EP1871947A1 - Composition for drop on demand finishing of a textile article - Google Patents
Composition for drop on demand finishing of a textile articleInfo
- Publication number
- EP1871947A1 EP1871947A1 EP06725251A EP06725251A EP1871947A1 EP 1871947 A1 EP1871947 A1 EP 1871947A1 EP 06725251 A EP06725251 A EP 06725251A EP 06725251 A EP06725251 A EP 06725251A EP 1871947 A1 EP1871947 A1 EP 1871947A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- finishing
- composition
- textile
- composition according
- nozzles
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
- D06M23/10—Processes in which the treating agent is dissolved or dispersed in organic solvents; Processes for the recovery of organic solvents thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
- B41J3/00—Typewriters or selective printing or marking mechanisms characterised by the purpose for which they are constructed
- B41J3/407—Typewriters or selective printing or marking mechanisms characterised by the purpose for which they are constructed for marking on special material
- B41J3/4078—Printing on textile
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06B—TREATING TEXTILE MATERIALS USING LIQUIDS, GASES OR VAPOURS
- D06B11/00—Treatment of selected parts of textile materials, e.g. partial dyeing
- D06B11/0056—Treatment of selected parts of textile materials, e.g. partial dyeing of fabrics
- D06B11/0059—Treatment of selected parts of textile materials, e.g. partial dyeing of fabrics by spraying
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
- D06M23/08—Processes in which the treating agent is applied in powder or granular form
Definitions
- the present invention relates to finishing textiles and more particularly to finishing of textiles by digital droplet deposition using drop-on-demand inkjet (DoD) techniques. It relates furthermore to finishing compositions specially adapted to this purpose and methods of performing such finishing.
- DoD drop-on-demand inkjet
- Textile upgrading is a totality of operations which have the purpose of giving textile the appearance and physical characteristics that are desired by the user. Textile upgrading comprises of, among other things, preparing, bleaching, optically whitening, colouring (dyeing and/or printing)and finishing a textile article.
- the conventional process for upgrading textile is built up (see figure 1) of a number of part -processes or upgrading steps, i.e. pre-treating the textile article (also referred to as the substrate), dyeing the substrate, coating the substrate, finishing the substrate and the post- treatment of the substrate.
- a known technique for printing textile is the so-called template technique. Ink is applied to cut-out leaves or elements, the templates, with which desired patterns such as letters and symbols can be applied to the substrate.
- Another known technique for printing textile is the so-called flatbed press technique, wherein the printed image lies in one plane with the parts of the print mould not forming a printing area.
- An example hereof is a so-called offset print, wherein the printing process takes place indirectly.
- dyeing of the substrate is another upgrading step.
- Dyeing is the application of a coloured chemical substance in a full plane, and then uniformly in one colour. Dyeing takes place at present by immersing the textile article in a dye bath, whereby the textile is impregnated with a coloured substance, visible on both sides of the substrate.
- Coating of a textile involves the application of a thin layer to the textile to endow it with particular functional properties such as to protect or increase the durability of the substrate.
- the usual techniques for applying a coating on solvent or water basis are the so-called “knife-over-roller", the “dip” and the “reverse roller” screen coaters.
- a solution, suspension or dispersion of a polymer substance in water is usually applied to the cloth and excess coating is then scraped off with a doctor knife.
- the coating formulation must be in a highly viscous, pasty form. For many functionalities, it is not possible to bring the formulation into such a viscous state without adversely affecting the functionality. This may be due to the fact that thickening agents are incompatible with the functional chemical.
- a further procedure sometimes employed for finishing of the textile is the use of immersion or bath techniques such as foularding.
- the textile is fully immersed in an aqueous solution containing the functional composition that is to be applied. Subsequent repeated cycles of drying, fixation and condensation are required to complete the operation. This leads to considerable use of resources, in particular water and energy.
- the solutions, suspensions or dispersions used for such techniques have low concentrations of the desired functional composition
- Each of the upgrading steps shown in figure 1 consists of a number of operations. Various treatments with different types of chemicals are required, depending on the nature of the substrate and desired end result.
- One drawback of the usual methods of upgrading is that per upgrading step (dyeing, coating, finishing) a number of cycles of unit operations have to be carried out to achieve the desired result.
- Three or more cycles of unit operations are often necessary for coating, which entails a relatively high environmental impact, a long throughput time and relatively high production costs.
- Four or more cycles of unit operations are even required for dyeing.
- the traditional dyeing process requires, for instance, the final operations of several rinses (washing and soaping) for rinsing out excess chemicals, such as thickening agent. Rinsing results in much use of water.
- a drying process usually consisting of a mechanical drying step using press-out rollers and/or vacuum systems followed by a thermal drying step, for instance using tenter-frames.
- a textile article may be printed using ink-jet printing technology to produce a graphic image.
- Ink formulations from the graphic (paper) printing sectors have generally been used for this purpose, as such formulations are already adapted for jet deposition.
- pigment particulate sizes and the relatively low solids contents make such inks most suitable for inkjet devices.
- Such formulations are not however entirely suitable for application to all textiles, in particular those where considerable absorbency is encountered.
- textile articles have been pretreated with a coating onto which ink droplets may be applied using standard graphic printing techniques.
- a process is known from United States patent No. US 4,702,742 in which a conventional printing device is used to print onto white cloth sheets.
- German patent application No. DE 199 30 866 in which both ink and a fixing solution are applied to a textile using a conventional inkjet head.
- Known methods are however only concerned with producing a graphic image and the formulations used are unsuitable as coatings for finishing.
- the previously proposed method provides the option of applying chemical substances in concentrated form and with an exact dosage.
- the desired upgrading result can thereby be achieved in only a single cycle of unit operations.
- the relatively high concentration with which the chemical substances may be applied furthermore makes interim drying almost unnecessary in many cases.
- the nozzles of the proposed device are preferably static with the textile being guided along the nozzles. This enables relatively high processing speeds and very precise forming of patterns.
- a further advantage of digital droplet deposition, is that it provides the possibility of on-demand delivery.
- compositions including antibiotics, moisture absorbents, water repellents, antistatic agents, ultraviolet rays absorbents, infrared rays absorbents, optical whitening agents, swelling agents, solvents, saponifier, embrittlement agent, inorganic granules, metal granules, magnetic material, flame retardants, resistance, oxidants, reducing agents, perfumes, etc.
- antibiotics moisture absorbents, water repellents, antistatic agents, ultraviolet rays absorbents, infrared rays absorbents, optical whitening agents, swelling agents, solvents, saponifier, embrittlement agent, inorganic granules, metal granules, magnetic material, flame retardants, resistance, oxidants, reducing agents, perfumes, etc.
- the document proposes impregnating a textile with a functional composition in the form of dots, wherein a mean dot diameter is 30 to 500microns and the occupied area ratio thereof is 3 to 95%.
- a mean dot diameter is 30 to 500microns and the occupied area ratio thereof is 3 to 95%.
- the document suggests the use of inkjet printing techniques, it identifies conventional inkjet devices as being unsuitable, in particular due to the high viscosity of traditional coating compositions.
- the document is concerned primarily with maintaining an identifiable droplet structure and preventing the droplets from running together.
- the document provides examples regarding the use of solutions but fails to address the problems of inkjet deposition of dispersions or suspensions.
- InkJet printers of various types are generally known for providing graphic images. Such printers may be desktop inkjet printers such as used in the office or home and are generally used for printing onto a particular type of paper substrate (printer paper), using small droplets ( ⁇ 20 pL) of water based inks containing colorants. Larger, industrial inkjet printers also exist for printing graphic images or date/batch codes onto products; these printers are typically printing onto non-porous substrates using solvent based inks containing colorants pigments. Such formulations are not however suitable for application to most textiles in particular due to lack of colour fastness.
- CIJ continuous inkjet
- droplets are continuously formed in the inkjet nozzles and are charged on ejection.
- an electric field droplets may either be directed to the substrate or into a gutter for recycling.
- Use of CIJ makes it possible to generate 64,000 to 125,000 droplets per second per droplet jet.
- This large number of droplets and a number of mutually adjacent heads over the whole width of the textile results in relatively high productivity and quality of the printed result.
- a production speed of the textile substrate of about 20 metres per minute can be realized.
- CIJ is most suitable in many cases, the cost per nozzle is generally very high.
- the specifications of the fluids to be jetted are sometimes very restrictive. They must be highly shear stable and must usually be provided with conductivity agents such as corrosive salts to enable them to carry the electrical charge. There is thus a desire to use other less complex and costly nozzles of the drop-on-demand (DoD) type.
- DoD drop-on-demand
- Drop-on-demand inkjets devices are generally well known from the desktop printing field. Such devices are in principle relatively cheap although high prices may be charged for commercial cartridges!
- Two main principles of droplet formation are common: piezoelectric actuation, whereby a droplet is formed by resonating the fluid using a piezo-actuator; and thermal actuation (bubblejet), where a droplet is ejected by local boiling of the fluid.
- Other methods of droplet formation are known that may be considered to fall into the category of DoD, such as valvejet devices in which miniature valves allow controlled passage of minute volumes of fluid.
- the principle of operation is in all cases that the droplet is formed in response to a signal. This is thus distinguished from the continuous CIJ devices in which droplets are continuously produced.
- a finishing composition for deposition by drop-on-demand inkjet technique onto a textile substrate comprising a dispersion or emulsion of a functional finishing agent in a vehicle, wherein the size of particles in the dispersion or emulsion of the finishing composition is less than 2 microns, preferably less than 1 micron, more preferably, less than 0.5 microns and not subject to flocculation or sedimentation.
- the term particle is intended to cover solid particles as present in dispersion and also liquid or gel like phases, present e.g. in emulsions.
- the maximum particle size will be less than 1 micron and for thermal inkjet may even need to be less than 0.5 microns. This value will also decrease as the percentage of solids in the composition increases above 10% but will rise as the nozzle diameter increases above 50 microns. It has been found most significant that the composition is of a consistent quality in this respect. Reference to particle size smaller than a given diameter is thus intended to refer to the D 99 diameter or better.
- the composition should also not be subject to flocculation or sedimentation. This is intended to mean that the composition does not form particles greater than the given values during prolonged use or when the inkjet device is idle during its normal use. It is understood that many compositions may e.g. form sediment during prolonged storage but that this may be overcome by appropriate mixing arrangements.
- finishing is understood to mean processes that use auxiliary chemicals to change the functionality of a textile substrate rather than merely providing it with a coloured design or changing its visual appearance as is the case with conventional inkjet printing use inks and dyes. These finishing techniques are meant to improve the properties of and/or add properties to the final product. In this context it is understood to encompass both coating and impregnating and also to include other physical treatments that upgrade the functionality of the substrate. A distinction will henceforth be made between colouring and finishing. Where necessary, finishing may be understood to exclude treatments involving the deposition of particles that are applied to the substrate only because of their absorption properties between 400 and 700 nm.
- finishing composition encompasses aqueous solutions, aqueous dispersions, organic solutions, organic dispersions, curable liquid mixtures and molten compounds that comprise an active component.
- the composition may be non-reactive with the substrate. In this manner, the composition may be applied to a greater diversity of substrates than would otherwise be the case.
- the term "textile” is intended to encompass all forms of textile article, including woven textiles, knitted textiles and non-woven textiles.
- the term is intended to exclude fibrous articles having two-dimensional rigidity such as carpets, paper and cardboard.
- These fibrous articles although sometimes referred to as textiles, are internally linked in such a way that they maintain a substantially fixed two-dimensional form. Even though they may be flexible in a third dimension they are not generally free to stretch or distort within the plane of the fibre layer, as is inherent in a true textile.
- the textile substrate is more than 100 meters in length and may be provided on a roll having a width of greater than 1 meter.
- Preferred textiles comprise cotton and/or other treated cellulosic fibres and also polyesters, polyamides, polyacrylnitril and acetates and triacetates or blends thereof.
- the vehicle is distilled, de-mineralized and/or de-ionized water, preferably present at between 60 and 90 wt% in the jetted composition.
- co-solvents include 2-pyrrolidone and isopropyl alcohol (IPA) present at from 0 to 5 wt%.
- IPA isopropyl alcohol
- the co-solvent can be used to improve the solubility of the finishing agent and/or its compatibility with other agents. Incompatibility between materials is a common formulation issue.
- the finishing composition may comprise a total of residual solids in the jetted composition of more than 5 wt%, preferably more than 10 wt% and most preferably more than 15 wt%. This leads to considerably less energy use in drying and allows greater operational speed. Particularly in the case of piezo actuation, up to 20% residual solids may be jetted. In this example, the particular case of UV cure formulations is excluded, as with these formulations effectively 100% residual solids may remain on curing.
- the finishing composition may further comprise a humectant, preferably present at from 10 to 35 wt% in the jetted composition.
- the humectant may usually be in the form of a low volatility, high boiling point liquid that helps prevent crusting of the nozzle when the jets are not active.
- Suitable humectants for water based systems include polyhydric alcohols, glycols, polyethylene glycol, polypropylene glycol, glycerol and n-methyl pyrrolidone (NMP). Although with certain formulations it may appear that more than 5% humectant is being used, it is in fact the case that the same material may also be present as a viscosity modifier.
- the finishing composition may also comprise a viscosity control agent, preferably present at from 2 to 15 wt% in the jetted composition.
- the viscosity control agent is an important ingredient for increasing reliability and quality as it controls the droplet formation and break up process.
- This material may also act as an active functional finishing component and provide some of the end user properties.
- high molecular weight polymers in solution should be avoided as their elasticity makes achieving jet break up difficult.
- a viscosity of 2 - 15 centipoise is desired for piezo -actuation while for thermal-actuation the viscosity may be 1 - 4 centipoise, as measured at the normal operating temperature of the nozzle.
- the finishing composition may further also comprise a wetting agent, preferably present at from 0.01 to 0.3 wt% in the jetted composition.
- the wetting agent may reduce foaming and may also lower surface tension and improve wetting of the nozzle and textile.
- Exemplary wetting agents include Surfynol 104E TM, Dynol 604 TM available from Air Products.
- the surface tension of the composition is between 28 and 50 dynes/cm. If the surface tension is too high, the composition will not wet the internals of the print head properly and will leave air pockets, which will prevent reliable deposition.
- the finishing composition may also comprise a biocide, preferably present at up to 0.5 wt% in the jetted composition.
- Biocide may be used to prevent bacteria growing in the composition - this may not be required if other components of the composition are sufficiently concentrated to kill bacteria.
- Exemplary biocides include l,2-benzisothiazolin-3- one and Proxel GXL TM available from Zeneca Specialties.
- a degassing agents may be included at up to 0.3 wt% in the jetted composition. This can serve to either scavenge or release dissolved gas from the fluid vehicle. Dissolved gas limits the maximum reliable firing frequency by creating air bubbles in the print head during operation.
- Suitable degassing agents include cyclohexanone oxime and Surfynol DF75 TM from Air Products.
- the finishing composition may further comprise a pH modifier, preferably present at up to 1 wt % in the jetted composition. The pH modifier may be used to maintain a pH at which the solids of the composition are stably dispersed, typically this is pH>7, so most modifiers are alkaline.
- the pH modifier may also be used to affect the chemistry of the interaction between the composition/active agent and the textile itself.
- Ammonia, morpholine, diethanolamine, triethanolamine and acetic acid are suitable pH modifiers.
- ceramic (piezo) print heads may be used.
- the finishing composition may also further comprise a corrosion inhibitor, preferably present at up to 0.2 wt% in the jetted composition. The corrosion inhibitor may be used to prevent unwanted ions present in the fluid (usually as impurities coming from the active components) from causing corrosion of the printer.
- the finishing agent may be chosen for its ability to withstand shear without degradation. In particular it should be stable to shear up to at least 10 5 /s. InkJet deposition is a high shear technique and so material that is not stable to high shear may decompose and block the print head nozzle and may also cease to provide the desired application or end user properties on the substrate. While the present invention is directed to finishing compositions for DoD, it is nevertheless considered that the composition would also be suitable for other jet deposition techniques where similar conditions of pressure, shear and nozzle diameter are encountered such as valve-jet type devices.
- the finishing composition may be based on a UV curable organic diluent, preferably present at between 75 and 95 wt% in the jetted composition.
- a UV curable organic diluent preferably present at between 75 and 95 wt% in the jetted composition.
- Such UV curing compositions are quick to cure, extremely durable and are ideal as carriers for certain agents.
- Particular to UV curing compositions is that substantially the total of the deposited material remains on the substrate.
- a solvent may however sometimes be added to reduce viscosity although generally this is not preferred.
- a photo-initiator may preferably be present at between 3 and 20 wt% in the jetted composition.
- the finishing agent may be any appropriate agent that can endow a functional property to a textile substrate.
- it may be selected from the group consisting of anti-static, anti-microbial, anti-viral, anti-fungal, medicinal, anti-pilling, non-crease, flame- retardant, water-repellant, UV-protective, deodorant, wear-resistant, slip -resistant, slip enhancing, grip enhancing, stain-resistant, oil resistant, adhesive, stiffening, softening, elasticity-enhancing, pigment-binding, conducting, semi-conducting, photo-sensitive, photovoltaic and light-emitting agents.
- a carrier for use with drugs or medicinal or biologically active agents a carrier may be used and the agent may be jetted at low temperatures e.g. below 4O 0 C.
- Appropriate carriers include cyclodextrines, fullerenes, aza-crown ethers and also polylactic acid (PLA). These carriers are ideally suited for attachment both to the textile fibres and to the agent. A review of these carriers is to be found in an article by Breteler et al. in Autex Research Journal, Vol. 2 No 4 entitled Textile Slow Release Systems with Medical Application, the contents of which are hereby incorporated by reference in their entirety. Alternate carriers, particularly for use with nano -particles, may be sol gel systems.
- the invention also relates to a method of finishing a textile comprising: providing a continuous supply of a textile substrate; providing an array of drop-on-demand inkjet nozzles; supplying to the nozzles a finishing composition according to any of the preceding claims; selectively dispensing the composition from the nozzles in a series of droplets to deposit a predetermined distribution of droplets onto the substrate.
- the droplets may be dispensed from the nozzles at velocities between 5 and 15 m/s.
- the droplets may also be formed at frequencies of up to 30 KHz.
- the nozzles are of the piezo-electric type. Such nozzles are considerably cheaper than CIJ nozzles and are less sensitive to the physical characteristics of the composition used. In particular, since greater viscosity and percentages of solids can be used, higher concentrations of active components may be jetted. Furthermore, for sensitive agents, less shear is encountered and by using ceramic heads, otherwise corrosive products may be handled.
- thermal print heads may be employed in cases where exposure to high temperature is not at issue or is otherwise desirable. It is also considered that valve-jet devices in which microscopic valves are periodically opened and closed could provide similar functionality when used with similar compositions as defined herein. [0042] Also preferable is that more than 30 g/m 2 of wet composition is deposited on the substrate, more preferably around 50 g/m 2 .
- the invention further relates to a textile article provided with a finish comprising the finishing composition as defined above or finished according to the method of the invention.
- Figure 1 shows a schematic block diagram of a conventional process for upgrading a substrate
- Figure 2 shows a view in perspective of a textile upgrader that may be employed in an embodiment of the invention
- Figure 3 is a schematic side view of the textile upgrader of figure 2;
- Figure 4 is a schematic front view of the textile upgrader of figure 2;
- Figure 5 is a cut-away schematic view of the textile upgrader of figure 2;
- Figure 6 is a schematic representation of a preferred sequence for performing the different treatment steps for upgrading
- Figure 7 is a schematic representation of an alternative preferred sequence for performing the upgrading steps;
- Figure 8 is a schematic representation of a further preferred sequence for performing the upgrading steps;
- Figure 9 shows a schematic view of a portion of woven textile coated according to the invention.
- Figure 10 is a cross section through the textile of Figure 9 along the line 10-10; and [0056] Figure 11 shows a similar view to Figure 10 through a coated textile in which smaller droplets have been used. DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS
- FIG. 2-5 show a textile upgrader 1 for performing the invention.
- the upgrader 1 is substantially as suggested in unpublished PCT application Nos PCT/EP2004/010732 and PCT/EP2004/010731 but uses drop on demand (DoD) finishing nozzles instead of continuous inkjet (CIJ) nozzles.
- Textile upgrader 1 is built up of an endless conveyor belt 2 driven using electric motors (not shown). On conveyor belt 2 can be affixed a textile article T for transport in the direction of arrow Pl along a housing 3 in which the textile undergoes a number of operations.
- the textile may be released and discharged in the direction of arrow P2.
- a large number of nozzles are arranged in housing 3.
- the nozzles are arranged on successively placed parallel beams 14.
- a first row 4, a second row 5, a third row 6 and so on are thus formed.
- the number of rows is variable (indicated in figure 5 with a dotted line) and depends among other factors on the desired number of operations.
- the number of nozzles per row is also variable and depends among other things on the desired resolution of the designs to be applied to the textile.
- the effective width of the beams is about 1 m
- the beams are provided with 8 fixedly disposed inkjet heads 12, each having about 2550 nozzles of around 35 ⁇ m.
- Each of the nozzles can generate a stream of droplets of ink, dye or finishing composition.
- FIG 5 is indicated with dotted lines that the different heads 12 are connected (electrically or wirelessly) by means of a network 15 to a central control unit 16, which comprises for instance a micro -controller or a computer.
- the drive of the conveyor belt 2 is also connected to the control unit via network 15'.
- the control unit can now actuate the drive and the individual nozzles as required.
- Also arranged per row of nozzles 4-11 is a double reservoir in which the finishing composition or dye to be applied is stored.
- the first row of nozzles 4 is provided with reservoirs 14a, 14b
- the second row 5 is provided with reservoirs 15a, 15b
- the third row 6 is provided with reservoirs 16a, 16b and so on.
- the appropriate substance is arranged in at least one of the two reservoirs of a row.
- the different reservoirs are filled with appropriate substances and the nozzles disposed in different rows are directed such that the textile article undergoes the correct treatment.
- reservoir 14a of the first row 4 contains cyan- coloured ink
- reservoir 15a of the second row 5 contains magenta-coloured ink
- reservoir 16a of the third row 6 contains yellow-coloured ink
- reservoir 17a of the fourth row 7 contains black coloured ink.
- the textile article is provided in rows 4-7 with patterns in a dyeing/printing treatment using CIJ nozzles of 50 microns.
- the reservoirs of the three subsequent rows 8-10 contain one or more finishing compositions according to the present invention, with which the treated textile can be coated in three passages using DoD thermal inkjet nozzles of 35 microns.
- the reservoir of the eighth row 11 contains a further finishing composition with which the printed and coated textile can be finished.
- the nozzles are DoD thermal inkjets having openings of 30 microns.
- the textile article T is preferably treated at the position of the fifth to the eighth row with infrared radiation coming from light sources 13 in order to influence the coating and/or the finishing.
- Figure 7 shows another situation in which the textile undergoes another treatment sequence.
- the textile article T is first of all dyed by guiding the textile along the first row 4 and second row 5 of nozzles. These rows 4, 5 have nozzles of 70 microns and apply a relatively smooth coloured coating onto the textile.
- the dyed textile is then coated as above, whereafter the final finishing step is carried out in the sixth and seventh rows 9,10.
- the textile article is first of all guided along the first row 4 of nozzles.
- the nozzles in row 4 are of about 70 microns and provide a smooth full background colour to the textile over the full width.
- the textile article is subsequently guided along the second row 5 and third row 6 by means of the conveyor belt, wherein patterns are printed onto the prepared surface. Good definition can be achieved in the printing steps at rows 5 and 6 using fine nozzles of between 30 and 50 microns.
- the textile is then guided along the fourth to sixth rows 7-9 to coat the dyed and printed textile in three passages, whereafter a final finishing treatment step is performed in the seventh and eighth rows 10,11.
- first reservoirs 14a, 15a, 16a are for instance used in each case for a first type of textile, while the second reservoirs 14b, 15b, 16b are used for another type of textile.
- Formulation Man 10 was loaded into a Trident Ultrajet IITM 32/96 (faceplate has 32 channels, 3 nozzles per channel) and the formulation primed relatively easily.
- the jet break up and droplet formation at different drop size settings for formulation Man 10 were captured using a VisionJet OpticaTM system, which captures images of drop formation during the jetting process.
- a pulse width of 17 ⁇ s the standard setting for this print head
- two droplets formed a main drop and satellite
- one droplet formed the satellite and main drop merge.
- the formulation is jetted through DoD nozzles of 50 microns at room temperature, at a rate of 10 g/m2.
- the selection of these parameters allow the depth of penetration of the water repellent to be controlled such that the droplet comes to lie on the surface of the textile.
- After jetting the textile article is cured by exposure to UV-light.
- the resultant layer has a weight of approximately 10 g/m2.
- Figure 9 shows a schematic view of a portion of woven textile 100 on which four pixels 102 of a water repellent coating material have been deposited.
- a formulation based on Example 1 using Bayguard TM as the active ingredient is considered appropriate.
- the textile 100 comprises fibres 104 arranged in a mesh with mesh openings 106 between the fibres 104.
- the fibre spacing is approximately 40 microns and the pixels 102 each have a diameter of approximately 100 microns.
- each pixel 102 effectively covers at least four complete openings 106. Additionally, it can be seen that the pixels 102 do not form a completely closed coating in that a pore 108 is formed between adjacent pixels 102.
- Figure 10 is a cross section through the textile 100 of Figure 9 along the line 10-10. It can be seen that the pixels 102 are generally located on the surface of the textile, spanning the openings 106 between adjacent fibres 104. Because of the viscous nature of the coating substance, each pixel 102 partially maintains its shape and although the pixels 102 flow together in the overlap region, the individual pixels are still discernable. It can furthermore be seen that the coating substance forming the pixel 102 partially envelopes the fibres 104 on the coated surface to form a good bond therewith. The viscosity of the coating substance is chosen to ensure the correct degree of impregnation of the material.
- Figure 11 shows a similar view to Figure 10 taken through a textile 100 in which smaller droplets 110 of a coating substance have been applied.
- the droplets 110 are of a similar size to the mesh opening 106 and tend to pass into and even through the openings.
- the resultant effect is less homogenous than in the case of Figure 10. It may be used to introduce a finishing composition into the substrate rather than provide a surface finish.
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Materials Engineering (AREA)
- Ink Jet Recording Methods And Recording Media Thereof (AREA)
- Ink Jet (AREA)
- Coloring (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Treatment Of Fiber Materials (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GBGB0505894.6A GB0505894D0 (en) | 2005-03-22 | 2005-03-22 | Composition for dot on demand finishing of a textile article |
PCT/EP2006/060969 WO2006100277A1 (en) | 2005-03-22 | 2006-03-22 | Composition for drop on demand finishing of a textile article |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1871947A1 true EP1871947A1 (en) | 2008-01-02 |
EP1871947B1 EP1871947B1 (en) | 2016-05-25 |
Family
ID=34531685
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP06725251.0A Not-in-force EP1871947B1 (en) | 2005-03-22 | 2006-03-22 | Composition for drop on demand finishing of a textile article |
Country Status (7)
Country | Link |
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US (1) | US20090045372A1 (en) |
EP (1) | EP1871947B1 (en) |
JP (1) | JP2008537573A (en) |
ES (1) | ES2587080T3 (en) |
GB (1) | GB0505894D0 (en) |
TW (1) | TW200700609A (en) |
WO (1) | WO2006100277A1 (en) |
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KR101453885B1 (en) | 2013-06-10 | 2014-11-03 | 주식회사 지오스에어로젤 | System for permeating textile and method for manufacturing textile using thereof |
KR101473813B1 (en) | 2013-07-15 | 2014-12-17 | 주식회사 지오스에어로젤 | Injection system for functional solution for textile and method for manufacturing textile using thereof |
KR101485784B1 (en) | 2013-07-24 | 2015-01-26 | 주식회사 지오스에어로젤 | Insulation composition with airogel for improving insulation and soundproof, and method for producting insulation textile using thereof |
GB201707428D0 (en) * | 2017-05-09 | 2017-06-21 | Applied Graphene Mat Plc ] | Composite moulding materials |
DE102020101672A1 (en) | 2019-03-22 | 2020-09-24 | Suchy Textilmaschinenbau Gmbh | Process for the refinement of flat textile materials by finishing |
TWI718692B (en) * | 2019-10-03 | 2021-02-11 | 財團法人紡織產業綜合研究所 | Sprayable water-repellent ink for digital printing process of fabric and water-repellent fabric |
ES2875698B2 (en) * | 2020-05-07 | 2022-03-11 | Torrecid Sa | COMPOSITION OF FLAME RETARDANT HYBRID INK |
JP2022103961A (en) | 2020-12-28 | 2022-07-08 | セイコーエプソン株式会社 | Printing apparatus, printing system, and printing method for printing apparatus |
EP4403693A1 (en) * | 2023-01-17 | 2024-07-24 | Swiss Performance Chemicals AG | Textile finishing process |
Family Cites Families (51)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR1568638A (en) * | 1967-06-13 | 1969-05-23 | ||
DE2020445A1 (en) * | 1970-04-27 | 1971-11-18 | Jakob Messner | Process for the continuous multicolored printing of web material using nozzles for the application of color and according to the speed controlled dye pressure and controlled nozzle open time |
BE790231A (en) * | 1971-10-18 | 1973-02-15 | North American Mills | APPARATUS AND METHOD FOR APPLYING COLORANTS AND / OR CHEMICALS TO FABRICS, TABLECLOTHS, STRANDS OR THREADS |
US3955032A (en) * | 1972-10-25 | 1976-05-04 | White Chemical Corporation | Flame retardants for natural and synthetic materials |
US4170883A (en) * | 1976-05-17 | 1979-10-16 | Milliken Research Corporation | Printing of pattern designs with computer controlled pattern dyeing device |
US4324117A (en) * | 1980-06-11 | 1982-04-13 | The Mead Corporation | Jet device for application of liquid dye to a fabric web |
US4434632A (en) * | 1981-11-25 | 1984-03-06 | Milliken Research Corporation | Apparatus for the application of liquids to moving materials |
DE3216731A1 (en) * | 1982-05-05 | 1983-11-10 | Hoechst Ag, 6230 Frankfurt | METHOD AND DEVICE FOR CONTINUOUSLY DYEING AND / OR FINISHING WET, TEXTILE PRODUCTS |
JPS62501301A (en) * | 1984-11-12 | 1987-05-21 | コモンウエルス サイエンテイフイツク アンド インダストリアル リサ−チ オ−ガナイゼイシヨン | Droplet flow alignment technology for jut printers |
US4702742A (en) * | 1984-12-10 | 1987-10-27 | Canon Kabushiki Kaisha | Aqueous jet-ink printing on textile fabric pre-treated with polymeric acceptor |
JPS61152874A (en) * | 1984-12-24 | 1986-07-11 | 東レ株式会社 | Fiber sheet having functional agent applied thereto in dot form |
US4650694A (en) * | 1985-05-01 | 1987-03-17 | Burlington Industries, Inc. | Method and apparatus for securing uniformity and solidity in liquid jet electrostatic applicators using random droplet formation processes |
EP0202656B1 (en) * | 1985-05-21 | 1992-01-29 | Canon Kabushiki Kaisha | Ink jet printing method |
JPS6385156A (en) | 1986-09-26 | 1988-04-15 | 東レ株式会社 | Method for obtaining functionaly pattern by ink jet method |
JPH0696333B2 (en) | 1987-11-21 | 1994-11-30 | 工業技術院長 | Method of adding information to cloth |
GB9100614D0 (en) * | 1991-01-11 | 1991-02-27 | Xaar Ltd | Ink composition |
US5310778A (en) * | 1992-08-25 | 1994-05-10 | E. I. Du Pont De Nemours And Company | Process for preparing ink jet inks having improved properties |
WO1995001404A1 (en) * | 1993-07-01 | 1995-01-12 | Tonejet Corporation Pty. Ltd. | Liquid ink jet ink |
JPH07258982A (en) * | 1994-03-17 | 1995-10-09 | Kanebo Ltd | Ink jet printed fabric having high fastness |
JPH08333531A (en) * | 1995-06-07 | 1996-12-17 | Xerox Corp | Water-base ink-jet ink composition |
US6255363B1 (en) * | 1995-09-29 | 2001-07-03 | 3M Innovative Properties Company | Liquid inks using a gel organosol |
US5853861A (en) * | 1997-09-30 | 1998-12-29 | E. I. Du Pont De Nemours And Company | Ink jet printing of textiles |
US6372842B1 (en) * | 1998-06-15 | 2002-04-16 | The Lubrizol Corporation | Methods of using an aqueous composition containing a water-soluble or water-dispersible synthetic polymer and resultant compositions formed thereof |
JP2000218930A (en) * | 1999-01-29 | 2000-08-08 | Mitsubishi Paper Mills Ltd | Ink jet recording cloth |
US6210474B1 (en) * | 1999-06-04 | 2001-04-03 | Eastman Kodak Company | Process for preparing an ink jet ink |
JP2001181987A (en) * | 1999-12-22 | 2001-07-03 | Canon Inc | Ink-jet printing method |
US6406138B1 (en) * | 2000-04-20 | 2002-06-18 | Hewlett-Packard Company | Polymer systems for high quality inkjet printing |
EP1152080A3 (en) * | 2000-04-29 | 2003-05-02 | Deotexis Inc. | Textile material and method for its production |
JP3863746B2 (en) | 2000-09-06 | 2006-12-27 | セーレン株式会社 | Inkjet printing method and inkjet printed matter |
US6538048B1 (en) * | 2000-11-09 | 2003-03-25 | Eastman Kodak Company | Ink jet printing method |
CA2425945C (en) * | 2000-11-09 | 2010-01-26 | 3M Innovative Properties Company | Weather resistant, ink jettable, radiation curable, fluid compositions particularly suitable for outdoor applications |
US6713542B2 (en) * | 2000-12-18 | 2004-03-30 | Cool Dot Ltd. | Method for producing a flame resistant cellulosic sheet material |
WO2002064877A2 (en) * | 2001-01-30 | 2002-08-22 | The Procter & Gamble Company | Coating compositions for modifying surfaces |
JP2002275769A (en) * | 2001-03-16 | 2002-09-25 | Seiren Co Ltd | Cloth for ink-jet dyeing and method for producing the same |
JP2002370443A (en) * | 2001-06-14 | 2002-12-24 | Konica Corp | Re-transferable ink jet image receiving sheet and image forming method |
DE10133643A1 (en) * | 2001-07-11 | 2003-01-30 | Clariant Gmbh | Water-based colorant preparations |
JP4261846B2 (en) * | 2001-09-28 | 2009-04-30 | キヤノン株式会社 | Method and apparatus for driving liquid discharge head |
US6644784B2 (en) * | 2001-10-30 | 2003-11-11 | Hewlett-Packard Development Company, L.P. | Method and apparatus for printing with multiple recording mechanisms |
JP2003201428A (en) * | 2002-01-07 | 2003-07-18 | Konica Corp | Disperse dye ink and method for ink-jet recording using the disperse dye ink |
TWI227724B (en) * | 2002-03-12 | 2005-02-11 | Rohm & Haas | Non-pigmented ink jet inks |
JP2003282704A (en) * | 2002-03-26 | 2003-10-03 | Nec Electronics Corp | Method of manufacturing semiconductor device with dual-damacene |
JP2003328283A (en) | 2002-05-02 | 2003-11-19 | Upepo & Maji Inc | Image-printed fiber product |
JP2004018544A (en) * | 2002-06-12 | 2004-01-22 | Konica Minolta Holdings Inc | Ink for ink-jet printing and method for ink-jet printing |
EP1371697A3 (en) * | 2002-06-14 | 2004-01-02 | Rohm And Haas Company | Polymeric binders for inkjet inks |
US6764173B2 (en) * | 2002-09-27 | 2004-07-20 | Eastman Kodak Company | Inkjet printing method |
JP4513255B2 (en) * | 2002-12-03 | 2010-07-28 | セイコーエプソン株式会社 | Ink composition for inkjet printing, printing method, and printed fabric |
JP2004276436A (en) * | 2003-03-17 | 2004-10-07 | Konica Minolta Holdings Inc | Recording device |
JP2004292468A (en) * | 2003-03-25 | 2004-10-21 | Konica Minolta Holdings Inc | Ink for inkjet, its manufacturing method, inkjet recording method using the same, and inkjet printing method |
JP4425559B2 (en) * | 2003-04-08 | 2010-03-03 | セーレン株式会社 | Fabric inkjet recording method and recording apparatus using ultraviolet curable ink |
US6811596B1 (en) * | 2003-05-12 | 2004-11-02 | Xerox Corporation | Phase change inks with improved image permanence |
JP2005047990A (en) * | 2003-07-30 | 2005-02-24 | Seiko Epson Corp | Inkjet ink for textile printing and inkjet textile printing method |
-
2005
- 2005-03-22 GB GBGB0505894.6A patent/GB0505894D0/en not_active Ceased
-
2006
- 2006-03-21 TW TW095109631A patent/TW200700609A/en unknown
- 2006-03-22 WO PCT/EP2006/060969 patent/WO2006100277A1/en not_active Application Discontinuation
- 2006-03-22 ES ES06725251.0T patent/ES2587080T3/en active Active
- 2006-03-22 US US11/886,876 patent/US20090045372A1/en not_active Abandoned
- 2006-03-22 JP JP2008502415A patent/JP2008537573A/en active Pending
- 2006-03-22 EP EP06725251.0A patent/EP1871947B1/en not_active Not-in-force
Non-Patent Citations (1)
Title |
---|
See references of WO2006100277A1 * |
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EP1871947B1 (en) | 2016-05-25 |
GB0505894D0 (en) | 2005-04-27 |
ES2587080T3 (en) | 2016-10-20 |
WO2006100277A1 (en) | 2006-09-28 |
TW200700609A (en) | 2007-01-01 |
US20090045372A1 (en) | 2009-02-19 |
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