Classifications

• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
  • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
  • D06P5/30—Ink jet printing
• • 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
  • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
  • D06M11/07—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof
  • D06M11/11—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with halogen acids or salts thereof
  • D06M11/155—Halides of elements of Groups 2 or 12 of the Periodic Table
• • 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
  • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
  • D06M11/58—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides
  • D06M11/64—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides with nitrogen oxides; with oxyacids of nitrogen or their salts
• • 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
  • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
  • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
  • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
  • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
  • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
  • D06P1/60—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing polyethers
  • D06P1/607—Nitrogen-containing polyethers or their quaternary derivatives
  • D06P1/6073—Nitrogen-containing polyethers or their quaternary derivatives containing CON=, OCON=, SO2N=, OSO2N= groups
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
  • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
  • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
  • D06P1/60—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing polyethers
  • D06P1/613—Polyethers without nitrogen
  • D06P1/6131—Addition products of hydroxyl groups-containing compounds with oxiranes
  • D06P1/6133—Addition products of hydroxyl groups-containing compounds with oxiranes from araliphatic or aliphatic alcohols
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
  • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
  • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
  • D06P1/60—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing polyethers
  • D06P1/613—Polyethers without nitrogen
  • D06P1/6136—Condensation products of esters, acids, oils, oxyacids with oxiranes
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
  • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
  • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
  • D06P1/673—Inorganic compounds
  • D06P1/67333—Salts or hydroxides

Definitions

• This invention pertains to inkjet printing on a pretreated fabric with colored inkjet inks, and to a pretreatment solution for the fabric that allows high quality printing thereon.
• Digital printing methods such as inkjet printing are becoming increasingly important for the printing of textiles and offer a number of potential benefits over conventional printing methods such as screen printing.
• Digital printing eliminates the set up expense associated with screen preparation and can potentially enable cost effective short run production.
• Inkjet printing furthermore allows visual effects such as tonal gradients and infinite pattern repeat sizes that cannot be practically achieved with a screen printing process.
• the present invention relates to a method of digitally printing a textile comprising the steps of:
• the aqueous pretreatment solution used in the method of the present invention is a nonionic latex polymer and a multivalent cationic salt solution. More preferably, the preteatment solution comprises a solution of a nonionic latex polymer and a multivalent cationic salt in water.
• aqueous pretreatment solution it is understood that the nonionic latex polymer may be present as a stable emulsion in the pretreatment solution.
• other ingredients can be added. Ingredient percentages mentioned hereinafter are weight percent based on the total weight of the final solution, unless otherwise indicated.
• the pretreatments for the particular textile substrates include a nonionic urethane latex polymer in order to further enhance the adhesion and/or washfastness of ink colorants on the textile fabric substrates. It has been found that pretreated textiles including a nonionic latex polymer provide high color density and saturation relative to untreated textiles, superior print quality relative to untreated textiles, reduction of wicking or bleeding relative to untreated textiles, and enhanced ink absorption relative to untreated textiles. Furthermore, the pretreatment formulations provide a washfast printed image when printing via an ink jet printing process.
• the nonionic latex polymer is added to the multivalent cationic salt solution.
• the nonionic latex polymer/multivalent cationic salt solution must be stable as a solution or as a stable emulsion to permit the treatment of the fabric. If the nonionic latex polymer gels, or its emulsion is not stable in the presence of the multivalent cationic salt solution, than it cannot be used as a pretreatment additive.
• a screening test for whether a nonionic latex polymer is stable in the presence of the multivalent cationic salt solution is to mix a 10 wt % polymer (on a dry basis) and a 15 wt % of calcium nitrate tetrahydrate and observe whether the solution/emulsion is stable. The stability observations at ambient temperature ( ⁇ 25 °) and at 10 minutes and 24 hours.
• the nonionic component must lead to a stable nonionic latex polymer/multivalent cationic solution/emulsion
• the nonionic component of the latex polymer comes from the incorporation of a nonionic reactant into the latex polymer.
• the nonionic components include ethylene oxide derivatives.
• the incorporation can occur during the polymerization step, or before after the polymerization step which prepares the latex polymer.
• the substitution can take the form of incorporating a glycol with sufficient (-CH 2 -CH 2 O-) n units to impart the nonionic stability.
• a polyurethane may have an alkyl polyethylene glycol incorporated into the nonionic polyurethane.
• the nonionic component can be the main component in nonionic latex polymer, as long as its properties satisfy the stability test described above.
• the nonionic latex polymer may also have ionic components incorporated into the polymer.
• ionic components such as acids may be used in the polyurethane reaction and a specific acid example is dimethylolpropionic acid.
• a specific acid example is dimethylolpropionic acid.
• the ionic component can be less than about 10 milliequivalents/gram, where the milliequivalent/gram calculation is based on the dry polymer weight.
• the solution should comprise sufficient nonionic latex polymer content and other ingredients to provide adequate infusion and/or coating of the textile with the nonionic latex polymer.
• the pretreatment will comprise at least about 0.5 wt% of the nonionic latex polymer, and amounts can be used up to the solution/emulsion stability of the particularly nonionic latex polymer utilized.
• the pretreatment will comprise from about 1 wt% to about 24 wt% of the nonionic latex polymer.
• the pretreatments of this invention comprise one or more multivalent cations.
• the effective amounts needed in a particular situation can vary, and some adjustment, as provided for herein, will generally be necessary.
• Multivalent indicates an oxidation state of two or more and, for an element "Z", are typically described as Z 2+ , Z 3+ , Z 4+ and so forth.
• multivalent cations may be referred to herein as Z x .
• the multivalent cations are substantially soluble in the aqueous pretreatment solution and preferably exist (in solution) in a substantially ionized state so that they are in a form where they are free and available to interact with textile when the textile is exposed to the pretreatment solution.
• Z x in the invention is selected from multivalent cations of the following elements: Mg, Ca, Sr, Ba, Sc, Y, La, Ti, Zr, V, Cr, Mn, Fe, Ru, Co, Rh, Ni, Pd, Pt, Cu, Au, Zn, Al, Ga, In, Sb, Bi, Ge, Sn, Pb.
• the multivalent cation comprises at least one of Ca, Ba, Ru, Co, Zn and Ga.
• the multivalent cation is Ca.
• Z x can be incorporated into pretreatment solution by addition in a salt form or by addition in an alkaline form and used as a base in the adjustment of the pretreatment solution pH.
• the associated anionic material can be chosen from any common anionic material, especially halides, nitrates and sulfates.
• the anionic form is chosen so that the multivalent cation is soluble in the aqueous pretreatment solution.
• the multivalent cationic salts can be used in their hydrated form.
• One or more multivalent cationic salts may be used in the pretreatment solution.
• the preferred multivalent cation salts are calcium chloride, calcium nitrate, calcium nitrate hydrate and mixtures thereof.
• the balance of the pretreatment solution is water.
• a pretreatment solution consisting essentially of a nonionic latex polymer and a multivalent cationic salt in water is particularly suitable.
• the solution should comprise sufficient multivalent cation content and other ingredients to provide adequate infusion and/or coating of the textile with the multivalent cation.
• the pretreatment will comprise at least about 0.5 wt% of the multivalent cation salt, and amounts can be used up to the solubility limits of the particularly multivalent cation salt or salts utilized.
• the pretreatment will comprise from about 1 wt% to about 30 wt% of the multivalent cation salt.
• the combined total weight of the nonionic latex polymer and the multivalent cation salt can be up to about 45 wt %.
• the fabric to be pretreated can be any fabric suitable for printing with colored inkjet inks, and is preferably a fabric comprising cotton and/or cotton blends.
• Application of the pretreatment to the fabric can be any convenient method and such methods are generally well-known in the art.
• One example is an application method referred to as padding.
• padding In padding, a fabric is dipped in the pretreatment solution, then the saturated fabric is passed through nip rollers that squeeze out the excess solution. The amount of solution retained in the fabric can be regulated by the nip pressure applied by the rollers.
• Other pretreatment techniques include spray application wherein the solution is applied by spraying on the face or face and back of the fabric. Spraying can be limited to the digitally printed area of the printed fabric. An example of where this limited spraying would be particularly applicable is in the digital printing of an image on preformed textile articles such as, for example, a T-shirts, caps, undergarments and like clothing articles.
• the pretreatment solution is applied to the fabric in a wet pick-up of from about 0.20 to about 7.5 grams of multivalent cationic (calcium) salt per 100 grams of fabric, more preferably from about 0.60 to about 6.0 grams of multivalent cationic (calcium) salt per 100 grams of fabric, and still more preferably from about 0.75 to about 5.0 grams of multivalent cationic (calcium) salt per 100 grams of fabric.
• the fabric may be dried in any convenient manner.
• the fabric is preferably substantially dry at the time of printing, such that the final percent moisture is (approximately) equal to the equilibrium moisture of the pretreated fabric at ambient temperature.
• the absolute amount of moisture in the fabric can vary somewhat depending on the relative humidity of the surrounding air.
• nonionic latex polymer remaining in the fabric after drying provide an interactive material that will interact with the inkjet inks during printing and improve the properties such washfastness of the printed textile It will be appreciated that sufficient nonionic latex polymer must be present to effect a brighter/more colorful image. Routine optimization will reveal appropriate nonionic polymer latex levels for a given printer and colored ink or ink set.
• the multivalent salts remaining in the fabric after drying provide an interactive material that will interact with the inkjet inks during printing. It will be appreciated that sufficient multivalent salts must be present to effect a brighter/more colorful image. Routine optimization will reveal appropriate multivalent salt levels for a given printer and colored ink or ink set.
• the colorant used for printing the colored image may be a dye or a pigment.
• Dyes include disperse dyes, reactive dyes, acid dyes and the like.
• the colored inkjet inks and the white ink are preferably aqueous and do not contain components that are UV curable.
• Pigmented inks are preferred.
• Pigmented inkjet inks suitable for use in the present method typically comprise a pigment dispersed in a vehicle.
• Aqueous vehicles are preferred.
• the pigment ink comprises an anionically stabilized pigment dispersed in an aqueous vehicle.
• aqueous vehicle refers to a vehicle comprised of water or a mixture of water and at least one water-soluble organic solvent (co-solvent) or humectant. Selection of a suitable mixture depends on requirements of the specific application, such as desired surface tension and viscosity, the selected colorant, and compatibility with substrate onto which the ink will be printed.
• water-soluble organic solvents and humectants include: alcohols, ketones, keto-alcohols, ethers and others, such as thiodiglycol, sulfolane, 2-pyrrolidone, 1,3- dimethyl-2-imidazolidinone and caprolactam; glycols such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, trimethylene glycol, butylene glycol and hexylene glycol; addition polymers of oxyethylene or oxypropylene such as polyethylene glycol, polypropylene glycol and the like; triols such as glycerol and 1,2,6-hexanetriol; lower alkyl ethers of polyhydric alcohols, such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl, diethylene glycol monoethyl ether; lower dialky
• An aqueous vehicle will typically contain about 30% to about 95% water with the balance (i.e., about 70% to about 5%) being the water-soluble solvent.
• Ink compositions typically contain about 60% to about 95% water, based on the total weight of the aqueous vehicle.
• Pigments suitable for being used with the multivalent pretreatment of the textile are those generally well-known in the art for aqueous inkjet inks.
• pigments are stabilized by dispersing agents, such as polymeric dispersants or surfactants, to produce a stable dispersion of the pigment in the vehicle.
• dispersing agents such as polymeric dispersants or surfactants
• SDP self-dispersible pigments
• Dispersed dyes are also considered pigments as they are insoluble in the aqueous inks used herein.
• anionic pigment dispersion an anionic surface charge
• carboxylic acid (carboxylate) groups ionizable carboxylic acid (carboxylate) groups.
• the pigments which are stabilized by added dispersing agents may be prepared by methods known in the art. It is generally desirable to make the stabilized pigment in a concentrated form.
• the stabilized pigment is first prepared by premixing the selected pigment(s) and polymeric dispersant(s) in an aqueous carrier medium (such as water and, optionally, a water-miscible solvent), and then dispersing or deflocculating the pigment.
• an aqueous carrier medium such as water and, optionally, a water-miscible solvent
• the dispersing step may be accomplished in a 2-roll mill, media mill, a horizontal mini mill, a ball mill, an attritor, or by passing the mixture through a plurality of nozzles within a liquid jet interaction chamber at a liquid pressure of at least 5,000 psi to produce a uniform dispersion of the pigment particles in the aqueous carrier medium (microfluidizer).
• the concentrates may be prepared by dry milling the polymeric dispersant and the pigment under pressure.
• the media for the media mill is chosen from commonly available media, including zirconia, YTZ and nylon.
• the pigment concentrate may be "let down” into an aqueous system.
• “Let down” refers to the dilution of the concentrate with mixing or dispersing, the intensity of the mixing/dispersing normally being determined by trial and error using routine methodology, and often being dependent on the combination of the polymeric dispersant, solvent and pigment.
• the dispersant used to stabilize the pigment is preferably a polymeric dispersant.
• Either structured or random polymers may be used, although structured polymers are preferred for use as dispersants for reasons well known in the art.
• the term "structured polymer” means polymers having a block, branched or graft structure. Examples of structured polymers include AB or BAB block copolymers such as disclosed in US5085698 ; ABC block copolymers such as disclosed in EP-A-0556649 ; and graft polymers such as disclosed in US5231131 .
• Other polymeric dispersants that can be used are described, for example, in US6117921 , US6262152 , US6306994 and US6433117 .
• Polymer dispersants suitable for use in the present invention comprise both hydrophobic and hydrophilic monomers.
• hydrophobic monomers used in random polymers are methyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, benzyl methacrylate, 2-phenylethyl methacrylate and the corresponding acrylates.
• hydrophilic monomers are methacrylic acid, acrylic acid, dimethylaminoethyl(meth)acrylate and salts thereof. Also quaternary salts of dimethylaminoethyl(meth)acrylate may be employed.
• pigments may be selected to make the ink.
• the term "pigment” as used herein means an insoluble colorant.
• the pigment particles are sufficiently small to permit free flow of the ink through the inkjet printing device, especially at the ejecting nozzles that usually have a diameter ranging from about 10 micron to about 50 micron.
• the particle size also has an influence on the pigment dispersion stability, which is critical throughout the life of the ink. Brownian motion of minute particles will help prevent the particles from flocculation. It is also desirable to use small particles for maximum color strength and gloss.
• the range of useful particle size is typically about 0.005 micron to about 15 micron.
• the pigment particle size should range from about 0.005 to about 5 micron and, most preferably, from about 0.005 to about 1 micron.
• the average particle size as measured by dynamic light scattering is less than about 500 nm, preferably less than about 300 nm.
• the selected pigment(s) may be used in dry or wet form.
• pigments are usually manufactured in aqueous media and the resulting pigment is obtained as water-wet presscake.
• presscake form the pigment is not agglomerated to the extent that it is in dry form.
• pigments in water-wet presscake form do not require as much deflocculation in the process of preparing the inks as pigments in dry form.
• Representative commercial dry pigments are listed in previously incorporated US5085698 .
• the ink may contain up to approximately 30%, preferably about 0.1 to about 25%, and more preferably about 0.25 to about 10%, pigment by weight based on the total ink weight. If an inorganic pigment is selected, the ink will tend to contain higher weight percentages of pigment than with comparable inks employing organic pigment, and may be as high as about 75% in some cases, since inorganic pigments generally have higher specific gravities than organic pigments.
• Self-dispersed pigments can be used and are often advantageous over traditional dispersant stabilized pigments from the standpoint of greater stability and lower viscosity at the same pigment loading. This can provide greater formulation latitude in final ink.
• SDPs and particularly self-dispersing carbon black pigments, are disclosed in, for example, US2439442 , US3023118 , US3279935 and US3347632 . Additional disclosures of SDPs, methods of making SDPs and/or aqueous inkjet inks formulated with SDP's can be found in, for example, US5554739 , US5571311 , US5609671 , US5672198 , US5698016 , US5707432 , US5718746 , US5747562 , US5749950 , US5803959 , US5837045 , US5846307 , US5851280 , US5861447 , US5885335 , US5895522 , US5922118 , US5928419 , US5976233 , US6057384 , US6099632 , US6123759 , US6153001 , US6221141 , US6221142 , US62
• Titanium dioxide is also an example of a pigment that can be used, and is potentially advantageous because it is white in color. Titanium dioxide can be difficult to disperse in an ink vehicle that is compatible with an ink jet printer system. Those dispersions and/or ink vehicles that provide inkjet stable titanium dioxide can be used with the nonionic latex polymer and multivalent cation pretreated textile.
• a combination of a graft and block copolymers are used as co-dispersants for the titanium dioxide pigment, such as described in US 2005/0282928 .
• This combination of dispersants is effective in stabilizing titanium dioxide pigment slurries and, furthermore, provides enhanced stability in the ink formulations.
• Other preferred titanium dioxide ink jet inks are described in US 2007/0060670 .
• the white ink can be used in an ink set as a process color. Alternatively, it can be used as an underlayer to the colored image. When used in the underlayer scheme, the colored inks are printed within 60 minutes of printing the white ink to optimize the colored image on the textile. The use of white ink followed by colored inks is particularly useful with colored textiles.
• ingredients may be formulated into the inkjet ink, to the extent that such other ingredients do not interfere with the stability and jetability of the finished ink, which may be readily determined by routine experimentation.
• Such other ingredients are in a general sense well known in the art.
• surfactants are added to the ink to adjust surface tension and wetting properties.
• Suitable surfactants include ethoxylated acetylene diols (e.g. Surfynols® series from Air Products), ethoxylated primary (e.g. Neodol® series from Shell and Tomadol® series from Tomah Products) and secondary (e.g. Tergitol® series from Union Carbide) alcohols, sulfosuccinates (e.g. Aerosol® series from Cytec), organosilicones (e.g. Silwet® series from GE Silicons) and fluoro surfactants (e.g. Zonyl® series from DuPont).
• Surfactants are typically used in the amount of about 0.01 to about 5% and preferably about 0.2 to about 2%, based on the total weight of the ink.
• Polymers may be added to the ink to improve durability.
• the polymers can be soluble in the vehicle or dispersed (e.g. "emulsion polymer” or “latex”), and can be ionic or nonionic.
• Useful classes of polymers include acrylics, styrene-acrylics and polyurethanes.
• a particularly useful preferred binder additive is a crosslinked polyurethane as described in US20050182154 , the disclosure of which is incorporated by reference herein for all purposes as if fully set forth.
• Biocides may be used to inhibit growth of microorganisms.
• Buffers may be used to maintain pH.
• Buffers include, for example, tris(hydroxymethyl)-aminomethane ("Trizma” or “Tris”).
• EDTA ethylenediaminetetraacetic acid
• IDA iminodiacetic acid
• EPDHA ethylenediamine-di(o-hydroxyphenylacetic acid)
• NTA nitrilotriacetic acid
• DHEG dihydroxyethylglycine
• CyDTA trans-1,2- cyclohexanediaminetetraacetic acid
• DTPA dethylenetriamine-N,N,N',N", N"-pentaacetic acid
• GEDTA glycoletherdiamine-N,N,N',N'-tetraacetic acid
• GEDTA glycoletherdiamine-N,N,N',N'-tetraacetic acid
• the amount of vehicle in an ink is typically in the range of about 70% to about 99.8%, and more typically about 80% to about 99%. Colorant is generally present in amounts up to about 10%. If a white ink is used, the white pigment can be up 25 % in concentration. Percentages are weight percent of the total weight of ink.
• ingredients when present, generally comprise less than about 15% by weight, based on the total weight of the ink.
• Surfactants when added, are generally in the range of about 0.2 to about 3% by weight based on the total weight of the ink.
• Polymers can be added as needed, but will generally be less than about 15% by weight based on the total weight of the ink.
• Ink jet inks typically have a surface tension in the range of about 20 dyne/cm to about 70 dyne/cm at 25°C. Viscosity can be as high as 30 cP at 25°C, but is typically somewhat lower.
• the ink has physical properties are adjusted to the ejecting conditions and printhead design. The inks should have excellent storage stability for long periods so as not clog to a significant extent in an ink jet apparatus. Further, the ink should not corrode parts of the ink jet printing device it comes in contact with, and it should be essentially odorless and non-toxic.
• Preferred pH for the ink is in the range of from about 6.5 to about 8.
• ink set refers to all the individual inks or other fluids an inkjet printer is equipped to jet.
• the ink set comprises at least two differently colored pigmented inkjet inks, and optionally one may be a white pigmented inkjet ink as described above.
• the ink set comprises at least three differently colored pigmented inkjet inks, wherein at least one is a cyan pigmented inkjet ink, at least one is a magenta pigmented inkjet ink, and at least one is a yellow pigmented inkjet ink.
• the ink sets may contain additional differently colored inks, as well as different strength versions of the CMYKW and other inks.
• the inks sets of the present invention can comprise full-strength versions of one or more of the inks in the ink set, as well as "light” versions thereof.
• Additional colors for the inkjet ink set may include, for example, orange, violet, green, red and/or blue.
• the present method relates to digitally printing a pretreated textile substrate. Typically, this involves the following steps:
• Printing can be accomplished by any inkjet printer equipped for handling and printing fabric.
• Commercial printers include, for example, the DuPontTM ArtistriTM 3210 and 2020 printers, and the Mimaki TX series of printers.
• inks and ink sets are available for use with these printers.
• Commercially available ink sets include, for example, DuPontTM ArtistriTM P700 and P5000 series inks.
• the amount of ink laid down on the fabric can vary by printer model, by print mode (resolution) within a given printer and by the percent coverage need to achieve a given color.
• the combined effect of all these considerations is grams of ink per unit area of fabric for each color.
• ink coverage is preferably from about 5 to about 17 grams of ink per square meter of fabric for colored inks (including black and white inks).
• a white ink is used as a background for the digitally printed image
• up to about twelve times more white ink may be used to obtain an enhanced final image.
• the white ink is initially printed onto the substrate in at least a portion of the area to be covered by the final image (the underprint portion), then the final image is printed at least over the underprint portion.
• the white ink can also be printed outside the boundaries of the final image (either as part of the initial background printing or subsequently as part of the image printing), for example, to generate a small, imperceptible boundary to the image, making the image appear to have a distinct boundary.
• the use of the white ink for printing a background for an image is particularly useful when printed onto colored (non-white) textiles.
• Fabric printed with colored inks will typically be post-treated according to procedures well-known in the textile printing art.
• the printed textiles may optionally be post processed with heat and/or pressure, such as disclosed in US20030160851 .
• Upper temperature is dictated by the tolerance of the particular textile being printed.
• Lower temperature is determined by the amount of heat needed to achieve the desired level of durability.
• fusion temperatures will be at least about 80°C and preferably at least about 140°C, more preferably at least about 160°C and most preferably at least about 180°C.
• Fusion pressures required to achieve improved durability can be very modest.
• pressures can be about 3 psig, preferably at least about 5 psig, more preferrable at least about 8 psig and most preferably at least about 10 psig. Fusion pressures of about 30 psi and above seem to provide no additional benefit to durability, but such pressures are not excluded.
• the duration of fusion is not believed to be particularly critical. Most of the time in the fusion operation generally involves bringing the print up to the desired temperature. Once the print is fully up to temperature, the time under pressure can be brief (seconds).
• DBTL dibutyltindilaurate
• DMPA dimethylol propionic acid
• EDA ethylene diamine
• IPDI isophoronediisocyanate
• TEA triethylamine
• TETA triethylenetetramine
• LHT polypropylene glycol triol, from Bayer and Desmophen C 1200 - a polyester carbonate diol from Bayer (Pittsburgh, PA) MPEG500 - Methyoxypolyethlene glycol from Dow Chemical (Midland, MI) Tegomer D-3403 - Polyether diol from Tego Chemie (Essen Germany)
• the flask temperature was raised to 50°C, then held at 50°C until NCO % was less than 2.03 %.
• Acetone (-310.0 g) was removed under vacuum, leaving a final dispersion of polyurethane with about 35.0% solids by weight and pH around 7.5.
• This polymer has 17 wt% or 3.9 meq. ethylene oxide unit.
• the flask temperature was raised to 50°C, then held for 30 minutes. 10 g DMPA followed by 7.5 g TEA was added to the flask via the addition funnel, which was then rinsed with 10 g acetone. The flask temperature was then raised again to 50°C and held at 50°C until NCO % was less than 1.25 %.
• Acetone was removed under vacuum, leaving a final dispersion of polyurethane with about 35.0% solids by weight and pH around 7.5.
• This polymer has 13wt% or 3.0 meq. ethylene oxide unit and 0.17 meq. COOH group.
• the flask temperature was raised to 50°C, then held for 30 minutes. 10 g DMPA followed by 7.5 g TEA was added to the flask via the addition funnel, which was then rinsed with 10 g acetone. The flask temperature was then raised again to 50°C and held at 50°C until NCO % was less than 1.47 %.
• Acetone was removed under vacuum, leaving a final dispersion of polyurethane with about 35.0% solids by weight pH around 7.5.
• This polymer has 11.3wt% or 2.6 meq. ethylene oxide unit and 0.18 meq. COOH group.
• the flask temperature was raised to 50°C, then held for 30 minutes. 15 g DMPA followed by 10 g TEA was added to the flask via the addition funnel, which was then rinsed with 10 g acetone. The flask temperature was then raised again to 50°C and held at 50°C until NCO % was less than 3.2 %.
• Acetone was removed under vacuum, leaving a final dispersion of polyurethane with about 35.0% solids by weight and pH around 7.5.
• This polymer has 7.4wt% or 1.7 meq. ethylene oxide unit and 0.27 meq. COOH group.
• This polymer has 3.9wt% or 0.09 meq. ethylene oxide unit and 0.042 meq. COOH group.
• the flask temperature was raised to 50°C, then held for 30 minutes.
• 30 g DMPA followed by 20 g TEA was added to the flask via the addition funnel, which was then rinsed with 10 g acetone.
• the flask temperature was then raised again to 50°C and held at 50°C until NCO % was less than 4.3 %.
• Acetone was removed under vacuum, leaving a final dispersion of polyurethane with about 35.0% solids by weight pH around 7.5.
• This polymer has 3.9wt% or 0.9 meq. ethylene oxide unit and 0.42 meq. COOH group.
• the flask temperature was raised to 50°C, then held for 30 minutes. 44.57 g DMPA followed by 25.2 g TEA was added to the flask via the addition funnel, which was then rinsed with 15.5 g acetone. The flask temperature was then raised again to 50°C and held at 50°C until NCO % was less than 1.23 %. This polymer has 0.36 meq. COOH group and no nonionic components.
• the Inventive Examples and Comparative Examples were tested for stability with a multivalent cationic salt solution.
• An amount of latex polymer to obtain 10 wt % in the final aqueous solution/emulsion was put into a beaker, the mixture stirred, then a 15 wt % calcium nitrate aqueous solution was added over about 5 minutes
• the dry polymer and the calcium nitrate tetrahydrate weight ratio was 10/15.
• the mixture was stirred for an additional 5 minutes. After 10 minutes and 24 hours, the solution/emulsion was observed for coagulation, gelling or other signs of instability.. If no coagulation was observed, it is rated compatible or stable.
• Table 1 Stability Test for Nonionic Latex Polymers with Multivalent Cationic Solution Inv Ex 1 Inv Ex 2 Inv Ex 3 Comp Ex 1 Comp Ex 2 Comp Ex 3 Stability with Calcium nitrate Compatible Compatible Compatible Coagulated Coagulated Coagulated Nonionic EO meq. 3.9 3.0 2.6 1.7 0.9 0 Anionic acid meq. 0 0.17 0.18 0.27 0.42 0.36
• the examples described below were done using an Epson 3000 ink jet printer, a Fast T-JetTM from US Screen Printing Institute (Tempe, AZ), the and prints were made on various substrates.
• the textile substrates used were 419 100 % cotton and 7409 65/35 polyester/cotton blend from Testfabrics Hanes Beefy T 100% cotton t-shirts, Hanes Heavy weight 100% cotton t-shirts, Hanes 50/50 polycotton cotton t-shirts, and a black fabric from Joann's Fabric (woven 100% cotton tweed). All test prints were fused at about 170°C for about 1 minute.
• Pigmented Inks were used for testing the nonionic latex polymer and multivalent cation pretreatment solution and comparison pretreatment formulations.
• the inks used were DuPontTM ArtistriTM P700 and P5000 series inks.
• the printed textile was tested for washfastness according to methods developed by the American Association of Textile Chemists and Colorists, (AATCC), Research Triangle Park, NC.
• AATCC Test Method 61-1996 "Colorfastness to Laundering, Home and Commercial: Accelerated ", was used.
• colorfastness is described as "the resistance of a material to change in any of its color characteristics, to transfer of its colorant(s) to adjacent materials or both as a result of the exposure of the material to any environment that might be encountered during the processing, testing, storage or use of the material.”
• Tests 2A and 3A were done and the color washfastness and stain rating were recorded. The ratings for these tests are from 1-5 with 5 being the best result, that is, little or no loss of color and little or no transfer of color to another material, respectively.
• Crock measurements were made using methodology described in AATCC Test Method 8-1996 .
• Pretreatment Solutions 1-6 Component (Wt%) as Calcium Nitrate Tetrahydrate as Calcium Nitrate Pretreatment Solution 1; Nonionic Latex Polymer Inv Ex 1 15 10.45 Pretreatment Solution 2; Nonionic Latex Polymer Inv Ex 2 15 10.45 Pretreatment Solution 3; Nonionic Latex Polymer Inv Ex 3 15 10.45 Pretreatment Solution 4*** 15 10.45 Comparative Pretreatment Solution 1 10 6.95 *** Pretreatment Solution 4 contains 10 % by weight (solids) of PermaxTM 200.
• Print Test Set A A 419 white cotton was printed with DuPontTM ArtistriTM P5000 CMYK Inks with various pretreatment conditions. Each example was pretreated by spraying the textile in an area about the same as the intended image to be printed, dried and printed with the Epson 3000 printer. The estimated amount of calcium nitrate hydrate on the T-shirt prior to printing was about 7.5 grams/square meter. 5 grams of nonionic latex polymer. Then the printed textile was fused at 170°C for 1 minute. The printed textile were tested for optical density, 2A and 3A wash fastness and wet and dry crock. Table 3 shows the results of this printing.
• Each pretreatment inventive example shows an improvement in optical density(OD), over the non pretreated sample and an improved washfastness and crock over the Comparison Pretreatment Solution example.
• Print Test Set B A 7409 polyester/cotton blend was printed with DuPontTM ArtistriTM P5000 CMYK Inks with various pretreatment conditions. Each example was pretreated by spraying the textile in an area about the same as the intended image to be printed, dried and printed with the Epson 3000 printer. The estimated amount of calcium nitrate hydrate on the T-shirt prior to printing was about 7.5 grams/square meter. 5 grams of nonionic latex polymer. Then the printed textile was fused at 170°C for 1 minute. The printed textile were tested for optical density, 2A and 3A wash fastness and wet and dry crock. Table 4 shows the results of this printing.
• Each pretreatment inventive example shows an improvement in optical density(OD), over the non pretreated sample and an improved washfastness and crock over the Comparison Pretreatment Solution example.

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• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Inorganic Chemistry (AREA)
• Ink Jet Recording Methods And Recording Media Thereof (AREA)
• Inks, Pencil-Leads, Or Crayons (AREA)
• Coloring (AREA)
• Treatment Of Fiber Materials (AREA)
• Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

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• 2006
  • 2006-09-15 US US11/521,992 patent/US20080092309A1/en not_active Abandoned
• 2007
  • 2007-09-14 EP EP07838417.9A patent/EP2059634B1/en active Active
  • 2007-09-14 JP JP2009528338A patent/JP5970152B2/ja active Active
  • 2007-09-14 WO PCT/US2007/020203 patent/WO2008033569A2/en not_active Ceased

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