EP1914343B1 - Beschichtung zur Behandlung von Substraten für Tintenstrahldruck , Verfahren zur Behandlung dieser Substrate und daraus hergestellte Artikel - Google Patents

Beschichtung zur Behandlung von Substraten für Tintenstrahldruck , Verfahren zur Behandlung dieser Substrate und daraus hergestellte Artikel Download PDF

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Publication number
EP1914343B1
EP1914343B1 EP08001346A EP08001346A EP1914343B1 EP 1914343 B1 EP1914343 B1 EP 1914343B1 EP 08001346 A EP08001346 A EP 08001346A EP 08001346 A EP08001346 A EP 08001346A EP 1914343 B1 EP1914343 B1 EP 1914343B1
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EP
European Patent Office
Prior art keywords
aqueous coating
coating formulation
substrate
total solids
substrates
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EP08001346A
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English (en)
French (fr)
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EP1914343A2 (de
EP1914343A3 (de
Inventor
Alison Salyer Bagwell
Kelly Dean Branham
Mary Elizabeth Farris-Kister
Leonard Eugene Zelazoski
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Kimberly Clark Worldwide Inc
Kimberly Clark Corp
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Kimberly Clark Worldwide Inc
Kimberly Clark Corp
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Priority claimed from US09/702,093 external-priority patent/US6838498B1/en
Application filed by Kimberly Clark Worldwide Inc, Kimberly Clark Corp filed Critical Kimberly Clark Worldwide Inc
Publication of EP1914343A2 publication Critical patent/EP1914343A2/de
Publication of EP1914343A3 publication Critical patent/EP1914343A3/de
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    • 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
    • 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
    • D06P1/38—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 reactive dyes
    • 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
    • D06P1/52—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 synthetic macromolecular substances
    • D06P1/5207—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • D06P1/5214—Polymers of unsaturated compounds containing no COOH groups or functional derivatives thereof
    • D06P1/5242—Polymers of unsaturated N-containing compounds
    • 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
    • D06P1/52—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 synthetic macromolecular substances
    • D06P1/5264—Macromolecular compounds obtained otherwise than by reactions involving only unsaturated carbon-to-carbon bonds
    • D06P1/5278—Polyamides; Polyimides; Polylactames; Polyalkyleneimines
    • 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
    • D06P1/64—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 low-molecular-weight organic compounds without sulfate or sulfonate groups
    • D06P1/642—Compounds containing nitrogen
    • D06P1/649—Compounds containing carbonamide, thiocarbonamide or guanyl groups
    • D06P1/6491—(Thio)urea or (cyclic) derivatives
    • 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
    • D06P1/6735—Salts or hydroxides of alkaline or alkaline-earth metals with anions different from those provided for in D06P1/67341

Definitions

  • the present invention relates to coatings for treating ink jet printable substrates, which are intended to receive images when printed by ink jet printing devices.
  • the present invention relates to coatings for treating textile substrates for ink jet printing, methods for treating said substrates, and articles produced therefrom. Such methods facilitate the use of such substrates in commonly available ink jet or laser printing devices, such as wide or narrow format ink jet and laser printers
  • Ink jet printing is a non-impact and non-contact printing method in which an electronic signal controls and directs droplets or a stream of ink that can be deposited on a wide variety of substrates.
  • Ink jet printing is extremely versatile in terms of the variety of substrates that can be treated, as well as the print quality and the speed of operation that can be achieved.
  • ink jet printing is digitally controllable. For these reasons, ink jet methodology has been widely adopted for industrial marking and labeling.
  • ink jet methodology has also found widespread use in architectural and engineering design applications, medical imaging, office printing (of both text and graphics), geographical imaging systems (e.g., for seismic data analysis and mapping), signage, in display graphics (e.g., photographic reproduction, business and courtroom graphics, graphic arts), and the like.
  • ink jet printing has now also been used to create an image on a variety of textile substrates.
  • the use of ink-jet printing to create an image on textile fabrics has allowed for the rapid visualization of an aesthetic design on fabric without the use of expensive and often wasteful screen printing techniques.
  • Such ink-jet printing methodology allows a designer or production facility to visualize a finished design in significantly less time than is usually necessary to bum a screen image of the design by typical screen printing methodology.
  • textile substrates also poses specific problems when printing or imaging via ink jet print methods, which are not found with common ink jet substrates (e.g. paper or coated paper).
  • the textile fibers can vary widely in composition, with each composition presenting a unique set of conditions for acceptable printing of the substrate.
  • cotton substrates may be very absorbent, such as in the case of aqueous-based inks.
  • ink is ejected from the ink channel of an ink jet printing device, it is rapidly absorbed into the fibers of the cotton substrate. Since these fibers are much larger than the fibers typically found in paper substrates, the color density or appearance of color brightness is signficantly diminished due to the lack of retention of the colorant at the surface of the fibers.
  • bleeding, mottle of the print pattern, and loss of image sharpness or clarity can often result from printing on the textile fabric itself.
  • synthetic fibers such as polyester may be poorly wet by the aqueous inks and such inks may be only retained in the interstitial spaces between the fibers. This limited ink retention also causes the print-quality related problems outlined above.
  • the permanence of the printed image on textile fabrics is often achieved commercially by some post-printing curing process such as heating, steaming, or chemical fixation. These processes tend to be inefficient, requiring further washing and drying steps to remove unfixed colorant from the fabric. It is therefore desirable to enhance the permanence of the printed image on ink jet printable substrates, either in the presence or absence of a post-printing curing process step.
  • Polymeric materials are typically used commercially to modify the properties of both natural and synthetic textile fibers and substrates. These polymeric treatments may alter textile appearance or hand, reduce shrinking, reduce flammability, or alter other properties of the fiber or substrate. Treatments may even be employed to enhance the ease of printing and/or print performance when commercial printing processes, such as rotary screen printing, are employed.
  • polyethylene oxide has been used to pretreat a starting cloth material so as to create an adequate textile substrate for ink-jet printing.
  • U.S. Patent number 5,781,216 to Haruta et al. the use of polyethylene oxide treated textile substrates are described as being highly capable of providing images of great color depth with sufficient brightness and sharpness, but free of objectionable color bleed. While Haruta discloses such a polyethylene oxide pretreatment with a cationizing agent, to thereby enhance the coloring ability of images, Haruta requires such treatment to thereafter be cured by additional heating, washing and drying steps.
  • EP 0605730 discloses printed cloths.
  • the cloths are preferably pretreated before being dyed to prevent bleeding of the dye liquid.
  • Such a treatment may involve a softening and water repellant agent.
  • Fixing agents such as sodium carbonate or sodium bicarbonate, hydrotropes and sizing agents may also be used.
  • Urea is listed as one possible hydrotrope and water soluble quaternized cationic polymers are listed as possible sizing agents.
  • imbibing solutions with sodium bicarbonate, sodium carbonate and urea are also known.
  • Such imbibing solutions are typically used by textile mills in ink pastes along with other additives such as thickeners, and not in conjunction with coating treatments on the textile substrates themselves prior to being printed.
  • the ink pastes are then rotary screen printed down onto the fabric substrates.
  • an ink jet paste delivery system can not be used for ink jet printing because of the physical constraints of the ink jet printer technology.
  • the salts in the pastes will corrode the ink jet printer heads.
  • Use of ink pastes are also a wasteful process. Furthermore, even with the use of such pastes in a convention screen printing process, the process experiences a large amount of dye wash off following printing.
  • ink jet printable substrate coatings and treatment methods which provide for high optical density with a minimum amount of bleeding on the substrate during and after imaging from ink jet printers.
  • ink jet printable substrate treatment methods which can be applied to textile fabric substrates.
  • methods for treating fabrics for receiving ink-jet ink formulations which methods allow for improved colorfastness and color intensity in a wide variety of textile substrates.
  • substrates which are not dependent upon an ink curing step for construction.
  • the color density and quality of the printed image, and the adhesion properties and/or colorfastness of acid and reactive dye-based ink jet ink formulations when applied to a variety of ink jet printable substrates can be improved by treating the substrates with coating formulations used in conjunction with imbibing solutions.
  • a wide array of textile fabric substrates can be treated to improve the colorfastness and washfastness of ink jet ink formulations.
  • the treatment formulations include an aqueous coating formulation containing solids and comprising a cationic polymer or copolymer, a cationic or non-ionic fabric softener, urea and either sodium bicarbonate, sodium carbonate, or a combination thereof for reactive dye based inks.
  • the treatment formulations include % cationic polymers or copolymers, and 5-20 % fabric softeners.
  • the formulations may also include 0-80% of a polymeric latex binder so as to increase washfastness. These percentages are based on solids. Total solids content for the formulations typically range from 10-50 %.
  • cationic polymer coatings in conjunction with a separate imbibing solution of either sodium bicarbonate or sodium carbonate and urea for reactive dye classes may be used.
  • the present methods provide pathways to the fixation of dyes, irrespective of chemical class or textile fabric substrate, and do so without the need of any further ink curing process beyond drying under ambient conditions.
  • efficacy of post printing processes such as steaming or curing may be enhanced by such formulations, reducing dye waste and further enhancing color vibrancy.
  • fixation of pigment or colorant may be enhanced by these formulations.
  • aqueous coatings and methods to improve the adhesion properties and/or colorfastness/color density and washfastness of ink jet printable substrates in the absence of a heating or post treatment curing step said methods including treating a textile substrate with an aqueous coating formulation including cationic polymers or copolymers and cationic or non-ionic fabric softeners.
  • the method comprises treating a textile substrate with an aqueous coating formulation including 5-95 % cationic polymers or copolymers, and 5-20 % fabric softeners. As has been stated earlier, these percentages are percent of total solids, unless otherwise stated.
  • the percent of the total solids is calculated by dividing the dry parts value for a particular component by the total dry parts of all of the components of the formulation.
  • the present invention is further directed to a treated ink jet printable substrate wherein the treatment comprises an aqueous coating formulation of cationic polymers or copolymers and cationic or non-ionic fabric softeners.
  • a desirable embodiment of the present invention is a treated ink jet printable substrate wherein the aqueous coating treatment comprises 5-95 % cationic polymers or copolymers, and 5-20 % fabric softeners.
  • the cationic copolymers function in the formulation to attract and fix oppositely charged anionic dye molecules to the substrates, and in particular, textile fabric substrates.
  • the polymers or copolymers may contain reactive residues or groups capable of crosslinking to the textile fibers, with themselves, or with other components present in the formulation.
  • Such cationic resins may incorporate charge groups in the main polymer chains or polymer backbones, or as side groups in the polymer chains.
  • An exemplary list of the structural formulas of such cationic polymers are illustrated in Figs. 1A-1C .
  • the cationic polymers for use in the coatings may include but are not limited to, polymers and copolymers of diallyldialkyammonium monomers such as diallyldimethylammonium chloride, cationic acrylate and acrylamide such as acryloxyethyldimethylammonium chloride or acrylamidoethyldimethylammonium chloride monomers, quartemized vinylpyridine such as methyl vinylpyridine chloride, and polyalkylamine polymers and copolymers.
  • Co-monomers in such systems may consist of ones which modify the flexibility, hydrophobicity, or mechanical properties of the polymer molecule.
  • reactive and/or self-condensing monomers may be included to enhance adhesion to the textile fiber or other components in the formulation.
  • cationic polymers with charged groups in the main chain include epihalohydrin-amine polymers such as RetenTM 204 LS and KymeneTM 557 LX polymers of Hercules Incorporated, of Wilmington, Delaware.
  • a specific example of a preferred cationic polymer resin is CP 7091 RV available from ECC International of Roswell, Georgia, with CP 7091 RV being a poly(diallyldimethlammonium chloride-co-diacetone acrylamide).
  • Suitable fabric softeners which may be used in accordance with the present inventive coatings/methods include, but are not limited to, Varisoft 222 of the Witco Corporation of Greenwich, Connecticut, Adogen 432 also of the Witco Corporation, Accosoft 550-75 of the Stepan Company of Northfield, Illinois, Alubrasoft Super 100 and Alubrasoft 116 of the BASF Corporation, Specialty Chemicals Division of Mt. Olive, New Jersey, and Ahcovel Base N-62 of ICI Surfactants or Hodgson Texiles Chemical of Mt. Holly, North Carolina.
  • the fabric softeners are cationic or nonionic and provide the attributes of print quality and image brightness to the printed textile substrate.
  • the fabric softener most suitable to a particular textile fabric substrate varies by fabric substrate. For instance, it has been found that the fabric softener Varisoft 222 performs better with cotton/banner fabric samples while Adogen 432 performs better with nylon/lycra samples.
  • the previously described coating treatments or formulations for ink jet printable substrates also include a latex binder in order to further enhance the adhesion and/or waterfastness of colorants on the textile fabric substrates. It has been found that coated ink jet receptive substrates including a latex binder provide high color density and saturation, superior print quality, reduction of wicking or bleeding, and enhanced ink absorption. Furthermore, the coating or treatment formulations provide a waterfast printed image when printing via an ink jet printing process, without the necessity of post-printing curing steps such as heating, steaming, chemical fixation, or radiation.
  • the present invention is also directed to a treated ink jet printable substrate wherein the treatment comprises an aqueous coating formulation of cationic polymers or copolymers, cationic or non-ionic fabric softeners, and a latex binder.
  • the treatment comprises an aqueous coating formulation of cationic polymers or copolymers, cationic or non-ionic fabric softeners, and a latex binder.
  • a desirable embodiment of the present invention is a treated ink jet printable substrate wherein the aqueous treatment formulation comprises 5-95 % cationic polymers or copolymers, 5-20 % fabric softeners and 0-80% latex binder.
  • the treatment or coating formulations in this alternate embodiment consist primarily of cationic polymers and copolymers, cationic or non-ionic fabric softeners and a water-insoluble polymer in the form of a latex dispersion or emulsion.
  • the treating formulation may include 0-80 % polymeric latex binder depending on the textile fabric substrate.
  • the latex reinforcing polymers may be either nonionic or cationic.
  • the latex materials may include vinylacetate, ethylene-vinylacetate, acrylate, styrene, and styrene-acrylate resins and other cationic or nonionic latexes. These resins may include reactive or self cross-linking groups in addition to inherent cationic functionality.
  • the aqueous coating formulations may also include other additives which effect the appearance or tactile properties of the finished substrate, such as optical brighteners. It should be recognized that all of the stated percentages are based on solids unless otherwise noted. Total solids content for the formulations typically range from 5-50 %, but desirably range from 5-32 %. More desirably the total solids content for the formulations range from 25-28 %.
  • Treatment formulations (compositions) for the textile substrates are made by adding the above components from stock solutions or dispersions, or as solids where appropriate, and mixing to homogeneity.
  • Application of the treatment formulation to the textile substrates may be carried out by any known means to those having ordinary skill in the art.
  • fabric substrates may be treated by a standard padding (dip and squeeze) method and dried in a forced air oven, although any suitable drying means of textiles known to those skilled in the art may be employed.
  • a textile substrate 20 is unwound from the incoming roll 30 and is then dipped in a saturator tank/bath 40 for sufficient time for it to become saturated with the treating formulation.
  • the textile substrate is then run through a pressurized nip roll set 44 and 48.
  • the pressure on the rolls should be in the range of 69-828 KPa (10-120 psig) but desirably in the range of 69-448,5 KPa (10-65 psig), depending on the type of textile fabric substrate utilized, and the total solids content of the treatment formulations used.
  • the pressurized nip rolls squeeze the coating evenly onto the substrate so as to penetrate the surface of the substrate.
  • the rolls may be either rubber or steel, however a set of rolls in which at least one roll being rubber is desirable.
  • the textile substrate is coursed through a drying means 50.
  • the drying means may include a tenter frame for holding the textile substrate, and may itself encompass multiple consecutive drying means depending on the nature of the substrate to be dried.
  • the drying temperature is desirably in the range from 200° F to 325° F (93.3 to 162.8° C), desirably between 220 to 250° F (104.4 to 121.1 °C).
  • the typical time for drying is between about 30 seconds and 3 minutes.
  • the finished treated textile substrate is taken up on a wind up roll 52.
  • the textile substrate may be rolled up for storage or moved to a second lamination process in preparation for ink jet printing.
  • the textile substrate may be laminated to a carrier backing for ease of printing.
  • dry pick-up ratios of the textile substrate may vary from 0.5% to 50%. Desirably, the dry pick-up ratios may vary from 3 to 20%. More desirably, the dry pick-up ratios may vary from 6 to 15%.
  • Wet pick-up ratios for the textile substrates are typically between 30-150%. Desirably such wet pick-up ratios are between 80-120%. Desirably for Dacron banners, the wet pick up ratios are between 40-120 %.
  • Substrates which may be treated in accordance with the present inventive methods are varied and include paper, fabric, films, and the like, although textile fabric substrates are preferred. Such fabrics may include cotton, silk, wool, polyester, rayon, nylon, and blends thereof.
  • the disclosed ink jet substrates may provide the benefits disclosed herein with or without further post-printing curing steps involving the use of heat, radiation or pressure. Ideally such treated substrates provide adhesion and/or colorfastness of the colorant with only ambient or room temperature curing or drying of the printed image. It should be noted however, that while not being necessary for the process, a post printing curing step may further enhance the colorfastness and washfastness of the printed image on the substrate.
  • the basis weight of the various fabrics which may be treated by these formulations may range from 2 ounces per square yard (osy) to 9 osy (67.7 to 304.65 g/m 2 ).
  • Dye classes which may be used in ink jet printers to be printed on such substrates include acid dyes, reactive dyes, direct dyes, azoic dyes, sulfur dyes, modified dyes, polymeric dyes, copolymerized dyes or other classes of colorants known to those skilled in the art. Furthermore, pigment colorants may be used in the ink jet printers to be printed on such substrates. Additionally, it has been found that when such substrate is printed with ink jet inks containing additives, such as those described in U.S. Application bearing Serial Number 09/109,681 filed July 2, 1998 and U.S. Patent No. 5,897,694 , such substrate treatments may be enhanced so as to provide enhanced colorfastness and washfastness.
  • such previously described treatment formulations may be used in a method to treat banner textile fabric substrates.
  • substrate materials include 100% cotton, 100 % polyester, !00% silk, nylon, rayon and blended materials, such as blends of cotton and polyester, as well as nonwoven materials.
  • an aqueous coating formulation including cationic polymers, fabric softeners, and latex polymer binders in accordance with the previously described methods enable the banner substrates to be ink jet printable, with improved colorfastness/ color density and washfastness, and with reduced color bleed.
  • the present invention is also directed to a treated ink jet printable banner substrate wherein the treatment comprises a formulation of cationic polymers or copolymers, fabric softeners, and an optional latex binder.
  • the treatment comprises a formulation of cationic polymers or copolymers, fabric softeners, and an optional latex binder.
  • a desirable embodiment of the present invention is a treated ink jet printable banner substrate wherein the aqueous treatment formulation includes between 5-95 % cationic polymers or copolymers, between 5-20 % cationic or non-ionic fabric softeners and between 0-80% latex binder.
  • articles produced by the above described methods employing treated textile substrates as described herein.
  • Such articles may include for example banners, wall coverings and other home furnishing products.
  • ink jet printed images applied to a treated substrate as described herein resists removal of said image from said substrate, even upon repeated contact of the printed substrate with water. Such repetitive contact can be the result of normal handling of an article, accidental exposure to liquid, and routine laundering of the article.
  • articles according to the present invention comprise a treated substrate containing an ink jet image printed thereon, the resulting image adheres sufficiently to said substrate to resist removal therefrom upon washing of said article.
  • Textile substrate samples were first printed with a test pattern using a commercial ink jet printer utilizing commercial ink jet inks containing acid, reactive, and/or direct dyes. Color density, color bleed, and print quality were evaluated on the samples as printed. These textiles included cotton poplin textile substrates. Duplicates of both sets of samples were washed using a washing method as described. Color density, color bleed, print quality or appearance, and color permanence were evaluated using the washed samples. Data from the preliminary examples is expressed in Table 1 which follows. TABLE 1 INK INK ADDITIVE FABRIC TREATMENT HEAT TREATMENT COLORFAST EVAL WATER DELTA E DETERG.
  • U.S. Silk, Inc. is located in New York, NY. Guilford Mills is located in New York, NY. Scher Fabrics, Inc. is located in New York, NY. Cranston Mills is located in Cranston, RI. Lorber Industries is located in Gardena, CA. Fisher Textiles is located in Indian Trail, NC.
  • treated textile samples were printed using an Encad Pro E (@ 300dpi) ink jet printer obtained from Encad Inc. of San Diego, California.
  • Encad GA, GS, or GO inks were employed using 4-Pass Enhanced Print Mode, that is with the printer passing over the textile substrate four times.
  • the printing head was preheated and option identified as number "7" was selected on the printer. This option enabled more ink to be expelled from the printer onto the substrates.
  • Dyes in the inks consisted of reactive, acid, and/or dyes and are described in Table 3 .
  • Sample sizes were typically 11 by 15 inches (27.9 by 38.1 cm). Additionally, a floral three color print, using lavender, green and magenta was used for testing, of approximately 14 by 25 inches (35.6 by 63.5 cm) in size. Where it was difficult to distinguish between shades of green, a neutral portion (that is free of ink) of the sample was also evaluated.
  • the textile samples were then washed out for approximately five minutes and then rinsed and drained of remaining water. Finally, the textile samples were rinsed with warm water (of between approximately 25-30° C) for two minutes followed by a rinse with cold water (of between approximately 10-20° C) for approximately one more minute.
  • a second set of samples were printed and subsequently steamed using a laboratory steamer for comparison.
  • a colorfastness level is characterized as poor, bleeding or wicking has occurred.
  • a washfastness level has been characterized as poor, the image has washed out.
  • a colorfastness and washfastness level has been characterized as good, the color vibrancy and image retention is noticeably better than the poor level.
  • the colorfastness and washfastness levels are characterized as excellent, the color properties and vibrancy are the highest levels with the highest color density.
  • Adhesive coated backing papers identified by the designation 6798 include a paper having a nominal thickness of 5.4 ml (137.2 ⁇ m), an initial adhesion value of 27 oz/in (300 g/cm), a tensile strength of 16 lbs/in (2.86 kg/cm), and an elongation capability of 10 %.
  • the batch formulations utilized are described in the following example summaries.
  • Example 1 (Comparative) Cationic copolymer CP 7091 RV (ECC International), poly(diallyldimethylammonium chloride-co-diacetone acrylamide), was obtained in a 49.3% stock solution in water. 20.3 wet parts of this solution (10 dry parts, or approximately 90-91 % of the total dry parts) were added to 70.3 parts water with mixing. 1.1 wet part ( 1 dry part, or approximately 9 % of the total dry parts) Varisoft® 222 fabric softener (90% in water) was added and the entire solution was mixed until homogeneous. This formulation was used to treat 100% cotton poplin via a padding application and dried as previously described.
  • ECC International ECC International
  • a portion of this sample was laminated to an adhesive paper carrier, printed with an ink jet printer and dried under ambient conditions.
  • the properties of the sample were evaluated for quality of the printed image, ink retention, and color density or saturation under the following conditions: 1) immediately after printing, 2) after printing and washing, 3) after printing and steaming, 4) after printing, steaming and washing.
  • the printed samples exhibited superior image quality with little or no bleed, excellent ink retention, and excellent color density. Samples that were steamed exhibited excellent enhancement of color and appearance. Washfastness of steamed samples and samples not post-treated with steam exhibited moderate retention of color when washed. This Example utilized the GS ink set.
  • Example 21 (Comparative) 50.7 wet parts cationic copolymer CP 7091 RV (ECC International) (49.3% in water)(25 dry parts, or approximately 18-19 % of the total dry parts) was added to 656.0 parts water with mixing.
  • Airflex® 540 latex emulsion (ethylene-vinyl acetate copolymer, 55.2% in water)(50 dry parts, or approximately 37 % of the total dry parts), 114.9 wet parts PrintRite® 591 acrylic emulsion (BF Goodrich, 43.5% in water)(50 dry parts, or approximately 37 % of the total dry parts), and 212.8 wet parts Varisoft® 222 fabric softener (4.7% in water) (10 dry parts, or approximately 7 % of the total dry parts) were added and the entire solution was mixed until homogeneous. This formulation was used to treat 100% cotton poplin via a padding application and dried. The sample was printed and evaluated using the process described in Example 1.
  • the printed sample exhibited superior image quality with little or no bleed, excellent ink retention, and excellent color density. Samples that were not steamed exhibited good retention of color when washed. Samples that were steamed exhibited excellent enhancement for color and appearance. Permanence of color to washing was dramatically increased compared to untreated samples. Little measurable washout was detected.
  • the Example utilized the GS ink set.
  • Example 24 (Comparative) 10.1 wet parts cationic copolymer CP 7091 RV (ECC International) (49.3% in water)(5 dry parts, or approximately 45 % of the total dry parts) was added to 48.8 parts water with mixing. 11.5 wet parts PrintRite® 591 acrylic emulsion (BF Goodrich, 43.5% in water)(5 dry parts, or approximately 45 % of the total dry parts), and 21.3 wet parts Varisoft® 222 fabric softener (4.7% in water) (1 dry part, or approximately 9 % of the total dry parts) were added and the entire solution was mixed until homogeneous. This formulation was used to treat 100% cotton poplin via a padding application and dried. The sample was printed and evaluated using the process described in Example 1.
  • the printed sample exhibited superior image quality with little or no bleed, excellent ink retention, and excellent color density. Samples that were not steamed exhibited good retention of color when washed. Samples that were steamed exhibited excellent enhancement for color and appearance. Washfastness of steamed samples and samples not post-treated with steam exhibited moderate retention of color when washed.
  • the Example utilized the GS ink set.
  • Example 28 (Comparative) 10.1 wet parts cationic copolymer CP 7091 RV (ECC International) (49.3% in water)(5 dry parts, or approximately 45 % of the total dry parts) was added to 51.2 parts water with mixing. 9.1 wet parts Airflex® 540 latex emulsion (ethylene-vinyl acetate copolymer, 55.2% in water)(5 dry parts, or approximately 45 % of the total dry parts), and 21.3 wet parts Varisoft® 222 fabric softener (4.7% in water)(1 dry part, or approximately 9 % of the total dry parts) were added and the entire solution was mixed until homogeneous. This formulation was used to treat 100% cotton poplin via a padding application and dried.
  • ECC International ECC International
  • the sample was printed and evaluated using the process described in Example 1.
  • the printed sample exhibited superior image quality with little or no bleed, excellent ink retention, and excellent color density. Samples that were not steamed exhibited good retention of color when washed. Samples that were steamed exhibited excellent enhancement for color and appearance. Permanence of color to washing was dramatically increased compared to untreated samples.
  • the Example utilized the GS ink set.
  • the present invention relates to treatments/coating formulations and related methods for treating textile substrates which enhance the color brilliance, adhesion, and/or waterfastness/detergentfastness of inkjet reactive dye, acid dye, and pigment based inks on textile fabric substrates when textile post treatment is desired (i.e. a heating step, such as steaming, oven heating, ironing, or other form of curative step), which utilizes an imbibing solution in conjunction with a substrate coating.
  • an imbibing solution shall mean a solution used to saturate a fabric such that it penetrates the interstitial spaces of the fabric.
  • the coating solution ( or treatment, as has earlier been described) itself may include the imbibing solution, or in the alternative, the coating solution and imbibing solution may be applied in separate application steps.
  • the treatment or coating formulations in the present invention consist primerily of cationic polymers, cationic or non-ionic fabric softeners, and other additives similar to those previously described.
  • an imbibing solution is used to further treat the fabric substrate.
  • an imbibing solution consisting of either sodium bicarbonate or sodium carbonate and urea, (for added color brilliance with post-treatment) is used with a aqueous coated fabric treatment.
  • the imbibing solution is desirably applied at a level of between 5-20 % by weight, more desirably 5-10 % by weight, depending on fabric type, and by using a standard saturation/padding method.
  • the sodium bicarbonate, sodium carbonate, or combination is present in the imbibing/coating solution in an amount between 3 and 10 percent of the total solids.
  • the urea is present in the combined imbibing/coating solution in an amount between 5 and 12 percent of the total solids.
  • Other additives may be included in the combined coating/imbibing solution such as wetting agents, and defoamers. If additives are present in the formulation, they are desirably present in an amount between 0.1 and 1 percent of the total solids.
  • the wetting agent Q2-511 may be included in the combined coating/imbibing solution.
  • dye fixatives may also be included in the coating formulation at less than 5 % of the total solids.
  • the sodium bicarbonate/sodium carbonate is also desirably present in an amount between 30 and 40 percent of the total solids.
  • the urea is present in the separate imbibing solution in an amount between 50 and 70 percent solids.
  • the imbibing solution may also include a wetting agent in solution as well as other additives in the same amounts as the prior embodiment.
  • Water is present in solution in an amount between 10 and 90 percent of the solution.
  • this imbibing solution embodiment is desirably used with the reactive colorant classes, including those which may be applied via ink jet printing processes such as the monochlorotriazines and/or vinyl sulfones.
  • Textile substrates for use with the treatment methods may include cotton, silk, linen, polyester, rayon, nylon, and blends thereof.
  • reactive dyes are used for cotton substrates
  • acid dyes are used for silk and nylon substrates.
  • the coating treatment and fixation treatment imbibing solution
  • the invention allows for the fixation of classes of dyes on substrates that they are not normally associated with, or which would not be done commercially because the fixation is not normally facile or efficient.
  • the disclosed ink jet receptive substrates that have been further treated with an imbibing solution provide high color density and saturation, superior print quality, reduction of wicking or bleeding, and enhanced ink absorption.
  • the coating or treatment formulations provide a color enhanced waterfast/detergentfast printed image when printed with an ink jet printing process with post-printing treatment steps, such as heating, steaming, chemical fixation, or radiation curing.
  • post-printing treatment steps such as heating, steaming, chemical fixation, or radiation curing.
  • a series of coatings were created including cationic polymers, fabric softeners, latex binders, other additives and water.
  • the coatings are identified below with the respective content percentages. It should be noted that certain coatings included an imbibing solution within their formulation while others did not, and an imbibing solution was therefore utilized in a separate application step. Batch sizes are expressed in grams.
  • Type C Separate Imbibing Solution referred to as Type C for use with cotton fabrics
  • Dyeset concentrations Polyamines
  • Dyeset Conc concentrations obtained from Sybron Chemicals of Wellford, South Carolina, along with Dyeset NOZ and Dyeset NFS.
  • Such materials are dye fixatives for reactive dyes.
  • the Q2-5211 which is a wetting agent, was obtained from Dow Coming.
  • the sodium bicarbonate can be obtained from VWR of Norcross, Georgia and Baker Chemical, and the Urea can be obtained from Baker Chemical.
  • Type H for cotton fabrics.
  • each of the samples were exposed on half of their area to D65/10° illuminant (standard day light) to determine whether any yellowing occurs.
  • a sample of each was also printed using the TX-1500 printer of Encad and a reactive ink set available from Kimberly-Clark Printing Technology, Inc. of Escondido, California under the designations 17960-17970.
  • the fabric sample Prior to printing, the fabric sample was first laminated to a backing as has been previously described in the first example set.
  • Examples of reactive dyes used included reactive blue 49 and black 5 available from companies such as DyStar and BASF corporation.
  • the reactive dye sets utilize vinyl sulfones and monochlorotriazines.
  • Type A was demonstrated to work well only after it had been steamed. Exposing Type A to a water wash was acceptable before steaming but detergent wash demonstrated considerable washout. Type B was demonstrated to work well without steaming but had some redepositing problems onto the fabric. Type C was demonstrated as having the most washout of all samples tested without steaming and having a visually impaired appearance. After steaming the results for Type C were very much improved.
  • Type D demonstrated positive results across all samples but failed the water spot test and printed samples. Only after washing and/or after steam and washing did Type D sample pass water spot testing. Type E demonstrated very acceptable results with water spotting occurring on printed sample only. Type E demonstrated poor results in detergent washing with no post processing steps. Type F demonstrated positive visual appearances as did Type H samples. Type G samples failed most testing. Types I, J and K each demonstrated relatively the same positive results, although type K was shown to be a better performer in terms of appearance and washability.
  • the water spot test comprised AATTC Test Method 104-1994. Essentially in this test, a drop of water is placed on a substrate and then rubbed down using a glass rod. The substrate is then observed to see if a water spot remains after the water dries. If a white circle appears then a water spot is considered to have been left.
  • reactive dye ink sets may be used with these coatings including those available from Kimberly-Ctark Printing Technology, Inc. under the designations, TXCR-500 Black, TXCR-520 Red, TXCR-523 Medium Red, TXCR-526 Scarlet, TXCR-530 Orange, TXCR-540 Yellow, TXCR-545 Golden Yellow, TXCR-550 Green, TXCR-560 Turquoise, TXCR-565 Medium Turquoise, TXCR-570 Blue, and TXCR-580 Gray. These reactive dye ink sets were tested with the above coatings by printing them through a Colorspan DM XII 12-color printer/ 600 dpi.
  • acid dye ink sets may be used with acid dye fixation solutions (Imbibing solutions).
  • Textile substrates which can use the acid dye sets include ones such as those with fibers that are dyeable with acid dyes, blended yams, as long as the ratio is at least 15% between nylon and other material such as Lycra, and polyamides.
  • Such acid dye sets are available from Kimberly-Clark Printing Technology, Inc. under the designation 17972-17975.
  • Additional acid dye sets are available from Kimberly-Clark Printing Technology, Inc. under the designations 7287-20-2 Black, 7287-27-2 Gray, 6869-184-5 Violet, 7287-21-1 Blue, 7287-24-2 Lt.
  • an inkjet solution to a conventional screen printing process using acid dyes and a treated substrate is provided.
  • Providing a digital alternative to this market will greatly reduce the cost for the manufacturing of textiles and will allow for more custom-made products to be produced.
  • Pigmented Ink Formulations may also be used in conjunction with the coating and imbibing solution formulations. It is particularly desirable to use Pigmented Ink formulations available from Kimberly-Clark Printing Technology, Inc. under the designations 17976-17979. Examples of the pigment dispersions include Acryjet Cyan, majenta, yellow and black available from the Rhom and Haas Corporation.
  • the coating/ treatment formulations and methods which are the subject of this invention provide ink jet printable textile substrates which possess characteristics of print and image quality, a noticeable color enhancement, color quality and density, ink retention capacity, and waterfastness and detergentfastness properties. Such formulations can be used to prepare articles of manufacture as previously described.

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  • Textile Engineering (AREA)
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Claims (18)

  1. Wässrige Beschichtungsformulierung, welche Feststoffe enthält, zum Verstärken von Bildvisualisierungen und zum Zurückhalten von Reaktivfarbstoff-basierten Farben, welche umfasst:
    a) Harnstoff
    b) einen Inhaltsstoff, welcher ausgewählt ist aus Natriumbikarbonat, Natriumkarbonat oder Kombinationen davon;
    dadurch gekennzeichnet, dass sie des Weiteren umfasst
    c) ein kationisches Polymer oder Copolymer; und
    d) einen kationischen oder nicht-ionischen Stoff-Weichmacher.
  2. Wässrige Beschichtungsformulierung gemäß Anspruch 1, wobei das kationische Polymer oder Copolymer in einer Menge von zwischen 5 bis 95% des Gesamtfeststoffgehalts vorhanden ist.
  3. Wässrige Beschichtungsformulierung gemäß Anspruch 1, wobei der Stoff-Weichmacher in einer Menge von zwischen 5 bis 20% des Gesamtfeststoffgehalts vorhanden ist.
  4. Wässrige Beschichtungsformulierung gemäß Anspruch 1, welche des Weiteren ein Latex-Bindemittel umfasst.
  5. Wässrige Beschichtungsformulierung gemäß Anspruch 4, wobei das Latex-Bindemittel in einer Menge von zwischen 0 bis 80% des Gesamtfeststoffgehalts vorhanden ist.
  6. Wässrige Beschichtungsformulierung gemäß Anspruch 1, wobei das Natriumbikarbonat, Natriumkarbonat oder eine Kombination davon in einer Menge von zwischen 3 und 10% des Gesamtfeststoffgehalts vorhanden ist.
  7. Wässrige Beschichtungsformulierung gemäß Anspruch 1, wobei der Harnstoff in einer Menge von zwischen 5 und 12% des Gesamtfeststoffgehalts vorhanden ist.
  8. Wässrige Beschichtungsformulierung gemäß Anspruch 1, welche des Weiteren Zusatzstoffe beinhaltet, welche ausgewählt sind aus der Gruppe beinhaltend Feuchtmacher, Entschäumer und Tenside.
  9. Wässrige Beschichtungsformulierung gemäß Anspruch 8, wobei die Zusatzstoffe in einer Menge von zwischen 0,1 und 1% des Gesamtfeststoffgehalts vorhanden sind.
  10. Verfahren zum Behandeln eines Substrats, um die Adhäsion, Farbfestigkeit und Waschbeständigkeit einer Reaktivfarbstoff-basierten Farbe zu verbessern, die mittels eines Druckers auf das Substrat gedruckt ist, und die einem Nachbehandlungsschritt nachfolgend dem Drucken ausgesetzt wird, wobei das Verfahren die Schritte umfasst:
    a) Bereitstellen eines Substrats; und entweder
    b1) Behandeln des Substrats mit einer wässrigen Beschichtungsformulierung, welche ein kationisches Polymer oder Copolymer, einen kationischen oder nicht-ionischen Stoffweichmacher, Harnstoff und einen Inhaltsstoff umfasst, welcher ausgewählt ist aus Natriumbikarbonat, Natriumkarbonat oder Kombinationen davon; oder
    b2) Behandeln des Substrats mit einer wässrigen Beschichtungsformulierung, welche ein kationisches Polymer oder Copolymer, und einen kationischen oder nicht-ionischen Stoffweichmacher umfasst; und dann Behandeln des Substrats mit einer wässrigen Aufsauglösung aus Harnstoff und einem Inhaltsstoff, welcher ausgewählt ist aus Natriumbikarbonat, Natriumkarbonat oder Kombinationen davon.
  11. Verfahren gemäß Anspruch 10, wobei in Schritt b1) das kationische Polymer oder Copolymer in der wässrigen Beschichtungsformulierung in einer Menge von zwischen 5 und 95% des Gesamtfeststoffgehalts vorhanden ist.
  12. Verfahren gemäß Anspruch 10, wobei in Schritt b1) der Stoffweichmacher in der wässrigen Beschichtungsformulierung in einer Menge von zwischen 5 und 20% des Gesamtfeststoffgehalts vorhanden ist.
  13. Verfahren gemäß Anspruch 10, wobei in Schritt b1) die wässrige Beschichtungsformulierung des Weiteren ein Latex-Bindemittel umfasst.
  14. Verfahren gemäß Anspruch 13, wobei das Latex-Bindemittel in der wässrigen Beschichtungsformulierung in einer Menge von zwischen 0 und 80% des Gesamtfeststoffgehalts vorhanden ist.
  15. Verfahren gemäß Anspruch 10, wobei in Schritt b1) der Harnstoff in der wässrigen βeschichtungsformulierung in einer Menge von zwischen 5 und 12% des Gesamtfeststoffgehalts vorhanden ist.
  16. Verfahren gemäß Anspruch 10, wobei in Schritt b1) das Natriumbikarbonat, Natriumkarbonat oder die Kombinationen davon in der wässrigen Beschichtungsformulierung in einer Menge von zwischen 3 und 10% des Gesamtfeststoffgehalts vorhanden sind.
  17. Verfahren gemäß Anspruch 10, welches des Weiteren die Schritte umfasst:
    c) Trocknen des Substrats;
    d) Drucken auf das Substrat mit einer Reaktivfarbstoff-basierten Farbe; und
    e) Nachbehandeln des bedruckten Substrats des Schritts d).
  18. Substrat, welches in Übereinstimmung mit dem Verfahren nach Anspruch 10 oder Anspruch 17 hergestellt wurde.
EP08001346A 1999-11-04 2000-10-31 Beschichtung zur Behandlung von Substraten für Tintenstrahldruck , Verfahren zur Behandlung dieser Substrate und daraus hergestellte Artikel Expired - Lifetime EP1914343B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US16374199P 1999-11-04 1999-11-04
US09/702,093 US6838498B1 (en) 1999-11-04 2000-10-30 Coating for treating substrates for ink jet printing including imbibing solution for enhanced image visualization and retention
EP00982068A EP1240383B1 (de) 1999-11-04 2000-10-31 Beschichtung von textilien für tintenstrahldruck

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EP00982068.9 Division 2000-10-31

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Publication number Priority date Publication date Assignee Title
EP0373573B1 (de) * 1988-12-14 1994-06-22 Ciba-Geigy Ag Aufzeichnungsmaterial für Tintenstrahldruck
JP2521896B2 (ja) * 1991-01-18 1996-08-07 日本製紙株式会社 インクジェット記録シ―ト
GB9120227D0 (en) * 1991-09-23 1991-11-06 Ici Plc Printing process and pretreatment composition
EP0605730B1 (de) 1992-07-27 2005-11-30 Kanebo, Ltd. Bedruckter stoff und verfahren zur herstellung
US5781216A (en) 1994-10-28 1998-07-14 Canon Kabushiki Kaisha Ink-jet printing cloth, textile printing method of the same and print resulting therefrom
US5897694A (en) 1997-01-06 1999-04-27 Formulabs Methods for improving the adhesion and/or colorfastness of ink jet inks with respect to substrates applied thereto, and compositions useful therefor
US6103364A (en) 1997-06-30 2000-08-15 Kimberly-Clark Worldwide, Inc. Ink jet printable, washable saturated cellulosic substrate
US6291023B1 (en) * 1998-04-22 2001-09-18 Sri International Method and composition for textile printing
CN103682358A (zh) 2012-09-24 2014-03-26 东丽先端材料研究开发（中国）有限公司 一种高分散性石墨烯组合物与制备方法及其应用于锂离子二次电池的电极
CA2976369A1 (en) 2015-02-13 2016-08-18 Yale University Biaryltriazole inhibitors of macrophage migration inhibitory factor

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