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WO2022050958A1 - Support d'enregistrement imprimable - Google Patents

Support d'enregistrement imprimable Download PDF

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Publication number
WO2022050958A1
WO2022050958A1 PCT/US2020/049533 US2020049533W WO2022050958A1 WO 2022050958 A1 WO2022050958 A1 WO 2022050958A1 US 2020049533 W US2020049533 W US 2020049533W WO 2022050958 A1 WO2022050958 A1 WO 2022050958A1
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WO
WIPO (PCT)
Prior art keywords
recording media
printable recording
polymer
cationic
coating composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US2020/049533
Other languages
English (en)
Inventor
Xiaoqi Zhou
Zhang-Lin Zhou
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hewlett Packard Development Co LP
Original Assignee
Hewlett Packard Development Co LP
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hewlett Packard Development Co LP filed Critical Hewlett Packard Development Co LP
Priority to PCT/US2020/049533 priority Critical patent/WO2022050958A1/fr
Publication of WO2022050958A1 publication Critical patent/WO2022050958A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D105/00—Coating compositions based on polysaccharides or on their derivatives, not provided for in groups C09D101/00 or C09D103/00
    • C09D105/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C09D11/322—Pigment inks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C09D11/324—Inkjet printing inks characterised by colouring agents containing carbon black
    • 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
    • D06P1/46—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 natural macromolecular substances or derivatives thereof
    • 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
    • D06P1/54—Substances with reactive groups together with crosslinking agents
    • 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

Definitions

  • Textile is a flexible material consisting of a network of natural or artificial fibers which form yarn or thread. Textiles have an assortment of uses in the daily life, such as clothing, bags, baskets, upholstered furnishings, window shades, towels, coverings for tables, beds, and other flat surfaces, and in art. Textiles are used in many traditional crafts such as sewing, quilting and embroidery. The coloration of the textile includes often the dyeing and printing. The dyeing is to apply colorant to the whole fabric network including yarn and thread. The printing is to place the specific design pattern in a special area under the design. Screen printing is a traditional method for fabric textile printing over decades. With the rapid development of digital printing technology, the inkjet printing is increasing its application range and volume in textile printing.
  • the inkjet printing method such as thermal inkjet and piezoelectric inkjet, dye sublimation inkjet and the alike have been under the investigation and some of the technology have successfully been commercialized in the printing industry. With these technologies, it is apparent that the image quality of printed images is strongly dependent on the construction of the recording media used.
  • Pre-treatment compositions or coatings can be applied to various textile media to improve printing characteristics and attributes of a printed image.
  • FIG. 1 is cross-sectional views of printable media according to some examples of the present disclosure.
  • Figure 3 is a flowchart illustrating a method for producing a printable media according to one example of the present disclosure.
  • pre-treatmenf a process as called “pre-treatmenf ’ can be applied to the surface of the recording media before printing and the composition is able to form a coating layer and form strong binding actions to the ink and media substrate, so that washing fastness, for examples, can be dramatically improved.
  • the pre-treatment refers to apply a special formulated chemical composition to the media substrate or textile substrate prior to printing.
  • the pre-treatment can also be called and referred to as coating composition.
  • Such coating composition is indeed coated on a base substrate.
  • the coating composition is coated onto a fabric base substrate and is thus called fabric coating composition.
  • the term “coating” and “coated” is used herein to describe the coating composition, or to describe a composition applied to a surface of a media substrate, such as a fabric base substrate.
  • the present disclosure is drawn to printable recording media comprising a fabric base substrate with an image-side and a back-side and a coating layer, applied to the image-side of the base substrate, comprising, at least, water, a cationic polysaccharide and a secondary cationic charged polymer.
  • the present disclosure relates also to a method for forming a printable recording media comprising: providing a fabric base substrate, with an image-side and a back-side; applying a coating layer comprising, at least, water, a cationic polysaccharide and a secondary cationic charged polymer, to the image-side of the base substrate; and drying the coating composition to remove water from the media substrate to leave a coating layer thereon.
  • the present disclosure further relates to a printing method comprising obtaining a printable recording media comprising a base substrate with an image-side and a back-side, and a coating layer, applied to the image-side of the base substrate, comprising, at least, water, a cationic polysaccharide and a secondary cationic charged polymer; and applying an ink composition onto said printable recording media to form a printed image.
  • the media is a coated printable recording media.
  • the coated printable media described herein is a coated fabric printable media.
  • coated it is meant herein that the printable recording media has been applied a coating composition.
  • coating composition refers to either a composition used to form a coating layer as well as the coating layer itself, the context dictating which is applicable.
  • a coating composition or coating that includes an evaporable solvent is referring to the compositional coating that is applied to a media substrate. Once coated on a media substrate and after the evaporable solvent is removed, the resulting coating layer can also be referred to as a coating.
  • the coating composition can be applied to various media to improve, for example, printing characteristics and attributes of an image.
  • the coating composition is a composition that is going to be applied to an uncoated printable recording media.
  • uncoated it is meant herein that the printable recording media has not been treated or coated by any composition.
  • the printable recording medium or printable media
  • the printable recording medium will provide printed images with good image quality and outstanding print durability such as washfastness, which is particularly useful for fabric substrates.
  • the durability of the printed ink on the coated fabric media can be tested by washing, for example by performing a washfastness test that includes five (5) standard washing machine cycles using warm water and a standard clothing detergent.
  • Figures 1 and 2 schematically illustrate some examples of the printable recording media as described herein.
  • Figure 3 is a flowchart illustrating an example of a method for producing the printable media.
  • Figures 1 and 2 illustrate the relative positioning of the various layers of the printable media without necessarily illustrating the relative thicknesses of the various layers. It is to be understood that the thickness of the various layers is exaggerated for illustrative purposes.
  • FIG. 1 illustrates the printable recording media (100) as described herein.
  • the printable recording media (100) encompasses a fabric base substrate or media substrate or bottom supporting substrate (110) and a coating layer (120).
  • the coating that can also be called image-receiving layer or ink-receiving layer
  • the coating layer composition is thus applied on one side, i.e. the image side, only and no other coating is applied on opposite side.
  • the image side with the coating layer is considered as the side where the image will be printed.
  • the printable media (100) has two surfaces: a first surface which might be referred to as the “image-receiving side”, “image surface” or “image side” (101) when coated with coating composition described herein, and a second surface, the opposite surface, which might be referred to as the “back surface” or “back-side” (102).
  • Figure 2 illustrates another example of the printable recording media (100) as described herein.
  • the printable media (100) encompasses a fabric base substrate (110) with coating layers (120) that are applied to both the “image side” (101) and the “back-side” (102) of the print media. In theory, both the image side and the back-side could be printed and functionalized as imagereceiving layer.
  • FIG. 3 An example of a method (200) for forming a printable recording media in accordance with the principles described herein, by way of illustration and not limitation, is shown in Figure 3.
  • such method encompasses providing (210) a fabric base substrate, with an image-side and a back-side, applying (220) a coating composition comprising, at least, water, a cationic polysaccharide and a secondary cationic charged polymer, to the image-side of the base substrate and drying (230) the coating composition to remove water from the substrate to leave a coating layer thereon.
  • the present disclosure relates thus also to a coated printable recording media, with an image-side (101) and a back-side (102), comprising a fabric base substrate (110) and a coating layer (120), that comprises, at least, at least, water, a cationic polysaccharide and a secondary cationic charged polymer.
  • a coating layer can be called “image-receiving layer” since, during the printing process, the ink will be directly deposited on its surface.
  • the printable recording media comprises a base substrate (110) and coating layers (120), comprising a cationic polysaccharide and a secondary cationic charged polymer, that are applied to both opposing sides of the base substrate.
  • the printable media (100) of the present disclosure is a media that comprises a fabric base substrate (110).
  • the fabric base substrate (110) can also be called bottom supporting substrate or fabric substrate.
  • the word “supporting” also refers to a physical objective of the substrate that is to carry the coatings layer and the image that is going to be printed.
  • fabric substrates useful in present disclosure include substrates that have fibers that may be natural and/or synthetic.
  • fabric as used to mean a textile, a cloth, a fabric material, fabric clothing, or another fabric product.
  • fabric structure is intended to mean a structure having warp and weft that is one of woven, non-woven, knitted, tufted, crocheted, knotted, and pressured, for example.
  • warp and “weft” refers to weaving terms that have their ordinary means in the textile arts, as used herein, e.g., warp refers to lengthwise or longitudinal yams on a loom, while weft refers to crosswise or transverse yarns on a loom.
  • fabric substrate does not include materials commonly known as any kind of paper (even though paper can include multiple types of natural and synthetic fibers or mixture of both types of fibers).
  • the paper thereon is defined as the felted sheet, roll and other physical forms that are made of various plant fibers (like trees or mixture of plant fibers) with synthetic fibers by laid down on a fine screen from a water suspension.
  • fabric substrates include both textiles in its filament form, in the form of fabric material, or even in the form of fabric that has been crafted into finished article (clothing, blankets, tablecloths, napkins, bedding material, curtains, carpet, shoes, etc.).
  • the fabric base substrate has a woven, knitted, non-woven or tufted fabric structure.
  • the fabric base substrate comprises wool, cotton, silk, linen, jute, flax, hemp, rayon, corn starch, tapioca, sugarcane, polyvinyl chloride, polyester, polyamide, polyimide, polyacrylic, polyacrylic polypropylene, polyethylene, polyurethane, polystyrene, polyaramid, polytetrafluoroethylene, polyethylene terephthalate, fiberglass, polytrimethylene, polycarbonate, polyester terephthalate, polybutylene terephthalate, or a combination thereof.
  • the fabric base substrate is woven, knitted, non-woven or tufted and comprises natural or synthetic fibers selected from the group consisting of wool, cotton, silk, rayon, thermoplastic aliphatic polymers, polyesters, polyamides, polyimides, polypropylene, polyethylene, polystyrene, polytetrafluoroethylene, fiberglass, polycarbonates polytrimethylene terephthalate, polyethylene terephthalate and polybutylene terephthalate.
  • the fabric base substrate is a synthetic polyester fiber.
  • the fabric base substrate (110) has a basis weight that is ranging from about 50 gsm to about 400 gsm. In some other examples, the basis weight of the fabric substrate can range from about 100 gsm to about 300 gsm.
  • the fabric base substrate can be a woven fabric where warp yams and weft yams are mutually positioned at an angle of about 90°.
  • This woven fabric includes, but is not limited to, fabric with a plain weave structure, fabric with twill weave structure where the twill weave produces diagonal lines on a face of the fabric, or a satin weave.
  • the fabric base substrate can be a knitted fabric with a loop structure including one or both of warp-knit fabric and weft-knit fabric.
  • the weft-knit fabric refers to loops of one row of fabric are formed from the same yam.
  • the warp-knit fabric refers to every loop in the fabric structure that is formed from a separate yarn mainly introduced in a longitudinal fabric direction.
  • the fabric base substrate can also be a non-woven product, for example a flexible fabric that includes a plurality of fibers or filaments that are one or both of bonded together and interlocked together by a chemical treatment process (e.g., a solvent treatment), a mechanical treatment process (e.g., embossing), a thermal treatment process, or a combination of two or more of these processes.
  • the fabric base substrate can include one or both of natural fibers and synthetic fibers. Natural fibers that may be used include, but are not limited to, wool, cotton, silk, linen, jute, flax or hemp. Additional fibers that may be used include, but are not limited to, rayon fibers, or those of thermoplastic aliphatic polymeric fibers derived from renewable resources, including, but not limited to, cornstarch, tapioca products, or sugarcanes. These additional fibers can be referred to as “natural” fibers.
  • the fibers used in the fabric base substrate includes a combination of two or more from the above-listed natural fibers, a combination of any of the above-listed natural fibers with another natural fiber or with synthetic fiber, a mixture of two or more from the above-listed natural fibers, or a mixture of any thereof with another natural fiber or with synthetic fiber.
  • the synthetic fiber that may be used in the fabric base substrate can be a polymeric fiber including, but not limited to, polyvinyl chloride (PVC) fibers, PVC-free fibers made of polyester, polyamide, polyimide, polyacrylic, polypropylene, polyethylene, polyurethane, polystyrene, polyaramid (e.g., Kevlar®) polytetrafluoroethylene (Teflon®) (both trademarks of E. I. du Pont de Nemours Company), fiberglass, polytrimethylene, polycarbonate, polyethylene terephthalate or polybutylene terephthalate.
  • PVC polyvinyl chloride
  • PVC-free fibers made of polyester, polyamide, polyimide, polyacrylic, polypropylene, polyethylene, polyurethane, polystyrene, polyaramid (e.g., Kevlar®) polytetrafluoroethylene (Teflon®) (both trademarks of E. I. du Pont de
  • the fibers include a combination of two or more of the above-listed polymeric fibers, a combination of any of the above-listed polymeric fibers with another polymeric fiber or with natural fiber, a mixture of two or more of the above-listed polymeric fibers, or a mixture of any of the above-listed polymeric fibers with another polymer fiber or with natural fiber.
  • the synthetic fiber includes modified fibers from above-listed polymers.
  • modified fibers refers to one or both of the polymeric fiber and the fabric as a whole having underwent a chemical or physical process such as, but not limited to, one or more of a copolymerization with monomers of other polymers, a chemical grafting reaction to contact a chemical functional group with one or both the polymeric fiber and a surface of the fabric, a plasma treatment, a solvent treatment, for example acid etching, and a biological treatment, for example an enzyme treatment or antimicrobial treatment to prevent biological degradation.
  • PVC-free means no polyvinyl chloride (PVC) polymer or vinyl chloride monomer units in the substrate.
  • the fabric base substrate contains both natural fiber and synthetic polymeric fiber.
  • the amount of synthetic polymeric fibers can represent from about 20 % to about 90 % of the total amount of fiber.
  • the amount of natural fibers can represent from about 10 % to about 80 % of amount of fiber.
  • the fabric base substrate may further contain additives including, but not limited to, one or more of colorant (e.g., pigments, dyes, tints), antistatic agents, brightening agents, nucleating agents, antioxidants, UV stabilizers, fillers and lubricants, for example.
  • colorant e.g., pigments, dyes, tints
  • antistatic agents e.g., antistatic agents, brightening agents, nucleating agents, antioxidants, UV stabilizers, fillers and lubricants
  • the fabric base substrate may be pre-treated in a solution containing the substances listed above before applying the coating composition.
  • the additives and pre-treatments are included to improve various properties of the fabric.
  • the fabric printable media (100) comprises a fabric base substrate (100) with an imageside (101) and a back-side (102) and coating layer, or ink-receiving layer (120), comprising, at least, water, a cationic polysaccharide and a secondary cationic charged polymer, that is directly applied to the image-side of the fabric base substrate.
  • the printable recording media has a coating composition that further comprises a reactive cross-linking agent, i.e. the coating composition can further comprise, as an optional ingredient, a reactive cross-linking agent.
  • the coating layer (120) is disposed on the image-side (101) of the fabric base substrate (110), at a coat-weight in the range of about 0.5 to about 20 gram per square meter (g/m 2 or gsm). In some other examples, the coating layer (120) is disposed, on the imageside (101) of the fabric base substrate (110), at a coat-weight in the range in the range of about 1 gsm to about 10 gsm. In yet some other examples, the coating layer (120) is disposed at a coatweight in the range of about 1 to about 6 gsm.
  • the coating layer (120) is disposed, on the image-side (101) of the fabric base substrate (110), at a coat-weight in the range of about 2 to about 5 gsm.
  • the coating layer (120) is disposed on both the imageside (101) and on the back-side (102) of the base substrate (110), at a coat-weight in the range of about 0.1 to about 10 gram per square meter (g/m2 or gsm), or in the range of about 1 gsm to about 6 gsm.
  • the printable recording media comprises a fabric base and a coating layer, including a cationic polysaccharide.
  • a cationic polysaccharide Whiteout being bound by any theory, it is believed that the cationic polysaccharide has strong film-forming capability and binding power to fabric base.
  • the cationic polysaccharide is present in coating composition, in an amount ranging from about 1 wt % active to about 90 wt % active based on a total weight of the coating composition. In further examples, the cationic polysaccharide is present in coating composition, in an amount ranging from about 5 wt % active to about 60 wt % active or from about 10 wt % active to about 50 wt % active based on a total weight of the coating composition. [0026] In some example, the ratio cationic polysaccharide/secondary cationic charged polymer is between 10/90 to 50/50. In some example, the ratio cationic polysaccharide/ secondary cationic charged polymer, that are present in coating composition, is between 30/70 to 20/80.
  • Suitable cationic polysaccharides are positively charged polysaccharides due to the presence of cationic functional groups.
  • Suitable polysaccharides for use herein include natural and semi-synthetic cationic polysaccharides.
  • suitable cationic functional groups include primary, secondary or tertiary amine groups or quaternary ammonium groups, which should be present in base form. In some examples, quaternary ammonium groups are present.
  • Such cationic polysaccharides are also called herein amino polysaccharides.
  • the cationic polysaccharide for use herein might be a polysaccharide such as cellulose with an excess of quaternary ammonium compound containing at least one group capable of reacting with polysaccharide hydroxyl groups.
  • the cationic polysaccharides are amino-polysaccharides, such as, for examples, chitin-based materials, chitosan materials and mixture thereof.
  • the cationic polysaccharides are linear cationic polysaccharides.
  • the cationic polysaccharides are modified linear polysaccharides with cationic charge center.
  • linear cationic polysaccharides used in the coating composition described herein are chitosan materials, meaning thus that it contains chitosan, modified chitosan, and/or chitosan salts. Chitosan is a partially or fully deacetylated form of chitin, a naturally occurring polysaccharide.
  • Chitosan is an amino-polysaccharide usually prepared by deacetylation of chitin (poly-beta(l,4)-N-acetyl-D-glucosamine). Chitosan is not a single, definite chemical entity but varies in composition depending on the conditions of manufacture. It may be equally defined as chitin sufficiently deacetylated to form soluble amine salts. Chitosan is the beta-(l-4) polysaccharide of D-glucosamine, and is structurally similar to cellulose.
  • the linear cationic polysaccharide used herein, can be a natural polymer composed of randomly distributed P-linked D-glucosamine and N-acetyl-D- glucosamine.
  • One other example of the linear polysaccharide used in the coating composition is cationic chitosan which consists of 2-acetamido-D-glucose and 2-amino-D-glucose units linked with glycosidic linkages, as shown below in Formula II, Where X can be Cl, NO3, CH3CO2; n is an integer above 5.
  • the cationic chitosan (Formula II) is produced by adding in acidic condition to chitosan (Formula I) as exemplified below.
  • Chitosan is a sustainable and environmental-friendly chemical having a cationic charge center which can help to crush and bind ink pigments and thus improve printing image quality and image durability. It is also considering as having strong film-forming character and binding power to fabric yarns which is readily able to physically block ink pigments’ penetration towards z-direction. Further, chitosan can be considered as compatible with second cationic polymer in the composition. Chitosan can be selected from deacetylated product of chitin polymer obtained, for example, from natural crustaceans or other sea animals.
  • the process for making chitosan from chitin resources can include, first, the removal and separation of proteins by sodium hydroxide (NaOH) then the dissolution and demineralization of calcium carbonate by acid (HC1), which can be are present in high concentrations. Such resulting product can be washed in order to obtain chitin. Resulting chitin can then be deacetylated in sodium hydroxide at 120 °C for 1 to 3 hours. Alkali helps in removal of protein and deacetylation of chitin simultaneously. After washing, in the last step, chitosan can be utilized for further applications in textiles.
  • NaOH sodium hydroxide
  • HC1 demineralization of calcium carbonate by acid
  • chitosan salts formed with an inorganic acid include, but are not limited to, chitosan hydrochloride, chitosan hydrobromide, chitosan phosphate, chitosan sulphonate, chitosan chloro-sulphonate, chitosan chloroacetate and mixtures thereof.
  • chitosan salts formed with an organic acid include, but are not limited to, chitosan formate, chitosan acetate, chitosan lactate, chitosan glycolate, chitosan malonate, chitosan epoxysuccinate, chitosan benzoate, chitosan adipate, chitosan citrate, chitosan salicylate, chitosan propionate, chitosan nitrilotriacetate, chitosan itaconate, chitosan hydroxy-acetate, chitosan butyrate, chitosan isobutyrate, chitosan acrylate, and mixtures thereof. It is also suitable to form a chitosan salt using a mixture of acids including, for example, both inorganic and organic acids.
  • the linear cationic polysaccharides can also be chitosan derivatives.
  • chitosan derivatives that can be used are, but not limited to, for example, carboxymethyl chitosan, chitosan oligosaccharide, chitosan nanoparticles.
  • the chitosan can be differentiated according to the degree of deacetylation (DOD). In one example, the DOD is 81%, and in another example, DOD is 93 and further in some examples, the DOD is 98%.
  • the molecular weight of chitosan can be in the range of about 250 to about 300 kDaltons.
  • Commercial chitosan can be available from various source such as, for examples, ChitoLytic Inc, Tidal Vision, and Aldrich Sigma Inc.
  • the printable recording media comprises a fabric base and a coating layer including a secondary cationic charged polymer.
  • the secondary cationic charged polymer can have cationic groups as part of the main chain, meaning that either cationic groups can exist on the backbone unit as part of the main chain (polymer backbone) or cationic groups can exist as an appending group directly attached to an element of the backbone unit(pendent group).
  • the secondary cationic charged polymer is a cationic polymer with multiple charge centers. This cationic polymer is referred to as a “second” cationic polymer because the polysaccharide previously described is also a cationic polymer.
  • the secondary cationic charged polymer is present in coating composition, in an amount ranging from about 50 wt % active to about 99 wt % active based on a total weight of the coating composition. In further examples, the secondary cationic charged polymer is present in coating composition, in an amount ranging from about 60 wt % active to about 90 wt % active based on a total weight of the coating composition; or from about 70 wt % active to about 80 wt % active based on a total weight of the coating composition.
  • the secondary cationic charged polymer can be a polyquatemium having reactive heterocyclic polymer.
  • the secondary cationic charged polymer is a quaternary amine-containing polymer.
  • the secondary cationic charged polymer is a quaternary polydiallyl-dimethylammonium polymer, a quaternary ionene-containing polymer, a quaternary epichlorohydrin amine polymer, a quaternary alkoxylated quaternary polyamine, a quaternary N,N-dimethylaminoethyl methacrylate, or a combination thereof.
  • Example quaternary amine-containing polymers that can be used include, for example, epichlorohydrin amine polymers, alkoxylated quaternary polyamines, polydiallyl-dimethylammonium polymers, quaternized ionene-containing polymers, N,N-dimethylaminoethyl methacrylate quaternary polymers, etc., or a combination thereof.
  • the quaternary amine-containing polymers can be included with any anionic counterion suitable for such polymers including halides, e.g., chloride, bromide, iodide, etc., or any other similarly charged anion.
  • the counterion used for the quaternary amine-containing polymer can be a variety of counterions associated with the various cationic polymers.
  • the quaternary amine-containing polymer can include a quaternary epichlorohydrin amine polymer, e.g., dimethylamine-epichlorohydrin copolymer.
  • Other similar quaternary amine-containing polymers can be used as well, including other alkoxylated quaternary polyamines.
  • the quaternary amine-containing polymer can include a dimethylamine-epichlorohydrin copolymer having the structure of Formula III.
  • the quaternary amine-containing polymer can be defined more generally as shown in Formula IV.
  • Formula IV where n is from 5 to 1,500, or can be from 10 to 500, from 20 to 400, from 20 to 250, or from 25 to 200; and X can be any suitable counter ion, such as a halogen, e.g., chloride, bromide, iodide, etc., or other similarly charged anion (for both examples, namely Formula III and Formula IV).
  • a halogen e.g., chloride, bromide, iodide, etc., or other similarly charged anion (for both examples, namely Formula III and Formula IV).
  • Formula III above is representative of Floquat® FL-2350, available from SNF (UK) Ltd., United Kingdom.
  • Formula IV above is representative of a more general formula of a quaternary polyamine (that may also be alkoxylated or dialkyoxylated at one or multiple R groups)
  • R can be linear or branched C2-C12 alkyl, C3-C12 hydroxyalkyl (which includes dihydroxyalkyl), C5-C12 aryl, C5-C12 alicyclic, C5-C16 alkyl aryl, or C5-C16 alkyl alicyclic
  • R1 can be linear or branched C1-C4 alkyl, C1-C4 hydroxyalkyl (which includes dihydroxyalkyl), C5-C12 aryl, C5- C12 alicyclic, C5-C16 alkyl aryl, or C5-C16 alkyl alicyclic.
  • R may be alkoxylated and R1 may be alkyl, aryl, or alkylaryl.
  • the secondary cationic charged polymer can be a quaternary amine- containing polymer that can include a polydiallyl-dimethylammonium, e.g., PolyDADMAC quaternary salt such as a chloride salt, as shown by example in Formula V, as follows:
  • n is from 5 to 1,500, or can be from 10 to 500, from 20 to 400, from 20 to 250, or from 25 to 200; and X can be any suitable counter ion, such as a halogen, e.g., chloride, bromide, iodide, etc., or other similarly charged anion.
  • a halogen e.g., chloride, bromide, iodide, etc., or other similarly charged anion.
  • the secondary cationic charged polymer is a quaternary amine- containing polymer that can be an ionene polymer, which is a polymer having ionic groups that are appended to the backbone unit as a side-chain, with an example including a quaternized poly(4-vinyl pyridine), having a general structure as shown in Formula VI, as follows:
  • X can be any suitable counter ion, such as a halogen, e.g., chloride, bromide, iodide, etc., or other similarly charged anion; and n can be from 5 to 1,500, or can be from 10 to 500, from 20 to 400, from 20 to 250, or from 25 to 200, for example.
  • a halogen e.g., chloride, bromide, iodide, etc., or other similarly charged anion
  • n can be from 5 to 1,500, or can be from 10 to 500, from 20 to 400, from 20 to 250, or from 25 to 200, for example.
  • the secondary cationic charged polymer including the quaternary amine-containing polymers described herein and shown in formulas III- VI, as well as others, can have a weight average molecular weight of from 1,000 Mw to 250,000 Mw, from 2,000 Mw to 200,000 Mw, from 2,000 Mw to 100,000 Mw, from 2,000 Mw to 75,000 Mw, from 2,000 Mw to 50,000 Mw, from 5,000 Mw 50,000 Mw, from 5,000 Mw to 30,000 Mw, or from 5,000 Mw to 20,000 Mw, for example.
  • a cross-linking agent (or cross-linker agent) can be optionally included in the coating composition.
  • the crosslinking agent or cross linker can be defined here as a chemical with functional groups capable to form a cross-linking reaction with other reactive groups such as amine, carboxyl, hydroxyl, and thiol on the surface of textile substrate, and binders of pigmented inks upon certain condition such as heating at 50oC to 200oC.
  • the cross-linking agent has to be compatible or dispersible with solvent, preferably with aqueous solvent like water to form a uniform solution without phase separation or gelling.
  • the reactive cross-linking agent can have a weight average molecular weight ranging from about 100 to about 3,000,000. In some examples, the weight average molecular weight of the reactive cross-linking agent ranges from about 100 to about 1,000,000; or from about 200 to about 500,000; or from about 300 to about 200,000 ; or from about 300 to about 100,000. In some other examples, the reactive cross-linking agent has a weight average molecular weight of 100,000 or less. In yet some other examples, the weight average molecular weight of the reactive cross-linking agent ranges from about 500 to about 40,000. Any weight average molecular weight throughout this disclosure is in Daltons.
  • the reactive cross-linking agent is present in the ink-receiving layer, in an amount ranging from about 0.5 wt % active to about 15 wt % active based on a total weight of the ink-receiving layer composition. In further examples, the reactive cross-linking agent is present in an amount ranging from about 1 wt % active to about 10 wt % active; or from about 4 wt % active to about 8 wt % active; or from about 2 wt % active to about 7 wt % active based on a total weight of the ink-receiving layer composition.
  • the crosslink agent is heterocyclic ammonium salt.
  • the heterocyclic ammonium salt is a polymeric salt consisting of four membered heterocyclic rings containing a quaternary ammonium as shown in the Formula VII :
  • R 3 is hydroxyl group, carboxy, acetoxy, alkoxy, amino or alkyl group, for example, at the 3 ’-position.
  • R 1 and R 2 are groups at the 1,1’ -nitrogen position and connecting the group to the backbone polymeric in long chain structure that can be polyamide chain and polyalkylenepolyamine chain.
  • the backbone polymeric structure includes, but is not limited to, polyethylene imine, polyamidoamine, the polyamidoaminester, or polyester backbone with pendant secondary amine groups.
  • R 3 is hydroxyl group, the structure is called azetidinium salts. Such azetidinium salts can be available from the reaction from either primary amine or secondary amine with epichlorohydrin by two-step reaction as shown in equations 1 and 2. q
  • the polymeric heterocyclic salt can be commercially available, for example, under the tradename Beetle® PT746 from BIP (Oldbury) Ltd, Polycup serial from Solenis, Inc such as Polycup® 8210, Polycup® 9200, Polycup® 7535, Polycup® 7360A, Polycup® 2000, Polycup® 172 and Polycup® 9700.
  • the reactive cross-linking agent is an azetidinium- containing polyamine polymer.
  • the reactive cross-linking agent is a polyamine epichlorohydrin resins.
  • the reactive cross-linking agent can be selected from the group consisting of poly(diallyldimethylammonium chloride); poly(methylene-co-guanidine) anion, wherein the anion is selected from the group consisting of hydrochloride, bromide, nitrate, sulfate, and sulfonates; a polyamine; poly(dimethylamine-co- epichlorohydrin); a polyethyleneimine; a polyamide epichlorohydrin resin; a polyamine epichlorohydrin resin; and a combination thereof.
  • the azetidinium-containing polyamine selected for use can include any of a number of cationic polyamines with a plurality of azetidinium groups.
  • an azetidinium group In an un-crosslinked state, as shown in Formula 2 below, an azetidinium group generally has a structure as follows:
  • Formula VIII [0047] As shown in Formula VIII, this structure is not intended to show repeating units, but rather merely a polymer that includes the azetidinium groups shown in Formula VIII, including azetidinium-containing polyamines having a weight average molecular weight from 1,000 Mw to 2,000,000 Mw, from 2,000 Mw to 1,000,000 Mw, from 5,000 Mw to 200,000 Mw, from 5,000 Mw to 100,000 Mw, or from 20,000 to 1,000,000 Mw, for example.
  • the asterisks (*) in Formula VIII represent portions of the various organic groups, polymeric portions, functional moieties, etc., for example.
  • the reactive cross-linking agent including the azetidinium- containing polyamine can be derived from the reaction of a polyalkylene polyamine (e.g. ethylenediamine, bishexamethylenetriamine, and hexamethylenediamine, for example) with an epihalohydrin (e.g. epichlorohydrin, for example) (referred to as PAmE resins).
  • a polyalkylene polyamine e.g. ethylenediamine, bishexamethylenetriamine, and hexamethylenediamine, for example
  • an epihalohydrin e.g. epichlorohydrin, for example
  • PAmE resins e.g. epichlorohydrin, for example
  • Ri can be a substituted or unsubstituted C2-C12 linear alkyl group and R2 is H or CH 3 .
  • Ri can be a C2-C10, C 2 -C 8 , or C 2 -C 6 linear alkyl group. More generally, there can be from 2 to 12 carbon atoms between amine groups (including azetidinium groups) in the azetidinium-containing polyamine. In other examples, there can be from 2 to 10, from 2 to 8, or from 2 to 6 carbon atoms between amine groups in the azetidinium-containing polyamine.
  • a carbon atom along the alkyl chain can be a carbonyl carbon, with the proviso that the carbonyl carbon does not form part of an amide group (i.e. Ri does not include or form part of an amide group).
  • a carbon atom of Ri can include a pendent hydroxyl group.
  • the number of units as shown in Formula IX can be any number of units that results in an azetidinium-containing polyamine having a weight average molecular weight from 1,000 Mw to 2,000,000 Mw, from 2,000 Mw to 1,000,000 Mw, from 5,000 Mw to 200,000 Mw, from 5,000 Mw to 100,000 Mw, or from 20,000 to 1,000,000 Mw, for example.
  • These units can be repeating along the polymer, along portions of the polymer, and/or can have other moieties between individual units shown in Formula IX.
  • the asterisks (*) in Formula IX represent portions of polymer that are not shown, but could include various organic groups, polymeric portions, functional moieties, etc., for example.
  • Non-limiting examples of commercially available azetidinium-containing polyamines that fall within these ranges of azetidinium group to amine groups include Crepetrol® 73, Kymene®736, Polycup® 1884, Polycup® 7360, and Polycup® 7360A, which are available from Solenis LLC (Delaware, USA). Other compounds from this or other companies can likewise be used. With more specific detail regarding the Polycup® family of azetidinium-containing polyamines, these resins tend to be formaldehyde-free, water-based cross-linking resins that are reactive with amine groups, carboxyl groups, hydroxyl groups, and thiol groups.
  • Polycup® 7360 is a thermosetting polyamine epichlorohydrin that can include the polymer in a fluid carrier at about 38 wt % solids and can have a range of viscosities from about 180 cP to about 300 cP at 25 °C, for example.
  • the reactive cross-linking agent could be a diallylazetidium salt (Formula X), a bis(2-methoxyethyl)azetidinium salt (Formula XI), a nonylpropylazetidinium salt (Formula XII), a undecylmethylazetidinium salt (Formula XIII) or a nonylpropargylazetidinium salt (Formula XIV).
  • the reactive cross-linking agent could be used a single reactive cross-linking agent or in combination with different reactive cross-linking agent.
  • the ink-receiving layer may also include other coating additives such as surfactants, rheology modifiers, defoamers, optical brighteners, biocides, pH controlling agents, dyes, and other additives for further enhancing the properties of the coating.
  • the total amount of optional coating additives may be in the range of 0 to 10 wt % based on the total amount of ingredients.
  • rheology modifier or rheology control agent is useful for addressing runnability issues. Suitable rheology control agents include polycarboxylate-based compounds, polycarboxylated-based alkaline swellable emulsions, or their derivatives.
  • the rheology control agent is helpful for building up the viscosity at certain pH, either at low shear or under high shear, or both.
  • a rheology control agent is added to maintain a relatively low viscosity under low shear, and to help build up the viscosity under high shear. It is desirable to provide a coating formulation that is not so viscous during the mixing, pumping and storage stages, but possesses an appropriate viscosity under high shear.
  • the printable recording media is prepared by using surface treatment compositions herein named a coating layer or coating composition.
  • a method of making a coated print media includes applying a coating composition as a layer to a media substrate and drying the coating composition to remove water from the media substrate to leave a coating composition, or an ink-receiving layer thereon.
  • a method (200) of making a printable recording media encompasses: providing (210) a fabric base substrate (110) with an image-side and a back-side; applying (210) an coating layer (120) comprising, at least, water, a cationic polysaccharide and a secondary cationic charged polymer to the image-side of the base substrate; and drying (220) the coating composition to remove water from the media substrate to leave a coating layer thereon.
  • the coating layer (120) is applied to the base substrate (110) on the image receiving side of the printable media.
  • the coating layer (120) is applied to the supporting fabric base substrate (110) on the image receiving side (101) and on the backside (102) of the printable media.
  • the coating layer (120) can be applied to the base substrate (110) by using any method appropriate for the coating application properties, e.g., thickness, viscosity, etc.
  • Non-limiting examples of methods include size press, slot die, blade coating, Meyer rod coating and padding coating.
  • a two rolls padding coating is used to apply the coating composition to a substrate (or other type of substrate).
  • the application of the coating composition can be carried out using padding procedures.
  • the fabric substrate can be soaked in a bath and the excess can be rolled out. More specifically, impregnated fabric substrates (prepared by bath, spraying, dipping, etc.) can be passed through padding nip rolls under pressure. The impregnated fabric, after nip rolling, can then be dried under heat at any functional time which is controlled by machine speed with peak fabric web temperature.
  • pressure can be applied to the substrate after impregnating the base substrate with the pre-treatment composition.
  • the surface treatment is accomplished in a pressure padding operation.
  • the fabric base substrate is firstly dipped into a pan containing treatment coating composition and is then passed through the gap of padding rolls.
  • the padding rolls (a pair of two soft rubber rolls or a metal chromic metal hard roll and a tough-rubber synthetic soft roll for instance), apply the pressure to composite-wetted textile material so that composite amount can be accurately controlled.
  • the pressure that is applied can be from 10 PSI to 150 PSI or, in some other examples, can be from 30 PSI to 70 PSI.
  • the coating layer can be applied in one single production run.
  • both sides of the substrate may be coated during a single manufacture pass, or each side is coated in a separate pass.
  • the coating composition is dried, it can form an ink-receiving layer. Drying can be by air drying, heated airflow drying, baking, infrared heated drying, etc. Other processing methods and equipment can also be used.
  • the coated media substrate can be passed between a pair of rollers, as part of a calendering process, after drying.
  • the calendering device can be any kind of calendaring apparatus, including but not limited to off-line super-calender, on-line calender, soft- nip calender, hard-nip calender, or the like.
  • the ink-receiving layer (120) can be calendered.
  • the calendaring can be done either in room temperature or at an elevated temperature and/or pressure.
  • the elevated temperature can range from 40°C to 60°C.
  • the calender pressure can range from about 100 psi to about 2,000 psi.
  • the image-receiving coating layer (120) can be dried using any drying method in the arts such as box hot air dryer.
  • the dryer can be a single unit or could be in a serial of 3 to 7 units so that a temperature profile can be created with initial higher temperature (to remove excessive water) and mild temperature in end units (to ensure completely drying with a final moisture level of less than 1-5 % for example).
  • the peak dryer temperature can be programmed into a profile with higher temperature at begging of the drying when wet moisture is high and reduced to lower temperature when web becoming dry.
  • the dryer temperature is controlled to a temperature of less than about 120°C to avoid reaction on reactive crosslink chemical agent, and the web temperature is controlled in the range of about 80 to about 100°C.
  • the operation speed of the coating/drying line is 20 to 30 meters per minute.
  • ink compositions can be applied by any processes onto the printable recording media.
  • the ink composition is applied to the printable recording media via inkjet printing techniques.
  • a printing method could encompasses obtaining a comprising a fabric base substrate with an image-side and a back-side, and an ink-receiving layer, applied to the image-side of the base substrate, comprising, at least, water, a cationic polysaccharide and a secondary cationic charged polymer and applying an ink composition onto said printable recording media to form a printed image.
  • Said printed image will have, for instance, enhanced image quality and image permanence.
  • the printed image can be dried using any drying device attached to a printer such as, for instance, an IR heater.
  • the ink composition, that is ejected on the coated fabric print media includes water, organic co-solvent, pigment having dispersant associated with or attached thereto, and polymer binder particles.
  • “ejecting” includes technologies where ink compositions or other fluids are ejected from jetting architecture, such as inkjet architecture.
  • Inkjet architecture can include thermal or piezo inkjet pens. Additionally, such architecture can be configured to print varying drop sizes such as less than 10 nanograms (ng), less than 20 ng, less than 30 ng, less than 40 ng, less than 50 ng, etc. These upper limits can, in one example, also provide the upper limit of various ranges, where 1 ng or 2 ng can represent the lower end of the various range.
  • Ink compositions that can be printed on the coated fabric printable media of the present disclosure can be pigmented ink with a binder polymer, such as latex binder particles, e.g., acrylic latex, or polyurethane particles. These solids can be carried by a liquid vehicle that includes water, organic cosolvent, and any of a number of other liquid ingredients, e.g., surfactant, biocide, sequestering agent, dispersing polymer, etc.
  • the polymer binder particles can include, in some more specific examples, imine-cross-linkable groups that are available for reaction with the imine-type cross-linking groups of the cross-linking polymer (found in the coating or the coated fabric print media, for example).
  • polyurethanes and/or latex polymers can be used for this purpose.
  • the polyurethane may be aliphatic (straight- chained, branched, and/or alicyclic) or aromatic, or may be any of a variety of types of polyurethane, including polyester-type, some specific examples of commercially available aliphatic waterborne polyurethanes include Sancure® 1514, Sancure® 1591, Sancure® 2260, and Sancure® 2026 (all of which are available from Lubrizol Inc.).
  • castor oil-based polyurethanes include Alberdingkusa® CUR 69, Alberdingkusa® CUR 99, and Alberdingkusa® CUR 991 (all from Alberdingk Boley Inc.).
  • Other examples can include polyester-type polyurethanes that may be carboxylated and/or sulfonated.
  • Impranil® DLN-SD Mw 133,000 Mw; Acid Number 5.2; Tg -47°C; Melting Point 175-200 °C
  • Impranil® DL 1380 from Covestro (Germany)
  • an example of an aromatic polyester-polyurethane binder that can be used is Dispercoll® U42.
  • Example components used to prepare the Impranil® DLN-SD or other similar anionic aliphatic polyester-polyurethane binders can include pentyl glycols, e.g., neopentyl glycol; C3 to C5 alkyl dicarboxylic acids, e.g., adipic acid; C4 to Cx alkyl diisocyanates, e.g., hexamethylene diisocyanate (HDI or HMDI); diamine sulfonic acids, e.g., 1- [(2-aminoethyl)amino]-methanesulfonic acid or 2-[(2-aminoethyl)amino]-ethanesulfonic acid; etc.
  • pentyl glycols e.g., neopentyl glycol
  • C3 to C5 alkyl dicarboxylic acids e.g., adipic acid
  • Example components used to prepare the Dispercoll® U42 or other similar aromatic polyester-polyurethane binders can include aromatic dicarboxylic acids, e.g., phthalic acid; C 4 to C « alkyl dialcohols, e.g., hexane- 1,6-diol; C 4 to C « alkyl diisocyanates, e.g., hexamethylene diisocyanate (HDI); diamine sulfonic acids, e.g., 2-[(2-aminoethyl)amino]-methanesulfonic acid or l-[(2-aminoethyl)amino]-ethanesulfonic acid; etc.
  • Other types of polyurethanes can also be used, such as polyether-type polyurethane, polycarbonate ester-polyether-type polyurethane, and/or polycarbonate-type polyurethane.
  • polyurethane polymeric compound examples include vinyl-urethane, acrylic urethane, polyurethane-acrylic, polyether polyurethane, polyester polyurethane, polycaprolactam polyurethane, or polyether polyurethane. Any of these examples may be aliphatic or aromatic.
  • the polyurethane may include aromatic polyether polyurethanes, aliphatic polyether polyurethanes, aromatic polyester polyurethanes, aliphatic polyester polyurethanes, aromatic polycaprolactam polyurethanes, or aliphatic polycaprolactam polyurethanes.
  • the polymer binder particles can be a latex polymer, such as a (meth)acrylic polymers, otherwise referred to as poly(meth)acrylate-based polymer or poly(meth)acrylates.
  • poly(meth)acrylates include polymers made by hydrophobic addition monomers, such as C1-C12 alkyl acrylates, carboxylic containing monomers (e.g., acrylic acid, methacrylic acid), vinyl ester monomers (e.g., vinyl acetate, vinyl propionate, vinyl benzoate, vinyl pivalate, vinyl-2-ethylhexanoate, vinyl versatate, etc.), vinyl benzene monomer, C1-C12 alkyl acrylamide and methacrylamide (e.g., t-butyl acrylamide, sec-butyl acrylamide, N,N-di methyl acrylamide, etc.), cross-linking monomers (e.g., divinyl benzene,
  • polymers made from the polymerization and/or copolymerization of alkyl acrylate, alkyl methacrylate, and/or vinyl esters may be used. Any of the listed monomers (e.g., hydrophobic addition monomers, aromatic monomers, etc.) may be copolymerized with styrene or a styrene derivative. As specific examples, polymers made from the copolymerization of alkyl acrylate, alkyl methacrylate, and/or vinyl esters, with styrene or styrene derivatives may also be useful.
  • monomers e.g., hydrophobic addition monomers, aromatic monomers, etc.
  • polymers made from the copolymerization of alkyl acrylate, alkyl methacrylate, and/or vinyl esters, with styrene or styrene derivatives may also be useful.
  • the latex polymer for example, can have an acid number from 0 mg KOH/g to 60 mg KOH/g, from 0 mg KOH/g to 50 mg KOH/g, from 5 mg KOH/g to 60 mg KOH/g, from 5 mg KOH/g to 50 mg KOH/g, or from 10 mg KOH/g to 40 mg KOH/g.
  • the latex polymer can also have a glass transition temperature from -30° C to 50° C, from -30° C to 35° C, from -30° C to 15° C, from 0° C to 50° C, from 0° C to 35° C, or from 0 C to 15° C, for example.
  • the polymer binder particles can include hybrid particles of the polyurethane and the latex polymer, for example.
  • a polyurethane core and a latex shell can be prepared as a polyurethane-latex hybrid by copolymerizing the latex monomers, e.g., for a (meth)acrylic latex polymer or styrene (meth)acrylic latex polymer, in the presence of polyurethane particles.
  • Surfactant can be used in some examples, but in other examples, surfactant can be omitted because the polyurethane can have properties that allow it to act as an emulsifier for the emulsion polymerization reaction.
  • An initiator can be added to start the polymerization of the latex monomers, resulting in the polyurethane-latex hybrid particles.
  • the pigment in the ink composition can include pigment colorant, for example.
  • the pigment can be present in an amount from 0.5 wt% to 12 wt%, from 0.5 wt% to 10 wt%, from 1 wt% to 8 wt%, or from 2 wt% to 6 wt% in the ink composition.
  • the pigment in the ink composition can be self-dispersed with a polymer, oligomer, or small molecule; or can be dispersed with a separate dispersant.
  • the pigment can be any of a number of pigments of any of a number of primary or secondary colors, or can be black or white, for example.
  • colors can include cyan, magenta, yellow, red, blue, violet, red, orange, green, etc.
  • the ink composition can be a black ink with a carbon black pigment.
  • the ink composition can be a cyan or green ink with a copper phthalocyanine pigment, e.g., Pigment Blue 15:0, Pigment Blue 15: 1; Pigment Blue 15:3, Pigment Blue 15:4, Pigment Green 7, Pigment Green 36, etc.
  • the ink composition can be a magenta ink with a quinacridone pigment or a co-ciystal of quinacridone pigments.
  • Example quinacridone pigments that can be utilized can include PR122, PR192, PR202, PR206, PR207, PR209, PO48, PO49, PV19, PV42, or the like. These pigments tend to be magenta, red, orange, violet, or other similar colors.
  • the quinacridone pigment can be PR122, PR202, PV19, or a combination thereof.
  • the ink composition can be a yellow ink with an azo pigment, e.g., PY74 and PY155.
  • pigments include the following, which are available from BASF Corp.: Paliogen® Orange, Heliogen® Blue L 690 IF, Heliogen® Blue NBD 7010, Heliogen® Blue K 7090, Heliogen® Blue L 7101F, Heliogen® Blue L 6470, Heliogen® Green K 8683, Heliogen® Green L 9140, Chromophtal® Yellow 3G, Chromophtal® Yellow GR, Chromophtal® Yellow 8G, Igrazin® Yellow 5GT, and Igralite® Rubine 4BL.
  • the following pigments are available from Degussa Corp.: Color Black FWI, Color Black FW2, Color Black FW2V, Color Black 18, Color Black, FW200, Color Black 5150, Color Black SI 60, and Color Black 5170.
  • the following black pigments are available from Cabot Corp.: Regal® 400R, Regal® 330R, Regal® 660R, Mogul® L, Black Pearls® L, Monarch® 1400, Monarch® 1300, Monarch® 1100, Monarch® 1000, Monarch® 900, Monarch® 880, Monarch® 800, and Monarch® 700.
  • the following pigments are available from Orion Engineered Carbons GMBH: Printex® U, Printex® V, Printex® 140U, Printex® 140V, Printex® 35, Color Black FW 200, Color Black FW 2, Color Black FW 2V, Color Black FW 1, Color Black FW 18, Color Black S 160, Color Black S 170, Special Black 6, Special Black 5, Special Black 4A, and Special Black 4.
  • the following pigment is available from DuPont: Ti- pure® R-101.
  • the following pigments are available from Heubach: Monastral® Magenta, Monastral® Scarlet, Monastral® Violet R, Monastral® Red B, and Monastral® Violet Maroon B.
  • the following pigments are available from Clariant: Dalamar® Yellow YT-858-D, Permanent Yellow GR, Permanent Yellow G, Permanent Yellow DHG, Permanent Yellow NCG-71, Permanent Yellow GG, Hansa Yellow RA, Hansa Brilliant Yellow 5GX-02, Hansa Yellow-X, Novoperm® Yellow HR, Novoperm® Yellow FGL, Hansa Brilliant Yellow 10GX, Permanent Yellow G3R-01, Hostaperm® Yellow H4G, Hostaperm® Yellow H3G, Hostaperm® Orange GR, Hostaperm® Scarlet GO, and Permanent Rubine F6B.
  • the following pigments are available from Sun Chemical: Quindo® Magenta, Indofast® Brilliant Scarlet, Quindo® Red R6700, Quindo® Red R6713, Indofast® Violet, L74-1357 Yellow, L75-1331 Yellow, L75-2577 Yellow, and LHD9303 Black.
  • the following pigments are available from Birla Carbon: Raven® 7000, Raven® 5750, Raven® 5250, Raven® 5000 Ultra® II, Raven® 2000, Raven® 1500, Raven® 1250, Raven® 1200, Raven® 1190 Ultra®, Raven® 1170, Raven® 1255, Raven® 1080, and Raven® 1060.
  • the following pigments are available from Mitsubishi Chemical Corp.: No. 25, No. 33, No. 40, No. 47, No. 52, No. 900, No.
  • the colorant may be a white pigment, such as titanium dioxide, or other inorganic pigments such as zinc oxide and iron oxide.
  • a cyan color pigment may include C.I. Pigment Blue -1, - 2, -3, -15, -15: 1,-15:2, -15:3, -15:4, -16, -22, and -60; magenta color pigment may include C.I. Pigment Red -5, -7, -12, -48, -48: 1, -57, -112, -122, -123, -146, -168, -177, -184, -202, and C.I. Pigment Violet- 19; yellow pigment may include C.I.
  • Black pigment may include carbon black pigment or organic black pigment such as aniline black, e.g., C.I. Pigment Black 1. While several examples have been given herein, it is to be understood that any other pigment can be used that is useful in color modification, or dye may even be used in addition to the pigment.
  • pigments and dispersants are described separately herein, but there are pigments that are commercially available which include both the pigment and a dispersant suitable for ink composition formulation.
  • Specific examples of pigment dispersions that can be used, which include both pigment solids and dispersant are provided by example, as follows: HPC-K048 carbon black dispersion from DIC Corporation (Japan), HSKBPG-l l-CF carbon black dispersion from Dom Pedro (USA), HPC-C070 cyan pigment dispersion from DIC, Cabojet® 250C cyan pigment dispersion from Cabot Corporation (USA), 17-SE-126 cyan pigment dispersion from Dom Pedro, HPF-M046 magenta pigment dispersion from DIC, Cabojet® 265M magenta pigment dispersion from Cabot, HPJ-Y001 yellow pigment dispersion from DIC, 16-SE-96 yellow pigment dispersion from Dom Pedro, or Emacol SF Yellow AE2060F yellow pigment dispersion from Sanyo (Japan),
  • the pigment(s) can be dispersed by a dispersant that is adsorbed or ionically attracted to a surface of the pigment or can be covalently attached to a surface of the pigment as a self-dispersed pigment.
  • the dispersant can be an acrylic dispersant, such as a styrene (meth)acrylate dispersant, or other dispersant suitable for keeping the pigment suspended in the liquid vehicle.
  • the styrene (meth)acrylate dispersant can be used, as it can promote 7t-stacking between the aromatic ring of the dispersant and various types of pigments.
  • the styrene (meth)acrylate dispersant can have a weight average molecular weight from 4,000 Mw to 30,000 Mw.
  • the styrene-acrylic dispersant can have a weight average molecular weight of 8,000 Mw to 28,000 Mw, from 12,000 Mw to 25,000 Mw, from 15,000 Mw to 25,000 Mw, from 15,000 Mw to 20,000 Mw, or about 17,000 Mw.
  • the styrene (meth)acrylate dispersant can have an acid number from 100 to 350, from 120 to 350, from 150 to 300, from 180 to 250, for example.
  • Example commercially available styrene-acrylic dispersants can include Joncryl® 671, Joncryl® 71, Joncryl® 96, Joncryl® 680, Joncryl® 683, Joncryl® 678, Joncryl® 690, Joncryl® 296, Joncryl® 671, Joncryl® 696 or Joncryl® ECO 675 (all available from BASF Corp., Germany).
  • Joncryl® 671, Joncryl® 71, Joncryl® 96, Joncryl® 680, Joncryl® 683, Joncryl® 678, Joncryl® 690, Joncryl® 296, Joncryl® 671, Joncryl® 696 or Joncryl® ECO 675 all available from BASF Corp., Germany.
  • the term “about” is used to provide flexibility to a numerical range endpoint by providing that a given value may be “a little above” or “a little below” the endpoint.
  • the degree of flexibility of this term can be dictated by the particular variable and would be within the knowledge of those skilled in the art to determine based on experience and the associated description herein.
  • the term “acid value” or “acid number” refers to the mass of potassium hydroxide (KOH) in milligrams that can be used to neutralize one gram of substance (mg KOH/g), such as the polyurethane disclosed herein. This value can be determined, in one example, by dissolving or dispersing a known quantity of a material in organic solvent and then titrating with a solution of potassium hydroxide (KOH) of known concentration for measurement.
  • the hard segments and soft segments can be used to calculate the glass transition temperature of the polymer with the hard and soft segments being calculated based on the various segments used as the homopolymer for the calculation.
  • a weight ratio range of about 1 wt% to about 20 wt% should be interpreted to include not only the explicitly recited limits of about 1 wt% and about 20 wt%, but also to include individual weights such as 2 wt%, 11 wt%, 14 wt%, and sub-ranges such as 10 wt% to 20 wt%, 5 wt% to 15 wt%, etc.
  • Table 2 illustrates the formulation of the coating compositions (in dry weight %) and their viscosity, solids and the amount to be applied to the textile-based substrate in order to produce the printable recording media as defined herein.
  • Deionized water is added to adjust the coating composition to the required solid content.
  • the viscosity is measured at room temperature (25°C) using a Viscosity viscometer.
  • the same images are printed on the experimental media samples EXP 0 to EXP 8 with a thermal inkjet pen (at 3 dpp ink with an A3410, available from HP Inc.).
  • the printed samples are cured by heating at 150 °C for 3 minutes.
  • the inks used for this printing examples are formulated based on the following recipe: 6 % of PUB DLN-SD, 6 % of glycerol, 0.5% of crodafosN3® acid, 1% of LEG-1, 0.22% of Aticide°B20, 0.3 % of surfynol ' 440, 3% of cyan pigment dispersion or 2.5% carbon black and balance of water.
  • Optical density is measured herein using an X-RITETM Spectrodensitometer (X-Rite Corporation), such as a Series 500 Densitometer.
  • washfastness can be defined as the optical density (OD) or delta E (AE) that is retained after standard washing machine. To test washfastness, the samples are washed for 5 cycles using a washing machine at 40 °C with detergent and then air dried.
  • the various coated samples are also evaluated to obtain initial optical density (OD) and L*a*b* color space values, which are represented in the following tables as “initial” values (i.e. pre-wash).
  • the printed fabric substrates are washed in a standard washing machine typically used to wash clothing, namely the WHIRLPOOL® WTW5000DW, with detergent.
  • the washing machine settings were set as follows: Soil level “medium,” temperature “warm,” e.g., about 40 °C, and wash setting “normal” with a single rinse cycle.
  • the full washing machine cycle is repeated for 5 full washes, air drying the printed fabric substrates between wash cycles. After the five fully washing cycles, optical density (OD) and L*a*b* values were again measured for comparison.
  • the delta E (AE) values were calculated using the 2000 standard denoted as AE 2 ooo- [0078]
  • the % change in optical density (AOD) and various AE values (AE 2000) are collected to compare the samples before washing and the samples after washing.
  • Table 3 illustrate the resulting printing performances and durability for images printed on experimental media samples.
  • Table 3 shows the summary of optical density, black optical density (KOD), cyan ink optical density (COD), and wash durability of the coated fabric media with the compositions having different cationic polysaccharide to secondary cationic charged polymer ratio. (For OD value, the higher the better; for Delta E, the lower the better). It can be seen that media with coated cationic polysaccharide composition improves both black optical density (KOD) and cyan ink optical density (COD) and wash durability comparing with un-treated same fabric.
  • EXP4 is a coating composition having a ratio of cationic poly saccharide/ secondary cationic charged polymer of 20:80.
  • the Table 4 shows the impact of pick-up weight of modification composition on optical density and wash durability. It can be seen that as low as 1 gsm of modification amount can trigger stable good wash durability for both cyan and black inks.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Ink Jet Recording Methods And Recording Media Thereof (AREA)

Abstract

L'invention concerne un support d'enregistrement imprimable comprenant un substrat de base en tissu ayant une face image et une face arrière et une couche de revêtement, appliquée sur la face image du substrat de base, comprenant au moins de l'eau, un polysaccharide cationique et un polymère chargé cationique secondaire. L'invention divulgue également le procédé de fabrication de ce support imprimable et le procédé d'impression l'utilisant.
PCT/US2020/049533 2020-09-04 2020-09-04 Support d'enregistrement imprimable Ceased WO2022050958A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/US2020/049533 WO2022050958A1 (fr) 2020-09-04 2020-09-04 Support d'enregistrement imprimable

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Application Number Priority Date Filing Date Title
PCT/US2020/049533 WO2022050958A1 (fr) 2020-09-04 2020-09-04 Support d'enregistrement imprimable

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017078728A1 (fr) * 2015-11-06 2017-05-11 Hewlett-Packard Development Company, L.P. Support d'enregistrement imprimable
WO2018048463A1 (fr) * 2016-09-09 2018-03-15 Hewlett-Packard Development Company, L.P. Support d'impression de tissu
US20190351659A1 (en) * 2015-09-29 2019-11-21 Hewlett-Packard Development Company, Lp. Printable media
WO2020131787A1 (fr) * 2018-12-18 2020-06-25 Hewlett-Packard Development Company, L.P. Composition de prétraitement et support imprimable

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20190351659A1 (en) * 2015-09-29 2019-11-21 Hewlett-Packard Development Company, Lp. Printable media
WO2017078728A1 (fr) * 2015-11-06 2017-05-11 Hewlett-Packard Development Company, L.P. Support d'enregistrement imprimable
WO2018048463A1 (fr) * 2016-09-09 2018-03-15 Hewlett-Packard Development Company, L.P. Support d'impression de tissu
WO2020131787A1 (fr) * 2018-12-18 2020-06-25 Hewlett-Packard Development Company, L.P. Composition de prétraitement et support imprimable

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