US20210310188A1 - Textile printing - Google Patents

Textile printing Download PDF

Info

Publication number
US20210310188A1
US20210310188A1 US17/266,964 US201817266964A US2021310188A1 US 20210310188 A1 US20210310188 A1 US 20210310188A1 US 201817266964 A US201817266964 A US 201817266964A US 2021310188 A1 US2021310188 A1 US 2021310188A1
Authority
US
United States
Prior art keywords
thermally curable
ink composition
pigment
curable ink
light source
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.)
Abandoned
Application number
US17/266,964
Other languages
English (en)
Inventor
Ronald A. Askeland
Blair A. Butler
Jie Zheng
Dennis Z. Guo
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
Assigned to HEWLETT-PACKARD DEVELOPMENT COMPANY, L.P. reassignment HEWLETT-PACKARD DEVELOPMENT COMPANY, L.P. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: ASKELAND, RONALD A., BUTLER, BLAIR A., GUO, DENNIS Z., ZHENG, JIE
Publication of US20210310188A1 publication Critical patent/US20210310188A1/en
Abandoned legal-status Critical Current

Links

Images

Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
    • D06P5/30—Ink jet printing
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • 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
    • D06P5/20—Physical treatments affecting dyeing, e.g. ultrasonic or electric
    • D06P5/2066—Thermic treatments of textile materials
    • D06P5/2077—Thermic treatments of textile materials after dyeing
    • 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
    • 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
    • D06P5/002—Locally enhancing dye affinity of a textile material by chemical means
    • 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
    • D06P5/20—Physical treatments affecting dyeing, e.g. ultrasonic or electric
    • D06P5/2066—Thermic treatments of textile materials
    • 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
    • D06P5/20—Physical treatments affecting dyeing, e.g. ultrasonic or electric
    • D06P5/2066—Thermic treatments of textile materials
    • D06P5/2083—Thermic treatments of textile materials heating with IR or microwaves

Definitions

  • Textile printing methods often include rotary and/or flat-screen printing.
  • Traditional analog printing typically involves the creation of a plate or a screen, i.e., an actual physical image from which ink is transferred to the textile.
  • Both rotary and flat screen printing have great volume throughput capacity, but also have limitations on the maximum image size that can be printed. For large images, pattern repeats are used.
  • digital inkjet printing enables greater flexibility in the printing process, where images of any desirable size can be printed immediately from an electronic image without pattern repeats.
  • Inkjet printers are gaining acceptance for digital textile printing.
  • Inkjet printing is a non-impact printing method that utilizes electronic signals to control and direct droplets or a stream of ink to be deposited on media.
  • FIG. 1 is a flow diagram illustrating an example of a printing method
  • FIG. 2 is a flow diagram illustrating an example of a printing method
  • FIGS. 3A and 3B are schematic diagram of different examples of a printing system disclosed herein;
  • FIG. 4 depicts black and white reproductions of originally colored photographs of control, example, and comparative black ink print swaths on cotton after washing;
  • FIG. 5 depicts black and white reproductions of originally colored photographs of control, example, and comparative cyan ink print swaths on cotton after washing;
  • FIG. 6 depicts black and white reproductions of originally colored photographs of control, example, and comparative black ink print swaths on nylon after washing;
  • FIG. 7 depicts black and white reproductions of originally colored photographs of control, example, and comparative cyan ink print swaths on nylon after washing;
  • FIG. 8 is a graph depicting the change in optical density (delta (A) OD) for the control, example, and comparative black and cyan ink print swaths;
  • FIG. 9 is a schematic illustration of a print and different exposure regions that was used in Example 2.
  • FIG. 10A depicts black and white reproductions of originally colored photographs of first example inks printed on cotton both before and after washing, where each print included a control region (untreated control) and an example region (treated with 395 nm UV LED);
  • FIG. 10B depicts black and white reproductions of originally colored photographs of the first example inks printed on cotton both before and after washing, where each comparative print was treated with a heat press;
  • FIG. 11A depicts black and white reproductions of originally colored photographs of second example inks printed on cotton both before and after washing, where each print included a control region (untreated control) and an example region (treated with 395 nm UV LED);
  • FIG. 11B depicts black and white reproductions of originally colored photographs of the second example inks printed on cotton both before and after washing, where each comparative print was treated with a heat press;
  • FIG. 12A depicts black and white reproductions of originally colored photographs of third example inks printed on cotton both before and after washing, where each print included a control region (untreated control) and an example region (treated with 395 nm UV LED); and
  • FIG. 12B depicts black and white reproductions of originally colored photographs of the third example inks printed on cotton both before and after washing, where each comparative print was treated with a heat press.
  • UV curing ultraviolet curing
  • the ink or other liquid used in printing includes a photoinitiator to initiate the photochemical reaction. This adds additional components to the overall printing process.
  • a thermally curable ink composition is coupled with rapid thermal curing by a narrow wavelength light source.
  • the thermally curable ink composition disclosed herein does not undergo a photochemical reaction (and thus does not include a photoinitiator) when exposed to the UV and/or IR radiation. Rather, the pigment in the ink absorbs the UV and/or IR radiation, and as a result, is heated. Because heating occurs through the pigment's absorption of the UV and/or IR radiation, the heating is selective, i.e., ink printed areas of the textile are heated, while non-printed areas of the textile remain unheated. Heating, and thus pigment fixation to the textile substrate, occur with 3 seconds or less of UV and/or IR exposure.
  • Washfastness refers to the ability of a print on a fabric to retain its color after being exposed to washing. Washfastness can be measured in terms of ⁇ E.
  • ⁇ E refers to the change in the L*a*b* values of a color (e.g., cyan, magenta, yellow, black, red, green, blue, white) after washing. ⁇ E can be calculated by different equations, such as the CIEDE1976 color-difference formula and the CIEDE2000 color-difference formula, both of which are set forth in the Examples section herein.
  • wt % active refers to the loading of an active component of a dispersion or other formulation that is present in the thermally curable ink composition or a pre-treatment composition.
  • the pigment may be present in a water-based formulation (e.g., a stock solution or dispersion) before being incorporated into the ink composition.
  • the wt % actives of the pigment accounts for the loading (as a weight percent) of the pigment that is present in the ink composition, and does not account for the weight of the other components (e.g., water, etc.) that are present in the formulation with the pigment.
  • wt % without the term actives, refers to either i) the loading (in the pre-treatment or thermally curable ink composition) of a 100% active component that does not include other non-active components therein, or ii) the loading (in the pre-treatment or ink composition) of a material or component that is used “as is” and thus the wt % accounts for both active and non-active components.
  • the thermally curable inkjet ink includes from about 1 wt % active to about 6 wt % active of a pigment that absorbs ultraviolet radiation, infrared radiation, or a combination thereof, based on a total weight of the thermally curable ink composition; from about 2 wt % active to about 20 wt % active of a polymeric binder, based on the total weight of the thermally curable ink composition; and an aqueous ink vehicle.
  • the pigment that is included in the thermally curable inkjet ink is capable of absorbing ultraviolet radiation having a wavelength ranging from about 10 nm to about 400 nm, infrared radiation having a wavelength ranging from about 760 nm to about 1 mm, or both ultraviolet and infrared radiation.
  • Carbon black is an example of a black UV and IR absorbing pigment.
  • suitable UV absorbing blue or cyan organic pigments include C.I. Pigment Blue 1, C.I. Pigment Blue 2, C.I. Pigment Blue 3, C.I. Pigment Blue 15, Pigment Blue 15:3, C.I. Pigment Blue 15:4, C.I. Pigment Blue 16, C.I. Pigment Blue 18, C.I. Pigment Blue 22, C.I. Pigment Blue 25, C.I. Pigment Blue 60, C.I. Pigment Blue 65, C.I. Pigment Blue 66, C.I. Vat Blue 4, and C.I. Vat Blue 60.
  • suitable UV absorbing magenta, red, or violet pigments include C.I. Pigment Red 1, C.I.
  • Pigment Red 2 C.I. Pigment Red 3, C.I. Pigment Red 4, C.I. Pigment Red 5, C.I. Pigment Red 6, C.I. Pigment Red 7, C.I. Pigment Red 8, C.I. Pigment Red 9, C.I. Pigment Red 10, C.I. Pigment Red 11, C.I. Pigment Red 12, C.I. Pigment Red 14, C.I. Pigment Red 15, C.I. Pigment Red 16, C.I. Pigment Red 17, C.I. Pigment Red 18, C.I. Pigment Red 19, C.I. Pigment Red 21, C.I. Pigment Red 22, C.I. Pigment Red 23, C.I. Pigment Red 30, C.I. Pigment Red 31, C.I. Pigment Red 32, C.I.
  • Pigment Violet 33 C.I. Pigment Violet 36, C.I. Pigment Violet 38, C.I. Pigment Violet 43, C.I. Pigment Violet 50 and any co-crystal of quinacridone pigments.
  • suitable UV absorbing yellow pigments include C.I. Pigment Yellow 1, C.I. Pigment Yellow 2, C.I. Pigment Yellow 3, C.I. Pigment Yellow 4, C.I. Pigment Yellow 5, C.I. Pigment Yellow 6, C.I. Pigment Yellow 7, C.I. Pigment Yellow 10, C.I. Pigment Yellow 11, C.I. Pigment Yellow 12, C.I. Pigment Yellow 13, C.I. Pigment Yellow 14, C.I. Pigment Yellow 16, C.I. Pigment Yellow 17, C.I. Pigment Yellow 24, C.I.
  • Pigment Yellow 34 C.I. Pigment Yellow 35, C.I. Pigment Yellow 37, C.I. Pigment Yellow 53, C.I. Pigment Yellow 55, C.I. Pigment Yellow 65, C.I. Pigment Yellow 73, C.I. Pigment Yellow 74, C.I. Pigment Yellow 75, C.I. Pigment Yellow 77, C.I. Pigment Yellow 81, C.I. Pigment Yellow 83, C.I. Pigment Yellow 93, C.I. Pigment Yellow 94, C.I. Pigment Yellow 95, C.I. Pigment Yellow 97, C.I. Pigment Yellow 98, C.I. Pigment Yellow 99, C.I. Pigment Yellow 108, C.I. Pigment Yellow 109, C.I.
  • Pigment Yellow 110 C.I. Pigment Yellow 113, C.I. Pigment Yellow 114, C.I. Pigment Yellow 117, C.I. Pigment Yellow 120, C.I. Pigment Yellow 122, C.I. Pigment Yellow 124, C.I. Pigment Yellow 128, C.I. Pigment Yellow 129, C.I. Pigment Yellow 133, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 147, C.I. Pigment Yellow 151, C.I. Pigment Yellow 153, C.I. Pigment Yellow 154, C.I. Pigment Yellow 155, C.I. Pigment Yellow 167, C.I. Pigment Yellow 172, C.I. Pigment Yellow 180, C.I. Pigment Yellow 185, and C.I. Pigment Yellow 213.
  • Solid pigments may be incorporated into the aqueous ink vehicle, or they may be part of a pigment dispersion that is incorporated into the aqueous ink vehicle.
  • the pigment dispersion may include a pigment and a separate dispersant, or may include a self-dispersed pigment. Whether separately dispersed or self-dispersed, the pigment can be any of a number of primary or secondary colors, or black or white.
  • the pigment may be any color, including, as examples, a cyan pigment, a magenta pigment, a yellow pigment, a black pigment, a violet pigment, a green pigment, a brown pigment, an orange pigment, a purple pigment, a white pigment, or combinations thereof.
  • the pigment is present in the thermally curable inkjet ink in an amount ranging from about 1 wt % active to about 6 wt % active of the total weight of the thermally curable inkjet ink. In another example, the pigment is present in the thermally curable inkjet ink in an amount ranging from about 1.5 wt % active to about 4 wt % active of the total weight of the thermally curable inkjet ink.
  • the pigment and separate dispersant or the self-dispersed pigment may be dispersed in water alone or in combination with an additional water soluble or water miscible co-solvent, such as 2-pyrrolidone, 1-(2-hydroxyethyl)-2-pyrrolidone, glycerol, 2-methyl-1,3-propanediol, 1,2-butane diol, diethylene glycol, triethylene glycol, tetraethylene glycol, or a combination thereof.
  • an additional water soluble or water miscible co-solvent such as 2-pyrrolidone, 1-(2-hydroxyethyl)-2-pyrrolidone, glycerol, 2-methyl-1,3-propanediol, 1,2-butane diol, diethylene glycol, triethylene glycol, tetraethylene glycol, or a combination thereof.
  • the liquid components of the pigment dispersion become part of the aqueous ink vehicle in the thermally curable inkjet ink.
  • the thermally curable inkjet ink also includes a polymeric binder.
  • the polymeric binder are selected from the group consisting of a polyester-polyurethane binder, a polyether-polyurethane binder, a polycarbonate-polyurethane binder, and a latex binder. In other example, hybrids of any of these binders may be used.
  • the thermally curable inkjet ink includes the polyester-polyurethane binder.
  • the polyester-polyurethane binder is a sulfonated polyester-polyurethane binder.
  • the sulfonated polyester-polyurethane binder can include diaminesulfonate groups.
  • the polyester-polyurethane binder is a sulfonated polyester-polyurethane binder, and is one of: i) an aliphatic compound including multiple saturated carbon chain portions ranging from C 4 to C 10 in length, and that is devoid of an aromatic moiety, or ii) an aromatic compound including an aromatic moiety and multiple saturated carbon chain portions ranging from C 4 to C 10 in length.
  • the sulfonated polyester-polyurethane binder can be anionic.
  • the sulfonated polyester-polyurethane binder can also be aliphatic, including saturated carbon chains as part of the polymer backbone or as a side-chain thereof, e.g., C 2 to C 10 , C 3 to C 8 , or C 3 to C 6 alkyl.
  • These polyester-polyurethane binders can be described as “alkyl” or “aliphatic” because these carbon chains are saturated and because they are devoid of aromatic moieties.
  • An example of an anionic aliphatic polyester-polyurethane binder that can be used is IMPRANIL® DLN-SD (CAS #375390-41-3; Mw 45,000 Mw; Acid Number 5.2; Tg ⁇ 47° C.; Melting Point 175-200° C.) from Covestro.
  • 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); C 4 to C 10 alkyldiol (e.g., hexane-1,6-diol); C 4 to C 10 alkyl dicarboxylic acids (e.g., adipic acid); C 4 to C 10 alkyl diisocyanates (e.g., hexamethylene diisocyanate (HDI)); diamine sulfonic acids (e.g., 1-[(2-aminoethyl)amino]-ethanesulfonic acid); etc.
  • pentyl glycols e.g., neopentyl glycol
  • C 4 to C 10 alkyldiol e.g., hexane-1,6-diol
  • the sulfonated polyester-polyurethane binder can be aromatic (or include an aromatic moiety) and can include aliphatic chains.
  • aromatic polyester-polyurethane binder that can be used is DISPERCOLL® U42 (CAS #157352-07-3).
  • 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 10 alkyl dialcohols (e.g., hexane-1,6-diol); C 4 to C 10 alkyl diisocyanates (e.g., hexamethylene diisocyanate (HDI)); diamine sulfonic acids (e.g., 1-[(2-aminoethyl)amino]-ethanesulfonic acid); etc.
  • aromatic dicarboxylic acids e.g., phthalic acid
  • C 4 to C 10 alkyl dialcohols e.g., hexane-1,6-diol
  • C 4 to C 10 alkyl diisocyanates e.g., hexamethylene diisocyanate (HDI)
  • diamine sulfonic acids
  • polyester-polyurethanes can also be used, including IMPRANIL® DL 1380, which can be somewhat more difficult to jet from thermal inkjet printheads compared to IMPRANIL® DLN-SD and DISPERCOLL® U42, but still can be acceptably jetted in some examples, and can also provide acceptable washfastness results on a variety of fabric types.
  • the polyester-polyurethane binders disclosed herein may have a weight average molecular weight (Mw, g/mol) ranging from about 20,000 to about 300,000.
  • Mw weight average molecular weight
  • the weight average molecular weight can range from about 50,000 to about 500,000, from about 100,000 to about 400,000, or from about 150,000 to about 300,000.
  • the polyester-polyurethane binders disclosed herein may have an acid number that ranges from about 1 mg/g KOH to about 50 mg/g KOH.
  • the term “acid number” refers to the mass of potassium hydroxide (KOH) in milligrams that is used to neutralize one gram of the sulfonated polyester-polyurethane binder.
  • KOH potassium hydroxide
  • a known amount of a sample of the polyester-polyurethane binder may be dispersed in water and the aqueous dispersion may be titrated with a polyelectrolyte titrant of a known concentration.
  • a current detector for colloidal charge measurement may be used.
  • An example of a current detector is the MUtek PCD-05 Smart Particle Charge Detector (available from BTG).
  • the current detector measures colloidal substances in an aqueous sample by detecting the streaming potential as the sample is titrated with the polyelectrolyte titrant to the point of zero charge.
  • An example of a suitable polyelectrolyte titrant is poly(diallyldimethylammonium chloride) (i.e., PolyDADMAC).
  • the acid number of the sulfonated polyester-polyurethane binder can range from about 1 mg KOH/g to about 200 mg KOH/g, from about 2 mg KOH/g to about 100 mg KOH/g, or from about 3 mg KOH/g to about 50 mg KOH/g.
  • the polyester-polyurethane binder has a weight average molecular weight (g/mol) ranging from about 20,000 to about 300,000 and an acid number ranging from about 1 mg KOH/g to about 50 mg KOH/g.
  • the average particle size of the polyester-polyurethane binders disclosed herein may range from about 20 nm to about 500 nm.
  • the sulfonated polyester-polyurethane binder can have an average particle size ranging from about 20 nm to about 500 nm, from about 50 nm to about 350 nm, or from about 100 nm to about 250 nm.
  • the particle size of any solids herein, including the average particle size of the dispersed polymer binder can be determined using a NANOTRAC® Wave device, from Microtrac, e.g., NANOTRAC® Wave II or NANOTRAC® 150, etc, which measures particles size using dynamic light scattering. Average particle size can be determined using particle size distribution data generated by the NANOTRAC® Wave device.
  • thermally curable inkjet ink examples include a polyether-polyurethane binder.
  • polyether-polyurethanes examples include IMPRANIL® LP DSB 1069, IMPRANIL® DLE, IMPRANIL® DAH, or IMPRANIL® DL 1116 (Covestro (Germany)); or HYDRAN® WLS-201 or HYDRAN® WLS-201K (DIC Corp. (Japan)); or TAKELAC® W-6061T or TAKELAC® WS-6021 (Mitsui (Japan)).
  • thermally curable inkjet ink examples include a polycarbonate-polyurethane binder.
  • polycarbonate-polyurethanes that may be used as the polymeric binder include IMPRANIL® DLC-F or IMPRANIL® DL 2077 (Covestro (Germany)); or HYDRAN® WLS-213 (DIC Corp. (Japan)); or TAKELAC® W-6110 (Mitsui (Japan)).
  • the thermally curable inkjet ink includes a latex polymer binder.
  • latex polymer generally refers to any dispersed polymer prepared from acrylate and/or methacrylate monomers, including an aromatic (meth)acrylate monomer that results in aromatic (meth)acrylate moieties as part of the latex.
  • the latex polymer may be devoid of styrene.
  • the latex particles can include a single heteropolymer that is homogenously copolymerized.
  • a multi-phase latex polymer can be prepared that includes a first heteropolymer and a second heteropolymer.
  • the two heteropolymers can be physically separated in the latex particles, such as in a core-shell configuration, a two-hemisphere configuration, smaller spheres of one phase distributed in a larger sphere of the other phase, interlocking strands of the two phases, and so on.
  • the first heteropolymer phase can be polymerized from two or more aliphatic (meth)acrylate ester monomers or two or more aliphatic (meth)acrylamide monomers.
  • the second heteropolymer phase can be polymerized from a cycloaliphatic monomer, such as a cycloaliphatic (meth)acrylate monomer or a cycloaliphatic (meth)acrylamide monomer.
  • the first or second heteropolymer phase can include the aromatic (meth)acrylate monomer, e.g., phenyl, benzyl, naphthyl, etc.
  • the aromatic (meth)acrylate monomer can be a phenoxylalkyl (meth)acrylate that forms a phenoxylalkyl (meth)acrylate moiety within the latex polymer, e.g. phenoxylether, phenoxylpropyl, etc.
  • the second heteropolymer phase can have a higher T g than the first heteropolymer phase in one example.
  • the first heteropolymer composition may be considered a soft polymer composition and the second heteropolymers composition may be considered a hard polymer composition.
  • the first heteropolymer composition can be present in the latex polymer in an amount ranging from about 15 wt % to about 70 wt % of a total weight of the polymer particle, and the second heteropolymer composition can be present in an amount ranging from about 30 wt % to about 85 wt % of the total weight of the polymer particle.
  • the first heteropolymer composition can be present in an amount ranging from about 30 wt % to about 40 wt % of a total weight of the polymer particle, and the second heteropolymer composition can be present in an amount ranging from about 60 wt % to about 70 wt % of the total weight of the polymer particle.
  • heteropolymer(s) or copolymer(s) can include a number of various types of copolymerized monomers, including aliphatic(meth)acrylate ester monomers, such as linear or branched aliphatic (meth)acrylate monomers, cycloaliphatic (meth)acrylate ester monomers, or aromatic monomers.
  • aliphatic(meth)acrylate ester monomers such as linear or branched aliphatic (meth)acrylate monomers, cycloaliphatic (meth)acrylate ester monomers, or aromatic monomers.
  • the aromatic monomer(s) selected for use can include an aromatic (meth)acrylate monomer.
  • aromatic (meth)acrylate does not include the copolymerization of two different monomers copolymerized together into a common polymer, e.g., styrene and methyl methacrylate. Rather, the term “aromatic (meth)acrylate” refers to a single aromatic monomer that is functionalized by an acrylate, methacrylate, acrylic acid, or methacrylic acid, etc.
  • the weight average molecular weight (g/mol) of the latex polymer can be from 50,000 to 500,000, for example.
  • the acid number of the latex polymer can be from 2 mg KOH/g to 40 mg KOH/g, from 2 mg KOH/g to 30 mg KOH/g, or 3 mg KOH/g to 26 mg KOH/g, or 4 mg KOH/g to 20 mg KOH/g, for example.
  • the latex polymer can be in acid form, such as in the form of a polymer with (meth)acrylic acid surface groups, or may be in its salt form, such as in the form of a polymer with poly(meth)acrylate groups.
  • any of the polyurethane-based polymeric binders may be present in the thermally curable inkjet ink in a total amount ranging from about 2 wt % active to about 15 wt % active of the total weight of the thermally curable inkjet ink.
  • the latex polymer can be present in the thermally curable inkjet ink at a relatively high concentration, e.g., from 5 wt % active to 20 wt % active, from 6 wt % active to 15 wt % active, or from 7 wt % active to 12 wt % active, for example.
  • the polymeric binder (prior to being incorporated into the thermally curable inkjet ink) may be dispersed in water alone or in combination with an additional water soluble or water miscible co-solvent, such as those described for the pigment dispersion. It is to be understood however, that the liquid components of the binder dispersion become part of the aqueous liquid vehicle in the thermally curable inkjet ink.
  • thermally curable inkjet ink also include a wax.
  • suitable waxes include those that are commercially available from Lubrizol, such as LIQUILUBETM 411, LIQUILUBETM 405, LIQUILUBETM 488, LIQUILUBETM 443, and LIQUILUBETM 454; from Michelman, such as ME80825, ME48040, ME98040M1, ME61335, ME90842, ME91240, and ML160; from Keim-Additec, such as ULTRALUBE® E-521/20, ULTRALUBE® E-7093, ULTRALUBE® 7095/1, ULTRALUBE® E-8046, ULTRALUBE® E-502V, and ULTRALUBE® E-842N, or from BYK, such as AQUACER® 2650, AQUACER® 507, AQUACER® 533, AQUACER® 515, AQUACER® 537, AQUASLIPTM 671, and AQUASLIPTM
  • the wax may be present in the thermally curable inkjet ink in a total amount ranging from greater than 0 wt % active to about 1.5 wt % active of the total weight of the thermally curable inkjet ink.
  • Other examples of the thermally curable inkjet ink do not include the wax.
  • the thermally curable inkjet ink includes the aqueous ink vehicle.
  • aqueous ink vehicle may refer to the liquid fluid with which the pigment (dispersion) and polymeric binder are mixed to form a thermal or a piezoelectric inkjet ink(s).
  • the vehicle may include a co-solvent, an anti-kogation agent, an anti-decel agent, a surfactant, a biocide, a chelating agent, a pH adjuster, or combinations thereof.
  • the vehicle consists of the co-solvent, the anti-kogation agent, the anti-decel agent, the surfactant, the biocide, a pH adjuster, or a combination thereof.
  • the vehicle consists of water and the co-solvent, the anti-kogation agent, the anti-decel agent, the surfactant, the biocide, a pH adjuster, or a combination thereof.
  • the vehicle consists of the anti-kogation agent, the anti-decel agent, the surfactant, the biocide, a pH adjuster, and water.
  • the vehicle consists of water and the co-solvent, the anti-kogation agent, the surfactant, the chelating agent, the biocide, a pH adjuster, or a combination thereof.
  • the vehicle may include co-solvent(s).
  • the co-solvent(s) may be present in an amount ranging from about 4 wt % to about 30 wt % (based on the total weight of the inkjet ink).
  • the vehicle includes glycerol.
  • co-solvents include alcohols, aliphatic alcohols, aromatic alcohols, diols, glycol ethers, polyglycol ethers, caprolactams, formamides, acetamides, and long chain alcohols.
  • Examples of such compounds include primary aliphatic alcohols, secondary aliphatic alcohols, 1,2-alcohols, 1,3-alcohols, 1,5-alcohols, ethylene glycol alkyl ethers, propylene glycol alkyl ethers, higher homologs (C 6 -C 12 ) of polyethylene glycol alkyl ethers, N-alkyl caprolactams, unsubstituted caprolactams, both substituted and unsubstituted formam ides, both substituted and unsubstituted acetamides, and the like.
  • Specific examples of alcohols may include ethanol, isopropyl alcohol, butyl alcohol, and benzyl alcohol.
  • EPHD 2-ethyl-2-(hydroxymethyl)-1,3-propane diol
  • 2-methyl-1,3-propanediol 1,2-butanediol
  • dimethyl sulfoxide 1,2-butanediol
  • alkyldiols such as 1,2-hexanediol.
  • the co-solvent may also be a polyhydric alcohol or a polyhydric alcohol derivative.
  • polyhydric alcohols may include ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, triethylene glycol, 1,5-pentanediol, 1,2-hexanediol, 1,2,6-hexanetriol, glycerin, trimethylolpropane, and xylitol.
  • polyhydric alcohol derivatives may include an ethylene oxide adduct of diglycerin.
  • the co-solvent may also be a nitrogen-containing solvent.
  • nitrogen-containing solvents may include 2-pyrrolidone, 1-(2-hydroxyethyl)-2-pyrrolidone, N-methyl-2-pyrrolidone, cyclohexylpyrrolidone, and triethanolamine.
  • An anti-kogation agent may also be included in the vehicle of a thermal inkjet formulation.
  • Kogation refers to the deposit of dried ink on a heating element of a thermal inkjet printhead.
  • Anti-kogation agent(s) is/are included to assist in preventing the buildup of kogation.
  • the anti-kogation agent may improve the jettability of the thermal inkjet ink.
  • the anti-kogation agent may be present in the thermal inkjet ink in an amount ranging from about 0.1 wt % active to about 1.5 wt % active, based on the total weight of the thermal inkjet ink.
  • the anti-kogation agent is present in the thermally curable inkjet ink in an amount of about 0.5 wt % active, based on the total weight of the thermally curable inkjet ink.
  • Suitable anti-kogation agents include oleth-3-phosphate (commercially available as CRODAFOSTM O3 A or CRODAFOSTM N-3A) or dextran 500k.
  • Other suitable examples of the anti-kogation agents include CRODAFOSTM HCE (phosphate-ester from Croda Int.), CRODAFOS® N10 (oleth-10-phosphate from Croda Int.), or DISPERSOGEN® LFH (polymeric dispersing agent with aromatic anchoring groups, acid form, anionic, from Clariant), etc.
  • the vehicle may include anti-decel agent(s).
  • Decel refers to a decrease in drop velocity over time with continuous firing.
  • Anti-decel agent(s) is/are included to assist in preventing decel.
  • the anti-decel agent may improve the jettability of the inkjet ink.
  • the anti-decel agent may be present in an amount ranging from about 0.2 wt % active to about 5 wt % active (based on the total weight of the inkjet ink).
  • the anti-decel agent is present in the thermally curable inkjet ink in an amount of about 1 wt % active, based on the total weight of the thermally curable inkjet ink.
  • ethoxylated glycerin having the following formula:
  • a+b+c ranges from about 5 to about 60, or in other examples, from about 20 to about 30.
  • the vehicle of the thermally curable inkjet ink may also include surfactant(s).
  • the surfactant may be present in an amount ranging from about 0.01 wt % active to about 5 wt % active (based on the total weight of the inkjet ink).
  • the surfactant is present in the inkjet ink in an amount ranging from about 0.05 wt % active to about 3 wt % active, based on the total weight of the thermally curable inkjet ink.
  • the surfactant may include anionic and/or non-ionic surfactants.
  • anionic surfactant may include alkylbenzene sulfonate, alkylphenyl sulfonate, alkylnaphthalene sulfonate, higher fatty acid salt, sulfate ester salt of higher fatty acid ester, sulfonate of higher fatty acid ester, sulfate ester salt and sulfonate of higher alcohol ether, higher alkyl sulfosuccinate, polyoxyethylene alkylether carboxylate, polyoxyethylene alkylether sulfate, alkyl phosphate, and polyoxyethylene alkyl ether phosphate.
  • anionic surfactant may include dodecylbenzenesulfonate, isopropylnaphthalenesulfonate, monobutylphenylphenol monosulfonate, monobutylbiphenyl sulfonate, monobutylbiphenylsul fonate, and dibutylphenylphenol disulfonate.
  • non-ionic surfactant may include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyglycerin fatty acid ester, polyoxyethylene alkylamine, polyoxyethylene fatty acid amide, alkylalkanolamide, polyethylene glycol polypropylene glycol block copolymer, acetylene glycol, and a polyoxyethylene adduct of acetylene glycol.
  • non-ionic surfactant may include polyoxyethylenenonyl phenylether, polyoxyethyleneoctyl phenylether, and polyoxyethylenedodecyl.
  • Further examples of the non-ionic surfactant may include silicon surfactants such as a polysiloxane oxyethylene adduct; fluorine surfactants such as perfluoroalkylcarboxylate, perfluoroalkyl sulfonate, and oxyethyleneperfluoro alkylether; and biosurfactants such as spiculisporic acid, rhamnolipid, and lysolecithin.
  • the vehicle may include a silicone-free alkoxylated alcohol surfactant such as, for example, TEGO® Wet 510 (EvonikTegoChemie GmbH) and/or a self-emulsifiable wetting agent based on acetylenic diol chemistry, such as, for example, SURFYNOL® SE-F (Air Products and Chemicals, Inc.).
  • a silicone-free alkoxylated alcohol surfactant such as, for example, TEGO® Wet 510 (EvonikTegoChemie GmbH) and/or a self-emulsifiable wetting agent based on acetylenic diol chemistry, such as, for example, SURFYNOL® SE-F (Air Products and Chemicals, Inc.).
  • Suitable commercially available surfactants include SURFYNOL® 465 (ethoxylatedacetylenic diol), SURFYNOL® 440 (an ethoxylated low-foam wetting agent) SURFYNOL® CT-211 (now CARBOWET® GA-211, non-ionic, alkylphenylethoxylate and solvent free), and SURFYNOL® 104 (non-ionic wetting agent based on acetylenic diol chemistry), (all of which are from Air Products and Chemicals, Inc.); ZONYL® FSO (a.k.a.
  • CAPSTONE® which is a water-soluble, ethoxylated non-ionic fluorosurfactant from Dupont
  • TERGITOL® TMN-3 and TERGITOL® TMN-6 both of which are branched secondary alcohol ethoxylate, non-ionic surfactants
  • TERGITOL® 15-S-3, TERGITOL® 15-S-5, and TERGITOL® 15-S-7 each of which is a secondary alcohol ethoxylate, non-ionic surfactant
  • all of the TERGITOL® surfactants are available from The Dow Chemical Co.
  • the chelating agent is another example of an additive that may be included in the aqueous ink vehicle.
  • the chelating agent is present in an amount greater than 0 wt % active and less than or equal to 0.5 wt % active based on the total weight of the thermally curable inkjet ink.
  • the chelating agent is present in an amount ranging from about 0.05 wt % active to about 0.2 wt % active based on the total weight of the thermally curable inkjet ink.
  • the chelating agent is selected from the group consisting of methylglycinediacetic acid, trisodium salt; 4,5-dihydroxy-1,3-benzenedisulfonic acid disodium salt monohydrate; ethylenediaminetetraacetic acid (EDTA); hexamethylenediamine tetra(methylene phosphonic acid), potassium salt; and combinations thereof.
  • Methylglycinediacetic acid, trisodium salt (Na3MGDA) is commercially available as TRILON® M from BASF Corp.
  • 4,5-dihydroxy-1,3-benzenedisulfonic acid disodium salt monohydrate is commercially available as TIRONTM monohydrate.
  • Hexamethylenediamine tetra(methylene phosphonic acid), potassium salt is commercially available as DEQUEST® 2054 from Italmatch Chemicals.
  • the vehicle may also include biocide(s) (i.e., antimicrobial agents).
  • biocide(s) i.e., antimicrobial agents.
  • the total amount of biocide(s) in the thermally curable inkjet ink ranges from about 0.1 wt % active to about 0.25 wt % active (based on the total weight of the inkjet ink).
  • the total amount of biocide(s) in the inkjet ink is about 0.22 wt % active (based on the total weight of the inkjet ink).
  • the biocide may be present in the pigment dispersion that is mixed with the vehicle.
  • biocides examples include the NUOSEPT® (Ashland Inc.), UCARCIDETM or KORDEKTM or ROCIMATM (Dow Chemical Co.), PROXEL® (Arch Chemicals) series, ACTICIDE® B20 and ACTICIDE® M20 and ACTICIDE® MBL (blends of 2-methyl-4-isothiazolin-3-one (MIT), 1,2-benzisothiazolin-3-one (BIT) and Bronopol) (Thor Chemicals), AXIDETM (Planet Chemical), NIPACIDETM (Clariant), blends of 5-chloro-2-methyl-4-isothiazolin-3-one (CIT or CMIT) and MIT under the tradename KATHONTM (Dow Chemical Co.), and combinations thereof.
  • NUOSEPT® Ashland Inc.
  • UCARCIDETM or KORDEKTM or ROCIMATM Low Chemical Co.
  • PROXEL® Arch Chemicals
  • the vehicle may also include a pH adjuster.
  • a pH adjuster may be included in the thermally curable inkjet ink to achieve a desired pH (e.g., a pH of about 8.5) and/or to counteract any slight pH drop that may occur over time.
  • the total amount of pH adjuster(s) in the thermally curable inkjet ink ranges from greater than 0 wt % to about 0.1 wt % (based on the total weight of the thermal inkjet ink).
  • the total amount of pH adjuster(s) in the thermally curable inkjet ink is about 0.03 wt % (based on the total weight of the thermally curable inkjet ink).
  • suitable pH adjusters include metal hydroxide bases, such as potassium hydroxide (KOH), sodium hydroxide (NaOH), etc.
  • the metal hydroxide base may be added to the thermal inkjet ink in an aqueous solution.
  • the metal hydroxide base may be added to the thermal inkjet ink in an aqueous solution including 5 wt % of the metal hydroxide base (e.g., a 5 wt % potassium hydroxide aqueous solution).
  • Suitable pH ranges for examples of the ink can be from pH 7 to pH 11, from pH 7 to pH 10, from pH 7.2 to pH 10, from pH 7.5 to pH 10, from pH 8 to pH 10, 7 to pH 9, from pH 7.2 to pH 9, from pH 7.5 to pH 9, from pH 8 to pH 9, from 7 to pH 8.5, from pH 7.2 to pH 8.5, from pH 7.5 to pH 8.5, from pH 8 to pH 8.5, from 7 to pH 8, from pH 7.2 to pH 8, or from pH 7.5 to pH 8.
  • the balance of the thermally curable inkjet ink is water.
  • deionized water may be used.
  • the water included in the thermally curable inkjet ink may be: i) part of the pigment dispersion and/or binder dispersion, ii) part of the vehicle, iii) added to a mixture of the pigment dispersion and/or binder dispersion and the vehicle, or iv) a combination thereof.
  • the thermally curable inkjet ink is a thermal inkjet ink
  • the liquid vehicle is an aqueous based vehicle including at least 70% by weight of water.
  • the thermally curable inkjet ink is a piezoelectric inkjet ink
  • the liquid vehicle is a solvent based vehicle including at least 50% by weight of the co-solvent.
  • a pre-treatment composition may be printed with the thermally curable inkjet ink.
  • the pre-treatment composition a fixing agent selected from the group consisting of a multivalent metal cation, a cationic polymer, and a combination of a multivalent metal cation and a cationic polymer, and an aqueous pre-treatment vehicle.
  • the pre-treatment composition include the multivalent metal salt without the cationic polymer.
  • the multivalent metal salt includes a multivalent metal cation and an anion.
  • the multivalent metal salt includes a multivalent metal cation selected from the group consisting of a calcium cation, a magnesium cation, a zinc cation, an iron cation, an aluminum cation, and combinations thereof; and an anion selected from the group consisting of a chloride anion, an iodide anion, a bromide anion, a nitrate anion, a carboxylate anion, a sulfonate anion, a sulfate anion, and combinations thereof.
  • the multivalent metal salt (containing the multivalent metal cation) may be present in any suitable amount.
  • the metal salt is present in an amount ranging from about 2 wt % to about 15 wt % based on a total weight of the pre-treatment composition.
  • the metal salt is present in an amount ranging from about 4 wt % to about 12 wt %; or from about 5 wt % to about 15 wt %; or from about 6 wt % to about 10 wt %, based on a total weight of the pre-treatment composition.
  • the pre-treatment composition include the cationic polymer without the multivalent metal salt.
  • the cationic polymer included in the pre-treatment composition has a weight average molecular weight (g/mol) of 100,000 or less. This molecular weight enables the cationic polymer to be printed by thermal inkjet printheads.
  • the weight average molecular weight of the cationic polymer ranges from about 800 to about 40,000. It is expected that a cationic polymer with a weight average molecular weight higher than 100,000 can be used for examples of the pre-treatment composition applied by piezoelectric printheads and analog methods.
  • the cationic polymer may have a weight average molecular weight higher than 100,000, such as, for example, up to 600,000.
  • Examples of the cationic polymer are 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; and poly(dimethylamine-co-epichlorohydrin).
  • the cationic polymer is present in an amount ranging from about 1 wt % active to about 10 wt % active based on a total weight of the pre-treatment composition. In further examples, the cationic polymer is present in an amount ranging from about 4 wt % active to about 8 wt % active; or from about 2 wt % active to about 7 wt % active; or from about 6 wt % active to about 10 wt % active, based on a total weight of the pre-treatment composition.
  • the multivalent metal cation is used in combination with the cationic polymer.
  • aqueous pre-treatment vehicle may refer to the liquid fluid in which the multivalent metal salt, or the cationic polymer, or the multivalent metal salt in combination with the cationic polymer, is/are mixed to form the pre-treatment composition.
  • the aqueous vehicle includes water and a co-solvent.
  • suitable co-solvents for the pre-treatment composition are water soluble or water miscible co-solvents that may be selected from the group consisting of glycerol, ethoxylated glycerol, 2-methyl-1,3-propanediol, trimethylolpropane, 1,2-propanediol, dipropylene glycol, and combinations thereof.
  • suitable examples of co-solvents include polyhydric alcohols or simple carbohydrates (e.g., trehalose).
  • pre-treatment composition co-solvent(s) may include alcohols (e.g., diols), ketones, ketoalcohols, ethers (e.g., the cyclic ether tetrahydrofuran (THF), and others, such as thiodiglycol, sulfolane, 2-pyrrolidone, 1-(2-hydroxyethyl)-2-pyrrolidone,1,3-dimethyl-2-imidazolidinone and caprolactam; glycols such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, trimethylene glycol, butylene glycol, and hexylene glycol; addition polymers of oxyethylene or oxypropylene such as polyethylene glycol, polypropylene glycol and the like; triols such as glycerol (as mentioned above) and 1,2,6-hexanetriol;
  • the total amount of the co-solvent(s) may be present in the pre-treatment composition in an amount ranging from about 5 wt % to about 25 wt % based on a total weight of the pre-treatment composition. The amounts in this range may be particularly suitable for the composition when it is to be dispensed from a thermal inkjet printhead. In another example, the total amount of the co-solvent(s) may be present in the pre-treatment composition in an amount ranging from about 10 wt % to about 18 wt % based on a total weight of the pre-treatment composition. The co-solvent amount may be increased to increase the viscosity of the pre-treatment composition for a high viscosity piezoelectric printhead.
  • water is present in addition to the co-solvent(s) and makes up a balance of the pre-treatment composition.
  • the weight percentage of the water present in the pre-treatment composition will depend, in part, upon the weight percentages of the other components.
  • the water may be purified water or deionized water.
  • An example of the pre-treatment composition further comprises an additive selected from the group consisting of a surfactant, a chelating agent, a buffer, a biocide, and combinations thereof.
  • the pre-treatment composition further include a surfactant.
  • the surfactant may be any surfactant that aids in wetting, but that does not deleteriously interact with the salt in the pre-treatment composition.
  • the surfactant in the pre-treatment composition is selected from the group consisting of a non-ionic surfactant and a zwitterionic surfactant.
  • the amount of the surfactant that may be present in the pre-treatment composition is 2 wt % active or less (with the lower limit being above 0) based on the total weight of the pre-treatment composition. In some examples, the amount of the surfactant ranges from about 0.05 wt % active to about 1 wt % active based on the total weight of the pre-treatment composition.
  • non-ionic surfactants include non-ionic fluorosurfactants, non-ionic acetylenic diol surfactants, non-ionic ethoxylated alcohol surfactants, non-ionic silicone surfactants, and combinations thereof.
  • alkoxylated surfactants such as TEGO® Wet 510 manufactured from Evonik
  • fluorinated POLYFOX® non-ionic surfactants e.g., PF159 non-ionic surfactants
  • silicone surfactants such as those from BYK® 340 series (e.g., BYK® 345, BYK® 346, BYK® 347, BYK® 348, BYK® 349) manufactured by BYK Chemie; or combinations thereof.
  • coco-betaine alkyl isothionates
  • the chelating agent is another example of an additive that may be included in the pre-treatment composition.
  • the chelating agent is present in an amount greater than 0 wt % active and less than or equal to 0.5 wt % active based on the total weight of the pre-treatment composition.
  • Any example of the chelating agent described in reference to the thermally curable inkjet ink may be used in the pre-treatment composition.
  • Buffers are another example of an additive that may be included in the pre-treatment composition.
  • the total amount of buffer(s) in the pre-treatment composition ranges from 0 wt % to about 0.5 wt % (with respect to the weight of pre-treatment composition). In another example, the total amount of buffer(s) in the ink is about 0.1 wt % (with respect to the weight of pre-treatment composition).
  • buffers examples include TRIS (tris(hydroxymethyl)aminomethane or Trizma), bis-tris propane, TES (2-[(2-Hydroxy-1,1-bis(hydroxymethyl)ethyl)amino]ethanesulfonic acid), MES (2-ethanesulfonic acid), MOPS (3-(N-morpholino)propanesulfonic acid), HEPES (4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid), DIPSO (3-(N,N-Bis[2-hydroxyethyl]amino)-2-hydroxypropanesulfonic acid), Tricine (N-[tris(hydroxymethyl)methyl]glycine), HEPPSO ( ⁇ -Hydroxy-4-(2-hydroxyethyl)-1-piperazinepropanesulfonic acid monohydrate), POPSO (Piperazine-1,4-bis(2-hydroxypropanesulfonic acid) dihydrate), EPPS (4-((hydroxy
  • Biocides are another example of an additive that may be included in the pre-treatment composition.
  • the total amount of biocide(s) in the pre-treatment composition ranges from about 0 wt % active to about 0.1 wt % active (with respect to the weight of the pre-treatment composition).
  • the total amount of biocide(s) in the pre-treatment composition ranges from about 0.001 wt % active to about 0.1 wt % active (with respect to the weight of the pre-treatment composition).
  • Any example of the biocide described in reference to the thermally curable inkjet ink may be used in the pre-treatment composition.
  • the pH of the pre-treatment composition can be less than 7. In some examples, the pH ranges from pH 1 to pH 7, from pH 3 to pH 7, from pH 4.5 to pH 7, etc.
  • the inkjet pre-treatment composition consists of the listed components and no additional components (such as water soluble polymers, water repellent agents, etc.).
  • the inkjet pre-treatment composition comprises the listed components, and other components that do not deleteriously affect the jettability of the fluid via a thermal- or piezoelectric inkjet printhead may be added.
  • Examples of the pre-treatment composition disclosed herein may be used in a thermal inkjet printer or in a piezoelectric printer to pre-treat a textile substrate.
  • the viscosity of the pre-treatment composition may be adjusted for the type of printhead that is to be used, and the viscosity may be adjusted by adjusting the co-solvent level and/or adding a viscosity modifier.
  • the viscosity of the pre-treatment composition may be modified to range from about 1 centipoise (cP) to about 9 cP (at 20° C.
  • the viscosity of the pre-treatment composition may be modified to range from about 2 cP to about 20 cP (at 20° C. to 25° C.), depending on the viscosity of the printhead that is being used (e.g., low viscosity printheads, medium viscosity printheads, or high viscosity printheads).
  • the pre-treatment composition includes the multivalent metal salt in an amount ranging from about 5 wt % to about 15 wt % based on the total weight of the pre-treatment composition; an additive selected from the group consisting of a non-ionic surfactant, a chelating agent, an antimicrobial agent, and combinations thereof; and the aqueous vehicle, which includes water and an organic solvent (e.g., the co-solvent).
  • an additive selected from the group consisting of a non-ionic surfactant, a chelating agent, an antimicrobial agent, and combinations thereof
  • the aqueous vehicle which includes water and an organic solvent (e.g., the co-solvent).
  • the textile fabric is selected from the group consisting of cotton fabrics, cotton blend fabrics, nylon fabrics, nylon blend fabrics, polyester fabrics, polyester blend fabrics, silk fabrics, silk blend fabrics, spandex, spandex blend fabrics, rayon, and rayon blend fabrics.
  • textile fabric is selected from the group consisting of cotton fabrics and cotton blend fabrics. Blends may include the listed material in combination with one or more other material(s).
  • An example of a tri-blend includes cotton, polyester and spandex.
  • organic textile fabrics and/or inorganic textile fabrics may be used for the textile fabric.
  • Some types of fabrics that can be used include various fabrics of natural and/or synthetic fibers.
  • Example natural fiber fabrics that can be used include treated or untreated natural fabric textile substrates, e.g., wool, cotton, silk, linen, jute, flax, hemp, rayon fibers, thermoplastic aliphatic polymeric fibers derived from renewable resources (e.g. cornstarch, tapioca products, sugarcanes), etc.
  • treated or untreated natural fabric textile substrates e.g., wool, cotton, silk, linen, jute, flax, hemp, rayon fibers, thermoplastic aliphatic polymeric fibers derived from renewable resources (e.g. cornstarch, tapioca products, sugarcanes), etc.
  • Example synthetic fibers used in the textile fabric/substrate can include polymeric fibers such as nylon fibers, 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 and Company, Delaware), fiberglass, polytrimethylene, polycarbonate, polyethylene terephthalate, polyester terephthalate, polybutylene terephthalate, or a combination thereof.
  • polymeric fibers such as nylon fibers, polyvinyl chloride (PVC) fibers, PVC-free fibers made of polyester, polyamide, polyimide, polyacrylic, polypropylene, polyethylene, polyurethane, polystyrene, polyaramid (e.g., Kevlar®
  • the fiber can be a modified fiber from the above-listed polymers.
  • modified fiber refers to one or both of the polymeric fiber and the fabric as a whole having undergone a chemical or physical process such as, but not limited to, 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, acid etching, or a biological treatment, an enzyme treatment, or antimicrobial treatment to prevent biological degradation.
  • fabric substrate do not include materials commonly known as any kind of paper (even though paper can include multiple types of natural and synthetic fibers or mixtures of both types of fibers).
  • Fabric substrates can include textiles in filament form, textiles in the form of fabric material, or textiles in the form of fabric that has been crafted into finished articles (e.g., clothing, blankets, tablecloths, napkins, towels, bedding material, curtains, carpet, handbags, shoes, banners, signs, flags, etc.).
  • the fabric substrate can have a woven, knitted, non-woven, or tufted fabric structure.
  • the fabric substrate can be a woven fabric where warp yarns and weft yarns can be mutually positioned at an angle of about 90°.
  • This woven fabric can include 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 substrate can be a knitted fabric with a loop structure.
  • the loop structure can be a warp-knit fabric, a weft-knit fabric, or a combination thereof.
  • a warp-knit fabric refers to every loop in a fabric structure that can be formed from a separate yarn mainly introduced in a longitudinal fabric direction.
  • a weft-knit fabric refers to loops of one row of fabric that can be formed from the same yarn.
  • the fabric substrate can be a non-woven fabric.
  • the non-woven fabric can be a flexible fabric that can include a plurality of fibers or filaments that are one or both 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 multiple processes.
  • FIG. 1 depicts an example of the printing method 100 .
  • an example the printing method 100 comprises: applying a thermally curable ink composition on a fabric substrate, the thermally curable ink composition including: from about 1 wt % active to about 6 wt % active of a pigment that absorbs ultraviolet radiation, infrared radiation, or a combination thereof, based on a total weight of the thermally curable ink composition; from about 2 wt % active to about 20 wt % active of a polymeric binder, based on a total weight of the thermally curable ink composition; and an aqueous ink vehicle (reference numeral 102 ); and selectively heating the pigment of the thermally curable ink composition applied on the fabric substrate by exposing the fabric substrate to an emission wavelength from a narrow wavelength light source for a total exposure time of 3 seconds or less, thereby thermally fixing the pigment to the fabric substrate (reference numeral 104 ).
  • total exposure time refers to the total time that the fabric having the ink printed thereon is exposed to the emission wavelength.
  • the total exposure time may take place during a single event where the light source is turned on (i.e., light source on event).
  • the total exposure time may take place over a series of light source on events that are shorter in duration than the total exposure time and whose sum equals the total exposure time.
  • light source on events may be separated by light source off events, during which the light source is turned off and the fabric is not exposed to the emission wavelength.
  • the total time to achieve pigment fixation is longer than the total exposure time due to the time periods when the light source is off. However, in these examples, the total exposure time is still 3 seconds or less because the fabric is not exposure to the light emission during the off events.
  • thermally curable ink composition may be used in the examples of the method 100 .
  • textile fabric may also be used in the examples of the method 100 .
  • the thermally curable ink composition may be ejected onto the textile fabric using any suitable applicator, such as a thermal inkjet printhead, a piezoelectric printhead, a continuous inkjet printhead, etc.
  • the applicator may eject the thermally curable ink composition in a single pass or in multiple passes.
  • single pass printing the cartridge(s) of an inkjet printer deposit the desired amount of the ink composition during the same pass of the cartridge(s) across the textile fabric.
  • the cartridge(s) of an inkjet printer deposit the desired amount of the ink composition over several passes of the cartridge(s) across the textile fabric.
  • the thermally curable ink composition is applied via analog methods, such as screen printing, spraying, roll-coating, cylindrical pad printing, etc.
  • the narrow wavelength light source is a light emitting diode having an emission wavelength ranging from about 10 nm to about 400 nm.
  • the narrow wavelength ultraviolet light source is a light emitting diode having an emission wavelength ranging from about 365 nm to about 395 nm.
  • the narrow wavelength ultraviolet light source is a 395 nm light emitting diode.
  • the narrow wavelength light source is a light emitting diode having an emission wavelength ranging from about 760 nm to about 1 mm.
  • the method 100 may include setting the narrow wavelength light source to a power setting ranging from about 3.5 W/cm 2 to about 10 W/cm 2 .
  • the power setting may depend, in part, upon the light source used, the total time for exposure, the distance between the light source and the textile fabric, etc. Higher power settings may be desirable for faster throughput systems.
  • the energy (radiant) exposure ranges from about 2 J/cm 2 to about 28 J/cm 2 . In a specific example, if a power of 10 W/cm 2 is applied for 1 second, the applied energy is 10 J/cm 2 .
  • the pigment in the printed ink When exposed to the UV or IR radiation, the pigment in the printed ink absorbs the ultraviolet light or infrared light and heats up to its fixation temperature. As such, exposure to the narrow wavelength light source fixes the ink on the textile fabric. It has been found that the narrow wavelength light source thermally cures the thermally curable ink composition disclosed herein within 3 seconds or less, and effectively fixes the pigment to the textile fabric without traditional UV curing components, such as photoinitiators.
  • the desired amount of the thermally curable ink composition is deposited in a single pass or in multiple passes, and then selective heating occurs.
  • the application of the thermally curable ink composition occurs prior to the selectively heating, and the selectively heating involves intermittent light source on events and light source off events.
  • the narrow wavelength light source is turned on, and during light source off events, the narrow wavelength light source is turned off.
  • the intermittent on and off events can effectively heat the pigment in the printed ink to its fixation temperature without overheating the pigment.
  • the light source on events may range from about 0.1 second to about 1.5 seconds. Since the total exposure time is 3 seconds or less, the number of light source on events will depend upon the duration of each on event and the desired total exposure time.
  • each light source on event when each light source on event is 1 second long, a total of three light source on events may take place so that the total exposure time is 3 seconds. A higher number of light source on events may be used when the on events are shorter in duration.
  • the light source off events may be long enough to allow the pigments to cool without allowing the pigments to return to their pre-exposure temperature.
  • the desired amount of the thermally curable ink composition is deposited in multiple passes, and selective heating occurs after each pass.
  • the applying of the thermally curable ink composition is accomplished in multiple print passes, and the method 100 further includes exposing the fabric substrate to the narrow wavelength light source after each print pass for a time less than the total exposure time.
  • the time for exposing the fabric substrate to the narrow wavelength light source after each print pass ranges from about 0.1 second to about 1.5 seconds. Since the total exposure time is 3 seconds or less, the duration of the exposure after each pass will depend upon the number of passes and the desired total exposure time. For example, when the ink is to be deposited in two printing passes and the total exposure time is 2 seconds, each of the exposures may take place for 1 second.
  • warming and/or cooling of the textile fabric may take place before and/or concurrently with UV and/or IR radiation exposure.
  • some examples of the method 100 include warming or cooling the fabric substrate having the thermally curable ink composition thereon at a temperature below a fixation temperature of the thermally curable ink composition: i) before the selectively heating; or ii) concurrently with the selectively heating; or iii) both before and concurrently with the selectively heating.
  • Warming may be accomplished with a heat source that is positioned above the textile fabric (e.g., an infrared heating lamp that provides radiative heating/warming) or below the fabric substrate (a conductive platen that provides conductive heating/warming).
  • a heat source that is positioned above the textile fabric (e.g., an infrared heating lamp that provides radiative heating/warming) or below the fabric substrate (a conductive platen that provides conductive heating/warming).
  • the temperature at which the fabric substrate is warmed ranges from about 60° C. to about 100° C.
  • the temperature at which the textile fabric is warmed ranges from about 70° C. to about 90° C. It is to be understood that this warming temperature range may vary, depending upon, e.g., the fixation temperature of the thermally curable ink. For example, if the fixation temperature of an ink were 160° C., the warming temperature may be any suitable temperature below 160° C.
  • Cooling may be accomplished with a cold air source that is positioned above the textile fabric or below the fabric substrate.
  • the temperature at which the fabric substrate is cooled ranges from about 20° C. to about 60° C. It is to be understood that this cooling temperature range may vary, depending upon, e.g., the fixation temperature of the thermally curable ink. For example, if the fixation temperature of an ink were 160° C., the cooling temperature may be any suitable temperature that enables the fabric substrate to reach 160° C. without overheating.
  • warming or cooling may be accomplished with any suitable bulk temperature control mechanism.
  • the warming or cooling takes place for an amount of time ranging from about 0.1 seconds to about 30 seconds. In another example, the warming or cooling takes place for an amount of time ranging from about 0.1 seconds to about 3 seconds. It is to be understood that this warming or cooling time range may vary, depending upon, e.g., the temperature at which warming or cooling takes place and whether warming or cooling is accomplished prior to and/or concurrently with the UV and/or IR radiation exposure. For example, if warming or cooling occurs concurrently with UV and/or IR radiation exposure, the time for warming or cooling may range from about 0.1 second up to 3 seconds.
  • the time for warming may be longer, e.g., up to 30 seconds. It is to be further understood that examples of the method 100 may be accomplished without warming/pre-heating or without cooling.
  • FIG. 2 depicts another example of the printing method 200 .
  • the printing method 200 comprises: applying a pre-treatment composition on a fabric substrate, the pre-treatment composition including: a fixing agent selected from the group consisting of a multivalent metal cation, a cationic polymer, and a combination of the multivalent metal cation and the cationic polymer; and an aqueous pre-treatment vehicle (reference numeral 202 ); applying a thermally curable ink composition on the fabric substrate, the thermally curable ink composition including: from about 1 wt % active to about 6 wt % active of a pigment that absorbs ultraviolet radiation, infrared radiation, or a combination thereof, based on a total weight of the thermally curable ink composition; from about 2 wt % active to about 20 wt % active of a polymeric binder, based on a total weight of the thermally curable ink composition; and an aqueous ink vehicle (reference numeral 202 ); applying
  • the pre-treatment composition may be used in the examples of the method 200 .
  • the pre-treatment composition may be applied digitally using inkjet technology.
  • the pretreatment composition can also be applied to fabric substrates via analog methods, e.g., spraying, roll-coating, cylindrical pad printing, etc. With these analog methods, the pre-treatment composition is applied to the entire fabric substrate.
  • thermally curable ink composition may be used in the examples of the method 200 .
  • the thermally curable ink composition may be ejected onto the textile fabric using any suitable applicator, such as a thermal inkjet printhead, a piezoelectric printhead, a continuous inkjet printhead, etc.
  • the applicator may eject the thermally curable ink composition in a single pass or in multiple passes as described in reference to the method 100 .
  • the thermally curable ink composition is applied via analog methods, such as screen printing, spraying, roll-coating, cylindrical pad printing, etc.
  • the narrow wavelength light source is a light emitting diode having an emission wavelength ranging from about 10 nm to about 400 nm.
  • the narrow wavelength ultraviolet light source is a light emitting diode having an emission wavelength ranging from about 365 nm to about 395 nm.
  • the narrow wavelength ultraviolet light source is a 395 nm light emitting diode.
  • the narrow wavelength light source is a light emitting diode having an emission wavelength ranging from about 760 nm to about 1 mm.
  • the method 200 may also include setting the narrow wavelength light source so that the energy exposure ranges from about 2 J/cm 2 to about 28 J/cm 2 .
  • the pigment in the printed ink When exposed to the UV or IR radiation, the pigment in the printed ink absorbs the ultraviolet or infrared light and heats up to its fixation temperature. As such, exposure to the narrow wavelength light source fixes the ink on the textile fabric.
  • the multivalent metal salt in the pre-treatment composition also interacts with pigment in the ink directly on the fabric substrate, which helps fix the pigment and improve the optical density.
  • the desired amount of the pre-treatment composition and of thermally curable ink composition is deposited in a single pass or in multiple passes, and then selective heating occurs.
  • the application of the pre-treatment composition occurs prior to the application of the thermally curable ink composition
  • the application of the thermally curable ink composition occurs prior to the selectively heating
  • the selectively heating involves intermittent light source on events and light source off events.
  • the narrow wavelength light source is turned on, and during light source off events, the narrow wavelength light source is turned off.
  • the intermittent on and off events can effectively heat the pigment in the printed ink to its fixation temperature without overheating the pigment.
  • the light source on events may range from about 0.1 second to about 1.5 seconds.
  • the number of light source on events will depend upon the duration of each on event and the desired total exposure time. For example, when each light source on event is 1 second long, a total of three light source on events may take place so that the total exposure time is 3 seconds. A higher number of light source on events may be used when the on events are shorter in duration.
  • the light source off events may be long enough to allow the pigments to cool without allowing the pigments to return to their pre-exposure temperature.
  • the desired amount of the thermally curable ink composition is deposited, the desired amount of the thermally curable ink composition is deposited in multiple passes, and selective heating occurs after each pass.
  • the application of the pre-treatment composition occurs prior to the application of the thermally curable ink composition, the applying of the thermally curable ink composition is accomplished in multiple print passes, and the method 200 further includes exposing the fabric substrate to the narrow wavelength light source after each print pass for a time less than the total exposure time.
  • the time for exposing the fabric substrate to the narrow wavelength light source after each print pass ranges from about 0.1 second to about 1 second. Since the total exposure time is 3 seconds or less, the duration of the exposure after each pass will depend upon the number of passes and the desired total exposure time.
  • the thermally curable ink composition is printed onto the printed pre-treatment composition while the pre-treatment composition is wet.
  • Wet on wet printing may be desirable because less pre-treatment composition may be applied during this process (as compared to when the pre-treatment composition is dried prior to ink application), and because the printing workflow may be simplified without the additional drying.
  • the thermally curable ink composition is printed onto the printed pre-treatment composition within a period of time ranging from about 0.01 second to about 30 seconds after the printed pre-treatment composition is printed.
  • the thermally curable ink composition is printed onto the previously applied pre-treatment composition within a period of time ranging from about 0.1 second to about 20 seconds; or from about 0.2 second to about 10 seconds; or from about 0.2 second to about 5 seconds after the previously applied composition is printed. Wet on wet printing may be accomplished in a single pass.
  • drying takes place after the application of the pre-treatment composition and before the application of the thermally curable ink composition. It is to be understood that in this example, drying of the pre-treatment composition may be accomplished in any suitable manner, e.g., air dried (e.g., at a temperature ranging from about 20° C. to about 80° C. for 30 seconds to 5 minutes), or by exposure to heat via any suitable heat source (e.g. for 3 seconds or less), and/or the like.
  • air dried e.g., at a temperature ranging from about 20° C. to about 80° C. for 30 seconds to 5 minutes
  • any suitable heat source e.g. for 3 seconds or less
  • warming or cooling of the textile fabric may take place before and/or concurrently with UV and/or IR radiation exposure.
  • some examples of the method 200 include warming or cooling the fabric substrate having the thermally curable ink composition thereon at a temperature below a fixation temperature of the thermally curable ink composition: i) before the selectively heating; or ii) concurrently with the selectively heating; or iii) both before and concurrently with the selectively heating.
  • Warming or cooling may be performed as described in reference to the method 100 .
  • FIGS. 3A and 3B schematic diagrams of two different printing systems 10 , 10 ′ including inkjet printheads 12 , or 12 and 14 , or 12 ′, or 12 ′ and 14 ′ and a narrow wavelength light source 18 or 18 ′.
  • the example system 10 shown in FIG. 3A illustrates a system for single pass printing and selective heating
  • the example system 10 ′ shown in FIG. 3B illustrates a system for multiple pass printing and single or multiple pass selective heating.
  • the textile fabric/fabric substrate 20 may be transported through the printing system 10 along the path shown by the arrow 22 .
  • a pagewide printhead 12 i.e., a series of printheads extending the width of the fabric substrate 20
  • a single color or multiple colors of the thermally curable ink composition 24 is/are inkjet printed directly onto fabric substrate 20 by the pagewide printhead 12 to form an ink layer.
  • the color(s), amount(s), and arrangement of the thermally curable ink composition(s) 24 that is/are applied depend upon the digital image from which the print is being generated.
  • the narrow wavelength light source 18 is operated to expose the fabric substrate 20 having the thermally curable ink composition(s) 24 printed thereon to UV and/or IR radiation 26 for a total exposure time of 3 seconds or less.
  • UV and/or IR radiation exposure may take place in one light source on event or in intermittent light source on events (where the narrow wavelength light source 18 is turned on an off while the fabric substrate 20 is positioned relative to the narrow wavelength light source 18 .
  • printing and selective heating of the pigment in the printed ink are each performed as the fabric substrate 20 is within proximity of the respective printer component.
  • some examples of the printing system 10 further include the inkjet printhead 14 , which contains and dispenses the pre-treatment composition 28 .
  • inkjet printhead 14 is a pagewide printhead that is in a fixed position relative to the fabric substrate 20 .
  • an example of the pre-treatment composition 28 disclosed herein is inkjet printed directly onto fabric substrate 20 .
  • the fabric substrate 20 is then moved to be exposed to printing and selective heating, While not shown, it is to be understood that the inkjet printhead 14 could be replaced with a mechanism that will apply the pre-treatment composition 28 in accordance with an analog method.
  • the mechanism could be an in-line or off-line sprayer, roll coater, etc.
  • a dryer may be positioned between the printheads 14 and 12 to dry the pre-treatment composition before the thermally curable inkjet ink is applied thereon.
  • the single pass printing and selective heating performed using the printing system 10 results in the printed article 30 on the fabric substrate 20 .
  • the heat absorbed by the pigment is sufficient to bind the pigment onto the fabric substrate 20 .
  • the heat to initiate fixation may range from about 100° C. to about 200° C.
  • the textile fabric/fabric substrate 20 may be transported through the printing system 10 ′ along the path shown by the arrow 22 ′.
  • printhead(s) 12 ′ is attached to a carriage (not shown) or other mechanism that moves the printhead 12 ′ relative to the fabric substrate 20 in the path shown by the arrow 32 .
  • a single color or multiple colors of the thermally curable ink composition 24 is/are inkjet printed directly onto fabric substrate 20 by the printhead(s) 12 ′ to form an ink layer.
  • the color(s), amount(s), and arrangement of the thermally curable ink composition(s) 24 that is/are applied depend upon the digital image from which the print is being generated. In this example, the total desired amount of thermally curable ink composition(s) 24 that is dispensed takes place over multiple passes of the printhead(s) 12 ′.
  • Exposure to the UV and/or IR radiation may occur after the multiple printing passes, or between each of the multiple printing passes.
  • the narrow wavelength light source 18 ′ is attached to a carriage (not shown) or other mechanism that moves the narrow wavelength light source 18 ′ relative to the fabric substrate 20 in the path shown by the arrow 32 .
  • the total exposure time is 3 seconds or less, whether exposure takes place in a single pass or multiple passes.
  • some examples of the printing system 10 ′ further include the inkjet printhead 14 ′, which contains and dispenses the pre-treatment composition 28 .
  • inkjet printhead 14 ′ is a printhead that is attached to a carriage (not shown) or other mechanism that moves the printhead 14 ′ relative to the fabric substrate 20 in the path shown by the arrow 32 .
  • the fabric substrate 20 is moved relative to the inkjet printhead 14 ′, an example of the pre-treatment composition 28 disclosed herein is inkjet printed directly onto fabric substrate 20 .
  • the printhead 12 ′ and the narrow wavelength radiation source 18 ′ are then moved to print and selectively heat.
  • the inkjet printhead 14 ′ could be replaced with a mechanism that will apply the pre-treatment composition 28 in accordance with an analog method.
  • the mechanism could be an in-line or off-line sprayer, roll coater, etc.
  • the multiple pass printing and single or multiple pass selective heating performed using the printing system 10 ′ results in the printed article 30 on the fabric substrate 20 .
  • the heat absorbed by the pigment is sufficient to bind the pigment onto the fabric substrate 20 .
  • the heat to initiate fixation may range from about 100° C. to about 200° C.
  • the fabric substrates used were cotton and nylon.
  • a pre-treatment composition, a cyan thermally curable ink, and a black thermally curable ink were used.
  • the pre-treatment composition is shown in Table 1 and the cyan and black thermally curable ink compositions are shown in Table 2.
  • a 395 nm light emitting diode (Hereaus lamp) was used. When operated at 50% power, the light source emitted 6.62 W/cm 2 .
  • the example print swaths on the cotton fabric were exposed to 6 exposures of 500 msec each, with a total energy of 19.87 J/cm 2 .
  • the example print swaths on the nylon fabric were exposed to 2 exposures of 100 msec each, with a total energy of 1.32 J/cm 2 .
  • UV radiation exposure took place after each of the ink passes.
  • comparative print swaths For some the comparative print swaths, a heat press alone was used. The comparative print swaths were exposed to 150° C. for 3 minutes using the heat press.
  • each of the example print swaths, comparative example print swaths, and the control print swaths was washed 5 times in a Kenmore 90 Series Washer (Model 110.289 227 91 ) with warm water (at about 40° C.) and detergent. Each print was allowed to air dry between each wash.
  • Photographs were taken of the swaths after washing to visibly compare the washfastness of the control, example, and comparative examples swaths. The results, which are reproduced in black and white, are shown in FIGS. 4 through 7 .
  • a control swath was generated next to an example swath, and another example swath was generated next to a comparative example swath.
  • Table 3 provides a key for FIGS. 4 and 5 , which show the various swaths printed on cotton.
  • Table 4 provides a key for FIGS. 6 and 7 , which show the various swaths printed on nylon.
  • the black example print swath E 1 printed on cotton and exposed to LED heating exhibited much better washfastness than the control black C 1 , and exhibited slightly better washfastness than the black comparative example print swath CE 1 printed on cotton and exposed to the heat press and the black comparative example print swath CE 2 printed on cotton and exposed to both LED and the heat press.
  • the cyan example print swath E 2 printed on cotton and exposed to LED heating exhibited much better washfastness than the control cyan C 2 , and exhibited slightly better washfastness than the cyan comparative example print swath CE 3 printed on cotton and exposed to the heat press and the cyan comparative example print swath CE 4 printed on cotton and exposed to both LED and the heat press.
  • the black example print swath E 3 printed on nylon and exposed to LED heating exhibited much better washfastness than the control black C 3 , and exhibited comparable or slightly better washfastness than the black comparative example print swath CE 5 printed on nylon and exposed to the heat press and the black comparative example print swath CE 6 printed on nylon and exposed to both LED and the heat press.
  • the cyan example print swath E 4 printed on nylon and exposed to LED heating exhibited much better washfastness than the control cyan C 4 , and exhibited comparable or slightly better washfastness than the cyan comparative example print swath CE 7 printed on nylon and exposed to the heat press and the cyan comparative example print swath CE 8 printed on nylon and exposed to both LED and the heat press.
  • LED exposure forms prints with improved washfastness on both cotton and nylon, when compared to prints formed with no heating or with heat press heating. LED exposure also speeds up the printing process, comparing. e.g., 3 minutes with the heat press versus 0.2 seconds or 3 seconds with the LED lamp.
  • thermoly curable ink composition Six examples of the thermally curable ink composition disclosed herein were prepared.
  • the example binder included in four of the example ink compositions was IMPRANIL® DLN-SD (an anionic aliphatic polyester-polyurethane binder, CAS #375390-41-3; Mw 45,000 Mw; Acid Number 5.2; Tg ⁇ 47° C.; Melting Point 175-200° C.) from Covestro.
  • IMPRANIL® DLN-SD an anionic aliphatic polyester-polyurethane binder, CAS #375390-41-3; Mw 45,000 Mw; Acid Number 5.2; Tg ⁇ 47° C.; Melting Point 175-200° C.
  • Table 4 The general formulation of these four example ink compositions is shown in Table 4, with the wt % active of each component that was used.
  • the weight percentage of the pigment dispersion represents the total pigment solids (i.e., wt % active pigment) present in the final ink formulations.
  • the amount of the pigment dispersion added to the example ink compositions was enough to achieve a pigment solids level equal to the given weight percent.
  • the weight percentage of the binder represents the total binder solids (i.e., wt % active binder) present in the final ink formulations.
  • a 5 wt % potassium hydroxide aqueous solution was added to each of the example ink compositions until a pH of about 8.5 was achieved.
  • the example binder included in another four of the example ink compositions was a latex polymer binder.
  • the general formulation of these four example ink compositions is shown in Table 6, with the wt % active of each component that was used.
  • example binder included in the last four of the example ink compositions was another type of latex polymer binder.
  • the general formulation of these four example ink compositions is shown in Table 7, with the wt % active of each component that was used.
  • the post-treatment that was performed on each region of a first set of prints is schematically shown in FIG. 9 .
  • the control regions at the left and right of each print
  • no post-treatment or curing was performed (this region is labeled “untreated control” in FIGS. 9-12 and Tables 8 and 9).
  • the example region at the middle of each print
  • the print was exposed to ultraviolet light for 1 second from a 395 nm light emitting diode operated at 50% energy (this region is labeled “LED exposed” in FIG. 9 and Tables 8 and 9 and “LED395, 50% energy, 1 sec” in FIGS. 10A, 11A, and 12A ).
  • the light source emitted 6.62 W/cm 2 .
  • the post-treatment that was performed on a second set of prints involved exposure to the heat press at 150° C. for about 3 minutes.
  • the initial optical density (initial OD) of each region of each print in the first set of prints was measured.
  • the initial optical density (initial OD) of each print in the second set of prints was also measured.
  • the prints in each set were washed 5 times in a Kenmore 90 Series Washer (Model 110.289 227 91) with warm water (at about 40° C.) and detergent. Each print was allowed to air dry between each wash.
  • the optical density (OD after 5 washes) of each region of each print in the first set of prints and of each print in the second set of prints was measured, and the percent change in optical density (% ⁇ OD) was calculated for each region and print.
  • each region or print is identified by the example ink composition, and the post-treatment (if any) used to generate the region or print.
  • the regions of the prints in the first set of prints exposed to ultraviolet light had a change in optical density of at least 37% less than the change in optical density of the regions of the same print that was untreated (i.e., the control).
  • the regions of the prints exposed to ultraviolet light had a change in optical density of at least 30% less than the change in optical density of the same color prints that were exposed to the heat press at 150° C. for 3 minutes.
  • Table 8 further shows, for the prints generated with the “example 3” ink compositions, that the regions of the prints exposed to ultraviolet light had a change in optical density of at least 16.5% less than the change in optical density of the same color prints that were exposed to the heat press at 150° C. for 3 minutes.
  • the prints were also tested for washfastness.
  • the L*a*b* values of a color e.g., cyan, magenta, yellow, black, red, green, blue, white
  • L* is lightness
  • a* is the color channel for color opponents green-red
  • b* is the color channel for color opponents blue-yellow.
  • the color change was then calculated using both the CIEDE1976 color-difference formula and the CIEDE2000 color-difference formula.
  • the CIEDE1976 color-difference formula is based on the CIELAB color space. Given a pair of color values in CIELAB space L* 1 ,a* 1 ,b* 1 and L* 2 ,a* 2 ,b* 2 , the CIEDE1976 color difference between them is as follows:
  • ⁇ E 76 ⁇ square root over ([( L* 2 ⁇ L* 1 ) 2 +( a* 2 ⁇ a* 1 ) 2 +( b* 2 ⁇ b* 1 ) 2 ]) ⁇
  • ⁇ E 76 is the commonly accepted notation for CIEDE1976.
  • the CIEDE2000 color-difference formula is based on the CIELAB color space. Given a pair of color values in CIELAB space L* 1 ,a* 1 ,b* 1 and L* 2 ,a* 2 ,b* 2 , the CIEDE2000 color difference between them is as follows:
  • ⁇ E 00 is the commonly accepted notation for CIEDE2000.
  • each region or print is identified by the example ink composition, and the post-treatment (if any) used to generate the region or print.
  • the ⁇ E 76 value and the ⁇ E 00 value of the regions of the prints exposed to ultraviolet light were at least 44% less than, respectively, the ⁇ E 76 value and the ⁇ E 00 value of the region of the same print that was untreated (i.e., the control prints).
  • the ⁇ E 76 value of the regions of the prints exposed to ultraviolet light were at least 26% less than the ⁇ E 76 value of the same color print that was exposed to the heat press at 150° C. for 3 minutes.
  • Table 9 further shows, for the prints generated with the “example 2” ink compositions, the ⁇ E 00 value of the regions of the prints exposed to ultraviolet light were less than or comparable to the ⁇ E 00 value of the region of the same color print that was exposed to the heat press at 150° C. for 3 minutes.
  • Table 9 shows, for the prints generated with the “example 3” ink compositions, the ⁇ E 76 value and the ⁇ E 00 value of the regions of the prints exposed to ultraviolet light were less than or comparable to, respectively, the ⁇ E 76 value and the ⁇ E 00 value of the same color print that was exposed to the heat press at 150° C. for 3 minutes.
  • FIGS. 10A, 11A, and 12A show the before and after photographs for the prints with the untreated control and example regions
  • the before and after photographs for the comparative prints exposed to the heat press are reproduced in black and white in FIGS. 10B, 11B, and 12B
  • FIGS. 10A and 10B show the prints formed with the example 1 inks
  • FIGS. 11A and 11B show the prints formed with the example 2 inks
  • FIGS. 12A and 12B show the prints formed with the example 3 inks.
  • the labeling in FIGS. 10A, 11A, and 12A follows the schematic in FIG. 9 .
  • ranges provided herein include the stated range and any value or sub-range within the stated range, as if such values or sub-ranges were explicitly recited.
  • from about 2 wt % to about 15 wt % should be interpreted to include not only the explicitly recited limits of from about 2 wt % to about 15 wt %, but also to include individual values, such as about 2.35 wt %, about 3.5 wt %, about 10 wt %, about 13.5 wt %, etc., and sub-ranges, such as from about 2.5 wt % to about 14 wt %, from about 4.5 wt % to about 12.5 wt %, etc.
  • when “about” is utilized to describe a value this is meant to encompass minor variations (up to +/ ⁇ 10%) from the stated value.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
US17/266,964 2018-11-29 2018-11-29 Textile printing Abandoned US20210310188A1 (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US2018/063043 WO2020112112A1 (fr) 2018-11-29 2018-11-29 Impression textile

Publications (1)

Publication Number Publication Date
US20210310188A1 true US20210310188A1 (en) 2021-10-07

Family

ID=70852411

Family Applications (1)

Application Number Title Priority Date Filing Date
US17/266,964 Abandoned US20210310188A1 (en) 2018-11-29 2018-11-29 Textile printing

Country Status (2)

Country Link
US (1) US20210310188A1 (fr)
WO (1) WO2020112112A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021262162A1 (fr) * 2020-06-24 2021-12-30 Hewlett-Packard Development Company, L.P. Ensemble de fluides pour impression textile

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2310704C2 (ru) * 2003-07-02 2007-11-20 Таркетт Сас Поверхностное покрытие с селективным тиснением и способ его изготовления

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7458673B2 (en) * 2003-10-29 2008-12-02 Konica Minolta Medical & Graphic Inc. Ink jet recording apparatus
EP2598332B1 (fr) * 2010-07-29 2019-08-28 Hewlett-Packard Development Company, L.P. Appareil d'impression à jet d'encre et procédé pour imprimer une encre durcissable aux ultraviolets (uv)
US9789706B2 (en) * 2015-04-10 2017-10-17 Electronics For Imaging, Inc. Removable ultraviolet curable dye sublimation inks

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2310704C2 (ru) * 2003-07-02 2007-11-20 Таркетт Сас Поверхностное покрытие с селективным тиснением и способ его изготовления

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Olsson. UV LED Inks: The Future of Narrow-web Printing? Nov 1, 2013. https://www.packagingimpressions.com/article/uv-led-inks-the-future-narrow-web-printing-just-passing-fad/all/ *

Also Published As

Publication number Publication date
WO2020112112A1 (fr) 2020-06-04

Similar Documents

Publication Publication Date Title
EP3762238B1 (fr) Fluide de pré-traitement par jet d'encre pour impression textile
US11365512B2 (en) Textile printing with inkjet inks
US11001965B2 (en) Textile printing with inkjet inks
WO2020046341A1 (fr) Ensemble de fluides d'impression textile
US20220186060A1 (en) Fluid set
US20210238436A1 (en) Fluid set for textile printing
US20210130636A1 (en) Fluid sets
US20230265303A1 (en) White inkjet ink
US20210310188A1 (en) Textile printing
US20220186432A1 (en) Dye discharge fluid
US20220073768A1 (en) Inkjet ink for textile printing
US11787962B2 (en) Inkjet ink for textile printing
WO2021262162A1 (fr) Ensemble de fluides pour impression textile
WO2022046112A1 (fr) Ensemble de fluide pour jet d'encre thermique
US20220396710A1 (en) Fixer composition
US20210246328A1 (en) Fixer composition
US20230151234A1 (en) White inkjet ink
WO2022182360A1 (fr) Composition d'encre pour jet d'encre thermique et kit d'impression textile
US20220081580A1 (en) Dye sublimation inkjet ink
US20210032487A1 (en) Inkjet inks for textile printing
WO2024076341A1 (fr) Encre blanche pour jet d'encre
WO2022173425A1 (fr) Ensemble de fluides pour impression textile

Legal Events

Date Code Title Description
AS Assignment

Owner name: HEWLETT-PACKARD DEVELOPMENT COMPANY, L.P., TEXAS

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:ASKELAND, RONALD A.;BUTLER, BLAIR A.;ZHENG, JIE;AND OTHERS;SIGNING DATES FROM 20181127 TO 20181128;REEL/FRAME:055506/0487

STPP Information on status: patent application and granting procedure in general

Free format text: DOCKETED NEW CASE - READY FOR EXAMINATION

STPP Information on status: patent application and granting procedure in general

Free format text: NOTICE OF ALLOWANCE MAILED -- APPLICATION RECEIVED IN OFFICE OF PUBLICATIONS

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO PAY ISSUE FEE