阅读说明：本技术 染料升华墨水热喷墨印刷法 (Dye sublimation ink thermal inkjet printing method ) 是由 H·杜莫克斯 S·M·克劳塞 V·J·林德奎斯特 于 2017-11-08 设计创作，主要内容包括：一种印刷方法包括选择染料升华墨水,其具有：分散染料着色剂分散体；选自甘油、乙氧基化甘油、2-甲基-1,3-丙二醇、二丙二醇及其组合的主要溶剂；选自非离子表面活性剂、阴离子表面活性剂及其组合的表面活性剂；选自缓冲剂、杀生物剂、螯合剂及其组合的添加剂；和余量水。向印刷头的加热电阻器施加包括超过热喷墨印刷头的启动能量(TOE)的裕度的运行能量,其中裕度为超过TOE大约10％至大约25％。从热喷墨印刷头将染料升华墨水i)直接印刷到织物基底上,或ii)印刷到转印介质上以在其上形成图像；和将图像转印到织物基底上。(A method of printing includes selecting a dye sublimation ink having: a disperse dye colorant dispersion; a primary solvent selected from the group consisting of glycerol, ethoxylated glycerol, 2-methyl-1, 3-propanediol, dipropylene glycol, and combinations thereof; a surfactant selected from the group consisting of nonionic surfactants, anionic surfactants, and combinations thereof; an additive selected from the group consisting of buffers, biocides, chelating agents, and combinations thereof; and the balance water. Operating energy comprising a margin above a start-up energy (TOE) of the thermal inkjet printhead is applied to the heater resistors of the printhead, wherein the margin is about 10% to about 25% above the TOE. Printing a dye sublimation ink from a thermal inkjet printhead i) directly onto a fabric substrate, or ii) onto a transfer medium to form an image thereon; and transferring the image to the fabric substrate.)

1. A method of printing, comprising:

a selective dye-sublimation ink comprising:

a disperse dye colorant dispersion;

a primary solvent selected from the group consisting of glycerol, ethoxylated glycerol, 2-methyl-1, 3-propanediol, dipropylene glycol, and combinations thereof;

a surfactant selected from the group consisting of nonionic surfactants, anionic surfactants, and combinations thereof;

an additive selected from the group consisting of buffers, biocides, chelating agents, and combinations thereof; and

the balance of water;

applying operating energy to a heating resistor of a thermal inkjet printhead including a margin in excess of a start-up energy (TOE) of the printhead, wherein the margin is about 10% to about 25% in excess of the TOE; and

transferring the dye-sublimation ink from the thermal inkjet print head:

i) direct thermal inkjet printing onto a fabric substrate; or

ii) thermal inkjet printing onto a transfer medium to form an image on the transfer medium; and

transferring the image from the transfer medium to a fabric substrate.

2. The printing method as claimed in claim 1, wherein the thermal inkjet printing is performed using jetting conditions selected from the group consisting of:

a voltage of about 18V to about 30V;

a pulse sequence of about 1.3 μ s to about 2.6 μ s;

an operating energy of about 0.9 μ J to about 1.1 μ J;

an ink chamber warming temperature in a range of about 35 ℃ to about 70 ℃; and

combinations thereof.

3. A printing method as claimed in claim 1, wherein the primary solvent is present in an amount of from about 10% to about 22% by weight based on the total weight of the ink, and wherein the dye sublimation ink further comprises a secondary solvent present in an amount of from 0% to about 7% by weight based on the total weight of the ink, wherein the disperse dye in the disperse dye colorant dispersion is more soluble in the secondary solvent than the primary solvent.

4. A printing method as claimed in claim 3, wherein the disperse dye colorant dispersion is present in an amount of from about 1% by weight active to about 7% by weight active based on the total weight of the ink.

5. A printing method as defined in claim 4 wherein the dye-sublimation ink comprises:

a sequestering agent present in an amount greater than 0 wt% active and less than 0.1 wt% active based on the total weight of the ink; and

a surfactant, wherein the surfactant is oleyl polyoxyethylene (3) ether phosphate present in an amount of about 0.1 wt% to about 0.75 wt% based on the total weight of the ink.

6. A printing process as claimed in claim 5, wherein the chelant is selected from methylglycinediacetic acid trisodium salt; 4, 5-dihydroxy-1, 3-benzenedisulfonic acid disodium salt monohydrate; ethylene diamine tetraacetic acid; hexamethylenediamine tetra (methylenephosphonic acid) potassium salt; and combinations thereof.

7. A printing method as claimed in claim 1, wherein the primary solvent comprises a combination of glycerol and ethoxylated glycerol.

8. The printing method as defined in claim 7 wherein the glycerol is present in an amount of from about 12 wt% to about 16 wt% based on the total weight of the ink, and wherein the ethoxylated glycerol is present in an amount of from greater than 0 wt% to about 5 wt% based on the total weight of the ink.

9. A printing method as in claim 1, wherein the disperse dye colorant dispersion has i) an average particle size of from about 50nm to about 200nm, and ii) from about 10 wt% dye solids to about 20 wt% dye solids and from about 4 wt% to about 7 wt% dispersant solids, based on the total weight of the colorant dispersion.

10. A printing method as in claim 1, wherein the disperse dye colorant dispersion is selected from the group consisting of a black disperse dye colorant dispersion, a cyan disperse dye colorant dispersion, a magenta disperse dye colorant dispersion, and a yellow disperse dye colorant dispersion.

11. A printing method as claimed in claim 3, wherein the secondary solvent is selected from 1, 2-propanediol, 1, 3-propanediol, propylene glycol, 2-pyrrolidone, tetrahydrofuran, diethylene glycol and combinations thereof.

12. A thermal inkjet printing method, comprising:

a selective dye-sublimation ink comprising:

a disperse dye colorant dispersion;

a primary solvent selected from the group consisting of glycerol, ethoxylated glycerol, 2-methyl-1, 3-propanediol, dipropylene glycol, and combinations thereof, wherein the primary solvent is present in an amount of from about 10 wt% to about 22 wt% based on the total weight of the ink;

a secondary solvent present in an amount of 0 wt% to about 7 wt%, based on the total weight of the ink;

a surfactant selected from the group consisting of nonionic surfactants, anionic surfactants, and combinations thereof;

an additive selected from the group consisting of buffers, biocides, chelating agents, and combinations thereof; and

the balance of water;

applying operating energy to a heating resistor of a thermal inkjet printhead including a margin in excess of a start-up energy (TOE) of the printhead, wherein the margin is about 10% to about 20% in excess of the TOE; and

transferring the dye-sublimation ink from the thermal inkjet print head:

i) direct thermal inkjet printing onto a fabric substrate; or

ii) thermal inkjet printing onto a transfer medium to form an image on the transfer medium; and

transferring the image from the transfer medium to a fabric substrate.

13. The thermal inkjet printing method as defined in claim 12 wherein the thermal inkjet printing is performed using jetting conditions selected from the group consisting of:

a voltage of about 18V to about 30V;

a pulse sequence of about 1.3 μ s to about 2.6 μ s;

an operating energy of about 0.9 μ J to about 1.06 μ J;

an ink chamber warming temperature in a range of about 35 ℃ to about 70 ℃; and

combinations thereof.

14. A thermal inkjet printing system, comprising:

a thermal inkjet printhead, comprising:

a base plate;

a further substrate defined on the base plate, the further substrate having at least one ink feed port and at least one ink chamber defined therein, wherein the at least one ink feed port is in operative and fluid communication with the at least one ink chamber and with the ink channel to supply ink thereto;

a nozzle plate disposed on a portion of the other substrate, the nozzle plate having at least one orifice defined therein, the at least one orifice being in fluid communication with the at least one ink chamber; and

a heater resistor operatively disposed on the backplane adjacent to and operatively associated with the at least one ink chamber and the at least one orifice;

wherein the ink chamber contains dye sublimation ink comprising:

a disperse dye colorant dispersion;

a primary solvent selected from the group consisting of glycerol, ethoxylated glycerol, 2-methyl-1, 3-propanediol, dipropylene glycol, and combinations thereof;

a surfactant selected from the group consisting of nonionic surfactants, anionic surfactants, and combinations thereof;

an additive selected from the group consisting of buffers, biocides, chelating agents, and combinations thereof; and

the balance of water; and

a printhead controller operatively connected to the heating resistor to activate the current to pass through the heating resistor to apply an operating energy comprising a margin in excess of a start-up energy (TOE) of the printhead, wherein the margin is about 10% to about 25% in excess of the TOE.

15. The thermal inkjet printing system as defined in claim 14 wherein the margin is about 15% above TOE.

Brief Description of Drawings

Features of examples of the present disclosure will become apparent by reference to the following detailed description and drawings, in which like reference numerals correspond to similar, but possibly different, components. For the sake of brevity, reference numerals or features having a previously described function may or may not be described in connection with other drawings in which they appear.

FIG. 1 is a flow chart illustrating two examples of printing methods;

FIG. 2 is a semi-schematic diagram in partial cross-sectional perspective showing one example of a heating resistor of an exemplary thermal inkjet printhead;

FIG. 3 is a semi-schematic diagram in partial cross-sectional perspective showing one example of an ink chamber of an exemplary thermal inkjet printhead;

FIG. 4 is a semi-schematic diagram in partial cross-sectional perspective showing one example of a nozzle plate of an exemplary thermal inkjet printhead;

FIG. 5 is a perspective view of one example of a thermal ink jet cartridge;

FIG. 6 is a schematic diagram of two examples of a printing system;

FIG. 7 is a graph depicting various printhead life stages for example black, cyan, magenta, and yellow thermal inkjet dye-sublimation inks in terms of drop velocity vs in meters per second (MDPN) in millions of drops per nozzle at different over-energy and power density values.

FIGS. 8A and 8B are graphs depicting average drop velocity in meters per second (FIG. 8A) and average drop weight in nanograms (FIG. 8B) for an exemplary black thermal inkjet dye-sublimation ink at two exemplary excess energy values and at various stages of printhead life in Millions of Drops Per Nozzle (MDPN);

FIGS. 9A and 9B are graphs depicting average drop velocity in meters per second (FIG. 9A) and average drop weight in nanograms (FIG. 9B) for an exemplary cyan thermal inkjet dye-sublimation ink at two exemplary excess energy values and at various stages of printhead life in Millions of Drops Per Nozzle (MDPN); and

fig. 10A and 10B are graphs depicting average drop velocity in meters per second (fig. 10A) and average drop weight in nanograms (fig. 10B) for an exemplary magenta thermal inkjet dye-sublimation ink at two exemplary excess energy values and at various stages of printhead life in Millions of Drops Per Nozzle (MDPN).

Detailed description of the invention

The development of man-made hydrophobic fibres (e.g. polyester) for the mass production of fabrics is problematic for conventional dyeing operations, since most dyes available at the time have no chemical affinity for the fabric. Disperse dyes (for dye sublimation inks) can be used to dye man-made hydrophobic fibers. Disperse dyes are a class of dyes that exhibit low or no solubility in water. Thus, disperse dyes use/include some form of dispersant (e.g., naphthalene sulfonic acid-formalin condensate, lignin sulfonic acid-formalin condensate, surfactants, etc.) to remain in a fluid form such as an inkjet ink.

Thermal inkjet printing involves electrically activating a resistor, which causes the resistor to rapidly heat and vaporize a thin film of ink adjacent the resistor, thereby ejecting ink drops from a printhead. The thermal interaction between the resistors and the ink may limit the types of inks that may be printed via a thermal inkjet printhead. This type of thermal interaction is not involved in piezoelectric inkjet printing, which may be one reason dye sublimation inks are typically formulated for piezoelectric printing.

However, it has been unexpectedly and accidentally discovered that examples of the methods of ejecting dye-sublimation inks in thermal inkjet printheads disclosed herein can achieve much longer printhead life while successfully printing dye-sublimation inks via thermal inkjet printheads.

Thermal inkjet printheads eject drops of appropriate volume using a certain minimum energy (referred to as "fire-on energy" (TOE) "). The activation energy may vary from print head design to print head design, and may also vary from sample to sample of a given print head design, e.g., due to manufacturing tolerances, etc. These tolerances add uncertainty in knowing how much energy is delivered to any given print head. Therefore, more energy (referred to as "excess energy" (OE)) is typically delivered to the average thermal inkjet printhead than is required to fire it to account for this uncertainty. Thus, thermal inkjet printers are configured to provide a fixed run/inkjet energy (excess energy/OE) that includes a margin over the activation energy. This fixed operating energy is greater than (because it includes the OE margin) the expected minimum start-up energy of the print head that the printer can accommodate.

Previous attempts to print dye sublimation inks with thermal inkjet printheads in the typical excess energy range of 30% to 50% have generally resulted in thermally induced failure modes. Some examples of such failure modes include resistor damage due to, for example, drive bubble cavitation (drive bubble cavitation), material build-up on the resistor (kogation) due to, for example, ink composition decomposition after repeated firing of the resistor, and ink material build-up within the firing chamber. Some commercially available dye sublimation inks were tested in thermal inkjet printheads and were able to print (well at 1 million drops per nozzle) approximately 10-15 milliliters of ink before thermally induced failure of the printhead.

However, it has been found that examples of the methods of the present disclosure can successfully print dye-sublimation inks by reducing the operating energy applied to the heating/ejection resistors of a thermal inkjet printhead (i.e., the operating energy includes an excess energy margin lower than in typical thermal inkjet printing). It has been found that the use of relatively low excess energy ejection parameters provides excellent printhead life while enabling acceptable dye sublimation ink drop velocities and drop weights. These results are reproducible between different pens (pens) and print heads. Such successful thermal inkjet printing of dye-sublimation inks is surprising, at least because it may have been expected that the ejection energy with a lower excess energy margin may be too low to consistently eject at an acceptable drop velocity/drop weight.

Referring now to fig. 1, an example of the dye-sublimation inks disclosed herein can be dispensed from a thermal inkjet printhead during an example of a printing method 100. One example of a method 100 (for direct printing) is shown at reference numerals 102, 104, and 106. Another example of a method 100 (for transfer) is shown at reference numerals 102, 104, 108 and 110.

One example of a printing method 100 of the present disclosure includes selecting a dye-sublimation ink comprising: a disperse dye colorant dispersion; a primary solvent selected from the group consisting of glycerol, ethoxylated glycerol, 2-methyl-1, 3-propanediol, dipropylene glycol, and combinations thereof; a surfactant selected from the group consisting of nonionic surfactants, anionic surfactants, and combinations thereof; an additive selected from the group consisting of buffers, biocides, chelating agents, and combinations thereof; and the balance water (as indicated by reference numeral 102). The method 100 further includes applying operating energy to the heater resistors of the thermal inkjet printhead including a margin in excess of a start-up energy (TOE) of the printhead, wherein the margin is about 10% to about 25% in excess of the TOE (as indicated by reference numeral 104); and sublimating the dye-sublimation ink from the thermal inkjet printhead: i) direct thermal inkjet printing onto a fabric substrate (as shown at reference numeral 106); or ii) thermal inkjet printing onto a transfer medium to form an image on the transfer medium (as shown at 108), and transferring the image from the transfer medium to a textile substrate (as shown at 110).

In another example of the printing method of the present disclosure, a dye sublimation ink is selected. The dye-sublimation ink includes: a disperse dye colorant dispersion; a primary solvent selected from the group consisting of glycerol, ethoxylated glycerol, 2-methyl-1, 3-propanediol, dipropylene glycol, and combinations thereof, wherein the primary solvent is present in an amount of from about 10 wt% to about 22 wt% based on the total weight of the ink; a secondary solvent present in an amount of 0 wt% to about 7 wt%, based on the total weight of the ink; a surfactant selected from the group consisting of nonionic surfactants, anionic surfactants, and combinations thereof; an additive selected from the group consisting of buffers, biocides, chelating agents, and combinations thereof; and the balance water. The exemplary method further includes applying operating energy to the heater resistors of the thermal inkjet printhead including a margin exceeding a start-up energy (TOE) of the printhead, wherein the margin is about 10% to about 20% above the TOE; and sublimating the dye-sublimation ink from the thermal inkjet printhead: i) direct thermal inkjet printing onto a fabric substrate; or ii) thermal inkjet printing onto a transfer medium to form an image on the transfer medium, and transferring the image from the transfer medium to a fabric substrate.

Referring now to fig. 2-5 together, an exemplary thermal inkjet printhead 10 generally includes a base plate 11 (e.g., made of silicon or another suitable material). The base plate 11 may include a plurality of layers (as shown in fig. 2) to operatively accommodate suitable electronic components to enable the printhead nozzles to fire. Printhead 10 further includes a substrate 12 (e.g., made of a polymer or other suitable material) defined on a base plate 11. The substrate 12 has at least one ink feed hole 14 and at least one ink chamber/reservoir 16 defined therein. In fig. 3, 4 ink feed holes 14 are shown, but it is understood that any desired number of ink feed holes 14 may be provided. The ink feed hole 14 is in operative (operative) and fluid communication with the ink chamber 16 and with the ink channel 13. In one example, one or more posts 15 may be disposed between the ink channel 13 and the ink feed hole 14 to filter the ink supply before the ink supply enters the ink chamber 16.

The ink chamber 16 is generally configured to repeatedly receive ink from an ink supply or source through the ink feed hole 14 and the ink channel 13 during an ink jet printing process. In one example, the printhead 10 may be incorporated with an ink cartridge 26 (see fig. 5), and the ink chamber 16 receives ink from one or more ink supply regions containing, for example, a volume of free ink and/or a capillary medium configured to store ink in individual capillaries. In another example, printhead 10 may be a separate unit that is operably connected (via appropriate tubing, etc.) to a remote supply of ink. In other words, the print head 10 may be integrated into the ink cartridge 26 (integrated print head: IPH); or the print head 10 may be integrated into a printer with a separate ink cartridge (IIC). It is to be understood that other configurations of the thermal inkjet printhead 10 are also contemplated herein.

The printhead 10 further includes a nozzle plate 18 disposed on the substrate 12. In one example, the nozzle plate 18 includes a plurality of orifices 20 (three of which are shown in FIG. 4). The orifice 20 is generally in fluid communication with the ink chamber 16 and is configured to eject an ink drop therethrough during an inkjet process (i.e., to push ink out of the printhead 10 through the orifice 20 during a thermal inkjet printing process).

A heater/ejection resistor 22 is operatively disposed on the backplane 11 adjacent to the one or more ink feed ports 14 and the one or more ink chambers 16. A heating/firing resistor 22 is also operatively associated with the orifice 20. Although fig. 4 depicts the heating/firing resistor 22 as being operatively associated with a single orifice 20, it is to be understood that the resistor 22 is also operatively associated with a plurality of orifices 20.

In one example of a thermal inkjet printhead 10, a series of ink chambers 16 receive liquid ink from an ink channel 13. A heater/firing resistor 22 is located opposite the nozzle/orifice 20 so that ink can collect between it and the orifice 20. The ejection of the ink drops is typically under the control of a microprocessor (not shown) whose signals are transmitted through electrical traces to the resistor 22. When an electrical printing pulse/current is passed through the inkjet firing/heating resistor 22 to heat it to the desired firing temperature, a small portion of the ink immediately adjacent to it vaporizes and ejects a droplet of ink from the printhead 10.

Fig. 5 is a semi-schematic view of an inkjet print cartridge 26 incorporating the print head 10 according to one example. Inkjet print cartridge 26 includes an internal ink reservoir (not shown) and a print head within ink cartridge body 27. The ink cartridge body 27 may include an ink reservoir contained entirely within the ink cartridge body 27, or may include a chamber within the ink cartridge body 27 that is fluidly connected to one or more off-axis ink reservoirs (not shown).

The printhead includes a nozzle plate 18 that includes an orifice 20 formed in a flexible polymer circuit (circuit). The flex circuit provides routing of conductive traces that are connected at one end to electrodes on the substrate and at the other end to contact pads 28. The print cartridge 26 is designed to be installed in a printer such that contact pads 28 on the front side of the flexible circuit contact the printer electrodes, thereby providing an externally generated stimulation signal to the print head. Each resistor 22 may act as an ohmic heater when selectively energized by one or more pulses applied to one or more contact pads 28, either sequentially or simultaneously.

The printhead controller 29 is operatively connected to the heating resistors 22 to activate the current to pass through the heating resistors 22 to apply operating energy including a margin exceeding a start-up energy (TOE) of the printhead 10, wherein the margin is about 10% to about 25% above the TOE.

It is understood that a single printhead 10 may include a plurality (e.g., 400 or some other desired number) of heating/firing resistors 22 and orifices 20. Although not shown, it is understood that printhead 10 comprises an integrated circuit that selectively transmits signals, such as from a microprocessor (operatively associated with printhead controller 29) capable of executing suitable computer readable instructions, to the required resistor(s) 22 and orifice(s) 20 to eject ink drops therefrom to produce an image directly on a fabric substrate or on a transfer medium.

The print cartridge 26 including the heater/ejector resistors 22 may be mounted in a carriage (not shown) of an inkjet printer. The carriage may move the print cartridge 26 across a print substrate (e.g., a fabric substrate or transfer medium) in the print/image area of the printer. The one or more orifices 20 associated with the resistor 22 may be arranged in one or more linear arrays of orifices. The one or more orifices 20 may be aligned parallel to the direction of movement of the print substrate through the printer and perpendicular to the direction of movement of the resistor 22 with the print cartridge 26. The control of the ejection of thermal inkjet dye sublimation ink from each orifice 20 results in the printing of characters or other images in a swath width (swath) across the fabric substrate or transfer medium.

Alternatively, the print cartridge 26 may be a page-wide print cartridge in fluid communication with an off-axis ink supply system. A page-wide print cartridge includes a print head bar that extends across the entire print/image area, so that the page-wide print cartridge is stationary during a printing operation.

One example of a thermal inkjet printing system according to the present disclosure includes a thermal inkjet printhead 10 including a base plate 11. A further substrate 12 is defined on the base plate 11, the further substrate 12 having at least one ink feed hole 14 and at least one ink chamber 16 defined therein, wherein the at least one ink feed hole 14 is in operative and fluid communication with the at least one ink chamber 16 and with the ink channel 13 for supplying ink thereto. A nozzle plate 18 is disposed on a portion of the other substrate 12, the nozzle plate 18 having at least one orifice 20 defined therein, the at least one orifice 20 being in fluid communication with the at least one ink chamber 16. A heater resistor 22 is operatively disposed on the backplane 11 adjacent to and operatively associated with the at least one ink chamber 16 and the at least one orifice 20. The ink chamber 16 contains dye sublimation ink. The dye-sublimation ink includes: a disperse dye colorant dispersion; a primary solvent selected from the group consisting of glycerol, ethoxylated glycerol, 2-methyl-1, 3-propanediol, dipropylene glycol, and combinations thereof; a surfactant selected from the group consisting of nonionic surfactants, anionic surfactants, and combinations thereof; an additive selected from the group consisting of buffers, biocides, chelating agents, and combinations thereof; and the balance water. The printhead controller 29 is operatively connected to the heating resistors 22 to activate the current to pass through the heating resistors 22 to apply operating energy including a margin in excess of a start-up energy (TOE) of the printhead, wherein the margin is about 10% to about 25% in excess of the TOE.

In another example of a thermal inkjet printing system, the margin is about 15% above the TOE.

Referring now to fig. 6, a schematic diagram of a printing system 30 includes a thermal inkjet printer 32 in a printing zone 34 of the printing system 30 and a dryer 36 located in a sublimation zone 38 of the printing system 30.

In one example, the fabric substrate 33 may be conveyed through the printing system 30 along a path indicated by arrow a to first feed the fabric substrate 33 to a printing zone 34 where one example of the thermal inkjet dye sublimation inks 24 disclosed herein are inkjet printed directly onto the fabric substrate 33 by the thermal inkjet printer 32 (e.g., from the print head 10 as described above) to form an ink layer on the fabric substrate 33. The ink layer disposed on the fabric substrate 33 may be heated in the print zone 34 (e.g., the air temperature in the print zone 34 may be about 10 ℃ to about 90 ℃) such that water may be at least partially evaporated from the ink layer. As an example, at least partial evaporation means that at least 50% of the water is removed. As another example, at least 80% of the water may be removed during evaporation. Generally, it is desirable to remove enough water from an area so that the color in that area does not transfer to the adjacent portion/opposing surface of the fabric substrate in contact with that area during/after rolling. The fabric substrate 33 (with the ink layer printed thereon) may then be transported to a sublimation zone 38 where the ink layer is heated or heated and exposed to pressure to sublimate the dye so that it permeates into the fabric substrate 33. This forms a printed article 40 comprising the image 37 formed on the fabric substrate 33.

In another example, transfer medium 42 may be conveyed through printing system 30 along a path indicated by arrow B to first feed transfer medium 42 to print zone 34 where an example of the thermal inkjet dye sublimation ink 24 disclosed herein is inkjet printed directly onto transfer medium 42 by thermal inkjet printer 32 (e.g., from printhead 10 as described above) to form an ink layer on transfer medium 42. Transfer medium 42 (having an ink layer printed thereon) may then be transported to sublimation zone 38 and into contact with fabric substrate 33. In the sublimation zone 38, the ink layer is heated or heated and exposed to pressure to sublimate the dye from the transfer medium 42 so that it permeates the permeable fabric substrate 33. This forms a printed article 40' including the image 37 formed on the fabric substrate 33.

In one example of the printing method 100, thermal inkjet printing is performed using jetting conditions selected from the group consisting of: a voltage of about 18V to about 30V; a pulse sequence of about 1.3 μ s to about 2.6 μ s; an operating energy of about 0.9 μ J to about 1.11 μ J; an ink chamber warming temperature in a range of about 35 ℃ to about 70 ℃; and combinations thereof. In one example, the ink chamber warming temperature is in a range of about 45 ℃ to about 65 ℃.

In another example of the printing method, thermal inkjet printing is performed using ejection conditions selected from the group consisting of: a voltage of about 18V to about 30V; a pulse sequence of about 1.3 μ s to about 2.6 μ s; an operating energy of about 0.9 μ J to about 1.06 μ J; an ink chamber warming temperature in a range of about 35 ℃ to about 70 ℃; and combinations thereof. In one example, the ink chamber warming temperature is in a range of about 45 ℃ to about 65 ℃.

In one example, the injection condition voltage may be about 27V to about 30V.

As used herein, a "pulse train" is the total time in microseconds of a precursor pulse (used to conduct heat into the ink film in direct contact with the surface of the resistor 22) applied to the heater resistor 22 plus dead time (dead time) (the period of no energy pulse between the precursor pulse and the fire-pulse) plus a fire pulse (used to establish drive bubble nucleation) applied to the heater resistor 22. For example, if the precursor pulse width is 0.25 μ s, the dead time is 0.6 μ s and the attack pulse width is 0.6 μ s, the pulse train is 1.45 μ s.

As mentioned herein, an example of the printing method 100 includes applying operating energy to the heating resistors 22 of the thermal inkjet printhead 10 that includes a margin that exceeds the start-up energy (TOE) of the printhead 10. In other words, the operating energy includes the amount of energy corresponding to TOE plus the amount of energy (margin) corresponding to excess energy (OE). In one example, the margin is about 10% to about 25% above the TOE. In another example, the margin is about 10% to about 20% above the TOE. In yet another example, the margin is about 15% over TOE.

It is to be understood that the operating energy depends on various factors, such as the size of the resistor 22, manufacturing tolerances, the accuracy of the electrical components in the printer, variations between printed components, the resistance of the cable, and the like. It is also understood that the elevated temperature to which the ink chamber is set is an adjustable parameter and has some effect on the TOE.

In one example, the operating energy may be determined by first determining the start-up energy (TOE) of the printhead 10. One example of determining the initiation energy at the time of manufacture involves applying high energy and observing drop ejection. The energy is then gradually reduced until ink drop ejection ceases. The start energy dot is an energy just above the dot where ink droplet ejection was stopped. This start-up energy may then be used, along with excess energy margin, to determine an operating voltage and write this voltage to the printhead assembly storage device.

In an exemplary printhead having heater resistors 22 with a surface area of about 620 square microns (length 29.8 μm, width 20.8 μm) and a firing temperature of ink chamber 16 set at about 45 ℃, the operating energy corresponding to TOE plus about 10% excess energy is about 0.96 μ J, the operating energy corresponding to TOE plus about 15% excess energy is about 1.02 μ J, the operating energy corresponding to TOE plus about 20% excess energy is about 1.06 μ J, and the operating energy corresponding to TOE plus about 25% excess energy is about 1.11 μ J.

Other exemplary values of TOE and excess energy (for exemplary black, cyan, magenta, and yellow thermal inkjet dye sublimation inks) for an exemplary printhead having heating resistors 22 with a surface area of about 620 square microns (length 29.8 μm, width 20.8 μm) and a warm-up temperature of the ink chamber 16 set at about 45 ℃ are shown in table 1 below.

TABLE 1

It is to be understood that these examples of operating energy are exemplary, as the TOE may vary from printer to printer and from printhead to printhead.

One example of a thermal ink jet dye sublimation ink disclosed herein comprises a dispersed dye colorant dispersion; a primary solvent selected from the group consisting of glycerol, ethoxylated glycerol, 2-methyl-1, 3-propanediol, dipropylene glycol, and combinations thereof; a surfactant selected from the group consisting of nonionic surfactants, anionic surfactants, and combinations thereof; an additive selected from the group consisting of buffers, biocides, chelating agents, and combinations thereof; and the balance water. In some examples, the thermal inkjet dye-sublimation ink consists of the listed components and is free of additional components (e.g., shear thinning agent, additional solvent, etc.). In other examples, thermal ink jet dye sublimation inks include the listed components, and other components may be added that do not adversely affect the jettability of the ink via the thermal ink jet print head.

Throughout this disclosure, the weight percentages referred to as "wt% actives" refer to the loading of the active components of the dispersion or other formulation present in the thermal ink jet dye sublimation ink. For example, the wt% actives of the disperse dye colorant dispersion allows for the loading (as a weight percentage) of reactive dye solids present in the ink, and does not allow for the weight of other components of the disperse dye colorant dispersion (e.g., co-solvents, water, etc.) in the ink-jet ink. The term "wt%" without the term "active" refers to a 100% active loading of other inactive components not included therein.

In the examples disclosed herein, the disperse dye colorant dispersion can be any color. In one example, the disperse dye colorant dispersion is selected from the group consisting of a black disperse dye colorant dispersion, a cyan disperse dye colorant dispersion, a magenta disperse dye colorant dispersion, and a yellow disperse dye colorant dispersion. Each disperse dye colorant dispersion comprises a disperse dye, a dispersant, and a disperse carrier.

The disperse dye included in the colorant dispersion may depend on the desired color of the thermal ink jet dye sublimation ink.

Black disperse dye colorant dispersions typically comprise a blend of disperse dyes, for example a blend of blue, brown and yellow disperse dyes, or a blend of blue, orange and violet disperse dyes, or a blend of blue, orange and yellow disperse dyes, or a blend of blue, magenta and yellow dyes. One example of a suitable blue, brown, and yellow disperse dye blend comprises disperse blue 360(DB360), disperse brown 27, and disperse yellow 54(DY 54). Some examples of suitable blue, orange and violet disperse dye blends include disperse blue 291: 1(DB 291: 1), disperse orange 29(DO29) and disperse violet 63 or DB 291: 1. DO29 and disperse violet 99. One example of a suitable blue, orange and yellow dye blend comprises DB360, disperse orange 25 and DY 54. One example of a suitable blue, magenta, and yellow dye blend includes disperse blue 77(DB77), disperse red 92, and disperse yellow 114(DY 114).

Cyan disperse dye colorant dispersions can include blue disperse dyes, such as disperse blue 27, disperse blue 60, disperse blue 73, DB77, disperse blue 87, disperse blue 257, DB 291: 1. disperse blue 359, DB360, disperse blue 367, and mixtures thereof.

Magenta disperse dye colorant dispersions can include red disperse dyes, such as disperse red 60, disperse red 82, disperse red 86: 1. disperse red 167: 1. disperse red 279 and mixtures thereof.

Yellow disperse dye colorant dispersions can include yellow disperse dyes such as DY54, disperse yellow 64, disperse yellow 71, disperse yellow 86, DY114, disperse yellow 153, disperse yellow 233, disperse yellow 245, and mixtures thereof.

The disperse dye colorant dispersion may comprise from about 10 wt% dye solids to about 20 wt% dye solids, based on the total weight of the colorant dispersion.

As mentioned above, each disperse dye colorant dispersion also includes a dispersant. The dispersant may be any suitable polymeric dispersant that can disperse the dye and be jetted through a thermal inkjet printhead.

Some examples of suitable polymeric dispersants for dispersing dye colorant dispersions include block acrylic copolymers, including A-B block copolymers, such as benzyl methacrylate-diblock copolymer and butyl methacrylate-diblock copolymer, and further examples of suitable polymeric dispersants include benzyl methacrylate-triblock copolymer, and benzyl methacrylate-triblock copolymer, such as ABC-triblock copolymer, and further examples of suitable polymeric dispersants include block acrylic copolymers, including ABC-triblock copolymer, and further examples of suitable block methacrylic acid-triblock copolymer, including low-ethoxy methacrylate-triblock copolymer, and further examples of suitable polymeric dispersants include block acrylic copolymers, such as benzyl methacrylate-triblock copolymer, and low-ethoxy methacrylate-triblock copolymer586. 671, 675, 678, 680, 683, 690, 693, and 695 (from BASF Corp.).

Examples of polymerization methods for forming the dispersant may include a radical method, a group transfer method (GTP), a Radical Addition Fragmentation (RAFT), an Atom Transfer Reaction (ATR), a special chain transfer polymerization technique (SCT), and the like. As an example, the dispersant may be a grafted acrylic copolymer made by SCT.

In other examples, the disperse dye may be a self-dispersing dye. The disperse dye may be exposed to a diazotisation treatment (in which charged radicals from the degraded azo are attached to the colorant) or to an ozone treatment (oxidation and functionalization with, for example, a carboxylic acid) or to a cross-linking treatment to render the dye self-dispersing.

The disperse dye colorant dispersion may comprise from about 4 wt% dispersant solids to about 7 wt% dispersant solids, based on the total weight of the colorant dispersion.

The average particle size of the solids (e.g., disperse dye and dispersant) in the disperse dye colorant dispersion can be from about 50nm to about 200 nm. In another example, the average particle size of the disperse dye is from about 100nm to about 200 nm. These particle sizes are particularly suitable for ejection through the orifices of a thermal inkjet printhead.

The dispersion vehicle can include water and a water-soluble or water-miscible cosolvent. Examples of water-soluble or water-miscible co-solvents in disperse dye colorant dispersions can include alcohols (e.g., glycols such as 1, 2-propanediol, 1, 3-propanediol, etc.), ketones, ketols, ethers (e.g., 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, 1, 3-propanediol (trimethylene glycol), butylene glycol, and hexylene glycol, addition polymers of ethylene oxide or propylene oxide such as polyethylene glycol, polypropylene glycol, etc., triols such as glycerol and 1, 2, 6-hexanetriol, lower alkyl ethers of polyhydric alcohols, such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, and diethylene glycol monoethyl ether; and lower dialkyl ethers of polyhydric alcohols, such as diethylene glycol dimethyl or diethyl ether.

One or more of these co-solvents can each be present in the disperse dye colorant dispersion in an amount of from about 1% to about 5% by weight, based on the total weight of the colorant dispersion. The balance of the disperse dye colorant dispersion is water, such as purified water or deionized water.

In one example, the disperse dye colorant dispersion has i) an average particle size of from about 50nm to about 200nm, and ii) from about 10 wt% dye solids to about 20 wt% dye solids and from about 4 wt% to about 7 wt% dispersant solids, based on the total weight of the colorant dispersion. In this example, the remainder of the disperse dye colorant dispersion may be one or more co-solvents and water.

To form the thermal ink jet dye sublimation inks disclosed herein, a disperse dye colorant dispersion is incorporated into an ink vehicle comprising a primary solvent, a surfactant, one or more additives, and water.

The disperse dye colorant dispersion may be incorporated into the ink vehicle in the presence of from about 1% by weight active to about 7% by weight active based on the total weight of the thermal inkjet dye-sublimation ink. In another example, the disperse dye colorant dispersion may be present in an amount from about 3% by weight active to about 5% by weight active based on the total weight of the thermal inkjet dye-sublimation ink. The wt% actives of the disperse dye colorant dispersion allows for the loading (as a weight percentage) of reactive dye solids present in the ink, and does not allow for the weight of other components of the disperse dye colorant dispersion (e.g., co-solvents, water, etc.) in the ink-jet ink.

The primary solvent is selected in part because the disperse dye is very insoluble in the primary solvent. The primary solvent is also selected in part because it also helps to maintain nozzle health of the thermal inkjet printhead and provides substantially consistent print quality over the life of the printhead. In one example, the primary solvent is selected from the group consisting of glycerol, ethoxylated glycerol, 2-methyl-1, 3-propanediol, dipropylene glycol, and combinations thereof. The primary solvent is present in an amount of about 10 wt% to about 22 wt% based on the total weight of the ink. It is to be understood that the total amount of primary solvent is within the given range, whether a single primary solvent or a combination of primary solvents is used. In one example, the primary solvent comprises a combination of glycerol and ethoxylated glycerol. In this example, the glycerol is present in an amount from about 12 wt% to about 16 wt% based on the total weight of the ink, and the ethoxylated glycerol is present in an amount from greater than 0 wt% to about 5 wt% based on the total weight of the ink.

The ink may further comprise a secondary solvent present in an amount of from 0 wt% to about 7 wt%, based on the total weight of the ink. In one example, the disperse dye in the disperse dye colorant dispersion is more soluble in the secondary solvent than the primary solvent and therefore constitutes less than 50% of the total solvent content (i.e., the primary solvent plus the secondary solvent, and excluding water) such that the disperse dye remains dispersed in the ink vehicle. Examples of secondary solvents are selected from the group consisting of 1, 2-propanediol, 1, 3-propanediol, propylene glycol, 2-pyrrolidone, tetrahydrofuran, diethylene glycol, and combinations thereof. The secondary solvent may be added to the ink vehicle or may be included as part of the disperse dye colorant dispersion. The co-solvent(s) are present in the disperse dye colorant dispersion in a relatively low amount (from 1 wt% to about 5 wt%, based on the total weight of the colorant dispersion) so that a portion of the co-solvent(s) is transferred to the inks disclosed herein, depending in part on the dispersion solids and the loading of the dispersion in the ink.

In one example, the primary solvent is present in an amount of about 10 wt% to about 22 wt% based on the total weight of the ink, and the dye-sublimation ink further comprises a secondary solvent present in an amount of 0 wt% to about 7 wt% based on the total weight of the ink, wherein the disperse dye in the disperse dye colorant dispersion is more soluble in the secondary solvent than the primary solvent.

The ink also includes a surfactant, which may be nonionic, anionic, or a combination thereof. In one example, the total amount of the one or more surfactants in the thermal ink jet dye sublimation ink is from about 0 wt% to about 2 wt% (relative to the weight of the thermal ink jet dye sublimation ink). In another example, the surfactant is present in an amount of 1 wt% or less. One or more surfactants may be included in thermal ink jet dye sublimation inks to aid jettability, control viscosity, improve lubricity, and prevent agglomeration of dispersed dye solids. Examples of suitable surfactants include oleyl polyoxyethylene (3) ether phosphate, non-oleyl polyoxyethylene (3) ether phosphate, and the likeIonic low-foaming surfactants, e.g. ethoxylated 2, 4, 7, 9-tetramethyl-5-decyne-4, 7-diol (as465(H L B13) from Evonik Industries) and other ethoxylated surfactants (available as440(H L B8) from Evonik Industries, or secondary alcohol ethoxylates (available as Evonik. RTM. TM.), as well as their use in the preparation of pharmaceutical preparations15-S-7(HLB 12.1)、15-S-9(H L B12.6), etc. available from The Dow chemical Co.) in one example, The surfactant is oleyl polyoxyethylene (3) ether phosphate, ethoxylated 2, 4, 7, 9-tetramethyl 5 decyne-4, 7-diol, or a combination thereof in some examples, it has been found that,465 and440 can impart a synergistic effect in wetting to the inks disclosed herein.

When included, the oleyl polyoxyethylene (3) ether phosphate may be present in an amount of about 0.1 wt% to about 0.75 wt% based on the total weight of the ink. In one example, the oleyl polyoxyethylene (3) ether phosphate is present in an amount of about 0.2 wt% to about 0.5 wt% based on the total weight of the ink. Oleyl polyoxyethylene (3) ether phosphate ester as CRODAFOS^TMO3A or Crodafos^TMN-3 acids were purchased from Croda. It is believed that the oleyl polyoxyethylene (3) ether phosphate may assist the chelating agent (when included) in effectively capturing the high amount of metal ions present in the ink (e.g. from the colorant dispersion) and that the chelating agent (when included) prevents the oleyl polyoxyethylene (3) ether phosphate from precipitating out of the ink. Such a combined guideA significant and unexpected reduction in kogation in thermal inkjet printheads is induced. Kogation refers to the deposition of dry ink on the heating element of a thermal inkjet printhead, and the combination of the oleyl polyoxyethylene (3) ether phosphate ester with the chelating agent helps to prevent build-up of kogation and extend the life of the printhead. These synergistic effects are unexpected in view of the small amounts of these two components and the relatively high amounts of metal ions (due to the disperse dye colorant dispersion) that may be present in the ink (e.g., about 4ppm to about 10 ppm).

As mentioned above, examples of the inks disclosed herein can further comprise one or more additives, such as chelating agents, buffers, biocides, and combinations thereof.

When included, the sequestering agent is present in an amount greater than 0 wt% active and less than 0.1 wt% active, based on the total weight of the ink. In one example, the chelating agent is present in an amount of about 0.04 wt% active to about 0.08 wt% active based on the total weight of the ink. The wt% actives of the chelant allows for the loading (as a weight percentage) of the active chelant present in the ink and does not allow for the weight of other components of the chelant solution (e.g., water) in the ink-jet ink.

In one example, the chelating agent is selected from methylglycine diacetic acid trisodium salt; 4, 5-dihydroxy-1, 3-benzenedisulfonic acid disodium salt monohydrate; ethylenediaminetetraacetic acid (EDTA); hexamethylenediamine tetra (methylenephosphonic acid) potassium salt; and combinations thereof. Methylglycinediacetic acid trisodium salt (Na)₃MGDA) can be used asM was purchased from BASF Corp. Disodium 4, 5-dihydroxy-1, 3-benzenedisulfonate monohydrate as TIRON^TMThe monohydrate was purchased. Hexamethylenediamine tetra (methylenephosphonic acid) potassium salt can be used2054 was purchased from Italmatch Chemicals.

The surfactant and the chelating agent and their respective amounts may depend in part on the colorant dispersion included in the ink. In one example, the sequestering agent is present in an amount greater than 0 wt% active and less than 0.1 wt% active based on the total weight of the ink; and the surfactant (oleyl polyoxyethylene (3) ether phosphate) is present in an amount of about 0.1 wt% to about 0.75 wt% based on the total weight of the ink. In this example, the chelating agent is selected from methylglycine diacetic acid trisodium salt; 4, 5-dihydroxy-1, 3-benzenedisulfonic acid disodium salt monohydrate; ethylenediaminetetraacetic acid (EDTA); and hexamethylenediamine tetra (methylenephosphonic acid) potassium salt. In another example, the ink is a black ink or a magenta ink, the chelant is present in an amount greater than 0 wt% active and less than 0.1 wt% active based on the total weight of the ink, and the surfactant is a combination of oleyl polyoxyethylene (3) ether phosphate ester and ethoxylated 2, 4, 7, 9-tetramethyl 5 decyne-4, 7-diol. In yet another example, the ink is a cyan ink or a yellow ink, the chelating agent is present in an amount greater than 0 wt% active and less than 0.1 wt% active based on the total weight of the ink, and the surfactant is an ethoxylated 2, 4, 7, 9-tetramethyl 5 decyne-4, 7-diol.

In one example, the thermal inkjet dye sublimation ink has a pH of about 7 to about 9.5 at the time of manufacture in another example, the thermal inkjet dye sublimation ink has a pH of about 8 to about 9 at the time of manufacture one or more pH adjusting agents, such as buffers, may be added to the ink to offset any slight pH reduction that may occur over time, the pH may decrease over time from about 0.5 units to about 1 unit after manufacture accordingly, the pH of the inks disclosed herein may be below the ranges given herein, depending in part on how much time has elapsed since manufacture, in one example, the total amount of one or more buffers in the ink is 0 wt% to about 0.5 wt% (relative to the weight of the thermal inkjet dye sublimation ink), in another example, the total amount of one or more buffers in the ink is about 0.1 wt% (relative to the weight of the thermal inkjet dye sublimation ink) examples of some suitable buffers include TRIS (hydroxymethyl) aminomethane or trisodium), 1, 3-bis [ TRIS (hydroxymethyl) aminopropane ] amine sulfonate, 1- (2-ethyl-2- (2-propane-2- (2-ethyl-2- (2-propane-2- (2- (2-hydroxyethyl-propane-2- (2-propane-piperazine-4-2-ethyl-2-piperazine-2-trisulfonic acid) trisulfonic acid, 1-2- (2-trishydroxyethyl-2-ethyl-2- (2-propane-2-ethyl-piperazine-2-4-2-piperazine-trisulfonic acid, 1-4-2-trisulfonic acid, 2-trisulfonic acid, 2-trishydroxyethyl-2-trisulfonic acid, 1-2-trisulfonic acid, 2-trishydroxyethyl-ethyl-2-.

In one example, the total amount of the one or more biocides in the thermal ink-jet dye-sublimation ink is from about 0 wt% actives to about 0.5 wt% actives (relative to the weight of the thermal ink-jet dye-sublimation ink). In another example, the total amount of the one or more biocides in the inkjet ink composition is from about 0.001 wt% actives to about 0.1 wt% actives (relative to the weight of the thermal inkjet dye sublimation ink). The wt% active of the biocide allows for the loading (as a weight percentage) of active biocide present in the ink, and does not allow for the weight of other components of the biocide (e.g., water) in the ink-jet ink.

Examples of suitable biocides include(Ashland Inc.)、UCARCIDE^TMOr KORDEK^TMOr ROCIMA^TM(Dow Chemical Co.)、(Arch Chemicals) series,B20 andm20 andMB L (blend of 2-methyl-4-isothiazolin-3-one (MIT), 1, 2-benzisothiazolin-3-one (BIT) and Bronopol) (Thor Chemicals), AXIDE^TM(Planet Chemical)、NIPACIDE^TM(Clariant) under the trade name KATHON^TM(Dow Chemical Co.) blends of 5-chloro-2-methyl-4-isothiazolin-3-one (CIT or CMIT) and MIT and combinations thereof.

It is to be understood that water is not considered a solvent or co-solvent in the inks disclosed herein, but is present in addition to one or more primary solvents and secondary co-solvents and constitutes the balance of the ink. Thus, the weight percent of water present in the thermal ink jet dye sublimation ink depends in part on the weight percent of the other components. The water may be purified water or deionized water.

To further illustrate the present disclosure, examples are given herein. It is understood that these examples are for illustration and are not to be construed as limiting the scope of the disclosure.

Examples