Heat activated ink jet ink

Abstract

A method of printing a liquid ink which is produced from a heat activated dye which is selected from a limited group of dyes which are capable of transfer at low energy. A printer which uses liquid ink, such as an ink jet printer, prints an image onto an intermediate substrate medium. The dyes contained in the ink are not substantially activated during the process of printing on to the medium. The image formed by the printed ink is transferred from the medium to a final substrate by the application of heat and pressure for a short period of time to activate the ink. The dye and dispersing/emulsifying agent(s) are selected from a limited group to produce an ink which permits thermal transfer at low energy, with the resulting image, as deposited on the final substrate, having an optical density of 1.0 or greater. Liquid ink is produced using heat activated dyes selected from a limited group of dyes that are capable of heat activation. The dyes are not substantially soluble in the liquid carrier, such as water. One or more emulsifying agents stabilize the ink formulation. A printer that uses liquid ink, such as an ink jet printer, is used to print the ink, and the dye is heat activated after printing.

Description

This application is a divisional of U.S. Ser. No. 08/710,171, filed Sep. 12, 1996, now U.S. Pat. No. 5,640,180, which is a continuation-in-part of U.S. Ser. No. 08/695,121, filed Aug. 5, 1996, now U.S. Pat. No. 5,642,141, which is a continuation-in-part of U.S. Ser. No. 08/565,999, filed Dec. 1, 1995, now U.S. Pat. No. 5,601,023, which is a continuation-in-part of U.S. Ser. No. 08/207,756, filed Mar. 8, 1994, now U.S. Pat. No. 5,487,614, and a continuation-in-part of U.S. Ser. No. 08/506,894, filed Jul. 25, 1995, which is a continuation-in-part of U.S. Ser. No. 08/299,736, filed Sep. 1, 1994, now U.S. Pat. No. 5,488,907.

FIELD OF THE INVENTION

particles particles and the liquid carrier, but must not materially insulate or otherwise materially inhibit the activation of the dye at the time of final transfer.

Agents having the required properties when used with some or all of the acceptable dyes include Lignosulfonate products such as Marasperse 52CP (Lignotech), Lignosol FTA (Lignotech), Lignosol SFX-65 (Lignotech), Marasperse CBA-1 (Lignotech), Temsperse S002 (Temfibre, Inc.) Stepsperse DF series (Stephan Co.), and Weschem NA-4 (Wesco Technologies, LTD), Kraft lignin products such as Diwatex XP (Lignotech), and Reax 85 (Westvaco), and oxylignin products such as Marasperse CBOS-6 and Vanisperse CB.

Other examples of emulsifying agents and dispersants are alkylaryl polyether alcohol nonionic surfactants, such as Triton X series (Octylphenoxy-polyethoxyethanol); alkylamine ethoxylates nonionic surfactants such as Triton FW series, Triton CF-10, and Tergitol (Union Carbide Chemicals); polysorbate products such as Tween (ICI Chemicals and Polymers); polyalkylene and polyalkylene modified surfactants, such as Silwet surfactants (polydimethylsioxane copolymers) and CoatOSil surfactants from OSI Specialties; alcohol alkoxylates nonionic surfactants, such as Renex, BRII, and Ukanil; Sorbitan ester products such as Span and Arlacel; alkoxylated esters/PEG products, such as Tween, Atlas, Myrj and Cirrasol surfactants from ICI Chemicals and Polymers; unsaturated alcohol products such as surfynol series surfactants from Air Products Co., alkyl phosphoric acid ester surfactant products, such as amyl acid phosphate, Chemphos TR-421; alkyl amine oxide such as Chemoxide series from Chemron Corporation; anionic sarcosinate surfactants such as Hamposyl series from Hampshire Chemical corporation; glycerol esters or polyglycol ester nonionic surfactants such as Hodag series from Calgene Chemical, Alphenate (Henkel-Nopco), Solegal W (Hoechst AG), Emultex (Auschem SpA); and polyethylene glycol ether surfactants such as Newkalgen from Takemoto Oil and Fat Co.

Multiple agents may be used in combination to improve the emulsification of the system and to stabilize the system, as long as the agents are not reactive and do not cause precipitation or otherwise negatively impact upon the emulsification process or the transfer process.

Organic solvents, cosolvents, and/or humectants can also be used as additional additives. Aliphatic and/or aromatic alcohols (thioalcohols), alkoxylated alcohols (thioalcohols), halogenated alcohols (thioalcohols) and carboxylated alcohols (thioalcohols), including mono-alcohol (thioalcohol), diol (thiodialcohol), triol (thiotrialcohol) and polyol (thiopolyalcohol), aminoxide, diamine, triamine material, may be used to improve dye dispersibility, solubility and/or stability in the final ink composition. Examples of solvent materials are diethylene glycol, DMSO and dipropylene glycol.

Other additives can also be introduced into the ink, such as surfactants, corrosion control agents, foam control agents, antioxidants, radiation stabilizers, thermal stabilizers, flame retarding agents, pH control agents, viscosity control agents, or surface (interfacial) tension control agents can be added during or after the emulsification process. Other materials, including dispersants, emulsifying agents, and stabilizers, may be included in the formulation by means of methods known in the art.

EXAMPLES

An example of a liquid ink composition usable in an ink jet printer is as follows:

Material                     Weight %

heat sensitive dye(s)        0.05-20%
dispersant/emulsifying agent 0.05-30%
solvent(s)/cosolvent(s)      0-45%
additive(s)                  0-15%
water                        40-98%
Total                        100%

The heat sensitive dye may be a red (magenta), blue (cyan), yellow or brown dye. The dispersant/emulsifying agent may be a sulfonated lignin such as Marasperse CBA-1. The additive(s) may be Tergitol 15-s-9, Triton X-165, Triton X-405 or Surfynol 465. The solvents and/or co-solvents may be diethlene glycol and/or thioglycol and/or 2-pyrrolidone and/or 1-methoxy 2-propanol.

Example A

30 grams of finely divided Spirit Blue Base (CAS# 68389-46-8) is mixed with 15 grams of Ultrazine NA (Lignotech, USA) and 500 grams of de-ionized water. An ultrasonic pulverizer is used to disperse the dye into the aqueous phase for approximately 30 minutes. Two (2.0) grams of Solsperse 27000 (Zenica Colors, USA) is added into the mixture, which is pulverized for another 10 minutes to achieve a stable emulsion. The mixture is filtered to remove particles larger than 0.25 microns. The printing ink for use in the ink jet printer is formulated from the emulsion as follows:

Material             Weight %

Emulsion             87.0
Glycol               4.0
1-methoxy.2-propanol 7.0
Ammonyx LO (1)       2.0
Total                100%

(1) Stepan Co

The resulting ink is printed by the HP 560 Deskjet printer onto plain copy paper in a dark cyan color, and is transferred from the paper medium or receiver onto a polyester fabric substrate by thermal transfer at 400° F. temperature with 40 lb. pressure applied for 20 seconds. The image as applied to the polyester fabric substrate has an optical density value of 1.4-1.5 for the cyan color as read by an X-Rite 418 densitometer.

Example B

Twenty (20) grams of Disperse Yellow 9 (CAS# 6373-73-5) is mixed with four (4) grams of Sulfynol 131 (Air Products) and 5.0 grams of glycerol (CAS# 56-81-5) and 480 grams of de-ionized water. The pulverizer is used to disperse the dye into the aqueous phase for approximately 25 minutes. One (1.0) gram of Sulfynol 104 E (Air Products) is added to the mixture and pulverized for another 10 minutes to produce an emulsion. The mixture is filtered to remove particles larger than 0.25 microns. The liquid ink for use in the ink jet printer is formulated as follows:

Material          Weight %

Emulsion          78.5
Diethylene Glycol 8.0
Thiodiethanol     5.0
Sulfynol 465      4.0
1-2.Propandiol    4.0
DEA               0.5
Total             100%

The resulting liquid ink is printed by a Canon Bubble Jet 4100 printer onto plain copy paper. The printed image is thermally transferred from the paper medium to a polyester textile substrate at 400° F., while applying 40 lb. pressure for 20 seconds. An intense yellow color having an optical density of 1.4, as measured by an X-Rite 418 densitometer with background correction, appears on the substrate.

Example C

Twenty-five (25) grams of finely divided Solvent Red 52 (CAS# 81-390), is mixed with twenty-two (22) grams of Transferin® N-38 (Boehme Filatex, Inc.) and one hundred and fifty (150) grams of de-ionized water. An ultrasonic pulverizer is used to finely divide the dye and to disperse and micronize the solid dye particles into the aqueous phase by operating the pulverizer for approximately Forty-five (45) minutes. Five (5) grams of Tergitol™ 15-S-15 (Union Carbide, USA). Ten (10) grams of 1,4-butanediol, and two hundred and twenty (220) grams of de-ionized water are then added into the dispersion and pulverized for an additional ten (10) minutes. The dispersion is then filtered to remove solid particulate have a dimension which is larger than 0.25 microns. A liquid ink is formulated using the homogenized emulsion as follows:

Component            Weight %


Emulsion             85.0
Tergitol ™ 15-S-9(1) 3.997
1-pyrrolidinone      2.0
1-ethoxy-2-propanol  6.0
IPA                  3.0
Kathon ® PFM(2)      0.003
Total                100%

(1)Union Carbide, USA
(2)Rohm & Haas Company

The liquid ink is then printed by an Epson Stylus Color Pro or Epson Stylus Color lls piezo electric ink jet printer to form an image on plain copy paper. The image is transferred from the paper to a polyester fabric substrate by the application of pressure and heat at a temperature of 400° F. for 25 seconds. The image as transferred has an optical density of 1.45 for the magenta color, as measured by an X-Rite 418 densitometer with background correction.

Claims

1. A liquid ink for use in ink jet printers prepared from heat activated dye solids, comprising:

	Material	Weight %
	heat sensitive dye solid	0.05-20%
	dispersant/emulsifying agent	0.05-30%
	solvent	0-45%
	water	40-98%
	Total	100%

2. A liquid ink for use in ink jet printers prepared from heat activated dye solids, as described in claim 1, further comprising 0.01% to 15% surfactant.

3. A liquid ink for use in ink jet printers prepared from heat activated dye solids, as described in claim 1, wherein said dispersant/emulsifying agent is a sulfonated lignin.

4. A liquid ink for use in ink jet printers prepared from heat activated dye solids, as described in claim 2, wherein said dispersant/emulsifying agent is a sulfonated lignin.

5. A liquid ink for use in ink jet printers prepared from heat activated dye solids, as described in claim 1, wherein said heat activated dye is a dye which, after the liquid ink is printed, transfers by the application of heat at a temperature which is not higher than 450° F. for no more than three and one-half minutes, with the resulting image, as deposited on the final substrate having an optical density of 1.0 or greater, as measured by an X-Rite 418 densitometer in the density operation mode with background corrections.

6. A liquid ink for use in ink jet printers prepared from heat activated dye solids as described in claim 5, further comprising 0.01% to 15% surfactant.

7. A liquid ink for use in ink jet printers prepared from heat activated dye solids as described in claim 5, wherein said dispersant/emulsifying agent is a sulfonated lignin.

8. A liquid ink for use in ink jet printers prepared from heat activated dye solids as described in claim 6, wherein said dispersant/emulsifying agent is a sulfonated lignin.

9. A liquid ink for use in ink jet printers prepared from heat activated dye solids as described in claim 1, further comprising 0.01% to 45% solvent.

10. A liquid ink for use in ink jet printers prepared from heat activated dye solids as described in claim 5, further comprising 0.01% to 45% solvent.

11. A liquid ink for use in ink jet printers prepared from heat activated dye solids as described in claim 6, further comprising 0.01% to 45% solvent.

12. A liquid ink for use in ink jet printers prepared from heat activated dye solids as described in claim 7, further comprising 0.01% to 45% solvent.

13. A liquid ink jet ink, comprising:

	Material	Weight %
	heat activated dye solids	0.05-20%
	at least one dispersant and emulsifying agent	0.05-30%
	solvent	0-45%
	water	40-98%
	Total	100%

14. A liquid ink jet ink as described in claim 13, further comprising 0.01% to 15% surfactant.

15. A liquid ink jet ink as described in claim 13, wherein said at least one dispersant and emulsifying agent is a sulfonated lignin.

16. A liquid ink jet ink as described in claim 13, wherein said heat activated dye is a dye which, after the liquid ink is printed, transfers by the application of heat at a temperature which is not higher than 450° F., for no more than three and one-half minutes, with the resulting image, as deposited on the final substrate, having an optical density of 1.0 or greater, as measured by an X-Rite 418 densitometer in the density operation mode with background corrections.

17. A liquid ink jet ink as described in claim 13, wherein said heat activated dye solids are finely divided.

18. A liquid ink jet ink as described in claim 13, wherein individual particles of said heat activated dye solids are 0.5 microns or less in size.

19. A liquid ink jet ink as described in claim 13, wherein said at least one dispersant and emulsifying agent comprises at least one dispersant and at least one emulsifying agent, and wherein said at least one emulsifying agent emulsifies said heat activated dye solids within the liquid ink.

20. A liquid ink jet ink, comprising:

	Material	Weight %
	heat activated dye solids	0.05-20%
	at least one dispersant and emulsifying agent	0.05-30%
	solvent	0-45%
	water	40-98%
	Total	100%

21. A liquid ink jet ink as described in claim 20, further comprising 0.01% to 15% surfactant.

22. A liquid ink jet ink as described in claim 20, wherein said at least one dispersant and emulsifying agent is a sulfonated lignin.

23. A liquid ink jet ink as described in claim 20, wherein said heat activated dye is a dye which, after the liquid ink is printed, transfers by the application of heat at a temperature which is not higher than 450° F., for no more than three and one-half minutes, with the resulting image, as deposited on the final substrate, having an optical density of 1.0 or greater, as measured by an X-Rite 418 densitometer in the density operation mode with background corrections.

24. A liquid ink jet ink as described in claim 20, wherein said heat activated dye solids are finely divided.

25. A liquid ink jet ink as described in claim 20, wherein individual particles of said heat activated dye solids are 0.5 microns or less in size.

26. A liquid ink jet ink as described in claim 20, wherein said at least one dispersant and emulsifying agent comprises at least one dispersant and at least one emulsifying agent, and wherein said at least one emulsifying agent emulsifies said heat activated dye solids within the liquid ink.