Ink jet printing method

Abstract

An ink jet printing method, comprising the steps of:

Description

FIELD OF THE INVENTION

[0016] This invention relates to an ink jet printing method for improving the light stability and waterfastness of a printed image containing an ink jet ink containing a water-soluble anionic dye and a cationic receiver.

BACKGROUND OF THE INVENTION

[0017] Inkjet printing is a non-impact method for producing images by the deposition of ink droplets in a pixel-by-pixel manner to an image-recording element in response to digital signals. There are various methods which may be utilized to control the deposition of ink droplets on the image-recording element to yield the desired image. In one process, known as continuous ink jet, a continuous stream of droplets is charged and deflected in an imagewise manner onto the surface of the image-recording element, while unimaged droplets are caught and returned to an ink sump. In another process, known as drop-on-demand ink jet, individual ink droplets are projected as needed onto the image-recording element to form the desired image. Common methods of controlling the projection of ink droplets in drop-on-demand printing include piezoelectric transducers and thermal bubble formation. Ink jet printers have found broad applications across markets ranging from industrial labeling to short run printing to desktop document and pictorial imaging.

[0018] The inks used in the various ink jet printers can be classified as either dye-based or pigment-based. A dye is a colorant which is molecularly dispersed or solvated by a carrier medium. The carrier medium can be a liquid or a solid at room temperature. A commonly used carrier medium is water or a mixture of water and organic co-solvents. Each individual dye molecule is surrounded by molecules of the carrier medium. In dye-based inks, no particles are observable under the microscope. Although there have been many recent advances in the art of dye-based ink jet inks, such inks still suffer from deficiencies such as low optical densities on plain paper and poor light-fastness. When water is used as the carrier medium, such inks also generally suffer from poor water-fastness.

[0019] An inkjet recording element typically comprises a support having on at least one surface thereof an ink-receiving or image-forming layer. The ink-receiving layer may be a polymer layer which swells to absorb the ink or a porous layer which imbibes the ink via capillary action.

[0020] Ink jet prints, prepared by printing onto ink jet recording elements, are subject to environmental degradation. They are especially vulnerable to water smearing, dye bleeding, coalescence and light fade. For example, since inkjet dyes are water-soluble, they can migrate from their location in the image layer when water comes in contact with the receiver after imaging. Highly swellable hydrophilic layers can take an undesirably long time to dry, slowing printing speed, and will dissolve when left in contact with water, destroying printed images. Porous layers speed the absorption of the ink vehicle, but often suffer from insufficient gloss and severe light fade.

[0021] EP Publication 1 002 660 A1 discloses an ink jet recording sheet containing an image-receiving layer containing a cationic polymer derived from a vinylbenzyltrialkylammonium salt. The specific examples of alkyl moieties in these salts include only methyl, benzyl and hydroxyethyl. However, there is a problem with these salts which contain alkyl moieties having methyl or benzyl groups in that the image formed in the image-receiving layer has poor light stability, as will be shown hereafter.

[0022] U.S. Pat. No. 4,575,465 relates to an inkjet recording sheet having an image-receiving layer containing a vinyl pyridine/vinylbenzyl quaternary salt copolymer. The example of the alkyl moiety in this salt disclosed is methyl.

[0023] U.S. Pat. No. 5,856,023 relates to an ink jet recording sheet having an image-receiving layer containing a vinylbenzyl quaternary ammonium salt terpolymer. At least one of the vinylbenzyl quaternary ammonium salt moieties contains three alkyl groups of 1 to 4 carbon atoms. There is a problem with these salts which contain alkyl moieties having 1 to 4 carbon atoms in that the image formed in the image-receiving layer has poor light stability, as will be shown hereafter.

[0024] It is an object of this invention to provide an inkjet printing method using anionic dyes that will provide images with improved light stability over the prior art using a receiving element having a particular mordant.

SUMMARY OF THE INVENTION

[0025] This and other objects are achieved in accordance with this invention which relates to an inkjet printing method, comprising the steps of:

[0026] A) providing an ink jet printer that is responsive to digital data signals;

[0027] B) loading the printer with ink-receptive elements comprising a support having thereon an image-receiving layer comprising a cationic polymer containing at least one ethylenically unsaturated monomer containing a trialkylammonium salt, each trialkylammonium salt containing at least one alkyl group having greater than 8 carbon atoms;

[0028] C) loading the printer with an ink jet ink composition comprising water, a humectant, and a water-soluble anionic dye; and

[0029] D) printing on the image-receiving layer using the ink jet ink in response to the digital data signals.

[0030] It has been found that use of the above dyes and image-receiving layer provides excellent light stability.

DETAILED DESCRIPTION OF THE INVENTION

[0031] Any anionic, water-soluble dye may be used in composition employed in the method of the invention such as a dye having an anionic group, e.g., a sulfo group or a carboxylic group. The anionic, water-soluble dye may be 5 any acid dye, direct dye or reactive dye listed in the COLOR INDEX but is not limited thereto. Metallized and non-metallized azo dyes may also be used as disclosed in U.S. Pat. No. 5,482,545, the disclosure of which is incorporated herein by reference. Other dyes which may be used are found in EP 802246-A1 and JP 09/202043, the disclosures of which are incorporated herein by reference. In a preferred embodiment, the anionic, water-soluble dye which may be used in the composition employed in the method of the invention is a metallized azo dye, a non-metallized azo dye, a xanthene dye, a metallophthalocyanine dye or a sulfur dye. Mixtures of these dyes may also be used. An example of an anionic dye which may be used in the invention is as follows: 1

[0032] The dye described above may be employed in any amount effective for the intended purpose. In general, good results have been obtained when the dye is present in an amount of from about 0.2 to about 5% by weight of the ink jet ink composition, preferably from about 0.3 to about 3% by weight. Dye mixtures may also be used.

[0033] Any cationic polymer can be employed in the invention provided it contains at least one at least one ethylenically unsaturated monomer containing a trialkylammonium salt, each trialkylammonium salt containing at least one alkyl group has greater than 8 carbon atoms, as described above. In a preferred embodiment of the invention, the cationic polymer has the formula 2

[0034] wherein:

[0035] R represents H or an alkyl group of from 1 to about 4 carbon atoms;

[0036] R1 and R2 each independently represents an alkyl group of from 1 to about 8 carbon atoms;

[0037] R3 represents an alkyl group of greater than 8 to about 20 carbon atoms;

[0038] Z represents at least one ethylenically unsaturated, nonionic monomer;

[0039] m represents a mole % of from about 5 to about 100;

[0040] n represents a mole % of from 0 to about 95; and

[0041] X represents an anion.

[0042] As noted above, Z in the formula represents at least one ethylenically unsaturated, nonionic monomer. Examples of these include styrene, alpha alkylstyrene where the alkyl group has 1 to 4 carbon atoms and the aromatic group may be substituted or part of a larger ring system. Other examples of Z include acrylate esters derived from aliphatic alcohols or phenols; methacrylate esters; acrylamides; methacrylamides; N-vinylpyrrolidone or suitably substituted vinylpyrrolidones; vinyl esters derived from straight chain and branched acids, e.g., vinyl acetate; vinyl ethers, e.g., vinyl methyl ether; vinyl nitrites; vinyl ketones; halogen-containing monomers such as vinyl chloride; and olefins, such as butadiene.

[0043] Specific examples of the cationic polymers useful in the invention include the following:

3
Invention
Polymer	m	n	R4	R5	R6
P-1	100	0	—(CH2)17CH3	—	—
P-2	50	50	—(CH2)17CH3	H	—COOCH2CH3
P-3	50	50	—(CH2)17CH3	—CH3	—COOCH2CH2OH
P-4	100	0	—(CH2)11CH3	—	—
P-5	50	50	—(CH2)11CH3	H	—C6H5

[0044] The cationic polymer employed in the invention may be used in an amount of amount from about 0.2 to about 32 g/m2, preferably from about 0.4 to about 16 g/m2.

[0045] The polymers of this invention can be prepared using conventional polymerization techniques including, but not limited to bulk, solution, emulsion, or suspension polymerization. They also can be partially crosslinked.

[0046] A binder may also be employed in the image-receiving layer. In a preferred embodiment, the binder is a hydrophilic polymer. Examples of hydrophilic polymers useful in the invention include poly (vinyl alcohol), polyvinylpyrrolidone, poly(ethyl oxazoline), poly-N-vinylacetamide, non-deionized or deionized Type IV bone gelatin, acid processed ossein gelatin, pig skin gelatin, acetylated gelatin, phthalated gelatin, oxidized gelatin, chitos an, poly(alkylene oxide), sulfonated polyester, partially hydrolyzed poly (vinyl acetate-co-vinyl alcohol), poly(acrylic acid), poly(1-vinylpyrrolidone), poly(s odium styrene sulfonate), poly(2-acrylamido-2-methane sulfonic acid), polyacrylamide or mixtures thereof. In a preferred embodiment of the invention, the binder is gelatin or poly(vinyl alcohol).

[0047] If a hydrophilic polymer is used in the image-receiving layer, it may be present in an amount of from about 0.02 to about 30 g/m2, preferably from about 0.04 to about 16 g/m2 of the image-receiving layer.

[0048] The weight ratio of cationic polymer to binder is from about 1:99 to about 8:2, preferably from about 1:9 to about 4:6.

[0049] Latex polymer particles and/or inorganic oxide particles may also be used in the binder in the image-receiving layer to increase the porosity of the layer and improve the dry time. Preferably the latex polymer particles and /or inorganic oxide particles are cationic or neutral. Examples of inorganic oxide particles include barium sulfate, calcium carbonate, clay, silica or alumina, or mixtures thereof. In that case, the weight % of particulates in the image receiving layer is from about 80 to about 95%, preferably from about 85 to about 90%.

[0050] The pH of the aqueous ink compositions employed in the invention may be adjusted by the addition of organic or inorganic acids or bases. Useful inks may have a preferred pH of from about 2 to 10, depending upon the type of dye being used. Typical inorganic acids include hydrochloric, phosphoric and sulfuric acids. Typical organic acids include methanesulfonic, acetic and lactic acids. Typical inorganic bases include alkali metal hydroxides and carbonates. Typical organic bases include ammonia, triethanolamine and tetramethylethlenediamine.

[0051] A humectant is employed in the ink jet composition employed in the invention to help prevent the ink from drying out or crusting in the orifices of the printhead. Examples of humectants which can be used include polyhydric alcohols, such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, tetraethylene glycol, polyethylene glycol, glycerol, 2-methyl-2,4-pentanediol 1,2,6-hexanetriol and thioglycol; lower alkyl mono- or di-ethers derived from alkylene glycols, such as ethylene glycol mono-methyl or mono-ethyl ether, diethylene glycol mono-methyl or mono-ethyl ether, propylene glycol mono-methyl or mono-ethyl ether, triethylene glycol mono-methyl or mono-ethyl ether, diethylene glycol di-methyl or di-ethyl ether, and diethylene glycol monobutylether; nitrogen-containing cyclic compounds, such as pyrrolidone, N-methyl-2-pyrrolidone, and 1 ,3-dimethyl-2-imidazolidinone; and sulfur-containing compounds such as dimethyl sulfoxide and tetramethylene sulfone. A preferred humectant for the composition employed in the invention is diethylene glycol, glycerol, or diethylene glycol monobutylether.

[0052] Water-miscible organic solvents may also be added to the aqueous ink employed in the invention to help the ink penetrate the receiving substrate, especially when the substrate is a highly sized paper. Examples of such solvents include alcohols, such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, t-butyl alcohol, iso-butyl alcohol, furfuryl alcohol, and tetrahydrofurfuryl alcohol; ketones or ketoalcohols such as acetone, methyl ethyl ketone and diacetone alcohol; ethers, such as tetrahydrofuran and dioxane; and esters, such as, ethyl lactate, ethylene carbonate and propylene carbonate.

[0053] Surfactants may be added to adjust the surface tension of the ink to an appropriate level. The surfactants may be anionic, cationic, amphoteric or nonionic.

[0054] A biocide may be added to the composition employed in the invention to suppress the growth of microorganisms such as molds, fungi, etc. in aqueous inks. A preferred biocide for the ink composition employed in the present invention is Proxel® GXL (Zeneca Specialties Co.) at a final concentration of 0.0001-0.5 wt. %.

[0055] A typical ink composition employed in the invention may comprise, for example, the following substituents by weight: colorant (0.05-5%), water (20-95%), a humectant (5-70%), water miscible co-solvents (2-20%), surfactant (0.1-10%), biocide (0.05-5%) and pH control agents (0.1-10%).

[0056] Additional additives which may optionally be present in the ink jet ink composition employed in the invention include thickeners, conductivity enhancing agents, anti-kogation agents, drying agents, and defoamers.

[0057] The ink jet inks employed in this invention may be employed in ink jet printing wherein liquid ink drops are applied in a controlled fashion to an ink receptive layer substrate, by ejecting ink droplets from a plurality of nozzles or orifices of the print head of an ink jet printer.

[0058] The image-recording layer used in the method of the present invention can also contain various known additives, including matting agents such as titanium dioxide, zinc oxide, silica and polymeric beads such as crosslinked poly(methyl methacrylate) or polystyrene beads for the purposes of contributing to the non-blocking characteristics and to control the smudge resistance thereof; surfactants such as non-ionic, hydrocarbon or fluorocarbon surfactants or cationic surfactants, such as quaternary ammonium salts; fluorescent dyes; pH controllers; anti-foaming agents; lubricants; preservatives; viscosity modifiers; dye-fixing agents; waterproofing agents; dispersing agents; UV-absorbing agents; mildew-proofing agents; mordants; antistatic agents, anti-oxidants, optical brighteners, and the like. A hardener may also be added to the ink-receiving layer if desired.

[0059] The support for the inkjet recording element used in the invention can be any of those usually used for ink jet receivers, such as paper, resin-coated paper, poly(ethylene terephthalate), poly(ethylene naphthalate) and microporous materials such as polyethylene polymer-containing material sold by PPG Industries, Inc., Pittsburgh, Pennsylvania under the trade name of Teslin®, Tyvek® synthetic paper (DuPont Corp.), and OPPalyte® films (Mobil Chemical Co.) and other composite films listed in U.S. Pat. No. 5,244,861.

[0060] The support used in the invention may have a thickness of from about 50 to about 500 μm, preferably from about 75 to 300 μm. Antioxidants, antistatic agents, plasticizers and other known additives may be incorporated into the support, if desired. In a preferred embodiment, paper is employed.

[0061] In order to improve the adhesion of the image-recording layer to the support, the surface of the support may be subjected to a corona-discharge-treatment prior to applying the image-recording layer.

[0062] In addition, a subbing layer, such as a layer formed from a halogenated phenol or a partially hydrolyzed vinyl chloride-vinyl acetate copolymer can be applied to the surface of the support to increase adhesion of the image recording layer. If a subbing layer is used, it should have a thickness (i.e., a dry coat thickness) of less than about 2 μm.

[0063] The image-recording layer may be present in any amount which is effective for the intended purpose. In general, good results are obtained when it is present in an amount of from about 2 to about 44 g/m2, preferably from about 6 to about 32 g/m2, which corresponds to a dry thickness of about 2 to about 40 μm, preferably about 6 to about 30 μm.

[0064] The following examples illustrates the utility of the present invention.

EXAMPLES

[0065] The following polymers were used as controls in the image receiving layers:

4
Control
Polymer	m	n	R4	R5	R6
CP-1	100	0	—CH3	—	—
CP-2	100	0	—(CH2)7CH3	—	—
CP-3	100	0	—(CH2)3CH3	—	—
CP-4	100	0	—CH2(C6H5)	—	—
CP-5	50	50	—CH3	H	—C6H5
CP-6	50	50	—(CH2)7CH3	H	—C6H5
CP-7	50	50	—(CH2)3CH3	H	—C6H5
CP-8	50	50	—CH2(C6H5)	H	—C6H5
CP-9	34	66	—(CH2)17CH3	H	—C6H4CH2N+(CH3)3Cl−

Example 1

Light Stability

Preparation of a water soluble, anionic dye ink composition, I-1

[0066] Ink I-1 containing Dye 1 was prepared by mixing the dye concentrate (3.1%) prepared as above with de-ionized water containing humectants of diethylene glycol (Aldrich Chemical Co.) and glycerol (Acros Co.), each at 6%, a biocide, Proxel GXL® biocide (Zeneca Specialties) at 0.003 wt %, and a surfactant, Surfynol 465 ® (Air Products Co.) at 0.05 wt. %.

[0067] The dye concentration was based on solution absorption spectra and chosen such that the final ink when diluted 1:1000, would yield a transmission optical density of approximately 1.0.

Preparation of Control Ink Recording Elements C-1 through C-9

[0068] The composite side of a polyethylene resin coated photographic grade paper based support was corona discharge treated prior to coating. Ink receptive layers were composed of a mixture of 0.86 g/m2 of cationic polymer CP-1 through CP-9, 7.75 g/m2 of pig skin gelatin and 0.09 g/m2 of S-00 12 μm poly(styrene) beads (ACE Chemical Co.), and coated from distilled water on the above mentioned paper support.

Preparation of Invention Ink Recording Elements E-1 through E-5

[0069] Recording elements E-1 through E-5 of the invention were coated the same as control receiver elements C-1 through C-9 except P-1 through P-5 were used in place of CP-1 through CP-9.

Printing

[0070] Elements E-1 through E-5 and control elements C-1 through C-9 were printed using an Epson 200® printer using I-1 ink described above. After printing, all images were allowed to dry at room temperature overnight, and the densities were measured at all steps using an X-Rite 820® densitometer.

[0071] The images were then subjected to a high intensity daylight fading test for 2 weeks, 50 Klux, 5400° K., approximately 25% rh. The Status A blue reflection density nearest to 1.0 was compared before and after fade and a percent density retained was calculated for the yellow dye with each receiver element. The results can be found in Table 1 below.

TABLE 1
Recording		Blue Density	Blue Density	% Retained
Element	Polymer	Before Fade	After Fade	After Fade
E-1	P-1	1.0	0.81	81
E-2	P-2	0.97	0.8	82
E-3	P-3	0.96	0.79	82
E-4	P-4	1.0	0.77	77
E-5	P-5	0.93	0.59	63
C-1	CP-1	0.98	0.47	48
C-2	CP-2	0.99	0.50	50
C-3	CP-3	0.99	0.48	49
C-4	CP-4	1.0	0.51	51
C-5	CP-5	0.96	0.50	52
C-6	CP-6	0.96	0.50	52
C-7	CP-7	0.90	0.50	55
C-8	CP-8	0.96	0.55	57
C-9	CP-9	0.91	0.52	57

[0072] The above results show that the recording elements E-1 through E-5 of the invention, as compared to the control recording elements C-1 through C-9, gave higher % retained density after high intensity daylight fading. Example 2

Light Stability for P-1 Level Series

[0073] Preparation of Invention Ink Recording Elements E-6 through E-10

[0074] Recording elements E-6 through E-10 of the invention were coated the same as described in Example 1, except the amounts of P-1 and pigskin gelatin were varied keeping the final layer thickness constant at 8.61 g/m2. The amounts of each are summarized in Table 2 below.

TABLE 2
Recording	g/m2 of	g/m2 of
Element	P-1	Pigskin Gelatin
E-6	0.16	8.45
E-7	0.43	8.18
E-8	0.70	7.91
E-9	0.86	7.75
E-10	1.67	6.94

Printing

[0075] Elements E-6 through E-10 and control elements C-1 and C-9 were printed as described in Example 1 above and the results can be found in Table 3 below.

TABLE 3
Recording		Blue Density	Blue Density	% Retained
Element	Polymer	Before Fade	After Fade	After Fade
E-6	P-1	0.96	0.81	84
E-7	P-1	0.93	0.74	80
E-8	P-1	0.93	0.72	78
E-9	P-1	0.95	0.71	75
E-10	P-1	1.04	0.84	81
C-1	CP-1	0.98	0.47	48
C-9	CP-9	0.91	0.52	57

[0076] The above results show that the recording elements E-6 through E-10 of the invention, as compared to the control recording elements C-1 and C-9 gave higher % retained density after high intensity daylight fading.

Example 3

Waterfastness

Preparation of a water soluble, anionic dye ink composition, I-2

[0077] Ink I-2 was prepared as described in Example 1 except Dye 2 (0.58%) was added in place of Dye 1.

Printing

[0078] Elements E-1, E-4 and E-5 and control recording elements C-1 and C-9 were printed as described in Example 1 except I-2 was used in place of I-1. After printing, all images were allowed to dry at room temperature overnight.

[0079] The images were then subjected to a waterfastness test (WF) which involves soaking each imaged receiver in room temperature, distilled water for 5 minutes and then allowing the image to dry at room temperature overnight. The image quality of each print was then visually ranked and assigned a value between 0 and 5. The visual ranking is an indirect measure of how well the dye is fixed (dye fixation) to the receiver layer. Zero represents no image degradation (better dye fixation) and 5 represents severe image degradation (poor dye fixation) and the results are summarized in Table 4 below.

TABLE 4
Recording Element	Polymer	WF Rank
E-1	P-1	0
E-4	P-4	0
E-5	P-5	3
C-1	CP-l	5
C-9	CP-9	2

[0080] The above results show that the recording elements E-1, E-4 and E-5 of the invention, as compared to the control recording element C-1 gave a lower WF rank (better dye fixation) after the waterfastness test than the control receiver element C-1. Although the WF rank for control recording element C-9 was better than recording element E-5 of the invention, the light stability was worse as was illustrated in Table 1 above.

[0081] The invention has been described in detail with particular reference to certain preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention.

Claims

1. An ink jet printing method, comprising the steps of: A) providing an ink jet printer that is responsive to digital data signals; B) loading said printer with ink-receptive elements comprising a support having thereon an image-receiving layer comprising a cationic polymer containing at least one ethylenically unsaturated monomer containing a trialkylammonium salt, each said trialkylammonium salt containing at least one alkyl group having greater than 8 carbon atoms; C) loading said printer with an ink jet ink composition comprising water, a humectant, and a water-soluble anionic dye; and D) printing on said image-receiving layer using said ink jet ink in response to said digital data signals.

2. The method of claim 1 wherein said cationic polymer has the formula

3. The method of claim 2 wherein Z is styrene.

4. The method of claim 2 wherein R1 and R2 are each CH3 and R3 is a linear alkyl group having greater than 8 to about 18 carbon atoms.

5. The method of claim 2 wherein X is chloride.

6. The method of claim 1 wherein said humectant is diethylene glycol, glycerol or diethylene glycol monobutylether.

7. The method of claim 1 wherein said image-receiving layer also contains a binder.

8. The method of claim 7 wherein said binder is a hydrophilic polymer.

9. The method of claim 8 wherein said hydrophilic polymer is gelatin or poly(vinyl alcohol).

10. The method of claim 8 wherein the weight ratio of cationic polymer to hydrophilic polymer is from about 1:99 to about 8:2.

11. The method of claim 1 wherein said anionic dye comprises about 0.2 to about 5% by weight of said ink jet ink composition.