USOO9284.

463B2

(12) United States Patent (10) Patent No.: US 9.284.463 B2

BrOWn et al. (45) Date of Patent: *Mar. 15, 2016

(54) SOLVENT-BASED INKJET INK 5,086,698 A 2, 1992 Wirz

FORMULATIONS 5,141,556 A 8, 1992 Matrick
5,169,436 A 12/1992 Matrick
5,169.438 A 12/1992 Matrick
(71) Applicant: Markem-Imaje Corporation, Keene, 5,265,315 A 11/1993 Hoisington et al.
NH (US) 5,275,646 A 1/1994 Marshall et al.
5,466,287 A 1 1/1995 Lyon
(72) Inventors: Benjamin J. Brown, Keene, NH (US); 5,514,207 A 5/1996 Fague
Richard C. Woudenberg, Keene, NH 33.87 A E. E; al.
(US); Richard J. Larson, Jr., Walpole, 5594,044 A 1/1997 SN
NH (US); Ann Benjamin, Keene, NH 5,659.346 A 8/1997 Moynihan et al.
(US); Corey Williams, Keene, NH (US) 5,725,641 A 3, 1998 MacLeod
5,755,860 A 5, 1998 Zhu
(73) Assignee: Markem-Imaje Corporation, Keene, 5,757,391 A 5/1998 Hoisington
NH (US) 5,837,042 A 11/1998 Lent et al.
5,888,287 A 3, 1999 Brown et al.
5,919,291 A 7/1999 Hotomi et al.
(*) Notice: Subject to any disclaimer, the term of this 5,919,293 A 7, 1999 MAN I.
patent is extended or adjusted under 35 5,932,631 A 8, 1999 Marritt et al.
U.S.C. 154(b) by 0 days. 5,935,308 A 8/1999 Siddiqui
5,973,027 A 10, 1999 Howald et al.
This patent is Subject to a terminal dis- 5,985,016 A 1 1/1999 Tsang et al.
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6,010,564. A 1, 2000 Zhu
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(65) Prior Publication Data H1967 H 6, 2001 Woolf
US 2014/0296405 A1 Oct. 2, 2014 (Continued)
Related U.S. Application Data FOREIGN PATENT DOCUMENTS
(63) Continuation of application No. 12/839,534, filed on DE 1982.771O 12/1999
Jul. 20, 2010, now Pat. No. 8,778,074. EP 04.08333 1, 1991
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(60) Provisional application No. 61/227,007, filed on Jul. EP 1412438 5, 2008
20, 2009 JP 59 142834 8, 1984
s JP 2001/O5717 4/2001
WO O1,25340 4/2001
(51) Int. Cl. WO 2004/028225 4/2004
C09D II/02 (2014.01) WO 2004/03.1308 4/2004
C09D II/38 (2014.01) WO 2005/OO7761 1, 2005
C09D II/36 (2014.01) (Continued)
C09D II/30 (2014.01)
(52) U.S. Cl. OTHER PUBLICATIONS
CPC ................ C09D 1 1/38 (2013.01); C09D II/30
(2013.01); C09D II/36 (2013.01) International Search Report and Written Opinion for PCT/US2010/
(58) Field of Classification Search 042520, mailed Nov. 23, 2010, 17 pages.
CPC ......... CO9D 1 1/30: CO9D 1 1/36: CO9D 1 1/38 “Langmuir and Langmuir-Blodgett Films: What and How?', online,
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St. licati - - - - - fief
ee appl1cauon Ille Ior 1965 R n1Story.
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htm. Finland) the Internet URL: http://www.ksvinc.com 1LB.
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Primary Examiner — Veronica F Faison
4,155,767 A 5/1979 Specht et al. (74) Attorney, Agent, or Firm — Fish & Richardson P.C.
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4,500,895 A 2f1985 Bucket al. (57) ABSTRACT
4,567,213 A 1, 1986 Bhatia
4,727,384 A 2f1988 Tsuda Solvent-based inkjet ink formulations including an organic
4,825,227 A 4, 1989 Fischbeck et al. Solvent, a resin, a Surfactant, and a colorant are provided. The
4.937,598 A 6, 1990 Hine et al. inks have many desirable attributes such as extended decap
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 US 9.284.463 B2
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U.S. Patent Mar. 15, 2016 US 9.284.463 B2

min.

FIG.

3 min.

FG, 2.

10 min.

F.G. 3

5 min.

F.G. 4

overnight

F.G. S.
 US 9,284.463 B2
1. 2
SOLVENT-BASED INKJET INK In one aspect of the disclosure, an inkjet ink includes an
FORMULATIONS organic solvent, a resin, a Surfactant, and a colorant. The
decap time of the ink can be at least about 1 minute.
CROSS REFERENCE TO RELATED In some implementations, the organic solvent includes a
APPLICATIONS fast solvent, an intermediate solvent, a slow solvent or their
mixtures. The fast solvent can be selected from the group
This application is a continuation of U.S. Utility applica consisting of methanol, ethanol, propanol, iso-propanol,
tion Ser. No. 12/839,534, filed on Jul. 20, 2010, which claims acetone, methyl ethyl ketone, methyl isobutyl ketone, pen
priority to U.S. Provisional Application Ser. No. 61/227,007, tane, hexane, heptane, methyl acetate, ethyl acetate, propyl
filed on Jul. 20, 2009. The entire contents of the foregoing 10 acetate, derivatives of the included solvents, and their mix
applications are hereby incorporated by reference. tures. In some examples, the intermediate solvent can be
selected from the group consisting of Cas alcohols, 1-meth
TECHNICAL FIELD oxy-2-propanol, 2-methoxy ethanol, 2-ethoxy ethanol,
1-methoxy-2-acetoxy propane, derivatives of the included
This disclosure relates to solvent-based inkjet ink formu 15 solvents, and their mixtures. The slow solvent can be selected
lations, products that include Such formulations, and to meth from the group consisting of tripropylene glycol monomethyl
ods of making and using the same. ether, tripropylene glycol-n-butyl ether, propylene glycol
phenyl ether, derivatives of the included solvents, and their
BACKGROUND mixtures.
In another aspect, the disclosure describes an inkjet ink
Inkjet printing typically involves ejecting inks from a com including a fast organic solvent (e.g., ethanol), a resin, a
ponent of an inkjet printer (e.g., from one or more nozzles of Surfactant (Such as a fluorosurfactant), and a colorant. The
a printhead) onto a Substrate. decap time of the ink can be at least about one hour.
Inkjet printhead noZZles can be designed to operate within In some implementations, the inkjet ink is substantially
specific viscosity ranges of inks and initial evaporation can 25 free of an intermediate organic solvent, a slow organic Sol
generally cause an increase in Viscosity that affects the ability vent, or combinations thereof.
of the nozzle to fire a drop of ink. Clogging can be caused by In some implementations, the inkjet ink has a drying time
evaporation of an organic solvent or water from the interface of less than about 2 seconds.
of the liquid at the surface and/or within the nozzle. The In some implementations, the fast solvent is selected from
inception of clogging may cause distortion of the printed 30 the group consisting of methanol, ethanol, propanol, iso
image or alphanumeric character. Eventually the clogged propanol, acetone, methyl ethyl ketone, methyl isobutyl
nozzle can fail to fire and no image will be generated. Con ketone, pentane, hexane, heptane, methyl acetate, ethyl
sequently, a printer service routine, Such as a printhead purge acetate, propyl acetate, derivatives of the included solvents,
operation, may be required on a regular basis to avoid printing and their mixtures.
defects. However, it may be desirable to service the printhead 35 In another aspect, the disclosure describes an inkjet ink
as infrequently as possible, as servicing the printhead can be including an intermediate organic solvent (e.g., a glycol ether
wasteful of ink and requires that the printer be unavailable for having at least about four carbon atoms), a resin, a surfactant
normal printing operations. (such as a fluoroSurfactant), and a colorant. The decap time of
A typical requirement for an inkjet ink is the ability to the ink can be at least about one hour.
remain in the fluid condition in a printhead nozzle opening on 40 In some implementations, the inkjet ink is substantially
exposure to air, which is the so-called “decap' condition. This free of a fast organic solvent, a slow organic solvent, or
ability can allow a nozzle to function normally after a period combinations thereof.
of non-use. Examples of Such periods of non-use may be In some implementations, the intermediate solvent is
during times of printer storage, maintenance, and/or during selected from the group consisting of Cas alcohols, 1-meth
normal operation of infrequently utilized printhead nozzles. 45 oxy-2-propanol, 2-methoxy ethanol, 2-ethoxy ethanol,
Decap is sometimes referred to in the art as “latency” and 1-methoxy-2-acetoxy propane, ethyl lactate, derivatives of
these two terms have been used interchangeably. The longer the included solvents, and their mixtures.
the decap time rating of the ink, the longer the downtimes that In another aspect, the disclosure describes an inkjet ink
can be handled or accommodated by the printer. For example, including a slow organic solvent, a resin, a surfactant (Such as
a long decap time reduces the need for servicing the print 50 a fluoroSurfactant), and a colorant. The decap time of the ink
head. can be at least about one day.
A longer decap time can be achieved, for example, by the In some implementations, the inkjet ink is substantially
use of certain less volatile solvents (a solvent with a lower free of a fast organic solvent, an intermediate organic solvent,
vapor pressure) in the ink formulation. However, such sol or combinations thereof.
vents do not dry quickly enough for high throughput printing 55 In some implementations, the slow organic Solvent
operations and thus Smearing of the print may result. There includes a glycol ether (optionally having at least about 10
fore, there is a need for inkjet inks that permit longer decap carbonatoms) or a dihydric alcohol (optionally having at least
time without sacrificing other beneficial properties, such as about 2 carbonatoms). The slow solvent can be selected from
fast drying time. the group consisting of tripropylene glycol monomethyl
60 ether, tripropylene glycol-n-butyl ether, propylene glycol
SUMMARY phenyl ether, derivatives of the included solvents, and their
mixtures.
The present disclosure includes systems and techniques In another aspect, the disclosure describes an inkjet ink
relating to Solvent-based inkjet ink formulations. The Subject including an organic solvent (such as a slow solvent), a fluo
matter described in this specification can be embodied in an 65 roSurfactant and optionally a resin.
inkjet ink that includes an organic Solvent, a resin, a Surfac Implementations of the disclosure may include one or
tant, and a colorant. more of the following features. In some implementations, the
 US 9,284.463 B2
3 4
ink can be used in a drop on demand inkjet printer (such as, slow organic solvent, or combinations thereof, and the ink has
thermal inkjet printer). The resin may be selected from the a drying time of less than about 2 seconds.
group consisting of rosin modified phenolic resin, phenolic In some implementations, the ink includes a fluoroSurfac
resin, styrene-acrylic resin, polyketone resin, derivatives of tant.
the included resins, and their mixtures. In some implementa 5 “Decap time' as used herein, refers to the period of time an
tions, the Surfactant includes a non-ionic Surfactant or an inkjet nozzle can be left uncapped and idle before the inkjet
ionic Surfactant. In some examples, the Surfactant includes a nozzle starts to fire an ink drop improperly. Improper firing
fluoroSurfactant, a siloxane-based Surfactant, an acetylenic includes no drop is fired, firing with either misdirection, loss
diol-based surfactant, a hydrocarbon-based surfactant, and/or of color, or unacceptable decrease of Velocity.
their mixtures. 10 “Relative evaporation rate' as used herein, refers to the
In some implementations, the fluoroSurfactant is selected evaporation rate value, as determined by the ASTM method
from the group consisting of polyethylene oxide-b-poly(tet D3359, relative to n-butyl acetate.
rafluoroethylene)polymers, 2-(perfluoroalkyl)ethyl stearate, It is to be further appreciated that certain features of the
anionic lithium carboxylate fluorosurfactant, anionic phos disclosure, which are, for clarity, described in the context of
phate fluoroSurfactant, anionic phosphate Surfactant, ampho 15 separate implementations, can also be provided in combina
teric quaternary ammonium-acetate fluorosurfactant, deriva tion in a single implementation. Conversely, various features
tives of the included fluorosurfactants, and their mixtures. which are, for brevity, described in the context of a single
The siloxane-based Surfactant, in some examples, can be implementation, can also be provided separately or in any
selected from the group consisting of polysiloxane-b-ethyl suitable sub-combination.
ene oxide, polysiloxane-b-propylene oxide, polysiloxane-b- The details of one or more implementations of the disclo
propylene oxide/ethylene oxide, derivatives of the included sure are set forth in the description below. Other features,
siloxane-based Surfactants, and their mixtures. objects, and advantages of the invention will be apparent from
In some implementations, the acetylenic diol-based Surfac the description and from the claims.
tant is selected from the group consisting of 2.4.7.9-tetram
ethyl-5-decyne-4,7-diol (TMDD), 2,5,8,11-tetramethyl-6- 25 BRIEF DESCRIPTION OF THE DRAWINGS
dodecyne-5,8-diol, derivatives of the included acetylenic
diol-based surfactants, and their mixtures. FIGS. 1-5 are a series of digital photographs of the first
In some implementations, the hydrocarbon-based Surfac three individual alpha numeric codes, taken at decap times of
tant is selected from the group consisting of polyoxyethylene 1 minute (FIG. 1), 3 minutes (FIG.2), 10 minutes (FIG.3), 15
(10) isooctylcyclohexyl ether, (1,1,3,3-tetramethylbutyl)phe 30 minutes (FIG. 4), and overnight (FIG.5), with the fast solvent
nyl-polyethylene glycol, polyethylene glycol tert-octylphe F-2 in a thermal inkjet cartridge.
nyl ether, polyoxyethylenesorbitan monopalmitate, deriva
tives of the included hydrocarbon-based surfactants, and their DETAILED DESCRIPTION
mixtures. The Surfactant can be present in an amount of less
than about 5% by weight of the ink, from about 0% to about 35 The present disclosure relates to solvent-based ink formu
1% by weight of the ink, or from about 1% to about 5% by lations. Such ink formulations can be advantageously used
weight of the ink. for improving decap time of a printhead in an inkjet printer.
In some implementations, the inkjet inks may have one or The decap times can be assessed by the number of marks a
more of the following attributes. The ink can have a drying printhead needs to make to obtain both a legible mark (Such
time of from about 0.5 second to about 10 seconds, a viscosity 40 as, of an alphanumeric code) and a perfect mark; both being
of from about 1 centipoise to about 25 centipoise, and a determined at arm’s length. The quality of the mark can be
surface tension of from about 20 dynes/cm to about 50 dynes/ determined in comparison to a control image generated
C. immediately after the ink is loaded into the printhead or the
In some implementations, the organic solvent has a relative cartridge. The lesser the number of marks a printhead needs to
evaporation rate of at least about 1.0, from about 0.01 to about 45 make to obtain a legible and perfect mark, the better would be
0.99, or less than about 0.01. The decap time of an ink can be the quality of the ink. In some implementations of this dis
at least about 10 hours. In some examples, the decap time of closure, the number of marks a printhead needs to make to
an ink with surfactant is from about 3 to about 10 fold greater obtain both a legible mark and a perfect mark is less then
than an ink without Surfactant. In some examples, the decap about 10, e.g., less then about 9, less then about 8, less then
time of the ink is at least about 15 minutes. 50 about 7, less then about 6, less then about 5, less then about 4,
Yet another aspect of the disclosure provides an inkjet ink less then about 3, or less then about 2. The longer decap times
including an organic solvent selected from the group consist can be achieved, for example, by use of Surfactants in inks
ing of a glycol ether, a glycol ether acetate, an alcohol, and without sacrificing other beneficial properties such as fast
their mixtures. The inkjet ink includes a resin, a fluoroSurfac drying times. The solvent in an ink can be selected based on
tant, and a colorant. 55 the desired dry time required for a substrate, and the ink
In another aspect, the disclosure describes a method of formulation can be tailored to extend its decap time without
forming a mark on a Substrate (such as a porous Substrate or compromising the desired dry time. The solvent-based ink
a non-porous Substrate). The method includes transferring an formulations of the disclosure can provide a decap time from
ink to the substrate to provide a mark on the substrate. about a few seconds to about at least a few days. In some
In another aspect, the disclosure describes an inkjet printer 60 implementations, the decap time is about 1 minute, e.g., about
including a printhead, a cartridge, and a reservoir including an 2 minutes, about 5 minutes, about 10 minutes, about 20 min
ink. In some implementations, the nozzle diameter of the utes, about 30 minutes, about 40 minutes, about 50 minutes,
printhead or the cartridge is from about 20 microns to about or about 60 minutes. In some implementations, the decap
100 microns. time is about 1 hour, e.g., about 2 hours, about 3 hours, about
In another aspect, the disclosure describes an inkjet ink 65 4 hours, about 5 hours, about 6 hours, about 7 hours, about 8
including a fast organic solvent, a resin and a colorant. The hours, about 9 hours, about 10 hours, about 11 hours, about 12
ink is Substantially free of an intermediate organic solvent, a hours, about 15 hours, about 18 hours, or about 21 hours. In
 US 9,284.463 B2
5 6
Some implementations, the decap time is about 1 day, e.g., and WO 2010/042105 (Barreto), the entire disclosures of
about 2 days, about 3 days, about 4 days, about 5 days, about which is incorporated herein by reference.
6 days, about 7 days, about 8 days, about 9 days, or about 10 The evaporation rate of a solvent can typically be deter
days. mined by the ASTM method D3359, and can be reported as a
In the case of inkjet printers with the inks described in this relative evaporation rate (RER), usually relative to n-butyl
disclosure, minimal intervention and/or maintenance may be acetate. Based on this RER, the solvents can be grouped in a
required over long idle times (i.e., decap times). For highly manner depending on the application envisioned. The Sol
volatile and intermediate volatility solvents, all nozzles can vents are categorized as a fast, intermediate and a slow solvent
recover after 1-2 images (such as an alpha numeric code) are according to their RERs: solvents having a RER greater than
printed after a certain decap time (this can be true for up to 10
1.0 can be grouped as fast solvents; solvents having a RER
about 24 hours idle time); for low volatility solvents, the idle from about 1.0 to about 0.01 can be grouped as intermediate
time may reach as long as 4 days after which all nozzles can solvents; and solvents having a RER less than about 0.01 can
be recovered without any ink purge cycles. The rapid recov be grouped as slow solvents. The RERs can typically be
ery of nozzles leads to good quality images (such as, a legible
image at arms length or a perfect image). The length of time 15 correlated with the volatility of a solvent. A fast solvent
until which the ink can consistently continue to produce a typically evaporates faster and can lead to rapidly increasing
legible and a perfect image in four or less attempts can be Viscosity of an ink. Although a solvent may be mentioned as
considered to be the decap time of that ink. a single chemical entity, derivatives of Such solvents can
Ink formulations can include solvent, resin, colorant, and include its structural isomers and other oligomers. The
Surfactant. Inks described herein typically have chemical and organic solvents described herein may either be used in an
physical properties that allow the inks to be jetted onto a anhydrous or wet form.
Substrate by an inkjet printer (e.g., by one or more nozzles of Examples of fast solvents can include methanol, ethanol,
a printhead of an inkjet printer). propanol, iso-propanol, acetone, methyl ethyl ketone, methyl
Drying time is an important attribute for solvent-based ink isobutyl ketone, pentane, hexane, heptane, methyl acetate,
formulations, especially inks using fast solvents. Though 25 ethyl acetate, propyl acetate, tert-butyl acetate, tert-butanol,
their decap time in the printhead is extended, the time tetrahydrofuran, and their mixtures.
required for ink printed onto a non-porous Substrate to In some implementations, the weight 96 of fast solvent in
become dry to touch, remains reasonable. Dry time is mea inks can be about 5%, e.g., about 10%, about 15%, about
Sured by printing an image onto a non-porous Substrate, e.g., 20%, about 25%, about 30%, about 35%, about 40%, about
oriented polypropylene, and allowing the printed image to be 30 45%, about 50%, about 55%, about 60%, about 65%, about
contacted by a stationary metal post at a prescribed time 70%, about 75%, about 80%, about 85%, about 90%, or about
following printing. Any smearing of the image indicates a 95%. In other implementations, the weight% of fast solvent
failure due to non-dry ink. In some implementations of this in inks can be greater than about 75%, e.g., greater than about
disclosure, the drying time is from about 0.5 second to about 80%, greater than about 85%, greater than about 90%, or
10 seconds, e.g., from about 1 second to about 9 seconds, 35 greater than about 95%.
from about 2 seconds to about 8 seconds, from about 3 sec Examples of intermediate solvents can include Cas alco
onds to about 7 seconds, or from about 4 seconds to about 6 hols (e.g., butanol, pentanol, hexanol, heptanol, octanol, and
seconds. In some other implementations, the drying time is the like), propylene glycol ethers (e.g., propylene glycol
about 0.5 second, e.g., about 1 second, about 2 seconds, about mono methyl ether, propylene glycol mono ethyl ether, pro
3 seconds, about 4 seconds, about 5 seconds, about 6 seconds, 40 pylene glycol n-propyl ether, propylene glycol n-butyl ether,
about 7 seconds, about 8 seconds, about 9 seconds, or about and the like), dihydric alcohols (e.g., ethylene glycol, propy
10 seconds. lene glycol, butylene glycol, and the like), 1-methoxy-2-ac
In some implementations, the Viscosity of the inks is about etoxy propane, cyclohexanone, and their mixtures.
5 centipoise, e.g., about 10 centipoise, about 11 centipoise, In some implementations, the weight '% of intermediate
about 12 centipoise, about 13 centipoise, about 14 centipoise, 45 solvent in inks can be about 5%, e.g., about 10%, about 15%,
about 15 centipoise, about 20 centipoise, or about 25 centi about 20%, about 25%, about 30%, about 35%, about 40%,
poise. In some implementations, the Viscosity of the inks is about 45%, about 50%, about 55%, about 60%, about 65%,
about 1 centipoise, e.g., about 2 centipoise, about 3 centi about 70%, about 75%, about 80%, about 85%, about 90%, or
poise, or about 4 centipoise. In some implementations, the about 95%. In other implementations, the weight% of inter
Viscosity of the inks is about 10 centipoise, e.g., about 11 50 mediate solvent in inks can be from about 60% to about 90%,
centipoise, about 12 centipoise, about 13 centipoise, or about e.g., from about 60% to about 80%, from about 70% to about
14 centipoise. 90%, or from about 70% to about 80%.
In some implementations, the ink has a surface tension of Examples of slow solvents can include, but are not limited
from about 20 dynes/cm to about 50 dynes/cm, e.g., from to, glycol ethers having at least about 10 carbon atoms (e.g.,
about 20 dynes/cm to about 30 dynes/cm, from about 30 55 at least about 11 carbonatoms, at least about 12 carbonatoms,
dynes/cm to about 40 dynes/cm, or from about 40 dynes/cm at least about 13 carbonatoms, at least about 14 carbonatoms,
to about 50 dynes/cm. or at least about 15 carbonatoms), dipropylene glycol methyl
Solvent ether, dipropylene glycol methyl ether acetate, dipropylene
Generally, the solvent can be any material that can dissolve glycol n-butyl ether, tripropylene glycol monomethyl ether,
the resin and other materials in the inkjet inks. Depending on 60 tripropylene glycol-n-butyl ether, propylene glycol phenyl
the choice of a Substrate for which an inkjet ink is targeted, a ether, and their mixtures. The RERs of certain glycol ethers
Solvent (such as an organic solvent) can be selected based on have been reviewed by Smith, R. L., in Environmental Health
the evaporation rate of a solvent. Certain non-aqueous inks Perspectives, Vol. 57, pp. 1-4 (1984), the entire disclosure of
have been disclosed in U.S. Patent Application Publications which is incorporated herein by reference. Examples of com
US 2005/0039634 (Hermansky), US 2009/0246377 (Robert 65 mercial solvents include “Dowanol TPM tripropylene glycol
son et al.), and US 2010/0098860 (Robertson et al.) and in methyl ether,” and “Dowanol PM propylene glycol methyl
published PCT applications WO 2010/042104 (Barreto et al.) ether available from Dow Chemical (Midland. Mich.).
 US 9,284.463 B2
7 8
In some implementations, the weight% of slow solvent in BASF), and Foral 85 hydrogenated rosinester resin, available
inks can be about 5%, e.g., about 10%, about 15%, about from Hercules Chemical Company, Inc.; 111 South Street,
20%, about 25%, about 30%, about 35%, about 40%, about Passaic, N.J. 07055.
45%, about 50%, about 55%, about 60%, about 65%, about Surfactant
70%, about 75%, about 80%, about 85%, about 90%, or about The Surfactant (Surface active agent) compound can serve
95%. In other implementations, the weight% of slow solvent to alter the Surface tension of the ink composition, and can be
in inks can be from about 5% to about 60%, e.g., from about anionic (Such as Sulfate esters, carboxylates, Sulfonates, or
5% to about 50%, from about 5% to about 40%, from about phosphonates), cationic, nonionic (such as polyol based,
5% to about 30%, from about 5% to about 20%, from about polyglycerols based, fluorocarbon based, siloxane-based,
20% to about 30%, from about 20% to about 40%, or from 10 alkyl phenol based, or polyoxyethylene based) or amphoteric
about 20% to about 50%. (such as phosphatides, imidazoline derivatives, or betaines)
In some implementations, the ink including a fast solventis Surfactant compound. Such as those described in "Surfactants
substantially free of the intermediate, or slow solvents. Sub and Interfacial Phenomena. Second Edition, M. J. Rosen,
stantially free refers to the weight % of a component being 1989, John Wiley and Sons, Inc., New York, pages 1-32, the
less than about 10%, e.g., less than about 9%, less than about 15 entire disclosures of which is incorporated herein by refer
8%, less than about 7%, less than about 6%, less than about CCC.
5%, less than about 4%, less than about 3%, less than about While not intending to be bound by any particular theory, it
2%, or less than about 1%. is believed that, consistent with the principles involving
The solvent can be non-toxic, environmentally friendly, Langmuir-Blodgett (LB) films and water, but herein applied
e.g., is EPA-approved and does not produce hazardous pol to liquid inks, Surfactant molecules in the inkjet ink formula
lutants, stable with respect to the materials in the ink, and/or tions can organize rapidly at the ink/air interface within the
cost effective for relatively large scale manufacturing. Other jetting nozzle. Typically, the ink surface within the opening of
Solvents can be used. the jetting nozzle, being a confined surface under tension, can
Resins cause the Surfactant molecules to organize in a dense manner.
The resin typically provides the ink with a desired viscos 25 Details of the teachings of Langmuir and Blodgett may be
ity, thermal stability, flexibility, and adhesion properties. The found at http://www.ksvinc.com/LB.htm (“Langmuir and
inks can include resins such as a rosin modified phenolic Langmuir-Blodgett Films: WHAT and HOW'?” KSV Instru
resin, a phenolic resin, a styrene-acrylic resin, a polyketone ments Oy (Helsinki, Finland)) or in the article entitled “Lang
resin, derivatives of the included resins, or their mixtures. The muir Blodgett Films.” I. R. Peterson, Journal of Physics, D
inks can include other types of resins such as polyvinyl 30 23, 4, (1990) 379-95, the entire disclosure of which is incor
butyral (PVB), acrylic, polyurethane, polyamide, polyvi porated herein by reference.
nylpyrrolidone (PVP), or vinyl resins. The inclusion of a surfactant within an ink formulation can
Examples of resins include, but are not limited to, acacia lead to a barrier in the form of a layer of surfactant at the
(gum arabic), gum ghatti, guargum; locust (carob) bean gum, interface of air and bulk ink, thereby reducing, and preferably
karaya gum (sterculia gum); gum tragacanth; chicle; highly 35 substantially eliminating, the ability of the solvent to evapo
stabilized rosin ester; tall oil; manila copais; corn gluten; rate from the bulk ink. By reducing the solvent evaporation
coumarone-indene resins; crown gum; damargum; p, alpha rate, and preferably entirely preventing solvent evaporation
dimethylstyrene; gum elemi; a rosinglycerol ester, an ethyl of the ink formulations, the decap time can be increased. At
ene vinyl acetate (EVA); a polyamide resin: ethylene oxide the same time, once an inkjet ink is jetted onto a substrate, fast
polymer and its adducts; ethylene oxide?propylene oxide 40 evaporation (i.e., fast drying time) can occur because the
copolymer and its adducts; galbanum resin; gellan gum, Surfactant molecules can spread out over a larger Surface area
ghatti gum, gluten gum; gualac gum, guarana gum; heptyl instead of being confined to a surface that is under tension.
paraben; cellulose resins, including methyl and hydroxypro Fluorosurfactants are surfactants that can either be ionic
pyl; hydroxypropyl methylcellulose resins; isobutylene-iso (with the fluorine-containing moiety being part of either the
prene copolymer; mastic gum, oatgum, opopanax gum, poly 45 cationic or the anionic part) or nonionic (Such as fluorocarbon
acrylamide; modified polyacrylamide resin; polylimonene; chain-containing alcohols). The fluoroSurfactants can be
polyisobutylene (min. MW 37,000); polymaleic acid; poly ethoxylated surfactants (i.e., polyethyleneoxide modified) or
oxyethylene derivatives; polypropylene glycol (MW 1200 polytetrafluoroalkylene surfactants. Ethoxylated surfactants
3000); polyvinyl acetate; polyvinyl alcohol; polyvinyl poly include one or more of ethylene oxide monomeric units.
pyrrolidone; polyvinyl pyrrolidone; rosin, adduct with 50 Polytetrafluoroalkylene surfactants include one or more of
fumaric acid, pentaerythritol ester, rosin, gum, glycerol ester, tetrafluoroalkylene units. Examples of fluorosurfactants
rosin, gum or wood, pentaerythritol ester, rosin, gum or include polyethylene oxide-b-poly(tetrafluoroethylene)poly
wood, partially hydrogenated, glycerol ester, rosin, gum or mers, 2-(perfluoroalkyl)ethyl Stearate, anionic lithium car
wood, partially hydrogenated, pentaerythritol ester, rosin, boxylate fluoroSurfactant, anionic phosphate fluoroSurfac
methyl ester, partially hydrogenated; rosin, partially dimer 55 tant, anionic phosphate Surfactant, amphoteric quaternary
ized, glycerol ester, rosin, partially hydrogenated; rosin and ammonium-acetate fluoroSurfactant, fluoroaliphatic poly
rosin derivatives; rosin, polymerized, glycerol ester, rosin, meric esters, their derivatives, and their mixtures. Examples
tall oil, glycerol ester, rosin, wood; rosin, wood, glycerol of commercial fluorosurfactants include Zonyl family of
ester, purified shellac, Styrene; styrene terpolymers; styrene fluorosurfactants (e.g., Zonyl FSO 100, Zonyl FSN, Zonyl
copolymers: Sucrose acetate isobutyrate; terpene resins, natu 60 FTS) and Capstone family of fluorosurfactants (available
ral and synthetic; turpentine gum, vinylacetate; Vinyl chlo from DuPont Chemicals, Wilmington, Del.), or Fluorad FC
ride-vinylidene chloride copolymer, Zanthan gum; and Zein. 170-C, FC 171, FC430 and FC431 available from 3M of St.
Examples of commercial resins include Joncryl family of Paul, Minn. Hermansky (see above) discloses the complete
resins (available from BASF), Reactol K3107 (a phenolic drying of the inks in the presence of Zonyl FSX surfactant.
resin from Hexion), Resin SK (a polyketone resin from 65 Siloxane-based surfactants are Surfactants which can be
Evonik), Alnovol PN320 (a novolak phenolic resin from copolymers of silyl ethers and epoxy (ethylene oxide, propy
Cytec), Laropal A81 (an aliphatic aldehyde resin from lene oxide) oligomers or polymers. Examples of siloxane
 US 9,284.463 B2
10
based surfactants include polysiloxane-b-ethylene oxide, provide an ink with, for example, a desired color and/or
polysiloxane-b-propylene oxide, polysiloxane-b-propylene opacity. Exemplary colors can include black, cyan, magenta,
oxide/ethylene oxide, their derivatives, and their mixtures. yellow, red, blue, green, brown, or their combinations.
Examples of commercial siloxane-based Surfactants include Examples of suitable pigments include Color Index Pig
copolymers such as SILWETR) copolymers including Silwet ment Black 7: Pigment Blue 15: Pigment Red 112, 146, 170
L-7604, available from GE Silicones; Troysol Q-148 and and 208; PigmentYellow 17 and 83; Pigment Green 7: carbon
5366 available from Troy Chemical. black, graphite; and pigment white titanium dioxide. Addi
Acetylenic diol-based surfactants are Surfactants which tional examples are disclosed in, e.g., U.S. Pat. No. 5,389,
can be acetylenic diols comprising hydrophobic groups at the 133, the entire disclosures of which is incorporated herein by
end of the acetylenic spacer and hydrophilic and/or hydro 10 reference. The pigment may also have a modifying group on
phobic ethers hanging off of the hydroxyl groups. Examples its surface, such as an oxygen-containing functionality (e.g.,
of acetylenic diol-based surfactants include, 2.4.7.9-tetram a carboxyl or phenol group). An example of a commercially
ethyl-5-decyne-4,7-diol (TMDD), 2,5,8,11-tetramethyl-6- available pigmented colorant can be “Special Black 4A
dodecyne-5,8-diol, their derivatives, and their mixtures. available from Evonik Degussa (Germany).
Examples of commercial acetylenic diol-based Surfactants 15 Examples of dyes include Orasol Pink 5BLG, Black RLI,
include Dynol series (Dynol 604) and Surfynol series (Sur Blue 2GLN, Red G, Yellow 2GLN, Blue GN, Blue BLN,
fynol 104, 420, 465, 485, TG-E, SE, etc.) available from Air Black CN, and Brown CR (all available from Ciba-Geigy,
Products. Inc., Mississauga, Ontario); Morfast Blue 100, Red 101, Red
Hydrocarbon-based surfactants are surfactants which can 104, Yellow 102, Black 101, and Black 108 (all available from
be polyoxyethylenated alkyl phenols (APE type), polyoxy Morton Chemical Company, Ajax, Ontario); and a mixture
ethylenated short chain alcohols (AE type), or long chain thereof.
organic acid esters. Examples of hydrocarbon-based Surfac Other Modifying Agents in the Formulations
tants include polyoxyethylene (10) isooctylcyclohexyl ether, The inkjet inks can contain Smaller amounts of other ingre
(1,1,3,3-tetramethylbutyl)phenyl-polyethylene glycol, poly dients without hindering the desired properties of the inks
ethylene glycol tert-octylphenyl ether, polyoxyethylenesor 25 Such ingredients can include dispersants, anti-foaming
bitan monopalmitate, their derivatives, and their mixtures. agents, wetting agents, viscosity modifiers, and light stabiliz
Examples of commercial hydrocarbon-based Surfactants CS.
include Triton X Series and Tergitol Series both from Dow Ink Preparation
Chemical; the TWEEN Series from ICI Americas; and the A pigment concentrate can be prepared by combining a
Igepal Series from Hallstar. 30 pigment with an amount of at least some (e.g., all) compo
The Surfactants can be present in varying amounts in the nents of an ink to be prepared to provide a concentrate having
inkjet ink, depending on the other ingredients. The surfac a higher concentration of pigment than the final ink. The
tants, as a weight% of the ink, can be present from about 0% pigment concentrate can improve pigment grinding and
to about 5%, e.g., from about 0% to about 1%, from about 1% reduce process time.
to about 2%, from about 2% to about 3%, from about 3% to 35 While not intending to be bound by any particular theory, it
about 4%, or from about 4% to about 5%. In some implemen is believed that in the pigment concentrate, the number den
tations, the Surfactants, as a weight '% of the ink, can be sity of pigment particles is increased, which allows for more
present from about 1.1% to about 5%, e.g., from about 1.1% particle-particle and particle-grinding media collisions,
to about 2%, from about 1.1% to about 3%, or from about which in turn decreases the period of time needed to reach a
1.1% to about 4%. In some implementations, the Surfactants, 40 desired particle size. Additionally, in the concentrate, the
as a weight% of the ink, can be present less than about 5%, particles have higher odds of coming in contact with dispers
e.g., less than about 4%, less than about 3%, less than about ant/surfactant molecules, if present. These materials can
2%, less than about 1%, or less than about 0.5%. The decap adsorb onto the surface of the particles so that the particles
time of an ink with a surfactant can increase from about 3 to with reduced size do not agglomerate. By increasing the odds
about 10 fold compared to an ink without a surfactant. In 45 of particle-dispersant collisions, the grind time can be
Some implementations, the decap time of an ink with a Sur reduced and the particle size stability can be increased.
factant can increase about 3 fold, e.g., about 4 fold, about 5 For example, to prepare a carbon black pigment concen
fold, about 6 fold, about 7 fold, about 8 fold, about 9 fold, or trate, the amount of dispersant to be used can be calculated
even about 10 fold compared to an ink without a surfactant. based on the desired pigment particle size, the calculated
The addition of Surfactants can provide an extended decap 50 pigment Surface area (Supplied by the pigment manufacturer),
time without compromising the drying time on a Substrate. or both. A fluid vehicle and dispersant can be charged into an
Surfactants can alter the viscosity of the ink formulations to appropriate vessel. The vehicle and dispersant can be mixed
some extent and can further prevent the viscosity of the inks until fully blended (some gentle heating may be necessary if
in the reservoir to alter minimally. For example, the viscosity the dispersant is a Solid). The vehicle/dispersant mixture can
of the inks can be from about 1 centipoise to about 25 centi 55 be moved to a high shear mixer and the pigment can be slowly
poise, e.g., from about 5 centipoise to about 20 centipoise, or charged. The materials can be milled to obtain a pigment
from about 10 centipoise to about 15 centipoise. The surfac COncentrate.
tants can alter the Surface tension of the inks at the air-ink For a liquid ink, all liquid ingredients can be mixed and, if
interface during idle time and can aid in decreasing the Sol necessary, the ink can be filtered through a desired filter.
vent evaporation rate. 60 Printers
Colorant A drop-on-demand inkjet printer can be defined as a piezo
The ink may include a colorant, which provides color to the driven system or a thermally driven system. In the case of the
ink. The ink can contain a Sufficient amount of a colorant that piezo system, a printer consists of electronics and Software
the ink has color, but not so much as to interfere with other necessary to control an ink reservoir and a piezo driven inkjet
desirable qualities, such as Surface tension or viscosity. 65 assembly (an array of inkjet nozzles arranged in a regular
An ink can include one or more colorants (e.g., one or more pattern), where a reservoir is either directly or indirectly
pigments, one or more dyes, or their mixtures). Colorants can attached to a printing assembly. Direct attachment results in
 US 9,284.463 B2
11 12
an integral printhead whereas indirect attachment results in a from liquid to gas, thus causing a rapid Volume expansion and
jetting assembly located some distance away from the reser Subsequently causing a droplet to eject from an orifice. In the
voir with the two components connected by an ink umbilical case of a piezo-based device a liquid ink is ejected from a
that delivers ink to the inkjet jetting assembly. In the case of printhead by activation of a piezo transformer (PZT), which
thermal inkjet system, a printer consists of electronics and 5 causes a pressure wave to be exerted upon the ink and an ink
Software necessary to drive a fully integrated reservoir and droplet can be ejected from an orifice. Both devices are
jetting assembly in a stand-alone holder organged together to referred to as drop-on-demand since a droplet of ink is ejected
increase image Swath or resolution. However, there are only when a heater or PZT material is activated. Each car
instances where a “bulk” ink reservoir can be used to feedink tridge or printhead contains an array of several orifices across
to a thermal inkjet assembly through an umbilical. The elec 10 its width. Activation of each orifice in Such an array is per
tronics and Software controls in both cases dictate when a formed methodically by the printer Such that an image is
drop is to be ejected from the inkjet assembly based on the formed drop-wise on a substrate, which is positioned a short
desired image to be printed. distance from the orifice array. The printers are designed Such
Drop on demand printers are described in more detail, e.g., that an orifice array and a substrate move relative to one
in U.S. Pat. No. 5,265,315; Thermal inkjet printheads are 15 another in order to form an image. In continuous ink jet
described, e.g., in U.S. Pat. Nos. 4,727,384 and 4,500,895: printing, a continuous stream of conductive ink droplets is
and, piezoelectric inkjet printheads are described in, e.g., U.S. ejected from a nozzle. The droplets are electrostatically
Pat. Nos. 4,825,227, 4,937,598, 5,659,346, 5,757,391, and deflected to address several vertical pixels as the substrate
7,052,117. The entire disclosures of these patents are incor moves relative to the nozzle. Inkdroplets that are not intended
porated herein by reference. or needed to form a desired image on the substrate are fully
Manufacturers of piezo inkjet assemblies include Dimatix, deflected into a gutter and recycled to the ink supply. CIJ inks
Xaar, and Xerox. Manufacturers of thermally driven inkjet contain an additive (such as, a conductive aid) that imparts
assemblies integrated to a reservoir (commonly referred to as conductivity and allows the droplets to be deflected. The
a thermal inkjet cartridge) include Hewlett Packard, Lex process of jetting ink droplets continuously and directing
mark, and Olivetti. 25 unneeded drops to the gutter allows the CIJ systems to utilize
The inks described can be utilized in either a piezo driven fast evaporating solvents without concern for decap and
or a thermally driven inkjet assembly by adjusting the Viscos nozzle clogging, as the nozzle is effectively never idle during
ity of an ink. In general, piezo driven inkjet assemblies can operation.
utilize inks with a viscosity between 7 cl’s and 25 cF’s depend In the case of inks that utilize fast evaporating solvents,
ing on the nozzle geometry, whereas thermally driven inkjet 30 upon contacting a substrate, which is typically non-porous
assemblies can utilize inks with a viscosity between 1 cl’s and and at room temperature, a solvent in the liquidink evaporates
5 cfs depending on the nozzle geometry. and a film forms on the substrate. In the case of inks that
Inkjet assemblies, both piezo and thermally driven sys utilize intermediate evaporating solvents, upon contacting a
tems, can be manufactured (such as by laser drilling, chemical Substrate, which is typically semi-porous and at room tem
etching) with different nozzle diameters depending on the 35 perature, a liquid ink dries by a combination of evaporation
desired drop Volume. In general, Smaller diameter nozzles can and absorption. In the case of inks that utilize slow evaporat
result in ejection of lower drop Volumes and larger diameter ing solvents, upon contacting a Substrate, which is typically
noZZles can result in ejection of higher drop Volumes. In the porous and at room temperature, a liquid ink flows rapidly
case of thermal inkjet assemblies, multiple nozzle diameters into the void spaces in the substrate and dries primarily by
can be integrated into a single jetting assembly such that 40 absorption. In all three cases of solvents, it is possible in some
multiple drop Volumes can be ejected from a single cartridge. settings to assist drying of the inks by adding an in-line drying
In some implementations, nozzle diameter can be from about capability. In some implementations of printing using the
20 microns to about 100 microns, e.g., from about 30 microns described inks, the drying of the inks on the substrate is
to about 100 microns, from about 40 microns to about 100 unassisted (such as without the use of external drying mecha
microns, from about 50 microns to about 100 microns, from 45 nisms e.g., fans).
about 60 microns to about 100 microns, from about 70 Substrates
microns to about 100 microns, from about 80 microns to The inks can be applied to either porous or non-porous
about 100 microns, or from about 90 microns to about 100 Substrates Such as flexible packaging films (for example,
microns. polypropylene, polyethylene, polyethylene terephthalate,
Printing Process 50 polystyrene, or poly(lactic acid) films), rigid plastic materials
Inks can be jetted by either thermal inkjet cartridges or (for example polypropylene, polyethylene, polyethylene
piezo drop on demand printheads. Examples of thermal inkjet terephthalate, polystyrene, poly(lactic acid), polyvinylchlo
cartridges are those commercially available from Hewlett ride materials), corrugated cardboard (for example, bleached,
Packard (such as HP45); Lexmark (such as Model 34); and unbleached, and coated cardboard), boxboard (for example,
Olivetti (such as IN501). Examples of piezo drop on demand 55 glossy coated, matte coated, and uncoated boxboards), bottle
printheads can include commercially available models from materials (for example, glass, polyethylene terephthalate,
Dimatix (such as Q or S Class) and Xaar (such as a XJ500). polyethylene, polypropylene, and poly(lactic acid) materi
Examples of thermal inkjet printers that would allow solvent als).
based inks to be jetted are: DeskJet model 710 from Hewlett Additionally, as indicated in each of Examples 1 through
Packard, the model Z845 from Lexmark, and the model 60 12, the solvent-based ink formulations can be tailored for a
Simple Way from Olivetti. Examples of piezo-based printers certain operating temperature, for a certain viscosity, and for
that would allow solvent-based inks to be jetted are: Markem a certain nozzle diameter, which defines the surface under
Imaje models 5200 and 4040. To print inks, an ink is loaded tension.
into a reservoir where it is either pumped or fed by gravity to Unless otherwise defined, all technical and scientific terms
a jetting chamber of a cartridge or printhead. In the case of the 65 used herein have the same meaning as commonly understood
thermal inkjet cartridge, a liquid ink is ejected from a print by one of ordinary skill in the art of solvent-based inkjet inks.
head by being rapidly heated, causing a rapid phase change Although methods and materials similar or equivalent to
 US 9,284.463 B2
13 14
those described herein can be used in the practice or testing, ULA Adapter at 72°F. using spindle 00 operating at 60 rpm
suitable methods and materials are described below. In case of spindle speed. The dry time was performed as described. Ink
conflict, the present specification, including definitions, will was loaded into a previously unfilled thermal inkjet cartridge,
control. In addition, the materials, methods, and examples are the printhead was purged and confirmed that all nozzles were
illustrative only and not intended to be limiting. 5 operable. An image was printed on a non-porous Substrate
and good image quality was immediately confirmed. The web
EXAMPLES speed was set at prescribed rate and the fixed post moved into
position. An image was printed on a Substrate and images
Example 1 allowed to pass by the fixed post. The images were inspected
10 for signs of smear that would indicate wet ink. The test was
Procedure for Making Inks and Pigmented performed at 150 dpi in process direction and 600 dpi in the
Concentrate cross process direction and dry time was recorded.
Procedure for Making Inks TABLE 1
Step 1: 15
A resin and solvent are measured into a glass beaker and Inks with fast solvents
the solution is stirred (with either a magnetic stirrer or a Ingredient F-1 F-2 F-3 F-4 F-5 F-6 F-7 F-8
propeller blade at about 200-400 rpm) at room temperature
until homogeneous. This will typically require between 10 Ethanol 93.4 91.4 91.4 91.3 90.0 91.4 92.4 90.4
and 200 minutes. The Surfactant is measured into a separate (anhydrous)
vessel and slowly added to the homogenous, stirring resin and Reacto K3107
Anovo PN430
2.9 2.9 2.9
3.0
2.9 2.9 2.9
Solvent Solution. The mixing was continued until homoge Joncryl 682 4.5
neous, but not for less than about 10 minutes. The colorant is Orasol Black 3.7 3.7 3.7 3.7 3.5 3.7 3.7 3.7
measured into a separate vessel. If colorant is a dye, no prior RLI
processing is necessary. If colorant is a pigmented dispersion, Zonyl FSO100 O.O 2.0 2.0 2.0
see Step 1A for the preparation of pigmented concentrate. 25 Zonyl FSN 2.0
The colorant is added slowly to the homogenous, stirring Silwet L7604 1.O
Triton X-100 3.0
Solution and continued to mix until colorant has been fully Dynol 604 2.O
incorporated into solution, but not for less than about 20 Viscosity 1.52 1.SS 1.94 1.70 16S 1.71 172 1.79
minutes. The Viscosity of ink was measured using Brookfield (cPs at 72° F.
DV series viscometer. The ink was loaded into a syringe and 30 Dry time O.S 1.5 1.25 -2 1.O O.S O.S 1.5
filtered through a 1.0 micron syringe filter (e.g., Whatman (a) 150 dpi (s)
Puradisc(R) 25GD; with GMF-150 media; p/n 6783-2510)
placed on the exit of the syringe. The filtered ink can now be
loaded into printer reservoir.
Step 1A: 35 Example 3
Procedure for Making Pigmented Concentrate:
The solvent was measured into a stainless steel vessel and
stirred using a high speed Cowles.(R) type blade at about 1000 Decap Testing for Fast-Solvents
rpm. The dispersant was measured into a separate vessel and
slowly added to the mixing solvent until homogeneous, but 40 Ink was loaded into a previously unfilled thermal inkjet
not for less than about 15 minutes. The pigment was measured cartridge, the printhead was purged and a control image con
into a separate vessel and slowly added to the mixing solvent sisting of 24 individual alpha numeric codes (in FIGS. 1-5,
until all of the pigment has been wetted by the solution. The “ENJOY BY 20 JUN 08” represents an alpha numeric code)
mixer speed was increased to about 2000-5000 rpm and was immediately generated. The printer was allowed to sit
mixed for about 30 minutes until the solution was homoge 45 idle for one minute and then an image consisting of 24 indi
neous and all of the pigment was wetted. The mixer was vidual alpha numeric codes was generated. The number of
stopped and the stainless steel vessel moved to Basket-style codes that had to be generated to obtain both a legible code at
media mill, Hockmeyer Micro; /16 gallon model. The media arms length (L*) and a perfect code (P) was recorded. The
mill was charged with appropriate media such as YTZ 0.4-0.6
mm ceramic material and processed at about 3000-4000 rpm printer was allowed to sit idle for 3 minutes and then an image
for not less than 2 hours or until Solution passes easily through 50 consisting of 24 individual alpha numeric codes was gener
a 1 micron filter (e.g., Whatman Puradisc(R) 25GD; with ated. This line of testing was continued for 5, 10, 15, 60
GMF-150 media; pin 6783-2510). This pigmented concen minutes and overnight. The results are presented in Table 2.
trate was used in Step 1 above. Two pigmented concentrates For the ink F-1, after 1 min. of decap time, the eighteenth code
were prepared. Pigmented Concentrate-1 containing 61.2% was legible whereas none of the codes were perfect. For the
glycol ether TPM, 10.2% Solsperse 32000, and 28.6% Spe 55 ink F-4, after 1 min. of decap time, the second code was both
cial Black 4A Pigment. Pigmented Concentrate-2 containing legible and perfect.
72.4% glycol ether TPM, 7.3% Solsperse 32000, and 20.3% FIGS. 1-5 are each the first three individual alpha numeric
Special Black 4A Pigment. codes generated with the ink F-2 after 1 min. (FIG. 1), 3 min.
Example 2 (FIG. 2), 10 min. (FIG. 3), 15 min. (FIG. 4), and overnight
60 (FIG. 5) decap times. The alpha numeric code on the right in
Inks with Fast Solvents each Figure is the first image generated. In FIG. 1, the first
legible image was the second image while the first perfect
The inks of the formulation F-1 to F-8 (Table 1) were image was the third image. In Table 2, the ink F-2 continues
prepared according to the method described in Example 1. to produce a legible and a perfect image for a decap time of at
Each column indicates the weight% of the ingredient in the 65 least about overnight (16 hours) while the ink F-6 was deter
final formulation. The viscosity of the inks in Table 1 were mined to produce a legible and a perfect image for a decap
measured using Brookfield DV Series Viscometer with a time of about 1 min.
 US 9,284.463 B2
15 16
TABLE 2
Decap Test Results
Time F-1 F-8

1 18 -24 2 3 1 3 2 2 S 8 1 1 >24 >24 12 14

3 >24 >24 3 4 2 3 2 2 na na 2 20 18 >24 9 11
5 >24 >24 1 4 1 3 1 2 na na 11 14 19 >24 11 12
10 >24 >24 1 2 2 2 1 2 S 8 10 15 20 24 14 20
15 >24 >24 1 1 2 2 1 2 2 3 12 10 17 19 11 14
60 >24 >24 1 1 1 1 2 2 1 1 7 10 18 20 9 10
overnight >24 >24 1 1 2 2 1 1 1 1 >24 >24 >24 >24 20 22

15 .
Example 4 immediately generated. The printer was allowed to sit idle for
30 seconds and then an image consisting of a matrix of indi
Inks with Fast Solvents vidual dots representing single nozzle firings was generated.
The printer was allowed to sit idle for 1 minute and then a
The inks of the formulation F-9 to F-14 (Table 3) can be 20 series of images were generated. This line of testing was
prepared according to the method described in Example 1. continued for 3, 5, 10, 15, and 30 minutes. The results are
Each column indicates the weight% of the ingredient in the presented in Table 5.
final formulation.

TABLE 3 TABLE 5
25
Inks with fast solvents Decap Test Results
Ingredient F-9 F-10 F-11 F-12 F-13 F-14 Idle time No. of drops fired before full recovery of iet
Ethanol 88-96 88-96 88-96 88-96 88-96 88-96 (min) I-1 I-2
Reacto K3107 2-4 2-4
30 O.S 104 30
Anovo PN430 2-4 2-4
1 140 34
Joncryl 682 2-4 2-4
Orasol Black RLI 3-5 3-5 3-5 3-5 3-5 3-5 3 176 34
5 175 17
Zonyl FSO100 O-3 O-3 O-3 10 189
Zonyl FSN 100 O-3 O-3 O-3 15 9
35 30 248 4

Example 5
Example 7
Inks with Intermediate Solvents
40
Inks with Intermediate Solvents
The inks of the formulation I-1, I-2, and I-6 (Table 4) were
prepared according to the method described in Example 1.
Each column indicates the weight% of the ingredient in the The inks of the formulations I-3 to I-5 (Table 6) can be
final formulation. The viscosity of the inks in Table 4 were prepared according to the method described in Example 1.
measured using Brookfield DV Series Viscometer with a 4s. final Each column indicates the weight% of the ingredient in the
formulation.
ULA Adapter at 72 F. using spindle 00 operating at 30 rpm
spindle speed.
TABLE 6
TABLE 4 50 Inks with intermediate solvents
Inks with intermediate solvents Ingredient I-3 I-4 I-5
Ingredient I-1 I-2 I-6 PM Solvent 72-80 72-80 72-80
Reactol K-3107 17-21
PM Solvent 77.7 76.2 76.2 Anovo PN430 17-21
Reactol K-3107 19.7 19.3 19.3 55 Joncryl 682 17-21
Orasol BlackRLI 2.6 2.5 2.5 Orasol Black RLI 2-3 2-3 2-3
Zonyl FSO 100 O 2 O Zonyl FSO 100 O-3 O-3 O-3
Zonyl FSN 100 O O 2
Viscocity, cPs at 10.4 10.7 10.6
40° C.
60 Example 8
Example 6 Inks with Slow Solvents

Decap Testing for Intermediate Solvents The inks of the formulation S-1 to S-4 (Table 7) were
65 prepared according to the method described in Example 1.
Ink was loaded into a Dimatix Skywalker 128/50 print Each column indicates the weight% of the ingredient in the
head. The printhead was purged and a control image was final formulation. The viscosity of the inks in Table 7 were
 US 9,284.463 B2
17 18
measured using Brookfield DV Series Viscometer with a jetting test was performed to assess the nozzle function; if
Small sample adapter at 40°C. using spindle 18 operating at fewer nozzles were functional than in the initial jettest, an ink
60 rpm spindle speed. purge was performed. The nozzle performance was reas
sessed after each Successive jet test until all of the original
TABLE 7 nozzles were functioning. The number of purges required to
Inks with slow solvents recover all nozzles was recorded (Table 9).
Ingredient S-1 S-2 S-3 S-4 TABLE 9
Dowanol TPM tripropylene glycol methyl 39 34.5 40.5 24 10
ether Decap Test Results
Pigmented Concentrate-2, (20.3% by weight 41 37 45 41
in TPM)
Foral 85 solution (35% by weight in TPM) 2O 27 13 2O number of purges
Zonyl FSO100 O 1.5 1.5 —
Surfynol 104 (20% solution in TPM) — 15 15
Viscosity, cPs at 40°C. 11.7 11.6 12.3 11.8 No. of days S-1 S-2

1 1 O
Example 9 4 4 O

Inks with Slow Solvents

The inks of the formulation S-5 to S-12 (Table 8) were Example 11

prepared according to the method described in Example 1.
Each column indicates the weight% of the ingredient in the 25
final formulation. The viscosity of the inks in Table 8 were Inks with Slow Solvents
measured using Brookfield DV Series Viscometer with a
Small sample adapter at 40°C. using spindle 18 operating at The inks of the formulation S-13 to S-16 (Table 10) can be
60 rpm spindle speed. prepared according to the method described in Example 1.
30
TABLE 8
Each column indicates the weight% of the ingredient in the
final formulation.
Inks with slow solvents
TABLE 10
Ingredient S-S S-6 S-7 S-8 S-9 S-10 S-11 S-12
35 Inks with slow solvents
Dowano TPM 30.8 3 O.S 29.S. 28.5 26 25.9 41.6 9
tripropylene Ingredient S-13 S-14 S-15 S-16
glycol
methyl ether Dowanol TPM tripropylene glycol 20-SO 20-50 S-35 5-35
Joncryl 682 17 17 17 17 13.3 6.2 8.O 17 methyl ether
(acrylic 40 Pigmented Concentrate-2, (20.3% 30-SO 30-SO 45-75
copolymer) by weight in TPM)
35% solution Pigmented Concentrate-1 45-55
in TPM Foral 85 solution (35% by weight in 1O-35 10-35
Pigmented 515 515 51.5 51.5 TPM)
Concen Joncryl 682 (acrylic copolymer) 35% S-20 S-20
trate-1 45 solution in TPM
Pigment 59.S 65.1 49 71 Zonyl FSO100 O-3 O-3 O-3.5 O-3.5
Concen Surfynol 104 (20% solution in TPM) O-3 O-3 O-3.5 O-3.5
trate-2,
(20.3%
carbon black
in TPM) 50
Zonyl FSO100 0.7 1 2 3 1.2 2.8 1.4 3 Example 12
Viscosity, cPs 18.1 18.9 19.6 20.4 17 15.7 12.9 18.6
at 40° C.

Ingredients are included as weight% Alternate Decap Testing for Intermediate Solvents
55
Example 10 Ink was loaded into a Dimatix Skywalker 128/50 print
head, the printhead was purged and a control image consist
Decap Test for the Slow Solvent Ink ing of 24 individual alpha numeric codes was immediately
generated. The printer was allowed to sit idle for 30 seconds
The Markem-Imaje Model 5600 printer was loaded with 60 and then an image consisting of 24 individual alpha numeric
the ink to be tested. The system was purged and a test image, codes was generated. The number of times the codes had to be
showing the proper function of each nozzle, was made. This generated to obtain both a legible code at arm’s length (L*)
test image allows the user to visually determine if any given and a perfect code (P) was recorded. The printer was allowed
noZZle is operating or not and if its directionality and Volume to sit idle for 1 minute and then an image consisting of 24
are proper. This jetting test was performed to assess initial 65 individual alpha numeric codes was generated. This line of
nozzle function, then allowed the printer to sit idle. After a testing was continued for 3, 5, 10, 15, 60 minutes and over
number of days (in this instance, either 1 day or 4 days), a night. The results are presented in Table 11.
 US 9,284,463 B2
19 20
TABLE 11 11. The ink of claim 10, wherein the fluorosurfactant is a
poly(ethylene oxide)-b-poly(tetrafluoroethylene) copolymer.
Decap Test Results 12. The ink of claim 1, wherein the surfactant is present in
Idle time I-1 I-2 I-6 an amount of from about 1.1% to about 5% by weight of the
5 ink.
(min) L* P* L* P* L* P* 13. The ink of claim 1, wherein the ink comprises:
O.S 2 2 2 3 2 3. greater than about 90% by weight of ethanol,
1 2 3. 1 1 2 3. a phenolic resin,
3 3. 4 2 3 2 3. from about 1.1% to about 5% by weight of the poly(ethyl
5
10
4.
4.
6
6
3
3
5
4
2
1.
3
2
10 ene oxide)-b-poly(tetrafluoroethylene) copolymer, and
15 >24 >24 3 6 1. 1. a colorant.
60 >24 >24 1 2 1. 1. 14. The ink of claim 13, wherein the ink comprises:
overnight >24 >24 2 2 1. 1 91.4% by weight of ethanol,
2.9% by weight of a phenolic resin,
A number of implementations have been described. Nev
15 2.0% by weight of the poly(ethylene oxide)-b-poly(tet
ertheless, it will be understood that various modifications can rafluoroethylene) copolymer, and
be made without departing from the spirit and scope of the 3.7% by weight of a colorant.
disclosure. Accordingly, other implementations are within 15. An inkjet ink, consisting of:
the scope of the following claims. one fast organic solvent,
For example, while ethanol has been described for fast one resin,
organic solvent, propanol or butanol can be used. one surfactant, and
one colorant.
All of the features disclosed in this specification may be 16. The ink of claim 15, wherein the fast organic solvent is
combined in any combination. Each feature disclosed in this Selected from the group consisting of methanol, ethanol, pro
specification may be replace by an alternative feature serving 25 panol, iso-propanol, acetone, methyl ethyl ketone, methyl
the same, equivalent, or similar purpose. Thus, unless isobutyl ketone, pentane, hexane, heptane, methyl acetate.
expressly stated otherwise, each feature disclosed is only an ethyl acetate, and propyl acetate.
example of a generic series of equivalent or similar features.
What is claimed is: 17. The ink of claim 16, wherein the fast organic solvent is
ethanol.
1. An inkjet ink, comprising:
a fast organic solvent,
30 18. The ink of claim 15, wherein the ink consists of greater
a resin, than about 90% by weight of the fast organic solvent.
a surfactant, and 19. The ink of claim 15, wherein the resin is selected from
a colorant, the group consisting of rosin modified phenolic resin, phe
wherein the ink is a thermal inkjet ink, has a drying time of nolic resin, styrene-acrylic resin, and polyketone resin.
less than about 2 seconds, and has a decap time of at least
35 20. The ink of claim 15, wherein the surfactant is a fluoro
about one hour. Surfactant, a siloxane-based surfactant, an acetylenic diol
2. The ink of claim 1, wherein the ink has a drying time of based surfactant, or a hydrocarbon-based surfactant.
less than about 1 second. 21. The ink of claim 20, wherein the surfactant is a fluoro
surfactant.
3. The ink of claim 1, wherein the ink has a decap time of 40 22. The ink of claim 21, wherein the fluorosurfactant is
at least about 10 hours.
4. The ink of claim 1, wherein the fast organic solvent is Selected from the group consisting of polyethylene oxide-b-
Selected from the group consisting of methanol, ethanol, pro poly(tetrafluoroethylene)polymers, 2-(perfluoroalkyl)ethyl
panol, iso-propanol, acetone, methyl ethyl ketone, methyl Stearate, anionic lithium carboxylate fluorosurfactant,
isobutyl ketone, pentane, hexane, heptane, methyl acetate, anionic phosphate fluorosurfactant, anionic phosphate sur
ethyl acetate, propyl acetate, and combinations thereof.
45 factant, and amphoteric quaternary ammonium-acetate fluo
rosurfactant.
5. The ink of claim 1, wherein the fast organic solvent is 23. The ink of claim 22, wherein the fluorosurfactant is a
ethanol.
6. The ink of claim 1, wherein the ink comprises greater poly(ethylene oxide)-b-poly(tetrafluoroethylene) copolymer.
than about 90% of the fast organic solvent. 24. The ink of claim 21, wherein the ink consists of from
7. The ink of claim 1, wherein the resin is selected from the
50 about 1.1% to about 5% by weight of the fluorosurfactant.
group consisting of rosin modified phenolic resin, phenolic 25. The ink of claim 15, wherein the ink consists of ethanol,
resin, styrene-acrylic resin, polyketone resin, and combina a phenolic resin, a poly(ethylene oxide)-b-poly(tetrafluoro
tions thereof. ethylene) copolymer, and a colorant.
8. The ink of claim 1, wherein the surfactant comprises a 26. The ink of claim 25, wherein the ink consists of:
fluorosurfactant, a siloxane-based surfactant, an acetylenic
55 greater than about 90% by weight of ethanol,
diol-based surfactant, a hydrocarbon-based surfactant, or a a phenolic resin,
combination thereof. from about 1.1% to about 5% by weight of the poly(ethyl
9. The ink of claim 8, wherein the surfactant comprises a ene oxide)-b-poly(tetrafluoroethylene) copolymer, and
fluorosurfactant. a colorant.
10. The ink of claim 9, wherein the fluorosurfactant is
60 27. The ink of claim 25, wherein the ink consists of:
selected from the group consisting of polyethylene oxide-b- 91.4% by weight of ethanol,
poly(tetrafluoroethylene)polymers, 2-(perfluoroalkyl)ethyl 2.9% by weight of a phenolic resin,
Stearate, anionic lithium carboxylate fluorosurfactant, 2.0% by weight of the poly(ethylene oxide)-b-poly(tet
anionic phosphate fluorosurfactant, anionic phosphate sur rafluoroethylene) copolymer, and
factant, amphoteric quaternary ammonium-acetate fluorosur 65 3.7% by weight of a colorant.
factant, and a combination thereof. ck ck ck ck ck