US007950794B2

(12) United States Patent (10) Patent No.: US 7,950,794 B2

Vanini (45) Date of Patent: May 31, 2011

(54) SOLVENT BASED INKJET INK (58) Field of Classification Search .................. 347/100;
FORMULATION 106731.13
See application file for complete search history.
(75) Inventor: Clelia Vanini, Como (IT) (56) References Cited
73) Assignee
(73) Assi : KIAN S.p.A.,
p.A., Lui CO) (IT
Luisago (CO) (IT) U.S. PATENT DOCUMENTS
(*) Notice: Subject to any disclaimer, the term of this s: A E. Eps et al.
rOOkS et al.
patent 1S extended O adjusted under 35 6,391,943 B2 ck 5/2002 Sarma et al. ................. 523,160
U.S.C. 154(b) by 1036 days. 2003/0107632 A1* 6/2003 Arita et al. ......... ... 347/100
2003/0203987 A1* 10, 2003 NOmoto et al. .... ... 523,160
(21) Appl. No.: 11/569,671 2004/022O298 A1* 11/2004 KOZee et al. ....... ... 523,160
2004/0266907 A1* 12/2004 Sugita et al. .................. 523,160
(22) PCT Filed: May 27, 2005 FOREIGN PATENT DOCUMENTS
EP 0509 688 10, 1992
(86). PCT No.: PCT/B2OOS/OO1481 WO WO98, 13430 4f1998
S371 (c)(1), WO WQ9922.62 429
(2), (4) Date: Jan. 31, 2007 wo WO 2004007626 A1 1, 2004
* cited by examiner
(87) PCT Pub. No.: WO2005/116149 Primary Examiner — Laura E Martin
PCT Pub. Date: Dec. 8, 2005 (74) Attorney, Agent, or Firm — Hess Patent Law Firm, PC;
Robert J. Hess
(65) Prior Publication Data
(57) ABSTRACT
US 2007/0263O18A1 Nov. 15, 2007 A solvent based ink formulation for inkjet printing, particu
O O larly on plastics and non-porous Surfaces, including 1-40% by
(30) Foreign Application Priority Data weight of a ketone solvent, 10-90% by weight of a mixture of
cosolvents, 0.1-10% by weight of a (co)polymer binder, 0.1-
May 28, 2004 (EP) ..................................... O4O12724 10% by weight of dispersants/wetting agents, and 0.1-10% of
(51) Int. Cl. plasticizers to give a formulation having flash point higher
C09D II/00 (2006.01) than 60.degree. C.
(52) U.S. Cl. ..................................... 347/100; 106/31.13 15 Claims, No Drawings
 US 7,950,794 B2
1. 2
SOLVENT BASED INKJET INK dye and a vehicle, the balance being water. Colour bleeding is
FORMULATION said to be avoided by using self aggregating components such
as Surfactants, that can generate micellae; the application is
FIELD OF THE INVENTION silent about paper cockle and curl problems, that in fact were
not solved.
The present invention relates to a solvent based formula A further problem is that water based inks have very poor
tion for inkjet inks, i.e. for inks to be used in inkjet printers. In performances on non-porous Substrates. Water-based inks
particular, this invention relates to ink formulations based on have poor adhesion on non-porous media because water has
a system comprising one or more organic solvents as opposed no solvency powerfor non-porous materials such as PVC and
to ink formulations containing radiation curable polymers, 10 other plastic materials, while organic solvents have it: this
i.e. to those inks that are substantially free from solvent (so means that organic solvent-based inks offer a better adhesion
called solvent-less systems). on these substrates than the water-based ones.
This problem became a major problem with the increase of
BACKGROUND OF THE INVENTION articles to be printed on non-porous, plasticized or plastic/
15 vinyl coated articles such as posters for outdoor advertising.
Inkjet printing is a well-known technique that involves It was proposed to use organic solvents and co-solvents
printing without the printing device contacting the printing (diluents and thinners) to replace water, in part or completely,
Substrate (non-impact printing). In the present invention we in the ink formulation.
refer to “Drop On Demand technology where ink drops are WO 98/13430 discloses inkjet ink compositions compris
created only when required either thermally (thermal tech ing a binder resin that is suitable for use with ethanol or
nology) or mechanically (piezo or valve technology) and acetone, that are the preferred solvents. The disclosed formu
jetted on the substrate forming small dots; the substrate can be lations are all containing about 80-85 wt % of ethanol (flash
very different, ranging from paper to plasticized Substrates point 13°C.) and/or acetone (flash point -20°C.) and are
such as labels or vinyl or polyolefin based or coated sub therefore highly flammable formulations. Thus, this solution
strates. During the printing step, the media can be heated to 25 proved to be not satisfactory because the amount of organic
temperatures of up to 80°C. Solvents required resulted in ink formulations that are classi
Because of this peculiar printing technique, inkjet inks fied as hazardous, often flammable and sometimes eventoxic.
have technical requirements quite different from the tradi Such ink formulations are therefore subject to the strict rules
tional inks; more particularly, inkjet inks require very accu for handling said materials.
rate control of viscosity and Surface tension and sometimes of 30 It was also proposed to use “oils” (e.g. long chain glycols,
electrical conductance. ethoxylated glycols, ethoxylated oils, ethoxylated fats,
Electrical conductance is a fundamental parameter espe ethoxylated fatty acids, ethoxylated alcohols and hydrocar
cially in Continuous Inkjet technology where drops are gen bons) to completely or partially replace water in the ink
erated continuously and then Switched to print using electro formulation; however, this solution proved to be of reduced
static devices: unlike in prior art, in the present invention 35 practicity: even if these oil-based or oil-containing inks are
electrical conductance has been considered an important usually non-hazardous and non-flammable and reliable in
parameter also in “Drop On Demand” technology. printing process (good head/nozzle stability, reliable running,
Solvent and solvent-less ink formulations are known for minimal printer maintenance), they have insufficient versa
inkjet printing. As is well known, in a solvent-based formu tility. In fact they are only intended for use on partially or
lation the solvent does not react to provide a final polymer, but 40 totally absorbent substrates, while their use is not recom
evaporates without entering the final dry ink formulation; mended on non-porous or glossy media.
contrary to this, in radiation curable ink formulations the U.S. Pat. No. 5,407,474 discloses an ink formulation for
Solvent is replaced by oligomers that are cured to provide a non porous Substrates; the formulation is comprising a flux
polymer that is part of the dry ink. An example of curable, and is designed for use on glass and ceramic only and the ink
solvent-less ink formulation is disclosed in WO 03/027162, 45 has to be subjected to firing to become permanent. Thus, the
where the UV curable composition comprises a curable dis ink formulation of this document has the drawback that it
persant. cannot be used on other Substrates than glass and ceramic
The invention formulations are solvent-based, i.e. they are (PVC cannot be fired in an oven) and that the presence of a
Substantially free from radiation curable oligomers that act as flux is detrimental to the ink viscosity. The solvent is selected
a solvent medium and the filming of the ink is obtained by 50 from water, alcohol, methylethylketone and their mixtures
evaporation of an organic solvent. The invention formulation and therefore this document relates to an ink having the same
are especially designed for inkjet printing onto a wide variety problems that are discussed above.
of non-porous Substrates such as plastic Substrates (especially
vinyl Substrates), but are also suitable for printing on metal, SUMMARY OF INVENTION
glass, ceramic, rubber and others. These ink formulations 55
can, however, also be used onto porous media like paper and There is therefore the need for an ink comprising a solvent
wood. Media to be printed can be either uncoated or coated that can solve the above mentioned problems and is suitable
with special coatings and primers for printing on non-porous Substrates prevents bleeding,
Within known solvent-based inks there several problems cockle and curling when printing on porous Substrates, while
deriving from the choice of the solvent system to be used. 60 avoiding hazard and flammability problems.
While water is a good solvent as far as it regards environment it is an aim of this invention to provide Such an inkjet ink
and hazard problems, it also is a Source of drawbacks deriving formulations.
from the use of water as a major solvent when paper is used as This aim is achieved by means of the present invention, that
a substrate, namely paper cockle and curl, and color bleeding. relates to a formulation for inkjet ink wherein the solvent is
EP 0509688 discloses a water based ink formulation com 65 substantially free from water and from alcohols such as
prising a maximum amount of 20% of an organic Solvent methanol, ethanol and similar lower alkyl alcohols, said ink
having low vapour pressure, 0.1 to 10 wt % of a water-soluble formulation comprising 0.1-10% by weight of a (co)polymer
 US 7,950,794 B2
3 4
binder, 1-40% by weight of an active organic solvent that defects such as “banding or “overspray” due to jet instability
completely dissolve the resin (binder), 10-90% by weight of and erratic satellite and ligament formation).
a mix of cosolvents, and 0.1-10% by weight of pigment, Another advantage is the low maintenance required for the
Solvent and co-solvents being selected to give a formulation printing machines, due to the purity and the stability of the
having flash point higher than 60°C. Other additives can be 5 ink, the consistency of the ink flow through ducts, dumpers
added in small amounts (up to 5%). and nozzles, and the good reliability of the jetting (jet stability
According to a preferred aspect of the invention, the active and no noZZle-crusting).
organic solvent is selected from ketones having high flash
point, i.e. a ketones having a flash point of 40° C. or higher, DESCRIPTION OF THE PREFERRED
10 EMBODIMENTS
and preferably of 50° C. or higher, and more preferably of 60°
C. or higher. Usually, the flash point of solvents and cosol
vents is within the range of 40°C. to 150° C., the flash point The inkjet ink of the present invention is a mild solvent ink
of the formulation being within the range of 60°C. to 150° C. with brilliant colors that produces photorealistic images that
All the above flash points are measured with Tag Closed 15 are water, scratch and light resistant: this results in the further
Cup method. advantage that there is no need of lamination of printed Sub
The high solvency power of ketones can offer improved strates, that can be used both indoor and outdoor.
dissolution properties at lower active solvent concentrations. The ink formulation according to the invention also show
The claimed formulation provides a correct balance of the Some resistance to commercial ethanol-containing cleaning
vehicle system that can also produce fast drying inks without products, thus making it possible to gently clean the indoor/
blocking head noZZles. The system is composed by a bal outdoor printed Substrates if necessary.
anced blend of more volatile and less volatile solvents and The ink formulation of the present invention typically com
cosolvents: the first evaporate from printed film quickly to prises one or more active solvents, one or more cosolvents,
give it a fast-drying effect, while the second keep the binder one or more binders and one or more pigments; additives
dissolved inside and outside the printhead nozzles to avoid 25 known in the art, such as dispersants, wetting agents, Surface
noZZle-crusting. tension control agents, viscosity control agents, evaporation
The formulation of the vehicle system can also provide control agents, anti-static agents, corrosion control agents,
Some conductivity to the ink (conductivity larger than 1 foam control agents, film enforcing agents and plasticizers
microSiemens/cm) to dissipate static charges. may also be present.
In fact the build-up of the charges that occur within the 30
The ranges of the relevant amounts are Summarized in the
printing device can cause many problems that affect printing following table, where the amounts are in percent by weight
quality: if the jetted drops are charged and the substrate is on the total formulation weight.
charged too, drops can be deviated from the correct trajectory
contributing to the so-called “overspray” effect: a printing TABLE 1
defect where lines are not well shaped because small drops 35
fall in wrong positions during the jetting. active solvents 1-40%
cosolvents 10-90%
The invention ink provides the user with several advan binders O. 1-10%
tages over prior art inkjet inks. pigments O. 1-10%
A first advantage is that the invention solvent-based ink dispersants, wetting agents O. 1-10%
will presently be classified a “NON HAZARDOUS AND 40 plasticizers O. 1-10%
NON FLAMMABLE” material not only for labelling regu anti-static agents (if needed) O-5%
viscosity control agents (if needed) O-5%
lations, but also for transport regulations: this means that no evaporation control agents (if needed) O-5%
special precautions are required for handling, storing and Surface tension control agents (if needed) O-5%
shipping it. corrosion control agents (if needed) O-5%
The invention ink is safe to use and virtually odor free so it 45 foam control agents (if needed) O-5%
film enforcing agents (if needed) O-5%
can be used in ink-jet printers without harmful fumes or light stabilizers (if needed) O-5%
expensive ventilation equipment. The almost high boiling
point (low volatility) and quite low vapour pressure (slow
evaporation rate) and the mild odour give to these solvents Preferred ranges are: from 1% to 25% by weight for active
low emissions level in the working environment. 50 solvents, 50% to 90% by weight for cosolvents, from 0.1% to
A further advantage of the formulation ink is its great 6% by weight for pigments, from 0.1% to 7% by weight for
versatility: these inks print with great results directly onto a binders; all other additives (dispersants/wetting agents, light
wide range of materials, including both coated and uncoated stabilizers, Surface tension control agents, viscosity control
media, and even low-quality Substrates to which it securely agents, evaporation control agents, anti-static agents, corro
bonds. Suitable media are all the plastic and PVC films 55 sion control agents, foam control agents, film enforcing
including white and translucent, adhesive and not adhesive agents and plasticizers) may be present in Small amounts.
substrates, but also rubber, PU and ABS films and many An ink formulation according to the present invention has
others can be safely printed with the invention formulation. advantageous characteristics; the formulation viscosity is
A still further advantage of the formulation ink is the high within the range of 4 to 50 cps, the surface tension is within
quality of the printed images (bright colors and high defini 60 the range of 25 to 50 mN/m and the evaporation rate is such as
tion) obtained using even a high speed print mode. to provide a printing speed of at least 70 m/h, all these values
Moreover the drying speed of the printed film is very good refer to data measured at room temperature, 25°C.
(the solvents efficiently leave the printed film) allowing to use Active Solvent.
the “roll-to-roll' printing mode. As above mentioned, the active solvent is a solvent that can
These are great advantages for end-users because high 65 dissolve the resin (i.e. the binder), ketones also have a great
quality images are obtained in a shorter time, that means a Solvency for many Substrates such as vinyl and plastic Sub
higher printing productivity with high quality (without Strates.
 US 7,950,794 B2
5 6
The active solvent is selected from ketones having flash diluents are selected from acetates, fatty esters and mixtures
point higher than 40°C., preferably higher than 50° C., and thereof, carbonates and propionates.
more preferably higher than 60°C. The high solvency power Exemplary acetates are 2-ethylhexyl acetate, cyclohexyl
of ketones can offer improved dissolution properties for the acetate, methylcyclohexanyl acetate, oxo-hexylacetate, oxo
binder at lower active solvent concentrations. heptyl acetate, ethylene glycol monoacetate, ethylene glycol
In fact the binder must be dissolved in a vehicle to allow diacetate, ethylene or diethylene glycol monoalkylether
further processing and final application. If the solvent has a acetates (methyl, ethyl, propyl, butyl), propylene or dipropy
stronger attraction to a polymerchain than the chain has for its lene glycol monoalkylether acetates (methyl, ethyl, propyl.
neighbouring chain, the secondary valency bonds between butyl), propylene glycol diacetate.
adjacent polymer chains break under the application of 10 Fatty esters suitable for the invention comprise the C-C,
kinetic energy, and the invading solvent displaces each poly esters of fatty acids, the alcohol esters of fatty acids and
glycol, glycerol and polyglyceryl esters of fatty acids.
mer chain from the next. Recombination of the polymer Exemplary fatty esters are butyrates, mixtures of dimethyl
chains is unlikely, because the solvent molecules are popu adipate and/or dimethyl glutarate and/or dimethyl Succinate;
lating the bonding sites. 15 alcohol or glycol or polyethylene glycols, glycerol or polyg
The degree to which the molecules of this dissolved “resin lyceryl laurates, oleates, Stearates and palmitates.
solution' interact with each other and other components of Other Suitable esters comprise acrylate esters, methacry
the formulation gives the viscosity of the final ink formula late esters, lactates, polyol benzoates, diethyl carbonate, pro
tion. pylene carbonate.
Suitable active solvents for the blend are aliphatic linear Propionate esters such as n-butyl propionate, n-pentyl pro
and branched ketones Such as methyl n-amylketone, methyl pionate and ethylene glycol monoethylether propionate are
iso-amylketone, methylhexyl ketone, methylheptyl ketone, also suitable.
4-methoxy-4-methyl-2-pentanone, ethylbutyl ketone, ethyl In the present invention the preferred amount of the mix
amyl ketone, di-n-propyl ketone, di-iso-butyl ketone, iso ture of these diluents in the final ink formulation is comprised
butyl heptyl ketone; cyclic ketones such as lactones (e.g. 25 between 30% and 80% and they are preferably selected from
gamma-butyrolactone, gamma-Valerolactone, from esa- to quite high flash-point esters such as acetates, fatty esters and
dodeca-lactones) cyclohexanone and its derivatives (methyl mixtures thereof, carbonates and propionates.
cyclohexanone, trimethyl cyclohexanone), N-methyl-2-pyr Referring to this invention preferred acetates can be ethyl
rolidone; other ketones such as diacetone alcohol, acetonyl ene or diethylene glycol monoalkylether acetates (methyl,
acetone, methylheptenone may also be used. 30 ethyl, propyl, butyl), propylene or dipropylene glycol
Preferably, the high flash-point active solvents are chosen monoalkylether acetates (methyl, ethyl, propyl, butyl), pro
between C7-Caliphatic linear or branched ketones and the pylene glycol diacetate, ethylene glycol diacetate, 2-ethyl
family of cyclic ketones as lactones, derivatives of cyclohex hexyl acetate.
anone and N-methyl-2-pyrrolidone. Preferred fatty esters are mixtures of dimethyl adipate,
Most preferably, the high flash-point active solvents are 35 dimethyl glutarate, dimethyl Succinate called dibasic esters.
cyclic ketones such as gamma-butyrolactone or 3.3,5-trim In the present invention a mixture of 10-25% of dimethyl
ethylcyclohexanone in a concentration within the range of 1% adipate, 55-65% of dimethyl glutarate and 15-25% of dim
to 25% by weight. ethyl Succinate is preferred (all percents by weight).
Cosolvents. The most preferred carbonate is propylene carbonate and
Cosolvents can act also as Viscosity control agents, Surface 40 the most preferred propionates are pentyl propionate and
tension control agents, evaporation control agents and anti ethylene glycol monoethylether propionate.
static agents determining the print quality. They can also be Suitable thinners are selected from linear and branched
quite aggressive towards Substrates and work with the active aliphatic monohydric alcohols with a carbonious chain longer
solvent. than Cs and polyhydric alcohols, glycol ethers and their
The correct balance of them can also produce fast drying 45 derivatives.
inks without blocking head nozzles: the more volatile cosol Preferred thinners are ethers are especially glycol ethers
vents evaporate from printed film quickly to give a fast-drying such as ethylene or diethylene or triethylene glycol
effect to it, while the less volatile of them keep the ink in monoalkylethers or dialkylethers (mono or di methylethers,
liquid form inside and outside the printhead nozzles to avoid mono or diethylethers, mono or di propylethers, mono or di
noZZle-crusting by air drying. 50 butylethers), propylene or dipropylene or tripropylene glycol
The almost high boiling point (low volatility) and quite low monoalkylethers or dialkylethers (mono or di methylethers,
vapour pressure (slow-evaporation rate) and the mild odour mono or diethylethers, mono or di propylethers, mono or di
give to these solvents low emissions level in the working butylethers), ethylene glycol monophenylether, ethylene gly
environment. col monobenzylether, ethylene glycol butylphenylether,
The balance of these cosolvents can also ensure some 55 diethylene glycol divinylether, tetraethylene glycol dimeth
conductivity to the ink (conductivity larger than 1 microSi ylether, propylene glycol monophenylether, propylene glycol
emens/cm) that becomes able to dissipate static charges p-cyclohexylphenylether, 1,3-butylene glycol monomethyl
avoiding Small drops falling in wrong positions during the ether, divinyl ether of butanediol, methoxytriglycol, ethox
jetting because of electrostatic deviations. ytriglycol, butoxytriglycol and glycerine ethers.
There are two categories possible of cosolvents: 60 In this invention preferred thinners are derivatives of glycol
diluents that, alone, cannot properly dissolve the resin, but ethers such as monoalkyl glycolethers and dialkyl glyco
work in combination with an active solvent; lethers in a concentration from 20% to 60%: more preferably
thinners that provide no solvency for the resin, but which between dialkylethers dipropylen glycol dimethylether is
are tolerated in blends and are used to lower viscosity. used.
In this invention suitable diluents are selected from esters 65 Wetting Agents and Dispersing Agents.
having flash point higher than 40° C. and preferably higher In the ink according to the invention, one or more Surfac
than 50° C. and more preferably higher than 60° C. Preferred tants can be used as dispersant, i.e. wetting agent. Suitable
 US 7,950,794 B2
7 8
Surfactants are known in the art and can be chosen between 81:3, 112, 122, 146, 170, 176, 184, 185: Pigment Violet 3,
the anionic, non-ionic, cationic and amphoteric types. Pigment Violet 19, Pigment Violet 23 and others similar are
In the present invention preferably the Surfactant is anionic, used.
non-ionic or polymeric (comb polymer or block copolymer). To give the right shade to cyan ink organic pigments such
Exemplary anionic Surfactant are soap, ethoxy carboxy as Pigment Blue 15:0, Pigment Blue 15:3, Pigment Blue 15:4,
lated, ester carboxylated, amide carboxylated, ester Sulpho Pigment Blue 60 and others similar are used.
nates, phosphate esters, alcohol Sulphates, alcohol ether Sul To give the right shade to yellow ink organic pigments such
phates, Sulphated alkanolamide ethoxylates, Sulphated oils as Pigment Yellow 1, 3, 14, 17, 55, 74, 83,97, 120, 139, 150,
and glycerides, nonylphenol ether Sulphates, ethane Sulpho 10
151, 155, 180 and others similar are used.
nates, paraffin Sulphonates, alkylbenzene Sulphonates, fatty To give the right shade to black ink an inorganic pigment
acid and ester Sulphonates, alkyl naphtalene Sulphonates, ole such as Pigment Black 7 (Carbon Black) is used.
fin Sulphonates, petroleum Sulphonates, lignin Sulphonates To give the right shade to orange ink organic pigments such
and derivatives, Sulphosuccinates and Sulphosuccinamates, as Pigment Orange 5, 13, 34, 71 and others similar are used.
amide Sulphonates. 15 To give the right shade to green ink organic pigments such
Non-ionic surfactant can be selected between acetylenic as Pigment Green 7 and Pigment Green 60 and others similar
Surfactants, alcohol ethoxylates, alkanolamides, amine are used.
oxides, phosphine oxides, Sulphoxides, mono/poly Saccha Many other organic pigments can be used in order to obtain
rides derivatives, ethoxylated alkanolamides, ethoxylated the desired ink colour, but also an inorganic pigment as TiO2
long-chain amines, ethylene oxide/propylene oxide copoly can be used to obtain a white ink.
mers, fatty acid ethoxylates, Sorbitan derivatives, ethylene These pigments are finely dispersed in the inks and their
glycol, propylene glycol, glycerol and polyglyceryl esters particles are characterized by a mean diameter of less than
plus their ethoxylated derivatives, alkyl amines, alkyl imida 0.2-0.3 microns.
Zolines, ethoxylated oils and fats, alkyl phenol ethoxylates. Anti-Static Agents.
In the present invention anionic and non-ionic Surfactants 25 Virtually all polymeric materials as the binder or the media
are preferably used in a concentration within the range of Substrate are good insulators. As a result, they are ineffective
0.1% to 10% by weight in the final formulation, and prefer in dissipating static charges and the gradual build-up of the
ably of 0.1 to 6.0%. charges can cause many problems that can affect printing
Binders. quality: if the jetted drops are charged and the Substrate is
One or more binders are essential in the formulation to 30 charged too, drops can be deviated from the original right
permanently fix the pigment to the substrate: vinyl resins are trajectory producing images not correctly defined (for
preferred in this application, but also acrylic resins can be examples lines are not well shaped).
used. The amount of binder is within the range of 0.1 to Inside the printing machines accumulation of static
10.0%, preferably within 0.1 to 7.0% and most preferably charges often happens because of the rubbing of different
35 Surfaces together (due to the quick moving of the printhead
within 0.15% to 5%, by weight of dry resin on the total for example).
formulation weight. Various solutions are therefore employed to reduce or
Films based on vinyl resins are nonoxidizing and perma eliminate the accumulation of static charge.
nently flexible and are characterized by absence of color and In the present invention the control of the static charge in
odor. These resins have low moisture vapor transmission rate 40 the ink can be accomplished by increasing the conductivity of
and low order of water absorbtion, so when properly pig the ink through incorporation of agents (solvents or additives)
mented, films based on them have excellent outdoor durabil that themselves conduct electricity.
ity. Additives with anti-static properties are cationic, anionic
The molecular weigth and the amount of binder in the final or non ionic Surfactants. The most prevalent cationic agents
formulation determine the viscoelastic behaviour of the ink 45 are quaternary ammonium salts, which are most effective in
and its behaviour during the drop formation and during the polar substance such as PVC. Anionic types include alkyl
jetting. sulfonates or phosphates combined with alkali metals. Non
An amount of polymer binder higher than 8% by weight of ionic types are mostly derived from fatty acid esters, ethano
dry resin will result injet instability and in problems with the lamides, mono and di-glycerides and ethoxylated and pro
printhead and capping system. 50 poxylated fatty amines. Due to their inherent low polarity,
Copolymers of different molecular weights are preferably non ionic antistats are highly effective in polyolefin applica
selected from vinyl chloride/vinyl acetate copolymers, car tions.
boxyl-modified vinyl chloride/vinyl acetate copolymers, Additives with anti-static properties can be also some poly
hydroxyl-modified vinyl chloride/vinyl acetate copolymers, mers (ex. polypyrroles) that have intrinsic conductivity that
epoxy-modified vinyl chloride/vinyl acetate copolymers. 55 can dissipate Surface charges.
In this invention vinyl chloride/vinyl acetate copolymers It was surprisingly found that alkylcarbonate cosolvents
(modified and non-modified) with molecular weights com Such as propylencarbonate act also as anti-static agent and can
prised in the range of 15000 to 44000 (referenced to polysty replace at least in part the known anti-static agents in any ink
rene standard) are preferred. formulation for inkjet printing, i.e. including known inkjet
Pigments. 60 ink formulations, and in particular in ink formulations
In the present invention organic and inorganic pigments are according to the present invention. A preferred anti-static
used to give the right colour to the inks: the selected pigments cosolvent is propylencarbonate and the amount of alkylcar
have brilliant colours that produce photorealistic images light bonate to be used is within the range of 1 to 20%.
resistant that can be used both for indoor and outdoor appli It therefore is an object of the present invention the use of
cations (without any lamination process). 65 alkylcarbonate cosolvents as anti-static agents in an ink for
To give the right shade to magenta ink organic pigments mulation for inkjet printing.
such as Pigment Red 2, 22, 48:1, 48:3, 49:1, 49:2, 53:1, 57:1, Plasticizer.
 US 7,950,794 B2
10
The addition of one or more plasticizers is useful in the -continued
formulation in order to enhance flexibility and help to mini Di-octylphtalate 2% by weight
mize solvent retention in the film. 2-Ethylhexyl acetate 15% by weight
When added to a polymer (the binder), they cause a Propylene glycol diacetate 12% by weight
decrease in its glass transition temperature that increases its Propylencarbonate 18% by weight
workability and flexibility. Dipropylen glycol dimethylether 30% by weight
Typical plasticizers are phtalates (diisooctyl phtalate, dii
sodecyl phtalate, butyl benzyl phtalate, butyl-2-ethylhexyl The ink is then filtered with a sub-micron absolute filter
phtalate, 2-ethylhexyl isodecyl phtalate), citrates (acetyl 10
(for example 0.6 micron porosity).
tributyl citrate, acetil triethylcitrate, tributyl citrate), epoxies The flash point of the formulation (Tag Closed Cup) is 63
(epoxidized soybean oil, 2-ethylhexyl epoxy tallate, epoxi C.
dized linseed oil), phosphate (tri(2-ethylhexyl)phosphate, The ink so obtained is presently classified as an "NON
triphenyl phosphate, tributyl phosphate) and adipate com HAZARDOUS AND NON FLAMMABLE material not
pounds. Monomeric plasticizers are more efficient than poly only for labelling regulations, but also for transport regula
15
meric plasticizers (adipic acid polyesters, azelaic acid poly tions and has great versatility: it prints with great results
esters, sebacic acid polyesters, blown castor oil, blown directly onto a wide range of materials, including both coated
soybean oil, blown linseed oil) but the last ones can provide and uncoated media, and even low-quality Substrates to which
special film characteristics such as low extractability or it securely bonds with no “mottling defects (i.e. ink drops do
migration. not coalesce on the media Surface avoiding uneven density).
In the present invention the amount of plasticizer is within A still further advantage of this ink is the high quality of the
the range of 0.1 to 6.0% by weight in order to lower the printed images (bright color and high definition) obtained
maintenance requirements for the printing machines prevent using even a high speed print mode.
ing nozzles-crusting and wipers-crusting and ensuring a cor Moreover the drying speed of the printed film is very good
rect consistency of the ink flow through ducts, dumpers and 25
(the solvents leave the printed film efficiently) allowing to use
noZZles. the roll-to-roll printing mode.
Additional Additives. Another advantage is the low maintenance required for the
The addition of one or more functional additives is not printing machines, due to the purity and the stability of the
required for most of applications, but if needed the formula ink, the consistency of the ink flow through tubes, dumpers
tion can also contain light stabilizers, Surface tension control 30
and nozzles, and the good reliability of the jetting (jet stability
agents, viscosity control agents, evaporation control agents, and no noZZle-crusting).
anti-static agents, corrosion control agents, foam control EXAMPLE 2
agents and film enforcing agents in Small amounts.
All the formulation components provide an ink with Sur A resin Solution is obtained by dissolving under stirring
face tension preferably controlled from 25 mN/m to 50 mN/m 35 20% by weight of a hydroxyl modified vinyl chloride/vinyl
(obtained by using proper Surfactants and cosolvents), vis acetate copolymer with molecular weight of 15000 (refer
cosity preferably within the range of 3 to 50 centipoises enced to polystyrene standard) in 3,3,5-trimethylcyclohex
(obtained by using proper binders and cosolvents) and con anone (80% by weight).
ductivity larger than 1 microSiemens/cm (obtained by using A pigmented dispersion is also prepared dispersing and
proper anti-static agents and/or and cosolvents). 40 milling Pigment Blue 15:3 (15% by weight) in ethylene gly
The invention will now be further described with reference
to the following non-limiting examples. col monobutylether acetate using a non-ionic Surfactant as
wetting/dispersing agent. The final dispersion must have a
EXAMPLE1 finess of less than 0.3 microns (mean diameter).
The resin solution is then added to the pigmented disper
A resin (binder) solution is obtained by dissolving under
45 sion by stirring and then aphtalate plasticizer is added always
stirring 20% by weight of a non-modified vinyl chloride/vinyl under stirring.
acetate copolymer with molecular weight 22000 (referenced Finally a cosolvents mixture of fatty esters comprising
to polystyrene standard) in 3,3,5-trimethylcyclohexanone 10-25% of dimethyl adipate, 55-65% of dimethyl glutarate
(80% by weight). and 15-25% of dimethyl succinate (DiBasicEster), ethylene
A pigmented dispersion is also prepared, by dispersing and
50 glycol monobutylether acetate, propylencarbonate and the
milling Pigment Red 122 (15% by weight) in ethylene glycol thinner (dipropylen glycol dimethylether) are added under
monobutylether acetate using a non-ionic Surfactant as wet stirring.
ting/dispersing agent. The final dispersion has mean diameter The ink formulation of example 2 is:
of the particles of less than 0.3 microns (average). 55
The resin Solution is then added to the pigmented disper
sion by stirring and then aphtalate plasticizer is added, always Resin Solution 8.5% by weight
by stirring. Pigmented dispersion 15% by weight
Finally, 2-ethylhexyl acetate, propylene glycol diacetate, Di-octylphtalate 3% by weight
propylencarbonate and dipropylen glycol dimethylether are Ethylene glycol monobutylether acetate 5% by weight
60 DiBasicEster 15% by weight
added under stirring. Propylencarbonate 19% by weight
The ink formulation of example 1 is: Dipropylen glycol dimethylether 34.5% by weight

The ink is then filtered with a sub-micron absolute filter

Resin Solution 8% by weight 65 (for example 0.6 micron porosity).
Pigmented dispersion 15% by weight The flash point of the formulation (Tag Closed Cup) is 64°
C.:
 US 7,950,794 B2
11 12
The ink so obtained can be classified as “NON HAZARD 4. An ink formulation according to claim 1, wherein said
OUSAND NON FLAMMABLE material not only for label mixture offatty esters comprises 10-25% of dimethyladipate,
ling regulations, but also for transport regulations and has 55-65% of dimethyl glutarate and 15-25% of dimethyl suc
great versatility. cinate; said carbonate is propylene carbonate and said propi
A still further advantage of this ink is the high quality of the onates are selected from pentyl propionate and ethylene gly
printed images (bright color and high definition) obtainable col monoethylether propionate.
even when using a high speed print mode: thanks to the quite 5. An ink formulation according to claim 1, wherein said
high conductivity of this formulation (greater than 2 micro thinner is dipropylene glycol dimethylether.
Siemens/cm) no “overspray” defect can be detected. 6. An ink formulation according to claim 1, wherein a
Moreover the drying speed of the printed film is very good 10 viscosity of the formulation is within a range of 3 to 50 cps, a
and the maintenance required for the printing machines is surface tension of the formulation is within a range of 25 to 50
low. mN/m and an evaporation rate of the formulation is such as to
The invention claimed is: provide a printing speed of at least 70 m/h.
1. An ink formulation for inkjet printing, which is free 7. An ink formulation according to claim 1, wherein the
from water and from lower alkyl alcohols, comprising
15 (co)polymer binder is a vinyl chloride/vinyl acetate copoly
1-25% by weight of one or more active solvents selected mer having a molecular weight within a range of 15000 to
from C7-C12 aliphatic linear or branched ketones, 44000 (referenced to polystyrene standard) and a concentra
cyclic ketones as lactones and derivatives of cyclohex tion within a range of 0.1%-7% by weight.
anone, pyrrolidones and mixtures thereof, 8. An ink formulation according to claim 1, wherein the ink
50-90% by weight of a mixture of cosolvents comprising has conductivity larger than 1 microSiemens/cm.
diluents that are esters selected from the group consist 9. An ink formulation according to claim 8, wherein one of
ing of acetates, mixtures of fatty acid esters, carbonates the cosolvents is propylene carbonate cosolvent in an amount
and propionates and mixtures thereof, in an amount within a range of 1 to 20% by weight.
within a range of 30 to 80% by weight of the ink formu 10. An ink formulation according to claim 9, wherein the
lation, and thinners selected from monoalkyl glyco 25 formulation includes anti-static agents within a range of 0 to
lethers and dialkyl glycolethers in an amount within a 5% by weight.
range of 20% to 60% by weight of the ink formulation, 11. An ink formulation according to claim 1, wherein the
0.1-10% by weight of a binder selected from a group con pigments are selected from organic and/or inorganic pig
sisting of vinyl resins, ments having mean particle diameterofless than 0.3 microns,
0.1-10% by weight of dispersants/wetting agents, and 30 an amount of said pigments being within a range of 0.1% to
0.1-10% by weight of pigments; the ink formulation hav 6% by weight.
ing a flash point higher than 60° C. 12. An ink formulation according to claim 1, wherein said
2. An ink formulation according to claim 1, wherein said dispersants/wetting agents include an anionic or non-ionic
active solvent amount is within the range of 5% and 15% by surfactant within a range of 0.1% to 6% by weight.
weight and said solvent is a cyclic ketone selected from
35 13. An ink formulation according to claim 1, comprising
gamma-butyrolactone, 3,3,5-trimethylcyclohexanone and alkylcarbonate cosolvents as anti-static agents in an ink for
mulation.
mixtures thereof.
3. An ink formulation according to claim 1, wherein said 14. An ink formulation according to claim 13, wherein said
diluents are selected from ethylene or diethylene glycol alkylcarbonate cosolvents include a propylene carbonate in
monoalkylether acetates (methyl, ethyl, propyl, butyl), pro 40 an amount within a range of 1 to 20% by weight.
pylene or dipropylene glycol monoalkylether acetates (me 15. An ink formulation according to claim 1, wherein the
thyl, ethyl, propyl, butyl), propylene glycol diacetate, ethyl formulation includes anti-static agents within a range of 0 to
ene glycol diacetate, 2-ethylhexyl acetate and mixtures 5% by weight.
thereof.