Patent Application
20100194836
The present invention is directed to aluminium effect pigments, an ink jet printing ink containing said aluminium effect pigments and to a method of printing as well as to a method of producing an ink jet printing ink and to the use of aluminium effect pigments in ink jet printing inks.
In ink jet printing technology, tiny drops of ink jet printing ink are projected directly on the surface of a substrate for printing without physical contact between the printing device and the substrate surface. The placement of each drop on the printing surface is controlled electronically. The ink jet printing technology has become an important technology for printing variable data and images on paper, cardboard, etc. on the one hand and on products such as, for example, cans, bottles, foils, etc. on the other hand. It is also possible to directly print on fragile objects such as eggs using ink jet technology. The ink jet technology allows to print these data and images at a high speed.
Various principles have been developed for drop generation in the past such as electrostatic, magnetic, piezoelectric, electro-thermal, mechanical micro-valve, and spark discharge technologies. Regardless of type of drop generation, the ink jet technology is basically classified into two basic categories, namely continuous ink jet —CIJ—and impulse or drop-on-demand—DOD—ink jet technology.
The continuous ink jet technology is characterised by pressurised ink discharge through a nozzle to generate drops of ink directed to the substrate surface in a continuous stream.
The impulse ink jet technology differs from the continuous ink jet technology in that the ink supply is maintained at or near atmospheric pressure. An ink drop is ejected from a nozzle only on demand when a controlled excitation is applied to the drop-generating transducer. The impulse ink jet (or drop-on-demand) technology is primarily used in colour printers.
In recent years colour printers have been developed allowing to produce colour prints with the basic colours yellow, cyan and magenta and occasionally black. These colours are widely used as process colours in established printing processes like lithography, gravure and flexo printing.
In order to further improve the quality of the colour prints, especially in view of the increasing applications for photo printing, so called “spot colours” are used. In offset printing a spot colour is any colour generated by a pure or mixed ink that is printed using a single run. These spot colours can include orange and green in addition to the four basic colours or any other colours which expand the colour gamut and vividness of a printed image.
EP 1 205 521 discloses a pigment preparation for an ink jet process according to which a wide variety of pigments can be used. When producing the pigment preparation all components are comminuted in a mill to obtain a particle size wherein preferably 99% of the particles have a particle size of below 1 μm. Pigments having a particle size of below 1 μm are more or less of spherical nature which are not able to produce a metallic appearance in a print.
JP 11-323223 A discloses an ink jet printing ink containing metallic pigments produced with pvd methods.
Also, WO 2006/101054 A1 describes ink jet printing inks containing pvd-metallic pigments.
Disadvantageously, it is not satisfactorily possible to produce ink jet prints, especially photo prints, having a metallic effect or metallic appearance with high quality such as high gloss, high lop and high hiding power at reasonable costs. The pvd-metallic pigments are very expensive and not easy to handle due to its strong tendency to agglomeration.
It is an objective of the present invention to provide aluminium effect pigments suitable for use in an ink jet printing ink as well as an ink jet printing ink allowing to produce prints having a metallic appearance and being in an acceptable range of costs. Another object of the invention is to provide aluminium effect pigments which do have a reduced tendency to agglomerate when used in an ink jet printing ink.
The objective is solved by providing aluminium effect pigments having the following properties:
a) a d50-value of the volume averaged particle size distribution curve in a range of about 1 μm to 15 μm
b) an average thickness h50 of 15 to 150 nm determined by counting their SEM images
c) an x-ray diffractogram measured on said aluminium effect pigments in essentially plane-parallel alignment showing main peaks which are not [111]- or [222]-reflections.
Preferred embodiments of the aluminium effect pigments of the present invention are specified in sub-claims 2 to 12.
Object underlying the present invention is also solved by an ink jet printing ink comprising the aluminium effect pigments of the present invention.
Preferred embodiments of the ink jet printing ink of the present invention are specified in sub-claims 14 to 24.
Furthermore, the object of the invention is solved by a method of printing comprising applying an ink jet printing ink of any of claims 13 to 24 on a surface of a substrate using preferably an ink jet printer.
A preferred embodiment is specified in sub-claim 26.
The object of the invention is also solved by a method of producing an ink jet printing ink according to any one of claims 13 to 24, comprising gently mixing aluminium effect pigments with components of ink jet printing inks such as solvents, diluents and/or binding agents. Gently mixing of the aluminium effect pigments means that the during the mixing process said aluminium effect pigments are not damaged, what would impair the superior optical properties, such as the reflectance.
Moreover, the object of the invention is solved by use of aluminium effect pigments of any one of claims 1 to 12 in ink jet printing inks. Preferably, the aluminium effect pigments are used in the preparation of an ink jet printing ink as claimed in any one of claims 13 to 24.
Finally, the object of the invention is solved by an article coated with aluminium effect pigments according to any one of claims 1 to 12 or with an ink jet printing ink of any one claims 13 to 24. Such an article can be, for example, paper, cardboard, foils made from plastic or metallic material, labels, bottles and containers made from glass, ceramic material, plastic material or metallic material, textiles, etc.
With the present invention it has surprisingly been discovered that it is possible to produce ink jet prints having a high class metallic appearance incorporating aluminium effect pigments into ink jet printing inks which have not been produced with expensive and cumbersome pvd-methods. Furthermore, the aluminium effect pigments of the present invention have a surprisingly reduced tendency to agglomerate when using in an ink jet printing ink. Thus, the aluminium effect pigments of the present invention can be more easily incorporated into ink jet printing inks compared to pvd aluminium pigments, i.e. aluminium pigments obtained by physical vapour deposition.
The quality of the prints is very similar to those which are obtained when using aluminium pigments produced by pvd-methods. The aluminium effect pigments of the present invention are produced by a wet grinding method. A process for obtaining ground aluminium effect pigments is described, for example, in the EP 1 613 702 A1 which is incorporated by reference therein. Briefly, the aluminium effect pigments are produced by grinding, preferably nearly spherical, aluminium particles in a ball mill or pearl mill.
The aluminium effect pigments of the present invention differ over those described in EP 1 613 702 A1 in terms of the specific combination of particle characteristics of the d50-value of the volume averaged particle size distribution curve of 1 μm to 15 μm and an averaged thickness h50 of 15 to 150 nm determined by counting from SEM images.
It turned out that aluminium effect pigments with the aforementioned combination of properties makes them suitable for use in an ink jet printing ink.
Aluminium effect pigments have a platelet-like form hence they act like micro-mirrors directly reflecting incident light. If the metal pigments are reduced to a size of less than 1 μm (d50), they are too small to act as a plate-like mirror. However, if the metal pigment flake size is 1 μm or more (d50-value), surprisingly these tiny metal flakes still act as aluminium effect pigments, i.e. are capable to reflect light in a uniform and directed manner.
If the average size is above 15 μm the pigments do not pass any more through the configuration such as tubes, channels, filters, nozzle, etc. of the ink jet configuration. Some part of the whole configuration would be clogged and the ink jet head would be practically inoperable.
The d50-value refers to the volume-averaged particle size distribution as measured with laser scattering methods. Such particle sizes are determined with instruments such as Cilas 1064.
To give the observer the most appealing view of an image containing aluminium effect pigments it is necessary that the aluminium effect pigments or flakes are not arranged randomly but essentially parallel to the surface of the substrate. In this case the incident light is reflected in a rather uniform way. If the aluminium effect pigments are randomly oriented in the ink jet printing ink the incident light is also randomly reflected which reduces the metallic brilliance and is not attractive to the observer.
After having applied the droplets of ink jet printing ink on a surface of a substrate the ink jet printing ink is dried or cured, for example, by applying heat and/or UV irradiation. This process occurs immediately after ink deposition on the substrate. The period of time for drying or curing is usually in the range of split seconds to minutes, depending on the drying or curing mechanism. During this very short period of time the aluminium effect pigments surprisingly orient essentially parallel to the surface of the printed ink.
Without wishing to be bound by theory it is currently believed that the small size of the aluminium effect pigments facilitates a rather quick orientation of the aluminium effect pigments in the ink droplets immediately after application.
According to a preferred embodiment of the invention, the aluminium effect pigments have a d50-value (Cilas) in a range of about 1 μm to 12 μm, preferably of about 1.5 μm to 8 μm, most preferably of about 2 μm to below 6 μm.
It turned out that a particle diameter or particle size in a range of 2 to 5 μm (d50-value Cilas) is very superior in terms of the metallic effect obtained after printing the ink jet printing ink.
Preferably, at least 99% of the particle size distribution curve (d99) is in a range of lower than about 14 μm. More preferably at least 99% of the particle size distribution curve is a range of lower than about 12 μm.
Moreover, it is preferred that the particle size distribution (PSD) of the aluminium effect pigments is very narrow. Preferably 100% of the aluminium effect particles (d100) have a particle size of less than 15 μm, further preferred less than 12 μm.
According to another preferred embodiment of the invention, 100% of the particle size distribution curve is in a range of between 0.5 to 8 μm, further preferred between 1 and 7 μm.
In order to use the established ink jet printing ink technology, it is mostly desirable to use aluminium effect pigments having a diameter at maximum up to 12 μm as, for example, the jet nozzle openings or other parts of the ink jet configuration are usually in a range of about 20 to 50 μm.
Basically, the limitations of the upper size of the aluminium effect pigments are determined by the dimensions of the whole printing configuration such as tubes, channels, filters and jet openings. The printing configuration must be such that it can work as a pump on the ink jet printing ink. If an ink jet print head is for example using a larger jet opening it is also possible to use larger aluminium effect pigments.
It has been shown that the ratio of average size, preferably absolute size, (d50-value Cilas) of the aluminium effect pigments to the diameter of the jet opening is advantageously in a range of 0.02 to 0.5 and preferably from 0.03 to 0.2 and most preferably from 0.04 to 0.12
Platelet-like metal pigments with these average sizes do easily fit through the jet nozzles of the jet print heads usually used.
The average thickness h50 of the aluminium effect pigments as determined by counting their SEM images is preferably 15 to 150 nm.
It turned out that, after applying the ink jet printing ink of the present invention on a substrate, very appealing aluminium effects of the printed ink jet printing ink can be only achieved with metal pigments with these very thin average thicknesses.
These aluminium effect pigments have an average thickness h50 of 15 to 150 nm determined by counting their SEM images as described above. More preferably the average thickness h50 is 15 to 100 nm and even more preferably 20 to 80 nm.
Also a very preferable average thickness h50 is 30 to below 80 nm. With such thin aluminium effect pigments very brilliant effects can be achieved. Besides high gloss and high flop the printings have a look of a liquid metal effect which is usually typical for pvd-pigments.
Less brilliant, but still reasonable metallic effects can be achieved with an average thickness h50 of 80 to 130 nm.
Below a h50 of 15 nm the pigments are too transparent and appear already quite dark due to their reduced reflective properties. Above a h50 of 150 nm the optical performance of the aluminium effect pigments decreases and pigment material is wasted because of the reduced hiding power, i.e. the specific coverage which is calculated as the coverage of aluminium effect pigments per weight.
Usually the particle thickness is determined by measuring the water coverage (according to DIN 55923) and/or by Scanning Electron Microscopy (SEM). The measurement of water coverage only yields an average thickness, but not the distribution of the particle thickness.
For PVD aluminium pigments with their known strong tendency to agglomerate this method cannot be used at all.
For this reason the average thickness of the aluminium effect pigments of the present invention was determined by SEM. Usually at least 100 particles are analysed in order to have a representative statistics.
The aluminium effect pigments of the present invention incorporated into the ink jet printing ink of the present invention differ significantly to pvd-pigments regarding their x-ray diffraction patterns. In order to characterise platelet like aluminium effect pigments by XRD method (X-ray Reflection Diffraction) the pigments are oriented in an essentially plane parallel orientation prior to measurement.
The x-ray diffractogram (XRD) measured on the aluminium effect pigments of the present invention in essentially plane-parallel alignment shows, usually one or two, main peaks which are not [111]- or [222]-reflections.
The measurement can be made on most X-ray diffractometers available on the market.
In the present invention the term “essentially plane-parallel alignment” means that at least 80% of the pigments are oriented in parallel to the substrate surface within a tolerance of +/−15° to the substrate surface.
The denomination “[111] plane” refers to Miller's indices. The [111] plane is the most densely packed diagonal plane of a face-centered cubic lattice.
The [111] reflection of the aluminium effect pigments of the present invention is weak, if visible at all. The [222] reflection is even more weaker and might not be detectable.
The main peaks of the aluminium effect pigments of the present invention are those of the [200] and/or [220] planes. It is especially preferred that the main peak is the one of the [200] plane.
The ratio of the peak intensities of the aluminium effect pigments of the present invention [111]/[200] is always <1. Preferably it is <0.5 and most preferably <0.1.
This result is contrasted by pvd-pigments: these pigments always exhibit main peaks corresponding to the reflexes of the [111]- or the [222]-planes.
These results reflect the well known fact that aluminium which is sputtered onto a foil forms essentially single crystals having the aforementioned reflectivity.
It is assumed that these results reflect the properties of the plastic state of deformation of the aluminium effect pigments during the grinding process. The usually polycrystalline aluminium powder, which is usually obtained by atomisation of molten aluminium, is subjected to strong shearing forces during the deforming grinding process, using usually balls or spheres as grinding body. The crystallites are sheared against each other whereas the most densely packed [111]-plane represents the plane of shearing. Because the grinding process naturally occurs perpendicular to the surface of the surface of the platelets the [111] planes are broken out of the plane surface. Consequently the peak intensity of the [111] and the second order [222]-planes are decreasing during the ongoing grinding process. At the same time the peaks corresponding to the [200] and the [220]-planes are intensified which finally become main peaks.
The relative width of the thickness distribution Δh resulting from counting the Scanning Electron Microscope images of the aluminium effect pigments and calculated from the respective number weighted cumulative distribution according to the formula
Δh=100(h90−h10)/h50 (I)
(“thickness span”) is preferably 30 to 140%,
wherein h90 is the number pigments covering 90% of the absolute height and h10 is the number pigments covering 10% of the absolute height and h50 is the number pigments covering 50% of the absolute height of said aluminium effect pigments.
Such pigments are principally disclosed in the WO 2004/087816 A2 which is incorporated by reference therein. However, the aluminium effect pigments of the present invention differ over the ones known from WO 2004/087812 A2 with respect to the specific combination of particle characteristics of the d50-value of the volume averaged particle size distribution curve of 1 μm to 15 μm and an averaged thickness h50 of 15 to 150 nm determined by counting from SEM images.
In a more preferable embodiment the number weighted cumulative distribution Δh ranges from 30 to 100% and most preferably from 30 to 70%.
Very much preferred are aluminium effect pigments with an average thickness h50 of 15 to 80 nm and a Δh of 30 to less than 70%.
Such thin particle thickness distribution curves of the aluminium effect pigments of the present invention surprisingly turned out to give optical effects after application of the ink jet printing ink of the present invention on a substrate with a very high gloss and flop-effect and liquid-metal-effect very similar to pvd-aluminium pigments.
A low Δh is necessary to obtain the desired high class optical effects. Pigments with a Δh above 140% do not stack properly in the ink jet printing ink. Furthermore, because of the very short time of orientation, a good orientation can only be achieved for pigments with a Δh of less than 140% and preferably less than 100%.
The ink jet printing ink of the present invention contains very thin aluminium effect pigments with rather narrow spans of the particle size and the particle thickness distribution curves as recited in claims to enable a uniform and short time of orientation of essentially all aluminium effect pigments during and after application of the ink jet printing ink of the present invention.
The aluminium effect pigments of the present invention exhibit very high hiding power compared to conventional aluminium effect pigments obtained by grinding methods.
The aluminium effect pigments of the present invention exhibit preferably a thickness distribution curve with a h90-value of under 110 nm and more preferably under 75 nm. The h95-value of the thickness distribution is preferably below 150 nm and more preferably below 120 nm. Additionally, the h99-value is preferably below 140 nm and more preferably below 90 nm.
Such a narrow thickness distribution of the aluminium effect pigments of the present invention leads to a very good stacking in the prints of the printed ink jet printing ink. Therefore, these pigments of the present invention exhibit very good gloss and flop effects.
The aspect ratio f of the aluminium effect pigments of the present invention is preferably in a range of about 30 to 500, more preferably the aspect ratio is in a range of about 35 to 300 and most preferably in a range of 40 to 200. The aspect ratio is the ratio of average particle size divided by average particle thickness and is represented by the following formula (II):
These aspect ratios have been proven useful in order to minimize the time for orientation of the aluminium effect pigments after application of the ink jet printing ink to the surface of substrate.
The aluminium effect pigments of the present invention used for the ink jet printing ink of the present invention can be of the leafing or the non-leafing type. According to a preferred embodiment of the invention the aluminium effect pigments are leafing pigments. Leafing pigments arrange themselves in an oriented manner, i.e. essentially parallel to the surface of substrate, at the surface of the ink jet printing ink after printed on a substrate whereas non-leafing pigments arrange themselves within the ink jet printing ink uniformly between substrate to which they are applied and the dried printing ink.
Preferably, leafing aluminium effect pigments are used in the present invention, so that the printed images obtained have a very brilliant and shiny appearance for the observer. The leafing behaviour can be induced by coating the aluminium effect pigments, for example, with stearic acid.
Ink jet printing inks containing aluminium pigments made by pvd-process have certain problems due to agglomeration and to settling of the aluminium particles in the ink jet printing ink. Such problems have been tried to overcome by using quite large amounts of dispersion additives and/or anti-settling agents.
Surprisingly, these problems are significantly less severe in the ink jet printing ink of the present invention.
While not wishing to be bound by theory it is assumed that these advantages are due to a certain roughness of the surface of the aluminium effect pigments of the present invention. The aluminium effect pigments of the present invention exhibit—due to their manufacturing process—a higher degree of roughness and of corrugation than pvd-pigments which have essentially a perfectly flat surface without corrugations. However, the higher degree of roughness of the aluminium effect pigments of the present invention prevents a completely plane-parallel attachment of the aluminium effect pigments to each other followed by a strong agglomeration of the pigments. Contrasting to pvd-pigments the aluminium effect pigments of the present invention can exhibit—on a very small scale—only punctual contacts between the platelets. Therefore, the enforcement of very short ranging attractive forces like van-der-Waals forces or of hydrogen-bonds are minimized and consequently agglomeration or aggregation processes are significantly reduced and preferably avoided at all.
In order to produce such novel aluminium effect pigments, aluminium is molten and subsequently atomized using well established technology. The spherical particles obtained by atomization are subsequently milled in a pearl mill or ball mill to the desired particle size of aluminium effect pigments. The process of ball milling or pearl milling metal particles is an established process known in the art as “Hall process”.
To obtain very thin pigments spherical balls made from a material with weight of 2 to 13 mg per sphere have to be used. Preferred balls are glass spheres. Furthermore fine an aluminium grit is preferably used as starting material for the production of aluminium effect pigments of the present invention being plate-like in shape.
The average particle size of the aluminium grit d50 used for the production of these thin aluminium effect pigments is <20 μm, more preferred <15 μm, still more preferred <10 μm and even more preferred <8 μm. In still another preferred embodiment of the invention the average particle size distribution is characterised as follows: d10<3 μm, d50<5 μm, d90<8 μm.
To obtain very thin aluminium effect pigments with a very tiny thickness distribution, e.g. an aluminium effect pigments having an average thickness h50 of 15 to 80 nm and a Δh of 30 to less than 70%, a very fine aluminium grit with a narrow size distribution is preferably used. Preferably, an aluminium grit with a particle size characteristics of dgrit,10<3.0 μm, dgrit,50<5.0 μm and dgrit,90<8.0 μm is used. More preferably, an aluminium grit with a particle size characteristics of dgrit, 10<0.6 μm, dgrit,50<2.0 μm and dgrit,90<4.0 μm is used.
Pursuant to another preferred embodiment of the invention the aluminium effect pigments are coated with a layer of corrosion inhibiting material.
The corrosion inhibiting material can be made of an encasing layer of metal oxide and/or organic polymeric material.
Preferably, the metal oxide layer comprises silica, alumina, titanium oxide, iron oxide and mixtures thereof. Most preferably, silica is used as a corrosion inhibiting layer. The average thickness of this metal oxide layer, preferably silicon oxide layer, is preferably between 10 and 40 nm, further preferred between 15 nm and 30 nm.
A layer of metal oxide may be applied to the surface of the metal pigments by hydrolysing soluble metal salts in the presence of agitated aluminium effect pigments. For example, metal chloride salts can be hydrolysed in water.
Preferably a sol-gel process for coating aluminium effect pigments with a layer of metal oxide is used. For example, an encapsulating layer of SiO2 may be applied by hydrolysing tetraalkoxysilanes, such as, for example, tetraethoxysilane or tetramethoxysilane in alcoholic media in the presence of agitated aluminium effect pigments, sufficient amounts of water and optionally catalysts such as acids or bases.
The amount of aluminium effect pigment in the ink jet printing ink of the present invention is preferably in a range from about 0.1 to 30% by weight, more preferably, from about 0.5 to 20% by weight and even more preferably, from about 1 to 15% by weight, based on the total weight of said ink jet printing ink.
According to another preferred embodiment of the invention the content of the aluminium effect pigment is in a range from about 2.5 to 8% by weight, based on the total weight of said ink jet printing ink.
According to another embodiment of the present invention the ink jet printing ink comprises a binding agent. Preferably, these ink jet printing inks are solvent based systems. The amount of binding agent is in a range of 1 to 99% by weight, based on the total weight of said ink jet printing ink.
Depending on the nature of the substrate to which the ink jet printing ink is to be applied, a binding agent is or is not to be included in the ink jet printing ink. If the binding agent is part of the substrate, e.g. a special ink jet printing paper containing adhesive substances it is not necessary that the ink jet printing ink contains a binding agent.
According to another preferred embodiment of the present invention the ink jet printing ink is based on solvent(s) or water and comprises a binding agent in a range of about 1 to 50% by weight, based on the total weight of said ink jet printing ink. Furthermore, it is preferred that the content of the binding agent amounts to about 2 to 35% by weight, based on the total weight of said ink jet printing ink. More preferably the content of the binding agent is in a range of about 3 to 25% by weight.
According to another preferred embodiment for radiation curing ink jet printing inks, especially for UV ink jet printing inks, the diluent is a reactive diluent, acting also as a binding agent. The amount of the reactive diluent, e.g. liquid oligomers and monomers, is in a range of 1 to 99% by weight, preferably 10 to 95% and more preferably 40 to 90% by weight, based on the total weight of said ink jet printing ink.
That is to say, according to an embodiment of the invention the reactive diluent can be a binding agent.
According to another preferred embodiment for radiation curing ink jet printing inks, especially for UV ink jet printing inks, the diluent is a non-reactive diluent
The binding agent can be any binding agent usually used in ink jet printing inks. Preferred, but not limited thereto, are the following binding agents: UV curable acrylic monomers and oligomers as well as resins of various families, like hydrocarbon resins, modified rosin resins, polyethylene glycol resins, polyamide resins, polyvinylbutyral resins, polyvinyl pyrrolidone resins, polyester resins, polyurethane resins, polyacrylic resins, polyacrylamide resins, polyvinylchloride resins, ketone resins, polyvinyl alcohol resins, modified cellulose or modified nylon resin or other resins soluble in organic solvents or mixtures thereof.
It is preferred that solvent or water based ink jet printing inks comprise a solvent content in an amount of about 10 to 95% by weight, based on the total weight of said ink jet printing ink. According to another preferred embodiment of the invention the content of solvent amounts to about 20 to 94% by weight and more preferably 50 to 93% by weight.
Any solvent or solvent mixture suitable with the ink jet printing ink technology can be used. Preferred solvents are water, alcohols, esters, ethers, thioethers, glycol ethers, glycol ether acetates, amines, amides, ketones and/or hydrocarbons or mixtures thereof.
Examples for alcohols are alkyl alcohols such as, e.g., methyl alcohol, ethyl alcohol, propyl alcohol, iso-propyl alcohol, butyl alcohol, pentyl alcohol, hexyl alcohol, fluorinated alcohols or mixtures thereof.
Examples of ketone solvents are acetone, methyl ethyl ketone or cyclohexanone, diisobutyl ketone, methyl propyl ketone, diacetone alcohol, N-methylpyrrolidone or mixtures thereof.
Examples of esters are methyl acetate, ethyl acetate, 1-methoxy-2-propylacetate propyl acetate, butyl acetate, methyl propionate or ethyl propionate glycolether acetates, butyl glycol acetate or mixtures thereof.
Examples of ether solvents are diethyl ether, dipropyl ether, tetrahydrofuran, dioxane ethylene glycol ethers, in particularly ethylene glycol ethyl ether or ethylene glycol methyl ether which are also marketed under the trademark Cellosolve®, methoxy propanol or mixtures thereof.
In addition, preferred examples of the organic solvents include a mixture of the diethylene glycol compound that is liquid under normal temperature and normal pressure and the dipropylene glycol or 1-methoxy-2-butylglycol compound that are liquid under normal temperature and normal pressure.
Examples of amine solvents are triethanolamine and dimethylethanolamine. Examples of amide solvents are N-methylpyrrolidone and 2-pyrrolidone.
The hydrocarbon can be selected from the group consisting of terpene hydrocarbons like pinene, limonene, terpinolene; aliphatic hydrocarbons like heptane, mineral spirits, Stoddard solvent and aromatic hydrocarbons like toluene, xylene, solvent naphta and mixtures thereof.
In another embodiment the ink jet printing ink of the present invention is a radiation curable ink, especially an UV curable ink, comprising said solvent in an amount of about 0 to 50% by weight, based on the total weight of said ink jet printing ink. More preferable the solvent content is 0 to 10% by weight, because in UV curable inks solvent usually are not necessary. According to a particularly preferred embodiment of the invention the UV curable ink jet printing ink does not contain a solvent.
According to another embodiment of the invention, the ink jet printing ink has a viscosity in a range of about 1 to 100 cps measured with the Brookfield viscometer LV Model DV-II+ using spindle no. 61 at 100 rpm at a temperature of 21° C. Preferably, the viscosity of the ink jet printing ink is in a range of about 3 cps to 30 cps, more preferred in a range of 5 to 20 cps.
The viscosity can be adjusted to accommodate the type of print head used, the substrate to be printed on, and/or the composition of the ink jet printing ink.
According to another embodiment of the invention, the ink jet printing ink has a surface tension from 20 to 50 mN/m. When the surface tension is less than 20 mN/m, the ink jet printing ink composition wetly spreads over the surface of the printer head for ink jet recording or exudes therefrom, resulting in difficulty of ejecting ink droplets in some cases. When the surface tension exceeds 50 mN/m, the ink composition does not wetly spread over a surface of the recording medium, resulting in failure to perform good printing in some cases.
Preferably, the ink jet printing ink comprises additives, for example dispersing agents, anti-settling agents, lubricants, humectants, surfactants, penetrants, pH-adjusters, biocides or mixtures thereof.
The dispersing agents aid to homogeneously disperse all components in the ink jet printing ink, more specifically the aluminium effect pigments, to avoid any tendency of agglomeration, if any. A dispersing agent may improve a homogenous dispersion of all components of the ink jet printing ink that can be dependent on the nature of the components used. Preferably, the dispersing agent is selected from the group consisting of fatty acids or mixtures thereof.
When an organic solvent is used, the ink jet printing ink composition of the invention can contain a dispersant. As the dispersant, there can be used any dispersant used in an ordinary ink composition such as a gravure ink, offset ink, intaglio ink or screen printing ink. In particular, it is preferred to use a dispersant effectively acting when the solubility parameter of the organic solvent is from 8 to 11. As such a dispersant, it is also possible to utilize a commercial product, and specific examples thereof include Solsperse 20000, 24000, 3000, 32000, 32500, 33500, 34000 and 35200 (Avecia K.K.) or Disperbyk-106, 111, 102, 161, 162, 163, 164, 166, 180, 190, 191 and 192 (BYK-Chemie GmbH).
In further preferred embodiments the ink jet printing ink compositions of the present invention contain antisettling agents. These substances are desired to prevent settling of the flaky aluminium effect pigments in the ink. Examples are Byk®-405 in combination with pyrogenic silica, modified ureas such as Byk®-410 and Byk®-411 or waxes like Byk Ceramat®237, Ceramat®250, Cerafak®103, Cerafak®106, or Ceratix®8461.
In aqueous ink formulations Byk®-420 is especially preferred.
The lubricants aid to improve the through-passing properties of the ink jet printing ink through the print head architecture. Preferably, the lubricant is selected from the group consisting of fatty acids such as stearic acid or oleic acid, fatty acid esters and mixtures thereof.
The humectants are used in water-based ink jet printing inks to avoid any drying out especially while in the print head. The humectants reduce the rate of evaporation and prevent precipitation of dyes, when evaporation occurs at the jet orifice. Preferably, the humectants are selected from the group consisting of polyols, such as glycols, glycerine, sorbitol, polyvinyl alcohols and mixtures thereof.
Biocides can be incorporated into ink jet printing inks in order to prevent growth of microorganisms. For example, polyhexamethylene biguanide, isothiazolones, isothiazolinones such as, e.g., 5-chloro-2-methyl-4-isothiazoline-3-one (CIT), 2-methyl-4-isothiazolin-3-one (MIT), etc. or mixtures thereof can be used.
In addition to aluminium effect pigments various colorants can be incorporated into the ink jet printing ink. For example, various black colorants such as C.I. Solvent Blacks 27, 28, 29, 35, 45; various blue colorants such as C.I. Direct Blues 86, 199; C.I. Solvent Blues 25, 44, 48, 67, 70; various red colorants such as C.I. Acid Red 52; C.I. Solvent Reds 49, 172; C.I. Disperse Red 60; C.I. Pigment Red 122; C.I. and/or various yellow colorants such as Acid Yellow 23; C.I. Direct Yellow 86; C.I. Disperse Yellow 119; C.I. Solvent Yellow 162; Solvent Yellow 146; C.I. Pigment Yellow 17 can be used in combination with the ink jet printing ink of the present invention.
The objective underlying the present invention is further solved by providing a method of printing, applying an ink jet printing ink of any one of claims 1 to 18 onto a surface of a substrate preferably using an ink jet printer.
Preferably the substrate is selected from the group consisting of coated or uncoated paper, coated or uncoated cardboard, plastics, metals, ceramics, glass, textiles and combinations thereof. Most preferred substrates are plastics.
The ink jet printing ink of the present invention can be applied to the substrate using a commercially available ink jet printer. Preferably, the ink jet printer has a container reserved for aluminium effect pigments containing ink jet printing ink. Before printing, the aluminium effect pigment containing ink jet printing ink is preferably sieved through a sieve with a mesh size suitable to remove possible remaining aggregated particles, which could clog the nozzle or other parts of the printing setup.
The objective of the present invention is further solved by a method of producing an ink jet printing ink according to any one of claims 13 to 24, comprising gently mixing the aluminium effect pigments of the present invention with components of ink jet printing inks, e.g. binding agent(s), solvent(s), additive(s), etc., as specified above in detail.
The ink jet printing ink composition of the invention can be prepared by the following method, for example: initially, the aluminium effect pigment of the present invention, optionally a dispersant, and liquid solvent and/or liquid binding agent and/or diluent are gently mixed, without damaging the aluminium effect pigments. Then, an ink jet printing ink is prepared by a ball mill, a pearl mill, a bead mill, an ultrasonic wave, a jet mill or the like to perform adjustment so as to have desired ink jet printing ink characteristics. Subsequently and optionally, liquid solvent and/or additives, for example, a dispersing aid, a viscosity adjusting agent and/or a binder resin are added or additionally added under stirring, thereby obtaining the ink jet printing ink of the present invention.
An important aspect of the claimed method is that, as mentioned before, the aluminium effect pigments are not damaged during the mixing process. The platelet structure of the aluminium effect pigments is to be preserved in order to maintain the special properties. A bending or twisting of aluminium effect pigments leads to a dramatic loss of the particular specular properties.
For example, the components of the ink jet printing ink of the present invention can be gently mixed using an ultrasonic bath followed by magnetic stirring.
The ink jet printing ink of the present invention can be used with any ink jet printing ink technology. The ink jet printing ink composition of the invention can be applied to various ink jet recording systems. That is to say, it can be applied to various ink jet recording systems such as an electric field controlling system in which ink jet printing ink is ejected utilising electrostatic attraction, a drop-on-demand system (or a pressure pulse system) in which ink is ejected utilising driving pressure of a piezoelectric element, and further, a bubble or thermal system in which ink is ejected utilising pressure developed by forming bubbles and allowing them to grow by high heat.
Preferably, the ink jet printing ink of the present invention is used with the continuous ink jet—CIJ—or impulse or drop-on-demand—DOD—ink jet technology
The invention is further illustrated by the following non-limiting examples. It is to be understood that only preferred embodiments are shown and described. It will be manifest to those skilled in the art that certain changes, various modifications and rearrangements of the parts may be made without departing from the spirit and the scope of the underlying inventive concept and that the same is not limited to the particular forms herein shown and described except insofar as indicated in the scope of the appended claims.
Barrels of aluminium were continuously fed and molten into an industrial oven (Company Induga; capacity: 2.5 tons). In a pre-cooker the molten aluminium was held at a temperature of 720° C. Several injectors working after the injector principle were dipping into the melt. The aluminium melt was atomised vertically upstairs. The atomising gas was compressed to about 20 bar and heated up to about 700° C. The aluminium grid cooled down and solidified during the flight through inert gas (nitrogen). The aluminium grit was collected in a cyclone yielding a grit characterised by a d50 of 14-17 μm. During further segregation the grit was fed into a multi-cyclone yielding a grit with a d50-value of 2.3-˜2.8 μm. Finally a very fine grit was collected in a filter. This grit had a d10-value of 0.4 μm, a d50-value of 1.0-1.9 μm and a d90-value of 2.0-3.8 μm.
A barrel mill (length: 32 cm, width: 19 cm) was fed with 4 kg glass spheres (diameter: 2 mm), 75 g of the fine aluminium grid from a), 200 g white spirit and 3.75 g oleic acid. Subsequently, the mixture was milled for 15 h at a rotation rate of 58 rpm yielding very thin aluminium flakes. The product was separated by rinsing with mineral spirit and subsequently screened during a wet sieving process using a sieve with 25 μm mesh. The fines were essentially freed from the mineral spirit using a suction filter and finally the pigments were made into a paste with isopropanol in a laboratory mixer to a solid content of about 50% by weight.
This pigment paste is called Pigment A in the following.
Pigment A was diluted with isopropanol to a 10% dispersion followed by crushing in a pearl mill (DRAIS PML H/V SuperTex) using stainless steel spheres (diameter: 0.7-0.9 mm). The milling duration was 4 h.
After crushing the pigment dispersion had a particle size distribution (psd*) with the following characteristics: D10=1.1 μm; D50=3.2 μm; D90=6.3 μm, D99=9.5 μm and D100=12.0 μm.
* measured with laser granulometer Cilas 1064 (Cilas, France).
After crushing the pigment dispersion was subjected to a solvent exchange process with PM (methoxypropanol) yielding a 50% by weight paste in a mixture of isopropanol and methoxypropanol.
This pigment paste is called Pigment B in the following.
Starting Pigment: Commercially available PVD Aluminum dispersion: “Metalure W (Dispersion in isopropanol with solid content of 20% by weight) sold by Eckart GmbH & Co. KG.
Particle Size Distribution (PSD): D10=3 μm; D50=11.5 μm; D90=19.0 μm
This pigment dispersion is called Pigment C in the following.
The Metalure W (Pigment C) dispersion was diluted to a 10% dispersion with isopropanol. Than the dispersion was crushed in a pearl mill (DRAIS PML H/V SuperTex) using stainless steel spheres (diameter: 0.7-0.9 mm). An additive was added (DisperByk 106) to prevent agglomeration of the metal pigments. The milling duration was 4 h.
The crushed pigments had a Particle Size Distribution (PSD)* characterized by: D10=0.6 μm; D50=2.2 μm; D90=4.6 μm; D100=10 μm.
The crushed pigment dispersion was further subjected to a solvent exchange process yielding a 30% dispersion in PG (Propylglycol)
The samples were prepared for the SEM investigation as described below:
The aluminium effect pigments B and D were in each case present in the form of a paste or dispersion and are each first washed with acetone and then dried.
A resin customarily used in electron microscopy, for example TEMPFIX (Gerhard Neubauer Chemikalien, D-48031 Munster, Germany), is applied to a sample plate and heated to softening on a hotplate. Subsequently, the sample plate is taken from the hotplate and the respective aluminium powder is scattered onto the softened resin. The resin becomes solid again as a result of cooling and the scattered aluminium effect pigments—due to the interplay between adhesion and the force of gravity—can be prepared standing almost vertically and fixed to the sample plate. As a result, the pigments can readily be measured laterally in the electron microscope. In the measurement of the thickness, the azimuthal angle α of the pigment is estimated relative to a plane normal to the surface and allowed for when evaluating the thickness heff according to the formula:
h
eff
=h
meas/cos α.
The cumulative breakthrough curve was plotted from the heff values with the aid of the relative frequencies of occurrence. At least about 100 particles were counted. From these data the h10, h50 and h90 values from the average thickness distribution could be estimated. As a measure of the mean thickness the h50 value was taken.
The pigments A and C were analysed by X-ray diffraction. A powder diffractometer of Thermoelektron (produced in Ecoblens, Switzerland, type X'iron) was used. The X-ray source was a copper tube and the Kα1,2-line was used as excitation source. The instrument had a set up according to a Bragg-Brentano-geometry. The measurements lasted several hours.
The pigments were washed with some acetone and a few drops of the pigment-aceton-dispersion were placed on a rotary disk and were dried at room temperature. During this procedure the pigments oriented in an essentially parallel configuration referring to the underground.
In
The diffractogram of pigment C (
In
Such reflexes are characteristic for an aluminium effect pigment in the state of a plastic deformation and therefore they reflect the physical state of an aluminium effect pigment during the grinding process.
1= low molecular weight Polyamide resin SI-18-129 supplied by Arizona chemical Savannah, GA, USA;
The solvent blend is heated to 75° C. and the resin portion gradually added. The mixture is agitated with a medium speed mixer until all resin particles have been dissolved.
The finished resin solution is cooled down to room temperature and then filtered through a sub-micron media filter.
4 parts Pigment B are added slowly to 96 Parts of Ink Vehicle A and stirred continuously for 15 minutes with a medium speed disperser. The mixture is then subsequently treated in an ultrasonic bath for additional 5 minutes.
The finished ink jet printing ink is then filtered through a 20 μm mesh filter to remove undesired oversize particles or agglomerates created during the manufacturing process.
The finished ink jet printing ink is transferred into a reservoir which allows continuous agitation with a stirrer. The ink jet printing ink is fed into a print head architecture fitted with the necessary peripheral equipment needed to operate the print head. The jetting temperature is adjusted to reach the desired fluid viscosity range of 8-20 cP.
Ink vehicle preparation as described in Example 1
4 parts Pigment D are added to 96 parts of Ink Vehicle A and stirred continuously for 30 minutes with a high speed disperser.
The finished ink jet fluid is then filtered through a 20 μm mesh filter to remove undesired oversize particles or agglomerates created during the manufacturing process.
The mixture is then subsequently treated in an ultrasonic bath for additional 5 minutes to ensure maximum dispersion.
The finished ink jet printing ink is transferred into a reservoir which allows continuous agitation with a stirrer. The ink jet printing ink is fed into a print head architecture with fitted with the necessary peripheral equipment needed to operate the print head. The jetting temperature is adjusted to reach the desired fluid viscosity range of 8-20 cP.
Starting Pigment: Aluminium effect pigments obtained by atomisation and milling as described in pigment A. except that a paste in 2-Hydroxy-2-methyl-1-phenyl-1-propanone with a solid content of 50% by weight was prepared.
30 parts of the aluminium effect pigment paste described above are dispersed in 30 parts isopropanol using a medium shear disperser.
After sufficient dispersion the mixture is then transferred to high performance media mill and milled until the average particle size of the pigment dispersion reaches a d50 of 2.5 μm+/−0.5. The average particle size distribution (PSD)* was d10=1.0 μm; d50=2.5 μm; d90=4.73 μm, and d100=10.3 μm.
* measured with laser granulometer Cilas 1064 (Cilas, France).
The slurry is then removed from the mill and placed into a rotary evaporator in order to remove the isopropanol. Once the isopropanol is removed the solid content is readjusted to 50% again with additional 2-Hydroxy-2-methyl-1-phenyl-1-propanone (Pigment E).
3= Miramer M3130, trade mark of MIWON Commercial Co., Ltd.
4= Lucirin TPO, trade mark of BASF
5= Miramer M200, trade mark of MIWON Commercial Co., Ltd.
6= EFKA, trade mark of Ciba Specialty Chemicals
5 parts of TPO were added to 40 parts of HDODA and gently heated under stirring until the TPO has completely dissolved. The temperature should not rise higher than 70° C. The stirring is continued until the mixture cooled down to 50° C. and then the other ingredients of the UV vehicle were added.
The finished vehicle is then filtered through a sub-micron media filter.
6 parts Pigment E are added to 94 parts of Ink Vehicle C and stirred continuously for 30 minutes with a high speed disperser. The temperature shall not exceed 50° C. The finished warm ink jet printing ink is then filtered through a 20 μm mesh filter to remove undesired oversize particles or agglomerates created during the manufacturing process.
After cooling the mixture is then subsequently treated in an ultrasonic bath for additional 10 minutes to ensure maximum dispersion.
The finished ink jet printing ink is transferred into a reservoir which allows continuous agitation with a stirrer. The ink is fed into a print head architecture with fitted with the necessary peripheral equipment needed to operate the print head. The jetting temperature is adjusted to reach the desired fluid viscosity range of 8-20 cP.
Starting pigment: Pigment Preparation C as used in Comparative example 2, except that a 20% dispersion of Metalure Win 2-Hydroxy-2-methyl-1-phenyl-1-propanone as solvent was used.
30 parts of the pvd-aluminium pigment dispersion described above are dispersed in 30 parts isopropanol using a medium shear disperser.
After sufficient dispersion the mixture is then transferred to high performance media mill and milled until the average particle size of the pigment dispersion reaches a d50 of 2.5 μm+/−0.5.
The average particle size distribution (PSD)* is D10=0.9 μm; D50=2.5 μm; D90=4.4 μm, and D100=9.9 μm.
* measured with laser granulometer Cilas 1064 (Cilas, France).
The slurry is then removed from the mill and placed into a rotary evaporator in order to remove the isopropanol. Once the isopropanol is essentially removed the solid content is readjusted to 30% again with additional 2-Hydroxy-2-methyl-1-phenyl-1-propanone (Pigment E).
10 parts Pigment E are added to 90 parts of Ink Vehicle C and stirred continuously for 30 minutes with a high speed disperser. The temperature shall not exceed 50° C. The finished warm ink jet printing ink is then filtered through a 20 μm mesh filter to remove undesired oversize particles or agglomerates created during the manufacturing process.
After cooling the mixture is then subsequently treated in an ultrasonic bath for additional 10 minutes to ensure maximum dispersion.
The finished ink jet printing ink is transferred into a reservoir which allows continuous agitation with a stirrer. The ink jet printing ink is fed into a print head architecture with fitted with the necessary peripheral equipment needed to operate the print head. The jetting temperature is adjusted to reach the desired viscosity range of 8-20 cP.
7= Pioloform BN 18 is a trademark of Wacker Polymer Systems GmbH & Co. KG, Germany
The solvent blend is heated to 75° C. and the resin portion gradually added. The mixture is agitated with a medium speed mixer until all resin particles have been dissolved.
The finished resin solution is cooled down to room temperature and then filtered through a sub-micron media filter.
4 parts Pigment A are added to 96 parts of Ink Vehicle A and stirred continuously for 30 minutes with a high speed disperser.
After sufficient dispersion the mixture is then transferred to high performance media mill and milled until the average particle size of the pigment dispersion reaches 2.8 μm+/−0.5. The average particle size distribution (PSD*) was d10=1.3 μm; d50=2.8 μm d90=5.6 and d100=11 μm.
* measured with laser granulometer Cilas 1064 (Cilas, France).
The finished ink jet printing ink is then filtered through a 20 μm mesh filter to remove undesired oversize particles or agglomerates created during the manufacturing process.
The mixture is then subsequently treated in an ultrasonic bath for additional 5 minutes to ensure maximum dispersion.
The finished ink jet fluid is transferred into a reservoir which allows continuous agitation with a stirrer. The ink is fed into a print head architecture with fitted with the necessary peripheral equipment needed to operate the print head. The jetting temperature is adjusted to reach the desired fluid viscosity range of 8-20 cP.
Ink Vehicle Preparation Based on Polyvinyl Butyral Resin: Ink Vehicle B as in Example 5.
4 parts Pigment C are added to 96 parts of Ink Vehicle B and stirred continuously for 30 minutes with a high speed disperser.
After sufficient dispersion the mixture is then transferred to high performance media mill and milled until the average particle size of the pigment dispersion reaches 2.8 μm+/−0.5. The average particle size distribution (PSD*) was d10=1.0 μm; d50=2.8 μm d90=5.1 and d100=10 μm.
*measured with laser granulometer Cilas 1064 (Cilas, France).
The finished ink jet printing ink is then filtered through a 20 μm mesh filter to remove undesired oversize particles or agglomerates created during the manufacturing process.
The mixture is then subsequently treated in an ultrasonic bath for additional 5 minutes to ensure maximum dispersion.
The finished ink jet printing ink is transferred into a reservoir which allows continuous agitation with a stirrer. The ink is fed into a print head architecture with fitted with the necessary peripheral equipment needed to operate the print head. The jetting temperature is adjusted to reach the desired fluid viscosity range of 8-20 cP.
The prints obtained when using the ink jet printing ink of the present invention had an optical appearance comparable to prints when using PVD-pigments, containing ink jet printing inks.
| Number | Date | Country | Kind |
|---|---|---|---|
| 07013985.2 | Jul 2007 | DE | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/EP08/05834 | 7/17/2008 | WO | 00 | 1/29/2010 |
