text:
|Publication number
|Publication type
|Application number
|PCT number
|Publication date
|Aug 26, 2008
|Filing date
|Nov 11, 2002
|Priority date
|Nov 13, 2001
|Fee status
|Also published as
|Publication number
|Yonetatsu Matsumoto, Peggy Diane Studer, Yong Zhao, Stefan Barny, Ranjana Changanbhai Patel
|Original Assignee
|Huntsman Advanced Materials Americas Inc.
|Export Citation
|BiBTeX, EndNote, RefMan
|Patent Citations (35), Non-Patent Citations (1), Referenced by (5), Classifications (22), Legal Events (6)
|External Links: USPTO, USPTO Assignment, Espacenet
The present invention relates to production of films composed of thin layers using ink jet processes, that is to say layers with a thickness below 10 μm, more preferably less than 5 μm, especially 1 to 2 μm and it is contemplated making layers thinner than 0.1 μm. The term "layer" is intended to cover a single thickness of deposited material that forms, or is one of several layers that form, a film and the term "film" is intended to cover both free-standing films and films supported on a substrate.
It is known from the prior art to apply thin layers and films to a substrate using many techniques, for example printing and screen-printing. Inkjet and laser printers will also produce thin films of ink.
It is known to use jet printing techniques to form three dimensional objects; for example in U.S. Pat. Nos. 5,059,226 and 5,140,937 there is disclosed the direct jetting of curable materials onto a substrate. In WO 97/48557 and WO 99/19900, there is described a method of forming three dimensional features on a surface using successive drops of inkjetted material to build up a deposit. The deposit is generally built up vertically to produce three dimensional objects, for example Braille characters and multi-layer optical and electrical devices.
Plastic layers and films capable of controlling electromagnetic radiation are important. U.S. Pat. No. 6,024,455 demonstrates the application of such plastic materials. The method described involves the melt co-extrusion of two (isotropic) polymers to produce a laminate film made up of hundreds of thin, alternating, layers of the two polymers. The layers are 0.1 μm thick or thinner.
To achieve controlled final optical properties, it is essential that the layers are dimensionally precise in the micro and macro dimensions, as well as optically clear.
Careful choice of the polymers gives control of light absorption, transmittance and reflection. High speed film web formation from the method described in U.S. Pat. No. 6,024,455 is clearly possible. However, it is difficult with this method to vary, readily the macro, micro and nano properties within each layer and between each layer.
The alignment of liquid crystal phases is usually brought about by a polyamide alignment layer that is in contact with the liquid crystals; U.S. Pat. No. 5,539,074. U.S. Pat. No. 5,567,349 and U.S. Pat. No. 5 593 617 disclose forming the alignment layer by polymerisation under polarised light of a layer that has been applied by spin coating. EP 1 227 347 discloses a process of jet printing an alignment layer followed by depositing a layer of cross-linkable liquid crystal in a volatile diluent.
U.S. Pat. No. 5,855,836 discloses a hot-melt system, in which a solid formulation is heated until it melts and is jet dispensed in a desired pattern on to a substrate. It then cools and solidifies, and the sequence is repeated to build a 3-dimensional object. The formulation includes a reactive component which is finally activated to cure the object. Since wax like materials are used, the formed layers are opaque and this method forms thick layers, e.g. 50 μm. Another disadvantage here is that the materials available are extremely limited. A related process is described in U.S. Pat. No. 5,059,266 and U.S. Pat. No. 5,140,937 involving direct jetting of curable materials. This is used for forming shaped 3 dimensional objects and not films.
It is also known to use red, green and blue filters in liquid crystal displays, which are deposited by jetting suitable pigments contained in suitable binders and solvents into a well.
One common feature with the prior art techniques is that the dispensed droplets of liquid are directed onto specific locations on a substrate so that the droplets adhere to the substrate in substantially the precise areas that the droplets land in order that the resulting deposit produces an image or print with as high (fine) a resolution as possible. This makes it hard to form a layer of substantially uniform thickness. In addition, when resins or curable resins are jet deposited they are generally supported in a volatile diluent.
There is an emerging need to produce on demand thin films made up of resins having active functionality for various purposes. For example: some polymeric resins have an active property, which may for example be physical, chemical, optical, electro-optical, magnetic or electrical (e.g. birefringence/wave guiding effects from liquid crystalline resins), or light emitting effects from organic/inorganic light emitting resins, electrical conducting effects from conducting resins. In particular, the capability to vary and integrate a variety of such active resins, in their active state (i.e. as tracks or patterns or circuits), within a layerwise plastic frame around the active resin is contemplated to be important in the future. In particular forming the active resin from suitable monomeric, oligomeric (pre-polymers) resin mixtures would allow greater flexibility in controlling the final active properties required.
In the field of security printing, the art is looking for new methods of creating authenticating materials that cannot be reproduced unlawfully and yet can readily be verified. Having these security features embedded within thin layers of polymeric material(s) would yield unusual effects in addition to the effects from the layering structure
U.S. Pat. No. 5,945,463 and U.S. Pat. No. 6,277,929 disclose a photocurable resin composition comprising a high molecular weight resin and a curable diluent that can be extruded to form a thick layer approx. 1 mm thick that is then photocured.
According to the present invention, there is provided a method of forming a film made up of at least one layer of at least one resin, which method comprises directing droplets of a liquid composition comprising:
The term "continuous layer" is intended principally to cover the situation when adjacent droplet relics spread out and join together to form a thin uninterrupted layer but is not intended to exclude either layers with occasional voids (although void-free layers are preferred) or layers that are deliberately shaped to form the overall shape of the article, e.g. to form wells and channels in layers by not depositing droplets in selected areas of an otherwise uninterrupted layer. Rather the expression "continuous layer" is intended to exclude layers made up solely of discrete unconnected areas as, for example, in the case of half tone printing.
The term "resin" used herein means a monomer, an oligomer or a polymer having a weight average molecular weight in excess of 500 daltons. It may be reactive, i.e. capable of cross-linking or polymerising, or non-reactive. It preferably has a physical, chemical, optical, electro-optical, magnetic or electrical activity. It may have a molecular weight higher than 750, e.g. higher than 1,000 daltons.
The term "droplet relic" means the layer of liquid formed by a droplet after impact with the substrate.
The viscosity of the liquid is important to allow the droplet relics the spread out. The droplet compositions used should have a viscosity of less than 70 cps, e.g. 2 to 70, e.g. 2 to 30 cps at room temperature or jetting temperature, if different, to provide the integration of adjacent droplets and to be compatible with commonly-used heads for producing the jets (e.g. piezojet systems). More preferably, the viscosity is 10-40 cps as a reasonable balance between fast jetting by piezo action and good resolution. Too low a viscosity can lead to loss of resolution due to excessive image spread and splatter and too high a viscosity can lead to unstable jetting conditions.
The jetted liquid used in the droplets contains a resin that can have a viscosity of from 2 to over 500 cps at room temperature; for examples compounds having molecular weight greater than 500 daltons will yield compositions that are high viscosity or are solid, and thus not readily jettable. The use of a diluent in the droplet composition reduces the viscosity of the resin and so allows it to be used in a composition that can be jetted.
Volatile solvents have been used in the prior art to bring the viscosity of a composition down to a level that allows them to be jetted. Such solvents can be problematical as the volatile solvent can evaporate, leaving high viscosity resin in the jetting equipment, causing jet nozzle blocking and resulting in patchy coatings with no easy continuity between droplets and within a droplet. This is especially problematic when jetting at elevated temperatures, e.g. above 40� C., generally above 50� C. and typically at 60-85� C., since such temperatures lead to increasing solvent loss. On the other hand, such temperatures are desirable for compositions having a high proportion of high molecular weight resins (e.g. with molecular weights above 400 or 500 daltons). Compositions having volatile solvents should therefore ideally be jetted at room temperature, which in turn means that they can only have a low content (<10%) of the resin in order to bring the viscosity of the liquid composition being jetted into the range of viscosities that can be jetted. Forming good quality films from such compositions, having a low content of the functional active resin of interest, is difficult. More powerful solvents may be used, such as chlorinated solvents, which can dissolve higher amounts of the active resins: however there are growing concerns regarding the environmental impact of these solvents.
We have found that reactive solvents or diluents (the term "reactive" and "curable" are used synonymously in describing the present invention), that is to say solvents and diluents that are cured following jetting, help considerably in achieving the low viscosity necessary to achieve stable jetting conditions when using compositions containing substantial amounts of the active resin or resin mixtures. The use of such reactive diluents also assists in the merging of adjacent droplet relics as they spread out following the impact of the droplet with the substrate. Most importantly, by careful selection/matching of the reactive diluent with a curable or non-curable resin of interest (including mixtures thereof), films can be achieved solely by jetting techniques that retain the activity/property sought from the resin. Nozzle blocking is reduced or eliminated and better quality films can be achieved, compared to those from compositions containing volatile solvents. Environmentally damaging solvents can also be avoided in this way.
Preferably, the reactive diluent is present in the range 10 to 80%, e.g. 30 to 60% or 40 to 70% by weight, more preferably 40 to 60% by weight. Too low a content of the diluent (e.g. less than 10%) with high molecular weight resins (e.g. greater than 500 daltons) can result in high viscosity compositions (e.g. >70 cps at 80� C.), necessitating higher operational temperatures (>100� C.) for the ink jet printhead. This can affect the stability of the resin held at such elevated temperature prior to jetting and can lead to a greater tendency of printhead nozzles to become blocked. A high content of the reactive diluent (e.g. >80%) can yield very good jetting properties at reasonable temperatures (<100� C.): however the final film properties can be impaired by the presence of large amounts of cured diluent. Thus, clearly these are scale-able composition ratios (i.e. ratios that can be varied), depending on the final resin activity required, and the best jetting and curing properties.
Although the droplets must be liquid, they may also contain suspended solids.
If the final product is a self-supporting film, it can be removed from the base substrate after the article is formed; however, the article will generally be retained on the base substrate and is preferably firmly adhered to that substrate.
By producing a droplet relic with a diameter of at least 1.4 times the diameter of the droplet, spaces between adjacent droplets can be "filled in". This is achieved according to the present invention by a suitable choice of the rheology (principally of the viscosity and surface tension) of the droplets and the jetting conditions taken in combination with the surface properties of the substrate. Any substrate may be used in the present invention, e.g. glass, plastics, metal etc, that allows liquid droplet relics to spread out and join with adjacent droplet relics to form a continuous layer. If the base substrate does not have suitable surface properties to cause such spreading, then the surface may be treated or coated. Naturally, since multiple layers may be deposited, a preceding layer can form the substrate for the deposit of a subsequent layer and so the materials of each deposited layer should be chosen to provide a suitable surface for the spreading of the droplets applied in subsequent layers.
Another important rheological characteristic in order to achieve blending of adjacent droplets to provide a layer of substantially uniform thickness is the surface tension of the liquid forming the droplets which should be less than 70 dynes cm−1 preferably less than 40 dynes cm−1 and will generally be in the range of 20-70 dynes cm−1 since this allows the droplet to blend smoothly with adjacent droplets, lines or complex patterns, forming thus a smooth layer; this provides the possibility of forming complex micro-properties in the thin layer by using droplets of different composition to form the layers (both within any layer and between layers).
Preferably the surface tension of the substrate should be of the same order of magnitude as the droplets.
As it will be appreciated, a droplet must remain liquid on impact with the substrate and must remain liquid for a period of time to allow it to spread out to form the required layer. It has been found that jetting at higher temperatures (e.g. 50� C., more generally 70� C. or higher) of curable materials in reactive diluents yields surprisingly thin films having required final properties. However, it is within the scope of the present invention for some of the droplets to be composed of a liquid that will not to spread out in the manner described above in which case such droplets will be embedded in the formed layer. This might be useful, for example, to form a line of precisely located non-spreading droplets that makes up a light guide or an electrically conductive path.
The ratio between the diameter of the final droplet relic on the substrate and the diameter of the droplet in flight is preferably substantially greater than 1.4:1 and most preferably at least 5:1 and more preferably at least 10:1, e.g. 15:1 or 20:1 or above. By allowing the droplets to spread to form the droplet relic, the thickness of the deposited layer naturally decreases and it is to achieve thin films that the present invention uses a substantial spacing between the deposited droplets. For example, a droplet relic having a diameter of 73 μm (36.5 μm radius) formed by the spreading out of a droplet of 20 μm diameter (10 μm radius) from a jet having a nozzle diameter of 20 μm will have a thickness of 1 μm. If the droplet relic spreads out to a diameter of 103.2 μm (radius 51.6 μm), the relic will have a thickness of 0.5 μm.
The diameter of the droplet relics will often be difficult to measure when adjacent relics merge; if the relic caused by individual droplets is not possible to discern in the deposited layer, it can be calculated by reference to the thickness of the layer and the diameter of the original droplets using the formula:
r 2 �t=4/3s 3
where r is the radius of the droplet relic;
In order to provide for a substantial spread of the droplets, the droplets should be jetted from a jet head at high speeds. The speed will depend on the degree of spread required and the viscosity of the liquid used. The droplets may generally be dispensed by the jetting head at velocities preferably between 0.5 and 2 m/s. more preferably 1 to 1.8 m/s. If the speed of the droplets is too high, it may spread unevenly and splatter. Thus, the speed will have to be set by trial and error according to rheology of the droplets and the substrate or, more likely, the rheology of the droplet should be selected on the basis of the jetting speed of the jetting head used. It is found that reactive diluents specifically aid spreading of the high-speed jetted droplet without break-up into random, uneven shape and consequent non-continuous films. The reactive diluent ideally should have a surface tension, and chemical/physical characteristics matched to those of the principal resin or curable component.
The use of elevated jetting temperatures e.g. above 40� C., generally above 50� C. and typically at 60-120� C., reduces the viscosity of compositions and allows them to be jetted: Such conditions help further in spreading the jetted droplet on the substrate to achieve the required thin film and this is especially beneficial when the substrate is thermally insulating (e.g. plastics surfaces)
Thus, the spreading of the droplet relics is a scaleable feature depending on a number of features, including original droplet size, viscosity of composition at the best jet operational temperature, surface tension of the droplet and the substrate and the jetting speeds achievable under stable jet conditions.
The droplets may be jetted at high jet firing frequency, preferably 5 to 20 kHz line frequency and preferably 40-100 kHz individual jet frequency. Future development may achieve higher frequencies, e.g. 300kHz, and such speeds may lead to higher droplet velocities.
Curing should be achieved as soon as possible after the droplets have spread out to form the layer (the term "curing" includes the polymerisation, isomerization and/or cross linking of the molecules and the liquid). Preferably, the curing involves a condensation reaction, as described below.
It has been found that curable (reactive) diluents not only enable the low viscosity required for jetting to be attained, but also surprisingly helps with the intimate mixing and curing of adjacent droplets in the same layer, and also increases the adherence of one layer to an earlier deposited layer in a multi-layer system. This effect yields much tougher laminar composites due to better adhesion inter and intra droplet. This adherence effect probably involves wetting, swelling, and partial dissolving phenomena, such that jetted droplets spread and blend smoothly without the presence of fracture and defect-forming voids. Reactive diluents are advantageous as they will become incorporated into the finally formed layer or film and, in contrast the use of non-reactive volatile solvents, will not give rise to vapour emission and/or free liquid within the layer. Troublesome drying regimes to remove residual non-reactive solvents can thus be avoided.
As stated above, the diluent is preferably present in the range 10 to 80%, e.g. 30 to 60% or 50 to 70%, more preferably 40 to 60%. It makes little difference whether percentages are measured by volume or by weight. It is appreciated that these are scaleable properties depending on layer thickness, number of reactive sites in the components in the curable droplets, e.g. hydroxy or amino number, and swelling characteristics of the cured layers on addition of the diluent/curable fluid resin.
The construction of a laminar article layer-by-layer allows different liquids to be jetted during the construction of each layer or in different whole layers or multi-layers, thus affording differing and unique micro and macro properties of strength, toughness and flexibility. The different liquids may form, after deposition and curing, a visual or machine-readable image. Random or repeating programmed patterns may be formed to achieve smooth, void free final properties. Deliberately designed repeating voids maybe formed surrounded by a toughened resin matrix to yield complex membranes. The techniques described above can be used for example to produce, tracks or patterns that have different refractive index from the surrounding area, and thus be used for wave-guiding purposes. The patterns may be disposed flat in one layer or be 3-dimensionally disposed over several layers.
Because each droplet is individually jetted, it is possible to jet the droplets from one or more different jetting heads and the droplets jetted from these heads may be the same or different. By applying droplets of differing compositions in any layer, it is possible to vary the layer pixel to pixel (i.e. droplet to droplet), line to line and/or layer to layer to build up a desired pattern of materials in thin layers. Thus thin complex laminar articles can be formed by jet printing techniques. When jetting different materials it is not necessary for the deposit thickness of each material in a layer to be the same. For example, a deposit making up part of a lens could have a thickness of 2 μm while the surrounding material could be made up of a much thinner layer, e.g. less than 1 μm thick.
In addition, two or more different liquids that together form the components of a curable resin may be jetted or sprayed simultaneously from adjacent jetting or spraying printheads such that the liquids combine either in flight or on the surface of the substrate. The components can also be jetted sequentially onto the same site to provide the curable composition. This process is particularly useful for jetting traditional two component adhesive resin mixtures, which have to be held separately until used.
The nozzle system employed in the present invention is preferably equivalent or identical to that used in inkjet printing systems, preferably piezo inkjet systems. Preferably, the size of the nozzle openings is as small as possible; with currently available inkjet systems, such openings are in the range of 10 to 50 cm. The size of the applied droplets may correspond to the size of the nozzle opening, i.e. in the range 10 to 50 μm, or may be bigger (80-100 microns): the nozzle openings may become in smaller in the future, e.g. about 1 μm or smaller, even as small as a few hundred nanometres, thus allowing correspondingly sized droplets to be applied.
Alternatively, the droplets can be in the form of so-called "microsprays" which are formed from droplets subjected to acoustic waves which break up the droplets into even finer droplets, see for example U.S. Pat. No. 6,182,907 (Mitsubishi Corporation) and U.S. Pat. No. 6,309,047 (Xerox Corporation). What is critical is that the jetted droplets and the droplets of the micro-spray should be directed at specific target locations on the substrate such that the droplets merge to form a continuous layer.
The process may include the step of varying the number of pixel drops, that is to say the number of droplets applied to each location and/or varying the volume of the applied liquid per pixel, per line applied and/or per layer, in order to achieve variable properties in the article. Another following jet may cover same previously addressed area.
Highly precise and complex layers can be fabricated with fine detail. Different fluids/components can be dispensed pixel-wise, line wise and layer wise within these address schemes, with further differentiation possible through clustering in the pixels, lines and layers in a random or configured manner, to provide even more material property variation. It is thus possible to apply, in a single pixel, several individual droplets (i.e. a cluster of droplets) to provide, for example, an optical lens by making the individual droplets of materials of different refractive index. Alternatively fractal patterns can be formed in an individual pixel. These patterns are part of the whole film layer.
By combining the compositions with programmable piezo (array) printhead technology, it is possible to vary micro-material properties of the formed laminar coating, to achieve strength, texture and variable macro properties. As pixel addressability with piezo printheads can be as fine as 20 μm spots, the resulting resolution can match the resolution achievable using laser address systems. This addressability will go even higher with the use of nanojet technology delivering picoliter volumes of liquid, or less.
The process lends itself very conveniently to the production of films from a digital representation held by a computer, and is particularly suitable for use with CAD systems. Thus, a film can be designed using CAD and light ray tracing software, the digital information can be converted to a series of laminae in digital form and the digital representation of the laminae can be used to control the delivery of the applied liquid sequentially on to successive layers of the deposited in order to reproduce the film. The techniques can be used for rapid prototyping and even rapid manufacture of specialist single or multi layer films. Thus the pattern of pixel-producing droplets in each layer can be designed using standard CAD design techniques incorporating ray tracing software (which can define detail within each pixel, e.g. refractive index) and the CAD program can be used for controlling printer heads in a manner that is known.
It is mentioned above that an image can be formed by applying different liquid compositions. Eye- and machine- readable images can also be formed by building pixels of a light modifying layer to a greater thickness than the surrounding areas either by making the film thicker in the desired location by increasing the density of the droplet deposits (i.e. depositing more droplets per unit area of the substrate) or by applying more than one droplet to a given pixel and/or by varying the compositions of the liquids used across the layer. The light modifying material may be for example a pigment or a dye or, as described below, a liquid crystal.
The whole process of forming single thin films or complex multi layer films can be done "web to web roll" as, for example in conventional rotogravure, with the jetting occurring in line at high speed. The different fluids can be dispensed one after another in a serial manner, as the substrate web moves past the printheads dispensing the different fluids. The web may be suitably primed or surface treated, in-line or off-line, to the manufacturing process.
In one embodiment, the substrate remains stationary and the jetting nozzles track across it. However, the nozzles may be held fixed and the substrate moved. In either case, the process can be applied simultaneously to a number of substrates by forming the layers on respective substrates and either moving the nozzles across the several substrates or moving the several substrates relative to the nozzles, which is particularly useful in forming large displays.
Polymers, oligomers, and/or monomers may be used as the resin in the jetted compositions. The resin may itself be curable.
The curable resins can involve compounds which can undergo condensation reactions. These reactions can be triggered either by thermosetting reactions such as epoxy/amine or isocyanate/polyol/amine etc., or by electromagnetically triggered cationic systems such as cyclic ether compounds (epoxy, oxetane, cycloaliphatic epoxy, etc), cyclic lactones, cyclic acetal compounds, cyclic thioether compounds, spiroorthoester compounds and vinyl compounds, plus cationic photo-initiator salts (e.g. diazonium, sulfonium, iodonium or ferrocenium), or radically cured systems such as acrylates, methacrylates, allyl urethane, urethane acrylates, epoxy-acrylates, unsaturated polyester compounds, plus radical photoinitiators (e.g. acetophenone series, benzion series, benzophenone series, thioxanthone series, phosphine oxides, alkyl borates, alkyl triphenyl borates, iodonium salts). Alternatively, they may undergo photo-dimerisation or a Diels Alder reaction, e.g. cinnamates.
In the thermosetting case, the reactants can be separately included in two liquids such that on jetting, the two components react to form the condensation product. In the photosetting case, the electromagnetic radiation can be administered imagewise in synchronisation with the liquid jet activation, pixel-by-pixel, line-by-line or a whole layer may be irradiated simultaneously. Suitable initiators should be employed.
Polymers of the type disclosed in U.S. Pat. No. 6,277,929 can also be used in the present invention.
Preferably, the curable diluent include ring opening compounds, e.g. epoxy, polyepoxy, thiiranes, aziridines, oxetanes, cyclic lactones, cyclic acetals; addition compounds such as vinyl-ethers; polymerising compounds such as ethylenic and (meth) acrylate, hydroxyacrylates, urethane acrylates and polyacrylates; hybrid compounds,. such as epoxy-ac)tlates, isocyanurate-epoxy, epoxy-silane advanced resins and polyurethane silanes; siloxanes containing ring opening or polymerising groups; and condensing resins such as isocyanates. The resin which is dissolved in the curable diluent may be a single component having similar reactive groups as the diluent, or may be a polymer made by polymerising the reactive diluent . The curable diluent may be a hybrid composition of above active components. The term "hybrid" is defined as containing compounds with two different reactive groups e.g. epoxy and acrylic or other functionalities, either in the same compound or in different compounds in the same composition. The resin layers may additionally contain additives such as fillers, reactive or not, organic fillers (e.g. core shell), inorganic fillers (glass spheres/fibres/flakes, alumina, silica, calcium carbonate etc), pigments, dyes, plasticisers, or pore formers etc. Nano particles may be dispersed in the jet fluids to achieve strengthening or optical effects.
In the preferred systems, the reactive diluent is a photopolymerisable vinyl type monomer, or an epoxy type monomer. The choice is dependent on the type of the resin being used in the composition: acrylate diluents may be used for acrylic resins and epoxide diluents for polyethers or photosensitive epoxy systems, and mixtures of acrylics and epoxide diluents for mixed resin or mixed photosensitive systems.
Representative examples of the photopolymerisable vinyl type monomer are hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate, 2-hydroxybutyl acrylate, etc.; mono- or diacrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, propylene glycol, etc.; acrylamides such as N,N-dimethylacrylamide, N-methylolacrylamide, etc.; aminoalk-yl acrylates such as N,N-dimethylaminoethyl acrylate, etc.; polyvalent acrylates of polyvalent alcohols or ethylene oxide or propylene oxide adducts thereof such as hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate, etc.; phenoxy acrylate, bisphenol A diacrylate and acrylates of ethylene oxide or propylene oxide adducts of these phenols, etc.; acrylates of glycidyl ethers such as glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, triglycidyl isocyanurate etc.; and melamine acrylate, and/or methacrylates corresponding to the above acrylates, etc.
Epoxy diluents include monoepoxides, such as n-butyl glycidyl ether, iso-octyl glycidyl ether, phenyl glycidylether, cresyl glycidyl ethers, glycidyl esters of mixed tertialy, aliphatic, monocarboxylicacids, glycidyl acrylate and glycidyl methacrylate; or di-epoxides such as diglycidyl-butane-diol, UVCUBE1500 bis cycloaliphatic epoxide; or oxetanes, furans; or vinyl ethers etc. if possible.
The diluents, e.g. acrylates, epoxides and hybrids, are preferable di-functional, as difunctionality can give useful crosslinking and film forming properties. However mixtures of mono- with di- and/or greater functionality may also be used.
The curable diluent preferably has a weight average molecular weight of less than 300 daltons.
The diluents as described above are used singly or as a mixture of two or more of them. The suitable range of an amount to be used is 20 to 300 parts by weight, preferably 30 to 150 parts by weight based on 100 parts by weight of the active resin compositions.
As indicated above, it may be that a first droplet is jetted and a second droplet is delivered over the first droplet as a trigger to cure the first droplet. Preferably, the active component in the second droplet may be a radiation photosensitive radical and/or cationic photoinitiator and/or a catalyst. The active component in the second liquid may comprise nano particles, either directly reactive via surface groups (such as epoxy, acrylic, hydroxy, amino etc) or contained as dispersions in an active component.
If the curable material in the droplets is photocurable, irradiation could take place pixel by pixel, line by line or layer by layer, and/or after several layers have been formed, and/or after all the layers have been formed. Preferably, electromagnetic radiation is employed. Suitable sources include UV light, microwave radiation, visible light, laser beams, and light emitting diode arrays, and other similar sources. Light management could involve light valve array technologies. The present invention can be applied to build up a thick deposit of resin composed of many layers. By curing each layer as it is deposited, it is possible to achieve superior properties resulting form homogeneous curing as compared to the situation when all the layers are cured simultaneously and as compared to curing a thick deposit of resin formed in one operation.
The irradiation maybe synchronised to the absorption and reactivity rates of the jet-applied liquid onto the previous cured layer material. This may involve the application of the electromagnetic irradiation after the liquid has ingressed to a degree into the previously formed thin layer, or the irradiation may be during the flight of the applied fluid from the jet device to the surface of the deposited previous cured layer. When forming alignment layers for liquid crystals (see below), the layer should also be irradiated following formation of the layer, to cure, e.g. by dimerisation, the photoactive groups of the linear photopolymerisable polymer (LPP), thereby forming a layer that orientates the liquid crystal molecules applied in a further step.
It will be appreciated that by using the techniques of the present invention, it is possible to build up three dimensional articles or films out of successive layers; especially in the form of laminated blocks and items with complex shapes. By varying the characteristics across the layers including layer thickness, as they are formed, optionally on a micro-scale, it is possible to instil desired a functionality in the finished article. This functionality can take many forms: many interesting proposals have been made for making optical, electro-optical and electrical components out of resins. Although the precise details of such devices do not form part of this invention, the present invention does allow a simple and effective way of making such components. Some details are nevertheless given below. In the case of optical components, the invention enables the optical properties of a component to be varied layer by layer and across each layer, and each layer can be of varying thickness and refractive index, thereby enabling complex optical multi-layer films to be produced.
Complex layer structured articles may be realised, having integrated complex shapes with laminar film blocks having optical, electro-optical, magnetic etc patterns, as well as macro-mechanical, colour and texture properties.
It is possible to build the component onto a substrate, which is then retained as part of the final finished article. Such a substrate might be a glass or a plastics sheet which could for example form part of an optical component.
The optical properties of the layers may be varied both within each layer and between layers, for example selective wavelength refractive/transmissive properties can be produced in random or patterned way. Furthermore, the layers can be of different thicknesses, involve different materials (thus varying the refractive index from layer to layer, in a random or patterned way) and each layer can itself be formed with a prescribed topography by varying its thickness over its extent. The topography between and in layers can be patterned, thus achieving optical effects. The patterns can be planar (i.e. within a layer) or can be 3-dimensionally disposed circuits within the laminar structure. Areas within a multi layer film maybe transparent or opaque. It will also be appreciated that, using the techniques of the present invention, it will be possible to produce so-called "smart cards" which might include high information content images, e.g. a hologram, a photograph (which could be digitally ink-jetted and coloured) or a watermark-like feature (which could be UV fluorescent). The laminar structure and the adhesive nature of the inter-laminar relationship leads to a considerable degree of security. This means that the structure can be used in situations where high-security printing is used, e.g. in authenticating software and other licensed copyright works, such as music and video carriers, or in security documents, security passes, identity cards, banking cards etc..
One important aspect of the present invention is its application to the deposition of liquid crystal alignment layers (so-called LPP (linear photopolymerisable polymer), which may be acrylic-based) and the subsequent deposition of a liquid crystal monomer layer (so-called LCM) that, on curing, forms liquid crystals (so-called LCP (liquid crystalline polymer)). Suitable materials are described in U.S. Pat. Nos. 5,539,074; 5,567,349 and 5,593,617 and available from the Applicant. Liquid crystals demonstrate birefringence, which occurs because the plane of polarised light is twisted as it passes though a layer of aligned liquid crystals. Birefringence can be seen by placing a liquid crystal layer between a pair of cross polarised filters. As the liquid crystal layer is rotated relative to the polarised filters, so the light transmitted through the sandwich formed by the polarisers and the liquid crystal layer changes in intensity. In addition, the colour of the transmitted light vary depending on the thickness of the liquid crystal layer. For example with a liquid crystal system available from the Applicant, CB 483, Staralign 2130 having a delta n value of 0.117, it is possible to alter the colour of light transmitted when placed between cross-polarisers by altering the thickness of an LCP layer as follows:
Thickness of liquid
crystal layer (μm)
The brightness of the light from the LCP can also be varied by a cholesteric LCP. The cholesteric layer reflects a narrow band of light and the efficiency of the reflection is dependent on the thickness of the LCP layer. Thus the ability of the present invention to deposit a thin layer of LCP can be used to tailor the colour and brightness of the light transmitted by the layer. By varying the thickness of the LCP and/or the orientation of the liquid crystals between delimited areas or domains within a layer (such that, within each area or domain, the layer is homogeneous and of uniform thickness), and optionally also building up several layers in each domain, a highly complex image can be formed reproducibly by an authorised manufacturer that is very difficult for any unauthorised person to replicate. The image may be machine readable. A film built up in this way can include artefacts deposited by the method of the present invention, e.g. a waveguide. disposed within a layer or three dimensionally within the surrounding layered structure in a seamless manner that makes unauthorised reproduction even harder to achieve. This means that an LCP formed in accordance with the present invention has special application for high security and smart cards and as a means of authentication of, for example, credit/debit cards, documents, certificates, software and audio products, as discussed above. Instead of LCPs, other resins, e.g. resins containing anti-counterfeit dyes, can be used for security and validation applications.
In the case of liquid crystalline polymers, the preferred diluent is an acrylate or methacrylate that preferably contains one or more aromatic ring, preferably a benzene ring, e.g. butanediol diacrylate, hexanediol diacrylate, isobornyl acrylate, phthalic acid mono hydroxyethyl acrylate, N-vinyl pyrrorydinone, tetrahydrofurfuryl acrylate, methyl methacrylate, propyleneglycol diacrylate, trietlyleneglycol acrylate, neopentylglycol diacrylate, cyclohexyl acrylate, lauryl acrylate, most preferably, benzyl acrylate and phenoxyethyl acrylates. It is preferred that the curable diluent is mono-functional.
Other specific applications for the present invention include:
Referring initially to
The invention may be carried into practice in various ways and some embodiments will now be described by way of illustration in the following Examples.
A Jetlab ink jet printer (obtainable from Microfab Technologies Ltd, Texas, USA) was used for jetting droplets onto a substrate. This equipment can precisely control the volume of jet droplet and printing pattern. The printer incorporates a piezo printhead. the temperature of which can be controlled, which enables the jetting of fluids at elevated temperatures that have an excessively high viscosity at room temperature.
The jet performance is dependent on physical properties of fluids such as viscosity and surface tension. Therefore, investigation of jet performances as a function of viscosity and surface tension was undertaken to find appropriate jet conditions for various fluids. A number of low-viscosity acyl ate monomers were selected due to their fast UV cure as well as good physical properties and jetted onto a substrate at room temperature.
Voltage (V)
Genomer 1230
Genomer 1223
Gray Valley,
Gray Valley, SR272
Gray Valley, SR508
The monomers referred to in Table 1 are:
The acrylates in Table 1 were sensitised to UV curing by using 3 wt % of IRGACURE 184 photoinitiator, obtainable from Ciba Specialty Chemicals in Basel, Switzerland.
The viscosities (measured using a Brookfield Digital Viscometer, Model HBTDCP, Spin Rate 100 rpm at room temperature) and dwell voltages for optimum jetting are listed in Table 1. Generally, it can be seen that lower viscosity fluids need lower dwell voltage for optimum jetting.
A number of droplets were directed at the same target area on a substrate at room temperature and the extent of spread of the resulting spot was measured on a video screen connected a digital (CCD) camera.
Each droplet had an in-flight diameter of approximately 50 μm. The number of droplets deposited on the spot was varied and the size of the spot (after spreading) was plotted against the number of droplets used to form the spot. The results for the jetting of various monomers onto a glass substrate are shown in
As can be seen, the spot size increases with the number of droplets but not, however, as a linear relationship. The degree of increase is reduced as the number of droplets increases.
PONPGDA droplets were jetted onto the same target on a glass slide and a polycarbonate disc. The results are shown in
As can be seen, the spot size of jet fluids on the polycarbonate substrate is much larger than that on the glass slide, because PONPGDA is more compatible at a molecular level with polycarbonate than with the glass slide. Thus, the hydrocarbon character of polycarbonate leads to better spreading.
Three fluids: PONPGDA, DPGDA and HDDA were jetted at room temperature onto the same target area of a glass slide coated with a thin film of UV-cured TPGDA. Of the three fluids, the surface tension of PONPGDA is lowest and is lower than that of the substrate TPGDA film. The spot size of PONPGDA is very large and a ring is formed, making it difficult to form a continuous film. The results from the other two fluids are shown in
Thus it can be seen:
Jetting a fluid (PONPGDA) whose surface tension is lower than that of substrate leads to poor film formation.
Fluid (HDDA) with higher surface tension than the substrate-forms a smaller spot size, which is not favourable to make very thin films.
Large spot size and good film formation is obtained from DPGDA which possesses approximately the same value of surface tension as the substrate (TPGDA).
A number of fluids were applied at room temperature by the ink jet printer described in Example 1 over an area of 1 cm�0.5 cm. The film thickness was controlled by optimising the number of droplets and the distance between adjacent spots. Normally, a small number of droplets and a larger distance between droplets is favourable to make a thin film. The in-flight diameter of each drop was 50 cm.
1. HDDA (see Example 1 for abbreviations) was applied onto a glass slide. Very good film formation was observed.
2. PONPGDA was applied on a polycarbonate disc. The fluid spread very well on the substrate and a thin film was formed. However, a slight corrosion of the substrate surface was observed after several hours.
3. DPGDA on TPGDA-coated glass slide. Good film formation and thin films (approximately 4 μm in thickness) were obtained. This shows possibilities to make multi-layer thin films.
A linear photopolarisable polymer (LPP) type F301. obtainable from Vantico A.G., Basel, Switzerland was dissolved in various solvents at concentrations of 0.3-1% (w/w). Low vapour pressure solvents or mixtures of such solvents were used to ensure a good film formation from droplets deposited on a substrate. Such solvents include cyclohexanone, cyclopentanone, ethyl-lactate, etc.. Other solvents that can be used to modify physical properties of polymer solution include methyl ethyl ketone (MEK), isopropanol and methyl isobutyl ketone. Room temperature jetting was used in order to avoid jet clogging due to solvent evaporation: under this circumstance, only low solid content in the solvents could be tolerated.
A diluted LPP solution was jetted onto a glass substrate by a piezo inkjet system as described in Example 1. The droplets were directed at an array of locations on the substrate by stepping the location of the head between droplets (see Table 2 for details of the step sizes). The droplet size varied from 100 to 500 μm, depending on wetting behaviour of droplets on the substrate and jetting conditions.
The dwell volts and printhead step properties were kept in a similar range. The interval distance between each droplet was set at a range of 50 to 500 μm, according to droplet size.
After the solvents were evaporated, a dry LPP film was formed. By using the above technique, a film with a thickness less than 1 μm was obtained. The shape of thin film can also be controlled. The results are set out in Table 2. It was relatively difficult to achieve good film formation from solvent compositions.
Step Size
of LPP F-
0.05 � 0.1
Uneven film because
evaporation of
cyclopentanone was not
slow enough.
0.1 � 0.1
Better film formation, but
not very uniform, because
relatively low dissolvability
of cyclohexanone.
0.1 � 0.1
Phase separation occurred
during film drying.
0.1 � 0.1
Good wetting ability and
film formation, however, pin
holes in the film due to
phase separation of solvents
during evaporation.
0.8 � 0.8
Uniform thin film with
thickness less than 1 μm.
In the following Examples 6 to 11, the following raw materials were used:
Material name
Curable Liquid Crystalline Acrylic
Vantico AG
Monomer Formulated in
Benzyl acrylate
Osaka Organic
Irgacure 369 photoinitiator
Ciba Specialty
Linearly Polymerisable Polymer
LPP StarAlign
Vantico AG
2110 ™
In Examples 6-11, the various formulations were prepared by mixing specified components under yellow light at room temperature until a homogeneous composition is obtained, as detailed below.
The compositions used in Examples 6 to 11 are set out in Table 4 below, together with the physical properties of the various liquids (viscosities and surface tensions, since jet performances are strongly influenced by such properties); all parts are by weight. The formulations are all stored at room temperature in brown bottles to avoid exposure to UV-visible light.
TABLE 4 Composition of the Formulations Material Examples 6, 7 Examples 8, 9 Examples 10, 11 OPALVA 2140 40.1 59.5 5.00 (Powder) Benzyl acrylate 59.3 39.9 0 (reactive solvent) Irgacure 369 0.6 0.6 0 Cyclopentanone 0 0 95 (non-reactive solvent) Total 100 100 100 % mass Viscosity (mPas) 21 67 3 Surface tension 37 37 28 (dynes/cm)
Two types of substrates were used in Examples 6-11:
In Example 6-11, a JetLab Printer (MicroFab Technologies Inc., Plano, Tex.) was used for jetting droplets of the compositions onto the above-described substrates. The volume of the jet droplet, drop density and printing patterns can be precisely controlled. The temperatures enabling stable jetting of the formulations are given in the Table 5 below. The objective was to obtain continuous films using the formulations described in Table 4 and using various drop densities at the best jetting conditions, as recorded in Table 5.
As will be seen, the substrate had a strong influence on the final film characteristics (See Table 5 below). Spreading of LCM (liquid crystalline monomer) formulations is poor on the plain glass substrate, i.e. not coated with any organic material, whereas thin films (less than 10 μm) were obtained on LPP coated glass plates.
After deposition, the samples were photochemically cured: before curing, the samples were heated at 60� C. in order to remove volatile materials. Heating also helps to orient the LCP layer (when LPP alignment layers are used, the orientation of the LCP layer is determined by the LPP layer). The LCP layers are then cured under nitrogen atmosphere using unpolarised, broad band either at regular UV exposure (e.g. high pressure mercury lamp, 500 mJ/cm2 at 365 nm) or at lower level exposure using "Black light", Model UVL-21, with a 4W UV lamp, from UVP Inc..
After curing, the layer thicknesses are measured with Alpha-Step� 500 Surface Profiler.
OPALVA 2140 was obtained as a powder by evaporating the cyclopentanone solvent * from the commercial product OPALVA 2140 CP 10. The powder comprises a liquid crystalline acrylic monomer, UV initiator, and stabiliser. 8.07 g of OPALVA 2140 powder and 101 mg of Irgacure 369 are mixed with 11.93 g of benzyl acrylate at room temperature and the mixture is stirred until a clear, slightly yellow homogeneous mixture is formed. The liquid formulation has a viscosity of 21 inPas at 25� C. and contains 40.1% active liquid crystalline monomer powder, 59.3% reactive solvent/diluent benzyl acrylate and 0.6% radical initiator Irgacure 369.
Single lines of the above composition were jetted onto the glass substrate, according to the conditions of Table 5. Thick lines (28 μm wide) were deposited, with little spreading (as compared to Example 7 below where the substrate was the LPP coated glass) to produce thin layers. The layers were cured, as set out above.
Birefringence (a characteristic of the liquid crystal material, seen as a bright line under crossed polarizers) appears fairly rapidly (1 to 5 min) after depositing. However, when continuous films are jetted, birefringence is recovered more slowly (>1 hour), especially for the thick films (>15 microns), deposited on untreated glass. The thicker the film, the slower is the birefringence recovery.
Benzyl acrylate curable diluent appears initially to destroy the liquid crystal organization of the LCP molecules. Careful curing restores the self organisation of the liquid crystalline materials. Curing with low UV energies seems to help the molecules to align. High intensity UV energies, on the other hand, cure rapidly the LCPs, such that the LC molecules cannot move, and, as a result, the optical display does not show any birefringence and the jetted film appears completely black under crossed polarizers even by rotating the sample.
Example 7 was identical to Example 6 except that LPP coated glass plates produced as set out in Example 5 were used instead of simple glass plates.
Thin, continuous films of 5.5 to 6 micron film thickness, of the composition described in Example 6, were obtained readily for drop densities higher than 5/mm, jetted at 60� C. This is in contrast to jetting directly on glass (Example 6). Thus the LPP layer enables greater spreading [4 times that of Example 6] of the deposited droplet, with better merging of adjacent droplets.
Non-continuous films were obtained for a drop density of 3 drops/mm or less.
The alignment of the LCP layer is facilitated by the LPP alignment layer and a film is readily obtained, showing bright / dark contrast when a jetted 2 layered composite film (i.e. a film formed by a LPP alignment layer and a LCP layer) is rotated under crossed polarisers. The LCP alignment is brought about by the LPP layer, and is best achieved for LCP layers thinner than 10 microns.
When thick LCP films (typically >15 μm obtained using drop densities of >20/mm) are jetted, no difference is noted between LPP-coated and non-coated glass plates: under these conditions, the LPP layer looses its role of alignment layer.
It is surprising that benzyl acrylate acting as a reactive diluent, facilitates good film formation, and, under certain controlled conditions (layer thickness, UV exposure conditions), does not interfere in the attainment of the required optical activity in the jetted OPALVA curable liquid crystalline monomer.
This example represents a film composed of 2 jetted layers (i.e. a LPP alignment layer and a LCP layer), each of thickness less than 10 microns and comprising different components and compositions.
11.98 g of OPALVA 2140 powder and 120 mg of Irgacure 369 are mixed with 8.02 g of benzyl acrylate at room temperature and the mixture is stirred until a clear homogeneous, slightly yellow mixture is formed. The liquid formulation has a viscosity of 67 mPas at 25� C. and contains 59.5% liquid crystalline monomer mixture, 0.6% radical initiator Irgacure 369, and 39.9% reactive diluent.
The composition was deposited as in Example 7 on an LPP coated plate, except that jetting was conducted at higher temperatures (75� C. instead of 60� C.), to account for the higher content of the OPALVA 2140 and higher resultant viscosity. This higher jetting temperature condition resulted in thinner, more homogenous films of 2.9 micron or 3.5 micron thickness respectively for Examples 8, 9. Coating thickness was assessed after full curing of the jetted film under nitrogen. The essential difference between Examples 8 and 9 is the greater spacing between the lines of the deposit in Example 8 as compared to Example 9 (see table 5).
Continuous films are obtained for drop density higher than 10/mm with appropriate line spacing. Birefringence recovery needs more time than for Examples 6, and 7, due to higher viscosity.
10 g of OPALVA 2140 CP 10 are mixed with 10 g of cyclopentanone. A clear and slightly yellow mixture is obtained. The liquid formulation has a low viscosity of 3 mPas at 25� C.
The composition was deposited as in Example 6 and 7 on and LPP coated plates at a droplet density of 10 (Example 10) and 20 (Example 11) droplets/mm. In the case of this non-reactive solvent-based formulation, thin films of 2.2 micron were obtained, but film homogeneity was poor, even at high drop densities (20/mm). There is patchy film formation. Thus the formulations of Examples 6, 7, 8, 9 containing the reactive diluent benzyl acrylate, yield surprisingly thin, good quality films, with retention of optical properties. The optical contrast for Examples 10 and 11 is also much weaker than observed for the corresponding benzyl acrylate-based formulations (Examples 6, 7 ,8, 9). Contrary to the time-effect of appearance of the optical effects in Examples 6, 7, 8 and 9, there were no time-effect on the optical performances in Examples 10, 11. However the quality of the deposits was poor.
The process conditions and results of Examples 6-11 are set out in Table 5
After the pattern B (See the Table 5 above) corresponding to Example 9 (drop density of 10/mm) is cured under low UV energy, lines of Formulation DPGDA (Acrylate formulation of Example 4) are jetted in-between the LCP 5 lines (Drop density=10 drops/mm). The pattern is completely cured under 500 mJ/cm2 at 365 nm.
In the following Examples 13 to 17, the compositions set out in Table 6 were used:
LCP IPE053: Liquid crystal polymer from OPAL, Vantico, Switzerland
SR339: Phenoxyethyl acrylate from Sartomer, i.e. a curable diluent
Cyclopentanone: Solvent from Aldrich, i.e. a non-curable diluent
Byk307: Silicone surface additive from Byk Chemie
In Examples 13 to 17, LCP fluids were jetted onto a glass plate coated with an optically aligned LPP coating from Example 5 using a single jet head supplied by Microfab Technologies Inc. Two representative fluids were jetted, which are Example 13, 47% LCP in a reactive diluent (SR339), and Example 16, 32% LCP in a mixture of reactive diluent SR399 and a non-reactive solvent (cyclopentanone). The printed LCP patterns were finally cured with a UV source (Fusion F450, 120W/cm2), using two passes at a speed of 10 m/min. The results are given in Table 7.
Per mm
thin film
Thus best films are achieved with the reactive diluent SR399 with droplets >20 drops per mm. Lower droplet rate per mm resulted in discontinuous films.
Fluids shown in Table 4 were jetted onto a LPP coated glass plate and cured by a UV source and the birefringence effect (optical anisotropy) was observed. Birefringence (LC effect) occurred in all the samples, even in Example 17, with only 30% LCP in the reactive diluent.
Example 13 (45% LCP ) composition was jetted onto a LPP coated glass plate, produced according to Example 5 and cured by TV radiation. Then the composition of Example 17 (30% LCP) was jetted on part of the Example 13 layer and then cured by UV. The birefringence effect was different between the Example 13 single layer and Example 13/17 multi-layers.
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|Citing Patent
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|U.S. Classification
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|International Classification
|Cooperative Classification
|European Classification
|Feb 24, 2005
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2 face robbery, stabbing chargesFebruary 04,20132 face robbery,
stabbing charges
BRATTLEBORO Two men are expected to answer charges today after allegedly stabbing and robbing a juvenile male.
Friday, police responded to Brattleboro Memorial Hospital after receiving a report of a youth who had been admitted with a stab wound after being robbed by two men near Elm St, according to police. Police described the juveniles injury as potentially serious, but minor.
Police said they learned one man had brandished a knife during the assault. An investigation led to the arrest of Anthony Gonzalez, 32, of Brattleboro, and Charles Trowell, 40, of Jersey City, N.J. Gonzalez was held on $5,000 bail, while Trowell who also had a warrant for his arrest from New Jersey for parole violations was held on $100,000 bail.
Both men are scheduled to be arraigned today in Brattleboro criminal court on robbery and assault charges. Trowel is also charged with being a fugitive from justice and will face extradition to Jersey at a later date.MORE IN This Just In
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Sweden to Halt Tax Cuts After Next Year to Buoy Public Finances
Swedes aren't likely to enjoy further reductions in income taxes after next year until at least 2017, Finance Minister Anders Borg said, citing constraints on public finances.
The government of the largest Nordic economy should instead use the limited fiscal maneuvering room to strengthen education and create jobs, Borg told reporters today in Norrkoeping, Sweden.
"It's not in the cards to make promises of big, broad tax cuts" in 2015 and 2016, Borg said. "It won't happen until we have significantly better public finances and an economy that shows that we're returning to a 1 percent surplus" of gross domestic product, he said.
Sweden's government last month said it will cut income taxes for a fifth time next year since coming to power in 2006 to boost demand. It won't reach its 1 percent of GDP surplus target until 2017 after stimulus measures depleted government coffers, the Finance Ministry said Sept. 18. Unemployment has risen in Sweden because of weak demand for its exports mainly from debt-stricken Europe. Sales abroad account for about half of Swedish output.
Sweden should still go ahead with more income-tax cuts once public finances improve since they encourage more people to join the labor force and work longer, Borg said.


text:
Sol Republic's New Tokidoki On-Ear Offerings
Partnering up with Japanese inspired lifestyle brand tokidoki, Sol Republic has launched a new pair of on-ear headphones. Offering a great degree of modularity and a chic, urban design, the headphones are also optimized for use with Apple products.
Audio Technica ATH-W3000 ANV Headphones - Number: 1697
Aiming to provide high-end audio performance, the Audio Technica ATH-W3000ANV is a premium and exclusive pair of headphones that look the part. The question is, will the product be able to deliver on the promise of top-notch sound, or will it fall short of the lofty mark expected? Read on for our evaluation.
Nokia Purity HD Stereo Headset - A Mixed Bag of Music
Priced at S$330, the on-ear Nokia Purity HD Stereo Headset by Monster is very travel-friendly, with its flat cables as well as the ability to be folded and stowed away neatly in the carrying case. We take it to the labs to see if its hefty price tag is justifiable.
Jays t-Jays Four - Good Bass with a Natural Tone
Like the older a-Jays Four, the t-Jays Four is also for use with Apple iPhones, but it also sports a few new features including 10mm dynamic drivers, and vented bass ports on the back of the ear buds to increase bass performance. We find out if it sounds as good as its specs suggest.
Fischer Audio FA-004 v2 - Into the Great Wide Open
Sporting a closed-back acoustic design with non-swivelling ear cups, the portable circumaural FA-004 v2 headphones features a headband padded in synthetic leather for maximum comfort. We find out if it sounds as good as it looks.
Corsair Vengeance 1500 7.1 Gaming Headset - Comfy, Cushy Cans
If you are a gamer and looking for that extra edge, maybe you should look into getting a better headset. With a good audio peripheral, you may be able to increase your reaction times. We take a look and see if the Corsair Vengeance 1500 can take your gaming to the next level.
SITEX 2012 - TVs & AV Products Buying Guide
Be sure to browse through our buying guide before you head down to SITEX 2012! We have a sumptuous spread of recommended audio-visual products for your consideration, including TVs, home theater systems, projectors, headphones, and media players.
Ultimate Ears 600vi - Unbiased Sound for Neutral Ears
The Ultimate Ears 600vi offers same features as the 600, plus an in-line microphone and controls. With other noise-isolating in-ear earphones out there, including models under the Ultimate Ears brand, how will this one stand out? Read on to see if our expectations were met.
Beyerdynamic T90 Open Back Headphones - Finely Balanced Quality
With its open back design and hefty asking price, the Beyerdynamic T90 is a headphone designed for the audiophile. We put it through its paces to see if its performance will be able to satisfy the demands of even the most demanding of music lovers?
Yamaha Novelties at IFA 2012
Yamaha has brought a treasure trove of products to IFA 2012, including new sound bars, desktop audio systems, and even a high-end CD player with a network-streaming client. Here are a few that caught our attention; fingers crossed that they will reach our shores soon.


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LINCOLN, Neb. -- A third man has emerged in the competition for starting quarterback at Nebraska.
Taylor Martinez was all the buzz during spring practice, and Saturday he showed why to the 77,936 fans who turned out at Memorial Stadium for the Red-White game.
The redshirt freshman threw for touchdowns on two of his first three series and rushed for a game-high 60 yards as his Red squad won 21-16.
Sophomore Cody Green led the White team to one touchdown and a field goal, passed for 155 yards and ran for 12.
Senior Zac Lee, the starter last season, was sidelined all spring after having surgery on his right (throwing) elbow.
Martinez appears well-suited for the direction the Cornhuskers want to take their offense. Offensive coordinator Shawn Watson plans to incorporate more quarterback runs, something the Huskers showed in the 33-0 Holiday Bowl win over Arizona.
Watson said Martinez is clearly the fastest quarterback and that it's only a matter of time before he hits the game field.
"We're not stupid," Watson said. "We're going to use talent. He's got talent. So we're going to use that talent."
Martinez completed 5 of 9 passes for 79 yards and had a tipped ball intercepted. He worked four full series in the first half before giving way to others.
His first two plays were designed runs, and he ran with confidence. Twice on his opening series he looked to pass, saw no one open and took off, the first time for 7 yards and the second for 10.
"I think you guys saw his speed," running back Rex Burkhead said. "He took control of the huddle and really ran with it."
The first time Martinez threw, he delivered the ball on a line to Tyler Legate for a 6-yard touchdown. He later hit Brandon Kinnie on a post pattern for 36 yards, with Kinnie dragging four defenders the last 5 yards to the end zone.
Martinez wasn't made available to reporters because coach Bo Pelini doesn't allow players who haven't been in a game to speak with the media.
"He's got a skill set that, honestly, you can't coach," Watson said. "He can put his foot in the dirt and just go. He's an instinctive runner. If something breaks down, he can make something big from it for us. And he's just getting better and better as a passer."
A couple long passes highlighted Green's day. He hit Niles Paul for 48 yards to set up a field goal. Two plays after he badly overthrew Mike Hays on a short sideline pass, he passed 72 yards for a touchdown to Will Henry.
Green said he was satisfied with his performance, but he believes the starting job is Lee's to lose.
"We all know that, just because he hasn't been here," Green said. "You've got to give him a chance to get in there and compete with us. This spring has really helped out everybody. You can see, we're all playing at a high level."
Watson said Lee will have to make up for lost time in preseason practices and that he can't assume he'll have an advantage over Green and Martinez because he started in 2009.
"He sees the young talent we have and what they bring to the table," Watson said. "Zac will bow up to it and compete. That's his nature."
Pelini said the play-calling would be basic, and that was the case except for two trick plays.
The Reds lined up in the wildcat formation, with Burkhead taking the direct snap. He threw quickly to cornerback-turned-receiver Prince Amukamara, who was engulfed by Pierre Allen and Terrence Moore for a 4-yard loss.
The White team's razzle-dazzle had a better outcome. Green threw a bounce-pass lateral toward the sideline to Mike McNeill, who fielded the ball and passed 31 yards to Paul.
"We gave each team a chance to make up a play of their own," Pelini said. "One worked, one didn't. We wanted to put Prince in there [on offense] and have a little fun with it."


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Iowa 21, Miami, Ohio 3
IOWA CITY, Iowa -- Fred Russell ran for 161 yards and a touchdown and Nathan Chandler threw for two scores as Iowa beat Miami of Ohio 21-3 in the season opener Saturday.
The Hawkeyes also intercepted Ben Roethlisberger four times and beat the RedHawks for the third straight season.
Russell carried the ball 22 times and had long runs of 59 and 66 yards, both in the second half. Chandler, making his first career start, was 12-of-19 for 129 yards. He also ran for 24 yards.
Iowa's defense, which gave up 343 yards passing to Roethlisberger last year, was more aggressive and tighter in coverage Saturday. Iowa recorded four sacks, held Miami to 50 yards rushing and didn't give up a pass longer than 26 yards.
Roethlisberger finished 27-of-42 for 250 yards.
Miami scored on its first possession, on a 21-yard field goal by Jared Parseghian. Roethlisberger looked sharp early, connecting on his first seven passes in marching Miami 77 yards in 15 plays.
Iowa answered on the next drive when Chandler threw a 7-yard TD pass to fullback Aaron Mickens.
The Hawkeyes seized momentum late in the half by capitalizing on a Miami mistake. With 32 seconds left and the ball at Miami 6, Roethlisberger was flushed from the pocket and wrapped in a defender's arms when he threw an interception that JovanJohnson returned 20 yards to the 1-yard line.
Russell scored two plays later, giving Iowa a 14-3 halftime lead.
Iowa safety Chris Smith erased Miami's only other first-half scoring chance when he intercepted Roethlisberger at the Iowa 3-yard line early in the second quarter.Johnson intercepted his second pass with 4:32 remaining when he jumped for the ball in the end zone, ending any hopes of a comeback.
This story is from ESPN.com's automated news wire. Wire index
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- National links: Reshuffling the top four


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By helping you earn miles or points toward airfare and hotel stays, travel rewards cards can be a great way to make your next trip more affordable. Whether you are a frequent business traveler wanting elite perks or a family looking to save money, you should be able to find a travel rewards card that's right for you.
How to Choose a Travel Credit Card
Looking for a new travel credit card?
You have our sympathy. There is simply WAY too many offers to choose from now.
But how do you find the right one for you?
It turns out, you can narrow down your search dramatically by deciding which one of the following links matter the most to you:
Save Money on Travel and Dining: Chase Sapphire Preferred
This card is a good fit if you want a hot deal or you plan to transfer points to one of Chase's airline or hotel partners.
Is it worth the annual fee? Read our review of the Chase Sapphire Preferred before you apply.
Tip: How to Meet Your Credit Card Minimum Spending Requirements
Travel Perks: American Express Platinum
This card is a good fit if you frequently travel and want Platinum benefits such as Airport Club Access, Platinum Concierge Service. Keep in mind, the travel-friendly benefits come at a price. There is a $450 annual fee and this is a charge card, not a credit card. In other words, you have to pay off your balance every month.
Is the Platinum Card worth it? Read our Platinum Card review before you decide.
Bonus Tip: If you frequently fly American Airlines, consider looking into the Starwood Preferred Guest credit card, which lets you transfer SPG points to AAdvantage. Plus, you get 5,000 bonus Starpoints when you transfer 20,000 Starpoints to an eligible SPG airline transfer partner such as American Airlines, Delta, and Hawaiian Airlines.
Vacation Credit Cards
Travel Credit Cards with No Annual Fee
Plus, right now, if you spend $1,000 on purchases within the first 90 days, you'll earn 20,000 bonus miles. 20,000 miles is enough to redeem for a $200 travel statement credit.
To learn more, read our Barclaycard Arrival review.
Airline Credit Cards
Plus, you can settle in sooner with Priority Boarding.
And right now, if you spend $1,000 on purchases within the first 3 months, you'll earn 30,000 bonus miles. One-way award tickets for domestic travel within and between the continental U.S., Alaska and Canada start at 10,000 miles (plus taxes and fees).
To learn more, read our Delta credit card review.
Hotel Credit Cards
Starpoints are good at over 1,200 hotels and resorts in nearly 100 countries. Starwood has 7 hotel categories, with the lowest level (category 1) costing you 2,000-3,000 points/night, the mid-range hotels (category 4) hotels costing you 10,000 points/night, and the highest (category 7) taking away 30,000-35,000 points/night. In other words, those 25,000 bonus Starpoints alone can result in a free night's stay at many Starwood properties.
What could hold you back from this tempting offer? There is a $95 annual fee ($0 introductory annual fee for the first year). Read our Starwood Preferred Guest credit card review to help you decide if the fee would be worth it to you.
There are over 4,200 hotels and resorts worldwide that accept Hilton HHonors points. Hilton has 10 hotel categories, with category 1 hotels costing 5,000 points/night and category 10 hotels charging 70,000-95,000 points/night. Mid-range category 5 hotels are just 30,000-40,000 points/night.
Wait, There's More Than Just Rewards to Consider
International Travel
Redeeming Points
Consider how you would like to book your reward travel: some cards require you to book through the card issuer's website, while others have more flexible options. Be sure to review the card's terms and conditions to see whether it has blackout dates or other restrictions on redeeming points.
Most travel and airline credit cards require very good to excellent credit to apply. Like most rewards cards, travel and airline credit card offers tend to charge higher interest rates compared to other types of credit cards, so if you don't plan on paying your balance in full each month, consider a low interest credit card instead.
Editorial Note: Any opinions, analyses, reviews or recommendations expressed in this article are those of the author's alone, and have not been reviewed, approved or otherwise endorsed by any card issuer. This site may be compensated through the Advertiser's affiliate programs.
Disclaimer: The information for the Discover it® Miles and Citi ThankYou® Premier Card have been collected independently by CreditDonkey. The card details on this page have not been reviewed or provided by the card issuer.
Travel Rewards Benefits
Travel rewards credit cards not only help you save money on expenses, such as flights and hotel rooms, they also usually offers points (or miles) that can be redeemed toward other discounts or benefits. A travel-focused credit card might also provide additional benefits when it is used to pay for travel expenses.
The majority of travel rewards credit cards work like regular rewards cards, with cardholders earning a certain number of points for each dollar spent on purchases using the card. The difference is that cards focused on travel rewards usually offer bonuses, either when you use them to pay for travel-related expenses, or when you redeem points for travel savings. Some examples may include:
A Focus on Business
Many credit cards aimed at businesspeople also emphasize travel rewards, as work-related travel remains common despite today's challenging economy:
Corporate Tie-ins
Some cards bear the name of a travel-related company, such as an airline or hotel chain, and provide even better bonuses for purchases at that particular business. Potential perks include:
Articles on Travel Rewards
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Planning a vacation? Hotel and transportation costs are high enough without the added costs of food, entertainment, and attractions. But, there are some easy ways to save money during your trip without sacrificing experience.
Best Adventure Travel Blogs
Are you game for an adventure? You can go on one without even leaving your seat with the best bloggers who write about their travel adventures.
Best Travel Food Blogs
Do you think the best way to experience the world is through your stomach? We can't always just hop on a plane, but we can get a taste of other cultures through travel food blogs. Read on for the top blogs to get your mouth watering.
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A travel credit card can be your next BFF (a loyal, rewarding one) or it can become an frenemy, by making you feel guilty that you're not using all of its benefits. There are many mistakes you can make along the way — starting with choosing one ...
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I have just upgraded from 2.6.5 to 2.7.
Easy as usual and all works except the title tag on my index pag fails.
I have a page and my set up uses this as my index via the settings in setting>reading>static page.
The title tag does show (when looking in the source code it is just a blank space.
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ALL other pages work (pages, posts, search, categories etc).
Any ideas why?
(BTW - I have tried different versions of the wp_title tag.... no difference.


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, Volume 26, Issue 3, pp 951-961
First online:
Short-term changes in biomass partitioning of two full-sib clones of Pinus taeda L. under differing fertilizer regimes over 4 months
- Jeremy P. StovallAffiliated withDepartment of Forest Resources and Environmental Conservation, Virginia Tech Email author
- , Thomas R. FoxAffiliated withDepartment of Forest Resources and Environmental Conservation, Virginia Tech
- , John R. SeilerAffiliated withDepartment of Forest Resources and Environmental Conservation, Virginia Tech
Rent the article at a discountRent now
* Final gross prices may vary according to local VAT.Get Access
Clonal forestry is a reality in the southeastern United States due to improvements in somatic embryogenesis of Pinus taeda L. Differences in below-ground carbon (C) allocation between individual genotypes could alter C sequestration and cycling in these clonal plantations. Biomass partitioning may vary between clones and in response to management practices, like fertilization. Our objective was to quantify differences in biomass partitioning due to fertilization in contrasting clones of P. taeda produced from the same full-sib cross. A two (clone)-by-two (fertilizer)-by-four (sequential harvest) factorial randomized complete block design was replicated eight times in a greenhouse for 4 months. Trees were destructively harvested monthly following fertilizer application, so changes in biomass partitioning could be determined. Both clones responded to fertilizer with a short-term reduction in root:shoot ratio and increase in foliar biomass. These changes were ephemeral, returning to control levels within 4 months. Fertilizer responses in below-ground partitioning were due to allometric differences in one clone, but were only attributable to altered rates of development in the other. Ephemeral changes in biomass partitioning in response to fertilizer application were consistent with a theory of short-term physiological response to increased nutrient availability fueling long-term fertilizer growth responses.
KeywordsAllometry Carbon allocation Intensive silviculture Varietal forestry
Reference tools
- Title
- Short-term changes in biomass partitioning of two full-sib clones of Pinus taeda L. under differing fertilizer regimes over 4 months
- Journal
Volume 26, Issue 3 , pp 951-961
- Cover Date
- 2012-06
- 10.1007/s00468-011-0673-4
- Print ISSN
- 0931-1890
- Online ISSN
- 1432-2285
- Publisher
- Springer-Verlag
- Additional Links
- Topics
- Keywords
- Allometry
- Carbon allocation
- Intensive silviculture
- Varietal forestry
- Industry Sectors
- Authors
- Jeremy P. Stovall (1) (2)
- Thomas R. Fox (1)
- John R. Seiler (1)
- Author Affiliations
- 1. Department of Forest Resources and Environmental Conservation, Virginia Tech, 228 Cheatham Hall (0324), Blacksburg, VA, 24061, USA
- 2. 419 East College St., SFA Station, Box 6109, Nacogdoches, TX, 75692, USA


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I have a web application which, among other things it does, listens on a socket for a connection for a message from a remote client. My problem arises when the user does a page refresh. After a page refresh, the application is getting reloaded and it's again trying to listen on the same port for which the there is an exception-"Address already in use."
Is there a way I can solve this?


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Micro Pigmentation & Training LtdRead MoreMicropigmentation & Training Ltd. is located in Marylebone. The salon offers permanent makeup for eyebrows, eyes and lips, which usually last for about two to five years. The salon has trained and qualified professionals to carry out the treatments and these professional explain each step of the treatment to the clients. Before the start of any treatment, the salon offers a full consultation to check the hair colour, eye colour and skin tone and then decides on a colour that would match. If necessary, colours are mixed to get the perfect colour to match the client's facial features. Once the treatment finishes, clients are given written advice on aftercare along with an aftercare balm to soothe the treated area. Clients can return two to four weeks after the treatment for a top up, which can involve adding colour, length and/or thickness. Semi-permanent make up courses Besides makeup treatments, Micropigmentation & Training Ltd. also offers training courses. Interested students can choose a basic intensive training course for four days which includes a home study manual, enhancing lower eyelashes, the application of top and lower eyeliner, hair stroke eyebrows and block eyebrows. In addition, students get thorough understanding of semi-permanent makeup, health and safety, clinical waste, how to minimise pain, methods of marketing, insurance and colour science. The salon also offers a refresher course, when semi-permanent makeup technicians can update their skills and learn new and advanced technologies. This course is taught on a one-on-one basis and is customised to the specific needs of the student.40 Harley StreetLondon, Greater London GB
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Discarded ltdRead MoreDiscarded ltd provide laser removal of unwanted tattoos in the Soho area of London. An active Q-switch Nd:yag laser is used to break down the ink particles in the skin to enable the body to naturally remove the particles away from the surface of the skin and therefore reducing or eliminating the appearance of the tattoo. It is not possible to remove all tattoos and the frequency and amount of sessions required will depend on the tattoo's size. It should also be noted that not everyone is suitable for laser removal treatment, for example those taking certain medications will be unable to use the service, however these issues can be discussed at the consultation appointment. Laser tattoo removal is a relatively new technology and a frequently asked question is whether or not the process of having a tattoo removed will be painful. Although mildly uncomfortable, a cryo machine is used to cool the area which is being treated and after the treatment, a cooling pack is applied to the area to help with any uncomfortable feelings which may be present after the process has completed. Each session varies in time from 10 - 40 minutes and is dependant on the size of the tattoo and what kind of treatment is required; whether the tattoo is to be eliminated as much as possible or if it requires toning down and fading in order that it can be more easily covered.21 Noel StreetLondon, Greater London GB
Beauty Aesthetics & Wellbeing ClinicRead MoreLocated on North End Road in Golders Green, Beauty Aesthetics and Wellbeing Clinic offers a variety of beauty services. These include facial rejuvenation, tattoo removal, varicose vein reduction, face/body thread lift, facial line correction, lip plump, deep tissue radiofrequency laser treatments, and Intense Pulse Light hair removals. Lipolysis therapies are also available, with options targeting skin conditions such as stretch marks, moles, warts and red patches.30 North End RoadLondon, Greater London GB
Studio M.ARead MoreOffering a broad range of hair and beauty services for men and women, the team of beauticians at Studio M.A have the expertise and experience needed to perform even those more advanced treatments such as tattoo removal and semi-permanent make-up. Thanks to the comprehensive array of services, bespoke packages for brides can be booked and carried out at the salon or outside of London. The products used at Studio M.A include Nioxin, Sebastian and Marrakech Oil.34 Bouverie StreetLondon, Greater London GB


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Chico & Brenda Manzie
member for 5 years, 7 months, 29 days
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Chico is a retired Newport News, Va. Firefighter.
Son of Rita (Cisneros) Manzie Senkbeil.
Brenda is a retired school bus driver.
Daughter of Alfred and Mary Jean Wood.
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Messages left for Chico & Brenda ... (36)
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Charles Christianson
Herman Augustus White
He is my great-great Uncle.
Can you connect me with any of his descendants?
Charles Christianson
Added by
Charles Christianson
on Jul 08, 2016 3:51 PM
Danny Driesel
Gary Fitting
Thank you for the transfer
Added by
Danny Driesel
on May 22, 2016 2:30 PM
Jennifer Garza
Memorial# 102364247
Thank you SO much for locating and posting a photo of the headstone of Eligio De La Garza. This is MUCH appreciated. Keep up the great work! :) ~Jenn
Added by
Jennifer Garza
on Jun 25, 2014 5:05 AM
David Olsen
Leopoldo Lopez
Thank you so much for the photos for Leopoldo. He was one of many men from the C Company 1st Battalion 5th Mechanized Infantry that was killed in Vietnam. Soon I will have them all back together again where they belong and they my work will be done.
Added by
David Olsen
on Jun 20, 2014 8:06 PM
Linda Riggs
thank you
Dear Chico & Brenda Manzie, thank you for putting in the picture of Martha Weisser and Earnest Weisser (Jimmy).
Linda Riggs
Added by
Linda Riggs
on Jun 15, 2014 5:02 PM
Charli Jones
Sarah Pollard
I saw the Sarah Pollard head stone and was wandering if this was taken at a cemetery for African Americans.
Thank you
Charli Jones
Added by
Charli Jones
on Jul 03, 2013 8:56 PM
Fran Chancellor
THANK you for the transfer!
Added by
Fran Chancellor
on Mar 04, 2013 8:14 AM
Mills Family
Chico & Brenda, thank you so much for creating the memorials & posting the headstone photos for the Mills family members & then the transfers. You are doing a terrific job!
Added by
on Jan 30, 2013 5:12 AM
Michael Briggs
Thank you!
Thank you for taking all of the headstone photographs that you did in Memorial Park Cemetery! Your time and effort are very much appreciated.
Michael W. Briggs
Added by
Michael Briggs
on May 03, 2012 7:30 PM
Joyce Blaylock
Helen Biddle
Thank you very much for the picture.
Added by
Joyce Blaylock
on May 03, 2012 2:06 AM
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