Patent Grant
10308825
The present invention relates to an ink composition. The present invention further relates to a method for preparing an ink composition. In addition, the present invention relates to a method for applying an image onto a recording medium.
Radiation-curable inkjet ink compositions are known in the art. These ink compositions comprise one or more radiation curable components. A special class of radiation curable inkjet ink compositions are phase change radiation curable inkjet ink compositions. These inks are fluid at elevated temperature and become solid—even if not yet cured—at lower temperatures. These inks are typically jetted at elevated temperatures. Phase change inks may become solid or semi-solid upon cooling down on a recording medium, e.g. a sheet of paper. As a result, spread of a droplet of ink on the recording medium may be decreased and color bleeding may be prevented. An example of a phase change radiation curable inkjet ink is a gelling radiation curable inkjet ink. Gelling radiation curable inkjet ink compositions typically comprise a gellant. Gellants are also known in the art as gelling agents or thickeners. Examples of gellants used in gelling radiation curable inkjet ink compositions are waxes, such as natural waxes and long chain carboxylic acids, and ketones.
The gelling behavior (e.g. viscosity of the droplet and speed of gelling) influences the behavior of the ink droplets on the recording medium. The behavior of the droplets may influence the visual appearance of the print.
It is therefore an object of the invention to provide a gelling radiation curable ink composition wherein the gelling behavior can be tuned.
It is a further object of the present invention to provide a gelling radiation curable ink composition that comprises alternative gellants.
The object of the invention is achieved in a radiation-curable inkjet ink composition comprising a radiation curable component, the radiation-curable inkjet ink composition further comprising a first and a second ester compound,
wherein the first ester compound is different from the second ester compound.
Radiation Curable Medium
The radiation curable inkjet ink composition may comprise a radiation curable medium. The radiation curable medium may comprise at least one radiation curable component. A radiation curable component is a component that may react (e.g. polymerize) under influence of suitable radiation, such as electromagnetic radiation, e.g. ultraviolet (UV) radiation. Examples of radiation curable components are epoxides and (meth)acrylates. (Meth-)acrylates may comprise one or more reactive groups for forming an acrylate polymer. The radiation curable medium may comprise one type of radiation curable compound or alternatively, the radiation curable medium may comprise a mixture of radiation curable compounds.
The radiation curable medium may further comprise at least one inhibitor. An inhibitor is a component that prevent (inhibits) unwanted polymerization of the radiation curable compound. Inhibitors may be added to the radiation curable inkjet ink composition to increase the shelf life of the ink composition.
The radiation curable medium may further comprise at least one photo initiator. A photo initiator is a component that improves the efficiency of curing; i.e. increases the polymerization rate when the ink composition is irradiated with suitable radiation, such as UV radiation.
The radiation curable medium may further comprise a solvent, such as water or an organic solvent. The solvent may be added to the radiation curable medium to tune ink properties, such as viscosity.
Further, additional components may be added to the radiation curable medium. For example, the radiation curable medium may comprise surfactants, antibacterial components and anti-fungi components.
Colorant
The radiation curable inkjet ink composition may further comprise a colorant, such as a pigment, a dye or a mixture thereof. Further, the radiation curable inkjet ink composition may comprise a mixture of dyes and/or a mixture of pigments. The colorant may provide the ink composition with a predetermined color.
Ester Compound
The radiation curable inkjet ink composition may further comprise a first ester compound.
According to the present invention the first ester compound consists essentially of a condensation product of a first reactant and a second reactant, wherein the first reactant is a compound A comprising at least 3 first functional groups, and wherein the second reactant comprises at least one compound B, wherein the at least one compound B comprises a second functional group, wherein the first functional group is a first group selected from a hydroxyl functional group and a carboxylic acid functional group and the second functional group is a second group selected from a hydroxyl functional group and a carboxylic acid functional group, wherein the first functional group is different from the second functional group.
Hence, the first ester compound may consist essentially of a condensation product of a first reactant and a second reactant, wherein the first reactant is a compound A comprising at least 3 hydroxyl functional group functional groups and wherein the second reactant comprises at least one compound B, wherein the at least one compound B comprises a carboxylic functional group. Alternatively, the ester compound may consist essentially of a condensation product of a first reactant and a second reactant, wherein the first reactant is a compound A comprising at least 3 carboxylic acid functional groups and wherein the second reactant comprises at least one compound B, wherein the at least one compound B comprises a hydroxyl functional group.
Preferably, compound B comprises only one second group. In case the second group is a hydroxyl functional group, the compound B preferably comprises only one hydroxyl functional group. In case the second group is a carboxylic acid group, the compound B preferably comprises only one carboxylic acid group.
The first ester compound formed by reacting the first reactant and the second reactant may be a nonlinear ester compound. The first ester compound may comprise at least three ester groups. The ester compound may provide the radiation curable inkjet ink composition with gelling properties.
The radiation curable inkjet ink composition may further comprise a second ester compound.
According to the present invention, the second ester compound consists essentially of a condensation product of a first reactant and a second reactant, wherein the first reactant is a compound A′ comprising at least 2 first functional groups, and wherein the second reactant comprises at least one compound B′, wherein the at least one compound B′ comprises a second functional group, wherein the first functional group is a first group selected from a hydroxyl functional group and a carboxylic acid functional group and the second functional group is a second group selected from a hydroxyl functional group and a carboxylic acid functional group, wherein the first functional group is different from the second functional group.
Hence, the second ester compound may consist essentially of a condensation product of a first reactant and a second reactant, wherein the first reactant is a compound A′ comprising at least 2 hydroxyl functional group functional groups and wherein the second reactant comprises at least one compound B′, wherein the at least one compound B′ comprises a carboxylic functional group. Alternatively, the ester compound may consist essentially of a condensation product of a first reactant and a second reactant, wherein the first reactant is a compound A′ comprising at least 2 carboxylic acid functional groups and wherein the second reactant comprises at least one compound B′, wherein the at least one compound B comprises a hydroxyl functional group.
Preferably, compound B′ comprises only one second group. In case the second group is a hydroxyl functional group, the compound B′ preferably comprises only one hydroxyl functional group. In case the second group is a carboxylic acid group, the compound B′ preferably comprises only one carboxylic acid group.
The second ester compound may comprise at least two ester groups. The second ester compound may provide the radiation curable inkjet ink composition with gelling properties.
The first ester compound may be different from the second ester compound.
The first ester compound and the second ester compound may be used as a gelling agent in a radiation-curable inkjet ink composition. The type of gellant used in a radiation curable inkjet ink composition may have an influence on the gelling behavior of the ink. For example, the temperature at which gelling starts and the speed of gelling may be influenced by the nature of the gellant. It is desired to tune the gelling behavior of the ink composition to the printing process such that optimum gelling behavior (and print quality) is obtained. It was found that tuning of the gelling behavior can be achieved by using two ester compounds as gelling agent, wherein the first and second ester compounds are different from one another, but wherein the molecular structure of the first and second ester compound is similar, i.e. wherein the ester compounds are compounds in accordance with the present invention. The viscosity of the ink at a certain temperature and the temperature at which gelling takes place (gelling temperature) of the ink can be tuned by using a first ester compound and a second ester compound in accordance with the present invention. In this way, spreading of an ink droplet on a recording medium after jetting can be controlled, which allows to prepare images having e.g. high gloss and do not show a visible swath boundary.
In an embodiment, the first ester compound consists essentially of a condensation product of a first reactant and x equivalents of a second reactant, wherein the first reactant is a compound A comprising x first functional groups, wherein x≥3 and wherein the second reactant comprises at least one compound B, wherein the at least one compound B comprises a second functional group, wherein the first functional group is a first group selected from a hydroxyl functional group and a carboxylic acid functional group and the second functional group is a second group selected from a hydroxyl functional group and a carboxylic acid functional group, wherein the first functional group is different from the second functional group, and the second ester compound consists essentially of a condensation product of a first reactant and y equivalents of a second reactant, wherein the first reactant is a compound A′ comprising at least y first functional groups, wherein y≥2 and wherein the second reactant comprises at least one compound B′, wherein the at least one compound B′ comprises a second functional group, wherein the first functional group is a first group selected from a hydroxyl functional group and a carboxylic acid functional group and the second functional group is a second group selected from a hydroxyl functional group and a carboxylic acid functional group, wherein the first functional group is different from the second functional group.
All reactive groups of compounds A and A′ may be converted into ester groups. Substantially no unreacted hydroxyl functional groups and/or carboxylic acid functional groups may be present anymore in the ester compounds once the first ester compound and second ester compound are formed.
In an embodiment, the second ester compound consists essentially of a condensation product of a first reactant and a second reactant, wherein the first reactant is a compound A′ comprising at least 3 first functional groups.
In an embodiment, the first ester compound may comprise at least four esters groups.
The second ester compound formed by reacting the first reactant and the second reactant may be a nonlinear ester compound. The second ester compound may comprise at least three ester groups.
The first ester compound and the second ester compound may be present in a total amount of 0.5 wt %-15 wt % based on the total weight of the radiation-curable inkjet ink composition. Preferably, the ester compound may present in an amount of 1.5 wt %-10.0 wt % based on the total weight of the radiation-curable inkjet ink composition, more preferably from 4.0 wt %-8.0 wt %.
In case the ink composition comprises less than 0.5 wt % of the ester compound, based on the total weight of the radiation-curable inkjet ink composition, then the increase in viscosity of the ink after printing on the recording medium may be insufficient to prevent color bleeding. Hence, too little ester compound may result in decreased print quality. The first ester compound may be present in an amount of 5 wt %-2000 wt % based on the amount of the second ester compound. Preferably, the first ester compound may be present in an amount of 10 wt %-1000 wt % based on the amount of the second ester compound.
The molecular structure of the first ester compound and the second ester compound may be similar. Without wanting to be bound to any theory, it is believed that the similar, but not identical molecular structures of the first and second ester compound, respectively, may allow to tune the phase change behavior of the radiation curable ink composition.
At high temperatures, the first and second ester compound may be fluid and may be dissolved in an ink composition. Hence, a radiation curable ink composition comprising the first and the second ester compound may be jetted at high temperatures. At lower temperatures, the viscosity of the ink may increase. When droplets of the ink composition are applied onto a recording medium, the temperature of the ink may decrease and consequently, the viscosity of the ink may decrease. This viscosity increase may result in pinning of the ink droplets. The temperature at which the viscosity increase takes place may be tuned by suitably selecting the first ester compound and the second ester compound. Further, the temperature at which the viscosity increase takes place may be tuned by selecting the amount and ratio of the first ester compound and the second ester compound. Hence, using an ink composition comprising two gelling agents may allow optimizing the gelling behavior of the ink composition with regard to the print process parameters.
An ink composition comprising a first ester compound and a second ester compound may show more than one viscosity increase; i.e. such ink composition may have two different gelling temperatures; a lower and a higher gelling temperature. However, these lower and higher gelling temperatures may be different from the gelling temperatures of an ink composition that comprises the first ester compound, but not the second ester compound or an ink composition that comprises the second ester compound, but not the first ester compound.
In an embodiment, the compounds A and A′ are selected from the group consisting of pentaerythritol, cyclodextrine, glycerol, dipentaerythritol, 2-(hydroxymethyl)-2-methylpropane-1,3-diol, 2-ethyl-2-(hydroxymethyl)propane-1,3-diol, 2-(hydroxymethyl)propane-1,3-diol, trimethylolethane, trimethylolpropane, trimethylolbutane and trimethylolpentane.
These compounds are compounds comprising at least 3 hydroxyl functional groups. When reacted with a carboxylic acid, ester compounds can be formed.
Esters obtainable by reacting a carboxylic ester with a compound A or compound A′ selected from the above listed group may be esters having a branched structure (i.e. non-linear esters). Without wanting to be bound to any theory, it is believed that a branched structure may decrease the tendency of the ester compound to crystallize when cooling down. Hence, ester compound obtainable from the above mentioned polyalcohol components may not crystallize when cooling down. This may improve the gloss of a print made with an ink composition comprising such ester compound. Methods for synthesizing ester compounds starting from a compound comprising a plurality of hydroxyl functional groups and a compound comprising a carboxylic acid group are known in the art.
The compound A and compound A′ may be the same or may be different. Preferably, compound A is different from compound A′.
In an embodiment, the compound B and the compound B′ are compounds according to formula I, wherein R is an alkyl group, an aryl group or an alkylaryl group, wherein R is a group having 5-30 carbon atoms.
R—C(O)OH formula I:
The compound B and compound B′ may be the same or may be different. Preferably, compound B is different from compound B′. Compounds according to formula I are suitable to form ester compounds in accordance with the present invention. The properties of the ester compound may be influenced by the choice of the functional group R. The nature of the R group may for example influence the melting point of the ester compound and the rate of diffusion of the ester compound in the inkjet ink composition. R may be an alkyl group, an aryl group or an alkylaryl group. When the functional group R comprises an aromatic unit, then pi-pi-interaction may occur. Pi-pi interaction may assist in forming the intermolecular network upon cooling of the ink composition comprising the ester compound, which may be beneficial for the increase in viscosity of the ink composition when cooling down.
The functional group R may be a group comprising 5-40 carbon atoms, preferably 10-25. When the functional group R comprises less than 5 carbon atoms, the ester compound may not show gelling behavior at printing conditions. When the functional group R comprises more than 40 carbon atoms, then the ester compound may not be fluid at jetting conditions, which may hamper the jetting of the inkjet ink composition. The ester compound may comprise only one type of functional group R. Alternatively, the ester compound may comprise a plurality of different R functional groups.
In the ink composition according to the present invention, compound A may be different from compound A′ and/or compound B may be different from compound B′.
In a further embodiment, the compound B and the compound B′ are fatty acids. Fatty acids are suitable for forming esters, when reacted with a compound comprising a hydroxyl functional group. The fatty acids may be saturated or non-saturated fatty acids. Non-saturated fatty acids may be monounsaturated fatty acids or polyunsaturated fatty acids. Non-saturated fatty acids comprise an alkene functional group. Upon curing of the ink, the alkene functional group may react and the ester compound may be incorporated in the network formed by the radiation-curable component.
When the compound B and the compound B′ are fatty acids, no so-called blooming of the ink may occur. Blooming is an unwanted phenomenon that may occur in ink composition, such as radiation-curable ink composition comprising a gelling agent. After being applied onto a recording medium, a gelling agent present in the ink may cool down and may solidify, thereby forming a three-dimensional network that increases the viscosity of the ink. However, in the course of time, the gelling agent may migrate to the surface of the ink layer, which may result in matt print appearance. The phenomenon of decreased gloss due to migration of the gelling agent is known as “blooming”. Without wanting to be bound to any theory, it is believed that by selecting compounds B and B′ to be fatty acids, amorphous ester compounds are obtained, that results in an ink composition that does not show blooming.
In an embodiment, the first ester compound is a fatty acid ester of pentaerythritol. Ester compounds of pentaerythritol may be suitable used as a gelling agent in a radiation-curable ink composition.
In a further embodiment, the first ester compound is pentaerythritoltetrastearate. Pentaerythritoltetrastearate is an ester obtainable by reacting pentaerythritol and stearic acid. Stearic acid (CH3(CH2)16COOH) is a fatty acid.
In an embodiment, the second ester compound is a fatty acid ester of glycerol. Ester compounds of glycerol may be suitable used as a gelling agent in a radiation-curable ink composition.
In a further embodiment, the second ester compound is glyceroltristearate. Glyceroltristearate is an ester obtainable by reacting glycerol and stearic acid. Stearic acid (CH3(CH2)16COOH) is a fatty acid.
In an embodiment, the radiation curable component is an acrylate having two or more acrylate functional groups. An acrylate may undergo a polymerization reaction when irradiated by suitable radiation, such as UV radiation. Hence, a polyacrylate polymer may be formed when an inkjet ink composition comprising an acrylate is cured, thereby hardening the ink. An acrylate molecule having two or more acrylate functional groups may react with two or more other acrylate molecules and hence, a polymeric network may be formed. Examples of acrylates having two or more acrylate functional groups are known in the art.
In a further embodiment, the ink composition further comprises a monofunctional acrylate. Presence of a monofunctional acrylate may improve the hardness and flexibility of the ink layer after curing.
In an aspect of the invention, a method for preparing a radiation-curable inkjet ink composition is provided, the method comprising the steps of:
The radiation-curable component and the ester compounds may be provided. Optionally, additional components may be provided, for example an additional solvent. The radiation-curable component and the ester compound may be provided neat or they may be provided in a solution or dispersion. Optionally, a colorant may be provided. In case the colorant is a pigment, the pigment is preferably provided as a dispersion, such as an aqueous pigment dispersion. The components may be provided at once, or the components may be added subsequently. The components may be added in any suitable order. In case a dispersible component is added (pigment and/or latex particles), such dispersible component may be preferably added after the other components of the ink composition are provided. Mixing of the components may be carried out at any suitable temperature, for example room temperature.
In an aspect of the invention, a method for applying an image onto a recording medium is provided, the method comprising the steps of:
In the method, an image is applied onto a recording medium. In the method, in step a), an image is applied to the recording medium. The image may be applied using an ink composition according to the present invention. The ink composition may be applied onto the recording medium in a predetermined fashion, e.g. in accordance with image files stored on suitable storing means. The image may be applied for example by jetting droplets of the radiation-curable inkjet ink composition using an inkjet print head. The recording medium may be a sheet-like medium, such as a sheet of paper or a sheet of vinyl. Alternatively, the recording medium may be a web, for example an endless belt. The web may be made of a suitable material. Optionally, the image may be dried after it has been applied onto the intermediate transfer member.
In the method, in step b), the radiation-curable inkjet ink composition is cured by irradiating the ink composition using UV radiation. The inkjet ink composition may be irradiated using a suitable source of radiation, such as a halogen lamp, a mercury lamp and/or a LED lamp. Optionally, a plurality of sources of radiation may be used to irradiate the inkjet ink composition.
These and further features and advantages of the present invention are explained hereinafter with reference to the accompanying drawings showing non-limiting embodiments and wherein:
In the drawings, same reference numerals refer to same elements.
The image receiving medium 2 may be a medium in web or in sheet form and may be composed of e.g. paper, cardboard, label stock, coated paper, plastic or textile. Alternatively, the image receiving medium 2 may also be an intermediate member, endless or not. Examples of endless members, which may be moved cyclically, are a belt or a drum. The image receiving medium 2 is moved in the sub-scanning direction Y over the flat surface 1 along four print heads 4a-4d provided with a fluid marking material.
The image receiving medium 2, as depicted in
A scanning print carriage 5 carries the four print heads 4a-4d and may be moved in reciprocation in the main scanning direction X parallel to the platen 1, such as to enable scanning of the image receiving medium 2 in the main scanning direction X. Only four print heads 4a-4d are depicted for demonstrating the invention. In practice an arbitrary number of print heads may be employed. In any case, at least one print head 4a-4d per color of marking material is placed on the scanning print carriage 5. For example, for a black-and-white printer, at least one print head 4a-4d, usually containing black marking material is present. Alternatively, a black-and-white printer may comprise a white marking material, which is to be applied on a black image-receiving medium 2. For a full-color printer, containing multiple colors, at least one print head 4a-4d for each of the colors, usually black, cyan, magenta and yellow is present. Often, in a full-color printer, black marking material is used more frequently in comparison to differently colored marking material. Therefore, more print heads 4a-4d containing black marking material may be provided on the scanning print carriage 5 compared to print heads 4a-4d containing marking material in any of the other colors. Alternatively, the print head 4a-4d containing black marking material may be larger than any of the print heads 4a-4d, containing a differently colored marking material.
The carriage 5 is guided by guiding means 6. These guiding means 6 may be a rod as depicted in
Each print head 4a-4d comprises an orifice surface 9 having at least one orifice 8, in fluid communication with a pressure chamber containing fluid marking material provided in the print head 4a-4d. On the orifice surface 9, a number of orifices 8 are arranged in a single linear array parallel to the sub-scanning direction Y, as is shown in
As depicted in
The ink jet printing assembly 3 may further comprise curing means 11a, 11b. As shown in
The first curing means 11a may emit a first beam of UV radiation, the first beam having a first intensity. The first curing means 11a may be configured to provide the radiation for the pre-curing step. The second curing means 11b may emit a second beam of radiation, the second beam of radiation having a second intensity. The second curing means 11b may be configured to provide the radiation for the post-curing step.
The carriage 12 is guided by guiding means 7. These guiding means 7 may be a rod as depicted in
The curing means may be energy sources, such as actinic radiation sources, accelerated particle sources or heaters. Examples of actinic radiation sources are UV radiation sources or visible light sources. UV radiation sources are preferred, because they are particularly suited to cure UV curable inks by inducing a polymerization reaction in such inks. Examples of suitable sources of such radiation are lamps, such as mercury lamps, xenon lamps, carbon arc lamps, tungsten filaments lamps, light emitting diodes (LED's) and lasers. In the embodiment shown in
The flat surface 1, the temperature control means, the carriage 5, the print heads 4a-4d, the carriage 12 and the first and second curing means 11a, 11b are controlled by suitable controlling means 10.
Materials
SR 9003 (propoxylated neopentyl glycol diacrylate) was obtained from Sartomer. Pentaerythritoltetrastearate was obtained from NOF. Glyceroltristearate was obtained from Sigma-Aldrich. All chemicals were used as received.
Methods
Viscosity
The viscosity is measured using an Anton Paar MCR 301 rheometer, with flat plate geometry. The viscosity is measured at shear rates ({dot over (γ)}) of 100 s−1. The ink compositions were provided to the rheometer at a temperature of 70° C. The ink compositions were kept at a constant temperature for 5 minutes, before the ink compositions started to cool down. During the viscosity measurements, the ink compositions were cooled down with a rate of 4° C. per minute starting at a temperature of 70° C. The measurement was stopped when a temperature of 10° C. was reached.
Several ink compositions were prepared. The ink compositions were prepared by adding gelling agent to a radiation curable medium, wherein the radiation curable medium consists of SR 9003 as radiation-curable monomer and mixing the components. The amount of gelling agent and of the radiation curable medium is shown in table 1. Ink compositions Ex 1, Ex 2 and Ex 3 are ink compositions according to the present invention. Ink composition Ex 1, Ex 2 and Ex 3 comprise pentaerythritoltetrastearate as a gelling agent and further comprise glyceroltristearate as a gelling agent.
Comparative ink compositions CE 1 and CE 2 were also prepared analogously; ink composition CE 1 comprises pentaerythritoltetrastearate as a gelling agent, ink composition CE 2 comprises glyceroltristearate as a gelling agent.
The ink compositions Ex 1, Ex 2, Ex 3, CE 1 and CE 2 are summarized in table 1.
The viscosity of each one of the ink compositions CE 1, CE 2, Ex 1, Ex 2 and Ex 3 was measured as a function of temperature in a temperature range of 10° C.-70° C. The viscosity of the five ink compositions as a function of temperature is shown in
The ink composition according to the present invention Ex 1 shows two changes in viscosity; one at about 38° C. and one at about 30° C. The ink composition according to the present invention Ex 2 shows two changes in viscosity; one at about 39° C. and one at about 26° C. The ink composition according to the present invention Ex 3 also shows two changes in viscosity; one at about 40° C. and one at about 21° C.
Gelling ink compositions are typically jetted at elevated temperatures. At the elevated temperature, the gelling ink compositions are in a liquid state; their viscosity is sufficiently low to be jetted. All five ink compositions shown in the examples and comparative examples are suitable to be jetted at elevated temperatures; their viscosity is 20 mPa·s or lower at temperatures from 45° C. to 70° C. At lower temperatures, the viscosity of the ink composition typically increases due to gelling of the ink droplets. The gelling temperature (the temperature at which a first viscosity increase takes place upon cooling down of the ink) differs for the ink compositions shown in
Upon further cooling down the ink compositions according to the present invention (Ex 1, Ex 2 and Ex 3), a second viscosity increase occurs for both ink compositions. Hence, even after the ink according to the present invention has formed a gel, the viscosity may increase further upon further cooling of the ink. This additional increase in viscosity may provide improved prevention of droplet spread.
Hence, an ink composition according to the present invention, comprising two gelling agents in accordance with the present invention may allow tuning of the gelling properties of a radiation-curable ink composition.
Detailed embodiments of the present invention are disclosed herein; however, it is to be understood that the disclosed embodiments are merely exemplary of the invention, which can be embodied in various forms. Therefore, specific structural and functional details disclosed herein are not to be interpreted as limiting, but merely as a basis for the claims and as a representative basis for teaching one skilled in the art to variously employ the present invention in virtually and appropriately detailed structure. In particular, features presented and described in separate dependent claims may be applied in combination and any combination of such claims are herewith disclosed. Further, the terms and phrases used herein are not intended to be limiting; but rather, to provide an understandable description of the invention. The terms “a” or “an”, as used herein, are defined as one or more than one. The term plurality, as used herein, is defined as two or more than two. The term another, as used herein, is defined as at least a second or more. The terms including and/or having, as used herein, are defined as comprising (i.e., open language). The term coupled, as used herein, is defined as connected, although not necessarily directly.
| Number | Date | Country | Kind |
|---|---|---|---|
| 14198894 | Dec 2014 | EP | regional |
| 15171059 | Jun 2015 | EP | regional |
This application is a Continuation of PCT International Application No. PCT/EP2015/080284, filed on Dec. 17, 2015, which claims priority under 35 U.S.C. 119(a) to Patent Application Nos. 14198894.9, filed in Europe on Dec. 18, 2014 and Ser. No. 15/171,059.7, filed in Europe on Jun. 8, 2015, all of which are hereby expressly incorporated by reference into the present application.
| Number | Name | Date | Kind |
|---|---|---|---|
| 9777091 | Fukuoka | Oct 2017 | B2 |
| 20130035428 | Carlini et al. | Feb 2013 | A1 |
| Number | Date | Country |
|---|---|---|
| 2 565 044 | Mar 2013 | EP |
| 2 679 640 | Jan 2014 | EP |
| Entry |
|---|
| International Search Report for PCT/EP2015/080264 (PCT/ISA/210) dated Feb. 16, 2016. |
| Written Opinion of the International Searching Authority for PCT/EP2015/080264 (PCT/ISA/237) dated Feb. 16, 2016. |
| Number | Date | Country | |
|---|---|---|---|
| 20170275481 A1 | Sep 2017 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | PCT/EP2015/080284 | Dec 2015 | US |
| Child | 15618679 | US |
