Apparatus and methods for printing on a curved surface

Abstract

Apparatus for printing onto an outer surface of a sample container, such as sample tubes and other containers for holding samples in an analytical laboratory. The apparatus has a printhead having an electromagnetic radiation source, a sample container holder, and a mechanism to (i) move the sample container outer surface relative to the printhead or (ii) move the printhead relative to the sample container outer surface. The apparatus is configured to maintain a distance between the sample container outer surface and the electromagnetic radiation source so as to provide for non-contact printing.

Description

APPARATUS AND METHODS FOR PRINTING ON A CURVED SURFACEFIELD

[0001] The present disclosure relates to printing on a curved surface, such as a sample container used in an analytical laboratory setting. The disclosure is applicable at least to equipment of the type used in high-throughput analytical laboratories, and also equipment used in smaller scale applications.BACKGROUND

[0002] Automation has revolutionized the operation of analytical and research laboratories. By integrating advanced robotics, instrumentation, and software, laboratory automation optimizes workflows, enhances process reproducibility, as well as reducing labor costs

[0003] At its core, laboratory automation aims to streamline experimental workflows by replacing manual tasks with automated processes. This involves the integration of robotic systems capable of performing a wide array of tasks, ranging from sample preparation and handling, sample analysis, output data analysis and storage.

[0004] Laboratory automation encompasses a diverse array of methodologies tailored to specific process requirements. Liquid handling robots, equipped with precision pipetting systems, enable accurate dispensing of reagents and samples, facilitating high-throughput screening and assay development. Integrated robotic workstations automate sample preparation workflows, including DNA extraction, purification, and amplification, revolutionizing genomics and molecular biology research. High-content imaging systems coupled with automated analysis software enable rapid acquisition and analysis of large-scale image datasets, empowering researchers in drug discovery and cell biology.

[0005] Automation is especially prevalent in high throughput analytical laboratories of the type used to analyze samples of clinical, environmental and industrial origin. Such laboratories aretasked with performing analysis on hundreds or thousands of individual samples per day, and automation is absolutely essential to operations.

[0006] Sample processing is also a feature of non-automated systems, such as in small-scale diagnostic laboratories and research environments.

[0007] Some processes in sample processing systems are carried out manually, or semi-manually with machine assistance.

[0008] It is often necessary to label sample containers in the laboratory. For example, secondary tubes are used for aliquoting, storing and transporting samples such as blood, blood components, urine, environmental samples, process samples from a primary tube in the laboratory for analysis on laboratory analysis. The choice of tube depends on the analyser and the intended use. Secondary tubes may be used also for archiving an aliquot of sample.

[0009] The process of labelling secondary tubes in a laboratory is a time consuming and / or wasteful process. If done by hand, this takes a significant amount of operator time and can be prone to error. If done by machine, waste is produced in the form of label rolls and processes must be implemented for the ordering, managing, and replacing of consumables in the system. Machines capable of performing this task also tend to utilize significant bench space due to the need to store and apply consumables.

[0010] Printing onto labels affixed to curved surfaces (such as a sample container surface) presents particular problems. Printing technologies often require even contact between the print head and the surface to be printed. Such contact is problematic when the print head must contact a curved surface, or the printing surface is otherwise non-planar or uneven.

[0011] It is an aspect of the present disclosure to provide an improvement in prior art printing apparatus. It is a further aspect of the present disclosure to provide a useful alternative to prior art printing apparatus.

[0012] The discussion of documents, acts, materials, devices, articles and the like is included in this specification solely for the purpose of providing a context for the present disclosure. It is not suggested or represented that any or all of these matters formed part of the prior art base or were common general knowledge in the field relevant to the present disclosure as it existed before the priority date of each provisional claim of this application.BRIEF DESCRIPTION OF THE DRAWINGS

[0013] The foregoing aspects and other features of the disclosed embodiment are explained in the following description, taken in connection with the accompanying drawings, wherein:

[0014] FIG. 1A is a diagrammatic illustration in lateral perspective view of an exemplary printer, with a sample tube disposed in a position ready for printing thereon.

[0015] FIG. IB is a diagrammatic illustration of a section taken through the line X-X’ of FIG. 1A

[0016] FIG. 2 is a diagrammatic illustration in lateral view of an exemplary one dimensional (linear) laser dynode array.

[0017] FIG. 3 is a diagrammatic illustration in lateral view of an exemplary two-dimensional laser dynode array.

[0018] FIG. 4 is a diagrammatic illustration in lateral view of an exemplary two-dimensional laser dynode array being used for non-contact printing onto a thermally activated label affixed to a cylindrical sample tube.

[0019] The drawings are not prepared to any particular scale or dimension and are not presented as being a completely accurate presentation of the various embodiments.SUMMARY

[0020] In a first aspect, but not necessarily the broadest aspect, there is provide an apparatus for printing onto an outer surface of a sample container, the apparatus comprising: a printhead having an electromagnetic radiation source, a sample container holder, and a mechanism to (i) move the sample container outer surface relative to the printhead or (ii) move the printhead relative to the sample container outer surface, wherein the apparatus is configured to maintain a distance between the sample container outer surface and the electromagnetic radiation source.

[0021] In one embodiment of the first aspect, the electromagnetic radiation source is configured to direct focused electromagnetic radiation onto an outer surface of a sample container held by the sample container holder, the outer surface being sensitive to the focused electromagnetic radiation such that a visually discernible marking appears on the outer surface in response to the focused electromagnetic radiation thereon.

[0022] In one embodiment of the first aspect, the electromagnetic radiation is capable of heating the sample container outer surface, and the sample container outer surface is heat sensitive.

[0023] In one embodiment of the first aspect, the electromagnetic radiation is laser electromagnetic radiation.

[0024] In one embodiment of the first aspect, the laser electromagnetic radiation is generated by a line or an array of diodes.

[0025] In one embodiment of the first aspect, the diodes are disposed in a staggered arrangement.

[0026] In one embodiment of the first aspect, the diodes are disposed on a wafer.

[0027] In one embodiment of the first aspect, the sample container outer surface is formed by: (i) a wall of the sample container, (ii) a material applied to a wall of the sample container, or (iii) a material incorporated into a wall of the sample container.

[0028] In one embodiment of the first aspect, the sample container holder is configured to hold a sample container used in a pathology laboratory, or another type of analytical laboratory.

[0029] In one embodiment of the first aspect, the sample container is used in a pathology laboratory, or another type of analytical laboratory has a capacity of between about 1 ml and about 50 ml.

[0030] In one embodiment of the first aspect, the sample container has a curved outer surface and / or is elongate.

[0031] In one embodiment of the first aspect, the apparatus comprises a mechanism for rotating a sample container held in the sample container holder about its central axis such that an outer surface of the sample container is moved past the printhead.

[0032] In one embodiment of the first aspect, the apparatus comprises one or more rollers configured to effect the rotation of the sample container about its central axis.

[0033] In one embodiment of the first aspect, the one or more rollers: (i) form a part of the sample container holder, (ii) are the sample container holder, or (iii) are proximal to the sample container such that the one or more rollers and the sample container holder contact a sample container.

[0034] In one embodiment of the first aspect, the apparatus is configured to print any one or more of the following onto a sample container outer surface: an optical code associated with a patient,a barcode associated with a patient, a QR code associated with a patient, a patient name, a patient identifier, a string of characters identifying a patient, a patient date of birth, a health insurance identifier, a social security identifier, a date and / or time the sample was obtained, a medical purpose for obtaining the sample, a bodily source of the sample, a treating practitioner name, a hospital name or a clinic name.

[0035] In a second aspect, there is provided an item of sample aliquot equipment comprising, or being in functional association with, the apparatus of any embodiment of the first aspect.

[0036] In a third aspect, there is provided a sample container used in a pathology laboratory, or another type of analytical laboratory, the sample container having an outer surface sensitive to laser electromagnetic radiation incident thereon such that an indicium appears on the sample container outer surface in response to the electromagnetic radiation, wherein the sample container outer surface is formed by: (i) a wall of the sample container, (ii) a material applied to a wall of the sample container, or (iii) a material incorporated into a wall of the sample container.

[0037] In one embodiment of the third aspect, the sample container has any one or more of the following printed onto an outer surface: an optical code associated with a patient, a barcode associated with a patient, a QR code associated with a patient, a patient name, a patient identifier, a string of characters identifying a patient, a patient date of birth, a health insurance identifier, a social security identifier, a date and / or time the sample was obtained, a medical purpose for obtaining the sample, a bodily source of the sample, a treating practitioner name, a hospital name or a clinic name.

[0038] In a fourth aspect, there is provided a method of printing onto an outer surface of a sample container used in a pathology laboratory, or another type of analytical laboratory, the method comprising the steps of: providing the apparatus of any embodiment of the first aspect,holding the sample container of any embodiment of the third aspect using the sample container holder of the apparatus, and causing or allowing the apparatus to print onto the sample container outer surface.

[0039] In one embodiment of the fourth aspect, the apparatus is caused or allowed to print any one or more of the following: an optical code associated with a patient, a barcode associated with a patient, a QR code associated with a patient, a patient name, a string of characters identifying a patient, a patient date of birth, a health insurance identifier, a social security identifier, a date and / or time the sample was obtained, a medical purpose for obtaining the sample, a bodily source of the sample, a treating practitioner name, a hospital name or a clinic name.DETAILED DESCRIPTION AND PREFERRED EMBODIMENTS

[0040] In one embodiment of the present disclosure, a tube having a blank thermally active label already applied thereto is inserted into an apparatus having a thermal print head, which is preferably of the non-contact type. Alternatively, the tube itself may be fabricated from a thermally active material. The tube is axially rotated such that the thermal print head passes over the label or thermally active material and in the course of doing so, causes an indicium or some other visual marking to be applied to the label.

[0041] Direct thermal printing is conventionally performed using labels on a roll rather than to labels pre-applied to a tube in the pathology space. The advantage of the present approach is the reduction in waste and consumable replacement for the end-user allowing for a more efficient workflow as well as the possibility for a smaller design footprint, saving bench space.

[0042] Reference is made to FIG. 1 A showing an exemplary apparatus (10) for printing marks on the outer surface of a sample tube. FIG. IB illustrates the section marked X-X’ in FIG. 1A. Illustrated is a printhead housing (15) having a slender elongate aperture (20) running along thevertical axis of the housing (15). Disposed vertically within the housing (15) is a one-dimensional array of laser diodes which form the printhead. The position and orientation of the array of laser diodes is indicated by the dashed line (25). The diode array (25) is similar to that illustrated in FIG 2, although longer.

[0043] The apparatus (10) comprises two rollers (30, 35) which are positioned so as to contact a pathology sample tube (40). The rollers (30,35) function in part to hold the tube (40) in the vertical orientation as drawn, aligned with the vertical aperture (20) and aligned also with the diode array (25). The base of tube (40) may rest on a support (not drawn) to prevent downward slippage.

[0044] The rollers (30, 35) are retained by a roller carrier (45) which maintains the rollers (30, 35) in mutual parallel spaced relation, and allows rotation of each roller (30, 35) about its respective shaft (30a, 30b). The roller carrier (45) is in turn connected to a mount structure (50). The connection between the roller carrier (45) and the mount structure (50) allows the roller carrier (45), and therefore also the rollers (30. 35) to swing away from the housing (15) thereby creating a large space between the rollers (30, 35) and the housing (15). The roller carrier (45) is swung away from the housing for the purpose of accepting a tube into the apparatus (10), and then swung towards the housing (15) so as to hold the tube (40) in place as shown in FIG. 1 A and FIG. IB.

[0045] The diode array (25) emits laser light, which passes out of the housing (15) via the vertical aperture (20). The laser light is directed onto the outer surface (40a) of the tube wall (40b). The outer surface (40a) is heat sensitive, and rapidly changes color upon exposure to laser light, thereby forming a marking.

[0046] The tube (40) is axially rotated by the rollers (30, 35) and in a manner synchronized by process control with the emission of laser light by the diode array (25) such that markings can be made across a large area of the outer surface (40a). Thus, the diode array (25) is pulsed under processor control to mark the outer surface (40a), with axial rotation of the tube (40) presentingfresh and unmarked outer surface (40a) to the diode array (25) which is then marked by a further pulse of the diode array (25), and so on until the required markings are made.

[0047] Axial rotation of the tube (40) is effected by rotation of at least one of the rollers (30, 35). In that regard, the mounting structure comprises a processor-controlled stepper motor (55) which turns the shaft (30b) via a meshing gear arrangement (60).

[0048] Once marking of the outer surface (40a) is completed, the roller carrier (45) is swung away from the housing (15) so as to allow removal of the tube (40). The swinging action may be performed manually, or by an electromechanical mechanism under processor control.

[0049] The tube (40) may be moved into and out of the apparatus (10) manually, semi-manually, robotically or by any other means. Where tube (40) movement is under processor control, movement is coordinated with pulsing of the diode array (25) and rotation of stepper motor (55).

[0050] The apparatus (10) may comprise idle rollers (not drawn) on either side of the vertical aperture (20) to improve accuracy, a sensor (not drawn) to detect and align any label on the tube (40) for printing, an optical code scanner (not drawn) to confirm printing quality of a bar code or QR code for example, a camera (not drawn) to ensure all required information has been correctly printed.

[0051] The outer surface (40a) upon which the markings are printed may be a heat sensitive material (such as a label fabricated from a heat sensitive paper, polymer or composite material which is applied to the tube wall (40b) by the user or by the tube manufacturer. Alternatively, the heat sensitive material may be incorporated into the external region of the tube wall (40b) so as to be exposable to the laser light. As a further alternative, the tube wall (40b) may itself be intrinsically heat sensitive.

[0052] Laser types potentially suitable in the context of the present disclosure include CO2, Fiber, green, blue, and ultraviolet lasers. Reference is made to FIG. 2 showing an exemplary type of laser, being a wafer-mounted diode laser array (100). A plurality of diodes (105a, 105b etc) are disposed to form a linear array. Each diode (105) is overlayed with a lens (110) which focusses laser light emitted by the diode (100) as required to form an accurate marking on the tube outer surface (40a).

[0053] Wafer level optics are optical products manufactured using semiconductor process on wafers. Wafer-level optics enables the design and manufacture of miniaturized optics at the wafer level using advanced semiconductor-like. Key advantages of wafer-level optics fabrication and integration include and the highly accurate assembly based on state-of-the-art lithography and bond-alignment technologies give a reduced form factor. Lens types such as convex and Fresnel lenses may be used. Seoul Precision optics Co., Ltd (Korea) is one supplier of wafer-level optics products.

[0054] Reference is made to FIG. 3 illustrating a two-dimensional laser diode array. Such an array is capable of marking a larger area than that of FIG. 2, and may therefore allow more rapid printing of information on the tube outer surface (40a). In the array of FIG. 3, it will be noted that the individual diodes are arranged in a staggered manner. Such arrangement improves any printed marking by increasing the density, the pattern or the quality of markings achievable by the laser.

[0055] In FIG. 2 or FIG. 3, each diode (105) of the array is individually addressable by a processor, or a control module under the instruction of a processor. Thus, each diode (105) in the array can be individually actuated (i.e. turned on and off in a pulsed manner) as required to provide the desired marking. The actuation of the individual diodes (105) is coordinated with rotation of the tube by a processor of the apparatus.

[0056] Any laser used is preferably of limited power, and incapable of ablating, etching or otherwise damaging any heat sensitive material printing surface, or the material from which the tube is fabricated. Lower power lasers are less expensive, safer and also do not cause the release of any significant amount of volatile material, smoke, or vapor that arise from the use of higher powered lasers that ablate or etch a material. The release of such materials necessitates the use of extraction equipment for occupational health and safety reasons.

[0057] In utilizing laser light for thermal printing, the present disclosure avoids the need for a traditional direct thermal printhead which comprises heated pins that directly contact the surface to be printed. Curved surfaces are difficult to print onto by conventional thermal printing methods, with unevenness in the surface presenting further problems. The laser-based non-contact thermal printing arrangement exploited by some embodiments of the present disclosure may overcome such problems. The use of lasers also avoids the need for a consumable ribbon, as required for thermal transfer printing.

[0058] While the embodiments of the drawings utilize multiple lasers, single laser embodiments will nevertheless be operable. When using a single laser beam the singular beam may be moved or scanned using a device such as a mirror controlled by a galvanometer. Another option is to move the laser using a motor-controlled motion stage. Another option is to maintain the laser beam stationary but to move the sample container in two dimensions. These options add cost, complexity, and size to the apparatus and are therefore less preferable.

[0059] Irrespective of the type of laser used, in a typical application print resolution in the range of 300dpi is desirable. This resolution requires the illuminated pixel by the laser beam to have a size of 0.084 mm or smaller.

[0060] Reference is made to FIG. 4 illustrating an embodiment of the apparatus configured to print text (patient name and date of birth) and a unique barcode onto a heat sensitive label (200), by laser light (300) emitted by a laser diode array (100 or 200). The diodes of the diode array (100 or 200) are electively actuated by the driver / controller (400).

[0061] A heat sensitive label or a heat sensitive material incorporated into a sample container may intrinsically change color upon exposure to heat. For example the label or material may char, or be otherwise degraded to cause a change in color. Alternatively, the label or material may comprise a thermochromic material that irreversibly changes color when heated. For example, a combination of leuco dyes, color developer and melt materials blended together and then micronized to reduce particle size may be used. These components are combined into a carrier forming an aqueous concentrate which changes from off white to a color permanently when heated above a predetermined temperature. As temperature increases, color density increases.

[0062] A commercially available thermal active label used for non-contact applications may be operable in the context of the present disclosure. It would be necessary to select a laser (in terms of wavelength and power) capable of causing the required color change. Suitable labels may include any direct thermal label product available from Thermal Labels Australia (thermallables.com.au) or Tiger Pack (tigerpak.com.au .

[0063] A sample container may have an irreversible thermochromic coating applied to an outside surface during manufacturing. Such coatings may comprise a dye incorporated into a microcapsule. The microcapsule releases the dye upon exposure to heat, leading to a color change.

[0064] A further alternative is to exploit certain coatings which change color upon the absorbance of laser light energy at, for example, around 780 nm. Such coating may comprise, a leuco dye, a hexaarylbiimidazole activator, an acid-generating source, an electromagnetic radiation absorber, and a stabilizing agent. The composition may include a liquid carrier, which can act to improvecoating performance, but which can be removed upon coating through a conventional liquid removal processes. Typically, at least a portion of the liquid carrier can be driven off or allowed to evaporate after the coating process is complete. The liquid carrier can include, but is not limited to, solvents such as methylethyl ketone, isopropyl alcohol or other alcohols, water, surfactants, and mixtures thereof.

[0065] Leuco dyes include members selected from the group consisting of amino-triarylmethanes, aminoxanthenes, aminothioxanthenes, amino-9,10-dihydro-acridines, aminophenoxazines, aminophenothiazines, aminodihydro-phenazines, aminohydrocinnamic acids and corresponding esters, 2(p-hydroxyphenyl)-4,5-diphenylimidazoles, indanones, and mixtures thereof. The leuco dye may be an aminotriarylmethane such as Leuco Crystal Violet

[0066] Generally, leuco dyes are substantially colorless, and upon removal of one or two hydrogen atoms, convert to a colored dye. A wide variety of specific leuco dyes within the above mentioned categories may be suitable for use.

[0067] Upon heat-induced oxidation, protonation, ring-opening, or the like, in the presence of an activator, the leuco dye can form a dye having a variety of optical characteristics. Although a wide range of compositions are suitable, the coating composition may contain at least about 3% by weight of leuco dye, and may be present at from about 4% and about 20% by weight. This weight ratio range assumes that the color forming composition (which includes the leuco dye), absorber, and stabilizing agent are in a common coating layer.

[0068] As stated, interaction between a leuco dye and an activator causes a chemical change in the leuco dye, thereby altering the color of the leuco dye from substantially white or colorless to substantially colored in appearance. The colored appearance can be generally a dark color such as black or deep colors having a high optical density. Generally, the chemical change in the leuco dye occurs upon application of a predetermined amount of heat. Activators suitable for use in thepresent invention are generally known as hexaarylbiimidazoles (HABIs) and can be chosen by those skilled in the art. Several non-limiting examples of suitable HABI activators include 2,2'- bis(2-ethoxyphenyl)-4,4',5,5'-tetraphenyl-2',l,l'-bi-lH-imidazole (o-EtO-HABI); 2-(o- chlorophenyl)-4,5-bis(m-methoxyphenyl)imidazole dimer (CMD-HABI); 2,2'-bis(2- chlorophenyl)-4,4',5,5'-tetraphenyl-l,l'-bi-lH-imidazole (o-Cl-HABI); 2-(2-methylphenyl)-2'-[2- (2-methylphenyl)-4,5-diphenyl-2H-imidazol-2-yl]-4,5-diphenyl-lH-imidazole (o-Me-HABI); 2,2',5-tris(2-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenylbiimidazole (TCDM-HABI); 2,2',4,4'-tetra(2-chlorophenyl)-5,5'-bis(3,4-dimethoxyphenyl)-2', I'-bi-l'-lH- imidazole (TCTM- HABI); 2,2'-di(2'-naphthalenyl)-4,4',5,5'-tetraphenyl-l,l'-bi-lH-imidazole (N-HABI); 2,2'-bis(l- naphthalenyl)-4,4'-bis(2-chlorophenyl-5,5'-bis(3-methoxyphenyl)-2',l'-bi-lH-imidazole (MCN- HABI); and 2,2'-bis(l-naphthalenyl)-4,4',5,5'-tetrakis(3-methoxyphenyl)-2,l'-bi-lH-imidazole (MN-HABI), and combinations thereof. In one aspect of the present invention, the HABI activator is o-EtO-HABI. Other HABI activators can be used in the present invention and are known to those skilled in the art. The coating compositions of the present invention can contain from about 6% to about 45% by weight of HABI activator in one embodiment. In another embodiment, the HABI activator can be present from about 20% and about 40% by weight. In a further detailed aspect, the HABI activator can be present at from about 25% to about 38% by weight.

[0069] A color forming composition may also include an acid-generating compound. The acidgenerating compound may be configured to react under the influence of either heat or IR radiation to provide either acids or radicals which form acids. The acid-generating compounds suitable for use in the present invention include halogen sources such as, but not limited to, tribromomethyl phenyl sulfone, 1,2-dibromotetrachloroethane, tristri chloromethyltriazine, dibromobenzylidene acetophenone, and mixtures thereof. In one aspect of the present invention, the halogen source can be tribromomethyl phenyl sulfone.

[0070] An electromagnetic radiation absorber may be part of a color changing coating composition, and can be applied as a separate layer which can be can be applied in a commonliquid carrier with the color forming composition and / or the stabilizing agent. The absorber can act as an energy sink, providing heat to surrounding areas upon interaction with an energy source. As a predetermined amount of heat is provided by the electromagnetic radiation absorber, matching of the electromagnetic radiation frequency and intensity to the absorber used can be carried out to optimize the system. The absorber can be present in the composition in an amount of between about 0.001% and about 10% by weight, and typically, between about 1% and about 5% by weight, although other weight ranges may be desirable depending on the activity of the particular absorber.

[0071] The absorber can be configured to be in a heat-conductive relationship with a leuco dye. For example, the absorber can be placed in the same layer as the leuco dye as part of an admixture, or may be in a separate layer. Thus, the absorber may be admixed with or in thermal contact with the color forming composition. The absorber may be applied to the substrate in a separate adjacent layer prior to or after applying the color forming composition as a layer. In one embodiment, consideration can also be given to choosing the absorber such that any light absorbed in the visible range does not adversely affect the graphic display or appearance of undeveloped leuco dye.

[0072] Although an inorganic compound can be used, the absorber typically is an organic compound, such as, but is not limited to polymethyl indoliums, metal complex IR dyes, indocyanine green, heterocyclic compounds and combinations thereof. Suitable polymethyl indolium compounds available from Aldrich Chemical Company include 2-[2-[2-chloro-3-[2-(l,3- dihydro-l,3,3-trimethyl-2H-indol-2-ylidene)-ethylidene]-l-cyclopenten-l-yl-ethenyl]-l,3,3- trimethyl-3H- indolium perchlorate; 2- [2-[2-Chloro-3 -[2-( 1 ,3 -dihydro- 1,3,3 -trimethyl-2H-indol- 2-ylidene)-ethylidene] - 1 -cy clopenten- 1 -yl-etheny 1] - 1 ,3 ,3 -trimethy 1-3H- indolium chloride; 2- [2- [2-chl oro-3 - [( 1 , 3 -dihydro-3 , 3 -dimethyl- 1 -propyl-2H-indol-2-y I i denejethy lidene] - 1 -cyclohexen- 1 -yl] ethenyl] -3 , 3 -dimethyl- 1 -propylindolium iodide; 2- [2-[2-chl oro-3 - [( 1 , 3 -dihydro- 1 ,3,3- trimethyl-2H-indol-2-ylidene)ethylidene]-l-cyclohexen-l-yl]ethenyl]-l,3,3-trimethylindolium iodide; 2-[2-[2-chloro-3-[(l,3-dihydro-l,3,3-trimethyl-2H-indol-2-ylidene)ethylidene]-l-cy cl ohexen-l-yl] ethenyl] -1,3, 3 -trimethylindolium perchlorate; 2-[2-[3-[(l,3-dihydro-3,3- dimethy 1- 1 -propy l-2H-indol-2-y lidene)ethy lidene] -2-(pheny Ithio)- 1 -cyclohexen- 1 -yl] ethenyl] - 3,3-dimethyl-l-propylindolium perchlorate; and mixtures thereof. In one aspect of the present invention, the IR absorber is 2- [2- [2-chl oro-3 -[2-( 1,3 -dihydro- 1,3,3 -trimethyl-2H-indol-2- ylidene)-ethylidene] - 1 -cyclopenten- 1 -yl-etheny 1] - 1 ,3 ,3 -trimethy l-3H-indolium perchlorate.

[0073] A stabilizing agent may also be included in the coating compositions. The stabilizing agent may be included in the color forming composition or present in a separate layer, and applied to the substrate after the color forming composition. The stabilizing agent may be a diarylguanidine dye salt to improve ambient light stability. Suitable diarylguanidine dye salts include salts of yellow, brown, and orange dyes having acid groups and a diarylguanidine such as diphenylguanidines, di- o-tolylguanidines, dixylylguanidines, and di-o-oxylguanidines. In one embodiment, the stabilizing agent is an admixture of a salt of metanil yellow or tartrazine, and di-o-tolyl-phenyl guanidine.

[0074] The di-o-tolyl-pne hl guanidine yellow dye not only significantly increases room light stability, but can provide a useful “background” color which is not excessively dark. Other suitable diarylguanidine dye salts includes the commercially available LUXOL dyes such as LUXOL Fast Brown K / G, LUXOL FAST YELLOW T, LUXOL Fast Orange GS, other LUXOL dyes, and similar compounds. Other colored dyes such as LUXOL Fast Red, Black, Blue and the like can also be used, however such darker dyes generally present a low contrast with the developed leuco dye. In one embodiment, the stabilizing agent can be mixed with a binder such as a cellulosic ester binder to form an overcoat composition. This overcoat composition can be applied to a suitable substrate subsequent to the color forming composition layer.

[0075] The stabilizing agent can be present at from about 5% by weight to about 20% by weight, and in one aspect from about 7% to about 15% by weight, such as about 10% by weight.

[0076] The stabilizing agent may further include a polyhydroxybenzophenone, hydroxylamine, triarylimidazole, hydroxyphenylbenzotriazole, and mixtures thereof. In one aspect of the present invention the stabilizing agent further comprises 2,2',4,4'-tetrahydroxy benzophenone. The stabilizer may further comprise a dibenzyl-hydroxylamine. Such additional stabilizers can be present up to about 20% by weight, independent of the above diarylguanidine dye salts. However, the total weight percent of stabilizers should generally be maintained below about 30% by weight. If present in a separate layer, these weight percentages can be altered.

[0077] The conditions under which a colour changing coating composition are developed may be varied according to the electromagnetic radiation frequency, heat flux, and exposure time. Variables such as spot size and laser power will also affect any particular system design and can be chosen based on the desired results. With these variables, an infrared radiation source can direct infrared radiation to the color forming composition. Further, leuco dye and / or activator concentration and proximity to one another can also be varied. Typically, the activator and the leuco dye are present in a common layer, and thus, concentration ratios can be considered for a desired affect. However, if the color forming composition comprises multiple layers itself, proximity can be considered.

[0078] Leuco dyes can be developed using lasers having from about 15 to 100 mW power usage, although lasers having a power outside this range can also be used. Typically, lasers having from about 30 mW to about 50 mW are readily commercially available. The spot size can be determined by considering the electromagnetic radiation source, and can range from about 1 to about 200 pm, though smaller or larger sizes can also be used. In one embodiment, a radiation spot size of between about 10 and about 60 pm can also be utilized.

[0079] Heat flux is a variable that may be altered, and may be from about 0.05 to 1.0 J / cm2 in one embodiment, and from about 0.05 to 0.4 J / cm2 in a second embodiment. Heat flux in these ranges allow for development of leuco dyes in less than about 100 microsec per dot in some embodiments,and less than about 35 and 20 microsec per dot in other embodiments. To illustrate an example where these variables can be brought together in a single embodiment, a sample container outer surface coated with a composition including a color forming composition, an activator, and a stabilizer can be developed using a spot size of 20 by 50 pm, a 45 mW laser, and 20 microsec exposure per dot in about 5 minutes. The images produced in accordance with the present invention can have a high optical density of about 1.1 OD or greater.

[0080] The apparatus may comprise one of more processors, processor / controllers, or controllers having access to program instructions configured to effect the printing of any desired marking. The program instructions may accept as input information relating to the marking, and to generate output in the form of a digital or analogue signal which directs a printhead (such as a laser diode array) to make the desired marking. The program instructions may also direct a motor to rotate the sample container in a coordinated manner to make the desired marking.

[0081] The present disclosure may be embodied in the form of program instructions executable by a processor of the present apparatus. The instructions may take the form of software or firmware or both. The program instructions may be configured to execute any method disclosed herein, including any steps of inputting information relating to a marking for printing. The program instructions may be stored on a physical medium such as solid state storage means, magnetic storage means, or optical storage means.

[0082] The apparatus may be in the form of a stand alone item of equipment that is dedicated to printing of information or other markings on the outer curved surface of a sample container. For example, the stand alone item equipment may be benchtop equipment used at a pathology sample collection office to printing patient identification marks on a primary sample tube, such as blood collection tube or a urine jar.

[0083] The apparatus may be incorporated into, or functionally associated with, any item of laboratory equipment for which sample container printing is involved. For example, equipment involving removing an aliquot from a primary tube and placing into a second tube will benefit because of the need to label the secondary tube with information present on the primary tube. The secondary tube may be used for archiving sample, or as sample input for an analysis instrument. Exemplary equipment includes a MLA Aliquot Benchtop apparatus.

[0084] Any features discussed in relation to a preferred embodiment, including any of the embodiments of the drawings, may be applied to any other preferred embodiment. Any such features may also be applied to any broader embodiment, including any embodiment defined by the claims or in the summary section of this specification.

[0085] It will be understood that the foregoing description is only illustrative of the aspects of the present disclosure. Various alternatives and modifications can be devised by those skilled in the art without departing from the aspects of the present disclosure. Accordingly, the aspects of the present disclosure are intended to embrace all such alternatives, modifications and variances that fall within the scope of any claims appended hereto. Further, the mere fact that different features are recited in mutually different dependent or independent claims does not indicate that a combination of these features cannot be advantageously used, such a combination remaining within the scope of the aspects of the present disclosure.

[0086] Any single feature or combination of features described herein may be implemented not only with the preferred embodiments disclosed herein, but also any other embodiment falling within the ambit of the present disclosure.

Claims

CLAIMS:

1. Apparatus for printing onto an outer surface of a sample container, the apparatus comprising: a printhead having an electromagnetic radiation source, a sample container holder, and a mechanism to (i) move the sample container outer surface relative to the printhead or (ii) move the printhead relative to the sample container outer surface, wherein the apparatus is configured to maintain a distance between the sample container outer surface and the electromagnetic radiation source.

2. The apparatus of claim 1, wherein the electromagnetic radiation source is configured to direct focused electromagnetic radiation onto an outer surface of a sample container held by the sample container holder, the outer surface being sensitive to the focused electromagnetic radiation such that a visually discernible marking appears on the outer surface in response to the focused electromagnetic radiation thereon.

3. The apparatus of claim 2, wherein the electromagnetic radiation is capable of heating the sample container outer surface, and the sample container outer surface is heat sensitive.

4. The apparatus of claim 2 or claim 3, wherein the electromagnetic radiation is laser electromagnetic radiation.

5. The apparatus of claim 4, wherein the laser electromagnetic radiation is generated by a line or an array of diodes.

6. The apparatus of claim 5, wherein the diodes are disposed in a staggered arrangement.

7. The apparatus if claim 5, wherein the diodes are disposed on a wafer.

8. The apparatus of any one of claims 1 to 7, wherein the sample container outer surface is formed by: (i) a wall of the sample container, (ii) a material applied to a wall of the sample container, or (iii) a material incorporated into a wall of the sample container.

9. The apparatus of any one of claims 1 to 8, wherein the sample container holder is configured to hold a sample container used in a pathology laboratory, or another type of analytical laboratory.

10. The apparatus of claim 9, wherein the sample container is used in a pathology laboratory, or another type of analytical laboratory has a capacity of between about 1 ml and about 50 ml.

11. Apparatus of any one of claims 1 to 10, wherein the sample container has a curved outer surface and / or is elongate.

12. The apparatus of any one of claims 1 to 11 comprising a mechanism for rotating a sample container held in the sample container holder about its central axis such that an outer surface of the sample container is moved past the printhead.

13. The apparatus of claim 12 comprising one or more rollers configured to effect the rotation of the sample container about its central axis.

14. The apparatus of claim 13, wherein the one or more rollers: (i) form a part of the sample container holder, (ii) are the sample container holder, or (iii) are proximal to the sample container such that the one or more rollers and the sample container holder contact a sample container.

15. The apparatus of any one of claims 1 to 14, configured to print any one or more of the following onto a sample container outer surface: an optical code associated with a patient, a barcode associated with a patient, a QR code associated with a patient, a patient name, a patient identifier, a string of characters identifying a patient, a patient date of birth, a health insurance identifier, a social security identifier, a date and / or time the sample was obtained, a medical purpose for obtaining the sample, a bodily source of the sample, a treating practitioner name, a hospital name or a clinic name.

16. An item of sample aliquot equipment comprising, or being in functional association with, the apparatus of any one of claims 1 to 15.

17. A sample container used in a pathology laboratory, or another type of analytical laboratory, the sample container having an outer surface sensitive to laser electromagnetic radiation incident thereon such that an indicium appears on the sample container outer surface in response to the electromagnetic radiation, wherein the sample container outer surface is formed by: (i) a wall of the sample container, (ii) a material applied to a wall of the sample container, or (iii) a material incorporated into a wall of the sample container.

18. The sample container of claim 17, having any one or more of the following printed onto an outer surface: an optical code associated with a patient, a barcode associated with a patient, a QR code associated with a patient, a patient name, a patient identifier, a string of characters identifying a patient, a patient date of birth, a health insurance identifier, a social security identifier, a date and / or time the sample was obtained, a medical purpose for obtaining the sample, a bodily source of the sample, a treating practitioner name, a hospital name or a clinic name.

19. A method of printing onto an outer surface of a sample container used in a pathology laboratory, or another type of analytical laboratory, the method comprising the steps of:providing the apparatus of any one of claims 1 to 15, holding the sample container of claim 16 using the sample container holder of the apparatus, and causing or allowing the apparatus to print onto the sample container outer surface.

20. The method of claim 19, wherein the apparatus is caused or allowed to print any one or more of the following: an optical code associated with a patient, a barcode associated with a patient, a QR code associated with a patient, a patient name, a string of characters identifying a patient, a patient date of birth, a health insurance identifier, a social security identifier, a date and / or time the sample was obtained, a medical purpose for obtaining the sample, a bodily source of the sample, a treating practitioner name, a hospital name or a clinic name.

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