WO2013059568A1

WO2013059568A1 - A method of manufacturing a glass phial including an indicia marking region

Info

Publication number: WO2013059568A1
Application number: PCT/US2012/060983
Authority: WO
Inventors: Thomas Hughes; Harald RITCHIE
Original assignee: Thermo Fisher Scientific Inc.
Priority date: 2011-10-20
Filing date: 2012-10-19
Publication date: 2013-04-25
Also published as: GB201118107D0

Abstract

A method of manufacturing a glass phial including an indicia marking region, comprises the step of curing a glass phial by heating it. After this step, a porous writing patch is applied to the phial, for example by applying and curing an ink or by applying a plastic writing patch, to form the indicia marking region which is capable of being marked by dye sublimation. The porous writing patch is cured at a low temperature so that the patch remains sufficiently porous to be printed on by a dye sublimation process. The ingression of the dye into the patch gives the indicia more resilience and protection from chemical or mechanical abrasion or damage.

Description

A METHOD OF MANUFACTURING A GLASS PHIAL

INCLUDING AN INDICIA MARKING REGION

FIELD OF THE INVENTION

[0001] The present invention relates to a method of manufacturing a glass phial or vial including an indicia marking region, and particularly but not exclusively to a laboratory glass phial including an indicia marking region which can be marked to accurately identify the phial.

BACKGROUND OF THE INVENTION

[0002] One method of marking a laboratory glass phial is writing on it by hand using a marker. A problem with this is that human error is a major cause of mis-identification of the phial. Also, the curved surface and small size of many phials makes marking by hand with a marker difficult. The markers used have limitations in the resistance of the marks made to chemicals used in the processing of the phials. Also, the marks can smudge if the phials are handled too soon afterwards.

[0003] Another method involves applying a printed label to the phial which tends to provide a more readable identification. A problem with the label is that it can become detached from the phial. Although chemically resistant adhesives can be used for the labels, the adhesive is reliant on the cleanliness of the phial surface to which the label is applied. The adhesion can also be affected when the phial is stored at a very low temperature.

[0004] Yet another method involves using a pre- referenced phial. The reference is applied during the manufacturing process of the phial or may be applied by a laser at the end of the manufacturing process, and the resulting reference is permanent in most cases. A problem with this method is that there is a significant increase in the cost of the phials, requiring a high volume of phials to be produced. Furthermore, the user is restricted to the references or indicia offered by the supplier and may have to change working practices as a result.

100051 Other methods involve automatically printing or marking the required references or indicia on the phials. The glass phials may be produced with a screen printed glass enamel patch to form a writing surface to receive the required reference, and after the writing surface has been screen printed, the phial may be cured at a temperature of 600°C to 650°C which also sterilizes the phial. The writing surface may be printed by ink jets and the phials cured using ultraviolet light. A plotter may mark the writing surface using markers that are chemically resistant. Hot foil printing may be used to print the required mark on the writing surface. A problem with the printing or marking methods is that the marked writing surface is susceptible to damage by scratching and abrasion. Furthermore, the curved surface of many phials provides limitations to the printing or marking. In addition, by curing the phial to sterilize it, a smooth glass writing surface is produced which is hard and impermeable and makes bonding of ink to the surface difficult as ink cannot penetrate into the patch forming the writing surface.

[0006 J It is an object of the present invention to provide a method to alleviate at least one of the above-mentioned problems.

SUMMARY OF THE INVENTION

[0007] According to the present invention there is provided a method of manufacturing a glass phial including an indicia marking region, comprising the steps of:

(a) curing a glass phial by heating it; and

(b) after step (a), applying a porous writing patch to the phial to form the indicia marking region which is capable of being marked by dye sublimation. [0008] According to the present invention there is provided a method of manufacturing a glass phial including an indicia marking region, comprising the steps of:

(a) sterilizing a glass phial by curing the phial by heating it; and

(b) after step (a), applying a porous writing patch to the phial to form the indicia marking region which is capable of being marked by dye sublimation.

[0009] According to another aspect of the present invention there is provided a method of manufacturing a glass phial including an indicia marking region, comprising the steps of: applying a porous writing patch to the phial to form the indicia marking region which is capable of being marked by dye sublimation, curing the applied porous writing patch at a temperature sufficiently low so that the patch remains porous and is not hardened to become

impermeable.

[0010J By applying the porous writing patch after curing and sterilizing the glass phial, the writing patch remains porous enabling applied dye to ingress or penetrate into the patch so that the dye becomes extremely resistant to surface abrasion, scratching and chemicals used in processing the phial. Herein, the term dye refers to any suitable colorant known in the art. The method enables high print quality and resolution and enables full colour photographic images to be printed. The print quality and resolution makes it possible to print barcodes as part of the indicia. The method enables the advantageous use of dye sublimation printing, among other printing or marking methods, to mark the indicia on the phial. Dye sublimation may provide a more permanent marking than a marking made with a pen for example, which is a conventional manner of marking phials. Prior art phials have not been receptive to marking by dye sublimation processes due to lack of a suitable writing surface. Instead of a glass phial, non-glass phials may be used in the method, for example a metal, plastic or a ceramic phial may be manufactured. Glass phials are preferred, however. The invention utilises the porous writing patch, which is cured at a lower temperature than prior art patched vials, so that the patch remains sufficiently porous to be printed on by a dye sublimation process. The ingression of the dye into the patch gives the indicia more resilience and protection from chemical or mechanical abrasion or damage.

[0011] The method may include step (c) comprising curing the porous writing patch after step (b). Step (c) may include heating the glass phial to accelerate the curing of the porous writing patch. Such heating may be to increase the rate of cross linking in the patch as described below. The glass phial may be heated to a temperature below the temperature of curing the phial by heating in step (a). This heating would be sufficiently low so that the patch remains porous and is not hardened to become impermeable. The step (c) comprising heating to accelerate curing the porous writing patch may comprise heating to a temperature of at least 80 °C, or for faster curing at least 100°C, preferably heating to a temperature of at least 120°C and more preferably heating to a temperature of at least 140°C. Whilst this heating to accelerate curing the porous writing patch may be to at least any of the aforementioned temperatures, this heating is preferably to a temperature below the temperature of curing the phial by heating in step (a). More preferably, this heating to accelerate curing the porous writing patch is to a temperature not greater than 300 °C, or not greater than 250 °C, and still more preferably to a temperature not greater than 200 °C, or not greater than 175 °C. For example, in a preferred embodiment, step (c) may include heating the phial in the range of 140°C to 175°C. This heating may be for a period of at least 30 minutes, e.g. 30 to 60 minutes.

[0012] The step of applying the porous writing patch may comprise applying an ink, especially a pad printing ink or screen printing ink. The ink, especially pad or screen printing ink, may comprise a multi component ink, especially a two component pad printing ink or a more than two component pad printing ink, and step (c) may comprise curing the ink, especially two component pad printing ink or more than two component pad printing ink, by cross-linking. The ink is thus preferably a cross-linking ink, especially a cross-linking pad printing ink. For example, curing the ink may comprise cross-linking at least two components of the multi component ink. Heating the phial may accelerate the cross-linking. Thus, the multi component ink preferably comprises at least two cross-linking components that cross-link. Step (c) may include heating the phial in one of the temperature ranges above to accelerate curing the porous writing patch, e.g. in the range of 140°C to 175°C and the heating may be for a period of time in the range of 30 to 60 minutes. This accelerates curing of the ink.

Ingredients of a suitable ink, especially a pad or screen printing ink, may comprise at least two cross-linking components. A suitable ink may comprise in a solvent: at least two cross-linking components and a colorant. The colorant may be a mixture of colorants. The colorant may be any suitable or desirable color for the patch. White is a preferred color for the patch in view of the desire to

subsequently mark the patch. A hardener is preferably added to the cross linking ink when the ink is ready to be applied to the phial. The ink applied to the phial thus more preferably comprises in a solvent: at least two cross-linking

components, a colorant and a hardener. An antistatic agent, e.g. in the form of an antistatic paste, may be added to the ink prior to applying it to the phial. Additional solvent may be added to thin the ink to the desired viscosity for applying to the phial.

[0013] Processing the phial in step (a) may involve curing the phial by heating it to a temperature of at least 550°C, preferably at least 600°C, and preferably heating it to a temperature in the range of 550°C to 650°C. Step (b) may comprise applying the porous writing patch so that it forms a ring around the phial. This enables easier orientation of the glass phial so that the porous writing patch can be marked. Where the porous writing patch does not extend fully around the phial, the phial may have an orientation feature so that the porous writing patch is in the correct location or position to be marked. The orientation feature may form part of the porous writing patch and may, for example, comprise a line or tab and the line may be vertical (i.e. relative to the phial being in a standing position). The orientation feature may comprise a tooth. [0014] The porous writing patch may comprise a plastic writing patch which may be applied to the phial by being bonded by, say, an adhesive. Step (c) may comprise curing, especially ultraviolet (UV) curing, of the plastic writing patch, or rather the adhesive, and the curing may be dependent on the adhesive used to bond the plastic writing patch to the phial.

[0015] The porous writing patch forms an indicia marking region on the phial that may be marked after step (b), and preferably after step (c). A method of marking an indicia marking region of a glass phial manufactured in accordance with the method of the invention preferably comprises marking the indicia marking region formed by the porous writing patch by a dye sublimation printing process. However, it will be understood that other manners of marking the phial

manufactured in accordance with the method of the invention may be employed, for example writing by hand with a pen, marking with a plotter pen, or printing using an ink jet printer.

[0016] A method of marking an indicia marking region of a glass phial manufactured in accordance with the above described method, may comprise applying a heated heating means, e.g. a heat pad or thermal print head, to a tape with dye so that dye from the tape ingresses into the porous writing patch by dye sublimation to mark the porous writing patch of the phial. The dye may be vaporised by the heated heating means to mark the porous writing patch.

Generally, in accordance with an aspect of the invention, there is provided a method of marking an indicia marking region of a phial, especially a phial manufactured in accordance with the above described method, which method comprises the steps of applying a heated heating means, e.g. a heat pad or thermal print head, to a tape with dye thereon so that dye from the tape ingresses into the porous writing patch by dye sublimation thereby to mark the porous writing patch of the phial.

[0017] The method of marking the indicia marking region, may include (i) depositing dye on the tape; and (ii) moving the tape between the heating means and the porous writing patch of the phial so that the dye on the tape is adjacent at least a portion of the porous writing patch. Step (i) may include providing a reference mark adjacent the dye on the tape; and step (ii) may include moving the tape until the reference mark is sensed to be in the vicinity of the heating means.

[0018] The phial may be provided with a curved surface to which the porous writing patch is applied so that the porous writing patch has a curved surface, i.e. when applied to the phial. The heated heating means may have a heated curved surface, shaped so as to press the tape against the curved surface of the porous writing patch.

[0019] The heated heating means may comprise a thermal print head.

This may be suitable for marking the porous writing patch when it comprises the plastic writing patch.

[0020] Generally, the method of marking by a dye sublimation printing process may be used to mark an indicia marking region of either a glass or non- glass phial, wherein the indicia marking region is formed by a porous writing patch. For example, the dye sublimation printing process may be used to mark an indicia marking region of a plastic phial. Therefore, in accordance with a further aspect of the invention, there is provided a method of marking an indicia marking region of a phial, comprising marking the indicia marking region by a dye sublimation printing process, wherein the indicia marking region is formed on the phial by a porous writing patch which is capable of being marked by dye sublimation.

[0021] Also provided by the invention is a phial marking device arranged to mark the porous writing patch of a laboratory phial. The device preferably has a heating means, more preferably with a curved surface, facing a phial holding clamp. The device preferably has means to move a portion of the tape between the heating means and the phial holding clamp. A portion of the tape with dye may be placed between the heating means and the phial holding clamp, which in use holds a phial with its writing patch facing the heating means. This may be performed whilst another portion of the tape is opposite a print head, such as an inkjet print head, which is located away from the heating means. The other portion of tape can be printed by the print head with dye to be marked onto the phial. The tape can be moved between the print head location and the heating means location. At the heating means location, the heated heating means can be applied to the tape with dye to mark the writing patch, i.e. to cause dye from the tape to ingress into the porous writing patch.

[0022) A container may be provided by the invention containing a plurality of stacks of phials, such as said glass phials. The container may be used in a method of marking the indicia marking region of the phial. The lowermost phial of any said stack may be removed and placed in a position so that the indicia marking region of the removed phial is marked by a dye sublimation process. The lowermost phial of any said stack may be removed and placed in a position, for example in the phial holding clamp, so that dye from the tape ingresses into the porous writing patch of the phial when the heated heating means is applied. The container preferably comprises a series of compartments wherein each

compartment is arranged to hold a stack of phials. Preferably, at the bottom portion of each compartment on one side of the container is an opening through which the lowermost phial of said stack may be removed. Preferably, at the bottom portion of each compartment on the opposing side of the container is another opening suitable for an ejector to enter the compartment and eject the lowermost phial of said stack of phials contained in the compartment. Each of the openings is preferably initially (e.g. before removal of a phial is required, such as during transit or storage) covered by a friable or removable material. The container may be tagged, for automatic identification and/or tracking, for example by RFID tag.

100231 Accordingly, in an aspect of the invention, there is provided a container containing a plurality of stacks of phials configured for use in a method of marking an indicia marking region on the phials, wherein the lowermost phial of any said stack may be removed and placed in a position so that the indicia marking region of the removed phial is marked by a dye sublimation process.

DETAILED DESCRIPTION OF EMBODIMENTS

[0024] Embodiments of the present invention will now be described, by way of example, with reference to the accompanying schematic drawings, in which:

1 025] Figure 1 is a perspective view of a glass phial manufactured in accordance with a first embodiment of the present invention;

[0026] Figure 2 is a flow diagram illustrating the method of manufacture in accordance with the first embodiment of the present invention;

[00271 Figure 3 is a perspective view of a packaging container for containing the glass phials;

[0028] Figure 4 is a sectional view taken along lines 4-4 of Figure 3;

[0029] Figure 5 is a view of a glass phial marking device for marking the glass phials manufactured in accordance with the first embodiment of the present invention;

[0030] Figures 6 and 7 are views of a phial being removed from the packaging container and into the glass phial marking device;

[0031] Figure 8 is a view of a heated heating pad of the glass phial marking device being applied to the glass phial; and

[0032] Figure 9 is a view of a modified glass phial marking device for marking glass phials manufactured in accordance with a second embodiment of the present invention.

[003 J Referring to Figure 1 of the accompanying drawings, a cylindrical laboratory glass phial 1 according to a first embodiment of the invention is manufactured to include an indicia marking region comprising a porous writing patch 2.

[00341 Referring to Figure 2, the glass phial is first cured and sterilized by heating it (step 10), A two component pad printing ink is applied to the phial to form the porous writing patch which is capable of being marked by dye

sublimation (step 20). It will be understood that in some embodiments a pad printing ink having more than two components may be used, or other types of printing ink may be used. The two component pad printing ink is specifically formulated for use with glass as well as ceramics and metals. It has a matt surface finish, is opaque and the ink is easy to process even when a multicoloured writing patch is to be produced. The two component pad printing ink is applied so that it forms the porous writing patch 2 as a ring around the phial 1 (see Fig. 1 ). Thus, the writing patch extends circumferentially around the phial. However, in some alternative embodiments, the writing patch may extend only around a part of the circumference of the phial. Alternatively to pad printing, screen printing ink and screen printing methods may also be used for printing the writing patch. Such screen printing inks may also be of two or more components.

[0035] The two component pad printing ink is then cured by chemical cross-linking. In order to accelerate the curing of the two component pad printing ink, the glass phial is reheated, and the reheating temperature is significantly below the temperature of heat applied earlier to sterilize the phial (step 30).

[0036] In a specific example of a preferred embodiment, the glass phial 1 is cured and sterilized by heating it to a temperature in the range of 550°C to 650°C. A two component pad printing ink is then applied. An example ink is a white pad printing ink supplied by Inkcups Now (USA): INC Sapphire CG Series. 160 White. The full list of ink ingredients used is given in the table below. Weight

Material [ % ] * [gram]

INC Sapphire CG Series.

Ink 100 50

160 White

Hardener 1000-HGL 0.5Kg 5 2.5

Solvent** ICN M-Thinner 12 6

Antistatic ICN Antistatic Paste 3 1 .5

Total: 60.0

* Percentage is calculated based on 50 gram of ink

100371 After the two component pad printing ink has been applied, the glass phial 1 is then reheated in the range of 140°C to 175°C for a period of time in the range of 30 to 60 minutes so that the porous writing patch 2 is fully resistant to dishwashing cycles and chemicals to be used in processing. Generally, a heating temperature of at least 100 °C for a period of 30 minutes is sufficient. If the two component print pad ink is left to simply crosslink, the resulting porous writing pad 2 would be ready for overprinting in less than 60 seconds and will be dust dry in 20 minutes at room temperature. Complete crosslinking would be realized in 7 to 8 days at room temperature.

100381 After a plurality of glass phials 1 have been manufactured as described above, they are packaged in a packaging container 40 illustrated in Figures 3 and 4. The phials 1 are placed in a series of compartments 41 between opposing sides 42, 43 of the packaging container 40 wherein each compartment 41 is arranged to hold a stack 44 of phials 1 (see Fig. 4). At the bottom portion of each opposing side 42, 43 of each compartment 41 is an opening 45, 46. One opening 45 is suitable for the phial 1 to pass through and the opposing opening 46 is suitable for an ejector arm 60 (see Figs. 6 and 7) to enter the compartment 41 and eject the lowermost phial of the stack 44 of phials contained in the compartment 41. Each opening 45, 46 is initially covered by a friable or removable material 47 and the tops of the compartments 41 are covered by a cover 48 (omitted from Fig. 3) after the compartments 41 have been filled with stacks 44 of phials 1.

[0039] Referring to Figures 5 to 8, a device 50 is arranged to mark the porous writing patch 2 of a laboratory glass phial 1 . Such a phial marking device is provided according to a still further aspect of the invention. The device 50 has a heat pad 51 with a curved surface 52 facing a phial holding clamp 53 below. A portion of a blank tape 54 is placed between the heat pad 51 and the phial holding clamp 53 and another portion of the tape 54 is opposite an inkjet print head 55 which is located away from the heat pad 51. The tape 54 can be moved by rollers 56.

[0040] An electronic control processor 57 is connected to the heat pad 51 , an actuator 58 for the heat pad 51 , the phial holding clamp 53, the inkjet print head 55 and the tape rollers 56, and controls them. A sensor 59 is located adjacent the phial holding clamp 53 and is also connected to the processor 57. The ejector arm 60 is located by a packaging container holder 61 and is connected to the device 50 for marking the phial 1 .

[0041] In use, the packaging container 40 is placed in the holder 61 and the ejector arm 60 is extended into the container 40 to eject the lowermost phial 1 of a stack 44 of phials into the phial holding clamp 53 which then clamps the phial 1. The arm 60 then retracts so that the phial 1 ' that was immediately above the removed phial 1 is aligned with the ejector arm 60.

[0042] A portion of the tape 54 opposite the inkjet print head 55 has a phial identification mark 62, formed by dye droplets printed on it by the inkjet print head 55 using a dye which the tape 54 is formulated to accept although a hot foil tape may be used instead. A reference mark 63 is printed adjacent the dye mark 62 by the inkjet print head 55 although a separate print head could print this. The tape portion with the dye mark 62 is moved by the rollers 56 until the sensor 59 detects the reference mark 63 which means that the tape portion with the dye mark 62 is between the heat pad 51 and the porous writing patch 2 with the dye mark 62' (shown dotted in Fig. 5) on the tape 54 facing the porous writing patch 2.

10043 J The pad 51 is heated and the pad actuator 58 is actuated to push the heated pad 51 towards the porous writing patch 2 (see Fig. 8). The curved surface 52 is shaped so as to press the tape 54 against the curved surface of the porous writing patch 2 applying equal pressure to the curved patch surface so that the tape 54 is evenly pressed. This applies the dye mark 62' on the tape 54 to the porous writing patch 2 by the dye droplets bursting and penetrating into the porous writing patch 2 and the applied mark is protected by the cross-linked two component pad printing ink of the porous writing patch 2 which is chemically resistant. Thus, dye from the tape 54 ingresses into the porous writing patch 2 by dye sublimation to mark the porous writing patch 2 of the phial 1 .

[0044] When marking of the phial 1 has finished, the phial holding clamp

53 releases the phial 1 and the ejector arm 60 ejects another phial V from the stack 44 into the clamp 53. The tape 54 is moved by the rollers 56 until a tape portion having another dye mark and reference mark is between the heat pad 51 and the phial in the clamp 53.

[0045] When all the phials have been ejected from one compartment 41 of the packaging container 40, the packaging container holder 61 moves the container 40 so that the ejector arm 60 can eject phials from the stack in the next compartment.

[0046] Referring to Figure 9, a cylindrical laboratory glass phial 70 according to a second embodiment of the invention has a plastic writing patch 71 applied as a ring around the phial 70 wherein the writing patch 71 is bonded to the phial 70 by adhesive. The writing patch 71 on the phial 70, and more specifically the adhesive, is then cured by ultraviolet light. 10047 J A device 80 for marking the plastic writing patch 71 of the laboratory glass phial 70 is a modification of the device 50 for marking the porous writing patch 2 of the laboratory glass phial 1 . Such a phial marking device is provided according to a yet further aspect of the invention. The device 80 does not have the inkjet print head or the heat pad with a curved surface of the device 50 but instead has a thermal print head 81 containing a series of heating elements 82 in a line perpendicular to the tape 83. The tape 83 used is a dye sublimation tape with ink on the side 84 of the tape 83 facing the plastic writing patch 71 of the phial 70. The tape 83 is pinched between the thermal print head 81 and the plastic writing patch 71 . This may be done by moving the thermal print head 81 and/or the clamp 53 containing the phial 70 towards the tape 83. Individual heating elements 82 of the thermal print head 81 are applied to the tape 83 so that dye on the opposite side 84 of the tape 83 is vapourised and ingresses into the plastic writing patch 71 to mark the plastic writing patch 71 of the phial 70 by dye sublimation.

[0048] The plastic writing patch 71 is porous to enable dye sublimation.

The plastic writing patch 71 is of a softer material than the porous writing patch 2 formed from two component pad printing ink and thus less heat needs to be applied for dye sublimation. This enables a thermal print head to be used to mark the writing patch.

[0049J Whilst particular embodiments have been described, it will be understood that various modifications may be made without departing from the scope of the invention. For example, the friable material 47 covering the openings 45, 46 on the packaging container 40 may be replaced by a removable film.

[0050] As used herein, including in the claims, unless the context indicates otherwise, singular forms of the terms herein are to be construed as including the plural form and vice versa. For instance, unless the context indicates otherwise, a singular reference, such as "a" or "an" means "one or more". [0051 ] Throughout the description and claims of this specification, the words "comprise", "including", "having" and "contain" and variations of the words, for example "comprising" and "comprises" etc, mean "including but not limited to", and are not intended to (and do not) exclude other components.

[0052] It will be appreciated that variations to the foregoing embodiments of the invention can be made while still falling within the scope of the invention.

Each feature disclosed in this specification, unless stated otherwise, may be replaced by alternative features serving the same, equivalent or similar purpose. Thus, unless stated otherwise, each feature disclosed is one example only of a generic series of equivalent or similar features.

[0053] The use of any and all examples, or exemplary language ("for instance", "such as", "for example", "e.g." and like language) provided herein, is intended merely to better illustrate the invention and does not indicate a limitation on the scope of the invention unless otherwise claimed. No language in the specification should be construed as indicating any non-claimed element as essential to the practice of the invention.

[0054] All or any of the features disclosed in this specification may be combined in any combination, except combinations where at least some of such features and/or steps are mutually exclusive. In particular, the preferred features of the invention are applicable to all aspects of the invention and may be used in any combination. Likewise, features described in non-essential combinations may be used separately (not in combination).

Claims

CLAIMS:

1 . A method of manufacturing a glass phial including an indicia marking region, comprising the steps of:

(a) curing a glass phial by heating it; and

2. The method as claimed in claim 1 , wherein step (a) comprises sterilizing the glass phial by curing the phial by heating it.

3. The method as claimed in claim 1 or 2, including step (c) comprising curing the porous writing patch after step (b).

4. The method as claimed in claim 3, wherein step (c) includes heating the glass phial to accelerate the curing of the porous writing patch.

5. The method as claimed in claim 4, wherein step (c) involves heating the glass phial to a temperature below the temperature of curing the phial by heating in step (a).

6. The method as claimed in any preceding claim, wherein the step of applying the porous writing patch comprises applying an ink.

7. The method as claimed in claim 6, wherein the step of applying the porous writing patch comprises applying a pad printing ink.

8. The method as claimed in claim 6, wherein applying the pad printing ink comprises applying a two component pad printing ink.

9. The method as claimed in claim 3 and any of claims 6 to 8, wherein step (c) comprises curing the ink by cross-linking.

10. The method as claimed in claims 4 and 9, wherein step (c) includes heating the phial to a temperature of at least 100°C,

1 1. The method as claimed in claim 10, wherein step (c) includes heating the phial in the range of 140°C to 175°C.

12. The method as claimed in claim 10 or 1 1 , wherein step (c) involves heating the phial for a period of time in the range of 30 to 60 minutes.

13. The method as claimed in any one of claims 1 to 6, wherein the step of applying the porous writing patch comprises applying a plastic writing patch.

14. The method as claimed in any preceding claim, wherein step (a) involves curing the phial by heating it to a temperature of at least 550°C.

15. The method as claimed in any preceding claim, wherein step (b) comprises applying the porous writing patch so that it forms a ring around the phial.

16. A method of marking an indicia marking region of a glass phial manufactured in accordance with any preceding claim, comprising marking the indicia marking region by a dye sublimation printing process.

17. The method as claimed in claim 16, comprising applying a heated heating means to a tape with dye so that dye from the tape ingresses into the porous writing patch by dye sublimation to mark the porous writing patch of the phial.

18. The method as claimed in claim 17, wherein the step of applying the heated heating means to the tape comprises applying a heated thermal print head to the tape.

19. The method as claimed in claim 17, including (i) depositing dye on the tape; and (ii) moving the tape between the heating means and the porous writing patch of the glass phial so that the dye on the tape is adjacent at least a portion of the porous writing patch.

20. The method as claimed in claim 19, wherein step (i) includes providing a reference mark adjacent the dye on the tape; and step (ii) includes moving the tape until the reference mark is sensed to be in the vicinity of the heating means.

21 . The method as claimed in claim 17, 19 or 20, including providing the glass phial with a curved surface to which the porous writing patch is applied so that the porous writing patch has a curved surface; and providing the heated heating means involves providing a heated curved surface, shaped so as to press the tape against the curved surface of the porous writing patch.

22. The method as claimed in any one of claims 17 to 21 , including the steps of providing a container containing a plurality of stacks of said glass phials, and removing the lowermost phial of any said stack and placing it in a position so that dye from the tape ingresses into the porous writing patch of the phial when the heated heating means is applied.

23. A method of manufacturing a glass phial including an indicia marking region, comprising the steps of: applying a porous writing patch to the phial to form the indicia marking region which is capable of being marked by dye sublimation, curing the applied porous writing patch at a temperature sufficiently low so that the patch remains porous and is not hardened to become impermeable.

24. A method of marking an indicia marking region of a phial, comprising marking the indicia marking region by a dye sublimation printing process, wherein the indicia marking region is formed on the phial by a porous writing patch which is capable of being marked by dye sublimation.

25. A phial marking device arranged to mark a porous writing patch of a phial, wherein the device has a heating means facing a phial holding clamp and further has means to move a portion of a tape with dye thereon between the heating means and the phial holding clamp, which in use holds a phial with a writing patch on the phial facing the heating means, whereby heating the heating means and applying the heated heating means to the portion of tape with dye causes dye from the tape to ingress into the writing patch.

26. The phial marking device of claim 25, further comprising a print head for applying dye to a portion of the tape, wherein the print head is located away from the heating means and wherein the means to move a portion of the tape can move the portion of tape between the location of the print head and the location of the heating means.

27. A container containing a plurality of stacks of phials configured for use in a method of marking an indicia marking region on the phials, wherein the lowermost phial of any said stack may be removed and placed in a position so that the indicia marking region of the removed phial is marked by a dye sublimation process.