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    • 专利摘要:
    polymeric members and methods for marking polymeric members are generally polymeric members and laser marking methods for producing visible markings on polymeric members, such as thin and/or curved surfaces. laser marking methods may include methods for laser marking straws with the step of adapting laser source properties to the properties of straws that are marked or with the step of laser marking straws that have photochromic dyes.
    公开号:BR112013026790B1
    申请号:R112013026790-9
    申请日:2012-04-17
    公开日:2022-01-04
    发明作者:Johnathan Charles Sharpe；Thomas B. Gilligan；Richard W. Lenz；Juan F. Moreno
    申请人:Inguran, Llc；
    IPC主号:
    专利说明:

    FIELD OF THE INVENTION
    [001] The present invention generally relates to polymeric members and laser marking methods for producing visible marks on polymeric members, and more particularly relates to laser-marked straws used to contain biological materials and methods for generating visible marks. into straws with a laser. BACKGROUND
    [002] Straws, such as straws with a capacity of 0.25 ml and straws with a capacity of 0.5 ml, can be used to transport and store biological products, biological materials, biological fluids, embryos, inseminated for the artificial insemination of an animal , semen, eggs, or the like and can be chilled or super chilled for storage. Marking individual straws is often desirable to identify the type of cells contained and their source.
    [003] Conventionally, straws can be serially processed through a printer prior to inputting contents for storage. Straws are typically highly narrow in diameter, ranging from 2 millimeters (“mm”) to 5 mm, and typically about 133 mm or about 280 mm in length. Therefore, the area on the outer surface on which marks can be printed may be limited. The straw printing job may be unsuitable for most types of impact printing, not only because of the non-planar surfaces to be printed on, but also because empty or fluid-filled plastic straws can dent or deform if subjected to pressure. located. Currently, printing on conventional cylindrical artificial insemination straws typically involves a mechanical system that accepts individual straws from a dispenser, which contains a plurality of straws, and passes the straws lengthwise near the print head of a jet printer. of stationary ink. The print head disperses ink droplets in appropriate volumes, trajectories and times to produce marks on one side along the length of the straw. This approach can produce visible marks in relation to the straw's secondary color to aid in identifying the contents of each straw. Marks typically applied to straws that, for example, contain inseminated for artificial insemination provide characters that can identify the semen source, animal name, date, company information, freezing batch, and sex selection characteristics such as being enriched for X-chromosome-bearing sperm or Y-chromosome-bearing sperm, or the like.
    [004] However, there are substantial unresolved issues associated with marking straws with an inkjet printer and the resulting ink marks. A substantial problem with inkjet printer marking straws is that characters may not be small enough and resolved enough to include all the necessary or desired information in the printable area of the straw. This problem can be exacerbated by international exchange requirements that now need additional information about individual straws. Additionally, the current resolution and accuracy of inkjet printing limits the complexity of characters that can be printed on the straw and may not be suitable for printing 1D, 2D, 3D or grayscale bar codes, logos, trademarks, or similar. Additionally, slight variations in the speed at which straws pass the inkjet print head can result in brand distortions such as pinched, stretched, or variable contrast marks.
    [005] Another substantial problem with branding straws by inkjet printer may be that inkjet printing is a one-time process that prevents printing on a straw multiple times. Conventional straw printers do not control straw orientation (rotation/rolling) in relation to the inkjet printhead. Thus, straws cannot be pre-printed with information that is constant between straws, such as company information, production location, trademarks, logos, or the like, and then reprinted at a subsequent date with variable information between straws such as identification code. (bull code), lot number, date or the like.
    [006] Another substantial problem with marking straws by an inkjet printer can be that the printed information may not be permanent. Inkjet printer ink can be soluble in a variety of solvents commonly used in the production of straws that contain biological products such as methyl alcohol, ethyl alcohol, acetone, ether, or the like. Consequently, information printed on inkjet printer ink can be readily removed by contact with such solvents. Similarly, information printed in inkjet printer ink can be removed by light abrasion.
    [007] Another substantial problem with marking straws by inkjet printer can be that consumables such as inkjet printer ink and thinner used to clean the inkjet printer can have a level of toxicity, can be spilled and time-consuming to clean, and can be costly.
    [008] Another substantial problem with impact marking or inkjet printer marking may be the relative ease of counterfeiting marks by uncertified manufacturers. Conventional marking is relatively large and uncomplicated and does not include authenticity markings.
    [009] Another substantial problem with impact marking or inkjet printer marking can be the lack of raised surfaces. Consequently, the marks cannot be interpreted by touch.
    [010] A wide variety of polymeric materials can be laser marked, such as liquid crystal polymer (LCP), polyethersulfone (PES), polyphenol sulphide (PES), polystyrene, polypropylene, polyethylene, polyethylene terephthalate (PET), polyvinyl chloride (PVC) and acrylonitrile butadiene styrene (ABS). However, laser beam induced marking of certain configurations of polymeric members such as straws that have an axial body defining an axial passage communicating between a pair of body ends continue to be marked using an inkjet printer with inkjet as described above. In particular, straws used for the storage of biological materials such as sex-sorted sperm, conventional semen, eggs, cells, embryos and similar cellular materials continue to be inkjet printed.
    [011] Previous attempts to brand such polymeric members by impinging a laser beam have resulted in markings that were too weak or resulted in brittleness, shrinkage, bending, drooping, or the like that rendered the polymeric member subsequently unsuitable for depositing the polymer. biological material, filling with biological liquids, cryogenic freezing of the polymeric member containing the biological material, storage, or handling.
    [012] The polymeric members and laser marking methods described in this document address each of these substantial problems of conventional straw marking. SUMMARY OF THE INVENTION
    [013] Accordingly, a broad object of the invention may be to provide a method of laser straw marking for marking the thin, curved surface of a straw, such as a cryopreservation straw. The laser beam may be optically focused to establish a laser beam spot of fixed dimensional threshold and adjustable fluence at each of a plurality of pixels located in the marking plane for an irradiation dwell period sufficient to produce a mark.
    [014] Another broad objective of the invention may be to provide methods for laser marking of straws that include adjusting laser beam characteristics within marking value ranges that allow visible marking of a variety of polymeric matrices of straws without straw deformation.
    [015] Yet another broad object of the invention may be to provide methods for laser marking of straws that include adjusting laser beam characteristics within marking value ranges that allow visible marking of a variety of polymeric matrices of straws without creating straw permeability. to biological materials that include, without limitation, pathogens such as bacteria and viruses.
    [016] Yet another broad object of the invention may be to provide a plurality of laser beam characteristics that to a plurality of tailored marking value ranges that allow a laser beam incidentally directed onto the marking plane of any one of a number of variety of straws differentiated by dispersed coloring, or dye, with the corresponding polymeric matrices to be visibly marked.
    [017] Another broad objective of the invention may be to provide methods for laser marking of straws that include laser beam characteristics adapted to characteristics of straws to reduce power and time requirements for marking straws.
    [018] Yet another broad object of the invention may be to provide a straw that has a thickness between about 0.1 mm and about 0.2 mm with visible laser engraved markings. Such a straw can retain a non-slanted shape and remain impermeable providing a suitable container for cryopreservation biological materials.
    [019] Another broad object of the invention may be to provide methods for laser marking of straws that include laser beam characteristics adapted to characteristics of straws, whereby the characteristics of straws can be modified for marking.
    [020] Yet another broad object of the invention may be to provide methods for marking a straw with a laser that provide increased protection against ultraviolet light.
    [021] Yet another objective of the invention may be to improve the properties of straws for marking with the inclusion of photochromic dyes that can selectively alter straw characteristics.
    [022] Of course, additional objects of the invention are revealed by all other areas of the specification, drawings and claims. BRIEF DESCRIPTION OF THE DRAWINGS
    [023] Figure 1 illustrates a diagram referring to modalities described in this document.
    [024] Figure 2 illustrates a diagram of particular computer media and control module media of modalities described in this document.
    [025] Figure 3 illustrates a perspective view of a laser-marked polymeric member in accordance with particular embodiments described herein.
    [026] Figure 4 illustrates a cross-sectional view of a laser-marked polymeric member according to particular embodiments described herein.
    [027] Figure 5 illustrates the results of assays in which a plurality of polymeric members is laser marked in accordance with certain modalities described herein.
    [028] Figure 6 illustrates a color wheel that indicates complementary primary and secondary colors.
    [029] Figure 7 illustrates a diagram referring to modalities described in this document.
    [030] Figure 8 illustrates a diagram referring to modalities described in this document.
    [031] Figure 9 illustrates a block diagram referring to the methods described in this document. DETAILED DESCRIPTION
    [032] Referring now firstly to Figure 1, a laser source (1) that operates to generate a laser beam (2) is illustrated. A non-limiting example of a laser source (1) may include a laser diode (3) that generates laser light (4) that travels within a fiber optic cable (5) to a laser head (6). At a fixed voltage, amperage (48) for the laser diode (3) can be adjusted to provide an adjustablely variable laser beam (2) within a power range. The laser head (6) can contain a laser crystal (7) and a Q switch (8). As a non-limiting example, the laser crystal (7) may be a vanadate (Nd:YVO4) laser crystal (7) which absorbs laser light (4) at 808 nanometers ("nm") from the laser diode. laser (3) and produces continuous waveform laser light (4) at a wavelength of 1064 nm. Q switching (8) acts to convert continuous waveform laser light (4) from laser crystal (7) (such as vanadate crystal) to series laser beam pulse(s) ( 9). The Q switch (8) can be opened and closed in the range of about 1000 to about 70,000 times per second. While the Q switch (8) is open, the stored energy from the laser crystal (7) emits a laser beam (2) until the Q switch (8) closes, which results in a laser beam pulse ( 9). The duration of the laser beam pulse (9) can be adjusted by a change in the switching rate of the Q switching (8). The above example of a laser source (1) is not intended to be limiting with respect to the numerous and wide varieties of laser source (1) that can be used to produce a laser beam (2) (either continuous or pulsed). ) that have a correspondingly wide range of waveform characteristics such as frequency or amplitude or both that may be suitable for use with the particular embodiments described herein. In particular, non-limiting examples of suitable laser sources (1) include Nd:YVO or YAG lasers (wavelength 1.064 nm), Nd:YVO or frequency doubled YAG lasers (wavelength 532 nm), and Excimer lasers (wavelength 193 nm, 351 nm).
    [033] The laser beam (2) emitted from the laser head (6), whether continuous or pulsed, can be received by one or a pair of scanning mirrors (10) (11), which can be referred to collectively as a driving element. The pair of scanning mirrors (10) (11) can be positioned to direct the laser beam (2) or each of the laser beam pulses (9) incident on a marking plane (12). Alternatively, acoustic-optical modulators and other refractory and reflective elements could be used to drive the laser beam (2). The laser beam (2) can also be optically focused to produce a laser beam spot (13) that has a threshold (14) of fixed dimension in the marking plane (12) by passing the laser beam (2) , or each of the laser beam pulses (9), through a focusing lens (15), such as an F-Theta lens. By optically focusing the laser beam (2) through the focusing lens (15), the threshold (14) of the laser beam spot (13) can be adjusted to a diameter in the range of about 20 microns to about 100 microns. Particular embodiments provide for a laser beam spot (13) incident on the marking plane (12) with a diameter of about 40 microns. If the power of the laser beam (2) is fixed, the smaller the dimension of the laser beam spot (13), the greater the fluency (62) of each of the laser beam pulses (9) incident on the plane of marking (12).
    [034] A plurality of pixels (16) can be assigned to a corresponding plurality of pixel locations (17) in relation to the marking plane (12). The plurality of pixel locations (17) may correspond to a marking pattern (50) that contains shape or text information, bar codes, logos, trademarks, or other representations of information. The laser beam spot (13) can be centered along one or more of the plurality of pixels (16) by operating the pair of scanning mirrors (10) (11). The step size (88), or spacing between the plurality of pixels (16), can be adjusted to increase or decrease the distance between any two of the plurality of pixel locations (17). If, for example, the laser beam spot (13) has a diameter of about 40 microns and the distance between any two of the plurality of pixels (16) is about 30 microns, series centered incidence of the laser beam (2) on any two of the plurality of pixels (16) will result in overlapping incidence of the laser beam (2) on the marking plane (12). If the laser beam spot (13) has a diameter of about 40 microns and the distance between any two of the pixel locations (17) is about 50 microns, then series-centered incidence of the laser beam (2) on any two of the plurality of pixels (16) will result in distant incidence of the laser beam (2) on the marking plane (12). Understandably, a smaller diameter laser beam spot (13) and a smaller distance between the plurality of pixel locations (17) can increase the resolution of a resulting visible mark (18) on the marking plane (12), but it can also increase the marking period (19) in which to complete the marking of the visible mark (18).
    [035] For each of the plurality of pixel locations (17), an irradiation dwell period (20) can be adjusted to increase or decrease the amount of time that the laser beam (2) remains at each of the plurality of pixel locations (17). As a non-limiting example, a relatively low fluence (62) of the laser beam (2) may need a longer irradiation dwell period (20) at each of the plurality of pixel locations (17) to achieve the same result. as compared to relatively high fluency (62) at each of the same plurality of pixel locations (17) acting on the same marking plane (12). The irradiation dwell period (20) can also be adjusted to encompass the duration of a laser beam pulse (9) or the duration of a plurality of laser beam pulses (9) in the same of the plurality of pixel locations. (17).
    [036] The term visible can be interpreted as visible by the naked eye, as well as by machine vision approaches, since at some stage straws can be 'read' by a device that is computer-based or has intelligence aspects. artificial that copies human functions. Similarly, the term visible markings (18) may include laser etched markings, such as holes, pits, charring, or other localized modifications of the surface depth or color of the surface that is marked that are visible to the naked eye or to vision approaches. of machine.
    [037] Producing visible markings (18) in a desired marking pattern (50) requires coordination of a variety of factors. One or more than one laser source (1) can produce laser beam pulses (9) at a coordinated rate, if pulsed, and can have a coordinated fluence (62) incident on the marking plane (12) that can be adjusted by varying laser beam power and/or threshold (14) of laser beam spot (13). The positioning of the pair of scanning mirrors (10) (11), or alternatively beam positioners, to direct the laser beam (2) incident on the marking plane (12) can be coordinated to control spacing between a plurality of pixel locations (17), as well as the irradiation residence period (20) of the laser beam (2) incident on each of the plurality of pixels (16). The scanning mirrors (10) (11), or other laser beam positioning mechanism, may be substituted for, or used in conjunction with, a carrier (52) movable with respect to the laser beam (2). For example, the carrier (52) can be coordinated with a carrier position controller (70) for movement in the longitudinal direction, while the scanning mirrors (10) (11) can direct the laser beam (2) orthogonally.
    [038] Referring now firstly to Figures 1 and 2, coordination of the factors described above can be controlled by a computer (21) that has a processing unit (22), a memory element (23), and a bus (24). ) which operably couples components of the computer (21), including, without limitation, the memory element (23) to the processing unit (22). The computer (21) may be a conventional computer (21) such as a personal computer or a laptop computer; however, the invention is not so limited. The processing unit (22) may comprise a central processing unit (CPU), or a plurality of processing units operating in parallel to process digital information. The bus (24) can be any of several types of bus configurations that include a memory bus or memory controller, a peripheral bus, and a local bus using any of a variety of bus architectures. The memory element (23) can be, without limitation, a read-only memory (ROM) (25) or a random access memory (RAM) (26), or both. A basic input/output system (89), which contains routines that assist in transferring data between computer components (21), such as during startup, may be stored in ROM (25). The computer (21) may additionally include a hard disk drive (27) for reading from and writing to a hard disk (28), a magnetic disk drive (29) for reading from and writing to a removable magnetic disk (30) , and an optical disc drive (31) for reading from and writing to a removable optical disc (32) such as a CD ROM or other optical media.
    [039] The hard disk drive (27), magnetic disk drive (29), and optical disk drive (31) are connected to the bus (24) by a hard disk drive interface (33), a magnetic disk drive (34), and an optical disk drive interface (35), respectively. The drives and their associated computer-readable media provide non-volatile storage of computer-readable instructions, data structures, program modules, and other data for the computer. It will be appreciated by those skilled in the art that any type of computer readable media that can store data that is accessible by the computer (21), such as magnetic cassettes, flash memory cards, digital video discs, Bernoulli cartridges, memory random access memory (RAMs), read-only memories (ROMs), and the like can be used in a variety of operating environments.
    [040] One or more laser control modules (36) or demarcation modules (37) and an operating system (38) (wired circuitry may be used in place of, or in combination with, software instructions ) can be stored on hard disk (28), magnetic disk (30), optical disk (32), ROM (25), or RAM (26), which can be served by the computer server. A computer user (51) can enter dialing commands (39) and dialing data (40) into the computer (21) through input devices (41), such as a keyboard (42) and a pointing device (43) such as a mouse, although other input devices (41) may be used such as a touch screen, joystick control device or the like. These and other input devices (41) are often connected to the processing unit (22) through a serial port interface (44) that can be coupled to the bus (24), but can be connected by other interfaces, such as a parallel port, game port, or a universal serial bus (USB). A monitor (68) or other type of display device may also be connected to the bus (24) via a monitor interface (67), such as a video adapter, or the like. In addition to the monitor (68), the computer (21) may additionally include other peripheral output devices (45), such as speakers and printers.
    [041] The laser control modules (36) provide a sequence of instructions executed by the processing unit (22). Execution of instructions by the processing unit (22) causes a laser control unit (46) to perform steps to generate laser control signals (47) for operation of the laser source (1) which includes the laser diode ( 3), amperage (48) for the laser diode (3) and any switch such as Q switching (8) to generate laser beam pulses (9).
    [042] The marking modules (37) provide a sequence of instructions executed by the processing unit (22). Execution of instructions by the processing unit (22) causes the marking control unit (49) to mark, in serial order, each of a plurality of pixels (16) at a plurality of pixel locations (17) that correspond to the marking pattern (50) that can be entered by the computer user (51). Execution of the instructions may produce a dial control signal (78a) to drive the pair of mirrors (10) (11) with a drive controller (69) to direct the laser beam (2) to each of the plurality of pixels (16) at each of the corresponding pixel locations (17) in the marking plane (12) for an assigned irradiation dwell period (20) in accordance with the marking pattern (50). In certain embodiments, execution of additional instructions may produce a dial control signal (78b) to operate a carrier position controller (70) to position a dial car (52). In certain embodiments, the instructions may provide marking control signals (78b) to manipulate the marking carriage (52) to serially position multiple straws (61) within the travel range (53) of the laser beam (2).
    [043] Referring now first to Figure 3, particular embodiments of the invention include a numerous and wide variety of polymeric members (54), particularly polymeric members (54) that have thin and/or curved surfaces. Particular embodiments of the polymeric members (54) have an axial body (55) that defines an axial passage (56) that communicates between a pair of body ends (57) (58) that include, but are not limited to, cylindrical vessels (59). ) that define a cylindrical passage (60) (as shown in Figure 3). As a non-limiting example, some embodiments regarding straws (61) for containing a variety of biological materials, and in certain embodiments, cryogenically frozen biological materials, such as embryos, semen, eggs, sperm cells, selected sperm cells by sex (subpopulations of sperm cells selected on the basis of being X-carrying or Y-carrying), sex-selected embryos, or the like. Straws (61), as a non-limiting example, may have a length of about 133 mm or about 280 mm with an outside diameter in the range of about 0.8 mm to about 5 mm and an inside diameter in the range of about 0.7mm to about 4.9mm and having a wall thickness in the range of about 0.1mm to about 0.2mm.
    [044] Figure 4 illustrates a cross-sectional view of the straw (61) seen in Figure 3. The inner surface (86) and outer surface (85) of the straw (61) can be seen as defining a straw thickness (87). Some depth of the visible mark (18) can also be seen in this cross-sectional view.
    [045] Table 1 provides a non-limiting list of straws (61) suitable for use with particular embodiments of the invention which may be obtained from IMV Technologies, 10, rue Clemenceau, 61300 L'Aigle, France, or other sources.


    [046] Modalities of polymeric members (54) that include conventional artificial insemination straws (61) are formed from polyvinyl chloride ("PVC") and polyethylene terephthalate ("PETG"). Additives such as carbon black, graphite, calcium silicates, zirconium silicates, zeolite, mica, kaolin, talc cordierite, and colorants such as organic pigments, inorganic pigments, photochromatic dyes, or polymer-compatible organic dyes can be dispersed by the entire polymer matrix (65) of the polymeric members (54). These polymers have been found to be impermeable to a wide range of biological materials including impermeability to hepatitis B and HIV-1 virus and other viruses, or the like, even when the straws containing the biological materials are cryogenically frozen. Benifla, Jean-Louis et al., “Safety of cryopreservation straws for human gametes or embryos: a preliminary study with human immunodeficiency virus 1”, Human Reproduction, Vol 15, no. 10, 2186 to 2189 (October 2000).
    [047] However, as described above, polymeric members (54) have not been laser marked previously, as attempts to generate a visible mark (18) in the marking plane (12) of polymeric members (54), which includes straws (61) ) such as those listed in Table 1 have resulted in either no visible mark (18) or a visible mark (18) that causes permeability and transfer of the contained biological materials or results in deformation of the polymeric member (54) to some extent that prevents the use of automated or manual downstream processes to fill the polymeric members (54) with biological materials, store, or utilize the polymeric member (54) for the intended purpose.
    [048] Figure 5 provides a tabular summary of the results obtained in tests in which a laser beam (2) was made incident on a marking plane (12) of certain modalities of a polymeric member (54) formed from a polymer of PVC to provide a length of about 133 mm with an outside diameter of about 4 mm and an inside diameter in the range of about 3.8 mm which results in a wall thickness of about 0.1 mm. Each assay was performed using a laser source (1) that includes a vanadate (Nd:YVO4) laser crystal (7) that absorbs laser light (4) at 808 nanometers (“nm”) from a laser diode (3) to produce a continuous waveform laser light (4) at a wavelength of 1064 nm, of doubled frequency to produce a laser beam (2) having a wavelength of 532 no. The laser beam (2) was switched using a Q-switch (8) to generate laser beam pulses (9) having a frequency of 10 kHz. The threshold (14) of the laser beam (2) incident on the marking plane (12) of each polymeric member (54) was set to establish a laser beam spot (13) having a diameter of about 40 μm . The fluency (62) of each of the plurality of laser beam pulses (9) was controlled by adjusting the amperage (48) of the current applied to the laser diode (3) to achieve an adjustable power range between 0.1 % and 100% of about 2 W. The step size (88), or distance between each of a plurality of pixel locations (16), was controlled by the marking module (37) of the computer (21) to establish a range of distance between any two of a plurality of pixels (17) (also referred to as "step size") within a range of about 30 µm and about 100 µm. The plurality of pixel locations (16) established by the marking module (37) of the computer (21) was adapted to a marking pattern (50) constant between trials. The laser beam (2) was centered incident on each of the plurality of pixels (16) included in the marking pattern (50) for an irradiation dwell period (20) controlled by the marking module (37) to reach a time of writing (63) to the marking pattern (50) in a range of about 2.4 seconds and about 14 seconds.
    [049] Referring now first to Figure 5, in accordance with the procedure described above, seventeen individual trials were conducted on a corresponding plurality of polymeric members (54) obtained from IMV Technologies, 10, rue Clemenceau, 61300 L'Aigle , France, which has catalog number 5702 (Red) (see key in Figure 5, upper left corner of each data grid). Fluency (62) of laser beam pulses (9) was adjusted between 0.1% and 100% of 2 W and the step size was adjusted between about 50 μm and about 100 μm as described above to generate various laser marking conditions. All other laser marking parameters were fixed at constant values between runs. As can be understood from the test results outlined in Figure 5, and consistent with conventional wisdom that polymeric members (54) cannot be laser marked, some of the marking conditions either did not produce a visible mark (18) or generated a visible mark (18), but resulted in permeability or deformation of the polymeric members (54) which rendered each of these polymeric members (54) unsuitable for the intended use of contained biological materials. Unexpectedly, in a restricted range of conditions shown by Figure 5, it was possible to laser mark (without creating permeability or deformation of the polymeric member (54)) this particular embodiment of a polymeric member (54) using a step size of 70 μm or 100 μm and, respectively, a power of between about 0.1% and 75% of 2 W or 100% of 2 W. Interestingly, at a step size of 100 μm, no visible markings (18 ) occurred at less than 75% of 2 W in power, while at a step size of 70 μm it was possible to visibly mark (18) each polymeric member (54) within the wide power range between about 0.1% and about 75% of 2 W.
    [050] Again referring primarily to Figure 5, according to the procedure described above, six individual trials were conducted on a corresponding plurality of polymeric members (54) obtained from IMV Technologies, 10, rue Clemenceau, 61300 L'Aigle , France, which have catalog number 5584 (Blue) (see key in Figure 5 upper middle of each data grid). Fluency (62) of laser beam pulses (9) was adjusted between 5% and 100% of 2 W and the step size was adjusted between about 40 μm and about 70 μm as described above to generate various marking conditions laser. All other parameters were fixed at constant values between trials. As can be understood from the test results outlined in Figure 5, and consistent with conventional wisdom, some of the marking conditions either did not produce a visible mark (18) or generated a visible mark (18), but resulted in permeability or deformation. of the polymeric members (54), which rendered each of these polymeric members (54) unsuitable for the intended use of contained biological materials. Again, unexpectedly, under a restricted range of conditions, it was possible to laser mark this particular modality of a polymeric member (54) using a step size of 50 μm and a power of between about 5% and 50% of 2 W. A lack of predictability is evidenced by the step size and useful power in laser marking polymeric members (54), catalog number 5567 (Red) which failed to produce visible marks (18) on polymeric members (54), number catalog number 5584 (Blue).
    [051] The remainder of the assays were performed according to the procedure described above on a variety of different polymeric members (54) obtained from IMV Technologies, 10, rue Clemenceau, 61300 L'Aigle, France, which have catalog number 5565 (Transparent), 5580 (Orange), 5575 (Yellow), and 5577 (Grey) (see the Key in Figure 5). For each particular embodiment of the polymeric member (54), the test conditions that produced a visible mark (18) without resulting in permeability or deformation of the polymeric member varied substantially; however, unexpectedly for each polymeric member modality, a restricted range of test conditions allowed the polymeric member (54) to be visibly marked (18) by incident laser beam (2) without resulting in permeability or deformation of the member. polymeric.
    [052] The results of the 37 tests showed that the conditions under which a laser beam (2) can induce a visible mark (18) on the marking plane (12) of a polymeric member (54) can vary substantially and unpredictably. between a plurality of polymeric members (54) differentiated by dispersed colorant (64) within corresponding polymeric matrices (65). However, for each modality of polymeric member (54), a restricted set of laser marking conditions can be established that allow visible marking (18) without resulting in permeability or deformation of each type of polymeric member (54).
    [053] One aspect relates to the desire to laser mark straws (61) rapidly while maintaining straw integrity to maintain biological materials. The systems and methods described refer to adjusting the residence period of irradiation (20) and fluency (62) based on the characteristics of the straws (61) in order to reduce damage to the straws (61) while producing visible marks (18). . Additionally, laser fluence (62), step size (88) and/or irradiation residence period (20) can be further reduced and laser marking can be further improved by coordinating or adapted additives (71), such as dyes (64) that have electromagnetic radiation absorbance properties with laser beams (2) of particular wavelengths. Figure 5 demonstrates the ability to reduce both laser power and time required using complementary dyes (64) and laser sources (1). Specifically, laser sources (1) may have laser beam wavelengths (2) adapted to certain electromagnetic radiation absorbance properties of the polymeric members (54) that are marked. The process of marking with a laser, such as engraving, results in both localized carbonization type “photodamage” and heat dissipation through a region that can result in skew and loss of integrity. The 37 trials demonstrated that it may be desirable to coordinate marking materials and laser sources in a way that tends to produce char type photodamage, as opposed to producing heat transfer that can tip a straw.
    [054] Results from 37 trials indicated that step size can be improved, reduced straw marking times, and laser fluency (62) can be reduced, which generally reduces straw damage and tilt (61), by coordinating or adapting an additive (71), such as a colorant (64), or dye, which has properties of absorbing electromagnetic radiation to the laser source (1), is added. Although some interplay exists between step size (88) and laser fluence (62), there is a level of unpredictability in producing visible marks (18) on thin polymeric members (54). However, a benefit can be seen for tailored dyes (64) with electromagnetic radiation absorbance properties that peak at or near the wavelength of the laser source (1). Examples of desirable electromagnetic radiation absorbance properties may be a maximum electromagnetic radiation absorbance wavelength or a local maximum electromagnetic radiation absorbance wavelength. Dyes (64), or dyes, which are visible complementary colors to the color at the laser wavelength can exhibit good absorbance properties at the wavelength of the laser source. In Figure 6 a color wheel illustrates the primary and secondary colors and related complementary colors.
    [055] Figure 5 demonstrates improved straw marking (61) when straw colors (61) are selected that match, or roughly match, the wavelength of the laser source (1). The 37 trials demonstrated that absorption of such adapted lasers and straws (61) provide the desired localized type of “photodamage” characterized by shallow holes and carbonization for enhanced contrast, whereas those laser emissions that are not so adapted result in less localized effects. which result in deeper holes, as well as more heat transferred to the surrounding area, and a greater tendency to tip the straws (61). Additionally, more power may be required to achieve the desired carbonization “photodamage” in straws and unadapted lasers that compound the tendency to tilt the straw (61).
    [056] In particular, Figure 5 illustrates results with good markings at low laser powers and at faster times by a 532 nm wavelength laser (“green”) on red straws. Red and green can be considered complementary colors, as a red dye exhibits good absorbance for light in the green range of the visible spectrum. Specifically, the red straw could be scored in 2.4 seconds using 75% of 2 W power or with as little as 10 mW in 4.25 seconds. Even at 25% power, the laser produced enough heat to tilt the red straw in 6.6 seconds. In contrast, the yellow dye was not able to produce visible marks at 50 mW in 4.25 seconds. The orange straw, which could have electromagnetic radiation absorbance characteristics close to those of a red straw, produced visible marks at 50% power in 4.5 seconds. In further contrast, the clear straw did not tilt to the mark for 14 seconds.
    [057] Several modalities described in this document refer to methods that emulate the behavior of red straws subjected to the 532 nm laser (green). Referring to Figure 7, such a method may include the step of obtaining a polymeric member (54), wherein the polymeric member (54) is formed from a polymeric matrix (65) that includes an additive with radiation-absorbing properties. electromagnetic. The additive may be a dye or colorant (64), which may have good electromagnetic radiation absorbance at certain wavelengths and even a maximum electromagnetic radiation absorbance wavelength. The electromagnetic radiation absorbance properties of the additive (71) can be adapted to the wavelength of the laser source (1), so that the colorant (64) tends to absorb the laser energy well. This concept can be referred to as “impedance matching”.
    [058] A marking plane (12) can be defined on the surface of the polymeric member (54). A laser beam (2) may be emitted from the laser source (1) and incidentally directed onto the marking plane (12) on the surface of the polymer member (54). The adapted laser beam (2) can then be incidentally optically focused onto the marking plane (12) on the surface of the polymeric member (54) to establish a laser beam point (13) having a threshold dimensional fixed (14). Finally, the polymeric member (54) can be visibly marked on the marking plane (12).
    [059] Adaptation of the laser source (1) with electromagnetic radiation-absorbing properties of the additive (71) may include substantially adapting the wavelength of the laser beam (2) to the wavelength of maximum absorbance of a dye (64) ) or a dye, or with wavelengths at which a dye (64) exhibits good absorbance of electromagnetic radiation (such as a local maximum). This adaptation can occur within the visible light spectrum of about 400 nm to 700 nm or in the ultraviolet frequency range of 250 nm to 400 nm. As an example, the adaptation of the maximum absorbance wavelength of a dye (64) and the wavelength of the laser beam (2) can occur at about 60 nm, or at about 40 nm. As another example, wavelength adaptation can largely be considered by selecting both light beam wavelengths (2) and dyes (64) with wavelengths of maximum absorbance characterized within the same primary or color family. secondary. In reference to the visible color of the dyes (64), this adaptation can also be considered in order to select lasers characterized as primary or secondary colors that are complementary to the visible colors of the dyes (64). Similarly, the straws (61) may be selected to include dyes or dyes (64) that are complementary in color to the wavelength of the laser source.
    [060] As another specific non-limiting example, the polymeric member (54) can be doped with an additive (71) that absorbs light in the ultraviolet frequency range well. The polymeric member (54) can then be marked with a laser source (1) operating at a wavelength in the ultraviolet range, such a 150 mW laser available from Vanguard operating at 355 nm, irrespective of the color of the member. polymer (54). An example of an additive (71) is a colorant (64) that absorbs light in the ultraviolet frequency range and may include photochromic dyes (73). Photochromic dyes (73) can be considered dyes that exhibit different spectra of absorption or emission of light in response to certain conditions. Exposure of the photochromic dye (73) to ultraviolet light, or natural light with an ultraviolet component, can be such a condition that it varies the dye's absorption or emission spectra (73). Photochromic dyes (73) may comprise dyes from the spironaphthoxazines and naphthopyrans families, which undergo chemical changes in their chemical structure in response to frequencies of electromagnetic radiation in particular that include light in the ultraviolet frequency range and are generally characterized by switching from transparent to a selected color when activated. Photochromic dyes (73) of this nature are commercially available as Reversacol™ dyes from James Robinson Ltd., Huddersfield, UK and are described in more detail in US patent documents 5,559,231 and 6,303,673, each of which which are incorporated herein by reference. These tinctures can be incorporated into clear straws or straws with any basal color that have a basal tincture (75). Compared to the 532nm green laser, the 355nm UV laser delivers higher energy photons that are applied at a higher frequency. The combination of higher energy photons and increased beam frequency can increase the resolution of laser engraving and reduce the time required to make a visible mark.
    [061] Additionally, 0.25 ml straws (61) can be constructed of PETG polyethylene terephthalate for their durable qualities. However, PETG is sensitive to ultraviolet light and becomes brittle and opaque when exposed to sunlight for a long time. For the same reason, an ultraviolet laser is expected to mark PETG straws (61) with high contrast. An ultraviolet laser source (1) can be used to engrave PETG straws (61) at increased speeds with reduced fluence (62). The use of an ultraviolet light source (1) may additionally provide the benefit of requiring substantially uniform fluence (62) and irradiation residence period (20) compared to the 532 nm laser independent of a straw basal color by the fact that basal colors may not show differences in UV laser absorbance. The addition of a photochromic dye (73) can further improve the ability to mark PETG straws (61) with an ultraviolet laser source (1) further reducing the fluence (62) required to make a visible mark.
    [062] As an example, the step of adapting a dye (64) with a laser source (1) can start by selecting a commercially available laser such as 266 nm, 355 nm, 532 nm or 1064 nm lasers at 150 mW or at 350 mW, available from Spectra Physics. The polymeric members (54), such as straws (61), can then be selected or produced to have properties that tend to absorb the wavelength of visible or ultraviolet light produced by the selected laser source (1). A colorant (64) may be dispersed in the polymeric matrix (65) of the polymeric member (54) for this purpose. As an example, the polymeric members (54) can be selected to have the photochromic dyes (73) for use with the 266nm and 355nm lasers. As another example, polymeric members (54) that absorb green light, such as red polymeric members (54), can be paired with laser sources (1) that operate at wavelengths characterized as green, such as 532 no. Similarly, laser sources (1) across the visible and ultraviolet light spectrum can be selected and adapted to complementary polymeric members (54). Table 2 illustrates commercially available laser sources (1) at common operating frequencies, although adjustable lasers are also available that can span a range of wavelengths. Each laser listed serves as an example only and many other lasers and laser wavelengths are contemplated within the scope of this invention. In table 2 the laser color is a generalization in reference to either the primary or secondary color to which the wavelength is closest.

    1 available from Spectra Physics2 available from Lexel Lasers3 available from James Robinson Ltd.
    [063] In another embodiment, the polymeric members (54) can be constructed of a polymeric matrix (65) with a colorant (64) or a dye, dispersed to achieve a desired color. The laser source (1) can then be adapted to complement the color of the polymer member (54).
    [064] In one embodiment, the fluence (62) of the laser beam (2) can be adjusted to produce a visible mark (18) on the tailored polymeric member (77). Creep (62) can be minimized in order to reduce a skew of the tailored polymeric member (77) while still producing a visible mark (18). The fluence (62) can be adjusted by adjusting the irradiation residence period (20) to accelerate a labeling of the polymeric members (54). The output power of the laser source (1) can also be reduced to adjust the fluency (62) of the laser beam (2).
    [065] Referring to Figure 8, another method may include obtaining a polymeric member (54) formed from a polymeric matrix (65) that includes a photochromic dye (73) that can undergo a transition from an inactive state to an activated state. The photochromic dye (73) can remain relatively colorless in the inactive state and can have a visible color selected in the on state. The photochromic dye (73) can be selected and adapted so that the visible color in the active state is complementary to the laser source (1) used for a marking. Such dyes tend to have good absorbance over at least some portion of the ultraviolet frequency range, but may also have good absorbance, or a wavelength of maximum local absorbance, which can be adapted to the wavelength of the laser source ( 1).
    [066] The method can continue with the activation of the photochromic dye(73). Once activated, the photochromic dye (73) can either transition from a transparent polymeric member (54) to a pre-selected color or it can have a combined effect with a basal dye (75) on the polymer matrix (65) and change the existing color of a polymer member (54). In both cases, when the visible color of the activated photochromic dye (73) is complementary to the wavelength of the laser source (1), the activated polymer member (79) can demonstrate improved absorbance to the laser source (1). resulting in improved markup.
    [067] The method can continue with defining a marking plane (12) on the surface of the polymeric member (54) and adapting a laser source (1) with an electromagnetic radiation absorbance property of the photochromic dye (73) in the activated state and activating the photochromic dye (73) on the polymer member (54) defining a labeling period. The period during which the photochromic dye (73) is activated can define a marking period and can be achieved with an ultraviolet lamp, an arc lamp or other source of electromagnetic radiation (81) that produces an activation energy (83) depending on the activating properties of the photochromic dye (73).
    [068] The laser source (1) can emit a laser beam (2) directed incident on the marking plane (12) on the surface of the polymeric member (54) during the marking period. The laser beam (2) can be optically focused incident on the marking plane (12) on the surface of the polymer member (54) to establish a laser beam spot (13) that has a fixed dimensional threshold resulting in visibly marking the polymeric member (54) in the marking plane (12) on the surface of the polymeric member (54) during the marking period.
    [069] The laser source (1) can be selected with a wavelength in the visible light frequency range from about 400 nm to about 700 nm and can be adapted to the wavelength of maximum absorption of the photochromic dye (73 ) in the activated state at about 60 nm, or at about 40 nm. Table 3 below illustrates the Reversacoltm product line of photochromic dyes and their wavelengths of maximum absorbance in the activated state.


    [070] The photochromic dye (73) can be characterized so as to have two local maxima in the light absorption spectra. The first local maximum may correspond to the ultraviolet frequency range, which indicates the energy that is absorbed in the reaction that causes a color shift. The second local maximum may be characteristic of the activated visible color. A photochromic dye can be adapted directly to a laser operating in the ultraviolet frequency range or it can have an activated state adapted to a particular laser. In the activated state such a photochromic dye can be dyed with a color that is complementary to the color of the laser source (1). Examples, as shown in Figure 6, include: a red activated photochromic dye and a green laser; a blue activated photochromic dye and an orange laser; a yellow activated photochromic dye and a violet laser; a green-activated photochromic dye and a red laser; an orange activated photochromic dye and a blue laser; and a violet-activated photochromic dye and a yellow laser.
    [071] As a non-limiting example, a straw containing any basal colorant may additionally be doped with the plum red photochromatic colorant available under the tradename ReversacolTM from James Robinson (UK). The photochromic dye can then be activated with an ultraviolet lamp or other ultraviolet light source. Once activated, a 532nm green laser, such as a Vangaurd 532, can be used to produce a visible mark on the straw. A straw doped with a photochromic dye adapted to the marking laser can be printed faster and with less power than straws that have unadapted basal dyes without photochromic additives.
    [072] In one embodiment, the activation step can be performed through the marking laser (1). As a non-limiting example, a green laser used for marking can interact with the polymer member (54) to produce frequency-doubled wavelengths of light. In such an embodiment, a green laser operating at 532 nm can undergo a frequency doubling to produce some light at a wavelength close to ultraviolet 266 nm. The amount of photons doubled in frequency in this way may be a small fraction of the total photons, but it may be enough to activate a photochromic dye (73) in the polymer member (54). In such an embodiment, a green laser can either mark a polymeric member (54) or activate the photochromic dye (73) on the polymeric member (54).
    [073] Certain embodiments also refer to the polymeric member apparatus (54) seen in Figures 7 and 8 for storing and transporting biological material. The polymeric member (54) may include an axial body (55) that defines an axial passage (56) between a pair of body ends (57) (58), and in particular a cylindrical body (59) that defines a cylindrical passage. (60). The cylindrical body (60) may have an outer surface (85) and may be formed from a polymeric matrix (65) that includes a photochromic dye (73). The photochromic dye (73) can be selected to change the color of the polymer member (54) in visible light or under ultraviolet light. In one embodiment, the polymeric member (54) can be activated by ultraviolet light and can also serve to protect biological materials from ultraviolet exposure. The apparatus may additionally include a plug for sealing the substantially tubular polymeric member.
    [074] The polymeric member may comprise a straw (61) for storing or transporting biological materials that include the same selected from: an amount of semen, an ova, an ovum, an anucleated cell, a plurality of sperm cells, an embryo, a plurality of sex-selected sperm cells, a sex-selected embryo, a pathogen, a bacterium, and a virus. The straw (61) can be between about 0.1 mm and 0.2 mm thick and can be constructed of polyvinyl chloride or polyethylene terephthalate. In some embodiments the materials may be marked as having thicknesses less than 0.5 mm.
    [075] In relation to Figure 9, a general method is illustrated (100). The method may start at step (102) with a definition of a marking plane (12). The marking plane (12) may be defined on a thin curved surface, such as a polymeric member (54) that has an axial body (55) that defines an axial passage (56) that communicates between a pair of body ends (56). 57/58). As an example, the marking plane (12) may be the outer surface of a cylindrical container (59) and as another example the marking plane (12) may be the outer surface of a 0.25 ml or 0.25 ml straw. 5 ml (61). The step of defining a marking plan (12) can be performed in the form of processing computer instructions described in Figure 2 and can be done alone or in conjunction with a user input (51). Using a computer (21) as described in relation to Figures 2 and 3, multiple marking planes can be defined on a plurality of straws for sequential marking.
    [076] In step (104) a laser beam (2) is generated, as by any of the previously described laser sources (1). In some embodiments, it may be desirable to select a laser source (1) with particular characteristics to facilitate the production of visible marks on thin curved surfaces. As an example, a wavelength or other operational characteristic of the laser source (1) can be coordinated with a color of the straws (61) that are marked. In such an embodiment, the polymeric member (54) may contain an additive (71), such as a colorant (64), or a dye, which can be doped into the polymeric matrix (65) of the polymeric member (54). A dye (64) can have electromagnetic radiation absorbance properties, such as an absolute or local maximum in the absorption spectra. The absolute or local maximum of the absorption spectra can be in the wavelength ranges of visible or ultraviolet light. For example, the absolute or local maximum of the absorbance spectra may be in the range of about 250 to 400 nm or in the range of about 400 nm to 700 nm. The absolute or local maximum of the absorbance spectra can also be adapted or slightly adapted to particular wavelengths of specified lasers, such as about 266 nm, 355 nm, 435 nm, 460 nm, 532 nm, 555 nm or 570 nm . In one embodiment, the laser source (1) may comprise a laser source (1) that operates at a wavelength of 355 nm and a dye (64) that has a local maximum in the absorbance spectra between about 300 nm and 380 nm.
    [077] As another example, the fluence (62), the irradiation residence period (20) and/or the step size (88) can be adjusted based on the material that is marked or based on the color of the curved surface. On the contrary, it may be desirable to select straw colors based on the laser source (1) to be used. In some embodiments, the straws (61) may be doped with photochromic dyes (73). Alternatively, only the portions of the straws (61) that comprise the marking plane (12) can be doped with photochromic dyes (73). A laser operating at the ultraviolet wavelength can be used to directly mark such straws doped with photochromic dyes.
    [078] In another embodiment, the straws (61) can be doped with a photochromic dye providing the straws with an active state and an inactive state. An arc lamp, an ultraviolet light source or other light source that generally contains light in the ultraviolet frequency can be used to switch the straws (61) from an inactive state to an active state. Straws (61) in the active state can exhibit different color properties and different laser absorbance properties compared to their inactive state.
    [079] In step (106) the laser beam can be focused on a plurality of pixel locations in the marking plane or in multiple marking planes. The step size and the irradiation residence period can be adjusted on a computer (21) based on the surface to be marked, the material to be marked, the color of the material to be marked or the activated color of the material to be marked. when activated. Such adjustments may be made for the purpose of visibly marking a surface without causing deformation of the member and without making the surface permeable.
    [080] In step (108) a visible mark (18) can be produced on the surface of the polymeric member (54). The polymeric member (54) can remain undeformed and impermeable after such marking.
    [081] As can be easily understood from the above, the basic concepts of the present invention can be incorporated in a variety of ways. The invention involves numerous and varied embodiments of a straw laser marker which includes the best mode and methods for using such embodiments of the straw laser marker to induce visible marks in a marking plane of a wide and numerous variety of polymeric members. , cylindrical containers and straws.
    [082] Accordingly, the particular modalities or elements of the invention disclosed by the description or shown in the figures or tables annexed to this patent application are not intended to be limiting, but rather illustrative of the numerous and varied modalities generically encompassed. by the invention or covered equivalents in relation to any particular element thereof. Furthermore, the specific description of a single embodiment or single element of the invention may not explicitly describe all possible embodiments or elements; many alternatives are implicitly revealed by the description and figures.
    [083] It should be understood that each element of an apparatus or each step of a method may be described by an apparatus term or a method term. Such terms may be substituted where desired to make explicit the implicitly broad coverage to which this invention is entitled. As an example, it should be understood that all steps of a method can be revealed as an action, a means to take that action, or as an element that causes that action. Similarly, each element of an apparatus can be revealed as the physical element or the action which that physical element facilitates. As an example, disclosure of a laser marker should be understood to encompass a disclosure of the act of laser marking -- whether explicitly discussed or not -- and conversely, if there is actually a disclosure of the act of laser marking, such disclosure is to be understood to encompass a development of a laser marker and even a means for laser marking. Such alternative terms for each element or step should be understood to be explicitly included in the description.
    [084] Furthermore, with respect to each term used, it is to be understood that unless its use in this patent application is inconsistent with such an interpretation, common dictionary definitions are to be understood as included in the description for each term as contained in the dictionary not abbreviated Random House Webster's, Second Edition, each definition hereby incorporated by reference.
    [085] Accordingly, it is to be understood that the applicant claims at least: i) each of the polymeric members, or straws, disclosed and described, ii) each of the straw laser marker methods disclosed and described herein , iii) the systems and related devices disclosed and described, iv) similar, equivalent and even implied variations of each of these devices and methods, v) the same alternative modalities that purchase each of the functions shown, disclosed or described, vi ) the same designs and alternative methods that fulfill each of the functions shown as being implied to fulfill what is disclosed and described, vii) each feature, component and step shown as separate and independent inventions, viii) the applications enhanced by the various systems or components disclosed, ix) the resulting products produced by such systems or components, x) methods and apparatus substantially as described above herein and with reference to any of the appended examples, xi) the various combinations and permutations of each of the foregoing disclosed elements.
    [086] The background section of this patent application provides a statement of the field to which the invention belongs. This section may also incorporate or contain paraphrases of certain US patents, patent applications, publications, or subject matter of the claimed invention that is useful in relating information, problems, or concerns about the state of technology to which the invention leans. Any US patent, patent application, publication, statement, or other information cited or incorporated herein is not intended to be interpreted, explained, or deemed to be prior art with respect to the invention.
    [087] The claims set forth in this specification, if any, are hereby incorporated by reference as part of this description of the invention, and the applicant expressly reserves the right to use all or a portion thereof of such claims as a description additional to support any or all of the claims or any element or component thereof and the applicant further expressly reserves the right to move any portion of or all of the content incorporated in such claims or any element or component thereof from the description to the claims or vice versa, as necessary, to define the subject matter for which protection is sought by this patent application or any subsequent patent application or a continuation, division or continuation patent application in part thereof, or to obtain any benefit, reduction of fees accordingly, or to comply with applicable laws, rules and regulations and patent of any country or treaty, and such content incorporated by reference shall survive the entire term of this patent application which includes any subsequent continuation, division or continuation patent application in part thereof or any restatement or extension therein. .
    [088] The claims presented in this specification, if any, are intended to further describe the divisions and limits of a limited number of preferred embodiments of the invention and should not be explained as the broadest embodiment of the invention or a complete listing of embodiments of the invention. that can be claimed. Applicant does not waive any right to develop additional claims based on the description presented above as a part of any continuation, division or continuation in part, or similar patent application.
    权利要求:
    Claims (30)
    [0001]
    1. Method for marking a polymeric member, comprising the steps of: a) defining a marking plane on the curved surface of a straw, the straw having an axial body defining an axial passage, the straw being formed from a polymeric matrix which includes an additive with at least one wavelength of maximum absorbance; b) adapting the wavelength of a laser source to the at least one wavelength of absorbance of the additive in the polymer matrix; c) generating a laser beam which has a fluence within a fixed dimensional threshold of a beam spot; d) focusing the laser beam spot at a plurality of pixel locations; and e) producing a visible mark on the straw marking plane.
    [0002]
    Method according to claim 1, characterized in that the additive with at least one wavelength of maximum absorbance comprises a dye with at least one wavelength of maximum absorbance.
    [0003]
    Method according to claim 2, characterized in that the step of adapting a laser with electromagnetic radiation absorbance properties of the additive further comprises substantially adapting the wavelength of the laser source to at least one wavelength of maximum absorbance of the laser. dye.
    [0004]
    Method according to claim 3, characterized in that the at least one wavelength of maximum absorbance of the dye and the wavelength of the laser are adapted to the visible light spectra having a wavelength between about 400 nm and around 700 nm.
    [0005]
    Method according to claim 3, characterized in that the at least one wavelength of maximum absorbance of the dye and the wavelength of the laser are adapted to about a wavelength selected from the group consisting of: 266 nm , 355nm, 435nm, 460nm, 532nm, 555nm and 570nm.
    [0006]
    Method according to claim 3, characterized in that the wavelength of maximum absorbance of the dye is in the ultraviolet frequency range which has a wavelength between about 250 nm and about 400 nm.
    [0007]
    A method according to claim 6, characterized in that the at least one maximum absorbance wavelength comprising a local maximum wavelength is in the ultraviolet frequency range at a wavelength between about 300 nm and about 380 nm. .
    [0008]
    A method as claimed in claim 2, further comprising the steps of: a) adjusting a fluence of the laser beam within the fixed dimensional threshold of the laser beam spot; and b) adjusting a residence time of irradiation of the laser beam spot on the marking plane on the surface of the polymeric member.
    [0009]
    Method according to claim 8, characterized in that the step of adapting the wavelength of a laser source with at least one wavelength of maximum absorbance of the dye further comprises the step of: minimizing the fluence of the laser beam required to produce a visible marking plane mark on the curved surface of the straw, and/or reduce the residence time of laser beam irradiation required to produce a visible marking plane mark on the curved surface of the straw, and/or reduce the laser energy output required to produce a visible mark in the marking plane on the curved surface of the straw.
    [0010]
    A method as claimed in claim 9, further comprising the steps of: a) selecting a laser that operates at a wavelength between about 250 nm and about 400 nm; and b) selecting a dye with a first wavelength of maximum absorbance between about 250 nm and about 400 nm.
    [0011]
    A method as claimed in claim 10, further comprising the steps of: a) selecting a laser that operates at a wavelength between about 300 nm and about 380 nm; and b) selecting a dye with a first wavelength of maximum absorbance between about 300 nm and about 380 nm.
    [0012]
    Method according to claim 9, characterized in that the dye comprises a photochromic dye and the laser source comprises a laser source that generates a laser beam in the ultraviolet wavelength range.
    [0013]
    Method according to claim 9, characterized in that the step of adapting the wavelength of a laser source to the at least one wavelength of maximum absorbance of the dye further comprises substantially adapting the wavelength of the laser source to a dye maximum absorbance wavelength, where the laser wavelength and the dye maximum absorbance wavelength are about 400 nm and about 700 nm and are adapted at about 40 nm.
    [0014]
    A method according to claim 3, further comprising the steps of: a) providing an activatable photosensitized cryopreservation straw, the cryopreservation straw including a polymer matrix, a photochromic dye, a non-photochromic dye; b) activating the photochromic dye within the polymer matrix with a source of electromagnetic radiation; c) arranging the plurality of pixel locations to produce a visible mark on the marking plane that contains identifying information for the cryopreservation straw.
    [0015]
    15. Method for marking a straw, characterized in that it comprises the steps of: a) defining a marking plane on the curved surface of a straw, the straw having an axial body defining an axial passage and being formed from a polymeric matrix containing a dye photochromic dye, whereby the photochromic dye has an activated state and an inactivated state; b) adapting a laser source to an electromagnetic radiation absorbance property of the photochromic dye in the activated state; c) activating the photochromic dye in the polymeric member; d) generating a laser beam that has a fluence within a fixed dimensional threshold of a beam spot; and e) focusing the laser beam spot on a plurality of pixel locations; and f) producing a visible mark on the marking plane of the polymeric member while the photochromic dye is in the activated state.
    [0016]
    Method according to claim 15, characterized in that the step of activating the photochromic dye further comprises the step of exposing the straw to a source of electromagnetic radiation.
    [0017]
    Method according to claim 16, characterized in that the step of exposing the straw to a source of electromagnetic radiation comprises exposing the straw to an ultraviolet lamp.
    [0018]
    A method according to claim 15, characterized in that the photochromatic dye has a wavelength of maximum absorption in the activated state.
    [0019]
    Method according to claim 18, characterized in that the step of adapting the laser source to the photochromic dye further comprises the step of selecting a laser source having a wavelength in the visible light frequency range of about 400 nm. at about 700 nm adapted to the wavelength of maximum absorption of the photochromic dye in the activated state, where the wavelengths are adapted at about 40 nm.
    [0020]
    A method according to claim 18, characterized in that the photochromic dye has a visible color in the activated state which is a complementary matched light source wavelength.
    [0021]
    A method according to claim 19, characterized in that the step of selecting a photochromic dye with an activated visible color complementary to the laser wavelength further comprises selecting a laser and the photochromic dye from among the following: an activated photochromic dye in red and a green laser; a blue activated photochromic dye and an orange laser; a yellow activated photochromic dye and a violet laser; a green-activated photochromic dye and a red laser; an orange activated photochromic dye and a blue laser; and a violet-activated photochromic dye and a yellow laser.
    [0022]
    Method according to claim 15, characterized in that the step of activating the photochromic dye in the straw is achieved through electromagnetic radiation doubled in frequency produced from the laser beam generated in step (d).
    [0023]
    23. A straw for containing a biological material, as claimed in claim 1, characterized in that it comprises: an axial body defining an axial passage between a pair of body ends, the axial body comprising a polymeric matrix and having a curved outer surface, a inner surface and a thickness between the outer surface and the inner surface, wherein the thickness between the outer surface and the inner surface is between about 0.1 mm and about 0.2 mm; and a laser engraved mark on the curved outer surface of the axial body, where the straw remains non-tilted and waterproof.
    [0024]
    A straw as claimed in claim 23, characterized in that the polymer matrix further comprises a dispersed colorant.
    [0025]
    A straw as claimed in claim 24, characterized in that the dispersed colorant is adapted to the wavelength of the laser used to produce the laser engraved mark.
    [0026]
    Straw according to claim 23, characterized in that the dispersed colorant comprises a photochromic dye.
    [0027]
    27. A straw for containing a biological material, characterized in that it comprises: a) an axial body defining an axial passage between a pair of body ends, the axial body having a curved outer surface and being formed of a polymeric matrix that includes a photochromic dye; and b) the photochromic dye selected to change color in visible light and/or in ultraviolet light; and c) a laser engraved mark on the outer surface of the axial body, where the straw remains non-tilted and impermeable.
    [0028]
    A polymeric receptacle as defined in claim 26, characterized in that the straw has a thickness of between about 0.1 mm and 0.2 mm.
    [0029]
    Straw according to claim 26, characterized in that the photochromic dye has an activated and an inactivated state and wherein a light in the ultraviolet or visible spectrum activates the photochromic dye and changes the color of the straw.
    [0030]
    A straw according to claim 26, characterized in that the photochromic dye provides protection for biological materials in the straw that are sensitive to ultraviolet light.
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    同族专利:
    公开号 | 公开日
    EP2699665A2|2014-02-26|
    US9358092B2|2016-06-07|
    WO2012145306A2|2012-10-26|
    CN103890162B|2016-08-17|
    US8865379B2|2014-10-21|
    BR112013026790A2|2017-05-02|
    US20140023813A1|2014-01-23|
    CA2833172A1|2012-10-26|
    WO2012145306A3|2014-03-06|
    CN103890162A|2014-06-25|
    EP2699665A4|2015-11-25|
    US20120264207A1|2012-10-18|
    CA2833172C|2020-06-02|
    CL2013003017A1|2014-07-11|
    CN106274107A|2017-01-04|
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    法律状态:
    2017-05-09| B15I| Others concerning applications: loss of priority|
    2017-07-11| B12F| Other appeals [chapter 12.6 patent gazette]|
    2018-09-18| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2020-08-18| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2021-06-08| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|
    2021-07-13| B350| Update of information on the portal [chapter 15.35 patent gazette]|
    2021-12-07| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2022-01-04| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 17/04/2012, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US201161476751P| true| 2011-04-18|2011-04-18|
    US61/476,751|2011-04-18|
    US201161483490P| true| 2011-05-06|2011-05-06|
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    PCT/US2012/033920|WO2012145306A2|2011-04-18|2012-04-17|Polymeric members and methods for marking polymeric members|
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