Method for manufacturing a sleeved product

Abstract

A method of activating the shrink characteristic of multi-layered film (1), the method comprising the steps of providing a multi-layered film comprising at least a base layer film (2) that comprises a shrinkable film, a photothermic layer (3), associated with the base layer film, and comprising a photothermic material, exposing the multi-layered film (1) to electromagnetic radiation in order for the photothermic material to generate heat and shrink the multi-layered film (1), wherein the electromagnetic radiation comprises UV-light having a peak wavelength between 200 nm and 399 nm, and at least 90% of the UV-light is within a bandwidth of ±30 nm of the peak wavelength.

Claims

1. A method of activating the shrink characteristic of a multi-layered film, the method comprising the steps of: (a) providing a multi-layered film comprising at least (i) a base layer film comprising a shrinkable film and defining one or more edge parts, (ii) a photothermic layer, associated with the base layer film and covering the base layer film except for one of the edge parts, and the photothermic layer comprising a photothermic material, wherein the base layer is substantially free from the photothermic material, and (iii) a design layer comprising a printing layer having the photothermic material, wherein the design layer forms a pattern of discontinuous regions; and (b) exposing the multi-layered film to electromagnetic radiation in order for the photothermic material to shrink the multi-layered film; wherein the electromagnetic radiation comprises UV-light having a peak wavelength between 200 nm and 399 nm, and at least 90% of the UV-light is within a bandwidth of ±30 nm of the peak wavelength.

2. The method according to claim 1, wherein the UV-light is emitted by a LED-UV emitter.

3. The method according to claim 1, wherein the photothermic layer is provided in direct contact with the base layer film.

4. The method according to claim 1, wherein the multi-layered film has a UV absorption of at least 50%, calculated from transmittance and reflectance as measured by IS013468-2.

5. The method according to claim 1, wherein the design layer comprises a colored ink composition.

6. The method according to claim 1, wherein the multi-layer film is substantially homogeneously shrunk independent from the pattern of discontinuous regions of the design layer.

7. The method according to claim 1, wherein the multi-layer film has a UV shrinkage of at least 15% in main shrinking direction as obtained by exposure to UV light of 6.0 J/cm2.

8. The method according to claim 1, wherein the base layer film has a free shrink in main shrinking direction of less than 10% after immersion in water at 60° C. for 10 sec.

9. The method according to claim 1, wherein the photothermic layer comprises a photothermic composition comprising one or more binder resins and from 3 to 80 wt.% of the photothermic material relative to the photothermic layer.

10. The method according to claim 9, wherein the photothermic material comprises UV-light absorbing material selected from the group consisting of (white) titanium dioxide (TiO2); (black) carbon black; (cyan) phtalocyanide; (magenta) quinacridone, diketopyrrolopyrrole, naphtol-based azo pigment, anthraquinone; (yellow) aceto acetic acid-and/or anhydride-based azo pigment; dioxiazine and benzotriazole UV absorber, benzo triazole, benzo phenone, salicylate, triazine and/or cyano acrylate type of UV absorber; and combinations thereof.

11. The method according to claim 9, wherein the photothermic material comprises from 20 to 80 wt.% of titanium dioxide relative to the photothermic layer.

12. The method according to claim 9, wherein the photothermic material comprises a transparent lacquer composition comprising a benzotriazole UV absorber.

13. A method for manufacturing a sleeved product, the method comprising: (a) arranging a sleeve around the product, the sleeve comprising: (i) a multi-layered film comprising at least a base layer film comprising a shrinkable film, a photothermic layer associated with the base layer film and comprising a photothermic material, wherein the base layer film is substantially free from the photothermic material, and a design layer comprising a printing layer having the photothermic material, wherein the design layer forms a pattern of discontinuous regions, and (ii) a seam area comprising two edge parts of the multi-layered film configured to be overlapped to form a seam, wherein the photothermic layer covers the base layer film except for one of the edge parts; and (b) exposing the sleeve to electromagnetic radiation in order for the photothermic material to shrink the multi-layered film, wherein the electromagnetic radiation comprises UV-light having a peak wavelength between 200 nm and 399 nm, and at least 90% of the UV-light is within a bandwidth of ±30 nm of the peak wavelength.

14. The method according to claim 13, wherein the sleeve is provided in a flat form and wrapped around a mandrel, whereby the two sleeve edge parts to be sealed overlap and/or contact each other in the seam area, and the edges are sealed to provide a tubular sleeve, whereafter the sleeve is opened and ejected around the product.

15. The method according to claim 13, wherein the sleeve is provided in a preformed tubular form and arranged around the product.

16. The method according to claim 13, wherein at least one of the edge parts does not comprise the photothermic layer in the seam area.

17. The method according to claim 13, wherein the electromagnetic radiation comprises UV-light having a peak wavelength of 365 nm, 385 nm or 395 nm, wherein at least 75% of the UV-light is within a bandwidth of ±10 nm of the peak wavelength.

Description

BRIEF DESCRIPTION OF THE FIGURES

(1) The accompanying figures are used to illustrate non-limiting exemplary embodiments of the present invention.

(2) FIG. 1A is a schematic view of a cross section through a first embodiment of a multi-layered film of the present invention;

(3) FIG. 1B is a schematic view of a cross section through a second embodiment of a multi-layered film of the present invention;

(4) FIG. 1C is a schematic view of a cross section through a third embodiment of a multi-layered film of the present invention;

(5) FIG. 1D is a schematic view of a cross section through a fourth embodiment of a multi-layered film of the present invention;

(6) FIG. 1E is a schematic view of a cross section through a fifth embodiment of a multi-layered film of the present invention;

(7) FIG. 1F is a schematic view of a cross section through a sixth embodiment of a multi-layered film of the present invention;

(8) FIG. 2 is a schematic view of a cross section through a seventh embodiment of a multi-layered film of the present invention;

(9) FIGS. 3A to 3C are a front view and two cross-sectional views of an eighth embodiment of a multi-layered film of the present invention;

(10) FIG. 4 shows a bottle that has been provided with a shrink sleeve comprising the multi-layered film of FIGS. 3A to 3C;

(11) FIGS. 5A to 5C show cross-sections of three further embodiments of a multi-layered film of the present invention in a seaming area; and

(12) FIGS. 6A and 6B show perspective views of method steps in the manufacturing of a sleeved product in accordance with embodiments of the invention.

DESCRIPTION OF EMBODIMENTS

(13) All of FIGS. 1A to 3 illustrate embodiments of multi-layered films configured to be shrunk by the method of activating the shrink characteristic of a multi-layered film of the present invention.

(14) In FIGS. 1A and 1, the multi-layered film 1 comprises a base layer film 2 and a photothermic layer 3. The layer 3 may also be a photothermic layer in case only one color is used. The layer 3 is a combined photothermic and design layer when more than one color is used such that a design may be noted. In FIG. 1A, the combined photothermic and design layer 3 has been printed on top of the base layer film 2, whereas in FIG. 1B, combined photothermic and design layer 3 has been printed below the base layer film 2. In FIGS. 1A to 3, a bottom or lower side of the film is defined as a side of the film that faces or touches a product surface when applied onto said product, whereas a top or upper side of the film relates to a side of the film that faces a UV light source when irradiated.

(15) In FIG. 1A, the combined photothermic and design layer 3 may be formed from a transparent lacquer. As well as having good UV absorption properties, this transparent lacquer may provide a protective layer. This is because when the film 1 of FIG. 1A is fitted around a product, it is the base layer film 2 that will be in contact with the product, and the combined photothermic and design layer 3 will form the top layer of the film 1.

(16) The combined photothermic and design layer 3 of the film 1 of FIG. 1B may also be formed from a transparent lacquer. However, in contrast to the first embodiment, it is the combined photothermic and design layer 3 of this second embodiment that will come into contact with a product. Therefore, in addition to providing good UV absorption, this embodiment protects the combined photothermic and design layer 3 against scratching.

(17) Alternatively, the combined photothermic and design layer 3 of the embodiment of FIGS. 1A and 1B may be formed from coloured inks, for example, black and white inks, where these inks also have good UV absorption properties.

(18) In FIGS. 1C to 1F, the multi-layered film 1 is provided with separate photothermic and design layers 4, 5.

(19) In the embodiment of FIG. 1C, the film 1 is provided with a photothermic layer 4 provided directly below the base layer film 2, and a separate design layer 5 provided on the photothermic layer 4. With this embodiment, the photothermic layer 4 may also comprise a transparent lacquer that has good UV absorption properties. Preferably, the photothermic layer 4 will act as a binder between the base layer film 2 and the design layer 5.

(20) FIG. 1D illustrates an embodiment of the invention comprising a photothermic layer 4 provided on the upper surface of the base layer film 2 and a design layer 5 provided on the lower surface of the base layer film 2. In this embodiment, the photothermic layer 4 may once again be formed from a transparent lacquer that has good UV absorption properties. As the lacquer is provided on top of the base layer film 2, the photothermic layer 4 will form the outer layer of the film 1 and so, preferably, the lacquer additionally provides a protective coat for the film 1.

(21) In addition, in FIGS. 1C and 1D, the design layer 5 forms the lowermost layer of the film 1. This means, therefore, that both the photothermic layer 4 and the base layer film 2 should be transparent so that the design can be seen when it is viewed through both the photothermic and base layer film (4, 2).

(22) In all of the embodiments of FIGS. 1A to 1D, the layer comprising the photothermic material (either the photothermic layer 4 or the combined photothermic and design layer 3) is provided directly on the base layer film 2.

(23) In contrast, in the embodiments of FIGS. 1E and 1F, the photothermic material is provided in a photothermic layer 4 that is in indirect contact with the base layer film 2. In other words, in the embodiments of FIGS. 1E and 1F, the design layer 5 lies between the base layer film 2 and the photothermic layer 4.

(24) In FIG. 1E, the film 1 is provided with a base layer film 2 as the outmost layer. A design layer 5 is then provided on the lower surface of this base layer film 2, and a photothermic layer 4 is provided below the design layer 5. In this embodiment, the photothermic layer 4 could comprise a transparent lacquer or coloured inks (such as black and white ink). Both the lacquer and the coloured inks would have good UV absorption properties.

(25) In the embodiment of FIG. 1F, the photothermic layer 4 and the design layer 5 are both provided on the upper surface of the base layer film 2. In particular, in this embodiment, the design layer 5 is sandwiched between the photothermic layer 4 and the base layer film 2. As the design layer 5 is positioned below the photothermic layer 4, the photothermic layer 4 must be transparent (for example, a transparent lacquer) or the design would not be visible.

(26) As the photothermic layer 4 is provided on an exposed surface of the film 1 in both of FIGS. 1E and 1F, this layer 4 can once again act as a protective layer. In the embodiments of FIGS. 1E and 1F, the photothermic layer 4 is protecting the design layer 5.

(27) The embodiment of FIG. 2 shows a film 1 comprising a combined photothermic and design layer 3 and a base layer film 2 comprising a multi-layered laminated film formed from five separate layers 2a, 2b, 2c, 2d, 2e. The multi-layered laminated film may have any number of layers, preferably three or five. The base layer film 2 comprising a multi-layered laminated film in the present embodiment comprises a core layer 2c of polystyrene (PS), two middle layers (2b, 2d) of a blend of polyethylene terephthalate (PET) and polystyrene (PET/PS), and two surface layers (2a, 2e) of polyethylene terephthalate (PET).

(28) FIG. 3A shows a front view of a multi-layered film 10 provided with a design. As shown in FIGS. 3B and 3C which respectively show a cross-section according to lines B-B‘ and A-A’, the film 10 comprises a base layer film 12, a photothermic layer 14 and a design layer 15. The horizontal direction (B-B′ direction) is the direction of main orientation. The photothermic layer 14 in this embodiment comprises a white ink composition 14a and a transparent lacquer composition 14b that includes a photothermic material, while the design layer 15 comprises a plurality of colored ink compositions comprising a pigment. The printed colored ink compositions (15a, 15b, 15c, . . . ) together define the design as best shown in FIG. 3A. The UV absorption and shrinkage of each of the printed colored ink compositions (15a, 15b, 15c, . . . ) are different depending on the used pigment in the printed colored ink compositions (15a, 15b, 15c, . . . ). Even if the multi-layer film 10 is comprised of partial design layers (15a, b, c) including different pigments, the complete area covered and not covered by design layers 15 can be shrunk and will not show a substantial difference of shrinkage ratio, because the multi-layer film 10 has a photothermic layer 14 that covers the complete area of the base layer film 12. As shown in FIG. 3C, a top and bottom end of the film 10 has a transparent area comprising a photothermic layer formed by a transparent lacquer composition.

(29) As shown in FIG. 3B, this photothermic layer 14 and the design layer 15 do not extend over the complete width 16 of the film 10 but leave some free area in which a seaming area 17a is applied for seaming in a next step. Seaming is performed by wrapping the film 10 around a product such that one end section (seaming area 17a) of the film 10 that is, for the purpose, provided with solvent or adhesive is brought in contact with another seaming area 17b at another end of the film 10, in accordance with arrow 11 and both seaming areas (17a, 17b) pressed against each other to provide the seam. It is noted that the seaming areas (17a, 17b) and the arrow 11 are shown to explain the relationship to the next step, but are not part of the cross-section of FIG. 3B. The arrangement shown makes it clear that shrinkage of the seaming area 17a can occur since a photothermic layer 14 is present in area 17b, even though the seaming area 17a is substantially free of photothermic material.

(30) Referring to FIG. 4, the film 10 when shrunk by a UV-light source forms a tight sleeve 18 around the product, which in the embodiment shown in FIG. 4 is a bottle 19, having a large diameter part 19a and a smaller diameter part 19b, a top part with a cap 19c, and a bottom part 19d. The bottom part 19d may also be provided with a shrunk film 10 if desired. In the sleeved configuration shown in FIG. 4, the photothermic layer 14 of white ink faces the outer surface of the bottle 19, while the base layer film 12 faces outside towards a radiation source for shrinking the sleeve. The method of the invention allows to tightly shrink a film 10 around a bottle 19 having large and small diameter parts (19a, 19b).

(31) FIGS. 5A to 5C show yet other embodiments of a multi-layered film 1 that may be subject to shrinkage in accordance with the invented method. The film 1 comprises a base layer film 2 and a printed layer 3, the latter comprises a design layer 31 and a photothermic layer 32. The base layer film 2 has an end part 22 that defines a seaming area 29 having a first end 29a and a second end 29b, as has already been explained above in the context of FIGS. 3A to 3C. In an overlapping arrangement, end part 22 is brought in line with other end part 21 of base layer film 2 and adhesively bonded in area 29. The embodiment of FIG. 5A has a backing print only, in that the design and photothermic layers (31, 32) are provided on a backside of the film 1 only. The embodiment of figure SA is formed after seaming the embodiment shown in FIG. 1E. The backside of the film 1 is the side facing a sleeved product surface. In the embodiment of figure SA, the photothermic layer 32 in end part 22 overlaps with the photothermic layer 32 in other end part 21.

(32) The embodiment of FIG. 5B has the design layer 31 printed on the backside, and the photothermic layer 32 printed on a surface side of the film 1. The embodiment of FIG. 5B is formed after seaming the embodiment shown in FIG. 1D. The surface side of the film 1 is the side facing away from a sleeved product surface, or, alternatively, facing towards a UV-light source during a shrinkage treatment. The embodiment of FIG. 5C finally has a combined design/photothermic layer (31, 32) printed on the backside, and a photothermic layer 32′ printed on a surface side of the film 1. In the embodiments of FIGS. 5A and 5C, the photothermic layer 32 covers substantially the complete area around the seaming area 29 in a circumferential direction 36. In the embodiment of FIG. 5B, there is a small gap 35 which is not covered by the photothermic layer 32, and therefore is not or less subject to shrinkage. Given the small width of the gap 35 in a circumferential direction 36, this is not much of a problem, because the main shrinking direction corresponds to the circumferential direction 36.

(33) FIGS. 6A and 6B finally disclose possible method steps in embodiments of the invented method. The method for manufacturing a sleeved product 40 comprises arranging a sleeve label 41 around a product, which, in the embodiment shown is a bottle 39. The sleeve 41 comprises an embodiment of a multi-layered film (1, 10) as shown in FIGS. 3 and 5. The sleeve 41 is arranged around the bottle 39 and then exposed to electromagnetic radiation emitted by a plurality of UV LED sources 44. The photothermic material present in the film (1, 10) generates heat and shrinks the multi-layered film (1, 10). As claimed, the electromagnetic radiation comprises UV-light having a peak wavelength between 200 nm and 399 nm, and at least 90% of the UV-light is within a bandwidth of ±30 nm of the peak wavelength.

(34) The sleeve 41 may be provided in a preformed tubular form, the sleeve 41 being cut from an elongated preformed sleeve 410 of the multi-layered film (1, 10) at a pitch 43 in a transverse direction 42 to the axis of the sleeve 41. The circumferential direction of the sleeve 410 corresponds to the main orientation and main shrinkage direction.

(35) In an alternative embodiment, the sleeve 41 is provided in the form of a flat film 50 and a piece of the flat film 50 is cut in a transverse direction 53 to a longitudinal axis of the flat film 50, and then wrapped around a cylindrical mandrel 51 that is rotated in a circumferential direction 52 of the mandrel 51. An edge part of the cut flat film 50 is provided with a strip of adhesive 54 which bonds two overlapping edge parts of the flat film 50 to provide the tubular sleeve 41. A machine direction of the flat film 50 corresponds to the main shrinkage and circumferential direction 52.

(36) To arrange the sleeve 41 around the bottle 39, the sleeve 41 is slightly opened and ejected around the bottle 39 in a direction 55. The sleeve 41 is then exposed to electromagnetic radiation emitted by a plurality of UV LED sources 44, which move relative to the sleeved bottle (39, 40). The relative movement may be achieved by moving the sleeved bottle (39,40) and/or by moving the UV light sources 44, for instance in a circular spinning movement.

(37) As shown in FIG. 6B, when the sleeve 41 is provided in the shape of a flat film 50, the film may also be wrapped immediately around the bottle 39 that is rotated in a circumferential direction 56 of the bottle 39. An edge part of the cut flat film 50 is provided with a strip of adhesive 54 which bonds two overlapping edge parts of the flat film to provide the tubular sleeve 41 around the bottle 39.

(38) UV devices suitable for producing the UV light required for embodiments of the invention include UV-LED lamps with the item code FE300 produced by Phoseon Technology. Details of three FE300 UV-LED lamps with peak wavelengths of 365 nm, 385 nm and 395 nm are outlined in Table 1 below.

(39) According to the invention, a UV-light source having a peak wavelength between 200 nm and 399 nm is used, whereby at least 90% of the UV-light is within a bandwidth of ±30 nm of the peak wavelength. A UV-light emitter having the claimed narrow wavelength distribution may be used, but it is also possible to use a UV light source having a wider wavelength distribution and filtering the light to obtain the claimed narrow wavelength distribution.

(40) Although the power of the UV-light source may be varied within a large range, a preferred power of the UV-light source ranges from 0.5-100 W/cm.sup.2, more preferably from 1-30 W/cm.sup.2, and most preferably from 3-20 W/cm.sup.2. Suitable UV-light emitters are for instance FE300 (365 nm): 3.3 W/cm.sup.2, and FE300 (385 nm): 5.5 W/cm.sup.2.

(41) The preferred UV LED devices may use any tip disposition, and one line type UV LED emitters such as FE300 (Phoseon), and/or multi line type UV LED emitters such as FJ 100 (Phoseon) may be used.

(42) Preferred lenses may have any shape and comprise rod lenses and flat lenses, whereby a rod lens is more preferred than a flat lens in order to keep the irradiation power at an even distance from the light source. The distance between the UV-light source and the product surface to be irradiated may be varied but is preferably close enough to prevent a large reduction of the irradiation power, which typically reduces with distance. A preferred distance between a product surface to be irradiated and a UV-light source is <75 mm, more preferably <50 mm, even more preferably <30 mm, and most preferably <20 mm.

(43) The product may be irradiated by the UV-light source in a device that allows irradiation of substantially the complete product surface once, or a few times. Preferably, a sleeved product that needs to be irradiated is moved relative to the UV-light source or sources. Movement may be achieved in any conceivable way, such as by hoisting or spinning a product and/or UV-light source, or a line or multi line of UV-light sources or sleeved products.

(44) In addition, for comparison, Table 1 also details an electrodeless lamp produced by Heraeus Noblelight. This lamp does not produce the UV-light required for the method of activating the shrink characteristic of a multi-layered film of the present invention.

(45) Tables 2 to 5 below detail the distribution of relative radiance of each of the lamps listed in Table 1.

(46) As can be seen from Tables 1 to 5, the lamps produced by Phoseon Technology all produce UV-light that is within ±30 nm of the peak wavelength.

(47) TABLE-US-00001 TABLE 1 UV Devices Percentage Percentage Percentage Peak Irradiated of intensity of intensity of intensity Itemcode wave wave in peak ± in peak ± in peak ± of UV Lamp length length 10 nm 3O mn 6O nm Type Light Supplier UV light I 365 nm 350 nm- 94% 100% 100% UV-LED FE300 Phoseon 380 nm Technology UV light II 385 nm 370 nm- 93% 100% 100% UV-LED FE300 Phoseon 400 nm Technology UV light III 395 nm 380 nm- 90% 100% 100% UV-LED FE300 Phoseon 410 nm Technology UVlight IV 365 nm 200 nm- 15%  18%  39% Flectrode- LIGHT Heraeus 500 nm less lamp HAMMER- Noblelight 10; H+

(48) TABLE-US-00002 TABLE 2 UV light I 365 nm Distribution of Relative Wavelength Range irradiance <350 nm  0% 350 nm-355 nm  1% 355 nm-360 nm  8% 360 nm-365 nm  30% 365 nm-370 nm  34% 370 nm-375 nm  22% 375 nm-380 nm  5% ≥380 nm  0% Total 100%

(49) TABLE-US-00003 TABLE 3 UV light II 385 nm Distribution of Wavelength Range Relative <370 nm  0% 370 nm-375 nm  1% 375 nm-380 nm  7% 380 nm-385 nm  27% 385 nm-390 nm  41% 390 nm-395 nm  19% 395 nm-400 nm  5% ≥400 nm  0% Total 100%

(50) TABLE-US-00004 TABLE 4 UV light III 395 nm Distribution of Wavelength Range Relative <390 nm  2% 390 nm-395 nm  15% 395 nm-400 nm  43% 400 nm-405 nm  30% 405 nm-410 nm  8% 410 nm-415 nm  2% Total 100%

(51) TABLE-US-00005 TABLE 5 UV light IV 365 nm Distribution of Wavelength Range Relative <300 nm  48% 300 nm-310 nm  4% 310 nm-320 nm  7% 320 nm-330 nm  1% 330 nm-340 nm  2% 340 nm-350 nm  0% 350 nm-360 nm  1% 360 nm-370 nm  13% 370 nm-380 nm  1% 380 nm-390 nm  1% 390 nm-400 nm  1% 400 nm-410 nm  6% 410 nm-420 nm  1% 420 nm-430 nm  1% ≥430 nm  13% Total 100%

(52) Base Layer

(53) The multi-layer films that are configured to be shrunk on the application of heat comprise a base layer. The base layer film of the multi-layered film comprises a shrinkable film, and preferably comprises over 95% of thermoplastic resin. Suitable types of base layer are detailed in Table 6 below. Their heat shrinkage in TD is shown in the Table 6.

(54) TABLE-US-00006 TABLE 6 Spec Heat Heat Heat Shrink Shrink Shrink Film Formulation ratio ratio ratio Thick- ST @60° C. @90° C. @150° C. ness Ratio for for for Name (μm) supplier Surface Core Middle (TD) 10 sec 10 sec 10 sec Haze Film I PETG TD Pentalabel ® 50 Klockner PETG 4-6R 0 65 77 2.0 shrink film LF- TG10F12- T45 Film II Hybrid Fancylap 40 GUNZE PETG Adhesive SBS 4-6R 0 70 78 4.0 multilayer HG8 layer TD shrink film Fain III Olefin Fancylap 50 GUNZE COC PP 4-6R 0 55 76 10.0 multilayer FL1 TD Film IV APET — 40 — APET* 4R 0 5 31 2.0 TD shrink (@90 d) film Film V Aclyic Label- 40 Jindal Aclylic PP BOPP 0 0 7 2.0 coated Lyte BOPP LL666 film

(55) The heat shrink ratio of the APET and BOPP films of Table 6 at 130° C. for 2 min is APET: 34%, and BOPP: 3%.

(56) Photothermic and Design Layers

(57) Shrinkable films adapted to be shrunk may also comprise ink in a photothermic layer and/or a design layer. Examples of such inks are listed in Table 7.

(58) These inks may be printed onto another layer of the film, for example the base layer film, using Gravure printing. The layers of printed ink may be 1.0 .mu.m thick. Titanium dioxide may be used in the white ink composition, for instance an amount of 50% by weight of the total white ink composition.

(59) Alternatively, a photothermic layer may comprise a clear lacquer (i.e. a “clear lac”). Suitable lacquers include Lacquers B and C listed in Tables 8-1 and 8-2.

(60) TABLE-US-00007 TABLE 7 Color inks for Photothermic layer or Design layer Color Code n. Name of color Inks medium Solvent Supplier White WB68-0AFG Pluritech White NITROBASE 50/50 EtAc/ Flint CLEAR TSDA CSWS-01- SLEEVEFLEX SOLVAFILM P nPr-Ac Sunchemical 21990 WHITE SL TV Cyan WZ61-15AF NITROBASE NITROBASE 2 TO 1 TSDA/ Flint CYAN CLEAR nPrAc YSBL-05- Finetap Cyan SOLVAFILM P nPr-Ac/EtAc Sunchemical 21519/JP01 SL TV/NC Vanish Magenta INZ61-36BF NITROBASE NITROBASE 2 TO 1 TSDA/ Flint MAGENTA CLEAR nPrAc YSBL-04- Finetap Magenta SOLVAFILM P nPr-Ac/EtAc Sunchemical 21521/JP01 SL TV/NC Vanish Yellow WZ61-55DF NITROBASE NITROBASE 2 TO 1 TSDA/ Flint YELLOW CLEAR nPrAc YSBL-02- Finelap Yellow SOLVAFILM P nPr-Ac/EtAc Sunchemical 21517/FJO9 SL TV/NC Vanish Black WZ61-96BF NITROBASE NITROBASE 2101 ISDA/ Flint BLACK CLEAR nPrAc YSBL-09- Finelap Black SOLVAFILM P nPr-Ac/EtAc Sunchemical 21524/JP01 SL TV;/NC *inks from Flint is used for example

(61) TABLE-US-00008 TABLE 8.1 Type Code n. Medium Solvent viscosity Supplier Lacquer W863- ELIOTECH SL n-propyl 18-20 sec Flint A OVSG CLEAR Acetate

(62) TABLE-US-00009 TABLE 8.2 Formulation (Base lacquer + UV absorber) Note Base UV Absorber Chemical name of Type lacquer UV absorber Solvent Viscosity type UV absorber Lacquer B Lacquer A Tinuvin Supplied n-propyl 18-20 Benzotriazol 2-(2H-benzotriazol-2-yl)- (100 wt %) 328 by BASF Acetate sec 4,6-ditertpentylphenol (3 wt %) Lacquer C Lacquer A Seesorb Supplied n-propyl 18-20 Benzophenone Tetrahydroxybenzophenone (100 wt %) 106 by Acetate sec (13 wt %) SHIPRO KASEI KAISHA LTD

Example 1

(63) Shrink films (i.e. films that are configured to be shrunk) were prepared using a base layer selected from Table 6. In addition, a photothermic layer was applied to this base layer. This photothermic layer comprised one of the Flint inks listed in Table 7, or a clear lacquer selected from those listed in Table 8-2. These films form working examples I-1 to I-11 in Table 9 below.

(64) Comparison examples I-1 to 1-7 listed in Table 9 comprise only a base layer (i.e. there is no photothermic layer). In comparison example I-8, the shrink film comprises Lacquer A in the printed layer. The printed Lacquer A does not comprise a photothermic material.

(65) UV light was applied to these shrink films using one of the UV lamps described in Table 1. The percentage shrinkage of these films by the UV light was then measured and the results of these shrinkage experiments are given in Table 9.

(66) TABLE-US-00010 TABLE 9 Flat Shrinkage without design layer Based Film (B) photothermic layer (P) Shinkage by UV UV UV UV UV 1.5 4 6 device TYPE abs % Ink type abs abs % J/cm2 J/cm2 J/cm2 Comparison example 1-1 UV light I Film I 8% —  8%  0% 0%  0%  0% Comparison example 1-2 UV light II Film I 8% —  8%  0% 0%  0%  0% Comparison example 1-3 UV llght III Film 1 8% —  8%  0% 0%  0%  0% Comparison example 1-4 UV light I Film II 9% —  9%  0% 0%  0%  0% Comparison example 1-5 UV light I Film III 7% —  7%  0% 0%  0%  0% Comparison example 1.6 UV light 11 Film IV 8% —  8%  0% 0%  0% Comparison example 1-7 UV light II Film V 7% —  7%  0% 0%  0%  0% Comparison example 1-8 UV right I Film I 8% Lacquer A  8%  0% 0%  0%  0% Working example 1-1 UV light I Film 1 8% Magenta 40% 32% 0%  0% 49% Working example 1-2 UV light I Film I 8% Cyan 88% 80% 0% 48% 77% Wolking example 1-3 UV light I Film 1 8% Yellow 40% 32% 0%  0% 71% Working example 1-4 UV light I Film I 8% Black 97% 89% 8% 63% 77% Working example 1-5 UV light I Film 1 8% White 94% 86% 6% 43% 77% Working example 1-7 UV light 1 Film II 9% White 93% 84% 0% 58% 74% Working example 1-8 UV light I Film III 7% White 94% 87% 4% 34% 70% Working example 1-9 UV light 11 Film IV 8% White 94% 86% 50% Working example 1-10 UV light II Film V 7% White 94% 87% 17% Working example 1-6 UV light I Film I 8% Lacquer B 87% 79% 0% 33% 74% Working example 1-11 UV light I Film I 8% Lacquer C 89% 81% 5% 45% 77%

(67) In the multi-layer films of Table 9, there is no design layer.

Example 2

(68) In Example 2, multi-layer films were prepared from a base layer, a photothermic layer and a design layer. Details of these multi-layer shrink films are listed in Table 10.

(69) The base layer was selected from those examples listed in Table 6, the photothermic layer comprises the white Flint ink listed in Table 7, and the design layer comprises additional flint inks of Table 7.

(70) UV light was applied to the films using one of the UV lamps listed in Table 1. The shrinkage of the multi-layer films of Example 2 was measured and the results are listed in Table 10.

(71) The working examples II-2, 4, 5 and the comparative example II-1 have a continuous backing white on design layer that is printed with a number of color inks (cyan, magenta, black, yellow) to eliminate overlap with each design ink below a base layer.

(72) In working example II-3 a continuous transparent lacquer comprising photothermic material shown as lacquer B in table 8 is printed on top of a base layer film together with a number of color inks (cyan, magenta, black, and yellow) to eliminate overlap with each design ink on the other side of the base layer film, meaning below the base layer film.

(73) When any color is described as a design layer in the table, it means that the part does not have a design layer.

(74) TABLE-US-00011 TABLE 10 Flat Shrinkage with design layer Free photothermic layer Design layer Free shrinkage Film UV UV UV Total layer Shrinkage (B) UV UV abs abs % abs % abs % UV (A) dispersion of by light UV abs % (B + P = (P = {circle around (2)} − (B + D = (D = {circle around (3)} − abs % Min by light shrinkage (2σ) Classif- device TYPE {circle around (1)} Color {circle around (2)}) {circle around (1)}) Color {circle around (3)}) {circle around (1)}) (B + P + D) abs % 0.4 J/cm2 0.4 J/cm2 ication Com- UV Film I 8% White 94% 86% — — — 94% 94% 37% 23% B parison light White 94% 86% Magenta 40% 32% 97% 54% example IV White 94% 86% Cyan 88% 80% 97% 59% II-1 White 94% 86% Black 97% 89% 97% 64% Free photothermic layer Design layer shrinkage Film UV UV UV Total layer Free Shrinkage dispersion of (B) UV UV abs abs % abs % abs% UV (A) by light shrinkage (2σ) by light UV abs % (B + P = (P = {circle around (2)} − (B + D = (D = {circle around (3)} − abs % Min 1.5 4 6 1.5 4 6 Classif- device TYPE {circle around (1)} Color {circle around (2)}) {circle around (1)}) Color {circle around (3)}) {circle around (1)}) (B + P + D) abs % J/cm2 J/cm2 J/cm2 J/cm2 J/cm2 J/cm2 ication Working UV Film I 8% White 94% 86% — — — 94% 94% 6% 43% 77% 7%  8% 3% A example light White 94% 86% Magenta 40% 32% 97% 6% 43% 75% II-2 I White 94% 86% Cyan 88% 80% 97% 0% 44% 75% White 94% 86% Yellow 40% 32% 97% 0% 49% 76% White 94% 86% Black 97% 89% 97% 0% 38% 73% Working UV Film I 8% Lacquer 87% 79% — — — 87% 87% 6% 37% 76 5% 10% 0% A example light Lacquer 87% 79% Magenta 40% 32% 90% 0% 27% 76 II-3 I Lacquer 87% 79% Cyan 88% 80% 90% 0% 36% 76 Lacquer 87% 79% Yellow 40% 32% 90% 0% 40% 76 Lacquer 87% 79% Black 97% 89% 90% 0% 36% 76 photothermic layer Design layer Film UV UV UV Total layer Free Shrinkage dispersion of Appearance UV UV abs abs % abs % abs % UV (A) by light shrinkage (2σ) after UV abs % (B + P = (P = {circle around (2)} − (B + D = (D = {circle around (3)} − abs % Min 1.5 4 6 1.5 4 6 Classif- device TYPE {circle around (1)} Color {circle around (2)}) {circle around (1)}) Color {circle around (3)}) {circle around (1)}) (B + P + D) abs % J/cm2 J/cm2 J/cm2 J/cm2 J/cm2 J/cm2 ication Working UV Film I 8% Whte 86% 78% — — — 86% 86% 48% 69% 76%  7%  5% 2% A example light White 86% 78% Magenta 31% 23% 93% 50% 63% 78% II-4 II White 86% 78% Cyan 85% 57% 97% 56% 68% 78% White 86% 78% Yellow 52% 44% 97% 50% 65% 77% White 86% 78% Black 98% 90% 97% 56% 68% 77% Working UV Film I 8% White 69% 61% — — — 69% 69% 36% 63% 76% 13% 12% 2% A example light White 69% 61% Magenta 33% 25% 87% 43% 71% 77% II-5 III Whew 69% 61% Cyan 45% 37% 87% 42% 68% 78% White 69% 61% Yellow 60% 52% 97% 47% 77% /8% White 69% 61% Black 94% 86% 97% 53% 77% 78% *Irradiation over 0.4 J/cm2 make film shrunk by radiation heat, not generating heat.

Example 3

(75) As with Example 2, the films of Example 3 comprise a base layer, a photothermic layer and a design layer. The multi-layer shrink films of Example 3 are listed in Table 11.

(76) The results of experiments conducted on the films of Example 3 are given in Table 11. The top part of Table 11 discloses experiments on the indicated films, whereas the bottom part of Table 11 describes the results of the carousel and around shrink test performed on working examples II-4. II-1 and III-2.

(77) TABLE-US-00012 TABLE 11 Shrink test of products pholothermic layer Design layer Total layer Film UV UV UV UV UV UV abs abs % abs % abs % abs % UV abs % (B + P = P = {circle around (2)} − (B + D = (D = {circle around (3)} − (B + P + Min device TYPE {circle around (1)} Color {circle around (2)}) {circle around (1)}) Color {circle around (3)}) {circle around (1)}) D) abs % Working UV Film II 9% White 86% 77% — — — 86% 86% example light II White 86% 77% Magent 32% 23% 93% III-1 White 86% 77% Cyan 65% 56% 97% White 86% 77% Yellow 53% 44% 97% White 86% 77% Black 98% 89% 97% Working UV Film III 7% White 86% 79% — — — 86% 86% example light II White 86% 79% Magent 31% 24% 93% III-2 White 86% 79% Cyan 64% 57% 97% White 86% 79% Yellow 52% 45% 97% White 86% 79% Black 98% 91% 97% Carousel Around UV Film Min shrink shrink device TYPE Abs % Classification Classificaiton Working UV light II Film I 86% A A example II-4 Working UV light II Film II 86% A A example III-1 Working UV light II Film III 86% A A example III-2

(78) Experiment to Analyze the Percentage of UV Absorption

(79) In Examples 1, 2 and 3, the UV absorption was measured using a UV spectrometer of the type Shimadzu UV-VIS Recording spectrophotometer UV-2401PC. The UV absorption was calculated from transmittance and reflectance as measured using the standard ISO13468-2 (=JIS K 7361-2).

(80) In Examples 1 to 3, the UV absorption of the multi-layer film and a part of multi-layer film or same formulations as the part of the multi-layer film was measured. Firstly, the transmittance and reflectance of the film were measured. Secondly, the UV absorption percentage was calculated using:
UV absorption %=100−(transmittance+reflectance)

(81) In addition, the UV absorption of the photothermic layer was measured. This was achieved by: (1) Measuring the UV absorption of only the base layer film (2) Measuring the UV absorption of the photothermic layer and the base layer film (3) Calculating the UV absorption of the photothermic layer as follows:
UV absorption of the photothermic layers=(2)−(1)

(82) A similar method was used to calculate the UV absorption of the design layer (if present).

(83) Free Shrink Test

(84) In the tables, the free shrinkage by light has also been measured.

(85) In the method used to measure the free shrinkage, samples of the multi-layered films were first prepared. These samples each had dimensions of: 50 mm in the transverse direction (TD) 15 mm in the machine direction (MD).

(86) Then: (1) Each sample was placed on a PET sheet that has not been treated with any coating. (2) Each sheet was then placed on a conveyer belt and passed under the UV light source in a constant condition. (3) The free shrinkage was then calculated using:

(87) Shrinkage (%)=(L.sub.0-L.sub.1)/L.sub.0*100; with L.sub.0: Length of transverse direction before irradiation L.sub.1: Length of transverse direction after irradiation In addition, the appearance of the shrunken sample was checked and classified either A or B:

(88) A—if there was an even shrink,

(89) B—if there was an uneven shrink

(90) In Examples 1 to 3, three samples of each example listed in the tables were used and the average value (i.e. the mean value) obtained from these three samples is given in the tables.

(91) Carousel Shrink Test

(92) In Example 3, a carousel shrink test was also performed. This test involved: (1) Preparing a lay-flat sample (a seamed tubular sleeve laid flat) that has a width of 72 mm and a cut height (or pitch) of 95 mm in size (2) The sample was then formed into a sleeve and arranged around a bottle so that a maximum shrinkage of 30% is required to fit the sleeve to the bottle (3) The bottle and sample were then placed in the middle of a set of six UV lights of type UV light II with a rod lens and spun around at 200 bpm (4) The sample was then irradiated with 7 J/cm of UV light II (5) After shrinking, the appearance was checked an classified as either A or B, where: A—indicates shrinking without concentration by colour influence B—indicates shrinking with concentration by colour influence.

(93) Around Light Shrink Test

(94) In Example 3, an around light shrink test was additionally performed. This test involved: (1) Preparing a lay-flat sample that is 72 mm by 95 mm in size (2) The sample was then formed into a sleeve and arranged around a bottle so that a maximum shrinkage of 30% is required to fit the sleeve to the bottle. (3) The bottle and sample were then placed in the middle of a set of four UV lights of type UV light II with a ROD lens. These four UV lights are arranged in a square configuration around the bottle. (4) The bottle was then moved vertically at a speed of 1 m/min through the middle of the square of UV lights so that the sample is irradiated at 24 J/cm.sup.2. (5) After shrinking, the appearance was checked and classified as for the carousel test.