EP1563028A2 - Coloured labels - Google Patents
Coloured labelsInfo
- Publication number
- EP1563028A2 EP1563028A2 EP03765021A EP03765021A EP1563028A2 EP 1563028 A2 EP1563028 A2 EP 1563028A2 EP 03765021 A EP03765021 A EP 03765021A EP 03765021 A EP03765021 A EP 03765021A EP 1563028 A2 EP1563028 A2 EP 1563028A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- label
- article
- transparent
- coloured
- colour
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000003292 glue Substances 0.000 claims abstract description 68
- 238000000034 method Methods 0.000 claims abstract description 55
- 230000008569 process Effects 0.000 claims abstract description 12
- 229920002678 cellulose Polymers 0.000 claims description 26
- 239000001913 cellulose Substances 0.000 claims description 26
- 239000000853 adhesive Substances 0.000 claims description 21
- 230000001070 adhesive effect Effects 0.000 claims description 21
- 238000004040 coloring Methods 0.000 claims description 18
- 239000000975 dye Substances 0.000 claims description 14
- 238000002372 labelling Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 239000011521 glass Substances 0.000 claims description 9
- 239000000049 pigment Substances 0.000 claims description 7
- 229920006378 biaxially oriented polypropylene Polymers 0.000 claims description 5
- 239000011127 biaxially oriented polypropylene Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 239000000976 ink Substances 0.000 claims description 5
- 239000012790 adhesive layer Substances 0.000 claims description 3
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 3
- 239000004626 polylactic acid Substances 0.000 claims description 3
- 229920000098 polyolefin Polymers 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims 2
- 238000009472 formulation Methods 0.000 claims 2
- 229920006254 polymer film Polymers 0.000 claims 1
- 101000872083 Danio rerio Delta-like protein C Proteins 0.000 abstract 3
- 239000003086 colorant Substances 0.000 description 11
- 238000005259 measurement Methods 0.000 description 10
- 229920001169 thermoplastic Polymers 0.000 description 9
- 239000004416 thermosoftening plastic Substances 0.000 description 8
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 5
- 229920000297 Rayon Polymers 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- -1 polyethylene phthalate Polymers 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 230000000007 visual effect Effects 0.000 description 3
- 229920000298 Cellophane Polymers 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004188 Virginiamycin Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 235000013405 beer Nutrition 0.000 description 2
- 239000001049 brown dye Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 230000000873 masking effect Effects 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229920006381 polylactic acid film Polymers 0.000 description 2
- 239000004627 regenerated cellulose Substances 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 239000005315 stained glass Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004826 Synthetic adhesive Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 235000013334 alcoholic beverage Nutrition 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229920001222 biopolymer Polymers 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000004456 color vision Effects 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000004069 differentiation Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000008393 encapsulating agent Substances 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000005308 flint glass Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 230000003278 mimic effect Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000005026 oriented polypropylene Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011236 particulate material Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000000985 reactive dye Substances 0.000 description 1
- 230000035807 sensation Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 235000015096 spirit Nutrition 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 235000014101 wine Nutrition 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65C—LABELLING OR TAGGING MACHINES, APPARATUS, OR PROCESSES
- B65C9/00—Details of labelling machines or apparatus
- B65C9/20—Gluing the labels or articles
- B65C9/22—Gluing the labels or articles by wetting, e.g. by applying liquid glue or a liquid to a dry glue coating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65C—LABELLING OR TAGGING MACHINES, APPARATUS, OR PROCESSES
- B65C9/00—Details of labelling machines or apparatus
- B65C9/0015—Preparing the labels or articles, e.g. smoothing, removing air bubbles
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/40—Adhesives in the form of films or foils characterised by release liners
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65C—LABELLING OR TAGGING MACHINES, APPARATUS, OR PROCESSES
- B65C9/00—Details of labelling machines or apparatus
- B65C9/0015—Preparing the labels or articles, e.g. smoothing, removing air bubbles
- B65C2009/0018—Preparing the labels
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/334—Applications of adhesives in processes or use of adhesives in the form of films or foils as a label
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2401/00—Presence of cellulose
- C09J2401/006—Presence of cellulose in the substrate
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2423/00—Presence of polyolefin
- C09J2423/006—Presence of polyolefin in the substrate
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/131—Glass, ceramic, or sintered, fused, fired, or calcined metal oxide or metal carbide containing [e.g., porcelain, brick, cement, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/14—Layer or component removable to expose adhesive
Definitions
- the present invention relates to the field of coloured labels such as (but not limited to) those labels fixed to an article with an aqueous adhesive applied thereto (so-called wet glue labels).
- the invention relates to those labels which achieve a no-label look on the article.
- Any suitable labels may be used in the invention such as labels comprising coloured transparent and/or translucent bio-polymeric films, for example films made from cellulose and/or polylactic acid.
- Labels made from thermoplastic films have been conventionally fixed onto an article with pressure sensitive adhesives (herein denoted as PSA) pre-coated onto the label facestock.
- PSA pressure sensitive adhesives
- Such label films include polyolefins, e.g. biaxially oriented polypropylene - BOPP).
- a PSA label facestock is dispensed from a release liner onto the article to be labeled.
- An alternative labeling method often used with a paper labels is to use a separate adhesive dispersed in an aqueous medium. The adhesive is applied as the label is fixed to the article. These are often referred to as wet glue labels but can also be called cold glue labels or just glue labels.
- alcoholic beverages such as beer, wine or spirits
- Packaging is a major part of the promotional mix especially at point of sale in supermarkets and the drive for differentiation amongst the manufacturers is furious.
- no-label' appearance has become fashionable for PSA labels as retailers have found many advantages from this new form of shelf appeal.
- the appearance of no-label is achieved by applying a transparent and/or translucent label to the article. If the label is transparent, printing on its reverse side (i.e. the "interior" side to be adhered to the article) appears to be directly applied to the article hence the term "no-label look".
- Such interior coats are better protected from wear and tear (rubbing, attack by solvents etc) as they are not on the exterior of the article.
- thermoplastic films have various disadvantages when used as the facestock for a transparent wet glue label.
- the properties of these thermoplastic films are different from the paper labels used on conventional wet glue machines.
- thermoplastic films have a higher barrier to moisture (they are not semi-permeable to water) and this causes a wet glue to take longer to dry (and hence more time for the label to fix in place) which can be disadvantageous on a high speed labelling line or where precise location of the label on the article is required.
- thermoplastic films are not an ideal replacement for a paper label on a conventional production line set up to apply a wet glue label to an article such as a bottle.
- Aqueous coatings are also not easily compatible with and do not adhere well to such thermoplastic films which are often hydrophobic without surface treatment of the film.
- the substrate conventionally used to prepare wet glue labels is paper which is not transparent.
- Thermoplastic films can be transparent but because of the previous stated disadvantages with thermoplastic films and wet glue coatings, it has been necessary to use pressure sensitive adhesives to provide an article with a no look label having acceptable performance.
- manufactures currently using labelling equipment for paper wet glue labels are faced with a significant capital outlay and disruption to change to equipment compatible with pressure sensitive labels if they wish to move to a no-label look.
- PCT/EP02/02726 describes use of wet glue method to apply a clear biopolymeric label (such as a cellulose film) to a transparent article to achieve a clear -label look without PSA.
- This method can use existing machinery suitable for paper wet glue labels yet allows use of biopolymeric labels which have various advantages over paper.
- the biopolymeric labels can be transparent or translucent to achieve a no-label look.
- a wet glue on a biopolymeric substrate can also dry in a reasonable time without the need to use exotic coatings.
- This method now provides an alternative route to a clear-label look for manufacturers without the disadvantages of changing an existing label line from wet glue to PSA.
- the contents of PCT/EP02/02726 are incorporated herein by reference.
- PSA labels have the pressure sensitive adhesive pre-applied during the production of the label stock.
- wet glue process requires that a wet adhesive is applied in situ to the label.
- the wet glue is applied to a glue roller then transferred to rubber covered palettes which transfer the glue onto the reverse of the label.
- the label is applied to articles such as glass or PET bottles at typical output speeds between 300 and 500 plus articles labelled per minute. At these line speeds and particularly with a range of conditions such as wet and dry and warm and cold bottles the applicant has found that the adhesive transfer characteristics of wet glue have been difficult to optimise to achieve a satisfactory no-label appearance of a wet glue label on a bottle comparable to the no-label appearance of a conventional PSA label.
- a label of a clear cellulose film can be applied to a clear flint glass bottle using a wet glue to achieve an acceptable appearance, unexpectedly this is not the case when coloured bottles are used.
- wet glue labelling coloured green, amber, brown or black glass bottles with clear cellulose labels or labels of thermoplastic polymer does not achieve a satisfactory no-label appearance.
- wet glue labels made from biopolymers (especially cellulose and/or polylactic acid) it will be appreciated that if a satisfactory means can be found to apply wet glue to other transparent or translucent facestock (e.g. thermoplastic film such as polyolefins for example BOPP) then the present invention applies equally to these substrates as the problem identified and solved herein arises mainly due to the nature of the wet glue label process compared to that used for PSA labels.
- biopolymers especially cellulose and/or polylactic acid
- EP 0664534 A discloses a heat shrinkable label (optionally made from a film of ethylene-vinyl acetate copolymer with an amount of vinyl acetate in the range of 1 to 6% by weight) where the refractive index of the label is in the range of 1.512 to 1.516 in the circumferential direction when fitted to the container, and is in the range of 1.513 to 1.520 in the vertical direction of the container, so that it is even more unlikely that wrinkling, slackening, etc. occur on a surface of the label when heated, as compared with a conventional label made of a polyethylene film. This deals with a completely different problem faced by a separate type of label to that of the present invention.
- EP 1124213 A discloses a clear PSA label where the PSA layer has at least one inorganic particulate material having a particle size not exceeding 50 ⁇ m and having a refractive index of between 1.4 and 1.6. This is stated to improve the transparency of the label of the bottle.
- WO 0130933 A discloses PSA labels where the pressure-sensitive adhesive has a refractive index of at least 1.48.
- the pressure-sensitive adhesives comprise at least one monomer containing a substituted or an unsubstituted aromatic moiety.
- US 6306242 discloses a method of applying a polymer label to an article with a hydrophilic adhesive by curing the label in situ after it has been applied to the article.
- the polymeric substrate for this hydrophilic adhesive is stated to include "clear, opaque or colored polypropylene" . This document does not appreciate the particular problem faced with achieving a no-label look using wet glue with a transparent label as for example no distinction is made between clear and coloured labels.
- L+A denotes a measurement made in a labelled region of an article i.e. in transmitted or reflected light (preferably in reflected light) through the combination of both a translucent or transparent label in situ (including its wet glue) and the translucent or transparent article;
- L denotes a measurement made in transmitted or reflected light (preferably reflected light) through a plain (i.e. unprinted) translucent or transparent label including (unless otherwise specified) through the wet glue applied to the side which will be the label interior side when on the bottle;
- A denotes a measurement made in transmitted or reflected light(preferably in reflected light) through translucent or transparent article (or translucent or transparent sub region thereof) unlabelled and without any wet glue applied.
- colour space measurements were taken from the front side of the sample as seen when the sample is located on the labelled article and the measurements were performed in reflected light .
- Equations 1 to 4 are defined in Equations 1 to 4 as follows (and where L, a and b are measured directly from the relevant sample):
- bottles of the invention exhibit the following values.
- the modulus of ⁇ C is less than about 5, more preferably less than about 4, most preferably less than about 3.5, for example about zero.
- the modulus of ⁇ L is less than about 7, more preferably less than about 4, most preferably less than about 3, for example about zero.
- the modulus of ⁇ E is less than about 8, more preferably less than about 6, most preferably less than about 4, for example about zero.
- the modulus of ⁇ H is less than about 7, more preferably less than about 5.5, most preferably less than about 2.5, for example about zero.
- Conveniently labelled bottles of the invention comprises those where the modulus of both ⁇ L and ⁇ E is less than about 4, more conveniently both less than about 3.
- Values of ⁇ C, ⁇ E and ⁇ H have been selected by experiment to define the region of CIE colour space for a label with respect to a given article which leads to an acceptable no-label look when that label is applied by a wet glue to the article. Without wishing to be bound by any theory the applicant believes that this is where the visual contrast between the label / adhesive / bottle assembly and the bottle is sufficiently low to achieve a no-label look.
- ⁇ L matched luminescence
- an otherwise matched coloured label can produce a satisfactory no-label look.
- appropriately selecting luminescence in addition to the other CIE parameters also helps to disguise visual blemishes caused by defects in the wet glue layer.
- An upper limit on the value of ⁇ L also ensures that a dark (e.g. black) label is not selected for use on a light (e.g. clear) bottle which would self evidently not result in a no-label look.
- CIE L, C, H colour space differences (cylindrical co-ordinates corresponding to the CIE Cartesian colour space L, a, b) are measured conventionally herein as the difference between the labelled article and the unlabelled article measured in reflected light through a transparent sample.
- CIE Commission Internationale d'Eclairage
- E L + E A [(a +A ) 2 + (b L+A ) 2 + (L +A ) 2 )] 1/2 , which describes the colour for the transparent / translucent region of the article with label attached thereto, as the sample;
- EL [(aj 2 + (b L ) 2 + (L L ) 2 )] 1/2 , which describes the colour for the label, as the sample;
- E A [(a A ) 2 + (b A ) 2 + (L A ) 2 )] 2 , which describes the colour for the transparent / translucent unlabelled article (such as a transparent bottle), as the sample.
- the modulus of transmitted colour ratio R tran s is greater than 0.9 preferably is substantially about 1.0.
- the transmitted colour ratio R trans which uses a composite measurement for the label plus article together can be distinguished from results obtained from more conventional colour matching which is based on reflected light.
- Two transparent coloured objects side by side may look the same, but when stacked on top of each other the colour can change and as such the methods described herein are superior in identifying and selecting that colour of wet glue label which is required to achieve an acceptable no-label appearance on a translucent article of given colour.
- Values for R trans and the equations herein can be used to determine optimal colour values for a label E to achieve a satisfactory no-label look for a given article of specified colour values E A and given the other values specified herein as optimal for example for parameters such as ⁇ C, ⁇ H and ⁇ L.
- the present invention relates to the surprisingly discovered need to minimise the visual sensation of contrast between the label and the bottle and its contents.
- Contrast can arise from differences in luminance.
- the applicant has surprisingly discovered that the acceptability of a no-label appearance depends on the intensity of scattered/reflected light from reflected and transmitted light through the sample. Contrast can also be at constant luminance due to differences in colour. Contrast can thus be defined in terms of standard (CIE Lab) measurements of colour and luminance (i.e. L a and b values). The optimum values are where the CIE differences between bottle and contents and film are as small as possible i.e. approach zero.
- a coloured, transparent / translucent polymeric label which is capable of being fixed to a pre-selected coloured transparent / translucent region of an article by a wet glue process to achieve a non-label look on the article, characterised in that: the colour parameters measured in CIE colour space of each of the label, labelled article and un-labelled article together satisfy conditions (a) and/or (b)
- the modulus of ⁇ C is less than about 10, preferably less than about 5, more preferably less than about 4, most preferably about 3.5, for example about zero, (such as ⁇ 0.5), where:
- the modulus of ⁇ L is less than about 7, preferably less than about 4, most preferably about 3, for example about zero, (such as ⁇ 0.5), where:
- the modulus of ⁇ E is less than about 10, more preferably less than about 6, most preferably about 4, for example about zero, (such as ⁇ 0.5), where:
- the modulus of transmitted colour ratio R tra n s is greater than 0.9 preferably is substantially about 1.0
- translucent means 'to show through' whereas the term “translucent” means 'to transmit and diffuse light so that objects beyond cannot be seen clearly'.
- translucent and transparent have been used herein interchangeably and the one term may be replaced by and/or has be used to imply the other throughout the specification and claims herein.
- any suitable transparent and/or translucent wet glue label facestock in combination with any suitable wet glue may be coloured as described herein to achieve a no-label appearance.
- Preferred wet glue labels that can be coloured as described herein are those preferred, embodied and exemplified in PCT/EP02/02726 but optionally any transparent and/or translucent labels also described in US 6306242 may also be coloured as described herein.
- More preferred facestock is cellulose, BOPP and/or polylactic acid film, most preferred is cellulose film or polylactic acid film, for example cellulose film.
- wet glue used to obtain the colour space values herein is the conventional wet glue described in the examples herein.
- the method of colour matching as described herein can be achieved by any suitable known method to colour a label for example one or more of the following and/or combinations thereof: a) colouring the label film directly by incorporating dyes and/or pigments therein; b) applying coloured lacquers to either or both surfaces by any suitable application method; c) colouring the surface of the substrates with coloured inks by any suitable print process; d) colouring a conventional clear wet glue in order to produce coloured translucent adhesive used in conjunction with a clear film; and/or e) colouring both the label film and the wet glue applied thereto
- the total desired colour of the label plus wet glue may be achieved by a partial combination from any of the above (or other) methods and/or by selection of a specific available colour of any suitable commercially available coloured film from a product range, should the known the film be measured to have the desired colour space values as calculated herein.
- Colouring can be achieved by use of pigments; dyes, such as powder dyes, liquid dyes, reactive dyes; and/or encapsulants of dyes and/or pigments.
- the specific colorants and the absolute and respective concentrations used will vary in each case as they depend on the colour space values which are required for the film and/or adhesive to achieve an improved no-label look on the selected article to be labelled. These values can be calculated for a given article as described herein.
- the colorant can be added into the liquid comprising dispersed cellulose (such as viscose) from which the cellulose film is regenerated.
- the process for colouring film can be achieved by a single calculation to achieve a suitable colour according to the method of the invention described herein.
- colouring can occur in real time as the label is applied to each article, for example by colouring the wet glue just before it is applied to the label.
- the colour of each article to be labelled can be sensed by suitable means (e.g. a camera or other sensor) and this information can be used to adjust (e.g. by a feeder of other means) the concentration and/or respective mix of the colorant(s) added to the adhesive applied to the next article to be labelled.
- suitable means e.g. a camera or other sensor
- This method provides a means to adjust for variations in the colour of individual bottles or batches of bottles (e.g. from different suppliers) so that the no-label look appearance of the labelled bottle remains optimal.
- Such a method of colouring the adhesive can also be used in combination with a coloured film.
- a film colour can be selected as described herein to provide an optimal no-label look for the average colour of the articles to be labelled.
- the wet glue can then be coloured in real time on the labelling line to adjust for smaller colour variations for each article and fine tune the no-label look appearance of each article.
- the label can be precisely matched to an article of any colour so a no-label appearance can be achieved for a much wider range of articles.
- one aspect of the present invention provides a method of reliably and reproducibly predicting in advance the colour and/or luminosity required of a label film to achieve a no label appearance when said label is applied by a wet glue method to a translucent article of given colour and luminosity (defined by its position in CIE colour space).
- the present invention is illustrated by the figures herein which are photographs of five bottles to which respectively as a comparison a clear, transparent cellulose label (Figure 1) and coloured (different browns) transparent cellulose labels of the invention ( Figures 2 & 3) had been applied by a wet glue process.
- Cellulose label film was produced as follows for both comparative labels and labels of and used in the method of the present invention as follows.
- a production machine was set up in a conventional manner to produce regenerated cellulose film from the well known viscose method.
- the viscose used had a cellulose content of 9.3% and the resultant film had a substance of 62 grams per square metre uncoated and 64.5 grams per square metre coated. Where a colorant was omitted the resultant film was a conventional clear and transparent cellulose film such as that available commercially from UCB under the trade mark Cellophane® 645 E711.
- cellulose films with a substances of 75 grams per square metre uncoated and 77.5 grams per square metre coated were also prepared and gave satisfactory results in the method of the present invention when tested analogously to the exemplified films herein.
- a suitable (e.g. brown) dye or pigment can be added to the viscose stream to be absorbed into the regenerated film.
- the colorant type and concentration
- the colorant may be selected such that the colour of the resultant film web satisfied the equations herein with respect to previously measured colour space values for the coloured (e.g. brown) glass bottles to be labelled. This produces a resultant film which is transparent and of the required colour to achieve a no-label appearance on a given coloured glass bottle (e.g. dark brown bottle filled with a very dark beer).
- One side of the optionally coloured cellulose film prepared as described above was coated with a conventional coating of vinyl chloride / vinyl acetate copolymer at a coat weight of 2.5 g per m 2 .
- a standard wet glue synthetic adhesive (50% water) was then applied to the same side as the copolymer during labelling by a conventional wet glue labelling apparatus. The applicant has found that this adhesive may be applied at coat weights from 2.5 to 3.5 g per m 2 and will still give satisfactory performance in the method of the present invention.
- the label films were applied to the bottles in a conventional way using unmodified (or only trivially modified) conventional labeling equipment set up for wet glue paper labels, to achieve a transparent label thereon.
- the colour space co-ordinates (CIE) for the various bottle / label combinations were measured conventionally in reflected light.
- the CIE data (Modulus values) obtained were given in the Tables below to 2 decimal places (dimensionless, no units). For each example there is a pair of data sets where #(i) refers to the bottle (whether empty or full as indicated) before labelling and #(ii) is data obtained after the relevant label had been applied.
- NA denotes "not applicable” (e.g. No-look label, ⁇ L, ⁇ H, ⁇ C, and ⁇ E were not determined for unlabelled bottles).
- Comp I was a label prepared from clear uncoloured transparent cellulose available commercially from UCB under the trade mark Cellophane® 645 E711.
- Comp II was a label where the colorant added to the cellulose was a blue colour unmatched (i.e. not satisfying the Equations 1 to 4 herein) to the colour of the brown bottle which was labelled.
- Comp III to VI are various comparative labelled bottle made using clear cellulose label applied (as described above) to a bottle of clear glass optionally filed with various brown dyes B to E. Tabl. e 1
- Bottles were labelled according to the invention as follows with reference to Tables 2 to 3 and Figures 2 to 3 herein.
- brown labels B1 and B2 in Examples 1 to 10 herein were coloured as described herein (by addition to a standard viscose bath with the film web speed the same in each case) using the following colorant mixture added at respective weight ratios (B1 and B2) of 20 and 9. (Each dye was available commercially from Colorantes Industriales) Colorant Weight ratio
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Abstract
There is described a coloured, transparent polymeric label which is capable of being fixed to a pre-selected coloured, transparent region of an article (optionally by a wet glue process) to achieve a non-label look on the article, characterised in that: the colour parameters measured in CIE colour space of each of the label, labelled article and un-labelled article together satisfy conditions (a) and/or (b) (a) (i) the modulus of DeltaC is less than about 5, more preferably less than about 4, most preferably about 3.5, for example about zero, where: DeltaC = CL+A-CA Equation 1 where CL+A = (aL+A<2> + bL+A<2>)<½> and CA= (aA<2> + bA<2>)<½> ; and (ii) the modulus of DeltaL is less than about 7, preferably less than about 4, most preferably about 3, for example about zero, where: DeltaL = LL+A - LA Equation 2; and (iii) the modulus of DeltaE is less than about 10, more preferablyless than about 6, most preferably about 4, for example about zero, where: DeltaE = (Deltaa<2> + Deltab<2> + DeltaL<2>)<½> Equation 3; where Deltaa = aL+A - aL and Deltab = bL+A- bL;; and (iv) the modulus of DeltaH is less than about 7, more preferably less than about 5.5, most preferably less than about 2.5, for example about zero, where: DeltaH = (DeltaE <2> + DeltaL<2> + DeltaC<2>)<½> Equation 4 and/or (b) the modulus of transmitted colour ratio (Rtrans) is greater than 0.9 preferably is substantially about 1.0, where Rtrans = 2 (EL+A) / (EL + EA) Equation 5 This provides a method for colour matching a label to a specific article such as a bottle to be labelled to provide a nolabel appearance on the article.
Description
COLOURED LABELS
The present invention relates to the field of coloured labels such as (but not limited to) those labels fixed to an article with an aqueous adhesive applied thereto (so-called wet glue labels). Preferably the invention relates to those labels which achieve a no-label look on the article. Any suitable labels may be used in the invention such as labels comprising coloured transparent and/or translucent bio-polymeric films, for example films made from cellulose and/or polylactic acid.
Labels made from thermoplastic films have been conventionally fixed onto an article with pressure sensitive adhesives (herein denoted as PSA) pre-coated onto the label facestock. Such label films include polyolefins, e.g. biaxially oriented polypropylene - BOPP). A PSA label facestock is dispensed from a release liner onto the article to be labeled. An alternative labeling method often used with a paper labels is to use a separate adhesive dispersed in an aqueous medium. The adhesive is applied as the label is fixed to the article. These are often referred to as wet glue labels but can also be called cold glue labels or just glue labels.
The market for alcoholic beverages such as beer, wine or spirits is more and more competitive and breweries need to find ways of capturing their audience and enticing them to purchase their product. Packaging is a major part of the promotional mix especially at point of sale in supermarkets and the drive for differentiation amongst the manufacturers is furious.
Recently a 'no-label' appearance has become fashionable for PSA labels as retailers have found many advantages from this new form of shelf appeal. The appearance of no-label is achieved by applying a transparent and/or translucent label to the article. If the label is transparent, printing on its reverse side (i.e. the "interior" side to be adhered to the article) appears to be directly applied to the article hence the term "no-label look". Such interior coats are better protected from wear and tear (rubbing, attack by solvents etc) as they are not on the exterior of the article.
However due to the process used to apply a wet glue label the conventional transparent plastic films (OPP, polyester- PE, polyethylene phthalate - PET) currently used in the PSA market have various disadvantages when used as the facestock for a transparent wet glue label. The properties of these thermoplastic films are different from the paper labels used on conventional wet glue machines.
For example thermoplastic films have a higher barrier to moisture (they are not semi-permeable to water) and this causes a wet glue to take longer to dry (and hence more time for the label to fix in place) which can be disadvantageous on a high speed labelling line or where precise location of the label on the article is required. Thus thermoplastic films are not an ideal replacement for a paper label on a conventional production line set up to apply a wet glue label to an article such as a bottle. Aqueous coatings are also not easily compatible with and do not adhere well to such thermoplastic films which are often hydrophobic without surface treatment of the film.
The substrate conventionally used to prepare wet glue labels is paper which is not transparent. Thermoplastic films can be transparent but because of the previous stated disadvantages with thermoplastic films and wet glue coatings, it has been necessary to use pressure sensitive adhesives to provide an article with a no look label having acceptable performance. Thus manufactures currently using labelling equipment for paper wet glue labels are faced with a significant capital outlay and disruption to change to equipment compatible with pressure sensitive labels if they wish to move to a no-label look.
The applicants co-pending application PCT/EP02/02726 describes use of wet glue method to apply a clear biopolymeric label (such as a cellulose film) to a transparent article to achieve a clear -label look without PSA. This method can use existing machinery suitable for paper wet glue labels yet allows use of biopolymeric labels which have various advantages over paper. The biopolymeric labels can be transparent or translucent to achieve a no-label look. A wet glue on a biopolymeric substrate can also dry in a reasonable time without the need to use exotic coatings. This method now provides an alternative route to a clear-label look for manufacturers without the disadvantages of changing an existing label line from wet glue to PSA. The contents of PCT/EP02/02726 are incorporated herein by reference.
However surprisingly the applicant has found that there are still issues that remain to provide an acceptable no-label appearance using a wet glue label compared to a PSA label.
PSA labels have the pressure sensitive adhesive pre-applied during the production of the label stock. In contrast the wet glue process requires that a wet adhesive is applied in situ to the label. The wet glue is applied to a glue roller then transferred to rubber covered palettes which transfer the glue onto the reverse of the label. In turn, the label is applied to articles such as glass or PET bottles at typical output speeds between 300 and 500 plus articles labelled per minute. At these line speeds and particularly with a range of conditions such as wet and dry and warm and cold bottles the applicant has found that the adhesive transfer
characteristics of wet glue have been difficult to optimise to achieve a satisfactory no-label appearance of a wet glue label on a bottle comparable to the no-label appearance of a conventional PSA label.
For example the applicant has found while a label of a clear cellulose film can be applied to a clear flint glass bottle using a wet glue to achieve an acceptable appearance, unexpectedly this is not the case when coloured bottles are used. For example wet glue labelling coloured green, amber, brown or black glass bottles with clear cellulose labels or labels of thermoplastic polymer does not achieve a satisfactory no-label appearance. Without wishing to be bound by any mechanism the applicant believes that due to the method of applying the adhesive there will be more under label defects compared to a PSA label. What is surprising is that these blemishes can more readily be seen with a clear transparent label on a transparent coloured article (such as a coloured glass or PET bottle) thus spoiling the illusion of a no-label appearance. Again without wishing to be bound by any mechanism the applicant speculates that this may be due to non-optimal optical contrast properties in the label / adhesive / bottle assembly.
Therefore if this unexpectedly observed problem is addressed it would enable a satisfactory or improved no-label appearance to be achieved by a wet glue label on a wider range (preferably any) colour or luminosity of article to be labelled, more preferably where the article (as well as the wet glue label) is translucent or transparent.
Although the disclosure herein relates mainly to wet glue labels made from biopolymers (especially cellulose and/or polylactic acid) it will be appreciated that if a satisfactory means can be found to apply wet glue to other transparent or translucent facestock (e.g. thermoplastic film such as polyolefins for example BOPP) then the present invention applies equally to these substrates as the problem identified and solved herein arises mainly due to the nature of the wet glue label process compared to that used for PSA labels.
Various documents exist which teach that optical properties of a label facestock or label adhesive may be modified.
EP 0664534 A (Fuji Seal) discloses a heat shrinkable label (optionally made from a film of ethylene-vinyl acetate copolymer with an amount of vinyl acetate in the range of 1 to 6% by weight) where the refractive index of the label is in the range of 1.512 to 1.516 in the circumferential direction when fitted to the container, and is in the range of 1.513 to 1.520 in the vertical direction of the container, so that it is even more unlikely that wrinkling, slackening,
etc. occur on a surface of the label when heated, as compared with a conventional label made of a polyethylene film. This deals with a completely different problem faced by a separate type of label to that of the present invention.
Some documents in the field of PSA labels teach of specific refractive index values for a PSA used in a transparent label.
EP 1124213 A (Heineken) discloses a clear PSA label where the PSA layer has at least one inorganic particulate material having a particle size not exceeding 50 μm and having a refractive index of between 1.4 and 1.6. This is stated to improve the transparency of the label of the bottle.
WO 0130933 A (3M) discloses PSA labels where the pressure-sensitive adhesive has a refractive index of at least 1.48. The pressure-sensitive adhesives comprise at least one monomer containing a substituted or an unsubstituted aromatic moiety.
References in the field of PSA labels are not relevant to the problem discovered by the applicant in the field of wet glue labels.
US 6306242 (Dronzek) discloses a method of applying a polymer label to an article with a hydrophilic adhesive by curing the label in situ after it has been applied to the article. On col. 5 lines 30 to 32 (and again on col. 8 lines 46 to 49) the polymeric substrate for this hydrophilic adhesive is stated to include "clear, opaque or colored polypropylene" . This document does not appreciate the particular problem faced with achieving a no-label look using wet glue with a transparent label as for example no distinction is made between clear and coloured labels.
It is an object of the invention to solve some or all of the problems identified herein, for example to provide a method of labelling articles with an improved no-label look.
In general the following subscripts are used herein and in the claims to denote various colour space parameters and measurements made herein:
"L+A" denotes a measurement made in a labelled region of an article i.e. in transmitted or reflected light (preferably in reflected light) through the combination of both a translucent or transparent label in situ (including its wet glue) and the translucent or transparent article; "L" denotes a measurement made in transmitted or reflected light (preferably reflected light) through a plain (i.e. unprinted) translucent or transparent label including (unless otherwise specified) through the wet glue applied to the side which will be the label interior side when on the bottle; and "A" denotes a measurement made in transmitted or reflected light(preferably
in reflected light) through translucent or transparent article (or translucent or transparent sub region thereof) unlabelled and without any wet glue applied.
Unless otherwise specified herein colour space measurements were taken from the front side of the sample as seen when the sample is located on the labelled article and the measurements were performed in reflected light .
In one method used in accordance with the present invention differences are measured between the labelled and unlabelled articles directly.
In this method ΔC, ΔL, ΔE and ΔH are defined in Equations 1 to 4 as follows (and where L, a and b are measured directly from the relevant sample):
ΔC = CL+A-CA Equation 1 where CL+A = (aL+A 2+bL+A 2)1 2 and CA= (aA 2+bA 2)1 2
ΔL = LL+A - LA Equation 2
ΔE = [Δa2 + Δb2 + ΔL2) \11/"2 Equation 3 where Δa = aL+A- ^L and Δb = bL+A- b
ΔH = (ΔE^ + ΔL^ + ΔC 2 1/2 Equation 4
Preferably and independently in each case labelled bottles of the invention exhibit the following values. The modulus of ΔC is less than about 5, more preferably less than about 4, most preferably less than about 3.5, for example about zero.
The modulus of ΔL is less than about 7, more preferably less than about 4, most preferably less than about 3, for example about zero.
The modulus of ΔE is less than about 8, more preferably less than about 6, most preferably less than about 4, for example about zero.
The modulus of ΔH is less than about 7, more preferably less than about 5.5, most preferably less than about 2.5, for example about zero.
Conveniently labelled bottles of the invention comprises those where the modulus of both ΔL and ΔE is less than about 4, more conveniently both less than about 3.
Values of ΔC, ΔE and ΔH have been selected by experiment to define the region of CIE colour space for a label with respect to a given article which leads to an acceptable no-label look when that label is applied by a wet glue to the article. Without wishing to be bound by any theory the applicant believes that this is where the visual contrast between the label / adhesive / bottle assembly and the bottle is sufficiently low to achieve a no-label look.
However the applicant has found that a specific range for ΔL (matched luminescence) is also required so an otherwise matched coloured label can produce a satisfactory no-label look. Without wishing to be bound by any theory the applicant believes that appropriately selecting luminescence in addition to the other CIE parameters also helps to disguise visual blemishes caused by defects in the wet glue layer. An upper limit on the value of ΔL also ensures that a dark (e.g. black) label is not selected for use on a light (e.g. clear) bottle which would self evidently not result in a no-label look.
CIE L, C, H colour space differences (cylindrical co-ordinates corresponding to the CIE Cartesian colour space L, a, b) are measured conventionally herein as the difference between the labelled article and the unlabelled article measured in reflected light through a transparent sample.
Each of the above parameters used herein is otherwise measured and/or defined as set out in the Commission Internationale d'Eclairage (CIE) standard C1E94 or by analogy with the methods used in this standard. The measurements were performed under standard reference test conditions as defined in CIE94 (except as modified herein) namely: CIE D65, CIE 10° Observer, 1000 Ix illuminance, gray background, minimal specimen separation, homogeneous specimen structure and normal colour vision and measurements made in reflected light as defined herein.
In an alternative or additional method used in accordance with the present invention differences are measured between the coloured sample and a clear uncoloured standard (label, labelled article and unlabelled articles).
As used herein a colour ratio in transmitted light (also denoted Rtrans) may be given from the ratio of the colour of the composite labelled article to the average colour of the separate label and the article. This can be defined in Equation 5 as: Rtrans = 2 -(EL+A) Equation 5
(EL + EA) where
EL+A = [(a +A)2 + (bL+A)2 + (L +A)2)]1/2, which describes the colour for the transparent / translucent region of the article with label attached thereto, as the sample; EL = [(aj2 + (bL)2 + (LL)2)]1/2, which describes the colour for the label, as the sample; and EA = [(aA)2 + (bA)2 + (LA)2)] 2, which describes the colour for the transparent / translucent unlabelled article (such as a transparent bottle), as the sample.
Preferably for optimal colour matching the modulus of transmitted colour ratio Rtrans is greater than 0.9 preferably is substantially about 1.0.
The transmitted colour ratio Rtrans which uses a composite measurement for the label plus article together can be distinguished from results obtained from more conventional colour matching which is based on reflected light. Two transparent coloured objects side by side may look the same, but when stacked on top of each other the colour can change and as such the methods described herein are superior in identifying and selecting that colour of wet glue label which is required to achieve an acceptable no-label appearance on a translucent article of given colour.
Values for Rtrans and the equations herein can be used to determine optimal colour values for a label E to achieve a satisfactory no-label look for a given article of specified colour values EA and given the other values specified herein as optimal for example for parameters such as ΔC, ΔH and ΔL.
The present invention relates to the surprisingly discovered need to minimise the visual sensation of contrast between the label and the bottle and its contents. Contrast can arise from differences in luminance. The applicant has surprisingly discovered that the acceptability of a no-label appearance depends on the intensity of scattered/reflected light from reflected and transmitted light through the sample. Contrast can also be at constant luminance due to differences in colour. Contrast can thus be defined in terms of standard (CIE Lab) measurements of colour and luminance (i.e. L a and b values). The optimum values are where the CIE differences between bottle and contents and film are as small as possible i.e. approach zero.
The applicant has also unexpectedly discovered that to a first approximation other parameters of the label or bottle (such as refractive indices, amount of reflection or difference between bottle surface and label or spectral analysis of glass versus label film) are less important to achieve the no-label appearance and need not be considered here.
Therefore broadly in accordance with the present invention there is provided a coloured, transparent / translucent polymeric label which is capable of being fixed to a pre-selected coloured transparent / translucent region of an article by a wet glue process to achieve a non-label look on the article, characterised in that: the colour parameters measured in CIE colour space of each of the label, labelled article and un-labelled article together satisfy conditions (a) and/or (b)
(a)(i) the modulus of ΔC is less than about 10, preferably less than about 5, more preferably less than about 4, most preferably about 3.5, for example about zero, (such as ± 0.5), where:
ΔC = C +A-CA Equation 1 where CL+A = (a +A 2 + bL+A 2)1 2 and CA = (aA 2 + bA 2)1/2 ;and
(ii) the modulus of ΔL is less than about 7, preferably less than about 4, most preferably about 3, for example about zero, (such as ± 0.5), where:
ΔL = LL+A - LA (Equation 2); and
(iii) the modulus of ΔE is less than about 10, more preferably less than about 6, most preferably about 4, for example about zero, (such as ± 0.5), where:
ΔE = (Δa2 + Δb2 + ΔL2)1/2 Equation 3; where Δa = aL+A- aL and Δb = bL+A- bL;; and (iv) the modulus of (ΔH) is less than about 7, more preferably less than about 5.5, most preferably less than about 2.5, for example about zero, (such as ± 0.5), where: ΔH = (ΔE2 - ΔL2 - ΔC2)1/2 Equation 4 and/or
(b) the modulus of transmitted colour ratio Rtrans is greater than 0.9 preferably is substantially about 1.0, where
Rtrans = 2 ( JΛ) Equation 5 (EL + EA)
The term "transparent" means 'to show through' whereas the term "translucent" means 'to transmit and diffuse light so that objects beyond cannot be seen clearly'. However in the context of the present invention (unless clearly meant otherwise) the terms translucent and transparent have been used herein interchangeably and the one term may be replaced by and/or has be used to imply the other throughout the specification and claims herein.
It will be appreciated that the any suitable transparent and/or translucent wet glue label facestock in combination with any suitable wet glue may be coloured as described herein to achieve a no-label appearance. Preferred wet glue labels that can be coloured as described herein are those preferred, embodied and exemplified in PCT/EP02/02726 but optionally any transparent and/or translucent labels also described in US 6306242 may also be coloured as
described herein. More preferred facestock is cellulose, BOPP and/or polylactic acid film, most preferred is cellulose film or polylactic acid film, for example cellulose film.
Unless otherwise specified herein where necessary the wet glue used to obtain the colour space values herein is the conventional wet glue described in the examples herein.
The method of colour matching as described herein can be achieved by any suitable known method to colour a label for example one or more of the following and/or combinations thereof: a) colouring the label film directly by incorporating dyes and/or pigments therein; b) applying coloured lacquers to either or both surfaces by any suitable application method; c) colouring the surface of the substrates with coloured inks by any suitable print process; d) colouring a conventional clear wet glue in order to produce coloured translucent adhesive used in conjunction with a clear film; and/or e) colouring both the label film and the wet glue applied thereto
It will be further appreciated that the total desired colour of the label plus wet glue may be achieved by a partial combination from any of the above (or other) methods and/or by selection of a specific available colour of any suitable commercially available coloured film from a product range, should the known the film be measured to have the desired colour space values as calculated herein.
Colouring can be achieved by use of pigments; dyes, such as powder dyes, liquid dyes, reactive dyes; and/or encapsulants of dyes and/or pigments.
Colorants which have been found to be used in the method of the present invention comprises blend of Crisofeniana G280 (yellow), Rojo Eliamina 8BLEC (red) and Azul Marina 15 REC (blue); or a blend of direct Yellow Colour Index (60% w/w), Direct Red Colour Index 81 (10% w/w), and Acid Blue Colour Index 113 (30% w/w).
However it will be appreciated that the specific colorants and the absolute and respective concentrations used will vary in each case as they depend on the colour space values which are required for the film and/or adhesive to achieve an improved no-label look on the selected article to be labelled. These values can be calculated for a given article as described herein.
For a regenerated cellulose film the colorant can be added into the liquid comprising dispersed cellulose (such as viscose) from which the cellulose film is regenerated. The process for colouring film can be achieved by a single calculation to achieve a suitable colour according to the method of the invention described herein.
Alternatively colouring can occur in real time as the label is applied to each article, for example by colouring the wet glue just before it is applied to the label. In this embodiment optionally the colour of each article to be labelled can be sensed by suitable means (e.g. a camera or other sensor) and this information can be used to adjust (e.g. by a feeder of other means) the concentration and/or respective mix of the colorant(s) added to the adhesive applied to the next article to be labelled. This method provides a means to adjust for variations in the colour of individual bottles or batches of bottles (e.g. from different suppliers) so that the no-label look appearance of the labelled bottle remains optimal.
Such a method of colouring the adhesive can also be used in combination with a coloured film. A film colour can be selected as described herein to provide an optimal no-label look for the average colour of the articles to be labelled. The wet glue can then be coloured in real time on the labelling line to adjust for smaller colour variations for each article and fine tune the no-label look appearance of each article.
The present invention of colour matching the label to the article shows some or all the following benefits (relative to a clear label):
Improved merging of the edges of the applied labels especially seen with with brown glass bottles. Improved masking of the micro bubbles trapped in the adhesive layer between the bottle surface and the inner face of the applied labels.
Improved masking of transferred marks or blemishes on the rubber plate, thus significantly widening the operating window with regard to surface defects or finish of the rubber application palettes used on a bottle line to transfer adhesive to the labels. Improved opacity of surface printed white inks which allows labels to be printed by the off set litho sheet fed process currently used to print the bulk of paper wet glue labels.
Elimination of the "wet T-shirt effect " seen when a single hit white ink is used as part of the label design colour palette.
The label can be precisely matched to an article of any colour so a no-label appearance can be achieved for a much wider range of articles.
Thus one aspect of the present invention provides a method of reliably and reproducibly predicting in advance the colour and/or luminosity required of a label film to achieve a no label appearance when said label is applied by a wet glue method to a translucent article of given colour and luminosity (defined by its position in CIE colour space). This is because the applicant has defined using the equations herein and parameter limits given herein for the variables in said equations a region of colour space relative to the article which the applicant has found by trial and error is sufficient to disguise the blemishes which unavoidably result from the wet glue method (compared say to a PSA label) when the labelled article is viewed in transmitted and/or reflected light through the transparent / translucent label - article assembly.
Further aspects, embodiments and preferred features of the invention are described in the claims.
The present invention is illustrated by the figures herein which are photographs of five bottles to which respectively as a comparison a clear, transparent cellulose label (Figure 1) and coloured (different browns) transparent cellulose labels of the invention (Figures 2 & 3) had been applied by a wet glue process.
The present invention will now be described in detail with reference to the following non limiting examples which are by way of illustration only. Firstly some common procedures are described.
Label preparation
Cellulose label film was produced as follows for both comparative labels and labels of and used in the method of the present invention as follows. A production machine was set up in a conventional manner to produce regenerated cellulose film from the well known viscose method. The viscose used had a cellulose content of 9.3% and the resultant film had a substance of 62 grams per square metre uncoated and 64.5 grams per square metre coated. Where a colorant was omitted the resultant film was a conventional clear and transparent cellulose film such as that available commercially from UCB under the trade mark Cellophane® 645 E711. In an alternative embodiment cellulose films with a substances of 75 grams per square metre uncoated and 77.5 grams per square metre coated were also prepared and gave satisfactory results in the method of the present invention when tested analogously to the exemplified films herein.
Optional label colouring
Optionally a suitable (e.g. brown) dye or pigment can be added to the viscose stream to be absorbed into the regenerated film. The colorant (type and concentration) may be selected such that the colour of the resultant film web satisfied the equations herein with respect to previously measured colour space values for the coloured (e.g. brown) glass bottles to be labelled. This produces a resultant film which is transparent and of the required colour to achieve a no-label appearance on a given coloured glass bottle (e.g. dark brown bottle filled with a very dark beer).
Adhesive
One side of the optionally coloured cellulose film prepared as described above was coated with a conventional coating of vinyl chloride / vinyl acetate copolymer at a coat weight of 2.5 g per m2. A standard wet glue synthetic adhesive (50% water) was then applied to the same side as the copolymer during labelling by a conventional wet glue labelling apparatus. The applicant has found that this adhesive may be applied at coat weights from 2.5 to 3.5 g per m2 and will still give satisfactory performance in the method of the present invention.
Bottles
Except where indicated the same type of clear bottle was used in each of the examples herein. However the bottles tested were filled with a solution of various dyes denoted B, C, D & E (or 'e' in the Figures 1 to 3) to mimic the effect of a range of various (brown) coloured bottles. Four particular shades and hues of brown liquid were prepared and in each case the same shade and hue of brown was denoted by the same letter B to E (in Figures 1 to 3 herein). It will be appreciated that it is irrelevant how the given colour was (as defined by CIE data herein) is achieved, for example B to E may be made a selection of a suitable dye(s) separately for each sample and/or the same dye(s) used at different concentrations in each sample. For comparison the labels were also applied to the empty clear bottle (denoted A). This technique provided a ready means to test many different shade and hue combinations of brown label on (simulated) brown bottle. It will be appreciated that this was for convenience as it was more difficult to obtain bottles having various graduations of brown.
Labelling
The label films were applied to the bottles in a conventional way using unmodified (or only trivially modified) conventional labeling equipment set up for wet glue paper labels, to achieve a transparent label thereon.
Using the method described herein (and in Equations 1 to 5 herein) the following CIE values were determined from experimental data for various labels applied to various glass bottles.
Results
The colour space co-ordinates (CIE) for the various bottle / label combinations were measured conventionally in reflected light. The CIE data (Modulus values) obtained were given in the Tables below to 2 decimal places (dimensionless, no units). For each example there is a pair of data sets where #(i) refers to the bottle (whether empty or full as indicated) before labelling and #(ii) is data obtained after the relevant label had been applied. NA denotes "not applicable" (e.g. No-look label, ΔL, ΔH, ΔC, and ΔE were not determined for unlabelled bottles).
Comparative Examples
The following comparative examples were prepared (Comps. I to VIII)
Labels (Comp I & II)
Comp I was a label prepared from clear uncoloured transparent cellulose available commercially from UCB under the trade mark Cellophane® 645 E711.
Comp II was a label where the colorant added to the cellulose was a blue colour unmatched (i.e. not satisfying the Equations 1 to 4 herein) to the colour of the brown bottle which was labelled.
Labelled bottles
Clear labels (Comp 111 to VIP
Comp III to VI are various comparative labelled bottle made using clear cellulose label applied (as described above) to a bottle of clear glass optionally filed with various brown dyes B to E.
Tabl. e 1
Comp Dve No-look label L a b ΔL ΔH ΔC ΔE lll(l) A (none) NA 26.15 0.45 -0.89 NA NA NA NA lll(ii) A (none) Pass 28.61 0.77 -0.52 2.46 0.49 -0.07 2.51
IV(i) B NA 24.16 1.16 0.11 NA NA NA NA
IV(ii) B Pass 26.21 0.69 -0.76 2.05 0.98 -0.14 2.27
V(i) C NA 22.21 0.72 -0.51 NA NA NA NA
V(ii) C Fail 27.89 0.22 -0.63 5.68 0.46 -0.22 5.71
Vl(i) D NA 20.13 0.05 -0.94 NA NA NA NA
V Vll((iiii)) D D F Faaiill 2 277..8866 - -00..0011 - -11..0066 7.73 0.06 0.12 7.73
Vll(i) E NA 25.21 0.19 -1.72 NA NA NA NA
Vll(ii) E Fail 30.56 -0.11 -1.30 5.35 0.29 -0.43 5.38
Each labelled bottle was visually inspected and given a crude "pass" or "fail" based on the blemishes seen on the label in reflected light and the overall illusion of no-label. Photographs of the labelled bottles evaluated are shown in Figure 1 herein. As can be seen from the data the applicant has surprisingly discovered (and contrary to what might be expected) not all clear (uncoloured) transparent labels are able to produce a satisfactory no-label look when applied to a bottle. This can be seen for example from Comps. V to VI when clear labels when applied to a dark coloured bottles ((simulated) brown bottles C to E) exhibit an unexpectedly high value for ΔL (luminance). Without wishing to be bound by any theory the applicant believed that (luminant) blemishes caused by uneven application of the adhesive can be seen particularly well through the clear label against the background of a dark bottle
Colour mismatched label and bottle (Comp VHP
For a further comparison a dark labels on a dark bottles was prepared where a blue cellulose label coloured as described herein was applied to a brown bottle and measured as described. This labelled bottle failed the no-look label test.
ΔL ΔC ΔH ΔE
Comp VIII = Brown Bottle / Comp Label II 6.3 7.76 7.54 12.52
The applicant has provided a means to solve the above identified problem as illustrated by the following examples according to the present invention.
Examples 1 to 10
Bottles were labelled according to the invention as follows with reference to Tables 2 to 3 and Figures 2 to 3 herein.
Labels
For each of the five bottles (one clear and four simulated brown) were labelled with a cellulose label as describes herein by a wet glue method. Two labels were used. Examples 1 to 5 used a dark brown label of a certain hue (denoted herein by B1 ) as shown in Figure 2 with reference to the data in Table 2. Examples 6 to 10 used a brown label of different lighter hue to B1 (denoted herein by B2) as shown in Figure 3 with reference to the data in Table 3. Conventional brown dyes were used to create (by the method as described herein) the two different shades (B1 & B2) of brown cellulose label used herein. These labels (B1 , B2) were applied to a clear bottles and various brown colours were simulated using dyes B to E. The label was applied using the wet glue process as described herein.
Results
Each labelled bottle was then rated visually for an appearance of a no-label look based on the blemishes seen on the label in reflected light and the overall illusion of no-label, based on ranking criteria given in Table A for each of the parameters ΔL, ΔH, ΔC and ΔE. The mean of the ranking values was tabulated as the "no-label look rating" for each example tested. These labelled bottles were also photographed and these are shown in Figure 2 (Table 2) and Figure 3 (Table 3) herein.
Table A
Parameterl // Rating values → 0 1 2 3. 4
ΔL > 7.0 < 7.0 < 4.0 < 3.5 * 0 (±0.5) ΔH > 7.0 < 7.0 < 5.5 < 2.5 « 0 (±0.5)
ΔC > 5.0 5.0 < 4.0 < 3.5 « 0 (±0.5)
ΔE > 8.0 < 8.0 < 6.0 < 4.0 ~ 0 (±0.5)
The CIE values were then related to those label / bottle combinations which passed to confirm the validity of the method of the present invention for pre-selecting those labels which will create an acceptable no-label look for a given bottle.
Table 2 (Label B1)
Ex Dve "No-label look rating" L a b ΔL ΔH ΔC ΔE
1 i A NA 26.23 0.18 -0.32 NA NA NA NA
1 ii A 2 25.03 0.54 4.86 1.20 2.55 4.52 5.33
2i B NA 22.89 0.51 -1.87 NA NA NA NA
2ii B VA 29.11 0.12 4.80 6.22 6.03 2.86 9.13
3i C NA 22.16 0.12 -2.16 NA NA NA NA
3ii C 2% 23.99 1.28 1.52 1.83 3.85 -0.18 4.26 4 4ii D D N NAA 2 244..3311 0 0..2211 - -11..1111 NA NA NA NA
4ii D 21/2 25.03 -0.15 4.50 0.71 4.50 3.37 5.66
5 E NA 23.68 -0.12 -1.72 NA NA NA NA
5ii E 2/2 25.26 -0.20 3.73 1.58 5.07 2.01 5.68
Table 3 (Label B2)
Ex Dve "No-label look rating" L a b ΔL ΔH ΔC ΔE
6i A NA 27.27 0.33 -1.24 NA NA NA NA
6ii A 21/ 23.48 1.32 1.35 3.79 2.70 0.61 4.69 7 7ii B B N NAA 2 255..3300 0 0..5544 - -11..5577 NA NA NA NA
7ii B 21/2 21.58 1.21 0.95 3.72 2.61 -0.12 4.54
8i C NA 22.93 0.07 -2.47 NA NA NA NA
8ii C 2% 23.99 1.28 1.52 1.06 4.13 -0.48 4.30
9i D NA 22.44 -0.03 -2.01 NA NA NA NA 9 9iiii D D 3 3V%Λ 2 222..7799 1 1..3322 1 1..1100 0.35 3.37 -0.29 3.41
10i E NA 22.45 -0.12 -2.38 NA NA NA NA
10ii E 21/ 25.44 1.12 1.26 2.98 3.78 -0.70 4.87
Colorant
The brown labels B1 and B2 in Examples 1 to 10 herein were coloured as described herein (by addition to a standard viscose bath with the film web speed the same in each case) using the following colorant mixture added at respective weight ratios (B1 and B2) of 20 and 9. (Each dye was available commercially from Colorantes Industriales)
Colorant Weight ratio
Direct Yellow Colour Index 12: 0.6
Direct Red Colour Index 81 : 0.1
Acid Blue Colour Index 1 13: 0.3 Total 1 .0
Examples 1 1 (0 to (vi) - Labelled brown bottle
Further dark brown glass bottles were labelled as described herein with reference to Table 4, these bottles are not shown in the photographs of Figures 1 to 3 herein. Various different coloured brown labels (denoted by Greek letters α to ε) were applied with a wet glue process to the same empty dark brown bottle. It will be appreciated that the given brown colour of label may be achieved by the selection of any suitable dye(s), pigment(s) and/or mixtures thereof at concentrations thereof. Each labelled bottle was tested as described above (Ex 11 (i) was the unlabelled bottle) and the data is given in Table 4.
Table 4
Ex Bottle Label Rating L a b ΔL ΔH ΔC ΔE
11 i Brown none NA 24.93 0.61 5.18 NA NA NA NA
11 ii Brown ( ) 31/2 27.59 0.68 3.80 2.66 0.27 -1.36 3.00
11 Hi Brown (β) 3 26.48 1.51 3.99 1.55 1.15 -0.95 2.15
1 1 iv Brown (Y) 3 22.17 1.39 3.04 2.77 1.29 -1.88 3.58
11v Brown (δ) 3% 22.82 0.52 4.08 2.11 0.05 -1.10 2.38
1 1vi Brown (ε) 3 24.38 0.91 1.76 0.56 1.16 -3.23 3.48
These various brown labels (Examples 11 (ii) to (vi)) were found to match the brown bottle to achieve a no-label look. A rating value calculated as for the "no label look rating" in Tables 2 and 3 above, compares favourable with the other examples. It can be seen that use of a colour and luminance matched label is particularly useful to achieve a no-label look on a dark coloured bottle.
Claims
1. A coloured, transparent polymeric label which is capable of being fixed to a preselected coloured transparent region of an article (optionally by a wet glue process) to achieve a non-label look on the article, characterised in that: the colour parameters measured in CIE colour space of each of the label, labelled article and un-labelled article together satisfy conditions (a) and/or (b):
(a) (i) the modulus ofΔC is less than about 5, more preferably less than about 4, most preferably about 3.5, for example about zero, where: ΔC = CL+A-CA Equation 1 where CL+A = (aL+A 2 + bL+A 2)1/2 and CA= (aA 2 + bA )1/2 ; and (ii) the modulus of ΔL is less than about 7, preferably less than about 4, most preferably about 3, for example about zero, where:
ΔL = LL+A - LA Equation 2; and (iii) the modulus of ΔE is less than about 10, more preferablyless than about 6, most preferably about 4, for example about zero, where:
ΔE = (Δa2 + Δb2 + ΔL2)1/2 Equation 3; where Δa = a +A - aL and Δb = b +A - bL;; and (iv) the modulus of ΔH is less than about 7, more preferably less than about 5.5, most preferably less than about 2.5, for example about zero, where: ΔH = (ΔE2 + ΔL2 + ΔC2)1 2 Equation 4 and/or
(b) the modulus of transmitted colour ratio (Rtr ns) is greater than 0.9 preferably is substantially about 1.0, where Rtrans = 2 (EI +A) Equation 5
(EL + EA)
2. A label as claimed in any preceding claim, in which the label comprises a polymer film made from cellulose, a cellulose derivative, a polyolefin and/or polylactic acid.
3. A label as claimed in the preceding claim, in which the label comprises cellulose film or BOPP film.
4. A method of preparing a coloured, transparent label that can be fixed by a wet glue on to a coloured transparent article and/or region thereof to achieve a no-label appearance thereon the method comprising the steps of
(a) measuring the L a b values of the article or region thereof (b) using Equations 1 to 5 and the parameter limits given herein to calculating corresponding L a b values required of a label.
(c) colouring a polymeric transparent label to have the L a b values calculated from step (b) where optionally the colouring method is selected from at least one of: (i) colouring the label directly by incorporating dyes or pigments therein;
(ii) applying transparent coloured compositions to either or both label surfaces; (iii) printing the surface of the label with pigmented or transparent inks; and/or (iv) colouring a clear wet glue formulation to produce coloured transparent adhesive layer when the glue is applied to the label: and/or (v) any combinations thereof which achieve the desired total colour space values
5. A method for preparing and/or applying a label to a coloured, transparent article and/or region thereof, the method comprising the steps of:
(a) coating a label as claimed in any preceding claim on at least one surface thereof with an aqueous composition with an adhesive dispersed therein;
(b) treating at least the opposite surface of the sheet, optionally both surfaces, to improve its printability,
(c) drying the film to remove excess water;
(d) applying the label to an article; and (e) optionally drying the article to affix the label thereon.
6. A method of labelling a coloured, transparent article and/or region thereof, thereof with a wet glue label to achieve a no-label appearance thereon, the method comprising the steps of (a) measuring the L a b of the article or region thereof
(b) using Equations 1 to 5 and the parameter limits given herein to calculating corresponding L a b values required of a label.
(c) colouring a polymeric transparent label to have the L*a*b values calculated from step (b), where optionally the colouring method is selected from at least one of: (i) colouring the label directly by incorporating dyes or pigments therein;
(ii) applying transparent coloured compositions to either or both label surfaces; (iii) printing the surface of the label with pigmented inks; and/or (iv) colouring a clear wet glue formulation to produce coloured, transparent adhesive layer when the glue is applied to the label: anό/or (v) any combinations thereof which achieve the desired total colour space values (d) applying the coloured label prepared in step (c) to the measured region of the article using a wet glue to achieve thereon a labelled article having a no-label appearance.
7. A label obtained or obtainable by a method as described in claim 4.
8. A label facestock comprising a label as claimed in any of claims 1 to 3 or 7 adjacent a release liner.
9. A labelled article where label has a no-label appearance thereon and where the article: (i) is obtained or obtainable by a method as described in claim 5 and/or 6, and/or
(ii) comprises a label as claimed in any of claims 1 to 3 and/or 7 fixed thereto with an aqueous adhesive composition.
10. An article as claimed in claim 9, which comprises a coloured, transparent glass or PET container.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB0216767A GB0216767D0 (en) | 2002-07-19 | 2002-07-19 | Coloured labels |
| GB0216767 | 2002-07-19 | ||
| GB0222170 | 2002-09-25 | ||
| GB0222170A GB0222170D0 (en) | 2002-09-25 | 2002-09-25 | Coloured labels |
| PCT/EP2003/007775 WO2004009721A2 (en) | 2002-07-19 | 2003-07-17 | Coloured labels |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP1563028A2 true EP1563028A2 (en) | 2005-08-17 |
Family
ID=30772037
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP03765021A Withdrawn EP1563028A2 (en) | 2002-07-19 | 2003-07-17 | Coloured labels |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US20060008602A1 (en) |
| EP (1) | EP1563028A2 (en) |
| JP (1) | JP2006512594A (en) |
| KR (1) | KR20050026497A (en) |
| AU (1) | AU2003254368A1 (en) |
| CA (1) | CA2492590A1 (en) |
| WO (1) | WO2004009721A2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8367415B2 (en) * | 2008-09-05 | 2013-02-05 | University Of South Carolina | Specific gene polymorphisms in breast cancer diagnosis, prevention and treatment |
| US8597752B1 (en) * | 2010-03-02 | 2013-12-03 | Myra Hersh | Repositionable self stick paint swatch for testing samples of paints on a wall |
| JP7082449B2 (en) * | 2018-10-31 | 2022-06-08 | ザ プロクター アンド ギャンブル カンパニー | Containers with perforated shrink sleeves and related processes |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NZ247073A (en) * | 1992-08-26 | 1994-12-22 | Lintec Corp | Pressure sensitive adhesive label sheet with label film being polyethylene resin of a density of .925-.95 g/cc |
| US5407718B1 (en) * | 1993-08-05 | 1999-03-02 | Avery Dennison Corp | Transparent paper label sheets |
| US5712031A (en) * | 1996-03-06 | 1998-01-27 | The Dow Chemical Company | Plastic adhesive labels for glass substrates |
| US6306242B1 (en) * | 1997-10-10 | 2001-10-23 | Peter J. Dronzek | Techniques for labeling of plastic, glass or metal containers or surfaces with polymeric labels |
| US6042930A (en) * | 1997-12-24 | 2000-03-28 | The Dow Chemical Company | Plastic heat-activated adhesive labels |
| GB0106410D0 (en) * | 2001-03-15 | 2001-05-02 | Ucb Sa | Labels |
| US20030102080A1 (en) * | 2001-12-05 | 2003-06-05 | Mallik Donald W. | Adhesive label, labeled item, and method for labeling item with polymer film label using water-based adhesive |
-
2003
- 2003-07-17 CA CA002492590A patent/CA2492590A1/en not_active Abandoned
- 2003-07-17 WO PCT/EP2003/007775 patent/WO2004009721A2/en not_active Ceased
- 2003-07-17 US US10/519,993 patent/US20060008602A1/en not_active Abandoned
- 2003-07-17 EP EP03765021A patent/EP1563028A2/en not_active Withdrawn
- 2003-07-17 KR KR1020057001011A patent/KR20050026497A/en not_active Abandoned
- 2003-07-17 AU AU2003254368A patent/AU2003254368A1/en not_active Abandoned
- 2003-07-17 JP JP2004522485A patent/JP2006512594A/en not_active Abandoned
Non-Patent Citations (1)
| Title |
|---|
| See references of WO2004009721A2 * |
Also Published As
| Publication number | Publication date |
|---|---|
| US20060008602A1 (en) | 2006-01-12 |
| WO2004009721A3 (en) | 2004-03-18 |
| HK1083518A1 (en) | 2006-07-07 |
| JP2006512594A (en) | 2006-04-13 |
| CA2492590A1 (en) | 2004-01-29 |
| AU2003254368A1 (en) | 2004-02-09 |
| WO2004009721A2 (en) | 2004-01-29 |
| KR20050026497A (en) | 2005-03-15 |
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