WO2010072784A1 - Scratch masking coating for glass containers - Google Patents
Scratch masking coating for glass containers Download PDFInfo
- Publication number
- WO2010072784A1 WO2010072784A1 PCT/EP2009/067798 EP2009067798W WO2010072784A1 WO 2010072784 A1 WO2010072784 A1 WO 2010072784A1 EP 2009067798 W EP2009067798 W EP 2009067798W WO 2010072784 A1 WO2010072784 A1 WO 2010072784A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- emulsion
- oil
- scratch
- surfactant
- esters
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/001—General methods for coating; Devices therefor
- C03C17/003—General methods for coating; Devices therefor for hollow ware, e.g. containers
- C03C17/005—Coating the outside
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
Definitions
- the present invention relates to the use of oil-in-water emulsions for improving glass surface appearance, particularly the external surfaces of glass containers. More particularly, the present invention relates to a scratch masking coating for glass bottles, which enhances appearance.
- Glass articles such as returnable bottles are handled a great number of times during manufacture, inspection, filling, shipping, washing etc. During such handling the bottles come into contact with various mechanical devices such as conveyors, inspection devices and the like as well as contact with other glass containers (such as bottles, jars, and the like) and surfaces such as boxes, shelves etc. This high degree of contact causes damage either by breakage, cracking, scratching or other defects of the surface.
- Coatings for glassware can comprise polymeric materials, which cure after application to the bottle surface, either at room temperature or upon heating.
- US Patent Number 4,273,834 discloses a specific organopolysiloxane and a curing catalyst that are applied to glass articles to mask abrasions. The material is cured on bottle surfaces at room temperature or under heating.
- US Patent Number 5,346,544 discloses triglyceride materials and fatty acid esters of isopropyl alcohol as a coating for glass containers which are emulsified in water, applied to glass bottles and dried at room temperature or with heating.
- US Patents Numbers 4,792,494 and 4,834,950 disclose the use of modified polyethylene preferably in the form of an aqueous dispersion to form a protective coating on glass surfaces. The coating is typically applied at the end of a hot end finishing process whereby residual heat of the glass aids drying in a conventional cold end coating process.
- US Patent Number 3,296,173 discloses a protective coating for glass comprising a reaction product of polyvinyl alcohol, an emulsified polyolefin and ammonium chloride. The coating is applied and heated whereby the composition reacts to produce a durable coating.
- returned bottles are treated with an anti-scuff coating during each wash/refill cycle.
- Coating systems that rely on heat to cure or dry an applied coating are not effective on lines where the glass bottles are cool.
- emulsion based coating systems instability of the emulsion on the glass surface is desired such that the emulsion breaks and the oil phase coating is deposited on the glass surface.
- Aqueous emulsion based coating systems often rely on emulsion destabilization by breaking due to water phase evaporation.
- moisture on the bottles such as from condensation can adversely impact such systems, and with some coatings, long cure times due to moisture such as from condensation can adversely impact a coating system. All current products known to date show poor or not satisfactory performances when applied on wet bottles, or on cold bottles which become wet due to condensation, for example during filling of glass bottles or containers, with cold stuffs, typically cold liquids, such as sparkling liquids, e.g.
- the applied product is diluted by the condensation water on the outside of the container, said dilution mainly resulting in a 'rinsing off' of the applied coating. Rinsing off would mean no coating at all.
- Solutions to this problem already exist, such as systems relying on emulsion destabilization through the addition of an emulsion destabilizer.
- Emulsions based upon high emulsifier concentration consist in using more concentrated emulsions, because the condensation water dilutes said emulsion.
- using more concentrated emulsions results in a not acceptable coating, since the amount of condensation water strongly varies, due to dew-point variations, so that the use of concentrated emulsions is not satisfying.
- An example of addition of emulsion destabilizer is disclosed in EP-A-1 731 227.
- the emulsion breaker is an acid, and the result is an improved performance of the desired coating, even in the presence of condensation on the outer parts of the glass containers.
- the main objectives of the present invention are to provide a formulation to be applied on returnable containers in order to face-lift or mask the white reflecting bands (scuff bands) that appear at the container-to-container (or other container to devices or surfaces) contact zones, because of intense glass to glass contact (or glass to devices and the like, as explained above), mainly during the filling process, after several trips of returnable glass containers.
- Another objective of the present invention is to provide a process for applying such formulation (a 'masking fluid'), in order to repair the visual aspect of such containers, since the presence of scuff bands strongly reduces the appearance of containers.
- a further objective of the present invention consists in providing an efficient scratch-masking or scuff-masking fluid, especially in case of filling conditions in which containers are filled with cold liquids, and water condensation of moisture at the container surface occurs.
- Still another objective is to provide an alternative solution to stable emulsion that would simply be rinsed off or strongly diluted, thereby avoiding the presence of significant higher concentration of active ingredients in the emulsion.
- Still another objective of the present invention is to avoid the use of acid additive as a destabilizer that would lead to corrosion issues, label issues, as well as security and environmental issues.
- the present invention relates to an improved formulation and an improved process for masking containers at these cold and wet conditions.
- Both laboratory tests and field experience showed that several parameters do influence the efficiency of masking, related to the emulsion stability.
- pH, water hardness or salt content of the water used for preparing the emulsion has impact.
- the present invention relies on the fact that, contrary to the currently used emulsions that generally comprise a high amount of surfactant, especially more than 20 weight% (wt%) , the use of less than 15 weight%, preferably less than 10 weight%, still more preferably less than 8 weight%, most preferably less than 5 weight% of surfactant in the scratch-masking composition provides excellent results, both in cold and wet conditions.
- the present invention is therefore the use of a formulation comprising from 0.1 wt% to 15 wt% of at least one surfactant and from 85 wt% to 99.9 wt% of at least one oil, in the form of an aqueous emulsion, as a scratch-masking coating on a glass surface.
- the above formulation comprises from 1 wt% to 10 wt% of at least one surfactant and from 90 wt% to 99 wt% of at least one oil. More preferably, the above formulation comprises from 1 .5 wt% to 8 wt% of at least one surfactant and from 92 wt% to 98.5 wt% of at least one oil. Even more preferably, the above formulation comprises from 1 .5 wt% to 5 wt% of at least one surfactant and from 95 wt% to 98.5 wt% of at least one oil. [0029] In the above formulation, any surfactant(s) and any oil(s) can be mixed together, provided that they are miscible the one in the other, and typically are able to form an aqueous oil-in-water emulsion.
- preferred formulations to be used as o ⁇ l- ⁇ n-water emulsions are liquid formulations, solid formulations being not convenient as scratch-masking coatings.
- the formulations for use in the present invention should therefore be in liquid form at operating conditions.
- any type of surfactant known by the skilled in the art is convenient for the formulation used in the present invention, provided that said surfactant is miscible within the oil(s).
- the surfactants can be non-ionic, anionic, cationic or zwitterionic.
- the surfactant(s) are non-ionic in order to avoid mixing problems with the oil(s), and, when anionic, to prevent salt formation when emulsified with ion- containing water.
- the surfactant(s) used in the present invention may be chosen from among: • alkoxylated (preferably ethoxylated and/or propoxylated) phenoxy alkyls;
- alkoxylated preferably ethoxylated and/or propoxylated
- primary or secondary alcohols such as, by way of non limiting examples, oleyl- or stearyl-alcohols
- alkoxylated (preferably ethoxylated and/or propoxylated) alkylamines such as, by way of non limiting examples, surfactants sold by CECA S.A., under the name Noramax ® , preferably Noramax ® S2, and Noramax ® S5;
- alkoxylated (preferably ethoxylated and/or propoxylated) acids such as, by way of non limiting examples, oleic acid and palmitic acid;
- alkoxylated (preferably ethoxylated and/or propoxylated) esters preferably glycerol esters
- the surfactants preferably comprise an average of up to 15 EO units per mole.
- the surfactant(s) are preferably chosen from among those listed in the European food additive list E numbers, more preferably from sections E400 to E499, and still more preferably from among the group of sorbitan esters, sections E491 to E496.
- the formulation for use in the present invention comprises at least one oil, which may be of any type known in the art.
- oil is meant any compound, oil or polymer, that is miscible with the surfactant(s) but not miscible with water and capable of forming an oil-in-water emulsion, that is to say an oil or polymer discontinuous phase in an aqueous or water continuous phase.
- Preferred oils may be for example chosen from among: • polyolefins such as paraffins oils;
- fatty esters preferably mono esters, having more than 10 carbon atoms, and preferably up to 40 carbon atoms;
- sorbitan esters or alkoxylated (preferably ethoxylated and/or propoxylated) sorbitan esters.
- formulations comprising at least one surfactant and at least one oil
- UV absorbers UV absorbers, light absorbers, impact absorbers; • and the like.
- Such additives may be added in the formulation oil(s) + surfactant(s) and/or in the oil-in-water ready-to-use emulsion and/or in the aqueous phase or water used for forming the emulsion.
- the s formulation for use in the present invention does not contain any additive, and preferably consists in a mixture of at least one oil and at least one surfactant, such as those described above.
- the formulation oil(s) + surfactant(s)
- oil-in-water emulsion that is to say a water continuous phase having dispersedo or emulsified therein an oil phase, wherein the oil phase is the scratch-masking coating.
- the emulsion is typically prepared by mixing an oil phase-containing surfactant(s) with an aqueous or water phase.
- the oil phase and surfactant can be supplied as a concentrate to be mixed with water by the end user to form thes treatment emulsion or supplied as a ready to use emulsion.
- the present invention also encompasses emulsions prepared by mixing water and at least one of the above-defined surfactants, then adding and mixing at least one of the above-defined oils, or prepared by mixing water and at least one of the above-defined oils, then adding and mixing at least one of the above-0 defined surfactants.
- the scratch-masking emulsion to be applied on the glass surface may be prepared by mixing at least one oil, at least one surfactant and water, in any order, so as to obtained the desired oil-in-water emulsion.
- the preferred concentration of the oil phase in the as applied emulsion iss from about 2% to 20% by weight, preferably from about 3% to 10% by weight, more preferably from 3% to 8% by weight of the total weight of the oil-in-water emulsion. Variations in water quality such as pH or hardness can impact the quality and stability of the final treatment emulsion when supplied as a concentrate for mixing with "local" water.
- the emulsion is obtained by thoroughly mixing water, at least one surfactant, and at least one oil, as described above. Any mixing device known in the art is appropriate, provided that, depending on parameters and layout, the amount of mixing energy is set in such a way that homogeneous emulsion is supplied to the applicator but of limited emulsion stability.
- the mixing energy devoted to the preparation of the above described oil- in-water emulsion should be set so that the emulsion is stable for a period time ranging from a few seconds to a few hours, and preferably for period of time that is adapted so as to supply a homogenous working liquid to the applicator. This period of time therefore depends on the flow lines, application devices, and the like.
- stable emulsion for a period of time is meant that no macroscopic phase separation (nearly complete breaking of the emulsion) occurs between the oil and the water during the time ranging from a few seconds to a few hours and preferably for period of time that is adapted so as to supply a homogenous working liquid to the applicator.
- the emulsion of the invention has a limited stability meaning that the emulsion will break on a time scale much longer then a few hours and preferably after a period of time that is adapted so as to supply a homogenous working liquid to the applicator.
- Any mixing means may be used to achieve an oil-in water-emulsion from water and the above described formulation.
- Typical mixers or emulsifying devices are those known in the art, and as non limiting examples, mention may be made of dynamic mixers, static mixers, ultra-sonic mixing devices, pumps, and the like.
- the present invention provides a process for applying a coating, typically a scratch-masking coating, to a glass container surface, such as bottles, that is adaptable to a variety of glass surface and application conditions.
- a coating typically a scratch-masking coating
- the coating provides for masking of scratches and abrasions on the glass container surface, which adversely impact its commercial value. For examples, scratches or abrasions on glass bottles, especially on returnable glass bottles used for beverages, result in an undesirable haze or white appearance, which decreases the value of the bottle.
- the process of the present invention provides a coating for glass containers that masks such scratches or abrasions. In addition, the coating can enhance the lubricity of the container surface.
- the coating of the present invention is applied in the form of an oil-in- water emulsion that may be applied via spray application, dipping or any other contact method (sponge, and the like). Spray application is the preferred method of application.
- the oil phase comprises the coating treatment for the glass surface.
- the process of the present invention provides for enhanced control of emulsion based glass surface masking coatings that is applicable in many types of application systems, such as those where the glass containers are warm as well as those where the glass containers are cold.
- the process of the present invention can be employed in a variety of bottle handling operations, warm as well as cold application temperatures, as well as be adapted to changing conditions such as water variations or changes in condensation due to variation in humidity in the surrounding area.
- the glass containers are considered as hot if their temperature is from 25°C to 100 0 C, preferably from 25°C to 65°C, more preferably from 25°C to 45°C and advantageously from 25°C to 40 0 C.
- the glass containers are considered as cold if their temperature is from 2°C to 25°C, preferably from 5°C to 22°C, more preferably from 6°C to 20°C and advantageously from 6°C to 18°C.
- the present invention provides a process for applying a scratch-masking coating to a glass surface, more specifically to a glass container surface, such as bottles, comprising at least the step of applying at least one scratch-masking oil-in-water emulsion as described above, onto at least one part of, or onto the entire, outer surface of said glass container.
- the process of the present invention comprises at least the following steps: • washing of the glass container,
- the washing of the glass container may be realised according to any method well known in the art, and for example using water, preferably hot water, more preferably together with one or more detergent, for example a base, such as sodium hydroxide.
- At least one lubricant can also be applied onto the outer surface of the glass container after washing. Such lubricants are known in the field, such as for example Tegoglass ® 3000 Plus provided by Arkema.
- the glass containers are then filled and capped, again according to known methods, with cold, tepid, or even warm liquids.
- the efficiency of the scratch-masking coating according to the present invention is not adversely affected by the condensation that may appear on the outer surface of the glass container, because of differences of temperatures between the glass container, the filled liquid, and/or the outer temperature and relative humidity of the environment.
- Labelling may be realised before or after applying the scratch-masking emulsion. Due to the neutral pH of the emulsions used in the present invention, and since said emulsions do contain only a low amount of surfactant, labels, and more particularly label dyes, are not, or only slightly, affected. [0066] In the present invention the pH is considered as neutral or almost neutral for a pH value between 5 and 8, preferably between 5.5 and 7.5 and more preferably between 6 and 7. [0067] The labelling step can therefore be realised before the scratch-masking coating step.
- the step consisting in applying the scratch-masking emulsion may thus be the last step before the newly washed, refilled and labelled glass containers are once again put on the market, and sold to the customers.
- the application equipment typically includes mixing and storage vessels, pumps, transfer and feed lines, spray apparatus and control and monitoring equipment.
- the equipment comprises one or more mixing vessel(s); dosing and circulating pump(s); mixing unit (can be the pump itself); circulation piping(s); applying means, such as spraying devices; and the like.
- the equipment may also comprise controlling means aiming at monitoring the process of applying the scratch-masking emulsion.
- controlling means may be for example optical means detecting the presence or the absence of a container in front of the applying means, and/or detecting the presence and the quantity of scuff bands or scratches, so that the minimum amount of emulsion is applied on the containers to obtain the best efficiency.
- the controlling means are monitored via a computer that may interact with the dosing pump(s) and applying means.
- the above described equipment may be encased within a "scratch-masking" cabinet that can be easily adapted to existing bottling lines, comprising the necessary equipment for washing, filling, capping and labelling glass containers, typically returnable glass bottles.
- a "scratch-masking" cabinet that can be easily adapted to existing bottling lines, comprising the necessary equipment for washing, filling, capping and labelling glass containers, typically returnable glass bottles.
- Bottle temperature 7.5 0 C
- Spray amount per bottle 0.5 mL per bottles (upper scuff band only); Storage conditions 22°C - 25°C, 100% relative humidity, 1 hour; Mixing means Dispermat ® , continuous at 20 % stirring power, 5 minutes.
- the various formulations are applied with the following conditions:
- the bottles are checked for assessing the scratch-masking efficacy, 24 hours after application, by visual observation of the bottle shoulder scuff band. For each bottle, a note is given, from 0 to 10, "0" meaning no coating and "10" meaning 100% masked.
- the emulsions are prepared with the following oils and surfactants:
- Cetiol ® SN [84878-33-1 ] Cetearyl Isononanoate, from Cognis;
- Ethoxylated secondary alcohols Softanol ® 30, 70, 90 200, from Ineos
- 2 Sorbitan and ethoxylated sorbitan: SMO and SML, from Evonik
- 3 Ethoxylated fatty glycerol esters: BL276, Tagat ® TO V, from Evonik.
- a first set of formulations is prepared using Cetiol ® SN as the oil. The results are presented in Table 1 below.
- An other set of formulations is prepared with the following characteristics: a) Opticoat ® 140 (from Arkema); b) Opticoat ® 140 + 1 mL of emulsion breaker (12 wt% of citric acid (CA) per litre of working solution); c) Emulsion formulation 97,5 % Cetiol ® SN + 2,5 % Softanol ® 70; d) Emulsion formulation 97,5 % Cetiol ® SN + 2,5 % SMO; e) Emulsion formulation 97,5 % Cetiol ® SN + 2,5 % Softanol ® 30; f) Emulsion formulation 97,5 % Cetiol ® SN + 2,5 % Softanol ® 90; g) Emulsion formulation 97,5 % Cetiol ® SN + 2,5 % Softanol ® 90; g) Emulsion formulation 97,5 % Cetiol ®
- Spray amount per bottle 0.5 mL per bottles (upper scuff band only) Storage conditions : 22°C - 25°C, 100% relative humidity, 1 hour
- Mixing time 5 minutes
- Mixing means Dispermat ® , 15%, 20 % , 25 % or 30% stirring power
- Spray pattern horizontal Bottle type : Coca Cola ® 25 cL ⁇ Number of bottles per test : 5.
- An other advantage of the present invention is that a neutral pH emulsion is applied, which has several significant advantages:
- Emulsion preparation was done with 30% stirring power of Dispermat ® stirrer.
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Surface Treatment Of Glass (AREA)
- Paints Or Removers (AREA)
- Details Of Rigid Or Semi-Rigid Containers (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
Description
Claims
Priority Applications (9)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
UAA201109226A UA109873C2 (en) | 2008-12-23 | 2009-12-22 | GLASS CONTAINERS FOR MASK SCREWS |
MX2011006796A MX343399B (en) | 2008-12-23 | 2009-12-22 | Scratch masking coating for glass containers. |
CA2747997A CA2747997A1 (en) | 2008-12-23 | 2009-12-22 | Scratch masking coating for glass containers |
BRPI0922519A BRPI0922519A2 (en) | 2008-12-23 | 2009-12-22 | scratch-resistant coating for glass containers |
MA33967A MA33322B1 (en) | 2008-12-23 | 2009-12-22 | Paint to hide scratches of glass containers |
DK09795788.0T DK2373591T3 (en) | 2008-12-23 | 2009-12-22 | Coating to cover scratches on glass containers |
CN200980157239.7A CN102325731B (en) | 2008-12-23 | 2009-12-22 | The cut masking coating of Glass Containers |
EP09795788.0A EP2373591B1 (en) | 2008-12-23 | 2009-12-22 | Scratch masking coating for glass containers |
ZA2011/04569A ZA201104569B (en) | 2008-12-23 | 2011-06-21 | Scratch masking coating for glass containers |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP08172678.8 | 2008-12-23 | ||
EP08172678A EP2202209A1 (en) | 2008-12-23 | 2008-12-23 | Scratch masking coating for glass containers |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2010072784A1 true WO2010072784A1 (en) | 2010-07-01 |
Family
ID=40627681
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2009/067798 WO2010072784A1 (en) | 2008-12-23 | 2009-12-22 | Scratch masking coating for glass containers |
Country Status (17)
Country | Link |
---|---|
EP (2) | EP2202209A1 (en) |
CN (1) | CN102325731B (en) |
AR (1) | AR076451A1 (en) |
BR (1) | BRPI0922519A2 (en) |
CA (1) | CA2747997A1 (en) |
CO (1) | CO6410237A2 (en) |
DK (1) | DK2373591T3 (en) |
MA (1) | MA33322B1 (en) |
MX (1) | MX343399B (en) |
NI (1) | NI201100127A (en) |
PA (1) | PA8855401A1 (en) |
PL (1) | PL2373591T3 (en) |
TW (1) | TWI469943B (en) |
UA (1) | UA109873C2 (en) |
UY (1) | UY32363A (en) |
WO (1) | WO2010072784A1 (en) |
ZA (1) | ZA201104569B (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9751799B2 (en) | 2012-10-03 | 2017-09-05 | Corning Incorporated | Physical vapor deposited layers for protection of glass surfaces |
US10717106B2 (en) | 2015-12-10 | 2020-07-21 | Ecolab Usa Inc. | Abrasion-masking composition for use with reusable containers and the method of using the same |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2336093A1 (en) * | 2009-12-14 | 2011-06-22 | Arkema Vlissingen B.V. | Process for scratch masking of glass containers |
HUE053264T2 (en) * | 2016-07-04 | 2021-06-28 | Diversey Inc | Method and composition for a stable oil-in-water emulsion for aesthetic improvement of food and beverage containers |
EP3502076A1 (en) * | 2017-12-22 | 2019-06-26 | Arkema B.V. | Process for treatment of glass containers |
SG11202005031YA (en) * | 2017-12-22 | 2020-07-29 | Arkema B V | Coating composition for glass containers |
FR3090677B1 (en) * | 2018-12-21 | 2021-11-19 | Arkema France | SCRATCH MASKING COATING SOLUTION FOR GLASS CONTAINERS |
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US4273834A (en) | 1978-10-14 | 1981-06-16 | Kirin Beer Kabushiki Kaisha | Masking of abrasion injury on glass articles |
JPS59145259A (en) * | 1983-02-09 | 1984-08-20 | Sapporo Breweries Ltd | Scratch coating composition for bottle |
JPS62128951A (en) * | 1985-11-27 | 1987-06-11 | Riken Vitamin Co Ltd | Composition for coating scratch on glass vessel |
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PT1560641E (en) * | 2002-11-14 | 2006-07-31 | Leuven K U Res & Dev | METHOD FOR THE PREPARATION OF EMULSES |
-
2008
- 2008-12-23 EP EP08172678A patent/EP2202209A1/en not_active Withdrawn
-
2009
- 2009-12-22 CN CN200980157239.7A patent/CN102325731B/en active Active
- 2009-12-22 BR BRPI0922519A patent/BRPI0922519A2/en not_active Application Discontinuation
- 2009-12-22 MX MX2011006796A patent/MX343399B/en active IP Right Grant
- 2009-12-22 UA UAA201109226A patent/UA109873C2/en unknown
- 2009-12-22 PL PL09795788.0T patent/PL2373591T3/en unknown
- 2009-12-22 MA MA33967A patent/MA33322B1/en unknown
- 2009-12-22 DK DK09795788.0T patent/DK2373591T3/en active
- 2009-12-22 WO PCT/EP2009/067798 patent/WO2010072784A1/en active Application Filing
- 2009-12-22 TW TW98144225A patent/TWI469943B/en not_active IP Right Cessation
- 2009-12-22 CA CA2747997A patent/CA2747997A1/en not_active Abandoned
- 2009-12-22 EP EP09795788.0A patent/EP2373591B1/en not_active Not-in-force
- 2009-12-23 PA PA20098855401A patent/PA8855401A1/en unknown
- 2009-12-23 AR ARP090105119A patent/AR076451A1/en active IP Right Grant
- 2009-12-23 UY UY0001032363A patent/UY32363A/en not_active Application Discontinuation
-
2011
- 2011-06-21 ZA ZA2011/04569A patent/ZA201104569B/en unknown
- 2011-06-22 NI NI201100127A patent/NI201100127A/en unknown
- 2011-06-23 CO CO11079052A patent/CO6410237A2/en not_active Application Discontinuation
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JPS59145259A (en) * | 1983-02-09 | 1984-08-20 | Sapporo Breweries Ltd | Scratch coating composition for bottle |
JPS62128951A (en) * | 1985-11-27 | 1987-06-11 | Riken Vitamin Co Ltd | Composition for coating scratch on glass vessel |
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AR076451A1 (en) | 2011-06-15 |
PA8855401A1 (en) | 2010-07-27 |
EP2373591B1 (en) | 2016-04-13 |
CN102325731B (en) | 2016-04-20 |
EP2373591A1 (en) | 2011-10-12 |
DK2373591T3 (en) | 2016-07-25 |
UA109873C2 (en) | 2015-10-26 |
MX2011006796A (en) | 2011-09-28 |
UY32363A (en) | 2010-06-30 |
MA33322B1 (en) | 2012-06-01 |
MX343399B (en) | 2016-11-03 |
TW201038501A (en) | 2010-11-01 |
TWI469943B (en) | 2015-01-21 |
PL2373591T3 (en) | 2016-11-30 |
CA2747997A1 (en) | 2010-07-01 |
CN102325731A (en) | 2012-01-18 |
BRPI0922519A2 (en) | 2017-05-30 |
NI201100127A (en) | 2012-10-29 |
ZA201104569B (en) | 2012-09-26 |
CO6410237A2 (en) | 2012-03-30 |
EP2202209A1 (en) | 2010-06-30 |
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