EP2009086A1 - Procédé de coloration de minéraux non-adsorbants et le produit ainsi obtenu - Google Patents
Procédé de coloration de minéraux non-adsorbants et le produit ainsi obtenu Download PDFInfo
- Publication number
- EP2009086A1 EP2009086A1 EP07012496A EP07012496A EP2009086A1 EP 2009086 A1 EP2009086 A1 EP 2009086A1 EP 07012496 A EP07012496 A EP 07012496A EP 07012496 A EP07012496 A EP 07012496A EP 2009086 A1 EP2009086 A1 EP 2009086A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- colouring
- adsorbent
- accordance
- procedure
- minerals
- 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.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 103
- 238000004040 coloring Methods 0.000 title claims abstract description 91
- 239000003463 adsorbent Substances 0.000 title claims abstract description 63
- 229910052500 inorganic mineral Inorganic materials 0.000 title claims abstract description 58
- 239000011707 mineral Substances 0.000 title claims abstract description 58
- 239000011230 binding agent Substances 0.000 claims abstract description 49
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 46
- 230000008569 process Effects 0.000 claims abstract description 44
- 239000003599 detergent Substances 0.000 claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 claims abstract description 12
- 239000000047 product Substances 0.000 claims description 69
- 238000007792 addition Methods 0.000 claims description 36
- 238000001035 drying Methods 0.000 claims description 30
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical group [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000000758 substrate Substances 0.000 claims description 17
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 13
- 238000002360 preparation method Methods 0.000 claims description 12
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 12
- 235000011152 sodium sulphate Nutrition 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000008187 granular material Substances 0.000 claims description 9
- 239000004115 Sodium Silicate Substances 0.000 claims description 7
- 238000001033 granulometry Methods 0.000 claims description 7
- 230000036571 hydration Effects 0.000 claims description 7
- 238000006703 hydration reaction Methods 0.000 claims description 7
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 7
- 238000011068 loading method Methods 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 239000002270 dispersing agent Substances 0.000 claims description 2
- 239000000725 suspension Substances 0.000 claims description 2
- 239000000049 pigment Substances 0.000 abstract description 22
- 230000008901 benefit Effects 0.000 abstract description 8
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 150000003839 salts Chemical class 0.000 description 9
- 238000005054 agglomeration Methods 0.000 description 6
- 230000002776 aggregation Effects 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000004150 EU approved colour Substances 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 229940006093 opthalmologic coloring agent diagnostic Drugs 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 239000003086 colorant Substances 0.000 description 3
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- OIQPTROHQCGFEF-UHFFFAOYSA-L chembl1371409 Chemical compound [Na+].[Na+].OC1=CC=C2C=C(S([O-])(=O)=O)C=CC2=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 OIQPTROHQCGFEF-UHFFFAOYSA-L 0.000 description 2
- FPVGTPBMTFTMRT-UHFFFAOYSA-L disodium;2-amino-5-[(4-sulfonatophenyl)diazenyl]benzenesulfonate Chemical compound [Na+].[Na+].C1=C(S([O-])(=O)=O)C(N)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 FPVGTPBMTFTMRT-UHFFFAOYSA-L 0.000 description 2
- 235000019233 fast yellow AB Nutrition 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- JMXROTHPANUTOJ-UHFFFAOYSA-H naphthol green b Chemical compound [Na+].[Na+].[Na+].[Fe+3].C1=C(S([O-])(=O)=O)C=CC2=C(N=O)C([O-])=CC=C21.C1=C(S([O-])(=O)=O)C=CC2=C(N=O)C([O-])=CC=C21.C1=C(S([O-])(=O)=O)C=CC2=C(N=O)C([O-])=CC=C21 JMXROTHPANUTOJ-UHFFFAOYSA-H 0.000 description 2
- 235000012736 patent blue V Nutrition 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- -1 sodium carbonate Chemical class 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/40—Dyes ; Pigments
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D11/00—Special methods for preparing compositions containing mixtures of detergents
- C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/046—Salts
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/08—Silicates
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/12—Water-insoluble compounds
- C11D3/122—Sulfur-containing, e.g. sulfates, sulfites or gypsum
Definitions
- This descriptive report refers, as its title indicates, to a procedure for colouring granulated non-adsorbent minerals and the product thus obtained of the type used in the field of chemical products and processes leading to coloured speckles used in the detergent industry being obtained, characterised in that it allows coloured granules, also known by the English tem "speckles", to be obtained which are particularly used as coloured speckles present in powdered detergents.
- These coloured granules are obtained from non-adsorbent mineral particles with a diameter of between 300 and 2,000 ⁇ m using a granular base of the same size, a binding agent and a colouring agent or pigment, all by means of a characteristic production procedure.
- the process is based on a non-adsorbent salt, preferably a monocrystal inorganic salt with a grain size of between 300 and 2,000 ⁇ m, preferably between 600 and 1,500 ⁇ m, of a hygroscopic nature in order to be able to fix the colouring agent, so these are mainly inorganic salts, such as sodium carbonate, sodium tripolyphosphate, sodium chloride, sodium sulphate among others.
- a non-adsorbent salt preferably a monocrystal inorganic salt with a grain size of between 300 and 2,000 ⁇ m, preferably between 600 and 1,500 ⁇ m, of a hygroscopic nature in order to be able to fix the colouring agent, so these are mainly inorganic salts, such as sodium carbonate, sodium tripolyphosphate, sodium chloride, sodium sulphate among others.
- the colouring agent is responsible for providing the desired colour to the inorganic salt and any pigment or colouring agent allowed in the detergent industry or any preparation thereof, which must have a granulometry between 0.01 and 15 ⁇ m, preferably between 0.01 and and 5 ⁇ m] is used.
- any pigment or colouring agent allowed in the detergent industry or any preparation thereof which must have a granulometry between 0.01 and 15 ⁇ m, preferably between 0.01 and and 5 ⁇ m] is used.
- Pigment Blue 15 Pigment Green 7, Pigment Yellow 3, Pigment Red 57, Yellow Food Colouring 3, Food Blue 5, Acid Green 1, Acid Yellow 4, among others.
- the binding agent is necessary to obtain a film, which fixes the colouring agent to the inorganic salt substrate, as it is a non-adsorbent material. This acts by generating a surface layer which fixes the colouring agent to the substrate and which is compatible with formulations in the detergent.
- binding agents which may be used and which are found in literature, we may cite among others, sodium silicate, different types of polymers, carboxymethyl cellulose (CMC), etc.
- the colouring procedure comprises a sequence of three main phases, which in their turn are divided into different intermediate steps.
- This colouring procedure is carried out in a industrial rotary mixer of the endless screw or mixing blade variety, with a jacket or encasing double wall equipped with a peripheral water heating circuit and also equipped with a hot air injection system inside.
- the appropriate temperature control and regulatory devices must be available both for water circulating in the jacket and for the hot air, to allow precise control of the working temperatures to prevent the formation and agglomeration of hydrated compounds.
- Figure -2- gives a graphic example of the evolution of temperature inside the mixer.
- Figure -3- shows a simplified view of the main elements, which the mixing device used in the invention must comprise.
- the procedure for colouring granulated, non-adsorbent minerals and the product thus obtained which forms the object of this invention consists of a characteristic sequence of phases (1,2,3) in which a non-adsorbent mineral (4) or substrate is mixed with a colouring agent (9) and a binding agent (11).
- the process is based on a non-adsorbent mineral (4), preferably a monocrystal inorganic salt with a grain size of between 300 and 2,000 ⁇ m, preferably between 600 and 1500 ⁇ m, so it is not necessary to carry out an agglomeration process for it to achieve the desired size and, given the monocrystalline nature of the product obtained, it is hard enough to withstand the effect of friction during mixing with the rest of the components.
- a non-adsorbent mineral (4) preferably a monocrystal inorganic salt with a grain size of between 300 and 2,000 ⁇ m, preferably between 600 and 1500 ⁇ m, so it is not necessary to carry out an agglomeration process for it to achieve the desired size and, given the monocrystalline nature of the product obtained, it is hard enough to withstand the effect of friction during mixing with the rest of the components.
- the colouring agent (9) can be fixed (9), so that sodium carbonate, sodium tripolysulphate, sodium chloride, sodium sulphate among others may be
- the colouring agent (9) is responsible for providing the desired colour to the non-adsorbent mineral (4) and for this any pigment or colouring agent allowed in the detergent industry or any preparation thereof, which must have a granulometry of between 0.01 and 15 ⁇ m, preferably between 0.01 and 5 ⁇ m, is used, thus maintaining its visibility and facilitating the homogeneity of the colour in the subsequent process and avoiding stains in the product because of a larger size.
- the commonest ones that may be used in the process we may cite: Pigment Blue 15, Pigment Green 7, Pigment Yellow 3, Pigment Red 57, Food yellow 3, Food Blue 5, Acid Green 1, Acid Yellow 4, among others.
- the binding agent (11) is necessary to obtain a film, which fixes the colouring agent (9) to the inorganic salt substrate. Moreover, being non-adsorbent materials, the pigment or colouring agent must be fixed to the grain.
- the binding agent (11) acts by generating a surface layer, which fixes the colouring agent (9) to the inorganic salt substrate (4), allowing it at the same time to be compatible with the formulations in the detergent.
- binding agents (11) which may be used in this process, we may cite among others, sodium silicate, different types of polymers, carboxymethyl cellulose (CMC), etc ., preferably soluble sodium silicate because of its readiness to form vitreous layers with the above features when its diluting water dries up.
- the colouring procedure characteristic of the invention comprises a sequence of three main phases, which in their turn are divided into different intermediate steps.
- the phase starts with the initial step of loading (5) the mixer (17) with the non-adsorbent mineral (4), where the step of heating the product (6) above its hydration temperature is carried out, if it has one. To do this, the jacket (18) is heated at the same time above this temperature and hot air is introduced into the mixer (17).
- the phase continues with the step of lowering the temperature (7) of the jacket (18) below the temperature of the product followed by the step of introducing (8) the colouring agent (9) in the form of a preparation.
- the jacket (18) be below the temperature of the product in order to avoid incrustations. This may be achieved in two ways: by keeping it constant just above the hydration temperature or by maintaining a constant difference with the temperature of the product.
- the colouring agent (9) will be added in suspension with water and, if necessary, with some kind of dispersant.
- concentration of colouring agent (9) in the preparation will be preferably between 15 %, to avoid using a lot of water which will evaporate afterwards, and 60 %, to allow a good mix and close contact between the substrate (4) and the colouring agent (9), as the medium which puts them in contact and allows them to join is water, although they are fixed by the binding agent (11) in the subsequent drying process.
- the addition to the mass will be made with sufficient time for mixing, preferably between 10 seconds and 5 minutes, depending on the mixing capacity of the equipment.
- the proportion of colouring agent (9) to be used in relation to the non-adsorbent mineral (4) varies between 0.001% and 10%, preferably between 0.01% and 1%.
- the introduction of the colouring agent (9) should be carried out preferably by means of spray nozzles or a shower to make mixing easier.
- step of adding (10) the binding agent (11) is carried out several times (13) to facilitate homogeneity and avoid incrustations.
- a drying step (12) is then carried out by introducing hot air into the mixer (17) to dry after each step of adding (10) a binding agent (11).
- the method of introducing this hot air, its rate of flow and temperature will result in less time and, therefore, greater production capacity, resulting in fewer operational costs.
- the temperature of the drying air must be preferably between 100 and 300° C, depending on the physical characteristics of the substrate (4), colouring agents (9) and binding agent (11) chosen.
- the rate of flow of hot air to be introduced should be such that it is sufficient to dry and keep the bed spongy if necessary, but avoiding elutriates (solid product carried away by the air) being produced. As high granulometry is involved, excessive amounts of elutriates are not generated and this solved by installing a sleeve filter or an air washer at the outlet for the exhaust air.
- the number of times (13) that the cycle of adding (10) and subsequent drying (12) steps is 5 by way of example, thus optimising the process in accordance with the type of mixer and product.
- the temperatures on addition (10) depend on the equipment, the number (13) of additions intended, the substrate (4) load, the temperature of the cooling jacket (18) and the characteristics of the drying air.
- the increase in temperatures between additions (10) should preferably be between 2 and 10° C. In this way a dry product will be obtained, preferably with humidity of less than 5% in weight.
- the method of adding (10) the binding agent (11) should enhance uniform distribution throughout the product without generating any kind of agglomerate (either of product or dry residue of the binding agent itself) and avoid giving rise to incrustations.
- adding is carried out over various steps emulating an on-going addition (10) and drying (12) process. That is to say, an addition (10) is made and we wait for this product to be dry enough for the next addition to be made.
- the number of additions (13) simulates an on-going process of addition and depends on the percentage of binding agent (11) necessary for each size of grain and substrate (4).
- the percentage addition of binding agent (11) may vary between 2 % and 10 %, the number of additions to fulfil the conditions of the first heading being a total of between 1 and infinity (exactly what an on-going addition process would be).
- a suitable number of additions is between 2 and 10. Below this amount there is the risk of generating incrustations and agglomerations and above, the process is affected energy wise.
- each one of the different additions (10) should be made in a way that allows a good mix.
- the addition to the mass will be made with sufficient mixing time, preferably between 10 seconds and 5 minutes, depending on the mixing capacity of the equipment.
- binding agent (11) should be by means of spray nozzles or a shower to make mixing easier.
- binding agent (11) will be added continuously throughout the drying process (12).
- a cooling process of the end product (16) must be carried out as otherwise the hygroscopic nature of the inorganic salts (4) being treated would cause condensation effects during storage.
- a suitable temperature for finishing the process and considering the product as finished (and cold) would be around 30-60° C.
- the cooling process is carried out by means of a step introducing cold air (14) and another simultaneous step introducing cold water (15) into the jacket (18). Cold is considered to be at a temperature around room temperature.
- the rotating speed of the mixing element (17) may be varied by controlling the rotating motor (20) in order to improve each one. These revolutions should not be excessive in order to avoid stirring the granules too violently causing them to break and fine materials to be produced.
- the following preferred values for each one of the above stages in a horizontal mixer (18) may be given:
- revolutions during the process will fluctuate between 1 and 150 rpm in the mixing element, depending on the type of product, equipment and process.
- the choice of the type of revolutions will directly influence the process time and, therefore the production capacity however, this will not have any great effect on the quality of the product.
- the mixer (17), which may be used for this invention, may be any of those used in industry, preferably the horizontal type with flat blades and having the following components:
- V/SA volume/surface area ratio of the jacket (18) should be optimised in order to avoid loss of energy and incrustations of the product.
- This volume/surface area ratio should likewise optimise the contact surface of drying air with the product and therefore increase the production capacity for a given volume. This ratio will be different depending on the type of mixer (17).
- the volume of product should be such that the formation of incrustations is prevented as, due to abrasion, they do not occur on the actual product bed.
- the occupied volume should be such as to allow mixing and minimise incrustations. In most equipment this percentage fluctuates between 50 and 100 % of the total volume of the equipment, which allows movement of the mixture.
- a production batch of coloured speckles of different colours is made, based on granular sodium sulphate with a constant jacket temperature, with the following mixer and process characteristics: Characteristics of the substrate.
- Characteristic Value Compound Granular sodium sulphate Average size 900 ⁇ m Apparent density 1.6 Kg/l Initial humidity 0.03 % Characteristics of the binding agent Characteristic Value Compound Soluble sodium silicate Percentage of total addition to substrate (in N additions) 5 % Characteristics of the different colouring agents Characteristic Value Colouring agent 1 (Green) Pigment Green 7 (35 %) Colouring agent 2 (Blue) Pigment Blue 15 (35 %) Colouring agent 3 (Orange) Food Yellow 3 (35 %) Percentage addition of preparation 0.20 % Characteristics of the mixer Characteristic Value Type of mixer Horizontal with flat blades Volume of mixer 3,000 litres V / SA ratio 0.26 m 3 /m 2 Characteristics of process Characteristic Value Substrate load 3,000 Kg.
- the sulphate thus obtained contains 97.4% pure sodium sulphate, higher than the methods currently used, since, as stated, the consumption of raw materials is less.
- the remaining properties (granulometry, density, etc.) remain very similar to the starting product as practically no grains have been broken.
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Detergent Compositions (AREA)
- Cosmetics (AREA)
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP07012496A EP2009086B1 (fr) | 2007-06-26 | 2007-06-26 | Procédé de coloration de minéraux non-adsorbants et le produit ainsi obtenu |
| ES07012496T ES2416281T3 (es) | 2007-06-26 | 2007-06-26 | Procedimiento de coloreado de minerales no adsorbentes y producto así obtenido |
| PL07012496T PL2009086T3 (pl) | 2007-06-26 | 2007-06-26 | Sposób barwienia minerałów o słabych właściwościach adsorpcyjnych i produkt otrzymany tym sposobem |
| UAA200807710A UA100110C2 (ru) | 2007-06-26 | 2008-06-05 | Способ окрашивания неадсорбирующих гранулированных минералов, продукт, полученный в результате его осуществления и применение |
| MX2008007645A MX2008007645A (es) | 2007-06-26 | 2008-06-12 | Procedimiento de coloreado de minerales no adsorbentes y producto asi obtenido. |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP07012496A EP2009086B1 (fr) | 2007-06-26 | 2007-06-26 | Procédé de coloration de minéraux non-adsorbants et le produit ainsi obtenu |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP2009086A1 true EP2009086A1 (fr) | 2008-12-31 |
| EP2009086B1 EP2009086B1 (fr) | 2013-03-27 |
Family
ID=38537723
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP07012496A Active EP2009086B1 (fr) | 2007-06-26 | 2007-06-26 | Procédé de coloration de minéraux non-adsorbants et le produit ainsi obtenu |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP2009086B1 (fr) |
| ES (1) | ES2416281T3 (fr) |
| MX (1) | MX2008007645A (fr) |
| PL (1) | PL2009086T3 (fr) |
| UA (1) | UA100110C2 (fr) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3318622A1 (fr) * | 2016-11-04 | 2018-05-09 | Sociedad Anónima Minera Catalano-Aragonesa | Particules colorées pour détergents et leur procédé de production |
Citations (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3850833A (en) | 1971-01-25 | 1974-11-26 | Colgate Palmolive Co | Scouring cleanser composition |
| US4097418A (en) | 1975-10-06 | 1978-06-27 | The Procter & Gamble Company | Granular colored speckles |
| US4162228A (en) | 1977-05-31 | 1979-07-24 | Lever Brothers Company | Process for preparing colored detergent flakes |
| EP0060728A1 (fr) | 1981-03-18 | 1982-09-22 | Unilever Plc | Procédé de fabrication de granules colorés pour détergents |
| EP0219328A2 (fr) | 1985-10-14 | 1987-04-22 | Unilever Plc | Composition détergente et son procédé de préparation |
| US4671886A (en) | 1985-11-25 | 1987-06-09 | The Procter & Gamble Company | Process for coloring granular product by admixing with pigment/diluent premix |
| GB2199338A (en) * | 1986-12-30 | 1988-07-06 | Unilever Plc | Coloured detergent particles |
| EP0289311A2 (fr) | 1987-04-30 | 1988-11-02 | Unilever Plc | Procédé de préparation d'une composition détergente granulaire |
| EP0344629A1 (fr) | 1988-06-03 | 1989-12-06 | Henkel Kommanditgesellschaft auf Aktien | Composition adsorbente granulaire avec une capacité de dégagement ameliorée |
| US5065883A (en) | 1990-09-17 | 1991-11-19 | Container Corporation Of America | Tamper evident closure |
| EP0556923A1 (fr) | 1992-02-18 | 1993-08-25 | Colorsil B.V. | Pigment de silicate mixte au zirconium dopé, procédé de préparation et produits contenant le pigment ou un pigment ainsi préparé |
| EP0702055A2 (fr) | 1994-09-14 | 1996-03-20 | Ciba-Geigy Ag | Pigments organiques prêts à être mélangés |
| US5605883A (en) | 1993-02-24 | 1997-02-25 | Iliff; Robert J. | Agglomerated colorant speckle exhibiting reduced colorant spotting |
| WO1998016615A1 (fr) * | 1996-10-15 | 1998-04-23 | The Procter & Gamble Company | Compositions particulaires colorees |
| EP0882125A1 (fr) | 1996-02-14 | 1998-12-09 | The Procter & Gamble Company | Procede d'obtention d'une composition de detergent a faible densite par agglomeration avec un double sel inorganique |
| EP0935343A1 (fr) | 1997-07-08 | 1999-08-11 | MASUDA, Tatsuji | Bascule rs |
| WO2000027980A1 (fr) * | 1998-11-06 | 2000-05-18 | The Procter & Gamble Company | Grains colores et compositions les renfermant |
| EP1305387A1 (fr) | 2000-07-31 | 2003-05-02 | Unilever Plc | Composition coloree a mouchetures et compositions particulaires de detergent de lessive contenant ladite composition |
| EP1627909A1 (fr) | 2004-07-22 | 2006-02-22 | The Procter & Gamble Company | Compositions détergentes contenant des particules colorées |
| WO2007006357A1 (fr) * | 2005-07-11 | 2007-01-18 | Unilever Plc | Granules delivrant un colorant |
-
2007
- 2007-06-26 EP EP07012496A patent/EP2009086B1/fr active Active
- 2007-06-26 PL PL07012496T patent/PL2009086T3/pl unknown
- 2007-06-26 ES ES07012496T patent/ES2416281T3/es active Active
-
2008
- 2008-06-05 UA UAA200807710A patent/UA100110C2/ru unknown
- 2008-06-12 MX MX2008007645A patent/MX2008007645A/es active IP Right Grant
Patent Citations (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3850833A (en) | 1971-01-25 | 1974-11-26 | Colgate Palmolive Co | Scouring cleanser composition |
| US4097418A (en) | 1975-10-06 | 1978-06-27 | The Procter & Gamble Company | Granular colored speckles |
| US4162228A (en) | 1977-05-31 | 1979-07-24 | Lever Brothers Company | Process for preparing colored detergent flakes |
| EP0060728A1 (fr) | 1981-03-18 | 1982-09-22 | Unilever Plc | Procédé de fabrication de granules colorés pour détergents |
| EP0219328A2 (fr) | 1985-10-14 | 1987-04-22 | Unilever Plc | Composition détergente et son procédé de préparation |
| US4671886A (en) | 1985-11-25 | 1987-06-09 | The Procter & Gamble Company | Process for coloring granular product by admixing with pigment/diluent premix |
| GB2199338A (en) * | 1986-12-30 | 1988-07-06 | Unilever Plc | Coloured detergent particles |
| EP0289311A2 (fr) | 1987-04-30 | 1988-11-02 | Unilever Plc | Procédé de préparation d'une composition détergente granulaire |
| EP0344629A1 (fr) | 1988-06-03 | 1989-12-06 | Henkel Kommanditgesellschaft auf Aktien | Composition adsorbente granulaire avec une capacité de dégagement ameliorée |
| US5065883A (en) | 1990-09-17 | 1991-11-19 | Container Corporation Of America | Tamper evident closure |
| EP0556923A1 (fr) | 1992-02-18 | 1993-08-25 | Colorsil B.V. | Pigment de silicate mixte au zirconium dopé, procédé de préparation et produits contenant le pigment ou un pigment ainsi préparé |
| US5605883A (en) | 1993-02-24 | 1997-02-25 | Iliff; Robert J. | Agglomerated colorant speckle exhibiting reduced colorant spotting |
| EP0702055A2 (fr) | 1994-09-14 | 1996-03-20 | Ciba-Geigy Ag | Pigments organiques prêts à être mélangés |
| EP0882125A1 (fr) | 1996-02-14 | 1998-12-09 | The Procter & Gamble Company | Procede d'obtention d'une composition de detergent a faible densite par agglomeration avec un double sel inorganique |
| WO1998016615A1 (fr) * | 1996-10-15 | 1998-04-23 | The Procter & Gamble Company | Compositions particulaires colorees |
| EP0935343A1 (fr) | 1997-07-08 | 1999-08-11 | MASUDA, Tatsuji | Bascule rs |
| WO2000027980A1 (fr) * | 1998-11-06 | 2000-05-18 | The Procter & Gamble Company | Grains colores et compositions les renfermant |
| EP1305387A1 (fr) | 2000-07-31 | 2003-05-02 | Unilever Plc | Composition coloree a mouchetures et compositions particulaires de detergent de lessive contenant ladite composition |
| EP1305387B1 (fr) * | 2000-07-31 | 2005-01-19 | Unilever Plc | Composition coloree a mouchetures et compositions particulaires de detergent de lessive contenant ladite composition |
| EP1627909A1 (fr) | 2004-07-22 | 2006-02-22 | The Procter & Gamble Company | Compositions détergentes contenant des particules colorées |
| WO2007006357A1 (fr) * | 2005-07-11 | 2007-01-18 | Unilever Plc | Granules delivrant un colorant |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3318622A1 (fr) * | 2016-11-04 | 2018-05-09 | Sociedad Anónima Minera Catalano-Aragonesa | Particules colorées pour détergents et leur procédé de production |
Also Published As
| Publication number | Publication date |
|---|---|
| ES2416281T3 (es) | 2013-07-31 |
| EP2009086B1 (fr) | 2013-03-27 |
| PL2009086T3 (pl) | 2013-10-31 |
| UA100110C2 (ru) | 2012-11-26 |
| MX2008007645A (es) | 2009-03-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US7748888B2 (en) | Apparatus for stabilizing plaster | |
| EP2531564B1 (fr) | Procédé pour la préparation de granules de noir de charbon | |
| ES2379855T3 (es) | Granulados de pigmento que contienen coadyuvantes de filtración inorgánicos | |
| CN101291885A (zh) | 低热膨胀铸造介质 | |
| CN107488049A (zh) | 一种Al2O3‑SiO2质球形轻质耐火材料骨料 | |
| EP2009086A1 (fr) | Procédé de coloration de minéraux non-adsorbants et le produit ainsi obtenu | |
| CN109942275B (zh) | 一种利用煤矸石生产的陶粒砂及其加工工艺 | |
| JPH0326795A (ja) | ゼオライト集塊形成工程および生成物 | |
| PL116770B1 (en) | Method of manufacture of pigment preparation for dyeingin the cake of linear polyesters | |
| KR20120016296A (ko) | 분말재료로부터 과립을 생산하는 방법 | |
| US5718755A (en) | Preparation and use of iron oxide black pigment granules | |
| CN108675779A (zh) | 一种复合铝铬砖及其制备方法 | |
| CN204768344U (zh) | 超微细硅树脂胶囊化磷系阻燃剂制备用加热搅拌装置 | |
| JP2008531454A (ja) | 泡ガラス粒状体を製造する方法 | |
| US3096291A (en) | Process of preparing dry granular compositions | |
| CN106544023A (zh) | 一种白光LED用小粒径LuAG绿粉的制备方法 | |
| CA2024800C (fr) | Methode pour ameliorer la fluidite du chlorure de cyanuryle solide | |
| CN107098681A (zh) | 一种可相变控温的瓷砖及其制备方法 | |
| RU2528814C2 (ru) | Способ получения стеклокерамзита и порокерамики из трепелов и опок | |
| JPH09241698A (ja) | 高嵩密度粒状洗剤組成物の製造方法 | |
| JP4152150B2 (ja) | ムライトウィスカーの製造方法 | |
| US3645004A (en) | Drying of efflorescent material | |
| WO2000036077A1 (fr) | Procede de preparation de detergents lessiviels en poudre | |
| RU2264364C2 (ru) | Способ улучшения формовочных и сушильных свойств глинистого сырья | |
| KR19980025533A (ko) | 과립 및 분말상의 츄잉껌 제조 방법 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
| AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC MT NL PL PT RO SE SI SK TR |
|
| AX | Request for extension of the european patent |
Extension state: AL BA HR MK RS |
|
| 17P | Request for examination filed |
Effective date: 20090618 |
|
| AKX | Designation fees paid |
Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC MT NL PL PT RO SE SI SK TR |
|
| 17Q | First examination report despatched |
Effective date: 20090917 |
|
| GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
| GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
| GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
| GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
| AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC MT NL PL PT RO SE SI SK TR |
|
| REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D |
|
| REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
| REG | Reference to a national code |
Ref country code: AT Ref legal event code: REF Ref document number: 603433 Country of ref document: AT Kind code of ref document: T Effective date: 20130415 |
|
| REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D |
|
| REG | Reference to a national code |
Ref country code: DE Ref legal event code: R096 Ref document number: 602007029278 Country of ref document: DE Effective date: 20130529 |
|
| REG | Reference to a national code |
Ref country code: RO Ref legal event code: EPE |
|
| REG | Reference to a national code |
Ref country code: DE Ref legal event code: R082 Ref document number: 602007029278 Country of ref document: DE Representative=s name: SCHAEFER, MATTHIAS, DIPL.-ING., DE Ref country code: DE Ref legal event code: R082 Ref document number: 602007029278 Country of ref document: DE Representative=s name: SCHAEFER, MATTHIAS W., DIPL.-ING., DE |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130327 Ref country code: BG Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130627 Ref country code: LT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130327 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20130605 Year of fee payment: 7 |
|
| REG | Reference to a national code |
Ref country code: AT Ref legal event code: MK05 Ref document number: 603433 Country of ref document: AT Kind code of ref document: T Effective date: 20130327 |
|
| REG | Reference to a national code |
Ref country code: LT Ref legal event code: MG4D |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130628 Ref country code: FI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130327 Ref country code: LV Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130327 Ref country code: SI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130327 |
|
| REG | Reference to a national code |
Ref country code: NL Ref legal event code: VDEP Effective date: 20130327 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 20130617 Year of fee payment: 7 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: EE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130327 Ref country code: CZ Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130327 Ref country code: IS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130727 Ref country code: NL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130327 Ref country code: PT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130729 Ref country code: SK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130327 Ref country code: AT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130327 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: RO Payment date: 20130618 Year of fee payment: 7 |
|
| REG | Reference to a national code |
Ref country code: PL Ref legal event code: T3 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CY Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130327 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: IT Payment date: 20130621 Year of fee payment: 7 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MC Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130327 Ref country code: DK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130327 |
|
| PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
| REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
| 26N | No opposition filed |
Effective date: 20140103 |
|
| REG | Reference to a national code |
Ref country code: IE Ref legal event code: MM4A |
|
| REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST Effective date: 20140228 |
|
| REG | Reference to a national code |
Ref country code: DE Ref legal event code: R097 Ref document number: 602007029278 Country of ref document: DE Effective date: 20140103 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20130630 Ref country code: IE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20130626 Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20130630 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20130701 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: PL Payment date: 20140626 Year of fee payment: 8 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: RO Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20140626 |
|
| GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20140626 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130327 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20140626 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20140626 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: TR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130327 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: HU Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO Effective date: 20070626 Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20130626 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: PL Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20150626 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20140630 |
|
| P01 | Opt-out of the competence of the unified patent court (upc) registered |
Effective date: 20230530 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: ES Payment date: 20230713 Year of fee payment: 17 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20240617 Year of fee payment: 18 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: ES Payment date: 20240701 Year of fee payment: 18 |