EP4314226A1 - Pastille détergente ayant une empreinte - Google Patents
Pastille détergente ayant une empreinteInfo
- Publication number
- EP4314226A1 EP4314226A1 EP22707746.8A EP22707746A EP4314226A1 EP 4314226 A1 EP4314226 A1 EP 4314226A1 EP 22707746 A EP22707746 A EP 22707746A EP 4314226 A1 EP4314226 A1 EP 4314226A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- printed
- detergent tablet
- detergent
- tablet
- printing
- 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.)
- Pending
Links
- 239000003599 detergent Substances 0.000 title claims abstract description 169
- 238000004806 packaging method and process Methods 0.000 claims abstract description 66
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000011888 foil Substances 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 239000002245 particle Substances 0.000 description 33
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 22
- 239000000049 pigment Substances 0.000 description 13
- 229920002451 polyvinyl alcohol Polymers 0.000 description 13
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 13
- 239000013543 active substance Substances 0.000 description 12
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 12
- 229920002678 cellulose Polymers 0.000 description 11
- 235000010980 cellulose Nutrition 0.000 description 11
- 238000009826 distribution Methods 0.000 description 11
- 238000005406 washing Methods 0.000 description 11
- 239000004372 Polyvinyl alcohol Substances 0.000 description 10
- 239000010457 zeolite Substances 0.000 description 10
- 239000011111 cardboard Substances 0.000 description 9
- 238000004140 cleaning Methods 0.000 description 9
- 238000011049 filling Methods 0.000 description 9
- 239000000454 talc Substances 0.000 description 8
- 229910052623 talc Inorganic materials 0.000 description 8
- 239000004753 textile Substances 0.000 description 8
- 239000002552 dosage form Substances 0.000 description 7
- 238000012546 transfer Methods 0.000 description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 239000001913 cellulose Substances 0.000 description 6
- 235000019589 hardness Nutrition 0.000 description 6
- 235000019359 magnesium stearate Nutrition 0.000 description 6
- 239000012463 white pigment Substances 0.000 description 6
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical class [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 5
- 239000012459 cleaning agent Substances 0.000 description 5
- 230000006835 compression Effects 0.000 description 5
- 238000007906 compression Methods 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 239000004408 titanium dioxide Substances 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 102000004190 Enzymes Human genes 0.000 description 4
- 108090000790 Enzymes Proteins 0.000 description 4
- 229910000004 White lead Inorganic materials 0.000 description 4
- 229910021536 Zeolite Inorganic materials 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 239000005022 packaging material Substances 0.000 description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 3
- 229920000168 Microcrystalline cellulose Polymers 0.000 description 3
- 239000004115 Sodium Silicate Substances 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 230000002902 bimodal effect Effects 0.000 description 3
- 235000013539 calcium stearate Nutrition 0.000 description 3
- 239000008116 calcium stearate Substances 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 3
- -1 chalk Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 description 3
- 235000019813 microcrystalline cellulose Nutrition 0.000 description 3
- 229920006280 packaging film Polymers 0.000 description 3
- 239000012785 packaging film Substances 0.000 description 3
- 150000004760 silicates Chemical class 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 239000001509 sodium citrate Substances 0.000 description 3
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical group O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 3
- 229940045872 sodium percarbonate Drugs 0.000 description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 3
- 229910052911 sodium silicate Inorganic materials 0.000 description 3
- 235000019794 sodium silicate Nutrition 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- FRKHZXHEZFADLA-UHFFFAOYSA-L strontium;octadecanoate Chemical compound [Sr+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O FRKHZXHEZFADLA-UHFFFAOYSA-L 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 2
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 2
- 239000005083 Zinc sulfide Substances 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 229910000410 antimony oxide Inorganic materials 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- RYZCLUQMCYZBJQ-UHFFFAOYSA-H lead(2+);dicarbonate;dihydroxide Chemical compound [OH-].[OH-].[Pb+2].[Pb+2].[Pb+2].[O-]C([O-])=O.[O-]C([O-])=O RYZCLUQMCYZBJQ-UHFFFAOYSA-H 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 2
- 238000012858 packaging process Methods 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- 229920003169 water-soluble polymer Polymers 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 229910052984 zinc sulfide Inorganic materials 0.000 description 2
- FMZMCVJBXLTPLT-UHFFFAOYSA-L zinc;barium(2+);sulfate;sulfide Chemical compound [S-2].[Zn+2].[Ba+2].[O-]S([O-])(=O)=O FMZMCVJBXLTPLT-UHFFFAOYSA-L 0.000 description 2
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000001218 confocal laser scanning microscopy Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000006735 deficit Effects 0.000 description 1
- 238000004851 dishwashing Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000010893 paper waste Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920006300 shrink film Polymers 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0047—Detergents in the form of bars or tablets
- C11D17/0065—Solid detergents containing builders
- C11D17/0073—Tablets
- C11D17/0078—Multilayered tablets
-
- 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
- C11D17/0047—Detergents in the form of bars or tablets
- C11D17/0065—Solid detergents containing builders
- C11D17/0073—Tablets
-
- 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
- C11D3/1233—Carbonates, e.g. calcite or dolomite
-
- 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
- C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
- C11D3/1246—Silicates, e.g. diatomaceous earth
- C11D3/128—Aluminium silicates, e.g. zeolites
-
- 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
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/22—Carbohydrates or derivatives thereof
- C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
Definitions
- the present invention relates to printed detergent tablets.
- the present invention relates to printed detergent tablets of a shrunk-on film pack, detergent supply forms which comprise these detergent tablets, and washing and cleaning methods using these detergent tablets.
- the detergent tablets also usually have coatings made of film materials, which, however, in the case of detergent tablets can be water-soluble or water-insoluble, with the water-insoluble film packaging having to be removed by the consumer before the detergent tablet can be used.
- Both water-soluble and water-insoluble film packaging offer the manufacturers of the corresponding dosing units the opportunity to provide the washing or cleaning agents with imprints such as product designations, product information, company names or advertising messages and symbols.
- the imprints can be applied not to the outer packaging of the tablets but to the tablets themselves before they are packaged with a preferably transparent water-soluble or water-insoluble film material.
- prints on packaging films can be distorted or reduced in quality during the packaging process, as is the case, for example, when printed packaging films are shrunk onto detergent tablets, the prints applied to the tablet surface go through the packaging process without any corresponding impairment.
- direct tablet printing has the disadvantage that in highly efficient processes with short process times, the printing ink applied to the tablet surface can rub off onto the inside of the applied packaging film in the subsequent packaging step.
- the application was based on the object of providing detergent portion units which can be produced by means of simplified processes, have high product stability and storage stability, in a simpler manner Way can be assembled using the smallest amounts of packaging materials and can be produced in an efficient manner.
- a printed detergent tablet comprising a) at least one phase of a compressed particulate premix, b) printing on the surface of the detergent tablet with a print resolution of 40 to 300 dpi, c) a film packaging shrunk onto the detergent tablet is suitable for solving these tasks the printing is at least partially covered.
- the printed detergent tablets comprise at least one phase.
- a phase is a macroscopic region of the detergent tablet which preferably comprises at least 5% by volume, preferably at least 15% by volume and in particular at least 25% by volume of the detergent tablet.
- Exemplary phases are tablet layers.
- the detergent tablet has only one phase.
- Single phase detergent tablets have side faces with identical surface properties. In these cases, it is not necessary to align the detergent tablet after tableting has taken place and before it is printed, for example to avoid undesirable interactions of the printing with ingredients or color or surface roughness of a side surface. Corresponding manufacturing processes are consequently less complex and more efficient.
- the detergent tablet has two or more layers. While the production of the tablets tends to become more complex as the number of layers increases, a tablet design with two or more layers simultaneously increases the degree of freedom with regard to the color design of the tablet. For example, it is possible to produce detergent tablets with differently colored layers.
- both the particle size distribution of the particulate premix used to produce the tablet and the degree of whiteness of the tablets produced from this premix affect the perceptibility and durability of the printing.
- both the absolute size of the particles and the proportion by weight of particles of a certain size are of influence.
- the particulate premix has a particle size distribution in which at least 70% by weight of the particles, preferably at least 80% by weight of the particles, have a particle size between 100 ⁇ m and 1000 ⁇ m. It is also preferred if the particulate premix has a particle size distribution in which at least 50% by weight of the particles have a particle size between 200 ⁇ m and 800 ⁇ m, preferably between 250 ⁇ m and 750 ⁇ m.
- the detergent tablet has two layered phases which differ in terms of their average particle size D50, the layer with the lower average particle size D50 being printed.
- the degree of whiteness of the tablet surface has proven to be particularly relevant for the perceptibility and legibility of the printing.
- detergent tablets are preferred in which at least 90%, preferably at least 95% and in particular at least 98% of the surface of the printed phase outside the printed area has a degree of whiteness which is defined by L*max in the range from 85 to 100, a *max ranges from -3 to +5 b*max ranges from +5 to -15.
- detergent tablets wherein at least 90%, preferably at least 95% and in particular at least 98% of the surface of the printed phase outside the printed area has a degree of whiteness which is defined by L*max is in the range from 95 to 100, a*max ranges from -1 to +2 b*max ranges from +2 to -4.
- Detergent tablets are particularly preferred, where at least 90%, preferably at least 95% and in particular at least 98% of the surface of the printed phase outside the printed area has a degree of whiteness which is defined by L*max is in the range from 98 to 100, a*max ranges from -1 to +1 b*max ranges from +1 to -11.
- Detergent tablets are very particularly preferred, where at least 90%, preferably at least 95% and in particular at least 98% of the surface of the printed phase outside the printed area has a degree of whiteness which is defined by L*max is in the range from 99 to 100, a* max is in the range of 0 b*max is in the range of 0.
- the detergent tablet has two layers which differ in terms of their degree of whiteness and the layer with the higher degree of whiteness has printing.
- These technical measures include, for example, the use of preferably particulate components with suitable degrees of whiteness; the use of pigments, in particular white pigments; the selection of a suitable particle size and particle size distribution of the premix to be tableted; the selection of a suitable compression pressure for tabletting the particulate premix the adjustment of a suitable surface roughness of the tablet outer surface
- the group of components of the particulate premix that are preferred because of their degree of whiteness includes, in particular, inorganic and organic salts.
- the group of preferred inorganic salts includes, in particular, sodium carbonate, sodium percarbonate, sodium bicarbonate, sodium sulfate, sodium silicate and zeolite.
- a preferred organic salt is sodium citrate. The use of urea is also preferred.
- Preferred particulate premixes include, based on their total weight, substances from the group sodium carbonate, sodium percarbonate, sodium hydrogen carbonate, sodium sulfate, sodium silicate, zeolite, sodium citrate and urea in amounts above 40% by weight, preferably above 50% by weight and in particular 55% up to 70% by weight.
- the pigments that can be used to improve the whiteness of the tablet surface include, for example, calcium carbonate, titanium dioxide, which can be in rutile or anatase crystal modification, zinc oxide, zinc sulfide, white lead (basic lead carbonate), barium sulfate, aluminum hydroxide, antimony oxide, lithopone (zinc sulfide -barium sulphate), kaolin, chalk, talc and/or mica.
- Titanium dioxide which can be in the rutile or anatase crystal modification, is particularly preferred.
- the mean particle size of such pigments is usually in the range from 0.004 ⁇ m to 50 ⁇ m. It is also possible to use pigments that have been surface-modified with dispersants.
- titanium dioxide pigments surface-modified with Al, Si, Zr or polyol compounds in particular in rutile form, as is sold, for example, under the trade names Kronos® 2132 (Kronos-Titan) or Hombitan® R 522 (Sachtleben Chemie GmbH). , used.
- the Tiona® RLL, AG and VC types from Solvay and the Bayertitan® RD, R, KB and AZ types from Bayer AG can also be used.
- white pigments are the stearates, in particular calcium stearate, magnesium stearate, strontium stearate and talc. Like the aforementioned white pigments, these white pigments can also be added to the particulate premix before tabletting. Alternatively, however, it is also possible to apply the white pigments, in particular the stearates, to the tablet surface during or after tabletting. This is achieved, for example, by applying the stearate to the surface of the stamp, with the stearate being transferred to the tablet surface during tableting, or by powdering or coating the tablet surface after tableting has taken place. The use of talc and magnesium stearate is particularly preferred as coating or powdering agent.
- the white pigments described above are preferably used in amounts of from 0.001 to 0.8% by weight, particularly preferably from 0.01 to 0.6% by weight, based on the total weight of the particulate premix. Particular preference is given to using these white pigments in detergent tablets which contain washing- or cleaning-active enzymes, since these enzymes can bring about an undesirable coloration of the detergent tablet surface.
- the white pigments can be added to the particulate premix as an integral part of the enzyme granules or as a separate active ingredient.
- the particle size distribution of the particulate premix in which at least 60 wt. While larger particles generally reduce the degree of whiteness at a given tableting pressure, the use of smaller particles increases abrasion during production and transport. With regard to the technical implementation of the printing and the durability of the print images obtained, printing using an inkjet printer has proven to be particularly advantageous.
- the print resolution is preferably 80 and 300 dpi and in particular 120 and 260 dpi.
- the surface of the printed phase is preferably 10% to 60%, in particular 20% to 45%, printed.
- Print motifs with curved contours have proven to be particularly suitable.
- Printed detergent tablet according to any of the previous points, wherein the printing covers 10% to 60%, preferably 20% to 45% of the printed phase.
- the printing is preferably completely covered by the shrunk-on film packaging.
- the printed surface and the surface of the printed phase outside the printed area preferably have a color difference DE above 20, particularly preferably above 40 and in particular above 60.
- An average roughness of at least one outer surface of the tablet of from 25 ⁇ m to 500 ⁇ m, preferably from 50 ⁇ m to 300 ⁇ m, has also proven advantageous for printability.
- the roughness describes the deviation of a real surface from an ideally smooth surface and is determined, for example, using confocal laser scanning microscopy.
- the printed area of the detergent tablet preferably has an average roughness of from 25 ⁇ m to 500 ⁇ m, preferably from 50 ⁇ m to 300 ⁇ m.
- the roughness values preferred according to the invention reduce abrasion of the moldings during production and transport and have an advantageous effect on the durability of the printing.
- the detergent tablets are preferably obtained by tabletting the particulate premixes using low compression forces. These low pressing pressures correlate with tablet hardnesses of preferably 50 N to 300 N and in particular 70 N to 200 N.
- the hardness of the tablets is measured by deforming the tablet until it breaks, the force acting on the side surfaces of the tablet and the maximum force the tablet withstands is determined.
- a tablet testing device from Sotax, for example, is suitable for determining the tablet hardness.
- the use of higher compression pressures generally achieves a higher degree of whiteness of the tablet surface due to the smoother tablet surface thereby achieved, these high compression pressures adversely affect tablet disintegration due to the likewise increased tablet hardness.
- the above tablet hardnesses of preferably 50 N to 300 N and in particular 70N to 200N are accompanied by sufficiently rapid tablet disintegration with a simultaneously advantageous degree of whiteness.
- Detergent tablets are both forms of supply for textile washing and forms of supply for cleaning hard surfaces such as ceramics, glass, metal or tiles.
- the detergent tablets preferably weigh from 14 g to 42 g, preferably from 20 g to 38 g, in particular from 24 g to 34 g.
- Preferred detergent tablets are cuboid.
- the cuboid detergent tablets comprise a bottom, a top and a lateral surface connecting the bottom and the top. It has also proven to be advantageous for the stability of the tablets if the edges delimiting the underside and the upper side are chamfered. In order to increase the stability of the moldings, it may also be advisable to round off the edges of the lateral surfaces connecting the undersides and the upper sides.
- the density of preferred detergent tablets is 1.1 g/cm 3 to 1.5 g/cm 3 , preferably 1.15 g/cm 3 to 1.3 g/cm 3 .
- the detergent forms according to the invention described below have comparatively high densities, for example densities in the range from 0.9 g/cm 3 to 1.4 g/cm 3 , preferably in the range from 1.05 g/cm 3 . cm 3 to 1.3 g/cm 3 .
- detergent tablets which contain at least one active substance from the group of builders, in particular at least one active substance from the group of zeolites, silicates and carbonates, preferably from the group of zeolites.
- the proportion by weight of these active substances in the total weight of the detergent tablet is preferably 5 to 60% by weight, in particular 10 to 50% by weight.
- detergent tablets which, based on their total weight, contain 5 to 60% by weight, in particular 10 to 50% by weight, of zeolite.
- active substances from the group of celluloses and cellulose derivatives preferably from the group of celluloses, microcrystalline celluloses and carboxymethyl celluloses, is also advantageous for the sharpness of the contours and durability of the printed image.
- the proportion by weight of these cellulose-based active substances in the total weight of the detergent tablet is preferably 2 to 50% by weight.
- preferred detergent tablets contain, based on their total weight, less than 10% by weight, preferably less than 5% by weight and in particular less than 1% by weight of an organic acid. Active substances are referred to as organic acids which are contained in the detergent tablets in acid form, i.e. not in the form of their salt.
- the detergent tablet contains less than 10% by weight, preferably less than 2% by weight, based on its total weight % and in particular no binder from the group of polyethylene glycols. Corresponding detergent tablets are preferred.
- the shrunk-on film packaging preferably consists of a water-soluble film material.
- the water-soluble film material may comprise one or more structurally distinct water-soluble polymer(s). Particularly suitable as water-soluble polymer(s) are polymers from the group of (possibly acetalized) polyvinyl alcohols (PVAL) and their copolymers.
- PVAL polyvinyl alcohols
- the shrunk-on film packaging consists preferably of at least 40% by weight, preferably at least 60% by weight and in particular at least 80% by weight of polyvinyl alcohol.
- the shrunk-on film packaging is preferably transparent.
- Water-soluble film materials are preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer whose molecular weight is in the range from 10,000 to 1,000,000 gmof 1 , preferably from 20,000 to 500,000 gmof 1 , particularly preferably from 30,000 to 100,000 gmof 1 and in particular from 40,000 to 80,000 gmof 1 .
- the preparation of the polyvinyl alcohol and polyvinyl alcohol copolymers typically involves the hydrolysis of intermediate polyvinyl acetate.
- Preferred polyvinyl alcohols and polyvinyl alcohol copolymers have a degree of hydrolysis of 70 to 100 mol %, preferably 80 to 90 mol %, particularly preferably 81 to 89 mol % and in particular 82 to 88 mol %.
- preferred polyvinyl alcohol copolymers include an ethylenically unsaturated carboxylic acid, its salt or its ester.
- Such polyvinyl alcohol copolymers particularly preferably contain, in addition to vinyl alcohol, sulfonic acids such as 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS), acrylic acid, methacrylic acid, acrylic esters, methacrylic esters or mixtures thereof.
- APMS 2-acrylamido-2-methyl-1-propanesulfonic acid
- outer packaging means known to the person skilled in the art in this area are suitable for further outer packaging of the printed detergent tablets provided with shrink film.
- the outer packaging takes place by means of a folding box.
- a detergent supply form comprising a) detergent tablets with a printed phase according to one of points 1 to 35, b) outer packaging in the form of a folding box, with a base surface, a top surface and the base surface and the top surface connecting side walls, wherein i) the Outer packaging has a filling level of 85% by volume to 99% by volume and ii) the outer packaging contains at least two washing tablets which are sorted in the outer packaging.
- the outer packaging is preferably designed as a one-piece folding box.
- Preferred overwraps have a flat bottom surface whose longest diagonal is greater than the height of the overwrap. This configuration of the outer packaging increases its stability and enables it to be opened and removed easily. It is particularly preferred if the outer packaging has a flat bottom surface, the largest diagonal of which is more than twice, preferably more than four times, the height of the outer packaging.
- the outer packaging has a cornered bottom surface, preferably a square bottom surface, very particularly preferably a rectangular bottom surface.
- the outer packaging has a cover surface that is plane-parallel to the base surface. Outer packaging in the form of a parallelepiped is particularly preferred.
- the outer packaging is resealable.
- adhesive, snap-in, snap-in or plug-in elements are suitable as closure elements, with adhesive and plug-in elements being particularly preferred.
- closure elements are plug-in closures or removable adhesive closures.
- the packaging materials are preferably based on renewable raw materials.
- the use of packaging materials based on cellulose and waste paper is particularly preferred.
- the outer packaging is made of cardboard.
- the advantages of cardboard lie in the great variability of the types and grammages available.
- Preferred cardboards have a grammage of 150 to 400 g/m 2 .
- Corrugated cardboard which has proven to be technically superior to cardboard in some respects, is used in a particularly preferred embodiment for manufacturing the outer packaging.
- Corrugated cardboard is characterized by its low weight and high strength and is a suitable medium for storage and transport, even in large containers.
- the outer packaging is designed as a box with a hinged lid.
- An essential feature of the detergent dosage form according to the invention is its high degree of filling of 85 to 99% by volume of the outer packaging.
- This high degree of filling not only reduces the amount of packaging material that can be used per detergent tablet, but also surprisingly increases the physical stability of the detergent tablets, both with regard to tablet breakage and with regard to tablet abrasion and the durability of the printing.
- the degree of filling of preferred outer packaging is 88% by volume and 99% by volume, preferably 92% by volume and 99% by volume.
- the “filling level” refers to that proportion of the inner volume of the outer packaging that is taken up by the detergent tablets in the outer packaging.
- the detergent supply form comprises at least ten, preferably at least twenty, particularly preferably at least thirty detergent tablets, which are arranged sorted in the outer packaging.
- Detergent supply forms have proven to be advantageous which comprise at least ten, preferably at least twenty, particularly preferably at least thirty detergent tablets, which are sorted in the outer packaging in such a way that each of the detergent tablets is in direct contact with at least three other detergent tablets.
- Another subject of the application is a method for producing a printed detergent tablet as described above, comprising the steps of a) providing a particulate premix, b) compressing the particulate premix to form a detergent tablet with at least one phase, c) printing the surface of the detergent tablet with a Print resolution between 40 and 300 dpi, d) transport of the printed detergent tablet to a packaging machine, e) wrapping the printed tablet in a foil pack and shrinking the foil pack in such a way that the shrunk-on foil pack covers the printing at least partially, preferably completely.
- the particulate premix in step b) is pressed with a pressure above 0.6 kN/cm 2 , preferably with a pressure above 1 kN/cm 2 , preferably with a pressure of 1 kN/cm 2 to 3 kN/cm 2 .
- Appropriate pressures have surprisingly proven to be advantageous with regard to the stability of the printed image. Due to the simultaneously better disintegration behavior, pressures of 1 kN/cm 2 to 2.5 kN/cm 2 are particularly preferred.
- the time between the end of the printing in step c) and the wrapping of the printed tablet in step e) is less than 180 seconds, preferably between 1 and 120 seconds, preferably between 1 and 10 seconds and in particular between 1 and 5 seconds.
- step e) the film packaging is preferably heat treated using an air stream at a temperature between 180°C and 650°C and subsequently shrunk onto the tablet.
- the detergent tablets according to the invention are suitable for cleaning textiles and for cleaning hard surfaces. Further subjects of the application are therefore methods for textile care or textile cleaning, in which a printed detergent tablet according to the invention is introduced into the dosing chamber or the washing drum of a textile washing machine and methods for dishwashing, in which a printed detergent tablet according to the invention is introduced into the dosing chamber or the interior of a dishwasher. Preferred washing or cleaning processes are carried out at liquor temperatures below 40.degree.
- items provided by this application include:
- a printed detergent tablet comprising a) at least one phase of a compressed particulate premix, b) printing on the surface of the detergent tablet with a print resolution of between 40 and 300 dpi; c) a foil packaging which is shrunk onto the detergent tablet and at least partially covers the printing.
- Printed detergent tablet according to point 1 wherein the detergent tablet has only one phase.
- Detergent tablet has two phases, preferably two layered phases.
- Printed detergent tablet according to any of the previous points, wherein the
- Detergent tablet has two layered phases, which differ in terms of their average particle size D50 and the layer with the lower average particle size D50 has a print.
- Printed detergent tablet according to one of the preceding points wherein the particulate premix has a particle size distribution in which at least 70% by weight of the particles, preferably at least 80% by weight of the particles have a particle size between 100 ⁇ m and 1000 ⁇ m.
- Printed detergent tablet according to any of the preceding points wherein the particulate premix has a bimodal particle size distribution with maxima in the range between 50 ⁇ m and 600 ⁇ m.
- Printed detergent tablet according to one of the preceding points the printing on the surface of the detergent tablet having a print resolution of between 80 and 300 dpi, preferably between 120 and 260 dpi.
- Printed detergent tablet according to one of the preceding points the printing having been applied using an inkjet printer.
- Printed detergent tablet according to any of the previous points wherein the printing covers 10% to 60%, preferably 20% to 45% of the printed phase.
- Printed detergent tablet according to one of the preceding points the printing having a curved contour.
- Detergent tablet according to one of the preceding points wherein the printed surface and the surface of the printed phase outside the printed area have a color difference DE above 20, preferably above 40 and in particular above 60.
- Printed detergent tablet according to one of the preceding points wherein at least 90%, preferably at least 95% and in particular at least 98% of the surface of the printed phase outside the printed area has a degree of whiteness which is defined by
- L*max ranges from 85 to 100
- a*max ranges from -3 to +5
- b*max ranges from +5 to -15.
- L*max ranges from 95 to 100
- a*max ranges from -1 to +2
- b*max ranges from +2 to -4.
- L*max ranges from 98 to 100
- a*max ranges from -1 to +1
- b*max ranges from +1 to -1.
- Detergent tablet in the printed area has an average roughness of 25 gm to 500 gm, preferably 50 gm to 300 gm.
- Detergent tablet has a tablet hardness of 50 N to 300 N and in particular from 70 N to 200 N.
- Printed detergent tablet according to one of the preceding points, wherein the particulate premix, based on its total weight, substances from the group sodium carbonate, sodium percarbonate, sodium bicarbonate, sodium sulfate, sodium silicate, zeolite, sodium citrate and urea in amounts above 40% by weight, preferably above 50% by weight and in particular from 55 to 70% by weight.
- the particulate premix contains a white pigment from the group of titanium dioxide, which can be present in rutile or anatase crystal modification, calcium carbonate, zinc oxide, zinc sulfide, white lead (basic lead carbonate), barium sulfate, aluminum hydroxide, antimony oxide, Lithopone (zinc sulphide barium sulphate), kaolin, chalk, talc and/or mica, preferably from the group titanium dioxide, which can be present in rutile or anatase crystal modification.
- a white pigment from the group of titanium dioxide, which can be present in rutile or anatase crystal modification, calcium carbonate, zinc oxide, zinc sulfide, white lead (basic lead carbonate), barium sulfate, aluminum hydroxide, antimony oxide, Lithopone (zinc sulphide barium sulphate), kaolin, chalk, talc and/or mica, preferably from the group titanium dioxide, which can be present in rutile or anatase
- the particulate premix comprises a white pigment from the group consisting of calcium stearate, magnesium stearate, strontium stearate and talc, in particular talc and magnesium stearate.
- Printed detergent tablet according to one of the above points, wherein the surface of the detergent tablet is powdered or coated with a white pigment, preferably a white pigment from the group consisting of calcium stearate, magnesium stearate, strontium stearate and talc, in particular from the group talc and magnesium stearate.
- a white pigment preferably a white pigment from the group consisting of calcium stearate, magnesium stearate, strontium stearate and talc, in particular from the group talc and magnesium stearate.
- Printed detergent tablet according to any one of the preceding points, wherein the particulate premix comprises, based on its total weight, a white pigment in amounts of from 0.001 to 0.8% by weight, preferably from 0.01 to 0.6% by weight.
- Printed detergent tablet according to any of the preceding items, wherein the particulate premix comprises enzyme and white pigment.
- Printed detergent tablet according to one of the preceding points, wherein the detergent tablet has at least one active substance from the group of builders, in particular at least one active substance from the group of zeolites, silicates and carbonates, preferably from the group of zeolites.
- Detergent tablets based on their total weight, at least one active substance from the group of builders, in particular at least one active substance from the group of zeolites, silicates and carbonates, preferably from the group of zeolites, in proportions by weight of 5 to 60% by weight, preferably 10 up to 50% by weight.
- Detergent tablet comprises at least one active ingredient from the group of celluloses and cellulose derivatives, preferably from the group of celluloses, microcrystalline celluloses and carboxymethyl celluloses.
- Detergent tablet comprises, based on its total weight, at least one active substance from the group of cellulose and cellulose derivatives, preferably from the group of celluloses, microcrystalline celluloses and carboxymethyl celluloses in proportions by weight of 2 to 50% by weight.
- Detergent tablet based on its total weight, comprises less than 10% by weight, preferably less than 2% by weight and in particular no binder from the group of polyethylene glycols.
- Detergent tablet has a cuboid three-dimensional shape.
- Detergent tablet has a weight of 14 g to 42 g, preferably 20 g to 38 g, in particular 24 g to 34 g.
- Detergent tablets have a density between 1.1 g/cm 3 and 1.5 g/cm 3 , preferably between 1.15 g/cm 3 and 1.3 g/cm 3 .
- Film packaging consists of at least 40% by weight, preferably at least 60% by weight and in particular at least 80% by weight of polyvinyl alcohol.
- Foil packaging is transparent.
- Detergent dosage form comprising a) detergent tablets with a printed phase according to any one of points 1 to 35; b) outer packaging in the form of a folding box, with a base surface, a top surface and side walls connecting the base surface and the top surface, wherein i) the outer packaging has a filling level of 85% by volume to 99% by volume and ii) the outer packaging has at least includes two washing tablets, which in the
- Outer packaging are sorted.
- Detergent supply form according to one of points 37 or 38, the outer packaging being resealable.
- Detergent dosage form according to one of points 37 to 39, wherein the outer packaging is made of cardboard.
- Detergent dosage form according to one of points 37 to 40, wherein the outer packaging is made of corrugated cardboard.
- Detergent dosage form according to one of points 37 to 41, wherein the outer packaging has a filling level of 88% by volume to 99% by volume, preferably from 92% by volume to 99% by volume.
- Detergent dosage form according to one of points 37 to 42, wherein the detergent dosage form comprises at least ten, preferably at least twenty, particularly preferably at least thirty detergent tablets.
- a method for producing a printed detergent tablet according to any one of the preceding points comprising the steps of a) providing a particulate premix b) compressing the particulate premix to form a detergent tablet having at least one phase; c) printing the surface of the detergent tablet with a print resolution of between 40 and 300 dpi; d) transporting the printed detergent tablet into a packaging machine; e) wrapping the printed tablet in a foil pack and shrinking the foil pack in such a way that the shrunk-on foil pack covers the printing at least partially, preferably completely.
- Method for textile care or textile cleaning in which a printed detergent tablet according to one of points 1 to 36 is introduced into the dosing chamber or the washing drum of a textile washing machine.
- Particulate premixes of the composition listed in the table below were compressed in a tablet press with compression forces of 10, 20 and 30 kN to form single-phase tablets (data in % by weight based on the particulate premix).
- the compressed surface area of the tablet was 16.75 cm 2 .
- 80% by weight of the particles of the particulate premix had a particle size between 100 ⁇ m and 1000 ⁇ m.
- the detergent tablets were printed over an area of 30% of their surface with a print resolution of 150, 300 and 600 dpi.
- the printed tablets were wrapped in a water-soluble polyvinyl alcohol film at intervals of 1 second, 10 seconds or 120 seconds.
- the film was subsequently pressed onto the tablet.
- the color transfer from the tablet surface to the inside of the shrunk-on film was determined. The results were categorized as follows:
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)
- Health & Medical Sciences (AREA)
- Inorganic Chemistry (AREA)
- Molecular Biology (AREA)
- Emergency Medicine (AREA)
- Detergent Compositions (AREA)
Abstract
La présente invention concerne une pastille détergente ayant une empreinte, comprenant : a) au moins une phase d'un prémélange sous forme de particules comprimées, b) une empreinte sur la surface de la pastille détergente avec une résolution d'impression comprise entre 40 et 300 dpi, c) un emballage de film rétréci sur la pastille détergente, qui recouvre au moins partiellement l'empreinte. L'invention concerne également un procédé pour la production de celle-ci.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP21164423 | 2021-03-23 | ||
PCT/EP2022/054726 WO2022199975A1 (fr) | 2021-03-23 | 2022-02-24 | Pastille détergente ayant une empreinte |
Publications (1)
Publication Number | Publication Date |
---|---|
EP4314226A1 true EP4314226A1 (fr) | 2024-02-07 |
Family
ID=75203083
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP22701193.9A Pending EP4314225A1 (fr) | 2021-03-23 | 2022-01-13 | Pastille d'agent de lavage |
EP22707746.8A Pending EP4314226A1 (fr) | 2021-03-23 | 2022-02-24 | Pastille détergente ayant une empreinte |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP22701193.9A Pending EP4314225A1 (fr) | 2021-03-23 | 2022-01-13 | Pastille d'agent de lavage |
Country Status (3)
Country | Link |
---|---|
US (1) | US20240010958A1 (fr) |
EP (2) | EP4314225A1 (fr) |
WO (2) | WO2022199897A1 (fr) |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19955240A1 (de) * | 1999-11-17 | 2001-05-23 | Henkel Kgaa | Verfahren zur Herstellung von Wasch- und Reinigungsmittelformkörpern |
GB9929843D0 (en) * | 1999-12-16 | 2000-02-09 | Unilever Plc | Process for preparing granular detergent compositions |
EP1167508A1 (fr) * | 2000-06-27 | 2002-01-02 | The Procter & Gamble Company | Pastilles nettoyantes et procédé de manufacture |
DE10245260A1 (de) * | 2002-09-27 | 2004-04-15 | Henkel Kgaa | Verfahren zur Herstellung umhüllter Wasch- oder Reinigungsmittel-Portionen |
-
2022
- 2022-01-13 EP EP22701193.9A patent/EP4314225A1/fr active Pending
- 2022-01-13 WO PCT/EP2022/050665 patent/WO2022199897A1/fr active Application Filing
- 2022-02-24 WO PCT/EP2022/054726 patent/WO2022199975A1/fr active Application Filing
- 2022-02-24 EP EP22707746.8A patent/EP4314226A1/fr active Pending
-
2023
- 2023-09-22 US US18/472,673 patent/US20240010958A1/en active Pending
Also Published As
Publication number | Publication date |
---|---|
US20240010958A1 (en) | 2024-01-11 |
EP4314225A1 (fr) | 2024-02-07 |
WO2022199897A1 (fr) | 2022-09-29 |
WO2022199975A1 (fr) | 2022-09-29 |
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