WO1997047721A1 - Improvements relating to lavatory cleaning blocks - Google Patents
Improvements relating to lavatory cleaning blocks Download PDFInfo
- Publication number
- WO1997047721A1 WO1997047721A1 PCT/EP1997/002501 EP9702501W WO9747721A1 WO 1997047721 A1 WO1997047721 A1 WO 1997047721A1 EP 9702501 W EP9702501 W EP 9702501W WO 9747721 A1 WO9747721 A1 WO 9747721A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- blocks
- perfume
- bleaching agent
- block
- sulphate
- Prior art date
Links
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
- C11D3/395—Bleaching agents
- C11D3/3955—Organic bleaching agents
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/37—Mixtures of compounds all of which are anionic
-
- 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
- C11D17/0056—Lavatory cleansing blocks
-
- 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
- C11D3/395—Bleaching agents
- C11D3/3951—Bleaching agents combined with specific additives
-
- 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
- C11D3/50—Perfumes
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
- C11D1/146—Sulfuric acid esters
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
Definitions
- the present invention relates to lavatory blocks including those which are intended, in use, to be located under the rim of a lavatory bowl or urinal such that, during a flushing cycle, water from the cistern flows over the block thereby dissolving a portion of the block.
- Such blocks are generally known in the art as 'rim blocks' and will be referred to as such or simply as 'blocks' herein.
- the invention also relates to so-called 'in-cistern' blocks which sit in the cistern of a lavatory or urinal and slowly dissolve in the water contained therein.
- Lavatory blocks produce foam, often produce a pleasing odour and can have germicidal properties. These germicidal properties can be due to the presence of bleaching species such as the so-called 'chlorine release agents ' , other oxygen bleaches such as peroxides and non- bleaching species such as quaternary ammonium compounds or halogated materials which do not release hypohalous acids in use.
- bleaching species such as the so-called 'chlorine release agents '
- other oxygen bleaches such as peroxides
- non- bleaching species such as quaternary ammonium compounds or halogated materials which do not release hypohalous acids in use.
- rim blocks generally comprise a surfactant component and a solubility retarding component or 'filler'.
- the surfactant component is an anionic surfactant which is present at a level of 5-85% by weight of the block.
- anionic surfactant systems are known for rim blocks. These comprise mixtures of two or more of primary alkyl sulphate (PAS), alkyl sulphates (AS) which may be branched, secondary alkyl sulphates (SAS) alkyl ether sulphates (AES) and alkyl benzene sulphonates (LAS) or the essentially pure surfactant materials.
- PAS primary alkyl sulphate
- AS alkyl sulphates
- AS secondary alkyl sulphates
- AES alkyl ether sulphates
- LAS alkyl benzene sulphonates
- US 4874536 discloses that AS/LAS mixtures can be used in blocks which are free of oxygen bleaching species.
- WO 95/11958 discloses the use of PAS/AES mixtures again in bleach-free blocks.
- WO 96/14392 discloses the use of PAS/LAS mixtures in bleach-free blocks.
- EP 0619367 discloses the presence of PAS/LES in bleach-free blocks.
- EP 0184416 discloses LAS/PAS in bleach free-blocks.
- GB 2178442 discloses the use of LAS/PAS mixtures in blocks which comprise two halogen bleaching agents.
- EP 0462643 discloses how blocks which comprise halogen bleaching agents can be improved by the incorporation therein of an oily liquid perfume component.
- the presence of the bleaching agent requires that relatively high levels of the perfume are present for moderate term stability.
- the bleaching agent also replaces a portion of the filler which is typically present. The presence of the perfume and bleach leads to a 'sticky' block which can be difficult to produce using the extrusion technique which is commonplace in manufacture of these blocks.
- a block should produce a copious foam when first installed, i.e. during the first 50-80 flushes and continue to produce copious foam during a significant part of the lifetime of the block.
- a lavatory block comprising:
- PAS and LAS form a phase which can adsorb some of the perfume present and prevent the development or expression of stickiness. This facilitates the manufacture of blocks by the process in which the mixture is extruded into a bar which is then cut into individual blocks. It also is believed that the combination of PAS together with ABS promotes the foaming and the perfume delivery from the block.
- a further aspect of the present invention subsists in the use of 3-15%wt primary alkyl sulphate and 15-50%wt of alkyl benezene sulphonate to reduce stickiness in a process for the manufacture of a lavatory block comprising 2-15%wt of oily liquid perfume and 2-30% of halogen bleaching agent.
- the preferred ratio of the primary alkyl sulphate and the alkyl benzene sulphonate is 1:1 to 1:5 in terms of PAS:LAS, most preferably around 1:3 in terms of PAS:LAS.
- Particularly suitable materials are PAS with an average alkyl chain length of C10-C16 and alkyl benzene sulphonate with an average alkyl chain length of C10-C16.
- the blocks according to the invention contain less than 5%wt of other surfactant components and more preferably the blocks are free of other surfactant components.
- the blocks according to the invention further comprise a processing aid to further assist in extrusion.
- processing aids include oils (including both mineral and silicone oils), esters (e.g. methyl decanoate) , liquid ketones (e.g. 2-decanone) , liquid tertiary alcohols (e.g 2-methyl hexan 2-ol) and polybutene.
- oils including both mineral and silicone oils
- esters e.g. methyl decanoate
- liquid ketones e.g. 2-decanone
- liquid tertiary alcohols e.g 2-methyl hexan 2-ol
- polybutene e.g. 2-methyl hexan 2-ol
- One suitable processing aid is an alkoxylated alcohol. It is preferred that the alkoxylated alcohol is an ethoxylated alcohol. When present the preferred level of alkoxylated alcohol is 0.75-2%wt.
- the preferred ethoxy chain length is 40-60 with an average ethoxy chain length of
- Suitable materials include Empilan KM 50/KF (TM) ex. Albright & Wilson.
- Another suitable process aid is a PEG monostearate.
- PEG 4000 Monostearate (100%) ex DAC is a suitable raw material.
- the blocks according to the invention are free of this processing aid.
- blocks according to the present invention comprise 0 to 50% by weight of an inert and/or electrolyte filler.
- blocks Preferably blocks contain 5-50%wt of filler.
- Suitable fillers include ionic (soluble) fillers and inert (insoluble) fillers.
- Suitable fillers include one or more of urea, sodium, magnesium and calcium carbonates, sodium chloride, borax, talc and sodium, magnesium and calcium sulphates.
- Preferred ionic fillers include sodium sulphate. It has been found advantageous to include at least sparingly soluble salts of the metals barium, cadmium, copper, iron, manganese or nickel so as to modify the in-use lifetime of the block.
- Preferred inert fillers include calcium carbonate.
- Typical levels of total filler range from 20-50%wt on product in total. Preferred levels of filler are 10-20%wt on product of ionic filler and 10-20% on product of inert filler. It is particularly preferred to use an approximately 50:50 mixture of sodium sulphate and calcium carbonate as the filler. Typical levels in product are 13-17%wt of each of calcium carbonate and sodium sulphate. It is generally preferred that for in-cistern blocks the inert filler is absent to prevent residues on block dissolution.
- inert filler is sparingly soluble, such as with calcite
- inert filler it has been found useful to employ an inert filler with a narrow cut large particle size such that dissolution and re-precipitation of the calcite is minimised.
- Calcitec SG TM has been found to be a suitable material.
- Suitable halogen bleaching agents are those which are at least sparingly soluble in water.
- the active chlorine bleaching agents are preferred.
- Suitable water-soluble, active chlorine, bleaching agents used in accordance with the invention include chlorinated cyanurates, phthalimides, p-toluene sulphonamides, azodicarbonamides, hydantoins, glycoluracils, amines and melamines.
- Other chlorine release agents such as calcium hypochlorite may be employed.
- the alkali metal salts of cyanurates are preferred.
- a particularly preferred bleaching agent comprises at least one N-chlorinated cyanuric acid derivative, more preferably sodium dichlorocyanurate (NaDCCA) .
- the bleaching agent is preferably present in an amount of 10 to 25% by weight, most preferably at around 15%wt.
- Oxidan DCN/WSG (TM) ex Sigma has been found to be a suitable bleaching agent.
- the blocks comprise 4-10% by weight of the perfume.
- Levels of 5-8% perfume are particularly preferred.
- This is most preferably the liquid oily perfume structurant of the kind described in the European patent application EP 167210. It will be understood that the liquid oily perfume must be stable in the presence of the particular water-soluble, active chlorine, bleaching agent selected. It is believed that substituted quinolines, cedryl methyl ether and cineole are all suitably stable perfume components.
- Suitable commercially available oily perfumes can be easily selected by testing them in combination with the water-soluble, active chlorine, bleaching agent.
- suitable bleach-stable perfumes are Verdeo 898, Bonanza 048 and Ponderosa 431 all ex IFF, and LB 132 ex Quest.
- Particularly preferred perfumes are Icebreaker Super Mod, Oxygen Supra Mod, Motebianco Supra, Montebianco Turbo7 and Lemonfit Supra (all TM) ex Givaudan Roure.
- Minor components will generally be present but are optional. These include colouring agents, and/or whitener ⁇ . These materials should be chosen such that they are compatible with the bleaching agent and do not react therewith to a significant extent.
- TM 'Sudangelb 150'
- Sandoz is an acceptable colouring agent as are Colanyl Green (TM) ex Hoechst and Dispers Blue (TM) ex BASF.
- Titanium dioxide is an acceptable whitener.
- a further optional minor component is a foam-boosting surfactant such as an amine oxide.
- Blocks according to the present invention are manufactured by an extrusion process as known in the art: i.e. the ingredients are mixed to form a dough, which is then extruded into a rod or bar which is cut into blocks of suitable lengths.
- the term block is not intended to limit the shape of the eventual product.
- the rod is generally cut into lengths which are long relative to their diameter and for cistern blocks the rod is cut into lengths which are short relative to their diameter.
- the blocks are extruded as a single composition, f > give a homogenous block.
- Rim blocks according to the present invention are typically used in a cage which is adapted to be suspended from the rim of the toilet bowl in such a manner that flush water flows over and through the cage when the cistern of the toilet is discharged.
- a particularly preferred embodiment of the present invention comprises a block according to the claims appended hereto in combination with a cage which retains the block, said cage being provided with a hook for attachment of the cage to the rim of a toilet bowl.
- Particularly preferred compositions are:
- Example 1 The components listed in Table 1 below were mixed in the proportions specified and extruded in the form of a bar which was then cut into blocks. All proportions are given in weight % as throughout the specification unless stated otherwise. Examples 1-2 and 4 are embodiments of the invention and example 3 is a comparative example.
- Perfume (Montebianco Turbo 7 [TM] ex. Givaudan Roure) was present at 6.5-7%, whitener (titanium dioxide) when present at 0.071 and colour (Colanyl Green ex. Hoechst) at 0.024% or less.
- compositions are given in the upper part of table 1 while foam height results obtained from toilet flushing experiments with formulations 1-4 are given in the lower part.
- foam height results the figure given is the foam height in cm which is attained directly after the flush.
Abstract
Description
Claims
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PL97330606A PL189534B1 (en) | 1996-06-12 | 1997-05-12 | Improvements related to toilet bars |
DE69702851T DE69702851T2 (en) | 1996-06-12 | 1997-05-12 | IMPROVEMENTS IN TOILET CLEANING BLOCKS |
AU28990/97A AU713578B2 (en) | 1996-06-12 | 1997-05-12 | Improvements relating to lavatory cleaning blocks |
EP97923089A EP0906410B1 (en) | 1996-06-12 | 1997-05-12 | Improvements relating to lavatory cleaning blocks |
BR9709668-7A BR9709668A (en) | 1996-06-12 | 1997-05-12 | Blocks for holy vessels |
CA002248093A CA2248093C (en) | 1996-06-12 | 1997-05-12 | Improvements relating to lavatory cleaning blocks |
JP50110698A JP3310985B2 (en) | 1996-06-12 | 1997-05-12 | Improvements on toilet cleaning blocks |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB9612218.9 | 1996-06-12 | ||
GBGB9612218.9A GB9612218D0 (en) | 1996-06-12 | 1996-06-12 | Improvements relating to lavatory cleaning blocks |
GBGB9705345.8A GB9705345D0 (en) | 1997-03-14 | 1997-03-14 | Improvements relating to lavatory cleaning blocks |
GB9705345.8 | 1997-03-14 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1997047721A1 true WO1997047721A1 (en) | 1997-12-18 |
Family
ID=26309492
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP1997/002501 WO1997047721A1 (en) | 1996-06-12 | 1997-05-12 | Improvements relating to lavatory cleaning blocks |
Country Status (15)
Country | Link |
---|---|
EP (1) | EP0906410B1 (en) |
JP (1) | JP3310985B2 (en) |
AR (1) | AR007550A1 (en) |
AU (1) | AU713578B2 (en) |
BR (1) | BR9709668A (en) |
CA (1) | CA2248093C (en) |
CZ (1) | CZ409798A3 (en) |
DE (1) | DE69702851T2 (en) |
ES (1) | ES2150773T3 (en) |
ID (1) | ID17251A (en) |
IN (1) | IN189775B (en) |
MY (1) | MY119184A (en) |
PL (1) | PL189534B1 (en) |
TR (1) | TR199802560T2 (en) |
WO (1) | WO1997047721A1 (en) |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1999040170A1 (en) * | 1998-02-04 | 1999-08-12 | Unilever Plc | Lavatory cleansing compositions |
WO1999040169A1 (en) * | 1998-02-04 | 1999-08-12 | Unilever Plc | Lavatory cleansing composition |
WO1999053013A1 (en) * | 1998-04-09 | 1999-10-21 | Unilever Plc | Toilet cleaning blocks |
WO1999053012A1 (en) * | 1998-04-09 | 1999-10-21 | Unilever Plc | Toilet cleaning blocks |
WO2000058433A1 (en) * | 1999-03-29 | 2000-10-05 | Unilever Plc | Lavatory cleansing compositions |
WO2000058434A1 (en) * | 1999-03-29 | 2000-10-05 | Unilever Plc | Lavatory cleansing compositions |
EP2110118A1 (en) | 2008-04-15 | 2009-10-21 | Takasago International Corporation | Malodour reducing composition and uses thereof |
US8580728B2 (en) | 2006-08-04 | 2013-11-12 | Takasago International Corporation | Use of fragrance compositions for the prevention of the development of indole base malodours from fecal and urine based soils |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7629043B2 (en) | 2003-12-22 | 2009-12-08 | Kimberly-Clark Worldwide, Inc. | Multi purpose cleaning product including a foam and a web |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0014979A1 (en) * | 1979-02-23 | 1980-09-03 | Henkel Kommanditgesellschaft auf Aktien | Process for producing rinsing blocks for the hygiene of water-closets |
EP0462643A1 (en) * | 1990-06-18 | 1991-12-27 | Unilever N.V. | Lavatory cleansing block |
EP0619367A1 (en) * | 1993-04-06 | 1994-10-12 | The Procter & Gamble Company | Lavatory blocks containing enzymes |
DE4439677A1 (en) * | 1994-11-07 | 1996-05-09 | Henkel Kgaa | Detergent piece for flush toilets |
-
1997
- 1997-05-12 CZ CZ984097A patent/CZ409798A3/en unknown
- 1997-05-12 PL PL97330606A patent/PL189534B1/en not_active IP Right Cessation
- 1997-05-12 WO PCT/EP1997/002501 patent/WO1997047721A1/en not_active Application Discontinuation
- 1997-05-12 CA CA002248093A patent/CA2248093C/en not_active Expired - Fee Related
- 1997-05-12 ES ES97923089T patent/ES2150773T3/en not_active Expired - Lifetime
- 1997-05-12 EP EP97923089A patent/EP0906410B1/en not_active Expired - Lifetime
- 1997-05-12 TR TR1998/02560T patent/TR199802560T2/en unknown
- 1997-05-12 DE DE69702851T patent/DE69702851T2/en not_active Expired - Lifetime
- 1997-05-12 JP JP50110698A patent/JP3310985B2/en not_active Expired - Fee Related
- 1997-05-12 BR BR9709668-7A patent/BR9709668A/en not_active IP Right Cessation
- 1997-05-12 AU AU28990/97A patent/AU713578B2/en not_active Ceased
- 1997-05-28 IN IN323BO1997 patent/IN189775B/en unknown
- 1997-06-10 ID IDP971978A patent/ID17251A/en unknown
- 1997-06-10 MY MYPI97002573A patent/MY119184A/en unknown
- 1997-06-11 AR ARP970102534A patent/AR007550A1/en unknown
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0014979A1 (en) * | 1979-02-23 | 1980-09-03 | Henkel Kommanditgesellschaft auf Aktien | Process for producing rinsing blocks for the hygiene of water-closets |
EP0462643A1 (en) * | 1990-06-18 | 1991-12-27 | Unilever N.V. | Lavatory cleansing block |
EP0619367A1 (en) * | 1993-04-06 | 1994-10-12 | The Procter & Gamble Company | Lavatory blocks containing enzymes |
DE4439677A1 (en) * | 1994-11-07 | 1996-05-09 | Henkel Kgaa | Detergent piece for flush toilets |
WO1996014392A1 (en) * | 1994-11-07 | 1996-05-17 | Henkel Kommanditgesellschaft Auf Aktien | Flush toilet cleansers in bar form |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1999040170A1 (en) * | 1998-02-04 | 1999-08-12 | Unilever Plc | Lavatory cleansing compositions |
WO1999040169A1 (en) * | 1998-02-04 | 1999-08-12 | Unilever Plc | Lavatory cleansing composition |
AU744375B2 (en) * | 1998-02-04 | 2002-02-21 | Unilever Plc | Lavatory cleansing compositions |
WO1999053013A1 (en) * | 1998-04-09 | 1999-10-21 | Unilever Plc | Toilet cleaning blocks |
WO1999053012A1 (en) * | 1998-04-09 | 1999-10-21 | Unilever Plc | Toilet cleaning blocks |
WO2000058433A1 (en) * | 1999-03-29 | 2000-10-05 | Unilever Plc | Lavatory cleansing compositions |
WO2000058434A1 (en) * | 1999-03-29 | 2000-10-05 | Unilever Plc | Lavatory cleansing compositions |
US8580728B2 (en) | 2006-08-04 | 2013-11-12 | Takasago International Corporation | Use of fragrance compositions for the prevention of the development of indole base malodours from fecal and urine based soils |
EP2110118A1 (en) | 2008-04-15 | 2009-10-21 | Takasago International Corporation | Malodour reducing composition and uses thereof |
Also Published As
Publication number | Publication date |
---|---|
AU713578B2 (en) | 1999-12-02 |
CA2248093C (en) | 2002-12-24 |
AR007550A1 (en) | 1999-11-10 |
JP3310985B2 (en) | 2002-08-05 |
EP0906410B1 (en) | 2000-08-16 |
AU2899097A (en) | 1998-01-07 |
DE69702851T2 (en) | 2001-01-04 |
EP0906410A1 (en) | 1999-04-07 |
ID17251A (en) | 1997-12-11 |
TR199802560T2 (en) | 1999-03-22 |
IN189775B (en) | 2003-04-19 |
JP2000505131A (en) | 2000-04-25 |
MY119184A (en) | 2005-04-30 |
CZ409798A3 (en) | 1999-07-14 |
ES2150773T3 (en) | 2000-12-01 |
PL189534B1 (en) | 2005-08-31 |
DE69702851D1 (en) | 2000-09-21 |
CA2248093A1 (en) | 1997-12-18 |
PL330606A1 (en) | 1999-05-24 |
BR9709668A (en) | 2000-05-09 |
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