EP0906410B1 - Improvements relating to lavatory cleaning blocks - Google Patents

Improvements relating to lavatory cleaning blocks Download PDF

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Publication number
EP0906410B1
EP0906410B1 EP97923089A EP97923089A EP0906410B1 EP 0906410 B1 EP0906410 B1 EP 0906410B1 EP 97923089 A EP97923089 A EP 97923089A EP 97923089 A EP97923089 A EP 97923089A EP 0906410 B1 EP0906410 B1 EP 0906410B1
Authority
EP
European Patent Office
Prior art keywords
blocks
perfume
block
bleaching agent
alkyl
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.)
Expired - Lifetime
Application number
EP97923089A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0906410A1 (en
Inventor
Marcella Margherita Leda Bartoletti
Ronald Meredith Morris
Roberto Paolo Tummiolo
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Unilever PLC
Unilever NV
Original Assignee
Unilever PLC
Unilever NV
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from GBGB9612218.9A external-priority patent/GB9612218D0/en
Priority claimed from GBGB9705345.8A external-priority patent/GB9705345D0/en
Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Publication of EP0906410A1 publication Critical patent/EP0906410A1/en
Application granted granted Critical
Publication of EP0906410B1 publication Critical patent/EP0906410B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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.
  • a number of different 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.
  • Suitable 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.
  • 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 around 50 being preferred.
  • 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.
  • 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 whiteners. 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, to 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.
  • compositions are: 4-15%wt primary alkyl sulphate 15-50%wt alkyl benzene sulphonate 2-30%wt at least one N-chlorinated cyanuric acid derivative, preferably NaDCCA 10-50%wt Sodium sulphate, calcium carbonate or a mixture thereof, 2-15%wt Perfume 0-5%wt Colour and/or optical brightener
  • 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.
  • Nonionic Empilan KM 50/KF TM, ex. Albright and Wilson
  • Process Aid PEG 4000 Monostearate 100% ex DAC Anionics (ABS) Nansa HS 80/GPF (TM, ex. Albright and Wilson) (PAS) Empicol LZ-V (TM, ex. Albright and Wilson) Bleaching agent Oxidan DCN/WSG (TM, ex Sigma).
  • 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. In the foam height results the figure given is the foam height in cm which is attained directly after the flush.

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  • 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)
  • Detergent Compositions (AREA)
  • Bidet-Like Cleaning Device And Other Flush Toilet Accessories (AREA)
  • Cleaning Implements For Floors, Carpets, Furniture, Walls, And The Like (AREA)
  • Sanitary Device For Flush Toilet (AREA)
EP97923089A 1996-06-12 1997-05-12 Improvements relating to lavatory cleaning blocks Expired - Lifetime EP0906410B1 (en)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
GBGB9612218.9A GB9612218D0 (en) 1996-06-12 1996-06-12 Improvements relating to lavatory cleaning blocks
GB9612218 1996-06-12
GB9705345 1997-03-14
GBGB9705345.8A GB9705345D0 (en) 1997-03-14 1997-03-14 Improvements relating to lavatory cleaning blocks
PCT/EP1997/002501 WO1997047721A1 (en) 1996-06-12 1997-05-12 Improvements relating to lavatory cleaning blocks

Publications (2)

Publication Number Publication Date
EP0906410A1 EP0906410A1 (en) 1999-04-07
EP0906410B1 true EP0906410B1 (en) 2000-08-16

Family

ID=26309492

Family Applications (1)

Application Number Title Priority Date Filing Date
EP97923089A Expired - Lifetime EP0906410B1 (en) 1996-06-12 1997-05-12 Improvements relating to lavatory cleaning blocks

Country Status (15)

Country Link
EP (1) EP0906410B1 (enrdf_load_stackoverflow)
JP (1) JP3310985B2 (enrdf_load_stackoverflow)
AR (1) AR007550A1 (enrdf_load_stackoverflow)
AU (1) AU713578B2 (enrdf_load_stackoverflow)
BR (1) BR9709668A (enrdf_load_stackoverflow)
CA (1) CA2248093C (enrdf_load_stackoverflow)
CZ (1) CZ409798A3 (enrdf_load_stackoverflow)
DE (1) DE69702851T2 (enrdf_load_stackoverflow)
ES (1) ES2150773T3 (enrdf_load_stackoverflow)
ID (1) ID17251A (enrdf_load_stackoverflow)
IN (1) IN189775B (enrdf_load_stackoverflow)
MY (1) MY119184A (enrdf_load_stackoverflow)
PL (1) PL189534B1 (enrdf_load_stackoverflow)
TR (1) TR199802560T2 (enrdf_load_stackoverflow)
WO (1) WO1997047721A1 (enrdf_load_stackoverflow)

Cited By (3)

* Cited by examiner, † Cited by third party
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
WO2025003018A1 (en) * 2023-06-30 2025-01-02 Unilever Ip Holdings B.V. Laundry composition
EP4574942A1 (en) * 2023-12-19 2025-06-25 Eurvest S.A. Sanitary composition for toilet cleaning, disinfecting and/or deodorizing

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1053294A1 (en) * 1998-02-04 2000-11-22 Unilever Plc Lavatory cleansing composition
EP1053296A1 (en) * 1998-02-04 2000-11-22 Unilever Plc Lavatory cleansing compositions
PL343345A1 (en) * 1998-04-09 2001-08-13 Unilever Nv Toilet cleaning blocks
EP1071741A1 (en) * 1998-04-09 2001-01-31 Unilever Plc Toilet cleaning blocks
TR200102763T2 (tr) * 1999-03-29 2002-04-22 Unilever N.V. Tuvalet temizleme bileşimleri
AU2911200A (en) * 1999-03-29 2000-10-16 Unilever Plc Lavatory cleansing compositions
US20080032912A1 (en) 2006-08-04 2008-02-07 Takasago International Corporation Use of fragrance compositions for the prevention of the development of indole base malodours from fecal and urine based soils
ES2530061T3 (es) 2008-04-15 2015-02-26 Takasago International Corporation Composición reductora del mal olor y usos de la misma

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2907029A1 (de) * 1979-02-23 1980-09-04 Henkel Kgaa Verfahren zur herstellung von abspuelbloecken fuer die toilettenhygiene
GB2178442B (en) 1985-06-14 1988-12-21 Jeyes Group Ltd Lavatory cleansing compositions
GB9013539D0 (en) * 1990-06-18 1990-08-08 Unilever Plc Lavatory cleansing block
EP0619366A1 (en) 1993-04-05 1994-10-12 The Procter & Gamble Company Lavatory blocks containing active oxygen
EP0619367A1 (en) * 1993-04-06 1994-10-12 The Procter & Gamble Company Lavatory blocks containing enzymes
DE4439677A1 (de) * 1994-11-07 1996-05-09 Henkel Kgaa Reinigungsmittelstück für Spültoiletten

Cited By (3)

* Cited by examiner, † Cited by third party
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
WO2025003018A1 (en) * 2023-06-30 2025-01-02 Unilever Ip Holdings B.V. Laundry composition
EP4574942A1 (en) * 2023-12-19 2025-06-25 Eurvest S.A. Sanitary composition for toilet cleaning, disinfecting and/or deodorizing

Also Published As

Publication number Publication date
BR9709668A (pt) 2000-05-09
EP0906410A1 (en) 1999-04-07
DE69702851D1 (de) 2000-09-21
IN189775B (enrdf_load_stackoverflow) 2003-04-19
WO1997047721A1 (en) 1997-12-18
AR007550A1 (es) 1999-11-10
DE69702851T2 (de) 2001-01-04
JP2000505131A (ja) 2000-04-25
ES2150773T3 (es) 2000-12-01
MY119184A (en) 2005-04-30
CA2248093A1 (en) 1997-12-18
PL330606A1 (en) 1999-05-24
JP3310985B2 (ja) 2002-08-05
CZ409798A3 (cs) 1999-07-14
AU2899097A (en) 1998-01-07
TR199802560T2 (xx) 1999-03-22
CA2248093C (en) 2002-12-24
AU713578B2 (en) 1999-12-02
PL189534B1 (pl) 2005-08-31
ID17251A (id) 1997-12-11

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