EP1165740B1 - Toilettenreinigungszusammensetzungen - Google Patents

Toilettenreinigungszusammensetzungen Download PDF

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Publication number
EP1165740B1
EP1165740B1 EP00912460A EP00912460A EP1165740B1 EP 1165740 B1 EP1165740 B1 EP 1165740B1 EP 00912460 A EP00912460 A EP 00912460A EP 00912460 A EP00912460 A EP 00912460A EP 1165740 B1 EP1165740 B1 EP 1165740B1
Authority
EP
European Patent Office
Prior art keywords
phase
block according
salt
lavatory cleansing
water
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
EP00912460A
Other languages
English (en)
French (fr)
Other versions
EP1165740A1 (de
Inventor
Marco Unilever Italia Spa Lever Faberge GALLI
Marco Unilever Italia Spa Lever Faberge OLIVA
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
Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Priority to EP00912460A priority Critical patent/EP1165740B1/de
Publication of EP1165740A1 publication Critical patent/EP1165740A1/de
Application granted granted Critical
Publication of EP1165740B1 publication Critical patent/EP1165740B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • C11D3/02—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
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/046—Salts
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/395—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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/50—Perfumes

Definitions

  • This invention is concerned with lavatory cleansing blocks which may be used to clean and/or perfume the flush water of a lavatory or urinal.
  • toilet blocks to impart cleansing and/or other components to the flush water of a lavatory or urinal is well known.
  • Such compositions may, for example, be immersed in the water of a lavatory or held under the rim of a toilet, in a suitable holder, for intermittent contact of the solid material with flush water.
  • these two approaches will be referred to herein respectively as 'cistern-blocks' and 'rim-blocks'
  • halogen release agents are, by their nature, powerful chemically reactive species, serving as halogenating or oxidising agents and it is consequently difficult to incorporate bleach-sensitive components such as perfumes and dyestuffs into blocks which contain bleaching agents.
  • the present invention provides a lavatory cleansing block comprising at least two phases one phase (phase 1) comprising a water insoluble salt as at least 50 wt% of the salt present within that phase and a second phase (phase 2) comprising a perfume and a water soluble salt such that the salts in both phases have the same anion.
  • the invention also relates to a process for producing the toilet blocks, described in the above paragraph, the process comprising the step of co-extruding the two phases to form a block.
  • the present invention preferably relates to a dual phase block.
  • Phase 1 of the block comprises a water insoluble salt as at least 50 wt% of the salt present, in the context of the present invention water insoluble salt refers to salts having a maximum solubility parameter of 0.05 gram per 100cc of water at 25°C.
  • the second phase (Phase 2) of the block comprises a perfume and a water soluble salt.
  • water soluble salt refers to salts having a solubility parameter of at least 0.5 gram per 100cc of water at 0°C, more preferably greater than 1 gram per 100 cc of water.
  • the salts in both phases should have the same anion.
  • phase 1 does not contain a water soluble salt having the same anion as the water insoluble salt.
  • the total level of water soluble salt having the same anion as the water insoluble salt within phase 2 is from 1 to 10 wt% of the total level of ingredients present in phase 2.
  • phase 2 further comprises a water insoluble salt having the same anion as the water soluble salt. More preferably the ratio of water soluble salt and the water insoluble salt both having the same anion within phase 2 of the toilet block is from 5:1 t 1:5. Most preferably the ratio of water soluble salt and the water insoluble salt both having the same anion within phase 2 of the toilet block is from 3:2 to 2:3.
  • a preferred water soluble salt for use with the present invention is sodium carbonate.
  • a preferred water insoluble salt for use with the present invention is calcium carbonate.
  • the total level of water insoluble salt in phase 1 is from 1 to 10 wt% of the total level of ingredients present in phase 1.
  • Blocks according to the present invention comprise 5 to 50 wt% to by weight of salt as a sum of the total ingredients of both phases inclusive of the anion present, more preferably 10-30 wt%.
  • the toilet blocks according to the invention may include an alcohol ethoxylate.
  • the alcohol ethoxylate preferably used in the present invention is ethoxylated with 8 or less moles of alkylene oxide, more preferably the alcohol ethoxylate is ethoxylated with 5 or less moles of alkylene oxide.
  • the alcohol ethoxylate has a carbon chain length of C 8 to C 22 , more preferably from C 8 to C 16
  • the alcohol ethoxylate is branched.
  • the alcohol ethoxylate has an H.L.B of 12 or less, more preferably an HLB of 10 or less, most preferably of 8 or less.
  • the alcohol ethoxylate should preferably have a cloud point of less than 65 when measured in water at a 1% solution.
  • the level of alcohol ethoxylate within the block is less than 5 wt% of the total weight of the block. More preferably the alcohol ethoxylate is in a separate phase to the perfume (that is phase 1). It is advantageous if the level of alcohol ethoxylate is from 0.5 to 6 wt % of the weight of the total composition (i.e. both phases), more preferably from 1.5 to 4 wt% of the weight of the total composition.
  • the blocks comprise up to 50% by weight of a at least sparingly water soluble bleaching agent.
  • levels of bleaching agents are 2-30% wt on product.
  • bleaching agent is used to mean both a bleaching agent and a precursor which produces a bleaching agent unless the context demands otherwise.
  • Suitable bleaching agents active-halide and active-oxygen bleaching agents particularly the so-called 'halogen release agents'.
  • 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. The alkali metal salts of cyanurates are preferred.
  • a particularly preferred bleaching agent is sodium dichlorocyanurate (NaDCCA).
  • the bleaching agent is typically present in an amount of 10-30% and most preferably at around 25%.
  • Oxidan DCN/WSG (TM) ex Sigma has been found to be a suitable bleaching agent.
  • the bleach resides in the same phase as the water insoluble salt (phase 1).
  • the composition will also contain a surfactant component which is anionic in nature.
  • This surfactant serves to provide a cleansing and foaming effect.
  • Suitable anionic surface active agents include alkali metal or ammonium alkylaryl sulphonates (especially alkyl benzene sulphonates), alkane sulphonates, alkyl sulphates and sarcosinates.
  • a surfactant system which comprises primary alkyl sulphate (PAS) together with other anionic surfactants.
  • PAS primary alkyl sulphate
  • the present invention provides a lavatory block comprising 1-15% wt (more preferably 1-5% wt) of a primary alkyl sulphate and 15-50%wt (more preferably 30-50%wt) of other anionic surfactants.
  • this mixed surfactant system is advantageous in that it reduces the stickiness of the block during manufacture.
  • the blocks with 1-5% PAS show improved wear characteristics.
  • the other anionic surfactants are sulphonates.
  • Suitable sulphonates include alkyl benzene sulphonate (ABS). It is believed that the combination of relatively low levels of PAS together with higher levels of ABS promotes the foaming and the perfume delivery from the block.
  • the total amount of surfactant when present may lie within wide limits.
  • the surfactant will generally be for 10 to 70% by weight of the composition, but more preferable that surfactant comprises from 20 to 50% by weight thereof.
  • the blocks according to the invention further comprise a processing aid to assist in extrusion.
  • processing aids include oils (including both mineral and silicone oils), esters (other than those derived from ethylenically unsaturated carboxyl group containing monomers), alcohol ethoxylates and polybutene.
  • the blocks comprise 2-15%wt of a hydrophobic oily liquid perfume.
  • the blocks more preferably comprise, 2-10%, more preferably 3-6% wt of the perfume. Levels of around 4% wt perfume are particularly preferred.
  • This oily perfume is typically of the kind described in the European patent application EP 167,210. It will be understood that the liquid oily perfume must be stable in the presence of the water-soluble, active chlorine, bleaching agent. Suitable oily perfumes can be easily selected by testing them in combination with the water-soluble, active chlorine, bleaching agent.
  • the toilet block may comprise two perfumes in this case it is preferable if the perfume present in each phase is at least 80 wt% of the total perfume present in that phase. More preferably different perfumes are present in phases.
  • bleach-stable perfumes examples include 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 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. Titanium dioxide is an acceptable whitener. Levels of colouring agents and/or whiteners as typically below 5% wt.
  • chelating agent such as ethylene diamine tetra-acetic acid or a derivative thereof, nitrolotriacetic acid, phosphonates of polyphosphates, metasilicates, boroheptonates, s.s-thylene-diamino disuccinate, dipicolinic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, or lower molecular weight polymeric materials capable of inhibiting crystal growth.
  • Further reducing agents such as alkali metal metabisulphates may be present to assist in the reduction of staining due to metals such as iron.
  • one phase of the blocks according to the present invention comprise 1-15% wt, more preferably 2-10% of a dyestuff on a carrier. It is preferable if the other phase of the block is totally coloured. In both cases it is preferable if the dye is water soluble.
  • a water-insoluble, gelling polymers may be used in compositions of the invention, these are polycarboxylic acids derived from one or more ethylenically unsaturated carboxyl group-containing monomers, especially ethylenically unsaturated carboxylic acids such as acrylic acid or maleic acid.
  • Suitable polymers include polyacrylic acid, polymaleic anhydride and copolymers of either of the aforementioned with ethylene, styrene and methyl vinyl ester. If present it is preferred that the polymer is cross-linked.
  • compositions in accordance with the invention may be produced by a variety of routes.
  • they may be prepared by a so-called "hot-melt” process comprising melting the fusible constituents of each phase of the block followed by adding the other components, and subsequently casting the melt into moulds or are formed into the desired final shape by a compression technique, i.e., a technique involving the steps of forming a mixture of the ingredients of the compositions and then compressing that mixture into the desired shape. The two phases so formed are then compressed together.
  • An especially preferred process is an extrusion process in which mixtures of the components of each phase are co-extruded into a solid bar or rod which is subsequently cut into pieces of the desired size.
  • compositions of the invention are used as free-standing lavatory cleansing blocks, these suitably have a weight from 30 to 150 gms.
  • weight of each phase is preferably approximately the same as each other (approximately in this context meaning that the weight of each phase varies within 20% from each other, more preferably within 10%).
  • compositions in accordance with the invention may also be formed into the final desired shape by a tabletting technique.
  • block is not intended to limit the shape of the eventual product.
  • the rod is cut into lengths which are short relative to their diameter.
  • the invention also provides a method of cleaning a lavatory or urinal using a block of a composition in accordance with the invention.
  • Toilet blocks were formed by an extrusion process in which the mixture of the components of each phase were co-extruded as a plastified mass through an aperture to form a billet and said billet is cut into tablets of appropriate size.
  • the toilet blocks had the following formulation: wt% of total block
  • Example A Phase 1 ABS 1 15 15 15 15 15 PAS 2 6 6 6 NaDCCA 11.25 11.25 11.25 CaCO 3 4.4 4.4 4.4 Na 2 SO 4 4.3 4.3 4.3 Alcohol ethoxylate 2EO 5 - - 3 Minors to 50 wt% Phase 2 ABS 1 17.4 17.4 17.4
  • PAS 2 2.5 2.5 2.5 CaCO 3 11.3 9.2 5.1 Na 2 SO 4 9.8 9.8 9.8 Na 2 CO 3 - 2.2 5.3 Perfume 3.5 3.5 3.5 Minors to 50 wt% ABS 1 Nansa HS 80/L ex Albright & Wilson PAS 2 PAS-Empicol LZ-V ex Albright & Wilson Coloured granules sodium carbonate ex Crosfield Alcohol ethoxylate 2EO 5 Loradac 2-24 2EO ex DAC.

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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)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Cosmetics (AREA)
  • Bidet-Like Cleaning Device And Other Flush Toilet Accessories (AREA)

Claims (12)

  1. Toilettenreinigungsblock enthaltend mindestens zwei Phasen, wobei eine Phase (Phase 1) ein wasserunlösliches Salz enthält, das mindestens 50 Gew.-% des Salzes in dieser Phase bildet, und eine zweite Phase (Phase 2), die ein Parfum und ein wasserlösliches Salz enthält, wobei die Salze in beiden Phasen das gleiche Anion haben.
  2. Toilettenreinigungsblock nach Anspruch 1, wobei Phase 2 weiterhin ein wasserunlösliches Salz mit dem gleichen Anion, wie das wasserlösliche Salz enthält.
  3. Toilettenreinigungsblock nach Anspruch 2, wobei das Verhältnis von wasserlöslichem Salz zu wasserunlöslichem Salz, die beide das gleiche Anion haben, 5:1 bis 1:5 ist.
  4. Toilettenreinigungsblock nach einem der vorhergehenden Ansprüche, wobei Phase 2 weiterhin ein bleichendes Material enthält.
  5. Toilettenreinigungsblock nach Anspruch 4, wobei das Bleichmittel ein Halogen freisetzendes Mittel ist.
  6. Toilettenreinigungsblock nach Anspruch 5, wobei das Bleichmittel Natriumdichlorcyanurat (NaDCCA) ist.
  7. Toilettenreinigungsblock nach einem der vorhergehenden Ansprüche, wobei das wasserlösliche Salz Natriumcarbonat ist.
  8. Toilettenreinigungsblock nach einem der vorhergehenden Ansprüche, wobei das wasserunlösliche Salz Calciumcarbonat ist.
  9. Toilettenreinigungsblock nach einem der vorhergehenden Ansprüche, wobei der Gehalt des wasserlöslichen Salzes mit dem gleichen Anion, wie das wasserunlösliche Salz, in Phase 2 von den gesamten in Phase 2 vorhandenen Inhaltsstoffen 1 bis 10 Gew.-% ausmacht.
  10. Toilettenblock nach einem der vorhergehenden Ansprüche, bei dem der Gesamtgehalt an wasserunlöslichem Salz in Phase 1 von den gesamten in Phase 1 vorhandenen Inhaltsstoffen 1 bis 10 Gew.-% ausmacht.
  11. Toilettenreinigungsblock nach einem der vorhergehenden Ansprüche, wobei Phase 1 weiterhin ein Alkoholethoxylat, das mit 8 oder weniger Mol Alkylenoxid ethoxyliert ist, enthält.
  12. Verfahren zur Herstellung eines Toilettenreinigungsblocks nach einem der vorhergehenden Ansprüche, wobei das Verfahren die Stufe umfasst, dass die zwei oder mehr Phasen coextrudiert werden, um den Block zu bilden.
EP00912460A 1999-03-29 2000-02-14 Toilettenreinigungszusammensetzungen Expired - Lifetime EP1165740B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP00912460A EP1165740B1 (de) 1999-03-29 2000-02-14 Toilettenreinigungszusammensetzungen

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP99302453 1999-03-29
EP99302453 1999-03-29
EP00912460A EP1165740B1 (de) 1999-03-29 2000-02-14 Toilettenreinigungszusammensetzungen
PCT/EP2000/001184 WO2000058434A1 (en) 1999-03-29 2000-02-14 Lavatory cleansing compositions

Publications (2)

Publication Number Publication Date
EP1165740A1 EP1165740A1 (de) 2002-01-02
EP1165740B1 true EP1165740B1 (de) 2004-04-28

Family

ID=8241298

Family Applications (1)

Application Number Title Priority Date Filing Date
EP00912460A Expired - Lifetime EP1165740B1 (de) 1999-03-29 2000-02-14 Toilettenreinigungszusammensetzungen

Country Status (13)

Country Link
EP (1) EP1165740B1 (de)
JP (1) JP2002540288A (de)
AR (1) AR023177A1 (de)
AT (1) ATE265521T1 (de)
AU (1) AU748762B2 (de)
BR (1) BR0007502B1 (de)
CA (1) CA2361266C (de)
DE (1) DE60010245T2 (de)
HU (1) HUP0200401A3 (de)
ID (1) ID30170A (de)
TR (1) TR200102763T2 (de)
WO (1) WO2000058434A1 (de)
ZA (1) ZA200105348B (de)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1553162B2 (de) * 2004-01-08 2011-04-20 Unilever N.V. Stückförmige Toilettenreinigungsmittel
US8984517B2 (en) 2004-02-04 2015-03-17 Intel Corporation Sharing idled processor execution resources
GB0428559D0 (en) 2004-12-31 2005-02-09 Jeyes Group Ltd Lavatory cleansing block
DE102008051173A1 (de) 2008-10-14 2010-04-15 Buck-Chemie Gmbh Haftendes Mittel zur Applikation auf einem Sanitärgegenstand
US8444771B2 (en) 2008-02-29 2013-05-21 Buck-Chemie Gmbh Method for cleaning and/or deodorizing toilet bowl or urinal using an adhesive agent
US8835371B2 (en) 2008-02-29 2014-09-16 Buck-Chemie Gmbh Adhesive agent for application on a sanitary object
DE102008012092A1 (de) 2008-02-29 2009-09-10 Buck- Chemie Gmbh Haftendes Mittel zur Applikation auf einem Sanitärgegenstand
PT2250245E (pt) 2008-02-29 2011-12-29 Buck Chemie Gmbh Agente adesivo para aplicação num objecto sanitário

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4460490A (en) * 1980-12-18 1984-07-17 Jeyes Group Limited Lavatory cleansing blocks
DE3225292A1 (de) * 1982-07-07 1984-01-12 Henkel KGaA, 4000 Düsseldorf Reinigungs- und desinfektionsmitteltablette fuer den wasserkasten von spueltoiletten
GB8417345D0 (en) * 1984-07-06 1984-08-08 Unilever Plc Para-dichlorobenzene-free lavatory cleansing blocks
GB8515181D0 (en) * 1985-06-14 1985-07-17 Jeyes Group Ltd Lavatory cleansing compositions
JPS6236500A (ja) * 1985-08-12 1987-02-17 花王株式会社 固形洗浄剤
US5759974A (en) * 1994-11-07 1998-06-02 Henkel Kommanditgesellschaft Auf Aktien Block-form cleaners for flush toilets
DE69702851T2 (de) * 1996-06-12 2001-01-04 Unilever N.V., Rotterdam Verbesserungen bezüglich toilettenreinigungsblöcke
GB2322632B (en) * 1997-02-20 2001-02-21 Reckitt & Colman Of India Ltd A toilet block composition

Also Published As

Publication number Publication date
EP1165740A1 (de) 2002-01-02
DE60010245D1 (de) 2004-06-03
HUP0200401A3 (en) 2004-03-01
AR023177A1 (es) 2002-09-04
CA2361266A1 (en) 2000-10-05
BR0007502B1 (pt) 2009-01-13
JP2002540288A (ja) 2002-11-26
BR0007502A (pt) 2001-10-02
HUP0200401A2 (hu) 2002-07-29
ZA200105348B (en) 2002-06-28
WO2000058434A1 (en) 2000-10-05
ID30170A (id) 2001-11-08
AU3422300A (en) 2000-10-16
CA2361266C (en) 2009-10-06
AU748762B2 (en) 2002-06-13
DE60010245T2 (de) 2005-04-14
ATE265521T1 (de) 2004-05-15
TR200102763T2 (tr) 2002-04-22

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