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WO1999053013A1 - Blocs nettoyants pour w-c - Google Patents

Blocs nettoyants pour w-c Download PDF

Info

Publication number
WO1999053013A1
WO1999053013A1 PCT/EP1999/001900 EP9901900W WO9953013A1 WO 1999053013 A1 WO1999053013 A1 WO 1999053013A1 EP 9901900 W EP9901900 W EP 9901900W WO 9953013 A1 WO9953013 A1 WO 9953013A1
Authority
WO
WIPO (PCT)
Prior art keywords
agent
toilet block
heavy metal
block according
metal ion
Prior art date
Application number
PCT/EP1999/001900
Other languages
English (en)
Inventor
Giuseppe Vincenzo Bolzoni
Ronald Meredith Morris
Marco Oliva
Roberto Tummiolo
Original Assignee
Unilever Plc
Unilever N.V.
Hindustan Lever Limited
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 N.V., Hindustan Lever Limited filed Critical Unilever Plc
Priority to PL99343344A priority Critical patent/PL343344A1/xx
Priority to HU0102361A priority patent/HUP0102361A3/hu
Priority to EP99915683A priority patent/EP1071741A1/fr
Priority to AU34167/99A priority patent/AU3416799A/en
Priority to CA002320776A priority patent/CA2320776A1/fr
Priority to BR9909498-3A priority patent/BR9909498A/pt
Publication of WO1999053013A1 publication Critical patent/WO1999053013A1/fr

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
    • C11D3/02—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
    • 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
    • C11D3/08—Silicates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3942—Inorganic per-compounds
    • 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

Definitions

  • the present invention relates to toilet blocks.
  • Toilet blocks are blocks of a slowly soluble material either in containers attached to the rim of a toilet (so-called 'rim-blocks') or in the cistern of the toilet (so-called 'cistern-blocks')-
  • the slowly soluble material can comprise a mixture of surfactant and optional filler as well as various functional ingredients such as perfumes dyestuffs and bleaches. Both types of block dissolve slowly in use: the rim block dissolving in the flush water that meets with it when the toilet is flushed and the cistern block dissolving in the water contained in the cistern between flushes.
  • Toilet blocks containing bleaching agents based on halogen release agents are known to be unstable, one way of countering this effect has been to include a source of certain metal ions as described in EP 0 341 836.
  • the present invention mitigates the problem of thermal heating within toilet blocks.
  • the present invention also improves the manufacturing process of toilet blocks.
  • a toilet block comprising:
  • the present invention further provides a method of preventing thermal heating within a toilet block by incorporation of a heavy metal ion deactivating agent within the formulation of said block.
  • a process for making a toilet block comprising the following steps :
  • the toilet blocks of the invention contain a bleaching agent and a heavy metal deactivating agent.
  • the blocks are thermally stable when stored in bulk.
  • the toilet blocks of the invention contain a bleaching agent.
  • the blocks comprise up to 50% by weight of an at least sparingly water soluble bleaching agent .
  • Typical 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.
  • the bleaching agents are in particulate or granular form.
  • Suitable bleaching agents include 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. 4 -
  • 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 heavy metal ion deactivating agent is a silicate or a periodate compound, more preferred are sodium silicate, magnesium silicate, or sodium periodate. Magnesium silicate is especially preferred.
  • a preferable mixture of heavy metal deactivating agent is sodium periodate and magnesium silicate in a ratio 5:1 to 1:5.
  • the level of heavy metal ion deactivating agent is from 0.05wt% to 5 wt% of the total composition, preferably from 0.1 wt% to 2.0 wt% of the total composition.
  • the ratio by weight of heavy metal deactivating agent to bleaching agent or precursor thereof is from 1:100 to 1:10, more preferably 1:60 to 1:20.
  • the heavy metal deactivating agent is combined with the particulate or granular bleaching agent, this is especially effective when the heavy metal deactivating agent is coated onto the particles or granules of bleaching agent .
  • a heavy metal ion deactivating agent is particularly beneficial with dual phase or multi phase toilet blocks, especially a dual phase toilet block having the bleaching agent or precursor thereof residing in only one phase.
  • the heavy metal deactivating agent is present in only one phase of a dual phase block it is preferably if the level of bleach within this phase is from 0.2 to 1% of the total weight of ingredients within that phase.
  • a surfactant may be present in the toilet block.
  • the surfactant component of the block may be anionic or nonionic in nature.
  • the surfactant serves to provide a cleansing and foaming effect and may, also act synergistically with the polymer component.
  • surfactant comprises up to 50%wt of the composition.
  • the surfactant component comprises one or more anionic surface active agents, optionally in combination with one or more nonionic surface active agents.
  • Suitable anionic surface active agents include alkali metal or ammonium alkylaryl sulphonates (especially alkyl benzene sulphonates) , alkane sulphonates, alkyl sulphates and sarcosinates .
  • Improved foaming properties can be obtained by the use of a surfactant system comprising primary alkyl sulphate (PAS) together with other anionic surfactants .
  • PAS primary alkyl sulphate
  • the present invention provides a lavatory cistern block comprising l-15%wt (more preferably l-5%wt) of a primary alkyl sulphate and 15-50%wt (more preferably 30-50%wt) of other anionic surfactants .
  • l-15%wt more preferably l-5%wt
  • 15-50%wt more preferably 30-50%wt
  • the other anionic surfactants is a sulphonate.
  • 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.
  • ABS alkyl benzene sulphonate
  • Suitable nonionic surfactants include polyethoxylated fatty alcohols, polyethoxylated fatty acids, polyethoxylated alkyl phenols, amine oxides and ethylene oxide/propylene oxide block copolymers .
  • the total amount of surfactant when present may lie within wide limits.
  • the surfactant will generally 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) and polybutene . 7 -
  • One particularly suitable processing aid is an alkoxylated alcohol. It is preferred that the alkoxylated alcohol is an ethoxylated alcohol . 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.
  • Polymers are an optional ingredient within the formulation of the toilet block. If present preferred polymers 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.
  • the carboxyl group-containing monomers may be polymerized alone or in combination with other ethylenically unsaturated monomers.
  • Preferred polymers are polymers of acrylic or methacrylic acid or maleic anhydride, or a co-polymer of one or more of the same either together or with other monomers. In general, polymers derived largely or wholly from the acidic monomers are preferred.
  • Suitable polymers include polyacrylic acid, polymaleic anhydride and copolymers of either of the aforementioned with ethylene, styrene and methyl vinyl ether. - 8
  • the polymer is crosslinked.
  • Such materials are available from a number of sources including materials available under the tradename CARBOPOL (TM) from B. F. Goodrich Company, the tradename SOKOLAN (TM) from the BASF Corporation and under the tradename POLYGEL (TM) from 3V Sigma.
  • the polymer is suitably present in an amount of from 0.5 to 20% by weight, more preferably from 1 to 5% by weight, most preferably around 2-3% by weight thereof.
  • blocks according to the present invention comprise 0 to 50% by weight of an inert non-polymeric and/or electrolyte filler.
  • blocks Preferably contain 5-50%wt, more preferably 10-30% of filler.
  • 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.
  • Preferred inert, non-polymeric fillers include calcium carbonate.
  • Typical levels of total filler range from 10-40%wt on product in total .
  • the toilet block is an in-cistern blocks
  • 10-30%wt of an ionic filler as the sole filler present to ensure stability and solubility of the block.
  • 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 15%wt of each of calcium carbonate and sodium sulphate .
  • 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.
  • 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 .
  • the most preferred perfume is Green Tank Harder (TM) ex. Givaudan Roure.
  • TM Colanyl Green (TM) ex Hoechst and Dispers Blue (TM) ex BASF.
  • a particularly preferred colouring agent is P. Green (CI 74260 ) .
  • Titanium dioxide is an acceptable whitener.
  • Levels of colouring agents and/or whiteners as typically below 5%wt. For colouring agents levels are typically in the range 0.0001-0. l%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.
  • An optional minor component is a foam-boosting surfactant.
  • Suitable surfactants include amine oxides.
  • compositions in accordance with the invention are formed by an extrusion process in which the mixture of the components which comprises is extruded as a plastified mass through an aperture to form a billet.
  • compositions of the invention are used as free-standing lavatory cleansing blocks, they have a weight from 30 to 150 grams, preferably 40-80 grams, 11 -
  • compositions are:
  • the invention also provides a method of cleaning a lavatory or urinal using a block of a composition in accordance with the invention.
  • Blocks were produced by mixing the raw materials together with the exception of perfume and NaDCCA. The perfume was then added to the mix followed by the addition of NaDCCA. The resulting dough was extruded (the entry part of the extruder being heated) and then cut into blocks of the desired shape.
  • NaDCCA 4 25.0 25.0 25.0 25.0 25.0 25.0 25.0 25.0
  • ABS Alkyl benzene sulphonate NANSA HS 80/LPF (TM) ex Albright & Wilson
  • PAS' Primary alkyl sulphate Empicol LZ-V (TM) ex
  • Polymer is Polygel DB (TM) high molecular weight-water insoluble, partially cross linked acrylic acid polymer ex Sigma 13
  • Example 5 powdered NaI ⁇ 4 is mixed with the NaDCC granules before the NaDCCA granules are added to the remaining ingredients within the formulation.

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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)

Abstract

L'invention concerne un bloc pour W-C comprenant a) un agent de blanchiment ou un précurseur de celui-ci et b) un agent de désactivation à base de ions métaux lourds.
PCT/EP1999/001900 1998-04-09 1999-03-22 Blocs nettoyants pour w-c WO1999053013A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
PL99343344A PL343344A1 (en) 1998-04-09 1999-03-22 Toilet cleaning blocks
HU0102361A HUP0102361A3 (en) 1998-04-09 1999-03-22 Toilet cleaning blocks, its preparation and a method of preventing heating within the toilet block
EP99915683A EP1071741A1 (fr) 1998-04-09 1999-03-22 Blocs nettoyants pour w-c
AU34167/99A AU3416799A (en) 1998-04-09 1999-03-22 Toilet cleaning blocks
CA002320776A CA2320776A1 (fr) 1998-04-09 1999-03-22 Blocs nettoyants pour w-c
BR9909498-3A BR9909498A (pt) 1998-04-09 1999-03-22 Bloco para vasos sanitários, e, processos para impedir o aquecimento térmico dentro de um bloco para vasos sanitários e para fabricar um bloco para vasos sanitários

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP98302784.8 1998-04-09
EP98302784 1998-04-09

Publications (1)

Publication Number Publication Date
WO1999053013A1 true WO1999053013A1 (fr) 1999-10-21

Family

ID=8234771

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1999/001900 WO1999053013A1 (fr) 1998-04-09 1999-03-22 Blocs nettoyants pour w-c

Country Status (9)

Country Link
EP (1) EP1071741A1 (fr)
AR (1) AR018836A1 (fr)
AU (1) AU3416799A (fr)
BR (1) BR9909498A (fr)
CA (1) CA2320776A1 (fr)
CZ (1) CZ20003729A3 (fr)
HU (1) HUP0102361A3 (fr)
PL (1) PL343344A1 (fr)
WO (1) WO1999053013A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1978080A1 (fr) * 2007-03-29 2008-10-08 Bolton Manitoba SpA Composition hygiénisante adhésive pour le nettoyage et/ou la désinfection et/ou parfumer des installations sanitaires

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4249274A (en) * 1979-12-03 1981-02-10 The Procter & Gamble Company Apparatus for sanitizing toilets
US4861511A (en) * 1987-06-26 1989-08-29 Nalco Chemical Company Toilet bowl cleaner and stain-inhibiting composition
EP0341836A2 (fr) * 1988-04-13 1989-11-15 JEYES GROUP plc Blocs de nettoyage pour cabinets d'aisance
EP0619367A1 (fr) * 1993-04-06 1994-10-12 The Procter & Gamble Company Blocs pour toilettes contenant des enzymes
WO1994026863A1 (fr) * 1993-05-14 1994-11-24 Block Drug Company, Inc. Bloc de nettoyage de toilettes
EP0688857A1 (fr) * 1994-06-24 1995-12-27 The Procter & Gamble Company Compositions de blanchiment à base d'hypochlorite
WO1997047721A1 (fr) * 1996-06-12 1997-12-18 Unilever Plc Perfectionnements relatifs aux blocs nettoyants pour w.-c.

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4249274A (en) * 1979-12-03 1981-02-10 The Procter & Gamble Company Apparatus for sanitizing toilets
US4861511A (en) * 1987-06-26 1989-08-29 Nalco Chemical Company Toilet bowl cleaner and stain-inhibiting composition
EP0341836A2 (fr) * 1988-04-13 1989-11-15 JEYES GROUP plc Blocs de nettoyage pour cabinets d'aisance
EP0619367A1 (fr) * 1993-04-06 1994-10-12 The Procter & Gamble Company Blocs pour toilettes contenant des enzymes
WO1994026863A1 (fr) * 1993-05-14 1994-11-24 Block Drug Company, Inc. Bloc de nettoyage de toilettes
EP0688857A1 (fr) * 1994-06-24 1995-12-27 The Procter & Gamble Company Compositions de blanchiment à base d'hypochlorite
WO1997047721A1 (fr) * 1996-06-12 1997-12-18 Unilever Plc Perfectionnements relatifs aux blocs nettoyants pour w.-c.

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1978080A1 (fr) * 2007-03-29 2008-10-08 Bolton Manitoba SpA Composition hygiénisante adhésive pour le nettoyage et/ou la désinfection et/ou parfumer des installations sanitaires

Also Published As

Publication number Publication date
HUP0102361A3 (en) 2002-02-28
PL343344A1 (en) 2001-08-13
BR9909498A (pt) 2000-12-12
AU3416799A (en) 1999-11-01
AR018836A1 (es) 2001-12-12
HUP0102361A2 (hu) 2001-10-28
CA2320776A1 (fr) 1999-10-21
EP1071741A1 (fr) 2001-01-31
CZ20003729A3 (cs) 2001-10-17

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