EP0462643A1 - Lavatory cleansing block - Google Patents

Lavatory cleansing block Download PDF

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Publication number
EP0462643A1
EP0462643A1 EP19910201409 EP91201409A EP0462643A1 EP 0462643 A1 EP0462643 A1 EP 0462643A1 EP 19910201409 EP19910201409 EP 19910201409 EP 91201409 A EP91201409 A EP 91201409A EP 0462643 A1 EP0462643 A1 EP 0462643A1
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EP
European Patent Office
Prior art keywords
weight
block according
lavatory
cleansing block
bleaching agent
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.)
Granted
Application number
EP19910201409
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German (de)
French (fr)
Other versions
EP0462643B1 (en
Inventor
Brian Stuart Joy
George Kerr Rennie
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
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Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Publication of EP0462643A1 publication Critical patent/EP0462643A1/en
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Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/04Water-soluble compounds
    • C11D3/046Salts
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047Detergents in the form of bars or tablets
    • C11D17/0056Lavatory cleansing blocks
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/12Water-insoluble compounds
    • C11D3/1233Carbonates, e.g. calcite or dolomite
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/395Bleaching agents
    • C11D3/3955Organic bleaching agents
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/50Perfumes
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds

Definitions

  • the present invention is concerned with lavatory cleansing blocks and a process for making them. More in particular, it relates to cleansing blocks which are intended for use as a cleansing, sanitizing and deodorizing block contained in a device which is hung below the rim of toilet bowls. The block is thereby activated by the flush water and effects its cleaning and sanitizing action each time the bowl is flushed with flush water from the cistern.
  • These so-called lavatory rim blocks are not in constant contact with water, as distinct from the so-called in-cistern type of cleansing blocks which are constantly immersed in the flush water cistern of lavatory bowls. It will be evident that such blocks will have completely different requirements as to structure, rate of wear, cracking, mushing and swelling properties, foam properties and perfume generation.
  • lavatory rim blocks are known in the art.
  • European patent application 167,210 discloses an extruded lavatory rim block which is free from para-dichloro benzene, comprising 40 to 90 % by weight of an anionic surfactant, 5 to 55 % by weight of an inert or electrolyte filler, and 5 to 15 % by weight of an oily liquid perfume, the weight ratio between the anionic surfactant and the filler, if electrolytic, being greater than 2.
  • EP-A-341836 discloses an extruded lavatory cleansing block with a good sanitising and cleansing effect, which block comprises an anionic surfactant and a chlorinated cuanuric acid derivative.
  • this block also comprises a third essential component being a source of specified metal ions, such as barium chloride, cadmium sulphate and calcium chloride, which component may be environmentally less acceptable.
  • this block is especially designed to be used in the cistern of a lavatory.
  • lavatory rim blocks which comprise: 30 to 80 % by weight of an anionic surfactant; 0 to 50 % by weight of an inert or electrolyte filler; 5 to 50 % by weight of a water-soluble bleaching agent; 5 to 15 % by weight of a hydrophobic structurant.
  • the weight ratio between the anionic surfactant and the filler, if electrolytic, is thereby preferably greater than 2.
  • water-soluble bleaching agents used in accordance with the invention are persulphates such as potassium monopersulphate and active chlorine bleaching agents such as alkali metal salts of dichloro cyanuric acid.
  • the preferred water-soluble bleaching agent is potassium dichlorocyanurate.
  • the bleaching agent is preferably present in an amount of 10 to 25 % by weight.
  • the blocks comprise 5-15 % by weight of a hydrophobic structurant.
  • a hydrophobic structurant This is preferably a liquid oily perfume, of the kind described in the European patent application 167,210. It will be understood that the liquid oily perfume must be stable in the presence of the water-soluble bleaching agent. Suitable oily perfumes can be easily selected by testing them in combination with the water-soluble bleaching agent. Examples of suitable bleach-stable perfumes are Verdeo 898, Bonanza 048 and Ponderosa 431 all ex IFF, and LB 132 ex Quest.
  • the perfume may be partially or totally replaced by another hydrophobic structurant, for example fatty acids or fatty alcohols, typically having 12 to 16 carbon atoms.
  • another hydrophobic structurant for example fatty acids or fatty alcohols, typically having 12 to 16 carbon atoms.
  • the anionic surfactant used in the block should have a relatively low perfume solubility and should only absorb water to optimize the ratio of oily liquid and lamellar phases to solid and inverted hexagonal phases.
  • Preferred anionic surfactants are sodium C9-C14 alkyl benzene sulphonates, sodium C11-C20 olefin sulphonates, sodium C11-C20 alkane sulphonates and sodium long chain C10-C14 alkyl sulphates or mixtures thereof, sodium alkyl benzene sulphonates being particularly preferred as the main surfactant component.
  • nonionic surfactants such as the ethoxylated fatty alcohol nonionics, fatty acid alkanolamides and amine oxides
  • surfactants such as nonionic surfactants such as the ethoxylated fatty alcohol nonionics, fatty acid alkanolamides and amine oxides
  • the filler used in the lavatory rim blocks of the present invention can be an electrolyte, such as sodium sulphate, sodium carbonate and a phosphorous containing sodium salt, e.g. sodium triphosphate, hexametaphospate, pyrophosphate, and orthophosphate.
  • the filer may also be an inert material such as calcite, clay or urea.
  • an electrolyte it is desirable to have a high ratio of surfactant to filler levels in the block, i.e. a high proportion of surfactant and a low proportion of electrolyte. It was found that the anionic surfactant/electrolyte filler weight ratio should be greater than about 2 in order to avoid excessive swelling in use and to provide adequate foam generation and stability. If an inert filler is used, the ratio of surfactant to filler proved to be not critical.
  • the blocks according to the invention can be made by mixing the ingredients to form a dough of suitable consistency which can then be extruded and cut into lengths to form blocks having the desired properties.
  • the lavatory rim blocks formed in accordance with the invention may also comprise non-surfactant nonionic polymeric materials such as polyethylene glycols, and minor ingredients such as dyes, germicides, fungicides and opacifiers, whereby the compatibility of such ingredients with the water-soluble bleaching agent must be observed.
  • non-surfactant nonionic polymeric materials such as polyethylene glycols
  • minor ingredients such as dyes, germicides, fungicides and opacifiers
  • Lavatory rim blocks were prepared from the ingredients listed in the following Table, wherein the amounts are given as % by weight. The ingredients were mixed to form a dough which was subsequently extruded in a conventional soap-extrusion apparatus and finally cut into lengths of approximately 8 cm. The obtained blocks had a weight of about 50 g.
  • the stability of the bleaching agent in the rim blocks was tested by placing them in a conventional rim block cage inside a lavatory bowl and flushing the toilet according to a standard pattern, whereafter the concentration of bleaching agent in the flush water was determined as well as the concentration of remaining bleaching agent in the block. It was found that the bleaching agent remained stable inside the blocks for some weeks, and that they continued to deliver KDCCA to the flush water for at least three weeks.

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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)

Abstract

A lavatory rim cleansing block comprising: 30 to 80 % by weight of an anionic surfactant; 0 to 50 % by weight of an inert or electrolyte filler; 5 to 50 % by weight of a water-soluble bleaching agent; 5 to 15 % by weight of a hydrophobic structurant, preferably an oily liquid perfume. The weight ratio between the anionic surfactant and the filler, if electrolytic, is preferably greater than 2 and the preferred water-soluble bleaching agent is potassium dichloro cyanurate.

Description

  • The present invention is concerned with lavatory cleansing blocks and a process for making them. More in particular, it relates to cleansing blocks which are intended for use as a cleansing, sanitizing and deodorizing block contained in a device which is hung below the rim of toilet bowls. The block is thereby activated by the flush water and effects its cleaning and sanitizing action each time the bowl is flushed with flush water from the cistern. These so-called lavatory rim blocks are not in constant contact with water, as distinct from the so-called in-cistern type of cleansing blocks which are constantly immersed in the flush water cistern of lavatory bowls. It will be evident that such blocks will have completely different requirements as to structure, rate of wear, cracking, mushing and swelling properties, foam properties and perfume generation.
  • Such lavatory rim blocks are known in the art.For instance, the European patent application 167,210 discloses an extruded lavatory rim block which is free from para-dichloro benzene, comprising 40 to 90 % by weight of an anionic surfactant, 5 to 55 % by weight of an inert or electrolyte filler, and 5 to 15 % by weight of an oily liquid perfume, the weight ratio between the anionic surfactant and the filler, if electrolytic, being greater than 2.
  • Whereas such blocks have good cleansing properties, they have a very limited sanitizing effect on the microorganisms which are always present in the toilet bowl.
  • EP-A-341836 (JEYES) discloses an extruded lavatory cleansing block with a good sanitising and cleansing effect, which block comprises an anionic surfactant and a chlorinated cuanuric acid derivative. However, this block also comprises a third essential component being a source of specified metal ions, such as barium chloride, cadmium sulphate and calcium chloride, which component may be environmentally less acceptable. Furthermore, this block is especially designed to be used in the cistern of a lavatory.
  • It is an object of the present invention to provide a lavatory rim block which possesses a good cleansing, sanitizing and perfume generating activity. Moreover, the blocks must be stable for a prolonged period under the humid conditions of a toilet bowl.
  • It has now been found that these and other objects may be achieved by means of the lavatory rim blocks according to the invention, which comprise: 30 to 80 % by weight of an anionic surfactant; 0 to 50 % by weight of an inert or electrolyte filler; 5 to 50 % by weight of a water-soluble bleaching agent; 5 to 15 % by weight of a hydrophobic structurant. The weight ratio between the anionic surfactant and the filler, if electrolytic, is thereby preferably greater than 2.
  • Surprisingly, the stability of the water-soluble bleaching agent inside the lavatory block proved to be very good, while at the same time the delivery of bleaching agent to the flush water was more than satisfactory and constant over a prolonged period.
  • Examples of water-soluble bleaching agents used in accordance with the invention are persulphates such as potassium monopersulphate and active chlorine bleaching agents such as alkali metal salts of dichloro cyanuric acid. The preferred water-soluble bleaching agent is potassium dichlorocyanurate. The bleaching agent is preferably present in an amount of 10 to 25 % by weight.
  • The blocks comprise 5-15 % by weight of a hydrophobic structurant. This is preferably a liquid oily perfume, of the kind described in the European patent application 167,210. It will be understood that the liquid oily perfume must be stable in the presence of the water-soluble bleaching agent. Suitable oily perfumes can be easily selected by testing them in combination with the water-soluble bleaching agent. Examples of suitable bleach-stable perfumes are Verdeo 898, Bonanza 048 and Ponderosa 431 all ex IFF, and LB 132 ex Quest.
  • However, the perfume may be partially or totally replaced by another hydrophobic structurant, for example fatty acids or fatty alcohols, typically having 12 to 16 carbon atoms.
  • The anionic surfactants which may be used in the present invention include for example alkali metal salts of alkyl substituted benzene sulphonates, alkali metal long chain alkyl sulphates, alkali metal ether sulphates derived from long chain alcohols and alkyl phenols, alkali metal alkane sulphonates, alkali metal olefin sulphonates and alkali metal sulphosuccinates, whereby the sodium salts are generally preferred. Most favoured are sodium alkyl benzene sulphonates.
  • Desirably, the anionic surfactant used in the block should have a relatively low perfume solubility and should only absorb water to optimize the ratio of oily liquid and lamellar phases to solid and inverted hexagonal phases.
  • Preferred anionic surfactants are sodium C₉-C₁₄ alkyl benzene sulphonates, sodium C₁₁-C₂₀ olefin sulphonates, sodium C₁₁-C₂₀ alkane sulphonates and sodium long chain C₁₀-C₁₄ alkyl sulphates or mixtures thereof, sodium alkyl benzene sulphonates being particularly preferred as the main surfactant component.
  • In addition, other types of surfactants, such as nonionic surfactants such as the ethoxylated fatty alcohol nonionics, fatty acid alkanolamides and amine oxides, may be incorporated as desired. However, they should not be present in amounts exceeding 20 % by weight, preferably 10 % by weight, because they could easily adversely affect the foaming properties and the rate of wear of the blocks.
  • The filler used in the lavatory rim blocks of the present invention can be an electrolyte, such as sodium sulphate, sodium carbonate and a phosphorous containing sodium salt, e.g. sodium triphosphate, hexametaphospate, pyrophosphate, and orthophosphate. The filer may also be an inert material such as calcite, clay or urea.
  • It was found that a high electrolyte content tends to suppress the solubility of the block to such an extent that there is insufficient active present in the bowl after flushing to generate a stable foam. Hence, if an electrolyte is used as the filler, it is desirable to have a high ratio of surfactant to filler levels in the block, i.e. a high proportion of surfactant and a low proportion of electrolyte. It was found that the anionic surfactant/electrolyte filler weight ratio should be greater than about 2 in order to avoid excessive swelling in use and to provide adequate foam generation and stability. If an inert filler is used, the ratio of surfactant to filler proved to be not critical.
  • The blocks according to the invention can be made by mixing the ingredients to form a dough of suitable consistency which can then be extruded and cut into lengths to form blocks having the desired properties.
  • The extrusion process can be suitably carried out using simple conventional extrusion equipment such as normally used for manufacturing soap bars.
  • The lavatory rim blocks formed in accordance with the invention may also comprise non-surfactant nonionic polymeric materials such as polyethylene glycols, and minor ingredients such as dyes, germicides, fungicides and opacifiers, whereby the compatibility of such ingredients with the water-soluble bleaching agent must be observed.
  • The invention will now be illustrated by means of the following non-limiting examples.
  • EXAMPLES 1-3
  • Lavatory rim blocks were prepared from the ingredients listed in the following Table, wherein the amounts are given as % by weight. The ingredients were mixed to form a dough which was subsequently extruded in a conventional soap-extrusion apparatus and finally cut into lengths of approximately 8 cm. The obtained blocks had a weight of about 50 g.
    Figure imgb0001
  • The stability of the bleaching agent in the rim blocks was tested by placing them in a conventional rim block cage inside a lavatory bowl and flushing the toilet according to a standard pattern, whereafter the concentration of bleaching agent in the flush water was determined as well as the concentration of remaining bleaching agent in the block. It was found that the bleaching agent remained stable inside the blocks for some weeks, and that they continued to deliver KDCCA to the flush water for at least three weeks.

Claims (12)

  1. A lavatory rim cleansing block comprising:
    30 to 80 % by weight of an anionic surfactant;
    0 to 50 % by weight of an inert or electrolyte filler;
    5 to 50 % by weight of a water-soluble bleaching agent;
    5 to 15 % by weight of a hydrophobic structurant.
  2. A lavatory cleansing block according to Claim 1, wherein the hydrophobic structurant is a liquid oily perfume.
  3. A lavatory cleansing block according to any one of the preceding Claims wherein the weight ratio between the anionic surfactant and the filler, if electrolytic, is greater than 2.
  4. A lavatory cleansing block according to any one of the preceding Claims comprising 10 to 25 % by weight of the water-soluble bleaching agent.
  5. A lavatory cleansing block according to any one of the preceding Claims wherein the water-soluble bleaching agent is an active chlorine bleaching agent.
  6. A lavatory cleansing block according to any one of the preceding Claims wherein the water-soluble bleaching agent is an alkali metal salt of dichloro cyanuric acid, preferably potassium dichloro cyanurate.
  7. A lavatory cleansing block according to any one of the preceding Claims comprising 50 to 80 % by weight of an anionic surfactant.
  8. A lavatory cleansing block according to any one of the preceding Claims wherein the anionic surfactant comprises C₉-C₁₄ alkylbenzene sulphonate.
  9. A lavatory cleansing block according to any one of the preceding Claims further comprising a nonionic surfactant in an amount of less than 10 % by weight.
  10. A lavatory cleansing block according to any one of the preceding Claims comprising 10 to 45 % by weight of an inert or electrolyte filler.
  11. A lavatory cleansing block according to any one of the preceding Claims comprising 7 to 12 % by weight of the oily liquid perfume.
  12. Process for preparing a lavatory block according to any one of the preceding Claims, whereby the ingredients are mixed to form a dough, which is then extruded and cut into blocks of suitable lengths.
EP91201409A 1990-06-18 1991-06-07 Lavatory cleansing block Revoked EP0462643B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9013539 1990-06-18
GB909013539A GB9013539D0 (en) 1990-06-18 1990-06-18 Lavatory cleansing block

Publications (2)

Publication Number Publication Date
EP0462643A1 true EP0462643A1 (en) 1991-12-27
EP0462643B1 EP0462643B1 (en) 1994-10-26

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ID=10677791

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EP91201409A Revoked EP0462643B1 (en) 1990-06-18 1991-06-07 Lavatory cleansing block

Country Status (9)

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EP (1) EP0462643B1 (en)
JP (1) JPH0765080B2 (en)
AU (1) AU628749B2 (en)
BR (1) BR9102494A (en)
CA (1) CA2044490C (en)
DE (1) DE69104780T2 (en)
ES (1) ES2063436T3 (en)
GB (1) GB9013539D0 (en)
ZA (1) ZA914661B (en)

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992018605A1 (en) * 1991-04-22 1992-10-29 Jeyes Limited Lavatory cleansing blocks
GB2273106A (en) * 1992-12-03 1994-06-08 Jeyes Group Plc Cleansing block
EP0619367A1 (en) * 1993-04-06 1994-10-12 The Procter & Gamble Company Lavatory blocks containing enzymes
EP0698080A1 (en) * 1993-05-14 1996-02-28 Block Drug Company Inc. Lavatory cleaning block
GB2300423A (en) * 1995-03-27 1996-11-06 Jeyes Group Plc Lavatory cleansing
WO1997043398A1 (en) * 1996-05-17 1997-11-20 S.C. Johnson & Son, Inc. Toilet cleansing block
WO1997044435A1 (en) * 1996-05-17 1997-11-27 S. C. Johnson & Son, Inc. Toilet cleansing block
WO1997047721A1 (en) * 1996-06-12 1997-12-18 Unilever Plc Improvements relating to lavatory cleaning blocks
US5817611A (en) * 1992-12-03 1998-10-06 Jeyes Group, Plc Lavatory cleansing blocks
WO1998047998A1 (en) * 1997-04-24 1998-10-29 S. C. Johnson & Son, Inc. Chlorinated in-tank toilet cleansing block
EP0879877A1 (en) * 1997-05-22 1998-11-25 Buck-Chemie GmbH & Co. Toilet cleaning block releasing active chlorine
WO1999040169A1 (en) * 1998-02-04 1999-08-12 Unilever Plc Lavatory cleansing composition
WO2003068902A1 (en) * 2002-02-11 2003-08-21 Jeyes Group Limited Cleansing blocks
WO2006056301A1 (en) 2004-11-23 2006-06-01 Buck-Chemie Gmbh Adhesive agent for sanitary cleaning and deodorization
WO2008100393A1 (en) * 2007-02-12 2008-08-21 S. C. Johnson & Son, Inc. Self-sticking disintegrating block for toilet or urinal
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
WO2016138186A1 (en) 2015-02-24 2016-09-01 Takasago International Corporation Enhanced perfume compositions
EP3211064A1 (en) 2016-02-24 2017-08-30 Takasago International Corporation Stimulating agent
WO2017146182A2 (en) 2016-02-24 2017-08-31 Takasago International Corporation Household product delivering warming and/or tingling sensations
WO2017146181A2 (en) 2016-02-24 2017-08-31 Takasago International Corporation Household product delivering cooling sensations

Families Citing this family (1)

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Publication number Priority date Publication date Assignee Title
DE102010043848A1 (en) * 2010-11-12 2012-05-16 Henkel Ag & Co. Kgaa Anionic surfactant spherical toilet stones

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EP0014979A1 (en) * 1979-02-23 1980-09-03 Henkel Kommanditgesellschaft auf Aktien Process for producing rinsing blocks for the hygiene of water-closets
EP0101402A1 (en) * 1982-07-07 1984-02-22 Henkel Kommanditgesellschaft auf Aktien Cleaning and disinfecting tablet for the flush tanks of flush toilets
EP0167210A2 (en) * 1984-07-06 1986-01-08 Unilever N.V. Para-dichlorobenzene-free lavatory cleansing blocks
EP0341836A2 (en) * 1988-04-13 1989-11-15 JEYES GROUP plc Lavatory cleansing blocks

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NL7902174A (en) * 1978-03-21 1979-09-25 Jeyes Group Ltd TOILET CLEANING BLOCKS.
GB2178442B (en) * 1985-06-14 1988-12-21 Jeyes Group Ltd Lavatory cleansing compositions

Patent Citations (4)

* Cited by examiner, † Cited by third party
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
EP0101402A1 (en) * 1982-07-07 1984-02-22 Henkel Kommanditgesellschaft auf Aktien Cleaning and disinfecting tablet for the flush tanks of flush toilets
EP0167210A2 (en) * 1984-07-06 1986-01-08 Unilever N.V. Para-dichlorobenzene-free lavatory cleansing blocks
EP0341836A2 (en) * 1988-04-13 1989-11-15 JEYES GROUP plc Lavatory cleansing blocks

Cited By (42)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2270084A (en) * 1991-04-22 1994-03-02 Jeyes Ltd Lavatory cleansing blocks
GB2270084B (en) * 1991-04-22 1995-05-10 Jeyes Ltd Lavatory cleansing blocks
WO1992018605A1 (en) * 1991-04-22 1992-10-29 Jeyes Limited Lavatory cleansing blocks
US5817611A (en) * 1992-12-03 1998-10-06 Jeyes Group, Plc Lavatory cleansing blocks
GB2273106A (en) * 1992-12-03 1994-06-08 Jeyes Group Plc Cleansing block
WO1994012612A1 (en) * 1992-12-03 1994-06-09 Jeyes Group Plc Lavatory cleansing blocks
GB2288814A (en) * 1992-12-03 1995-11-01 Jeyes Group Plc Lavatory cleansing blocks
AU678416B2 (en) * 1992-12-03 1997-05-29 Jeyes Group Limited Lavatory cleansing blocks
EP0619367A1 (en) * 1993-04-06 1994-10-12 The Procter & Gamble Company Lavatory blocks containing enzymes
EP0698080A1 (en) * 1993-05-14 1996-02-28 Block Drug Company Inc. Lavatory cleaning block
GB2300423A (en) * 1995-03-27 1996-11-06 Jeyes Group Plc Lavatory cleansing
US6294510B1 (en) 1995-03-27 2001-09-25 Jeyes Group Limited Halogen-releasing composition for lavatory cleansing
AU714770B2 (en) * 1996-05-17 2000-01-13 S.C. Johnson & Son, Inc. Toilet cleansing block
US5990061A (en) * 1996-05-17 1999-11-23 S. C. Johnson & Son, Inc. Toilet cleansing block
WO1997043398A1 (en) * 1996-05-17 1997-11-20 S.C. Johnson & Son, Inc. Toilet cleansing block
AU717373B2 (en) * 1996-05-17 2000-03-23 S.C. Johnson & Son, Inc. Toilet cleansing block
WO1997044435A1 (en) * 1996-05-17 1997-11-27 S. C. Johnson & Son, Inc. Toilet cleansing block
US5945390A (en) * 1996-05-17 1999-08-31 S. C. Johnson & Son, Inc. Toilet cleansing block
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Also Published As

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DE69104780D1 (en) 1994-12-01
JPH04252300A (en) 1992-09-08
ZA914661B (en) 1993-02-24
BR9102494A (en) 1992-01-21
CA2044490C (en) 1996-12-17
AU628749B2 (en) 1992-09-17
JPH0765080B2 (en) 1995-07-12
GB9013539D0 (en) 1990-08-08
CA2044490A1 (en) 1991-12-19
ES2063436T3 (en) 1995-01-01
DE69104780T2 (en) 1995-03-02
AU7838691A (en) 1991-12-19
EP0462643B1 (en) 1994-10-26

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