EP1554368A1 - Schmutzabweisendes reinigungsmittel - Google Patents

Schmutzabweisendes reinigungsmittel

Info

Publication number
EP1554368A1
EP1554368A1 EP03773307A EP03773307A EP1554368A1 EP 1554368 A1 EP1554368 A1 EP 1554368A1 EP 03773307 A EP03773307 A EP 03773307A EP 03773307 A EP03773307 A EP 03773307A EP 1554368 A1 EP1554368 A1 EP 1554368A1
Authority
EP
European Patent Office
Prior art keywords
carbon atoms
group
detergent composition
soiling
hydrocarbon group
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
EP03773307A
Other languages
English (en)
French (fr)
Other versions
EP1554368B2 (de
EP1554368B1 (de
Inventor
Mari Johnson Professional Kk Yagi
Mitsuo Johnson Professional Kk Sado
Aki Johnson Professional Kk Abe
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.)
Diversey Inc
Original Assignee
JohnsonDiversey Inc
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
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=32232634&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP1554368(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by JohnsonDiversey Inc filed Critical JohnsonDiversey Inc
Publication of EP1554368A1 publication Critical patent/EP1554368A1/de
Application granted granted Critical
Publication of EP1554368B1 publication Critical patent/EP1554368B1/de
Publication of EP1554368B2 publication Critical patent/EP1554368B2/de
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
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/373—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones
    • C11D3/3742—Nitrogen containing silicones
    • 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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0036—Soil deposition preventing compositions; Antiredeposition 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
    • C11D3/43—Solvents
    • 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
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces

Definitions

  • the present invention relates to an anti-soiling detergent composition that possesses excellent storage stability and has a sustained anti-soiling effect on cleaned surfaces in addition to exhibiting superior detergency.
  • the soil in baths comprises proteins and other nitrogenous compounds, fatty acid metal salts, or the like
  • the soil in washstands comprises fatty acid metal salts and the like
  • the soil in restrooms comprises urolith deposits, soil that is based on fecal matter, urine, and other types of excrement, and the like.
  • Examples of disclosed detergents that combine an anti-soiling effect and contain such organopolysiloxanes include compositions for bathtub cleaning that contain amino-modified organopolysiloxanes and nonionic surfactants, inhibit redeposition of water-formed deposits, and have protective action on bathtub materials (refer, for example, to Japanese Patent Application Laid-open No. S51-83608), as well as detergent compositions that contain specific organopolysiloxane and provide delustering and surface protection to bath fixtures (refer, for example, to Japanese Patent Application Laid-open No. H3-197596).
  • a detergent composition for the desoiling and antibacterial cleaning of hard surfaces that contains specific cationic surfactants, cation-based bactericidal agents, and hydrophilic organopolysiloxanes and has an anti-soiling effect and antibacterial action (refer, for example, to Japanese Patent Application Laid-open No. 2000-198999).
  • Japanese Patent Application Laid-open Nos. S51-83608 and H3-197596 disclose detergent compositions that have excellent anti-soiling effects and detergency with respect to water- formed deposits and soil, but there is no mention of an anti-soiling effect on water stains, nor is there any disclosure made concerning sustained anti-soiling effects or storage stability, which are believed to be important in practical terms.
  • Japanese Patent Application Laid-open No. 2000-198999 discloses a detergent composition that has an excellent anti- soiling effect on water stains.
  • An object of the present invention is to provide a detergent composition that combines an excellent anti-soiling effect on cleaned surfaces, preserves this anti-soiling effect, and exhibits excellent storage stability in addition to having excellent detergency.
  • the object is to provide an anti-soiling detergent composition that can be used to advantage for cleaning and anti-soiling of hard surfaces such as those of plastic, stainless steel, porcelain, tile, glass, ceramic, granite/terrazzo, and other natural stone materials in restrooms, washstands, baths, and other damp locations; particularly, for cleaning and anti- soiling of water stains on hard surfaces such as those of tile, glass, and ceramic in restroom and washstands.
  • an anti-soiling detergent composition that has an excellent anti-soiling effect on cleaned surfaces, preserves this anti-soiling effect, and exhibits excellent storage stability in addition to having excellent detergency can be obtained by combining a polyetheramide-modified organopolysiloxane and/or amino-modified organopolysiloxane, a surfactant, a metal chelating agent, and water.
  • the present invention was perfected on the basis of this discovery.
  • an anti-soiling detergent composition which comprises an anti-soiling detergent composition which comprises:
  • the anti-soiling detergent composition of the invention may also contain (E) 0.01 to 5 mass% of a thickener in addition to components (A) to (D).
  • the anti-soiling detergent composition of the invention may further contain (F) 0.1 to 20 mass% of a water-soluble solvent in addition to the above components.
  • the anti-soiling detergent composition of the present invention contains components (A), (B), (C), and (D) as essential ingredients.
  • the component (A) used in the present invention is a polyetheramide-modified organopolysiloxane and/or amino-modified organopolysiloxane, and it is added with the purpose of endowing the cleaned surface with an anti-soiling effect.
  • the polyetheramide-modified organopolysiloxane of component (A) used in the present invention may be a organopolysiloxane having polyoxyethylene groups and amido groups expressed by average compositional formula (1)
  • a and d are zero or positive numbers
  • b and c are positive numbers such that 1.9 ⁇ a + b + c + d ⁇ 2.2
  • R 1 is a hydrogen atom, a hydroxyl group, or a substituted or unsubstituted monovalent hydrocarbon group with 1 to 6 carbon atoms.
  • Such monovalent hydrocarbon groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, and other alkyl groups; phenyl, tolyl, xylyl, and other aryl groups; benzyl, phenethyl, and other aralkyl groups; and 3-chloropropyl, 3,3,3-trifluoropropyl, and other halo-substituted alkyl groups.
  • R 2 is a monovalent hydrocarbon group with 1 to 6 carbon atoms, specific examples of which include methyl, ethyl, propyl, butyl, pentyl, hexyl, vinyl, and phenyl groups.
  • Q 1 is a divalent organic group having an amido group expressed by general formula (2) or (3)
  • R and R are divalent hydrocarbon groups with 2 to 18 carbon atoms, specific examples of which include ethylene, propylene, butylene, isobutylene, pentamethylene, octamethylene, decamethylene, dodecamethylene, and cyclohexyl groups.
  • R 4 and R 6 are hydrogen atoms or monovalent hydrocarbon groups with 1 to 6 carbon atoms, specific examples of which include methyl, ethyl, propyl, butyl, pentyl, hexyl, and other alkyl groups; phenyl, tolyl, xylyl, and other aryl groups; benzyl, phenethyl, and other aralkyl groups; and 3-chloropropyl, 3,3,3-trifluoropropyl, and other halo-substituted alkyl groups.
  • X is a monovalent organic group expressed by general formula (4)
  • R 7 is a divalent hydrocarbon group with 2 to 18 carbon atoms, specific examples of which include ethylene, propylene, butylene, isobutylene, pentamethylene, octamethylene, decamethylene, dodecamethylene, and cyclohexyl groups.
  • R 8 is a divalent hydrocarbon group with 3 to 10 carbon atoms, specific examples of which include propylene, isopropylene, butylene, and isobutylene groups.
  • Y is a group selected from among hydrogen atoms, alkyl groups, acyl groups, and isocyanic groups, examples of which include methyl, ethyl, propyl, acetyl, and propionyl groups.
  • Q is a monovalent organic group having a polyoxyalkylene group expressed by general formula (5) -R 9 iO j -(C 2 H 4 O) k -(R 10 O) m -Z (5) where / andj are each 0 or 1 ; k is a positive integer of 1 or greater; m is zero or a positive number of 1 or greater; and R 9 is a divalent hydrocarbon group with 2 to 18 carbon atoms, specific examples of which include ethylene, propylene, butylene, isobutylene, pentamethylene, octamethylene, decamethylene, dodecamethylene, and cyclohexyl groups.
  • R 10 is a divalent hydrocarbon group with 3 to 10 carbon atoms, specific examples of which include propylene, isopropylene, butylene, and isobutylene groups.
  • Z is a group selected from among hydrogen atoms, alkyl groups, acyl groups, and isocyanic groups, examples of which include methyl, ethyl, propyl, acetyl, and propionyl groups.
  • the molecular structure of the polyetheramide-modified organopolysiloxane maybe not only linear but also branched, cyclic, or reticulated.
  • the polyetheramide-modified organopolysiloxane having such amido groups and polyoxyethylene groups may, for example, be a compound expressed by the following general formula.
  • R 11 is -(CH 2 ) 3 NHCO(CH 2 )qO(CH 2 CH 2 O) r (CH 2 ) s H, where n is 10 to 1000, p is 1 to 100, q is 1 to 100, r is 2 to 20, and s is 0 to 20.
  • R 12 is -JCH 2 ) 3 NH(CH 2 ) 2 NHCO(CH 2 ) w H
  • R 13 is -(CH 2 ) 3 O(CH 2 CH 2 O) x (CH 2 CHCH 3 O) y (CH 2 ) z H
  • t is 10 to 1000
  • u is 1 to 100
  • v is 1 to 100
  • w is 1 to 20
  • x is 2 to 20
  • y 0 to 20
  • z is 0 to 20.
  • R cl is -(CH 2 ) 3 NHCO(CH 2 ) m4 O m5 (CH 2 CH 2 O) m6 (CH 2 CHCH 3 O) m7 (CH 2 ) m8 H;
  • R c2 is -(CH 2 ) 3 ⁇ (CH 2 CH 2 O) m 9(CH 2 CHCH 3 O) m ⁇ o(CH 2 ) n ⁇ ⁇ 1 D 1 ;
  • E 1 and E 2 which maybe the same or different, are R cl , R c2 , -OH, or -(CH 2 ) p ⁇ H, and preferably -CH 3 ;
  • D 1 is -H or -COCH 3 ;
  • ml is 10 to 1000;
  • m2 is 1 to 100;
  • m3 is 0 to 100;
  • m4 is 1 to 100;
  • m5 is 0 or 1;
  • m6 is 0 to 20;
  • m7 is
  • R c3 is -(CH 2 ) 3 NH(CH 2 ) 2 NHCO(CH 2 ) m ⁇ 5 O m t 6 (CH 2 CH 2 O) ml7 (CH 2 CHCH 3 O) ml 8 (CH 2 ) ml9 H;
  • R c4 is -(CH 2 ) 3 O(CH 2 CH 3 O) m2 o(CH 2 CHCH 3 O) m2 ⁇ (CH 2 ) m22 D 2 ;
  • E 3 and E 4 which maybe the same or different, are R c3 , R c4 , -OH, or -(CH 2 ) p2 H, and preferably -CH 3 ;
  • D 2 is -H or -COCH 3 ;
  • ml2 is 10 to 1000;
  • ml3 is 1 to 100;
  • ml4 is 0 to 100;
  • ml5 is 1 to 100;
  • ml6 is 0 or 1;
  • G 2 is (CH 2 ) 3 NH(CH 2 ) 2 NHCO(CH 2 ) 3 O(CH 2 CH 2 O) ⁇ oC 12 H 25 .) [Chemical Formula 11]
  • G 3 is (CH 2 ) 3 O(CH 2 CH 2 O) 10 (CH 2 CHCH 3 O) ⁇ oH
  • G 4 is (CH 2 ) 3 NHCO(CH 2 ) 3 O(CH 2 CH 2 O) 6 C 10 H 21 .
  • the polyetheramide-modified organopolysiloxane of component (A) used in the present invention may also be a organopolysiloxane having an amino group, polyoxyethylene group, and amido group expressed by average compositional formula (6)
  • a and d are zeros or positive numbers; b, c, and el are positive numbers such that 1.9 ⁇ a + b + c + d + el ⁇ 2.2; and R 1 is a hydrogen atom, a hydroxyl group, or a substituted or unsubstituted monovalent hydrocarbon group with 1 to 6 carbon atoms.
  • Such monovalent hydrocarbon groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, and other alkyl groups; phenyl, tolyl, xylyl, and other aryl groups; benzyl, phenethyl, and other aralkyl groups; and 3-chloropropyl, 3,3,3-trifluoropropyl, and other halo-substituted alkyl groups.
  • R 2 is a monovalent hydrocarbon group with 1 to 6 carbon atoms, specific examples of which include methyl, ethyl, propyl, butyl, pentyl, hexyl, vinyl, and phenyl groups.
  • Q 1 is a divalent organic group having an amido group expressed by general formula (2) or (3)
  • R 3 and R 5 are divalent hydrocarbon groups with 2 to 18 carbon atoms, specific examples of which include ethylene, propylene, butylene, isobutylene, pentamethylene, octamethylene, decamethylene, dodecamethylene, and cyclohexyl groups.
  • R 4 and R 6 are hydrogen atoms or monovalent hydrocarbon groups with 1 to 6 carbon atoms, specific examples of which include methyl, ethyl, propyl, butyl, pentyl, hexyl, and other alkyl groups; phenyl, tolyl, xylyl, and other aryl groups; benzyl, phenethyl, and other aralkyl groups; and 3-chloropropyl, 3,3,3-trifluoropropyl, and other halo-substituted alkyl groups.
  • X is a monovalent organic group expressed by general formula (4)
  • R 7 is a divalent hydrocarbon group with 2 to 18 carbon atoms, specific examples of which include ethylene, propylene, butylene, isobutylene, pentamethylene, octamethylene, decamethylene, dodecamethylene, and cyclohexyl groups.
  • R 8 is a divalent hydrocarbon group with 3 to 10 carbon atoms, specific examples of which include propylene, isopropylene, butylene, and isobutylene groups.
  • Y is a group selected from among hydrogen atoms, alkyl groups, acyl groups, and isocyanic groups, examples of which include methyl, ethyl, propyl acetyl, and propionyl groups.
  • Q is a monovalent organic group having a polyoxyalkylene group expressed by general formula (5)
  • R 9 is a divalent hydrocarbon group with 2 to 18 carbon atoms, specific examples of which include ethylene, propylene, butylene, isobutylene, pentamethylene, octamethylene, decamethylene, dodecamethylene, and cyclohexyl groups
  • R 10 is a divalent hydrocarbon group with 3 to 10 carbon atoms, specific examples of which include propylene, isopropylene, butylene, and isobutylene groups
  • Z is a group selected from among hydrogen atoms, alkyl groups, acyl groups, and isocyanic groups, examples of which include methyl, ethyl, propyl, acetyl, and propionyl groups.
  • the total amount of the primary and secondary amino groups of general formula (7) or (8) contained in the polyetheramide-modified organopolysiloxane molecules is preferably within a range of 0.15 to 0.45 mass%.
  • the anti-soiling effect has inferior sustainability because of the poor adsorption of the polyetheramide-modified organopolysiloxane on the cleaned surfaces, whereas the composition has inferior storage stability when the content exceeds 0.45 mass%.
  • the molecular structure of the polyetheramide-modified organopolysiloxane may be not only linear but also branched, cyclic, or reticulated.
  • the polyetheramide-modified organopolysiloxane having such amido groups, polyoxyethylene groups, and amino groups may, for example, be a compound expressed by the following general formula.
  • R 14 is -(CH 2 ) 3 O(CH 2 CH 2 O) n5 (CH 2 CHCH 3 O)n 6 (CH 2 ) n7 D 3 ;
  • R 15 is -(CH 2 ) 3 NH 2 ;
  • R 16 is -CCH 2 ) 3 NHCO(CH 2 ) n8 O n9 (CH 2 CH 2 O) nl o(CH 2 CHCH 3 O) n ⁇ (CH 2 ) n ⁇ 2 H;
  • E 5 and E 6 which may be the same or different, are R 14 , R 15 , R 16 , -OH, or - ⁇ CH 2 ) p3 H, and preferably -CH 3 ;
  • D 3 is -H or -COCH 3 ;
  • nl is 10 to 1000;
  • n2 is 0 to 100;
  • n3 is 1 to 100;
  • n4 is 1 to 100;
  • n5 is 2 or 20;
  • n6 is
  • R 17 is -(CH 2 ) 3 O(CH 2 CH 2 O)ni 7 (CH 2 CHCH 3 O)ni 8 (CH 2 )ni9D 4 ;
  • R 18 is -(CH 2 ) 3 NH(CH 2 ) 2 NH 2 ;
  • R 19 is -(CH 2 ) 3 NH(CH 2 ) 2 NHCO(CH 2 ) n2 oO n2 i(CH 2 CH 2 O) n22 (CH 2 CHCH 3 O)n 3 (CH 2 ) n24 H;
  • E 7 and E 8 which may be the same or different, are R 17 , R 18 , R 19 , -OH, or -(CH 2 ) p4 H, and preferably -CH 3 ;
  • D 4 is -H or -COCH 3 ;
  • nl3 is 10 to 1000;
  • nl4 is 0 to 100;
  • nl5 is 1 to 100;
  • nl ⁇ is l
  • G 17 is -(CH 2 ) 3 O(CH 2 CH 2 O) ⁇ 0 C ⁇ 0 H 21
  • G 18 is -(CH 2 ) 3 NH(CH 2 ) 2 NH 2
  • G 19 is -(CH 2 ) 3 NH(CH 2 ) 2 NHCOCH 2 O(CH 2 CH 2 O) 4 CioH 21 .
  • the amino-modified organopolysiloxane of component (A) used in the present invention is commonly known as amino-modified organopolysiloxane, which is commercially available. It is possible, for example, to use an amino-modified product of a organopolysiloxane in which some of the methyl groups in the polydimethylsiloxane are substituted by at least one type of group selected from organic groups having amino groups or substituted amino groups, such as aminomethyl, aminoethyl, aminopropyl, aminobutyl, and other aminoalkyl groups, as well as aminoethyl-substituted aminopropyl and other aminoalkyl-substituted aminoalkyl groups (other substituents may also be contained).
  • R' and R" are divalent hydrocarbon groups with 1 to 10 carbon atoms, al is zero or a positive number of 1 or greater, and bl is a positive number of 1 or greater.
  • the same groups as those described above can be cited as examples of the divalent hydrocarbon groups with 1 to 10 carbon atoms.
  • Using a polyetheramide-modified organopolysiloxane for component (A) is more preferred from the standpoint of storage stability.
  • the admixed amount of component (A) is selected from the range of 0.05 to
  • component (A) is preferably within a range of 0.1 to 8 mass% because of considerations related to the anti-soiling effect and storage stability, and even more preferably within a range of 0.1 to 5 mass% because of considerations related to economic efficiency.
  • Component (A) may be used singly or as a combination of two or more ingredients.
  • the surfactant of component (B) used in the present invention is admixed with the purpose of removing the soil adhered to the cleaned surface and solubilizing the polyetheramide-modified organopolysiloxane and/or amino-modified organopolysiloxane, which is component (A).
  • At least one type of surfactant selected from among nonionic surfactants, amphoteric surfactants, and cationic surfactants is used as the surfactant of component (B) because of considerations related to the anti-soiling effect, which is the effect possessed by component (A).
  • nonionic surfactants examples include polyoxyalkylene alkyl ethers, polyoxyalkylene alkenyl ethers, polyoxyalkylene alkyl phenyl ethers, alkyl polyglucosides, fatty acid polyglycerine esters, fatty acid sugar esters, and fatty acid alkanolamides.
  • polyoxyalkylene alkyl ethers, alkyl polyglucosides, and fatty acid alkanolamides are preferred among these nonionic surfactants because of considerations related to detergency, and polyoxyalkylene alkyl ethers and alkyl polyglucosides are even more preferred because of considerations related to economic efficiency.
  • amphoteric surfactants include alkyl carboxybetaines, alkyl sulfobetaines, alkyl hydroxysulfobetaines, alkyl amidobetaines, imidazohnium betaines, alkyl diaminoethyl glycines, dialkyl diaminoethyl glycines, alkyl amine oxides, alkyl ether amine oxides, and amide/amine oxides.
  • alkyl carboxybetaines alkyl sulfobetaines, alkyl hydroxysulfobetaines, alkyl amidobetaines, alkyl amine oxides, alkyl ether amine oxides, and amide/amine oxides are preferred among these amphoteric surfactants because of considerations related to detergency, and alkyl amidobetaines and alkyl amine oxides are even more preferred because of considerations related to economic efficiency.
  • cationic surfactants examples include alkyl trimethylammonium salts, dialkyl dimethylammonium salts, alkyl trimethylammonium salts, alkyl dimethylammonium adipates, benzalkonium salts, benzethonium salts, pyridinium salts, imidazohnium salts, and biguanide compounds.
  • the counterions of these cationic surfactants are halogen ions and the like.
  • dialkyl dimethylammonium salts alkyl dimethylammonium adipates, benzalkonium salts, benzethonium salts, and biguanide compounds are preferred among these cationic surfactants because of considerations related to bactericidal properties and economic efficiency, and benzalkonium chloride and dialkyl dimethylammonium chlorides are even more preferred because of considerations related to the anti-soiling effect.
  • These surfactants may be used singly or as combination of two or more components, and can be appropriately selected and used in accordance with detergency on the soil, foaming properties, rinsing properties, mildness on the skin, damage to the material, ease of wiping, and other required performance attributes.
  • the admixed amount of component (B) is selected from the range of 0.1 to 30 mass% of the composition.
  • the detergency and the anti-soiling effect of component (A) will be limited if this amount is less than 0.1 mass%, and the increase in detergency will reach saturation and the economic efficiency will actually decline if more than 30 mass% is admixed.
  • the amount in which the surfactant is admixed is preferably within a range of 1 to 30 mass%, based on the total mass of the composition, because of considerations related to detergency, and even more preferably within a range of 1 to 15 mass% because of considerations related to economic efficiency.
  • Examples of the metal chelating agent of component (C) used in the present invention include hydroxycarboxylic acids, aminocarboxylic acids, phosphoric acids, phosphonic acids, phosphonocarboxylic acids, water-soluble macromolecular polymers, salts thereof, and other compounds that are soluble in water and have a chelating capacity. These may be used singly or as combinations of two or more compounds.
  • the metal chelating agent is admixed with the purpose of obtaining enhanced detergency.
  • hydroxycarboxylic acids include acetic acid, adipic acid, monochloroacetic acid, oxalic acid, succinic acid, oxydisuccinic acid, carboxymethylsuccinic acid, carboxymethyloxysuccinic acid, glycolic acid, diglycolic acid, lactic acid, tartaric acid, carboxymethyltartaric acid, citric acid, malic acid, gluconic acid, and salts thereof.
  • aminocarboxylic acids include nitrilotriacetic acid, iminodiacetic acid, ethylenediamine tetraacetic acid, diethylenetriamine pentaacetic acid, N-hydroxyethyl ethylenediamine acetic acid, ethylenediamine tetrapropionic-acetic acid, methyl glycine diacetic acid, triethylenetetramine hexaacetic acid, ethylene glycol diether diamine tetraacetic acid, hydroxyethyliminodiacetic acid, cyclohexane-l,2-diaminotetraacetic acid, djenkolic acid, and salts thereof.
  • phosphoric acids examples include orthophosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, metaphosphoric acid, hexametaphosphcric acid, phytic acid, and other condensed phosphoric acids, as well as salts thereof.
  • Examples of phosphonic acids include ethane- 1,1-diphosphonic acid, ethane- 1,1,2-triphosphonic acid, 1-hydroxyethane- 1,1-diphosphonic acid, derivatives thereof, l-hydroxyethane-l,l,2-triphosphonic acid, ethane- l,2-dicarboxy-l,2-diphosphonic acid, methane hydroxyphosphonic acid, aminotrimethylene phosphonic acid, and salts thereof.
  • phosphonocarboxylic acids examples include 2-phosphonobutane-l,2-dicarboxylic acid, l-phosphonobutane-2,3,4-tricarboxylic acid, ⁇ -methylphosphonosuccinic acid, and salts thereof.
  • water-soluble macromolecular polymers examples include polyacrylic acid, polymaleic acid, copolymers of acrylic acid and maleic acid, polyaconitic acid, poly- ⁇ -hydroxyacrylic acid, polymethacrylic acid, and salts thereof.
  • metal chelating agents may be used in the form of acids or as partial or complete salts.
  • salts include salts of potassium, sodium, and other alkali metals; monoalkanolamines, diethanolamine, triethanolamine, and other alkanolamine salts; and ammonium salts.
  • Hydroxycarboxylic acids, aminocarboxylic acids, alkali metal salts thereof, and alkanolamine salts are preferred among these metal chelating agents because of considerations related to the impact on the environment, and hydroxycarboxylic acids, aminocarboxylic acids, and sodium salts thereof are even more preferred because of considerations related to economic efficiency.
  • the admixed amount of component (C) is selected from the range of 0.1 to 20 mass% of the composition.
  • a limited detergency improving effect will be produced if this amount is less than 0.1 mass%, and the detergency improving effect will reach saturation, the composition will have poor storage stability, and the economic efficiency will actually be low if more than 20 mass% is admixed.
  • the amount in which the metal chelating agent is admixed is preferably within a range of 1 to 20 mass%, based on the total mass of the composition, because of considerations related to detergency, and even more preferably within a range of 1 to 15 mass% because of considerations related to economic efficiency.
  • Purified water, deionized water, soft water, distilled water, and tap water can be cited as examples of the water, or component (D), used in the present invention. These types of water may be used singly or as a combination of two or more types. Among these, tap water and deionized water are preferably used because of considerations related to economic efficiency and storage stability.
  • water refers to the sum of water provided from the outside and water contained as the aqueous solution or crystal water derived from the components that constitute the anti-soiling detergent composition of the present invention. This water is admixed in such a way that the entire anti-soiling detergent composition constitutes 100%.
  • a thickener can also be admixed as component (E) according to need together with essential components (A) to (D).
  • Component (E) is admixed in order to make the anti-soiling detergent composition of the present invention more usable through a thickening effect; particularly, to improve usability when spraying is employed or when a non-horizontal surface is cleaned, and hence to enhance detergency on non-horizontal surfaces.
  • thickener examples include xanthan gum, carageenan, guar gum, gum arable, locust bean gum, alginate, carboxymethylcellulose, and other thickening polysaccharides, as well as carboxyvinyl polymers, crosslinked polyacrylic acids, and salts thereof.
  • xanthan gum and carboxyvinyl polymers are preferred among these because of considerations related to the stability of the composition.
  • the admixed amount of component (E) is selected from the range of 0.01 to 5 mass% of the composition. An inferior anti-soiling effect will be produced if this amount is less than 0.01 mass%, and the composition will become excessively viscous and difficult to handle, and the economic efficiency will actually be low if more than 5 mass% is admixed.
  • the amount in which the thickener is admixed is preferably within a range of 0.05 to 2 mass%, based on the total mass of the composition, because of considerations related to the ease of operation, and even more preferably within a range of 0.05 to 1 mass% because of considerations related to economic efficiency.
  • a water-soluble solvent may be admixed as component (F) according to need together with essential components (A) to (D).
  • Component (F) contributes to further improvements in detergency, particularly, detergency in relation to organic soil.
  • Alcohols such as ethanol, propanol, isopropanol, butanol, and other monohydric alcohols; ethylene glycol, diethylene glycol, isoprene glycol, propylene glycol, and other alkylene glycols; and glycerin, polyglycerin, 1,3-butanediol, and other polyhydric alcohols
  • Glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monophenyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether
  • lower alcohols with a carbon number of 1 to 5 glycol ethers, and terpene-based hydrocarbon solvents are preferred because of considerations related to detergency, and the following solvents are even more preferred because of considerations related to detergency, stability, and water solubility: lower alcohols with a carbon number of 1 to 5, propylene glycol monomethyl ether, propylene glycol monobutyl ether, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monobutyl ether, and limonene.
  • the admixed amount of component (F) is selected from the range of 0.1 to 20 mass% of the composition.
  • Detergency will be limited if this amount is less than 0.1 mass%, and the increase in detergency will reach saturation, the economic efficiency will actually decline, and the composition will have unsatisfactory storage stability if more than 20 mass% is admixed.
  • the amount in which the water-soluble solvent is admixed is preferably 1 to 15 mass% because of considerations related to detergency and storage stability, and is more preferably 1 to 10 mass% because of considerations related to economic efficiency, based on the total mass of the composition.
  • the stock solution for the anti-soiling detergent composition of the present invention is adjusted to a pH of 5 to 9, and preferably 6 to 8, taking into account the absence of any adverse effect on the material of the cleaning object, and biological and environmental safety.
  • the pH can be adjusted using a substance that displays alkalinity and a substance that displays acidity.
  • alkaline substances that can be used for pH adjustment include sodium hydroxide, potassium hydroxide, and other alkali hydroxides; sodium carbonate, potassium carbonate, and other carbonates; sodium silicate, potassium silicate, and other silicates; monoethanolamine, diethanolamine, and other amines; and ammonia.
  • acidic substances that can be used for pH adjustment include hydrochloric acid, sulfuric acid, and other inorganic acids, as well as citric acid, acetic acid, and other organic acids.
  • component (C) If an organic acid that corresponds to component (C) is used as the pH regulator, it must be taken into account that component (C) should be admixed in a ratio that does not fall outside the range of 0.1 to 20 mass%.
  • Fragrances, dyes, pigments, bactericides, preservatives, and the like may also be admixed as needed in addition to the aforementioned components into the anti-soiling detergent composition of the present invention as long as the objects of the present invention are not compromised.
  • the anti-soiling detergent composition of the present invention can be used to advantage for cleaning and desoiling hard surfaces that are in repeated contact with tap water and are prone to developing water stains; particularly, the hard surfaces of restrooms, washstands, baths, and the like.
  • the materials of such cleaned surfaces include plastics, stainless steel, porcelain, tile, glass, ceramics, granite/terrazzo, and other natural stone materials.
  • the anti-soiling detergent composition of the present invention may be used either as a stock solution or after being diluted with water or warm water in accordance with the degree of soiling of the cleaned surface.
  • the degree of dilution can be up to 50 times, based on considerations related to detergency and anti-soiling effect.
  • cleaning methods in which the anti -soiling detergent composition of the present invention can be used include the following.
  • a sponge or the like is impregnated with the anti-soiling detergent composition of the present invention, and a hard surface is scrubbed and rinsed.
  • a cleaned surface is sprinkled with the anti-soiling detergent composition of the present invention, scrubbed with a sponge or the like, and rinsed.
  • a cleaned surface is sprayed with the anti-soiling detergent composition of the present invention, allowed to stand for a while, and rinsed.
  • nonwoven fabric or the like is impregnated with the anti-soiling detergent composition of the present invention, affixed, allowed to stand for a while, and rinsed.
  • a towel or duster is impregnated with the anti-soiling detergent composition of the present invention, the soil is wiped off, and the surface is wiped with a moist towel.
  • pH METER F-12 manufactured by Horiba
  • pH METER F-12 was used to measure the pH value of a prepared stock solution of an anti-soiling detergent composition at 25°C in accordance with JIS Z-8808: 1984.
  • (2) Detergency Test 1 Simulated Restroom Soil [Preparation of Simulated Restroom Soil] 0.5 g of lanolin was dissolved in 5 mL of chloroform, 495 mL of ethanol was added for dilution, and an ethanol solution was prepared. A preparation obtained by dissolving 10 g of ferric chloride in 500 mL of water and adding the resulting solution to the ethanol solution was applied in the exact quantity of 1 mL to ceramic tile (SPKC-100/L00; white; 10 cm x 10 cm; manufactured by INAX) whose surface had been pre-roughened with sandpaper (No.
  • a preparation obtained by dissolving 2.5 g of oleic acid, 2.5 g of triolein, 0.25 g of albumin, and 4.75 g of calcium stearate in 60 g of chloroform was uniformly applied in the exact quantity of 1 mL to slide glass (7.6 cm x 2.6 cm). The slide glass was dried overnight at room temperature and used as a test piece.
  • test piece A stock solution of each composition was fed dropwise onto the test piece, and the test piece was scrubbed with a Conradi stick wrapped in tissue paper (Kim Wipe, manufactured by Crecia), which was moved back and forth 15 times to conduct the detergency test. Following testing, the test piece was rinsed for 10 seconds with a certain amount of tap water and dried at room temperature. The mass of the test piece was measured before and after the test, and the cleaning ratio was determined using the formula shown below.
  • Ceramic tile (SPKC-100/L00; white; 10 cm x 10 cm; manufactured by INAX) was cleaned using a sponge (4 cm x 8 cm) with 2 mL of a stock solution of each composition, rinsed for 20 seconds with a certain amount of tap water, and dried at room temperature to obtain a test piece.
  • Five drops of a solution obtained by dissolving 1 g of ferric chloride in 100 g of water were dropped in spots onto the test piece by using a dropping pipette, and the test piece was then baked for 3 hours at 105°C and allowed to cool at room temperature.
  • the soil was scrubbed off from the test piece with moistened tissue paper (Kim Wipe, manufactured by Crecia), and soil removal was visually evaluated.
  • moistened tissue paper Karl Wipe, manufactured by Crecia
  • the urinals, toilet bowls, and washstands were scrubbed with a sponge by using a stock solution of each composition, and the scrubbed surfaces were then rinsed with running water.
  • the surfaces were scrubbed with a moistened sponge and merely rinsed with without using any detergent.
  • a stock solution of each composition was used in the same manner as on day 1, and the surfaces were scrubbed with a sponge and rinsed with water.
  • the urinals, toilet bowls, and washstands were scrubbed with a sponge by using a stock solution of each composition, and the scrubbed surfaces were then rinsed with running water.
  • the surfaces were scrubbed with a moistened sponge and merely rinsed with without using any detergent.
  • a stock solution of each composition was used in the same manner as on day 1, and the surfaces were scrubbed with a sponge and rinsed with water.
  • Organopolysiloxane 1 A polyetheramide-modified organopolysiloxane expressed by the chemical formula
  • Organopolysiloxane 2 A polyetheramide-modified organopolysiloxane expressed by the chemical formula [Chemical Formula 21]
  • Organopolysiloxane 3 A polyetheramide-modified organopolysiloxane expressed by the chemical formula
  • G 12 is (CH 2 ) 3 O(CH 2 CH2O) 8 C, 2 H 2 5
  • G 13 is (CH 2 ) 3 NHCOCH 2 O(CH 2 CH 2 O) 4 C ⁇ 2 H 25 .)
  • Organopolysiloxane 6 Polyether-modified organopolysiloxane (Registered trade name: KF-6011, manufactured by Shin-Etsu Silicones) * Organopolysiloxane 7: Polydimethylsiloxane
  • Nonionic surfactant 1 Alkyl polyglucoside
  • Nonionic surfactant 2 Polyoxyethylene alkyl ether (Registered trade name: Naroakty-ID70, manufactured by Sanyo Chemical Industries)
  • Nonionic surfactant 3 Polyoxyethylene alkyl ether (Registered trade name: Lutensol TO8, manufactured by BASF)
  • Amphoteric surfactant 1 Alkylamidopropyl betaine (Registered trade name: TegoBetain LI OS, manufactured by Goldschmidt)
  • Amphoteric surfactant 2 Alkylamine oxide (Registered trade name: Barlox 12, manufactured by Lonza)
  • Anionic surfactant 1 Sodium alkyl ether sulfonate
  • Anionic surfactant 2 Sodium alkylbenzenesulfonate (Registered trade name: Taycapower LN2450, manufactured by Tayca)
  • Thickener 2 Xanthan gum (registered trade name: Kelzan, manufactured by Kelco)
  • compositions of examples 1 to 28 deliver satisfactory performance in terms of test items such as detergency, anti-soiling effect, sustainability of the anti-soiling effect, and storage stability.
  • an inferior and poorly sustainable anti-soiling effect is provided by the compositions of comparative examples 1 to 6, which are devoid of the polyetheramide-modified organopolysiloxane and/or amino-modified organopolysiloxane of component (A), or by the composition of comparative example 7, in which the content of component (A) is too low.
  • Inferior storage stability is exhibited by the compositions of comparative examples 8 and 9, in which more than 10 mass% of component (A) is admixed.
  • compositions of examples 7 to 11, 12, and 26 to 28 were used to clean restrooms, washstands, and mirrors in stores, offices, residences, and the like in the same manner as in the tests of sustainability of the anti-soiling effect, and it was found that adequate detergency was exhibited and that satisfactory results were obtained in terms of sustainability of the anti- soiling effect as well.

Landscapes

  • 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)
  • Cosmetics (AREA)
EP03773307A 2002-10-25 2003-10-21 Schmutzabweisendes reinigungsmittel Expired - Lifetime EP1554368B2 (de)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
JP2002310790 2002-10-25
JP2002310790 2002-10-25
JP2003356224 2003-10-16
JP2003356224A JP4463521B2 (ja) 2002-10-25 2003-10-16 水回りの硬表面用防汚洗浄剤組成物
PCT/US2003/033396 WO2004039931A1 (en) 2002-10-25 2003-10-21 Anti-soiling detergent composition

Publications (3)

Publication Number Publication Date
EP1554368A1 true EP1554368A1 (de) 2005-07-20
EP1554368B1 EP1554368B1 (de) 2007-03-07
EP1554368B2 EP1554368B2 (de) 2010-02-24

Family

ID=32232634

Family Applications (1)

Application Number Title Priority Date Filing Date
EP03773307A Expired - Lifetime EP1554368B2 (de) 2002-10-25 2003-10-21 Schmutzabweisendes reinigungsmittel

Country Status (12)

Country Link
EP (1) EP1554368B2 (de)
JP (1) JP4463521B2 (de)
KR (1) KR20050073583A (de)
AT (1) ATE356188T1 (de)
AU (1) AU2003280001B2 (de)
BR (1) BR0315635A (de)
CA (1) CA2502606C (de)
DE (1) DE60312361T3 (de)
ES (1) ES2279184T3 (de)
MX (1) MXPA05004414A (de)
NZ (1) NZ539507A (de)
WO (1) WO2004039931A1 (de)

Families Citing this family (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4647956B2 (ja) * 2004-08-20 2011-03-09 小林製薬株式会社 防汚剤組成物
JP5252826B2 (ja) * 2007-04-17 2013-07-31 ディバーシー株式会社 硬質表面用洗浄剤組成物
US7597766B2 (en) * 2007-08-03 2009-10-06 American Sterilizer Company Biodegradable detergent concentrate for medical instruments and equipment
PL2260094T3 (pl) * 2008-04-04 2012-01-31 Unilever Nv Zastosowanie cytrynianu jako środka czyszczącego do powierzchni twardych
JP2010275440A (ja) * 2009-05-29 2010-12-09 Murakami Corp 親水性回復剤および親水性回復方法
JP5663181B2 (ja) * 2010-03-30 2015-02-04 小林製薬株式会社 トイレ洗浄用組成物
JP2013001771A (ja) * 2011-06-14 2013-01-07 Neos Co Ltd 液状カビ防除洗浄剤組成物
JP5579761B2 (ja) * 2012-02-20 2014-08-27 エコラボ合同会社 液体洗浄剤組成物
JP6158065B2 (ja) * 2013-12-16 2017-07-05 花王株式会社 硬質表面用洗浄剤組成物
JP2016169308A (ja) * 2015-03-12 2016-09-23 株式会社ソフト９９コーポレーション 撥水型ウインドウォッシャー液
JP6777446B2 (ja) * 2015-07-14 2020-10-28 花王株式会社 硬質表面用洗浄剤組成物
JP2017165829A (ja) * 2016-03-15 2017-09-21 木村石鹸工業株式会社 トイレ用撥水性洗浄剤組成物
US10433545B2 (en) 2016-07-11 2019-10-08 Ecolab Usa Inc. Non-streaking durable composition for cleaning and disinfecting hard surfaces
JP6652484B2 (ja) * 2016-12-13 2020-02-26 アース製薬株式会社 硬質表面用洗浄組成物
JP6585145B2 (ja) * 2016-12-13 2019-10-02 アース製薬株式会社 水洗トイレ用洗浄組成物
JP7308010B2 (ja) * 2016-12-28 2023-07-13 小林製薬株式会社 表面平滑化剤
JP2019081722A (ja) * 2017-10-30 2019-05-30 花王株式会社 殺黴剤組成物
JP7170528B2 (ja) * 2018-12-25 2022-11-14 ライオン株式会社 トイレ用の液体洗浄剤組成物
JP7405522B2 (ja) * 2019-06-28 2023-12-26 小林製薬株式会社 トイレ便器用コーティング剤
JP7321797B2 (ja) * 2019-06-28 2023-08-07 小林製薬株式会社 トイレ便器用コーティング剤
JP7346247B2 (ja) * 2019-10-31 2023-09-19 アース製薬株式会社 トイレの汚れ防止組成物
JP7642337B2 (ja) * 2020-09-29 2025-03-10 セッツ株式会社 洗浄剤組成物、スプレーボトル型洗浄剤、ウェットワイパー及び物品表面の洗浄方法
JP7759721B2 (ja) * 2020-10-06 2025-10-24 山崎産業株式会社 液状防汚用組成物及び防汚方法
JP7748180B2 (ja) * 2020-12-04 2025-10-02 山崎産業株式会社 液状防汚洗浄剤組成物及び防汚方法
JP7752648B2 (ja) * 2022-03-25 2025-10-10 山崎産業株式会社 硬質表面用の液状抗菌性付与洗浄剤組成物及び抗菌性付与方法
JP7801269B2 (ja) * 2022-03-28 2026-01-16 山崎産業株式会社 硬質表面への汚れ付着抑制用液状洗浄剤組成物及び汚れ付着抑制方法
WO2025142775A1 (ja) * 2023-12-25 2025-07-03 ダウ・東レ株式会社 新規共変性シリコーン、それを含む共変性シリコーン組成物、それを含む液体洗剤およびその製造方法
WO2025142774A1 (ja) * 2023-12-25 2025-07-03 ダウ・東レ株式会社 共変性シリコーン組成物、それを含む液体洗剤およびその製造方法

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4859359A (en) * 1988-03-25 1989-08-22 Dyna-5, Inc. Hard surface cleaning and polishing compositions
EP0353388A3 (de) * 1988-07-29 1990-09-19 Dyna-5, Inc. Bodenbehandlungsprodukt
US5514302A (en) † 1992-09-25 1996-05-07 S.C. Johnson & Son, Inc. Fabric cleaning shampoo compositions
CA2235358A1 (en) * 1997-04-21 1998-10-21 Masahiro Takahashi Surface modifier composition
CA2235198A1 (en) * 1997-04-21 1998-10-21 Masahiro Takahashi Polyoxethylene alkyl ether fatty acid amide modified organopolysiloxane composition
GB2329902B (en) * 1997-10-01 2002-01-09 Reckitt & Colman Inc Aqueous emulsion cleaning composition
US6425959B1 (en) * 1999-06-24 2002-07-30 Ecolab Inc. Detergent compositions for the removal of complex organic or greasy soils

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2004039931A1 *

Also Published As

Publication number Publication date
AU2003280001B2 (en) 2009-07-16
EP1554368B2 (de) 2010-02-24
WO2004039931A1 (en) 2004-05-13
CA2502606C (en) 2009-01-06
NZ539507A (en) 2007-06-29
ATE356188T1 (de) 2007-03-15
JP2004162041A (ja) 2004-06-10
DE60312361T2 (de) 2007-07-12
JP4463521B2 (ja) 2010-05-19
DE60312361T3 (de) 2010-06-10
ES2279184T3 (es) 2007-08-16
KR20050073583A (ko) 2005-07-14
MXPA05004414A (es) 2005-07-26
DE60312361D1 (de) 2007-04-19
EP1554368B1 (de) 2007-03-07
AU2003280001A1 (en) 2004-05-25
BR0315635A (pt) 2005-08-23
CA2502606A1 (en) 2004-05-13

Similar Documents

Publication Publication Date Title
EP1554368B2 (de) Schmutzabweisendes reinigungsmittel
US7375068B2 (en) Anti-soiling detergent composition comprising a polyetheramide-modified organopolysiloxane
US4501680A (en) Acidic liquid detergent composition for cleaning ceramic tiles without eroding grout
ES2412707T5 (es) Composición detergente líquida para lavado de vajillas a mano
ES2638446T3 (es) Composición de limpieza
EP0698660B1 (de) Reinigungsmittel für harte Oberflächen
CN1120349A (zh) 清洁组合物及其使用方法
ES2354956T3 (es) Composición limpiadora de superfices duras , ácida , líquida.
US20060074004A1 (en) Light duty liquid detergent composition
JP2020180287A (ja) 食器手洗い用液体洗浄組成物
JP3264878B2 (ja) 液体洗浄剤組成物
US5439609A (en) Aqueous cleaning composition for hard surfaces
JPH1112596A (ja) 食器用液体洗浄剤組成物
KR19990036296A (ko) 산성 세정용 조성물
WO2019054260A1 (ja) 硬質表面用液体洗浄剤組成物
JP2003523480A (ja) 条痕のないふき取り不要の洗浄組成物
JP3558907B2 (ja) 硬表面防汚抗菌洗浄剤組成物
CN100540644C (zh) 抗染污清洁剂组合物
JP2797571B2 (ja) 洗浄剤組成物
JPH1143689A (ja) 硬質表面用洗浄剤組成物
JPH10219292A (ja) 硬質表面用洗浄剤組成物
JPH09235592A (ja) 液体洗浄剤組成物
JP2025185774A (ja) 食器用液体洗浄剤組成物
JPH1025493A (ja) 液体クレンザー組成物
HK1005994B (en) Detergent composition for hard surface

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20050415

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL LT LV MK

DAX Request for extension of the european patent (deleted)
GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAL Information related to payment of fee for publishing/printing deleted

Free format text: ORIGINAL CODE: EPIDOSDIGR3

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK TR

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20070307

Ref country code: CH

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20070307

Ref country code: BE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20070307

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20070307

Ref country code: LI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20070307

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20070307

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REF Corresponds to:

Ref document number: 60312361

Country of ref document: DE

Date of ref document: 20070419

Kind code of ref document: P

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20070607

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20070807

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2279184

Country of ref document: ES

Kind code of ref document: T3

ET Fr: translation filed
REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20070307

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20070307

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20070307

PLAX Notice of opposition and request to file observation + time limit sent

Free format text: ORIGINAL CODE: EPIDOSNOBS2

26 Opposition filed

Opponent name: THE PROCTER & GAMBLE COMPANY

Effective date: 20071206

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20070307

NLR1 Nl: opposition has been filed with the epo

Opponent name: THE PROCTER & GAMBLE COMPANY

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20070608

PLBB Reply of patent proprietor to notice(s) of opposition received

Free format text: ORIGINAL CODE: EPIDOSNOBS3

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20071031

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20071022

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20070307

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20070307

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20070607

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20071021

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20070908

PUAH Patent maintained in amended form

Free format text: ORIGINAL CODE: 0009272

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: PATENT MAINTAINED AS AMENDED

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20091026

Year of fee payment: 7

Ref country code: TR

Payment date: 20091006

Year of fee payment: 7

27A Patent maintained in amended form

Effective date: 20100224

AK Designated contracting states

Kind code of ref document: B2

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK TR

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20091024

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20091030

Year of fee payment: 7

Ref country code: IT

Payment date: 20091026

Year of fee payment: 7

REG Reference to a national code

Ref country code: NL

Ref legal event code: VDEP

Effective date: 20100304

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100604

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100304

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20101102

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20110630

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20101021

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20101021

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20131028

Year of fee payment: 11

Ref country code: DE

Payment date: 20131029

Year of fee payment: 11

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 60312361

Country of ref document: DE

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20141021

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20141021

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20150501