EP1554368B2 - Schmutzabweisendes reinigungsmittel - Google Patents

Schmutzabweisendes reinigungsmittel Download PDF

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Publication number
EP1554368B2
EP1554368B2 EP03773307A EP03773307A EP1554368B2 EP 1554368 B2 EP1554368 B2 EP 1554368B2 EP 03773307 A EP03773307 A EP 03773307A EP 03773307 A EP03773307 A EP 03773307A EP 1554368 B2 EP1554368 B2 EP 1554368B2
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EP
European Patent Office
Prior art keywords
soiling
detergent composition
carbon atoms
mass
group
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EP03773307A
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English (en)
French (fr)
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EP1554368A1 (de
EP1554368B1 (de
Inventor
Mari Johnson Professional Kk Yagi
Mitsuo Johnson Professional Kk Sado
Aki Johnson Professional Kk Abe
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Diversey Inc
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JohnsonDiversey Inc
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—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. More specifically, 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 as defined in claim 1, a surfactant, a metal chelating agent, and water.
  • the present invention was perfected on the basis of this discovery.
  • the present invention provides an anti-soiling detergent composition as defined in claim 1.
  • 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 polyetheramide-modified organopolysiloxane of component (A) used in the present invention is a organopolysiloxane having an amino group, polyoxyethylene group, and amido group expressed by average compositional formula (6) R 1 a R 2 b Q 1 c Q 2 d Q 3 e1 SiO (4-a-b-c-d-e1)/2 (6)
  • a and d are zeros or positive numbers; b, c, and e 1 are positive numbers such that 1.9 ⁇ a+b+c+d+e1 ⁇ 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 e O f -(C 2 H 4 O) g -(R 8 O) h -Y (4), where e and f are each 0 or 1, and g and h are zeros or positive integers of 1 or greater.
  • 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 2 is a monovalent organic group having a polyoxyalkylene group expressed by general formula (5) -R 9 i O j -(C 2 H 4 O) k -(R 10 O) m -Z (5), where i and j are each 0 or 1; k is a positive integer of 1 or greater; m is zero or a positive integer of 1 or greater; 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; and Z is a group selected from among hydrogen atoms, alkyl groups, acyl groups, and isocyanic groups, examples of which
  • Q 3 is a divalent organic group having an amino group expressed by general formula (7) or (8).
  • R 3 to R 6 are the same as above.
  • 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) n6 (CH 2 ) n7 D 3 ;
  • R 15 is -(CH 2 ) 3 NH 2 ;
  • R 16 is -(CH 2 ) 3 NHCO(CH 2 ) n8 O n9 (CH 2 CH 2 O) n10 (CH 2 CHCH 3 O) n11 (CH 2 ) n12 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 ;
  • n1 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 0 to 20;
  • R 17 is -(CH 2 ) 3 O(CH 2 CH 2 O) n17 (CH 2 CHCH 3 O) n18 (CH 2 ) n19 D 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 ) n20 O n21 (CH 2 CH 2 O) n22 (CH 2 CHCH 3 O) n23 (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 ;
  • n13 is 10 to 1000;
  • n14 is 0 to 100;
  • n15 is 1 to 100;
  • n 16 is 1 to 100;
  • n17
  • G 14 is -(CH 2 ) 3 O(CH 2 CH 2 O) 5 C 12 H 25
  • G 15 is -(CH 2 ) 3 NH 2
  • G 16 is -(CH 2 ) 3 NHCOCH 2 O(CH 2 CH 2 O) 5 C 12 H 25 .
  • G 17 is -(CH 2 ) 3 O(CH 2 CH 2 O) 10 C 10 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 C 10 H 21 .
  • the admixed amount of component (A) is selected from the range of 0.05 to 10 mass%, based on the total mass of the composition. An inferior anti-soiling effect will be produced if this amount is less than 0.05 mass%, and the increase in the anti-soiling effect will reach saturation and the economic efficiency will actually be low if more than 10 mass% is admixed.
  • the admixed amount of 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 and 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, imidazolinium 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, imidazolinium 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.
  • 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-1,2-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, 1-hydroxyethane-1,1,2-triphosphonic acid, ethane-1,2-dicarboxy-1,2-diphosphonic acid, methane hydroxyphosphonic acid, aminotrimethylene phosphonic acid, and salts thereof.
  • phosphonocarboxylic acids examples include 2-phosphonobutane-1,2-dicarboxylic acid, 1-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 arabic, 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.
  • water-soluble solvents may be used singly or as combinations of two or more components, and can be appropriately selected and used in accordance with detergency on the soil, damage to the material, ease of wiping, and other required performance attributes.
  • 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.
  • the anti-soiling detergent compositions shown in Tables 1 to 8 were prepared and subjected to various tests.
  • the numerical values for the components in the tables refer to the content (mass%) of each component.
  • the pH was adjusted as needed with the aid of a pH regulator such as acetic acid, sulfuric acid, or sodium hydroxide, and the sum of components (A) to (F), the pH regulator, and arbitrary components was 100 mass% total.
  • a pH regulator such as acetic acid, sulfuric acid, or sodium hydroxide
  • the anti-soiling detergent compositions thus obtained were evaluated for test parameters such as pH, detergency, anti-soiling effect, sustainability of the anti-soiling effect, and storage stability by the test methods and in accordance with the grading system described below, and the results are presented as well in Tables 1 to 8 below.
  • 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.
  • lanolin 0.5 g was dissolved in 5 mL of chloroform, 495 mL of ethanol was added for dilution, and an ethanol solution was prepared.
  • the coated tile was baked for 1 hour at 145°C and allowed to cool at room temperature, yielding a test piece.
  • 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 ⁇ 2.6 cm). The slide glass was dried overnight at room temperature and used as a test piece.
  • Ceramic tile (SPKC-100/L00; white; 10 cm ⁇ 10 cm; manufactured by INAX) was cleaned using a sponge (4 cm ⁇ 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.
  • 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.
  • compositions were placed overnight in an incubator set to -15°C (model HRF-90P, manufactured by Hoshizaki), allowed to freeze, and then caused to thaw at room temperature. This cycle was repeated five times, and the condition of the composition after 8 hours had elapsed since the start of thawing was visually observed. An evaluation was made based on the following grading system.
  • 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 and 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 comparative examples 15 and 16 which are devoid of the metal chelating agent of component (C), or by the composition of comparative example 17, in which too little of component (C) is admixed. It can also be seen that inferior storage stability is exhibited by the composition of comparative example 18, in which more than 20 mass% of component (C) 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.

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Claims (7)

  1. Ein schmutzabweisendes Reinigungsmittel, enthaltend:
    (A) 0,05 bis 10 Masse-% eines mit Polyetheramid modifizierten Organopolysiloxans,
    (B) 0,1 bis 30 Masse-% zumindest eines Tensids, ausgewählt aus nicht-ionischen Tensiden, amphoteren Tensiden und kationischen Tensiden,
    (C) 0,1 bis 20 Masse-% eines Metallchelatbildners und
    (D) Wasser,
    wobei das mit Polyetheramid modifizierte Organopolysiloxan der Komponente (A) ein mit Polyetheramid modifiziertes Organopolysiloxan ist, dessen mittlere Zusammensetzung durch die folgende Formel (6) wiedergegeben wird:

            R1 aR2 bQ1 cQ2 dQ3 e1SiO(4-a-b-c-d-e1)/2     (6)

    wobei a und d null oder positive Zahlen sind; b, c und e1 positive Zahlen sind, so dass 1,9 ≤ a + b+ c + d +e1 ≤ 2,2; R1 ein Wasserstoffatom, eine Hydroxylgruppe oder eine substituierte oder unsubstituierte monovalente Kohlenwasserstoffgruppe mit 1 bis 6 Kohlenstoffatomen ist; R2 eine monovalente Kohlenwasserstoffgruppe mit 1 bis 6 Kohlenstoffatomen ist; Q1 eine Gruppe ist, die durch die allgemeine Formel (2) oder (3) wiedergegeben wird:
    Figure imgb0019
    Figure imgb0020
     wobei R3 und R5 bivalente Kohlenwasserstoffgruppen mit 2 bis 18 Kohlenstoffatomen sind; R4 und R6 Wasserstoffatome oder monovalente Kohlenwasserstoffgruppen mit 1 bis 6 Kohlenstoffatomen sind; X eine Gruppe ist, die durch die allgemeine Formel (4) wiedergegeben wird:

            -R7 eOf-(C2H4O)g-(R8O)h-Y     (4)

    wobei e und f jeweils 0 oder 1 sind; g und h null oder positive ganze Zahlen von 1 oder größer sind; R7 eine bivalente Kohlenwasserstoffgruppe mit 2 bis 18 Kohlenstoffatomen ist; R8 eine bivalente Kohlenwasserstoffgruppe mit 3 bis 10 Kohlenstoffatomen ist; Y ein Wasserstoffatom, eine monovalente Kohlenwasserstoffgruppe mit 1 bis 18 Kohlenstoffatomen, eine Acylgruppe oder eine Isocyansäuregruppe ist; Q2 eine Gruppe ist, die durch die allgemeine Formel (5) wiedergegeben wird:

            -R9 iOj-(C2H4O)k-(R10O)m-Z     (5),

    wobei i und j jeweils 0 oder 1 sind; k eine positive ganze Zahl von 1 oder größer ist; m null oder eine positive ganze Zahl von 1 oder größer ist; R9 eine bivalente Kohlenwasserstoffgruppe mit 2 bis 18 Kohlenstoffatomen ist; R10 eine bivalente Kohlenwasserstoffgruppe mit 3 bis 10 Kohlenstoffatomen ist; und Z ein Wasserstoffatom, eine monovalente Kohlenwasserstoffgruppe mit 1 bis 18 Kohlenstoffatomen, eine Acylgruppe oder eine Isocyansäuregruppe ist; wobei d und g nicht beide gleichzeitig null sein können; Q3 eine Gruppe ist, die durch die allgemeine Formel (7) oder (8) wiedergegeben wird:
    Figure imgb0021
    Figure imgb0022
     wobei R3 und R5 bivalente Kohlenwasserstoffgruppen mit 2 bis 18 Kohlenstoffatomen sind; und R4 und R6 Wasserstoffatome oder monovalente Kohlenwasserstoffgruppen mit 1 bis 6 Kohlenstoffatomen sind.
  2. Das schmutzabweisende Reinigungsmittel gemäß Anspruch 1, zusätzlich zu den Komponenten (A) bis (D) enthaltend (E) 0,01 bis 5 Masse-% eines Verdickungsmittels.
  3. Das schmutzabweisende Reinigungsmittel gemäß Anspruch 1 oder 2, zusätzlich zu den obigen Komponenten enthaltend (F) 0,1 bis 20 Masse-% eines wasserlöslichen Lösungsmittels.
  4. Das schmutzabweisende Reinigungsmittel gemäß einem der Ansprüche 2 bis 3, wobei das Verdickungsmittel der Komponente (E) zumindest eine Verbindung ist, die ausgewählt wird aus verdickenden Polysacchariden, Carboxyvinylpolymeren, vernetzten Polyacrylsäuren, und deren Salzen.
  5. Das schmutzabweisende Reinigungsmittel gemäß einem der Ansprüche 3 bis 4, wobei das wasserlösliche Lösungsmittel der Komponente (F) zumindest eine Verbindung ist, die ausgewählt wird aus Alkoholen, Glycolethern und Kohlenwasserstofflösungsmitteln auf Terpenbasis.
  6. Das schmutzabweisende Reinigungsmittel gemäß einem der Ansprüche 1 bis 5, wobei das schmutzabweisende Reinigungsmittel für Anwendungen auf harten Oberflächen verwendet wird.
  7. Das schmutzabweisende Reinigungsmittel gemäß einem der Ansprüche 1 bis 6, wobei das schmutzabweisende Reinigungsmittel für Anwendungen in Toiletten, Waschbecken, Bädern und anderen Feuchträumen verwendet wird.
EP03773307A 2002-10-25 2003-10-21 Schmutzabweisendes reinigungsmittel Expired - Lifetime EP1554368B2 (de)

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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
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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
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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
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