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
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/38—Cationic compounds
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/18—Hydrocarbons
  • C11D3/188—Terpenes
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/50—Perfumes
• • 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
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/38—Cationic compounds
  • C11D1/62—Quaternary ammonium compounds

Definitions

• the present invention relates to a cleaning composition, in particularly, to a cleaning composition comprising a cationic surfactant and a Citrus essential oil component, and methods of removing filth from a substrate surface, especially a hard surface using the same.
• the sanitation issues of the dining-room, kitchen and the periphery thereof have attracted more attention, which focus on the cleaning and removing dirt from the surfaces of various utensils in the dining-room and kitchen (e.g., exhaust fan, culinary hearth, etc.) and the periphery thereof (e.g., walls, door and windows, tables, etc.), so that the detergents useful for cleansing the dirt of dining-room, kitchen and the periphery thereof play a very important role in the use of detergents. It is estimated that the consumption of relevant detergents in China has reached several hundred thousand tons every year.
• an oily dirt mainly consists of edible oil(s), especially vegetable oil(s) with a high unsaturated degree (e.g., bean oil in which the content of greases having diene bond(s) is as high as 60%), which are vaporized at a high temperature and tend to produce an oxidative polymerization at a high temperature.
• vegetable oil(s) with a high unsaturated degree e.g., bean oil in which the content of greases having diene bond(s) is as high as 60%
• Such an oily dirt blends and meshes with other oily dirts to form a viscous oily dirt like oil paint. Meanwhile, the dirt accumulates with time and becomes more viscous, even become clotty, thereby adding to the cleansing difficulties.
• the traditional detergent for cleaning heavy oily dirts in the kitchen comprises traditional anionic or nonionic surfactant, builders and water.
• This cleaning composition achieves a favorable decontamination effect by adding a nonionic surfactant compound for emulsifying oily dirt.
• ethylene glycol butyl ether is used as a solvent
• sodium metasilicate is used for providing an alkali condition for saponifying oily dirt
• sodium tripolyphosphate is used as a builder. It is also proposed in U. S. Patent US 4,921,692 that a favorable decontamination effect can be obtained by using a compound of nonionic surfactant and amine oxide as a penetrant, ethanolamine for adjusting an alkali condition, and sodium tripolyphosphate as a builder.
• Japanese Patent JP2000192083 discloses a new cleaning composition for kitchen comprising a new fucose, amino acid surfactant and fatty acid surfactant components, in which the fucose can be degraded by decomposing into two glucose molecules.
• this cleaning composition neither contains any harmful substances, nor irritates skin or hurts hands.
• this cleaning composition is greatly reduced in the decontamination effect, and can hardly remove heavy dirt in kitchen.
• Chinese Patent Application Publication No. CNl, 408, 833 proposes a formulation containing a tea essential oil.
• the tea essential oil is nontoxic and fresh, and has an anti- bacterial function and a relative strong decontamination and oil removing ability.
• tea essential oil is only used frequently in toothpastes and cosmetics at present.
• the use of a tea essential oil in a cleaning composition will incur a sharp increase of the cost, therefore it is impractical.
• a cleaning composition should not contain phosphorus, and should have a low VOC (Volatile Organic Compounds) level, a reasonable alkali level and a low cost.
• VOC Volatile Organic Compounds
• An object of the present invention is to solve the problems existing in the above-mentioned traditional kitchen cleaning compositions for removing heavy dirt and degreasing. See Vol. 56 in “Surfactant Science” series, Marcel Dekker, New York, 1996, including in particular Chapter 2 entitled “Alkylarylsulfonates: History, Manufacture, Analysis and Environmental Properties", pages 39-108, "Surfactant Science” series, Vol. 73, Marcel Dekker, New York, 1998 and “Surfactant Science” series, Vol. 40, Marcel Dekker, New York, 1992. See also WO97/22,683 filed on May 17, 1996, WO98/40,452 filed on February 24, 1998 and Chinese Patent Application No.CNl,702,162A filed on May 31, 2005. Documents referenced herein are incorporated in their entirety.
• a cleaning composition comprising a combination of a cationic surfactant and a Citrus essential oil and capable of removing oil with an improved efficiency, a low irritant, a decreased causticity, a high degradability and a low cost.
• an aspect of the invention is to provide a cleaning composition comprising:
• Another aspect of the invention is to provide a cleansing method for removing filth from a substrate surface comprising a step of bringing the substrate into contact with a liquid phase and/or gas phase cleaning composition (or placing the substrate in the composition), said composition comprising: (a) 0.5 % to 30 % by weight of a cationic surfactant based on the total weight of the composition; (b) 0.01 % to 5 % by weight of a
• Citrus essential oil based on the total weight of the composition; and (c) balance amount of a carrier.
• the cleaning composition of the invention may be applied directly or after being diluted with enough water or other carriers in advance.
• the cleaning composition of the invention may comprise many variants, including: Variant 1.
• Variant 2 The cleaning composition as described previously, wherein the cationic surfactant comprises quaternary ammonium salt type compounds.
• Variant 3 The cleaning composition as described previously, wherein the quaternary ammonium salt is selected from a group consisting of a tetra-alkyl quaternary ammonium salt compound having one long-chain alkyl and three short-chain alkyls, a tetra-alkyl quaternary ammonium salt compound having two long-chain alkyls and two short-chain alkyls, a tri-alkyl benzyl quaternary ammonium salt compound, and mixtures thereof, wherein the long-chain alkyl means an alkyl having 6 to 30 carbon atoms, and the short-chain alkyl means an alkyl having 1 to 5 carbon atoms.
• the quaternary ammonium salt is selected from a group consisting of a tetra-alkyl quaternary ammonium salt compound having one long-chain alkyl and three short-chain alkyls, a tetra-alkyl quaternary ammonium salt compound having two
• Variant 4 The cleaning composition as described previously, wherein the short-chain alkyl means an alkyl having 1 to 3 carbon atoms.
• Variant 5 The cleaning composition as described previously, wherein the cationic surfactant is an ethoxylated coco alkyl quaternary ammonium salt.
• Variant 6. The cleaning composition as described previously, wherein the content of the cationic surfactant is about 2-20 %, more preferably 5-15 % by weight of the composition.
• Variant 7. The cleaning composition as described previously, wherein the Citrus essential oil is a substance containing or consisting substantially of at least one of the following compounds: limonene CAS 5989-27-5 and terpene CAS 68647-72-3.
• Variant 8 The cleaning composition as described previously, wherein the content of the Citrus essential oil is 0.1-5 %, more preferably 0.5-3 % by weight of the composition.
• Variant 9 The cleaning composition as described previously, further comprising an additional surfactant other than a cationic surfactant.
• Variant 10 The cleaning composition as described previously, wherein the additional surfactant is a nonionic surfactant.
• Variant 11 The cleaning composition as described previously, wherein the non-ionic surfactant is a fatty alcohol polyoxyethylene ether.
• Variant 12 The cleaning composition as described previously, wherein the nonionic surfactant is selected from the group consisting of branched or linear primary alcohol ethoxylate, branched or linear secondary alcohol ethoxylate, branched or linear alkylphenol ethoxylate, branched or linear alkylamine ethoxylate, branched or linear alkyl ether amine ethoxylate, branched or linear alcohol type alkoxylate, branched or linear alkyl glucoside, or mixtures thereof.
• the nonionic surfactant is selected from the group consisting of branched or linear primary alcohol ethoxylate, branched or linear secondary alcohol ethoxylate, branched or linear alkylphenol ethoxylate, branched or linear alkylamine ethoxylate, branched or linear alkyl ether amine ethoxylate, branched or linear alcohol type alkoxylate, branched or linear alkyl glucoside, or mixtures thereof.
• Variant 13 The cleaning composition as described previously, wherein the content of the additional surfactant is 0.1-10% by weight of the composition.
• Variant 14 The cleaning composition as described previously, wherein the content of the additional surfactant is 0.5-5% by weight of the composition.
• Variant 15 The cleaning composition according to variant 1, wherein the assistant component is one selected from the group consisting of builder, solvent, colorant, pH regulator, buffering agent, chelating agent, preservative, bactericide, defoaming agent, foam-forming agent, foam stabilizing agent, film-forming agent, solubilizer, anti-deposition agent, thickening agent, dispersant, enzyme, enzyme boosters, perfume, clay and mixtures thereof.
• the assistant component is one selected from the group consisting of builder, solvent, colorant, pH regulator, buffering agent, chelating agent, preservative, bactericide, defoaming agent, foam-forming agent, foam stabilizing agent, film-forming agent, solubilizer, anti-deposition agent, thickening agent, dispersant, enzyme, enzyme boosters, perfume, clay and mixtures thereof.
• the assistant component is one selected from the group consisting of builder, solvent, colorant, pH regulator, buffering agent, chelating agent, preservative, bactericide, defoaming agent
• Variant 17 The cleaning composition as described previously, wherein the builder is an organic builder.
• Variant 18 The cleaning composition as described previously, wherein the builder is one selected from the group consisting of an organic base, ethers, alcohols, and mixtures thereof.
• Variant 19 The cleaning composition as described previously, wherein the organic base is one selected from the group consisting of mono-, di- or triethanolamine, cocinic acid diethanolamine and the like.
• Variant 20 The cleaning composition as described previously, wherein the builder is one selected from the group consisting of diethylene glycol butyl ether, propylene glycol methyl ether, propylene glycol butyl ether, propylene glycol propyl ether, propylene glycol dimethyl ether, ethylene glycol butyl ether, and mixtures thereof.
• Variant 21 The cleaning composition as described previously, wherein the builder is ethanolamine and/or diethylene glycol butyl ether.
• Variant 22 The cleaning composition as described previously, wherein the assistant component is a solvent.
• Variant 23 The cleaning composition according to variant 22, wherein the solvent is a volatile organic compound.
• Variant 24 The cleaning composition as described previously, wherein the content of the assistant component is 0.01-20% by weight of the composition.
• Variant 25 The cleaning composition as described previously, wherein the content of the assistant component is 0.01-10% by weight of the composition.
• Variant 26. The cleaning composition as described previously, wherein the content of the assistant component is 0.1-5% by weight of the composition.
• Variant 27 The cleaning composition as described previously, wherein pH value of the formulated liquid of the composition at 2O 0 C is 12 or less.
• Variant 28 The cleaning composition as described previously, wherein pH value of the formulated liquid of the composition at 2O 0 C is 9 ⁇ 11.5.
• Variant 29 The cleaning composition as described previously, wherein the carrier is water.
• Variant 30 As a particular preferable embodiment, the cleaning composition of the invention, based on the total weight of the composition, comprises:
• the cleaning composition of the invention has a wonderful balance among oil removing efficiency, irritation, corrosion, degradability and cost.
• the cleaning composition has a high oil removing efficiency, a low irritation, corrosion and odor of solvent, a high degradability and a low cost.
• the cleaning composition is applicable especially for removing animal and vegetable oily dirt on the hard surfaces of dining-room, kitchen, food processor and the like, e.g., for cleaning exhaust fan, culinary hearth, refrigerator, kitchen walls, doors and windows, etc.
• the cleaning composition must contain both a cationic surfactant component and a Citrus essential oil component.
• the most preferred quaternary ammonium salt is selected from a group consisting of a tetra-alkyl quaternary ammonium salt having one liposoluble long chain and three short chains (preferably a Ci_ 5 alkyl such as methyl), tetra-alkyl quaternary ammonium salt having two liposoluble long chains and two short chains, three alkyl benzyl amine and mixtures thereof.
• said long chain may be a linear or branched hydrocarbon, or may contain an aromatic ring.
• said long chain means an alkyl having 6-30 carbon atoms and said short chain means an alkyl having 1-5 carbon atoms, particularly an alkyl having 1-3 carbon atoms.
• Ethoxylated coco alkyl quaternary ammonium salts such as Berol series quaternary ammonium salts, particularly Berol 226 manufactured by Akzo Nobel, are most preferred.
• the inventors of the present invention have found that the complex of these preferable quaternary ammonium salts surfactants and Citrus essential oils can bring about unexpected advantages or effects far superior to the prior art cleaning compositions.
• the cationic surfactants can be used in the form of a single surfactant or a mixture of cationic surfactants, which depends on the cationic surfactant products available from the suppliers.
• the content of said cationic surfactants or mixtures thereof is preferably about 0.5-30% by weight, more preferably 2-20% by weight and still more preferably 5-15% by weight of the cleaning composition according to the present invention.
• Citrus means these plants among rue family Citrus and mainly includes mandarin oranges, tangerine oranges ⁇ Citrus reticulata Blanco), oranges, lemons, pomelos ⁇ Citrus grandis Osbeck), high oranges or other Hybrid Citrus Varieties. Said oranges include limes ⁇ Citrus aurantium Linn), sweet oranges ⁇ Citrus sinensis Osbeck), bitter oranges (Neroli) and so on.
• the Citrus essential oils mentioned in the present invention are colorless transparent liquids and have the fragrance of an orange.
• the main components of the Citrus essential oils are terpene compounds.
• the Citrus essential oils are actually a kind of special vegetable oils insoluble or slightly soluble in water and have a fragrance.
• the main components of said Citrus essential oils are terpenes, aromatic hydrocarbons, alcohols, aldehydes, ketones, ethers, esters, phenols and so on.
• the main component of the sweet Citrus oils, bitter Citrus oils and lemon oils is limonene.
• Cirus essential oils means the extracts obtained by the method in which the parts of natural Citrus vegetables such as the roots, stems, leafs, flowers, fruits, seeds or barks are subjected to steam distillation, compression, extraction, adsorption and so on, for example, by the FMC process, Brown process or the process disclosed in Chinese patent application publication No. CN1,7O2,162A, which is introduced herein as a part of the specification of the present invention.
• any other materials comprising or being substantially comprised of at least one selected from the group consisting of limonene CAS 5989-27-5, terpene CAS 68647-72-3, and mixtures thereof are also within the scope of the term "Citrus essential oils" used herein.
• the cleaning compositions herein comprise 0.01 - 5 %, preferably 0.1 - 5 %, more preferably 0.5 - 3 % by weight of the Citrus essential oils.
• Citrus plants are rich in China, but they are processed only in a simple way such as exporting fresh fruits, producing cans, expressing juice and the like.
• the present invention not only improves the cleaning effects but also more valuably utilizes the Citrus plants, especially citrus skins, by combining the low cost Citrus essential oils and the cationic surfactant in the widely used cleaning compositions.
• water may be used as a carrier to constitute the balance of the cleaning composition.
• Water is often used as the filler solvent or constitutes the balance of the concentration in the cleaning compositions according to the present invention.
• the cleaning compositions can, and preferably will, contain various other optional components.
• other surfactant than the cationic surfactant, builder and solvent can be listed as examples.
• the present invention further comprises other surfactant(s) than the cationic surfactant.
• the other surfactant(s) than the cationic surfactant can be selected from a group consisting of nonionic surfactant, zwitterionic surfactant, amine oxide surfactant, and mixtures thereof.
• the other surfactant(s) generally comprises 0.1 - 10%, preferably 0.5 - 5 %, by weight of the cleaning composition.
• the cleaning composition according to the present invention optionally, but preferably, comprises one or more nonionic surfactants.
• the nonionic surfactant can remove the fat-type dirt more effectively than a surfactant carrying a charge. Therefore, it is often used in a general-purpose cleaning composition for cleaning a hard surface, such as worktable of a kitchen, bathroom appliances, floor and the like.
• Conventional nonionic and amphoteric surfactants include C 12 -C 18 alkyl ethoxylates (AE) including the so-called narrow peaked alkyl ethoxylates and C 6 -Ci 2 alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxylates/propoxylates).
• AE alkyl ethoxylates
• C 6 -Ci 2 alkyl phenol alkoxylates especially ethoxylates and mixed ethoxylates/propoxylates.
• N-alkyl polyhydroxy fat acid amides can also be used. Typical examples thereof include the C 12 -C 18 N-methylglucamides. See WO 9,206,154.
• Other sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as Cio-Ci8N-(3-methoxypropyl) glucamide.
• the N-propyl to N-hexyl C 12 -C 18 glucamides can be used for low sudsing.
• C10-C20 conventional soaps may also be used. If high sudsing is desired, the branched C 10 -C 16 soaps may be used. Examples of nonionic surfactants are described in U.S. Patent No. 4,285,841, Barrat et al, issued August 25, 1981.
• these surfactants include fatty alcohol polyoxyethylene ether series, for example, such as branched or linear primary alcohol ethoxylates, branched or linear secondary alcohol ethoxylates, branched or linear alkylphenol ethoxylates, branched or linear alkylamine ethoxylates, branched or linear alkyl ether amine ethoxylates, branched or linear alcohol type alkoxylates, branched or linear alkyl glucosides, or mixtures thereof.
• fatty alcohol polyoxyethylene ether series for example, such as branched or linear primary alcohol ethoxylates, branched or linear secondary alcohol ethoxylates, branched or linear alkylphenol ethoxylates, branched or linear alkylamine ethoxylates, branched or linear alkyl ether amine ethoxylates, branched or linear alcohol type alkoxylates, branched or linear alkyl glucosides, or
• compositions herein also optionally contain amine oxide surfactants of the formula: R 1 (EO) x (PO) y (BO) z N(O)(CH 2 R') 2 qH 2 O (I)
• R 1 (EO) x (PO) y (BO) z N(O)(CH 2 R') 2 qH 2 O
• R 1 (EO) x (PO) y (BO) z N(O)
• R 1 is a hydrocarbyl moiety having chain- length of from about 8 to about 18.
• R 1 may be somewhat longer, having a chain-length in the range C 12-24 .
• the invention also encompasses amine oxides wherein x+y+z is different from zero, specifically x+y+z is from about 1 to about 10, R 1 is a primary alkyl group containing about 8 to about 24, preferably from about 12 to about 16 carbon atoms; in these embodiments, y + z is preferably 0 and x is preferably from about 1 to about 6, more preferably from about 2 to about 4; EO represents ethyleneoxy, PO represents propyleneoxy; and BO represents butyleneoxy.
• amine oxides can be prepared by conventional synthetic methods, e.g., by the reaction of alkylethoxysulfates with dimethylamine followed by oxidation of the ethoxylated amine with hydrogen peroxide.
• Highly preferred amine oxides herein are solids at ambient temperature, more preferably they have melting-points in the range of 30 0 C to 90 0 C.
• Amine oxides suitable for use herein are available commercially from a number of suppliers, including Akzo Chemie, Ethyl Corp., and Procter & Gamble. See McCutcheon's compilation and Kirk-Othmer's review article for alternate amine oxide manufacturers.
• Preferred commercially available amine oxides are the solid, dihydrate ADMOX 16 and ADMOX
• Preferred embodiments include dodecyldimethylamine oxide dihydrate, hexadecyldimethylamine oxide dihydrate, octadecyldimethylamine oxide dihydrate, hexadecyltris(ethyleneoxy)dimethyl-amine oxide, tetradecyldimethylamine oxide dihydrate, and mixtures thereof.
• R' is H in certain of the preferred embodiments
• R' is CH 2 OH, such as hexadecylbis(2-hydroxyethyl)amine oxide, tallowbis(2-hydroxyethyl)amine oxide, stearylbis(2-hydroxyethyl)amine oxide and oleylbis(2- hydroxyethyl)amine oxide.
• Solvents may, but preferably, be contained in the cleaning composition according the present invention.
• the solvent can penetrate into and dissolve the oily dirt thereby fully decomposing and effectively removing it.
• the solvent together with water constitute the balance of the cleaning composition according to the present invention.
• Solvents are broadly defined as compounds that are liquid at temperatures of 20 ° C-
• solvents tend to exist as discrete entities rather than as broad mixtures of compounds.
• Preferred solvents are volatile organic compound. More particularly, solvents of this invention contain from about 1 to about 35 carbon atoms, and contain linear, branched or cyclic hydrocarbon moieties of no more than about 8 carbon atoms.
• the non-aqueous polar solvents having very weak detergent function are further preferred, for example, such as ethanol, propanol, isopropanol, ethylene glycol, propylene glycol, 2-methyl pyrrolidinone, and mixtures thereof. Preferred among these solvents is isopropanol.
• compositions herein preferably contain up to about 10% by weight of the solvent.
• Organic builders suitable for the purposes of the present invention include, but not restricted to, organic bases such as mono-, di- or triethanol amine, cocinic acid diethanol amine; ethers and alcohols, for example, such as diethylene glycol (mono)butyl ether, propylene glycol methyl ether, propylene glycol butyl ether, propylene glycol propyl ether, propylene glycol dimethyl ether, ethylene glycol butyl ether and the like. Among them preferred are ethanolamine and diethylene glycol butyl ether.
• the compositions herein comprise about 0.01-10 %, preferably 0.1-5%, by weight of the builders. Lower or higher levels of builder, however, are not meant to be excluded.
• those builders discussed below can also be used in the present cleaning composition without any particular limitation on their kinds and amounts as long as they will not prevent the objects of the present invention from being achieved.
• Organic builders suitable for the purposes of the present invention include, but not restricted to, a wide variety of polycarboxylate compounds.
• polycarboxylate refers to compounds having a plurality of carboxylate groups, preferably at least 3 carboxylate groups.
• Polycarboxylate builder can generally be added to the composition in an acid form, but can also be added in the form of a neutralized salt. When utilized in a salt form, alkali metals, such as sodium, potassium, and lithium, or alkanolammonium salts are preferred. Included among the polycarboxylate builders are a variety of categories of useful materials.
• polycarboxylate builders encompass the ether polycarboxylates, including oxydisuccinate, as disclosed in Berg, U.S. Patent 3,128,287, issued April 7, 1964, and Lamberti et al, U.S. Patent 3,635,830, issued January 18, 1972. See also "TMS/TDS" builders of U.S. Patent 4,663,071, issued to Bush et al, on May 5, 1987.
• Suitable ether polycarboxylates also include cyclic compounds, particularly alicycic compounds, such as those described in U.S. Patents 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903.
• organic builders include the ether hydroxypolycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1,3,5-trihydroxy benzene-2,4,6- trisulphonic acid, and carboxymethyloxy succinic acid, the various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediamine tetraacetic acid and nitrilotriacetic acid, as well as polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.
• polyacetic acids such as ethylenediamine tetraacetic acid and nitrilotriacetic acid
• polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene
• the cleaning compositions can, and preferably will, contain various other optional components.
• Such optional components may be in either liquid or solid form.
• the optional components may either dissolve in the liquid phase or may be dispersed within the liquid phase in the form of fine particles or droplets.
• examples of those other optional composition components include, but not limited to, colorants, pH adjusters, buffering agents, chelating agents, preservatives, filler salts, bactericides, antifoams, foaming agents, foam stabilizing agents, film-forming agents, solubilizers, anti-deposition agents, thickeners, dispersants, enzymes, enzyme boosters, perfumes, clays, and mixtures thereof.
• the cleaning composition comprises about 0.01-5% by weight of the other optional composition component.
• the cleaning compositions herein may also optionally contain one or more types of inorganic builders beyond those listed hereinbefore that also function as alkalinity sources.
• inorganic builders can include, for example, silicate builders, carbonate builders and aluminosilicate builders.
• silicate builders are the alkali metal silicates, particularly those having a SiO 2 INa 2 O ratio in the range 1.6:1 to 3.2:1 and layered silicates, such as the layered sodium silicates described in U.S. Patent 4,664,839, issued May 12, 1987 to H. P. Rieck.
• NaSKS-6 is the trademark for a crystalline layered silicate marketed by Hoechst (commonly abbreviated herein as 'SKS-6"). Unlike zeolite builders, the Na SKS-6 silicate builder does not contain aluminum. NaSKS-6 has the delta-Na 2 Si2 ⁇ 5 morphology form of layered silicate. It can be prepared by methods such as those described in German DE-A-3,417,649 and DE-A-3, 742,043.
• SKS-6 is a highly preferred layered silicate for use herein, but other such layered silicates, such as those having the general formula NaMSi x ⁇ 2 ⁇ + ryH 2 O wherein M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0, can be used herein.
• Various other layered silicates available from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11 in alpha, beta and gamma forms, respectively. As noted above, the de Ka-Na 2 Si 2 Os
• silicates are most preferred for use herein.
• Other silicates may also be useful, such as for example magnesium silicate, which can serve as a stabilizing agent for oxygen bleaches and as a component of foam control systems.
• carbonate builders are the alkaline earth and alkali metal carbonates as disclosed in German Patent Application No. 2,321,001 published on November 15, 1973.
• Ahmuinosilicate builders are useful in the present invention.
• Aluminosilicate builders can be a significant builder ingredient in cleaning composition formulations.
• Aluminosilicate builders include those having the empirical formula: M z (zA10 2 ) y ] xH 2 0 wherein z and y are integers of at least 6, the molar ratio of z to y is in the range from about 1.0 to about 0.5, and x is an integer from about 15 to about 264.
• aluminosilicate ion exchange materials are commercially available. These aluminosihcates can be crystalline or amorphous in structure and can be naturally-occurring aluminosilicates or synthetically derived. A method for producing alunnnosilicate ion exchange materials is disclosed in U.S. Patent 3,985,669, Krummel, et al, issued October 12, 1976. Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X.
• the crystalline aluminosilicate ion exchange material has the formula: Na 12 [(AlO 2 )i 2 (SiO 2 ) i2 ] xH 2 0 wherein x is from about 20 to about 30, especially about 27.
• This material is known as Zeoite A.
• the aluminosilicate has a particle size of about 0.1-10 microns in diameter.
• Such optional inorganic builders can include, for example, aluminosilicates such as zeolites. Aluminosilicate zeolites, and their use as builders are more fully discussed in Corkill et al., U.S. Patent No. 4,605,509; issued August 12, 1986, the disclosure of which is incorporated herein by reference. Also crystalline layered silicates, such as those discussed in this '509 U.S. patent, are also suitable for use in the cleaning compositions herein. If utilized, optional inorganic builders can comprise from about 2% to 15% by weight of the compositions herein.
• the cleaning compositions herein may also optionally contain one or more types of enzymes.
• enzymes can include proteases, amylases, cellulases and lipases.
• Such materials are known in the art and are commercially available. They may be incorporated into the cleaning compositions herein in the form of suspensions, "marumes" or "prills".
• Another suitable type of enzyme comprises those in the form of slurries of enzymes in nonionic surfactants, e.g., the enzymes marketed by Novo Nordisk under the tradename
• LDP Enzymes added to the compositions herein in the form of conventional enzyme prills are especially preferred for use herein. Such prills will generally range in size from about 100 to 1,000 microns, more preferably from about 200 to 800 microns and will be suspended throughout the non-aqueous liquid phase of the composition. Prills in the compositions of the present invention have been found, in comparison with other enzyme forms, to exhibit especially desirable enzyme stability in terms of retention of enzymatic activity over time. Thus, compositions which utilize enzyme prills need not contain conventional enzyme stabilizing such as must frequently be used when enzymes are incorporated into the cleaning compositions.
• the cleaning compositions herein will typically comprise from about 0.001% to 5%, preferably from about 0.01% to 1% by weight of a commercial enzyme preparation.
• Protease enzymes for example, are usually present in such commercial preparations at levels sufficient to provide from 0.005 to 0.1 Anson units (AU) of activity per gram of composition.
• the cleaning compositions herein may also optionally contain a chelating agent which serves to chelate metal ions, e.g., iron and/or manganese ions, within the cleaning compositions herein.
• a chelating agent which serves to chelate metal ions, e.g., iron and/or manganese ions, within the cleaning compositions herein.
• Such chelating agents thus serve to form complexes with metal impurities in the composition which would otherwise tend to deactivate composition components such as the peroxygen bleaching agent.
• Amino carboxylates useful as optional chelating agents include ethylenediamine tetraacetates,N-hydroxy ethylenediaminetriacetates, nitrilotriacetates, ethylene-diamine tetrapropionates, triethylenetetraamine hexacetates, diethylenetriamine pentaacetates, ethylenediamine disuccinates and ethanol diglycines.
• the alkali metal salts of these materials are preferred.
• Amino phosphonates are also suitable for use as chelating agents in the compositions of this invention when at least low levels of total phosphorus are permitted in cleaning compositions, and include ethylenediamine tetrakis(methylene phosphonates) as
• these amino phosphonates do not contain alkyl or alkenyl groups with more than about 6 carbon atoms.
• Preferred chelating agents include hydroxyethyldiphosphonic acid (HEDP), diethylene triamine penta acetic acid (DTPA), ethylenediamine disuccinic acid (EDDS) and dipicolinic acid (DPA) and salts thereof.
• the chelating agent may, of course, also act as a builder during use of the compositions herein.
• the chelating agent if employed, can comprise from about 0.1% to 4% by weight of the compositions herein. More preferably, the chelating agent will comprise from about 0.2% to 2% by weight of the cleaning compositions herein.
• the cleaning compositions herein may also optionally contain a polymeric material which serves to enhance the ability of the composition to maintain its solid particulate components in suspension.
• a polymeric material which serves to enhance the ability of the composition to maintain its solid particulate components in suspension.
• Such materials may thus act as thickeners, viscosity control agents and/or dispersing agents.
• Such materials are frequently polymeric polycarboxylates but can include other polymeric materials such as polyvinylpyrrolidone (PVP) or polyamide resins.
• Polymeric polycarboxylate materials can be prepared by polymerizing or copolymerizing suitable unsaturated monomers, preferably in their acid form.
• Unsaturated monomeric acids that can be polymerized to form suitable polymeric polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenemalonic acid.
• the presence in the polymeric polycarboxylates herein of monomeric segments, containing no carboxylate radicals such as vinylmethyl ether, styrene, ethylene, etc. is suitable provided that such segments do not constitute more than about 40% by weight of the polymer.
• Particularly suitable polymeric polycarboxylates can be derived from acrylic acid.
• acrylic acid-based polymers which are useful herein are the water-soluble salts of polyacrylic acid.
• the average molecular weight of such polymers in the acid form preferably ranges from about 2,000 to 100,000, more preferably from about 2,000 to 10,000, even more preferably from about 4,000 to 7,000, and most preferably from about 4,000 to 5,000.
• Water-soluble salts of such acrylic acid polymers can include, for example, the alkali metal salts.
• Soluble polymers of this type are known materials. Use of polyacrylates of this type in cleaning compositions has been disclosed, for example, Diehl, U.S. Patent 3,308,067, issued March 7, 1967. Such materials may also perform a builder function.
• the optional thickening, viscosity control and/or dispersing agents should be present in the compositions herein to the extent of from about 0.1% to 4% by weight. More preferably, such materials can comprise from about 0.5% to 2% by weight of the cleaning compositions herein.
• the cleaning compositions herein may also optionally contain conventional brighteners, suds suppressors, dyes and/or perfume materials.
• brighteners, suds suppressors, silicone oils, dyes and perfumes must of course, be compatible and non-reactive with the other composition components in a non-aqueous environment, If present, brighteners suds suppressors, dyes and/or perfumes will typically comprise from about 0.0001% to 2% by weight of the compositions herein.
• Polymeric soil release agents are characterized by having both hydrophilic segments, to hydrophilize the surface of hydrophobic fibers, such as polyester and nylon, and hydrophobic segments, to deposit upon hydrophobic fibers and remain adhered thereto through completion of washing and rinsing cycles and, thus, serve as an anchor for the hydrophilic segments. This can enable stains occurring subsequent to treatment with the soil release agent to be more easily cleaned in later washing procedures.
• polymeric soil release agents useful herein include U.S. Patent 4,721,580, issued January 26, 1988 to Gosselink; U.S. Patent 4,000,093, issued December 28, 1976 to Nicol, et al.; European Patent Application 0 219 048, published April 22, 1987 by Kud, et al.; U.S. Patent 4,702,857, issued October 27, 1987 to Gosselink; U.S. Patent 4,968,451, issued November 6, 1990 to J.J. Scheibel.
• Commercially available soil release agents include the SOKALAN type of material, e.g., SOKALAN HP-22, available from BASF (Germany). Also see U.S. Patent 3,959,230 to Hays, issued May 25, 1976 and U.S. Patent 3,893,929 to Basadur issued July 8, 1975. Examples of this polymer include the commercially available material ZELCON 5126 (from Dupont) and MILEASE T (from
• polymeric soil release agents include the terephthalate polyesters of U.S. Patent 4,711,730, issued December 8, 1987 to Gosselink et al, the anionic end-capped oligomeric esters of U.S.Patent 4,721,580, issued January 26, 1988 to Gosselink, and the block polyester oligomeric compounds of U.S. Patent 4,702,857, issued October 27, 1987 to Gosselinic.
• Preferred polymeric soil release agents also include the soil release agents of U.S. Patent 4,877,896, issued October 31, 1989 to Maldonado et al.
• soil release agents will generally comprise from about 0.01% to about 10.0%, by weight, of the cleaning compositions herein, typically from about 0.1% to about 5%, preferably from about 0.2% to about 3.0%.
• the present composition can be formulated at a concentration sufficient to be used.
• the product can be sprayed onto a surface to be cleaned and then wiped off by a suitable material such as cloth, paper towel or the like.
• the composition herein can be formulated into a form of concentrate and be diluted before use.
• the composition herein can be packaged by a packaging container including a spraying apparatus, for example, such as a pump, an aerosol propellant, an injection valve and the like.
• the heavy duty cleaning compositions of the present invention can be made by mixing and blending the desired ingredients with the desired solvent.
• Berol 226 (a cationic surfactant), from Akzol Nobel Company;
• Test method 1 decontamination ability test
• a man-made oily dirt was formulated by adding 5 % of glyceryl monostearate, based on the total mass of the oily dirt, into a mixture of tallow oil (a butter produced by Bright).
• the oily dirt was placed into a beaker on an electric furnace, heated up to 180 ° C and maintained the temperature while stirring for 10 minutes, then naturally cooled to a desired 80 ° C for ready (the room temperature is 20 " C).
• a clean 75 mm x 26 mm x 2 mm slide glass for a microscope was provided and weighted (the weight is recorded as MO).
• the slide glass was immersed into the oily dirt for 1 ⁇ 2 seconds, then taken out and aired at the room temperature for 12 hours to obtain a test piece, and then accurately weighted with an analytical balance (the weight is recorded as Ml).
• a mechanical stirrer and a 300 ml glass beaker were provided. 200 ml of test liquid was poured into the glass beaker and then the test piece was carefully put into the glass beaker using a long forceps. Then the test liquid was stirred at 1000 rpm provided that the stirring paddle would not contact the test piece. After 5 minutes, the stirring was stopped. The test liquid was poured off and the test piece was taken out of the glass beaker and put into a dry oven at 35 ° C . After being dryed for 2 hours, the test piece was weighted (the weight is recorded as M2). Dirt removal ratio is calculated according to the following equation:
• Test method 2 test method of skin irritative response The cleaning composition was dropped onto one side of a four-layered gauze with a size of 2.5 cm x 2.5 cm and then the gauze was applied onto a skin. After 4 hours, the gauze was removed, the remained cleaning composition was removed by warm water or a non-irritative solvent. The skin irritative response degree was observed after removing the cleaning composition from the skin. The scores and the irritability were remarked according to the following Table 1 and Table 2.
• Example 1 Into a reaction kettle, 600 g of water were charged, and 20 g of 23E7, 60 g of Berol 226, 40 g of diethylene glycol monobutyl ether, and 5 g of D-limonene were added at room temperature under atmospheric pressure. The materials were stirred for 30 minutes until a homogeneous mixture was obtained. Then, 5 g monoethanolamine were added thereto. The materials became homogeneous after being stirred for 30 minutes. Finally, the remainder water was supplemented, and the materials were stirred for 30 minutes.
• Example 2 Into a reaction kettle, 600 g of water were charged, and 20 g of 23E7, 60 g of Berol 226, 40 g of diethylene glycol monobutyl ether, and 5 g of D-terpene were added at room temperature under atmospheric pressure. The materials were stirred for 30 minutes until a homogeneous mixture was obtained. Then, 5 g monoethanolamine were added thereto. The materials became homogeneous after being stirred for 30 minutes. Finally, the remainder water was supplemented, and the materials were stirred for 30 minutes.
• Example 3 Into a reaction kettle, 600 g of water were charged, and 20 g of 23E7, 60 g of Berol 226, and 5 g of D-limonene were added at room temperature under atmospheric pressure.
• the materials were stirred for 30 minutes until a homogeneous mixture was obtained. Then, 5 g monoethanolamine were added thereto. The materials became homogeneous after being stirred for 30 minutes. Finally, the remainder water was supplemented, and the materials were stirred for 30 minutes.
• Example 4 Into a reaction kettle, 600 g of water were charged, and 20 g of 23E7, 60 g of Berol 226, 40 g of diethylene glycol monobutyl ether, and 5 g of D-limonene were added at room temperature under atmospheric pressure. The materials were stirred for 30 minutes until a homogeneous mixture was obtained. Finally, the remainder water was supplemented, and the materials were stirred for 30 minutes.
• Example 5 Into a reaction kettle, 600 g of water were charged, and 60 g of Berol 226, 40 g of diethylene glycol monobutyl ether, and 5 g of D-limonene were added at room temperature under atmospheric pressure. The materials were stirred for 30 minutes until a homogeneous mixture was obtained. Then, 5 g of monoethanolamine were added thereto. The materials became homogeneous after being stirred for 30 minutes. Finally, the remainder water was supplemented, and the materials were stirred for 30 minutes.
• Example 6 Into a reaction kettle, 400 g of water were charged, and 300 g of 23E7, 5 g of Berol 226, 40 g of diethylene glycol monobutyl ether, and 50 g of D-limonene were added at room temperature under atmospheric pressure. The materials were stirred for 30 minutes until a homogeneous mixture was obtained. Then, 5 g monoethanolamine were added thereto. The materials became homogeneous after being stirred for 30 minutes. Finally, the remainder water was supplemented, and the materials were stirred for 30 minutes.
• Example 7 Into a reaction kettle, 600 g of water were charged, and 20 g of 23E7, 100 g of Berol 226, 40 g of diethylene glycol monobutyl ether, and 5 g of D-limonene were added at room temperature under atmospheric pressure. The materials were stirred for 30 minutes until a homogeneous mixture was obtained. Then, 5 g monoethanolamine were added thereto. The materials became homogeneous after being stirred for 30 minutes. Finally, the remainder water was supplemented, and the materials were stirred for 30 minutes.
• Example 8 Into a reaction kettle, 600 g of water were charged, and 20 g of 23E7, 200 g of Berol 226, 40 g of diethylene glycol monobutyl ether, and 5 g of D-limonene were added at room temperature under atmospheric pressure. The materials were stirred for 30 minutes until a homogeneous mixture was obtained. Then, 5 g of monoethanolamine were added thereto. The materials became homogeneous after being stirred for 30 minutes. Finally, the remainder water was supplemented, and the materials were stirred for 30 minutes.
• Example 9 Into a reaction kettle, 400 g of water, 300 g of Berol 226, 40 g of diethylene glycol monobutyl ether, and 5 g of D-limonene were added at room temperature under atmospheric pressure. The materials were stirred for 30 minutes until a homogeneous mixture was obtained. Then, 5 g of monoethanolamine were added thereto. The materials became homogeneous after being stirred for 30 minutes. Finally, the remainder water was supplemented, and the materials were stirred for 30 minutes.
• Example 10 Into a reaction kettle, 600 g of water, 80 g of Berol 226, 40 g of diethylene glycol monobutyl ether, and 0.1 g of D-limonene were added at room temperature under atmospheric pressure. The materials were stirred for 30 minutes until a homogeneous mixture was obtained. Then, 5 g of monoethanolamine were added thereto. The materials became homogeneous after being stirred for 30 minutes. Finally, the remainder water was supplemented, and the materials were stirred for 30 minutes.
• Example 11 Into a reaction kettle, 600 g of water were charged, and 20 g of 23E7, 60 g of Berol 226, 40 g of diethylene glycol monobutyl ether, and 10 g of D-limonene were added at room temperature under atmospheric pressure. The materials were stirred for 30 minutes until a homogeneous mixture was obtained. Then, 5 g of monoethanolamine were added thereto. The materials became homogeneous after being stirred for 30 minutes. Finally, the remainder water was supplemented, and the materials were stirred for 30 minutes.
• Example 12 Into a reaction kettle, 600 g of water were charged, and 80 g of 23E7, 60 g of Berol 226, 40 g of diethylene glycol monobutyl ether, and 30 g of D-limonene were added at room temperature under atmospheric pressure. The materials were stirred for 30 minutes until a homogeneous mixture was obtained. Then, 5 g of monoethanolamine were added thereto. The materials became homogeneous after being stirred for 30 minutes. Finally, the remainder water was supplemented, and the materials were stirred for 30 minutes.
• Example 13 Into a reaction kettle, 300 g of water, 300 g of Berol 226, 40 g of diethylene glycol monobutyl ether, and 50 g of D-limonene were added at room temperature under atmospheric pressure. The materials were stirred for 30 minutes until a homogeneous mixture was obtained. Then, 5 g of monoethanolamine were added thereto. The materials became homogeneous after being stirred for 30 minutes. Finally, the remainder water was supplemented, and the materials were stirred for 30 minutes.
• Example 14 Into a reaction kettle, 600 g of water, 12O g of dodecyl dimethylamine oxide, 40 g of diethylene glycol monobutyl ether, and 5 g of D-limonene were added at room temperature under atmospheric pressure. The materials were stirred for 30 minutes until a homogeneous mixture was obtained. Then, 5 g of monoethanolamine were added thereto. The materials became homogeneous after being stirred for 30 minutes. Finally, the remainder water were supplemented, and the materials were stirred for 30 minutes.
• Example 15 Into a reaction kettle, 600 g of water, 120 g of AO- 14-2, 40 g of diethylene glycol monobutyl ether, and 5 g of D-limonene were added at room temperature under atmospheric pressure. The materials were stirred for 30 minutes until a homogeneous mixture was obtained. Then, 5 g of monoethanolamine were added thereto. The materials became homogeneous after being stirred for 30 minutes. Finally, the remainder water was supplemented, and the materials were stirred for 30 minutes.
• Comparative Examplel Into a reaction kettle, 600 g of water were charged, and 20 g of 23E7, 40 g of Berol 226, and 40 g of diethylene glycol monobutyl ether were added at room temperature under atmospheric pressure. The materials were stirred for 30 minutes until a homogeneous mixture is obtained. Then, 5 g of monoethanolamine were added thereto. The materials became homogeneous after being stirred for 30 minutes. Finally, the remainder water was supplemented, and the materials were stirred for 30 minutes.
• Comparative Example2 Into a reaction kettle, 600 g of water were charged, and 20 g of 23E7, 40 g of diethylene glycol monobutyl ether, and 5 g of D-limonene were added at room temperature under atmospheric pressure. The materials were stirred for 30 minutes until a homogeneous mixture was obtained. Then, 5 g of monoethanolamine were added thereto. The materials became homogeneous after being stirred for 30 minutes. Finally, the remainder water was supplemented, and the materials were stirred for 30 minutes.
• Berol 226 was replaced by dodecyldimethylamine oxide; **: Berol 226 was replaced by AO- 14-2.
• Example 2 The inventors compared the cleaning composition obtained in Example 1 with two commercial products selected randomly (hereinafter refer as commercial product A and commercial product B, respectively). The results were shown in Table 4 below.

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