CN111212896B - Detergent composition comprising hydrate forming salt particles coated with betaine - Google Patents
Detergent composition comprising hydrate forming salt particles coated with betaine Download PDFInfo
- Publication number
- CN111212896B CN111212896B CN201880066768.5A CN201880066768A CN111212896B CN 111212896 B CN111212896 B CN 111212896B CN 201880066768 A CN201880066768 A CN 201880066768A CN 111212896 B CN111212896 B CN 111212896B
- Authority
- CN
- China
- Prior art keywords
- detergent composition
- composition
- solid detergent
- hydrate
- forming salt
- 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.)
- Active
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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
-
- 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
- C11D1/88—Ampholytes; Electroneutral 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
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/046—Salts
Abstract
The present invention relates to solid detergent compositions having improved solubility. The present inventors have investigated to provide solid detergent compositions with improved solubility under cold water conditions, in particular at temperatures below 10 ℃, more preferably below 5 ℃, and towards a way of providing coated filler agents for detergent compositions which inhibit the formation of crystal agglomerates which are difficult to disperse and dispense. After a considerable amount of research aimed at solving this problem, the inventors have found that it is possible to obtain filler agents with high dispersibility and solubility in cold water at temperatures lower than 10 ℃, more preferably lower than 5 ℃, by at least partially coating the hydrate-forming salt with zwitterionic compounds of the betaine type.
Description
Technical Field
The present invention relates to solid detergent compositions having improved solubility. More particularly, it relates to solid laundry detergent compositions containing hydrate forming salts having improved cold water solubility.
Background
The problems of providing improved dispensing, dispersing and easy dissolving laundry detergent powders are well known and have been addressed many times in the past. It is undesirable, for example, to have a slow dispensing and low solubility solid laundry composition that forms a residue in the drawer of many automatic washing machines.
Also, in some areas, cold water at about 10 ℃ or less is typically used to wash fabrics during the winter season. Under such washing conditions, noticeable lumps form in the dispensing drawer of the washing machine, which can appear as visible solid white lumps in the drawer and on the washed fabrics. This problem is further exacerbated when the order of addition to the washing machine is laundry detergent product first, clothes second and water last.
During the release of cold water into the washing machine, the water gradually penetrates into the mass of solid detergent composition without applying significant physical or mechanical power thereto and hydrates the surfactant and hydrates present in the composition to form a salt. Surfactants, especially anionic surfactants, present in detergent compositions form a highly viscous paste-like phase. The hydrated water-soluble salt precipitates in crystalline form, which further hardens the viscous paste phase of the surfactant. The crystals formed are also linked to each other to transform the phase itself into a firm, hydrated solid phase that is difficult to disperse or dissolve by the subsequent application of mechanical force. The detergent composition remains insoluble under such conditions during ordinary washing times. This phenomenon is undesirable for users.
Some prior art documents have attempted to solve the problem of low dispersion and dissolution of detergent compositions in cold water, mainly due to the presence of hydrate-forming crystalline salts.
In EP229671a2(Kao,1987) a high density particulate detergent composition is disclosed in which high dispersibility and solubility in cold water is achieved by particles comprising water soluble crystalline inorganic salts which carry organic material thereon having a melting point of 40 ℃ or less which inhibits hydration of the coated particles. The organic substance is defined as a nonionic surfactant. The nonionic surfactants include polyoxyethylene, polyhydric alcohols, and alkanolamide surfactants.
When suitable conditions exist, hydrated salts can be easily formed in the powder dispensing drawer of the washing machine during low temperatures. Low water content, low temperature, is a particularly favorable condition for hydrate formation. The formation of hydrates often results in the loss of surfactant available for washing and these can deposit on fabrics, which resemble white stain-like spots on washed fabrics.
The present inventors have investigated to provide solid detergent compositions with improved solubility under cold water conditions, in particular at temperatures below 10 ℃, more preferably below 5 ℃, and towards a way of providing coated filler agents for detergent compositions which significantly inhibit the formation of crystal agglomerates which are difficult to disperse and distribute.
Disclosure of Invention
After a considerable amount of research with the aim of solving this problem, the inventors have found that it is possible to obtain coated filler agents with high dispersibility and solubility in cold water at temperatures below 10 ℃, more preferably below 5 ℃, by at least partially coating the hydrate-forming salts with zwitterionic compounds of the betaine type. Accordingly, in a first aspect, the present invention provides a coated filler agent for a solid detergent composition comprising a hydrate forming salt and a zwitterionic compound of the betaine type, wherein the hydrate forming salt is at least partially coated by the zwitterionic compound. In a second aspect, the present invention provides a filler composition according to the invention having the coated filler agent and a water-soluble salt.
In a third aspect, the present invention provides the use of a coated filler agent or filler composition according to the present invention in a detergent composition for providing improved solubility.
These and other aspects, features and advantages will become apparent to those of ordinary skill in the art upon review of the following detailed description and appended claims. For the avoidance of doubt, any feature of one aspect of the invention may be used in any other aspect of the invention. The word "comprising" means "including," but not necessarily "consisting of. In other words, the listed steps or options need not be exhaustive. It should be noted that the examples given in the following description are intended to illustrate the invention, and are not intended to limit the invention to those examples per se. Similarly, all percentages are weight/weight percentages unless otherwise indicated. Except in the operating and comparative examples, or where otherwise explicitly indicated, all numbers in this description indicating amounts of material or conditions of reaction, physical properties of materials and/or use are to be understood as modified by the word "about". Numerical ranges expressed in the format "x to y" are understood to include x and y. When multiple preferred ranges are described in the format of "x to y" for a particular feature, it is to be understood that all ranges combining the different endpoints are also contemplated.
Detailed Description
In a first aspect, the present invention relates to a coated filler agent for a solid detergent composition comprising a hydrate forming salt and a zwitterionic compound of the betaine type, wherein the hydrate forming salt is at least partially coated by the zwitterionic compound.
Coated filler agents
Zwitterionic compounds
The coated filler of the present invention comprises zwitterionic compounds of the betaine type.
The zwitterionic compounds of the betaines are preferably zwitterionic surfactants or zwitterionic polymers, preferably zwitterionic surfactants. Suitable zwitterionic surfactants are known in the art and include, for example, those derivatives broadly described as aliphatic quaternary ammonium, phosphonium, and sulfonium compounds, in which the aliphatic radicals can be straight or branched chain, wherein one of the aliphatic substituents contains from about 8 to about 18 carbon atoms and one contains an anionic group, e.g., carboxy, sulfonate, sulfate, phosphate, or phosphonate.
Specific examples of suitable zwitterionic surfactants include alkyl betaines such as coco dimethyl carboxymethyl betaine, lauryl dimethyl alpha-carboxyethyl betaine, cetyl dimethyl betaine, lauryl bis (2-hydroxyethyl) carboxymethyl betaine, stearyl bis (2-hydroxypropyl) carboxymethyl betaine, oleyl dimethyl gamma-carboxypropyl betaine and lauryl bis (2-hydroxypropyl) alpha-carboxyethyl betaine, alkylamidopropyl betaine and alkyl sulfobetaine, such as coco dimethyl sulfopropyl betaine, stearyl dimethyl sulfopropyl betaine, lauryl dimethyl sulfoethyl betaine, lauryl bis (2-hydroxyethyl) sulfopropyl betaine, cocamidopropyl hydroxysulfobetaine, and alkylamidopropyl hydroxysulfobetaine. Preferred examples of phosphobetaines (phospho-betaines) include, but are not limited to, propyl phosphobetaine monosodium, cocamidoethyl phosphobetaine disodium, cocamido 3-hydroxypropyl phosphobetaine disodium, lauryl myristoylamido 3-hydroxypropyl phosphobetaine.
Useful betaines have the structure given in formula 1:
wherein
R1: is an alkyl group having 1 to 14 carbon atoms, preferably 1 to 2 carbon atoms, preferably straight or branched.
R2: is an alkyl group having 1 to 14 carbon atoms, preferably 1 to 2 carbon atoms, preferably straight or branched.
R3: alkyl having 6 to 14 carbon atoms, preferably 10 to 14 carbon atoms, preferably straight-chain or branched, or
In addition, useful betaines have the structure given in formula 2:
wherein
R1: is an alkyl group having 1 to 14 carbon atoms, preferably 1 to 2 carbon atoms, preferably straight or branched.
R2: is an alkyl group having 1 to 14 carbon atoms, preferably 1 to 2 carbon atoms, preferably straight or branched.
R3: is an alkyl group having 6 to 14 carbon atoms, preferably 10 to 14 carbon atoms, preferably straight or branched, or
Particularly useful betaines are, for example, 3- (dodecyldimethylammonium) propane-1-sulfonate and 3- (tetradecyldimethylammonium) ethane-1-sulfonate.
The zwitterionic surfactant is most preferably a carbobetaine (carbo-betaine), a sulfobetaine, a phosphobetaine, a carboxybetaine, or mixtures thereof.
The zwitterionic compound is preferably a zwitterionic polymer. Preferred zwitterionic polymers include, but are not limited to, poly (phosphobetaine methacrylate), poly (sulfobetaine methacrylate), poly (carboxybetaine methacrylate), poly (serine methacrylate).
The zwitterionic compounds of the betaines are present in an amount in the range from 0.5 to 20% by weight, based on the coated filler. Preferably, the amount of zwitterionic compound in the coated filler agent is at least 1 wt%, still preferably at least 2.5 wt%, further preferably at least 3 wt% and most preferably at least 5 wt%, based on the coated filler agent, but typically not more than 10 wt%, still preferably not more than 15 wt% and most preferably not more than 20 wt%.
The zwitterionic compounds of the betaines according to the invention coat the hydrates at least partially to form salts. More preferably, the zwitterionic compound completely covers the hydrate-forming salt.
Hydrate forming salts
The coated filler agent of the present invention comprises a hydrate forming salt. The hydrate-forming salts of the invention are at least partially coated with zwitterionic compounds of the betaine type.
Non-limiting examples of hydrate-forming salts are sulfates, carbonates or bicarbonates of alkaline earth metals or alkali metals and mixtures thereof.
Preferred examples of hydrate-forming salts according to the invention are selected from sodium carbonate, sodium sulphate, sodium bicarbonate, sodium tripolyphosphate, sodium pyrophosphate, sodium orthophosphate, magnesium sulphate or mixtures thereof. Preferably, the hydrate forming salt is sodium carbonate, sodium sulfate or a mixture thereof.
The present invention is particularly suitable for any salt that exhibits a significant change in solubility with decreasing temperature. This is particularly suitable for salts which readily crystallize from aqueous solutions at relatively low temperatures to form crystals which readily bond together to form a robust structure. Without being bound by theory, it is believed that this crystal formation inhibits the dispersibility and solubility of the detergent composition. Among the known salts for use in detergent compositions, sodium carbonate generates a large amount of heat upon hydration, and dissolves even in cold water to form a solution having a high concentration, while generating heat. This heat is then absorbed by the surrounding low temperature and as the temperature decreases, the solubility of the hydrated salt decreases, the salt precipitates as crystals. At a temperature of 32 ℃ or lower, sodium carbonate is in the form of its decahydrate, and it has a large amount of crystal water. Hydration increases the volume of insoluble crystals, and such hydrated crystals readily bond together to form a more robust structure. Thus, the problem of residue formation is particularly higher in compositions containing sodium carbonate.
The hydrate forming salt is present in an amount ranging from 80 to 99 wt% based on the coated filler agent. Preferably, the amount of hydrate forming salt in the coated filler agent is at least 80 wt%, still preferably at least 85 wt%, further preferably at least 87 wt% and most preferably at least 90 wt%, but generally not more than 99 wt%, still preferably not more than 97.5 wt% and most preferably not more than 95 wt%, based on the coated filler agent.
Method for producing coated filler agents
Any method known in the art for coating may be used in the present invention.
Preferably, the process for preparing the coated filler agent comprises the steps of:
a. providing a hydrate forming salt;
b. applying a coating onto the hydrate forming salt by spraying or decanting a zwitterionic compound of the betaine type or intimately mixing the hydrate forming salt with the zwitterionic compound, or preparing a slurry of the hydrate forming salt with the zwitterionic compound and subsequently drying the slurry.
One preferred coating method comprises spraying or decanting the zwitterionic compound onto the hydrate-forming salt. During the coating process, the hydrates are continuously mixed to form the salts. Preferably, the hydrate forming salt is placed in a plow shear mixer or other high speed mixer, which can maintain the high speed rotation of the hydrate forming salt during the coating process. The coated filler agent obtained from this process is according to the invention and the zwitterionic compound at least partially covers or coats the hydrate forming salt. In another preferred method, the hydratable salt is placed in a Sigma or z-blender during the coating process, wherein the zwitterionic compound is continuously sprayed or decanted onto the hydrate-forming salt.
Another method of preparing the coated filler agent of the invention comprises a first step of preparing an aqueous slurry comprising a hydrate forming salt and a zwitterionic compound, after which the slurry is dried, preferably by a spray drying route, the coated filler agent obtained being according to the invention wherein the zwitterionic compound at least partially covers the hydrate forming salt.
Filler composition
According to a second aspect of the present invention, a filler composition having the coated filler agent of the first aspect and a water-soluble salt is disclosed.
Water-soluble salt
The filler composition according to the second aspect of the invention comprises a water-soluble salt having a solubility in distilled water of greater than 30 grams per 100mL when measured at a temperature of 10 ℃, the water-soluble salt being present separately from the hydrate-forming salt. Preferably, the water-soluble salt has a solubility of at least 35 g/100 mL, more preferably at least 40 g/100 mL, even more preferably at least 45 g/100 mL.
Non-limiting examples of water-soluble salts include potassium carbonate, potassium chloride, potassium formate, potassium acetate, sodium chloride, sodium acetate, sodium formate, calcium acetate, magnesium chloride, sodium dihydrogen phosphate, potassium hydrogen sulfate, magnesium acetate, sodium fumarate. More preferably, the water soluble salt is selected from sodium chloride, sodium acetate or sodium formate.
Preferably, the amount of water-soluble salt in the filler composition is at least 5 wt%, still preferably at least 10 wt%, further preferably at least 15 wt% and most preferably at least 20 wt%, but generally not more than 40 wt%, still preferably not more than 50 wt% and most preferably not more than 60 wt%, based on the filler composition.
Detergent composition
According to a third aspect of the present invention, there is disclosed a solid detergent composition comprising a coated filler agent according to the first aspect or a filler composition according to the second aspect of the present invention. Solid detergent compositions according to the present invention encompass powders as well as a wide variety of cast and extruded forms including, for example, pellets, blocks, granules and tablets. It is to be understood that the term "solid" refers to the state of the solid detergent composition under the intended storage conditions and use of the detergent composition. Generally, it is expected that the detergent composition will remain solid when provided at temperatures up to about 100 ° F. Preferably, the solid detergent composition is a powder, tablet, granule or particulate composition.
In some embodiments, the detergent composition is provided in unit dosage form. Unit dose refers to a unit size of the detergent composition such that the entire unit is used during a single wash cycle. When the solid detergent composition is provided as a unit dose, it is preferably provided as a cast solid, an extruded granule or pellet, or a tablet having a size of between about 1 gram to about 50 grams. In other embodiments, the cast solid, extruded pellet, or tablet has a size between 50 grams and up to 250 grams, or the extruded solid has a weight of about 100 grams or greater.
Moreover, it is to be understood that the solid detergent composition may be provided as a cast solid, an extruded pellet, or a tablet, such that a plurality of solids may be obtained in a package having a size of between about 40 grams and about 11,000 grams.
In other embodiments, the solid detergent composition is provided in the form of a multi-purpose solid, such as a cake or a plurality of pellets, and can be reused to produce an aqueous detergent composition for multiple wash cycles. In some embodiments, the solid detergent composition is provided as a powder, cast solid, extruded cake, or tablet having a mass of between about 5 grams and 10 kilograms. In some embodiments, the multipurpose form of the solid detergent composition has a mass of between about 1 to 10 kilograms, more preferably 1 to 5 kilograms.
Preferably, the solid detergent composition comprises from 2 wt% to 40 wt% of the coated filler agent. Preferably, the amount of coated filler in the solid detergent composition is at least 2 wt%, further preferably at least 5 wt%, further preferably at least 10 wt% and most preferably at least 15 wt%, but generally not more than 30 wt%, further preferably not more than 35 wt% and most preferably not more than 40 wt%, based on the detergent composition.
In a further embodiment of the invention, the detergent composition comprises a filler composition having a coated filler agent and a water-soluble salt.
The detergent composition preferably comprises the filler composition in an amount of at least 5 wt%, further preferably at least 8 wt%, further preferably at least 10 wt% and most preferably at least 15 wt%, but generally not more than 30 wt%, further preferably not more than 40 wt% and most preferably not more than 50 wt%, based on the weight of the detergent composition.
Surface active agent
Preferably, the detergent composition comprises a surfactant selected from anionic, nonionic, zwitterionic, cationic or amphoteric surfactants.
Anionic surfactants
Suitable anionic detergent compounds which may be used are typically water-soluble alkali metal salts of organic sulphuric and sulphonic acids having an alkyl group containing from about 8 to about 22 carbon atoms, the term alkyl being used to include the alkyl portion of higher acyl groups.
Examples of suitable synthetic anionic detergent compounds are sodium and potassium alkyl sulphates, especially by reacting higher C' s8To C18Alcohols (e.g. derived from tallow or coconut oil) sulphated, alkyl C9To C20Sodium and potassium benzene-sulphonates, especially linear secondary alkyl C10To C15Sodium benzenesulfonate; and sodium alkyl glyceryl ether sulfates, especially higher from tallow or coconut oilAlcohols and those ethers of synthetic alcohols derived from petroleum.
The anionic surfactant is preferably selected from: linear alkyl benzene sulfonate; an alkyl sulfate; alkyl ether sulfates; soap; alkyl (preferably methyl) ester sulfonates, and mixtures thereof.
Most preferred anionic surfactants are selected from: linear alkyl benzene sulfonate; an alkyl sulfate; alkyl ether sulfates and mixtures thereof. Preferably, the alkyl ether sulphate is C having an average of 1 to 3EO (ethoxylate) units12To C14N-alkyl ether sulfates. Sodium lauryl ether sulphate is particularly preferred (SLES). Preferably, the linear alkylbenzene sulfonate is C11To C15Sodium alkyl benzene sulfonate. Preferably, the alkyl sulfates are linear or branched C12To C18Sodium alkyl sulfate. Sodium dodecyl sulfate is particularly preferred (SDS, also known as primary alkyl sulfate). Preferably, the solid detergent composition comprises from 2 wt% to 80 wt% anionic surfactant.
Nonionic surfactant
The nonionic surfactant component preferably comprises an alcohol ethoxylate. Alcohol ethoxylates are formed from the reaction of primary or secondary alcohols with ethylene oxide. Typically, aliphatic C8To C18The linear or branched primary or secondary alcohol is reacted with ethylene oxide in the desired molar amount to obtain the alcohol ethoxylate. Preferred alcohol ethoxylates have 2 to 40, preferably 3 to 30, more preferably 5 to 20 ethylene oxide 20 units attached to the aliphatic chain.
The surfactant may be selected from the surfactants described in "Surface Active Agents" by Schwartz & Perry, Vol.1, Interscience 1949, Schwartz, Vol.2 of Perry & Berch, Interscience 1958, Current edition "McCutcheon's Emulsifiers and Detergents" issued by the Manufacturing conditioners Company or "Tenside-Taschenbuch", H.Stache, 2 nd edition, Carl Hauser Verlag, 1981. Preferably, the surfactant used is saturated.
Suitable nonionic detergent compounds which may be used include, inter alia, those having a hydrophobic group and a reactive hydrogen atomWith alkylene oxides, in particular ethylene oxide alone or together with propylene oxide, as well as aliphatic alcohols, acids, amides or alkylphenols. A specific nonionic detergent compound is C6To C22Alkylphenol-ethylene oxide condensates, usually 5 to 25 EO, i.e. 5 to 25 units of ethylene oxide per molecule, and aliphatic C8To C18Condensation products of linear or branched primary or secondary alcohols with ethylene oxide, typically 5 to 40 EO.
The total amount of surfactant present in the composition is preferably at least 5 wt%, more preferably at least 10 wt%. More preferably, the total amount of surfactant is from 15 to 65 wt%, preferably from 10 to 50 wt%.
In addition to the aforementioned nonionic and/or anionic surfactants, other surfactants such as cationic surfactants and amphoteric/zwitterionic surfactants such as betaines may also be present.
Builders and chelating agents
The builder material may be selected from 1) calcium sequestrant materials, 2) deposition materials, 3) calcium ion exchange materials, and 4) mixtures thereof. Examples of calcium sequestrant builder materials include alkali metal polyphosphates such as sodium tripolyphosphate, and organic sequestrants such as ethylenediamine tetraacetic acid. Examples of deposition builder materials include sodium orthophosphate.
Examples of calcium ion exchange builder materials include various types of water-insoluble crystalline or amorphous aluminosilicates of which zeolites are well known representatives, for example zeolite ｃA, zeolite B (also known as zeolite P), zeolite C, zeolite X, zeolite Y and zeolite P-type, as described in EP- ｃA-0,384,070.
The detergent composition may also optionally contain relatively low levels of organic detergent builder or chelant materials. Examples include alkali metals, citrates, succinates, malonates, carboxymethylsuccinates, carboxylates, polycarboxylates, and polyacetylcarboxylates. Specific examples include oxydisuccinic acid (oxydisuccinic acid), mellitic acid, benzenepolycarboxylic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, alkyl or alkenylsuccinic acid, nitrilotriacetic acidSodium, potassium and lithium salts of acetic acid and citric acid. Other examples are DEQUESTTMWhich are sequestrants of the organic phosphonate type marketed by Monsanto, and alkane hydroxyphosphonates.
Other suitable organic builders include the higher molecular weight polymers and copolymers known to have builder properties. For example, such materials include suitable polyacrylic acids, polymaleic acids, and polyacrylic acid/polymaleic acid copolymers and salts thereof, such as by BASF under the name SOKALANTMThose that are sold.
If used, the builder material may comprise from about 0.5 to 20% by weight of the composition, preferably from 1% to 10% by weight. Preferred levels of builder are less than 10% by weight of the composition, preferably less than 5% by weight. Preferably, the laundry detergent formulation is a non-phosphate building laundry detergent formulation, i.e. containing less than 1 wt% phosphate.
Shading dye
Hueing dyes deposit onto fabrics during the washing or rinsing step of the washing process, providing visible hueing to the fabrics. Toning of white laundry may be done in any color depending on user preference. Blue and violet are particularly preferred hues, so that the preferred dye or dye mixture is one that imparts a blue or violet hue on white fabrics. The hueing dye used is preferably blue or violet. The hueing dye chromophore is preferably selected from: monoazo, disazo, triphenylmethane, triphenol dioxazine, phthalocyanine, naphthalactam, azine, and anthraquinone. Most preferably, monoazo, disazo, azine and anthraquinone. Most preferably, the dye bears at least one sulfonate group. Preferred shading dyes are selected from direct dyes, acid dyes, hydrophobic dyes, cationic dyes and reactive dyes.
If included, the hueing dye is present in the composition in the range of 0.0001 to 0.01 wt%.
Fluorescent agent
The composition preferably comprises a fluorescent agent (optical brightener). Fluorescent agents are well known, and many such fluorescent agents are commercially available. Typically, these fluorescent agents are provided and used in the form of their alkali metal salts, e.g., sodium salts. The total amount of fluorescer or fluorescers used in the composition is typically from 0.005 to 2 wt%, more preferably from 0.01 to 0.1 wt%. Preferred classes of fluorescers are: distyrylbiphenyl compounds, such as Tinopal (trade mark) CBS-X, diamine distyrylbisonic acid compounds, such as Tinopal DMS pure Xtra and Blankophor (trade mark) HRH, and pyrazoline compounds, such as Blankophor SN. Preferred fluorescent agents are: sodium 2- (4-styryl-3-sulfophenyl) -2H-naphtho (napthol) [1,2-d ] triazole, disodium 4,4' -bis { [ (4-anilino-6- (N-methyl-N-2-hydroxyethyl) amino-1, 3, 5-triazin-2-yl) ] amino } stilbene-2-2 ' -disulfonate, disodium 4,4' -bis { [ (4-anilino-6-morpholinyl-1, 3, 5-triazin-2-yl) ] amino } stilbene-2-2 ' -disulfonate, and disodium 4,4' -bis (2-sulfostyryl) biphenyl.
Perfume
Preferably, the composition comprises a perfume. The perfume is preferably 0.001 to 3 wt%, most preferably 0.1 to 1 wt%. Many suitable examples of fragrances are provided in CTFA (Cosmetic, Toiletryand Fragrance Association)1992International layers Guide, published by CFTA Publications, and OPD 1993Chemicals layer Directory 80th annual edition, published by Schnell publishing Co.
It is common for multiple perfume components to be present in a formulation. In the compositions of the present invention, it is envisaged that four or more, preferably five or more, more preferably six or more, or even seven or more different perfume components will be present.
Polymer and method of making same
The composition may comprise one or more polymers. The polymer may assist the cleaning process by helping to break up (retail) dirt in the solution or suspension and/or prevent dye transfer. The polymer may also assist in the soil removal process. Dye transfer, anti-redeposition and soil release polymers are described in further detail below.
The composition may comprise one or more polymers. Examples are carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, poly (ethylene glycol), poly (vinyl alcohol), ethoxylated polyamines, polycarboxylates such as polyacrylates, maleic/acrylic acid copolymers and lauryl methacrylate/acrylic acid copolymers.
Dye transfer inhibitors
Modern detergent compositions often use polymers as so-called "dye transfer inhibitors". These prevent migration of the dye, especially during long soaking times. Typically, such dye transfer inhibiting agents include polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, manganese phthalocyanines, peroxidases, and mixtures thereof, and are typically present at levels of 0.01 to 10 wt%, based on the total amount in the laundry composition.
Anti-redeposition polymers
Antiredeposition polymers are designed to suspend or disperse soils. Typically the 25 anti-redeposition polymer is an ethoxylated and or propoxylated polyethyleneimine or polycarboxylate material. For example, acrylic-based homopolymers or copolymers available from Dow Chemical under the trademark ACUSOL, from Akzonobel under the trademark Alcosperse, or from BASF under the trademark Sokolan.
Soil release polymers
Examples of suitable soil release polymers include poly (vinyl esters) (e.g., C)1-C6Vinyl ester), preferably poly (vinyl acetate) grafted onto a polyalkylene oxide backbone. Commercially available soil release agents of this kind include SOKALAN-type materials such as SOKALAN HP-22 available from BASF (West Germany). Further suitable soil release polymers of different types include the commercially available materials ZELCON 5126 (from DuPont) and millase T (from ICI). If present, the soil release polymer may be included at a level of from 0.01 to 10 wt% based on the total amount of the laundry composition. Further examples of soil release polymers are terephthalic acid/diol copolymers sold under the tradenames Texcare, Reel-o-tex, Gerol, Marloquest, Cirrasol.
Enzyme
Enzymes may also be present in the formulation. Preferred enzymes include proteases, lipases, pectate lyases, amylases, cutinases, cellulases, mannanases.
According to another aspect of the invention is disclosed the use of a coated filler agent of the first aspect or a filler composition of the second aspect in a detergent composition for improving cold water solubility and/or dispersibility.
The invention will now be explained in more detail by means of non-limiting examples of compositions according to the invention.
Examples
Example 1: evaluation of solubility and dispersibility
To determine the solubility of the hydrate forming salts in the coated filler agent, different compositions were prepared and tested in the following manner. The compositions tested are given in table 1.
10g of the composition with hydrate forming salt given in Table 1 were placed in a beaker. To this was added 100mL of water maintained at a temperature of 5 ℃ and allowed to stand for 5 minutes. After 5 minutes, the solution was gently mixed 5 times clockwise and 5 more times counterclockwise using a glass rod. The solution was then slowly decanted to separate the solid portion. The collected residue was dried at a temperature of 60 ℃, and the weight of the residue was weighed and recorded in table 1.
In example 1, 10 grams of sodium sulfate (hydrate forming salt) was placed in a plow shear mixer and rotated at high speed, 0.05 grams of sulfobetaine was sprayed onto the salt during mixing, and after 5 minutes of mixing, a filler was obtained and tested for solubility.
In example 2, a coated filler agent was prepared similarly to example 1, followed by the addition of sodium chloride to obtain a filler composition. Similarly, in example 3, different filler compositions with sodium chloride and potassium carbonate were obtained.
In example B, the filler agent was prepared similarly to example 1 except that the sulfobetaine was replaced with a given amount of Neodol EO7 (ethoxylated nonionic surfactant).
TABLE 1
The table above shows that when sodium sulphate (hydrate forming salt) is at least partially coated with sulphobetaine according to the invention (example 2), the best solubility results are obtained when dissolved at 5 ℃. The table also shows that the solubility of the filler agent is low and the residues formed in examples a and B, which have no coating or are coated with compounds outside the scope of the invention, are hard. The further filler compositions of examples 2 and 3 with coated filler agent and water soluble salt show improved solubility and the nature of the residue is also soft.
Example 2: evaluation of solubility and dispersibility of solid detergent composition
3 different solid detergent compositions as shown in table 2 were evaluated. 100 grams of each solid detergent composition was packaged in a sachet and kept at a temperature of 5 ℃ for 24 hours. 100 grams of each solid detergent composition was then poured into the powder dispensing drawer of a three-star automatic top loading washing machine. Water maintained at a temperature of 5 ℃ was brought into contact with the powders given in table 2 at the desired flow rate, followed by fluff (fuzzy) circulation. The residue remaining in the powder dispensing drawer at the end of the cycle was taken and dried at a temperature of 60 ℃ for 24 hours. After drying, the residue was weighed and the amount of residue was determined as provided in table 2.
TABLE 2
The table above shows that when sodium sulphate (hydrate forming salt) is at least partially coated with sulphobetaine according to the invention (example 4), the best solubility results are obtained when dissolved at 5 ℃. The further filler composition of example 5 with coated filler agent and water soluble salt showed improved solubility and dispersibility compared to the detergent composition of comparative example C with only hydrate forming salt.
It will be appreciated that the illustrated embodiments provide coated filler agents having hydrate forming salts at least partially coated with zwitterionic compounds, providing improved cold water solubility and dispersibility.
It should be understood that the specific forms of the invention herein illustrated and described are intended to be representative only, as certain changes may be made therein without departing from the clear teachings of the disclosure. Although the invention has been described with reference to specific embodiments, it will be appreciated by those skilled in the art that the invention may be embodied in many other forms.
Claims (11)
1. A coated filler agent for a solid detergent composition comprising a zwitterionic compound that is a hydrate-forming salt and a betaine, wherein the hydrate-forming salt is at least partially coated by the zwitterionic compound, wherein the hydrate-forming salt is selected from alkaline earth or alkali metal sulfates, carbonates or bicarbonates, and mixtures thereof, wherein the zwitterionic compound is a zwitterionic surfactant selected from carbobetaine/carboxybetaine, sulfobetaine, phosphobetaine, or mixtures thereof, wherein the zwitterionic surfactant is present in an amount of 0.5 to 20 wt% based on the coated filler agent, and wherein the hydrate-forming salt is present in an amount of 80 to 99 wt% based on the coated filler agent.
2. The coated filler agent of claim 1, wherein the hydrate-forming salt is selected from sodium carbonate, sodium sulfate, or mixtures thereof.
3. A filler composition comprising the coated filler agent of any preceding claim and a water-soluble salt having a solubility in distilled water of greater than 30 grams per 100mL when measured at a temperature of 10 ℃, the water-soluble salt being present separately from the hydrate-forming salt.
4. The filler composition of claim 3, wherein the water soluble salt is selected from sodium chloride, sodium formate, or sodium acetate.
5. A solid detergent composition comprising a coated filler agent according to claim 1 or 2 or a filler composition according to claim 3 or 4.
6. The solid detergent composition according to claim 5, wherein the coated filler agent is present in an amount of from 2 wt% to 40 wt% based on the solid detergent composition.
7. The solid detergent composition according to claim 5, wherein the filler composition is present in an amount of from 5 wt% to 50 wt% based on the solid detergent composition.
8. A solid detergent composition according to claim 5 or 6, wherein the composition is a powder, tablet or particulate composition.
9. A solid detergent composition according to claim 5 or 6, wherein the composition is a granular composition.
10. The solid detergent composition according to any one of claims 5 to 7, wherein the composition comprises from 2 wt% to 80 wt% anionic surfactant.
11. Use of a coated filler agent according to claim 1 or 2 or a filler composition according to claim 3 or 4 in a solid detergent composition for improving cold water solubility and/or dispersibility.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP17196421 | 2017-10-13 | ||
| EP17196421.6 | 2017-10-13 | ||
| PCT/EP2018/074304 WO2019072468A1 (en) | 2017-10-13 | 2018-09-10 | Detergent composition comprising hydrate-forming salt particles coated with betaine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111212896A CN111212896A (en) | 2020-05-29 |
| CN111212896B true CN111212896B (en) | 2021-07-09 |
Family
ID=60083878
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201880066768.5A Active CN111212896B (en) | 2017-10-13 | 2018-09-10 | Detergent composition comprising hydrate forming salt particles coated with betaine |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP3694967B1 (en) |
| CN (1) | CN111212896B (en) |
| PH (1) | PH12020550146A1 (en) |
| WO (1) | WO2019072468A1 (en) |
| ZA (1) | ZA202001682B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116617181B (en) * | 2023-07-21 | 2023-09-22 | 山东国邦药业有限公司 | Tilmicosin granule, and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1233275A (en) * | 1996-03-15 | 1999-10-27 | 美国安利有限公司 | Free-flowing agglomerated nonionic surfactant detergent composition and process for making same |
| CN1263481A (en) * | 1997-06-10 | 2000-08-16 | 罗狄亚公司 | Fluids containing viscoelastic surfactant and methods for using the same |
| CN101868526A (en) * | 2007-11-16 | 2010-10-20 | 花王株式会社 | Detergent builder granule |
| CN102492573A (en) * | 2011-12-06 | 2012-06-13 | 大连晟骊商贸有限公司 | Laundry sheet |
| CN103849495A (en) * | 2014-03-17 | 2014-06-11 | 刘良贵 | Detergent for kitchenware and manufacture method thereof |
| GB2516261A (en) * | 2013-07-16 | 2015-01-21 | Solent Internat Ltd | Cleaning product |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3768509D1 (en) | 1986-01-17 | 1991-04-18 | Kao Corp | HIGH DENSITY GRANULATED DETERGENT. |
| CA2001927C (en) | 1988-11-03 | 1999-12-21 | Graham Thomas Brown | Aluminosilicates and detergent compositions |
-
2018
- 2018-09-10 EP EP18762870.6A patent/EP3694967B1/en active Active
- 2018-09-10 CN CN201880066768.5A patent/CN111212896B/en active Active
- 2018-09-10 WO PCT/EP2018/074304 patent/WO2019072468A1/en unknown
-
2020
- 2020-03-16 PH PH12020550146A patent/PH12020550146A1/en unknown
- 2020-03-17 ZA ZA2020/01682A patent/ZA202001682B/en unknown
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1233275A (en) * | 1996-03-15 | 1999-10-27 | 美国安利有限公司 | Free-flowing agglomerated nonionic surfactant detergent composition and process for making same |
| CN1263481A (en) * | 1997-06-10 | 2000-08-16 | 罗狄亚公司 | Fluids containing viscoelastic surfactant and methods for using the same |
| CN101868526A (en) * | 2007-11-16 | 2010-10-20 | 花王株式会社 | Detergent builder granule |
| CN102492573A (en) * | 2011-12-06 | 2012-06-13 | 大连晟骊商贸有限公司 | Laundry sheet |
| GB2516261A (en) * | 2013-07-16 | 2015-01-21 | Solent Internat Ltd | Cleaning product |
| CN103849495A (en) * | 2014-03-17 | 2014-06-11 | 刘良贵 | Detergent for kitchenware and manufacture method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| PH12020550146A1 (en) | 2021-02-08 |
| WO2019072468A1 (en) | 2019-04-18 |
| ZA202001682B (en) | 2021-07-28 |
| EP3694967A1 (en) | 2020-08-19 |
| BR112020007310A2 (en) | 2020-09-29 |
| CN111212896A (en) | 2020-05-29 |
| EP3694967B1 (en) | 2021-10-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2573996C (en) | A highly water-soluble solid laundry detergent composition that forms a clear wash liquor upon dissolution in water | |
| EP2252680B1 (en) | Laundry treatment composition comprising polymeric lubricants | |
| CA2616734C (en) | A solid laundry detergent composition comprising alkyl benzene sulphonate, carbonate salt and carboxylate polymer | |
| WO2009112296A1 (en) | Laundry treatment compositions | |
| WO2013139702A1 (en) | Laundry detergent particles | |
| CA2616656C (en) | A solid laundry detergent composition comprising alkyl benzene sulphonate and a hydratable material | |
| AU2017267050B2 (en) | Liquid laundry detergent compositions | |
| CN111212896B (en) | Detergent composition comprising hydrate forming salt particles coated with betaine | |
| JP2004536927A (en) | Method of making a substantially anhydrous structured surfactant paste and detergent composition containing the same | |
| AU653408B2 (en) | Zeolite based spray-dried detergent compositions and process for preparing same | |
| EP2103677A1 (en) | Laundry treatment compositions | |
| WO2015017206A2 (en) | Method of making granular detergent compositions comprising polymers | |
| EP1529833A1 (en) | Detergent particles | |
| EP4133043A1 (en) | Laundry detergent composition | |
| CN111971372B (en) | Dye particle | |
| AU2017267127B2 (en) | Liquid laundry detergent compositions | |
| BR112020007310B1 (en) | COATED BURGER, BURGER COMPOSITION SOLID DETERGENT COMPOSITION USE OF A COATED BURGER | |
| WO2022268728A1 (en) | Unit dose cleaning composition | |
| WO2015017182A2 (en) | Method of making granular detergent compositions comprising surfactants | |
| CN104822816B (en) | Detergent composition | |
| EP2252681B1 (en) | Laundry treatment compositions | |
| EP2521764A1 (en) | Detergent formulation containing spray dried granule |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20210812 Address after: Rotterdam Patentee after: Unilever Intellectual Property Holdings Ltd. Address before: Rotterdam Patentee before: Netherlands Unilever Co.,Ltd. |
|
| TR01 | Transfer of patent right |