JP2007532713A - Detergent composition - Google Patents

Abstract

The invention relates to a method of preparing an aqueous detergent dispersion comprising mixing at least one silane compound, colloidal silica particles, and a detergent to form an aqueous detergent dispersion comprising silanized colloidal silica particles. The invention also relates to a dispersion obtainable by the method and to the use thereof.

Description

  The present invention relates to a detergent composition comprising silane-modified silica particles.

  Detergent compositions are currently used in many cleaning applications, including the cleaning of hard and soft surfaces such as textiles, and many other applications in household and industrial applications.

  US Patent Application 2002/0111287 A1 discloses a method for obtaining a detergent composition comprising hydrophilic silicate-containing particles. However, it has been found that these types of detergent compositions are not always sufficiently stable and can easily precipitate over time, which of course is detrimental to the cleaning effect.

  Thus, it would be desirable to provide a stable and preferably highly concentrated aqueous detergent dispersion that can be used in such applications. It would also be desirable to provide a convenient and inexpensive method for producing such dispersions.

  The present invention relates to a method for preparing an aqueous detergent dispersion, which comprises mixing at least one silane compound, colloidal silica particles, and a detergent to produce an aqueous detergent dispersion containing silane-treated colloidal silica particles.

  This method can be performed without environmental hazards and health issues for process workers handling the components of the resulting aqueous detergent dispersion.

Mixing of the silane and colloidal silica particles is preferably carried out continuously at a temperature from about 20 ° C to about 95 ° C, more preferably from about 50 ° C to about 75 ° C, most preferably from about 60 ° C to about 70 ° C. It is preferable that Silane is controlled at a temperature of about 60 ° C. under vigorous stirring (this is from about 0.01 to about 100, preferably from about 0.1 to about 10, per 1 nm ² of colloidal silica surface area (of colloidal silica particles) And more preferably from about 0.5 to about 5, most preferably from about 1 to about 2 silane molecules). The addition of silane can be continued for an appropriate time depending on the rate of addition, the amount of silane to be added, and the desired degree of silane treatment. However, the addition of silane is preferably continued for about 5 hours, more preferably about 2 hours, until a suitable amount of silane is added. The amount of silane added to the colloidal silica particles is preferably from about 0.1 to about 6, preferably from about 0.3 to about 3, and most preferably from about 1 to about 2 silanes per 1 nm ² of surface area of the colloidal silica particles. Is a molecule. This continuous addition of silane to the colloidal particles may be particularly important when preparing highly concentrated silane-treated silica sol dispersions having a silica content of up to about 80% by weight. However, the silane content is suitably from about 20% to about 80%, preferably from about 25% to about 70%, most preferably from about 30% to about 60%.

  The colloidal silica particles and silane are preferably mixed at a weight ratio of silane to silica of from about 0.01 to about 1.5, more preferably from about 0.05 to about 1, and most preferably from about 0.1 to about 0.5.

  The one or more silane compounds are preferably diluted with water prior to mixing it with the colloidal silica particles, suitably from about 1: 8 to about 8: 1, preferably from about 3: 1 to about 1: 3. It is preferred to produce a premix of silane and water, most preferably in a weight ratio of about 1.5: 1 to about 1: 1.5. The silane-water solution thus obtained is substantially transparent and easily mixed with colloidal silica particles. During the continuous addition of silane to the colloidal silica particles, the mixing preferably lasts from about 1 second to about 30 minutes, preferably from about 1 minute to about 10 minutes after addition of the stopped silane.

  According to one embodiment, the organosiloxane or silicone is not mixed into an aqueous dispersion for preparing silicone coatings of silica particles or silane-modified silica particles.

  The mixing of the present invention may be carried out at a pH from about 1 to about 13, preferably from about 6 to about 12, more preferably from about 7.5 to about 11, and most preferably from about 9 to about 10.5.

  The term “stable”, particularly with respect to “stable dispersions”, is preferably at least about 2 months, more preferably at least about 4 months, at normal storage at room temperature, ie from about 15 ° C. to about 35 ° C. Most preferably means a stable compound, mixture or dispersion that does not substantially gel or precipitate within a period of at least about 5 months.

  The relative increase in viscosity of the dispersion after 2 months of preparation is preferably less than about 100%, more preferably less than about 50%, and most preferably less than about 20%. The relative increase in viscosity of the dispersion after 4 months of preparation is preferably less than about 200%, more preferably less than about 100%, and most preferably less than about 40%.

  Colloidal silica particles (also referred to herein as silica sols) are, for example, precipitated silica, microsilica (silica fume), pyrogenic silica (fumed silica) or silica with sufficient purity, and these It may be derived from a mixture.

The colloidal silica particles and silica sols of the present invention may be modified and may contain other elements such as amines, aluminum and / or boron, which may be present in the particles and / or continuous phase. Boron-modified silica sols are described, for example, in US Pat. No. 2,630,410. The aluminum modified silica particles suitably have an Al ₂ O ₃ content of from about 0.05% to about 3% by weight, preferably from about 0.1% to about 2% by weight. Procedures for preparing aluminum-modified silica sols are further described in, for example, Iler, K. Ralph, “Silica Chemistry”, pages 407-409, John Wiley & Sons (1979) and US Pat. No. 5,368,833.

The colloidal silica particles suitably have an average particle diameter ranging from about 2 nm to about 150 nm, preferably from about 3 nm to about 50 nm, and most preferably from about 5 nm to about 40 nm. Preferably, the colloidal silica particles is from about 20 m ² / g to about 1500 m ² / g, preferably from about 50 m ² / g to about 900 meters ² / g, most preferably from about 70m ² / g to about 600 meters ² / Has a specific surface area of up to g.

  The colloidal silica particles preferably have a narrow particle size distribution, i.e. a low relative standard deviation in particle size. The relative standard deviation of the particle size distribution is the ratio of the standard deviation of the particle size distribution to the average particle size (number basis). The relative standard deviation of this particle size distribution is preferably less than about 60% (number basis), more preferably less than about 30% (number basis), and most preferably less than about 15% (number basis).

The colloidal silica particles are preferably stabilized cations such as K ⁺ , Na ⁺ , Li ⁺ , NH ₄ ⁺ , organic cations, primary amines, secondary amines, tertiary amines so as to form an aqueous silica sol. And in the presence of quaternary amines, or mixtures thereof, are preferably dispersed in an aqueous solvent. However, also a dispersion comprising an organic solvent such as lower alcohol, acetone or mixtures thereof is suitably from about 1% to about 20%, preferably from about 1% to about 10% by volume of the total solvent volume. %, Most preferably from about 1% to about 5% by volume. However, it is preferred to use an aqueous silica sol free from further solvents. The colloidal silica particles are preferably negatively charged. Suitably, the silica content in the sol is from about 20% to about 80%, preferably from about 25% to about 70%, most preferably from about 30% to about 60% by weight. . The higher the silica content, the thicker the resulting silane-treated colloidal silica dispersion. The pH of the silica sol is suitably from about 1 to about 13, preferably from about 6 to about 12, and most preferably from about 7.5 to about 11. However, for an aluminum modified silica sol, the pH is suitably from about 1 to about 12, preferably from about 3.5 to about 11.

  The silica sol preferably has an S value from about 20 to about 100, more preferably from about 30 to about 90, and most preferably from about 60 to about 90.

  It has been found that dispersions having S values within these ranges can improve the stability of the resulting dispersion. This S value characterizes the degree of aggregation of the colloidal silica particles, i.e. the degree of formation of aggregates or microgels. This S value was measured and calculated according to the formula shown in J. Phys. Chem. 60 (1956), 955-957 by Iler, R.K. & Dalton, R.L.

This S value depends on the silica content, viscosity, and density of the colloidal silica particles. A high S value indicates a low microgel content. This S value represents, for example, the amount (wt%) of SiO ₂ present in the dispersed phase of the silica sol. The degree of microgel can be controlled during the manufacturing process, for example, as further described in US Pat. No. 5,368,833.

  The silane compound can form a stable covalent siloxane bond (Si-O-Si) with a silanol group, or can be bonded to the silanol group on the surface of colloidal silica particles, for example, by hydrogen bonding. Thus, the silica particles are surface-modified by this method.

  Suitable silane compounds include tris- (trimethoxy) silane, octyltriethoxysilane, methyltriethoxysilane, methyltrimethoxysilane; isocyanate silanes such as tris- [3- (trimethoxysilyl) propyl] isocyanurate; gamma- Mercaptopropyltrimethoxysilane, bis- (3- [triethoxysilyl] propyl) polysulfide, beta- (3,4-epoxycyclohexyl) -ethyltrimethoxysilane; epoxy group (epoxysilane), glycidoxy group and / or glycid Silanes containing a xylpropyl group, such as gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxypropylmethyldiethoxysilane, (3-glycidoxypropyl) trimethoxysilane, (3-glycidoxypropyl) Hexyltrimethoxysilane Beta- (3,4-epoxycyclohexyl) -ethyltriethoxysilane; silanes containing vinyl groups such as vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris- (2-methoxyethoxy) silane, vinylmethyldimethoxysilane, vinyl Triisopropoxysilane; gamma-methacryloxypropyltrimethoxysilane, gamma-methacryloxypropyltriisopropoxysilane, gamma-methacryloxypropyltriethoxysilane, octyltrimethyloxysilane, ethyltrimethoxysilane, propyltriethoxysilane, phenyltri Methoxysilane, 3-mercaptopropyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, dimethyldimethoxysilane, 3-chloropropylto Ethoxysilane, 3-methacryloxypropyltrimethoxysilane, i-butyltriethoxysilane, trimethylethoxysilane, phenyldimethylethoxysilane, hexamethyldisiloxane, trimethylsilyl chloride, vinyltriethoxysilane, hexamethyldisilizan, and mixtures thereof Is mentioned. U.S. Pat. No. 4,927,749 discloses further suitable silanes that can be used in the present invention. However, the most preferred silanes are epoxy silanes and silane compounds containing glycidoxy or glycidoxypropyl groups, in particular gamma-glycidoxypropyltrimethoxysilane and / or gamma-glycidoxypropylmethyldiethoxysilane.

  The term detergent refers to all ingredients that the detergent may constitute (these may be present in the prepared aqueous detergent dispersion). This includes surfactants, builders, auxiliary builders, fillers, enzymes, pH adjusters, hydrophilizing agents, optical brighteners, dye transfer inhibitors, such as CMC, bleaching chemicals such as hydrogen peroxide, activators, Complexing agents, softeners, fragrances, viscosity modifiers and other ingredients typically used in liquid detergents may be included. Furthermore, any detergent ingredients such as those described in WO 01/83662, US Pat. No. 6,713,303, EP 929639, WO 91/09100 or US2002 / 0111287 found in liquid detergents may also be used.

  The detergent is preferably added after the silane-treated or silane-modified silica particles are formed. This detergent is preferably mixed with silane-treated colloidal silica particles at room temperature.

  Preferred detergent components mixed with the silane modified silica particles will be described in more detail below. Preferably, the detergent, i.e., the total amount of detergent ingredients, is mixed to produce a total detergent content in the resulting aqueous detergent dispersion of from about 2% to about 80% by weight. According to one embodiment, the total detergent content in the aqueous detergent dispersion is preferably from about 2% to about 10%, most preferably from about 2% to about 5%. According to another embodiment, the total detergent content in the aqueous detergent dispersion is preferably from about 50% to about 80%, most preferably from about 60% to about 70% by weight. According to yet another embodiment, the total detergent content in the aqueous detergent dispersion is preferably from about 30% to about 50%, most preferably from about 40% to about 50% by weight.

  The surfactant or surfactant may be an anionic, nonionic, cationic, amphoteric and / or zwitterionic surfactant.

Preferred anionic surfactants of the sulfonate type are preferably the known (C ₉ -C ₁₃ ) -alkylbenzene sulfonates, alpha-olefin sulfonates and alkane sulfonates. Also suitable are esters of sulfo fatty acids or di-salts of alpha-sulfo fatty acids. Further suitable anionic surfactants are treated with sulfuric acid as obtained during the preparation by esterification of 1 mol monoglycerol with 1 to 3 mol fatty acid or during transesterification of triglycerides with 0.3 to 2 mol glycerol. Fatty acid glycerol esters, which are monoesters, diesters and triesters and mixtures thereof. Suitable alkyl sulfates are in particular (C ₁₂ -C ₁₈ ) -fatty alcohols such as lauryl alcohol, myristyl alcohol, cetyl alcohol or stearyl alcohol, and fatty alcohols obtained from coconut oil, palm oil and palm shell oil. Sulfuric acid monoesters of mixtures (which may further comprise a fraction of unsaturated alcohols, such as oleyl alcohol).

  Further suitable anionic surfactants may be selected from, for example, alcohol-ethoxy sulfates, alkali metal sarcosinates or alkyl ester sulfonates.

  Suitable further anionic surfactants are in particular soaps. Saturated fatty soaps such as lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid salts, and especially derived from natural fatty acids such as coconut fatty acid, palm shell fatty acid or beef tallow fatty acid A soap mixture is preferred. The anionic surfactants may be in the form of their sodium, potassium or ammonium salts and in the form of soluble salts of organic bases such as monoethanolamine, diethanolamine or triethanolamine. The anionic surfactants are preferably in the form of their sodium or potassium salts, particularly sodium salts.

Particularly preferred nonionic surfactants are alkyl alkoxylates, gluconamides and alkyl polyglycosides. Of the alkyl alkoxylates, it is preferred to use ethoxylated alcohols. Preferred ethoxylated alcohols have, for example, C ₁₁ -alcohols with 3, 5, 7, 8 and 11 EO units, 3, 6, 7, 8, 10 or 13 EO units (C ₁₂ -C ₁₅ ). Alcohols with 4, 7 or 8 EO units (C ₁₄ -C ₁₅ ) -Alcohols with 8, 11, 15, 20, 25, 50 or 80 EO units (C ₁₆ -C ₁₈ ) -Alcohols And mixtures thereof. The degree of ethoxylation shown is a statistical average that may be an integer or a fraction for a particular product. In addition to these, it is also possible to use fatty alcohol-EO / PO adducts, for example RTM. Genapol brands 3970, 2909 and 2822 from Clariant GmbH. Further suitable surfactants are of the formula R ₂ —CO—N (R ₃ ) —Z, where R ₂ CO is an aliphatic acyl group having 6 to 22 carbon atoms, R ₃ is hydrogen, An alkyl or hydroxyalkyl group having 1 to 4 carbon atoms, and Z is a linear or branched polyhydroxyalkyl group having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups) Polyhydroxy fatty acid amide. Preferably, alkyl glycosides of the formula RO (G) _x can be used, wherein R is predominantly linear or methyl-branched, in particular methyl-branched at the 2-position, 8-22, preferably 12-18. And G is a glycose unit having 5 or 6 carbon atoms, preferably glucose. The degree of oligomerization, x (which indicates the distribution of monoglycosides and oligoglycosides) is any desired number from 1 to 10, preferably 1.2 to 1.4. Also preferred are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters having 1 to 4 carbon atoms in the alkyl chain.

Examples of suitable cationic surfactants are quaternary ammonium compounds, cationic polymers and hair care formulations and also emulsifiers of the type used in fabric conditioners. As cationic surfactants, ammonium surfactants such as alkyldimethylammonium halides and the formula [R ² (OR ³ ) _y ] [R ⁴ (OR ³ ) _y ] ₂ R ⁵ N ⁺ X ⁻ (wherein , R ² is an alkyl group or alkylbenzyl group having about 8 to about 18 carbon atoms in the alkyl chain, and each R ³ is —CH ₂ CH ₂ —, —CH ₂ CH (CH ₃ ). -, -CH ₂ CH (CH ₂ OH)-, -CH ₂ CH ₂ CH _2- , and a mixture thereof, each R ⁴ is C ₁ -C ₄ alkyl, C ₁ -C ₄ Hydroxyalkyl, benzyl, ring structure formed by joining two R ⁴ groups, —CH ₂ CHOHCHOHCOR6CHOH—CH ₂ OH (where R ⁶ is a hexose or a hexose polymer having a molecular weight of about 1000 or less) , and is selected from the group consisting of hydrogen (if y is not 0), R ⁵ is the same as R ^4, or is an alkyl chain, the carbon atoms of R ² plus R ⁵ Those surfaces having counts of about 18 or less, each y from 0 to about 10, the sum of y values from 0 to about 15, and X is any compatible anion) An activator is mentioned.

  Other cationic surfactants useful in the present invention are also described in US Pat. No. 4,228,044 issued to Cambre on October 14, 1980.

  Amphoteric surfactants can be incorporated into the detergent dispersion. These surfactants are widely used as aliphatic derivatives of secondary or tertiary amines, or heterocyclic secondary amines and aliphatic derivatives of tertiary amines (the aliphatic groups may be linear or branched). Can be described. One of the aliphatic substituents contains at least about 8 carbon atoms, typically from about 8 to about 18 carbon atoms, and at least one of the anionic water solubilizing groups such as carboxy, sulfonate, Contains sulfate. See US Pat. No. 3,929,678, column 19, lines 18-35, issued December 30, 1975 to Laughlin et al. For examples of amphoteric surfactants.

  Also, zwitterionic surfactants can be mixed into the detergent dispersion. These surfactants are widely described as secondary amine and tertiary amine derivatives, heterocyclic secondary amine and tertiary amine derivatives, or quaternary ammonium compounds, quaternary phosphonium compounds or tertiary sulfonium compound derivatives. obtain. See US Pat. No. 3,929,678, column 19, lines 38-22, line 48, issued December 30, 1975 to Laughlin et al. For examples of zwitterionic surfactants. Amphoteric surfactants and zwitterionic surfactants are generally used in combination with one or more anionic surfactants and / or nonionic surfactants.

Said builders are crystalline aluminosilicates, alkali metal carbonates, bicarbonates, sesquicarbonates, phosphates such as alkali metal orthophosphates, alkali metal pyrophosphates and alkali metal polyphosphates such as tripolyphosphate , Ammonium, crystalline phyllosilicate, crystalline alkali metal silicate (not including layer structure and / or X-ray amorphous alkali metal silicate), zeolite, such as zeolite A (eg, zeolite 4A), zeolite B, zeolite P, Zeolite X, or zeolite HS, zeolite MAP, silicate, eg, crystalline layered disilicate [eg, formula NaMSi _{x + 1} · yH ₂ O (wherein M is sodium or hydrogen, x is a number from 1.9 to 4) There, and y is a number from 0 to 20) of], amorphous disilicates (e.g., Buriteshiru ^{T M} ), polycarboxylates, citrates, sulfates, borates or mixtures thereof are preferred. Preferred organic detergent builders for the purposes of the present invention include a wide variety of polycarboxylate compounds. As used herein, “polycarboxylate” refers to a compound having a plurality of carboxylate groups, preferably at least three carboxylates. The polycarboxylate builder can generally be added to the dispersion in the acid form, but can also be added in the form of a neutralized salt. When utilized in salt form, alkali metal salts such as sodium, potassium, and lithium salts, or alkanol ammonium salts are preferred. Among the polycarboxylate builders are included various categories of beneficial materials. One important category of polycarboxylate builders includes ether polycarboxylates. Several ether polycarboxylates have been disclosed for use as detergent builders. Examples of useful ether polycarboxylates are disclosed in Berg US Pat. No. 3,128,287 issued April 7, 1964 and Lamberti et al. US Pat. No. 3,635,830 issued January 18, 1972. And oxydisuccinate.

As a particular type of ether polycarboxylate useful as a builder in the present invention, it may also be represented by the general formula: CH (A) (COOX) -CH (COOX) -O-CH (COOX) -CH (COOX) (B) In which A is H or OH, B is H or —O—CH (COOX) —CH ₂ (COOX), and X is H or a salt-forming cation). For example, when A and B are both H in the above general formula, the compound is oxydisuccinic acid and its water-soluble salt. When A is OH and B is H, the compound is monosuccinic tartrate (TMS) and its water-soluble salts. When A is H and B is —O—CH (COOX) —CH ₂ (COOX), the compound is disuccinic tartrate (TDS) and its water-soluble salts. Mixtures of these builders are particularly preferred for use herein. Particularly preferred is a mixture of TMS and TDS in a weight ratio of about 97: 3 to about 20:80 TMS to TDS. These builders are disclosed in US Pat. No. 4,663,071, issued May 5, 1987 to Bush et al.

  Suitable ether polycarboxylates include cyclic compounds, particularly alicyclic compounds such as those described in U.S. Pat.Nos. 3,923,679, 3,835,163, 4,158,635, 4,120,874 and 4,102,903. Also mentioned.

Other useful detergent builders include the structure: HO- [C (R) (COOM) -C (R) (COOM) -O] _n -H, where M is hydrogen or a cation (the resulting salt is Water soluble), preferably an alkali metal cation, ammonium cation or substituted ammonium cation, n being from about 2 to about 15 (preferably n is from about 2 to about 10, more preferably N is on average from about 2 to about 4), and each R is the same or different and is selected from hydrogen, C _1-4 alkyl or C _1-4 substituted alkyl (preferably R is hydrogen). ] The ether hydroxy polycarboxylate represented by these is mentioned.

  Still other ether polycarboxylates include copolymers of maleic anhydride and ethylene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid, and carboxymethyloxysuccinic acid. .

  Organic polycarboxylate builders also include various alkali metal salts, ammonium salts and substituted ammonium salts of polyacetic acid. Examples include ethylenediaminetetraacetic acid and sodium, potassium, lithium, ammonium and substituted ammonium salts of nitrilotriacetic acid.

  Further, polycarboxylates such as merit acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof can be mentioned.

  Citrate builders such as citric acid and its soluble salts (especially the sodium salt) are polycarboxylate builders of particular importance for heavy duty liquid detergent formulations, but can also be used in granule dispersions.

  Other carboxylate builders include the carboxylated carbohydrates disclosed in US Pat. No. 3,723,322 issued to Diehl on March 28, 1973.

Further, among the detergent components of the present invention, 3,3-dicarboxy-4-oxa-1,6-hexanedioate disclosed in US Pat. No. 4,566,984 issued to Bush on January 28, 1986, and its Related compounds are preferred. Beneficial succinic acid builders include C ₅ -C ₂₀ alkyl succinic acids and their salts. A particularly preferred compound of this type is dodecenyl succinic acid. The alkyl succinic acid is typically of the general formula R—CH (COOH) CH ₂ (COOH), ie a derivative of succinic acid, where R is a hydrocarbon, for example C ₁₀ -C ₂₀ alkyl or Alkenyl, preferably C ₁₂ -C ₁₆ , or R may be substituted with hydroxyl, sulfo, sulfoxy or sulfone substituents, all as described in the above patent.

  The succinate builder is preferably used in the form of water-soluble salts thereof (including sodium salt, potassium salt, ammonium salt and alkanol ammonium salt). Specific examples of succinate builders include lauryl succinate, myristyl succinate, palmityl succinate, 2-dodecenyl succinate (preferred), 2-pentadecenyl succinate and the like. Lauryl succinate is the preferred builder of this group and is described in European Patent Application No. 0,200,263 published on November 5, 1986. Examples of useful builders also include sodium and potassium carboxymethyloxymalonate, carboxymethyloxysuccinate, cis-cyclo-hexane-hexacarboxylate, cis-cyclopentane-tetracarboxylate, water-soluble polyacrylates (about These polyacrylates having molecular weights up to 2,000 or more can also be used effectively as dispersants), and copolymers of maleic anhydride and vinyl methyl ether or ethylene.

  Another suitable polycarboxylate is the polyacetal carboxylate disclosed in US Pat. No. 4,144,226, issued March 13, 1979 to Crutchfield et al. These polyacetal carboxylates can be prepared by combining an ester of glyoxylic acid and a polymerization initiator under polymerization conditions. The resulting polyacetal carboxylate ester is then coupled to chemically stable end groups to stabilize the polyacetal carboxylate against rapid depolymerization in alkaline solution, converted to the corresponding salt, and added to the surfactant .

  Polycarboxylate builders are also disclosed in US Pat. No. 3,308,067, issued March 7, 1967 to Diehl. Such materials include water-soluble salts of aliphatic carboxylic acids such as homopolymers and copolymers of maleic acid, itaconic acid and methylenemalonic acid.

Other organic builders known in the art can also be used. For example, monocarboxylic acids with long chain hydrocarbyls and their soluble salts can be utilized. These would include materials commonly referred to as “soaps”. A chain length of C ₁₀ -C ₂₀ is typically utilized. The hydrocarbyl may be saturated or unsaturated.

  Examples of such carboxylic acids are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acid, aminocarboxylic acid, nitrilotriacetic acid (NTA) (provided that its use is ecological) As long as it is not unsafe), and mixtures thereof. Preferred salts are salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acid and mixtures thereof. These acids themselves may also be used. Apart from their builder effect, these acids also typically have the nature of an acidifying component and can therefore be used to establish relatively low and mild pH in detergents. In this connection, mention may be made in particular of citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and mixtures thereof.

  The hydrophilizing agent is ethanol, n- or i-propanol, butanol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl Ether, propylene glycol ethyl ether or propylene glycol propyl ether, dipropylene glycol monomethyl ether or dipropylene glycol monoethyl ether, diisopropylene glycol monomethyl ether or dipropylene glycol monoethyl ether, methoxytriglycol, ethoxytriglycol or butoxytriglycol , 1-Butoxyethoxy-2-propano , 3-methyl-3-methoxybutanol, propylene glycol t-butyl ether, alcohol, more particularly C1-4 alkanol, glycol, polyethylene glycol (preferably with a molecular weight in the range of 100 to 100,000, more particularly 200 to 10,000. And polyols, such as sorbitol and mannitol, and polyethylene glycol, carboxylic esters, polyvinyl alcohol, ethylene oxide / propylene oxide block copolymers, and mixtures thereof as described above, which are liquid at room temperature.

H ₂ O ₂ (this is the preferred bleach) and compounds that produce H ₂ O _{2 in} water that can be used as bleach, sodium perborate tetrahydrate, sodium perborate monohydrate and sodium percarbonate Is particularly important. Other useful bleaches include, for example, persulfates and mixed salts with persulfates, such as salts commercially available as Caroato®, peroxypyrophosphate, citrate perhydrate and H ₂ O ₂ . The resulting persalt or peracid, such as perbenzoate, peroxophthalate, diperazeleic acid, diperdodecanedioic acid or phthaloiminoperacid, such as phthaliminopercaproic acid.

  Bleaching systems that may be included in the detergent are active chlorine carriers and / or organic or inorganic active oxygen carriers, bleach activators such as TAED, TAGU, SNOBS (sodium nonoylbenzenesulfonate), PAG (pentaacetylglucose) Alternatively, diacylated diperoxycarboxylic acid, bleach catalyst, enzyme for removing discoloration, perborate and / or percarbonate are preferable. The pH adjuster is preferably sodium carbonate, citric acid, sodium citrate and / or bicarbonate.

  The detergent may also contain an enzyme. Enzymes suitable for use in the dispersion are enzymes from the classes of oxidases, proteases, lipases, cutinases, amylases, pullulanases, cellulases, hemicellulases, xylanases and peroxidases and mixtures thereof, for example proteases such as BLAP®. (Trademark), Optimase (registered trademark), Opticlean (registered trademark), Maxacal (registered trademark), Maxapem (registered trademark), Alcalase (registered trademark), Esperase (registered trademark) and / or Sabinase (registered trademark); Amylase, For example, Termamyl (R), Amylase-LT (R), Maxamil (R), Duramil (R) and / or Perfect (R) OxAm; Lipase, e.g. Lipolase (R), Lipomax ( Registered trademark), Fast (R) and / or Lipozyme (TM); cellulase, for example, a Seruzaimu (R) and / or Karazeme ®. For example, as described in European Patent No. 0564478 or International Patent Application WO 94/23005, an enzyme that may be used as needed may be adsorbed to a support and / or encapsulated in a membrane material. They may be protected against premature inactivation.

  The present invention also relates to aqueous detergent dispersions obtained from the methods specified herein. The present invention also relates to an aqueous detergent dispersion comprising the silane-treated colloidal silica particles described herein and a detergent. The detergent and silane-treated silica particles are preferably uniformly dispersed in the aqueous phase.

  The aqueous detergent dispersion is up to about 80% by weight, preferably from about 0.01% to about 20%, more preferably from about 0.1% to about 10%, most preferably from about 0.3% to about 5%. Up to% (dry) silica may be included.

  The aqueous detergent dispersion preferably has a detergent content of from about 2% to about 80% by weight. Preferred detergent contents are as described herein.

  The stability of the dispersion facilitates its handling and application during use. This is because it allows storage and does not need to be prepared on site just before use. Thus, already prepared dispersions can be used directly and easily. The dispersion is also beneficial in the sense that it does not involve dangerous amounts of toxic solvent components. This dispersion is preferably a substantially aqueous dispersion. However, according to one embodiment, a suitable organic solvent miscible with water is from about 1% to about 20% by volume of the total dispersion volume, preferably from about 1% to about 10%, most preferably May be included in the substantially aqueous dispersion in an amount from about 1% to about 5% by volume. This is due to the fact that for certain applications, a certain amount of organic solvent may be present without harmful environmental effects.

  Depending on the size of the silica particles, the weight ratio of silane to silica, the type of silane compound, the reaction conditions, etc., the dispersion may be colloidal silica that is not silane-treated, at least to some extent, in addition to silane-treated colloidal silica particles. Particles may also be included. Suitably, at least about 40 wt%, preferably at least about 65 wt%, more preferably at least about 90 wt%, and most preferably at least about 99 wt% of the colloidal silica particles are silane treated (silane modified). In addition to the silane in the form of silane groups or silane derivatives bonded to the surface of the silica particles, the dispersion may also contain unbound silane compounds that are freely dispersed to at least some extent. Suitably, the silane compound comprises at least about 40% by weight, preferably at least about 60% by weight, more preferably at least about 75% by weight, more preferably at least about 90% by weight, and most preferably at least about 95% by weight. Bonded to the surface of the silica particles.

  Suitably, at least about 1% (several basis) of the silanol surface groups of the colloidal silica particles can be bonded to the silane groups of the silane compound, preferably at least about 5%, more preferably at least about 10%, Preferably at least about 30% and most preferably at least about 50% are bound to the silane group.

  The weight ratio of total silane content to total silica content in the dispersion is preferably from about 0.01 to about 1.5, more preferably from about 0.05 to about 1, and most preferably from about 0.1 to about 0.5. The total content of silica includes the silica in the modified silane treated silica particles and unmodified silica particles, which may also be present in the prepared dispersion. The total content of silane is based on all freely dispersed silanes and all bonded silane groups or derivatives.

  The detergent dispersion can be used to treat hard surfaces, but can also be used to treat the surfaces of fibers and fabrics.

  Hard surfaces are in particular those found in the home, i.e. surfaces comprising stone, ceramic, wood, plastic, metals such as stainless steel, floor coverings such as carpets. The cleaner dispersion may be of different types, such as a glass cleaner, an all purpose cleaner, a bath cleaner, a kitchen cleaner, and the like.

  Fabric surfaces include synthetic fabrics and natural fabrics, and the particles used according to the present invention are used, for example, in the treatment of cotton and cotton / wool blends for fabric pre-treatment and post-treatment and fabric washing. It is preferable. The particles may also be used for textile processing in the textile industry, in which case they may be used for both permanent and temporary processing of the textile.

  The detergent dispersion is also preferably used as a dishwashing detergent, dishwashing detergent, dishwashing cleaner and rinse aid. This detergent dispersion may also be used as an automotive cleaner and paint cleaner for manual use and for automatic use in car washers. This detergent dispersion may also be used in an anti-redeposition treatment, for example for coil coating.

  Now that the invention has been described, it will be clear that the invention may be varied in many ways. Such variations are not to be regarded as a departure from the spirit and scope of the invention, but all such modifications as would be obvious to one skilled in the art are intended to be included within the scope of the invention. . The following examples show more specific details of the reaction, but the following general principles may be disclosed herein. The following examples further illustrate the methods by which the described invention can be practiced and are not intended to limit the scope thereof.

All parts and percentages represent parts by weight and percentages by weight, unless otherwise specified.
[Example]

  Table 1 lists the liquid detergents used in the following examples.

  Table 2 lists the silica sols used in the following examples, with the addition of Silquest A-187 (gamma-glycidoxypropoxy-trimethoxysilane), some of which are available from General Electric Silicones. Silane modified. In the deionized silica sol, that is, most of the anions and cations were removed by ion exchange. The silane modified deionized sol was silane modified following the deionization process. The weight ratio of silane to silica shown in Table 2 is based on the dry content of silane and colloidal silica in the product.

The particle size Dp for each sol in Table 2 is based on the specific surface area of the unmodified sol for each particle size, respectively.
[Example 1]

  The colloidal silica dispersions listed in Table 2 were added to the liquid detergents listed in Table 1 under good agitation according to Table 3. The amount of detergent to which this colloidal silica dispersion is added is 100 g unless otherwise stated. Stability was adjusted initially and finally after precipitation for 1 month storage at 55 ° C. for precipitation and separation (heterogeneous sample). This stability was adjusted by optical inspection.

From Table 3, it can be clearly seen that the detergent dispersion containing the silane-modified silica sol was much more stable than the unmodified silica-based detergent dispersion.
[Example 2]

  The performance of the silane-modified sol in detergent application had the same technical effect as can be seen from Table 4 below.

  1.5 g of silica sol aqueous product was added to 100 g of Ajax double action (glass cleaner) with good stirring at room temperature. The cleaner was then used as described below.

  Method: An external window was used for the test. Detergent (including silica sol) was sprayed onto a vertical window, then excess was removed with a rubber scraper. The window was dried for 5 minutes. A standard soil (Krefeld) solution (1%) was sprayed onto a portion of the cleaned window. Also, water was sprayed on another part of the cleaned window. The spread and wetting of the soil was investigated (spread and soil release). Hydrophilicity was shown by wetting of the sprayed water. The window was further dried for 5 minutes. Water was sprayed onto the window. This soil removal was investigated. As can be clearly seen from Table 4, the soil removal, release and spread of the detergent dispersion 2-4 is much better than the criterion 1 without silica sol.

Claims (11)

  A method for preparing an aqueous detergent dispersion comprising mixing at least one silane compound, colloidal silica particles, and a detergent to produce an aqueous detergent dispersion containing silane-treated colloidal silica particles.   The method of claim 1, wherein the silane compound is epoxy silane.   The method according to claim 1 or 2, wherein the silane compound is an epoxy silane having a glycidoxy group.   4. A method according to any preceding claim, wherein the silane and silica particles are mixed at a silane to silica weight ratio of about 0.01 to about 1.5.   The method of any of claims 1 to 4, wherein the silane is mixed with silica particles in a weight ratio of about 0.05 to about 1 silane to silica.   An aqueous dispersion obtained from the method according to claim 1.   An aqueous dispersion comprising silane-treated colloidal silica particles and a detergent.   The method of claim 6 or 7, wherein the silica content is about 0.01 wt% to about 20 wt%.   The dispersion of any of claims 6 to 8, wherein the weight ratio of silane to silica is from about 0.01 to about 1.5.   Use of the dispersion according to any of claims 6 to 9 for cleaning applications.   Use of the dispersion according to any one of claims 6 to 9 for re-deposition prevention treatment.