JPH06506006A - liquid or paste detergent - Google Patents

Abstract

New washing products form suspensions of crystalline, stratified sodium silicates and other components typical of washing products in liquid non-ionic surface-active agents or in mixtures of such surface-active agents with organic solvents selected from the group composed of glycols, glycolethers and glycerine, whereas these washing products should not contain more than 30 wt. % water. The silicates used are compounds having the general formula: NaMSIx?O2x+1?.yH2?O, in which M stands for sodium or hydrogen, x is a number between 1.9 and 4 and y is a number from 0 to 20.

Description

[Detailed description of the invention] liquid or paste detergent The present invention relates to liquids or pastes containing silicates and nonionic surfactants. Concerning detergent.

Because phosphates can contribute to eutrophication of surface waters, virtually all Phosphate, which was present as a builder in many detergents, has been replaced by other compounds that act similarly. Efforts to replace chemical compounds have been ongoing for a long time. requirements that are expected to be met A substitute that satisfies virtually all of the above was discovered in the 1970s in the form of zeolite. Zeolites have since replaced most phosphates in detergents. However, efforts are still being made to find other phosphate substitutes. very recently proposed the general formula NaMSiwoxx. 1・yH2o [where M is sodium or hydrogen, or a number from 1.9 to 4, and y is a number from 0 to 20. ] Regarding crystalline layered sodium silicate (European Patent Application No. 164514) European Patent Application No. 337217 and European Patent Application No. 337219). now In addition, some of them can be used alone or in detergents by adding them to phosphate. In contrast to the amorphous silicate described in that literature, the crystalline layered silicate It shows remarkable binding strength towards aluminum and magnesium ions. Therefore, I will quote it first. In the literature, crystalline layered silicates have been used in soft water and as solid detergent ingredients. We advocate the use of

However, these crystalline layered silicates also It is also known that it becomes unstable and turns into amorphous silicate. Aini (, layer) Defects in this structure are always accompanied by loss of calcium and magnesium binding strength. As a result, one of the basic effects that detergent builders are supposed to have is lost. Therefore, These crystalline layered disilicates can be used in liquid or pasty detergents. Appeared.

Surprisingly, it is now known that if a detergent containing a liquid phase of a certain composition is given, the liquid and that crystalline layered silicates can be used in pasty detergents. In this liquid phase, crystalline layered disilicates are It has been found that these substances exist in a suspended state.

In the present invention, M is sodium or is hydrogen, X is a number from 1.9 to 4, and y is a number from O to 20. ] The present invention relates to a liquid or paste detergent containing crystalline layered sodium silicate. child site 1; t, formula R-(0-CHI-CH2-8OH(I) [wherein R is a long chain primary or secondary alkyl group containing 8 to 20 carbon (C) atoms, n is a number from 3 to 20. ] and optionally a glycerol. an organic solvent selected from the group consisting of coals and glycol ethers, and Suspend in a liquid phase containing up to 30% by weight (based on total detergent) of water. water in liquid phase Particular preference is given to detergents containing up to 20% by weight, especially up to 10% by weight.

The new detergent allows the decomposition of crystalline layered sodium silicate to last longer than typical detergent storage periods. can be suppressed to the extent that it is no longer difficult. The builder effect is achieved during the cleaning process. It remains intact to the extent that it is needed. Another advantage is that inorganic peroxides It can be said to be well combined with the detergent of the present invention.

The crystalline layered sodium silicate used in the present invention is a natural mineral (e.g. It may be a kanemite. However, it is described in various forms in the literature. Synthetically produced layered silicates are preferred. Formula NaMSitOs - Silicates represented by yH20 are particularly preferred, and the β-form and NazSi20s The and delta forms are particularly preferred. Crystalline layered sodium silicate is available as a liquid or paste. In the detergent, preferably 10 to 50% by weight (based on the total detergent), more preferably 20-40% by weight present. In detergents, crystalline layered sodium silicate is preferred. or in the form of ultrafine particles of 100 μm or less, more preferably 3011 μm or less. It is preferable to do so.

The liquid phase in which the crystalline layered sodium silicate is suspended contains, as a basic component, the formula (I) Nonionic surfactants represented by, optionally glycols and glycol ethers. 30% by weight (based on total detergent) of organic solvent selected from the group consisting of: Contains up to The water content should be between 0.5 and 20% by weight (based on the total detergent). It is preferable that the amount does not exceed 10% by weight. The water is in the form of hydration water of solid salts or water that is added to the detergent in a similarly bound form. In addition, the flow of this phase The composition of the liquid phase should be selected such that the temperature is below 15°C, especially below 10°C. is preferred. Liquid nonionic surfactant and/or sufficient amount of organic solvent and These figures can easily be reached by using water and/or water accordingly. Ru.

The nonionic surfactant represented by formula (1) suitable for use in the present invention is ethylene Oxide (EO) 3-20 μl and 8-20 carbon atoms, preferably 10-1 It is an adduct with a long chain primary or secondary alcohol containing 8 carbon atoms.

The nonionic surfactant contains 4 to 10 ol of ethylene oxide (EO) and Clt. -+S saturated or unsaturated fatty alcohol or C1□-18 oxoalcohol Preferably, it is an adduct with 1 mol of coal. Examples of such surfactants As, CI 1/l 4 coconut oil alcohol + ethylene oxide (EO) 3 mol, CI2/II coconut oil alcohol + ethylene oxide (EO) 5■01 , and oleyl/cetyl alcohol + ethylene oxide (E O) 10+o l, and oxoalcohol of CIl/I3 + 7 mo of ethylene oxide (EO) l is mentioned. The nonionic surfactant represented by formula (I) is used in the detergent of the present invention. Preferably 10 to 60% by weight, more preferably 10 to 40% by weight .

Forming the liquid phase of the detergent of the invention together with the nonionic surfactant (I) and optionally water Suitable organic solvents that may be used include, inter alia, water-soluble glycols and glycol ethers. 111 (eg glycerol). In a preferred embodiment, other organic No additional solvents are used. Glycols have 2 to 6 carbons in the molecule. atoms, and dimers and oligomers of propylene glycol, and preferably is preferably a glycol containing ethylene glycol that is liquid at room temperature. stomach. The glycol ethers used are methanol, ethanol, and propatool. or butanol and mono-, di-, or tri-glycols It is preferable that it is a monoester of. Ethers have up to 10 carbons per molecule Preferably, it contains atoms. The organic solvent content may be up to 30% by weight Preference is given to especially between 0.5 and 10% by weight (based on total detergent).

Another preferred component of the liquid or paste detergent of the present invention is a bleaching agent. It is an inorganic peroxide that acts as a In the simplest case, some of the water present in the liquid phase is May be replaced with an equal weight of hydrogen peroxide. However, mainly in the undissolved state, It is therefore preferable to use solid inorganic peroxides which are also present in detergents in suspended form. Delicious. Perporate tetrahydrate, perperate-hydrate and percarbonate The adduct of hydrogen peroxide (HzO2) and sodium carbonate, also known as Particularly preferred. Solid inorganic peroxides, like crystalline layered sodium silicate, In detergents, it is preferable to use it in the form of ultrafine particles. Solids in the detergent of the present invention The inorganic peroxide content may be up to 30% by weight, but preferably between 5 and 30% by weight. , more preferably between 10 and 25% by weight.

In addition to the components already mentioned, the detergents according to the invention may contain other active substances. like this Typical chemicals found in liquid and pasty detergents with other ingredients such as The additives do not affect the stability of the detergent. The ingredients are primarily other types surfactants, especially nonionic and anionic surfactants, other organic or is an inorganic building block, as well as sequestering agents, foam control agents, anti-deposition agents and bleaching agents. It is an activator. Further examples of such auxiliaries and adducts include optical brighteners, detergents, These include purification enhancers, enzymes, dyes, fragrances, inorganic salts and preservatives. Washing of the present invention The total content of the active substances and auxiliaries in the preparations is usually up to 50% by weight, preferably It is between 0.5 and 20% by weight. Individual components dissolved or suspended may be present in detergents.

Among other nonionic surfactants, ethylene oxide and propylene oxy or fatty acids, fatty acid amides or alkyl acids containing 12 to 18 carbon atoms. phenols and alkyl glycosides (e.g. alkyl glucosides or glucosides) (alkyl polyglucosides obtained from long-chain primary alcohols) It is. These alkyl gelcondos contain 10 to 14 carbon atoms in the alcohol component. Preferably it contains 1 to 3 glucose units per elementary atom and molecule.

Also, amine oxide type nonionic surfactants (e.g. N-coco alkyl Ru-N,N-dimethylamine oxide and N-tallow alkyl-N,N-dihyde lokidiethylamine oxide) and fatty acid alkanolamide type noni Ionic surfactants are also suitable. The amount of these nonionic surfactants present is Typically, up to the amount of nonionic surfactant of formula (I) present, preferably Up to half that amount.

Suitable synthetic anionic surfactants include, in particular, sulfonate and sulfate surfactants. It is an anionic surfactant of type 1. A suitable surfactant of the sulfonate type is , an alkylbenzene sulfonate containing an alkyl group of ce-+s, an olefin sulfonates, i.e. alkenes and hydroxyalkanesulfonates, and , for example, monoolefins of ClZ−+S containing terminal double bonds or internal double bonds. After sulfonating the sulfonate with sulfur trioxide gas, the sulfonated product is subjected to alkaline hydrolysis. or a type of disulfonate obtained by acid hydrolysis. Also C11-1 After sulfochloridation or sulfoxylation of the alkanes of No. 11, hydrolysis or Alkanesulfonates obtained by neutralization, or olefins and α-sulfolipids Fatty acids (e.g. hydrogenated coconut oil, palm kernel oil or alpha-sulfonated fatty acids of tallow fatty acids) alkanesulfonate obtained by adding bisulfite to (methyl or ethyl ester) Nate is also suitable. Suitable surfactants of the sulfate type may be natural or synthetic. primary alcohols, i.e. fatty alcohols (e.g. coconut oil fatty alcohols) oleyl, tallow fatty alcohol, oleyl, lauryl, myristyl, palmityl or is a sulfuric acid monoester of stearyl alcohol) or Cl0-! . oxo is a sulfuric acid monoester of an alcohol or a secondary alcohol with a similar chain length . Also, aliphatic primary ethoxylated with 1 to 611 ol of ethylene oxide (EO) Sulfate monoesters of alcohols and sulfate monoesters of ethoxylated secondary alcohols Noesters are also suitable.

Also suitable are sulfated fatty acid alkanolamides and sulfated fatty acid monoglycerides. It is. In particular, anionic surfactants based on natural raw materials can be used for detergent-active soaps, That is, it is a C0-U fatty acid salt. The anionic surfactant is used in the detergent of the present invention. in its sodium salt form or organic bases, especially monoethanolamine. It is preferably present in the form of soluble salts with , jetanolamine, and triethanolamine. Delicious. The amount of anionic surfactant in the detergent of the present invention is the total amount of nonionic surfactant. It is preferably less than the amount of nonionic surfactant, especially half the amount of the total nonionic surfactant. is preferable. The content is preferably between 5 and 20% by weight (relative to total detergent). Yes.

Particularly suitable cationic surfactants contain up to two carbon atoms each bonded to a nitrogen atom. In addition to the three relatively short chain alkyl groups with children, there are also long chain 01°-18 alkyl groups It is a quaternary ammonium compound containing groups. two or three relatively short chains Alkyl may even close to form a ring (eg, a pyridine ring). That's it Examples of such compounds include N,N,N-trimethyl-N-tetradecylammoni Um chloride and N,N-dimethyl-N-hydroxyethyl-N-dodecyl Ammonium hydrogen sulfate is mentioned.

Betaine surfactants have an anionic group as one of the relatively short alkyl substituents. Predominantly long-chain quaternary ammonium compounds, generally containing carboxyl groups It is. One example of a betaine surfactant is N,N-dimethyl-N-coconut oil. Examples include alkylaminoacetate.

The detergent of the present invention contains crystalline layered sodium silicate alone as a builder. Preferably, but also other organic and/or inorganic soluble or insoluble molecules der may also be present in the detergent. Typically, these additional builders increase the amount of layered silicates. It is present in an amount not exceeding, preferably less than half the amount of silicate. especially , the amount of additional builders present is from 0.1 to 5% by weight (based on total detergent).

Particularly suitable additional builders are alkaline reactive salts, especially alkali metal salts, It can only precipitate or form complexes with calcium ions. (, together with surfactants, causes a synergistic increase in cleaning power, and also reduces the precipitation of sewage waste. Shows preventive power. Among the inorganic salts, water-soluble alkali metal metaphosphates and Even more important are alkali metal polyphosphates, especially pentasodium trisphosphate. .

The organic builder is an aminopolycarboxylic acid type sequestering agent (e.g. trilotriacetic acid, ethylenediaminetetraacetic acid, and higher congeners) .

Suitable phosphorus-containing organic complexing agents include alkane polyphosphonic acids, aminopolyphosphonic acids and hydroxyalkane polyphosphonic acids, and phosphonopolycarboxylic acids (e.g. For example, methanediphosphonic acid, dimethylaminomethane-1,1-diphosphonic acid, Minotrimethylenephosphonic acid, ethylenediaminetetramethylenephosphonic acid, diamine Ethylenetriaminepentamethylenephosphonic acid, 1-hydroxyethane-1,1 -diphosphonic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, etc. It is a water-soluble salt of compound). These sequestering agents also act as stabilizers for compounds. may be present in relatively small amounts. Among organic builders, calcium ions and complex salts form Of particular importance are nitrogen (N)-free and phosphorus (P)-free polycarboxylic acids. Yes, low molecular weight compounds (e.g. citric acid, 2,2-hydroxyethane monophosphate or or carboxymethylhydroxysuccinic acid and in the form of water-soluble salts from 350 to about 1. carboxylic acid polymers with molecular weights in the range of 500,000. especially Preferred polycarboxylate polymers range from 500 to 175,000 molecules. in particular a molecular weight in the range of 10,000 to 100,000. Po Recarboxylate polymers include, for example, polyacrylic acid, poly-alpha-hydroxy Copolymers of cyacrylic acid and polymaleic acid and carboxylic acid monomers polymers (e.g. acrylic acid and maleic acid, or other ethylenically unsaturated compounds ( for example, copolymers with vinyl methyl ether).

Also included are water-soluble salts of polyglyoxylic acid.

Particularly suitable water-insoluble inorganic builders are as phosphate replacements in detergents. Zeolite type A, described in detail in German patent application no. 2412837 It is a finely divided synthetic sodium alumosilicate containing bound water. cation exchange Sodium alumosilicate can be used in its typical hydrated, microcrystalline form. Sunawa However, cation-exchanged sodium alumosilicate has almost no particles larger than 30 um. Preferably, 80% of the particles are smaller than 101. stomach.

Its calcium binding strength, measured according to German Patent Application No. 2412837 is in the range of 100 to 200 ag Cab/g. In particular, zeolite Na Zeolite NaA, such as X and a mixture of NaA and NaX, are suitable. deer However, in the detergent of the present invention, the zeolite is an inorganic peroxide, especially perporate. It is preferable to use it only when there is no

Suitable inorganic non-complexing salts include bicarbonates, carbonates, borates, sulfates. Alkali gold amorphous silicates, also known as silicates or “washed alkyls” It is a genus salt. Other builders that can also be used due to their hydrotropic properties is non-capillary active and C! -9 of sulfonic acids, carboxylic acids and sulfocarboxylic acids salts (e.g. alkanes, benzene, toluene, xylene or cumenesulfonic acid) , sulfobenzoic acid, sulfophthalic acid, sulfoacetic acid, sulfosuccinic acid alkali gold and acetic acid or lactic acid salts).

Suitable foam control agents are, for example, C2°-14 fatty acid salts or especially those with alkyl groups. Salts of long-chain N-alkylaminotriazines containing 8 to 18 carbon atoms in or a salt of a CD-4° aliphatic ketone. Optionally supplementing with ultra-fine silica Paraffin oil and silicone oil dispersions are preferred. For example, a soap place content up to 5% by weight (based on total detergent), but paraffin oil and silico In the case of oils, it is typically much less (e.g., about 0.05-0.5% by weight).

Suitable anti-deposition agents include, in particular, cellulose ethers (e.g. carboxymethyl ethers). Lulose, methyl cellulose, hydroxyalkyl cellulose, and methyl Droxyethyl cellulose, methyl hydroxypropyl cellulose and methyl cal mixed ethers such as boxymethylcellulose), and also different cellulose ethers mixtures of carboxymethylcellulose and methylcellulose, especially mixtures of carboxymethylcellulose and methylcellulose It is a thing.

In order to enhance its bleaching effect, the detergent of the present invention contains, in addition to an inorganic peroxide, a bleaching agent. May contain sex agents. Bleach activators contain peroxynicarponic acid or its like in the cleaning solution. It is an unlying agent that forms a salt of and reacts with hydrogen peroxide. Typical bleach activator Examples include ethylenediaminetetraacetic acid, pentaacetylglucose and diacetate. Examples include tildioxohexahydrotriazine. Also, N-acyl compounds and In addition to O-acyl compounds, anhydrides can also be used. Mostly in the liquid phase of some detergents Bleach activator that remains undissolved, i.e. bleach that exists mostly in suspension Preference is given to using activators. The bleach activator may contain up to 6% by weight, especially from 2 to 5%. Preferably it is present up to % by weight (based on total detergent).

A particularly suitable optical brightener in detergents is 4,4-bis-(2''-anilino-4'' -morpholino-1,3,5-1-diazinyl-62-amino)-stilbene-2 , 2'-disulfonic acid alkali metal salt or jetano group instead of monophorino group. It is a compound with a similar structure containing an amino group. Other suitable brighteners include substituted diphthyl Phenylstyryl type brighteners (e.g. 4,4-bis-(2-sulfostyryl) )-diphenyl, 4,4'-bis-(4-chloro-3-sulfostyryl)-dif phenyl and 4-(4-chlorostyryl-4°-(2-sulfostyryl)-diph phenyl alkali metal salt).

Detergency enhancers are long-chain polar compounds that themselves have no surface activity. However, it can increase the cleaning power of surfactants present in detergents. like that Examples of compounds include coconut oil amine + 2101 ethylene oxide (EO) and Adducts of glycerol and long-chain α-olefin epoxides may be mentioned.

Suitable enzymes are proteases, lipases and amylases or mixtures thereof. An enzyme selected from the group consisting of: Bacillus subtilis, Bacillus licheniformis (Ba bacteria such as Cillus licheniformis) and Actinobacteria Particularly suitable are enzymes obtained from the species of Theria or from fungi. Enzyme decomposes early can be embedded in an encrusting material to protect against

The method of manufacturing the detergent of the present invention is not difficult at all. In the simplest case, mix all ingredients cormorant. Premixing the components such that they later form a liquid phase and in the resulting liquid It is best to add the ingredients to be suspended and mix homogeneously therewith. solid component In the case of detergents, the suspended solid particle size involves washing the detergent with water and then reducing it further to a smaller size. Although it is possible to It is preferable to start. The maximum The viscosity of the final detergent is determined. Therefore, this value can be adjusted widely by selecting appropriate components. May vary within a range. For example, organic solvents can be added to reduce the viscosity. , thickening ingredients (eg, soap) can be added to increase the viscosity. present invention liquid detergent, when measured at a temperature of 20°C using a B-type viscometer, is about 1,000 to in the range of about 5.000 mPa, s, especially about 2.000 to about 4.0001 Pa , s. Particularly high physical stability is preferred. The viscosity of detergent powder is quite high.

The detergent of the present invention is mainly used as a laundry detergent. Its active substance content Depending on the circumstances, the detergent of the present invention may be used as a stand-alone detergent or as a detergent additive. Ru. However, when provided with appropriately selected active substances, the detergents of the invention can also be used in household It can also be used for cleaning hard surfaces, both in the industrial sector. of suspension Due to its stability, the detergent can also be automatically dosed.

Example Weigh and combine all ingredients and homogenize the mixture in a ceramic ball mill. (running time for 5 minutes) and apply a single dose of pasty detergents A and B listed below. It was prepared as 50g.

Both detergents were stored for 4 weeks at 40°C in sealed polyethyline bags. This period After this period, there was no evidence of phase separation. The crystalline layered structure of disilicate is preserved. This was shown by X-ray reflection. No loss of active oxygen due to manganese titration This was confirmed.

international search report Continuation of front page (72) Inventor: Schwatke, Carl, Federal Republic of Germany, Day-5090 Leh Vakusen 3, Taubenveke No. 25 (72) Inventor: Hemann, Gigli Nde Federal Republic of Germany Day-4005 Meerbusch, im Bachgrund 2 3#r

Claims (1)

[Claims] 1. General formula NaMSixO2k+1・yH2O [where M is sodium or water x is a number from 1.9 to 4, and y is a number from 0 to 20. ] Crystallinity indicated by A liquid or paste detergent containing layered sodium silicate; ricate has the formula R-(O-CH2-CH2-)■OH [wherein R is 8 to 20 long-chain primary or secondary alkyl group containing carbon (C) atoms, n being a number from 3 to 20 It is. ], and optionally glycols and glycols. an organic solvent selected from the group consisting of coal ethers and glycerol, and Suspended in a liquid phase containing up to 30% (by weight of total detergent) water; Paste detergent. 2. Crystalline layered sodium silicate has the formula NaMSi2O5.yH2O The detergent according to claim 1. 3. As crystalline layered sodium silicate, β-form and/or Na2Si2O5 The detergent according to claim 2, wherein the δ-isomer exists. 4. Claims 1 to 3 wherein the water content is up to 20% by weight, preferably up to 10% by weight. Detergent listed in any of the above. 5. 10 to 50% by weight of crystalline layered sodium silicate, preferably 20 to 40% by weight amount%, 10 to 60% by weight, preferably 10% by weight of the nonionic surfactant represented by formula (I) ~40% by weight, 5 to 30% by weight of inorganic peroxide, preferably 10 to 25% by weight, and 0 to 30% of organic solvent. 30% by weight, preferably 0.5-10% by weight, water 0-30% by weight, preferably 0.5-20% by weight and Containing typical detergent ingredients from 0 to 50% by weight, preferably from 0.5 to 20% by weight. The detergent according to any one of claims 1 to 3. 6. Nonionic surfactant, 4 to 10 mol of ethylene oxide (EO) and 10 Group consisting of adducts with 1 mol of long-chain alcohols containing ~18 carbon atoms The detergent according to claim 5, selected from: 7. Inorganic peroxides can be added to sodium perborate hydrate, sodium percarbonate and their like. A detergent according to claim 5 selected from the group consisting of a mixture of. 8. The detergent according to claim 5, which is in the form of a paste.