WO1990013623A1 - Detergent paste substantially free of water and containing no phosphate - Google Patents
Detergent paste substantially free of water and containing no phosphate Download PDFInfo
- Publication number
- WO1990013623A1 WO1990013623A1 PCT/EP1990/000648 EP9000648W WO9013623A1 WO 1990013623 A1 WO1990013623 A1 WO 1990013623A1 EP 9000648 W EP9000648 W EP 9000648W WO 9013623 A1 WO9013623 A1 WO 9013623A1
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- WIPO (PCT)
- Prior art keywords
- weight
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- content
- acid
- free
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Classifications
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- 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
- C11D3/12—Water-insoluble compounds
- C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
- C11D3/1246—Silicates, e.g. diatomaceous earth
- C11D3/128—Aluminium silicates, e.g. zeolites
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- 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
- C11D1/66—Non-ionic compounds
- C11D1/83—Mixtures of non-ionic with anionic compounds
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- 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
- C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
- C11D17/003—Colloidal solutions, e.g. gels; Thixotropic solutions or pastes
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
- C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid compositions
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- 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
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
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- 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
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
Definitions
- the present invention relates to a pasty, phosphate-free, essentially water-free detergent which is distinguished by high storage stability and improved dispersibility and solubility in water.
- Pasty detergents have the advantage over powdered agents that they can be handled and dosed dust-free. They are therefore also suitable for automatic dosing devices. Their problem is that they have to be sufficiently flowable in a larger temperature range, which considerably limits the freedom from recipes, especially if high proportions of solid active substances are to be incorporated into the paste. On the other hand, it is required that the agents do not separate during storage, which is difficult to reconcile with the requirement for good flowability and correspondingly reduced viscosity. Furthermore, the aim is not to use solvents and suspension stabilizers, since they do not contribute to washing performance when used. Finally, when cold water is added, in particular during the washing-in process in the washing machine, they should not form tough, difficult to disperse gels, but should dissolve quickly and completely.
- DE 12 79 878 (GB 1205 711) describes a pasty, essentially anhydrous agent, the liquid phase of which consists of non-ionic surfactants and lower alcohols.
- Sodium tripolyphosphate (TPP) and soda are used as skeleton salts, and sodium perborate monohydrate as bleaching agent.
- TPP Sodium tripolyphosphate
- soda soda are used as skeleton salts, and sodium perborate monohydrate as bleaching agent.
- the solids are finely ground and suspension stabilizers in the form of finely divided silica are additionally added to the agent.
- No. 4,115,308 describes pasty detergents which can be water-free and in this case contain large proportions of solvents, such as triethanolamine, polyethylene glycol or free fatty alcohols. These additives do not contribute to the washing effect of the agents.
- the majority of the pastes also contain tripolyphosphate in proportions of 32 to 35% by weight.
- the paste-like compositions according to DE 28 25 218 (US Pat. No. 4,315,812) are also extremely phosphate-rich with fractions of 30 to 35% by weight Na tripolyphosphate.
- the agents contain finely divided silicon dioxide in proportions of approximately 2% by weight.
- Phosphate-free detergent pastes which, however, contain high proportions of water-soluble builder substances which are also problematic for environmental reasons, such as nitrolotriacetate or phosphonates (between 38 and 55% by weight) are known from DE 2054855.
- the compositions contain larger proportions of alcohols as solvents and small amounts of soap in the form of the alkali or alkaline earth metal salts as a suspension stabilizer.
- EP 30 096 teaches that in liquid to pasty detergents, the solids, consisting of skeleton salts and persalts, have to be ground to particle sizes below 10 ⁇ m in order to avoid segregation of the pastes during storage.
- the skeleton salts consist essentially of polyphosphonates.
- Alkali silicates and organic builder salts can also be present, but no further details are given here.
- the surfactant component consists exclusively of liquid nonionic surfactants. Anionic surfactants are not included in the pastes. The necessity of having to grind the solids to a very small grain size requires a considerable expenditure of equipment and time.
- the paste-like agents mentioned essentially contain phosphates as builder salts.
- P-free detergents require a different overall concept compared to P-containing detergents in order to avoid a decrease in the cleaning ability.
- This development is already well advanced with powder detergents, while with pasty agents the problems are much greater due to the limited choice with regard to the usable raw materials.
- Particular problems arise with pastes in which the phosphate is to be replaced by zeolite. Because of the water insolubility of the zeolites, these are particularly difficult to disperse in cold water. The experience gained with phosphate-containing agents cannot therefore be easily transferred to phosphate-free, high proportions of zeolite-containing liquid concentrates.
- EP 295 525 discloses a pasty detergent which does not flow under the influence of gravity, and a method for automatic Dosing this agent in the washing machine known.
- the agent contains nonionic surfactants and builder salts dispersed therein.
- the high viscosity of the agents and their tendency to form viscous, difficult to disperse gels when mixed with cold water requires the use of mechanical conveying and dispersing devices, such as pumps, agitators and injectors, and process control. Although they enable a high degree of automation, exact dosing and trouble-free operation, they also require corresponding investments.
- the object was therefore to develop a phosphate-free liquid detergent which is resistant to segregation and whose viscosity or flowability is selected such that it can also be metered without any outlay on equipment. Furthermore, the agent should be rapidly and completely dispersible and soluble in cold water without the formation of tough and poorly dispersible gels.
- the invention with which these objects are achieved is a pasty, phosphate-free, essentially water-free detergent concentrate, characterized by a content of
- the water content of the compositions is less than 4% by weight, preferably less than 2% by weight. According to this definition, free water, ie. H. not as water of hydration or water bound to zeolite.
- the viscosity of the agents is generally between 10.00 and 70,000 mPa-s, preferably 15,000 and 60,000 mPa-s and in particular up to 50,000 mPa « s (illi-Pascal x see).
- the agents are therefore still flowable and can be metered by hand, but on the other hand can also be fed to the washing machines by means of automatic metering and washing devices.
- the proportion of Na-alkylbenzenesulfonate (component A), which is generally referred to in industry as dodecylbenzenesulfonate, is preferably 3 to 6% by weight.
- Component (B) consists of alkoxylated, preferably ethoxylated, linear alcohols or their mixtures with alcohols (oxo alcohols) having 8 to 18 carbon atoms which are methyl-branched in the 2-position. Alcohols with 8 to 16 carbon atoms are preferably saturated. Those with 18 carbon atoms are preferably unsaturated and consist, for example, of oleyl alcohol.
- the number of ethylene glycol ether groups (E0) is 2 to 10, preferably 3 to 8 and should preferably be coordinated with respect to the alcohol residue in such a way that the ethoxylates or ethoxylate mixtures have a pour point below 10 ° C., preferably below 5 ° C.
- Nonionics from this class are C ⁇ o-14-coconut alcohols with 3 - 8 EO, Oley alcohol with 5 - 10 E0, C ⁇ o-14-oxo alcohols with 3 - 8 EO and Ci2-i5-0xo alcohols with 3 - 7 EO, as well as their mixtures.
- Alcohol alkoxylates of the general formulas are also useful
- R- (E0) a - (P0) b- (E0) c and R- (P0) x - (E0) y - (P0) z in the EO for an ethylene glycol ether residue, PO for a propylene glycol ether residue, a for numbers from 1 to 10, b for numbers 1 to 3, c for the numbers 0 to 10 with (a + c) - 5 to 15, x for the numbers 1 to 3, y for the numbers 3 to 10 and z for the numbers 0 to 3 stand with (x + z) 1 to 4.
- the aforementioned ethoxylates and alkoxylates can be mixed with one another in any manner.
- the proportion of the surfactant component (B) is on average 20 to 40% by weight, preferably 25 to 35% by weight.
- the total amount of surfactants is 20 to 35% by weight, preferably 22 to 33% by weight.
- Component (C) consists of hydrated, Fe-crystalline, synthetic zeolite of the NaA type. Suitable zeolites have practically no particles larger than 30 ⁇ m and preferably consist at least 80% of particles smaller than 10 ⁇ m. Their calcium binding capacity, which is determined according to the information in DE 24 12837, is in the range from 100 to 200 mg CaO / g.
- the zeolite content of the agents is, on hydrated based on zeolite, 35 to 65% by weight, preferably 37 to 60% by weight and in particular 50 to 57% by weight.
- Suitable polycarboxylates which are to be assigned to component (D) and can be used either alone or in a mixture are monomeric polycarboxylates, such as citric acid and nitrilotriacetic acid (NTA) in the form of the sodium salts. If citric acid is used exclusively, its proportion (based on acid) is preferably 8 to 15% by weight. If only NTA is used, its proportion (based on acid) is preferably 3 to 10% by weight.
- Preferred components of component (D) are polymeric or copolymeric carboxylic acids in the form of the sodium salts.
- Suitable homopolymers are polyethacrylic acid and preferably polyacrylic acid, for example those with a molecular weight of 800 to 200,000.
- polyacrylic acid Of particular interest are low-molecular, low-viscosity polyacrylic acids which do not adversely affect the fluidity of the liquid concentrates, but at the same time still have sufficient sequestering power.
- Such polyacrylic acids have a molecular weight of 1,000 to 50,000. They are in the means as. Sodium salts, but mostly not all acid groups are neutralized.
- the polyacrylic acid content of the agents, based on acid, can be 3 to 10, preferably 4 to 8,% by weight.
- Suitable copolymers are those of acrylic acid with methacrylic acid or copolymers of acrylic acid, methacrylic acid or maleic acid with vinyl ethers, such as vinyl methyl ether or vinyl ethyl ether, furthermore with vinyl esters, such as vinyl acetate or vinyl propionate, acrylamide, methacrylamide and with ethylene, propylene or styrene.
- vinyl ethers such as vinyl methyl ether or vinyl ethyl ether
- vinyl esters such as vinyl acetate or vinyl propionate
- acrylamide methacrylamide
- ethylene, propylene or styrene ethylene, propylene or styrene.
- the proportion thereof in the interest of sufficient water solubility is not more than 60 mole percent, preferably less than 50 mole percent.
- Copolymers of acrylic acid or methacrylic acid with maleic acid such as are characterized, for example, in EP 25551-B1 have proven to be particularly suitable.
- copolymers containing 50 to 90% by weight of acrylic acid or methacrylic acid and 50 to 10% by weight of maleic acid are particularly preferred.
- Copolymers in which 60 to 85% by weight of acrylic acid and 40 to 15% by weight of maleic acid are present are particularly preferred.
- the content of such (co) polymers in the compositions, based on free acid, can be up to 10% by weight, preferably 3 to 8% by weight.
- Anhydrous soda and sodium silicate are suitable as washing alkalis (component E).
- the sodium silicate can have a Na ⁇ : Si ⁇ 2 ratio of 1: 0.9 to 1: 3.5. Waterglass with a ratio of 1: 2 to 1: 3.5 and metasilicate with a ratio of 1: 1 to 1: 1.5 are preferred.
- the proportion of washing alkalis is 0 to 20, preferably 0 to 10% by weight, the proportion of soda preferably up to 10% by weight and that of sodium silicate preferably up to 7% by weight.
- suspension stabilizers can be added to the compositions in proportions of up to 5% by weight, preferably from 0.2 to 3% by weight.
- Alkaline soaps in particular sodium soaps from fatty acids with 12 to 22 carbon atoms, preferably saturated, are suitable Finely divided silica, such as precipitated or thermally produced silica (Aerosil) or diatomaceous earth, is also suitable. Mixtures of soap and finely divided silica can also be used.
- cellulose ethers with graying-inhibiting action such as sodium carboxymethyl cellulose and their mixtures with other cellulose ethers, such as methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose or mixed ethers, such as methyl hydroxyethyl cellulose, methyl carboxymethyl cellulose or ethyl hydroxyethyl cellulose.
- Cellulose ethers and (co) polymers can advantageously be used together.
- the graying inhibitor content of the agents can be up to 1.5% by weight, preferably up to 0.5% by weight.
- enzymes in particular proteases, amylases and their mixtures, fragrances and customary optical brighteners, in particular optical brighteners with substantivity for cellulose fibers (cotton) from the class of the substituted bis-triazinylstilbene disulfonic acids and the sulfonated distyryl, which are usually used in proportions of 0.05 to 0.5% by weight.
- agents for improving the flowability can also be added.
- hydrotropes such as alkylbenzenesulfonate with 1 to 3 carbon atoms in the alkyl groups, such as toluene, Cu ol or xylene sulfonate.
- C9..13 alkylbenzenesulfonates they do not contribute to the detergency of the agents and are therefore less preferred.
- Solvents such as lower alcohols and ether alcohols and polyethylene glycols with a molecular weight of 200 to 1,000 can also be used.
- the proportion of polyglycols can be up to 10% by weight. Alcohols can be used in the same amount, but they are less preferred.
- the water content of the funds should be as low as possible, since free
- Water increases the viscosity of the agents and thus complicates the processing and dosing of the agents. Water contents of less than 3% by weight, in particular less than 1.5% by weight, are therefore particularly preferred.
- the agents are prepared by mixing and homogenizing the solid, finely divided constituents with the liquid nonionic surfactants, in particular with the liquid surfactant mixture. Surprisingly, it was found that about half of the solid alkylbenzenesulfonates behave like liquid constituents and thus favor the incorporation of high solids contents. At the same time, they lower the viscosity of the agents or enable higher proportions of solids. They also improve the dispersing properties of the agents in cold tap water.
- the mixture is expediently ground while the constituents are combined or subsequently, for example in a colloid mill or on a roller mill, so that the particle size of the suspended solids is less than 50 ⁇ m, preferably between 5 and 40 ⁇ m.
- the proportion of coarse particles (over 80 ⁇ m) should preferably be less than 5% by weight.
- the agents are generally used in a concentration of 4 to 12 g / 1, preferably 5 to 10 g / 1, with softened, ie. H. to a degree of hardness of less than 2 ° dH, in particular less than 1 ° dH, softened water is used to prepare the wash liquor.
- the agents are characterized by a high washability and a low, non-disturbing foam development during use. Surprisingly, it has been found that the agents are extraordinarily stable against segregation even under long-term storage under changing climatic conditions and dissolve and distribute completely within a short time even at water temperatures of 5 ° C.
- OA-424 oxo alcohol C o-12 with E0 » 2P0 and 4E0
- CO-16 cetyl oleyl alcohol with 65% oleyl alcohol + 1P0
- the polyacrylate had a molecular weight of 5,000.
- the copolymer was composed of acrylic acid and maleic acid (3: 1) and had a molecular weight of approximately 70,000. Both polymer salts were used in the form of the Na salts.
- the Na citrate was present as a dihydrate.
- the NaA type zeolite had a water content of 20%.
- the Na salt of 4,4'-bis (2-anilino-4-morpholino-l, 3,5-triazin-6-yl-amino) -stilbene-2,2'-disulfonic acid was used as the optical brightener .
- the soap consisted of a sodium tallow soap.
- the silica designated SiO 2 consisted of diatomaceous earth.
- the enzyme consisted of a protease-amylase mixture " (3: 2).
- the content of unbound water was less than 0.5% by weight.
- the contents given in the table mean percentages by weight.
- component (B ) the acid content is given in brackets.
- Example 1 42000 mPa-s
- Example 2 49000 mPa-s
- Example 3 29000 mPa-s
- Example 4 32000 mPa-s
- the agents proved to be stable in storage, i.e. no recognizable sedimentation occurred within a period of 6 weeks.
- the solution speed at 4.5 ° C and 21 ° C determined under standardized conditions was excellent.
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Abstract
The concentrated detergent paste substantially free of water and containing no phosphate contains (A) 2 to 7 % wt. sodium alkylbenzole sulphonate with linear C9-13? alkyl chains, (B) 20 to 40 % wt. non-ionic tensides with linear alkyl or alkylene groups with 10 to 18 C atoms, (C) 35 to 65 % wt. synthetic, fine-crystalline, water-containg zeolith of type NaA, (D) 3 to 15 % wt. of at least one organic polycarboxylate builder (related to free acids), (E) 0 to 20 % wt. alcaline washing agents of the sodium carbonate and sodium silicate class, (F) 0 to 5 % wt. of a suspension stabiliser and (G) other common detergent components. The sum of components (C) and (D) should not exceed 70 % wt. and the setting point of component (B) should be below 10C.
Description
"Pastöses, phosphatfreies, im wesentlichen wasserfreies Waschmit- tel" "Pasty, phosphate-free, essentially water-free detergent"
Die vorliegende Erfindung betrifft ein pastöses, phosphatfreies, im wesentlichen wasserfreies Waschmittel, das sich durch eine hohe Lagerstabilität und eine verb?sserte Dispergierbarkeit und Lös¬ lichkeit in Wasser auszeichnet.The present invention relates to a pasty, phosphate-free, essentially water-free detergent which is distinguished by high storage stability and improved dispersibility and solubility in water.
Pastöse Waschmittel besitzen gegenüber pulverförmigen Mitteln den Vorteil, daß sie staubfrei gehandhabt und dosiert werden können. Sie eignen sich daher auch für automatische Dosiervorrichtungen. Ihre Problematik besteht darin, daß sie in einem größeren Tempe¬ raturbereich hinreichend fließfähig sein müssen, was die Rezep¬ turfreiheit erheblich einengt, insbesondere wenn hohe Anteile an festen Wirkstoffen in die Paste eingearbeitet werden sollen. An¬ dererseits wird verlangt, daß sich die Mittel während der Lagerung nicht entmischen, was mit der Forderung nach einer guten Fließfä¬ higkeit und entsprechend verringerter Viskosität nur schwer ver¬ einbar ist. Weiterhin wird angestrebt, keine Lösungsmittel und Suspensionsstabilisatoreπ zu verwenden, da sie bei der Anwendung nichts zur Waschleistung beitragen. Schließlich sollen sie bei Zugabe von kaltem Wasser, insbesondere bei dem Einspülprozeß in der Waschmaschine, keine zähen, schwer dispergierbaren Gele bil¬ den, sondern sich schnell und vollständig lösen. Diese Gefahr ist insbesondere dann gegeben, wenn die Mittel hohe Anteile an nicht- ionischen Tensiden enthalten.
In DE 12 79 878 (GB 1205 711) ist ein pastöses, im wesentlichen wasserfreies Mittel beschrieben, dessen flüssige Phase aus nicht¬ ionischen Tensiden und niederen Alkoholen besteht. Als Gerüstsalze werden Natriumtripolyphosphat (TPP) und Soda, als Bleichmittel Natriu perborat-moπohydrat eingesetzt. Um ein Entmischen der Pa¬ sten bei der Lagerung zu vermeiden, werden die Feststoffe fein gemahlen und dem Mittel zusätzlich Suspensionsstabilisatoren in Form feinteiliger Kieselsäure zugesetzt. Aus DE 22 33 771 (US 38 50831) sind Waschpasten bekannt, die als flüssige Phase Gemische aus nichtionischen Tensiden und Polyolen und als Gerüstsalze Phosphate, Citrat und Nitrilotriacetat enthalten. Auch Wasserglas, d. h. ein schwach alkalisch reagierendes Silikat der Zusammenset¬ zung Na θ : Siθ2 = 1 : 3,3, kann anwesend sein.Pasty detergents have the advantage over powdered agents that they can be handled and dosed dust-free. They are therefore also suitable for automatic dosing devices. Their problem is that they have to be sufficiently flowable in a larger temperature range, which considerably limits the freedom from recipes, especially if high proportions of solid active substances are to be incorporated into the paste. On the other hand, it is required that the agents do not separate during storage, which is difficult to reconcile with the requirement for good flowability and correspondingly reduced viscosity. Furthermore, the aim is not to use solvents and suspension stabilizers, since they do not contribute to washing performance when used. Finally, when cold water is added, in particular during the washing-in process in the washing machine, they should not form tough, difficult to disperse gels, but should dissolve quickly and completely. This danger arises in particular if the agents contain high proportions of non-ionic surfactants. DE 12 79 878 (GB 1205 711) describes a pasty, essentially anhydrous agent, the liquid phase of which consists of non-ionic surfactants and lower alcohols. Sodium tripolyphosphate (TPP) and soda are used as skeleton salts, and sodium perborate monohydrate as bleaching agent. In order to avoid separation of the pastes during storage, the solids are finely ground and suspension stabilizers in the form of finely divided silica are additionally added to the agent. DE 22 33 771 (US 38 50831) discloses washing pastes which contain mixtures of nonionic surfactants and polyols as the liquid phase and phosphates, citrate and nitrilotriacetate as the structural salts. Water glass, ie a weakly alkaline-reacting silicate of the composition Na θ: Siθ2 = 1: 3.3, can also be present.
In US 4 115 308 sind pastöse Waschmittel beschrieben, die wasser¬ frei sein können und in diesem Falle große Anteile an Lösungsmit¬ teln, wie Triethanolamin, Polyethylenglykol oder freien Fettalko¬ holen enthalten. Diese Zusätze tragen nichts zur Waschwirkung der Mittel bei. Außerdem enthalten die Pasten in der Mehrzahl Tripolyphosphat in Anteilen von 32 bis 35 Gew.-%. Ausgesprochen phosphatreich mit Anteilen von 30 bis 35 Gew.-% Na-Tripolyphosphat sind auch die pastenförmigen Mittel gemäß DE 28 25 218 (US 4 315 812). Als Dispersionsstabilisator enthalten die Mittel feintei- liges Siliciumdioxid in Anteilen von ca. 2 Gew.-%. Phosphatfreie Waschmittelpasten, die jedoch hohe Anteile an wasserlöslichen, aus Umweltgründen ebenfalls problematischen Buildersubstanzen, wie Nitrolotriacetat oder Phoshponaten (zwischen 38 und 55 Gew.-%) enthalten, sind aus DE 2054855 bekannt. Zusätzlich enthalten die Mittel größere Anteile an Alkoholen als Lösungsmittel sowie ge¬ ringe Mengen an Seife in Form der Alkali- oder Erdalkalisalze als Suspensionsstabilisator.
EP 30 096 lehrt, daß man in flüssigen bis pastösen Waschmitteln die Feststoffe, bestehend aus Gerüstsalzen und Persalzen, auf Korngrößen unter 10 μm vermählen muß, um ein Entmischen der Pasten während der Lagerung zu vermeiden. Die Gerüstsalze bestehen im wesentlichen aus Polyphosphonaten. Auch Alkalisilikate und orga¬ nische Buildersalze können anwesend sein, jedoch werden hierzu keine näheren Angaben gemacht. Die Tensidkomponente besteht aus¬ schließlich aus flüssigen nichtionischen Tensiden. Anionische Tenside sind in den Pasten nicht enthalten. Die Notwendigkeit, die Feststoffe auf eine sehr kleine Korngröße vermählen zu müssen, erfordert einen erheblichen apparativen und zeitlichen Aufwand.No. 4,115,308 describes pasty detergents which can be water-free and in this case contain large proportions of solvents, such as triethanolamine, polyethylene glycol or free fatty alcohols. These additives do not contribute to the washing effect of the agents. The majority of the pastes also contain tripolyphosphate in proportions of 32 to 35% by weight. The paste-like compositions according to DE 28 25 218 (US Pat. No. 4,315,812) are also extremely phosphate-rich with fractions of 30 to 35% by weight Na tripolyphosphate. As a dispersion stabilizer, the agents contain finely divided silicon dioxide in proportions of approximately 2% by weight. Phosphate-free detergent pastes, which, however, contain high proportions of water-soluble builder substances which are also problematic for environmental reasons, such as nitrolotriacetate or phosphonates (between 38 and 55% by weight) are known from DE 2054855. In addition, the compositions contain larger proportions of alcohols as solvents and small amounts of soap in the form of the alkali or alkaline earth metal salts as a suspension stabilizer. EP 30 096 teaches that in liquid to pasty detergents, the solids, consisting of skeleton salts and persalts, have to be ground to particle sizes below 10 μm in order to avoid segregation of the pastes during storage. The skeleton salts consist essentially of polyphosphonates. Alkali silicates and organic builder salts can also be present, but no further details are given here. The surfactant component consists exclusively of liquid nonionic surfactants. Anionic surfactants are not included in the pastes. The necessity of having to grind the solids to a very small grain size requires a considerable expenditure of equipment and time.
Die genannten pastenför igen Mittel enthalten im wesentlichen Phosphate als Buildersalze. Im Interesse einer minimalen Abwas¬ serbelastung ist jedoch eine weitgehende Phosphatfreiheit anzu¬ streben. P-freie Waschmittel erfordern jedoch gegenüber P-haltigen Mitteln ein geändertes Gesamtkonzept, um einen Abfall des Reini¬ gungsvermögens zu vermeiden. Bei pulverförmigen Waschmitteln ist diese Entwicklung schon weit fortgeschritten, während bei pastösen Mitteln die Probleme wegen der beschränkten Auswahlmöglichkeit hinsichtlich der brauchbaren Rohstoffe sehr viel größer sind. Be¬ sondere Probleme ergeben sich bei solchen Pasten, in denen das Phosphat durch Zeolith ersetzt werden soll. Diese lassen sich wegen der Wasserunlöslichkeit der Zeolithe besonders schlecht in kaltem Wasser dispergieren. Die an phosphathaltigen Mitteln gewonnenen Erfahrungen lassen sich daher nicht ohne weiteres auf phosphatfreie, hohe Anteile an Zeolith enthaltenden Flüssigkonzentraten übertragen.The paste-like agents mentioned essentially contain phosphates as builder salts. In the interest of minimal pollution of the wastewater, however, it is desirable to be largely free of phosphates. P-free detergents, however, require a different overall concept compared to P-containing detergents in order to avoid a decrease in the cleaning ability. This development is already well advanced with powder detergents, while with pasty agents the problems are much greater due to the limited choice with regard to the usable raw materials. Particular problems arise with pastes in which the phosphate is to be replaced by zeolite. Because of the water insolubility of the zeolites, these are particularly difficult to disperse in cold water. The experience gained with phosphate-containing agents cannot therefore be easily transferred to phosphate-free, high proportions of zeolite-containing liquid concentrates.
Aus EP 295 525 ist ein pastöses, unter dem Einfluß der Schwerkraft nicht fließendes Waschmittel sowie ein Verfahren zum automatischen
Dosieren dieses Mittels in die Waschmaschine bekannt. Das Mittel enthält als flüssige Komponente nichtionische Tenside sowie darin dispergierte Buildersalze. Die hohe Viskosität der Mittel und ihre Neigung beim Mischen mit kaltem Wasser viskose, schwer dispergierbare Gele zu bilden, erfordert die Anwendung mecha¬ nischer Förder- und Dispergiervorrichtungen, wie Pumpen, Rührwerke und Injektoren sowie eine Prozeßsteuerung. Sie ermöglichen zwar einen hohen Automatisierungsgrad, eine exakte Dosierung und einen störungsfreien Betrieb, erfordern aber andererseits entsprechende Investitionen.EP 295 525 discloses a pasty detergent which does not flow under the influence of gravity, and a method for automatic Dosing this agent in the washing machine known. As a liquid component, the agent contains nonionic surfactants and builder salts dispersed therein. The high viscosity of the agents and their tendency to form viscous, difficult to disperse gels when mixed with cold water requires the use of mechanical conveying and dispersing devices, such as pumps, agitators and injectors, and process control. Although they enable a high degree of automation, exact dosing and trouble-free operation, they also require corresponding investments.
Es bestand somit die Aufgabe, ein phosphatfreies flüssiges Wasch¬ mittel zu entwickeln, das gegen Entmischen beständig ist und des¬ sen Viskosität bzw. Fließfähigkeit so gewählt ist, daß es sich auch ohne apparativen Aufwand und dosieren läßt. Weiterhin soll das Mittel in kaltem Wasser schnell und vollständig dispergierbar und löslich sein, ohne daß es zur Bildung zäher und schlecht dis- pergierbarer Gele kommt.The object was therefore to develop a phosphate-free liquid detergent which is resistant to segregation and whose viscosity or flowability is selected such that it can also be metered without any outlay on equipment. Furthermore, the agent should be rapidly and completely dispersible and soluble in cold water without the formation of tough and poorly dispersible gels.
Gegenstand der Erfindung, mit der diese Aufgaben gelöst werden, ist ein pastöses, phosphatfreies, im wesentlichen wasserfreies Waschmittelkonzentrat, gekennzeichnet durch einen Gehalt anThe invention with which these objects are achieved is a pasty, phosphate-free, essentially water-free detergent concentrate, characterized by a content of
A) 2 bis 7 Gew.-% an Natrium-Alkylbenzolsulfonat mit linearen Cg_i3-Alkylkettenf A) 2 to 7 wt .-% of sodium alkylbenzenesulfonate with linear Cg_i3 alkyl chains f
B) 20 bis 40 Gew.-% an nichtionischen Tensiden mit linearen, 10 bis 18 C-Atome aufweisenden Alkyl- oder Alkenylgruppen,B) 20 to 40% by weight of nonionic surfactants with linear alkyl or alkenyl groups having 10 to 18 carbon atoms,
C) 35 bis 65 Gew.-% an synthetischem, feinkristallinem, wasser¬ haltigem Zeolith vom Typ NaA,C) 35 to 65% by weight of synthetic, finely crystalline, water-containing zeolite of the NaA type,
D) 3 bis 15 Gew.-% mindestens eines organischen Polycarboxylat- Builders (bezogen auf freie Säure),D) 3 to 15% by weight of at least one organic polycarboxylate builder (based on free acid),
E) 0 bis 20 Gew.-% an Waschalkalien aus der Klasse Natriu carbonat
und Natriumsilikat, F) 0 bis 5 Gew.-% eines Suspensionsstabilisators, mit der Maßgabe, daß die Summe der Bestandteile (C) und (D) 70 Gew.-% nicht übersteigt.E) 0 to 20% by weight of washing alkalis from the sodium carbonate class and sodium silicate, F) 0 to 5% by weight of a suspension stabilizer, with the proviso that the sum of the components (C) and (D) does not exceed 70% by weight.
Der Wassergehalt der Mittel beträgt weniger als 4 Gew.-%, vor¬ zugsweise weniger als 2 Gew.-%. Als Wasser gilt gemäß dieser De¬ finition freies, d. h. nicht als Hydratwasser oder an Zeolith ge¬ bundenes Wasser.The water content of the compositions is less than 4% by weight, preferably less than 2% by weight. According to this definition, free water, ie. H. not as water of hydration or water bound to zeolite.
Die Viskosität der Mittel liegt im allgemeinen zwischen 10.00 und 70.000 mPa-s, vorzugsweise 15.000 und 60.000 mPa-s und insbeson¬ dere bis 50.000 mPa«s ( illi-Pascal x see). Die Mittel sind somit noch fließfähig und von Hand dosierbar, können aber andererseits auch mittels automatischer Dosier- und Waschvorrichtungen den Waschmaschinen zugeführt werden.The viscosity of the agents is generally between 10.00 and 70,000 mPa-s, preferably 15,000 and 60,000 mPa-s and in particular up to 50,000 mPa « s (illi-Pascal x see). The agents are therefore still flowable and can be metered by hand, but on the other hand can also be fed to the washing machines by means of automatic metering and washing devices.
Der Anteil an Na-Alkylbenzolsulfonat (Komponente A), das in der Technik meist pauschal als Dodecylbenzolsulfonat bezeichnet wird, beträgt vorzugsweise 3 bis 6 Gew.-%.The proportion of Na-alkylbenzenesulfonate (component A), which is generally referred to in industry as dodecylbenzenesulfonate, is preferably 3 to 6% by weight.
Die Komponente (B) besteht aus alkoxylierten, vorzugsweise ethoxy- lierten linearen Alkoholen bzw. deren Gemischen mit in 2-Stellung methylverzweigten Alkoholen (Oxo-Alkoholen) mit 8 bis 18 C-Atomen. Alkohole mit 8 bis 16 C-Atomen sind vorzugsweise gesättigt. Solche mit 18 C-Atomen sind vorzugsweise ungesättigt und bestehen bei¬ spielsweise aus Oleylalkohol . Die Zahl der Ethylenglykolethergrup- pen (E0) beträgt 2 bis 10, vorzugsweise 3 bis 8 und soll in Bezug auf den Alkoholrest vorzugsweise so abgestimmt sein, daß die Eth- oxylate bzw. Ethoxylatgemische einen Stockpunkt von unter 10° C, vorzugsweise von unter 5° C aufweisen. Besonders geeignete
Nonionics aus dieser Klasse sind Cιo-14-Cocosalkohole mit 3 - 8 EO, Oleylakohol mit 5 - 10 E0, Cχo-14-Oxoalkohole mit 3 - 8 EO und Ci2-i5-0xoalkohole mit 3 - 7 EO, sowie deren Gemische.Component (B) consists of alkoxylated, preferably ethoxylated, linear alcohols or their mixtures with alcohols (oxo alcohols) having 8 to 18 carbon atoms which are methyl-branched in the 2-position. Alcohols with 8 to 16 carbon atoms are preferably saturated. Those with 18 carbon atoms are preferably unsaturated and consist, for example, of oleyl alcohol. The number of ethylene glycol ether groups (E0) is 2 to 10, preferably 3 to 8 and should preferably be coordinated with respect to the alcohol residue in such a way that the ethoxylates or ethoxylate mixtures have a pour point below 10 ° C., preferably below 5 ° C. Particularly suitable Nonionics from this class are Cιo-14-coconut alcohols with 3 - 8 EO, Oley alcohol with 5 - 10 E0, Cχo-14-oxo alcohols with 3 - 8 EO and Ci2-i5-0xo alcohols with 3 - 7 EO, as well as their mixtures.
Gut brauchbar sind auch Alkoholalkoxylate der allgemeinen FormelnAlcohol alkoxylates of the general formulas are also useful
R-(E0)a-(P0)b-(E0)c und R-(P0)x-(E0)y-(P0)z in der EO für einen Ethylenglykolether-Rest, PO für einen Propylenglykolether-Rest, a für Zahlen von 1 bis 10, b für Zahlen 1 bis 3, c für die Zahlen 0 bis 10 mit (a + c) - 5 bis 15, x für die Zahlen 1 bis 3, y für die Zahlen 3 bis 10 und z für die Zahlen 0 bis 3 mit (x + z) = 1 bis 4 stehen. Bevorzugte Nonionics dieser Klasse sind Oleylalkohol mit 1 - 2 PO und 4 - 8 EO, Cs-12-Oxoalkohle mit a = 2 bis 6, b = 1 bis 2 und c = 2 bis 6 und Cχo-14-Oxoalkohole bzw. Cιo-14-Fettalkohole mit x = 1 bis 2 und y = 5 bis 12 gemäß vorstehenden Formeln. Ebenso können die vorgenannten Ethoxylate und Alkoxylate in be¬ liebiger Weise miteinander vermischt sein.R- (E0) a - (P0) b- (E0) c and R- (P0) x - (E0) y - (P0) z in the EO for an ethylene glycol ether residue, PO for a propylene glycol ether residue, a for numbers from 1 to 10, b for numbers 1 to 3, c for the numbers 0 to 10 with (a + c) - 5 to 15, x for the numbers 1 to 3, y for the numbers 3 to 10 and z for the numbers 0 to 3 stand with (x + z) = 1 to 4. Preferred nonionics of this class are oleyl alcohol with 1 - 2 PO and 4 - 8 EO, Cs-12-oxo alcohol with a = 2 to 6, b = 1 to 2 and c = 2 to 6 and Cχo-14-oxo alcohols or Cιo- 14-fatty alcohols with x = 1 to 2 and y = 5 to 12 according to the formulas above. Likewise, the aforementioned ethoxylates and alkoxylates can be mixed with one another in any manner.
Der Anteil der Tensidkomponente (B) im Mittel beträgt 20 bis 40 Gew.-%, vorzugsweise 25 bis 35 Gew.-%. Die Gesamtmenge der Tenside beträgt 20 bis 35 Gew.-%, vorzugsweise 22 bis 33 Gew.-%.The proportion of the surfactant component (B) is on average 20 to 40% by weight, preferably 25 to 35% by weight. The total amount of surfactants is 20 to 35% by weight, preferably 22 to 33% by weight.
Die Komponente (C) besteht aus hydratisierte , fe-'nkristallinem, synthetischem Zeolith vom Typ NaA. Geeignete Zeolithe weisen praktisch kein Teilchen größer als 30 μm auf und bestehen vor¬ zugsweise zu wenigstens 80 % aus Teilchen einer Größe kleiner als 10 μm. Ihr Calciumbindevermögen, das nach den Angaben in DE 24 12837 bestimmt wird, liegt im Bereich von 100 bis 200 mg CaO/g. Der Gehalt der Mittel an Zeolith beträgt, auf hydratisier-
ten Zeolith bezogen, 35 bis 65 Gew.-%, vorzugsweise 37 bis 60 Gew.-% und insbesondere 50 bis 57 Gew.-%.Component (C) consists of hydrated, Fe-crystalline, synthetic zeolite of the NaA type. Suitable zeolites have practically no particles larger than 30 μm and preferably consist at least 80% of particles smaller than 10 μm. Their calcium binding capacity, which is determined according to the information in DE 24 12837, is in the range from 100 to 200 mg CaO / g. The zeolite content of the agents is, on hydrated based on zeolite, 35 to 65% by weight, preferably 37 to 60% by weight and in particular 50 to 57% by weight.
Geeignete, der Komponente (D) zuzurechnende Polycarboxylate, die entweder allein oder im Gemisch eingesetzt werden können, sind monomere Polycarboxylate, wie Citronensäure und Nitrilotriessig- säure (NTA) in Form der Natriumsalze. Sofern ausschließlich Ci¬ tronensäure eingesetzt wird, beträgt deren Anteil (auf Säure be¬ zogen) vorzugsweise 8 bis 15 Gew.-%. Sofern ausschließlich NTA eingesetzt wird, beträgt dessen Anteil (auf Säure bezogen) vor¬ zugsweise 3 bis 10 Gew.-%.Suitable polycarboxylates which are to be assigned to component (D) and can be used either alone or in a mixture are monomeric polycarboxylates, such as citric acid and nitrilotriacetic acid (NTA) in the form of the sodium salts. If citric acid is used exclusively, its proportion (based on acid) is preferably 8 to 15% by weight. If only NTA is used, its proportion (based on acid) is preferably 3 to 10% by weight.
Bevorzugte Bestandteile der Komponente (D) sind poly ere bzw. co¬ polymere Carbonsäuren in Form der Natriumsalze. Geeignete Homo- polymere sind Poly ethacrylsäure und bevorzugt Polyacrylsäure, beispielsweise solche mit einem Molekulargewicht von 800 bis 200.000. Von besonderem Interesse sind niedermolekulare niedrig¬ viskose Polyacrylsäuren, die das Fließvermögen der Flüssigkonzen¬ trate nicht nachteilig beeinflussen, gleichzeitig aber noch ein ausreichendes Sequestrierungsvermögen besitzen. Derartige Poly¬ acrylsäuren weisen ein Molekulargewicht von 1.000 bis 50.000 auf. Sie liegen in den Mitteln als. Natriumsalze vor, wobei jedoch meist nicht sämtliche Säuregruppen neutralisiert sind. Der Gehalt der Mittel an Polyacrylsäure kann auf Säure bezogen 3 bis 10, vorzugs¬ weise 4 bis 8 Gew.-% betragen.Preferred components of component (D) are polymeric or copolymeric carboxylic acids in the form of the sodium salts. Suitable homopolymers are polyethacrylic acid and preferably polyacrylic acid, for example those with a molecular weight of 800 to 200,000. Of particular interest are low-molecular, low-viscosity polyacrylic acids which do not adversely affect the fluidity of the liquid concentrates, but at the same time still have sufficient sequestering power. Such polyacrylic acids have a molecular weight of 1,000 to 50,000. They are in the means as. Sodium salts, but mostly not all acid groups are neutralized. The polyacrylic acid content of the agents, based on acid, can be 3 to 10, preferably 4 to 8,% by weight.
Geeignete Copolymere sind solche der Acrylsäure mit Methacrylsäure bzw. Copolymere der Acrylsäure, Methacrylsäure oder Maleinsäure mit Vinylethern, wie Vinylmethylether bzw. Vinylethylether, ferner mit Vinylestern, wie Vinylacetat oder Vinylpropionat, Acrylamid, Methacrylamid sowie mit Ethylen, Propylen oder Styrol. In solchen
copolymeren Säuren, in denen eine der Komponenten keine Säurefunk¬ tion aufweist, beträgt deren Anteil im Interesse einer ausreichen¬ den Wasserlöslichkeit nicht mehr als 60 Molprozent, vorzugsweise weniger als 50 Molprozent. Als besonders geeignet haben sich Co¬ polymere der Acrylsäure bzw. Methacrylsäure mit Maleinsäure er¬ wiesen, wie sie beispielsweise in EP 25551-B 1 charakterisiert sind. Es handelt sich dabei um Copoly erisate, die 50 bis 90 Gew.-% Acrylsäure bzw. Methacrylsäure und 50 bis 10 Gew.-% Maleinsäure enthalten. Besonders bevorzugt sind solche Copolymere, in denen 60 bis 85 Gew.-% Acrylsäure und 40 bis 15 Gew.-% Maleinsäure vorliegen. Der Gehalt der Mittel an derartigen (Co-)Polymeren kann, auf freie Säure bezogen, bis zu 10 Gew.-%, vorzugsweise 3 bis 8 Gew.-% betragen.Suitable copolymers are those of acrylic acid with methacrylic acid or copolymers of acrylic acid, methacrylic acid or maleic acid with vinyl ethers, such as vinyl methyl ether or vinyl ethyl ether, furthermore with vinyl esters, such as vinyl acetate or vinyl propionate, acrylamide, methacrylamide and with ethylene, propylene or styrene. In such copolymeric acids in which one of the components has no acid function, the proportion thereof in the interest of sufficient water solubility is not more than 60 mole percent, preferably less than 50 mole percent. Copolymers of acrylic acid or methacrylic acid with maleic acid, such as are characterized, for example, in EP 25551-B1 have proven to be particularly suitable. These are copolymers containing 50 to 90% by weight of acrylic acid or methacrylic acid and 50 to 10% by weight of maleic acid. Copolymers in which 60 to 85% by weight of acrylic acid and 40 to 15% by weight of maleic acid are present are particularly preferred. The content of such (co) polymers in the compositions, based on free acid, can be up to 10% by weight, preferably 3 to 8% by weight.
Als Waschalkalien (Komponente E) eignen sich wasserfreie Soda und Natriumsilikat. Das Natriumsilikat kann ein Verhältnis Na θ:Siθ2 von 1:0,9 bis 1:3,5 aufweisen. Bevorzugt sind Wasserglas mit einem Verhältnis von 1:2 bis 1:3,5 und Metasilikat mit einem Verhältnis von 1:1 bis 1:1,5. Der Anteil der Waschalkalien beträgt 0 bis 20, vorzugsweise 0 bis 10 Gew.-%, wobei der Anteil der Soda vorzugs¬ weise bis 10 Gew.-% und der an Natriumsilikat vorzugsweise bis 7 Gew.-% beträgt.Anhydrous soda and sodium silicate are suitable as washing alkalis (component E). The sodium silicate can have a Na θ: Siθ2 ratio of 1: 0.9 to 1: 3.5. Waterglass with a ratio of 1: 2 to 1: 3.5 and metasilicate with a ratio of 1: 1 to 1: 1.5 are preferred. The proportion of washing alkalis is 0 to 20, preferably 0 to 10% by weight, the proportion of soda preferably up to 10% by weight and that of sodium silicate preferably up to 7% by weight.
Fakultativ können den Mitteln Suspensions-Stabilisatoren (Kompo¬ nente F) in Anteilen bis zu 5 Gew.-% vorzugsweise von 0,2 bis 3 Gew.-% zugemischt werden. Geeignet sind Alkaliseifen, insbesondere Natriumseifen von Fettsäuren mit 12 bis 22 C-Atomen, bevorzugt gesättigten
Weiterhin eignet sich feinteilige Kieselsäure, wie gefällte oder auf thermischem Wege hergestellte Kieselsäure (Aerosil) bzw. Diatomeenerde. Auch Gemische aus Seife und feinteiliαe Kieselsäure sind brauchbar.
Weitere fakultative Bestandteile sind Celluloseether mit vergrau- ungsinhibierender Wirkung, wie Na-Carboxymethylcellulose und deren Gemische mit anderen Celluloseethern, wie Methylcellulose, Ethyl- cellulose, Hydroxyethylcellulose, Hydroxypropylcellulose oder Mischether, wie Methyl-hydroxyethylcellulose, Methylcarboxmethyl- cellulose oder Ethyl-hydroxyethylcellulose. Celluloseether und (Co-)Polymere können mit Vorteil gemeinsam verwendet werden. Der Gehalt der Mittel an Vergrauungsinhibitoren kann bis zu 1,5 Gew.-%, vorzugsweise bis 0,5 Gew.-% betragen.Optionally, suspension stabilizers (component F) can be added to the compositions in proportions of up to 5% by weight, preferably from 0.2 to 3% by weight. Alkaline soaps, in particular sodium soaps from fatty acids with 12 to 22 carbon atoms, preferably saturated, are suitable Finely divided silica, such as precipitated or thermally produced silica (Aerosil) or diatomaceous earth, is also suitable. Mixtures of soap and finely divided silica can also be used. Further optional components are cellulose ethers with graying-inhibiting action, such as sodium carboxymethyl cellulose and their mixtures with other cellulose ethers, such as methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose or mixed ethers, such as methyl hydroxyethyl cellulose, methyl carboxymethyl cellulose or ethyl hydroxyethyl cellulose. Cellulose ethers and (co) polymers can advantageously be used together. The graying inhibitor content of the agents can be up to 1.5% by weight, preferably up to 0.5% by weight.
Als weitere fakultative Bestandteile kommen Enzyme, insbesondere Proteasen, Amylasen und deren Gemische, Duftstoffe und übliche optische Aufheller in Frage, insbesondere optische Aufheller mit Substantivität für Cellulosefasern (Baumwolle) aus der Klasse der substituierten Bis-triazinylstilben-disulfonsäuren und der sulfo- nierten Distyryle, die üblicherweise in Anteilen von 0,05 bis 0,5 Gew.-% eingesetzt werden.Other optional components are enzymes, in particular proteases, amylases and their mixtures, fragrances and customary optical brighteners, in particular optical brighteners with substantivity for cellulose fibers (cotton) from the class of the substituted bis-triazinylstilbene disulfonic acids and the sulfonated distyryl, which are usually used in proportions of 0.05 to 0.5% by weight.
Darüber hinaus können noch Mittel zur Verbesserung der Fließfähig¬ keit zugesetzt werden. Hierzu zählen bekannte Hydrotrope, wie Al- kylbenzolsulfonat mit 1 bis 3 C-Atomen in den Alkylgruppen, wie Toluol-, Cu ol- oder Xylolsulfonat. Im Gegensatz zu den C9..13- Alkylbenzolsulfonaten tragen sie jedoch nichts zur Waschkraft der Mittel bei und sind daher weniger bevorzugt. Brauchbar sind ferner Lösungsmittel, wie niedere Alkohole und Etheralkohole sowie Poly- ethylenglykole mit einem Molekulargewicht von 200 bis 1.000. Der Anteil an Polyglykolen kann bis 10 Gew.-% betragen. Alkohole kön¬ nen in gleicher Menge eingesetzt werden, sie sind jedoch weniger bevorzugt.
Der Wassergehalt der Mittel soll möglichst gering sein, da freiesIn addition, agents for improving the flowability can also be added. These include known hydrotropes, such as alkylbenzenesulfonate with 1 to 3 carbon atoms in the alkyl groups, such as toluene, Cu ol or xylene sulfonate. In contrast to the C9..13 alkylbenzenesulfonates, however, they do not contribute to the detergency of the agents and are therefore less preferred. Solvents such as lower alcohols and ether alcohols and polyethylene glycols with a molecular weight of 200 to 1,000 can also be used. The proportion of polyglycols can be up to 10% by weight. Alcohols can be used in the same amount, but they are less preferred. The water content of the funds should be as low as possible, since free
Wasser die Viskosität der Mittel erhöht und somit die Verarbeitung und die Dosierung der Mittel erschwert. Wassergehalte von weniger als 3 Gew.- , insbesondere weniger als 1,5 Gew.-% sind daher be¬ sonders bevorzugt.Water increases the viscosity of the agents and thus complicates the processing and dosing of the agents. Water contents of less than 3% by weight, in particular less than 1.5% by weight, are therefore particularly preferred.
Die Herstellung der Mittel erfolgt durch Mischen und Homogenisie¬ ren der festen, feinteiligen Bestandteile mit den flüssigen nichtionischen Tensiden, insbesondere mit dem flüssigen Tensidgemisch. Überraschenderweise wurde festgestellt, daß auch die festen Alkylbenzolsulfonate etwa zur Hälfte ihres Anteils sich wie flüssige Bestandteile verhalten und somit das Einarbeiten ho¬ her Feststoffanteile begünstigen. Sie erniedrigen gleichzeitig die Viskosität der Mittel bzw. ermöglichen höhere Anteile an Fest¬ stoffen. Außerdem verbessern sie die Dispergiereigenschaften der Mittel in kaltem Leitungswasser. Zweckmäßigerweise wird das Ge¬ misch während des Vereinigens der Bestandteile oder anschließend daran vermählen, beispielsweise in einer Kolloidmühle bzw. auf einem Walzenstuhl, so daß die Korngröße der suspendierten Fest¬ stoffe unter 50 μm, vorzugsweise zwischen 5 bis 40 μm liegt. Der Anteil grober Teilchen (über 80 μm) soll bevorzugt unter 5 Gew.-% liegen.The agents are prepared by mixing and homogenizing the solid, finely divided constituents with the liquid nonionic surfactants, in particular with the liquid surfactant mixture. Surprisingly, it was found that about half of the solid alkylbenzenesulfonates behave like liquid constituents and thus favor the incorporation of high solids contents. At the same time, they lower the viscosity of the agents or enable higher proportions of solids. They also improve the dispersing properties of the agents in cold tap water. The mixture is expediently ground while the constituents are combined or subsequently, for example in a colloid mill or on a roller mill, so that the particle size of the suspended solids is less than 50 μm, preferably between 5 and 40 μm. The proportion of coarse particles (over 80 μm) should preferably be less than 5% by weight.
Die Mittel werden im allgemeinen in einer Konzentration von 4 bis 12 g/1, vorzugsweise 5 bis 10 g/1 eingesetzt, wobei zweckmäßiger¬ weise enthärtetes, d. h. auf einen Härtegrad von weniger 2° dH, insbesondere weniger als 1 °dH enthärtetes Wasser zum Ansetzen der Waschlauge verwendet wird.The agents are generally used in a concentration of 4 to 12 g / 1, preferably 5 to 10 g / 1, with softened, ie. H. to a degree of hardness of less than 2 ° dH, in particular less than 1 ° dH, softened water is used to prepare the wash liquor.
Die Mittel zeichnen sich durch ein hohes Waschvermögen und eine geringe, nicht störende Schaumentwicklung bei der Anwendung aus.
Überraschend hat sich gezeigt, daß die Mittel auch bei langdau¬ ernder Lagerung unter wechselnden Klimabedingungen außerordentlich stabil gegen Entmischen sind und sich innerhalb kurzer Zeit auch bei Wassertemperaturen von 5 °C vollständig lösen und verteilen.
The agents are characterized by a high washability and a low, non-disturbing foam development during use. Surprisingly, it has been found that the agents are extraordinarily stable against segregation even under long-term storage under changing climatic conditions and dissolve and distribute completely within a short time even at water temperatures of 5 ° C.
B e i s p i e l eB e i s p i e l e
Die Zusammensetzung der Mittel, bezogen auf nichtwäßrige Bestand¬ teile, ist Tabelle 1 zu entnehmen. Es bedeuten: ABS = Natriumsalz einer linearen Cιo_i3-Alkylbenzolsulfon- säure (mittlere Alkylkettenlänge Cn g) 0A-6 = Oxoalkohol Cχ2-13 mit 6E0The composition of the compositions, based on non-aqueous constituents, is shown in Table 1. It means: ABS = sodium salt of a linear Cιo_i3-alkylbenzenesulfonic acid (average alkyl chain length Cn g) 0A-6 = oxo alcohol Cχ2-13 with 6E0
OA-424 = Oxoalkohol C o-12 mit E0» 2P0 und 4E0 OA-424 = oxo alcohol C o-12 with E0 » 2P0 and 4E0
CO-16 = Cetyl-Oleylalkohol mit 65 % Anteil Oleylalkohol + 1P0CO-16 = cetyl oleyl alcohol with 65% oleyl alcohol + 1P0
+ 6E0+ 6E0
Das Na-Silikat wies die Zusammensetzung Na2θ:Siθ2 = 1:2,4 auf. Das Polyacrylat besaß ein Molekulargewicht von 5 000. Das Copolymere setzt sich aus Acrylsäure und Maleinsäure (3:1) zusammen und wies ein Molekulargewicht von ca. 70 000 auf. Beide Polymersalze kamen in Form der Na-Salze zum Einsatz. Das Na-Citrat lag als Dihydrat vor. Der Zeolith vom Typ NaA wies einen Wassergehalt von 20 % auf. Als optische Aufheller kam das Na-Salz der 4,4'-Bis-(2-anilino-4- morpholino-l,3,5-triazin-6-yl-amino)-stilben-2,2'-disulfonsäure zum Einsatz. Die Seife bestand aus einer Na-Talgseife. Die mit Siθ2 bezeichnete Kieselsäure bestand aus Diatomenerde. Das Enzym bestand aus einem Protease-Amylase-Gemisch" (3:2). Der Gehalt an nicht gebundenem Wasser lag unter 0,5 Gew.-%. Die in der Tabelle angegebenen Gehalte bedeuten Gewichtsprozente. Im Falle der Kom¬ ponente (B) ist der Säureanteil in Klammern angegeben.
The Na silicate had the composition Na2θ: Siθ2 = 1: 2.4. The polyacrylate had a molecular weight of 5,000. The copolymer was composed of acrylic acid and maleic acid (3: 1) and had a molecular weight of approximately 70,000. Both polymer salts were used in the form of the Na salts. The Na citrate was present as a dihydrate. The NaA type zeolite had a water content of 20%. The Na salt of 4,4'-bis (2-anilino-4-morpholino-l, 3,5-triazin-6-yl-amino) -stilbene-2,2'-disulfonic acid was used as the optical brightener . The soap consisted of a sodium tallow soap. The silica designated SiO 2 consisted of diatomaceous earth. The enzyme consisted of a protease-amylase mixture " (3: 2). The content of unbound water was less than 0.5% by weight. The contents given in the table mean percentages by weight. In the case of component (B ) the acid content is given in brackets.
Beispielexample
Komponente Bestandteil 1 2 3 4Component Component 1 2 3 4
A ABS 5,0 6,0 3,0 5,0A ABS 5.0 6.0 3.0 5.0
B 0A 6 3,9 3,9 3,7 4,0B 0A 6 3.9 3.9 3.7 4.0
OA 422 25,3 25,6 27,3 -OA 422 25.3 25.6 27.3 -
CO 16 . . . 25,0CO 16. . . 25.0
C Zeolith 57,0 55,9 37,3 51,1C zeolite 57.0 55.9 37.3 51.1
D Polyacrylat 6,1 6,2 - -D polyacrylate 6.1 6.2 - -
(Säure) (5,2) (5,3)(Acid) (5.2) (5.3)
Citrat - - 18,6 -Citrate - - 18.6 -
(Säure) (12,1)(Acid) (12.1)
Copolymer - - - 5,0Copolymer - - - 5.0
(Säure) (4,4)(Acid) (4.4)
E Na-Silikat - - 5,0 -E Na silicate - - 5.0 -
Soda - - - 5,0Soda - - - 5.0
F Seife - - - 2,0F soap - - - 2.0
Siθ2 - - 2,0 -Siθ2 - - 2.0 -
opt. Aufheller 1,0 0,8 1,0 1,0opt. Brightener 1.0 0.8 1.0 1.0
Enzym 1.3 1,2 1,7 1,5Enzyme 1.3 1.2 1.7 1.5
Parfüm 0,4 0,4 0,4 0,4
Die mit einem Rotations-Viskosimeter bei 20 °C bestimmte Viskosi¬ tät betrug:Perfume 0.4 0.4 0.4 0.4 The viscosity determined using a rotary viscometer at 20 ° C. was:
Beispiel 1: 42000 mPa-s Beispiel 2: 49000 mPa-s Beispiel 3: 29000 mPa-s Beispiel 4: 32000 mPa-sExample 1: 42000 mPa-s Example 2: 49000 mPa-s Example 3: 29000 mPa-s Example 4: 32000 mPa-s
Die Mittel erwiesen sich als lagerstabil, d.h. innerhalb einer Standzeit von 6 Wochen trat keine erkennbare Sedimentierung auf. Die unter standardisierten Bedingungen bestimmte Lösungsgeschwin¬ digkeit bei 4,5 °C und 21 °C war ausgezeichnet. Von jeweils 10 g Paste, eingerührt in 1 Liter Wasser, waren nach 2 Minuten bzw. 5 Minuten folgende prozentuale Anteile gelöst:The agents proved to be stable in storage, i.e. no recognizable sedimentation occurred within a period of 6 weeks. The solution speed at 4.5 ° C and 21 ° C determined under standardized conditions was excellent. The following percentages of 10 g paste, stirred into 1 liter water, were dissolved after 2 minutes and 5 minutes:
4,5 °C 21 °C 2 Min. 5 Min. 2 Min.4.5 ° C 21 ° C 2 min. 5 min. 2 min.
Beispiel 1 95,9 100 % 100 % Beispiel 2 94,8 100 % 100 %
Example 1 95.9 100% 100% Example 2 94.8 100% 100%
Claims
1. Pastöses, phosphatfreies, im wesentlichen wasserfreies Wasch¬ mittelkonzentrat, gekennzeichnet durch einen Gehalt an1. Pasty, phosphate-free, essentially water-free detergent concentrate, characterized by a content of
A) 2 bis 7 Gew.-% an Natrium-Alkylbenzolsulfonat mit linearen Cg-i3-Alkylketten,A) 2 to 7% by weight of sodium alkylbenzenesulfonate with linear Cg-i3 alkyl chains,
B) 20 bis 40 Gew.-% an nichtionischen Tensiden mit linearen, 10 bis 18 C-Atome aufweisenden Alkyl- oder Alkenylgruppen,B) 20 to 40% by weight of nonionic surfactants with linear alkyl or alkenyl groups having 10 to 18 carbon atoms,
C) 35 bis 65 Gew.-% an synthetischem, feinkristalline , was¬ serhaltigem Zeolith vom Typ NaA,C) 35 to 65% by weight of synthetic, finely crystalline, water-containing zeolite of the NaA type,
D) 3 bis 15 Gew.-% mindestens eines organischen Polycarboxy- latBuilders (bezogen auf freie Säure),D) 3 to 15% by weight of at least one organic polycarboxylate builder (based on free acid),
E) 0 bis 20 Gew.-% an Waschalkalien aus der Klasse Natriumcarbonat und Natriumsilikat,E) 0 to 20% by weight of washing alkalis from the class sodium carbonate and sodium silicate,
F) 0 bis 5 Gew.-% eines Suspensionsstabilisators,F) 0 to 5% by weight of a suspension stabilizer,
G) sowie sonstigen üblichen Waschmittelbestandteilen mit der Maßgabe, daß die Summe der Bestandteile (C) und (D) 70 Gew.-% nicht übersteigt.G) and other usual detergent ingredients with the proviso that the sum of the ingredients (C) and (D) does not exceed 70% by weight.
2. Mittel nach Anspruch 1, gekennzeichnet durch einen Gehalt an 3 bis 6 Gew.-% der Komponente A.2. Composition according to claim 1, characterized by a content of 3 to 6 wt .-% of component A.
3. Mittel nach einem oder mehreren der Ansprüche 1 und 2, ge¬ kennzeichnet durch einen Gehalt von 25 bis 35 Gew.-% der Kom¬ ponente B, die einen Stockpunkt von unter 10 °C, vorzugsweise unter 5 °C, aufweist.3. Composition according to one or more of claims 1 and 2, characterized by a content of 25 to 35% by weight of component B, which has a pour point of below 10 ° C, preferably below 5 ° C.
4. Mittel nach einem oder mehreren der Ansprüche 1 bis 3, ge¬ kennzeichnet durch einen Gehalt an 37 bis 60 Gew.-% der Kom¬ ponente C. 4. Composition according to one or more of claims 1 to 3, characterized by a content of 37 to 60% by weight of component C.
5. Mittel nach einem oder mehreren der Ansprüche 1 bis 4, ge¬ kennzeichnet durch einen Gehalt an 3 bis 10 Gew.-% bezogen auf Säure, an homopoly erer und copolymerer Acrylsäure.5. Composition according to one or more of claims 1 to 4, characterized by a content of 3 to 10% by weight, based on acid, of homopolymeric and copolymeric acrylic acid.
6. Verfahren zur Herstellung der Mittel nach einem oder mehreren der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß man die Mischung der Bestandteile auf eine Korngröße der Feststoffe unter 50 μm zerkleinert. 6. A process for the preparation of the agent according to one or more of claims 1 to 5, characterized in that the mixture of the constituents is comminuted to a grain size of the solids below 50 microns.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DEP3914504.2 | 1989-05-02 | ||
DE19893914504 DE3914504A1 (en) | 1989-05-02 | 1989-05-02 | PASTOESES, PHOSPHATE-FREE, IN ESSENTIAL WATER-FREE DETERGENT |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1990013623A1 true WO1990013623A1 (en) | 1990-11-15 |
Family
ID=6379940
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP1990/000648 WO1990013623A1 (en) | 1989-05-02 | 1990-04-23 | Detergent paste substantially free of water and containing no phosphate |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0395976A1 (en) |
DE (1) | DE3914504A1 (en) |
PT (1) | PT93931A (en) |
WO (1) | WO1990013623A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1993023521A1 (en) * | 1992-05-19 | 1993-11-25 | Henkel Kommanditgesellschaft Auf Aktien | Process for producing pasty washing agents |
US5456850A (en) * | 1988-12-14 | 1995-10-10 | Henkel Kommanditgesellschaft Auf Aktien | Fluid to pasty washing agent containing bleach |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB9025624D0 (en) * | 1990-11-26 | 1991-01-09 | S B Chemicals Limited | Liquid built detergent concentrates |
DE4109247A1 (en) * | 1991-03-21 | 1992-09-24 | Henkel Kgaa | LIQUID OR PASTE-DETECTED DETERGENT |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2283222A1 (en) * | 1974-08-29 | 1976-03-26 | Henkel & Cie Gmbh | LIQUID PASTE CONCENTRATES FOR WASHING AND CLEANING PRODUCTS |
FR2283951A1 (en) * | 1974-09-06 | 1976-04-02 | Colgate Palmolive Co | Detergent and cleasing paste - esp for automatic clothes- or dish-washing contg zeolite molecular sieve, surfactant and water |
GB2176799A (en) * | 1985-06-21 | 1987-01-07 | Unilever Plc | Detergent composition in paste form |
EP0234867A2 (en) * | 1986-02-20 | 1987-09-02 | The Clorox Company | Concentrated non-phosphate detergent paste compositions |
EP0295525A2 (en) * | 1987-06-15 | 1988-12-21 | Henkel Kommanditgesellschaft auf Aktien | Mechanical washing process |
-
1989
- 1989-05-02 DE DE19893914504 patent/DE3914504A1/en not_active Withdrawn
-
1990
- 1990-04-23 WO PCT/EP1990/000648 patent/WO1990013623A1/en unknown
- 1990-04-23 EP EP90107660A patent/EP0395976A1/en not_active Withdrawn
- 1990-04-30 PT PT9393190A patent/PT93931A/en not_active Application Discontinuation
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2283222A1 (en) * | 1974-08-29 | 1976-03-26 | Henkel & Cie Gmbh | LIQUID PASTE CONCENTRATES FOR WASHING AND CLEANING PRODUCTS |
FR2283951A1 (en) * | 1974-09-06 | 1976-04-02 | Colgate Palmolive Co | Detergent and cleasing paste - esp for automatic clothes- or dish-washing contg zeolite molecular sieve, surfactant and water |
GB2176799A (en) * | 1985-06-21 | 1987-01-07 | Unilever Plc | Detergent composition in paste form |
EP0234867A2 (en) * | 1986-02-20 | 1987-09-02 | The Clorox Company | Concentrated non-phosphate detergent paste compositions |
EP0295525A2 (en) * | 1987-06-15 | 1988-12-21 | Henkel Kommanditgesellschaft auf Aktien | Mechanical washing process |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5456850A (en) * | 1988-12-14 | 1995-10-10 | Henkel Kommanditgesellschaft Auf Aktien | Fluid to pasty washing agent containing bleach |
WO1993023521A1 (en) * | 1992-05-19 | 1993-11-25 | Henkel Kommanditgesellschaft Auf Aktien | Process for producing pasty washing agents |
US5518645A (en) * | 1992-05-19 | 1996-05-21 | Henkel Kommanditgesellschaft Auf Aktien | Process for the production of paste-form detergents |
Also Published As
Publication number | Publication date |
---|---|
EP0395976A1 (en) | 1990-11-07 |
PT93931A (en) | 1991-01-08 |
DE3914504A1 (en) | 1990-11-08 |
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