EP2007863B1 - Granulés d'un produit lavant ou nettoyant sensible - Google Patents
Granulés d'un produit lavant ou nettoyant sensible Download PDFInfo
- Publication number
- EP2007863B1 EP2007863B1 EP07728143A EP07728143A EP2007863B1 EP 2007863 B1 EP2007863 B1 EP 2007863B1 EP 07728143 A EP07728143 A EP 07728143A EP 07728143 A EP07728143 A EP 07728143A EP 2007863 B1 EP2007863 B1 EP 2007863B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- granules
- weight
- washing
- enzyme
- cleaning agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Not-in-force
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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
- C11D3/50—Perfumes
- C11D3/502—Protected perfumes
- C11D3/505—Protected perfumes encapsulated or adsorbed on a carrier, e.g. zeolite or clay
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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
- C11D17/0034—Fixed on a solid conventional detergent ingredient
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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
- C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
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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
- C11D3/38—Products with no well-defined composition, e.g. natural products
- C11D3/386—Preparations containing enzymes, e.g. protease or amylase
- C11D3/38672—Granulated or coated enzymes
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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
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3902—Organic or inorganic per-compounds combined with specific additives
- C11D3/3905—Bleach activators or bleach catalysts
- C11D3/3935—Bleach activators or bleach catalysts granulated, coated or protected
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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
- C11D3/40—Dyes ; Pigments
- C11D3/42—Brightening agents ; Blueing agents
Definitions
- the present application relates to granules of sensitive detergent or cleaning agent ingredients, to processes for producing such granules, to corresponding detergents and cleaners and to the use of suitable components for producing such granules.
- a fundamental alternative to this is the preparation of enzymes in liquid form, which are usually incorporated in over-flowing liquid or gel detergents and cleaners.
- these ingredients are not physically protected against the negative effects of other ingredients of the detergents and cleaners in question.
- This disadvantage can be compensated for some ingredients by adding chemical agents; For example, by adding inhibitors, proteases are prevented from hydrolyzing other enzyme molecules.
- the negative effects of alternating freezing and thawing can be compensated for example by the addition of polyols.
- other ingredients, particularly bleaching agents are difficult to prevent from adversely affecting sensitive ingredients during storage.
- the enzymes are added to liquid agents in solid form by WO 99/00471 A1 and WO 99/00478 A1 disclosed.
- the enzymes are formulated into so-called prills, which are also customary for use in solid compositions, that is to say without protection beyond this solid form.
- both are anhydrous.
- the first of these applications teaches the teaching of matching these solid particles with respect to their density to that of the medium, that is below 1.7 g / ml, in order to ensure a sufficient stability of the particles during storage.
- the second of these applications teaches in this context the doctrine to increase the cleaning performance of the enzymes contained by adding the compound ethylenediamine-N, N'-disuccinic acid (EDDS) or salts thereof.
- EDDS ethylenediamine-N, N'-disuccinic acid
- WO 00/29534 A1 discloses the preparation of granules in which various layers are applied to an inert core or support. This may also include an enzyme layer, which is obligatorily covered to the outside by one or more protective layers.
- protective layers for the enzyme herein are disclosed the materials titanium dioxide, methyl cellulose (Methocel A15), polyethylene glycol (PEG 600), polyvinyl alcohol (Elvanol 51-05) and a specific nonionic surfactant (Neodol 23-6.5). According to the description, these granules have high stability values and low dust levels.
- the applicability in liquid, and anhydrous or mainly anhydrous means is claimed, but not proven. A possible use for predominantly aqueous agents is not considered at all.
- PEG-containing coatings for enzyme-containing granules for this application go out WO 96/38527 A1 and WO 97/39116 A1 out.
- the PEG-containing layer may in each case also contain titanium dioxide.
- a fundamental one For example, interchangeability of PEG and PVA for these purposes is disclosed WO 00/63336 A1 ,
- a liquid applied coating system for sensitive ingredients that can also enter into aqueous media also reveals EP 1586241 A1 , It consists of 60-95% by weight of wax, 3-25% by weight of fatty acid, 0-20% by weight of additives and content of alkali metal ions sufficient to be at least 70% of the total amount of free To neutralize carboxyl groups of the fatty acid. That is, it is a wax / soap / fatty acid mixture.
- the registration EP 356239 A2 discloses a system according to which enzymes are uniformly distributed or coated in a protective special polymer material (matrix) (polymeric shell). These are physically stable when stored in a low-water, liquid detergent or cleaning agent, which ensures the integrity of the enzymes, and they disintegrate only at the moment of dilution with water at the beginning of the washing process. Basically the same solution is revealed WO 92/20771 A1 for liquid detergent formulations with a water content of up to 60 wt .-%.
- the registrations WO 2005/028603 A1 and WO 2005/028604 A1 disclose liquid detergents and cleaners having a water content of up to 70% by weight in which contained enzymes are stabilized by being encapsulated in a gel. This is each formed by using special silanes. Even in these cases, it comes during storage to protect the encapsulated ingredients and only on dilution in the aqueous wash to release them.
- the registration US 2005/0245418 A1 describes the encapsulation of enzymes in a water-soluble gel for use in aqueous detergents and cleaners.
- EP 653485 A1 It turns out to dissolve or suspend sensitive ingredients such as enzymes in an oil and to trap these oil drops in polymer capsules. These capsules are designed so that they can be added to a liquid medium, for example a detergent with up to 35 wt .-% water and only then burst open and release their contents, if in the wash liquor further dilution takes place.
- a liquid medium for example a detergent with up to 35 wt .-% water
- Another compartmentalization method is used WO 03/106607 A1 out.
- enzymes or enzyme crystals in the aqueous phase can be stably maintained by surfactants in a hydrophobic silicone environment, with the silicone phase in turn being stabilized via surfactants in a hydrophilic outer phase.
- granules are to be understood as a solid form of preparation in which a plurality of ingredients - in this case components (a), (b), (c) and optionally (d) - are not in the form of a powder but in Form of discrete particles or granules (granules, granules) are provided. In sum, these are referred to as granules.
- Granules generally have no harmonious geometric shape; their surface can be rather smooth, uneven or even jagged. The mass is in many cases more or less porous.
- the sensitive detergent or cleaning agent ingredient is processed together with components (b) and (c) into a largely uniform granulate.
- a particulate carrier material (b) is a solid, room-temperature, pulverulent or particulate material prior to incorporation in granules according to the application, which is chemically inert to such an extent that it is below the production, processing and Storage conditions of the granules reacts with any other of the ingredients of the granules or agent in an affecting the overall efficiency of the granules extent. Due to its structure, it is capable of physically binding liquids or gelatinous or pasty substances to its surface to a certain extent, so that it can also be referred to as an adsorbent in connection with the present invention.
- these are: talc, silicic acid, metal oxides, in particular aluminum oxides, silicates, in particular phyllosilicates, sodium aluminum silicates, bentonites and / or aluminosilicates (zeolites) and / or titanium dioxide.
- organic compounds such as polyvinyl alcohol (PVA) in particular at least partially hydrolyzed PVA. It is particularly advantageous if these compounds fulfill an additional benefit, for example a builder function when using the washing or cleaning agent.
- PEG has not been found to be particularly advantageous so that it is at least not included in the present invention as a characterizing feature of a preferred embodiment of the adsorbent, and most preferably is not included as part of the adsorbent.
- a binder (c) is a solid, pasty (waxy) or liquid material which is chemically inert to such an extent that it can not be mixed with any other of the conditions of manufacture, processing and storage of the granules Ingredients of the granules or agent in an affecting the overall effectiveness of the granules extent reacts. It is one of (b) different stuff. It is or becomes at least so viscous under the conditions of granule production that it virtually glues the other ingredients together. In this case, in particular, the physicochemical interaction with the adsorbent of importance, which causes the resulting mass to a total homogeneous phase, which is then convertible into individual granules.
- the other ingredients and in particular the ingredient to be formulated are included.
- the interaction between the two components (b) and (c) is responsible for the physical stability of the granule particles.
- Suitable binders are inorganic or organic substances which have the properties described, for example non-cross-linked, polymeric compounds selected from the group: polyacrylates, polymethacrylates, methacrylic acid-ethyl acrylate copolymers, polyvinylpyrrolidones, substituted polysaccharides, especially cellulose ethers, polyvinyl alcohols (PVA), preferably partially hydrolyzed polyvinyl alcohols and / or ethoxylated polyvinyl alcohols and their copolymers and mixtures.
- PVA polyvinyl alcohols
- Polyethylene glycol has not been found to be particularly advantageous in this regard, so that it is not a preferred embodiment of the binder and most preferably is not included as part of the binder.
- Some compounds such as PVA are suitable both as component (b) and as component (c) due to their adsorption properties and their co-existing binding effect. They can be used according to the invention as (c) if they have not already been presented as (b).
- optionally further ingredients (d) are in principle to be understood as meaning all compounds which are chemically inert to such an extent that they are not subject to any of the ingredients of the granules or composition in any of the conditions of preparation, processing and storage of the granules react to the overall effectiveness of the granules impairing extent.
- plasticizers are compounds or mixtures that can be added to improve the manufacturing process of the granules.
- water-dispersible organic compounds Preferably, they are selected from the following group: water-dispersible organic compounds, water-dispersible organic polymers, polyethylene glycols (PEG), in particular short-chain PEG, fatty acids or salts of fatty acids, triacetin and / or triethyl citrate or polyfunctional alcohols such as 1,2-propanediol or glycerol.
- PEG polyethylene glycols
- fatty acids or salts of fatty acids triacetin and / or triethyl citrate or polyfunctional alcohols such as 1,2-propanediol or glycerol.
- solubility improvers also called swelling agents, disintegration aids or disintegrants.
- swelling agents also called disintegration aids or disintegrants.
- disintegration aids compounds or mixtures that can be added to improve the solubility of the granules the moment they are According to the invention actually disintegrate, namely at the moment of application of the agent concerned.
- For washing and cleaning agents are generally used in dilute form, that is added to an aqueous wash liquor. In this moment of strong dilution with water, water diffuses into the granules, which then burst open and release their ingredient, so that it can take effect.
- solubility enhancers this disintegration process can be improved.
- a temporal regulation such as in the form that the granulated ingredient is only slightly later than one or more other ingredients of the agent in solution.
- a temporal regulation such as in the form that the granulated ingredient is only slightly later than one or more other ingredients of the agent in solution.
- the solubility improvers make up a weight fraction of 0-50% by weight (based on the granules).
- they are selected from the group consisting of water-soluble inorganic salts, monosaccharides, preferably glucose, oligosaccharides, and swelling agents, especially compounds suitable as disintegrants, in particular cellulose, compacted cellulose, cellulose derivatives and / or crosslinked organic polymers, preferably crosslinked polyvinylpyrrolidones or crosslinked polyacrylates.
- optional ingredients include, for example, water, enzyme stabilizers, dyes, color pigments, pH buffer substances, antioxidants, density regulating compounds and / or other ingredients. Preferably they account for a weight fraction of 0-40 wt .-% (based on the granules).
- ingredients may also be, for example, resulting from the enzyme production and not completely separated fermentation media components. Their presence is especially then advantageous if they exert a stabilizing influence on the enzyme. If the ingredient is a more complicated chemical compound, such as a perfume, it may also be associated with other intermediates or stereoisomers resulting from the synthesis and not completely separated.
- ingredients may be compounds which exert an additional effect in the context of the later intended use for the granulate in a washing or cleaning agent and which may thus also be referred to as a "benefit agent".
- water is generally supplied merely as an ancillary substance, for example via the aqueous enzyme preparation.
- a certain amount of water can give the pulp to be processed a favorable consistency.
- a certain equilibrium content of water is established which, however, does not impair the overall integrity of the particles.
- the proportion of water increases so suddenly that the particles completely disintegrate.
- An ingredient also included in (d) is thus water.
- the water content of the granules is regulated in particular by the manner of their preparation. For example, in fluidized-bed spray granulation, an aqueous mixture of ingredients removes a substantial portion of the water by evaporation.
- an incorporated liquid enzyme preparation is controlled.
- Enzyme stabilizers are contained in enzyme-containing granules as preferred further ingredients in particular. They serve especially during storage as protection against damage such as inactivation, denaturation or decay, for example by physical influences, oxidation or proteolytic cleavage.
- proteolysis is particularly preferred, especially if the agents also contain proteases.
- Preferred granules of the invention or agents, see below) contain stabilizers for this purpose.
- One group of stabilizers are reversible protease inhibitors.
- Benzamidine hydrochloride, borax, boric acids, boronic acids or their salts or esters are frequently used for this purpose, including, in particular, derivatives with aromatic groups, for example ortho, meta or para-substituted phenylboronic acids, in particular 4-formylphenylboronic acid, or the salts or Esters of the compounds mentioned.
- peptide aldehydes that is oligopeptides with a reduced C-terminus, especially those of 2 to 50 monomers are used for this purpose.
- the peptidic reversible protease inhibitors include ovomucoid and leupeptin.
- specific, reversible peptide inhibitors for the protease subtilisin and fusion proteins from proteases and specific peptide inhibitors are suitable.
- enzyme stabilizers are amino alcohols such as mono-, di-, triethanol- and -propanolamine and mixtures thereof, aliphatic carboxylic acids up to C 12 , such as succinic acid, other dicarboxylic acids or salts of said acids. End-capped fatty acid amide alkoxylates are also suitable for this purpose. Some organic acids used as builders can additionally stabilize an enzyme.
- Lower aliphatic alcohols but especially polyols, such as glycerol, ethylene glycol, propylene glycol, sorbitol or di-glycerol phosphate are other frequently used enzyme stabilizers against physical influences.
- polyols such as glycerol, ethylene glycol, propylene glycol, sorbitol or di-glycerol phosphate are other frequently used enzyme stabilizers against physical influences.
- calcium and / or magnesium salts are used, such as calcium acetate or calcium formate.
- Polyamide oligomers or polymeric compounds such as lignin, water-soluble vinyl copolymers or cellulose ethers, acrylic polymers and / or polyamides stabilize the enzyme preparation, inter alia, against physical influences or pH fluctuations.
- Polyamine N-oxide-containing polymers act simultaneously as Enzyme stabilizers and as color transfer inhibitors.
- Other polymeric stabilizers are linear C 8 -C 18 polyoxyalkylenes.
- alkylpolyglycosides can stabilize the enzymatic components of the agent according to the invention and, preferably, are capable of additionally increasing their performance.
- Crosslinked N-containing compounds preferably perform a dual function as soil release agents and as enzyme stabilizers. Hydrophobic, nonionic polymer stabilizes in particular an optionally contained cellulase.
- Reducing agents and antioxidants increase the stability of the enzymes to oxidative degradation;
- sulfur-containing reducing agents are familiar, for example sodium sulfite and reducing sugars.
- peptide-aldehyde stabilizers for example of polyols, boric acid and / or borax, the combination of boric acid or borate with reducing salts and succinic acid or other dicarboxylic acids or the combination of boric acid or borate with polyols or polyamino compounds and with reducing salts.
- the effect of peptide-aldehyde stabilizers is favorably enhanced by the combination with boric acid and / or boric acid derivatives and polyols, and still further by the additional action of divalent cations, such as calcium ions.
- Dyes may be added to improve the aesthetic appearance of the granule particles or to draw on the laundry during use of the detergent or cleaner. They are advantageously incorporated so that they are evenly distributed throughout the particle. They are known per se in the prior art.
- Color pigments can also serve to enhance the aesthetic appearance of the granule particles. They can also be distributed uniformly in the particle. In this case, however, in particular the aspect is in the foreground to cover the particle surface with color pigments in order to cover the intrinsic color of the granules. This too is known per se in the prior art.
- a commonly used white pigment is titanium dioxide.
- pH buffer substances can be incorporated to protect the respective ingredients during storage against pH influences such as from the surrounding medium. However, they can also be incorporated in order to emerge from the particle into the wash liquor at the same time as the ingredient is being used, and then to influence the pH of the wash medium. In this way, a pH shift can be triggered, for example, to improve its effectiveness at the same time as the release of an enzyme with a certain pH activity profile.
- antioxidants can be incorporated to provide protection against atmospheric oxygen or other oxidizing compounds during storage.
- density-regulating compounds in granules is known per se.
- the density can be reduced or the density can be increased by adding clay or silicate crystals.
- This is advantageous for matching the bulk density of the particles to the bulk density of solid detergents and cleaners in order to prevent segregation processes during transport or storage.
- an adjustment to the density of the agent concerned can be achieved in the same way so that the granules are homogeneously distributed macroscopically homogeneously in the agent in question and ideally neither sediment nor float on the surface.
- disintegration is to be understood as meaning the disintegration of the granules that is to be observed macroscopically.
- a slight, which does not significantly affect the activity of the granulated ingredients, possibly swelling of the granules in a strongly water-containing environment is not meant hereby and can certainly be observed with granules according to the invention.
- a slight abrasion occurs, which is optionally observed in a liquid or gel preparation containing the particles of the invention as a suspended matter and / or leads to a slight turbidity.
- storage means storage of the respective mixture at a constant 23 ° C. for at least 24 h and increasingly preferably for at least 30 h, 36 h, 42 h, 48 h, 3 days, 4 days, 5 days, 6 days and most preferably for at least 7 days to understand. It takes place in an outwardly hermetically sealed, not evacuated vessel, wherein the volume of the air phase does not exceed that of the measuring liquid.
- the reference system is an aqueous buffer system consisting of 16% sodium sulfate and 3% sodium citrate, pH 5.0 ⁇ 0.1.
- the liquid containing the granules is subjected to a sieve test. It is quantitatively given without applying a pressure or vacuum through a sieve having a smaller mesh size than the granules, so that the granules are retained by the sieve.
- the mesh size of the screen may be 280 ⁇ m.
- the sieve is washed with an equal sodium sulfate / sodium citrate solution and finally with dist. Rinsed with water. A performance of this detection is described in Example 11, which was additionally shaken during incubation at low speed, which is not absolutely necessary according to the invention.
- a non-disintegration according to the invention is then considered when more than 50% by weight of the initially weighed-in particle mass (before stirring into the solution) remains on the sieve after the sieve residue has dried. More preferably, more than 60, 70, 80, 90 and most preferably more than 95% of the originally weighed particulate mass remains on the screen.
- the disintegration index for the particles in question is defined as the quotient of the particle mass (residue) remaining on the sieve and the originally weighed particle mass and is given as weight% residue, the residue being determined after the particles have been incubated at 23 ° C.
- aqueous Buffer system consisting of 16% sodium sulfate and 3% sodium citrate in water, pH 5.0 ⁇ 0.1 were stored for a defined period of time. The period is at least 24 hours, and more preferably at least 30 hours, 36 hours, 42 hours, 48 hours, 3 days, 4 days, 5 days, 6 days, and most preferably at least 7 days.
- the numerical value of the disintegration index is therefore the higher, the fewer particles are disintegrated during the storage period and are not retained on the sieve.
- a non-disintegration according to the invention is present when the disintegration index is at least 50%. Increasingly, the disintegration index is 60, 70, 80, 90, and most preferably more than 95%.
- the solution according to the invention can be applied to all ingredients specified above in connection with the present invention. Because they are all fundamentally equally endangered, especially against oxidation, and are protected according to the invention in principle in the same way.
- the extent of disintegration can not be related to the substantial retention of the mass of the particles, but to the maintenance of the enzyme activity.
- the enzyme activity can be determined depending on the processed enzyme according to known methods. Thus, it has been shown experimentally that in the granules described in the examples not only the majority of the initially weighed particle mass (before stirring into the solution) remained on the sieve, but also a large part of the enzymatic activity. This is more than 50%, and more preferably more than 60, 70, 80, 90, and most preferably more than 95%. In contrast, granules of the prior art, which had a structurally different structure, showed significantly worse values.
- the components (b) and (c) are present in a weight% ratio of (b) to (c) of from 1: 5 to 20: 1, more preferably from 1: 5 to 5: 1.
- Concrete mixing ratios are to be optimized experimentally in a particular case that on the one hand not too large excess of adsorbent remains, which makes the mass to be brittle, and on the other hand no excessive excess of binder remains, which could lead to the resulting mass to sticky and difficult to process. It should be considered that also the other components exert an influence on the nature of the material and the granule particles according to their respective properties.
- a substance that can be used for several of these components can only be counted once, so that in each case a granulate according to the invention is always at least a mixture of components (a) with (b) and a different component (c). is.
- the essence of the invention is to obtain granules with favorable properties in such a way that adsorbents and binders are matched to one another in a complementary manner.
- an optimum of the respective proportions must be determined experimentally.
- Example 2 of the present application are granules with about 5 wt .-% of component (a) (enzyme), 31 wt .-% of component (b), 22 wt .-% of component (c) and below (d ) a proportion of 24 wt .-% plasticizer, 8 wt .-% Lösigesverêter and about 10 wt .-% water.
- a part of the particulate carrier material, namely the TiO 2 which in itself accounts for 8% by weight of the total mass of the granules, also serves as a color pigment in the formulation specified therein.
- Example 3 discloses granules with only about 5 wt .-% of component (a) (enzyme), 78 wt .-% of different Components (b), 7 wt .-% of component (c) and a water content (d) of about 10 wt .-%.
- proportions of adsorbent (b) above 50% by weight, preferably above 60% by weight and especially above 70% by weight, are particularly advantageous if the optional further ingredients are used (D) is largely dispensed with, that is, together they make up less than 40 wt .-%, preferably less than 30 wt .-% and more preferably less than 20 wt .-% of the granules.
- Preferred embodiments of the present invention form such described granules according to the invention, wherein the sensitive detergent or cleaning agent ingredient (a) is a perfume, an optical brightener, a bleach activator or an enzyme, preferably an enzyme, more preferably an oxidation-stabilized enzyme is.
- the sensitive detergent or cleaning agent ingredient (a) is a perfume, an optical brightener, a bleach activator or an enzyme, preferably an enzyme, more preferably an oxidation-stabilized enzyme is.
- Fragrances are added to laundry detergents or cleaners to improve the aesthetics of the products and provide consumers with a visually and sensory "typical and unmistakable" product in addition to washing or cleaning performance.
- a fragrance In order to be perceptible, a fragrance must be volatile, whereby besides the nature of the functional groups and the structure of the chemical compound, the molecular weight also plays an important role. For example, most odorants have molecular weights up to about 200 daltons, while molecular weights of 300 daltons and above are more of an exception. Due to the different volatility of fragrances, the odor of a perfume or fragrance composed of several fragrances changes during evaporation, whereby the odor impressions in "top note”, “heart or middle note” (middle note or body) and “base note” (end note or dry out) divided.
- the top note of a perfume or fragrance is not only from volatile compounds, while the base note for the most part consists of less volatile, that is adherent fragrances.
- the base note for the most part consists of less volatile, that is adherent fragrances.
- more volatile fragrances can be bound to certain fixatives, preventing them from evaporating too quickly.
- the subsequent classification of the fragrances in "more volatile” or “adherent” fragrances so nothing is said about the olfactory impression and whether the corresponding fragrance is perceived as the head or middle note.
- fragrances individual fragrance compounds, for example, the synthetic products of the ester type, ethers, aldehydes, ketones, alcohols and hydrocarbons can be used.
- Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethylmethylphenyl glycinate, allylcyclohexyl propionate, styrallyl propionate and benzyl salicylate.
- the ethers include, for example, benzyl ethyl ether, to the aldehydes, for example, the linear alkanals having 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones for example the ionone, ⁇ -isomethylionone and methyl cedryl ketone , the alcohols include anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons mainly include the terpenes such as limonene and pinene.
- fragrances are used, which together produce an attractive fragrance.
- perfumes may also contain natural fragrance mixtures such as those available from vegetable sources, for example, pine, citrus, jasmine, patchouly, rose or ylang-ylang oil.
- the content of detergents or cleaners of fragrances is up to 2% by weight of the total formulation. In the design of granules according to the invention, suitable for the use in detergents and cleaners are provided, this must be considered accordingly.
- Alternative embodiments of the present invention are granules of optical brighteners. This class of ingredients, especially for textile detergents, leads to a perceived positive impression of the cleaned laundry.
- Preferred embodiments of this aspect of the invention are derivatives of diaminostilbenedisulfonic acid or its alkali metal salts.
- Suitable salts are, for example, salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulphonic acid or compounds of similar construction which, instead of the morpholino Group carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group.
- brighteners of the substituted diphenylstyrene type may be present, for example, the alkali salts of 4,4'-bis (2-sulfostyryl) -diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) -diphenyl, or 4 - (4-chlorostyryl) -4 '- (2-sulfostyryl).
- Mixtures of the aforementioned brightener can be used.
- Particularly suitable are mixtures of optical brighteners of a distyryl-biphenyl derivative and a stilbentriazine derivative. These brightener types can be used in any desired mixing ratios.
- Such brighteners are available, for example, under the trade name Tinopal from Ciba.
- detergents may also contain bleach activators. Due to their reactivity, it is within the scope of the present invention to formulate these ingredients in the form of granules according to the invention.
- bleach activators it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid.
- Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups.
- polyacylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular 1,3,4,6 Tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), acylated hydroxycarboxylic acids, such as triethyl-O-acetylcitrate (TEOC), Carboxylic anhydrides, in particular phthalic anhydride, isatoic anhydride and / or succinic an
- Hydrophilic substituted acyl acetals and acyl lactams are also preferably used. Combinations of conventional bleach activators can also be used. Likewise, nitrile derivatives such as cyanopyridines, nitrile quats, for example N-alkylammonium acetonitriles, and / or cyanamide derivatives can be used.
- Preferred bleach activators are sodium 4- (octanoyloxy) benzenesulfonate, n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), undecenoyloxybenzenesulfonate (UDOBS), sodium dodecanoyloxybenzenesulfonate (DOBS), decanoyloxybenzoic acid (DOBA, OBC 10) and / or dodecanoyloxybenzenesulfonate ( OBS 12), as well as N-methylmorpholinum acetonitrile (MMA).
- n-nonanoyl or isononanoyloxybenzenesulfonate n- or isononanoyloxybenzenesulfonate
- UOBS undecenoyloxybenzenesulfonate
- DOBS dodecanoyloxybenzenesulfonate
- Further bleach activators preferably used in the context of the present application are compounds from the group of cationic nitriles, in particular cationic nitriles of the formula in the R 1 is -H, -CH 3 , a C 2-24 alkyl or alkenyl radical, a substituted C 2-24 alkyl or alkenyl radical having at least one substituent from the group -Cl, -Br, - OH, -NH 2 , -CN, an alkyl or alkenylaryl radical having a C 1-24 -alkyl group, or represents a substituted alkyl or alkenylaryl radical having a C 1-24 -alkyl group and at least one further substituent on the aromatic ring, R 2 and R 3 are independently selected from -CH 2 -CN, -CH 3 , -CH 2 -CH 3 , -CH 2 -CH 2 -CH 3 , -CH (CH 3 ) -CH 3 , -CH 2 -
- Bleach activators can in the usual amount range from 0.01 to 20 wt .-%, preferably in amounts of 0.1 to 15 wt .-%, in particular 1 wt .-% to 10 wt .-%, based on the total washing or Detergent composition, be included. In the design of granules according to the invention, which are intended for use in detergents and cleaners, this must be taken into account accordingly.
- Preferred embodiments of the present invention are granules of enzymes.
- This inherently established class of ingredients leads to a corresponding improvement in the cleaning performance of the agents concerned.
- These enzymes are basically of natural origin; Starting from the natural molecules, improved variants are available for use in detergents or cleaning agents, which are preferably used accordingly.
- Agents provided with granules according to the invention preferably contain enzymes in total amounts of 1 ⁇ 10 -8 to 5 percent by weight, based on active protein. In the design of granules according to the invention, which are intended for use in detergents and cleaners, this must be taken into account accordingly.
- the protein concentration can be determined by known methods, for example the BCA method (bicinchoninic acid, 2,2'-biquinolyl-4,4'-dicarboxylic acid) or the biuret method ( Gornall AG, CS Bardawill and MM David, J. Biol. Chem., 177 (1948), pp. 751-766 ).
- BCA method bicinchoninic acid, 2,2'-biquinolyl-4,4'-dicarboxylic acid
- the biuret method Gornall AG, CS Bardawill and MM David, J. Biol. Chem., 177 (1948), pp. 751-766 .
- component (a) comprises one or more hydrolytic enzymes and / or oxidoreductases, more preferably ⁇ -amylases, proteases, lipases, cutinases, hemicellulases, cellulases, ⁇ -glucanases, Oxidases, catalases, peroxidases and / or laccases, among these particularly preferred oxidation-stabilized ⁇ -amylases, proteases, lipases, cutinases, hemicellulases, cellulases, ⁇ -glucanases, oxidases, peroxidases and / or laccases.
- hydrolytic enzymes and / or oxidoreductases more preferably ⁇ -amylases, proteases, lipases, cutinases, hemicellulases, cellulases, ⁇ -glucanases, Oxidases, catalases, peroxidases and / or laccases, among these particularly preferred oxidation-
- Preferred embodiments of this article form such enzyme granules, wherein the enzyme is one or a mixture of the following enzymes: protease, amylase, cellulase, hemicellulase, oxidase and perhydrolase, preferably an oxidation stabilized of these respective enzymes.
- subtilisin type examples thereof are the subtilisins BPN 'and Carlsberg, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase, proteinase K and the subtilases, but not the subtilisins in the narrower sense Proteases TW3 and TW7.
- subtilisin Carlsberg in a developed form under the trade names Alcalase ® from Novozymes A / S, Bagsvaerd, Denmark.
- the subtilisins 147 and 309 are sold under the trade names Esperase ®, or Savinase ® from Novozymes. From the protease from Bacillus lentus DSM 5483 ( WO 91/02792 A1 ) derive from the name under the name BLAP ® variants, which in particular in WO 92/21760 A1 . WO 95/23221 A1 . WO 02/088340 A2 and WO 03/038082 A2 to be discribed. Other useful proteases from various Bacillus sp. and B. gibsonii go out of the patent applications WO 03/054185 A1 . WO 03/056017 A2 . WO 03/055974 A2 and WO 03/054184 A1 out.
- proteases are, for example, under the trade names Durazym ®, relase ®, Everlase® ®, Nafizym, Natalase ®, Kannase® ® and Ovozymes ® from Novozymes, under the trade names Purafect ®, Purafect ® OxP and Properase.RTM ® by the company Genencor, that under the trade name Protosol® ® from Advanced Biochemicals Ltd., Thane, India, under the trade name Wuxi ® from Wuxi Snyder Bioproducts Ltd., China, under the trade names Proleather® ® and protease P ® by the company Amano Pharmaceuticals Ltd., Nagoya, Japan, and the enzyme available under the name Proteinase K-16 from Kao Corp., Tokyo, Japan.
- amylases which can be prepared according to the invention are the ⁇ -amylases from Bacillus licheniformis, B. amyloliquefaciens or B. stearothermophilus, and also their further developments improved for use in detergents or cleaners.
- the enzyme from B. licheniformis is available from Novozymes under the name Termamyl ® and from Genencor under the name Purastar® ® ST. Development products of this ⁇ -amylase are available from Novozymes under the trade names Duramyl ® and Termamyl ® ultra, from Genencor under the name Purastar® ® OxAm and from Daiwa Seiko Inc., Tokyo, Japan, as Keistase ®.
- the ⁇ -amylase from B. amyloliquefaciens is marketed by Novozymes under the name BAN ®, and variants derived from the ⁇ -amylase from B. stearothermophilus under the names BSG ® and Novamyl ®, likewise from Novozymes.
- ⁇ -amylase from Bacillus sp. A 7-7 (DSM 12368) and in the application WO 02/44350 A2 described cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948).
- CGTase cyclodextrin glucanotransferase
- DSM 9948 cyclodextrin glucanotransferase
- amylolytic enzymes belonging to the sequence space of ⁇ -amylases can be used, which in the application WO 03/002711 A2 is defined, and the ones in the application WO 03/054177 A2 to be discribed.
- fusion products of said molecules can be used, for example those from the application DE 10138753 A1 or point mutations of it.
- Granules according to the invention may contain lipases or cutinases, in particular because of their triglyceride-cleaving activities, but also in order to obtain suitable ones Precursors generate in situ peracids.
- lipases originally obtainable from Humicola lanuginosa (Thermomyces lanuginosus) or further developed, in particular those with the amino acid exchange D96L. They are sold, for example, by Novozymes under the trade names Lipolase ®, Lipolase Ultra ®, LipoPrime® ®, Lipozyme® ® and Lipex ®.
- the cutinases can be used, which were originally isolated from Fusarium solani pisi and Humicola insolens.
- useable lipases are available from Amano under the designations Lipase CE ®, Lipase P ®, Lipase B ®, or lipase CES ®, Lipase AKG ®, Bacillis sp.
- Lipase® , Lipase AP® , Lipase M- AP® and Lipase AML® are available.
- the lipases, or cutinases can be used, the initial enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii.
- Granules according to the invention especially if they are intended for the treatment of textiles, contain cellulases, depending on the purpose as pure enzymes, as enzyme preparations or in the form of mixtures in which the individual components complement each other advantageously in terms of their various performance aspects.
- These performance aspects include, in particular, contributions to the primary washing performance, the secondary washing performance of the composition (anti-redeposition effect or graying inhibition) and softening (fabric effect), up to the exercise of a "stone-washed" effect.
- EG endoglucanase
- Novozymes A useful fungal, endoglucanase (EG) -rich cellulase preparation, or its further developments are offered by Novozymes under the trade name Celluzyme ®.
- Further commercial products of this company are Cellusoft® ® and Renozyme ®. The latter is based on the registration WO 96/29397 A1 , Performance-enhanced cellulase variants go, for example, from the application WO 98/12307 A1 out.
- WO 97/14804 A1 disclosed cellulases used; For example, it revealed 20 kD EG Melanocarpus, available from AB Enzymes, Finland, under the trade names Ecostone® ® and Biotouch ®. Further commercial products from AB Enzymes are Econase® ® and ECOPULP ®. Other suitable cellulases from Bacillus sp. CBS 670.93 and CBS 669.93 are in WO 96/34092 A2 disclosed, the Bacillus sp. CBS 670.93 from the company Genencor under the trade name Puradax ® is available. Further commercial products of the company Genencor are "Genencor detergent cellulase L" and IndiAge ® Neutra.
- Granules according to the invention for use in detergents or cleaners can, in particular for the removal of certain problem soiling, comprise further enzymes which are combined under the term hemicellulases.
- Suitable mannanases for example, under the name Gamanase ® and Pektinex AR ® from Novozymes, under the name Rohapec ® B1 L from AB Enzymes, under the name Pyrolase® ® from Diversa Corp., San Diego, CA, USA, and under the name Purabrite ® from Genencor Int., Inc., Palo Alto, CA, USA.
- a suitable ⁇ -glucanase from a B. alcalophilus for example, from the application WO 99/06573 A1 out.
- the obtained from B. subtilis ⁇ -glucanase is available under the name Cereflo ® from Novozymes.
- granules according to the invention may also contain oxidoreductases, for example oxidases, oxygenases, catalases (which react as peroxidase at low H 2 O 2 concentrations), peroxidases, such as halo, chloro, bromo, lignin, glucose or Manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases).
- oxidoreductases for example oxidases, oxygenases, catalases (which react as peroxidase at low H 2 O 2 concentrations), peroxidases, such as halo, chloro, bromo, lignin, glucose or Manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases).
- Suitable commercial products Denilite® ® 1 and 2 from Novozymes should be mentioned.
- advantageous systems for an enzymatic perhydrolysis can be applied to the application WO
- choline oxidases are disclosed WO 2004/058955 A2
- Modified proteases with pronounced, at this point also advantageously usable perhydrolase activity, in particular for achieving a mild bleaching in laundry detergents go from the application WO 2004/058961 A1 out.
- a combined enzymatic bleaching system comprising an oxidase and a perhydrolase describes the application WO 2005/124012 . Further perhydrolases which can be used according to the invention are also disclosed WO 2005/056782 A2 , Advantageously, it is additionally preferred to add organic, particularly preferably aromatic, compounds which interact with the enzymes in order to enhance the activity of the relevant oxidoreductases (enhancers) or to ensure the flow of electrons (mediators) at greatly varying redox potentials between the oxidizing enzymes and the soils.
- organic, particularly preferably aromatic, compounds which interact with the enzymes in order to enhance the activity of the relevant oxidoreductases (enhancers) or to ensure the flow of electrons (mediators) at greatly varying redox potentials between the oxidizing enzymes and the soils.
- the enzymes used in granules according to the invention are either originally from microorganisms, such as the genera Bacillus, Streptomyces, Humicola, or Pseudomonas, and / or are produced by biotechnological methods known per se by suitable microorganisms, such as transgenic expression hosts of the genera Bacillus or by filamentous fungi ,
- the purification of the relevant enzymes is conveniently carried out by conventional methods, for example by precipitation, sedimentation, concentration, filtration of the liquid phases, microfiltration, ultrafiltration, exposure to chemicals, deodorization or suitable combinations of these steps.
- the enzymes can be formulated according to the invention together with accompanying substances, for example from the fermentation or with stabilizers.
- liquid enzyme preparations for example coming directly from the fermentative preparation, is incorporated into the slurry for the preparation of the granules in aqueous solution.
- liquid enzyme preparations are also commercially available, especially proteases and amylases designed for use in detergents and cleaners.
- liquid protease preparations having an enzyme protein content of 0.1 to 50%, preferably 5 to 40%, particularly preferably 10 to 35% They may optionally by methods known in the art (for example, concentration via rotary evaporation or dilution by adding buffer) to a suitable concentration for further processing.
- Granules according to the invention contain as component (b) (adsorbent) one or more of the compounds selected from the group: talc, silicic acid.
- polyvinyl alcohols which are available as white-yellowish powders or granules with degrees of polymerization in the range from about 500 to 2500 (molar masses of about 20,000 to 100,000 g / mol), have degrees of hydrolysis of 98 to 99 and 87 to 89 mol%, respectively So still a residual content of acetyl groups.
- Fully saponified polyvinyl alcohols have a glass transition temperature of 85 ° C and a melting point of 228 ° C.
- the corresponding values for partially hydrolyzed (87 - 89%) products are significantly lower at approx. 58 ° C and 186 ° C, respectively.
- the latter are the "partially hydrolyzed" PVA which is particularly suitable according to the invention.
- Granules containing these components (b) have remarkable stability and, when used as part of a detergent formulation, have excellent solubility under application conditions. This is evidenced by the examples of the present application.
- Granules according to the invention contain as component (c) (binder) one or more of the compounds selected from the group: polyacrylate, polymethacrylate, polyvinylpyrrolidone, substituted polysaccharide, in particular cellulose ethers, polyvinyl alcohol (PVA), in particular partially hydrolyzed PVA or ethoxylated PVA, a copolymer of the abovementioned Compounds, in particular methacrylic acid-ethyl acrylate copolymer, more preferably a combination of two or three of these compounds.
- binder one or more of the compounds selected from the group: polyacrylate, polymethacrylate, polyvinylpyrrolidone, substituted polysaccharide, in particular cellulose ethers, polyvinyl alcohol (PVA), in particular partially hydrolyzed PVA or ethoxylated PVA, a copolymer of the abovementioned Compounds, in particular methacrylic acid-ethyl acryl
- Suitable substances which may be mentioned are the crosslinked polyvinylpyrrolidone Collidone CL (commercial product of BASF, Ludwigshafen) and the methacrylic acid-ethylacrylate copolymers Eudragit L100 (Degussa, Frankfurt / M.) and Collicoat MEA (BASF).
- Preferred embodiments of the present invention form granules according to the invention comprising, as part of component (d) (plasticizer), one or more compounds selected from the group: water-dispersible organic compound or water-dispersible organic polymer, in particular polyethylene glycol (PEG), especially short-chain PEG, Fatty acid or salt a fatty acid, triacetin, triethyl citrate and / or polyhydric alcohol, preferably fatty acid or salt of a fatty acid, more preferably sodium stearate and / or sodium oleate.
- PEG polyethylene glycol
- Fatty acid or salt a fatty acid triacetin, triethyl citrate and / or polyhydric alcohol, preferably fatty acid or salt of a fatty acid, more preferably sodium stearate and / or sodium oleate.
- component (d) For granules with these parts of component (d) were characterized by a remarkable stability and when used in the context of a washing or cleaning agent formulation by an excellent solubility under conditions of use. This is evidenced by the examples of the present application.
- Preferred embodiments of the present invention form granules according to the invention containing, as part of component (d) (solubility improver), one or more compounds selected from the group: water-soluble inorganic salt, monosaccharide, in particular glucose, oligosaccharide, polysaccharide, in particular cellulose, compacted cellulose or Cellulose derivative, crosslinked organic polymer, in particular crosslinked polyvinylpyrrolidone or crosslinked polyacrylate.
- component (d) solubility improver
- water-soluble inorganic salt monosaccharide, in particular glucose, oligosaccharide, polysaccharide, in particular cellulose, compacted cellulose or Cellulose derivative
- crosslinked organic polymer in particular crosslinked polyvinylpyrrolidone or crosslinked polyacrylate.
- component (d) For granules with these parts of component (d) were characterized by a remarkable stability and when used in the context of a washing or cleaning agent formulation by an excellent solubility under conditions of use. This is evidenced by the examples of the present application.
- disintegrants due to their action, increase their volume upon ingress of water, on the one hand the intrinsic volume increased (swelling), on the other hand, on the release of gases, a pressure can be generated, which can decay the granular particles into smaller particles.
- disintegration aids are, for example, carbonate / citric acid systems, although other organic acids can also be used.
- Swelling disintegration aids are, for example, synthetic polymers such as polyvinylpyrrolidone (PVP) or natural polymers or modified natural substances such as cellulose and starch and their derivatives, alginates or gasein derivatives.
- Disintegrating agents based on cellulose are used as preferred disintegrating agents in the context of the present invention.
- a further embodiment of the present invention relates to a granulate according to the invention, which is additionally coated with a single or multiple coating.
- This additional coating serves, in particular, for the additional protection of the ingredients, but can also serve other purposes, for example delaying the release, improving the bulk material properties, for example lowering the dust rate, increasing the stability and / or improving the optical image.
- a ball coater (turbojet) can be used, described in the thesis by Karin Wöstheinrich, "Possible applications of the Weglin-Kugelcoaters HKC 05-TJ including simulations", as an online dissertation under the URL http: // w210.ub.unituebingen.de/dbt/volltexte/2000/134/index.html. can be viewed (accessed on 5/5/2005).
- the granules particles preferably enzyme particles
- the coating material is sprayed on via a top sprayer. This is done under drying conditions, ie 40-45 ° C, so that the product has about 35-38 ° C and remains dry.
- Preferred such methods and process products are characterized in that the enzyme granules particles are coated with an aqueous emulsion based on silicone oil.
- the polymer in the form of an aqueous solution, for example as an aqueous PEG solution.
- the coating and surfactant such as nonionic surfactant with about 80 EO can be used.
- a granules coated according to the invention wherein the coating consists of more than 50 wt .-% of one or more of the following compounds: water-dispersible substances, water-dispersible and / or water-soluble polymer, fatty acid, salt Fatty acid, fatty alcohol, paraffin, polyvinyl acetate, polyacrylate, polymethacrylate, methacrylic acid-ethyl acrylate copolymer, polyvinyl pyrrolidone, cellulose ethers, polyvinyl alcohol and ethoxylated polyvinyl alcohol.
- water-dispersible substances water-dispersible and / or water-soluble polymer
- fatty acid salt Fatty acid
- fatty alcohol paraffin
- polyvinyl acetate polyacrylate
- polymethacrylate methacrylic acid-ethyl acrylate copolymer
- polyvinyl pyrrolidone polyvinyl pyrrolidone
- cellulose ethers polyvinyl
- it is a polymer-coated granules according to the invention, wherein the water-soluble polymer is polyacrylate or a methacrylic acid-ethyl acrylate copolymer and / or the cellulose ether is methylcellulose (MC), hydroxyethylcellulose (HEC), hydroxypropylcellulose (HPC), hydroxypropylmethylcellulose (HPMC) or carboxymethylcellulose (CMC).
- MC methylcellulose
- HEC hydroxyethylcellulose
- HPC hydroxypropylcellulose
- HPMC hydroxypropylmethylcellulose
- CMC carboxymethylcellulose
- Example 4 granules according to the invention having an additional polymer coating have increased stability values.
- a coating was made with a commercially available polyacrylate (methacrylic acid-ethyl acrylate copolymer (1: 1)), which gave excellent stability values.
- a commercially available polyacrylate methacrylic acid-ethyl acrylate copolymer (1: 1)
- Kollicoat MEA from BASF.
- the coating additionally contains one or more fillers selected from the group of inorganic particles, preferably silicate or alumina, more preferably talc.
- Such fillers may be used, for example, to influence the overall plasticity of the coating in question and / or of the particles obtained in order to improve their diffusion-tightness or to regulate the bulk density of the particles.
- it is a coated granules according to the invention, wherein the coating additionally contains one or more plasticizers selected from the group: triethyl citrate, triacetin, polyhydric alcohol, in particular 1,2-propanediol, and polyethylene glycol.
- plasticizers selected from the group: triethyl citrate, triacetin, polyhydric alcohol, in particular 1,2-propanediol, and polyethylene glycol.
- Example 4 the coating was carried out with a commercially available polyacrylate (methacrylic acid-ethyl acrylate copolymer (1: 1)) to which 5% (based on the coating polymer) was further added as a plasticizer. This has had a positive effect on the processability of the material and thus ultimately on the advantageous properties of the resulting coated granules.
- a commercially available polyacrylate methacrylic acid-ethyl acrylate copolymer (1: 1)
- the coating additionally contains color pigment, preferably titanium dioxide.
- color pigments according to the invention serve to improve the optical appearance of the granules and can also have an overall positive effect on the plasticity of the respective material. Analogously, it is within the scope of the present invention to impart these properties to the coating or the coating material.
- it is an inventive coated granules, wherein the coating additionally contains one or more compounds acting as antioxidants.
- Antioxidants are known per se to the person skilled in the art. For example, it is common to increase the stability of enzymes to oxidative degradation by sulfur-containing reducing agents, sodium sulfite and reducing sugars to antioxidants (see above). Further compounds which may be mentioned as being suitable at this point are, for example, ascorbic acid, tocopherol, gallates, thiosulfate-substituted phenols, hydroquinones, catechols and aromatic amines, and also organic sulfides, polysulfides, dithiocarbamates, phosphites, phosphonates and vitamin E.
- it is a coated granules according to the invention, wherein the coating is 5 to 100 wt .-%, preferably 10 to 80 wt .-%, particularly preferably 15 to 60 wt .-% of the uncoated granules.
- This information refers to the ready-made granules. At the moment of manufacture, these values may still be slightly different because granules, even after their coating, are usually subjected to a drying step. This reduces the water content of both the core and the coating, which may also result in differences in the ratio of water to each other. This is the case, for example, when comparatively dilute, that is to say particularly water-containing, enzyme preparations have been incorporated into the core or when it has been coated with an aqueous suspension of a per se hydrophobic coating material. In the latter case, the water content of the finally obtained coating is significantly lower than that of the core.
- an inventive uncoated or coated granules having an average particle diameter of 100 to 3000 microns, preferably 200 to 2500 microns, more preferably 400 to 2000 microns.
- This size depends on the one hand after the manufacturing process, after which coated granules usually have a slightly larger diameter than uncoated. On the other hand, it depends on the field of application. Furthermore, these size ranges have been found to be advantageous to achieve a rapid disintegration and release of the ingredients at the moment of use of the funds in question and also to give the product a special aesthetic impression.
- the size of the particles can be regulated according to variations known per se to those skilled in the art for the preparation of the particles, in particular the uncoated particles.
- those granules obtainable by extrusion in which 90% of all particles are within a range of ⁇ 20% of the mean size are preferred. This can be controlled via the nozzle plate.
- a preferred embodiment of the present invention is an uncoated or coated granulate according to the invention having an average density of from 1.00 to 1.50, preferably from 1.02 to 1.30, particularly preferably from 1.05 to 1.15 g / ml.
- the density of the granules described in Example 4 of the present application is in each case about 1.29 g / ml.
- a further subject of the present invention are processes for the preparation of each granulate according to the invention.
- An advantageous procedure, based on a liquid, concentrated aqueous enzyme preparation can be described as follows:
- the enzyme concentrate is added to the advantageously previously prepared dry, powdery to granular mixture of a composition relevant to the invention.
- the water content of the mixture should be chosen so that when working with stirring and impact tools in granular, at room temperature not Transfer adhesive particles and plastically deform and extrude using higher pressure.
- the free-flowing premix is then processed in a known manner in a kneader and a connected extruder to a plastic, homogeneous as possible mass, the mass as a result of mechanical processing to temperatures between 15 and 80 ° C, in particular 40 ° C and 60 ° C, in particular to 45 ° C to 55 ° C can heat.
- an extrusion temperature of below 60 ° C and an extrusion pressure in the range of 30 to 130 bar, in particular in the range of 50 to 90 bar.
- the material leaving the extruder is passed through a perforated disc with subsequent doctor blade and thereby comminuted to form cylindrical particles of defined size.
- the diameter of the holes in the perforated disc is 0.7 to 1.2 mm, preferably 0.8 to 1.0 mm. It may also be advantageous not to cut off the mass emerging from the nozzle plate of the extruder immediately at the nozzle head, but to interpose a cooling section, after which the granulation takes place in a cutting device.
- the particles present in this form can then be dried, rounded and / or coated. It has proven to be advantageous to spheronize the cylindrical particles leaving the extruder and chopper prior to wrapping, that is to round and deburr them in suitable apparatus.
- a device which consists of a cylindrical container with stationary, solid side walls and a base plate rotatably mounted friction plate. Devices of this type are widely used in the art under the trade name Marumerizer® and, for example, in US Pat DE 2137042 and DE 2137043 described.
- dust-like fractions with a particle size of less than 0.1 mm, in particular less than 0.4 mm, and any coarse fractions with a particle size of more than 2 mm, in particular more than 1.6 mm can be removed by sieving or air classification and optionally returned to the production process.
- the beads are continuously or batchwise, preferably using a fluidized bed dryer, at inlet air temperatures of preferably 35 ° C to 70 ° C and in particular in a Product temperature of not more than 60 ° C to the desired residual moisture content of, for example, 2 wt .-% to 10 wt .-%, in particular 3 wt .-% to 8 wt .-%, based on total granules, dried, if they previously had higher water contents have shown.
- liquid preparation of the sensitive ingredient (a) to be incorporated in particular a liquid enzyme preparation. It can be added by a separate liquid metering device at any point of the process length of the extruder, while the components (b), (c) and (d) are supplied at the beginning of the process length as free-flowing granules or as a powder.
- Another object of the present invention are detergents or cleaners containing a sensitive ingredient in the form of granules of the invention.
- solid, liquid or gel detergents and cleaners which contain sensitive ingredients, especially enzymes with good protection against other, especially bleaching, ingredients.
- This form of packaging is physically largely stable to perform its protective function. On the other hand, it shows in the application, that is at the moment of dilution by the aqueous wash liquor a good release behavior, so that the enzymes are readily available in an active form, and leave virtually no residue on the laundry.
- a washing or cleaning agent is to be understood as meaning every conceivable type of detergent, both concentrates and undiluted agents, for use on a commercial scale, in the washing machine or in hand washing or cleaning.
- detergents for textiles, carpets, or natural fibers for which according to the present invention the term laundry detergent is used.
- laundry detergent include, for example, dishwashing detergents for dishwashers or manual dishwashing detergents or cleaners for hard surfaces such as metal, glass, porcelain, ceramics, tiles, stone, painted surfaces, plastics, wood or leather; for such according to the present invention, the term cleaning agent is used.
- Embodiments of the present invention include all known in the art and / or all appropriate dosage forms of Detergents or cleaning agents according to the invention. These include in particular solid, pulverulent, means, possibly also of several phases, compressed or uncompressed; further include, for example: extrudates, granules, tablets or pouches, packed both in large containers and in portions.
- a washing or cleaning agent according to the invention optionally contains further ingredients such as enzyme stabilizers (see above), surfactants, for example nonionic, anionic and / or amphoteric surfactants, and / or bleaching agents, and / or builders and optionally further customary ingredients, among which are the following: other, in particular the enzymes already mentioned above, sequestering agents, electrolytes, optical brighteners, grayness inhibitors, silver corrosion inhibitors, dye transfer inhibitors, foam inhibitors, abrasives, dyes and / or fragrances, as well as microbial Active ingredients and / or UV absorbents.
- enzyme stabilizers see above
- surfactants for example nonionic, anionic and / or amphoteric surfactants, and / or bleaching agents, and / or builders and optionally further customary ingredients, among which are the following: other, in particular the enzymes already mentioned above, sequestering agents, electrolytes, optical brighteners, grayness inhibitors, silver corrosion inhibitors, dye transfer inhibitors,
- the enzyme granules according to the invention or produced by the process according to the invention is used for the production of solid, in particular particulate detergents or cleaners, which can be obtained by simply mixing the enzyme granules with other powder components customary in such agents.
- the enzyme granules preferably have average particle sizes Range from 0.7 to 2.0 mm.
- the granules according to the invention preferably contain less than 2% by weight, in particular not more than 1.4% by weight, of particles having a particle size outside the range from 0.4 to 2.0 mm.
- the method is not limited to these particle sizes, but covers a wide range of particle sizes corresponding to the field of application; usually the average particle diameter (d 50 ) is between 0.1 and more than 2 mm.
- washing or cleaning agent which is predominantly liquid, gel or pasty and preferably hydrous.
- the bleach-containing liquid or gel-containing compositions according to the invention are preferably heavy-duty detergents for textile cleaning, which have a flow behavior which the user perceives as aesthetically pleasing and / or good manufacturability.
- the density of the composition described in Example 5 of the present application is about 1.094 g / ml while that of the particles incorporated therein is about 1.29 g / ml. This shows that both densities do not necessarily have to be identical, but can differ within a certain range. Because there are other surface effects (charges, hydrophobicity / hydrophilicity effects, etc.) added, which are to be compensated experimentally in detail. Furthermore, a stabilization of the particles takes place in suspension the flow behavior of the agents. In particular, in liquid or gel compositions, the presence of a flow limit provides effective stabilization of the particle phase.
- Preferred embodiments of this subject matter are detergents or cleaning compositions according to the invention containing a bleaching agent selected from the group: enzymatic bleaching system, inorganic bleaching system, organic bleaching system or a mixture thereof.
- Bleaching systems for use in detergents and cleaners are known per se and have already been described above. Enzymatic systems have also been described above and can be added in inventive compositions in granulated form according to the invention or in another way, as long as at least one granule according to the invention is present. This may, for example, also be the substrate of such a bleaching enzyme (see above).
- Preferred embodiments of this aspect of the invention are detergents and cleaners according to the invention: wherein the bleaching agent is present in the liquid or gel agent as particles, preferably as coated particles.
- Preferred embodiments of this aspect of the invention are detergents and cleaners according to the invention, wherein the sensitive ingredient is an oxidative enzyme.
- the oxidative enzyme is protected against acting compounds, for example against the highly concentrated surfactants of a liquid detergent formulation.
- enzyme and substrate can be at least largely separated from one another in this way, so that it comes to a reaction between the two only at the moment of use, that is, the bursting of the granular particles at high dilution with water. In this way, the substrate is not prematurely consumed and is almost completely available for the desired use.
- the present invention is also realized by suitable uses to make sensitive detergent or makemiltelinhaltsstoffe in the form of granules comparatively stable.
- the sensitive detergent or cleaning agent ingredient is a perfume, an optical brightener, a bleach activator or an enzyme, preferably an enzyme, more preferably an oxidation-stabilized enzyme.
- the mixture was then homogenized and plasticized on a process length of 28 ⁇ D.
- the enzyme mass was discharged through a round-strand die (diameter 1 mm) onto a conveyor belt and, after a cooling distance of 1 m, passed into a granulator type 881203 (from Brabender). The resulting cylindrical extrudate particles were mechanically rounded.
- extrudate (granulate E2) was prepared from the following constituents: No. Quantity [g] ingredient 1 110 Polyvinyl alcohol (Erkol ® M05 / 290) 2 120 Sodium stearate (Riedel / Fluka) 3 40 Sodium aluminum silicate (Wessalith ® 4000) 4 40 glucose 5 80 Alumina (Disperal P3 ®) 6 40 Titanium dioxide (Kronos) 7 516 Liquid protease preparation (as in Example 1)
- granules consist of about 5% pure enzyme; the remaining components are thus contained in the following quantities: (b) 31% by weight of particulate carrier material consisting of Wessalith, Dispersal and TiO 2 , (c) 22% by weight of binder, consisting of PVA, (d) 24% by weight. % Plasticizer, consisting of sodium stearate, 8% by weight solubility improver, consisting of glucose and about 10% water. A portion of the particulate carrier material, namely the TiO 2 , which in itself accounts for 8% of the total mass of the granules, also serves as a color pigment. The weight ratio of (b) to (c) was about 1.4: 1.
- these granules also contained 78% by weight of the particulate carrier material (b) (sodium aluminum silicate, PVA or sodium sulfate) and 7% by weight. % of the binder (c) (polyacrylate). The weight ratio of (b) to (c) was about 11: 1.
- the ready-made granules E3c, E4c and E5c thus contained a coating which in each case constituted about 21% of the mass of the granule core.
- the density of the coated granules was in each case about 1.29 g / ml.
- Liquid heavy-duty detergents of the following compositions were prepared, the amount in% by weight being based on the active ingredient content in each case: No. amount ingredient [% By weight of active substance] 1 16.5 Sodium linear alkyl benzene sulfonate (commercial product Maranil ®, from Cognis, Dusseldorf). 2 10 Nonionic surfactant (C 12-18 fatty alcohol ethoxylate (7 EO); commercial product Dehydol ® LT 7; Cognis). 3 1 Hydroxyethane-1,1-diphosphonic acid Na4 salt (HEDP; Sequion ® 10 H 60; Fa Polygon Chemie, Olten, Switzerland).
- HEDP Hydroxyethane-1,1-diphosphonic acid Na4 salt
- PAP Phthalimidoperoxyhexanoic acid
- the preparation was carried out by the water was placed in a stirred tank and to the xanthan was added. After swelling the xanthan (30 min), the sulfate was added. Thereafter, the addition of the surfactants and the other raw materials in the order listed, with stirring. The pH was adjusted to 5.0 ⁇ 0.2 by concentrated NaOH.
- the formulations F1, F2, F3c, F4c, F5c and V1 and V2 prepared according to the preceding example were stored at a storage temperature of 25 ° C in gas-tight glass bottles. After periods of 1, 2, 4 and 8 weeks, the enzyme activity was determined using a "continuous flow apparatus" (Skalar, Erkelenz). The method is based on the cleavage of casein, staining of the hydrolysis products with trinitrobenzenesulfonic acid and their photometric determination. In principle, any other protease activity determination method which is not impaired by surfactants present can also be used.
- V1 The commercially available enzyme granules in V1 show a higher but by no means satisfactory stability. The granulation and coating has therefore been insufficient to prevent exposure to the bleaching agent during storage. Further, it was observed in V1 that its granules disintegrate over time.
- the uncoated granules E1 and E2 are already characterized by a significantly longer lasting high enzyme activity, which in fact means a higher enzyme stability. This is particularly noteworthy because the recipe in question contains more than 50 wt .-% water. Both granules remained unchanged in shape, that is they did not disintegrate.
- E1 granule core with PVA, sodium stearate, sodium aluminum silicate, aluminum oxide and titanium dioxide
- a coating according to Example 4 polyacrylate / triethyl citrate
- Example 2 No. amount amount ingredient [G] [Wt .-%] 1 80 13 Polyvinyl alcohol (viscosity 4.5 ⁇ 0.5, saponification number 270-310 mg KOH / g, commercial product Erkol M05 / 290 from Erkol, Tarragona, Spain) 2 80 13 Sodium oleate (Riedel-de Ha ⁇ n / Sigma-Aldrich, Seelze, Germany) 3 60 9.7 Sodium stearate (Riedel-de Ha ⁇ n / Sigma-Aldrich, Seelze, Germany) 4 60 9.7 Sodium sulfate (Riedel-de Ha ⁇ n / Sigma-Aldrich, Seelze, Germany) 5 80 13 crosslinked polyvinylpyrrolidone (commercial product Collidon ® CL of the Fa.
- Liquid protease preparation commercial product containing about 10% by weight of pure enzyme protein stabilized by point mutagenesis against oxidation, balance: water and 1,2-ethylene glycol as stabilizer, about 160,000 HPU / g
- this formulation contained, with No. 6, approximately 4.2% by weight of enzyme as the sensitive ingredient (a), with Nos. 1 and 4 together, 22.7% by weight of component (b), with No. 5 13 wt .-% of component (c), with Nos. 2 and 3 together 22.7 wt .-% plasticizer as part of component (d) and as the predominant remainder water.
- Example 1 No. amount amount ingredient [G] [Wt .-%] 1 80 16 Polyvinyl alcohol (viscosity 4.5 ⁇ 0.5, saponification number 270-310 mg KOH / g, commercial product Erkol M05 / 290 from Erkol, Tarragona, Spain) 2 60 12 Sodium stearate (Riedel-de Ha ⁇ n / Sigma-Aldrich, Seelze, Germany) 3 80 16 Sodium sulfate (Riedel-de Ha ⁇ n / Sigma-Aldrich, Seelze, Germany) 4 80 16 cross-linked polyvinylpyrrolidone (commercial product Collidon CL from BASF, Ludwigshafen) 5 200 40 Liquid protease preparation (commercial product containing about 10% by weight of pure enzyme protein stabilized by point mutagenesis against oxidation, balance: water and 1,2-ethylene glycol as stabilizer, about 160,000 HPU / g)
- this formulation contained, with No. 5, approximately 4% by weight of enzyme as component (a), with Nos. 1 and 3 together, 32% by weight of component (b), with No. 4 16% by weight of component ( c), with No. 2 12 wt .-% plasticizer as part of component (d) and as the predominant remainder water.
- Example 2 No. amount amount ingredient [Wt .-%] [Wt .-%] 1 80 16 Polyvinyl alcohol (viscosity of 4.5 ⁇ 0.5; Sapontechnisches number 270-310 mg KOH / g; commercial product Erkol ® M05 / 290 Fa Erkol, Tarragona, Spain.) 2 60 12 Sodium stearate (Riedel-de Ha ⁇ n / Sigma-Aldrich, Seelze, Germany) 3 60 12 Sodium sulfate (Riedel-de Ha ⁇ n / Sigma-Aldrich, Seelze, Germany) 4 20 4 Methacrylic acid-ethyl acrylate copolymer (commercial product Eudragit ® L100.
- this formulation contained, with No. 6, approximately 4% by weight of enzyme as component (a), with Nos. 1 and 3 together 28% by weight of component (b), with Nos. 4 and 5 20% by weight.
- component (c) with No. 2 12 wt .-% plasticizer as part of component (d) and as the predominant remainder water.
- the sieve was dried for 48 h at 35 ° C. and the granules remaining in the sieve were weighed out and related to the initial value. In each case duplicate determinations were carried out.
- the granule K1 disintegrates significantly more than 50%. In addition, it has been observed that in these granules, the majority of the enzyme-containing active layer peels off.
- the granules E7, E7c, E8, E8c, E5c according to the invention show values well above 50%, which means that the majority of the granules are not disintegrated in the test solution during storage (and even with shaking). So they meet the requirements of the invention.
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Claims (13)
- Produit de granulation d'un constituant sensible d'agent de lavage ou de nettoyage, contenant les composants suivants :(a) le constituant sensible d'agent de lavage ou de nettoyage ;(b) de 10 à 80 % en poids d'une matière de support particulaire choisie parmi le groupe comprenant : le talc, l'acide silicique, l'oxyde d'aluminium, un silicate, en particulier du silicate stratifié et/ou du silicate de sodium-aluminium, la bentonite, l'aluminosilicate, un sulfate, le dioxyde de titane et/ou l'alcool polyvinylique, en particulier l'alcool polyvinylique partiellement hydrolysé, de manière particulièrement préférée une combinaison de deux ou de trois de ces composés ;(c) de 3 à 50 % en poids d'un constituant différent de (b), à titre de liant, choisi parmi le groupe comprenant : du polyacrylate, du polyméthacrylate, de la polyvinylpyrrolidone, du polysaccharide substitué, en particulier de l'éther cellulosique, de l'alcool polyvinylique, en particulier de l'alcool polyvinylique partiellement hydrolysé ou de l'alcool polyvinylique éthoxylé, un copolymère d'acide méthacrylique-acrylate d'éthyle, de manière particulièrement préférée une combinaison de deux ou de trois de ces composés ; et(d) de manière facultative, d'autres constituants différents de (b) et (c) :qui présente un indice de désintégration d'au moins 50 % après 24 heures, déterminé avec un tamis possédant une largeur de maille de 280 µm, et dans lequel les composants (b) et (c) sont présents dans un rapport, en % en poids, de (b) à (c) de 1 : 5 à 20 : 1, de manière particulièrement préférée de 1 : 5 à 5 : 1.de 0 à 50 % en poids de plastifiant ;de 0 à 50 % en poids d'agent améliorant la solubilité et/oude 0 à 40 % en poids d'eau, de stabilisateurs enzymatiques, de colorants, de pigments colorés, de substances faisant office de tampon pour le pH, d'antioxydants, de composés régulateurs de la densité et/ou d'autres constituants ;
- Produit de granulation selon la revendication 1, contenant, à titre de partie du composant (d) (agent améliorant la solubilité), un ou plusieurs composés choisis parmi le groupe comprenant : un sel inorganique soluble dans l'eau, un monosaccharide, en particulier le glucose, un oligosaccharide, un polysaccharide, en particulier la cellulose, de la cellulose rendue compacte ou un dérivé de cellulose, un polymère organique réticulé, en particulier de la polyvinylpyrrolidone réticulée ou du polyacrylate réticulé.
- Produit de granulation selon l'une quelconque des revendications 1 ou 2, qui est en outre revêtu d'une enduction simple ou multiple, en particulier d'une enduction qui est constituée, à concurrence de plus de 50 % en poids, par un ou plusieurs des composés suivants : des substances aptes à être dispersées dans l'eau, un polymère apte à être dispersé dans l'eau et/ou soluble dans l'eau, un acide gras, un sel d'acide gras, un alcool gras, de la paraffine, de l'acétate de polyvinyle, du polyacrylate, du polyméthacrylate, un copolymère d'acide méthacrylique-acrylate d'éthyle, de la polyvinylpyrrolidone, de l'éther cellulosique, de l'alcool polyvinylique et de l'alcool polyvinylique éthoxylé, en particulier un produit de granulation possédant une densité moyenne de 1,00 à 1,50, de préférence de 1,02 à 1,30, de manière particulièrement préférée de 1,05 à 1,15 g/ml.
- Procédé pour la préparation d'un produit de granulation selon l'une quelconque des revendications 1 à 3, en particulier d'un produit de granulation dans lequel l'adsorbant (b) est déposé au préalable principalement sous la forme d'une substance sèche et le composant enzymatique (a) est incorporé sous la forme d'une préparation liquide.
- Agent de lavage ou de nettoyage, contenant un constituant sensible sous la forme d'un produit de granulation selon l'une quelconque des revendications 1 à 3.
- Agent de lavage ou de nettoyage selon la revendication 5, qui est présent principalement sous forme liquide, sous forme de gel ou sous forme pâteuse, et de préférence qui est aqueux, en particulier un agent de ce type qui possède une teneur en eau de manière plus préférée de 5 à 95, de 10 à 90, de 20 à 80, de 30 à 70, de 40 à 60, de 45 à 55 % en poids, et de manière tout particulièrement préférée qui possède une teneur en eau de 50 % en poids.
- Agent de lavage ou de nettoyage selon la revendication 6, qui possède une teneur en sel inorganique de 3 à 30 % en poids, de préférence de 5 à 20 % en poids, de manière particulièrement préférée de 7 à 10 % en poids dans la phase liquide, en forme de gel, respectivement pâteuse.
- Agent de lavage ou de nettoyage selon l'une quelconque des revendications 6 à 7, qui possède une densité de 1,00 à 1,50 g/ml, de préférence de 1,02 à 1,30 g/ml, de manière particulièrement préférée de 1,05 à 1,15 g/ml.
- Agent de lavage ou de nettoyage selon l'une quelconque des revendications 5 à 8, contenant un agent de blanchiment choisi parmi le groupe comprenant : un système de blanchiment enzymatique, un système de blanchiment inorganique, un système de blanchiment organique ou un de leurs mélanges.
- Agent de lavage ou de nettoyage selon la revendication 9, dans lequel, en ce qui concerne l'agent de blanchiment, il s'agit :(i) de H2O2 ou d'un système formant du H2O2, en particulier un percarbonate ;(ii) de H2O2 ou d'un système formant du H2O2, respectivement en combinaison avec un précurseur d'acide peroxycarboxylique, en particulier de la tétraacétyléthylènediamine (TAED) ;(iii) un acide peroxycarboxylique préformé, en particulier l'acide 1,12-diperdodécanedioïque (DPDDA), l'acide phtalimidoperoxy-hexanoïque (PAP), de manière particulièrement préférée, le PAP ;(iv) d'une combinaison de (a), (b) et/ou (c).
- Agent de lavage ou de nettoyage selon la revendication 9 ou 10, dans lequel l'agent de blanchiment est présent, dans l'agent sous forme liquide ou sous forme de gel, sous la forme de particules, de préférence sous la forme de particules enrobées.
- Agent de lavage ou de nettoyage selon l'une quelconque des revendications 5 à 11, dans lequel le constituant sensible est une enzyme oxydante.
- Utilisation des composants:(b) de 10 à 80 % en poids d'une matière de support particulaire choisie parmi le groupe comprenant : le talc, l'acide silicique, l'oxyde d'aluminium, un silicate, en particulier du silicate stratifié et/ou du silicate de sodium-aluminium, la bentonite, l'aluminosilicate, un sulfate, le dioxyde de titane et/ou l'alcool polyvinylique, en particulier l'alcool polyvinylique partiellement hydrolysé, de manière particulièrement préférée une combinaison de deux ou de trois de ces composés ;(c) de 3 à 50 % en poids d'un constituant différent de (b), à titre de liant, choisi parmi le groupe comprenant : du polyacrylate, du polyméthacrylate, de la polyvinylpyrrolidone, du polysaccharide substitué, en particulier de l'éther cellulosique, de l'alcool polyvinylique, en particulier de l'alcool polyvinylique partiellement hydrolysé ou de l'alcool polyvinylique éthoxylé ; et(d) de manière facultative, d'autres constituants différents de (b) et (c) :de 0 à 50 % en poids de plastifiant ;de 0 à 50 % en poids d'agent améliorant la solubilité et/oude 0 à 40 % en poids d'eau, de stabilisateurs enzymatiques, de colorants, de pigments colorés, de substances faisant office de tampon pour le pH, d'antioxydants, de composés régulateurs de la densité et/ou d'autres constituants, pour préparer, via un mélange intime de ces composants avec un constituant sensible d'agent de lavage ou de nettoyage, un produit de granulation de ce constituant sensible d'agent de lavage ou de nettoyage, qui présente un indice de désintégration d'au moins 50 % après 24 heures et dans lequel les composants (b) et (c) sont présents dans un rapport, en % en poids, de (b) à (c) de 1 : 5 à 20 : 1, de manière particulièrement préférée de 1 : 5 à 5 : 1.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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PL07728143T PL2007863T3 (pl) | 2006-04-20 | 2007-04-16 | Granulat wrażliwego składnika środków piorących lub czyszczących |
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Application Number | Priority Date | Filing Date | Title |
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DE102006018780A DE102006018780A1 (de) | 2006-04-20 | 2006-04-20 | Granulat eines sensitiven Wasch- oder Reinigungsmittelinhaltsstoffs |
PCT/EP2007/053678 WO2007122126A1 (fr) | 2006-04-20 | 2007-04-16 | Granulés d'un produit lavant ou nettoyant sensible |
Publications (2)
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EP2007863A1 EP2007863A1 (fr) | 2008-12-31 |
EP2007863B1 true EP2007863B1 (fr) | 2011-10-19 |
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Application Number | Title | Priority Date | Filing Date |
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EP07728143A Not-in-force EP2007863B1 (fr) | 2006-04-20 | 2007-04-16 | Granulés d'un produit lavant ou nettoyant sensible |
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Country | Link |
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US (1) | US20090156454A1 (fr) |
EP (1) | EP2007863B1 (fr) |
JP (1) | JP2009534493A (fr) |
AT (1) | ATE529499T1 (fr) |
DE (1) | DE102006018780A1 (fr) |
ES (1) | ES2373994T3 (fr) |
PL (1) | PL2007863T3 (fr) |
WO (1) | WO2007122126A1 (fr) |
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EP2859082B1 (fr) | 2012-06-08 | 2019-07-31 | The Procter and Gamble Company | Particules esthétiques visuellement contrastantes possédant une solubilité dans l'eau accrue, particulièrement utiles pour une combinaison avec des compositions pulvérulentes ou granulaires |
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CN111286204B (zh) * | 2020-03-12 | 2021-08-20 | 复旦大学 | 一种遇含水溶剂快速溶解或分散的高分子复合物及其制备方法和应用 |
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2006
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-
2007
- 2007-04-16 ES ES07728143T patent/ES2373994T3/es active Active
- 2007-04-16 AT AT07728143T patent/ATE529499T1/de active
- 2007-04-16 EP EP07728143A patent/EP2007863B1/fr not_active Not-in-force
- 2007-04-16 PL PL07728143T patent/PL2007863T3/pl unknown
- 2007-04-16 JP JP2009505861A patent/JP2009534493A/ja active Pending
- 2007-04-16 WO PCT/EP2007/053678 patent/WO2007122126A1/fr active Application Filing
-
2008
- 2008-10-20 US US12/254,350 patent/US20090156454A1/en not_active Abandoned
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2859082B1 (fr) | 2012-06-08 | 2019-07-31 | The Procter and Gamble Company | Particules esthétiques visuellement contrastantes possédant une solubilité dans l'eau accrue, particulièrement utiles pour une combinaison avec des compositions pulvérulentes ou granulaires |
US11407965B2 (en) | 2017-07-31 | 2022-08-09 | Dow Global Technologies Llc | Detergent additive |
WO2019121311A1 (fr) | 2017-12-21 | 2019-06-27 | Buck Group AG | Additif parfumant pour le linge |
Also Published As
Publication number | Publication date |
---|---|
ATE529499T1 (de) | 2011-11-15 |
ES2373994T3 (es) | 2012-02-10 |
EP2007863A1 (fr) | 2008-12-31 |
PL2007863T3 (pl) | 2012-03-30 |
JP2009534493A (ja) | 2009-09-24 |
US20090156454A1 (en) | 2009-06-18 |
DE102006018780A1 (de) | 2007-10-25 |
WO2007122126A1 (fr) | 2007-11-01 |
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