JP2002500270A - Detergent dish for dishwasher containing soil release agent polymer - Google Patents

Abstract

  (57) [Summary] The present invention provides a molded article containing a builder, an alkali source, a bleach, an enzyme and a surfactant. When the active ingredient (I) containing a component selected from the group consisting of soil release agents is present in an amount of more than 80% by weight of the amount present in a molded body region of 40% by volume or less, high storage stability is obtained. Thus, a very strong detergent molded article having a good aroma and a predetermined solubility can be obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION

TECHNICAL FIELD [0001] The present invention relates to the production and use of detergent moldings, in particular tablets used at home, especially for machines, and detergent moldings. Examples of the tablet include a dishwasher detergent tablet, a laundry detergent tablet, a bleach tablet, a stain remover tablet, and a water softener tablet.

[0002] Detergent compacts, especially tablets, have several advantages over powder compositions, such as ease of handling, ease of dosing, and small packaging capacity.

[0003] Unfortunately, tablets are required to achieve their full dimensional stability and fracture resistance.
Certain problems arise due to the relatively high pressure required to compress the powdered components. In other words, tablets are often subjected to large compressive forces,
Sensitive detergent components (bleaches, fragrances, enzymes, silver protectors, dyes, surfactants, etc.) may have poor storage stability or may have a higher level of stability than other detergent forms containing the same amount of ingredients. Its performance (especially performance against dairy products such as tea and milk, and stains such as starch)
In some cases, the delicate material to be washed is insufficiently protected, and the disintegration and solubility during use of the detergent are impaired.

According to the prior patent literature, some of these problems are said to have been solved.

However, in many cases, consumers cannot reproduce the performance benefits of the patent literature. Accordingly, manufacturers of detergent moldings face an important challenge of providing tablets that will satisfy consumers.

[0006] Therefore, the problem to be solved by the present invention is high performance and easy to handle,
In addition, a detergent molded article having high storage stability, a minimum packaging capacity, an excellent aroma characteristic, a predetermined solubility characteristic and the like that are sufficiently satisfied by a consumer, and a tablet mainly used in a machine especially at home. In particular, to provide laundry detergent tablets, stain remover tablets, water softener tablets and the like.

DISCLOSURE OF THE INVENTION Surprisingly, the above-mentioned object can be attained by allowing certain active ingredients (I) in a molded article to be mainly present in an area of the molded article of 40% by volume or less. There was found.

Accordingly, the present invention provides a molded article containing a builder, an alkali source, a bleaching agent, an enzyme and a surfactant, wherein 80% by weight of the active ingredient (I) containing a component selected from the group consisting of soil release agents is contained. The molded article is characterized by being present in an area of the molded article of not more than 40% by volume in an amount exceeding 40% by volume.

In addition to the components selected from the group consisting of soil release agents, the active ingredient (I) comprises chlorine bleach, oxygen bleach, bleach activator, silver protectant, soil release agent, enzyme, interface It may be an activator, a component (or compound) for controlling solubility, or the like. However, the active ingredient (I) may also be a mixture of these ingredients.

According to a preferred embodiment of the present invention, the active ingredient (I) includes, in addition to a component selected from the group consisting of soil release agents, a solubility controlling component, a bleaching agent, a bleaching activator, A mixture containing at least one other substance selected from the group consisting of a silver protective agent, an enzyme, and a surfactant.

The solubility, surface area, compressibility, storage stability and the like of the region of the molded product containing the active ingredient (I) can have an important influence on the properties of the whole tablet molded product.

According to the invention, preferably, the active ingredient (I) is present in an amount of more than 80% by weight, preferably more than 90% by weight, more preferably more than 95% by weight, most preferably The region of the compact containing 100% by weight is precisely spatially surrounded by the other components of the compact in three directions.

According to one preferred embodiment of the invention, the active ingredient (I) is present in an amount of more than 80% by weight of the amount present, preferably more than 90% by weight, more preferably 95% by weight. More than
Most preferably, the at least one compacted area, contained in an amount of 100% by weight, has a rate of more than 5%, preferably more than 10%, more preferably more than the dissolution rate of the remaining area of the compact. It can be dissolved at a rate of more than 50%, particularly preferably more than 100%.

According to the invention, preferably, the active ingredient (I) comprises more than 80% by weight of the amount present, preferably more than 90% by weight, more preferably 95% by weight. Greater than 40% by volume of the compact, preferably 5 to 30% by volume, more preferably 10 to 25% by volume, most preferably 15 to 20% by volume, in an amount of more than 100% by weight In the compact region.

[0015] Storage at normal home environmental conditions, ie, temperature 15-30 ° C./humidity 5-55% (preferably 15-35%), for 30 days (preferably 60 days, more preferably 90 days). During the period, the shaped body regions containing more than 80% by weight of the amount of active ingredient (I) present increase their weight by not more than 50% by weight, preferably not more than 40% by weight, more preferably not more than 40% by weight. If it is less than 30% by weight, particularly preferably less than 20% by weight, most preferably less than 10% by weight, most preferably less than 5% by weight, the overall properties of the shaped body may be affected in a desirable way. Can be.

Further, under normal home environment conditions, that is, at a temperature of 15 to 30 ° C./humidity of 5 to 55% (preferably 15 to 35%) for 30 days (preferably 60 days, more preferably 90 days) During the storage period, the shaped body region containing more than 80% by weight of the active ingredient (I) present has a weight loss of not more than 50% by weight, preferably not more than 40% by weight, more preferably not more than 40% by weight. If not more than 30% by weight, particularly preferably not more than 20% by weight, most preferably not more than 10% by weight, most preferably not more than 5% by weight, the overall properties of the compact may be affected in a desirable way. Can be.

[0017] Further, under normal home environment conditions, that is, at a temperature of 15 to 30 ° C / humidity of 5 to 55% (preferably 15 to 35%) for 30 days (preferably 60 days, more preferably 90 days). During the storage period, the colored molded body region or the colored component has an absorption maximum of a 1% solution of less than 100 wavenumbers, preferably less than 50 wavenumbers.
Wave number or less, more preferably 30 wave number or less, particularly preferably 20 wave number or less, most preferably 10 wave numbers or less
Below the wavenumber, and most preferably below 5 wavenumbers, the overall properties of the shaped body can be affected as desired.

Further, the molded article of the present invention may contain the active ingredient (I) in an amount of more than 80% by weight, preferably more than 90% by weight, more preferably more than 95% by weight, most preferably more than 95% by weight. Preferably
If the region of the compact, which is contained in an amount of 100% by weight, is spatially accurately surrounded by the other components of the compact in three directions, it has a good influence on the properties of the compact.

Solubility Solubility can be affected by solubility promoting ingredients / compounds (disintegrants) or solubility retarding ingredients / compounds.

Suitable disintegrants are any disintegrants known from the prior art [in particular, Roem
pp (9th edition, volume 6, page 4,440) and Voigt "Lehrbuch der pharmazeutischen Techno
logie "(6th edition, 1998). Particularly suitable disintegrants are substances such as starch, cellulose, cellulose derivatives, alginate, dextran, cross-linked polyvinylpyrrolidone; disintegrant systems containing weak acids and carbonates, especially citric and tartaric acids with bicarbonate or carbonate And polyethylene glycol sorbitan fatty acid esters.

The use of disintegrants is known from the patent literature. Thus, according to DE 938 566, the acetylsalicylic acid is converted to the granular form prior to compression and, after careful but complete drying, the dried granules are coated with highly dispersed silica. The acetylsalicylic acid granules, which have been powdered with highly dispersed silica, can then be mixed with the powder or other forms of the tablet in tablet form and compressed into tablets. The barrier layer of highly dispersed silica not only functions as an insulating layer, but also protects against undesired reactions and contributes to the rapid disintegration of the tablet after prolonged storage.

According to the disclosure of DE 12 28 029, the powder mixture is mixed without pre-granulation with cellulose powder and optionally with highly dispersed silica, and the resulting mixture is
Tablets are preferably made by milling and compression.

According to DE 41 21 127, disintegrants which are particularly effective for the production of pharmaceutical tablets comprise a coating material immobilized on the surface of cellulose particles. This disintegrant is used in particulate form,
It is said that an average particle size of less than 200 μm is particularly advantageous. Thus, in general, in conventional disintegrants for tablets, such as those belonging to the first group of disintegrants described above, the disintegrant is converted to other tablets in the form of very fine particles, fine particles or granules before the compression step. Either the ingredients are mixed or the disintegrant is coated or powdered with other tablet ingredients.

According to the disclosure of EP-B-0 523 099, the disintegrants employed in the manufacture of medicaments can also be used in detergent or cleaning compositions. Disclosed disintegrants include swellable layered silicates such as bentonite, starch / cellulosic natural materials and derivatives thereof, alginate and other potato starch, methylcellulose and / or hydroxypropylcellulose. These disintegrants can be mixed or mixed with the granules to be compressed.

Also according to the disclosure of WO-A-96 / 06156 it is advantageous to incorporate a disintegrant in the detergent tablet. Also in this case, examples of typical disintegrants include sugars such as microcrystalline cellulose and sorbitol, layered silicates, particularly bentonite / smectite type fine particle swellable layered silicates. In addition, effervescent substances such as citric acid, bisulfate, bicarbonate, carbonate and percarbonate are also exemplified as possible disintegrants.

EP-A-0 466 485, EP-A-0 522 766, EP-A-0 711 827, EP-A-0 711 828 and EP
-A-0 716 144 discloses the manufacture of detergent tablets using compressed granular material with a particle size of 180-2,000 μm. The resulting tablet can have both a uniform and a non-uniform structure. According to EP-A-0 522 766, particles containing at least a surfactant and a builder are coated with a binder / disintegrant solution / dispersion. Binder /
As disintegrants, in particular, polyethylene glycol is used, and as other binders / disintegrants, disintegrants as described above, for example starch and its derivatives, commercially available cellulose derivatives, for example crosslinked and modified cellulose, microcrystalline cellulose fibers ,
Crosslinked polyvinylpyrrolidone, layered silicate, and the like are exemplified. In addition, weak acids such as citric acid and tartaric acid used in combination with a carbonate-containing source can also be used as a coating material, and these acids exhibit a foaming action upon contact with water, and according to Roempp's definition, the second group Belongs to the disintegrant.

[0027] The disclosure of DE 197 10 254 (not yet published) is incorporated herein by reference. The disintegrants disclosed in this document have a dust content of at most 1% by weight, preferably less than 1% by weight, and a particle size of less than 10% by weight of the total amount of the disintegrant granules containing the dust is less than 0.2 mm. Such a particle size distribution (sieve analysis). Advantageously, at least 90% by weight of the disintegrant granules have a particle size of at least 0.2 mm and at most 3 mm. Such disintegrants are particularly suitable for the purposes of the present invention.

Also suitable are disintegrators belonging to the group consisting of the organic acids, for example, citric acid, citric acid / bicarbonate mixtures, cellulose and its derivatives. If a disintegrant is present in the shaped body, the dissolution time of the entire shaped body is preferably shorter than the processing time required for the main washing cycle of the prior art dishwasher, less than 40 minutes, preferably 30 minutes. Less than a minute, more preferably less than 20 minutes, and most preferably less than 10 minutes.

In general, paraffins, microwaxes, high molecular weight polyethylene glycols and the like disclosed in detail in the prior art can be used as solubility retarders. The mixtures disclosed in DE 197 27 073 (currently unpublished) are particularly suitable for use in the present invention, the disclosure of which is hereby incorporated by reference.

When the molded article contains a component for dissolving the solubility, the entire dissolution time (20 minutes of cold water)
C) is preferably longer than the pre-rinse cycle time of a commercial dishwasher, more than 5 minutes, preferably more than 10 minutes.

Description of the General Form of the Molded Article The molded article of the present invention can be obtained from prior patent documents and standard technical documents (for example, Riedel, Die Ta
It can take any three-dimensional form, as described in blette). The shaped body region containing the active ingredient (I) is also not restricted to a particular three-dimensional form. However, for practical reasons, dimensions greater than 5 mm in one spatial direction are preferred.

DESCRIPTION OF THE SPECIFIC FORM OF THE MOLD In accordance with one preferred embodiment of the present invention, the present invention provides a uniform or non-uniform shaped body having a known structure.

The moldings according to the invention are in particular cylindrical tablets, which are preferably between 15 and 60 m
m, more preferably 30 ± 10 mm in diameter. The height of such a tablet is preferably between 5 and 30 mm, more preferably between 15 and 28 mm. Particularly preferably, the diameter of the shaped body has been found to be 32, 33, 34, 35, 36, 37, 38 or 39 mm. In certain particularly preferred embodiments, the height of the tablet is 24, 25, 26, 27 or 28 mm.

However, a square, rectangle, trapezoid, ellipse, irregular shape or the like can be advantageously used as the bottom surface of the molded body. The length of the ridge is preferably 15 to 60 mm, more preferably 30 ± 10 mm.

The weight of each molded product (particularly, tablet) is 15 per molded product or tablet.
6060 g is preferred, and 20-40 g is more preferred. In contrast, the density of the shaped body or tablet usually appears to be greater than 1 kg / dm ³ , preferably 1.1-1.4 kg / dm ³ .

According to the present invention, depending on the particular application, the hardness range of the water, the nature of the soil to be removed, etc., one or more molded bodies, for example 2 to 4 molded bodies, in particular tablets Can be used. Other compacts of the present invention can have even smaller (eg, as small as 10 mm) diameters or dimensions.

As used herein, the term “homogeneous molded article” refers to a component of the molded article (excluding the molded article region containing the active ingredient (I)) in which the difference between each component and the active substance Means a compact that is distributed so uniformly as to be indistinguishable to the naked eye. of course,
The solid granular structure used can be identified. According to one preferred embodiment of the invention, there is only one other shaped body region (layer) except for the shaped body region containing the active ingredient (I).

Accordingly, the term “heterogeneous shaped body” as used herein refers to the active ingredient (
The components other than I) mean a molded article that does not need to be uniformly distributed. As a simple example, heterogeneous shaped bodies can be produced, for example, by the addition of different colorant components and / or different fragrance components.

Another example, which is treated according to the invention as a non-uniform (non-uniform) molding, is that, besides the molding region containing the active ingredient (I), several layers (phases), ie at least 2 This is the case when a molded body composed of two layers is compressed. For example, these various layers can have different disintegration and dissolution rates and / or can contain different components. Thereby, the molded body can obtain advantageous performance characteristics.
For example, if a tablet contains more than one component that can adversely affect each other, these components can be separated from each other. In a cleaning apparatus, a layer that incorporates one (or more) components into a faster, disintegrating and / or dissolving layer, while dissolving the other components more slowly, if the cleaning conditions are arranged in a particular order. So that one of the components can be pre-acted or
Alternatively, the reaction can be terminated by the time the dissolution of the other components starts.

According to one preferred embodiment of the invention, in addition to the shaped body region containing the active ingredient (I), there are two layers as separate layers. Particularly preferably, the volume ratio of these two layers is between 10: 1 and 1:10, preferably between 5: 1 and 1: 5, more preferably between 2: 1 and 1: 2.

In another particularly preferred embodiment, as further layers, there are three or more layers.

The layer structure of the shaped body can take the form of a stack, in which the inner layer can dissolve at its edges before the outer layer has completely dissolved or collapsed. However, as an alternative, another layer may be placed on the lateral side of the inner layer to completely surround the inner layer, thereby preventing / delaying premature dissolution of the components of the inner layer. Can be.

According to another preferred embodiment of the present invention, the tablet comprises at least three layers (ie 2
One outer layer + at least one inner layer). In this case, the peroxy bleach is present in at least one of the inner layers, while no peroxy bleach is present in the two outer layers (stacked tablets) or the outermost layers (shell or jacket tablets). In another possible embodiment, the peroxy bleach and the bleach activator or the bleach catalyst and / or the enzyme can be present spatially separated from one another in the same tablet / mold. Such an embodiment has the advantage that in the shaped body of the invention, any danger of undesired interactions can be eliminated.

According to one preferred embodiment of the present invention, the bleaching component, especially the chlorine component, does not form a layer with the fragrance component. According to another preferred embodiment of the present invention, the silver protectant component does not comprise a bleach component. According to another preferred embodiment of the invention, the solubility controlling component is constituted together with a bleach activator. According to another preferred embodiment of the present invention, the solubility controlling component is constituted together with the enzyme. According to another preferred embodiment of the present invention, the solubility controlling component is constituted together with a bleaching agent. According to another preferred embodiment of the present invention, the solubility controlling component is comprised together with a silver protectant component. According to another preferred embodiment of the present invention, the solubility controlling component comprises at least 50% by weight, preferably 70% by weight of the total amount of the surfactant or the total surfactant mixture.
More preferably more than 90% by weight.

Method for Producing a Molded Article The molded article of the present invention can be produced by any of the methods usually used for producing molded articles.

According to some embodiments, the shaped body region containing the active ingredient (I) is surrounded in liquid form (very commonly in solution and / or melt form), optionally at an elevated temperature, It has proved to be particularly suitable to introduce the components into the preformed recesses and then to solidify the shaped body regions by conventional methods (very commonly drying and / or cooling). Also, the viscosity should be greater than 1,500 mPas, preferably greater than 2,000 mPas, more preferably from 2,000 to 15,000 mPas, most preferably from 2,500 to 7,000 mPas, particularly preferably from 3,000 to 4,000 mPas. Turned out to be particularly effective.

The carrier component active ingredient (I) has proven to be particularly effective when combined with a molten carrier material. The molten carrier material is, as a rule, at room temperature or in particular above room temperature,
It is a substance that solidifies.

According to the invention, particularly suitable carrier materials are nonionic surfactants (registered trademark:
Dehypon T104, registered trademark: Dehypon LS54, registered trademark: Dehydol LS30, registered trademark:
Lutensol AT80), polyethylene glycol of various molecular weights (PEG400, 12,000), soap (registered trademark: Lorol C16), stearate (registered trademark: Cutina GMS), thickening caustic soda and meltable salts such as sodium carbonate decahydrate And so on. The strengths and weaknesses of each component can be replicated by experts in testing.

According to the invention, a particularly preferred melting component (fusible component) is a wax. The term `` wax '' as used herein generally refers to a material that melts without decomposition at temperatures above 40 ° C. and has a relatively low viscosity and is non-viscous at temperatures slightly above the melting point. Means a natural or synthetic substance. Wax consistency and solubility are highly temperature dependent.

The wax wax in accordance with the sampling source, three groups, i.e. natural wax is classified into chemical modified wax Contact and synthetic waxes.

Natural waxes include, for example, candelilla wax, carnauba wax, wood wax, esparto wax, colcrow, Guaruma wax, rice bran oil wax, sugarcane wax, Ouricury wax, or montan wax; beeswax, shellac Animal waxes such as wax, whale wax, lanolin (wool wax) and tail gland oil; mineral waxes such as ceresin and ozokerite (ground wax); and petrochemical waxes such as petrolatum, paraffin wax and microwax.

The chemically modified wax includes, for example, hard wax, montan ester wax, Sassol (Sass
ol) wax, hydrogenated jojoba wax and the like.

[0053] Synthetic waxes are generally understood to be polyalkylene waxes and polyalkylene glycol waxes.

The term “wax” as used herein also includes, for example, so-called wax alcohols. Wax alcohols are C ₂₈ -C ₄₀ fatty alcohol water insoluble relatively high molecular weight. Wax alcohols are present as a major constituent of many natural waxes, for example in the form of wax esters of relatively high molecular weight fatty acids (waxic acid). Examples of wax alcohols include lignoceryl alcohol (1-tetracosanol), melisyl alcohol, and the like. The molten component may contain wool wax alcohol, such as lanolin, which is a triterpene and considered to be a steroid alcohol. According to the invention, fatty acid glycerol esters and fatty acid alkanolamides and, if desired, water-insoluble or substantially water-insoluble polyalkylene glycol compounds can also be used, at least in part, as one component of the melt component.

The molten component preferably contains mainly paraffin wax. That is, at least 50% by weight, preferably 50% by weight or more of the molten component is composed of paraffin wax. In the jacket melt component, the content of paraffin wax is about 60% by weight, 70% or 80% by weight is especially preferred, higher paraffin wax content, for example a content of more than 90% by weight is most preferred. is there. According to a preferred embodiment of the present invention, the molten component is paraffin wax in its entirety.

According to the present invention, the paraffin wax does not contain any hydrolyzable groups, and thus is not hydrolyzed in an alkaline detergent environment in contrast to wax esters and the like. Advantages over natural wax.

The paraffin wax is composed of an alkane as a main constituent, and a small amount of isoalkane and cycloalkane. The paraffin wax used in the present invention preferably does not contain any components having a melting point higher than 70 ° C, more preferably higher than 60 ° C. In paraffin, high-melting alkane components leave undesirable wax residues on surfaces such as dishes to be washed when the wash liquor temperature is reduced to the above temperature. This should be avoided since wax residues generally leave an unpleasant appearance on the cleaning surface. The jacket melting component of the present invention preferably contains at least one paraffin wax having a melting point of about 57C to about 60C.

The paraffin wax used in the present invention is preferably at ambient temperature (typically about 10 to about 30).
° C) and contains a high content of alkanes, isoalkanes and cycloalkanes. According to the invention, the wax component, which is solid at room temperature, is more preferably used in a higher proportion and present in the wax. The impact / wear resistance of the jacket melt component increases as the percentage of solid wax component increases, resulting in longer lasting protection of the jacketed particles. When the oil or liquid wax component is contained at a high concentration, the jacket melt component has a reduced strength and pores are formed, so that the particles formed from the melt component are exposed to the environment as described above. .

At an unusually low temperature, for example below 0 ° C., the solidified molten component can collapse by impact or friction. To improve the stability at such low temperatures, additives can be incorporated into the molten components. Suitable additives must have the following requirements: they must be completely miscible with the molten wax, must not substantially alter the melting range of the jacket melt component, and must have low temperature elasticity of the solidified melt component. To improve,
In general, do not increase the permeability of the solidified molten component to moisture / moisture and do not increase the viscosity of the melt of the jacket material so that processing is difficult or impossible. Suitable additives reduce the brittleness of jackets consisting essentially of paraffin at low temperatures, such as EVA copolymers, methyl esters of hydrogenated resin acids, polyethylene, copolymers of ethyl acrylate and 2-ethylhexyl acrylate, and the like. Is mentioned.

In addition to paraffin, the molten component can contain one or more of the above-mentioned waxes or wax-like substances as its main constituent. Basically, the properties of the mixture for forming the jacket should be such that the jacket is at least substantially insoluble in water. Solubility in water is about 10 m at a temperature of about 30 ° C
The solubility should not exceed g / l and less than 5 mg / l is preferred.

The mixtures disclosed in DE 197 10 254 (not yet published) are particularly suitable for the purposes of the present invention, the disclosure of which is incorporated herein.

According to another preferred embodiment of the invention, a part of the shaped body and / or the components of the shaped body are irradiated with microwaves in order to have a good effect on their strength, moisture content and solubility. Can be treated by exposure to

However, each component may be simply compressed. In this case, in addition to powders and granules, microtablets and compacts smaller in size than the final compact can be used.

[0064] As used soil release agent present invention, the specific active ingredient (I) is a so-called soil release agent, which, after the first wash, or prevent re-contamination of the surface, already It is a substance that promotes separation of the removed dirt.

The soil release agent used in the present invention includes any known compounds. For example, cationic polymers described in the following documents are particularly suitable.

According to EP-A-0 167 382, EP-A-0 342 997 and DE-OS 26 16 404, cationic polymers are added to cleaning compositions to create streaks on the surface of dishes and the like. Can be washed without leaving.

EP-A-0 167 382 discloses a liquid cleaning composition containing a cationic polymer as a thickening agent. Particularly preferred cationic polymers include hydroxypropyltrimethylammonium guar, copolymers of aminoethyl methacrylate and acrylamide, and copolymers of dimethyldiallylammonium chloride and acrylamide.

EP-A-0 342 997 discloses a multipurpose cleaning agent comprising a cationic polymer, in particular employing polymers containing imino groups.

DE-OS 26 16 404 discloses a glass cleaning composition containing a cationic cellulose derivative. By adding this cationic cellulose derivative to the composition, better drainage is ensured, and washing is performed so that no streaks remain on the glass surface.

EP-A-0 467 472 discloses, for example, hard surface cleaning compositions containing cationic homopolymers and / or copolymers as soil release agents. These polymers contain quaternized ammonium alkyl methacrylate groups as monomer units. These compounds are used to treat hard surfaces so that dirt can be more easily washed off the hard surfaces during the second wash.

Particularly suitable cationic polymers as soil release agents are: copolymers such as trialkylammonium alkyl acrylates (methacrylates) or acrylamide monomers; dialkyl diallyl ammonium salts; ethers or esters of polysaccharides; Polymer-like reaction products with side-chain ammonium groups, especially guar, cellulose and starch derivatives; ethylene oxide polyadducts of compounds containing ammonium groups; quaternary ethyleneimine polymers, and polyamides and polyesters containing quaternary side groups.

Further, as the soil release agent, natural polyuronic acid and its related substances are also suitable, and a polyampholyte and / or a hydrophobized polyampholyte are also suitable.

Enzymes According to the present invention, the washing performance of detergents / detergents is improved by adding 0 to 5% by weight of enzymes, based on the total amount of detergents / detergents, and under more mild conditions. The same quality cleaning performance can be guaranteed. The most commonly used enzymes include lipolytic enzymes (lipases), starch hydrolases (amylases), cellulases and proteolytic enzymes (proteases). Preferred proteases are
For example, BLAP® 140 (Biozym), Optimase® M-440 and Opti
clean® M-250 (Solvay Enzymes); Maxacal® CX and Max
apem (registered trademark) or Esperase (registered trademark) (Gist Brocades), Savinase (registered trademark) (Novo) and the like. Particularly preferred cellulases and lipases are Celluzym® 0.7T and Lipolase® 30T, respectively (Novo Nordisk). Particularly suitable amylases are Duramyl® and Termamyl® 60T and Termamyl® 90T (Novo), Amylase-LT® (Solvay Enzymes) and Maxamyl® P5000 (Gist Brocades). Other enzymes can also be used.

Oxygen bleach The specific active ingredient (I) used in the present invention is an oxygen bleach, preferably an alkali metal perborate and a hydrate thereof, and an alkali metal percarbonate. And
In the present invention, it is preferable to use sodium perborate (monohydrate or tetrahydrate) or sodium percarbonate and its hydrate. Persulfates can also be used.

However, organic peracids can be used as other representative oxygen bleaches.
Examples of suitable organic acids are, in particular, the very effective phthalimidoperoxycaproic acids, but in principle other known peracids can also be used.

[0076] As used bleach activators present invention, the specific active ingredient (I) is a bleach activator. Known bleach activators are compounds containing one or more N- or O-acyl groups, for example compounds selected from anhydrides, esters, imides and acylated imidazoles or oximes. Examples include tetraacetylethylenediamine (TAED), tetraacetylmethylenediamine (TAMD), tetraacetylhexylenediamine (TAHD), pentaacetylglucose (PAG), 1,5-diacetyl-2,2-
Examples include dioxohexahydro-1,3,5-triazine (DADHT) and isatoic anhydride (ISA).

[0077] bleach activators used are the perhydrolysis (perhydro lysis) conditions, aliphatic peroxocarboxylic acids, preferably C _{1 ~ 10} (preferably C _{2 ~ 4} are) aliphatic Peruokisoka carboxylic acid And / or compounds that form unsubstituted or substituted perbenzoic acids. Substances containing O- and / or N-acyl groups and / or unsubstituted or substituted benzoyl groups having the stated number of carbon atoms are preferred. Suitable bleach activators include polyacylated alkylenediamines, especially tetraacetylethylenediamine (TAED), acylated triazine derivatives, especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT) ), Acylated glycolurils, especially tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS)
Carboxylic anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate, and 2,5-diacetoxy-2,5-hydrofuran, n-methylmorpholinium acetonitrile methyl sulfate ( MMA). Further suitable bleach activators include enol esters (DE 196
16 693 and DE 196 16 767), acetylated sorbitol, mannitol and mixtures thereof (EP 0 525 239, SORMAN), acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetylfructose, tetraacetylxylose and Octaacetyl lactose, acetylated (optionally N-alkylated) glucamine and gluconolactone and / or N-acylated lactam,
For example, N-benzoylcaprolactam (WO94 / 27970, WO94 / 28102, WO94 / 2810
3, WO95 / 00626, WO95 / 14759 and WO95 / 17498). It is also preferred to use hydrophilically substituted acylacetals (DE 196 16 769) and acyl lactams (German Patent Applications DE 196 16 770 and WO 95/14075). Also,
Combinations of the usual bleach activators (DE 44 43 177) can also be used. Such bleach activators are used in conventional amounts, preferably 1 to 10% by weight, more preferably 2 to 8% by weight, based on the total detergent / washing agent.

Bleaching Catalyst In addition to or instead of the conventional bleach activators described above, sulfonimides (
European patents EP 0 446 982, EP 0 453 003) and / or bleach-promoting transition metal salts or complexes can be used as so-called bleach catalysts. Examples of suitable transition metal compounds include, in particular, the following: German Patent Application DE 195 2
9 905 described manganese-, iron-, cobalt-, ruthenium- or molybdenum-selenium complexes and their N-analogs (German Patent Application DE 196 20 267), manganese- described in German Patent Application DE 195 36 082, Iron-, cobalt-, ruthenium- or molybdenum-carbonyl complexes, manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper containing nitrogen-containing tripod ligands according to DE 196 05 688 Complexes, cobalt-, iron according to German Patent Application DE 196 20 411
-, Copper- and ruthenium-ammine complexes, manganese, copper and cobalt complexes described in German Patent Application DE 44 16 438, cobalt complexes described in European Patent Application EP 0 272 030, manganese complexes described in European Patent Application EP 0 693 550 Manganese, iron, cobalt and copper complexes according to EP 0 392 592, EP 0 443 651 or EP 0 458 397, EP 0 458 398, EP 0 549 271, EP 0 549 272, EP 0 A manganese complex according to 544 490 and EP 0 544 519. Combinations of bleach activators with transition metal bleach catalysts are known, for example, from German patent applications DE 196 13 103 and WO 95/27775. Preferably, polyacylated alkylenediamines, especially tetraacetylethylenediamine (TAED), N-acylimides, especially N-nonanoylsuccinimides (NO
SI), an acylated phenolsulfonate, especially a bleach activator selected from the group consisting of n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), MMA, in a dose of detergent / wash Based on the entire agent, preferably
Up to 10% by weight, more preferably 0.1 to 8% by weight, most preferably 2 to 8% by weight, particularly preferably 2 to 6% by weight.

Bleaching-promoting transition metal complexes, especially complexes containing Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru as central atom, preferably salts of manganese and / or cobalt and / or The complex, more preferably the cobalt (ammine) complex, cobalt (acetate) complex, cobalt (carbonyl) complex, chloride of cobalt or manganese, and manganese sulfate are present in representative amounts. The preferred dose is preferably in an amount of up to 5% by weight, more preferably in an amount of 0.0025 to 1% by weight, most preferably in an amount of 0.01 to 0.25% by weight, based on the total detergent / cleaning agent. . However, in special cases, higher amounts of bleach activator can also be used.

Anticorrosive The dishwasher detergent of the present invention can contain an anticorrosive as an active ingredient (I) to protect tableware or the dishwasher itself. Silver protectants are particularly important for the protection of dishwashers. Known anticorrosives, for example DE 43 25 922, DE
The substances described in 41 28 672 and DE 43 38 724 can be used. In particular, silver protectants selected from the group consisting of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and transition metal salts or complexes can generally be used. Benzotriazole and / or alkylaminotriazole are particularly preferred. in addition,
Dishwashing detergents often include active chlorine-containing anticorrosives, which can significantly reduce corrosion of silver surfaces. According to the above references, chlorine-free dishwashing detergents comprise, in particular, redox-active organic compounds containing oxygen and nitrogen, such as dihydric and trihydric phenols, examples of which include hydroquinone, pyrocatechol , Hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol, and derivatives of these compounds. Also often, salt and complex inorganic compounds, such as Mn,
Metal salts such as Ti, Zr, Hf, V, Co, Ce are also used. Of these, transition metal salts selected from the group consisting of salts and / or complexes of manganese and / or cobalt are preferred, and cobalt (ammine) complexes, cobalt (acetate) complexes,
Cobalt (carbonyl) complexes, chlorides of cobalt or manganese and manganese sulfate are particularly preferred. Zinc compounds can also be used to prevent corrosion of tableware.

Other Detergent / Detergent Components According to the molded article of the present invention, as long as the other detergent / detergent components satisfy the above-mentioned requirements for the molded article area of the present invention, the above-mentioned active ingredient (I) is All can function as other detergent / cleaning ingredients.

Builders Water-soluble and water-insoluble builders can be used in the detergents / cleaners of the present invention, especially for sequestering calcium and magnesium ions. Water-soluble builders are preferred as builders because they generally have less tendency to form insoluble residues on tableware and hard surfaces. In accordance with the present invention, representative builders, which may be present in an amount of 10-90% by weight, based on the total composition, include low molecular weight polycarboxylic acids and salts thereof, homopolymer / copolymer polycarboxylic acids and salts thereof, carbonates, Phosphates and silicates. Similarly, water-insoluble builders that can be used in the present invention include zeolites and mixtures of zeolites with the above builders.

Preferably, trisodium citrate, pentasodium tripolyphosphate, sodium bicarbonate, gluconate and the like are used, and silicate builders such as disilicate and / or metasilicic acid are used.

Alkali Source An alkali source can be present as a further component. Examples of the alkali source include an alkali metal hydroxide, an alkali metal carbonate, an alkali metal hydrogencarbonate, an alkali metal sesquicarbonate, an alkali metal silicate, an alkali metal metasilicate, and a mixture of these substances. According to the invention, alkali metal carbonates, in particular sodium carbonate, sodium hydrogen carbonate or sodium sesquicarbonate, are preferably used.

[0085] Builder systems containing a mixture of tripolyphosphate and sodium carbonate are particularly preferred.

Another particularly suitable builder system contains a mixture of tripolyphosphate, sodium carboxylate and sodium disilicate.

Surfactant The specific active ingredient (I) used in the present invention is a surfactant. In principle, any type of surfactant can be used as active ingredient (I). Preferably, non-ionic surfactants, especially low-foaming non-ionic surfactants, can be used, but other low-foaming surfactants can also be used. Particular preference is given to using alkoxylated alcohols, in particular ethoxylated and / or propoxylated alcohols, alkylpolyglycosides, alkylpolyglucamides and the like.

Alkoxylated alcohol The term "alkoxylated alcohol" as used herein refers to the reaction product of an alkylene oxide and an alcohol. According to the present invention, preferably, the ethylene oxide used, also alcohol as an alkylene oxide, relatively long-chain alcohols, e.g., C ₁₀ -C ₁₈ alcohols, preferably C ₁₂ -C ₁₆ alcohols, more suitably is _{C 11, C 12, C 13} , C 14, C 15, C 16, C 17 and C _18, such as the use alcohol. Generally, starting from n moles of ethylene oxide and 1 mole of alcohol, depending on the reaction conditions,
Complex mixtures of adducts with different degrees of ethoxylation are formed. According to another preferred embodiment of the invention, a mixture of alkylene oxides is used, preferably a mixture of ethylene oxide and propylene oxide. If desired, end-capped alcohol ethoxylates can also be used in the present invention, which can be obtained by etherification with a short-chain alkyl group, preferably a butyl group, in the final step.
According to the invention, highly ethoxylated fatty alcohols or mixtures of this highly ethoxylated fatty alcohol with end-capped fatty alcohol ethoxylates are particularly preferred.

Alkyl polyglycosides Alkyl polyglycosides are surfactants which can be obtained by the reaction of sugars and alcohols in the usual way, depending on the production process employed, monoalkylated oligomeric or polymeric saccharide mixtures. Is obtained. Preferred alkyl polyglycosides are alkyl polyglucosides. According to a preferred embodiment of the present invention, the alcohol is a long-chain fatty alcohol or a mixture thereof, and the sugar has a degree of oligomerization of 1-10.

Polyhydroxylamide (Glucamide) of Fatty Acid Polyhydroxylamide (glucamide) of fatty acid is a reaction product obtained by reductively aminating a sugar (glucose) with ammonia and acylating the same. As acylating agents, long-chain fatty acids, long-chain fatty acid esters or long-chain fatty acid chlorides are generally used. When methylamine or ethylamine is used in place of ammonia in the reductive amination treatment, a secondary amide is formed (for example, SOEFW Journal, 11
9 (1993) 794-808). The fatty acid moiety, it is good suitable to use a carbon chain length of C ₆ -C _12.

Colored molded body region The molded body region of the molded body can be colored. As a particularly preferred specific example,
In the molded body, at least one region or all regions among the plurality of molded body regions can be colored with different colors. According to one preferred embodiment of the present invention, it is colored red. According to another preferred embodiment of the invention, it is colored green. According to yet another preferred embodiment of the present invention, it is colored yellow. According to yet another preferred embodiment of the present invention, the mixture is colored in a mixture of various colors.

Storage stability The storage stability of the shaped body is particularly important. According to a preferred embodiment of the present invention,
During normal household environmental conditions, i.e., a temperature of 15-30C / humidity 5-55% (preferably 15-35%) and a storage period of 30 days (preferably 60 days, more preferably 90 days), The increase in the weight of the shaped body region containing the active ingredient (I) is up to 50% by weight, preferably up to 40% by weight, more preferably up to 30% by weight, most preferably up to 20% by weight, particularly advantageously Is less than 10% by weight, most preferably less than 5% by weight.

According to another preferred embodiment of the present invention, normal domestic environmental conditions, ie a temperature of 15
During storage for 30 days (preferably 60 days, more preferably 90 days) at -30 ° C / humidity 5-55% (preferably 15-35%), the active substance of the active ingredient (I) The loss is less than 50% by weight, preferably less than 40% by weight, more preferably less than 30% by weight, most preferably less than 20% by weight, and very particularly preferably less than 10% by weight, most preferably less than 5% by weight. % By weight or less.

According to another preferred embodiment of the present invention, normal domestic environmental conditions, ie, a temperature of 15
-30 ° C / humidity 5-55% (preferably 15-35%) and storage period of 30 days (preferably 60 days, more preferably 90 days) during the storage period of 30 days (preferably 60 days, more preferably 90 days). The absorption maximum of a 1% solution is at most 100 wavenumbers, preferably at most 50 wavenumbers, more preferably at most 30 wavenumbers, most preferably at most 20 wavenumbers, particularly preferably at most 10 wavenumbers, particularly preferably at most 10 wavenumbers. 5 or less.

Example The following components were mixed and compressed into a compact. Components shown in parentheses in the table are examples of the corresponding substance group, and other substances described in this specification can be used instead. The starting compositions belong to the preferred embodiments of the present invention.

[0096] In the detergent performance measurement test, the selected specific active ingredient (I) was transferred to the molded body area of the present invention. In the other molding areas, the particular active ingredient (I) selected was reduced or completely removed according to the invention before the test was carried out.

In Table 1 below, Ra means possible starting composition and Va means test composition (number =% by weight).

[Table 1]

The builder system of the starting composition can have the composition in Table 2 below (all other components are the same as a).

[Table 2]

Examples of alternative starting compositions (R) and test compositions (V) of the present invention are shown in Table 3 below (
Numerical value = wt%).

[Table 3]

Further examples (% by weight) of the starting composition (R) and the test composition (V) according to the invention are given in Table 4 below.

[Table 4]

Further examples (% by weight) of the starting composition (R) and the test composition (V) according to the invention are given in Table 5 below.

[Table 5]

Further examples (% by weight) of the starting composition (R) and the test composition (V) according to the invention are given in Table 6 below.

[Table 6]

Further examples (% by weight) of the starting composition (R) and the test composition (V) according to the invention are given in Table 7 below.

[Table 7]

Further examples (% by weight) of the starting composition (R) and the test composition (V) according to the invention are given in Table 8 below.

[Table 8]

Another starting composition (R) (% by weight) and a test composition (V) were tested.

[Table 9]

If the moldings according to the invention contain several layers, each composition can consist of the components of an individual layer. In other words, in such a case, the proportions are based on the composition of each layer, rather than on the whole composition as usual.

Each composition may, of course, contain only small amounts of other components typical for MDWM (eg, fillers, preservatives, etc.), in which case the content of the other components should be changed accordingly. It is.

The production of the shaped bodies according to the invention comprises, in another context, the steps known to the expert in the art. A preferred embodiment of the molded article of the present invention comprises a concave portion in the tablet, in which the active ingredient (I) is present. The production is preferably carried out by forming a concave portion in the molded body and filling the formed concave portion with the active ingredient (I). This recess can be formed by a Korsch rotary press. In this example, a Fette tableting machine was used. Select a circular tablet press die (26 x 36 mm), use a punch to form a recess with a depth of 5 mm on one side, and select the bottom of this recess to be able to inject a volume of 1 ml. After that, the surface of the tablet was smoothed again.

Next, the liquid mixture of paraffin and active substance (I) was poured and cooled. This cooling process can be facilitated by conventional methods and equipment.

When a polymer was used as the soil release agent, the second substance (paraffin) could be removed due to the specific thermoplastic properties of the polymer.

As described above, according to the present invention, in the corresponding composition around the filled molding region, the active ingredient (I) has its dosage reduced beforehand. In this example and the test, the active ingredient (I) was removed from the surrounding area.

The tablets of the present invention have been found to be superior when compared to homogeneous tablets and several commercially available tablets in which the active ingredient form does not correspond to the present invention.

The properties of the detergents / detergents of the present invention were tested using enzyme-based stains as an example and compared to known detergents / detergents.

The detergent / cleaner of the present invention was also tested for its various properties under conditions simulating actual conditions of use by non-technically trained testers and compared to uniform tablets. did. Except for detergent / detergent dosage instructions and general safety instructions, the tester did not give any instructions on detergent / detergent handling when testing using a commercial dishwasher. This comparative test gave particularly good results. In particular, the cleaning action was evaluated to be good.

In the test, the starting compositions Ra and Va1 were used, a comparative sample containing the surfactant active substance (I) in a homogeneous distribution in the tablet, and the active chlorine as another component (particularly the enzyme). A sample containing the surfactant active substance (I) according to the present invention so as to be largely separated from the (component) was employed.

The test results using the soil release agent active ingredient (I) were obtained at 55 ° C. by a standard program. In the mixture corresponding to composition Ra or Va1, up to 2% by weight of polyuronic acid, cationic polymer and hydrophobized polyampholyte were used independently of one another, but the builder was omitted. The cleaning performance on milk and starch based soils obtained by the following cleaning cycle was 10-30% better than the untreated samples.

The above cleaning performance was able to be identified even when paraffin was not used.
However, this cleaning performance could be similarly identified using paraffin with a melting point of 40-44 ° C. This washing performance is even more remarkable for paraffin having a melting point of 46 to 48 ° C. Furthermore, the cleaning performance is particularly pronounced with paraffins having a melting point of 57-60 ° C.

As shown by the above results, the tablets of the present invention are superior to the conventional dishwasher detergent tablets.

In the following example, a melt dispersion of a soil release agent polymer in a shell forming material was prepared. A tablet having a concave portion (weight 24 g) was produced by compression using a punch having a projection. The composition is given in Table 11 below, in weight percent based on the premix (and thus the recessed tablet).

[0120]

Table 10 Composition of premix (% by weight)

The melt dispersions SDE 1 to SDE 3 were prepared by heating the shell-forming material and stirring it in the solid active substance (soil release agent). Their compositions are given in Table 12 below in weight percent based on the melt.

[Table 11] ☆ Hydroxycellulose, quaternary (Amerchol)

The molten dispersion was introduced into the above-described molded body and cooled. Before filling, the compact
Each molded body weighed 24 g and was filled with 1.3 g of the molten dispersion. Melt dispersion SDE 1
The cleaning performance of molded articles E1 to E5 filled with SDE5 was tested against various stains. For this test, milk, egg yolk and autoflakes were used to form a soil paste for testing, which was washed in a commercial dishwasher.

The cleaning performance of the tablet against stains was visually evaluated by an expert on a scale of 0 to 10. Note that the evaluation point “0” indicates that cleaning was not performed at all, and the evaluation point “10” indicates a state in which dirt was completely removed.

The scoring points for soil removal were measured under 55 ° C./water 16 ° d hardness cleaning conditions (ie, “hardness conditions”) in the main cleaning cycle. The dishwasher used was Miele
G 590 (general purpose program). Table 13 below compares the cleaning performance of tablets E1-E3 with unfilled tablet V.

[Table 12]

As shown by the above results, the tablets E1 to E3 of the present invention are superior to the comparative tablet V.

────────────────────────────────────────────────── ─── Continued on the front page (72) Thomas Müller-Kirschbaum, Federal Republic of Germany Day-42653 Solingen, Lutzowstrasse 75 Otto-Hahnstrasse 185 (72) Inventor Thomas Mailer Federal Republic of Germany Day 40593 Düsseldorf, Göppinger Straße 4 (72) Inventor Hans-Josef Beerwien Federal Republic of Germany Day 41439 Dolmagen, Karl-Friedrich -Schinkel-Strasse 43 (72) Inventor Bernd Richter Germany Day-42799 Reichlingen, In den Weiden # 61 F-term (reference) 4H003 AC05 AC08 AC23 BA17 DA01 DA03 DA19 EA08 EA09 EA15 EA16 EA20 EB02 EB03 EB08 EB12 EB20 EB21 EB22 EB24 EB26 EB36 EB40 EB42 EC01 EC02 EE05 EE07 FA15 FA16 FA25 FA43

Claims (20)

[Claims] 1. A molded article containing a builder, an alkali source, a bleaching agent, an enzyme and a surfactant, in an amount exceeding 80% by weight of the active ingredient (I) containing a component selected from the group consisting of soil release agents. Is a molded body characterized by being present in a molded body region of 40% by volume or less. 2. The shaped body region of 1 to 30% by volume, preferably 2 to 25% by volume, especially 3 to 20% by volume of the shaped body, represents more than 90% by weight of said active ingredient (I). 2. The shaped body according to claim 1, comprising an amount of more than 95% by weight, preferably of 100% by weight. 3. The active ingredient (I) is a substance selected from the group consisting of chlorine bleach, oxygen bleach, bleach activator, silver protectant, enzyme, solubility controlling component and other components. 2. The molded article according to claim 1, which is a mixture. 4. The method according to claim 1, wherein the at least one oxygen-based bleach is a substance selected from the group consisting of alkali metal perborates, alkali metal percarbonates, organic peracids and hydrogen peroxide. The molded article according to any one of the above. 5. The active ingredient (I) is a mixture of a soil release agent and a molten component selected from the group consisting of surfactants, paraffins, microwaxes and relatively high molecular weight polyethylene glycols. 5. The molded article according to any one of 1 to 4. 6. A bleach activator which is preferably a polyacylated alkylenediamine, especially tetraacetylethylenediamine (TAED), an N-acylimide, especially N-nonanoylsuccinimide (NOSI), an acylated phenolsulfonate, especially n-nonanoyl or Isononanoyloxybenzenesulfonate (n- or iso-NOBS
) And n-methylmorpholinium acetonitrile methyl sulfate (MMA), and / or manganese salts or complexes, cobalt salts or complexes, preferably cobalt (amine) complexes, cobalt ( (Acetate) complex, cobalt (carbonyl) complex, a substance selected from the group consisting of cobalt chloride, manganese chloride and manganese sulfate, and the amount thereof is preferably 1 to 10% by weight, based on the total amount of the molded body. The molded article according to any one of claims 1 to 5, more preferably 2 to 8% by weight. 7. The builder as a gluconate, a low molecular weight polycarboxylic acid and its salts, homopolymer and copolymer polycarboxylic acids and their salts, carbonates, phosphates and silicates, preferably citrate. One or more substances selected from the group consisting of silicate builders such as trisodium silicate and / or pentasodium tripolyphosphate, sodium carbonate, sodium bicarbonate, sodium gluconate, disilicate and metasilicate; The molded article according to any one of claims 1 to 6, which is used. 8. The molded product according to claim 1, wherein the builder system includes a mixture of tripolyphosphate, sodium carbonate, and sodium silicate. 9. The surfactant is a non-ionic surfactant, preferably a low-foaming non-ionic surfactant, more preferably an alkoxylated and / or propoxylated fatty alcohol, an alkyl polyglycoside. The molded article according to any one of claims 1 to 8, wherein the molded article is selected from the group consisting of, alkyl polyglucamide and a mixture thereof. 10. The silver protecting agent, wherein at least one substance selected from the group consisting of triazole, benzotriazole, bisbenzotriazole, aminotriazole, alkylaminotriazole and a salt or complex of a transition metal, preferably benzotriazole The molded article according to any one of claims 1 to 9, wherein a triazole and / or an alkylaminotriazole is used. 11. The transition metal salt is a manganese salt or complex, a cobalt salt or complex, preferably a cobalt (amine) complex, a cobalt (acetate) complex, a cobalt (carbonyl) complex, a cobalt chloride, a manganese chloride. 11. The molded article according to claim 10, wherein the molded article is selected from the group consisting of manganese sulfate. 12. The molded article according to claim 1, wherein the solubility controlling component is selected from the group consisting of paraffins, microwaxes and high molecular weight polyethylene glycols. 13. The molded article according to claim 1, wherein the solubility controlling component is selected from the group consisting of an organic acid such as citric acid, a mixture of citric acid and bicarbonate, cellulose and a cellulose derivative. . 14. The molded article according to claim 1, wherein the bleaching component, particularly the chlorine bleaching agent, does not constitute one layer together with the fragrance component. 15. The silver protective agent is not constituted together with a bleaching component.
5. The molded article according to any one of 4. 16. The molded article according to claim 1, wherein the solubility controlling component is constituted together with a bleaching activator. 17. The solubility controlling component is constituted together with an enzyme.
7. The molded article according to any one of 6. 18. The molded article according to claim 1, wherein the solubility controlling component is constituted together with a bleaching agent. 19. The solubility controlling component is constituted together with a silver protecting agent.
19. The molded article according to any one of 1 to 18. 20. The solubility controlling component is at least 50% by weight, preferably at least 50% by weight.
20. The shaped body according to any one of claims 1 to 19, comprising a surfactant in an amount exceeding 70% by weight, more preferably in an amount exceeding 90% by weight.