JP2002500268A - Detergent molded product with special volume ratio - Google Patents

Abstract

  (57) [Summary] The present invention provides that component (I) is present in an amount greater than 80%, preferably greater than 90%, more preferably greater than 95%, most preferably 100% by weight of the amount present. Disclosed are detergent / detergent moldings, characterized in that they are contained in an area of the molding which occupies not more than 40% by volume of the molding in volume.

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 against tea, milk, starch and other stains) is reduced, and in some cases, the protection of delicate materials to be washed out is insufficient, and the disintegration and solubility when using detergents are impaired Will be.

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 problem is caused by the fact that a certain component (I) (hereinafter also referred to as an active component (I)) in a molded article is mainly converted into 40 volumes of the molded article. It was found that the problem could be solved by arranging it in the area of the compact occupying less than 10%.

Accordingly, the present invention relates to a molded article containing a builder, a bleaching agent and a surfactant, wherein the component (I) is present in an amount of more than 80% by weight of the amount present, preferably more than 90% by weight, More preferably in an amount of more than 95% by weight, most preferably in an amount of 100% by weight, up to 40% by volume of the shaped body, preferably 1 to 30% by volume, more preferably 2 to 25% by volume, most preferably A molded article characterized in that it is preferably contained in a molded article region occupying 3 to 20% by volume.

The active ingredient (I) is a bleaching agent selected from chlorine-based and / or oxygen-based bleaching agents, a bleaching activator, a silver protecting agent, a soil release agent, an enzyme, a surfactant or a component for controlling solubility ( Or a compound). However, the active ingredient (I) may also be a mixture of these ingredients.

According to one preferred embodiment of the present invention, the active ingredient (I) comprises a solubility controlling ingredient, a bleach, a bleach activator, a silver protectant, a soil release agent, an enzyme and a surfactant. A mixture with at least one other substance selected from the group.

[0011] The solubility, surface area, compressibility, etc. of the region of the shaped body containing the active ingredient (I) can have an important influence on the properties of the whole tablet.

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 molded article region containing 100% by weight has a rate of more than 5%, preferably more than 10%, more preferably 50%, than the dissolution rate of the remaining area of the molded article. It is possible to dissolve at a rate above, particularly preferably above 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 (surface area), preferably 5 to 30% by volume, more preferably 10 to 25% by volume, most preferably 15 to It can be present in the 20% by volume compact area.

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.

The disclosure of EP-B-0 523 099 states that the disintegrants employed in the manufacture of pharmaceuticals 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.

The disclosure content of DE 197 10 254 (not disclosed at this time) 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.

Disintegrants belonging to the group consisting of organic acids are also suitable, and include, for example, citric acid, a mixture of citric acid / bicarbonate, 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 delaying the solubility, the entire dissolution time (cooled water 20
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 or standard technical documents (eg, 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 mold having a known structure.

The moldings according to the invention are in particular cylindrical tablets, which are preferably 15 to 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 body (particularly, tablet) is 15 per molded body 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 moldings, for example 2 to 4 moldings, 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 the difference between each component of the molded article (excluding the molded article region containing the active ingredient (I)) and 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 region (layer), except for the shaped region containing the active ingredient (I).

Thus, 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 a preferred embodiment of the present 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 be dissolved 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 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 single 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 comprising the active ingredient (I) is surrounded in liquid form (very commonly in solution and / or melt form), optionally at elevated temperatures, 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,
Any substance that solidifies may be used.

According to the present invention, a particularly suitable carrier material is a nonionic surfactant (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.

The use of the mixtures mentioned in the now unpublished DE 197 27 073, the disclosure of which is specifically incorporated herein as part of the present specification, is particularly suitable for the purposes of the present invention. I have.

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.

Oxygen bleaches Specific active ingredients (I) used according to the invention are oxygen bleaches, preferably alkali metal perborates and hydrates thereof, and alkali metal percarbonates. 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 bleaching agents. Examples of suitable organic acids are, in particular, the very effective phthalimidoperoxycaproic acids, but in principle other known peracids can also be used.

[0050] According to bleach activator present invention can be as active ingredients (I), using 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-dioxohexahydro. Examples thereof include -1,3,5-triazine (DADHT) and isatoic anhydride (ISA).

The 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 / detergent.

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.

Bleach-promoting transition metal complexes, especially complexes containing Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru as central atom, preferably salts and / or complexes of manganese and / or cobalt 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 may 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. Soil release agent The specific active ingredient (I) used in the present invention is a so-called soil release agent, which prevents the re-contamination of the surface after the first washing and the soil which has already been removed. It is a substance that promotes the separation of

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 cleaner 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.

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) 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 to sequester 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.

[0069] 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.

Surfactants In principle, any type of surfactant can be used. 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 As used herein, the term "alkoxylated alcohol" 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 oligomers or saccharide mixtures of polymers. 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.

In the test for measuring the detergent performance, the selected specific active ingredient (I) was transferred to the molding 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 above starting composition can have the composition in Table 2 below (all other components being 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]

When the molding of the invention contains 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 of 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.

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 aspect does not correspond to the present invention.

The detergents / detergents of the present invention were tested for their storage stability in comparison to known detergents / detergents. The detergents / cleaners of the present invention were also tested for their ability to remove black tea stains in comparison to known detergents / cleaners. In addition, the detergents / detergents of the present invention were tested for their ability to remove enzymatic stains as compared to known detergents / detergents.

The detergent / cleaning agent 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.

Particularly good results were obtained when a soil release agent was used as active ingredient (I). In the mixtures corresponding to compositions Ra or Va1, up to 2% by weight of polyuronic acid, cationic polymers and hydrophobized polyampholytes 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.

In another cleaning test, a sample with the following starting composition Ra was used: The starting composition Ra comprises active chlorine (dichlorocyanurate) bleaching components, on the one hand, in a homogeneous distribution in the tablet, on the other hand, according to the invention, the active chlorine contains other components, in particular enzyme-containing components. Contained in such a state that it is largely separated from The homogenous tablets had significantly poor storage stability after 2 weeks, and as a result could not obtain a satisfactory cleaning action on milk and starch stains. In the present invention, a bleaching component having a completely ordinary composition is applied to the presence of the bleached component in the molded body region which is a concave portion in this example. This effect is even more pronounced when using a mixture of chlorine component and paraffin at 55 ° C. in a standard program. The cleaning performance was improved even immediately after production. Its effect improved over the storage period. In particular, tea, milk, meat, egg and starch mixtures are better than tablets without compacted areas (ie tablets with uniformly distributed active ingredient (I)) and commercial dishwasher detergent tablets. , Was removed much more effectively.

This effect was observed even when paraffin having a melting point of 40 to 44 ° C. was used. This effect was even more pronounced with paraffin having a melting point of 46-48 ° C. The cleaning effect was also significantly improved with paraffin having a melting point of 57-60 ° C.

In another cleaning test, a sample with the following starting composition Ra was used: This starting composition Ra contains a small amount of a metal catalyst (manganese catalyst, cobalt catalyst (cobalt-pentaaminechloro catalyst)), and simultaneously disperses the n-methylformolinium acetonitrile methylsulfate bleaching system component in a tablet. It contains the active ingredient (I) according to the invention in such a way that it is largely separated from the other ingredients, in particular the enzyme-containing ingredients. The storage stability was remarkably inferior, so that a satisfactory washing action could not be obtained for milk and starch stains.

In the present invention, a bleaching component having a completely ordinary composition is applied to the presence of a bleached component in the molded body region which is a concave portion in this example.

This cleaning effect is even more pronounced when using a mixture of chlorine component and paraffin at 55 ° C. in a standard program. The cleaning performance was improved even immediately after production. Its effect improved over the storage period. In particular, milk, boiled meat, eggs and starch mixtures are much more likely to be used than tablets without compacted areas (ie tablets with a uniformly distributed active ingredient (I)) and commercial dishwasher detergent tablets. Effectively removed.

This effect was observed even when paraffin having a melting point of 40 to 44 ° C. was used. This effect was even more pronounced with paraffin having a melting point of 46-48 ° C. Further, the cleaning effect was remarkably improved even with paraffin having a melting point of 57 to 60 ° C.

In another cleaning test, the surfactant is contained, on the one hand, in a homogeneous distribution in the tablet, and, on the other hand, according to the invention, the active ingredient (I) is separated from other ingredients, in particular enzyme-containing ingredients. Samples contained in such a way that they were largely separated were used. In this cleaning test, the final rinsing effect was evaluated. A mixture of surfactant and paraffin was used at 55 ° C. according to a standard program. The results obtained were better than those obtained with tablets having no shaped body areas, ie tablets having a homogeneously distributed active ingredient (I) and commercial dishwasher detergent tablets.

From the above results, it is clear that the tablets of the present invention are better than the prior art dishwasher detergent tablets.

────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Christian Nich, Federal Republic of Germany Day-40591 Düsseldorf, Otto-Hahn-Strasse No. 185 (72) Inventor Jürgen Höhler Federal Republic of Germany-Day 40593 Wech No. 20 (72) Inventor Hans-Joseph Behrweiann Federal Republic of Germany-Day 41439 Dolmagen, Karl-Friedrich-Schinkel-Strasse No. 43 (72) Inventor Thomas Müller-Kirschbaum Federal Republic of Germany Day-42653 Solinge Lutzowstrasse 75 (72) Inventor Thomas Holderbaum Germany-40789 Holheim, Monheim Strasse No. 11 F-term (reference) 4H003 AC08 BA01 BA09 DA01 DA03 DA17 EA09 EA15 EA16 EB02 EB16 EB20 EB24 EB26 EB36 EC01 EC02 EE05 FA12 FA16 FA32

Claims (42)

[Claims] 1. A molded article containing a builder, an alkali source, a bleaching agent, an enzyme and a surfactant, wherein component (I) comprises more than 80% by weight of the amount present, preferably more than 90% by weight. Amount, more preferably more than 95% by weight, most preferably 100% by weight, up to 40% by volume of the compact, preferably 1 to 30% by volume, more preferably 2 to 25% by volume. A molded body characterized in that it is contained in a molded body region most preferably occupying 3 to 20% by volume. 2. The molded article according to claim 1, wherein the component (I) is a chlorine bleach and / or an oxygen bleach. 3. The molded article according to claim 1, wherein the component (I) is a bleach activator. 4. The molded article according to claim 1, wherein the component (I) is a silver protective agent and / or a soil release agent. 5. The molded article according to claim 1, wherein the component (I) is an enzyme and / or a surfactant. 6. The molded article according to claim 1, wherein the component (I) is a component for controlling solubility. 7. Component (I) is a bleaching agent and / or a bleaching activator and / or a silver protective agent and / or a soil release agent and / or an enzyme and / or a surfactant and / or a component for controlling solubility. And / or a mixture of other components.
The molded article according to 1. 8. Component (I) is a component for controlling solubility and at least one other component selected from the group consisting of a bleaching agent, a bleaching activator, a silver protecting agent, a soil release agent, an enzyme and a surfactant. 2. The molded article according to claim 1, which is a mixture with: 9. The method according to claim 1, wherein a substance selected from the group consisting of an alkali metal perborate, an alkali metal percarbonate, an organic peracid and hydrogen peroxide is used as the at least one oxygen bleaching agent. The molded article according to any one of the above. 10. The at least one bleaching agent, trichlorocyanuric acid,
The molded article according to any one of claims 1 to 9, wherein the molded article is a substance selected from the group consisting of dichlorocyanurate, monochlorocyanurate, hypochlorite, and other typical chlorine bleaching agents. 11. A bleach activator, preferably a polyacylated alkylenediamine, especially tetraacetylethylenediamine (TAED), an N-acylimide, especially an N-acylimide.
Nonanoyl succinimide (NOSI), acylated phenol sulfonate, especially n-
Nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NO
BS), n-methylmorpholinium acetonitrile methyl sulfate (MMA), and / or a bleach accelerating transition metal complex, especially Mn, Fe, Co, Cu,
Complexes containing Mo, V, Ti and / or Ru, preferably salts and / or complexes of manganese and / or cobalt, more preferably cobalt (ammine) complexes, cobalt (acetate) complexes, cobalt (carbonyl) complexes The molded article according to any one of claims 1 to 10, wherein a) complex, cobalt or manganese chloride and / or manganese sulfate is used. 12. 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. Trisodium acid and / or pentasodium tripolyphosphate, sodium carbonate, sodium bicarbonate,
The molded article according to any one of claims 1 to 11, wherein one or more substances selected from the group consisting of silicate builders such as sodium gluconate, disilicate and metasilicate are used. 13. The molded article according to claim 1, wherein the builder system comprises a mixture of a tripolyphosphate and sodium carbonate. 14. The molded article according to claim 1, wherein the builder system includes a mixture of tripolyphosphate, sodium carbonate, and sodium disilicate. 15. The surfactant may be a nonionic surfactant, preferably a low foaming nonionic surfactant, more preferably an alkoxylated and / or propoxylated fatty alcohol, an alkyl polyglycoside. The molded article according to any one of claims 1 to 14, wherein the molded article is selected from the group consisting of, alkyl polyglucamide and a mixture thereof. 16. The silver protecting agent according to claim 1, 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 is used. 16. The molded article according to any one of items 15 to 15. 17. The molded article according to claim 16, wherein benzotriazole and / or alkylaminotriazole is used as the silver protective agent. 18. The transition metal salt may be manganese salt or complex, cobalt salt or complex, preferably cobalt (amine) complex, cobalt (acetate) complex, cobalt (carbonyl) complex, cobalt chloride, manganese chloride. 17. The molded article according to claim 16, which is selected from the group consisting of manganese sulfate and manganese sulfate. 19. The molded article according to claim 1, further comprising at least one solubility controlling component. 20. The molded article according to claim 19, further comprising a dissolution retarder selected from the group consisting of paraffin, microwax, and high molecular weight polyethylene glycol. 21. The molded article according to claim 20, wherein a total dissolution time of the molded article is longer than a pre-rinse cycle period of a normal dishwasher. 22. An organic acid such as citric acid, a mixture of citric acid and bicarbonate,
20. The molded article according to claim 19, further comprising a dissolution accelerator selected from the group consisting of cellulose and cellulose derivatives. 23. The compact of claim 22, wherein the total dissolution time of the entire compact is shorter than the main wash cycle period of a conventional dishwasher. 24. A compact according to claim 1, wherein there is only one other compact region. 25. The molded product according to claim 1, wherein two other molded product regions are present. 26. The volume ratio for the other two compact regions is 10: 1 to 1:
The molded article according to claim 25, wherein the ratio is preferably from 5: 1 to 1: 5, more preferably from 2: 1 to 1: 2. 27. The molded body according to claim 1, wherein three or more other molded body regions are present. 28. The molded article according to claim 1, wherein the bleaching component, in particular, the chlorine bleaching agent does not constitute one layer together with the fragrance component. 29. The silver protective agent is not constituted together with the bleaching component.
9. The molded article according to any one of 8. 30. The molded article according to claim 1, wherein the solubility controlling component is constituted together with a bleaching activator. 31. The solubility-controlling component is constituted together with an enzyme.
The molded article according to any one of 0. 32. The molded article according to claim 1, wherein the solubility controlling component is constituted together with a bleaching agent. 33. The solubility controlling component is constituted together with a silver protecting agent.
33. The molded article according to any one of 1 to 32. 34. The solubility controlling component is constituted together with a surfactant or a surfactant mixture, and its dose is at least 50% by weight, preferably 70% by weight of the total amount of the surfactant or the surfactant mixture. The molded product according to any one of claims 1 to 33, wherein the amount is more than 90% by weight, more preferably more than 90% by weight. 35. The molding according to claim 1, wherein one or more molding regions or all molding regions are colored differently. 36. The molded article according to claim 1, wherein one of the colors is red. 37. The molded article according to claim 1, wherein one of the colors is green. 38. The molded article according to claim 1, wherein one of the colors is yellow. 39. The molded article according to claim 1, wherein the color is a mixed color of various colors. 40. Under normal domestic environmental conditions, ie, 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 increase in the weight of the shaped area (area occupying 40% or less of the shaped body surface area) containing more than 80% by weight of the component (I) is not more than 50% by weight, preferably 40% by weight. 40% by weight or less, more preferably 20% by weight or less, particularly preferably 10% by weight or less, particularly preferably 5% by weight or less. Molded body. 41. Under normal household environmental conditions, ie, 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 loss of weight of the shaped areas containing more than 80% by weight of component (I) (areas occupying less than 40% of the shaped body surface area) is less than 50% by weight, preferably 40% by weight. 50% by weight or less, more preferably 20% by weight or less, particularly preferably 10% by weight or less, most preferably 5% by weight or less. The molded article according to the above. 42. Under normal home environment conditions, ie, 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 absorption maximum of a 1% solution of the colored molded product region or the coloring component is 100 wave numbers or less, preferably 50 wave numbers or less, more preferably 30 wave numbers or less, most preferably 20 wave numbers or less, and Particularly preferably less than 10 wavenumbers, most preferably less than 5 wavenumbers.
The molded article according to any one of the above.