EP0879877B1 - Toilet cleaning block releasing active chlorine - Google Patents

Abstract

Toilet cleaning block contains at least 10 wt.% surfactant, at least 20 wt.% inorganic salt, 1-30 wt.% active chlorine source (I) and solid perfumes (II) and it is solid at room temperature and contains O or N. Also claimed is the production of the block by extruding the composition and cutting the strand into blocks of suitable size.

Description

The invention relates to an active chlorine-releasing toilet cleaning block, in particular a toilet cleaning block to be attached to the edge of the bowl and a method for manufacturing the toilet cleaning block.

Of course, such blocks must have the desired cleaning and disinfecting effects unfold. It is also necessary that the toilet area is fresh and disinfected smells, because consumers consider the smell as a measure of the cleaning and disinfectant power of the block.

In the case of cleaning blocks that release active chlorine, the desired "disinfectant smell" achieved by the chlorine released. However, since the pure chlorine smell is not The well-known toilet cleaning blocks contain enough fresh and pleasant smells additionally perfume oils.

Perfume oils are solutions of various essential oils. In order to meet the ideas of consumers, the well-known active chlorine-releasing cleaning blocks perfume oils in concentrations of approx 10% used.

For example, EP 0462 643 B1 describes a formulation with 8% by weight of a hydrophobic, liquid perfume oil in an active chlorine-releasing toilet cleaning block proposed.

Perfume oils are relatively expensive. When using active chlorine releasing agents together Oxidation is also common for substances and perfume oils and / or chlorination of individual or all components of the perfume oils, which is natural is undesirable.

The object of the invention is a new active chlorine-releasing cleaning block To provide that smells nice and inexpensive to manufacture and a Specify procedures for manufacturing the cleaning and disinfection block.

This object is solved by the features of claims 1 and 14.

Amazingly, it has been found that by sharing solid, Fragrances containing oxygen and / or nitrogen with active chlorine-releasing Compounds to reinforce the desired disinfectant reminder Odor occurs, d. H. that the smell of chlorine and / or fragrance same concentration as in the well-known toilet cleaning blocks with perfume oil is much more intense.

The solid fragrances are also much cheaper than perfume oils and as a result The concentration of fragrance and / or of the synergetic smell effect can active chlorine-releasing agents compared to the known recipes for the same Odor intensity can be reduced. Of course, the respective concentration of the Fragrance of the desired smell and the desired odor intensity from.

Solid fragrance substances are understood to mean all substances that have a more or less strong smell and a melting point above 20 ° C.

Particularly suitable as oxygen-containing fragrances are the substances which at least one aromatic together with an ester and / or ether and / or Contain carboxylic acid and / or carbonyl group, such as 4'-methoxyacetophenone (Acetanisole), benzophenone, cinnamyl cinnamate (cinnamyl alcohol cinnamate), 4-acetyl-6-tert-butyl-1,1-dimethylindane, Coumarin, para-cresylphenyl acetate, methyl naphthyl ketone, Phenylacetic acid, α-trichloromethylbenzyl acetate, acetylisoeugenol, Benzyl isoeugenol, piperonylacetone, ethyl vanillin, p-hydroxyphenyl-butan-2-one, Hydroquinone dimethyl ether, β-naphthyl methyl ether, phenylethyl salicylate, 5-propenyl-2-ethoxyphenol and vanillin.

As oxygen-containing fragrances with a cyclic aliphatic group or an aliphatic heterocycle, for example maltol, ethyl maltol, 4-tert-butyl-cyclohexanol or 4-tert-butylcyclohexan-2-one can be used. Of course, there are also others, a cyclic aliphatic group or one solid fragrances containing aliphatic heterocycle possible.

From the group of monocyclic or polycyclic solid terpenes or sesquiterpenes find preferably borneol, camphor, cedrol, isobomeol, menthol and Thymol application. Of course, other solid terpenes or sesquiterpenes, in particular also non-cyclic.

Suitable fragrances containing nitrogen are preferably indole and indole derivatives like Indoflor ®.

Many of the solid fragrances containing oxygen or nitrogen are also organic degradable. Another advantage of the solid containing oxygen or nitrogen Fragrance is also that they are often non-irritating and not harmful to health are.

Due to their stability against active chlorine-releasing substances, especially Na dichloroisocyanurate, the fragrances are 4'-methoxyacetophenone (acetanisole), borneol, Camphor, cedrol, isoborneol and 4-tert. Butyl cyclohexanol preferred.

Among these particularly stable fragrances are borneol, cedrol, isoborneol and 4th. Butyl-cyclohexanol also as non-irritant and not harmful to health Fragrances.

However, less fragrances which are stable against Na dichloroisocyanurate can also be used be used if they are protected with an oxidation inhibitor. Under Oxidation inhibitors are generally understood to mean all the substances that cause oxidation or reduce or even prevent chlorination of the solid fragrance. Such substances are advantageously selected as oxidation inhibitors which are used in the toilet cleaning block anyway. So can be used as an extrusion aid such substances can be selected that act as oxidation inhibitors Act. For example, it can also act as an oxidation inhibitor Castor ethoxylate, especially castor ethoxylate with less than 80 EO, than Extrusion aids are used.

When using the less stable against the active chlorine-releasing substance solid fragrances, it is also possible to coat the fragrance by coating or microencapsulating to protect. For example, mono-, oligo- or polysaccharides, especially sugar, or water-soluble plastics such. B. polyvinyl alcohol be used.

The toilet cleaning blocks according to the invention contain essential components at least 10% by weight of surfactants, at least 20% by weight of inorganic salts, between 1 and 30% by weight, preferably between 5 and 25% by weight, particularly preferably between 10 and 20% by weight of active chlorine-releasing substances and solid fragrance containing oxygen or nitrogen.

In particular, mono-, di- or Trichior isocyanuric acid or its salts or a chlorinated hydantoin compound proven, sodium dichloroisocyanurate is particularly preferred.

The synergetic odor effect occurs particularly strongly when the concentration ratio between the active chlorine releasing agent and the solid fragrance between 5: 1 and 3: 1, preferably between 4.5: 1 and 3.3: 1 and in particular between 3.5: 1 and 4: 1.

Suitable, preferred and particularly preferred ranges [% by weight] of the individual substance classes are listed in the table below: Range [wt%] Preferred range [% by weight] Particularly preferred range [% by weight] substance class a.) 10-60 10-50 10-50 anionic surfactant b.) 0-20 0-20 0-20 nonionic surfactant c.) 0-10 0-5 0-5 amphoteric surfactant d.) 0-5 0-5 0-5 Lactobionic acid or lactobionic acid derivative e.) 20-80 40-75 40-75 inorganic salt f.) 0.5-10 1-7 3-6 solid fragrance G.) 0-5 0-5 0.5-5 colour H.) 1-30 5-25 10-20 active chlorine-releasing substance i.) 0-5 0-5 0-5 complexing j.) 0-20 0-20 0-20 flush regulator k.) 0-40 0-40 0-40 Acid that dissolves limescale and urine l.) 0-20 0-20 0-20 extrusion aids m.) 0-5 0-5 0-5 other additives

In a preferred embodiment, the block according to the invention consists of approximately 10 to 60% by weight, preferably 10 to 50% by weight, of anionic surfactant (a). In particular, those selected from the groups consisting of alkyl sulfate, fatty alcohol sulfate, fatty alcohol ether sulfate and alkylbenzenesulfonate or mixtures thereof are used. Alkyl chain lengths of the alkyl radicals of the fatty acid constituents of C ₈ -C _{18 are} preferred.

Nonionic surfactants (b) can optionally be used. Here are suitable especially the adducts of 3 to 80 moles of ethylene oxide with 1 mole of one aliphatic compound having essentially 8 to 20 carbon atoms selected are from the group of alcohols and fatty acids. But also alkyl aromatic Compounds such as alkylphenols are suitable here. The proportion of non-ionic Surfactants in the agent according to the invention can be up to 20% by weight.

The amphoteric surfactants (c) use 0 to 10% by weight, preferably 0 to 5% by weight of a fatty acid amidopropyl betaine with a C ₅ -C ₂₁ fatty acid content. Betaine coconut fatty acid is preferably used as the fatty acid. It is advantageous that this amphoteric surfactant can be combined as desired with the anionic and optionally nonionic surfactant used in each case or the anionic and optionally nonionic surfactants.

The cleaning block can contain 0 to 5% by weight of lactobionic acid or at least one lactobionic acid derivative (d) included. The total proportion of components (c) and (d) 0.5 to 10% by weight. Components (c) and / or (d) essentially serve as a foaming agent. When using lactobionic acid or lactobionic acid derivative as a foaming agent, the amount added can be achieved with the same foaming effect of foaming agents compared to conventional formulations by about half or reduce more.

The agent according to this preferred embodiment can be 20 to 80% by weight inorganic Salt (s), preferably 40 to 75% by weight of an inorganic salt which is selected from the group consisting of the alkali and / or alkaline earth salts of sulfuric acid, phosphoric acids, nitrogen acids, carbonic acid or hydrochloric acid or contain mixtures thereof. This allows the consistency and rinsing behavior of the cleaning block favorably.

As a further optional component, the agent according to the invention can be color (g) contain. Pigments and dyes are generally suitable as color components. If you want to achieve that the cleaning block should be colored as such, will preferably added color in the form of pigments. On the other hand, it can also be desired to be removed from the cleaning block during a rinse Detached components in the form of a colored solution visible to the consumer become. In order to achieve such a colored solution, dyes are preferred choose as part of the remedy. Also a combination of pigment (s) and Dyes) is possible.

The agent according to the invention can contain 0 to 5% by weight of complexing agent (i), which are used against water hardness and for complex formation with heavy metal ions become. The respective amounts of the complexing agent are corresponding the complexing ability of the agent and according to the desired Rinsing speed selected.

To ensure that the block according to the invention has a defined service life and that the same amounts are rinsed from the block in each case rinse regulators (j) can be used. Suitable for this especially the salts of aromatic sulfonic acids, for example sodium cumene sulfonate or sodium toluenesulfonate. Dipropylene glycol can also be used for the same purpose be used. If the latter connection is used, their share of the cleaning block can even be kept extremely low. In As a rule, a proportion of up to 5% by weight is then sufficient. In the field of salts the proportion of aromatic sulfonic acids is up to 20% by weight finished funds.

Lime and urine scale dissolving acids (k) can be added to the block to prevent limestone deposits from forming in toilet bowls or around to remove existing deposits again. Acids such as Amidosulfonic acid and citric acid as well as other organic acids. You can up to a proportion of 40% by weight can be contained in the finished composition.

Furthermore, the block according to the invention can contain extrusion aids (I). These serve to be able to shape the raw mass of the agent in the appropriate composition. Suitable extrusion aids are, for example, polyethylene glycol. It is usually sufficient to use up to 20% by weight of extrusion aids. However, since other constituents of the cleaning block also enable better shapability of the cleaning composition, the proportion of extrusion aid added can be very much less than 20% by weight or the addition of such an agent can be dispensed with entirely. The other constituents of the cleaning block composition, which also make it easier to form, include dipropylene glycol, which can optionally be used as a rinse regulator. Optional liquid acids can also be used for this purpose. Furthermore have proven as an extrusion aid C _13/15 oxoalcohol and Rhizinusethoxylate, each with less than 80 ethoxy groups.

The agent according to the invention can be in addition to the previously mentioned components contain other conventional additives (m) up to a proportion of 5% by weight. To such additional additives include, for example, enzymes such as savinase, cellulase, Protease and lipase as well as preservatives.

The invention also relates to a method for producing an inventive Cleaning blocks, in which a mass of suitable composition is produced by means of the extrusion process. The pre-mixed Mass formed into an endless strand by means of an extruder and this then in Cut pieces or blocks of a suitable size. The size of the pieces is variable and can be selected according to the purpose. Usually will cut the pieces so that after cutting blocks weighing them of about 20 to 100 g, preferably 20 to 50 g.

1. Zusammensetzung eines Toilettenreinigungsblocks unter Verwendung eines gegenüber Natriumdichlorisocyanurat weitgehend stabilen Riechstoffs

a) Der mittels Extrusion hergestellte Toilettenreinigungsblock mit der nachfolgend aufgeführten Zusammensetzung zeigt gute Reinigungseigenschaften, zersetzt sich nicht und zeigt einen angenehmen, intensiven, erfrischenden Geruch. Er wird als sogenannter "Rim-Block" verwendet. Gesamtgehalt Gew.% Alkylbenzolsulfonat Natriumsalz 40 Toluolsulfonat 3 Natriumchlorid 20 Diisocyanurat Natriumsalz 15 Talkfettalkoholethoxylat mit 25 EO 4 Farbe 0,1 C_13/15 Oxoalkoholethoxylat mit 7 EO 3 Campher 4 Natriumsulfat ad 100

b) Andere Geruchsnoten können erzielt werden, wenn 4'-Methoxyacetophenon (Acetanisol), Borneol, Cedrol, Isobomeol oder 4-tert. Butyl-Cyclohexanol, ebenfalls in einer Konzentration von etwa 4 Gew.% anstelle von 4 Gew.% Campher in der Zusammensetzung von 1a) verwendet werden. Auch diese Toilettenreinigungsblöcke zeichnen sich durch einen intensiven, erfrischenden und angenehmen Geruch aus und sind beständig.

c) Auch mit einer Mischung aus 2 Gew.% Bomeol und 2 Gew.% Isoborneol wurden intensiv erfrischend riechende Toilettenreinigungsblöcke hergestellt.

2. Zusammensetzung eines Toilettenreinigungsblocks unter Verwendung eines weniger gegen Natriumdichlorisocyanurat stabilen Riechstoffs Anstelle von C_13/15 Oxoalkoholethoxylat mit 7 EO wird Rhizinusethoxylat mit 40 EO als Extrusionshilfsmittel und Oxidationsinhibitor und anstelle von 4 Gew% Campher wird 4,0 Gew% Menthol in der Rezeptur gemäß 1a) verwendet.

3. Vergleich der Geruchsintensität Es wurde bei gleicher Konzentration an Dichlorisocyanurat die Intensität des Chlorgeruchs verglichen und Toilettenreinigungsblocks mit folgender Zusammensetzung hergestellt: Beispiel 1 Beispiel 2 Beispiel 3 Alkylbenzolsulfonat Natriumsalz 40 40 40 Toluolsulfonat 3 3 3 Natriumchlorid 20 20 20 Talkfettalkoholethoxylat mit 25 EO 4 4 4 Farbe 0,1 0,1 0,1 C_13/15 Oxoalkoholethoxylat mit 7 EO 3 3 3 Dichlorisocyanurat Natriumsalz 15 15 15 Campher 0 4 0 Parfümöl 0 0 4 Natriumsulfat ad 100 ad 100 ad 100 Chlor-Geruchsintensität Normal Intensiv Normal Sonstiger Geruch --- Camphergeruch Parfümölgeruch

The invention is explained in more detail below on the basis of preferred exemplary embodiments:

1. Composition of a toilet cleaning block using a fragrance that is largely stable to sodium dichloroisocyanurate

a) The toilet cleaning block manufactured by extrusion with the following composition shows good cleaning properties, does not decompose and shows a pleasant, intense, refreshing smell. It is used as a so-called "rim block". total content Wt.% Alkylbenzenesulfonate sodium salt 40 toluenesulfonate 3 sodium chloride 20 Diisocyanurate sodium salt 15 Talc fatty alcohol ethoxylate with 25 EO 4 colour 0.1 C _13/15 oxo alcohol ethoxylate with 7 EO 3 camphor 4 sodium sulphate ad 100

b) Other smell notes can be achieved if 4'-methoxyacetophenone (acetanisole), borneol, cedrol, isobomeol or 4-tert. Butyl-cyclohexanol, also in a concentration of about 4% by weight instead of 4% by weight camphor in the composition of 1a) can be used. These toilet cleaning blocks are also characterized by an intense, refreshing and pleasant smell and are durable.

c) Intensively refreshing-smelling toilet cleaning blocks were also produced with a mixture of 2% by weight of Bomeol and 2% by weight of Isoborneol.

2. Composition of a toilet cleaning block using a fragrance less stable to sodium dichloroisocyanurate Instead of C _13/15 oxo alcohol ethoxylate with 7 EO, castor ethoxylate with 40 EO as extrusion aid and oxidation inhibitor and instead of 4% by weight camphor, 4.0% by weight menthol is in the recipe 1a) used.

3. Comparison of the Odor Intensity The intensity of the chlorine odor was compared at the same concentration of dichloroisocyanurate and toilet cleaning blocks were produced with the following composition: example 1 Example 2 Example 3 Alkylbenzenesulfonate sodium salt 40 40 40 toluenesulfonate 3 3 3 sodium chloride 20 20 20 Talc fatty alcohol ethoxylate with 25 EO 4 4 4 colour 0.1 0.1 0.1 C _13/15 oxo alcohol ethoxylate with 7 EO 3 3 3 Dichloroisocyanurate sodium salt 15 15 15 camphor 0 4 0 perfume oil 0 0 4 sodium sulphate ad 100 ad 100 ad 100 Chloro-odor intensity normal Intensive normal Other smell --- Camphergeruch Perfume oil odor

The toilet cleaning blocks showed the same concentration of dichloroisocyanurate sodium salt in Example 1 (without added perfume component) and 3 (Adding perfume oil as a perfuming component) Chlorine smell more comparable Intensity, whereas the toilet cleaning block according to Example 2 has the same concentration of dichloroisocyanurate sodium salt with an addition of the solid fragrance Campher developed a significantly more intense smell of chlorine.

Claims (14)

1. Toilet cleaning block which comprises at least 10% by weight of surfactants, at least 20% by weight of inorganic salts, between 1 and 30% by weight of substances which release active chlorine, and a fragrance which is solid at room temperature, comprises oxygen or nitrogen and is added in solid form.
2. Block according to Claim 1, characterized in that the oxygen-containing solid fragrance is chosen from the group of aromatic compounds which contain an ester and/or ether and/or carboxylic acid and/or carbonyl group.
3. Block according to Claim 1, characterized in that the oxygen-containing fragrance is chosen from the group of cyclic aliphatics or aliphatic heterocycles.
4. Block according to Claim 1, characterized in that the oxygen-containing fragrance is chosen from the group of monocyclic or polycyclic solid terpenes or sesquiterpenes.
5. Block according to Claim 4, characterized in that the fragrance is borneol, camphor, cedrol, isoborneol, menthol or thymol.
6. Block according to Claim 1, characterized in that the nitrogen-containing fragrance is indole or an indole compound.
7. Block according to one of the preceding claims, characterized in that the block comprises an oxidation inhibitor.
8. Block according to one of Claims 1 to 7, characterized in that the concentration of the fragrance is between 0.5 and 10% by weight, in particular between 3 and 6% by weight.
9. Block according to one of Claims 1 to 8, characterized in that the block comprises two or more fragrances.
10. Block according to one of the preceding claims, characterized in that the concentration of the substance which releases active chlorine is between 5 and 25% by weight, in particular 10 to 20% by weight.
11. Block according to one of the preceding claims, characterized in that the agent which releases active chlorine is mono-, di- or trichloroisocyanuric acid or salts thereof or a chlorinated hydantoin compound.
12. Block according to one of the preceding claims, characterized in that the concentration ratio between the agent which releases active chlorine and the solid fragrance is between 5:1 and 3:1, preferably between 4:1 and 3.3:1 and in particular between 3.5:1 and 4:1.
13. Block according to one of Claims 1 to 12 consisting of a) 10-60% by weight of anionic surfactant b) 0-20% by weight of nonionic surfactant c) 0-10% by weight of amphoteric surfactant d) 0-5% by weight of lactobionic acid or at least one lactobionic acid derivative e) 20-80% by weight of inorganic salt f) 0.5-10% by weight of solid fragrance which contains oxygen or nitrogen g) 0-5% by weight of colorant h) 1-30% by weight of substance which releases active chlorine i) 0-5% by weight of complexing agent j) 0-20% by weight of wash-off regulator k) 0-40% by weight of acid which dissolves limescale and urine scale l) 0-20% by weight of extrusion auxiliaries m) 0-5% by weight of further additives.
14. Process for the preparation of a toilet cleaning block, characterized in that a composition according to one of Claims 1 to 13 is made into a strand using an extruder, and this strand is cut into blocks of suitable size.