Apparatus And Process For Production Of A Water-Soluble Shell, And Washing Or Cleansing Agent Portion Packs Comprising Said Water-Soluble Shell And Containing A Viscoelastic, Solid Filling Substance
20210301228 · 2021-09-30
Inventors
- Matthias Sunder (Duesseldorf, DE)
- Peter Schmiedel (Duesseldorf, DE)
- Mareile Job (Leverkusen, DE)
- Boray TORUN (Duesseldorf, DE)
- Katja Gerhards (Duesseldorf, DE)
- Steffen Ristau (Duesseldorf, DE)
- Thomas WEBER (Weimar (Lahn), DE)
- Maria Trinchera (Huerth, DE)
Cpc classification
B29C33/34
PERFORMING OPERATIONS; TRANSPORTING
B29C35/02
PERFORMING OPERATIONS; TRANSPORTING
B29K2029/04
PERFORMING OPERATIONS; TRANSPORTING
B29C33/565
PERFORMING OPERATIONS; TRANSPORTING
B29C33/02
PERFORMING OPERATIONS; TRANSPORTING
International classification
Abstract
An apparatus for production of a water-soluble shell for holding a filling substance, having a tank filled with a melt of a shell material, wherein the shell material contains a polymer and is water-soluble and is solid under standard conditions, and a male mold movably arranged in the region of the tank and automatically lowerable into the melt and withdrawable from the tank in order to form a water-soluble shell. The invention also relates to a corresponding process and to a corresponding shell and to a corresponding portion pack for use as a washing or cleaning agent.
Claims
1. An apparatus for production of a water-soluble shell for holding a filling substance, comprising a tank filled with a melt of a shell material, wherein the shell material contains a polymer and is water-soluble and is solid under standard conditions, and a male mold movably arranged in the region of the tank and automatically lowerable into the melt and withdrawable from the tank in order to form a water-soluble shell from the shell material.
2. The apparatus according to claim 1, wherein the male mold has a temperature regulator.
3. The apparatus according to claim 1, wherein the tank substantially has an inverted shape of the male mold.
4. The apparatus according to claim 1, wherein the male mold, which is movably arranged in the region of the tank, is automatically lowerable into the melt and withdrawable from the tank in order to remove it from the shell material to form a water-soluble shell resting on the male mold.
5. The apparatus according to claim 1, wherein at least one further tank having at least one further melt of a further shell material is provided, wherein the male mold having the shell resting thereon is automatically lowerable into the further melt and withdrawable from the further melt in order to form a further water-soluble shell resting against the water-soluble shell resting on the male mold.
6. The apparatus according to claim 5, wherein the shell materials have different optical properties in the solid state.
7. The apparatus according to claim 1, wherein one end of the male mold has a portion comprising a filling substance.
8. The apparatus according to claim 1, wherein the male mold is designed in such a way that a rigid shell lying thereon cannot be stripped off.
9. The apparatus according to claim 8, wherein the male mold is wider in a distal region than in a proximal region.
10. The apparatus according to claim 8, wherein the male mold has an unevenness.
11. The apparatus according to claim 8, wherein the male mold can be set in vibration.
12. A process for production of a water-soluble shell for holding a filling substance, wherein an apparatus according to claim 1 is provided, the male mold is lowered into the melt at a temperature below a melting temperature of the melt so that a contact surface of the male mold is covered with shell material, a shell is formed by solidifying the shell material on the male mold, and the male mold having a shell adhering to it is lifted out of the tank before, after, or during solidification, and the shell is detached from the male mold.
13. The process according to claim 12, wherein the male mold is lowered into the melt to a depth which is greater than a maximum width of the male mold.
14. The process according to claim 12, wherein the shell is detached by rolling it out or turning it inside out.
15. The process according to claim 12, wherein one end of the male mold has a portion comprising a filling substance and the portion is separated when the shell is detached, so that the shell having the filling substance is replaced.
16. A shell for a portion pack suitable for use as a washing or cleaning agent, produced by a process according to claim 12.
17. A portion pack as a washing or cleaning agent containing (a) a shell made from a melt of a polymer-containing and water-soluble shell material which is solid under standard conditions, and (b) a viscoelastic and solid filling substance in the above-mentioned shell, containing, based on the total weight of said filling substance, (i) a total amount from 0.1 to 70 wt. % of at least one surfactant, and (ii) a total amount of at least 0.5 wt. % of at least one organic gelator compound having a molar mass of <1000 g/mol, a solubility in water of less than 0.1 g/L (20° C.), and a structure containing at least one hydrocarbon structural unit having 6 to 20 carbon atoms, and, in addition, an organic structural unit covalently bonded to the aforementioned hydrocarbon unit, which has at least two groups selected from —OH, —NH—, or mixtures thereof, and (iii) optionally water.
18. The portion pack according to claim 17, wherein the above-mentioned at least one filling substance has a storage modulus of between 10.sup.3 Pa and 10.sup.8 Pa and a loss modulus (in each case at 20° C., with a deformation of 0.1% and a frequency of 1 Hz), and the storage modulus in the frequency range between 10.sup.−2 Hz and 10 Hz is at least twice as great as the loss modulus.
19. The portion pack according to claim 17, wherein the organic gelator compound is selected from benzylidene alditol compound, diketopiperazine compound, dibenzylcystine compound, hydrogenated castor oil, hydroxystearic acid, N—(C.sub.8-C.sub.24)-hydrocarbyl glyconamide, or mixtures thereof.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
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DETAILED DESCRIPTION OF THE INVENTION
[0175]
[0176] In the region of the tank, a male mold 6a is movable in an initial state, namely vertically movable by means of an actuator (not shown here), the male mold 6a being automatically lowerable into the melt 4 and withdrawable from the melt 4.
[0177] In a subsequent step, a male mold 6b is lowered into the melt 4, i.e., arranged in such a way that at least a part of the male mold 6b is located below the surface of the melt.
[0178] The male mold 6a is submerged in the melt 4 over a length which is greater than the maximum width of the male mold 6b. Due, among other things, to the temperature difference between the melt 4 and male mold 6b as well as the stickiness and viscosity of the melt 4, as well as the specific heat capacity thereof, a layer of shell material 5 is formed in this state, which layer rests on the male mold 6b and adjoins it.
[0179] A male mold 6c is removed from the tank 3 and the melt 4 in a further subsequent step. A solid, gel-like, water-soluble shell 2 has formed therefrom by cooling the shell material 5 resting against the male mold 6c. The shell 2 does not have to be gel-shaped.
[0180] The male mold 6a; 6b; 6c has a temperature regulator (not shown in detail) on the inside, in order to accelerate the cooling and solidification of the shell 2, and to influence or predetermine the thickness of the shell 2.
[0181] In
[0182] In a first state, a tank 3a is only partially filled with a melt 4 of a shell material 5. In a second state, the male mold 6b is lowered into the tank 3b, as a result of which the melt 4 is displaced, so that its level rises and the male mold 6b is effectively lowered into the melt 4. In a third state, the male mold 6c is lifted out of the tank 3c, a shell 2 made of the shell material 5 adhering to the male mold 6c. The tank 3c is now empty, but a residual amount of melt 4 or shell material 5 can also remain there.
[0183] In
[0184] In the region of the tank 3a, a male mold 6a is arranged above it in an initial state, the male mold 6a being automatically lowerable into the melt 4a and withdrawable from the melt 4a.
[0185] In a subsequent step, a male mold 6b is lowered into the melt 4a with the granular material 7 contained therein. Due, among other things, to the temperature difference between the melt 4a and the male mold 6b as well as the stickiness, viscosity, and specific heat capacity of the melt 4a and the amount, density, and specific heat capacity of the granular material 7, a layer of shell material 5a is formed in this state, which layer rests against the male mold 6b and adjoins it, in any case integrates with it.
[0186] A male mold 6c is removed from the tank 3a and the melt 4a in a further subsequent step. By cooling the shell material 5a resting on the male mold 6c, a solid, water-soluble shell 2a containing granular material 7 has formed therefrom.
[0187] Subsequently, as shown on male molds 6d and 6e, a male mold 6d having a first shell 2a adjoining is lowered into the second melt 4b of a second shell material 5b without granular material, so that a second shell 2b is formed which encloses the first shell 2a. In the final state, the male mold 6f is lifted out of the second melt 4b and the adjacent shells 2a, 2b are cooled so that they solidify and form a shell 2 composed of two layers.
[0188] The first shell 2a is opaque, while the second shell 2b is at least partially transparent, so that the first shell 2a and the granular material 7 contained therein are visible from the outside.
[0189] According to
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[0191]
[0192]
[0193]
[0194]
[0195] First, in a first step 101, an apparatus as described above for production of a water-soluble shell 2 is provided, comprising a tank 3 filled with a melt 5 of a shell material 4 and a male mold 6. Then, in a step 102, the male mold 6 is lowered into the melt 4 at a temperature below a melting temperature of the melt 4, so that a contact surface of the male mold 6 is covered with the shell material 5. This allows a shell 2 to be formed in a step 103 by solidification of the shell material 5 on the male mold 6. Before, after, or during the solidification in accordance with step 103, the male mold 6 is lifted out of the melt in a step 104, so that a shell 2 is provided on the male mold 6, which is detached from the male mold 6 in a step 105. In a step 106, the shell 2 is cured further by hot air drying and in a step 107 a protective layer (not shown here) is vapor-deposited onto the shell 2. The shell 2 is thus provided.
[0196] In a step 108, the shell 2 is filled with at least one filling substance 9. Subsequently, the shell 2 can optionally be closed in a step 109 by means of sealing with a water-soluble film, as a result of which a portion pack is provided for use as a washing or cleaning agent 12.
[0197] Another subject matter of the invention is a portion pack for use as a washing or cleaning agent, in particular as a textile washing agent or dishwashing agent, containing [0198] (a) a shell made from a melt of a polymer-containing and water-soluble shell material that is solid under standard conditions, and [0199] (b) a viscoelastic, solid filler substance contained in said shell, containing, based on the total weight of the above-mentioned filling substance, [0200] (i). a total amount of from 0.1 to 70 wt. % of at least one surfactant, [0201] and [0202] (ii). a total amount of at least 0.5 wt. % of at least one organic gelator compound with a molar mass <1000 g/mol, a solubility in water of less than 0.1 g/L (20° C.) and a structure containing at least a hydrocarbon structural unit with 6 to 20 carbon atoms (preferably at least one carbocyclic, aromatic structural unit) and additionally an organic structural unit covalently bonded to the aforementioned hydrocarbon unit, which has at least two groups selected from —OH, —NH—, or mixtures thereof [0203] and [0204] (iii). optionally water.
[0205] For this subject matter of the invention, it is preferred to use the embodiments of the shell material described above as preferred for the shell of the portion pack (vide supra).
[0206] It is also preferred if the shell of the portion pack is produced according to the process described above (vide supra).
[0207] It is preferred according to the invention if the viscoelastic, solid filling substance is incorporated firmly into the shell of the portion pack. This is preferably done in that the viscoelastic, solid filling substance is formed in the shell by curing a liquid composition.
[0208] It is preferred according to the invention if the shell of the portion pack has an opening. The viscoelastic, solid filling substance of the portion pack is visible and accessible through this opening. This increases, for example, the speed at which the portion pack according to the invention dissolves during use, since the water supplied in the washing or cleaning process can immediately come into direct contact with the filling sub stance.
[0209] The stability of the portion pack and the dissolving or dispersing power of the portion pack is further improved, when the above-mentioned filling substance has a storage modulus between 10.sup.3 Pa and 10.sup.8 Pa, (preferably between 10.sup.4 Pa and 10.sup.8 Pa, particularly preferably in a range from 10.sup.5 Pa to 10.sup.7 Pa) and a loss modulus (in each case at 20° C., with a deformation of 0.1% and a frequency of 1 Hz), and the storage modulus in the frequency range between 10.sup.−2 Hz and 10 Hz is at least twice as great as the loss modulus, preferably five times greater than the loss modulus, particularly preferably at least ten times greater than the loss modulus.
[0210] The viscoelastic, solid filling substance according to the invention is preferably transparent or translucent. If a filling substance according to the invention has a residual light power (transmission) of at least 20% based on the reference measurement in the spectral range between 380 nm and 780 nm, it is considered transparent within the meaning of the invention.
[0211] The transparency of the viscoelastic, solid filling substance according to the invention can be determined using various methods. The Nephelometric Turbidity Unit (NTU) is frequently used as an indication of transparency. It is a unit, used e.g. in water treatment, for measuring turbidity e.g. in liquids. It is a unit of turbidity measured using a calibrated nephelometer. High NTU values are measured for clouded compositions, whereas low values are determined for clear, transparent compositions.
[0212] The HACH Turbidimeter 2100Q from Hach Company, Loveland, Colo. (USA), is used with the calibration substances StabICal Solution HACH (20 NTU), StabICal Solution HACH (100 NTU) and StabICal Solution HACH (800 NTU), all of which can also be produced by Hach Company. The measurement is filled with the composition to be analyzed in a 10 ml measuring cuvette having a cap and is carried out at 20° C.
[0213] At an NTU value (at 20° C.) of 60 or more, viscoelastic, solid filling substances have a perceptible turbidity within the meaning of the invention, as can be seen with the naked eye. It is therefore preferred if the viscoelastic, solid filling substance according to the invention has an NTU value (at 20° C.) of at most 120, more preferably at most 110, more preferably at most 100, particularly preferably at most 80.
[0214] In the scope of the present invention, the transparency of the viscoelastic, solid filling substances according to the invention was determined by a transmission measurement in the visual light spectrum over a wavelength range of from 380 nm to 780 nm at 20° C. To do this, a reference sample (water, deionized) is first measured in a photometer (Specord S 600 from AnalytikJena) with a cuvette (layer thickness 10 mm) that is transparent in the spectrum to be examined. The cuvette is then filled with a sample of the filling substance according to the invention and measured again. The sample is filled in the liquid state and solidified in the cuvette and then measured.
[0215] It is preferred if the viscoelastic, solid filling substance according to the invention has a transmission (20° C.) of particularly preferably at least 25%, more preferably at least 30%, more preferably at least 40%, in particular at least 50%, very particularly preferably at least 60%.
[0216] It is very particularly preferred if the viscoelastic, solid filling substance according to the invention has a transmission (at 20° C.) of at least 30% (in particular of at least 40%, more preferably of at least 50%, particularly preferably of at least 60%) and an NTU value (at 20° C.) of at most 120 (more preferably at most 110, more preferably at most 100, particularly preferably at most 80).
[0217] The shell of the portion pack and/or the viscoelastic, solid filling substance of the portion pack can be printed with text or graphic motifs.
[0218] The viscoelastic, solid filling substance according to the invention contains, based on the total weight thereof, a total amount of from 0.1 to 70 wt. % of surfactant. Suitable surfactants according to the invention are preferably anionic surfactants, nonionic surfactants, zwitterionic surfactants, amphoteric surfactants or cationic surfactants.
[0219] Preferred viscoelastic, solid filling substances contain, based on their total weight, a total amount of 5 to 70 wt. %, more preferably 5 to 65 wt. %, more preferably 5 to 60 wt. %, more preferably 10 to 70 wt. %, more preferably 10 to 65 wt %, more preferably 10 to 60 wt %, more preferably 15 to 70 wt %, more preferably 15 to 65 wt %, more preferably 15 to 60 wt %, particularly preferably 20 to 70 wt. %, more preferably 20 to 65 wt. %, more preferably 20 to 60 wt. %, very particularly preferably 25 to 70 wt. %, more preferably 25 to 65 wt. %, more preferably 25 to 60 wt. %, further preferably 30 to 70 wt. %, more preferably 30 to 65 wt. %, more preferably 30 to 60 wt. % of at least one surfactant. These surfactant compositions are particularly suitable for treating textiles, but in particular for use in a washing machine for textile washing. It is in turn particularly preferable for the viscoelastic, solid filling substance to contain at least one anionic surfactant and optionally also at least one nonionic surfactant.
[0220] Preferred embodiments of a viscoelastic, solid filling substance according to the invention for use as a dishwashing agent, in particular for use in a dishwasher, each contain, based on the weight of the composition, 0.1 to 5.0 wt. %, in particular 0.2 to 4.0 wt. %, of at least one surfactant.
[0221] A viscoelastic, solid filling substance that is preferred according to the invention is characterized in that it contains at least one anionic surfactant. Viscoelastic, solid filling substances according to the invention having anionic surfactant are particularly suitable for washing textiles, particularly preferably for use in a washing machine for washing textiles. Preferred viscoelastic, solid filling substances according to the invention, which are suitable as dishwashing agents (in particular for use in a dishwasher), each contain, based on the weight of the viscoelastic, solid filling substance according to the invention, 0 to 1 wt. %, in particular 0 to 0.5 wt. %, particularly preferably 0 to 0.25 wt. %, of anionic surfactant.
[0222] If the viscoelastic, solid filling substance according to the invention contains anionic surfactant and is used as a textile washing agent, it is preferred that, based on the total weight of the composition, anionic surfactant is contained in a total amount of 5 to 70 wt. %, more preferably 5 to 60 wt. %, more preferably 10 to 70 wt. %, in particular 10 to 60 wt. %, particularly preferably 10 to 40 wt. %, more preferably 25 to 40 wt. %.
[0223] Regardless of the field of application of the viscoelastic, solid filling substances according to the invention, sulfonates and/or sulfates can preferably be used as the anionic surfactant.
[0224] Surfactants of the sulfonate type that can be used are preferably C.sub.9-13 alkylbenzene sulfonates, olefin sulfonates, i.e. mixtures of alkene and hydroxyalkane sulfonates, and disulfonates, as obtained, for example, from C.sub.12-18 monoolefins having a terminal or an internal double bond by way of sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products. C.sub.12-18 alkane sulfonates and the esters of α-sulfofatty acids (ester sulfonates) are also suitable, for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.
[0225] Particularly preferred viscoelastic, solid filling substances according to the invention, in particular textile washing agents, contain at least one compound of the formula (T-1) as the anionic surfactant,
##STR00001##
where
R′ and R″ are, independently of one another, H or alkyl, and together contain 9 to 19, preferably 9 to 15 and in particular 9 to 13, C atoms, and Y.sup.+ is a monovalent cation or the nth part of an n-valent cation (in particular Na.sup.+).
[0226] The alkali salts and in particular the sodium salts of the sulfuric acid half-esters of C.sub.12-C.sub.18 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol or stearyl alcohol, or of C.sub.10-C.sub.20 oxo alcohols and the half-esters of secondary alcohols having these chain lengths are preferred as alk(en)yl sulfates. From a washing perspective, C.sub.12-C.sub.16 alkyl sulfates, C.sub.12-C.sub.15 alkyl sulfates and C.sub.14-C.sub.15 alkyl sulfates are preferred. 2,3-alkyl sulfates are also suitable anionic surfactants.
[0227] Fatty alcohol ether sulfates, such as the sulfuric acid monoesters of straight-chain or branched C.sub.7-21 alcohols ethoxylated with 1 to 6 mol ethylene oxide, such as 2-methyl-branched C.sub.9-11 alcohols having, on average, 3.5 mol ethylene oxide (EO) or C.sub.12-18 fatty alcohols having 1 to 4 EO, are also suitable.
[0228] Other suitable anionic surfactants are soaps. Saturated and unsaturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, (hydrogenated) erucic acid and behenic acid, and in particular soap mixtures derived from natural fatty acids, such as coconut, palm kernel, olive oil or tallow fatty acids.
[0229] The anionic surfactants, and the soaps, can be present in the form of sodium, potassium, magnesium or ammonium salts thereof. The anionic surfactants are preferably present in the form of the ammonium salts thereof. Preferred counterions for the anionic surfactants are the protonated forms of choline, triethylamine, monoethanolamine or methylethylamine.
[0230] In a very particularly preferred embodiment, the viscoelastic, solid filling substance according to the invention, in particular as a textile washing agent, contains an alkyl benzene sulfonic acid, in particular C.sub.9-13 alkyl benzene sulfonic acid, neutralized with monoethanolamine, and/or fatty acid neutralized with monoethanolamine.
[0231] A preferred viscoelastic, solid filling substance according to the invention contains at least one anionic surfactant selected from the group consisting of C.sub.8-18 alkylbenzene sulfonates, olefin sulfonates, C.sub.12-18 alkane sulfonates, ester sulfonates, alkyl sulfates, alkenyl sulfates, fatty alcohol ether sulfates and mixtures thereof.
[0232] In the scope of a preferred embodiment, the viscoelastic, solid filling substance according to the invention, in particular as a washing or cleaning agent, contains at least one nonionic surfactant.
[0233] The at least one nonionic surfactant can be any known nonionic surfactant that is suitable for the purpose according to the invention.
[0234] In the scope of a preferred embodiment, the viscoelastic, solid filling substance contains at least one nonionic surfactant.
[0235] Preferred embodiments of a viscoelastic, solid filling substance according to the invention as a dishwashing agent, in particular for use in a dishwasher, each contain, based on the weight of the composition, 0.1 to 5.0 wt. %, in particular 0.2 to 4.0 wt. %, of at least one nonionic surfactant.
[0236] Preferred embodiments of a viscoelastic, solid filling substance according to the invention as a textile washing agent, in particular for use in a washing machine, each contain, based on the weight of the composition, 1.0 to 25 wt. %, preferably 2.5 to 20.0 wt. %, more preferably 5.0 to 18.0 wt. %, of at least one nonionic surfactant.
[0237] The at least one nonionic surfactant can be any known nonionic surfactant that is suitable for the purpose according to the invention.
[0238] In a preferred embodiment of the invention, the viscoelastic, solid filling substance described herein contain, as a nonionic surfactant, at least one fatty alcohol alkoxylate having the following formula (T-2),
##STR00002##
where R′ is a linear or branched C.sub.8-C.sub.18 alkyl functional group, an aryl functional group or alkylaryl functional group, XO is independently an ethylene oxide (EO) or propylene oxide (PO) group, and m is an integer from 1 to 50. In the above formula, R′ represents a linear or branched, substituted or unsubstituted alkyl functional group. In a preferred embodiment of the present invention, R.sup.I is a linear or branched alkyl radical having 5 to 30 carbon atoms, preferably 7 to 25 carbon atoms, and in particular 10 to 19 carbon atoms. Preferred functional groups R′ are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl functional groups and mixtures thereof, the representatives that have an even number of carbon atoms being preferred. Particularly preferred functional groups R′ are derived from fatty alcohols having 12 to 19 carbon atoms, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or from oxo alcohols having 10 to 19 carbon atoms.
[0239] XO in formula (T-2) is an ethylene oxide (EO) or a propylene oxide (PO) group, preferably an ethylene oxide group.
[0240] The index m in formula (T-2) is an integer from 1 to 50, preferably from 2 to 20, and more preferably from 2 to 10. In particular, m is 3, 4, 5, 6 or 7. The solid, viscoelastic filling substance according to the invention may contain mixtures of nonionic surfactants which have different degrees of ethoxylation.
[0241] In summary, particularly preferred fatty alcohol alkoxylates are those of formula (T-3)
##STR00003##
where k=9 to 17, and m=3, 4, 5, 6, or 7. Very particularly preferred representatives are fatty alcohols having 10 to 18 carbon atoms and 7 EO (k=11 to 17, m=7).
[0242] Fatty alcohol ethoxylates of this kind are available under the trade names Dehydol® LT7 (BASF), Lutensol® A07 (BASF), Lutensol® M7 (BASF), and Neodol® 45-7 (Shell Chemicals).
[0243] Particularly preferably, the solid, viscoelastic filling substances according to the invention contain nonionic surfactants from the group of alkoxylated alcohols. Nonionic surfactants that are preferably used are alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 C atoms and, on average, 1 to 12 mol ethylene oxide (EO) per mol of alcohol, in which the alcohol functional group can be linear or preferably methyl-branched in the 2 position, or can contain linear and methyl-branched functional groups in admixture, as are usually present in oxo alcohol functional groups. However, alcohol ethoxylates having linear functional groups of alcohols of native origin having 12 to 18 C atoms, for example from coconut, palm, tallow fatty or oleyl alcohol, and an average of 2 to 8 EO per mol of alcohol, are particularly preferred. Preferred ethoxylated alcohols include, for example C.sub.12-14-alcohols having 3 EO or 4 EO, C.sub.8-11-alcohol having 7 EO, C.sub.13-15-alcohols having 3 EO, 5 EO, 7 EO or 8 EO, C.sub.12-18-alcohols having 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C.sub.12-14-alcohol with 3 EO and C.sub.12-18-alcohol with 5 EO.
[0244] Preferred alcohol ethoxylates have a narrowed homologue distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols having more than 12 EO can also be used in particular as cleaning agents for automatic dishwashing. Examples of these are tallow fatty alcohols with 14 EO, 25 EO, 30 EO, or 40 EO.
[0245] Ethoxylated nonionic surfactants are particularly preferably used which were obtained from C.sub.6-20 monohydroxy alkanols or C.sub.6-20 alkyl phenols or C.sub.16-20 fatty alcohols and more than 12 mol, preferably more than 15 mol, and in particular more than 20 mol, ethylene oxide per mol of alcohol. A particularly preferred nonionic surfactant is obtained from a straight-chain fatty alcohol having 16 to 20 carbon atoms (C.sub.16-20 alcohol), preferably from a C.sub.18 alcohol and at least 12 mol, preferably at least 15 mol and in particular at least 20 mol, ethylene oxide. Of these, what are referred to as “narrow range ethoxylates” are particularly preferred.
[0246] Surfactants that are preferably used come from the group of the alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols and mixtures of these surfactants with structurally complex surfactants such as polyoxypropylene/polyoxyethylene/polyoxypropylene ((PO/EO/PO) surfactants). Such (PO/EO/PO) nonionic surfactants are also characterized by good foam control.
[0247] In the context of the present invention, low-foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units have been found to be particularly preferred nonionic surfactants, in particular for cleaning agents for automatic dishwashing. Among these, in turn, surfactants having EO-AO-EO-AO blocks are preferred, with one to ten EO groups or AO groups being bonded to one another before a block of the other group follows. Here, nonionic surfactants of general formula (T-4) are preferred
##STR00004##
are preferred, in which R.sup.1 represents a straight-chain or branched, saturated or mono- or polyunsaturated C.sub.6-24 alkyl or alkenyl functional group; each R.sub.2 and R.sub.3 group is selected, independently of one another, from —CH.sub.3, —CH.sub.2CH.sub.3, —CH.sub.2CH.sub.2—CH.sub.3, —CH(CH.sub.3).sub.2; and the indices w, x, y and z represent, independently of one another, integers from 1 to 6.
[0248] Preferred nonionic surfactants of the above formula can be prepared using known methods, from the corresponding alcohols R.sup.1—OH and ethylene or alkylene oxide. The R.sup.1 radical in the above formula can vary depending on the origin of the alcohol. If native sources are used, the R.sup.1 functional group has an even number of carbon atoms and is generally unbranched, with the linear functional groups of alcohols of native origin having 12 to 18 C atoms, such as coconut, palm, tallow fatty or oleyl alcohol, for example, being preferred. Some examples of alcohols that are available from synthetic sources are the Guerbet alcohols or functional groups that are methyl-branched or linear and methyl-branched in the 2 position in admixture, such as those usually present in oxo alcohol functional groups. Irrespective of the approach taken in the production of the alcohol used in the nonionic surfactants contained in the viscoelastic, solid filling substance, nonionic surfactants are preferred in which R.sup.1 represents an alkyl functional group having 6 to 24, preferably 8 to 20, particularly preferably 9 to 15, and in particular 9 to 11, carbon atoms in the above formula.
[0249] Besides propylene oxide, butylene oxide in particular is worthy of consideration as an alkylene oxide unit that is contained alternately with the ethylene oxide unit in the preferred nonionic surfactants. However, other alkylene oxides in which R.sup.2 and R.sup.3 are selected, independently of one another, from —CH.sub.2CH.sub.2—CH.sub.3 and —CH(CH.sub.3).sub.2 are also suitable. Preferably, nonionic surfactants of the above formula are used in which R.sup.2 and R.sup.3 represent a —CH.sub.3 functional group; w and x represent, independently of one another, values of 3 or 4; and y and z represent, independently of one another, values of 1 or 2.
[0250] Further preferably used nonionic surfactants, in particular for viscoelastic, solid filling substances for use as cleaning agents for automatic dishwashing, are nonionic surfactants of general formula (T-5)
R.sup.1O(AlkO).sub.xM(OAlk).sub.yOR.sup.2 (T-5)
where R.sup.1 and R.sup.2 represent, independently of one another, a branched or unbranched, saturated or unsaturated, optionally hydroxylated alkyl radical having 4 to 22 carbon atoms; Alk represents a branched or unbranched alkyl radical having 2 to 4 carbon atoms; x and y represent, independently of one another, values of between 1 and 70; and M represents an alkyl radical from the group CH.sub.2, CHR.sup.3, CR.sup.3R.sup.4, CH.sub.2CHR.sup.3 and CHR.sup.3CHR.sup.4, where R.sup.3 and R.sup.4 represent, independently of one another, a branched or unbranched, saturated or unsaturated alkyl radical having 1 to 18 carbon atoms.
[0251] Preferred in this case are nonionic surfactants of general formula (T-6)
R.sup.1—CH(OH)CH.sub.2—O(CH.sub.2CH.sub.2O).sub.xCH.sub.2CHR(OCH.sub.2CH.sub.2).sub.y—CH.sub.2CH(OH)—R.sup.2 (T-6),
where R, R.sup.1 and R.sup.2, independently of one another, represent an alkyl radical or alkenyl radical having 6 to 22 carbon atoms; x and y, independently of one another, represent values of between 1 and 40.
[0252] Preferred in this case are, in particular, compounds of general formula (T-7)
R.sup.1—CH(OH)CH.sub.2—O(CH.sub.2CH.sub.2O).sub.xCH.sub.2CHR(OCH.sub.2CH.sub.2).sub.yO—CH.sub.2CH(OH)—R.sup.2 (T-7)
in which R represents a linear, saturated alkyl radical having 8 to 16 carbon atoms, preferably 10 to 14 carbon atoms, and R.sup.1 and R.sup.2 represent, independently of one another, an alkyl radical or alkenyl radical having 6 to 22 carbon atoms, and n and m represent, independently of one another, values of from 20 to 30. Such compounds can be obtained, for example, by reacting alkyl diols HO—CHR—CH.sub.2—OH with ethylene oxide, a reaction with an alkyl epoxide being performed subsequently in order to close the free OH functions during formation of a dihydroxy ether.
[0253] Preferred nonionic surfactants are in this case, in particular for viscoelastic, solid filling substances for use as cleaning agents for automatic dishwashing, those of general formula (T-8)
R.sup.1—CH(OH)CH.sub.2O-(AO).sub.w-(AO).sub.x-(A″O).sub.y-(A′″O).sub.z—R.sup.2 (T-8)
where [0254] R.sup.1 represents a straight-chain or branched, saturated or mono- or polyunsaturated C.sub.6-24-alkyl or alkenyl radical; [0255] R.sup.2 represents hydrogen or a linear or branched hydrocarbon radical having 2 to 26 carbon atoms; [0256] A, A′, A″ and A′″ represent, independently of one another, a functional group from the group —CH.sub.2CH.sub.2, —CH.sub.2CH.sub.2—CH.sub.2, —CH.sub.2—CH(CH.sub.3), —CH.sub.2—CH.sub.2—CH.sub.2—CH.sub.2, —CH.sub.2—CH(CH.sub.3)—CH.sub.2—, —CH.sub.2—CH(CH.sub.2—CH.sub.3), [0257] w, x, y and z represent values between 0.5 and 120, it being also possible for x, y and/or z to be 0.
[0258] By adding the above-mentioned nonionic surfactants of general formula (T-8)
R.sup.1—CH(OH)CH.sub.2O-(AO).sub.w-(A′O).sub.x-(A″O).sub.y-(A′″O).sub.z—R.sup.2 (T-8)
hereinafter also referred to as “hydroxy mixed ethers,” the cleaning performance of preparations according to the invention can surprisingly be significantly improved, specifically in comparison to systems that contain alternative nonionic surfactants, such as those from the group of polyalkoxylated fatty alcohols.
[0259] By using these nonionic surfactants having one or more free hydroxyl groups on one or both terminal alkyl functional groups, the stability of the enzymes that may be additionally contained in the viscoelastic, solid filling substances according to the invention can be significantly improved.
[0260] In particular, those end-capped poly(oxyalkylated) nonionic surfactants are preferred, in particular for cleaning agents for automatic dishwashing, which, according to the following formula (T-10)
##STR00005##
in addition to a radical R.sup.1, which represents linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 2 to 30 carbon atoms, preferably having 4 to 22 carbon atoms, also have a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R.sup.2 having 1 to 30 carbon atoms, where n represents values of between 1 and 90, preferably values of between 10 and 80, and in particular values of between 20 and 60. Surfactants of the above formula are particularly preferred in which R.sup.1 represents C.sub.7 to C.sub.13, n represents a whole natural number from 16 to 28, and R.sup.2 represents C.sub.8 to C.sub.12.
[0261] Surfactants of the formula are particularly preferred, in particular for viscoelastic, solid filling substances for use as cleaning agents for automatic dishwashing
R.sup.1O[CH.sub.2CH(CH.sub.3)O].sub.x[CH.sub.2CH.sub.2O].sub.yCH.sub.2CH(OH)R.sup.2,
in which R.sup.1 represents a linear or branched aliphatic hydrocarbon functional group having 4 to 18 carbon atoms or mixtures thereof, R.sup.2 denotes a linear or branched hydrocarbon functional group having 2 to 26 carbon atoms or mixtures thereof, x represents values of between 0.5 and 1.5, and y represents a value of at least 15. The group of these nonionic surfactants includes for example the C.sub.2-26 fatty alcohol (PO).sub.1-(EO).sub.15-40-2-hydroxyalkyl ethers, in particular including the C.sub.8-10 fatty alcohol (PO).sub.1-(EO).sub.22-2-hydroxydecyl ethers.
[0262] Preferred in particular are those end-group-capped poly(oxyalkylated) nonionic surfactants, in particular for viscoelastic, solid filling substances for use as cleaning agents for automatic dishwashing, which are of the formula
R.sup.1O[CH.sub.2CH.sub.2O].sub.x[CH.sub.2CH(R.sup.3)O].sub.yCH.sub.2CH(OH)R.sup.2,
in which R.sup.1 and R.sup.2 represent, independently of one another, a linear or branched, saturated or mono- or polyunsaturated hydrocarbon functional group having 2 to 26 carbon atoms, R.sup.3 is selected, independently of one another, from —CH.sub.3, —CH.sub.2CH.sub.3, —CH.sub.2CH.sub.2—CH.sub.3, —CH(CH.sub.3).sub.2, but preferably represents —CH.sub.3, and x and y represent, independently of one another, values of between 1 and 32, with nonionic surfactants where R.sup.3=—CH.sub.3 and having values for x of from 15 to 32 and for y of from 0.5 and 1.5 being very particularly preferred.
[0263] Further preferably used nonionic surfactants, in particular for viscoelastic, solid filling substances for use as cleaning agents for automatic dishwashing, are the end-capped poly(oxyalkylated) nonionic surfactants of the formula
R.sup.1O[CH.sub.2CH(R.sup.3)O].sub.x[CH.sub.2].sub.kCH(OH)[CH.sub.2].sub.jOR.sup.2,
in which R.sup.1 and R.sup.2 represent linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R.sup.3 represents H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl or 2-methyl-2-butyl radical, x represents values between 1 and 30, and k and j represent values between 1 and 12, preferably between 1 and 5. If the value x is >2, each R.sup.3 in the above formula R.sup.1O[CH.sub.2CH(R.sup.3)O].sub.x[CH.sub.2].sub.kCH(OH)[CH.sub.2]OR.sup.2 can be different. R.sup.1 and R.sup.2 are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon functional groups having 6 to 22 carbon atoms, with functional groups having 8 to 18 C atoms being particularly preferred. For the functional group R.sup.3, H, —CH.sub.3 or —CH.sub.2CH.sub.3 are particularly preferred. Particularly preferred values for x are in the range of from 1 to 20, in particular from 6 to 15.
[0264] As described above, each R.sup.3 in the above formula can be different if x is >2. In this way, the alkylene oxide unit in square brackets can be varied. For example, if x represents 3, the functional group R.sup.3 can be selected in order to form ethylene oxide (R.sup.3=H) or propylene oxide (R.sup.3=CH.sub.3) units, which can be joined together in any sequence, for example (EO)(PO)(EO), (EO)(EO)(PO), (EO)(EO)(EO), (PO)(EO)(PO), (PO)(PO)(EO) and (PO)(PO)(PO). The value 3 for x has been selected here by way of example and can by all means be greater, in which case the range of variation increases as the values for x increase and includes a large number of (EO) groups combined with a small number of (PO) groups, for example, or vice versa.
[0265] Particularly preferred end-capped poly(oxyalkylated) alcohols of the above formula have values of k=1 and j=1, such that the previous formula is simplified to R.sup.1O[CH.sub.2CH(R.sup.3)O].sub.xCH.sub.2CH(OH)CH.sub.2OR.sup.2. In the formula mentioned last, R.sup.1, R.sup.2 and R.sup.3 are as defined above and x represents numbers from 1 to 30, preferably from 1 to 20, and in particular from 6 to 18. Surfactants in which the radicals R.sup.1 and R.sup.2 have 9 to 14 C atoms, R.sup.3 represents H, and x assumes values from 6 to 15 are particularly preferred. Finally, the nonionic surfactants of general formula R.sup.1—CH(OH)CH.sub.2O-(AO).sub.w—R.sup.2 have proven to be particularly effective, in which [0266] R.sup.1 represents a straight-chain or branched, saturated or mono- or polyunsaturated C.sub.6-24-alkyl or alkenyl radical; [0267] R.sup.2 represents a linear or branched hydrocarbon radical having 2 to 26 carbon atoms; [0268] A represents a radical from the group CH.sub.2CH.sub.2, CH.sub.2CH.sub.2CH.sub.2, CH.sub.2CH(CH.sub.3), preferably CH.sub.2CH.sub.2, and [0269] w represents values between 1 and 120, preferably 10 to 80, particularly 20 to 40.
[0270] The group of these nonionic surfactants includes, for example, the C.sub.4-22 fatty alcohol-(EO).sub.10-80-2-hydroxyalkyl ethers, in particular including the C.sub.8-12 fatty alcohol-(EO).sub.22-2-hydroxydecyl ethers and the C.sub.4-22 fatty alcohol-(EO).sub.40-80-2-hydroxyalkyl ethers.
[0271] Furthermore, the viscoelastic, solid filling substance according to the invention may contain amine oxide as a nonionic surfactant. In principle, all the amine oxides found in the prior art for this purpose, i.e. compounds that have the formula R.sup.1R.sup.2R.sup.3NO, where each of R.sup.1, R.sup.2 and R.sup.3 is, independently of one another, an optionally substituted hydrocarbon chain having 1 to 30 carbon atoms, can be used as the amine oxide. Amine oxides that are particularly preferably used are those in which R.sup.1 is an alkyl having 12 to 18 carbon atoms and R.sup.2 and R.sup.3 are, independently of one another, an alkyl having 1 to 4 carbon atoms, in particular alkyl dimethyl amine oxides having 12 to 18 carbon atoms. Examples of representatives of suitable amine oxides are N-coconut-alkyl-N,N-dimethyl amine oxide, N-tallow alkyl-N,N-dihydroxyethyl amine oxide, myristyl-/cetyl dimethyl amine oxide or lauryl dimethyl amine oxide.
[0272] Suitable nonionic surfactants include alkyl glycosides of general formula RO(G).sub.x, for example, in which R corresponds to a primary straight-chain or methyl-branched aliphatic radical, in particular an aliphatic radical that is methyl-branched in the 2 position, having 8 to 22, preferably 12 to 18, C atoms, and G is the symbol that represents a glycose unit having 5 or 6 C atoms, preferably glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably between 1.2 and 1.4.
[0273] Another class of preferably used nonionic surfactants, which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain.
[0274] Other suitable surfactants are the polyhydroxy fatty acid amides, which are known as PHFAs.
[0275] Other nonionic surfactants that can be used may be, for example, [0276] polyol fatty acid esters, [0277] alkoxylated triglycerides, [0278] alkoxylated fatty acid alkyl esters of formula R.sup.3CO—(OCH.sub.2CHR.sup.4).sub.wOR.sup.5, [0279] in which R.sup.3CO represents a linear or branched, saturated and/or unsaturated acyl functional group having 6 to 22 carbon atoms, R.sup.4 represents hydrogen or methyl, and R.sup.5 represents linear or branched alkyl functional groups having 1 to 4 carbon atoms, and w is 1 to 20, [0280] hydroxy mixed ethers, [0281] sorbitan fatty acid esters and addition products of ethylene oxide to sorbitan fatty acid esters such as the polysorbates, [0282] sugar fatty acid esters and addition products of ethylene oxide to sugar fatty acid esters, [0283] addition products of ethylene oxide to fatty acid alkanolamides and fatty amines, or [0284] fatty acid-N-alkyl glucamides.
[0285] The viscoelastic, solid filling substance according to the invention described herein may also contain a plurality of the nonionic surfactants described above.
[0286] According to the invention, particularly preferred viscoelastic, solid filling substances, in particular as textile washing agents, each contain, based on the total weight, a total amount of [0287] 10 to 60% by weight, in particular 25 to 40% by weight, of at least one anionic surfactant, and [0288] 2 to 35% by weight, in particular 18 to 28% by weight, of at least one nonionic surfactant.
[0289] Very particularly preferred viscoelastic, solid filling substances according to the invention for use as textile washing agents contain, according to the invention, at least one surfactant combination as described below for the compositions (A) to (D): [0290] (A) viscoelastic, solid filling substance containing, as a surfactant, in each case based on the total weight of the viscoelastic, solid filling substance, at least a total amount of [0291] 10 to 60 wt. % of at least one anionic surfactant, at least one C.sub.9-13-alkyl benzene sulfonate being contained as an anionic surfactant, and [0292] 2 to 35 wt. % of at least one nonionic surfactant, at least one alkoxylated alcohol having 8 to 18 carbon atoms and on average 4 to 12 mol ethylene oxide (EO) per mol of alcohol being contained as a nonionic surfactant. [0293] (B) viscoelastic, solid filling substance containing, as a surfactant, in each case based on the total weight of the viscoelastic, solid filling substance, at least a total amount of [0294] 10 to 60 wt. % of at least one anionic surfactant, at least 5 to 60 wt. % of at least one C.sub.9-13-alkyl benzene sulfonate being contained as an anionic surfactant, and [0295] 2 to 35 wt. % of at least one nonionic surfactant, at least 2 to 35 wt. % of at least one alkoxylated alcohol having 8 to 18 carbon atoms and on average 4 to 12 mol ethylene oxide (EO) per mol of alcohol being contained as a nonionic surfactant. [0296] (C) viscoelastic, solid filling substance containing, as a surfactant, in each case based on the total weight of the viscoelastic, solid filling substance, at least a total amount of [0297] 25 to 40 wt. % of at least one anionic surfactant, at least one C.sub.9-13-alkyl benzene sulfonate being contained as an anionic surfactant, and [0298] 18 to 28 wt. % of at least one nonionic surfactant, at least one alkoxylated alcohol having 8 to 18 carbon atoms and on average 4 to 12 mol ethylene oxide (EO) per mol of alcohol being contained as a nonionic surfactant. [0299] (D) viscoelastic, solid filling substance containing, as a surfactant, in each case based on the total weight of the viscoelastic, solid filling substance, at least a total amount of [0300] 25 to 40 wt. % of at least one anionic surfactant, at least 25 to 40 wt. % of at least one C.sub.9-13-alkyl benzene sulfonate being contained as an anionic surfactant, and [0301] 18 to 28 wt. % of at least one nonionic surfactant, at least 18 to 28 wt. % of at least one alkoxylated alcohol having 8 to 18 carbon atoms and on average 4 to 12 mol ethylene oxide (EO) per mol of alcohol being contained as a nonionic surfactant.
[0302] When providing all of the aforementioned solid, viscoelastic filling substances with a specific amount of selected surfactant, the amounts of the individual surfactant components are of course to be selected within the stated quantity ranges of the individual surfactant components so that the specified total amount of surfactant is adhered to.
[0303] Preferred viscoelastic and solid filling substances are characterized in that, based on their total weight, the organic gelator compound is contained in the above-mentioned filling substance in a total amount of 0.5 to 10.0 wt. %, in particular 0.8 to 5.0 wt. %, more preferably between 1.0 wt. % and 4.5 wt. %, very particularly preferably between 1.0 and 4.0 wt. %.
[0304] In preferred viscoelastic and solid filling substances, the organic gelator compound is selected from benzylidene alditol compound, diketopiperazine compound, dibenzylcystine compound, hydrogenated castor oil, hydroxystearic acid, N—(C.sub.8-C.sub.24)-hydrocarbyl glyconamide, or mixtures thereof. A selection from at least one benzylidene alditol compound is particularly preferred.
[0305] Very particularly preferred viscoelastic and solid filling substances are characterized in that the above-mentioned filling substance contains at least one benzylidene alditol compound of the formula (I) as the organic gelator compound
##STR00006##
wherein
*- represents a covalent single bond between an oxygen atom of the alditol backbone and the provided functional group,
n represents 0 or 1, preferably 1,
m represents 0 or 1, preferably 1,
R.sup.1, R.sup.2 and R.sup.3 represent, independently of one another, a hydrogen atom, a halogen atom, a C.sub.1-C.sub.4 alkyl group, a cyano group, a nitro group, an amino group, a carboxyl group, a hydroxyl group, a —C(═O)—NH—NH.sub.2 group, a —NH—C(═O)—(C.sub.2-C.sub.4-alkyl) group, a C.sub.1-C.sub.4 alkoxy group, a C.sub.1-C.sub.4 alkoxy C.sub.2-C.sub.4 alkyl group, with two of the functional groups forming, together with the remainder of the molecule, a 5-membered or 6-membered ring,
R.sup.4, R.sup.5, and R.sup.6 independently represent a hydrogen atom, a halogen atom, a C.sub.1-C.sub.4alkyl group, a cyano group, a nitro group, an amino group, a carboxyl group, a hydroxyl group, a —C(═O)—NH—NH.sub.2 group, a —NH—C(═O)—(C.sub.2-C.sub.4-alkyl) group, a C.sub.1-C.sub.4-alkoxy group, a C.sub.1-C.sub.4-alkoxy-C.sub.2-C.sub.4-alkyl group, wherein two of the radicals form, together with the remainder of the molecule, a 5- or 6-membered ring.
[0306] Due to the stereochemistry of the alditols, it should be mentioned that the above-mentioned benzylidene alditols according to the invention are suitable in the L configuration or in the D configuration or in a mixture of the two. Due to natural availability, the benzylidene alditol compounds are preferably used according to the invention in the D configuration. It has been found to be preferable for the alditol backbone of the benzylidene alditol compound according to formula (I) contained in the above-mentioned filling substance to be derived from D-glucitol, D-mannitol, D-arabinitol, D-ribitol, D-xylitol, L-glucitol, L-mannitol, L-arabinitol, L-ribitol, or L-xylitol.
[0307] Particularly preferred are those above-mentioned filling substances which are characterized in that R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5 and R.sup.6 according to the benzylidene alditol compound of formula (I) mean, independently of one another, a hydrogen atom, methyl, ethyl, chlorine, fluorine, or methoxy, preferably a hydrogen atom.
[0308] n according to benzylidene alditol compound of formula (I) preferably represents 1.
[0309] m according to benzylidene alditol compound formula (I) preferably represents 1.
[0310] More than very particularly preferably, the viscoelastic and solid filling substance according to the invention contains, as a benzylidene alditol compound of formula (I), at least one compound of formula (I-1)
##STR00007##
where R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5 and R.sup.6 are as defined in formula (I). Most preferably, according to formula (I-1), R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5 and R.sup.6 represent, independently of one another, a hydrogen atom, methyl, ethyl, chlorine, fluorine, or methoxy, preferably a hydrogen atom.
[0311] Most preferably, the benzylidene alditol compound of formula (I) is selected from 1,3:2,4-di-O-benzylidene-D-sorbitol; 1,3:2,4-di-O-(p-methylbenzylidene)-D-sorbitol; 1,3:2,4-di-O-(p-chlorobenzylidene)-D-sorbitol; 1,3:2,4-di-O-(2,4-dimethylbenzylidene)-D-sorbitol; 1,3:2,4-di-O-(p-ethylbenzylidene)-D-sorbitol; 1,3:2,4-di-O-(3,4-dimethylbenzylidene)-D-sorbitol, or mixtures thereof.
[0312] Preferred viscoelastic, solid filling substances contain at least one 2,5-diketopiperazine compound of the formula (I) as the organic gelator compound
##STR00008##
wherein
R.sup.1, R.sup.2, R.sup.3 and R.sup.4 independently of one another represent a hydrogen atom, a hydroxy group, a (C.sub.1-C.sub.6)-alkyl group, a (C.sub.2-C.sub.6)-alkenyl group, a (C.sub.2-C.sub.6)-acyl group, a (C.sub.2-C.sub.6)-acyloxy group, a (C.sub.1-C.sub.6)-alkoxy group, an amino group, a (C.sub.2-C.sub.6)-acylamino group, a (C.sub.1-C.sub.6)-alkylaminocarbonyl group, an aryl group, an aroyl group, an aroyloxy group, an aryloxy group, an aryl (C.sub.1-C.sub.4)-alkyloxy group, an aryl (C.sub.1-C.sub.3)-alkyl group, a heteroaryl group, a heteroaryl (C.sub.1-C.sub.3)-alkyl group, a (C.sub.1-C.sub.4)-hydroxyalkyl group, a (C.sub.1-C.sub.4)-aminoalkyl group, a carboxy(C.sub.1-C.sub.3)-alkyl group, wherein at least two of the radicals R.sup.1 to R.sup.4 can form a 5- or 6-membered ring together with the rest of the molecule,
R.sup.5 stands for a hydrogen atom, a linear (C.sub.1 to C.sub.6)-alkyl group, a branched (C.sub.3 to C.sub.6)-alkyl group, a (C.sub.3 to C.sub.6)-cycloalkyl group, a (C.sub.2-C.sub.6)-alkenyl group, a (C.sub.2-C.sub.6)-alkynyl group, a (C.sub.1-C.sub.4)-hydroxyalkyl group, a (C.sub.1-C.sub.4)-alkoxy-(C.sub.1-C.sub.4)-alkyl group, a (C.sub.1-C.sub.4)-acyloxy-(C.sub.1-C.sub.4)-alkyl group, an aryloxy-(C.sub.1-C.sub.4)-alkyl group, an O-(aryl-(C.sub.1-C.sub.4)-alkyl)oxy-(C.sub.1-C.sub.4)-alkyl group, a (C.sub.1-C.sub.4)-alkylsulphanyl-(C.sub.1-C.sub.4)-alkyl group, an aryl group, an aryl-(C.sub.1-C.sub.3)-alkyl group, a heteroaryl group, a hetroaryl-(C.sub.1-C.sub.3)-alkyl group, a (C.sub.1-C.sub.4)-hydroxyalkyl group, a (C.sub.1-C.sub.4)-aminoalkyl group, an N—(C.sub.1-C.sub.4)-alkylamino-(C.sub.1-C.sub.4)-alkyl group, an N,N—(C.sub.1-C.sub.4)-dialkylamino-(C.sub.1-C.sub.4)-alkyl group, an N—(C.sub.2-C.sub.8)-acylamino-(C.sub.1-C.sub.4)-alkyl group, an N—(C.sub.2-C.sub.8)-acyl-N—(C.sub.1-C.sub.4)-alkylamino-(C.sub.1-C.sub.4)-alkyl group, an N—(C.sub.2-C.sub.8)-Aroyl-N—(C.sub.1-C.sub.4)-alkylamino-(C.sub.1-C.sub.4)-alkyl group, an N,N—(C.sub.2-C.sub.8)-diacylamino-(C.sub.1-C.sub.4)-alkyl group, an N-(aryl-(C.sub.1-C.sub.4)-alkyl)amino-(C.sub.1-C.sub.4)-alkyl group, an N,N-di(aryl-(C.sub.1-C.sub.4)-alkyl)amino-(C.sub.1-C.sub.4)-alkyl group, a (C.sub.1-C.sub.4)-carboxyalkyl group, a (C.sub.1-C.sub.4)-alkoxycarbonyl-(C.sub.1-C.sub.3)-alkyl group, a (C.sub.1-C.sub.4)-acyloxy-(C.sub.1-C.sub.3)-alkyl group, a guanidino-(C.sub.1-C.sub.3)-alkyl group, an aminocarbonyl-(C.sub.1-C.sub.4)-alkyl group, an N—(C.sub.1-C.sub.4)-alkylaminocarbonyl-(C.sub.1-C.sub.4)-alkyl group, an N,N-Di((C.sub.1-C.sub.4)-alkyl) aminocarbonyl-(C.sub.1-C.sub.4)-alkyl group, an N—(C.sub.2-C.sub.8)-acylaminocarbonyl-(C.sub.1-C.sub.4)-alkyl group, an N,N—(C.sub.2-C.sub.8)-diacylaminocarbonyl-(C.sub.1-C.sub.4)-alkyl group, an N—(C.sub.2-C.sub.8)-acyl-N—(C.sub.1-C.sub.4)-alkylaminocarbonyl-(C.sub.1-C.sub.4)-alkyl group, an N-(aryl-(C.sub.1-C.sub.4)-alkyl) aminocarbonyl-(C.sub.1-C.sub.4)-alkyl group, an N-(aryl-(C.sub.1-C.sub.4)-alkyl)-N—(C.sub.1-C.sub.6)-alkylaminocarbonyl-(C.sub.1-C.sub.4)-alkyl group, or an N,N-di(aryl-(C.sub.1-C.sub.4)-alkyl)aminocarbonyl-(C.sub.1-C.sub.4)-alkyl group.
[0313] It is preferred according to the invention if R.sup.3 and R.sup.4 according to formula (II) represent a hydrogen atom. According to the invention it is particularly preferred if R.sup.2, R.sup.3 and R.sup.4 according to formula (II) represent a hydrogen atom. Very particularly preferred viscoelastic and solid filling substances according to the invention therefore contain at least one 2,5-diketopiperazine compound according to formula (II-a)
##STR00009##
wherein R.sup.1 and R.sup.5 are defined under formula (II) (vide supra).
[0314] It has been found to be preferred if the radical R.sup.1 according to formula (II) and according to formula (II-a) binds in the para position of the phenyl ring. For the purposes of the present invention, preference is therefore given to filling substances according to the invention which contain at least one 2,5-diketopiperazine compound according to formula (II-b),
##STR00010##
wherein R.sup.1 and R.sup.5 are defined as above under formula (II) (vide supra). The numbers 3 and 6 positioned on the ring atoms in formula (II-b) only mark positions 3 and 6 of the diketopiperazine ring, as they are generally used in the scope of the invention for naming all 2,5-diketopiperazines according to the invention.
[0315] The 2,5-diketopiperazine compounds of the formula (II) have centers of chirality at least on the carbon atoms in positions 3 and 6 of the 2,5-diketopiperazine ring. The numbering of ring positions 3 and 6 was illustrated by way of example in formula (II-b). The 2,5-diketopiperazine compound of the formula (II) of the filling substance according to the invention is preferably the configuration isomer 3 S, 6S, 3R, 6S, 3 S, 6R based on the stereochemistry of the carbon atoms at the 3 and 6 position of the 2,5-diketopiperazine ring, 3R, 6R, or mixtures thereof, particularly preferably 3S, 6S.
[0316] Preferred portion packs contain in the above-mentioned filling substance at least one 2,5-diketopiperazine compound of the formula (II) as an organic gelator compound selected from 3-benzyl-6-carboxyethyl-2,5-diketopiperazine, 3-benzyl-6-carboxymethyl-2,5-diketopiperazine, 3-benzyl-6-(p-hydroxybenzyl)-2,5-diketopiperazine, 3-benzyl-6-iso-propyl-2,5-diketopiperazine, 3-benzyl-6-(4-aminobutyl)-2,5-diketopiperazine, 3,6-di(benzyl)-2,5-diketopiperazine, 3,6-di(p-hydroxybenzyl)-2,5-diketopiperazine, 3,6-di(p-(benzyloxy)benzyl)-2,5-diketopiperazine, 3-benzyl-6-(4-imidazolyl)methyl-2,5-diketopiperazine, 3-benzyl-6-methyl-2,5-diketopiperazine, 3-benzyl-6-(2-(benzyloxycarbonyl)ethyl)-2,5-diketopiperazine, or mixtures thereof. In turn, compounds with the aforementioned configuration isomers are preferably suitable for selection.
[0317] It is also possible for the portion packs according to the invention to contain at least one diarylamidocystine compound of the formula (III) in their above-mentioned filling substance as the organic gelator compound
##STR00011##
wherein
X.sup.+, independently of each other, stands for a hydrogen atom or an equivalent of a cation,
R.sup.1, R.sup.2, R.sup.3, and R.sup.4, independently of each other, stand for a hydrogen atom, a halogen atom, a C.sub.1-C.sub.4 alkyl group, a C.sub.1-C.sub.4 alkoxy group, a C.sub.2-C.sub.4 hydroxyalkyl group, a hydroxyl group, an amino group, an N—(C.sub.1-C.sub.4 alkyl)amino group, an N,N-Di(C.sub.1-C.sub.4 alkyl)amino group, an N—(C.sub.2-C.sub.4 hydroxyalkyl)amino group, an N,N-Di(C.sub.2-C.sub.4 hydroxyalkyl)amino group, or R.sup.1 with R.sup.2 or R.sup.3 with R.sup.4 forms a 5- or 6-segment annulated ring, which in turn can each be substituted with at least one group from C.sub.1-C.sub.4 alkyl group, C.sub.1-C.sub.4 alkoxy group, C.sub.2-C.sub.4 hydroxyalkyl group, hydroxyl group, amino group, N—(C.sub.1-C.sub.4 alkyl)amino group, N,N-Di(C.sub.1-C.sub.4 alkyl)amino group, N—(C.sub.2-C.sub.4 hydroxyalkyl)amino group, N,N-Di(C.sub.2-C.sub.4 hydroxyalkyl)amino group.
[0318] Each of the stereocenters contained in the compound of the formula (III) can independently represent the L or D stereoisomer. It is preferable according to the invention for the above-mentioned cystine compound of formula (III) to be derived from the L stereoisomer of the cysteine.
[0319] The above-mentioned filling substances can contain at least one compound of formula (III), in which R.sup.1, R.sup.2, R.sup.3, and R.sup.4, independently of each other, stand for a hydrogen atom, a halogen atom, a C.sub.1-C.sub.4 alkyl group, a C.sub.1-C.sub.4 alkoxy group, a C.sub.2-C.sub.4 hydroxyalkyl group, a hydroxyl group, or R.sup.1 with R.sup.2 or R.sup.3 with R.sup.4 forms a 5- or 6-segment annulated ring, which in turn can each be substituted with at least one group from C.sub.1-C.sub.4 alkyl group, C.sub.1-C.sub.4 alkoxy group, C.sub.2-C.sub.4 hydroxyalkyl group, or hydroxyl group. In particular, those filling substances which contain N,N′-dibenzoylcystine (R.sup.1=R.sup.2=R.sup.3=R.sup.4 hydrogen atom; X.sup.+=independently of each other, for a hydrogen atom or an equivalent of a cation), in particular N,N′-dibenzoyl-L-cystine, as a diarylamidocystine compound of formula (III) are particularly suitable.
[0320] The N—(C.sub.5-C.sub.24)-hydrocarbyl glyconamide compounds suitable as organic gelator compounds preferably have the formula (IV)
##STR00012##
wherein
n is 2 to 4, preferably 3 or 4, in particular 4;
R.sup.1 is selected from hydrogen, C.sub.1-C.sub.16 alkyl radicals, C.sub.1-C.sub.3 hydroxy or methoxyalkyl radicals, preferably C.sub.1-C.sub.3 alkyl, hydroxyalkyl, or methoxyalkyl radicals, particularly preferably methyl;
R.sup.2 is selected from C.sub.5-C.sub.24 alkyl radicals, C.sub.5-C.sub.24 monoalkenyl radicals, C.sub.5-C.sub.24 dialkenyl radicals, C.sub.5-C.sub.24 trialkenyl radicals, C.sub.5-C.sub.24 hydroxyalkyl radicals, C.sub.5-C.sub.24-hydroxyalkenyl residues, C.sub.1-C.sub.3 hydroxyalkyl residues or methoxy-C.sub.1-C.sub.3-alkyl residues, preferably C.sub.8-C.sub.18 alkyl residues and mixtures thereof, more preferably C.sub.8, C.sub.10, C.sub.12, C.sub.14, C.sub.16, and C.sub.18 alkyl radicals and mixtures thereof, most preferably C.sub.12 and C.sub.14 alkyl radicals or a mixture thereof.
[0321] In particularly preferred embodiments, the remainder
##STR00013##
is a residue derived from a glycuronic acid, in particular the glycuronic acid of a hexose (n=4). In particular, glucuronic acid should be mentioned as a preferred residue. R.sup.1 is preferably H or a short-chain alkyl radical, in particular methyl. R.sup.2 is preferably a long-chain alkyl radical, for example a C.sub.8-C.sub.18 alkyl radical.
[0322] Compounds of the formula (IV-1) are therefore very particularly preferred
##STR00014##
where R.sup.2 has the meanings given for formula (IV).
[0323] The filling substance according to the invention of the portion pack according to the invention optionally contains water. It is preferred if in the above-mentioned filling substance water is contained in a total amount of 0 to 30 wt. %, more preferably 0 and 30 wt. %, particularly preferably 0 to 25 wt. %, more preferably 0 and 25 wt. %, very particularly preferably 0 to 20 wt. %, more preferably 0 and 20 wt. %, based on the total weight of the filling substance. The proportion of water in the filling substance is very particularly preferably 20 wt. % or less, more preferably 15 wt. % or less, even more preferably 12 wt. % or less, in particular between 4 and 11 wt. %. The quantities in wt. % refer to the total weight of the filling substance in each case.
[0324] Viscoelastic, solid filling substances that can be used with preference are characterized in that they additionally contain at least one organic solvent with a molecular weight of at most 500 g/mol. It is again particularly preferred if the above-mentioned organic solvent is selected from (C.sub.2-C.sub.8)-alkanols with at least one hydroxyl group (very particularly preferably from ethanol, ethylene glycol, 1,2-propanediol, glycerin, 1,3-propanediol, n-propanol, isopropanol, 1,1,1-trimethylolpropane, 2-methyl-1,3-propanediol, 2-hydroxymethyl-1,3-propanediol), triethylene glycol, butyl diglycol, polyethylene glycols having a weight-average molar mass M.sub.w of at most 500 g/mol, glycerol carbonate, propylene carbonate, 1-methoxy-2-propanol, 3-methoxy-3-methyl-1-butanol, butyl lactate, 2-isobutyl-2-methyl-4-hydroxymethyl-1,3-dioxolane, 2,2-dimethyl-4-hydroxymethyl-1,3-dioxolane, dipropylene glycol, or mixtures thereof.
[0325] Said organic solvent is particularly preferably contained in the above-mentioned at least one filling substance in a total amount of 5 to 40 wt. %, in particular 10 to 35 wt. %, based on the total weight of the above-mentioned at least one filling substance.
[0326] It is preferred according to the invention if the viscoelastic and solid filling substance is present in the portion pack as a molded body.
[0327] A molded body is a single body that stabilizes itself in the shape imparted to it. This dimensionally stable body is formed from a molding compound (e.g., a composition) in such a way that this molding compound is deliberately brought into a predetermined shape, for example, by pouring a liquid composition into a casting mold (for example, the shell according to the invention) and then curing the liquid composition, for example in the scope of a sol-gel process. All conceivable shapes are possible, such as spheres, cubes, cuboids, round discs, tubs, bowls, prisms, octas, tetrahedra, egg shapes, dogs, cats, mice, horses, torsos, busts, pillows, automobiles, oval discs with an embossed trademark, and much more.
[0328] It is preferred according to the invention if the molded body of the viscoelastic, solid filling substance has a weight of at least 1 g, preferably at least 5 g, particularly preferably at least 10 g.
[0329] It is preferred according to the invention if the molded body according to the invention of the viscoelastic, solid filling substance has a weight of at most 80 g, in particular at most 70 g, particularly preferably at most 50 g, very particularly preferably at most 40 g, most preferably at most 30 g. In this context, the aforementioned minimum weights of the molded body are particularly preferred.
[0330] The molded body of the viscoelastic, solid filling substance very particularly preferably has a weight of 10 to 80 g, in particular 10 to 70 g, more preferably 10 to 50 g, most preferably 10 to 30 g, for example 15 g or 25 g. It is again preferred if the above-mentioned molded body contains surfactant in the total amounts marked as preferred (vide supra).
[0331] According to the invention, preferred viscoelastic, solid filling substances additionally contain at least one active ingredient selected from polyalkoxylated polyamine, soil-release active ingredient, enzyme, builders, complexing agents, optical brighteners (preferably in portion packs for textile washing), pH adjusters, perfume, dyes, dye transfer inhibitors or the mixtures thereof.
[0332] It is preferred according to the invention if the viscoelastic, solid filling substance according to the invention (in particular as a textile washing agent) contains at least one polyalkoxylated polyamine in addition to the surfactant.
[0333] In the scope of the present invention and its individual aspects, the polyalkoxylated polyamine is a polymer having an N-atom-containing backbone which carries polyalkoxy groups on the N atoms. The polyamine has primary amino functions at the ends (terminus and/or side chains) and preferably both secondary and tertiary amino functions internally; optionally, it may also have merely secondary amino functions internally, such that a linear polyamine, and not a branched chain polyamine, is produced. The ratio of primary to secondary amino groups in the polyamine is preferably in the range of from 1:0.5 to 1:1.5, in particular in the range of from 1:0.7 to 1:1. The ratio of primary to tertiary amino groups in the polyamine is preferably in the range of from 1:0.2 to 1:1, in particular in the range of from 1:0.5 to 1:0.8. The polyamine preferably has an average molar mass in the range of from 500 g/mol to 50,000 g/mol, in particular from 550 g/mol to 5,000 g/mol. The N atoms in the polyamine are separated from one another by alkylene groups, preferably by alkylene groups having 2 to 12 C atoms, in particular 2 to 6 C atoms, although it is not necessary for all the alkylene groups to have the same number of C atoms. Ethylene groups, 1,2-propylene groups, 1,3-propylene groups, and mixtures thereof are particularly preferred. Polyamines which carry ethylene groups as the above-mentioned alkylene group are also referred to as polyethyleneimine or PEI. PEI is a polymer that is particularly preferred according to the invention and has an N-atom-containing backbone.
[0334] The primary amino functions in the polyamine can carry 1 or 2 polyalkoxy groups and the secondary amino functions can carry 1 polyalkoxy group, although it is not necessary for every amino function to be alkoxy group-substituted. The average number of alkoxy groups per primary and secondary amino function in the polyalkoxylated polyamine is preferably from 1 to 100, in particular from 5 to 50. The alkoxy groups in the polyalkoxylated polyamine are preferably polypropoxy groups which are directly bound to N atoms, and/or polyethoxy groups which are bound to potentially present propoxy functional groups and to N atoms which do not carry propoxy groups.
[0335] Polyethoxylated polyamines are obtained by reacting polyamines with ethylene oxide (abbreviated to EO). The polyalkoxylated polyamines containing ethoxy and propoxy groups are preferably obtainable by reacting polyamines with propylene oxide (abbreviated to PO) and subsequent reaction with ethylene oxide.
[0336] The average number of propoxy groups per primary and secondary amino function in the polyalkoxylated polyamine is preferably from 1 to 40, in particular from 5 to 20.
[0337] The average number of ethoxy groups per primary and secondary amino function in the polyalkoxylated polyamine is preferably from 10 to 60, in particular from 15 to 30.
[0338] If desired, the terminal OH function polyalkoxy substituents in the polyalkoxylated polyamine can be partially or completely etherified with a C.sub.1-C.sub.10 alkyl group, in particular a C.sub.1-C.sub.3 alkyl group.
[0339] Polyalkoxylated polyamines which are particularly preferred according to the invention can be selected from polyamine reacted with 45EO per primary and secondary amino function, PEIs reacted with 43EO per primary and secondary amino function, PEIs reacted with 15EO+5PO per primary and secondary amino function, PEIs reacted with 15PO+30EO per primary and secondary amino function, PEIs reacted with 5PO+39.5EO per primary and secondary amino function, PEIs reacted with 5PO+15EO per primary and secondary amino function, PEIs reacted with 10PO+35EO per primary and secondary amino function, PEIs reacted with 15PO+30EO per primary and secondary amino function and PEIs reacted with 15PO+5EO per primary and secondary amino function. A very particularly preferred alkoxylated polyamine is PEI having a content of from 10 to 20 nitrogen atoms reacted with 20 units of EO per primary or secondary amino function of the polyamine.
[0340] A further preferred subject of the invention is the use of polyalkoxylated polyamines which can be obtained by reacting polyamines with ethylene oxide and optionally also propylene oxide. If polyamines polyalkoxylated with ethylene oxide and propylene oxide are used, the proportion of propylene oxide in terms of the total amount of the alkylene oxide is preferably from 2 mol. % to 18 mol. %, in particular from 8 mol. % to 15 mol. %.
[0341] The viscoelastic, solid filling substance according to the invention additionally contains preferably, based on the weight thereof, polyalkoxylated polyamines, in a total amount of from 0.5 to 12 wt. %, in particular from 5.0 to 9.0 wt. %.
[0342] In a further preferred embodiment, the viscoelastic, solid filling substance according to the invention, in particular as a textile washing agent, additionally contains at least one soil release active ingredient. Substances which allow the removal of dirt are often referred to as soil-release active ingredients or as soil repellents since they are capable of making the treated surface, preferably textiles, repellant to soil. Owing to their chemical similarity to polyester fibers, particularly effective active ingredients which allow the removal of dirt, but can also exhibit the desired effect on fabrics made of other materials, are copolyesters containing dicarboxylic acid units, alkylene glycol units and polyalkylene glycol units. Such polyesters which allow the removal of dirt and the use thereof, preferably in washing agents for textiles, have long been known.
[0343] For example, polymers of ethylene terephthalate and polyethylene oxide terephthalate in which the polyethylene glycol units have molecular weights of from 750 to 5,000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate is from 50:50 to 90:10, and the use thereof in washing agents are described in the German patent DE 28 57 292. Polymers that have a molecular weight of from 15,000 to 50,000 and consist of ethylene terephthalate and polyethylene oxide terephthalate in which the polyethylene glycol units have molecular weights of from 1,000 to 10,000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate is from 2:1 to 6:1 can be used in washing agents according to the German laid-open application DE 33 24 258. European patent EP 066 944 relates to textile treatment agents containing a copolyester of ethylene glycol, polyethylene glycol, aromatic dicarboxylic acid and sulfonated aromatic dicarboxylic acid in certain molar ratios. European patent EP 185 427 discloses polyesters that are end-capped with methyl or ethyl groups and have ethylene and/or propylene terephthalate and polyethylene oxide terephthalate units, and washing agents containing soil-release polymers of this kind. European patent EP 241 984 relates to a polyester which, in addition to oxyethylene groups and terephthalic acid units, also contains substituted ethylene units and glycerol units. European patent EP 241 985 discloses polyesters which, in addition to oxyethylene groups and terephthalic acid units, contain 1,2-propylene, 1,2-butylene and/or 3-methoxy-1,2-propylene groups and glycerol units, and which are end-capped with C.sub.1 to C.sub.4 alkyl groups. European patent EP 253 567 relates to soil-release polymers that have a molar mass of from 900 to 9,000 and consist of ethylene terephthalate and polyethylene oxide terephthalate, wherein the polyethylene glycol units have molecular weights of from 300 to 3,000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate is from 0.6 to 0.95. European patent application EP 272 033 discloses polyesters that are end-capped at least in portions with C.sub.1-4 alkyl or acyl functional groups and that have polypropylene terephthalate and polyoxyethylene terephthalate units. European patent EP 274 907 describes sulfoethyl-end-capped soil-release polyesters containing terephthalate. In European patent application EP 357 280, soil-release polyesters having terephthalate, alkylene glycol and poly-C.sub.2-4 glycol units are produced by sulfonation of unsaturated end groups.
[0344] In a preferred embodiment of the invention, the viscoelastic, solid filling substance according to the invention contains at least one polyester which allows the removal of dirt, containing the structural units EI to E-III or EI to E-IV,
##STR00015##
in which
a, b and c each represent, independently of one another, a number from 1 to 200,
d, e and f each represent, independently of one another, a number from 1 to 50,
g represents a number from 0 to 5,
Ph is a 1,4-phenylene functional group,
sPh represents a 1,3-phenylene functional group substituted with a —SO.sub.3M group in position 5,
M represents Li, Na, K, Mg/2, Ca/2, Al/3, ammonium, mono-, di-, tri- or tetraalkylammonium, the alkyl function groups of the ammonium ions being C.sub.1-C.sub.22 alkyl functional groups or C.sub.2-C.sub.10 hydroxyalkyl functional groups or any desired mixtures thereof,
R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5 and R.sup.6 each represent, independently of one another, hydrogen or a C.sub.1-C.sub.18 n- or iso-alkyl group,
R.sup.7 represents a linear or branched C.sub.1-C.sub.30 alkyl group or a linear or branched C.sub.2-C.sub.30 alkenyl group, a cycloalkyl group having 5 to 9 carbon atoms, a C.sub.6-C.sub.30 aryl group or a C.sub.6-C.sub.30 arylalkyl group, and
[0345] Polyfunctional unit represents a unit having 3 to 6 functional groups capable of esterification reaction.
[0346] Preference is given to those polyesters in which R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5 and R.sup.6 are each, independently of one another, hydrogen or methyl, R.sup.7 represents methyl, a, b and c are each, independently of one another, a number from 1 to 200, in particular 1 to 20, particularly preferably 1 to 5, very preferably a and b=1 and c can be a number from 2 to 10, d is a number between 1 and 25, in particular between 1 and 10, particularly preferably between 1 and 5, e is a number between 1 and 30, in particular between 2 and 15, particularly preferably between 3 and 10, and f is a number between 0.05 and 15, in particular between 0.1 and 10, and particularly preferably between 0.25 and 3. Polyesters of this kind can be obtained, for example, by polycondensation of terephthalic acid dialkyl ester, 5-sulfoisophthalic acid dialkyl ester, alkylene glycols, optionally polyalkylene glycols (where a, b and/or c>1) and polyalkylene glycols capped at one end (corresponding to unit E-III). It should be noted that, for numbers a, b, c>1, there is a polymer backbone and thus the coefficients can assume, as an average, any value within the specified interval. This value reflects the number-average molecular weight. An ester of terephthalic acid having one or more difunctional, aliphatic alcohols is considered as unit (E-I), with ethylene glycol (R.sup.1 and R.sup.2 each being H) and/or 1,2-propylene glycol (R.sup.1=H and R.sup.2=—CH.sub.3 or vice versa) and/or shorter-chain polyethylene glycols and/or poly[ethylene glycol-co-propylene glycol] having number-average molecular weights of from 100 to 2,000 g/mol being preferably used. The structures can contain, for example, 1 to 50 units (E-I) per polymer chain. An ester of 5-sulfoisophthalic acid having one or more difunctional, aliphatic alcohols is considered as unit (E-II), with the above-mentioned esters preferably being used in this case. There can be, for example, 1 to 50 units (E-II) in the structures. Poly[ethylene glycol-co-propylene glycol] monomethyl ethers having average molecular weights of from 100 to 2,000 g/mol and polyethylene glycol monomethyl ethers of general formula CH.sub.3—O—(C.sub.2H.sub.4O).sub.n—H where n=1 to 99, in particular 1 to 20 and particularly preferably 2 to 10, are preferably used as polyalkylene glycol monoalkyl ethers according to unit (E-III) that are nonionically capped at one end. Since the theoretical maximum average molecular weight, to be achieved using quantitative conversion, of a polyester structure is specified by the use of such ethers that are capped at one end, the preferred use amount of structural unit (E-III) is that which is necessary for achieving the average molecular weights described below. With the exception of linear polyesters which result from structural units (E-I), (E-II) and (E-III), the use of crosslinked or branched polyester structures is also in accordance with the invention. This is expressed by the presence of a crosslinking polyfunctional structural unit (E-IV) having at least three to at most 6 functional groups capable of an esterification reaction. Acid, alcohol, ester, anhydride or epoxy groups, for example, can be named as functional groups in this case. Different functionalities in one molecule are also possible. Examples of this are citric acid, malic acid, tartaric acid and gallic acid, particularly preferably 2,2-dihydroxymethylpropionic acid. Polyhydric alcohols such as pentaerythrol, glycerin, sorbitol and/or trimethylolpropane can also be used. These may also be polyvalent aliphatic or aromatic carboxylic acids, such as benzene-1,2,3-tricarboxylic acid (hemimellitic acid), benzene-1,2,4-tricarboxylic acid (trimellitic acid), or benzene-1,3,5-tricarboxylic acid (trimesic acid). The weight proportion of crosslinking monomers, based on the total mass of the polyester, can be up to 10 wt. %, in particular up to 5 wt. %, and particularly preferably up to 3 wt. %, for example. The polyesters, containing the structural units (El), (E-II) and (E-III) and optionally (E-IV), generally have number-average molecular weights in the range of from 700 to 50,000 g/mol, it being possible to determine the number-average molecular weight by means of size-exclusion chromatography in aqueous solution, using calibration with reference to closely distributed polyacrylic acid Na salt standards. Preferably, the number-average molecular weights are in the range of from 800 to 25,000 g/mol, in particular from 1,000 to 15,000 g/mol, particularly preferably from 1,200 to 12,000 g/mol. Preferably, solid polyesters having softening points above 40° C. are used according to the invention as a component of the particle of the second type; said polyesters preferably have a softening point of between 50 and 200° C., particularly preferably between 80° C. and 150° C., and extremely preferably between 100° C. and 120° C. The polyesters can be synthesized according to known processes, for example by the above-mentioned components first being heated at normal pressure by adding a catalyst and then forming the required molecular weights in the vacuum by hyperstoichiometric amounts of the glycols used being distilled off. The known transesterification and condensation catalysts, such as titanium tetraisopropylate, dibutyltin oxide, alkaline or alkaline earth metal alcoholates, or antimony trioxide/calcium acetate, are suitable for the reaction. Reference is made to EP 442 101 for further details.
[0347] The viscoelastic, solid filling substance according to the invention can additionally contain at least one enzyme as a washing or cleaning agent. In principle, all the enzymes found in the prior art for textile treatment can be used in this regard. This at least one enzyme is preferably one or more enzymes which can develop catalytic activity in a surfactant-containing liquor, in particular a protease, amylase, lipase, cellulase, hemicellulase, mannanase, pectin-cleaving enzyme, tannase, xylanase, xanthanase, ß-glucosidase, carrageenanase, perhydrolase, oxidase, oxidoreductase and mixtures thereof. Preferred hydrolytic enzymes include in particular proteases, amylases, in particular α-amylases, cellulases, lipases, hemicellulases, in particular pectinases, mannanases, ß-glucanases, and mixtures thereof. Proteases, amylases and/or lipases and mixtures thereof are particularly preferred, and proteases are very particularly preferred. These enzymes are in principle of natural origin; starting from the natural molecules, variants that have been improved for use in washing or cleaning agents are available, which are preferably used accordingly.
[0348] Among the proteases, the subtilisin-type proteases are preferred. Examples of these are the subtilisins BPN′ and Carlsberg, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, the subtilisin DY, and the enzymes thermitase, proteinase K and proteases TW3 and TW7, which belong to the subtilases but no longer to the subtilisins in the narrower sense. Subtilisin Carlsberg is available in a developed form under the trade name Alcalase® from Novozymes A/S, Bagsvaerd, Denmark. Subtilisins 147 and 309 are marketed by Novozymes under the trade names Esperase® and Savinase®, respectively. The protease variants marketed under the name BLAP® are derived from the protease from Bacillus lentus DSM 5483. Other proteases that can be used are, for example, the enzymes available under the trade names Durazym®, Relase®, Everlase®, Nafizym®, Natalase®, Kannase® and Ovozyme® from Novozymes, the enzymes available under the trade names Purafect®, Purafect® OxP, Purafect® Prime, Excellase® and Properase® from Genencor, the enzyme available under the trade name Protosol® from Advanced Biochemicals Ltd., Thane, India, the enzyme available under the trade name Wuxi® from Wuxi Snyder Bioproducts Ltd., China, the enzymes available under the trade names Proleather® and Protease P® from Amano Pharmaceuticals Ltd., Nagoya, Japan, and the enzyme available under the name Proteinase K-16 from Kao Corp., Tokyo, Japan. Also, the proteases from Bacillus gibsonii and Bacillus pumilus are particularly preferably used.
[0349] Examples of amylases that can be used according to the invention are α-amylases from Bacillus licheniformis, from B. amyloliquefaciens or from B. stearothermophilus, as well as the developments thereof that have been improved for use in washing or cleaning agents. The enzyme from B. licheniformis is available from Novozymes under the name Termamyl® and from Genencor under the name Purastar®ST. Development products of this α-amylase are available from Novozymes under the trade names Duramyl® and Termamyl®ultra, from Genencor under the name Purastar®OxAm, and from Daiwa Seiko Inc., Tokyo, Japan, as Keistase®. The α-amylase from B. amyloliquefaciens is marketed by Novozymes under the name BAN®, and derived variants from the α-amylase from B. stearothermophilus are marketed under the names BSG® and Novamyl®, also by Novozymes. Furthermore, for this purpose the α-amylases from Bacillus sp. A 7-7 (DSM 12368) and cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948) are to be emphasized. Fusion products of all mentioned molecules can also be used. Furthermore, the developments of the α-amylase from Aspergillus niger and A. oryzae, available under the trade name Fungamyl® from Novozymes, are suitable. Other commercial products that can advantageously be used are, for example, Amylase-LT®, and Stainzyme® or Stainzyme Ultra® or Stainzyme Plus®, the latter also from Novozymes. Variants of these enzymes that can be obtained by point mutations may also be used according to the invention.
[0350] Examples of lipases or cutinases that can be used according to the invention, which are contained in particular due to their triglyceride-cleaving activities, but also in order to produce peracids in situ from suitable precursors, are the lipases that can be originally obtained or developed from Humicola lanuginosa (Thermomyces lanuginosis), in particular those with the amino acid exchange D96L. These are marketed for example by Novozymes under the trade names Lipolase®, Lipolase®Ultra, LipoPrime®, Lipozyme® and Lipex®. Furthermore, the cutinases that have been isolated originally from Fusarium solani pisi and Humicola insolens can be used, for example. Lipases that can also be used are available from Amano under the names Lipase CE®, Lipase P®, Lipase B®, and Lipase CES®, Lipase AKG®, Bacillus sp. Lipase®, Lipase AP®, Lipase M-AP® and Lipase AML®. From Genencor, the lipases or cutinases of which the starting enzymes have been isolated originally from Pseudomonas mendocina and Fusarium solanii can be used, for example. The preparations M1 Lipase® and Lipomax® originally marketed by Gist-Brocades, the enzymes marketed by Meito Sangyo KK, Japan, under the names Lipase MY-30®, Lipase OF® and Lipase PL®, and the product Lumafast® from Genencor should be mentioned as other important commercial products.
[0351] Depending on their purpose, cellulases can be present as pure enzymes, as enzyme preparations or in the form of mixtures in which the individual components are advantageously complementary in terms of their different performance aspects, in particular in portion packs for textile washing. These performance aspects include in particular the contributions of the cellulase to the primary washing performance of the agent (cleaning performance), to the secondary washing performance of the agent (anti-redeposition effect or graying inhibition), to softening (fabric effect), or to providing a “stone-washed” effect. A usable fungal cellulase preparation that is rich in endoglucanase (EG) and the developments thereof are provided by Novozymes under the trade name Celluzyme®. The products Endolase® and Carezyme®, also available from Novozymes, are based on 50 kD-EG and 43 kD-EG, respectively, from H. insolens DSM 1800. Other commercial products from this company that can be used are Cellusoft®, Renozyme® and Celluclean®. It is also possible to use, for example, 20 kD-EG from Melanocarpus, which are available from AB Enzymes, Finland under the trade names Ecostone® and Biotouch®. Further trade products from AB Enzymes are Econase® and Ecopulp®. Other suitable cellulases are from Bacillus sp. CBS 670.93 and CBS 669.93, wherein those from Bacillus sp. CBS 670.93 are available from Genencor under the trade name Puradax®. Other commercial products from Genencor are “Genencor detergent cellulase L” and IndiAge®Neutra. Variants of these enzymes that can be obtained by point mutations may also be used according to the invention. Particularly preferred cellulases are Thielavia terrestris cellulase variants, cellulases from Melanocarpus, in particular Melanocarpus albomyces, EGIII-type cellulases from Trichoderma reesei, or variants that can be obtained therefrom.
[0352] Furthermore, other enzymes which can be grouped together under the term “hemicellulases” can be used in particular to remove specific problematic stains on the substrate. These include, for example, mannanases, xanthan lyases, xanthanases, xyloglucanases, xylanases, pullulanases, pectin-cleaving enzymes, and β-glucanases. The β-glucanase obtained from Bacillus subtilis is available from Novozymes under the name Cereflo®. Hemicellulases that are particularly preferred according to the invention are mannanases which are marketed, for example, under the trade names Mannaway® by Novozymes or Purabrite® by Genencor.
[0353] In the context of the present invention, the pectin-cleaving enzymes also include enzymes having the names pectinase, pectate lyase, pectin esterase, pectin demethoxylase, pectin methoxylase, pectin methylesterase, pectase, pectin methylesterase, pectinesterase, pectin pectyl hydrolase, pectin depolymerase, endopolygalacturonase, pectolase, pectin hydrolase, pectin polygalacturonase, endopolygalacturonase, poly-α-1,4-galacturonide, glycanohydrolase, endogalacturonase, endo-D-galacturonase, galacturan 1,4-α-galacturonidase, exopolygalacturonase, poly(galacturonate) hydrolase, exo-D-galacturonase, exo-D-galacturonanase, exopoly-D-galacturonase, exo-poly-α-galacturonosidase, exopolygalacturonosidase, or exopolygalacturanosidase. Examples of enzymes that are suitable in this regard are available for example under the names Gamanase®, Pektinex AR®, X-Pect® or Pectaway® from Novozymes, under the names Rohapect UF®, Rohapect TPL®, Rohapect PTE100®, Rohapect MPE®, Rohapect MA plus HC, Rohapect DA12L®, Rohapect 10L®, Rohapect B1L® from AB Enzymes, and under the name Pyrolase® from Diversa Corp., San Diego, Calif., USA.
[0354] Of all these enzymes, particularly preferred are those which have been stabilized in a comparatively stable manner against oxidation or by means of point mutagenesis, for example. This includes in particular the aforementioned commercial products Everlase® and Purafect®OxP as examples of proteases of this kind and Duramyl® as an example of an α-amylase of this kind.
[0355] The viscoelastic, solid filling substance according to the invention contains enzymes preferably in total amounts of from 1×10.sup.−8 to 5 wt. % based on active protein. Preferably, the enzymes are contained in a total amount of from 0.001 to 2 wt. %, more preferably from 0.01 to 1.5 wt. %, even more preferably from 0.05 to 1.25 wt. %, and particularly preferably from 0.01 to 0.5 wt. %.
[0356] The use of builder substances (builders) such as silicates, aluminum silicates (particularly zeolites), salts of organic di- and polycarboxylic acids, as well as mixtures of these substances, preferably water-soluble builder substances, can be advantageous.
[0357] In an embodiment that is preferred according to the invention, the use of phosphates (including polyphosphates) is largely or completely omitted. In this embodiment, the viscoelastic, solid filling substance according to the invention preferably contains less than 5 wt. %, particularly preferably less than 3 wt. %, in particular less than 1 wt. %, phosphate(s). Particularly preferably, the viscoelastic, solid filling substance according to the invention is, in this embodiment, completely phosphate-free, i.e., the compositions contain less than 0.1 wt. % phosphate(s).
[0358] The builders include in particular carbonates, citrates, phosphonates, organic builders, and silicates. The proportion by weight of the total builders with respect to the total weight of the viscoelastic, solid composition according to the invention is preferably from 15 to 80 wt. % and in particular 20 to 70 wt. % for dishwashing detergents.
[0359] Some examples of organic builders that are suitable according to the invention are the polycarboxylic acids (polycarboxylates) that can be used in the form of their sodium salts, polycarboxylic acids being understood as those carboxylic acids that carry more than one, in particular two to eight, acid functions, preferably two to six, in particular two, three, four, or five acid functions in the entire molecule. As polycarboxylic acids, dicarboxylic acids, tricarboxylic acids, tetracarboxylic acids, and pentacarboxylic acids, in particular di-, tri-, and tetracarboxylic acids, are thus preferred. The polycarboxylic acids can also carry additional functional groups such as hydroxyl or amino groups, for example. For example, these include citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, saccharic acids (preferably aldaric acids, for example galactaric acid and glucaric acid), aminocarboxylic acids, in particular aminodicarboxylic acids, aminotricarboxylic acids, aminotetracarboxylic acids such as nitrilotriacetic acid (NTA), glutamic-N,N-diacetic acid (also called N,N-bis(carboxymethyl)-L-glutamic acid or GLDA), methyl glycine diacetic acid (MGDA) and derivatives thereof and mixtures thereof. Preferred salts are the salts of the polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, GLDA, MGDA, and mixtures thereof.
[0360] Other substances that are suitable as organic builders are polymeric polycarboxylates (organic polymers with a plurality of (in particular greater than ten) carboxylate functions in the macromolecule), polyaspartates, polyacetals, and dextrins.
[0361] Besides their building effect, the free acids also typically have the property of an acidification component. Particularly noteworthy here are citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid, and any mixtures thereof.
[0362] Particularly preferred viscoelastic, solid filling substances according to the invention contain one or more salts of citric acid, i.e., citrates, as one of their substantial builders. These are contained in the viscoelastic, solid filling substances according to the invention (in particular for washing textiles) preferably in a proportion of 0.3 to 10 wt. %, in particular from 0.5 to 8 wt. %, particularly from 0.7 to 6.0 wt. %, particularly preferably 0.8 to 5.0 wt. %, based in each case on the total weight of the filling substance. One or more salts of citric acid are contained in the viscoelastic, solid filling substances according to the invention (in particular for cleaning hard surfaces, in particular for washing dishes), preferably in a proportion of from 2 to 40 wt. %, in particular from 5 to 30 wt. %, more particularly from 7 to 28 wt. %, particularly preferably from 10 to 25 wt. %, very particularly preferably from 15 to 20 wt. %, in each case relative to the total weight of the composition.
[0363] The viscoelastic, solid filling substances according to the invention can contain, in particular, phosphonates as a further builder. A hydroxy alkane and/or amino alkane phosphonate is preferably used as a phosphonate compound. Of the hydroxy alkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) has particular significance. Possible preferable aminoalkane phosphonates include ethylenediamine tetramethylene phosphonate (EDTMP), diethylenetriamine pentamethylene phosphonate (DTPMP) and the higher homologues thereof. Phosphonates are preferably contained in viscoelastic, solid filling substances according to the invention in amounts of from 0.1 to 10 wt. %, in particular in amounts of from 0.5 to 8 wt. %, very particularly preferably from 2.5 to 7.5 wt. %, in each case relative to the total weight of the composition.
[0364] The combined use of citrate, (hydrogen) carbonate and phosphonate is particularly preferred (particularly for use in dishwashing agents). These can be used in the aforementioned quantities. In particular, amounts of from 10 to 25 wt. % citrate, 10 to 30 wt. % carbonate (or hydrogen carbonate), and 2.5 to 7.5 wt. % phosphonate are used in this combination in the viscoelastic, solid filling substances according to the invention, in each case based on the total weight of the composition.
[0365] Additional particularly preferred viscoelastic, solid filling substances according to the invention, in particular for use as washing or cleaning agents, preferably as dishwashing agents, more preferably as automatic dishwashing agents, are characterized in that, in addition to citrate and (hydrogen) carbonate and, in some cases, phosphonate, they contain at least one additional phosphorus-free builder. In particular, it is selected from aminocarboxylic acids, the additional phosphorus-free builder preferably being selected from methyl glycine diacetic acid (MGDA), glutamic acid diacetate (GLDA), aspartic acid diacetate (ASDA), hydroxyethyliminodiacetate (HEIDA), iminodisuccinate (IDS), and ethylenediamine disuccinate (EDDS), particularly preferably from MGDA or GLDA. An example of a particularly preferred combination is citrate, (hydrogen) carbonate, and MGDA as well as, optionally, phosphonate.
[0366] The proportion by weight of the additional phosphorous-free builder, in particular of the MGDA and/or GLDA, is preferably from 0 to 40 wt. %, in particular from 5 to 30 wt. %, more particularly from 7 to 25 wt. %. The use of MGDA or GLDA, in particular MGDA, is particularly preferred as granular material. Advantageous in this regard are MGDA granules that contain as little water as possible and/or have a lower hygroscopicity (water absorption at 25° C., normal pressure) than non-granulated material powders. The combination of at least three, in particular at least four builders from the above group has proven to be advantageous for the cleaning and rinsing performance of portion packs according to the invention, in particular portion packs for use as dishwashing agents, preferably automatic dishwashing agents. Besides those, additional builders can also be contained.
[0367] Polymeric polycarboxylates are also suitable as organic builders. These are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a relative molecular mass of from 500 to 70,000 g/mol. Suitable polymers are in particular polyacrylates which preferably have a molecular mass of from 1,000 to 20,000 g/mol. Due to their superior solubility, the short-chain polyacrylates, which have molar masses of from 1,100 to 10,000 g/mol, and particularly preferably from 1,200 to 5,000 g/mol, can in turn be preferred from this group.
[0368] Viscoelastic, solid filling substances according to the invention can also contain, as a builder, crystalline layered silicates of general formula NaMSi.sub.xO.sub.2x+1.y H.sub.2O, where M represents sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, with 2, 3, or 4 being particularly preferred values for x, and y represents a number from 0 to 33, preferably from 0 to 20. It is also possible to use amorphous sodium silicates with a modulus Na.sub.2O:SiO.sub.2 of 1:2 to 1:3.3, preferably of 1:2 to 1:2.8 and in particular of 1:2 to 1:2.6, which are preferably delayed in dissolution and have secondary washing properties.
[0369] An optical brightener is preferably selected from the substance classes of distyrylbiphenyls, stilbenes, 4,4′-diamino-2,2′-stilbene disulfonic acids, coumarins, dihydroquinolones, 1,3-diarylpyrazolines, naphthalic acid imides, benzoxazole systems, benzisoxazole systems, benzimidazole systems, pyrene derivatives substituted with heterocycles, and mixtures thereof.
[0370] Particularly preferred optical brighteners include disodium-4,4′-bis-(2-morpholino-4-anilino-s-triazin-6-ylamino)stilbene disulfonate (for example available as Tinopal® DMS from BASF SE), disodium-2,2′-bis-(phenyl-styryl)disulfonate (for example available as Tinopal® CBS from BASF SE), 4,4′-bis[(4-anilino-6-[bis(2-hydroxyethyl)amino]-1,3,5-triazin-2-yl)amino]stilbene-2,2′-disulfonic acid (for example available as Tinopal® UNPA from BASF SE), hexasodium-2,2′-vinylenebis[(3-sulphonato-4,1-phenylene)imino[6-(diethylamino)-1,3,5-triazin-4,2-diyl]imino]bis-(benzene-1,4-disulfonate) (for example available as Tinopal® SFP from BASF SE), 2,2′-(2,5-thiophendiyl)bis[5-1,1-dimethylethyl)-benzoxazole (for example available as Tinopal® SFP from BASF SE) and/or 2,5-bis(benzoxazol-2-yl)thiophene.
[0371] It is preferable for the dye transfer inhibitor to be a polymer or a copolymer of cyclic amines such as vinylpyrrolidone and/or vinylimidazole. Polymers suitable as a dye transfer inhibitor include polyvinylpyrrolidone (PVP), polyvinylimidazole (PVI), copolymers of vinylpyrrolidone and vinylimidazole (PVP/PVI), polyvinylpyridine-N-oxide, poly-N-carboxymethyl-4-vinylpyridium chloride, polyethylene glycol-modified copolymers of vinylpyrrolidone and vinylimidazole, and mixtures thereof. Particularly preferably, polyvinylpyrrolidone (PVP), polyvinylimidazole (PVI) or copolymers of vinylpyrrolidone and vinylimidazole (PVP/PVI) are used as a dye transfer inhibitor. The polyvinylpyrrolidones (PVP) used preferably have an average molecular weight of 2,500 to 400,000 and are commercially available from ISP Chemicals as PVP K 15, PVP K 30, PVP K 60 or PVP K 90, or from BASF as Sokalan® HP 50 or Sokalan® HP 53. The copolymers of vinylpyrrolidone and vinylimidazole (PVP/PVI) used preferably have a molecular weight in the range of from 5,000 to 100,000. A PVP/PVI copolymer is commercially available from BASF under the name Sokalan® HP 56, for example. Other dye transfer inhibitors that can be extremely preferably used are polyethylene glycol-modified copolymers of vinylpyrrolidone and vinylimidazole, which for example are available from BASF under the name Sokalan® HP 66.
[0372] In the scope of a preferred embodiment according to the invention, the viscoelastic, solid filling substance according to the invention contains solid particles (also referred to as particles in the following). Such dispersed solid particles are to be understood as solid substances which do not dissolve in the liquefied phase of the filling substance according to the invention and are present as a separate phase at temperatures of up to 5° C. units above the sol-gel temperature of the viscoelastic and solid filling substance according to the invention. During the production of the viscoelastic filling substances according to the invention, these particles are suspended in the liquid phase above the sol-gel temperature and then the liquid phase is cooled below the sol-gel temperature to obtain the viscoelastic filling substance according to the invention.
[0373] The solid particles are preferably selected from polymers, pearlescing pigments, microcapsules, speckles, bleaching agents (for example sodium percarbonate), or mixtures thereof.
[0374] Within the meaning of the present invention, microcapsules include any type of capsule known to a person skilled in the art, but in particular core-shell capsules and matrix capsules. Matrix capsules are porous molded bodies that have a structure similar to a sponge. Core-shell capsules are molded bodies that have a core and a shell. Capsules that have an average diameter X.sub.50.3 (volume average) of from 0.1 to 200 preferably from 1 to 100 more preferably from 5 to 80 particularly preferably from 10 to 50 μm and in particular from 15 to 40 μm are suitable as microcapsules. The average particle size diameter X.sub.50.3 is determined by sieving or by means of a Camsizer particle size analyzer from Retsch.
[0375] The microcapsules of the invention preferably contain at least one active ingredient, preferably at least one odorant. These preferred microcapsules are perfume microcapsules.
[0376] In a preferred embodiment of the invention, the microcapsules have a semi-permeable capsule wall (shell).
[0377] A semi-permeable capsule wall within the meaning of the present invention is a capsule wall that is semi-permeable, i.e. continuously releases small quantities of the capsule core over time, without the capsules e.g. being destroyed or opened e.g. by tearing. These capsules continuously release small quantities of the active ingredient contained in the capsule, e.g. perfume, over a long period of time.
[0378] In another preferred embodiment of the invention, the microcapsules have an impermeable shell. An impermeable shell within the meaning of the present invention is a capsule wall that is substantially not permeable, i.e. releases the capsule core only by the capsule being damaged or opened. These capsules contain significant quantities of the at least one odorant in the capsule core, and therefore when the capsule is damaged or opened, a very intense fragrance is provided. The fragrance intensities thus achieved are generally so high that lower quantities of the microcapsules can be used in order to achieve the same fragrance intensity as for conventional microcapsules.
[0379] In a preferred embodiment of the invention, the viscoelastic, solid filling substance according to the invention contains both microcapsules having a semipermeable shell and microcapsules having an impermeable shell. By using both types of capsule, a significantly improved fragrance intensity can be provided over the entire laundry cycle.
[0380] In another preferred embodiment of the invention, the surfactant composition according to the invention may also contain two or more different microcapsule types having semipermeable or impermeable shells.
[0381] High-molecular compounds are usually considered as materials for the shell of the microcapsules, such as protein compounds, for example gelatin, albumin, casein and others, cellulose derivatives, for example methylcellulose, ethylcellulose, cellulose acetate, cellulose nitrate, carboxymethylcellulose and others, and especially also synthetic polymers such as polyamides, polyethylene glycols, polyurethanes, epoxy resins and others. Preferably, melamine formaldehyde polymer, melamine urea polymer, melamine urea formaldehyde polymer, polyacrylate polymer or polyacrylate copolymer are used as the wall material, i.e. as the shell. Capsules according to the invention are for example, but not exclusively, described in US 2003/0125222 A1, DE 10 2008 051 799 A1 or WO 01/49817.
[0382] Preferred melamine formaldehyde microcapsules are produced by melamine formaldehyde precondensates and/or the C.sub.1-C.sub.4 alkyl ethers thereof in water, by the at least one odor modulator compound and optionally other ingredients, such as at least one odorant, being condensed in the presence of a protective colloid. Suitable protective colloids are e.g. cellulose derivatives, such as hydroxyethyl cellulose, carboxymethyl cellulose and methylcellulose, polyvinylpyrrolidone, copolymers of N-vinylpyrrolidone, polyvinyl alcohols, partially hydrolyzed polyvinyl acetates, gelatin, arabic gum, xanthan gum, alginates, pectins, degraded starches, casein, polyacrylic acid, polymethacrylic acid, copolymerisates of acrylic acid and methacrylic acid, sulfonic acid group-containing water-soluble polymers having a content of sulfoethyl acrylate, sulfoethyl methacrylate or sulfopropyl methacrylate, and polymerisates of N-(sulfoethyl)-maleinimide, 2-acrylamido-2-alkyl sulfonic acids, styrene sulfonic acids and formaldehyde and condensates of phenol sulfonic acids and formaldehyde.
[0383] It is preferable for the surface of the microcapsules used according to the invention to be coated entirely or in part with at least one cationic polymer. Accordingly, at least one cationic polymer from polyquaternium-1, polyquaternium-2, polyquaternium-4, polyquaternium-5, polyquaternium-6, polyquaternium-7, polyquaternium-8, polyquaternium-9, polyquaternium-10, polyquaternium-11, polyquaternium-12, polyquaternium-13, polyquaternium-14, polyquaternium-15, polyquaternium-16, polyquaternium-17, polyquaternium-18, polyquaternium-19, polyquaternium-20, polyquaternium-22, polyquaternium-24, polyquaternium-27, polyquaternium-28, polyquaternium-29, polyquaternium-30, polyquaternium-31, polyquaternium-32, polyquaternium-33, polyquaternium-34, polyquaternium-35, polyquaternium-36, polyquaternium-37, polyquaternium-39, polyquaternium-43, polyquaternium-44, polyquaternium-45, polyquaternium-46, polyquaternium-47, polyquaternium-48, polyquaternium-49, polyquaternium-50, polyquaternium-51, polyquaternium-56, polyquaternium-57, polyquaternium-61, polyquaternium-69 or polyquaternium-86 is suitable as a cationic polymer for coating the microcapsules. Polyquaternium-7 is very particularly preferred. The polyquaternium nomenclature used in the scope of the present application for the cationic polymers is taken from the declaration for cationic polymers according to the International Nomenclature of Cosmetic Ingredients (INCI declaration) for cosmetic raw materials.
[0384] Microcapsules that can preferably be used have an average diameter X.sub.50.3 in the range of 1 to 100 μm, preferably from 5 to 95 μm, in particular from 10 to 90 μm, for example from 10 to 80 μm.
[0385] The shell of the microcapsules surrounding the core or (filled) cavity preferably has an average thickness in the range of from approximately 5 to 500 nm, preferably of from approximately 50 nm to 200 nm, in particular of from approximately 70 nm to approximately 180 nm.
[0386] Pearlescing pigments are pigments that have a pearlescent shine. Pearlescing pigments consist of thin sheets that have a high refraction index, and partially reflect the light and are partially transparent to the light. The pearlescent shine is generated by interference of the light hitting the pigment (interference pigment). Pearlescing pigments are usually thin sheets of the above-mentioned material, or contain the above-mentioned material as thin, multilayered films or as components arranged in parallel in a suitable carrier material.
[0387] The pearlescing pigments that can be used according to the invention are either natural pearlescing pigments such as fish silver (guanine/hypoxanthine mixed crystals from fish scales) or mother of pearl (from ground seashells), monocrystalline, sheet-like pearlescing pigments such as bismuth oxychloride and pearlescing pigments with a mica base and a mica/metal oxide base. The latter pearlescing pigments are mica that has been provided with a metal oxide coating.
[0388] Pearlescing pigments with a mica base and mica/metal oxide base are preferred according to the invention. Mica is a phyllosilicate. The most important representatives of these silicates are muscovite, phlogopite, paragonite, biotite, lepidolite, and margarite. In order to produce the pearlescing pigments in conjunction with metal oxides, mica, primarily muscovite or phlogopite, is coated with a metal oxide. Suitable metal oxides are, inter alia, TiO.sub.2, Cr.sub.2O.sub.3, and Fe.sub.2O.sub.3. Interference pigments and colored luster pigments are obtained as pearlescing pigments according to the invention by suitable coating. These pearlescing pigment types additionally have color effects as well as a glittering optical effect. Furthermore, the pearlescing pigments that can be used according to the invention also contain a color pigment that does not derive from a metal oxide.
[0389] The grain size of the pearlescing pigments that are preferably used is preferably between 1.0 μm and 100 μm, particularly preferably between 10.0 and 60.0 μm, at an average diameter X.sub.50.3 (volume average).
[0390] Within the meaning of the invention, “speckles” are understood to mean macroparticles, in particular macrocapsules, that have an average diameter X.sub.50.3 (volume average) of more than 300 μm, in particular from 300 to 1,500 μm, preferably from 400 to 1,000 μm.
[0391] Speckles are preferably matrix capsules. The matrix is preferably colored. The matrix is formed for example by gelation, polyanion-polycation interactions or polyelectrolyte-metal ion interactions, and this is well known in the prior art, just like the production of particles using these matrix-forming materials. An example of a matrix-forming material is alginate. For the production of alginate-based speckles, an aqueous alginate solution, optionally also containing the active ingredient or active ingredients to be included, is subject to dripping and is then cured in a precipitation bath containing Ca.sup.2+ ions or Al.sup.3+ ions. Alternatively, other matrix-forming materials may be used instead of alginate.
[0392] In a preferred embodiment, the viscoelastic, solid filling substances according to the invention, in particular as dishwashing agents, contain, as an additional component, at least one zinc salt as a glass corrosion inhibitor. The zinc salt can be an inorganic or organic zinc salt. The zinc salt to be used according to the invention preferably has a solubility in water of greater than 100 mg/1, preferably greater than 500 mg/1, particularly preferably greater than 1 g/l, and in particular greater than 5 g/l (all solubilities at 20° C. water temperature). The inorganic zinc salt is preferably selected from the group comprising zinc bromide, zinc chloride, zinc iodide, zinc nitrate, and zinc sulfate. The organic zinc salt is preferably selected from the group comprising zinc salts of monomeric or polymeric organic acids, particularly from the group of zinc acetate, zinc acetyl acetonate, zinc benzoate, zinc formiate, zinc lactate, zinc gluconate, zinc ricinoleate, zinc abietate, zinc valerate, and zinc-p-toluene sulfonate. In an embodiment that is particularly preferred according to the invention, zinc acetate is used as a zinc salt. The zinc salt is preferably contained in viscoelastic, solid filling substances according to the invention in an amount of from 0.01 wt. % to 5 wt. %, particularly preferably in an amount of from 0.05 wt. % to 3 wt. %, in particular in an amount of from 0.1 wt. % to 2 wt. %, based on the total weight of the composition. In addition or alternatively to the aforementioned salts (particularly the zinc salts), polyethylene imines such as those which are available under the name Lupasol® (BASF) can preferably be used as glass corrosion inhibitors in an amount of from 0 to 5 wt. %, in particular 0.01 to 2 wt. %.
[0393] Examples of viscoelastic, solid filling substances that can be used (particularly for washing agent portion packs) are filling substances F1 to F3 in the following table:
TABLE-US-00002 F1 F2 F3 [wt. %] [wt. %] [wt. %] C.sub.11-13 alkylbenzene sulfonic acid 23.0 26.0 23.0 C.sub.13-15 alkyl alcohol branched at 24.0 27.0 24.0 the 2 position, ethoxylated with 8 mol ethylene oxide Glycerin 9.0 9.0 9.0 2-aminoethanol 6.8 6.8 6.8 Ethoxylated polyethyleneimine 5.0 5.0 5.0 C.sub.12-18 fatty acid 7.5 7.5 7.5 Diethylenetriamine- 0.6 0.6 0.6 N,N,N′,N′N″-penta (methylenephosphonic acid), heptasodium salt (sodium DTPMP) 1,2-propylene glycol 4.5 4.5 4.5 Ethanol 4.0 4.0 4.0 Sodium bisulfite 0.1 0.1 0.1 Denatonium benzoate 0.001 0.001 0.001 Soil-release polymers of 1.0 1.0 0.6 ethylene terephthalate and polyethylene oxide terephthalate Copolymer from — — 0.15 N-vinyl pyrrolidone and N-vinylimidazole (dye transfer inhibitor) 1,3:2,4-di-O-benzylidene- 1.2 1.2 1.2 D-sorbitol Perfume, dye, protease, 1.7 1.7 1.5 amylase, lipase, (without (without cellulase, optical brightener dye) optical brightener) Water up to 100 up to 100 up to 100
[0394] It is preferred if the portion pack according to the invention contains, as further filling substance, as little free-flowing, granular mixture of a solid composition as possible and the further filling substance is in particular free of free-flowing, granular mixture of a solid composition. A granular mixture is formed from a large number of loose, solid particles, which in turn comprise what are known as grains. A grain is a name for the particulate constituents of powders (grains are the loose, solid particles), dusts (grains are the loose, solid particles), granular material (loose, solid particles are agglomerates of several grains), and other granular mixtures. The free-flowing ability of a granular mixture relates to its ability to flow freely under its own weight out of a flow-test funnel having an outlet of 16.5 mm diameter. A preferred portion pack according to the invention is characterized in that pourable, granular mixture is contained in an amount of 0 to 4 wt. %, in particular from 0 to 3, particularly preferably from 0 to 1 wt. %, very particularly preferably from 0 to 0.5 wt. %, each based on the total weight of all filling substances contained in the portion pack.
[0395] Items 1 to 55 below show specific embodiments of the invention. The reference signs of the figures have been given below only for clarification and not to restrict the scope of items 1 to 55: [0396] 1. An apparatus (1) for production of a water-soluble shell (2) for holding a filling substance (9), comprising a tank (3) filled with a melt (4) of a shell material (5), wherein the shell material (5) contains a polymer and is water-soluble and is solid under standard conditions, and a male mold (6) movably arranged in the region of the tank (3) and automatically lowerable into the melt (4) and withdrawable from the tank (3), to form, from the shell material (5), a water-soluble shell (2) resting on the male mold (6) (which shell preferably rests on the male mold (6) after the male mold (6) has been removed from the tank (3)). [0397] 2. The apparatus (1) according to item 1, wherein the male mold (6) has a temperature regulator. [0398] 3. The apparatus (1) according to one of the preceding items, wherein the tank (3) substantially has an inverted shape of the male mold (6). [0399] 4. The apparatus (1) according to one of the preceding items, wherein the shell material (5) contains at least one active ingredient. [0400] 5. The apparatus (1) according to one of the preceding items, wherein the shell material (5) contains at least one bittering agent, in particular denatonium benzoate. [0401] 6. The apparatus (1) according to one of the preceding items, wherein the shell material (5) is elastic (preferably under standard conditions). [0402] 7. The apparatus (1) according to one of the preceding items, wherein the melt (4) contains a granular material (7). [0403] 8. The apparatus (1) according to item 7, wherein the granular material (7) contains at least one active ingredient.
[0404] 9. The apparatus (1) according to one of the preceding items, wherein at least one further tank (3b) having at least one further melt (4b) of a further shell material (5b) is provided, wherein the male mold (6) having the shell (2; 2a) resting thereon is automatically lowerable into the further melt (4b) and withdrawable from the further melt (4b) in order to form a further water-soluble shell (2b) resting against the water-soluble shell (2; 2a) resting on the male mold (6). [0405] 10. The apparatus (1) according to item 9, wherein the shell materials (5a, 5b) contain different active ingredients and/or the melts (4a, 4b) contain different granular materials (7). [0406] 11. The apparatus (1) according to one of items 9 to 10, wherein the shell materials (5a, 5b) have different optical properties in the solid state. [0407] 12. The apparatus (1) according to one of the preceding items, wherein one end of the male mold (6) has a portion comprising a filling substance (9). [0408] 13. The apparatus (1) according to one of the preceding items, wherein the male mold (6) is designed in such a way that a rigid shell (2) lying thereon cannot be stripped off. [0409] 14. The apparatus (1) according to item 13, wherein the male mold (6) is wider in a distal region than in a proximal region. [0410] 15. The apparatus (1) according to one of items 13 to 14, wherein the male mold (6) has an unevenness (11). [0411] 16. The apparatus (1) according to one of the preceding items, wherein the male mold (6) can be set in vibration. [0412] 17. A process for production of a water-soluble shell (2) for holding a filling substance (9), wherein [0413] an apparatus (1) according to one of items 1 to 16 is provided, [0414] a melt (4) is produced from shell material (5), wherein the contents of the shell material, which are solid under standard conditions, are preferably comminuted before melting in such a way that a powder with an average particle size X.sub.50.3 (volume average) of less than 100 μm is present, [0415] the male mold (6) is lowered into the melt at a temperature below a melting temperature of the melt (4) so that a contact surface of the male mold (6) is covered with shell material (5), [0416] a shell (2) is formed by solidifying the shell material (5) on the male mold (6), and [0417] the male mold (6) having a shell (2) adhering to it is lifted out of the tank (3) before, after, or during solidification, and [0418] the shell (2) is detached from the male mold (3). [0419] 18. The process according to item 17, wherein the male mold (6) is lowered into the melt (4) to a depth which is greater than a maximum width of the male mold (6). [0420] 19. The process according to one of items 17 or 18, wherein the shell (2) is detached by rolling it out or turning it inside out. [0421] 20. The process according to one of items 17 to 19, wherein one end of the male mold (6) has a portion comprising a filling substance (9) and the portion is separated when the shell (2) is detached, so that the shell (2) having the filling substance (9) is replaced. [0422] 21. The process according to one of items 17 to 20, wherein the shell (2) is detached under the action of sound waves, in particular ultrasonic waves. [0423] 22. The process according to one of items 17 to 21, wherein the shell (2) is cured by hot air drying. [0424] 23. The process according to one of items 17 to 22, wherein a layer is vapor-deposited onto the shell (2). [0425] 24. The process for production of a portion pack (12) for use as a washing or cleaning agent, comprising the steps that [0426] a shell (2) is provided by a process according to one of items 17 to 23, [0427] the shell (2) is filled with at least one viscoelastic and solid filling substance (9), and [0428] optionally the shell (2) is closed. [0429] 25. The process according to item 24, wherein viscoelastic, solid filling substance (9) is formed in the shell (2) by curing a liquid composition introduced into the shell (2). [0430] 26. The process according to item 24 or 25, wherein the filling substance (9) contains, based on the total weight of the above-mentioned filling substance (9), [0431] (i) a total amount of from 0.1 to 70 wt. % of at least one surfactant, [0432] and [0433] (ii) a total amount of at least 0.5 wt. % of at least one organic gelator compound with a molar mass <1000 g/mol, a solubility in water of less than 0.1 g/L (20° C.) and a structure containing at least a hydrocarbon structural unit with 6 to 20 carbon atoms (preferably at least one carbocyclic, aromatic structural unit) and additionally an organic structural unit covalently bonded to the aforementioned hydrocarbon unit, which has at least two groups selected from —OH, —NH—, or mixtures thereof [0434] and [0435] (iii) optionally water. [0436] 27. The process according to item 26, characterized in that the organic gelator compound is selected from benzylidene alditol compound, diketopiperazine compound, dibenzylcystine compound, hydrogenated castor oil, hydroxystearic acid, N—(C.sub.8-C.sub.24)-hydrocarbyl glyconamide, or mixtures thereof. [0437] 28. A shell (2) for a portion pack (12) suitable for use as a washing or cleaning agent, produced by a process according to one of items 17 to 23. [0438] 29. A portion pack (12) for use as a washing or cleaning agent containing [0439] (a) a shell (2) made from a melt (4) of a polymer-containing and water-soluble shell material (5) which is solid under standard conditions, and [0440] (b) a viscoelastic and solid filling substance (9) in the above-mentioned shell (2), containing, based on the total weight of said filling substance (9), [0441] (i) a total amount of from 0.1 to 70 wt. % of at least one surfactant, [0442] and [0443] (ii) a total amount of at least 0.5 wt. % of at least one organic gelator compound with a molar mass <1000 g/mol, a solubility in water of less than 0.1 g/L (20° C.) and a structure containing at least a hydrocarbon structural unit with 6 to 20 carbon atoms (preferably at least one carbocyclic, aromatic structural unit) and additionally an organic structural unit covalently bonded to the aforementioned hydrocarbon unit, which has at least two groups selected from —OH, —NH—, or mixtures thereof [0444] and [0445] (iii) optionally water. [0446] 30. The portion pack (12) according to item 29, characterized in that at least one polymer is contained as a polymer of the shell material, selected from (optionally acetalized) polyvinyl alcohol (PVOH), copolymers of polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene oxide, gelatin, cellulose, and the derivatives thereof, acrylic acid-containing polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters, polyethers, and mixtures thereof, preferably from (optionally acetalized) polyvinyl alcohol (PVOH), copolymers of polyvinyl alcohol, polyethylene oxide, gelatin, and mixtures thereof. [0447] 31. The portion pack (12) according to one of items 29 or 30, characterized in that the shell (2) additionally contains at least one bitter substance, in particular denatonium benzoate. [0448] 32. The portion pack (12) according to one of items 29 to 31, characterized in that the shell (2) is produced by a process according to one of items 24 to 27. [0449] 33. The portion pack (12) according to one of items 29 to 32, characterized in that the above-mentioned at least one filling substance (9) has a storage modulus of between 10.sup.3 Pa and 10.sup.8 Pa, preferably between 10.sup.4 Pa and 10.sup.8 Pa and a loss modulus (in each case at 20° C., with a deformation of 0.1% and a frequency of 1 Hz), and the storage modulus in the frequency range between 10.sup.−2 Hz and 10 Hz is at least twice as great as the loss modulus, preferably five times greater than the loss modulus, particularly preferably at least ten times greater than the loss modulus. [0450] 34. The portion pack (12) according to one of items 29 to 33, characterized in that the storage modulus of the above-mentioned at least one filling substance (9) is in a range from 10.sup.5 Pa to 10.sup.7 Pa. [0451] 35. The portion pack (12) according to one of items 29 to 34, characterized in that the organic gelator compound is selected from benzylidene alditol compound, diketopiperazine compound, dibenzylcystine compound, hydrogenated castor oil, hydroxystearic acid, N—(C.sub.5-C.sub.24)-hydrocarbyl glyconamide, or mixtures thereof [0452] 36. The portion pack (12) according to one of items 29 to 35, characterized in that the above-mentioned at least one filling substance (9) contains at least one benzylidene alditol compound of the formula (I) as the organic gelator compound
##STR00016## [0453] wherein [0454] *- represents a covalent single bond between an oxygen atom of the alditol backbone and the provided functional group, [0455] n represents 0 or 1, preferably 1, [0456] m represents 0 or 1, preferably 1, [0457] R.sup.1, R.sup.2, and R.sup.3 represent, independently of one another, a hydrogen atom, a halogen atom, a C.sub.1-C.sub.4 alkyl group, a cyano group, a nitro group, an amino group, a carboxyl group, a hydroxy group, a —C(═O)—NH—NH.sub.2 group, a —NH—C(═O)—(C.sub.2-C.sub.4-alkyl) group, a C.sub.1-C.sub.4 alkoxy group, a C.sub.1-C.sub.4 alkoxy C.sub.2-C.sub.4 alkyl group, with two of the functional groups forming together with the remainder of the molecule a 5-membered or 6-membered ring, [0458] R.sup.4, R.sup.5, and R.sup.6 represent, independently of one another, a hydrogen atom, a halogen atom, a C.sub.1-C.sub.4 alkyl group, a cyano group, a nitro group, an amino group, a carboxyl group, a hydroxyl group, a —C(═O)—NH—NH.sub.2 group, a —NH—C(═O)—(C.sub.2-C.sub.4-alkyl) group, a C.sub.1-C.sub.4 alkoxy group, a C.sub.1-C.sub.4 alkoxy C.sub.2-C.sub.4 alkyl group, with two of the functional groups forming, together with the remainder of the molecule, a 5-membered or 6-membered ring. [0459] 37. The portion pack (12) according to item 36, characterized in that the alditol backbone according to formula (I) is derived from D-glucitol, D-mannitol, D-arabinitol, D-ribitol, D-xylitol, L-glucitol, L-mannitol, L-arabinitol, L-ribitol, or L-xylitol. [0460] 38. The portion pack (12) according to one of items 36 or 37, characterized in that R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5 and R.sup.6 are, independently of one another, a hydrogen atom, methyl, ethyl, chlorine, fluorine, or methoxy, preferably a hydrogen atom. [0461] 39. The portion pack (12) according to one of items 29 to 38, characterized in that the above-mentioned at least one filling substance (9) contains at least one benzylidene alditol compound of the formula (I-1) as the organic gelator compound
##STR00017## [0462] where R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5 and R.sup.6 are as defined in item 36. [0463] 40. The portion pack (12) according to one of items 29 to 39, characterized in that the above-mentioned filling substance, as the organic gelator compound, is at least one benzylidene alditol compound from 1,3:2,4-di-O-benzylidene-D-sorbitol; 1,3:2,4-di-O-(p-methylbenzylidene)-D-sorbitol; 1,3:2,4-di-O-(p-chlorobenzylidene)-D-sorbitol; 1,3:2,4-Di-O-(2,4-dimethylbenzylidene)-D-sorbitol; 1,3:2,4-di-O-(p-ethylbenzylidene)-D-sorbitol; 1,3:2,4-Di-O-(3,4-dimethylbenzylidene)-D-sorbitol, or mixtures thereof. [0464] 41. The portion pack (12) according to one of items 29 to 40, characterized in that, the organic gelator compound is contained in a total amount of 0.5 to 10.0 wt. %, in particular 0.8 to 5.0 wt. %, more preferably 1.0 wt. % and 4.5 wt. %, very particularly preferably 1.0 and 4.0 wt. %, based on the total weight of the viscoelastic and solid filling substance. [0465] 42. The portion pack (12) according to one of items 29 to 41, characterized in that, water is contained in the above-mentioned at least one filling substance (9) in a total amount of 0 to 25 wt. %, in particular from 0 to 20 wt. %, more preferably from 0 to 15 wt. %, based on the total weight of the above-mentioned at least one filling substance (9). [0466] 43. The portion pack (12) according to one of items 29 to 42, characterized in that the above-mentioned at least one filling substance (9) additionally contains at least one organic solvent having a molecular weight of at most 500 g/mol (preferably selected from (C.sub.2-C.sub.8) alkanols having at least one hydroxyl group (particularly preferably ethanol, ethylene glycol, 1,2-propanediol, glycerin, 1,3-propanediol, n-propanol, isopropanol, 1,1,1-trimethylolpropane, 2-methyl-1,3-propanediol, 2-hydroxymethyl-1,3-propanediol), triethylene glycol, butyl diglycol, polyethylene glycols having a weight-average molar mass M.sub.w of at most 500 g/mol, glycerol carbonate, propylene carbonate, 1-methoxy-2-propanol, 3-methoxy-3-methyl-1-butanol, butyl lactate, 2-isobutyl-2-methyl-4-hydroxymethyl-1,3-dioxolane, 2,2-dimethyl-4-hydroxymethyl-1,3-dioxolane, dipropylene glycol, or mixtures thereof). [0467] 44. The portion pack (12) according to item 43, characterized in that the above-mentioned organic solvent is contained in the above-mentioned at least one filling substance (9) in a total amount of 5 to 40 wt. %, in particular of 10 up to 35 wt. %, based on the total weight of the above-mentioned at least one filling substance (9). [0468] 45. The portion pack (12) according to one of items 29 to 44, characterized in that in the above-mentioned filling substance, at least one anionic surfactant, preferably at least one anionic surfactant is contained selected from the group consisting of C.sub.8-18 alkyl benzene sulfonates, olefin sulfonates, C.sub.12-18 alkane sulfonates, ester sulfonates, alkyl sulfates, alkenyl sulfates, fatty alcohol ether sulfates, and mixtures thereof. [0469] 46. The portion pack (12) according to one of items 29 to 45, characterized in that the above-mentioned filling substance contains at least one anionic surfactant of the formula (T-1),
##STR00018## [0470] where [0471] R′ and R″ are, independently of one another, H or alkyl, and together contain 9 to 19, preferably 9 to 15 and in particular 9 to 13, C atoms, and Y.sup.+ is a monovalent cation or the nth part of an n-valent cation (in particular Na.sup.+). [0472] 47. The portion pack (12) according to one of items 29 to 45, characterized in that the above-mentioned filling substance contains at least one nonionic surfactant. [0473] 48. The portion pack (12) according to one of items 29 to 45, characterized in that the above-mentioned filling substance contains at least one nonionic surfactant of the formula (T-2)
R.sup.2—O—(XO).sub.m—H, (T-2) [0474] where [0475] R.sup.2 represents a linear or branched C.sub.8-C.sub.18 alkyl group, an aryl group or an alkyl aryl group, [0476] XO represents, independently of one another, an ethylene oxide (EO) group or a propylene oxide (PO) group, [0477] m represents integers of from 1 to 50. [0478] 49. The portion pack (12) according to one of items 29 to 48, characterized in that surfactant is contained in the above-mentioned filling substance in a total amount of 5 to 70 wt. %, more preferably 5 to 65 wt. %, more preferably 5 to 60 wt. %, more preferably 10 to 70 wt. %, more preferably 10 to 65 wt %, more preferably 10 to 60 wt %, more preferably 15 to 70 wt %, more preferably 15 to 65 wt %, more preferably 15 to 60 wt %, particularly preferably 20 to 70 wt. %, more preferably 20 to 65 wt. %, more preferably 20 to 60 wt. %, very particularly preferably 25 to 70 wt. %, more preferably 25 to 65 wt. %, more preferably 25 to 60 wt. %, further preferably 30 to 70 wt. %, more preferably 30 to 65 wt. %, more preferably 30 to 60 wt. %. [0479] 50. The portion pack (12) according to one of items 29 to 49, characterized in that surfactant is contained in the above-mentioned filling substance in a total amount of 0.1 to 5.0 wt. %, in particular 0.2 to 4.0 wt. %, based on the total weight of said filling substance. [0480] 51. The portion pack (12) according to one of items 29 to 50, characterized in that the above-mentioned at least one filling substance (9) is in the form of a molded body. [0481] 52. The portion pack (12) according to item 51, characterized in that the molded body has a weight of at least 1 g, particularly preferably at least 5 g, very particularly preferably from 10 to 30 g. [0482] 53. The portion pack (12) according to one of items 29 to 52, characterized in that it is water-soluble. [0483] 54. The portion pack (12) according to one of items 29 to 53, characterized in that the above-mentioned filling substance is transparent. [0484] 55. The portion pack (12) according to one of items 29 to 54, characterized in that, based on the total weight of all filling substances contained in the portion pack, free-flowing, granular mixture is contained in an amount of 0 to 4 wt. %, in particular 0 to 3, particularly preferably from 0 to 1 wt. %.
[0485] For a configuration of the portion pack for use as a washing agent, the above items 1 to 49 and 51 to 55 are particularly preferred.
[0486] For a configuration of the portion pack for use as a dishwashing agent, the above items 1 to 44, 47, 48 and 51 to 54 are particularly preferred.
[0487] The invention is not restricted to the embodiments mentioned above. Deviations from this are also conceivable. For example, any number of male molds, for example arranged in parallel, can be provided. The portion pack can also be sealed by closure with a form-fitting cover, for example made from the shell material.
LIST OF REFERENCE SIGNS
[0488] 1 apparatus [0489] 2 shell [0490] 3 tank [0491] 4 melt [0492] 5 shell material [0493] 6 male mold [0494] 7 granulate [0495] 8 end of male mold [0496] 9 filling substance [0497] 10 parting surface [0498] 11 unevenness [0499] 12 portion pack for use as a washing or cleaning agent [0500] 13 cover [0501] 101-108 steps