DE10021165A1 - Active substance release system - Google Patents

Abstract

Disclosed is a system for the (controlled) release and/or absorption of active ingredients and/or substances, containing a mesoporous support material, wherein one or several active ingredients and/or substances are incorporated or can be incorporated.

Description

The present invention relates to a system for the (controlled) release of active substances. and / or active substances containing a porous carrier material in which one or more Active substances and / or active substances are stored.

The dosage and release of active ingredients can depend on respective application, in different ways. So active and Active ingredients are fed directly to the respective application, so that these substances are immediately available. The substances to be dosed can also be made up in such a way that it is delayed, d. H. delayed or in another location.

Various release systems are in particular from the pharmaceutical industry known, the controlled and / or delayed release of the active substances (active pharmaceutical ingredients) enable. With a controlled release the Active and / or active ingredients released in metered amounts. The delayed release means that the active ingredient is only released some time after dosing.

Substances that are to be released in a controlled or delayed manner are often used in Form of capsules offered. The capsule walls have such a structure that the Substances are controlled and / or delayed dosed or released. The release can either via semipermeable membranes or by delayed dissolution or destroy the capsule walls.

The release systems also serve to protect sensitive and volatile Substances in encapsulated form from outside influences or premature release to be protected.

The adsorption processes are opposed to the release mechanism. With these components from the environment are adsorbed by appropriate materials, i. H. chemically or physically bound.  

In British patent application GB 2 296 261 A compositions for Treatment of textiles described that a mesoporous molecular sieve in a sufficient amount to eliminate bad smells. The Mesoporous Molecular sieve has a pore size of about 15 Å to about 100 Å with a Si Atom to Al atom <50: 1, preferably <200: 1 and in particular <300: 1. The particles have a size of about 1 µm to about 50 µm. The mesoporous structure is characterized by a receive so-called template reaction, d. H. the molecular sieve is made from suitable Si and Al compounds prepared in the presence of surfactants. Such porous crystalline Materials are described, for example, in international patent application WO 91/111390 discloses, these materials being used as support materials for catalysts.

With regard to the variety of active ingredients, which are based on the most varied Areas are used and thus metered, there is a constant need, more To develop release systems. Surprisingly, it was found that a Carrier system that has a mesoporous structure, binds active and / or active substances and releases these substances at a desired time.

The present invention accordingly relates to a system for (controlled) Release and / or absorption of active and / or active substances containing a Mesoporous carrier material in which one or more active and / or active substances are introduced or can be introduced.

The release system according to the invention is suitable for incorporation into a large number of Agents in which either active and / or active ingredients are protected from external influences and / or these substances are to be released or delayed released.

The active and / or active ingredients can be selected from all conceivable substances that to be controlled in any area or released with a time delay. The active and / or active substances in the sense of the present invention are both substances that are solid anchored in the mesoporous carrier material, i.e. chemically bound, and in bound form can develop their activity, or the (initially in the carrier material included and then) released by the system to their after the release To develop activity, as well as substances that are undesirable in free form or have undesirable effects and from the system, d. H. from the mesoporous Carrier material, picked up and removed from their environment.  

As concrete examples of active substances and / or active substances, e.g. B. fragrances, dyes and Fluorescent agents, surfactants, wash-active substances, bleaches, bleach activators, UV Protective substances, polymers, foam inhibitors, graying inhibitors, inorganic salts, Hydrotopes, silicone oils, soil release compounds, optical brighteners, graying inhibitors ren, anti-shrink agents, anti-crease agents, color transfer inhibitors, antimicrobial Active substances, germicides, fungicides, antioxidants, corrosion inhibitors, fatty substances, lecithin, Preservatives, pearlescent agents or mixtures thereof may be included. Can continue the agents contain electrolytes, preferably sodium, magnesium or calcium chloride, as well as pH adjusting agents such as organic or inorganic acids, pharmaceuticals, antibac terial substances, biocides, enzymes, adhesive components such as amines, cosmetic effect substances such as vitamins, moisturizing substances, oils, herbal and plant extracts, agents for Textile care and pre- or post-treatment for laundry and cleaning, such as fabric softener components, antistatic agents, ironing aids, phobing and impregnating agents, swelling and Anti-slip agents, finishing agents, are called.

Particularly preferred as active ingredients are those substances which are found in washing and Detergents or in cosmetic products have a nourishing effect. Examples vitamins such as vitamin E (α-tocopherol) and panthenol are used for caring components (Provitamin B5), beta-carotene (provitamin A), antidandruff agent, UV protection agent, emollients (cosmetic oils), silicone oils, conditioners, glycerin, polymers for firming effects in Hair, cationic polymers, components for textile finishing and finishing, such as Impregnating agents, finishing agents, finishing agents, foam boosters, components for the Easy care equipment, handle variators and soil release equipment, anti-foaming agents, Antistatic, antimicrobial and fungicidal agents, etc. and any other components that have a nourishing effect on textiles, skin and hair.

In particular, oxidic materials such as those of the Elements Si, Al, B, Ge and groups IIIa, IIb, IVb, Vb, VIb of the periodic table of the Elements Be, Sn, Pb, Bi, Co, Fe, Co, Ne, Ce, Mn or mixtures thereof are suitable.

The mesoporous support material used according to the invention preferably has a such a pore structure that the release of the introduced active and / or Active ingredients can be controlled.

The active and / or active substances are usually in the pores of the carrier material stored. They can be physically or chemically bound to the surface. In One possible embodiment has the surface of the porous carrier material  functional groups to which the active and / or active substances are chemically bound can be.

Another object of the present invention is a method for producing mesoporous carrier materials with active and / or active substances applied thereon, the characterized in that an oxide precursor in an aqueous solvent in The presence of a surfactant component is hydrolyzed, the precipitate that forms filtered off and then calcined.

Examples of suitable oxide precursors for the preparation of the invention carrier materials used can be used are alkylsilanes, alkoxysilanes, Alkylalkoxysilanes, organoalkoxysilanes, the radicals being, in addition to the alkyl groups, also allyl, Aminoalkyl, hydroxyalkyl groups, etc. can be bound. In a preferred one Embodiment are the carrier materials using the in the Organosilanes described in EP-A-0 941 761. These organosilanes and / or their Condensation products are built up in situ with a maximum of 4 silicon atoms.

The organosilanes used preferably have the general formulas 1a to Id

R ¹ 2R ² SiX (Ia)

R ¹ R ² SiX ₂ (Ib)

R ² SiX ₃ (Ic)

SiX ₄ (Id)

X ₃ Si-R ³ -SiX ₃ (Ie),

in which R ^{1 is} a monovalent, optionally halogen-substituted and optionally interrupted by ether oxygen atoms hydrocarbon radical each having 1 to 18 carbon atoms or a hydrogen atom, R ^{2 has} the meanings of R ¹ or a monovalent hydrocarbon radical having 1 to 12 carbon atoms per radical, which is replaced by one or several groups of the formulas -NR ¹ -, -S-, -O-, -CO-O- can be interrupted and with one or more groups of the formulas -SH, -OH, -NR ¹ ₂ , -Cl, -COOH , -O-CO- CR ³ = CH ₂ , R ^{3 is} a divalent alkyl radical having 1 to 6 carbon atoms or the phenylene group and X is a group -OR ⁴ , an acetoxy, amino, acid amide, oximino group or represents a chlorine atom, R ^{4 represents} a hydrogen atom or an alkyl radical having 1 to 8 carbon atoms per radical, which can be interrupted by ether oxygen atoms.

Examples of radicals R ¹ are alkyl radicals, such as the methyl, ethyl, n-propyl, iso-propyl, 1-n-butyl, 2-n-butyl, iso-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert. Pentyl radical; Hexyl radicals, such as the n-hexyl radical; Heptyl residues, such as the n-heptyl residue; Octyl radicals, such as the n-octyl radical and iso-octyl radicals, such as the 2,2,4-trimethylpentyl radical; Nonyl radicals, such as the n-nonyl radical; Decyl radicals, such as the n-decyl radical; Dodecyl radicals, such as the n-dodecyl radical; Octadecyl radicals, such as the n-octadecyl radical; Cycloalkyl radicals, such as the cyclopentyl, cyclohexyl, cycloheptyl radicals and methylcyclohexyl radicals; Aryl radicals, such as the phenyl, naphthyl and anthryl and phenane thryl radical; Alkaryl radicals, such as o-, m-, p-tolyl radicals; Xylyl residues and ethylphenyl residues; and aralkyl radicals, such as the benzyl radical, the α- and the β-phenylethyl radical.

The alkyl radicals having 1 to 10, in particular up to 6, carbon atoms, in particular the methyl and ethyl radical, are preferred. Examples of alkyl radicals R ¹ which are substituted by an ether oxygen atom are the methoxyethyl and ethoxyethyl radical. Examples of halogenated radicals R ¹ are haloalkyl radicals, such as the 3,3,3-trifluoro-n propyl radical, the 2,2,2,2 ', 2', 2'-hexafluoroisopropyl radical, the heptafluoroisopropyl radical and haloaryl radicals, such as the o-, m- and p-chlorophenyl.

Examples of aliphatic unsaturated radicals R ¹ are alkenyl radicals, such as the vinyl, 5-hexenyl, 2,4-divinylcyclohexylethyl, 2-propenyl, allyl, 3-butenyl and 4-pentenyl radical; and alkynyl radicals, such as the ethynyl, propargyl and 2-propynyl radical.

Preferred radicals R ² are radicals of the formulas - (CH ₂ ) _s -SH, - (CH ₂ ) _s -OH, - (CH ₂ ) _s -Cl, - (CH ₂ ) _t - COOH, - (CH ₂ ) _s -NH (C ₆ H ₁₁ ), - (CH ₂ ) _s -NH ₂ , - (CH ₂ ) _s -NH (CH ₃ ), - (CH ₂ ) _s -NH- (CH ₂ ) _s -NH ₂ , - (CH ₂ ) _s -O- (CH ₂ ) _s -CH ₃ , - (CH ₂ ) _s - [- O- (CH ₂ ) _t ] _s -O- (CH = CH ₂ ) - (CH ₂ ) _s -O-CO-CH = CH ₂ , where s is 1, 2, 3, 4, 5 or 6 and t is 1 to 18, in particular 6 to 12.

On average, X has a value of at least 2.05, preferably at least 2.1, in particular at least 2, 3 calculated per molecule of organosilane of the general formulas Ia to Ie.

The organosilane composition is preferably chosen so that the organopolysiloxane of the general formula II formed as an envelope wall

[R ¹ ₂ R ² SiO _1/2 ] _x [R ¹ R ² SiO _2/2 ] _y [R ² SiO _3/2 ] _z [SiO _4/2 ] _u [SiO _3/2 -R ³ -SiO _{3 / 2} ] _v (II)

corresponds to, in which x is 0 to 60 mol%, y is 0 to 95 mol%, z is 0 to 100 mol%, u is 0 to 50 mol% and v is 0 to 100 mol% and, R ¹ , R ² and R ³ are have the meanings given above.

× is preferably 0 to 30 mol%, y 0 to 50 mol%, z 50 to 100 mol%, u 0 to 20 Mol% and v 0 to 50 mol%.

The hydrolysis and polycondensation can also be carried out in the presence of catalysts be performed. The catalysts can be acidic or basic, are preferred basic catalysts used.

Examples of basic hydrolysis and condensation catalysts are aminosilanes, through Hydrolysis of ammonia-releasing compounds, such as divinyltetramethyldisilazane, hexams thyldisilazane, organic amine compounds such as n-hexylamine, triethylamine, diethylamine, Tributylamine, piperidine, diazabicyclooctane, organic hydroxides, especially quaternary Hydrocarbon ammonium hydroxides such as tetramethyl ammonium hydroxide, tetrabutyl ammonium hydroxide, trimethylbenzylammonium hydroxide and inorganic hydroxides such as Sodium hydroxide, lithium hydroxide, potassium hydroxide, and a mixture of the above. Ver bonds.

Particularly preferred basic catalysts are the aminosilanes of the general formula III,

XaSi- [R ⁶ _b -NR ⁵ ] _C -R ⁶ -N (R ⁵ ) ₂ (III)

in the
R ^{5 is} a hydrogen atom or an alkyl radical with 1 to 8 carbon atoms per radical, R ^{6 is} a divalent alkyl radical with 1 to 6 carbon atoms, a the values 1, 2 or 3, b the values 1, 2, 3 or 4 and c the values 0 , 1, 2 or 3 mean and X has the above meanings.

The aminosilanes of the general formula III are in the one forming the envelope Organopolysiloxane incorporated. This allows the polarity of the envelope wall Organopolysiloxanes are influenced. X is preferably methoxy or Alkoxy residues.

Preferred examples of aminosilanes of the general formula III are Aminopropyltrimethoxysilane, aminoethylaminopropyltrimethoxysilane and N- Cyclohexylaminopropyltrimethoxysilane.

In the hydrolysis and condensation, the catalyst is preferably used in amounts of 0.1 up to 30% by weight, based on the weight of the organosilanes and / or their  Condensation products of the general formulas Ia to Ie used. The basic ones Catalysts can be the organosilanes and / or their condensation products or aqueous phase (variants (A) and (B)) or immiscible liquid phase (Variant (C)) can be added.

The radicals R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ as well as the indices a, b, c, m, n, u, v, x, y and z can each independently be the same in the above formulas or be different.

As surfactants, in the presence of which the mesoporous carrier materials are produced , cationic and nonionic surfactants are particularly suitable.

Examples of cationic surfactants are quaternary ammonium compounds, cationic Polymers and emulsifiers, such as those found in hair care products and also in agents for Textile finish can be used, such as. B. quaternary imidazolinium compounds, protonated alkylamine compounds, quaternized protein hydrolyzates, polyquaternium Polymers, cationic quaternary sugar derivatives, cationic alkyl polyglucosides, cationic polyacrylates, copolymers of PVP and dimethylaminomethacrylate, Copolymers of vinylimidazole and vinylpyrrolidone, aminosilicone polymers and - copolymers, polyquaternized polymers, cationic chitin - based biopolymers and their derivatives, cationic silicone oils, alkylamidoamines, quaternary ester compounds as well as any mixtures of the above.

Suitable examples are quaternary ammonium compounds of the formulas (IV) and (V),

wherein R ⁷ and R ^{8 are} an acyclic alkyl radical having 12 to 24 carbon atoms, R ^{9 is} a saturated C ₁ -C ₄ alkyl or hydroxyalkyl radical, R ^{10 is} either R ⁷ , R ⁸ or R ⁹ and COR ¹¹ and COR ¹² each represents an aliphatic acyl radical having 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds and R ^{13 represents} H or OH, where d, e and f can each independently have the value 1, 2 or 3 and Y is either a halide, methosulfate, methophosphate or phosphate ion, as well as mixtures of these compounds. Compounds which contain alkyl radicals having 16 to 18 carbon atoms are particularly preferred.

Examples of cationic compounds of the formula (IV) are Didecyldimethylammonium chloride, ditallow dimethylammonium chloride or dihexadecylammo nium chloride. Examples of compounds of the formula (IV) are methyl-N- (2-hydroxyethyl) -N, N- di (tallow acyl oxyethyl) ammonium methosulfate, bis (palmitoyl) ethyl hydroxyethyl methyl ammonium methosulfate or methyl-N, N-bis (acyloxyethyl) -N- (2-hydroxyethyl) ammonium methosulfate. If quaternized compounds of formula (V) are used, the unsaturated ones Having alkyl chains, the acyl groups are preferred, their corresponding ones Fatty acids have an iodine number between 5 and 25, preferably between 10 and 25 and in particular between 15 and 20 and which have a cis / trans isomer ratio (in % By weight) of 30:70, preferably greater than 50:50 and in particular greater than 70:30 to have.

In addition to the quaternary compounds described above, other known compounds can also be used, such as quaternary imidazolinium compounds of the formula (VI)

wherein R ¹⁴ and R ¹⁵ each represent a saturated alkyl radical having 12 to 18 carbon atoms, R ¹⁶ an alkyl radical having 1 to 4 carbon atoms or H and Z represents an NH group or oxygen and A is an anion.

Further suitable quaternary compounds are described by formula (VII)

wherein R ^{11 represents} a C _1-4 alkyl, alkenyl or hydroxyalkyl group, R ¹⁸ and R ¹⁹ each independently represent a C _8-28 alkyl group and g is a number between 0 and 5.

In addition to the compounds of the formulas (IV) to (VII), short-chain, water-soluble, quaternary ammonium compounds are used, such as trihydroxyethylmethylammo nium methosulfate or the alkyltrimethylammonium chlorides and bromides, dialkyldimethyl ammonium chlorides and bromides and trialkyl methyl ammonium chlorides and bromides, e.g. B. Cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylam monium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride, Tricetylmethylammonium chloride and hexadecyltrimethylammonium bromide.

Protonated alkylamine compounds as well as the non-quaternized, protonated ones Precursors of the cationic emulsifiers are suitable.

The quaternized compounds represent further cationic compounds which can be used according to the invention Protein hydrolyzates, e.g. B. Quaternized Wheat Protein Hydrolyzate Gluadin® WQ, Gluadin® WQT (manufacturer: Cognis Deutschland GmbH).  

Suitable cationic polymers include the polyquaternium polymers as described in CTFA Cosmetic Ingredient Dictionary (The Cosmetic, Toiletry and Fragrance, Inc., 1997) to be discribed. Examples are in particular cationic cellulose derivatives, which are also known as Merquats designated polymers Polyquaternium-6, Polyquaternium-7; Polyquaternium-10- Polymers (Ucare Polymer JR 400; Amerchol;), Polyquaternium-4 copolymers, such as Graft copolymers with a cellulose skeleton and quaternary ammonium groups, which over Allyldimethylammonium chloride are bound, cationic guar derivatives, such as guar hydroxypropyl triammonium chloride, e.g. B. Cosmedia Guar (Manufacturer: Cognis Germany GmbH), cationic quaternary sugar derivatives, e.g. B. the commercial product Glucquat®100, ge according to CTFA nomenclature a "Lauryl Methyl Gluceth-10 Hydroxypropyl Dimonium Chloride", cationic alkyl polyglucosides (APG derivatives), cationic polyacrylates, such as Eudragit® RL 30 D (manufacturer: Röhm), copolymers of PVP and Dimethylaminomethacrylate, copolymers of vinylimidazole and vinylpyrrolidone, aminosilicone polymers and copolymers.

Polyquaternized polymers (e.g. Luviquat Care from BASF) and also cationic chitin-based biopolymers and their derivatives, for example the one below the trade name Hydagen DCMF, CMFP, HCMG (manufacturer: Cognis Germany GmbH) available chitosan and chitosan derivatives.

Also suitable according to the invention are cationic silicone oils such as those in the Commercially available products Q2-7224 (manufacturer: Dow Corning; a stabilized trimethyl silylamodimethicone), Dow Corning 929 emulsion (containing a hydroxylamino mo differentiated silicone, also called amodimethicone), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker), Abil®-Quat 3270 and 3272 (manufacturer: Th. Goldschmidt; diquaternary polydimethylsiloxanes, quaternium-80), and silicone quat Tegopren® 6922 (manufacturer: Th. Goldschmidt).

Also alkylamidoamines, especially fatty acid amidoamines like the one under the name Tego Amid®S 18 available stearylamidopropyldimethylamine can be used.

Quaternary can also be used and is also very readily biodegradable Ester compounds, so-called "esterquats", such as those under the trademark Stepantex® distributed methylhydroxyalkyldialkoyloxyalkylammonium methosulfate or the under Dehyquart® known products from Cognis.  

Suitable nonionic surfactants are selected, for example, from alkoxylated ones Fatty alcohols, such as fatty alcohol polyethylene glycol ether, fatty alcohol polyethylene / polypropylene glycol colethers and mixed ethers, which may be end group capped, copolymers Ethylene oxide and propylene oxide, hydroxyalkyl polyethylene glycol ethers, alkyl glycosides, amine oxides, fatty acid alkanolamides, polyhydroxy fatty acid amides and any mixtures the previous one.

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. In particular, however, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for. B. from coconut, palm, tallow or oleyl alcohol, and preferred by average 2 to 8 EO per mole of alcohol. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO to 7 EO, C _9-11 alcohol with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C _12-14 alcohol with 3 EO and C _12-18 alcohol with 7 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol holoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO. Nonionic surfactants which contain EO and PO groups together in the molecule can also be used according to the invention. Here block copolymers with EO-PO block units or PO-EO block units can be used, but also EO-PO-EO copolymers or PO-EO-PO copolymers. Of course, mixed alkoxylated nonionic surfactants can also be used, in which EO and PO units are not distributed in blocks but statistically. Such products can be obtained by the simultaneous action of ethylene and propylene oxide on fatty alcohols.

Particularly preferred examples of alkoxylated fatty alcohols are the fatty alcohol polyethylene glycol colether, fatty alcohol polyethylene / polypropylene glycol ether and mixed ether, which may be endgrup can be pen-sealed and copolymers of ethylene oxide and propylene oxide.

Examples of fatty alcohol polyethylene glycol ethers are those with the formula (VIII)

R ²⁰ O- (CH ₂ CH ₂ O) _h H (VIII)

in which R ^{20 is} a linear or branched alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms and h is a number from 1 to 5.

The substances mentioned are known commercial products. Typical examples are addition products of an average of 2 or 4 moles of ethylene oxide with technical C _12/14 coconut oil alcohol (Dehydol® LS-2 or LS-4, from Cognis Deutschland GmbH) or addition products of average 4 moles of ethylene oxide over C _14/15 oxo alcohols (Dobanol®45-4, Shell). The products can have a conventional or narrow homolog distribution.

Fatty alcohol polyethylene / polypropylene glycol ethers are understood to mean nonionic surfactants of the formula (IX)

in which R ^{21 represents} a linear or branched alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms, i for numbers from 1 to 0 and k for numbers from 1 to 4.

These substances are also known commercial products. Typical examples are addition products of an average of 5 moles of ethylene oxide and 4 moles of propylene oxide with technical C _12/14 coconut fatty alcohol (Dehydol® LS-54, from Cognis Deutschland GmbH), or 6.4 moles Ethylene oxide and 1.2 mol of propylene oxide over technical C _10/14 coconut fatty alcohol (Dehydol®LS-980, from Cognis Deutschland GmbH).

Mixed ethers are to be understood as end group-locked fatty alcohol polyglycol ethers with the formula (X)

in the R ²² for a linear or branched alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms, I for numbers from 1 to 10, m for 0 or numbers from 1 to 4 and R ²³ for an alkyl radical has 1 to 4 carbon atoms or a benzyl radical.

Typical examples are mixed ethers of the formula (X) in which R ^{22 stands} for a technical C _12/14 cocoalkyl radical, l for 5 or 10, m for 0 and R ²³ for a butyl group (Dehypon®LS-54 or LS -104, Cognis Deutschland GmbH). The use of mixed ethers which are closed with butyl or benzyl groups is particularly preferred for technical reasons.

Hydroxyalkyl polyethylene glycol ethers are compounds with the general formula (XI)

in the
R ^{24 represents} hydrogen or a straight-chain alkyl radical having 1 to 16 carbon atoms,
R ^{25 is} a straight-chain or branched alkyl radical having 4 to 8 carbon atoms,
R ^{26 represents} hydrogen or an alkyl radical having 1 to 16 carbon atoms and
n for a number from 7 to 30
stand, with the proviso that the total number of carbon atoms contained in R ²⁴ and R ^{25 is} 6 to 16.

In addition, alkyl glycosides of the general formula R ²⁷ O (G) _X can also be used as further nonionic surfactants, in which R ^{27 is} a primary straight-chain or methyl branched, in particular in the 2-position methyl branched aliphatic radical having 8 to 22, preferably 12 to 18 C atoms and G is the symbol which stands for a glycose unit with 5 or 6 C atoms, preferably for glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is an arbitrary number between 1 and 10; x is preferably 1.2 to 1.4.

Another class of nonionic surfactants that are used especially in solid agents are, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fat acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain.  

Also nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dime thylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can be suitable.

Other suitable surfactants are polyhydroxy fatty acid amides of the formula XII,

in the R ²⁸ CO for an aliphatic acyl radical with 6 to 22 carbon atoms, R ²⁹ for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups stands. The polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.

The group of polyhydroxy fatty acid amides also includes compounds of the formula XIII,

in which R ³⁰ for a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ³¹ for a linear, branched or cyclic alkyl radical or an aryl radical with 2 to 8 carbon atoms and R ³² for a linear, branched or cyclic alkyl radical or Aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, C _1-4 alkyl or phenyl radicals being preferred and [Z] standing for a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propxylated derivatives of this residue.

[Z] is preferably obtained by reductive amination of a sugar, for example Glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy or N-aryloxy-substituted compounds can then, for example, by reaction with  Fatty acid methyl esters in the presence of an alkoxide as a catalyst in the desired Polyhydroxy fatty acid amides are transferred.

The carrier materials can be produced in an acidic or alkaline medium become. The pore structure can be adjusted depending on the pH value. So z. B. when carrying out the reaction in an alkaline environment, preferably using cationic compounds such as cetrytrimethylammonium bromide as a template usually hexagonal structures, i.e. H. long channels are formed, which are an optimal passage for the stored substances and thus the active substances to be released. By varying the pH between pH 11 and pH 10, the Tailor the size of the pores in a limited size range.

The reaction is usually carried out in an excess of solvent. By the suitable choice of the surfactant component as well as the choice of the surfactant silicate Ratio can polycondensation products with hexagonal, cubic, vesicular or lamellar pores are obtained, the pore size in the range between 2 and can be 50 nm. Small pore sizes are preferably obtained when low molecular weight surfactants are used. Large pores are obtained through use of amphiphilic block copolymers such as EO-PO-EO polymers.

The active ingredient and / or active ingredient to be stored can be used directly in the manufacturing reaction of the mesoporous carrier materials are inserted or subsequently into the mesoporous Carrier material are introduced.

In a preferred embodiment of the present invention, the hydrolysis of the Oxide precursor already in the presence of the active substance. If the hydrolysis takes place in the presence of the Active and / or active substances to be stored, the size of the pores can be influenced by these substances.

In a further embodiment of the present invention, the Mesoporous carrier material is produced and then the active and / or Active substance applied to the material obtained in a manner known per se.

In a preferred embodiment of the present invention, the release of the Substances controlled by the pore structure and / or size of the carrier material.  

The release of substances that are not chemically anchored to the carrier material takes place by diffusion from the highly ordered (mostly hexagonal) pore structures. The Release of firmly anchored substances can e.g. B. by hydrolysis of the bond in a suitable medium and subsequent diffusion from the highly ordered pores occur.

In the manufacture of the carrier materials, the pore size can be adjusted in a targeted manner the release mechanism and speed can be adjusted. This is before all possible via the choice of the surfactant used or the substance to be stored. Also by changing the pore geometry (e.g. cubic-bicontinuous or lamellar The release kinetics can be controlled instead of hexagonal.

In a preferred embodiment, the pore walls can be modified in such a way that that they have an anchoring option, such as functional groups, for the active and / or Active ingredients, such as enzymes. Such a modification of the pore walls would have The advantage that sensitive substances such as enzymes are bound to the pore walls and not be destroyed by other components. The modification can either be in situ, d. H. in the implementation of oxide precursors in the reaction medium in the presence of Surfactants can be obtained by a suitable choice of organo-substituted oxide precursors. Alternatively, a modification after calcination can be carried out using Organosilicon compounds are generated. It can be both hydrophilic Modifications (e.g. with aminoethyltrimethoxysilane) or hydrophobic modifications (e.g. with octadecyltrichlorosilane) of the mesoporous oxide material.

Another object of the present invention is accordingly the use of Release or adsorption systems according to the invention in washing and cleaning agents, in agents for skin and hair cleaning and care, on surfaces, in adhesives, in dye particles, cosmetics, shampoos, conditioners, (room) fragrances, toilet Gels, leveling compounds, grouting compounds, fillers, adhesive tapes, scented candles Surfaces etc.

In addition to the release systems used according to the invention, such agents contain all the usual other ingredients that may be present in such agents.

In one possible embodiment of the present invention, the washing and Detergent for cleaning hard surfaces, including dishes  used. Agents for cleaning hard surfaces are usually liquid to gel-shaped.

In a further embodiment of the present invention, the washing and Detergent used for textile treatment. Examples of textile treatment agents are textile detergents, such as universal detergents and mild detergents, textile pretreatment Detergents and stain treatment agents, as well as post-treatment agents such as fabric softener. In a further embodiment, the agents for textile treatment are combination products, which also contain the components for textile cleaning and textile care, e.g. B. a Universal or mild detergent, the components for textile care in the form of release system according to the invention included.

Yet another object of the present invention is a care and maintenance product This cleanses the skin, which contains the usual components contained in such agents characterized that furthermore a release system from a mesoporous Carrier material and one or more active substances and / or active substances applied to it is included.

Yet another object of the present invention is a care and maintenance product This cleanses the skin, which contains the usual components contained in such agents characterized in that it contains a mesoporous carrier material, which may or may not has several active substances and / or active substances applied thereon, which is suitable for this Substances that are on the skin or are secreted from it, to record.

Liquid and lumpy are examples of skin care and cleansing agents Washing, showering and bathing preparations, body creams and lotions, tanning agents, Face creams, eye care products, facial tonic and also the products of the decorative Cosmetics such as lipsticks and lip gloss, make-up and face powder, mascara, To name eyeliner, eye pencils, eye shadow preparations, nail care products, etc. Further Examples are so-called combination products, which are simultaneously a cleaning and a have a nourishing effect on the skin, e.g. B. skin cleanser that Release system according to the invention, in which active ingredients with lipid-replenishing agents and / or caring properties are applied to the porous carrier material, contain.  

Another item is a means of cleaning and maintaining hair, containing common ingredients, which is characterized by the one Release system from a porous carrier material and one or more thereon contains applied active substances and / or active substances.

Examples of agents for cleaning and maintaining hair are hair shampoos, Hair care products such as hairdressing creams, lotions and gels, hair fixatives, hair sprays, Hair pomade, hair rinses and spa packs, hair shaping agents, hair dye and bleaching agents. Other examples are so-called combination products that have a cleansing and nourishing effect on the hair at the same time, e.g. B. Hair shampoos in which nourishing substances act as active ingredients on the porous Carrier material are applied.

Another object of the present invention is a washing and cleaning agent, which, in addition to the usual ingredients, a release system from a mesoporous Carrier material and one or more active substances and / or active substances applied thereon contains.

Another object of the present invention is a washing and cleaning agent, which contains a mesoporous carrier material in addition to the usual ingredients optionally has one or more active substances and / or active substances applied thereon and is suitable for substances that are on the substrate to be cleaned, to record.

Such agents can be in liquid to gel or solid form and in of any shape that is advantageous for the respective application.

If the agents are in liquid to gel form, they are usually aqueous preparations, which may also contain other water-miscible organic solutions agents and thickeners. To the organic miscible with water agents count z. B. Hydrophilizing agents. The production of liquid up Gel-like preparations can be carried out continuously or batchwise by simple mixing of the components, if necessary at an elevated temperature.

Examples of hydrophilizing agents are mono- or polyhydric alcohols, alkanolamines or glycol ethers, provided they are miscible with water. The hydrophilizing agents are preferably selected from ethanol, n- or i-propanol, butanols, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl glycol monomethyl, dipropylene -, or -ethyl ether, di-isopropylene glycol mono methyl or -ethyl ether, methoxy, ethoxy or butoxytriglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene-glycol-t-butyl ether alcohols, in particular C ₁ -C ₄ alkanols, glycols, polyethylene glycols, preferably with a molecular weight between 100 and 100,000, in particular between 200 and 10,000, and polyols, such as sorbitol and mannitol, and also polyethylene glycol which is liquid at room temperature, carboxylic acid esters, polyvinyl alcohols, ethylene oxide propylene oxide Block copolymers and any mixtures of the above.

One or more of a liquid composition can be used to adjust the viscosity or thickening systems are added. The viscosity of the compositions can using standard methods (e.g. Brookfield RVD-VII viscometer 20 rpm and 20 ° C, spindle 3) are measured and is preferably in the range of 100 up to 5000 mPas. Preferred compositions have viscosities from 200 to 4000 mPas, with values between 400 and 2000 mPas being particularly preferred.

Suitable thickeners are inorganic or polymeric organic compounds. It can mixtures of several additives can also be used.

The inorganic thickeners include, for example, polysilicic acids and clay minerals such as montmorillonites, zeolites, silicas and bentonites.

The organic thickeners come from the groups of natural polymers, the modified natural polymers and the fully synthetic polymers. These too Swelling agents, mostly high-molecular substances, absorb the liquids, swell and eventually change into viscous real or colloidal solutions.

Natural polymers that are used as thickeners are included in for example agar-agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, Guar flour, locust bean gum, starch, dextrins, gelatin and casein.

Modified natural products mainly come from the group of modified starches and Celluloses, examples include carboxymethyl cellulose and other cellulose ethers, Hydroxyethyl and propyl cellulose and core meal ether called.  

A large group of thickeners, widely used in a wide variety Find application areas are the fully synthetic polymers such as polyacrylic and Polymethacrylic compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimines, Po lyamides and polyurethanes.

The thickeners can be used in an amount of up to 10% by weight, preferably from 0.05 to 5% by weight. and particularly preferably from 0.1 to 3% by weight, based on the finished combination settlement, be included.

In addition, surfactant thickeners can also be used, e.g. B. alkyl polyglycosides such as C _8-10 alkyl polyglucoside (APG® 220, manufacturer: Cognis Deutschland GmbH); C _12-14 alkyl polyglucoside (APG® 600, manufacturer: Cognis Deutschland GmbH).

The means in solid form include e.g. B. powders, compacts, such as granules and moldings (tablets) The individual forms can be produced by methods known from the prior art, such as by spray drying, granulation and pressing. The compositions in solid form can also be packaged in suitable packaging systems, the packaging system preferably having a moisture vapor transmission rate of 0.1 g / m ² / day to less than 20 g / m ² / day when the packaging system is at 23 ° C and a relative equilibrium humidity of 85% is stored.

The agents can contain all the ingredients customary for the respective application. It is also possible to use the substances mentioned above as active ingredients in free form as well as the surfactants and cationic compounds mentioned.

Other ingredients for detergents and cleaning agents include tensides and Builders to name.

Anionic, nonionic, cationic, amphoteric and zwitterionic can be used as surfactants Surfactants are used. Examples include nonionic and cationic surfactants the above-mentioned surfactants used to manufacture the porous carrier material can be referred.

Anionic surfactants used are, for example, those of the sulfonate and sulfate type. The surfactants of the sulfonate type are preferably C _9-13 -alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfates such as are obtained, for example, from C _12-18 monoolefins with a terminal or internal double bond by sulfonation Gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Also suitable are alkanesulfonates obtained from C _12-18 alkanes, for example by sulfochlorination or sulf oxidation with subsequent hydrolysis or neutralization. Likewise, the esters of a-sulfo fatty acids (ester sulfonates), e.g. B. the a-sulfonated methyl ester of hydrogenated coconut, palm kernel or tallow fatty acids.

As alk (en) yl sulfates, the alkali and especially the sodium salts of sulfuric acid are half-esters of C ₁₂ -C ₁₈ fatty alcohols, for example made from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ - Oxo alcohols and those half esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned, which contain a synthetic, straight-chain alkyl radical produced on a petrochemical basis. The C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates as well as C ₁₄ -C ₁₅ alkyl sulfates are preferred from the point of view of washing technology. 2,3-Alkyl sulfates, which are produced, for example, according to US Pat. Nos. 3,234,258 or 5,075,041 and can be obtained as commercial products from Shell Oil Company under the name DAN®, are also suitable anionic surfactants.

Other suitable anionic surfactants are sulfonated fatty acid glycerol esters. Under fatty acid glyce The mono-, di- and triesters as well as their mixtures are to be understood as Rinestern, as in the production by esterification of a monoglycerin with 1 to 3 moles of fatty acid or obtained in the transesterification of triglycerides with 0.3 to 2 mol of glycerol. Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated Fatty acids with 6 to 22 carbon atoms, for example caproic acid, caprylic acid, Capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.

The sulfuric acid monoesters of the straight-chain or branched C _7-21 alcohols ethoxylated with 1 to 6 moles of ethylene oxide, such as 2-methyl-branched C _9-11 alcohols with an average of 3.5 moles of ethylene oxide (EO) or C _{12 18} fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight.

Other suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain C _8-18 fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below). Again, sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution are particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.

Other suitable anionic surfactants include soaps, in particular can be used in powdery form and at higher pH values. Suitable are ge saturated and unsaturated fatty acid soaps, such as the salts of lauric acid, myristic acid, Pal mitic acid, stearic acid, hydrogenated erucic acid and behenic acid and in particular from natural fatty acids, e.g. B. coconut, palm kernel, olive oil or tallow fatty acids derived Soap mixtures.

The anionic surfactants including the soaps can be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or tri ethanolamine. The anionic surfactants are preferably in the form of their sodium or potassium salts, especially in the form of the sodium salts.

So-called gemini surfactants can be considered as further surfactants. Below are in generally understood such compounds that two hydrophilic groups and two hydro possess phobic groups per molecule. These groups are usually separated by a so-called called "spacers" separated from each other. This spacer is usually a carbon chain, which should be long enough that the hydrophilic groups have a sufficient distance so that they can act independently of one another. Such surfactants are characterized in generally due to an unusually low critical micelle concentration and the Ability to greatly reduce the surface tension of the water. In In exceptional cases, however, the term Gemini surfactants does not only refer to dimeric, but also understood trimeric surfactants.

Suitable Gemini surfactants are, for example, sulfated hydroxy mixed ethers of dimer alcohol bis- and trimer alcohol tris sulfates and ether sulfates. End group capped dimers and trimeric mixed ethers are particularly characterized by their bi- and multifunctionality. So the end-capped surfactants mentioned have good wetting properties and are low-foaming, so that they are particularly suitable for use in mechanical  Washing or cleaning processes are suitable. Gemini can also be used. Polyhydroxy fatty acid amides or poly-polyhydroxy fatty acid amides.

Zwitterionic surfactants are surface-active compounds that contain at least one quaternary ammonium group and at least one -COO ^⊖ or -SO ₃ ^⊖ group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines such as the N-alkyl-N, N-dimethylammonium glycinate, for example the cocoalkyl-dimethylammonium glycinate, N-acylaminopropyl-N, N-dimethylammoniumglycina te, for example the cocoacylaminopropyl-dimethylammonium glycinate, and 2-alkyl- 3-car boxymethyl-3-hydroxyethyl-imidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group, as well as the cocoacylaminoethylhydroxyethylcarboxymethylglycinate. A preferred zwitterionic surfactant is the fatty acid amide derivative known under the CTFA name Cocamidopropyl Betaine.

Ampholytic surfactants are understood to mean those surface-active compounds which, in addition to a C _8-18 -alkyl or -acyl group, contain at least one free amino group and at least one -COOH or -SO ₃ H group in the molecule and are capable of forming internal salts are. Examples of suitable ampholytic surfactants are N-alkylglycine, N-alkylpropionic acid, N-alkylaminobutyric acid, N-alkyliminodipropionic acid, N-hy droxyethyl-N-alkylamidopropylglycine, N-alkyltaurine, N-alkylsarcosine, 2-alkylaminopropionic acid and alkylaminoacetic acid each with about 8 up to 18 carbon atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate and C _12-18 acyl sarcosine.

Detergents and cleaning agents can also all usually be used for such agents contain suitable builders, in particular zeolites, silicates, carbonates, organic Cobuilder and - where there are no ecological prejudices against their use - also that Phosphates.

Suitable crystalline, layered sodium silicates have the general formula NaMSi _x O _{2x + 1} .H ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4. Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicates Na ₂ Si ₂ O ₅ .yH ₂ O are preferred.

Amorphous sodium silicates with a modulus Na ₂ O: SiO ₂ of 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, can also be used are delayed in dissolving and have secondary washing properties. The delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying. In the context of this invention, the term “amorphous” is also understood to mean “X-ray amorphous”. This means that the silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle. However, it can very well lead to particularly good builder properties if the silicate particles deliver washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred. Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.

Fine crystalline, synthetic and bound water containing zeolite is preferred Zeolite A and / or P. Zeolite P is Zeolite MAP® (commercial product from Crosfield) particularly preferred. However, zeolite X and mixtures of A, X are also suitable and / or P.

Zeolites from Fau are further preferred and particularly suitable zeolites to call jasit type. The mineral faujasite belongs to the zeolites X and Y. the faujasite types within the zeolite structure group 4, which are characterized by the double Subunit D6R is marked (compare Donald W. Breck: "Zeolite Molecular Sieves ", John Wiley & Sons, New York, London, Sydney, Toronto, 1974, page 92). To Zeo lith structure group 4 includes the minerals Cha in addition to the faujasite types mentioned bazit and gmelinit as well as the synthetic zeolites R (Chabazit-Typ), S (Gmelinit-Typ), L and ZK-5. The latter two synthetic zeolites have no mineral Analogues.

Zeolites of the faujasite type are composed of β-cages which are linked tetrahedrally via D6R subunits, the β-cages being arranged in a manner similar to the carbon atoms in the diamond. The three-dimensional network of faujasite-type zeolites has pores of 2.2 and 7.4 Å, the unit cell also contains 8 cavities with a diameter of approx. 13 Å and can be determined using the formula Na ₈₆ [(AlO ₂ ) ₆₆ (SiO ₂ ) ₁₀₆ ] .264 H ₂ O. The network of zeolite X contains a void volume of approximately 50%, based on the dehydrated crystal, which represents the largest empty space of all known zeolites (zeolite Y: approx. 48% void volume, faujasite: approx. 47% void volume). (All data from: Donald W. Breck: "Zeolite Molecular Sieves", John Wiley & Sons, New York, London, Sydney, Toronto, 1974, pages 145, 176, 177).

In the context of the present invention, the term “zeolite of the faujasite type” denotes all three zeolites that form the faujasite subgroup of zeolite structure group 4. Next Zeolite X also includes zeolite Y and faujasite and mixtures of these compounds usable according to the invention, the pure zeolite X being preferred. Also mixtures or Cocrystallizates of zeolites of the faujasite type with other zeolites that are not mandatory Zeolite structure group 4 must be used.

The aluminum silicates that can be used are commercially available, and the Methods for their presentation are described in standard monographs.

Examples of commercially available X-type zeolites can be described by the following formulas:

Na ₈₆ [(AlO ₂ ) ₈₆ (SiO ₂ ) ₁₀₆ ] .x H ₂ O,
K ₈₆ [(AlO ₂ ) ₈₆ (SiO ₂ ) ₁₀₆ ] .x H ₂ O,
Ca ₄₀ Na ₆ (AlO ₂ ) ₈₆ (SiO ₂ ) ₁₀₆ ] .x H ₂ O,
Sr ₂₁ Ba ₂₂ [(AlO ₂ ) ₈₆ (SiO ₂ ) ₁₀₆ ] .x H ₂ O,

in which x can have values between 0 and 276 and the pore sizes from 8.0 to 8.4 Å exhibit.

A co-crystallizate of zeolite X and zeolite A (approx. 80% by weight zeolite X), which is sold by CONDEA Augusta SpA under the brand name VEGOBOND AX®, is also commercially available and can preferably be used in the context of the present invention and through the formula

nNa ₂ O. (1-n) K ₂ O.Al ₂ O _3. (2-2.5) SiO _2. (3.5-5.5) H ₂ O

can be described. The zeolite can be used both as a builder in one granular compound used, as well as a kind of "powdering" of the entire pressing mixture are used, usually both ways to Incorporation of the zeolite into the premix can be used. Suitable zeolites have an average particle size of less than 10 µm (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22 % By weight of bound water.

It goes without saying that the generally known phosphates are also used as buildersub punching possible, provided that such use is not avoided for ecological reasons should be. Among the multitude of commercially available phosphates are the alkali metal phosphates with particular preference for pentasodium or pentapotassium tri phosphate (sodium or potassium tripolyphosphate) in the detergent and cleaning agent ind struck the greatest importance.

Alkali metal phosphates is the general term for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which one can distinguish between metaphosphoric acids (HPO ₃ ) _n and orthophosphoric acid H ₃ PO _{4 in} addition to higher molecular weight representatives. The phosphates combine several advantages: They act as alkali carriers, prevent limescale deposits on machine parts and lime incrustations in tissues and also contribute to cleaning performance.

In particular, polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic Cobuilder (see below) and phosphonates are used. These classes of substances will described below.

Usable organic builders are, for example, those in the form of their Polycarboxylic acids that can be used are sodium salts, with polycarboxylic acids being such Carboxylic acids are understood that carry more than one acid function. For example these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, Maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, and Mixtures of these. Preferred salts are the salts of polycarboxylic acids such as  Citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and Mixtures of these.

The acids themselves can also be used. The acids have besides their buil the effect typically also the property of an acidifying component and serve thus also for setting a lower and milder pH value of washing or rice cleaning agents. In particular, citric acid, succinic acid, glutaric acid, adi pinic acid, gluconic acid and any mixtures of these.

Polymeric polycarboxylates are also suitable as builders, for example the Alka limetal salts of polyacrylic acid or polymethacrylic acid, for example those with a molecular weight of 500 to 70,000 g / mol.

For the purposes of this document, the molecular weights given for polymeric polycarboxylates are weight-average molecular weights M _{W of} the respective acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was made against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship to the polymers investigated. This information differs significantly from the molecular weight information for which polystyrene sulfonic acids are used as standard. The molecular weights measured against polystyrene sulfonic acids are generally significantly higher than the molecular weights given in this document.

Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of Have 2000 to 20,000 g / mol. Because of their superior solubility, this can Group in turn the short-chain polyacrylates, the molar masses from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, may be preferred.

Also suitable are copolymeric polycarboxylates, especially those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid. As special copolymers of acrylic acid with maleic acid which have 50 to 90% by weight have proven suitable Contain acrylic acid and 50 to 10 wt .-% maleic acid. Your relative Molecular weight, based on free acids, is generally 2,000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol.  

The (co) polymeric polycarboxylates can be either as a powder or as an aqueous solution be used. The content of (co) polymeric polycarboxylates in the agent is before preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.

To improve water solubility, the polymers can also allylsulfonic acids, such as for example, allyloxybenzenesulfonic acid and methallylsulfonic acid, as a monomer.

Biodegradable polymers of more than two ver. Are also particularly preferred different monomer units, for example those that act as monomers salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or as a mono contain more salts of acrylic acid and 2-alkylallylsulfonic acid as well as sugar derivatives.

Further preferred copolymers are those which are preferably acrolein and Have acrylic acid / acrylic acid salts or acrolein and vinyl acetate.

Likewise, other preferred builder substances are polymeric aminodicarboxylic acids, de ren salts or their precursors. Polyaspa are particularly preferred Ragic acids or their salts and derivatives.

Other suitable builder substances are polyacetals, which are produced by the implementation of Dial dehydrogenated with polyol carboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups have pen, can be obtained. Preferred polyacetals are made from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyolcar receive bonic acids such as gluconic acid and / or glucoheptonic acid.

Other suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates obtained by partial hydrolysis of starches that can. The hydrolysis can be carried out according to customary methods, for example acid or enzyme catalysis based procedures. They are preferably hydrolysis products with average molecular weights in the range of 400 to 500000 g / mol. There is a polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30 preferred, DE being a common measure of the reducing effect of a Polysac charids compared to dextrose, which has a DE of 100. Both are usable Maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with a higher molar mass range from 2000 to 30000 g / mol.  

The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function. A product oxidized at C _{6 of} the saccharide ring can be particularly advantageous.

Also oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine di succinate, are other suitable cobuilders. This is ethylenediamine-N, N'-disuccinate (EDDS) preferably used in the form of its sodium or magnesium salts. Continue to be In this connection, glycerol disuccinates and glycerol trisuccinates are also preferred. Suitable amounts are in formulations containing zeolite and / or silicate at 3 to 15% by weight.

Other useful organic cobuilders are, for example, acetylated hydroxycarboxylic acid ren or their salts, which may optionally also be in lactone form and wel che at least 4 carbon atoms and at least one hydroxyl group and maximum contain two acid groups.

Another class of substances with cobuilder properties are the phosphonates it is especially hydroxyalkane or aminoalkanephosphonates. Among the Hydroxyalkanephosphonaten is the 1-hydroxyethane-1,1-diphosphonate (HEDP) from special of importance as a cobuilder. It is preferably used as the sodium salt, the Disodium salt neutral and the tetrasodium salt reacts alkaline (pH 9). As an aminoalkane phosphonates are preferably ethylenediaminetetramethylenephosphonate (EDTMP), Diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologues in Question. They are preferably in the form of the neutral sodium salts, e.g. B. as Hexasodium salt of EDTMP or as hepta and octa sodium salt of DTPMP. HEDP is preferably used as the builder from the class of the phosphonates. The Aminoalkanephosphonates also have a strong ability to bind heavy metals. Accordingly, it may be preferred, especially if the compositions also contain bleach be to use aminoalkanephosphonates, in particular DTPMP, or mixtures of to use the phosphonates mentioned.

In addition, all compounds that are capable of complexes with alkaline earths train as cobuilders.

As enzymes, which also act as active substances on active materials can be used, come from the class of oxidases, proteases, Lipa  sen, cutinases, amylases, pullulanases, cellulases, hemicellulases, xylanases and Peroxidases and mixtures thereof, for example proteases such as BLAP®, Optimase®, Opticlean®, Maxacal®, Maxapem®, Alcalase®, Esperase® and / or Savinase®, amylases such as Termamyl®, Amylase-LT®, Maxamyl®, Duramyl® and / or Purafect® OxAm, lipases such as Lipolase®, Lipomax®, Lumafast® and / or Lipozym®, Cellulases like Celluzyme® and or Carezyme®. Made from mushrooms or Bacteria such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus, Humicola lanuginosa, Humicola insolens, Pseudomonas pseudoalcaligenes or Pseudomonas cepacia obtained enzymatic agents. Any enzymes used can, as for example in the European patent EP 0 564 476 or in the International patent applications WO 94/23005 described, adsorbed on carriers and / or embedded in coating substances in order to protect them against premature inactivation protect. They are preferably used in amounts of up to 10% by weight, in particular of 0.2% by weight to 2% by weight, with enzymes stabilized against oxidative degradation are particularly preferred.

Among the compounds which serve as bleaching agents and supply H ₂ O ₂ in water, sodium perborate tetrahydrate, sodium perborate monohydrate and sodium percarbonate are of particular importance. Other useful bleaching agents are, for example, persulfates and mixed salts with persulfates, such as the salts available under the trade name CAROAT®, peroxypyrophosphates, citrate perhydrates and H ₂ O2-delivering peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, diperdodecthalopanoic acid or phthaloic acid such as phthaloic acid or phthaloic acid. Organic peracids, alkali perborates and / or alkali percarbonates are preferably used in amounts of 0.1 to 40% by weight, preferably 3 to 30% by weight, in particular 5 to 25% by weight.

To when washing and cleaning at temperatures of 60 ° C and below, and to achieve an improved bleaching effect, particularly in the pre-treatment of laundry, bleach activators can be incorporated into the detergent tablets or can be applied to the carrier materials described above. As bleach activators can compounds that are aliphatic under perhydrolysis conditions Peroxocarboxylic acids with preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid can be used. Substances containing O and / or N-acyl groups of the number of carbon atoms mentioned are suitable and / or optionally substituted benzoyl groups. Multiple are preferred acylated alkylenediamines, especially tetraacetylethylenediamine (TAED), acylated  Triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular 1,3,4,6-tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n- Nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), acylated Hydroxycarboxylic acids, such as triethyl-O-acetyl citrate (TEOC), carboxylic anhydrides, in particular phthalic anhydride, isatoic anhydride and / or succinic anhydride, Carboxamides, such as N-methyldiacetamide, glycolide, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate, isopropenylacetate, 2,5-diacetoxy-2,5- dihydrofuran and enol esters as well as acetylated sorbitol and mannitol respectively Mixtures containing these substances, acylated sugar derivatives, in particular Pentaacetylglucose (PAG), Pentaacetylfructose, Tetraacetylxylose and Octaacetyllactose as well as acetylated, optionally N-alkylated glucamine or gluconolactone, triazole or Triazole derivatives and / or particulate caprolactams and / or caprolactam derivatives, preferably N-acylated lactams, for example N-benzoylcaprolactam and N-acetylcaprolactam. Hydrophilically substituted acyl acetals acyl lactams can also are preferably used. Combinations of conventional bleach activators can also be used be used. Similarly, nitrile derivatives such as cyanopyridines, nitrile quats, e.g. B. N- Alkyammonium acetonitrile, and / or cyanamide derivatives are used. Preferred Bleach activators are sodium 4- (octanoyloxy) benzene sulfonate, n-nonanoyl or Isononanoyloxybenzenesulfonate (n- or iso-NOBS), undecenoyloxybenzenesulfonate (UDOBS), Sodium dodecanoyloxybenzenesulfonate (DOBS), decanoyloxybenzoic acid (DOBA, OBC 10) and / or dodecanoyloxybenzenesulfonate (OBS 12), and N-methylmorpholinum acetonitrile (MMA). Such bleach activators are in the usual range of 0.01 to 20% by weight, preferably in amounts of 0.1 to 15% by weight, in particular 1% by weight to 10 wt .-%, based on the total composition.

In addition to the conventional bleach activators or in their place, too so-called bleach catalysts can be included. These substances are bleach-enhancing transition metal salts or transition metal complexes such as for example Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes. Also Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands as well as Co, Fe, Cu and Ru amine complexes are suitable as bleaching catalysts.

Cosmetic products, d. H. Skin and hair cleansing and care products can also be used have all the usual ingredients suitable in such agents, the active ingredients and / or active substances both in the form of the release / adsorption according to the invention systems as well as in free or in the form of micro / nanocapsules.  

In a further embodiment, the release / adsorb according to the invention tion system in adhesives, e.g. B. used in two-component adhesive. In this Embodiment can the porous carrier material as an active substance one of the reactive Contain adhesive components or crosslinkers, with a slow release of the Crosslinker component from the carrier material and the reaction between the two Components expires.

Another area of application of a release system according to the invention is the use in Two-component coating agents, such as paints etc. Here, too, it is possible to use the two Lacquer components, one of which is in the form of the release system according to the invention is available in a package (pharmaceutical form).

In a further embodiment of the present invention, the active substances used are one Dye. It has been found that the luminosity of dyes is intensified can if this on porous carrier material, in particular in a carrier material mesoporous structure. By intensifying the luminosity, the Amount of expensive dyes can be reduced in many areas of application, resulting in a Cost savings leads. Suitable dyes are, for example, anionic dyes, e.g. B. anionic nitroso dyes. A possible colorant is, for example, Sudan red, Naphthol green (Color Index (Cl) Part 1: Acid Green 1; Part 2: 10020), which is a commercial product for example as Basacid® Green 970 from BASF, Ludwigshafen, and Mixtures of these with suitable blue dyes. Coming as additional colorants Pigmosol® Blue 6900 (Cl 74160), Pigmosol® Green 8730 (Cl 74260), Basonyl® Red 545 FL (Cl 45170), Sandolan® Rhodamine EB400 (Cl 45100), Basacid® Yellow 094 (Cl 47005), Sicovit® Patentblau 85 E 131 (Cl 42051), Acid Blue 183 (CAS 12217-22-0, Cl Acidblue 183), Pigment Blue 15 (Cl 74160), Supranol® Blue GLW (CAS 12219-32-8, C1 Acidblue 221), Nylosan® Yellow N-7GL SGR (CAS 61814-57-1, Cl Acidyellow 218) and / or Sandolan® Blue (C1 Acid Blue 182, CAS 12219-26-0).

Other dyes are those known from hair dyes direct dyes. Direct dyes are usually Ni trophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols. Preferred direct dyes are those under the international names or Trade names HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, Basic Yellow 57, HC Orange 1, Disperse Orange 3, HC Red 1, HC Red 3, HC Red 13, HC Red BN, Basic Red 76,  HC Blue 2, HC Blue 12, Disperse Blue 3, Basic Blue 7, Basic Blue 26, Basic Blue 99, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Basic Violet 2, Basic Violet 14, Acid Violet 43, Disperse Black 9, Acid Blac 52, Basic Brown 16 and Basic Brown 17 are known Compounds and 1,4-bis - (- hydroxyethyl) amino-2-nitrobenzene, 3-nitro-4- (β- hydroxyethyl) aminophenol, 4-amino-2-nitrodiphenylamine-2'-carboxylic acid, 6-nitro-1,2,3,4- tetrahydroquinoxaline, 2-hydroxa-1,4-naphthoquinone, hydroxyethyl-2-nitro-toluidine, picramine acid, 2-amino-6-chloro-4-nitrophenol, 4-ethylamino-3-nitrobenzoic acid and 2-chloro-6- ethylamino-1-hydroxy-4-nitrobenzene.

Other dyes that can be used in the field of hair dyes Dye precursors known compounds are used such as developer and Coupler components.

Primary aromatic amines with a. Are usually used as developer components further, in the para or ortho position, free or substituted hydroxy or Amino group, diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazole derivatives as well as 2,4,5,6-tetraaminopyrimidine and its derivatives. Are special representatives for example p-phenylenediamine, p-toluenediamine, 2,4,5,6-tetraaminopyrimidine, p- Aminophenol, N, N-bis (2-hydroxyethyl) -p-phenylenediamine, 2- (2,5-diaminophenyl) ethanol, 2- (2,5-diaminophenoxy) ethanol, 4-amino-3-methylphenol, 2-aminomethyl-4-aminophenol, 4- Amino-2-diethylaminomethylphenol, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6- diaminopyrimidine, 2,5,6-triamino-4-hydroxypyrimidine and 1,3-N, N'-bis (2'-hydroxyethyl) -N, N'- bis (4'-aminophenyl) diamino-propan-2-ol.

As examples of coupler components, m-phenylenediamine derivatives, naphthols, Re sorcinol and resorcinol derivatives, pyrazolones and m-aminophenol derivatives are mentioned. As Coupler substances are particularly suitable 1-naphthol, 1,5-, 2,7- and 1,7-dihydroxy naphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinol monomethyl ether, m-phenylenediamine, 1-phenyl-3-methyl-pyrazolon-5, 2,4-dichloro-3-aminophenol, 1,3-bis- (2,4- diaminophenoxy) propane, 2-chloro-resorcinol, 4-chloro-resorcinol, 2-chloro-6-methyl-3-aminophe nol, 2-amino-3-hydroxypyridine, 2-methylresorcinol, 5-methylresorcinol and 2-methyl-4-chloro-5- aminophenol.

In a possible embodiment of this embodiment, the surfaces of the Carrier material reactive groups with corresponding groups in the Dye molecules can react so that the dyes on the support material is anchored.  

In a further embodiment of the present invention, the active and / or Active ingredient adsorbed from the environment. In this embodiment, this removes Carrier material undesirable substances from the environment, e.g. B. odorants, dirt, Skin and hair fat, sebum, etc. If the system according to the invention as Laundry after-treatment agents, e.g. B. used in a rinse cycle and remains on the Textiles, re-soiling can be delayed.

In a further embodiment, the release system according to the invention is used as Coating on surfaces, e.g. B. on ceramics, sheets, etc. which may already be can be pretreated or painted. Such a coating can e.g. B. as Color coating, corrosion protection and / or impregnation etc. are used. The Release system can also do this in the form of a (thin) film by reaction generated directly on the surface. In this embodiment, the porous Carrier material as active ingredient reactive components or antioxidants or catalysts etc. pp. included, with a slow release of the reactive component from the Carrier material takes place on the surface and the reaction between the surface and another component or coating expires.  

Examples

400 g of water, 10 g of cetyltrimethylammonium bromide (Aldrich), 100 g of concentrated hydrochloric acid and 45 g of tetraethyl orthosilicate were mixed at 35 ° C. with stirring to produce a mesoporous carrier material HEM-1. A fine precipitate was formed, which had a hexagonal arrangement of the pores with a diameter of approx. 3.6 nm (see Fig. 1, 2, 3).

To prepare another mesoporous carrier material HEM-2, 400 g of water, 36 g of Dehyquart A (Cognis), 100 g of concentrated hydrochloric acid and 45 g of tetraethyl orthosilicate 35 ° C mixed with stirring. A fine precipitate formed, which was hexagonal Arrangement of the pores had a diameter of about 3.9 nm.

To produce a further mesoporous carrier material HEM-3, 960 g of water, 16 g of Pluronic P 123 (BASF), 52 g of concentrated hydrochloric acid and 37 ml of tetraethyl orthosilicate were mixed at 35 ° C. with stirring. A fine precipitate was formed, which had a hexagonal arrangement of the pores with a diameter of approx. 10.6 nm (see Fig. 4).

For the production of a mesoporous carrier material HEM-4 with enclosed therein 400 g of water, 10 g of cetyltrimethylammonium bromide and 100 g of concentrated dye Hydrochloric acid, 0.6 g Sudan red and 45 g tetraethyl orthosilicate mixed at 35 ° C with stirring. A fine precipitate formed, which had a hexagonal arrangement of the pores 3.9 nm in diameter.

For the production of a mesoporous carrier material HEM-5 with enclosed therein 400 g water, 10 g cetyltrimethylammonium bromide, 100 g concentrated perfume Hydrochloric acid, 1 g diphenyl ether and 45 g tetraethyl orthosilicate at 35 ° C with stirring mixed. A fine precipitate formed, which was a hexagonal arrangement of the Pores with a diameter of about 4.2 nm.

To prepare a mesoporous carrier material with an antibacterial active ingredient HEM-6 enclosed therein, 960 g of water, 16 g of Pluronic P 123 (BASF), 52 g of concentrated hydrochloric acid, 2 g of phenol and 37 ml of tetraethyl orthosilicate were mixed at 35 ° C. with stirring. A fine precipitate was formed, which had a hexagonal arrangement of the pores with a diameter of approx. 11.4 nm (see Fig. 1).

Immobilization of enzymes

For the production of an organically modified mesoporous carrier material HEM-7 for 400 g of water, 10 g of cetyltrimethylammonium bromide, 100 g concentrated hydrochloric acid, 4 g aminopropyltriethoxysilane and 41 g tetraethyl orthosilicate mixed at 35 ° C with stirring. A fine precipitate formed, the one had hexagonal arrangement of the pores with a diameter of about 3.7 nm. The The precipitate was washed with ethanol and dried in a drying oven.

For the production of another organically modified mesoporous carrier material HEM-8 960 g of water, 16 g of Pluronic P 123 (BASF), 52 g of concentrated hydrochloric acid, 4 g Aminopropyltriethoxysilane and 33 ml of tetraethylorthosilicate mixed at 35 ° C with stirring. A fine precipitate formed, which had a hexagonal arrangement of the pores 10.8 nm in diameter. The precipitate was washed with ethanol and dried in a drying oven.

The immobilization of enzymes (e.g. papain, trypsin, ovalbumin, conalbumin, Cytochrome C, peroxidase etc.) in the silicate carrier materials (HEM-1, HEM-7, HEM- 8) is carried out by adsorption in a buffer solution at a defined pH. Evidence of Adsorption takes place with the help of UV spectroscopy. For example, 5 mg conalbumin at pH 7.0 in a 0.005 M phosphate buffer at 4 ° C for 2 h with shaking at 0.25 g HEM-7 adsorbed. The adsorption properties depend on both the pore size of the Carrier material as well as the molecular weight of the enzymes. In HEM-1 could Cytochrome C absorbed at pH <7 as well as papain and trypsin at pH <7 become. However, peroxidase could not be immobilized. In HEM-8 could Conalbumin and ovalbumin can be immobilized. It was also found that a Silanization of the pore walls with octadecyltrichlorosilane (1% in toluene) after adsorption of the Enzymes with octadecyltrichlorosilane delayed the release kinetics. Subsequent treatment of enzyme-adsorbed HEM-1 with Aminopropyltriethoxysilane (5% in methylene chloride) delayed the Kinetics of release of the enzymes.  

Covalent modification of mesoporous silicates

The organically modified mesoporous carrier materials of type HEM-7 and HEM-8 by reactive anchoring with an appropriately functionalized dye, Fragrance or other active ingredients are also covalently linked. This will the aminipropyl-modified silicate in a suitable solvent with the reactive Active ingredient or dye implemented.

Test of the matting properties of silicates

Gel base consisting of water, Gylcerin carbonate and Carbopol ETD 2001 each with 1% silicate HEM-1 or 1% talc. These gels are used in one Half-side test procedure applied 50 mg each to the right half of the forehead, while the left a palcebo (consisting of water, glycerol carbonate and Carbopol ETD 2001) was applied becomes. Subsequently, the gloss of the skin is reduced in a measurement period of 5 hours determined by image analysis.

Claims (24)

1. System for the release of active substances and / or active substances, characterized in that it contains a mesoporous carrier material, into which one or more active substances and / or active substances are or can be introduced. 2. System according to claim 1, characterized in that the active and / or Active substances are selected from fragrances, dyes and fluorescent agents, Surfactants, detergent substances, bleaching agents, bleach activators, UV Protective substances, polymers, foam inhibitors, graying inhibitors, inorganic salts, hydrotopes, silicone oils, soil release compounds, optical brighteners, graying inhibitors, anti-shrink agents, Anti-crease agents, color transfer inhibitors, antimicrobial agents, Germicides, fungicides, antioxidants, corrosion inhibitors, fatty substances, lecithin, Preservatives, pearlescent agents or mixtures thereof may be included. Farther the agents can contain electrolytes, preferably sodium, magnesium or Calcium chloride, as well as pH adjusting agents, such as organic or inorganic acids, Pharmaceuticals, antibacterial substances, biocides, enzymes, adhesive components, such as amines, cosmetic active ingredients, such as vitamins, moisturizing substances, oils, Herbal and plant extracts, agents for textile care and pre- or post-treatment during washing and cleaning, such as fabric softener components, antistatic agents, Ironing aids, phobing and impregnating agents, swelling and anti-slip agents, Finishing agents, as well as any mixtures of the above. 3. System according to claim 1 or 2, characterized in that as Carrier materials oxidic materials of the elements Si, Al, B, Ge and the Groups IIIa, IIb, IVb, Vb, VIb of the periodic table of the elements Be, Sn, Pb, Bi, Co, Fe, Co, Ne, Ce, Mn or mixtures thereof can be used. 4. System according to any one of claims 1 to 3, characterized in that the Release of the introduced active and / or active substances through the pore structure of the Material is controlled. 5. System according to any one of claims 1 to 4, characterized in that the Surface of the porous support material has functional groups.   6. System according to claim 5, characterized in that active and / or active ingredients bound to the surface of the carrier material via the functional groups are. 7. Process for the production of a controlled release system Active ingredients, characterized in that a hydrolyzable oxide precursor in Presence of surfactants and possibly active substances and / or active substances of the hydrolysis is subjected. 8. The method according to claim 7, characterized in that the oxide precursor is selected from hydrolyzable compounds of the elements Si, Al, B, Ge, Be, Sn, Pb, Bi, Co, Fe, Co, Ne, Ce, Mn and elements of groups IIIa, IIb, IVb, Vb, VIb of the periodic table mixtures thereof. 9. The method according to claim 8, characterized in that the oxide precursor is selected from alkylsilanes, alkoxysilanes, alkylalkoxysilanes, Organoalkoxysilanes, where as residues in addition to the alkyl groups, also allyl, Aminoalkyl, hydroxyalkyl groups, etc. can be bound. 10. The method according to claim 9, characterized in that organosilanes with the general formulas Ia to Id are used as oxide precursors,
R ¹ ₂ R ² SiX (Ia)
R ¹ R ² SiX ₂ (Ib)
R ² SiX ₃ (Ic)
SiX ₄ (Id)
X ₃ Si-R ³ -SiX ₃ (Ie),
in which R ^{1 is} a monovalent, optionally halogen-substituted and optionally interrupted by ether oxygen atoms hydrocarbon radical each having 1 to 18 carbon atoms or a hydrogen atom, R ^{2 has} the meanings of R ¹ or a monovalent hydrocarbon radical having 1 to 12 carbon atoms per radical, which is replaced by one or several groups of the formulas -NR ¹ -, S-, -O-, -CO-O- can be interrupted and with one or more groups of the formulas -SH, -OH, -NR ¹ ₂ , -Cl, -COOH, -O-CO-CR ³ = CH ₂ , R ^{3 is} a divalent alkyl radical having 1 to 6 carbon atoms or the phenylene group and X is a group -OR ⁴ , an acetoxy, amino, acid amide, oximino group or a Chlorine atom, R ^{4 represents} a hydrogen atom or an alkyl radical with 1 to 8 carbon atoms per radical, which can be interrupted by ether oxygen atoms. 11. The method according to any one of claims 7 to 10, characterized in that the Surfactants are cationic surfactants that are selected from quaternary Ammonium compounds, quaternary imidazolinium compounds, protonated Alkylamine compounds, quaternized protein hydrolyzates, polyquaternium Polymers, cationic quaternary sugar derivatives, cationic Alkyl polyglucosides, cationic polyacrylates, copolymers of PVP and Dimethylaminomethacrylate, copolymers of vinylimidazole and vinylpyrrolidone, Aminosilicone polymers and copolymers, polyquaternized polymers, cationic chitin-based biopolymers and their derivatives, cationic Silicone oils, alkylamidoamines, quaternary ester compounds and any Mixtures of the foregoing. 12. The method according to any one of claims 6 to 11, characterized in that the Surfactants are nonionic surfactants which are selected from the group alkoxylated Fatty alcohols, such as fatty alcohol polyethylene glycol ether, fatty alcohol polyethylene / polypro pylene glycol ether and mixed ether, which may be end group capped, Copolymers of ethylene oxide and propylene oxide, hydroxyalkyl polyethylene glycol ethers, alkyl glycosides, amine oxides, fatty acid alkanolamides, polyhydroxy fatty acid amides and any mixtures of the foregoing. 13. The method according to any one of claims 6 to 11, characterized in that it is in acidic or alkaline environment is carried out. 14. The method according to any one of claims 6 to 13, characterized in that the Process is carried out in the presence of the active ingredient and / or active ingredient. 15. The method according to any one of claims 6 to 14, characterized in that the Pore structure of the carrier materials formed modified with functional groups becomes. 16. The method according to claim 15, characterized in that the active and / or Active substances are bound to the carrier material via the functional groups.   17. Use of the system according to one of claims 1 to 6 in washing and Cleaning agents, in agents for skin and hair cleaning and care Surfaces, in adhesives, in dye particles, cosmetics, shampoos, Conditioners, (room) fragrances, toilet gels, fillers, grouts, Fillers, adhesive tapes, scented candles and on surfaces. 18. Use of the system according to one of claims 1 to 6 for the adsorption of Odors, soiling, skin and hair fat, sebum. 19. Agent for the care and cleaning of the skin, the usual contained in such agents Contains components, characterized in that further a release system of a mesoporous support material and one or more on it applied active and / or active substances is contained. 20. Agent for the care and cleaning of the skin, the usual contained in such agents Contains components, characterized in that it is a mesoporous Contains carrier material, which may have one or more active ingredients applied to it. and / or active substances, which is suitable substances that are on the Skin or be separated from it. 21. Detergents and cleaning agents containing common ingredients, thereby characterized that there is a release system from a mesoporous Carrier material and one or more active and / or applied thereon Contains active substances. 22. Detergent and cleaning agent containing usual ingredients, thereby characterized in that it has a mesoporous support material and so is suitable for substances that are on the substrate to be cleaned, to record. 23. Surface coating containing a system according to one of claims 1 to 6. 24. Surface coating according to claim 23, characterized in that the Embodiment is the release system according to the invention as Color coating, corrosion protection and / or impregnation is used.