EP1948773A1 - Fragrant consumer products comprising oxidizing agents - Google Patents

Fragrant consumer products comprising oxidizing agents

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Publication number
EP1948773A1
EP1948773A1 EP06806237A EP06806237A EP1948773A1 EP 1948773 A1 EP1948773 A1 EP 1948773A1 EP 06806237 A EP06806237 A EP 06806237A EP 06806237 A EP06806237 A EP 06806237A EP 1948773 A1 EP1948773 A1 EP 1948773A1
Authority
EP
European Patent Office
Prior art keywords
weight
acid
methyl
agent
agents
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP06806237A
Other languages
German (de)
French (fr)
Other versions
EP1948773B1 (en
Inventor
Peter Schmiedel
Wolfgang Von Rybinski
Andreas Bauer
Sören HÖLSKEN
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP1948773A1 publication Critical patent/EP1948773A1/en
Application granted granted Critical
Publication of EP1948773B1 publication Critical patent/EP1948773B1/en
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39Organic or inorganic per-compounds
    • C11D3/3945Organic per-compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/50Perfumes

Definitions

  • the present invention relates to a consumable product containing oxidizing agent, which comprises a fragrance composition, said fragrance composition containing a certain minimum amount of fragrances of certain classes.
  • oxidizing agent which comprises a fragrance composition, said fragrance composition containing a certain minimum amount of fragrances of certain classes.
  • the consumer products are, for example, washing or cleaning agents or, for example, also cosmetics
  • fragrances in typical consumer products usually serves two different purposes.
  • the products should be scented as such, on the other hand, the objects on which the products are to be scented. or detergent should give the freshly cleaned surfaces or freshly washed laundry a "freshly cleaned" olfactory impression that should last as long as possible, on the other hand, the sometimes very strong odor of detergents and cleaners should be covered
  • the fragrance of the consumer product eg a washing or cleaning agent
  • a washing or cleaning agent ultimately also provides a welcome opportunity for differentiation in the face of an ever more confusing supply of products, for example in the field of detergents and cleaners
  • the consumer therefore usually wants to acquire a product which not only works well, but also appeals to its aesthetic sensibility, for example by the product as such or objects treated with it developing a fragrance.
  • the consumer expects stains on textiles or cosmetics Moreover, it expects that at least the product, but also the treated object will smell pleasant at all.
  • This expectation on the part of the consumer is even so pronounced that, for example, in the case of a cleaned object appropriate fragrance expected missing this fragrance (eg "Citrusf ⁇ sche" in toilet cleaners), the consumer even doubts the actual active power of the product
  • a particular problem in this case is a perfuming of products with an ability to oxidize.
  • a perfume often, especially after storage, leads to significant product instabilities, so that, for example, an originally fragrant perfumed product after a few weeks of storage odorously changed in a dramatic negative way, so that it is not even neutral, but even repugnant.
  • the product thus becomes unusable or unsaleable as a result of perfuming.
  • a consumable product containing oxidizing agents preferably washing or cleaning agent or cosmetic product comprising a fragrance composition
  • at least 50 wt .-% preferably at least 60 wt .-%, advantageously at least 65 wt .-%, in a more advantageous manner at least 70 wt .-%, more preferably at least 75 wt .-%, in turn advantageously at least 80 wt .-%, in a particularly advantageous manner at least 85 wt .-%, in particular at least 90 wt .-% of the fragrances contained are selected from those fragrances which are at least one of the following classes of substances attributable saturated alcohols, preferably primary, secondary, and / or tertiary saturated, optionally branched or optionally cyclic alcohols, saturated esters, optionally branched or cyclic saturated esters saturated ethers, optionally branched or cyclic saturated ether aromatics with saturated substituents, optionally branched en
  • the consumption product according to the invention is preferably a washing or cleaning agent or a cosmetic agent but they can also be used for industrial, institutional or commercial purposes.
  • the detergents or cleaners are, in particular, liquid detergents or cleaners, also in spray form, but solid detergents or cleaners, in particular also in tablet form, piece form or powder form, are preferred.
  • Agents which are particularly preferred for the purposes of the invention are detergents and cleansing preparations, preferably for cleaning, treatment and / or care of fibers or textile articles, ie textile washing, textile care, textile treatment, textile aftertreatment agents and conditioners of all kinds. These also include separate bleaching agents, such as stain salts, liquid bleaches, detergency boosters. They can be used both as a detergent additive as well as for pretreatment.
  • These include curtain detergents and special detergents for white laundry.
  • Dishwashing agents in particular those for automatic dishwashing and hard surface cleaners, are among the preferred cleaning agents.
  • Particularly preferred cleaning agents which include the care agents for the purposes of this application, are e.g. in particular also all-purpose cleaners or special cleaners such as preferably car care or cleaner, oven cleaner, bathroom cleaner, decalcifier, facade cleaner, window cleaner, stain remover, floor care products, floor cleaner, glass ceramic hob cleaner, (hand) dishwashing detergent, stove cleaner or care products, leather cleaners or care products, metal cleaning agents , Furniture cleaner or care products, pipe cleaner, sanitary cleaner, scouring agent, carpet cleaner or care products, toilet cleaner, toilet flush cleaner for hanging in the toilet bowl or the cistern, the aforementioned each in solid or liquid form.
  • the most preferred cleaning agents include, in particular, the machine dishwashing detergents.
  • the preferred cleaning agents include i.a. also the toilet cleaner or toilet cleaner, ie products for cleaning toilet bowls and urinals, which are preferably as powder, tablets, shaped bodies or liquids, preferably gels offered.
  • oxidizing agents and fragrances as well as other common ingredients such as preferably surfactants, they may preferably contain organic acids (e.g., citric acid and / or lactic acid) or, preferably, sodium bisulfate, amidosulfuric acid, or phosphoric acid to remove lime deposits or so-called urine stones.
  • organic acids e.g., citric acid and / or lactic acid
  • sodium bisulfate, amidosulfuric acid, or phosphoric acid to remove lime deposits or so-called urine stones.
  • these preferably give small amounts of acid, surfactant, oxidizing agent and / or fragrance and thereby slow down the preparation of soiling.
  • Typical constituents, in particular of a solid toilet cleaner, preferably powder may, for example, preferably be selected from the following: anionic surfactants, preferably 0-40 wt.%, Advantageously 0.1-30 wt.%, In particular 15-20 wt. % nonionic surfactants, preferably 0-10% by weight
  • organic acids or acid salts preferably 3-50% by weight, preferably 5-10% by weight
  • inorganic acids or acid salts preferably 3-95% by weight, in particular 25-90% by weight
  • Alkalis preferably 0-10% by weight, in particular up to 5% by weight
  • Neutral salts preferably 0-30% by weight
  • Sodium carbonate preferably 0-10% by weight
  • Cellulose preferably 0-5% by weight, in particular 1-2% by weight,
  • - complexing agent preferably 0-10 wt .-%, in particular 0.1 to 5 wt .-%
  • Dye preferably ⁇ 1% by weight
  • Perfume preferably 0.01-10% by weight
  • Oxidizing agent preferably 0.01-25 wt .-%, in particular 0.1-20 wt .-%, wherein the wt .-% - in each case based on the total average.
  • Typical constituents of a particularly liquid WC cleaner may be e.g. preferably be selected from the following: anionic surfactants, preferably 0-30 wt .-%, advantageously 0.1-20 wt .-%, in particular 1-10 wt -.% Nonionic surfactants, preferably 0-20 wt .-%, in particular 1 -10% by weight of organic acids or acid salts, preferably 0-50% by weight, advantageously 4-40
  • % By weight, in particular 3-30% by weight of inorganic acids or acid salts, preferably 0-5% by weight, in particular 0-2% by weight
  • Neutral salts preferably 0-10% by weight
  • Cellulose preferably 0-5% by weight
  • Dye preferably ⁇ 1% by weight
  • Perfume preferably 0.01-10% by weight, in particular 0.05-5% by weight
  • Thickening agents e.g. Xanthan, preferably 0-5% by weight
  • Oxidizing agent preferably 0.01-25 wt .-%, in particular 0, 1-20 wt .-%, wherein the wt .-% indication in each case based on the total mean.
  • Typical components of a rinsing cleaner (solid) for hanging in the toilet bowl or the cistern may preferably be selected from the following: Surfactants, for example APG, fatty alcohol ethoxylates, fatty alkyl sulfates, fatty alkyl ether sulfates, linear alkylbenzenesulfonates, alkanesulfonates etc., preferably in amounts of 0-40% by weight, in particular 15-30% by weight,
  • Acids or acidic salts for example formic acid, acetic acid, citric acid, amidosulfonic acid, sodium hydrogensulfate, coconut fatty acids, etc., preferably in amounts of 0-20% by weight, in particular 0.1-15% by weight,
  • Complexing agents for example sodium citrate, sodium phosphonate, preferably in amounts of 0-10% by weight, in particular 0.1-5% by weight,
  • Fillers for example sodium sulphate, preferably in amounts of 0-60% by weight, in particular 0.1-30% by weight,
  • Dye preferably ⁇ 1% by weight
  • Perfume preferably 0.01-10% by weight, in particular 0.05-5% by weight of oxidizing agent, preferably 0.01-25% by weight, in particular 0.1-20% by weight, the percent by weight indicating in each case based on the total mean
  • Winding boxes may preferably be selected from the following
  • Surfactants for example APG, fatty alcohol ethoxylates, fatty alkyl sulfates, fatty alkyl ether sulfates, linear alkylbenzenesulfonates, alkanesulfonates etc., preferably in amounts of 0-30% by weight, in particular 5-20% by weight,
  • Acids or acidic salts for example formic acid, acetic acid, citric acid, amidosulfonic acid, sodium hydrogensulfate, coconut fatty acids, etc., preferably in amounts of 0-10% by weight, in particular 0.1-5% by weight,
  • Complexing agent for example sodium citrate, sodium phosphonate, preferably in amounts of 0-10% by weight, in particular 0.1-5% by weight, water, solvent, preferably 0-99% by weight, dye, preferably ⁇ 1% by weight fragrance , preferably 0.01-10% by weight of oxidizing agent, preferably 0.01-25% by weight, in particular 0.1-20% by weight, the percentage by weight in each case being based on the total agent
  • the preferred cleaning agents include, inter alia, the pipe cleaning agents or Abflußremi- ger These are preferably strong alkaline preparations, which are usually the elimination of pipe blockages of organic materials - such as hair, fat, food residues, soaps deposits etc - serve Zur Formation of H 2 -GaS with a sparkling effect can serve as additives of AI or Zn powder.
  • Possible ingredients, in addition to oxidizing agents and fragrances, are preferably alkalis, alkaline salts and neutral salts.
  • preferably sodium nitrate and sodium chloride are also contained in pipe cleaners bath i- ger form may preferably contain hypochlorite.
  • there are also drain cleaner on Enzymbasis. Acid preparations are also possible.
  • Oxidizing agent is preferably present in amounts of 0.01 to 60 wt .-%, in particular in amounts up to 40 wt .-%, fragrances preferably in amounts of 0.01-10 wt .-%, wherein the wt .-% statement in each case based on the total mean.
  • all-purpose cleaners are universally applicable cleaners for all hard surfaces in household and commercial, which are wet or damp wipeable. As a rule, these are neutral or weakly alkaline or weakly acidic products, in particular liquid products.
  • all-purpose cleaners may contain ingredients selected from the following: surfactants [e.g. Alkanesulfonates (SAS), alkylbenzenesulfonates (LAS), alkylpolyglucosides (APG), fatty alcohol polyglycol ether sulfates (FAES), fatty alcohol polyglycol ethers (FAE, FAEO), preferably 0-25% by weight, in particular 0.1 to 20% by weight
  • surfactants e.g. Alkanesulfonates (SAS), alkylbenzenesulfonates (LAS), alkylpolyglucosides (APG), fatty alcohol polyglycol ether sulfates (FAES), fatty alcohol polyglycol ethers (FAE, FAEO),
  • Trisodium citrate, sodium nitrilotriacetic acid salt, sodium phosphonate, pentasodium triphosphate preferably 0-10% by weight, especially 0.1 to 5% by weight, of solvent and hydrotrope [e.g. Ethanol, propylene glycol ether, sodium toluene or cumene sulfonate], preferably 0-10% by weight, in particular 0.1 to 5% by weight of dyes, preferably ⁇ 1% by weight
  • Perfume preferably 0.01-10% by weight, in particular 0.05-5% by weight preservative
  • Oxidizing agent preferably 0.01-30% by weight, especially 0.1-20% by weight of acids, e.g. Acetic acid, citric acid, maleic acid, preferably 0.1-10% by weight, in particular 0.1-5% by weight in the case of weakly alkaline all-purpose cleaners, also alkalis, e.g. Sodium hydroxide solution, soda, preferably 0-5 wt .-% water, preferably 0-99 wt .-%, wherein the wt .-% - in each case based on the total mean.
  • acids e.g. Acetic acid, citric acid, maleic acid
  • alkalis e.g. Sodium hydroxide solution, soda, preferably 0-5 wt .-% water, preferably 0-99 wt .-%, wherein the wt .-% - in each case based on the total mean.
  • disinfecting all-purpose cleaners contain antimicrobial agents (e.g., alcohols, quaternary ammonium compounds, amphoteric surfactants, triclosan) or more oxidizing agents, e.g. preferably> 1% by weight, the percentage by weight being based on the total agent.
  • antimicrobial agents e.g., alcohols, quaternary ammonium compounds, amphoteric surfactants, triclosan
  • oxidizing agents e.g. preferably> 1% by weight, the percentage by weight being based on the total agent.
  • the preferred cleaning agents include, among others, the sanitary cleaners. These are products for cleaning in the bathroom and toilet.
  • the alkaline sanitary cleaners are preferably used to remove grease, while the acidic sanitary cleaners are used primarily for the removal of limescale.
  • Sanitary cleaners have advantageous wise also a significant disinfecting effect, especially the strong alkaline, chlorine-containing sanitary cleaner.
  • the components of alkaline sanitary cleaners may contain ingredients, selectable from the following: anionic surfactants, preferably 0-10 wt .-%, in particular 1-5 wt .-% of nonionic surfactants, preferably 0-5 wt .-%, in particular 1-3 wt .-% sodium hydroxide, preferably 0-10 wt .-%, in particular 1-5 wt .-% oxidizing agent, for example Sodium hypochlorite or calcium hypochlorite or hydrogen peroxide, preferably 0.01-10% by weight, in particular 1-5% by weight of perfume, preferably 0.01-10% by weight, in particular 0.05-5% by weight, of water, preferably 0-99 wt .-%, wherein the wt .-% - is in each case based on the total average.
  • anionic surfactants preferably 0-10 wt .-%, in particular 1-5 wt .-% of nonionic surfactants, preferably
  • Acid sanitary cleaners preferably contain no alkalis, but acid or acid salts, preferably in amounts of 0.01-30 wt .-%, wherein the wt .-% - refers to the total average.
  • oven cleaners are e.g. strongly alkaline with sodium hydroxide, sodium metasilicate, 2-aminoethanol.
  • they also preferably contain anionic and / or nonionic surfactants, preferably water-soluble solvents and preferably thickeners such as polycarboxylates, carboxymethylcellulose, as well as oxidizing agents and fragrances.
  • the preferred cleaning agents include, inter alia, the metal cleaning agents. These are cleaners for certain metal types such as stainless steel or silver.
  • Stainless steel cleaners preferably contain not only acids (preferably up to 3% by weight, eg citric acid, lactic acid), surfactants (in particular up to 5% by weight, preferably nonionic and / or anionic surfactants), water also solvents (preferably up to 15% by weight). %) to eliminate greasy soiling and other substances such. As thickeners and preservatives. Very fine polishing bodies are also contained in products for preferably glossy stainless steel surfaces. Silver cleaning agents, in turn, are preferably acidified.
  • complexing agents eg thiourea, sodium thiosulfate
  • Typical offer forms are cleaning cloths, dip baths, pastes, liquids.
  • copper and non-ferrous metal cleaners eg for brass and bronze
  • polishing agents and preferably also ammonium soaps and / or complexing agents are used.
  • the preferred cleaning agents include the glass cleaner or window cleaner. These are preferably used to eliminate in particular fatty greasy soil from glass surfaces. They preferably contain substances which are advantageously selectable from the following: anionic and / or nonionic surfactants (in particular up to 5% by weight),
  • Anti-fogging agent etc, wherein the wt .-% indication in each case based on the total mean.
  • cleaning agents include i.a. also all special cleaning agents, e.g. such as ceramic hobs, as well as carpet and upholstery cleaners and stain removers.
  • Products preferred according to the invention are also car care products.
  • the preferred car care products include u.a. Paint preservatives, paint polishes, paint cleaners, washing preservatives, shampoos for car wash, car wash and wax products, polishes for decorative metals, protective films for decorative metals, plastic cleaner, tar remover, window cleaner, engine cleaner etc.
  • the cleaners of the invention can be used in general for cleaning surfaces such as glass, porcelain, plastic, textiles, leather, paints or wood.
  • the institutional or commercial cleaners which are usually made available in the form of large containers, are preferably for the operational cleaning and hygiene, e.g. designed in public buildings, schools, office buildings, hotels, restaurants and hospitals, such products are preferably designed so that preferably a safe surface disinfection can be guaranteed.
  • oxidizing agent e.g. > 1 wt .-% or> 3 wt .-% or> 5 wt .-%, wherein the wt .-% indication in each case based on the total mean.
  • Technical cleaners are generally used in industry, namely in particular in the beverage, metal, food, cosmetic and pharmaceutical industries used, for example as a cleaner for car washes, Tankwagen- u. Aircraft cleaner.
  • particularly low-foaming surfactants for example special nonionic surfactants, such as ethylene oxide-propylene oxide block copolymers and so-called end-capped alkyl ethoxylates
  • particularly low-foaming surfactants for example special nonionic surfactants, such as ethylene oxide-propylene oxide block copolymers and so-called end-capped alkyl ethoxylates
  • larger amounts of oxidizing agent may be contained, for example,> 1% by weight or> 3% by weight or> 5% by weight, the weight percentage being based in each case on the total agent
  • inventively preferred cosmetic agents include in particular
  • those for skin care such as, preferably, bath preparations, skin cleansers, skin care products, ocular cosmetics, lip care products, nail care products, personal care products, foot care products
  • dentifrice and oral care such as, preferably, oral and oral care products, dentifrices, denture cleaners, denture adhesives
  • those for hair care such as, preferably, shampoos, hair care preparations, hair hardening agents, hair treatment agents, hair lotions, hair styling agents, hair dyes, bleaching agents
  • Preferred ingredients of the consumer products according to the invention in particular of the cosmetic agents, can be defined by their function. Of course, some ingredients may also be multifunctional
  • Preferred ingredients of the consumer products of the invention may be selected from the following: a) Absorbents
  • Antioxidants preferably present in a separate form from the oxidizing agent
  • Combability aids in hair care products They generally reduce the electrostatic charge on objects, such as the hair surface. Hair can be combed much easier, h) binders
  • surface-active substances which are preferably capable of stably dispersing immiscible liquids such as oil and water, o) emulsion stabilizers
  • moisturizers are used for preferably selective removal of body hair, q) moisturizers
  • oral care substances may, for example, be the basis for, for example, liquid cosmetic preparations or else be part of solid products w) oral care substances
  • Reducing agent preferably present in a separate form from the oxidizing agent
  • UV absorber / light filter substances are able to filter certain UV rays and can thus protect the skin, for example, from premature light-induced aging as well as from sunburn.
  • denaturant ee)
  • ingredients can be contained according to a preferred embodiment in the products according to the invention, preferably cosmetic agents.
  • emulsions such as W / O, O / W, PIT emulsions (emulsions according to US Pat Phase inversion theory called PIT), microemulsions and multiple emulsions, coarse, unstable, single or multi-phase shaking mixtures, gels, sprays, pouches, aerosols and foam aerosols.
  • the products according to the invention are advantageously able, in particular in comparison with oxidant-free compositions, improved performances, in particular cleaning performances, e.g. with regard to the removal of stains, in particular colored stains. Furthermore, they are advantageously able to achieve more effective hygiene performance in the material to be treated (eg textiles, dishes, hard surfaces, etc.), in particular in comparison with oxidant-free compositions, by improving the destruction of bacteria and other microorganisms, in particular with regard to one significant reduction in germ count. Furthermore, the fragrance composition according to the invention contributes to a pleasant odor of the entire composition, in particular washing or cleaning agent or cosmetic and thus increases its acceptance by the consumer.
  • Another advantage of the invention is that such a product is stable on storage, in particular as regards the stability of the oxidizing agent as well as the perfuming of the product.
  • the scent impression of the perfumed composition according to the invention advantageously does not change even during prolonged storage over several weeks.
  • the activity of the oxidizing agent advantageously does not diminish significantly more than in the absence of perfuming even after prolonged storage for several weeks. Both advantageously also apply to liquid funds.
  • the perfume composition contained in the agent according to the invention contains at least 91% by weight, preferably at least 92% by weight, advantageously at least 94% by weight, more preferably at least 96% by weight, even more preferably at least 98% by weight, more preferably at least 99% by weight, in particular even 100% by weight of such fragrances, which at least one of saturated alcohols, preferably primary, secondary, and / or tertiary saturated, optionally branched or optionally cyclic alcohols, saturated esters, optionally branched or cyclic saturated esters saturated ethers, optionally branched or cyclic saturated ether - aromatics with saturated substituents, if necessary with branched, saturated substituents
  • Nitriles optionally unsaturated in conjugation with the nitrile group, saturated acetals, optionally branched or cyclic saturated acetals, saturated hemiacetals, the percentages by weight being based on the total amount of fragrance
  • the perfume composition contained in the agent according to the invention contains at least 50% by weight, at least 60% by weight, at least 70% by weight, at least 80% by weight, at least 90% by weight or at least 91% by weight, preferably at least 92% by weight, advantageously at least 94% by weight, more preferably at least 96% by weight, even more preferably at least 98% by weight, more preferably at least 99% by weight, in particular even 100% by weight of fragrances, selected from citronitrile, ortho-tert-butylcyclohexyl acetate, cyclohexylsahcylate, (+) - (1 l R, 3S, 6S) -1- (2 l , 2 l , 6'-tri-methyl-1'-cyclohexyl) -3- hexanol, (-) - (1 1 S 1 SR 1 R) -I - (2 ⁇ 2 ⁇ 6'-tri-methyl-r-cyclohexyl) -3-hexanol, (-
  • allyl (cyclohexyloxy) acetate 2,4-dimethylethyl 1, 3-d ⁇ oxolan-2-ethyl acetate, 3,12-Tr ⁇ decad ⁇ en-n ⁇ t ⁇ l, amyl acetate, isoamyl acetate, ethyl phenylacetate, 2-Propenylphenoxyacetat, Isobornylacetat, Dimethylbenzylcarbinylacetat, hexyl acetate, cresyl acetate (para), Isobutylphenyl- acetate, Butylcyclohexylacetat- cis-para-tert , Butylcyclohexylacetate trans-para-tert, hydroxymethyl alcohol, 2,6-dimethylheptan-2-ol, decanol, octanol, 2,6-dimethylcyclo [4 4 0] decan-1-ol (0
  • fragrances can be used in particular in liquid agents with great success in the context of the invention
  • Corresponding fragrance compositions even with highly reactive oxidizing agents such as peroxycarboxylic acids, which may advantageously be selected from mono- and diperoxycarboxylic acids, in particular dodecanediperoxyacid or preferably imidoperoxycarboxylic acids, more preferably 6-phthalimidoperoxycaproic acid (6-phthalimidoperoxyhexanoic acid, PAP), provide exceptional stability results, in particular Look at PAP.
  • the potency of the oxidizing agent remains very well preserved even after prolonged storage, advantageously also in liquid agents.
  • the fragrance of the fragrance composition remains very well preserved even after prolonged storage, advantageously also in liquid agents.
  • the product contains certain minimum values of fragrances, namely at least 0.01% by weight or 0.05% by weight, advantageously at least 0.1% by weight, in a considerably advantageous manner at least 0.15% by weight. -%, more preferably at least 0.2 wt .-%, in a further advantageous manner at least 0.25 wt .-%, more preferably at least 0.3 wt .-%, in a very advantageous manner at least 0.35 Wt .-%, in a particularly advantageous manner at least 0.4 wt .-%, in a particularly advantageous manner at least 0.45 wt .-%, in a significantly advantageous manner at least 0.5 wt .-%, in a very significantly advantageous manner at least 0.55 wt .-%, in an extremely advantageous manner at least 0.6 wt .-%, most advantageously at least 0.65 wt .-%, in an extremely advantageous manner at least 0.7 wt .-%, in exceptionally advantageous manner at least 0.75
  • the product contains larger amounts of fragrances, namely at least 1 wt .-%, advantageously at least 2 wt .-%, in a considerably advantageous manner at least 5 wt .-%, more preferably at least 10 wt .-%, in a further advantageous manner at least 13 wt .-%, more preferably at least 14 wt .-%, in a very advantageous manner at least 15 wt .-%, in a particularly advantageous manner at least 16 wt .-%, in a particularly advantageous manner at least 17% by weight, in a significantly advantageous manner at least 18% by weight, in a very advantageous manner at least 19% by weight, in particular at least 20% by weight, of perfumes, based on the total product.
  • fragrances namely at least 1 wt .-%, advantageously at least 2 wt .-%, in a considerably advantageous manner at least 5 wt .-%, more preferably at least 10 wt .-%, in a further
  • the product therefore contains certain maximum values of perfume oil, namely, for example, not more than 30% by weight, 25% by weight, 20% by weight or 15% by weight, advantageously not more than 10% by weight.
  • fragrances within the meaning of the invention are in accordance with the usual definition, i. they are usually substances that are perceptible by their smell, especially pleasant smell. These preferably also include the flavorings.
  • the fragrances used today are above all essential oils, flower oils, extracts from plant and animal drugs, from natural products, isolated components (isolates) as well as semi-synthetic and fully synthetic uniform fragrances.
  • any conceivable oxidizing agent may be used, e.g. Perborates, percarbonates, hydrogen peroxide, sodium hypochlorite, dichromate, dithionite, permanganate, chlorine, concentrated sulfuric acid, organic peracids, chlorine, hypochlorite, chlorine dioxide, peroxides, etc.
  • oxidizing agent any conceivable oxidizing agent may be used, e.g. Perborates, percarbonates, hydrogen peroxide, sodium hypochlorite, dichromate, dithionite, permanganate, chlorine, concentrated sulfuric acid, organic peracids, chlorine, hypochlorite, chlorine dioxide, peroxides, etc.
  • a number of advantageously usable bleaching agents are mentioned below.
  • the oxidizing agents preferably bleaching agents, may preferably be coated.
  • the coating can serve to reduce the interaction with other ingredients, but this is not completely successful.
  • the oxidizing agent is an oxidative bleaching agent, preferably based on oxygen, with particular preference being given to peroxycarboxylic acids.
  • the agent according to the invention contains a peroxycarboxylic acid, which is advantageously selected from mono- and diperoxycarboxylic acids, in particular dodecanediperoxyacid or preferably imidoperoxycarboxylic acids, more preferably 6-phthalimidoperoxycaproic acid (6-phthalimidoperoxyhexanoic acid, PAP) and / or wherein the Peroxycarboxylic acid at atmospheric pressure has a melting point above 25 ° C, in particular above 35 ° C, preferably above 45 0 C, preferably above 50 ° C, more preferably above 100 0 C.
  • a peroxycarboxylic acid which is advantageously selected from mono- and diperoxycarboxylic acids, in particular dodecanediperoxyacid or preferably imidoperoxycarboxylic acids, more preferably 6-phthalimidoperoxycaproic acid (6-phthalimidoperoxyhexanoic acid, PAP) and / or wherein the Peroxycarboxylic acid at
  • the oxidizing agent in particular the peroxycarboxylic acid, is present in granular form, preferably coated, the mass of the coating advantageously being from 0.1 to 30% by weight, based on the total of the particles containing the oxidizing agent, preferably Granules.
  • "Essentially” means here that, preferably in the case of a freshly prepared product, advantageously at least 50, 55, 60, 65, 70, 75% by weight of the oxidizing agent are present in granular form, the statement wt% here referring to the total amount of oxidizing agent Means, in particular after a storage period, also present a proportion of the oxidizing agent in dissolved form
  • the agent according to the invention contains at least 0.01% by weight of surfactants
  • the surfactant content of the entire composition z B is 0.1-60% by weight, preferably 1-50% by weight, advantageously 5-45% by weight, more preferably 10-40% by weight, in particular 15-30% by weight
  • the lower limit of the surfactant content may also be at a value of preferably 1% by weight, 2% by weight, 3% by weight, 4% by weight, 5% by weight, 6 % By weight, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, % By weight, 17% by weight, 18% by weight, 19% by weight, 20% by weight, 21% by weight, 22% by weight, 23% by weight, 24% by weight, 25% by weight, 26 % By weight, 27% by weight, 28% by weight, 29% by weight or 30% by weight, based on the total agent
  • the lower limit of surfactant may in particular even be even higher values, for example at a value of preferably 35% by weight, 40% by weight, 45% by weight,
  • the upper limit of surfactant can also be used, for example, at a value of preferably 65% by weight, 60% by weight, 55% by weight, 50% by weight, 45% by weight, 40% by weight, 35% by weight, 30% by weight. % or 25% by weight or even only at values such as 20% by weight, 19% by weight, 18% by weight, 17% by weight, 16% by weight, 15% by weight, 14% by weight, 13% by weight %, 12% by weight, 11% by weight or 10% by weight It is, for example, also possible to suitably combine the stated lower limit and upper limits from the abovementioned data, for example to represent a surfactant content of 4-18% by weight It is also possible that 0% by weight of surfactant is included
  • anionic surfactants such as, for example, (linear) alkylbenzenesulfonates, fatty alcohol sulfates or alkanesulfonates etc., preferably in amounts of from 0.1 to 30% by weight, and / or nonionic surfactants, for example alkylpolyglycol ethers, alkylpolygluco - side or amine oxides, etc., preferably in amounts of, for example, from 0.1 to 30% by weight, in each case based on the total agent
  • the agent according to the invention may also contain cationic surfactants, for example in amounts of 0.01% by weight or 0.05% by weight to 30% by weight.
  • the agent according to the invention is cationic surfactant-free, which means the agent is less than 10% by weight, preferably less than 5% by weight, advantageously less than 3% by weight, more preferably less than 1% by weight, even more preferably less than 0.5% by weight, in particular 0% by weight of cationic surfactant
  • the agent according to the invention contains electrolytes, in particular inorganic and / or organic salts, in particular phosphate, citrate and / or sulfate, more preferably sodium sulfate, preferably in amounts of at least 0.1% by weight, advantageously at least 3% by weight. %, in particular in amounts of 5 to 30 wt .-%, each based on the total agent. It is also possible that 0 wt .-% electrolyte is included
  • the agent of the invention contains complexing agents, e.g. Nitrilotriacetic acid, ethylenediaminetetraacetic acid or phosphonate etc., preferably in amounts of up to 30% by weight or up to 20% by weight, in particular 0 to 10% by weight, advantageously from 0.1 to 5% by weight , based on the total agent, so is a further preferred embodiment of the invention. Particularly advantageous are complexing agents, e.g. Nitrilotriacetic acid, ethylenediaminetetraacetic acid or phosphonate etc., preferably in amounts of up to 30% by weight or up to 20% by weight, in particular 0 to 10% by weight, advantageously from 0.1 to 5% by weight , based on the total agent, so is a further preferred embodiment of the invention. Particularly advantageous are complexing agents, e.g. Nitrilotriacetic acid, ethylenediaminetetraacetic acid or phosphonate etc., preferably in amounts of up to 30% by weight or up to 20% by weight,
  • nitrogen-free chelating agents such as e.g. preferably alkali metal polyphosphonates, mono- or polyphosphonic acids, in particular 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP), citrate and / or short-chain dicarboxylic acids.
  • nitrogen-free chelating agents such as e.g. preferably alkali metal polyphosphonates, mono- or polyphosphonic acids, in particular 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP), citrate and / or short-chain dicarboxylic acids.
  • 1-hydroxyethylidene-1, 1-diphosphonic acid is most preferred. It is also possible that 0 wt .-% complexing agent is included.
  • complexing agents can be used according to the invention to preferably inactivate or bind heavy metal ions, which in particular can act as catalysts of oxidation processes and thus lead to degradation of oxidizing agent, e.g. Peroxycarboxylic acids, such as PAP, and which, for example, via water pipes or metallic components of the production plants or via raw materials or ingredients in the agent according to the invention, e.g. Detergents or cleaners, can be registered.
  • oxidizing agent e.g. Peroxycarboxylic acids, such as PAP
  • the agent according to the invention also contains enzymes, in particular e.g. Proteases, amylases, catalases, peroxidases, cellulases and / or lipases, and / or enzyme stabilizers, preferably in amounts of from 0 to 10% by weight, based in each case on the total agent. It is also possible that 0 wt .-% enzyme is included.
  • enzymes in particular e.g. Proteases, amylases, catalases, peroxidases, cellulases and / or lipases, and / or enzyme stabilizers, preferably in amounts of from 0 to 10% by weight, based in each case on the total agent. It is also possible that 0 wt .-% enzyme is included.
  • the agent according to the invention contains builders (builders).
  • the builder content of the agent is, for example, 0-99% by weight, preferably 1-60% by weight, advantageously 2-50% by weight. even more advantageously 3-60% by weight, more preferably 5-50% by weight, in particular 6-40% by weight.
  • the lower limit of the builder content but also at a value of preferably 7 wt .-%, 8 wt .-%, 9 wt .-%, 10 wt .-%, 11 wt .-%, 12 wt.
  • the lower limit may in particular even be at even higher values, for example at a value of preferably 35% by weight, 40% by weight, 45% by weight, 50% by weight, 55% by weight or 60% by weight. -%.
  • the upper limit of the builder content may also be at a value of preferably 70% by weight, 71% by weight, 72% by weight, 73% by weight, 74% by weight, 75% by weight. %, 76 wt%, 77 wt%, 78 wt%, 79 wt%, 80 wt%, 81 wt%, 82 wt%, 83 wt%, 84 wt.%, 85 wt.%, 86 wt.%, 87 wt.%, 88 wt.%, 89 wt.%, 90 wt.%, 91 wt.%, 92 wt .-%, 93 wt .-%, 94 wt .-% or 95 wt .-% are.
  • the upper limit can also be at lower values, e.g. at a value of preferably 65 wt .-%, 45 wt .-%, 35 wt .-%, 30 wt .-%, 25 wt .-%, 20 wt .-%, 15 wt .-%, 10 wt. -% or 5 wt .-%. It may also be possible within the meaning of another embodiment that no builder, ie 0% by weight, is contained.
  • preferably also very little builder may be present, e.g. more than 0.1 wt .-%, more than 0.5 wt .-% or more than 1 wt .-%, but advantageously less than 30 wt .-%, preferably less than 20 wt .-%, in particular less than 10 wt .-%.
  • the inventive composition contains as builder in particular fatty acids, preferably saturated and / or branched fatty acids, especially having a melting point below 4O 0 C 1 is preferably less than 30 0 C, and / or citric nen yarn and / or citrate, preferably in amounts of, for example, from 0 to 15% by weight, and / or polyacrylates, preferably in amounts of, for example, from 0 to 15% by weight, and / or phosphonates, where the term% by weight refers in each case to the total Means relates.
  • fatty acids preferably saturated and / or branched fatty acids, especially having a melting point below 4O 0 C 1 is preferably less than 30 0 C
  • / or citric nen yarn and / or citrate preferably in amounts of, for example, from 0 to 15% by weight
  • polyacrylates preferably in amounts of, for example, from 0 to 15% by weight
  • / or phosphonates where the term% by weight refers in each case to the
  • the agent according to the invention has at least substantially no halide ions, in particular no chloride ions, the amount of halide ions, in particular chloride ions, advantageously being at most 500 ppm, preferably at most 100 ppm, in particular at most 30 ppm, then a preferred embodiment is present. Because the Applicant has surprisingly found that a high halide, in particular chloride ion concentration, as may be common in conventional detergents and cleaners due to contamination of some raw materials or ingredients, especially in liquid agents to increased degradation of oxidizing agents, such as For example, peroxycarboxylic acids can lead.
  • a reduction of the halide concentration, in particular the chloride ion concentration lead to a reduced degradation of the oxidizing agent, for example the peroxycarboxylic acid.
  • a low chloride ion concentration can be achieved according to the invention, for example, by the use of methylsulfate, phosphate, tosylate or cumene sulfonate compounds or by the use of low-chloride raw materials or ingredients (eg use of essentially halide-free components, eg halide-free surfactants, halide-free phosphates). phonates etc.).
  • the agent is in liquid form, preferably in aqueous or nonaqueous form, which is advantageously a dispersion, preferably an emulsion or suspension, then a preferred embodiment is present.
  • the agent may also be present as a pouch.
  • the invention can be e.g. liquid heavy-duty detergents with outstanding washing performance, especially in the area of bleachable stains in connection with a very appealing perfuming both in the product and on the laundry realize.
  • the fragrance impression in the product is subject to no change even during prolonged storage and the perfuming does not show a destabilizing effect on the bleaching agent.
  • the agent which is present in particular in liquid form, according to a further preferred embodiment has a pH of advantageously at most 7, in particular a pH of 3.5 to 7, preferably from 4.0 to 6.5, particularly preferably from From 4.5 to 6, very particularly preferably from about 5 to, and / or, if it is a liquid agent, it may preferably be at least one water-miscible solvent having a low dissolving power, preferably glycerol, for the peroxycarboxylic acid, in particular imidoperoxycarboxylic acid. contain.
  • Bleaching agents in particular those based on peroxycarboxylic acids, such as PAP, can be stabilized relatively effectively in an acid environment, in particular at a pH of around 6.
  • liquid agents in particular liquid detergents and cleaners can be carried out for example by adding acids or acidic salts
  • acids or acidic salts According to the invention are preferred bisulfates, bicarbonates and organic polycarboxylic acids, for example It is also possible to use the phosphonates or citrates which can be used as complexing agents as phosphonic acids or citric acid and then to adjust the desired pH by adding alkalis.
  • ionic surfactant for example LAS, is also possible as acid , wherein the pH can be adjusted by subsequent addition of sodium hydroxide solution
  • the agents of the invention can, in a preferred embodiment contain at least one fatty acid this case are saturated and / or branched fatty acids, especially having a melting point below 3O 0 C, preferable in the invention
  • Isocarb- 16 ® Sasol be used in the inventive washing or cleaning agents
  • the agents according to the invention may advantageously have a citric acid or citrate content.
  • Citric acid or citrate may, for example, lead to a degradation of peroxycarboxylic acids, especially PAP.
  • citric acid or citrates it may be advantageous to use citric acid or citrates in the agent according to the invention, for example the detergent or cleaning agent (for example as builder and / or as complexing agent)
  • composition according to the invention may also be of gel-like or paste-like consistency.
  • the agent is pourable, preferably it has a viscosity between 100 and 10000 mPas at a shear rate of 30 s -1 and a temperature of 25 ° C.
  • the agent is present in solid form, preferably as a powder
  • the powder is predominantly (for example, in amounts of> 50% by weight,> 60% by weight,> 70% by weight,> 80% by weight,> 90% by weight or> 95% by weight). based on the total powder) of uniform, preferably almost spherical or elliptical particles formed.
  • the ellipsoid is similar to the ball, but longitudinal axis and transverse Axes are different.
  • the powder can also consist of other embodiments of particles, the majority as well
  • lamellar plaque and the like or at least approximately lamellar
  • (f) are strand-like or at least approximately strand-like.
  • the lower limit for the bulk density can also be set at a value of preferably 250, 300,
  • the lower limit is even higher, e.g. at 800g / L.
  • the upper limit for the bulk density may be at a value of preferably 1450, 1400, 1350,
  • the upper limit is even lower, e.g. at a value of preferably 700, 650, 600, 550 or 500 g / L.
  • the solid agent is a compactate, available e.g. by operations such as pressing, rolling, briquetting, pelletizing, extruding, agglomerating or related compaction processes, this is a further preferred embodiment.
  • the agent in solid form is a shaped body, preferably a tablet or a block or a strand.
  • a shaped body preferably a tablet or a block or a strand.
  • multiphase or multilayer shaped bodies may be preferred.
  • solid pouches e.g. Powder in the pouch.
  • the content of inorganic salt, particularly preferably sodium sulfate, in the dispersion (of the liquid agent) can be selected such that at a temperature which is around 5 ° C. , in particular to 1O 0 C, preferably around 15 ° C, is less than the warehouse or storage temperature (about 2O 0 C) of the dispersion, substantially there is a dispersion in which the aqueous phase is saturated with the inorganic salt.
  • the content of organic salt, particularly preferably sodium sulfate are chosen such that at about O 0 C to 15 0 C, in particular O 0 C to 10 0 C, preferably 0 0 C to 5 0 C, essentially one with the inorganic salt saturated dispersion is obtained.
  • the content of inorganic salt, particularly preferably sodium sulfate, in the dispersion 5 to 30 wt .-%, in particular 10 to 30 wt .-%, preferably 15 to 30 wt .-%, based on the total formulation.
  • the content of inorganic salt, more preferably sodium sulfate, in the agent according to the invention, preferably liquid agent, in particular liquid detergent or cleaning agent be chosen such that the surfactants are at least substantially inactivated in the agent, in particular by salting out, ie Inducing a phase separation in a low-surfactant, continuous phase and a preferably lamellar, generally highly viscous, crystalline or liquid-crystalline surfactant-rich phase, preferably by introducing at least one sulfate compound, particularly preferably sodium sulfate.
  • the formulation preferably washing or cleaning agent formulation, in particular dissolution of the organic peroxycarboxylic acid is at least substantially prevented or at least reduced.
  • the term "continuous phase” is understood to mean the dispersant with the constituents or ingredients dissolved therein (for example salts, surfactants, etc.).
  • the dispersant is preferably water.
  • the surfactants which may possibly lead to a deactivation of the oxidizing agent, are at least partially inactivated, which can be done in particular by salting out, the surfactants from the particular micellar, active form can be converted into a preferably lamellar, crystalline or liquid-crystalline form (crystal or liquid crystal formation), which is dispersed in a nearly surfactant-free continuous phase.
  • the dispersed liquid crystal itself which can be separated, for example, by centrifugation, should be as highly viscous as possible.
  • the content of free or active surfactants, ie present in micellar form in the liquid agents, preferably liquid detergents and cleaners formulations or in the continuous phase of the liquid detergent formulations according to the invention may therefore according to a preferred embodiment preferably be very low, advantageously not more than 1%.
  • the concentration of an inorganic salt, particularly preferably sodium sulfate, in the agent according to the invention, preferably liquid agent, in particular liquid detergent or cleaning agent should be chosen so that in the continuous phase of the undiluted washing or cleaning agent advantageously less than 1% dissolved surfactant is present and when the temperature is lowered, especially at temperature drops to 0 0 C, no crystallization of the salt, preferably sulfate, takes place.
  • the agents according to the invention may preferably have a correspondingly adapted or optimized surfactant ratio.
  • the content of alkyl polyglycol ethers may preferably be as low as possible. In a preferred embodiment, the content of nonionic surfactants even approaches zero.
  • Corresponding formulations may be used as surfactants, e.g. contain only (linear) alkylbenzenesulfonates and / or (secondary) alkanesulfonates and can show excellent stability of the bleaching agent.
  • the product according to the invention in particular washing, care or cleaning agent, at least one, preferably more, active components, in particular washing, care and / or cleaning active components, advantageously selected from the group comprising anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, acidifiers, alkalizing agents, anti-wrinkle compounds, antibacterial agents, antioxidants, anti redeposition agents, antistatics, builders, bleaches, bleach activators, bleach stabilizers, bleach catalysts, ironing aids, cobuilders, anti-shrinkage agents, electrolytes, Enzymes, colorants, colorants, dyes, color transfer inhibitors, fluorescers, fungicides, germicides, odor-complexing substances, adjuvants, hydrotropes, rinse aids, complexing agents, preservatives, corrosion inhibitors, optical brighteners , Perfume carriers, pearlescers, pH adjusters, repellents and impregnating agents, poly
  • Skin-care active substances are all those active substances which give the skin a sensory and / or cosmetic advantage.
  • Skin-care active substances are preferably selected from the following substances: a) waxes such as, for example, carnauba, spermaceti, beeswax, lanolin and / or derivatives thereof and others.
  • Hydrophobic plant extracts c) Hydrocarbons such as squalene and / or squalane d) Higher fatty acids, preferably those having at least 12 carbon atoms, for example lauric acid, stearic acid, behenic acid, myristic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid, isostearic acid and / or multiple times unsaturated fatty acids and others.
  • esters preferably such as Cetyloctanoat, lauryl lactate, My ⁇ styllactat, Cetyllactat, Isopropylmynstat , My ⁇ styl myristate, isopropyl palmitate, isopropyl adipate, butyl stearate, decyl oleate, cholesterol isoleostearate, glycerol monostearate, glyceryl distearate, glycerol stearate, alkyl lactate, alkyl citrate and / or alkyl tartrate and other g) lipids such as cholesterol, ceramides and / or sucrose esters and other h) vitamins such as for example,
  • Anionic surfactants are preferably present in the products according to the invention.
  • Suitable anionic surfactants are, for example, those of the sulfonate and sulfates type.
  • the surfactants of the sulfonate type are preferably C 9 .
  • Suitable anionic surfactants are sulfonated fatty acid glycine esters.
  • Fatty acid glycylesters are understood as meaning the mono-, di- and diesters and mixtures thereof, as in the preparation by esterification of a monoglycerine with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 mol of glycene are obtained.
  • Preferred sulfated fatty acid glycine esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capnic acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid
  • Alk (en) ylsulfates are the alkali metal salts and in particular the sodium salts of the sulfuric monoesters of C 12 -C 18 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myriphenyl, cetyl or stearyl alcohol or the C 10 -C 20 Oxyalcohols and those half-esters of secondary alcohols of these chain lengths are also preferred.
  • Alk (en) ylsulfates of said chain length which contain a synthetic, petrochemical-based straight-chain alkyl radical which has an analogous degradation behavior as the adequate compounds based on oleochemicals Raw Materials Of washing technology interest, the C 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates and C 4 -C 1 s alkyl sulfates are preferred. Also 2,3-alkyl sulfates, as commercial products of the Shell Oil Company under the name DAN ® can be obtained, are suitable anionic surfactants
  • 21 -alcohols such as 2-methyl-branched C 9 11 alcohols having an average of 3.5 moles of ethylene oxide (EO) or C 12 .
  • 18- fatty alcohols with 1 to 4 EO are suitable They are particularly in detergents due to their high foaming behavior preferably only in relatively small amounts, for example in amounts of 1 to 5 wt -%, used
  • Suitable anionic surfactants are, for example, the partial esters of di- or polyhydroxyalkanes, mono- and disaccharides, polyethylene glycols with the ene adducts of maleic anhydride and at least monounsaturated carboxylic acids having a chain length of from 10 to 25 carbon atoms with an acid number of from 10 to 140
  • Preferred anionic surfactants have, in addition to an unbranched or branched, saturated or unsaturated, aliphatic or aromatic, acyclic or cyan, optionally alkoxylated alkyl radical having 4 to 28, preferably 6 to 20, especially 8 to 18, particularly preferably 10 to 16, extremely preferred 12 to 14 carbon atoms, two or more anionic, especially two, acid groups, preferably carboxylate, sulfonate and / or sulfate groups, in particular a carboxylate and a sulfate group, examples of these compounds are the ⁇ -sulfo fatty acid salts, the acylglutamates, the Monoglycene disulfates and the alkyl ethers of Glycenndisul- fats and in particular the below-described monoester sulfosuccinates
  • Particularly preferred anionic surfactants are the sulfosuccinates, sulfosuccinamates and sulfosuccinamides
  • the sulfosuccinates are the salts of the mono- and di-esters of sulfosuccinic acid HOOCCH (SO 3 H) CH 2 COOH, while the sulfosuccinamates include the salts of the monoamides of sulfosuccinic acid and the sulfosuccinamides the salts of the diamides of Sulfosuccinic acid understands.
  • the salts are preferably alkali metal salts, ammonium salts and mono-, di- or trialkanolammonium salts, for example mono-, di- or triethanolammonium salts, in particular lithium, sodium, potassium or ammonium salts, particularly preferably sodium or ammonium salts , most preferably sodium salts.
  • one or both carboxyl groups of the sulfosuccinic acid is preferably with one or two identical or different unbranched or branched, saturated or unsaturated, acyclic or cyclic, optionally alkoxylated alcohols having 4 to 22, preferably 6 to 20, in particular 8 to 18 , more preferably 10 to 16, most preferably 12 to 14 carbon atoms esterified.
  • esters of unbranched and / or saturated and / or acyclic and / or alkoxylated alcohols in particular unbranched, saturated fatty alcohols and / or unbranched, saturated, with ethylene and / or propylene oxide, preferably ethylene oxide, alkoxylated fatty alcohols having a degree of alkoxylation of 1 to 20, preferably 1 to 15, in particular 1 to 10, more preferably 1 to 6, most preferably 1 to 4.
  • the monoesters are preferred in the context of the present invention over the diesters.
  • a particularly preferred sulfosuccinate is Sulfobernsteinklarylpolyglykolester-di-Na- trium salt (lauryl EO sulfosuccinate, di-sodium salt; INCI Disodium Laureth Sulfosuccinate), for example, as Tego ® sulfosuccinate F 30 (Goldschmidt) with a sulfosuccinate of 30 weight .-% is commercially available.
  • one or both carboxyl groups of the sulfosuccinic acid forms preferably with a primary or secondary amine having one or two identical or different, unbranched or branched, saturated or unsaturated, acyclic or cyclic, optionally alkoxylated alkyl radicals with 4 to 22, preferably 6 to 20, in particular 8 to 18, more preferably 10 to 16, most preferably 12 to 14 carbon atoms carries, a carboxylic acid amide.
  • Particular preference is given to unbranched and / or saturated and / or acyclic alkyl radicals, in particular unbranched, saturated fatty alkyl radicals.
  • sulfosuccinates and sulfosuccinamates designated according to INCI, which are described in more detail in the International Cosmetic Ingredient Dictionary and Handbook: Ammonium Dinonyl Sulfosuccinates, Ammonium Lauryl Sulfosuccinates, Diammo- Dimethicone Copolyol Sulfosuccinate, Diammonium Lauramido-MEA Sulfosuccinate, Diamonium Lauryl Sulfosuccinate, Diammonium Oleamido PEG-2 Sulfosuccinate, Diamyl Sodium Sulfosuccinate, Dicapryl Sodium Sulfosuccinate, Dicyclohexyl Sodium Sulfosuccinate, Diheptyl Sodium Sulfosuccinate, Dihexyl Sodium Sulfosuccinate, Diisobutyl Sodium Sulfosuccinate, Dioctyl Sodium Sulfos
  • anionic surfactants in the composition according to the invention can vary within wide ranges, depending on the purpose of the agent in question.
  • an agent according to the invention may contain very large amounts of anionic surfactant, preferably up to an order of magnitude of up to 40, 50 or 60% by weight or more.
  • an agent according to the invention may contain only very small amounts of anionic surfactant, for example less than 15 or 10% by weight or less than 5% by weight or even less.
  • anionic surfactants may advantageously be present in the compositions according to the invention in amounts of from 2 to 35% by weight and in particular from 5 to 30% by weight, with concentrations above 10% by weight and even above 15% by weight may find particular preference.
  • the product according to the invention contains anionic surfactants, preferably in amounts of at least 0.1% by weight.
  • soaps may be present in the compositions according to the invention.
  • Particularly suitable are saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular of natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.
  • the content of the soap soaps, independently of other anionic surfactants, is preferably not more than 3% by weight, and more preferably 0.5 to 2.5% by weight.
  • the anionic surfactants and soaps may be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine. Preferably, they are in the form of their sodium or potassium salts, especially in the form of the sodium salts.
  • Anionic surfactants and soaps may also be prepared in situ by incorporating into the spray-dried composition the anionic surfactant acids and optionally fatty acids which are then neutralized by the alkali carriers in the spray-dried composition.
  • nonionic surfactants may also be included in the compositions of the invention, both in solid and in liquid compositions.
  • their content may be up to 2 or 3 or 5 wt .-%.
  • It may also contain greater amounts of nonionic surfactant, for example, up to 5 wt% or 10 wt% or 15 wt% or 20 wt% or 30 wt% or even more if it is is appropriate.
  • Useful lower limits may be at values of 1, 2, 3 or 4 wt .-%.
  • the nonionic surfactants are in relatively large amounts, ie up to 50% by weight, advantageously from 0.1 to 40% by weight, particularly preferably from 0.5 to 30 and in particular from 2 to 25% by weight, in each case based on the total agent included.
  • the product according to the invention contains nonionic surfactants, preferably in amounts of at least 0.1% by weight.
  • nonionic surfactants are presented below.
  • the agents according to the invention can preferably also contain cationic surfactants.
  • Suitable cationic surfactants are, for example, surface-active quaternary compounds, in particular having an ammonium, sulfonium, phosphonium, iodonium or arsonium group.
  • Particularly preferred cationic surfactants are the quaternary, partially antimicrobial ammonium compounds (QAV, INCI quaternary ammonium compounds) according to the general formula (R ') (R ") (R"') (R IV ) N + X " , in which R 1 to R ⁇ v identical or different dz ⁇ - alkyl radicals 1 C 7-28 - aralkyl radicals or heterocyclic radicals, wherein two or in the case of an aromatic inclusion as in pyridine even three radicals together with the nitrogen atom, the heterocycle, for example a pyridinium or Imidazoliniumtress , form, represent and X "are halide ions, sulfate ions, hydroxide ions or similar anions.
  • at least one of the radicals has a chain length of 8 to 18, in particular 12 to 16, carbon atoms.
  • QACs are prepared by reacting tertiary amines with alkylating agents, e.g. Methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethylene oxide produced.
  • alkylating agents e.g. Methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethylene oxide produced.
  • alkylating agents e.g. Methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethylene oxide produced.
  • alkylating agents e.g. Methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethylene oxide produced.
  • alkylating agents e.g. Methyl chloride, benzyl chloride, dimethyl sulfate, dodecy
  • Suitable QACs are, for example, benzalkonium chloride (N-alkyl-N, N-dimethylbenzylammonium chloride, CAS No. 8001-54-5), benzalkone B (mp-dichlorobenzyl-dimethyl-C 1-4 -alkylammonium chloride, CAS No. 58390-78 -6), benzoxonium chloride (benzyldodecyl-bis- (2-hydroxyethyl) -ammonium chloride), cetrimonium bromide (N-hexadecyl-N, N-trimethyl-ammonium bromide, CAS No.
  • benzotrium chloride N, N-dimethyl-N- [2- [2- [p- (1,1,3,3-tetramethylbutyl) phenoxy] ethoxy] ethyl] benzylammonium chloride, CAS No. 121-54-0
  • Dialkyldimethylammonium chlorides such as di-n-decyldimethylammonium chloride (CAS No. 7173-51-5-5), didecyldimethylammonium bromide (CAS No. 2390-68-3), dioctyldimethylammoniumchloric, 1-cetylpyridinium chloride (CAS No 123-03-5) and thiazoline iodide (CAS No.
  • QACs are the benzalkonium chlorides having C 8 -C 18 -alkyl radicals, in particular C 1 -C -acyl-benzyl-dimethylammonium chloride.
  • a particularly preferred QAC Kokospentaethoxymethylammoniummethosulfat (INCI PEG-5 Cocomonium Methosulfate; Rewoquat CPEM ®).
  • anionic surfactants In order to avoid possible incompatibilities of the antimicrobial cationic surfactants with anionic surfactants optionally present in the composition according to the invention, as far as possible anionic surfactant-compatible and / or optionally cationic surfactant are used or, in a particular embodiment of the invention, cationic surfactants are completely dispensed with
  • compositions according to the invention are described. These too may preferably be present in the compositions according to the invention.
  • compositions according to the invention may contain one or more cationic surfactants, advantageously in amounts, based on the total composition, of from 0 to 30% by weight, more preferably from 0 to 20% by weight, preferably 0.01 to 10% by weight, in particular 0.1 to 5% by weight Suitable minimum values may also be present at 0.5, 1, 2 or 3% by weight.
  • the product according to the invention contains cationic surfactants, preferably in quantities of at least 0.1% by weight
  • agents according to the invention such as, preferably, cleaning agents, care agents and detergents, may also contain amphoteric surfactants. These will be described in more detail below, in particular in connection with conditioning agents and plasticizers
  • the agents according to the invention may contain one or more amphoteric surfactants, advantageously in amounts, based on the total composition, of from 0 to 30% by weight, more preferably greater than 0 to 20% by weight, preferably 0 , 01 to 10% by weight, in particular 0.1 to 5% by weight
  • compositions according to the invention may be inorganic and organic builders.
  • the inorganic builders include water-insoluble or non-water-soluble ingredients, such as aluminosilicates and, in particular, zeolites
  • the agent according to the invention contains no phosphate and / or no zeolite.
  • the agent may also possible for the agent to comprise Zeohth. It may then be preferred that this zeohth content, based on the total weight of the agent, is less than 5% by weight, preferably not more than 4% by weight, not more than 3% by weight or not more than 2% by weight
  • the agent according to the invention has a zeolite content of at least 10% by weight, for example at least 15% by weight or at least 20% by weight or at least 30% by weight or even beyond, for example at least 50% by weight. % having.
  • Soluble builders may preferably contain the agent according to the invention in amounts of 10% by weight to 30% by weight, preferably 15% by weight to 25% by weight and particularly preferably 18% by weight to 20% by weight on the total weight of the agent, with sodium carbonate as the soluble builder being particularly preferred.
  • the agent according to the invention contains less than 10% by weight, for example less than 5% by weight, of soluble builder.
  • Useful finely crystalline, synthetic and bound water-containing zeolite is preferably zeolite A and / or P.
  • zeolite P for example, zeolite MAP (R) (commercial product of Crosfield) is particularly preferred.
  • zeolite X and mixtures of A, X and / or P are particularly preferred.
  • zeolite X and mixtures of A, X and / or P are particularly preferred.
  • zeolite X co-crystallized sodium / potassium aluminum silicate of zeolite A and zeolite X, which as VEGOBOND AX ® (a product of Condea Augusta SpA) Trade is available. This product is described below.
  • VEGOBOND AX ® a product of Condea Augusta SpA
  • the zeolite may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3 wt .-%, based on zeolite, of ethoxylated C 12 -C 18 -FeK- alcohols with 2 to 5 ethylene oxide groups, C 12 -C 14 fatty alcohols having 4 to 5 ethylene oxide groups or ethoxylated isotridecanols.
  • Suitable zeolites have an average particle size of preferably less than 10 ⁇ m (volume distribution, measuring method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
  • zeolites are faujasite-type zeolites. Together with the zeolites X and Y, the mineral faujasite belongs to the faujasite types within the zeolite structure group 4, which are characterized by the double-six-membered subunit D6R. In addition to the faujasite types mentioned, the zeolite structural group 4 also includes the minerals chabazite and gmelinite as well as the synthetic zeolites R (chabazite type), S (gmelinite type), L and ZK-5. The latter two synthetic zeolites have no mineral analogs.
  • Faujasite-type zeolites are composed of ⁇ -cages linked by tetrahedral D6R subunits, with the ⁇ -cages resembling the carbon atoms in the diamond.
  • the three-dimensional network of the faujasite-type zeolites suitable according to the invention has pores of 2.2 and 7.4 ⁇ , and the unit cell also contains 8 cavities with a diameter of approximately 13 A and can be represented by the formula Na 86 [(Al 2 O) 86 (SiO 2) 1 o6] 264 H 2 O describe.
  • the network of zeolite X contains a void volume of about 50%, based on the dehydrated crystal, which represents the largest void space of all known zeolites (zeolite Y: approx. 48% void volume, faujasite: approx. 47% void volume).
  • zeolite type zeolite denotes all three zeolites which form the faujasite subgroup of the zeolite structure group 4.
  • zeolite Y and faujasite and mixtures of these compounds are also suitable according to the invention, with pure zeolite X being preferred.
  • Mixtures or cocrystallizates of faujasite-type zeolites with other zeolites, which need not necessarily belong to the zeolite structure group 4, are also suitable according to the invention, with preferably at least 50% by weight of the faujasite-type zeolites being suitable.
  • the suitable aluminum silicates are commercially available and the methods for their preparation are described in standard monographs.
  • zeolite A-LSX which corresponds to a cocrystal of zeolite X and zeolite A and in its anhydrous form has the formula (M 2 / n O + M'2 / n O) Al 2 O 3 zSiO 2 , wherein M and M 'may be alkali or alkaline earth metals and z is a number from 2.1 to 2.6.
  • VEGOBOND AX by the company CONDEA Augusta SpA
  • Y-type zeolites are also commercially available and can be obtained, for example, by the formulas
  • the particle sizes of the suitable zeolites are advantageously in the range from 0.1 ⁇ m to 100 ⁇ m, preferably from 0.5 ⁇ m to 50 ⁇ m and in particular from 1 ⁇ m to 30 ⁇ m, in each case measured by standard particle size determination methods.
  • all of the inorganic constituents contained should preferably be water-soluble. Therefore, builders other than the zeolites mentioned are used in these embodiments.
  • polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 C atoms and at least 3 hydroxyl groups.
  • Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • dextrins for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches.
  • the hydrolysis can be carried out by customary, for example acid or enzyme catalyzed processes.
  • it is hydrolysis products having average molecular weights in the range of 400 to 500,000 g / mol.
  • a polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30 is preferred, DE being a common measure of the reducing action of a polysaccharide compared to dextrose, which has a DE of 100 , is.
  • DE dextrose equivalent
  • 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.
  • Ethylenediamine-N, N '-di-succinate (EDDS) is preferably in the form of its sodium or magnesium salts.
  • glycerol disuccinates and glycerol trisuccinates are also preferred in this context. Suitable amounts are, for example, 3 to 15 wt .-%, based on the total agent.
  • organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be present in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.
  • phosphonates are in particular hydroxyalkane or aminoalkanephosphonates.
  • hydroxyalkane phosphonates 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a co-builder. It is preferably used as the sodium salt, the disodium salt neutral and the tetrasodium salt alkaline (pH 9).
  • Preferred aminoalkane phosphonates are ethylenediamine tetramethylene phosphonate (EDTMP), diethylene triamine pentamethylene phosphonate (DTPMP) and their higher homologs.
  • the builder used here is preferably HEDP from the class of phosphonates.
  • the aminoalkanephosphonates also have a pronounced heavy metal binding capacity. Accordingly, in particular if the agents also contain bleach, it may be preferable to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.
  • phosphates in particular pentasodium triphosphate, optionally also pyrophosphates and orthophosphates, which act primarily as precipitants for calcium salts.
  • Phosphates are predominantly used in automatic dishwasher detergents, but in some cases also in detergents.
  • Alkali metal phosphates is the summary term for the alkali metal (especially sodium and potassium) salts of various phosphoric acids, in which one can distinguish metaphosphoric acids (HPO 3 ), and orthophosphoric H 3 PO 4 in addition to high molecular weight representatives.
  • the phosphates combine several advantages: they act as alkali carriers, prevent lime deposits on machine parts or lime incrustations in fabrics and also contribute to the cleaning performance.
  • Sodium dihydrogen phosphate, NaH 2 PO 4 exists as a dihydrate (density 1, 91 like '3 , melting point 60 °) and monohydrate (density 2.04 like ' 3 ). Both salts are white powders which are very soluble in water and which lose the water of crystallization on heating and at 200 ° C into the weak acid diphosphate (disodium hydrogen diphosphate, Na 2 H 2 PaO 7 ), at higher temperature in sodium trimetaphosphate (Na 3 P 3 O 9 ) and Maddrell's salt (see below).
  • NaH 2 PO 4 is acidic; It arises when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed.
  • Potassium dihydrogen phosphate (potassium phosphate primary or monobasic, potassium bisphosphate, KDP), KH 2 PO 4 , is a white salt of density 2.33 "3 , has a melting point of 253 ° [decomposition to form potassium polyphosphate (KPO 3 ) X ] and is easily soluble in water.
  • Disodium hydrogen phosphate (secondary sodium phosphate), Na 2 HPO 4 , is a colorless, very slightly water-soluble crystalline salt. It exists anhydrous and with 2 mol. (Density 2.066 like “3 , water loss at 95 °), 7 mol. (Density 1, 68 like '3 , melting point 48 ° with loss of 5 H 2 O) and 12 mol. Water (density 1, 52 like '3 , melting point 35 ° with loss of 5 H 2 O), becomes anhydrous at 100 ° and on more intense heating in the diphosphate Na 4 P 2 O 7 over. Disodium hydrogen phos- phate is prepared by neutralization of phosphoric acid with soda solution using phenolphthalein as an indicator. Di-potassium hydrogen phosphate (secondary or dibasic potassium phosphate), K 2 HPO 4 , is an amorphous, white salt that is readily soluble in water.
  • Decahy- hydrate (corresponding to 19-20 % P 2 O 5 ) has a melting point of 10O 0 C and in anhydrous form (corresponding to 39-40% P 2 O 5 ) has a density of 2.536 like "3 .
  • Trisodium phosphate is readily soluble in water under alkaline reaction and is prepared by evaporation of a solution of exactly 1 mole of disodium phosphate and 1 mole of NaOH.
  • Tripotassium phosphate (tertiary or tribasic potassium phosphate), K 3 PO 4 , is a white, deliquescent, granular powder with a density of 2.56 '3 , has a melting point of 1340 ° and is readily soluble in water with an alkaline reaction. It arises, for example, when heating Thomasschlacke with coal and potassium sulfate. Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred over the corresponding sodium compounds in the detergent industry.
  • Tetrasodium diphosphate (sodium pyrophosphate), Na 4 P 2 O 7 , exists in anhydrous form (density 2.534 '3 , melting point 988 °, also indicated 880 °) and as decahydrate (density 1, 815-1, 836 like ' 3 , melting point 94 ° with loss of water). Both substances are colorless crystals which are soluble in water with an alkaline reaction.
  • Na 4 P 2 O 7 is formed on heating of disodium phosphate to> 200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dewatering the solution by spraying. The decahydrate complexes heavy metal salts and hardness agents and therefore reduces the hardness of the water.
  • Potassium diphosphate (potassium pyrophosphate), K 4 P 2 O 7 , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33% '3 , which is soluble in water, the pH being 1% Solution at 25 ° 10.4.
  • Condensation of the NaH 2 PO 4 or of the KH 2 PO 4 gives rise to relatively high molecular weight sodium and potassium phosphates, in which cyclic representatives, the sodium or potassium metaphosphates and chain-type, the sodium or potassium polyphosphates, can be distinguished.
  • cyclic representatives, the sodium or potassium metaphosphates and chain-type, the sodium or potassium polyphosphates can be distinguished.
  • melting or annealing phosphates melting or annealing phosphates
  • Graham's salt Kurrolsches
  • Maddrell's salt All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.
  • pentasodium triphosphate Na 5 P 3 Oi 0 (sodium tripolyphosphate)
  • 10O g of water dissolve at room temperature about 17 g, at 60 ° about 20 g, at 100 ° about 32 g of the salt water-free salt; after two hours of heating the solution to 100 ° caused by hydrolysis about 8% orthophosphate and 15% diphosphate.
  • pentasodium triphosphate In the preparation of pentasodium triphosphate, phosphoric acid is reacted with soda solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dehydrated by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentakaliumtriphos-phat, K 5 P 3 O 10 (potassium tripolyphosphate), for example, in the form of a 50% by weight solution (> 23% P 2 O 5 , 25% K 2 O) in the trade. The potassium polyphosphates are widely used in the washing and cleaning industry. Furthermore, there are also sodium potassium tripolyphosphates, which can also be used in the context of the present invention. These arise, for example, when hydrolyzed sodium trimetaphosphate with KOH:
  • carbonates and silicates are used as inorganic builder substances.
  • crystalline, layered sodium silicates of the general formula NaMSi x 0 2x + 1 yH 2 O, where M is sodium or hydrogen, x is a number from 1, 6 to 4, preferably 1, 9 to 4.0 and y is one Number is from 0 to 20 and preferred values for x are 2, 3 or 4.
  • crystalline silicates are preferably subsequently added to the direct or post-treated spray-drying product.
  • Preferred crystalline layer silicates of the formula given are those in which M is sodium and x is 2 or
  • both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 O 5 yH 2 O are preferred.
  • Such compounds are commercially available, for example, under the name SKS® (from Clariant).
  • SKS-6 ® is a ⁇ -sodium di-silicate having the formula
  • Na 2 Si 2 O S yH 2 O, SKS-7 ® is predominantly a beta-sodium disilicate. Reaction with acids (eg citric acid or carbonic acid) produces kanemite from the ⁇ -sodium disilicate
  • NaHSi 2 O 5 yH 2 O commercially available under the names SKS- 9® or SKS- 10® (from Clariant). It may also be advantageous to use chemical modifications of these phyllosilicates. So can For example, the alkalinity of the layered silicates are suitably influenced. Phyllosilicates doped with phosphate or with carbonate have altered crystal morphologies in comparison with the ⁇ -sodium disilicate, dissolve more rapidly and show an increased calcium binding capacity in comparison to ⁇ -sodium disilicate.
  • phyllosilicates of the general empirical formula x Na 2 O • y SiO 2 • z P 2 O 5 in which the ratio x to y is a number 0.35 to 0.6, the ratio x to z a number of 1.75 to 1200 and the ratio y to z of a number of 4 to 2800 is known.
  • the solubility of the layered silicates can also be increased by using particularly finely divided layered silicates.
  • compounds from the crystalline layer silicates with other ingredients can be used.
  • compounds with cellulose derivatives which have advantages in the disintegrating action, as well as compounds with polycarboxylates, for example citric acid, or polymeric polycarboxylates, for example copolymers of acrylic acid, may be mentioned.
  • the preferred builder substances also include amorphous sodium silicates having a modulus Na 2 O: SiO 2 of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2, 6, which have secondary washing properties.
  • amorphous is also understood to mean "X-ray amorphous”. This means that the silicates in X-ray diffraction experiments do not give sharp X-ray reflections typical of crystalline substances, but at best one or more maxima of the scattered X-radiation, which have a width of several degrees of diffraction angle.
  • the silicate particles provide blurred or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of size 10 to a few hundred nm, with values of up to max. 50 nm and in particular up to max. 20 nm are preferred.
  • Such so-called X-ray amorphous silicates which also have a dissolution delay compared with conventional water glasses, are known.
  • Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.
  • the content of the (X-ray) amorphous silicates in particular zeolite-free compositions is preferably 1 to 10 wt .-%, which corresponds to a preferred embodiment of the invention.
  • Particularly preferred inorganic water-soluble builders are alkali metal carbonates and alkali metal bicarbonates, with sodium and potassium carbonate and especially sodium carbonate being among the preferred embodiments.
  • the content of alkali metal carbonates in particular zeolite-free compositions can vary within a very broad range and is preferably from 5 to 40% by weight, in particular from 8 to 30% by weight, the content of alkali metal carbonates usually being higher than (X-ray). ) amorphous silicates.
  • Useful organic builders are, for example, usable in the form of their alkali and especially sodium polycarboxylic acids, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for environmental reasons , as well as 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 thereof. The acids themselves can also be used.
  • the acids typically also have the property of an acidifying component and thus also serve, for example in the granules according to the invention, for setting a lower and milder pH of detergents and cleaners.
  • an acidifying component for example, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.
  • polymeric polycarboxylates for example the alkali metal salts of polyacrylic acid or of polymethacrylic acid, for example those having a relative molecular mass of 500 to 70,000 g / mol.
  • the molecular weights stated for polymeric polycarboxylates are weight-average molar masses M w of the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the polymers investigated. These data differ significantly from the molecular weight data, in which polystyrene sulfonic acids are used as standard. The molar masses measured against polystyrenesulfonic acids are generally significantly higher than the molecular weights specified in this document.
  • compositions according to the invention may also contain polymers, in particular as carriers for the perfume oils (fragrances).
  • Suitable polymers which can also be used as carriers in combination with perfume include, in particular, polyacrylates which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molar masses of from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, may again be preferred from this group.
  • copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid.
  • Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
  • Their relative molecular weight, based on free acids is generally from 2000 to 70000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol.
  • the content of the organic builder substances may vary within a broad range. Preference is given to contents of from 2 to 20% by weight, in particular contents of not more than 10% by weight being particularly preferred
  • the agents according to the invention may contain components from the classes of the grayness inhibitors (soil carriers), the neutral salts and / or the fabric softening auxiliaries (for example cationic surfactants), which is preferred
  • Graying inhibitors have the task to keep suspended from the fiber debris suspended in the fleet and so prevent the re-accumulation of dirt
  • water-soluble colloids are mostly organic nature suitable, for example, the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
  • water-soluble polyamides containing acidic groups are suitable for this purpose.
  • soluble starch preparations and starch products other than those mentioned above can be used, eg degraded starch, aldehyde starches, etc Polyvinylpyrrolidone is also useful.
  • cellulose ethers such as carboxymethylcellulose (Na salt), 1 -methylcellulose, hydroxyalkylcellulose and mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and the like d their mixtures, and polyvinylpyrrolidone, for example, in amounts of preferably 0.1 to 5% by weight, based on the means used
  • a typical example of a suitable representative of the neutral salts is sodium sulfate. It can be used in amounts of, for example, from 0 to 60% by weight, preferably from 2 to 45% by weight
  • Suitable plasticizers which are described in more detail below, are, for example, swellable phyllosilicates of the type of corresponding montmorillonites, for example bentonite, as well as cationic surfactants
  • the content of water on average depends, inter alia, on whether the composition is in liquid or solid form, and is therefore preferably 0 to less than 100% by weight and in particular 0.5 to 95% by weight, with values of not more than 5% by weight.
  • Particular preference is given in particular to solid or non-aqueous liquid agents Not included in the case of the solid compositions is the water adhering to any aluminosilicates such as zeolite
  • the composition according to the invention contains water in an amount of more than 20% by weight, advantageously more than 30% by weight, in more advantageously more than 40 wt .-%, more preferably more than 50 wt .-%, in particular 60 to 95 wt .-%, particularly preferably 70 to 93 wt .-% and most preferably 80 to 90 wt .-%.
  • the agent according to the invention can, if it is a solid, have an excellent trickling behavior.
  • the agent according to the invention is substantially solid, preferably in powdery, pressed or granular form.
  • the particles can be post-treated, for example, by rounding the particles of the agent.
  • the rounding can be done in a standard roundabout.
  • the rounding time is not longer than 4 minutes, especially not longer than 3.5 minutes. Rounding times of a maximum of 1.5 minutes or less are particularly preferred.
  • An inventive agent in particulate form can in particular with nonionic surfactants, perfume oil (fragrances) and / or foam inhibitors or formulations containing these ingredients, preferably with amounts up to 20 wt .-% of active ingredient, in particular with amounts of 2 to 18 wt. -% active substance, in each case based on the aftertreated product, in a conventional manner, preferably in a mixer or optionally a fluidized bed, post-treatment.
  • an agent according to the invention may also be post-treated or powdered with solids, preferably in amounts of up to 15% by weight, in particular in amounts of from 2 to 15% by weight, based in each case on the total weight of the post-treated agent.
  • Bicarbonate, carbonate, zeolite, silica, citrate, urea or mixtures thereof, in particular in amounts of from 2 to 15% by weight, based on the total weight of the aftertreated product, can preferably be used as solids for the aftertreatment.
  • the aftertreatment can be carried out in an advantageous manner in a mixer and / or by means of Verrunder.
  • an agent according to the invention is aftertreated with nonionic surfactants, which may also contain, for example, optical brighteners and / or hydrotropes, perfume (fragrances), and / or a solution of optical brightener and / or foam inhibitors or preparation forms containing same May contain ingredients.
  • nonionic surfactants may also contain, for example, optical brighteners and / or hydrotropes, perfume (fragrances), and / or a solution of optical brightener and / or foam inhibitors or preparation forms containing same May contain ingredients.
  • these ingredients or preparation forms containing these ingredients are preferably applied in liquid, molten or pasty form to the particulate agent, which is to be acted upon.
  • the aftertreatment with the substances mentioned here in a conventional mixer only for example in a 2-wave mixer within a maximum of 1 minute, preferably within 30 seconds and for example within 20 seconds, the time information for Addition and mixing time is done.
  • nonionic surfactants are described in more detail. These nonionic surfactants can be applied to the particulate agents in an aftertreatment step. Of course, all nonionic surfactants but can advantageously be directly in the composition according to the invention, liquid or solid, foaming or gel may be included.
  • 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 residue can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture may contain, as they are usually present in Oxoalkoholresten.
  • alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, palm kernel, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred.
  • the preferred ethoxylated alcohols include, for example, C 12 -C 14 -alcohols with 3 EO or 4 EO, C 9 -C 11 -alkyl with 7 EO, C 13 -C 15 -alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12 -C 18 -alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12 -C 14 -AlkOhOl with 3 EO and C 12 -C 18 -alcohol with 7 EO.
  • the stated degrees of ethoxylation represent statistical averages, which may be an integer or a fractional number for a particular product.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow rank ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples of these are (TaIg) fatty alcohols with 14 EO 1 16 EO, 20 EO, 25 EO, 30 EO or 40 EO.
  • Preferred nonionic surfactants are one or more ethylene oxide (EO) and / or propylene oxide (PO) alkoxylated, unbranched or branched, saturated or unsaturated C 10 . 22 alcohols having a degree of alkoxylation of up to 30, preferably ethoxylated C 10-18 fatty alcohols having an ethoxylation degree of less than 30, preferably 1 to 20, in particular 1 to 12, more preferably 1 to 8, most preferably 2 to 5, for example C 12 .
  • EO ethylene oxide
  • PO propylene oxide
  • nonionic surfactants and alkyl glycosides of the general formula RO (G) x can be used in which R is a primary straight-chain or methyl-branched, especially in the 2-position methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which 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 from 1 to 10; preferably x is 1, 1 to 1, 4.
  • nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants, in particular together with alkoxylated fatty alcohols and / or alkyl glycosides, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, as described for example in Japanese Patent Application JP 58/217598 or which are preferably prepared according to the method described in International Patent Application WO-A-90/13533.
  • Particularly preferred are C 12 -C 8 fatty acid methyl esters with an average of 3 to 15 EO, in particular with an average of 5 to 12 EO.
  • Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.
  • alkoxylated amines advantageously ethoxylated and / or propoxylated, in particular primary and secondary amines having preferably 1 to 18 carbon atoms per alkyl chain and an average of 1 to 12 MoI ethylene oxide (EO) and / or 1 to 10 MoI propylene oxide (PO) per Mole of amine.
  • EO MoI ethylene oxide
  • PO MoI propylene oxide
  • compositions according to the invention which are particularly suitable for automatic dishwashing, in particular dishwashing compositions in the form of tablet tablets, such as tabs, all surfactants are suitable in principle as surfactants.
  • the nonionic surfactants described above and especially the low-foaming nonionic surfactants are particularly preferred for this purpose.
  • Particularly preferred are the alkoxylated alcohols, especially the ethoxylated and / or propoxylated alcohols.
  • the person skilled in the art generally means, under alkoxylated alcohols, the reaction products of alkylene oxide, preferably ethylene oxide, with alcohols, preferably in the context of the present invention, the longer-chain alcohols C 10 to C 18 , preferably C 12 to C 16 , such as C 11 -, C 12 - , C 13 , C 14 , C 15 , C 16 , C 17 and C 18 alcohols.
  • the longer-chain alcohols C 10 to C 18 , preferably C 12 to C 16 , such as C 11 -, C 12 - , C 13 , C 14 , C 15 , C 16 , C 17 and C 18 alcohols.
  • n moles of ethylene oxide and one mole of alcohol give rise to a complex mixture of addition products of varying degrees of ethoxylation, depending on the reaction conditions.
  • a further embodiment consists in the use of mixtures of the alkylene oxides, preferably the mixture of ethylene oxide and propylene oxide.
  • compositions according to the invention may also contain foam inhibitors, for example foam-inhibiting paraffin oil or foam-inhibiting silicone oil, for example dimethylpolysiloxane.
  • foam inhibitors for example foam-inhibiting paraffin oil or foam-inhibiting silicone oil, for example dimethylpolysiloxane.
  • foam inhibitors for example foam-inhibiting paraffin oil or foam-inhibiting silicone oil, for example dimethylpolysiloxane.
  • foam inhibitors for example foam-inhibiting paraffin oil or foam-inhibiting silicone oil, for example dimethylpolysiloxane.
  • foam inhibitors for example foam-inhibiting paraffin oil or foam-inhibiting silicone oil, for example dimethylpolysiloxane.
  • foam inhibitors for example foam-inhibiting paraffin oil or foam-inhibiting silicone oil, for example dimethylpolysiloxane.
  • additives which are solid at room temperature paraffin waxes, silicic acids, which may also be rendered hydrophobic in
  • Foam-inhibiting paraffin oils which are suitable for use and which may also be present in admixture with paraffin waxes are generally complex mixtures without a sharp melting point.
  • the melting range is usually determined by differential thermal analysis (DTA) and / or the solidification point. This is the temperature at which the paraffin passes from the liquid to the solid state by slow cooling.
  • Paraffins with less than 17 carbon atoms are not useful according to the invention, their proportion in the paraffin oil mixture should therefore be as low as possible and is preferably below the limit significantly measurable by conventional analytical methods, for example gas chromatography.
  • paraffins are used, which solidify in the range of 2O 0 C to 70 0 C.
  • paraffin wax mixtures may contain different proportions of liquid paraffin oils.
  • the liquid fraction at 40 ° C. is as high as possible, even without being 100% at this temperature.
  • Preferred paraffin wax mixtures have at 4O 0 C a liquid content of at least 50 wt .-%, in particular from 55 wt .-% to 80 wt .-%, and at 6O 0 C, a liquid content of at least 90 wt .-%. This has the consequence that the paraffins at temperatures down to at least 7O 0 C, preferably down to at least 60 0 C are flowable and pumpable.
  • paraffins contain as far as possible no volatile components.
  • Preferred paraffin waxes contain less than 1 wt .-%, in particular less than 0.5 wt .-% at 11O 0 C and atmospheric pressure vaporizable fractions.
  • Paraffins which can be used according to the invention can be obtained, for example, under the trade names Lunaflex® from Guer and Deawax® from DEA Mineralöl AG.
  • the paraffin oils may contain at room temperature solid bisamides derived from saturated fatty acids containing 12 to 22, preferably 14 to 18, carbon atoms and alkylenediamines having 2 to 7 carbon atoms.
  • Suitable fatty acids are lauric, myristic, stearic, arachic and behenic acids and mixtures thereof, such as are obtainable from natural fats or hardened oils, such as tallow or hydrogenated palm oil.
  • Suitable diamines are, for example, ethylenediamine 1, 3-propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, p-phenylenediamine and toluenediamine.
  • Preferred diamines are ethylenediamine and hexamethylenediamine.
  • Particularly preferred bisamides are bis-myristoyl-ethylenediamine, bispalmitoyl-ethylenediamine, bis-stearoyl-ethylenediamine and mixtures thereof and the corresponding derivatives of hexamethylenediamine.
  • the products according to the invention can preferably be mixed with further constituents, in particular detergents, care and / or cleaning agents or cosmetic ingredients.
  • further constituents in particular detergents, care and / or cleaning agents or cosmetic ingredients.
  • ingredients of detergents and cleaners and which raw materials can usually be added are, for example, substances such as bleaching agents, bleach activators and / or bleach catalysts, enzymes, temperature-sensitive dyes, etc., which of course may also be contained directly in the composition.
  • the agent may comprise UV absorbers, which are advantageously applied to the treated fabrics and improve the lightfastness of the fibers and / or the lightfastness of other formulation ingredients.
  • UV absorber are organic substances (sunscreen) to understand, which are able to absorb ultraviolet rays and the absorbed energy in the form of longer-wave radiation, eg heat to give back.
  • Compounds having these desired properties include, for example, the non-radiative deactivating compounds and derivatives of benzophenone having substituents in the 2- and / or 4-position.
  • substituted benzotriazoles phenyl-substituted acrylates (cinnamic acid derivatives) in the 3-position, optionally with cyano groups in the 2-position, salicylates, organic Ni complexes and natural substances such as umbelliferone and the endogenous urocanic acid.
  • phenyl-substituted acrylates in the 3-position
  • salicylates optionally with cyano groups in the 2-position
  • organic Ni complexes such as umbelliferone and the endogenous urocanic acid.
  • the biphenyl and especially stilbene derivatives commercially available as Tinosorb ® FD or Tinosorb ® FR ex Ciba.
  • UV-B absorbers there may be mentioned 3-benzylidene camphor or 3-benzylidene norcamphor and its derivatives, eg 3- (4-methylbenzylidene) camphor; 4-aminobenzoic acid derivatives, preferably 2-ethylhexyl 4- (dimethylamino) benzoate, 2-octyl 4- (dimethylamino) benzoate and 4-dimethylaminobenzoic acid amide; Esters of cinnamic acid, preferably 2-ethylhexyl 4-methoxycinnamate, 4-methoxycinnamic acid propyl ester, 4-methoxycinnamic acid iso-amyl ester, 2-cyano-3,3-phenylcinnamic acid 2-ethylhexyl ester (octocrylene); Esters of salicylic acid, preferably 2-ethylhexyl salicylate, 4-salicylic acid isopropylbenzyl
  • 2-phenylbenzimidazole-5-sulfonic acid and its alkali metal, alkaline earth metal, ammonium, alkylammonium, alkanolammonium and glucammonium salts Sulfonic acid derivatives of benzophenones, preferably 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its salts
  • Sulfonic acid derivatives of 3-Benzylidencamphers such as 4- (2-oxo-3-boryl-nylidenemethyl) benzenesulfonic acid and 2-methyl-5- (2-oxo-3-bomylidene) sulfonic acid and salts thereof.
  • UV-A filter in particular derivatives of benzoylmethane come into question, such as 1- (4'-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1, 3-dione, 4-tert-butyl 4'-methoxydibenzoylmethane (Parsol 1789), 1-phenyl-3- (4'-isopropylphenyl) -propane-1,3-dione and enamine compounds.
  • the UV-A and UV-B filters can also be used in mixtures.
  • insoluble photoprotective pigments namely finely dispersed, preferably nano-metal oxides or salts, are also suitable for this purpose.
  • suitable metal oxides are in particular zinc oxide and titanium dioxide and, in addition, oxides of iron, zirconium, silicon, manganese, aluminum and cerium and mixtures thereof.
  • silicates (talc) barium sulfate or zinc stearate can be used.
  • the oxides and salts are already used in the form of the pigments for skin-care and skin-protecting emulsions and decorative cosmetics.
  • the particles should have an average diameter of less than 100 nm, preferably from 5 to 50 nm and in particular from 15 to 30 nm. They may have a spherical shape, but it is also possible to use those particles which have an ellipsoidal or otherwise deviating shape from the spherical shape.
  • the pigments can also be surface treated, i. hydrophilized or hydrophobized.
  • Typical examples are coated titanium dioxides, e.g. Titanium dioxide T 805 (Degussa) or Eusolex® T2000 (Merck).
  • Suitable hydrophobic coating agents are in particular silicones and in particular trialkoxyoctylsilanes or simethicones. Micronized zinc oxide is preferably used. Further suitable UV light protection filters can be found in the relevant prior art.
  • the UV absorbers are advantageously contained in amounts of from 0.01% to 5% by weight, preferably from 0.03% to 1% by weight, in the composition. They can also be added to the product later, for example together with other substances.
  • the agents according to the invention if they are solid, can also be in the form of a tablet or shaped article, as has already been shown.
  • tablette or “shaped bodies” are dimensionally stable, solid bodies, irrespective of the manner of their preparation. Such bodies can be produced, for example, by crystallization, molding, injection molding, reactive or thermal sintering, (co) extrusion, powdering, pastillation or compacting processes such as calendering or tableting.
  • the preparation of the "tablets" or “shaped bodies” by tabletting is particularly preferred in the context of the present application.
  • the tablet is thus preferably made of compressed, particulate material.
  • Solid compositions according to the invention may preferably contain disintegration aids.
  • Suitable swellable disintegration aids are, for example, bentonites or other swellable silicates. It is also possible to use synthetic polymers, in particular the superabsorbents or cross-linked polyvinylpyrrolidone used in the hygiene sector.
  • polymers based on starch and / or cellulose are used as swellable disintegration aids.
  • These base substances can be processed alone or in mixture with other natural and / or synthetic polymers to swellable disintegrating agents.
  • a cellulosic material or pure cellulose can be converted by pressure transfer into secondary particles by granulation, compaction or other application, which swell on contact with water and thus serve as a disintegrant.
  • Wood pulp which has been obtained by thermal or chemical-thermal processes from wood or wood chips (sawdust, sawmill waste) has proven to be suitable as a cellulosic material.
  • This cellulose material from the TMP process (thermomechanical pulp) or the CTMP process (chemothermomechanical pulp) can then be compacted by application of pressure, preferably roller compacted and converted into particle form.
  • pressure preferably roller compacted and converted into particle form.
  • pure cellulose can also be used in a completely analogous manner, although it is more expensive from the raw material base.
  • both microcrystalline and amorphous finely divided cellulose and mixtures thereof can be used.
  • the primary fiber length of the cellulose or cellulose used in the cellulosic material should be less than 200 .mu.m, preference being given to primary fiber lengths of less than 100 .mu.m, in particular less than 50 .mu.m.
  • the secondary particles ideally have a particle size distribution in which preferably more than 90 wt .-% of the particles have sizes above 200 microns.
  • a certain proportion of dust can contribute to an improved storage stability of the tablets produced therewith. Shares of a fine dust content of less than 0.1 mm up to 10 wt .-%, preferably up to 8 wt .-% may be present in the agents used in the invention with disintegrant granules.
  • the agents according to the invention can be present in the form of a conditioning agent and / or conditioner substrate and contain the appropriate components.
  • conditioning is preferably to be understood as meaning the avivating treatment of textiles, fabrics and fabrics. Conditioning gives the textiles positive properties, such as improved softness, increased gloss and color brilliance, improved fragrance impression, reduction of felting, ironing relief by reducing the sliding properties, reducing the creasing behavior and the static charge and a color transfer inhibition in dyed textiles ,
  • compositions according to the invention may comprise plasticizer components.
  • plasticizer components examples include quaternary ammonium compounds, cationic polymers and emulsifiers, as are used in hair care products and also in agents for Textilavivage.
  • softening compounds which will also be described in more detail below, can be present in all inventive compositions, but especially in the conditioners or in compositions with the desired softening effect.
  • Suitable examples are quaternary ammonium compounds of the formulas (III) and (IV),
  • R and R 1 is an acyclic alkyl radical having 12 to 24 carbon atoms
  • R 2 is a saturated C 1 -C 4 alkyl or hydroxyalkyl radical
  • R 3 is either R, R 1 or R 2 or is a aromatic residue stands.
  • X " represents either a halide, methosulfate, methophosphate or phosphate ion and mixtures of these Examples of cationic compounds of the formula (III) are didecyldimethylammonium chloride, ditallowdimethylammonium chloride or dihexadecylammonium chloride.
  • Ester quats are so-called ester quats. Esterquats are characterized by excellent biodegradability.
  • R 4 is an aliphatic alkyl radical having 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds
  • R 5 is H, OH or O (CO) R 7
  • R 6 is, independently of R 5, H, OH or O (CO) R 8
  • R 7 and R 8 are independently of each represents an aliphatic alk (en) yl radical having 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds
  • m, n and p can each independently of one another have the value 1, 2 or 3.
  • X " can be either a halide, methosulfate, methophosphate or phosphate ion and mixtures thereof
  • Preferred compounds are those for R 5, the group 0 (CO) R 7 and for R 4 and R 7 are alkyl radicals having 16 to 18 carbon atoms included. Especially preferred are compounds in which R 6 is also OH.
  • Examples of compounds of 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 (acyl-oxy-ethyl) -N- (2-hydroxy-ethyl) -ammonium-methosulphate are quaternized compounds of the formula (IV) having unsaturated alkyl chains, the acyl groups are preferred whose corresponding fatty acids have an iodine value between 5 and 80, preferably between 10 and 60 and in particular between 15 and 45 and which have a cis / trans isomer ratio (in parts by weight).
  • Stepan under the tradename Stepantex ® Methylhy- droxyalkyldi-alkoyloxyalkylammoniummethosulfate or those known under Dehyquart ® Cognis products known under or Rewoquat ® manufactured by Goldschmidt-Witco.
  • Further preferred compounds are the diester quats of the formula (V) 1 which are obtainable under the name Rewoquat® W 222 LM or CR 3099 and, in addition to the softness, also provide stability and color protection.
  • R 21 and R 22 are each independently an aliphatic radical having 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds.
  • R s is H or a saturated alkyl radical having 1 to 4 carbon atoms
  • R 10 alternatively also O (CO)
  • R 20 wherein R 20 is an aliphatic, saturated or unsaturated alkyl radical having 12 to 18 carbon atoms, and Z is an NH group or oxygen and X "is an anion.
  • q can take integer values between 1 and 4.
  • R14 CH 2 - O (CO) R 16 wherein R 12, R 13 and R 14 independently are a C 4 -Atkyl-, alkenyl or hydroxyalkyl group is of one another, R 15 and R 16 are each independently selected a C 8 _2 8 -Alkyl group and r is a number between 0 and 5.
  • short-chain, water-soluble, quaternary ammonium compounds such as trihydroxyethylmethylammonium methosulfate or the alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, e.g. Cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride.
  • quaternary ammonium compounds such as trihydroxyethylmethylammonium methosulfate or the alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, e.g. Cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride,
  • protonated alkylamine compounds which have plasticizing effect, as well as the non-quaternized, protonated precursors of cationic emulsifiers are suitable.
  • cationic compounds which can be used according to the invention are the quaternized protein hydrolysates.
  • Suitable cationic polymers include the polyquaternium polymers as referred to in the CTFA Cosmetic Ingredient Dictionary (The Cosmetic, Toiletry and Fragrance, Inc., 1997), in particular the Polyquaternium-6, Polyquaternium-7, also referred to as Merquats, Polyquaternium-10 polymers (Ucare Polymer IR 400, Amerchol), polyquaternium-4 copolymers such as graft copolymers having a cellulose backbone and quaternary ammonium groups attached via allyldimethylammonium chloride, cationic cellulose derivatives such as cationic guar such as guar hydroxypropyl triammonium chloride, and similar quaternized guar derivatives (eg Cosmedia Guar, manufacturer: Cognis GmbH), cationic quaternary sugar derivatives (cationic alkyl polyglucosides), eg.
  • CTFA Cosmetic Ingredient Dictionary The Cosmetic, Toiletry and Fragrance, Inc., 1997)
  • Polyquaternized polymers for example Luviquat Care from BASF
  • cationic biopolymers based on chitin and derivatives thereof for example, under the trade designation chitosan ® (manufacturer: Cognis) polymer obtainable.
  • cationic silicone oils such as the commercially available products Q2-7224 (manufactured by Dow Corning, a stabilized trimethylsilyl-modimeth-icon), Dow Corning 929 emulsion (containing a hydroxylamino-modified silicone, also referred to as amodimethicones is SM-2059 (manufacturer): General Electric), SLM-55067 (manufacturer: Wacker) Abil ® -Quat 3270 and 3272 (manufacturer: Goldschmidt-Rewo; diquaternary polydimethylsiloxanes, quaternium-80), and Silicone quat Rewoquat ® SQ 1 ( Tegopren® ® 6922, manufacturer: Goldschmidt-Rewo).
  • Q2-7224 manufactured by Dow Corning, a stabilized trimethylsilyl-modimeth-icon
  • Dow Corning 929 emulsion containing a hydroxylamino-modified silicone, also referred
  • the alkylamidoamines may be in their quaternized or, as shown, their quaternized form.
  • R 17 can be an aliphatic alk (en) yl radical having 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds, s can assume values between 0 and 5.
  • R 18 and R 19 are each independently H 1 C 1-4 alkyl or hydroxyalkyl.
  • Preferred compounds are fatty acid amidoamines, such as the propyldimethylamine Stearylamido- obtainable under the name Tego Amid ® S 18 or the 3-9124 available Talgamido- propyl-trimethylammo-nium methosulfate under the name Stepantex ® X, which is a good conditioning effect by dye transfer-inhibiting Effect and especially characterized by their good biodegradability.
  • fatty acid amidoamines such as the propyldimethylamine Stearylamido- obtainable under the name Tego Amid ® S 18 or the 3-9124 available Talgamido- propyl-trimethylammo-nium methosulfate under the name Stepantex ® X, which is a good conditioning effect by dye transfer-inhibiting Effect and especially characterized by their good biodegradability.
  • alkylated quaternary ammonium compounds of which at least one alkyl chain is interrupted by an ester group and / or amido group, in particular N-methyl-N (2-hydroxyethyl) -N, N- (ditalgacyloxyethyl) ammonium methosulfate.
  • Suitable nonionic plasticizers are, in particular, polyoxyalkylene glycol alkanoates, polybutylenes, long-chain fatty acids, ethoxylated fatty acid ethanolamides, alkyl polyglycosides, in particular sorbitan mono-, di- and triester and fatty acid esters of polycarboxylic acids.
  • plasticizers may be used in amounts of from 0.1 to 80% by weight, usually from 0.1 to 70% by weight, preferably from 0.2 to 60% by weight and in particular from 0.5 to 40 Wt .-%, in each case based on the total agent to be included.
  • Conditioners according to the invention may preferably contain one or more anionic surfactants, in particular those which have already been described above.
  • Conditioners according to the invention may preferably contain one or more nonionic surfactants, in particular those which have already been described above.
  • gemini surfactants come into consideration. These are generally understood as meaning those compounds which have two hydrophilic groups and two hydrophobic groups per molecule. These groups are usually separated by a so-called “spacer". This spacer is typically a carbon chain that should be long enough for the hydrophilic groups to be spaced sufficiently apart for them to act independently of each other. Such surfactants are generally characterized by an unusually low critical micelle concentration and the ability to greatly reduce the surface tension of the water. In exceptional cases, however, the term gemini surfactants is understood to mean not only dimeric but also trimeric surfactants.
  • Suitable gemini surfactants are, for example, sulfated hydroxy mixed ethers or dimer alcohol bis- and trimer tris sulfates and ether sulfates.
  • End-capped dimeric and trimeric mixed ethers are characterized in particular by their bi- and multi-functionality.
  • the end-capped surfactants mentioned have good wetting properties and are low foaming, so that they are particularly suitable for use in machine washing or cleaning processes.
  • gemini-polyhydroxy fatty acid amides or poly-polyhydroxy fatty acid amides, as described in the relevant prior art.
  • surfactants are polyhydroxy fatty acid amides of the following formula
  • 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 following formula R 24 -OR 25
  • R-CO-N- [Z] in the R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
  • R 24 is a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms
  • R 25 is a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, wherein C 1-4 alkyl or phenyl radicals are preferred and [Z] is a linear polyhydroxyalkyl radical whose alkyl chain having at least two hydroxyl groups substituted, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this radical.
  • [Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a reduced sugar for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy- or N-aryloxy-substituted compounds can then be converted into the desired polyhydroxy fatty acid amides, for example, by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
  • the agents according to the invention preferably also contain amphoteric surfactants.
  • the betaines represent an important class.
  • Betaines are known surfactants which are predominantly produced by carboxyalkylation, preferably carboxymethylation of aminic compounds.
  • the starting materials are condensed with halocarboxylic acids or their salts, in particular with sodium chloroacetate, wherein one mole of salt is formed per mole of betaine.
  • unsaturated carboxylic acids such as acrylic acid is possible.
  • betaines are the carboxyalkylation products of secondary and in particular tertiary amines which follow the formula (IX),
  • R 28 in the R 26 is alkyl and / or alkenyl radicals having 6 to 22 carbon atoms
  • R 27 is hydrogen or alkyl radicals having 1 to 4 carbon atoms
  • R 28 is alkyl radicals having 1 to 4 carbon atoms
  • n is from 1 to 6
  • X 1 is an alkali and / or alkaline earth metal or ammonium.
  • Typical examples are the carboxymethylation products of hexylmethylamine, hexyldimethylamine, octyldimethylamine, decyldimethylamine, dodecylmethylamine, dodecyldimethylamine, dodecylethylmethylamine amine, C ⁇ m cocoalkyldimethylamine, myristyldimethylamine, cetyldimethylamine, stearyldimethylamine, stearylethyl-methylamine, oleyldimethylamine, C 16/ 8- tallowalkyldimethylamine and technical mixtures thereof.
  • R 31 is CO for an aliphatic acyl radical having 6 to 22 carbon atoms and 0 or 1 to 3 double bonds
  • m is a number from 1 to 3 and R 29 , R 30 , n and X 2 are as defined above.
  • Typical examples are reaction products of fatty acids having 6 to 22 carbon atoms, namely caproic, caprylic, capric, lauric, myristic, palmitic, palmitic, stearic, isostearic, oleic, elaidic, petro-, linoleic acid gadoleic, behenic, and, which are condensed with sodium chloroacetate erucic acid and technical mixtures with N, N-dimethylaminoethylamine, N 1 N- dimethylaminopropylamine, N, N-diethylaminoethylamine and N, N-diethylaminopropylamine.
  • Preference is given to the use of a condensation product of C 8 / i 8 coconut fatty acid N, N-dimethylaminopropylamide with sodium chloroacetate.
  • R 32 is an alkyl radical having 5 to 21 carbon atoms
  • R 33 is a hydroxyl group
  • These substances are also known substances which can be obtained, for example, by cyclizing condensation of 1 or 2 moles of fatty acid with polyfunctional amines, such as, for example, aminoethyl-ethanolamine (AEEA) or diethylenetriamine.
  • AEEA aminoethyl-ethanolamine
  • the corresponding carboxyalkylation products are mixtures of different open-chain betaines.
  • Typical examples are condensation products of the above mentioned fatty acids with AEEA, preferably imidazolines based on lauric acid or C, in turn, 12 /, which are then betainized with sodium coconut oil fatty acid 4 i.
  • compositions according to the invention are in liquid form, for example in the form of conditioning agents or liquid detergents etc.
  • the use of both liquid organic solvents and water can be indicated.
  • the agents according to the invention therefore optionally contain solvents.
  • Solvents that can be used in the compositions according to the invention originate, for example, from the group of monohydric or polyhydric alcohols, alkanolamines or glycol ethers, provided they are miscible with water in the concentration range indicated.
  • the solvents are preferably selected from ethanol, n- or i-propanol, butanols, glycol, propane- or butanediol, glycerol, diglycol, propyl- or butyldiglycol, hexylene glycol, 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 ether, butoxy propoxy-propanol (BPP), dipropylene glycol monomethyl, or ethyl ether,
  • glycol ethers are available under the trade names Arcosolv ® (Arco Chemical Co.) or Cellosolve ®, carbitol ® or Propasol ® (Union Carbide Corp.); this includes for example ButylCarbitol® ®, hexyl carbitol ®, MethylCarbitol® ®, and carbitol ® itself, (2- (2-ethoxy) ethoxy) ethanol.
  • Arcosolv ® Arco Chemical Co.
  • Cellosolve ® Cellosolve ®
  • carbitol ® or Propasol ® Union Carbide Corp.
  • ButylCarbitol® ® hexyl carbitol ®
  • MethylCarbitol® ® MethylCarbitol®
  • carbitol ® itself, (2- (2-ethoxy) ethoxy) ethanol.
  • the choice of glycol ether can be readily made by one skilled in the art on the
  • Pyrrolidone solvents such as N-alkyl-pyrrolidones, for example N-methyl-2-pyrrolidone or NC 8 - C 12 -alkyl-pyrrolidone, or 2-pyrrolidone, can also be used.
  • N-alkyl-pyrrolidones for example N-methyl-2-pyrrolidone or NC 8 - C 12 -alkyl-pyrrolidone, or 2-pyrrolidone
  • glycerol derivatives in particular glycerol carbonate.
  • Alcohols which may be preferably used as cosolvents in the present invention include low molecular weight liquid polyethylene glycols, for example, polyethylene glycols having a molecular weight of 200, 300, 400 or 600.
  • Further suitable cosolvents are other alcohols, for example (a) lower alcohols such as ethanol, propanol, isopropanol and n-butanol, (b) ketones such as acetone and methyl ethyl ketone, (c) C 2 -C 4 polyols such as a diol or a triol, for example ethylene glycol, propylene glycol, glycerol or mixtures thereof. Particularly preferred is from the class of diols 1, 2-octanediol.
  • the inventive composition contains one or more solvents from the group comprising C 1 - to C 4 -Monoalko-hole, C 2 - to C 6 glycols, C 3 - to C 2 glycol ethers and glycerol, in particular ethanol ,
  • the inventive C 3 - to C 12 glycol ethers contain alkyl or alkenyl groups having less than 10 carbon atoms, preferably up to 8, especially up to 6, more preferably 1 to 4 and most preferably 2 to 3 carbon atoms.
  • Preferred C 1 to C 4 monoalcohols are ethanol, n-propanol, isopropanol and tert-butanol.
  • Preferred C 2 -C 6 -glycols are ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,5-pentanediol, neopentyl glycol and 1,6-hexanediol, in particular ethylene glycol and 1,2-propylene glycol.
  • Preferred C 3 - to C 2 glycol ethers are di-, tri-, tetra- and pentaethylene glycol, di-, tri- and tetrapropylammonium pylenglykol, Propylenglykolmonotertiärbutylether and propylene glycol monoethyl ether as well as pursuant propanol INCI designated solvent Butoxydiglycol, butoxyethanol, butoxyisopropanol, butoxy, Butyloctanol, ethoxydiglycol, ethoxyethanol, ethyl hexanediol, isobutoxypropanol, isopentyldiol, 3-methoxybutanol, methoxyethanol, methoxyisopropanol and methoxymethylbutanol.
  • the agent according to the invention may contain one or more solvents in an amount of usually up to 40% by weight, preferably 0.1 to 30% by weight, in particular 2 to 20% by weight, more preferably 3 to 15 wt .-%, most preferably 5 to 12 wt .-%, for example, 5.3 or 10.6 wt .-%, each based on the total agent included.
  • the agent according to the invention in particular the conditioning agent, may optionally contain one or more complexing agents.
  • Chelating agents also called sequestering agents, are ingredients that are capable of complexing and inactivating metal ions, for example, to prevent their adverse effects on the stability or appearance of the agents, for example clouding. On the one hand, it is important to complex the incompatible with numerous ingredients calcium and magnesium ions of water hardness. The complexation of the ions of heavy metals such as iron or copper retards the oxidative decomposition of the finished agents.
  • the following complexing agents designated according to INCI are suitable: Aminotrimethylene Phosphonic Acid, Beta-Alanine Diacetic Acid, Calcium Disodium EDTA, Citric Acid, Cyclodextrin, Cyclohexanediamine Tetraacetic Acid, Diammonium Citrate, Diammonium EDTA, Diethylenetriamine Pentamethylene Phosphonic Acid, Dipotassium EDTA, Disodium Azacyloheptane Diphosphonate, Disodium EDTA, Disodium Pyrophosphate, EDTA, Etidronic Acid, Galactic Acid, Gluconic Acid, Glucuronic Acid, HEDTA 1 Hydroxypropyl Cyclodextrin, Methyl Cyclodextrin, Pentapotassium Triphosphate, Pentasodium Aminotrimethylene Phosphonates, Pentasodiene, Ethylenediamines, Tetramethylene Phosphonates, Pentasodium Pentetates, Pentta
  • Preferred complexing agents are tertiary amines, in particular tertiary alkanolamines (aminoalkanol).
  • the alkanolamines have both amino and hydroxy and / or ether groups as functional groups.
  • Particularly preferred tertiary alkanolamines are tri-ethanolamine and tetra-2-hydroxypropyl-ethylenediamine (N, N, N ', N'-tetrakis (2-hydroxy-propyl) ethylenediamine).
  • Particularly preferred combinations of tertiary amines with Zinkricinoleat and one or more ethoxylated fatty alcohols as nonionic solubilizers and optionally solvents are described in the prior art.
  • a particularly preferred complexing agent is etidronic acid (1-hydroxyethylidene-1, 1-diphosphonous acid, 1-hydroxyethyl-1, 1-diphosphonic acid, HEDP, acetophosphonic acid, INCI Etidronic Acid) including their salts.
  • the agent according to the invention accordingly contains etidronic acid and / or one or more of its salts as complexing agent.
  • the agent according to the invention contains a complexing agent combination of one or more tertiary amines and one or more other complexing agents, preferably one or more complexing acids or their salts, in particular triethanolamine and / or tetra-2-hydroxypropylethylenediamine and etidronic acid and / or one or more of their salts.
  • the agent according to the invention in particular conditioner, optionally contains one or more viscosity regulators, which preferably act as thickener.
  • the viscosity of the agent may be measured using standard methods (e.g., Brookfield viscometer RVD-VII at 20 U / min and 2O 0 C 1 spindle 3) are measured.
  • Preferred liquid to gel compositions may have viscosities of 20 to 4000 mPas, with values between 40 and 40 mPas and 2000 mPas may be particularly preferred.
  • Suitable thickeners are inorganic or polymeric organic compounds. It is also possible to use mixtures of several thickeners.
  • the inorganic thickeners include, for example, polysilicic acids, clay minerals such as montmorillonites, zeolites, silicas, aluminum silicates, phyllosilicates and bentonites.
  • the organic thickeners are derived from the groups of natural polymers, modified natural polymers and fully synthetic polymers.
  • Naturally derived polymers which are used as thickeners are, for example, xanthan gum, agar agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, guar gum, gellan gum, locust bean gum, starch, dextrins, gelatin and casein.
  • Modified natural substances are derived primarily from the group of modified starches and celluloses, examples being carboxymethylcellulose and other cellulose ethers, hydroxyethyl and propylcellulose, highly etherified methylhydroxyethylcellulose and core flour ethers.
  • a large group of thickeners which find wide use in a variety of applications, are the fully synthetic polymers such as polyacrylic and polymethacrylic compounds, which may be crosslinked or uncrosslinked and optionally cationically modified, vinyl polymers, polycarboxylic acids, polyethers, activated Polyamide derivatives, castor oil derivatives, polyimines, polyamides and polyurethanes.
  • polyacrylic and polymethacrylic compounds which may be crosslinked or uncrosslinked and optionally cationically modified, vinyl polymers, polycarboxylic acids, polyethers, activated Polyamide derivatives, castor oil derivatives, polyimines, polyamides and polyurethanes.
  • polymers examples include acrylic resins, ethyl acrylate-acrylamide copolymers, acrylic ester-methacrylic acid-ester copolymers, ethyl acrylate-acrylic acid-methacrylic acid copolymers, N-methylolmeth-acrylamide, maleic anhydride-methyl vinyl ether copolymers, polyether-polyol copoly -mere as well as butadiene-styrene copolymers.
  • thickeners are derivatives of organic acids and their alkoxide adducts, for example aryl polyglycol ethers, carboxylated nonylphenol ethoxylate derivatives, sodium alginate, diglycerol monoisostearate, nonionic ethylene oxide adducts, coconut fatty acid diethanolamide, isododecenemene succinic anhydride and galactomannan.
  • organic acids and their alkoxide adducts for example aryl polyglycol ethers, carboxylated nonylphenol ethoxylate derivatives, sodium alginate, diglycerol monoisostearate, nonionic ethylene oxide adducts, coconut fatty acid diethanolamide, isododecenemene succinic anhydride and galactomannan.
  • Thickeners from the mentioned classes of substances are commercially available and are described, for example, under the trade names Acusol®-820 (methacrylic acid (stearyl alcohol-20-EO) ester-acrylic acid copolymer, 30% in water, Rohm & Haas), Da-pral®-GT -282-S (alkyl polyglycol ether, Akzo), Deuterol® polymer-11 (dicarboxylic acid co-polymer, Schöner GmbH), Deuteron®-XG (anionic heteropolysaccharide based on ⁇ -D-glucose, D-manose, D -Glucuronic acid, Schöner GmbH), Deuteron®-XN (nonionic polysaccharide, Schöner GmbH), Dicrylan®-thickener-0 (ethylene oxide adduct, 50% in water).
  • Acusol®-820 methacrylic acid (stearyl alcohol-20-EO) ester-acrylic acid copolymer, 30% in water, Rohm & Ha
  • the agent according to the invention in particular conditioning agent, optionally contains one or more enzymes.
  • Suitable enzymes are, in particular, those from the classes of the hydrolases, such as the proteases, esterases, lipases or lipolytic enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of said enzymes. All of these hydrolases in the wash contribute to the removal of stains such as proteinaceous, greasy or starchy stains and graying. In addition, cellulases and other glycosyl hydrolases may contribute to color retention and to enhancing the softness of the fabric by removing pilling and microfibrils. Oxireductases can also be used for bleaching or inhibiting color transfer.
  • hydrolases such as the proteases, esterases, lipases or lipolytic enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of said enzymes. All of these hydrolases in the wash contribute to the removal of stains such as proteinaceous, greasy or starchy stains and graying.
  • enzymatic agents obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus ichicheniformis, Streptomyceus griseus and Humicola insolens.
  • Bacillus subtilis Bacillus ichicheniformis
  • Streptomyceus griseus and Humicola insolens.
  • subtilisin-type proteases and in particular proteases derived from Bacillus lentus are used.
  • lipolytic enzymes or from protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic enzymes and cellulase, but in particular protease and / or lipase-containing mixtures or mixtures with lipolytic enzymes of particular interest.
  • lipolytic enzymes are the known cutinases.
  • Peroxidases or oxidases have also proved suitable in some cases.
  • Suitable amylases include in particular ⁇ -amylases, iso-amylases, pullulanases and pectinases.
  • cellulases are preferably cellobiohydrolases, endoglucanases and ß-Glucosi-denen, which are also called cellobiases, or mixtures thereof used. Since different cellulase types differ by their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases.
  • the enzymes may be adsorbed as a shaped body to carriers or embedded coated to protect against premature decomposition.
  • the proportion of enzymes, enzyme mixtures or enzymes For example, zymgranulate may be about 0.1 to 5% by weight, preferably 0.12 to about 2% by weight, based on the total agent.
  • the agents according to the invention may contain bleaching agents.
  • bleaching agents include sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Other useful bleaching agents are, for example, peroxopyrophosphates, citrate perhydrates and H 2 O 2 -producing peracidic salts or peracids, such as persulfates or persulfuric acid.
  • the urea peroxohydrate percarbamide which can be described by the formula H 2 N-CO-NH 2 H 2 O 2 , is also useful.
  • the means for cleaning hard surfaces for example in automatic dishwashing
  • they can, if desired, also contain bleaching agents from the group of organic bleaches, although their use is in principle also possible with detergents for textile laundry.
  • Typical organic bleaching agents are the diacyl peroxides, such as, for example, dibenzoyl peroxide.
  • Other typical organic bleaches are the peroxyacids, examples of which include the alkyl peroxyacids and the aryl peroxyacids.
  • Preferred representatives are the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy- ⁇ -naphthoic acid and magnesium monoperphthalate, the aliphatic or substituted aliphatic peroxy acids, such as peroxylauric acid, peroxystearic acid, ⁇ -phthalimidoperacycaproic acid (phthalimidoperoxyhexanoic acid, PAP), O-carboxybenzamidoperoxycaproic acid, N -nonylamidoperadipic acid and N-nonenylamidopersuccinates, and aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelic acid, diperoxysebacic acid, diperoxybrassic acid, the diperoxyphthalic acids, 2-decyldiperoxy- butane-1,4-diacid
  • Dyes can be used in the composition according to the invention, wherein the amount of one or more dyes is to be chosen so low that remain after application of the agent no visible residues.
  • the agent according to the invention is free of dyes.
  • the agent according to the invention may preferably contain one or more antimicrobial agents or preservatives in an amount of usually 0.0001 to 3 wt.%, Preferably 0.0001 to 2 wt.%, In particular 0.0002 to 1 wt. more preferably 0.0002 to 0.2% by weight, most preferably 0.0003 to 0.1% by weight.
  • Antimicrobial agents or preservatives are distinguished depending on the antimicrobial spectrum and mechanism of action between bacteriostats and bactericides, fungistats and fungicides, etc. Important substances from these groups are, for example, benzalkonium chlorides, alkylarylsulfonates, halophenols and phenol mercuriacetate.
  • the terms antimicrobial effect and antimicrobial agent in the context of the teaching of the invention have the usual meaning.
  • Suitable antimicrobial agents are preferably selected from the groups of the alcohols, amines, aldehydes, antimicrobial acids or their salts, carboxylic acid esters, acid amides, phenols, phenol derivatives, diphenyls, diphenylalkanes, urea derivatives, oxygen, nitrogen acetals and formals , Benzamidines, isothiazolines, phthalimide derivatives, pyridine derivatives, antimicrobial surface-active compounds, guanidines, antimicrobial amphoteric compounds, quinolines, 1,2-dibromo-2,4-di-cyanobutane, iodo-2-propyl-butyl-carbamate, iodine, iodophores, Per - oxo compounds, halogen compounds and any mixtures of the above.
  • the antimicrobial agent may be selected from ethanol, n-propanol, i-propanol, 1,3-butanediol, phenoxyethanol, 1,2-propylene glycol, glycerol, undecylenic acid, benzoic acid, salicylic acid, dihydracetic acid, o-phenylphenol, N-methylmorpholine-acetonitrile (MMA), 2-benzyl-4-chlorophenol, 2,2'-methylenebis (6-bromo-4-chlorophenol), 4,4'-di-chloro-2 'hydroxydiphenyl ether (dichlorosilane), 2,4,4'-trichloro-2'-hydroxydiphenyl ether (trichlosan), chlorhexidine, N- (4-chlorophenyl) -N- (3,4-dichlorophenyl) -urea, N, N '- (1, 10-decanediyldi-1-pyridinyl-4-ylid
  • halogenated xylene and cresol derivatives such as p-chlorometacresol or p-chloro-meta-xylene, and natural antimicrobial agents of plant origin (for example, from spices or herbs), of animal and microbial origin.
  • antimicrobial surface-active quaternary compounds a natural antimicrobial agent of plant origin and / or a natural antimicrobial agent of animal origin, most preferably at least one natural antimicrobial agent of plant origin from the group comprising caffeine, theobromine and theophylline and essential oils such as eugenol, thymol and geraniol, and / or at least one natural antimicrobial agent of animal origin from the group, comprising enzymes such as protein from milk, lysozyme and lactoperoxidase, and / or at least one antimicrobial surface-active quaternary compound with an ammonium, sulfonium, phosphonium, iodonium - or Arsonium distr, peroxo compounds and chlorine compounds are used.
  • bacteriocins are preferably used.
  • Glycine, glycine derivatives, formaldehyde, compounds which readily split off formaldehyde, formic acid and peroxides are preferably used.
  • quaternary ammonium compounds QAV
  • Benzalkonium chloride etc.
  • Benzalkonium halides and / or substituted benzalkonium halides are for example commercially available as Barquat ® ex Lonza, Marquat® ® ex Mason Variquat ® ex Witco / Sherex and Hyamine, ® ex Lonza and as Bardac ® ex Lonza.
  • antimicrobial agents are N- (3-chloroallyl) hexaminium chloride such as Dowicide and Dowicil ® ® ex Dow, Benzethonium- chloride such as Hyamine ® 1622 ex Rohm & Haas, methylbenzethonium as Hyamine ® 1ox ex Rohm & Haas, cetylpyridinium chloride such as Cepacol ex Merrell Labs.
  • the agents according to the invention may optionally contain ironing aids for improving the water absorbency, the rewettability of the treated textiles and for ease of ironing the treated textiles.
  • ironing aids for improving the water absorbency, the rewettability of the treated textiles and for ease of ironing the treated textiles.
  • silicone derivatives can be used in the formulations. These additionally improve the rinsing out of the wash-active formulations by their foam-inhibiting properties.
  • Preferred silicone derivatives are, for example, polydialkyl or alkylaryl siloxanes in which the alkyl groups have one to five carbon atoms and are completely or partially fluorinated.
  • Preferred silicones are polydimethylsiloxanes, which may optionally be derivatized and then amino-functional or quaternized or Si-OH, Si-H and / or Si-Cl bonds.
  • the viscosities of the preferred silicones at 25 0 C in the range between 100 and 100,000 mPas, wherein the silicones in amounts between 0.2 and 5 wt .-%, based on the total composition can be used.
  • the agents according to the invention in particular conditioning agents, can be obtained by all known techniques known to the person skilled in the art.
  • the agents can be obtained, for example, by mixing directly from their raw materials, optionally with the use of high-shear mixing equipment.
  • in particular conditioning agents it is recommended to melt, where appropriate, any plasticizer components present and to subsequently disperse the melt in a solvent, preferably water.
  • the polymerizable betaine esters of the formula (I) which can be used according to the invention or polymers which can be prepared from them according to the invention can be incorporated into the conditioning agents by simple admixing.
  • the conditioning agents are preferably present as fabric softeners. They are usually introduced into the rinse cycle of an automatic washing machine.
  • Another object of the invention is a substrate, in particular conditioning substrate, which is impregnated and / or coated with an agent according to the invention, which thus contains the fragrance composition according to the invention and oxidizing agent.
  • Conditioning substrates according to the invention are mainly used in textile treatment and in particular in textile drying processes.
  • the substrate material is preferably made of porous sheet-like cloths. They may consist of a fibrous or cellular flexible material which has sufficient thermal stability for use in the dryer and which can retain sufficient quantities of impregnating or coating agent to effectively condition fabrics without significant bleeding or bleeding during storage By means of done.
  • These wipes include cloths of woven and non-woven synthetic and natural fibers, felt, paper or foam, such as hydrophilic polyurethane foam.
  • Nonwovens are generally defined as adhesively bonded fibrous products having a mat or layered fibrous structure, or those comprising fibrous mats in which the fibers are randomly or randomly distributed.
  • the fibers may be natural such as wool, silk, jute, hemp, cotton, flax, sisal or ramie; or synthetically, such as rayon, cellulose esters, polyvinyl derivatives, polyolefins, polyamides or polyesters. In general, any fiber diameter or titer is suitable for the present invention.
  • the non-woven used here Fabrics do not tend to rupture or disintegrate due to the random or random arrangement of fibers in the nonwoven material that impart excellent strength in all directions, for example, when used in a household tumble dryer.
  • nonwoven fabrics suitable as substrates in the present invention are known, for example, from WO 93/23603.
  • Preferred porous and flat cleaning cloths consist of one or different fiber materials, in particular of cotton, refined cotton, polyamide, polyester or mixtures of these.
  • the cleaning substrates in fabric form preferably have an area of from 10 to 5000 cm 2 , preferably from 50 to 2000 cm 2 , in particular from 100 to 1500 cm 2 and particularly preferably from 200 to 1000 cm 2 .
  • the grammage of the material is usually between 20 and 1000 g / m 2 , preferably from 30 to 500 g / m 2 and in particular from 50 to 150 g / m 2 .
  • Conditioning substrates can be obtained by impregnation or impregnation or else by melting the agents or conditioners according to the invention onto a substrate.
  • the invention further provides for the use of a conditioning agent or a conditioning substrate according to the invention in a textile conditioning process, such as, for example, a final rinse, a textile drying process and a textile drying process or textile drying process.
  • Preferred agents according to the invention are liquid detergents, preferably containing surfactant (s) and other customary ingredients of detergents and cleaners.
  • suitable liquid detergent as a thickening system based in each case on the total agent a) 0, 1 to 5 wt .-% of a polymeric thickener, b) 0.5 to 7 wt .-% of a boron compound and c) 1 to 8 wt. -% of a complexing agent, included.
  • aqueous, higher-viscosity liquid detergents whose content of surfactant (s) is above 35% by weight.
  • Suitable thickening agents also called swelling agents, e.g. Alginates or agar-agar have been described above.
  • Preferred aqueous liquid detergents contain as thickening system 0.2 to 4 wt .-%, preferably 0.3 to 3 wt .-% and in particular 0, 4 to 1, 5 wt .-%, of a polysaccharide.
  • a preferred polymeric thickener is xanthan gum, a microbial anionic heteropolysaccharide produced by Xanthomonas campestris and some other species under aerobic conditions and having a molecular weight of from 2 to 15 million daltons.
  • Xanthan is formed from a chain of ⁇ -1,4-linked glucose (cellulose) with side chains.
  • the structure of the subgroups consists of glucose, mannose, glucuronic acid, acetate and Pyruvate, where the number of pyruvate units determines the viscosity of xanthan gum.
  • Liquid detergents of the invention may preferably contain a boron compound which is used in amounts of from 0.5 to 7% by weight.
  • boron compounds useful in the present invention are boric acid, boric oxide, alkali borates such as ammonium, sodium and potassium ortho-, meta- and pyroborates, borax in its various stages of hydration and polyborates such as alkali metal pentaborates.
  • Organic boron compounds such as esters of boric acid can also be used.
  • Preferred liquid detergents contain 0.5 to 4 wt .-%, preferably 0.75 to 3 wt .-% and in particular 1 to 2 wt .-% boric acid and / or sodium tetraborate.
  • liquid detergents according to the invention may contain 1 to 8% by weight of a complexing agent.
  • Particularly preferred liquid detergents contain citric acid or sodium citrate, preference being given to liquid detergents which contain from 2.0 to 7.5% by weight, preferably from 3.0 to 6.0% by weight and in particular from 4.0 to 5.0 Wt .-% sodium citrate.
  • the liquid detergents according to the invention preferably contain surfactant (s), wherein anionic, nonionic, cationic and / or amphoteric surfactants are used. From an application point of view, preference is given to mixtures of anionic and nonionic surfactants, wherein the proportion of nonionic surfactants may preferably be greater than the proportion of anionic surfactants.
  • surfactant s
  • sugars and / or sugar derivatives such as alkyl polyglucosides or cyclodextrins can also be done.
  • liquid detergents according to the invention contain oxidizing agents and fragrances in accordance with the invention. This applies to all means which have been designated as being according to the invention in the context of this description.
  • liquid detergent of the following composition, wt .-% each based on the total average 16.5 wt .-% linear alkylbenzenesulfonate 10 wt .-% C12-18-fatty alcohol + 7-ethoxy units 1 wt .-% 1-hydroxyethane -1, 1-diphosphonic acid 3 wt .-% sodium citrate 8 wt .-% sodium sulfate
  • Example 1 The formulation of Example 1 was perfumed with a perfume oil I, which included fragrances according to the invention, so that more than 50 wt .-% of the fragrances contained were selected from such fragrances, which at least one of the following classes were attributable saturated alcohols saturated saturated esters ether
  • Example 1 The formulation of Example 1 was perfumed with a conventional perfume oil II typical for washing-things, i.a. including:
  • OTBCA 85% cis-2-tert-butylcyclohexyl acetate / 15% trans-2-tert-butylcyclohexyl acetate
  • Vertofix Coeur juniper, Juniperus mexicana, extract, acetylated, [3R]
  • the degree of preservation of the bleach PAP was at weekly intervals during storage at 25 ° C over a period of 4 weeks for the composition of the invention, ie the liquid detergent according to Example 1 with the perfume of Example 2 (corresponds to "detergent A according to the invention"), and the comparative composition thus the liquid detergent according to Example 1 with that with the conventional detergent perfume from Example 3 (equivalent to Comparative detergent B) assessed.
  • the content of bleach was determined by iodometric titration.
  • the initial content (3% absolute) was set as 100%.
  • the following table shows the bleach contents (in%) after the respective storage times (in weeks) at 25 ° C:
  • Detergent A (according to the invention) 100 99 96 93 89

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Abstract

Fragrant consumer products comprising oxidizing agents are described, which may be, for example, detergents or cleaners or, for example, also cosmetics. These consumer products comprise certain minimum amounts of fragrances of certain classes of substances. They are characterized by very good (storage) stability, both with regard to the fragrance of the product, and also with regard to the potency of the oxidizing agent.

Description

„Oxidationsmittel enthaltende, wohlriechende Verbrauchsprodukte" "Oxidizing agent-containing, fragrant consumable products"
Die vorliegende Erfindung betrifft ein Oxidationsmittel enthaltendes Verbrauchsprodukt, welches eine Riechstoffzusammensetzung umfasst, wobei diese Riechstoffzusammensetzung eine bestimmte Mindestmenge an Riechstoffen bestimmter Stoffklassen enthält Bei den Verbrauchsprodukten handelt es sich z B um Wasch- oder Reinigungsmittel oder z B auch um KosmetikaThe present invention relates to a consumable product containing oxidizing agent, which comprises a fragrance composition, said fragrance composition containing a certain minimum amount of fragrances of certain classes. The consumer products are, for example, washing or cleaning agents or, for example, also cosmetics
Der Einsatz von Riechstoffen in typischen Verbrauchsprodukten wie z B Wasch- oder Reinigungsmitteln dient in der Regel zwei unterschiedlichen Zwecken Zum einen sollen die Produkte als solche beduftet werden, zum anderen sollen die Objekte, auf welche die Produkte wirken, beduftet werden Am Beispiel der Wasch- oder Reinigungsmittel sollen die frisch gereinigten Flächen oder die frisch gewaschene Wäsche einen „frisch gereinigten" Geruchseindruck vermitteln, der möglichst lange anhalten soll, zum anderen soll der zum Teil recht starke Eigengeruch der Wasch- und Reinigungsmittel überdeckt werdenThe use of fragrances in typical consumer products such as detergents usually serves two different purposes. On the one hand, the products should be scented as such, on the other hand, the objects on which the products are to be scented. or detergent should give the freshly cleaned surfaces or freshly washed laundry a "freshly cleaned" olfactory impression that should last as long as possible, on the other hand, the sometimes very strong odor of detergents and cleaners should be covered
Für viele Konsumenten liefert der Duft des Verbrauchsproduktes, z B eines Wasch- oder Reinigungsmittels letztendlich auch eine willkommene Möglichkeit der Differenzierung angesichts eines immer unübersichtlicher werdenden Angebotes an Produkten, z B im Bereich der Wasch- und ReinigungsmittelFor many consumers, the fragrance of the consumer product, eg a washing or cleaning agent, ultimately also provides a welcome opportunity for differentiation in the face of an ever more confusing supply of products, for example in the field of detergents and cleaners
Der Verbraucher möchte deshalb in der Regel ein Produkt erwerben, welches nicht nur gut wirkt, sondern auch sein ästhetisches Empfinden anspricht, z B indem das Produkt als solches oder damit behandelte Objekte einen Wohlgeruch entfalten So erwartet der Verbraucher z B , dass Anschmutzungen auf Textilien oder auch auf harten Oberflachen mit einem entsprechenden Produkt entfernt werden, und überdies erwartet er auch, dass zumindest das Produkt, am besten aber auch das behandelte Objekt angenehm riechen Diese Erwartungshaltung des Verbrauchers ist sogar derart ausgeprägt, dass er z B bei einem gereinigten Objekt auch einen entsprechenden Duft erwartet Fehlt dieser Duft (z B "Citrusfπsche" bei WC-Reinigern), zweifelt der Verbraucher sogar an der tatsächlich vorhandenen Wirkleistung des ProduktesThe consumer therefore usually wants to acquire a product which not only works well, but also appeals to its aesthetic sensibility, for example by the product as such or objects treated with it developing a fragrance. For example, the consumer expects stains on textiles or cosmetics Moreover, it expects that at least the product, but also the treated object will smell pleasant at all. This expectation on the part of the consumer is even so pronounced that, for example, in the case of a cleaned object appropriate fragrance expected missing this fragrance (eg "Citrusfπsche" in toilet cleaners), the consumer even doubts the actual active power of the product
Nachteihgerweise ist eine geeignete Parfumierung von Produkten, insbesondere mit Blick auf die Parfumierung preiswerter Massenprodukte wie z B Wasch- oder Reinigungsmitteln aber nicht nur kostspielig, sondern teilweise auch, z B infolge von Inkompatibilitäten von Inhaltsstoffen mit den empfindlichen Riechstoffen, nur in sehr unzureichender Weise realisierbar, was die Geruchsquali- tät der beduften Produkte anbetrifftNachteihgerweise is a suitable perfuming of products, especially with a view to the perfuming of low-cost mass products such as detergents or cleaners but not only costly, but partially, for example, due to incompatibilities of ingredients with the fragrances sensitive, only in very inadequate manner feasible As far as the odor quality of the scented products is concerned
Ein besonderes Problem stellt dabei eine Parfumierung von Produkten mit Oxidationsvermogen dar Hier wird in vielen Fällen sogar ganz auf eine Parfumierung verzichtet, weil eine Parfumierung solcher Produkte oftmals, insbesondere nach Lagerung, zu erheblichen Produktinstabilitäten führt, so dass sich z.B. ein ursprünglich wohlriechend parfümiertes Produkt nach einigen Wochen der Lagerung geruchlich in dramatischer Weise negativ verändert, so dass es dann nicht einmal mehr neutral, sondern sogar abstoßend wirkt. Das Produkt wird also infolge der Parfümierung unbrauchbar oder unverkäuflich.A particular problem in this case is a perfuming of products with an ability to oxidize. Here, in many cases even completely dispensed with a perfume, because a perfume Such products often, especially after storage, leads to significant product instabilities, so that, for example, an originally fragrant perfumed product after a few weeks of storage odorously changed in a dramatic negative way, so that it is not even neutral, but even repugnant. The product thus becomes unusable or unsaleable as a result of perfuming.
Vor diesem Hintergrund war es die an die vorliegende Erfindung gestellte Aufgabe, eine Möglichkeit bereitzustellen, Probleme bei der Parfümierung von Produkten mit Oxidationsvermögen zu mindern.Against this background, it was the object of the present invention to provide a way to alleviate problems in perfuming products with oxidizing power.
Gelöst wird diese Aufgabe durch ein Oxidationsmittel enthaltendes Verbrauchsprodukt, vorzugsweise Wasch- oder Reinigungsmittel oder kosmetisches Produkt, umfassend eine Riechstoffzusammensetzung, wobei zumindest 50 Gew.-%, vorzugsweise zumindest 60 Gew.-%, vorteilhafterweise zumindest 65 Gew.-%, in vorteilhafterer Weise zumindest 70 Gew.-%, in noch vorteilhafter Weise zumindest 75 Gew.-%, in wiederum vorteilhafter Weise zumindest 80 Gew.-%, in besonders vorteilhafter Weise zumindest 85 Gew.-%, insbesondere zumindest 90 Gew.-% der enthaltenen Riechstoffe aus solchen Riechstoffen ausgewählt sind, welche zumindest einer der folgenden Stoffklassen zuordenbar sind gesättigte Alkohole, vorzugsweise primäre, sekundäre, und/oder tertiäre gesättigte, ggf. verzweigte oder ggf. zyklische Alkohole, gesättigte Ester, ggf. verzweigte oder zyklische gesättigte Ester gesättigte Ether, ggf. verzweigte oder zyklische gesättigte Ether Aromaten mit gesättigten Substituenten, ggf. mit verzweigten, gesättigten Substituenten Nitrile, ggf. ungesättigt in Konjugation mit der Nitrilgruppe gesättigte Acetale, ggf. verzweigte oder zyklische gesättigte Acetale gesättigte Halbacetale, wobei die Gew.-%-Angabe auf die gesamte Riechstoffmenge bezogen ist.This object is achieved by a consumable product containing oxidizing agents, preferably washing or cleaning agent or cosmetic product comprising a fragrance composition, wherein at least 50 wt .-%, preferably at least 60 wt .-%, advantageously at least 65 wt .-%, in a more advantageous manner at least 70 wt .-%, more preferably at least 75 wt .-%, in turn advantageously at least 80 wt .-%, in a particularly advantageous manner at least 85 wt .-%, in particular at least 90 wt .-% of the fragrances contained are selected from those fragrances which are at least one of the following classes of substances attributable saturated alcohols, preferably primary, secondary, and / or tertiary saturated, optionally branched or optionally cyclic alcohols, saturated esters, optionally branched or cyclic saturated esters saturated ethers, optionally branched or cyclic saturated ether aromatics with saturated substituents, optionally branched en, saturated substituents nitriles, optionally unsaturated in conjugation with the nitrile group saturated acetals, optionally branched or cyclic saturated acetals saturated hemiacetals, wherein the wt .-% - refers to the total amount of fragrance.
Bei dem erfindungsgemäßen Verbrauchsprodukt, wobei im folgenden die Begriffe „Verbrauchsprodukt", „Produkt" und „Mittel" synonym verwendet werden, handelt es sich vorzugsweise um ein Wasch- oder Reinigungsmittel oder um ein kosmetisches Mittel. Die erfindungsgemäßen Verbrauchsprodukte können sowohl im Haushalt Verwendung finden, aber sie können auch für industrielle und institutionelle bzw. gewerbliche Zwecke Verwendung finden.The consumption product according to the invention, the terms "consumable product", "product" and "agent" being used interchangeably hereinafter, is preferably a washing or cleaning agent or a cosmetic agent but they can also be used for industrial, institutional or commercial purposes.
Bei den Wasch- oder Reinigungsmitteln handelt es sich insbesondere um flüssige Wasch- oder Reinigungsmittel, auch in Sprayform, jedoch sind auch feste Wasch- oder Reinigungsmittel, insbesondere auch in Tablettenform, Stückform oder Pulverform, bevorzugt. Im Rahmen der Erfindung besonders bevorzugte Mittel sind Waschmittel sowie Waschpflegemittel, vorzugsweise zur Reinigung, Behandlung und/oder Pflege von Fasern bzw. textiler Gegenstände, also Textilwasch-, Textilpflege-, Textilbehandlungs-, Textilnachbehandlungsmittel und Conditioner aller Art. Dazu zählen auch separate Bleichmittel, wie Fleckensalze, flüssige Bleichen, Waschkraftverstärker. Sie können sowohl als Waschmittel-Additiv wie auch zur Vorbehandlung verwendet werden. Dazu zählen auch Hygienespüler, welche vorzugsweise dem letzten Spülgang zugesetzt werden und einen antimikrobiellen Wirkstoff bzw. Oxidantien sowie vorzugsweise nichtionische Tenside enthalten. Dazu zählen auch Gardinenwaschmittel sowie Spezialwaschmittel für weiße Wäsche.The detergents or cleaners are, in particular, liquid detergents or cleaners, also in spray form, but solid detergents or cleaners, in particular also in tablet form, piece form or powder form, are preferred. Agents which are particularly preferred for the purposes of the invention are detergents and cleansing preparations, preferably for cleaning, treatment and / or care of fibers or textile articles, ie textile washing, textile care, textile treatment, textile aftertreatment agents and conditioners of all kinds. These also include separate bleaching agents, such as stain salts, liquid bleaches, detergency boosters. They can be used both as a detergent additive as well as for pretreatment. These include hygiene rinse, which are preferably added to the last rinse and contain an antimicrobial agent or oxidants and preferably nonionic surfactants. These include curtain detergents and special detergents for white laundry.
Zu den bevorzugten Reinigungsmittel zählen unter anderem auch Geschirrspülmittel, insbesondere solche für das maschinelle Geschirrspülen und Reiniger für harte Oberflächen. Besonders bevorzugte Reinigungsmittel, zu denen im Sinne dieser Anmeldung auch die Pflegemittel zählen, sind z.B. insbesondere auch Allzweckreiniger oder Spezial-Reiniger wie vorzugsweise Autopflegemittel bzw.- reiniger, Backofenreiniger, Badreiniger, Entkalkungsmittel, Fassadenreiniger, Fensterreiniger, Fleckentfernungsmittel, Fußbodenpflegemittel, Fußbodenreiniger, Glaskeramikkochfeldreiniger, (Hand-)Geschirrspülmittel, Herdreiniger oder -Pflegemittel, Lederreiniger oder -Pflegemittel, Metallputzmittel, Möbelreiniger oder -Pflegemittel, Rohrreinigungsmittel, Sanitärreiniger, Scheuermittel, Teppichreiniger oder -Pflegemittel, WC-Reiniger, WC-Spülreiniger zum Einhängen in das WC-Becken oder den Spülkasten, vorgenannte jeweils in fester oder flüssiger Form.Dishwashing agents, in particular those for automatic dishwashing and hard surface cleaners, are among the preferred cleaning agents. Particularly preferred cleaning agents, which include the care agents for the purposes of this application, are e.g. in particular also all-purpose cleaners or special cleaners such as preferably car care or cleaner, oven cleaner, bathroom cleaner, decalcifier, facade cleaner, window cleaner, stain remover, floor care products, floor cleaner, glass ceramic hob cleaner, (hand) dishwashing detergent, stove cleaner or care products, leather cleaners or care products, metal cleaning agents , Furniture cleaner or care products, pipe cleaner, sanitary cleaner, scouring agent, carpet cleaner or care products, toilet cleaner, toilet flush cleaner for hanging in the toilet bowl or the cistern, the aforementioned each in solid or liquid form.
Zu den bevorzugtesten Reinigungsmitteln zählen insbesondere die Maschinengeschirrspülmittel.The most preferred cleaning agents include, in particular, the machine dishwashing detergents.
Zu den bevorzugten Reinigungsmitteln zählen u.a. auch die Toilettenreiniger bzw. WC-Reiniger, also Produkte zur Reinigung von WC-Becken sowie Urinalen, welche vorzugsweise als Pulver, Tabletten, Formkörper oder Flüssigkeiten, vorzugsweise Gele, angeboten werden. Neben Oxida- tionsmitteln und Riechstoffen sowie anderen üblichen Inhaltsstoffen wie vorzugsweise Tensiden können sie vorzugsweise organische Säuren (z.B. Citronensäure und/oder Milchsäure) oder vorzugsweise Natriumhydrogensulfat, Amidoschwefelsäure oder Phosphorsäure zur Entfernung von Kalkablagerungen oder so genannten Urinsteinen enthalten. Zum Einhängen in das WC-Becken oder den Spülkasten werden Spülreiniger verwendet, diese geben vorzugsweise geringe Mengen an Säure, Tensid, Oxidationsmittel und/oder Riechstoff ab und verlangsamen dadurch das Ansetzen von Verschmutzungen.Among the preferred cleaning agents include i.a. also the toilet cleaner or toilet cleaner, ie products for cleaning toilet bowls and urinals, which are preferably as powder, tablets, shaped bodies or liquids, preferably gels offered. In addition to oxidizing agents and fragrances, as well as other common ingredients such as preferably surfactants, they may preferably contain organic acids (e.g., citric acid and / or lactic acid) or, preferably, sodium bisulfate, amidosulfuric acid, or phosphoric acid to remove lime deposits or so-called urine stones. For hanging in the toilet bowl or cistern flushing detergents are used, these preferably give small amounts of acid, surfactant, oxidizing agent and / or fragrance and thereby slow down the preparation of soiling.
Typische Bestandteile insbesondere eines festen WC-Reinigers, vorzugsweise Pulver, können z.B. vorzugsweise aus folgenden ausgewählt sein: anionische Tenside, vorzugsweise 0-40 Gew.-%, vorteilhafterweise 0,1-30 Gew.-%, insbesondere 15-20 Gew.-% - nichtionische Tenside, vorzugsweise 0-10 Gew. -%Typical constituents, in particular of a solid toilet cleaner, preferably powder, may, for example, preferably be selected from the following: anionic surfactants, preferably 0-40 wt.%, Advantageously 0.1-30 wt.%, In particular 15-20 wt. % nonionic surfactants, preferably 0-10% by weight
- organische Säuren bzw. saure Salze, vorzugsweise 3-50 Gew.-%, vorzugsweise 5-10 Gew.-%organic acids or acid salts, preferably 3-50% by weight, preferably 5-10% by weight
- anorganische Säuren bzw. saure Salze, vorzugsweise 3-95 Gew.-%, insbesondere 25-90 Gew.-%inorganic acids or acid salts, preferably 3-95% by weight, in particular 25-90% by weight
- Alkalien, vorzugsweise 0-10 Gew. -%, insbesondere bis 5 Gew.-%Alkalis, preferably 0-10% by weight, in particular up to 5% by weight
- Natriumhydrogencarbonat, vorzugsweise 0-30 Gew.-%Sodium hydrogencarbonate, preferably 0-30% by weight
- Neutralsalze, vorzugsweise 0-30 Gew.-%Neutral salts, preferably 0-30% by weight
- Natriumcarbonat, vorzugsweise 0-10 Gew.-%Sodium carbonate, preferably 0-10% by weight
- Cellulose, vorzugsweise 0-5 Gew.-%, insbesondere 1 - 2 Gew.-%,Cellulose, preferably 0-5% by weight, in particular 1-2% by weight,
- Komplexbildner, vorzugsweise 0-10 Gew.-%, insbesondere 0,1 bis 5 Gew.-%- complexing agent, preferably 0-10 wt .-%, in particular 0.1 to 5 wt .-%
- Farbstoff, vorzugsweise <1 Gew.-%Dye, preferably <1% by weight
- Riechstoff, vorzugsweise 0,01-10 Gew.-%Perfume, preferably 0.01-10% by weight
- Oxidationsmittel, vorzugsweise 0,01-25 Gew.-%, insbesondere 0,1-20 Gew.-%, wobei die Gew.-%-Angabe jeweils auf das gesamte Mittel bezogen ist.- Oxidizing agent, preferably 0.01-25 wt .-%, in particular 0.1-20 wt .-%, wherein the wt .-% - in each case based on the total average.
Typische Bestandteile eines insbesondere flüssigen WC-Reinigers, können z.B. vorzugsweise aus folgenden ausgewählt sein: anionische Tenside, vorzugsweise 0-30 Gew.-%, vorteilhafterweise 0,1-20 Gew.-% insbesondere 1-10 Gew. -% nichtionische Tenside, vorzugsweise 0-20 Gew.-%, insbesondere 1-10 Gew.-% organische Säuren bzw. saure Salze, vorzugsweise 0-50 Gew.-%, vorteilhafterweise 4-40Typical constituents of a particularly liquid WC cleaner may be e.g. preferably be selected from the following: anionic surfactants, preferably 0-30 wt .-%, advantageously 0.1-20 wt .-%, in particular 1-10 wt -.% Nonionic surfactants, preferably 0-20 wt .-%, in particular 1 -10% by weight of organic acids or acid salts, preferably 0-50% by weight, advantageously 4-40
Gew.-%, insbesondere 3-30 Gew.-% anorganische Säuren bzw. saure Salze, vorzugsweise 0-5 Gew.-%, insbesondere 0-2 Gew.-%% By weight, in particular 3-30% by weight of inorganic acids or acid salts, preferably 0-5% by weight, in particular 0-2% by weight
Natriumhydrogencarbonat, vorzugsweise 0-10 Gew.-%Sodium hydrogencarbonate, preferably 0-10% by weight
Neutralsalze, vorzugsweise 0-10 Gew.-%Neutral salts, preferably 0-10% by weight
Cellulose, vorzugsweise 0-5 Gew.-%Cellulose, preferably 0-5% by weight
Farbstoff, vorzugsweise <1 Gew.-%Dye, preferably <1% by weight
Riechstoff, vorzugsweise 0,01-10 Gew.-%, insbesondere 0,05-5 Gew.-%Perfume, preferably 0.01-10% by weight, in particular 0.05-5% by weight
Verdickungsmittel, z.B. Xanthan, vorzugsweise 0-5 Gew.-%Thickening agents, e.g. Xanthan, preferably 0-5% by weight
Wasser, vorzugsweise 0-99 Gew.-%Water, preferably 0-99% by weight
Oxidationsmittel, vorzugsweise 0,01-25 Gew.-%, insbesondere 0, 1-20 Gew.-%, wobei die Gew.-%-Angabe jeweils auf das gesamte Mittel bezogen ist.Oxidizing agent, preferably 0.01-25 wt .-%, in particular 0, 1-20 wt .-%, wherein the wt .-% indication in each case based on the total mean.
Typische Bestandteile eines Spülreinigers (fest) zum Einhängen in das WC-Becken oder den Spülkasten können vorzugsweise aus folgenden ausgewählt sein: Tenside, z B APG, Fettalkoholethoxylate, Fettalkylsulfate, Fettalkylethersulfate, lineare Alkyl- benzolsulfonate, Alkansulfonate usw , vorzugsweise in Mengen von 0-40 Gew -%, insbesondere 15-30 Gew -%,Typical components of a rinsing cleaner (solid) for hanging in the toilet bowl or the cistern may preferably be selected from the following: Surfactants, for example APG, fatty alcohol ethoxylates, fatty alkyl sulfates, fatty alkyl ether sulfates, linear alkylbenzenesulfonates, alkanesulfonates etc., preferably in amounts of 0-40% by weight, in particular 15-30% by weight,
Säuren bzw saure Salze, z B Ameisensäure, Essigsäure, Zitronensäure, Amidosulfonsaure, Natriumhydrogensulfat, Kokosfettsäuren usw , vorzugsweise in Mengen von 0-20 Gew -%, insbesondere 0,1-15 Gew -%,Acids or acidic salts, for example formic acid, acetic acid, citric acid, amidosulfonic acid, sodium hydrogensulfate, coconut fatty acids, etc., preferably in amounts of 0-20% by weight, in particular 0.1-15% by weight,
Komplexbildner, z B Natπumcitrat, Natπumphosphonat, vorzugsweise in Mengen von 0-10 Gew -%, insbesondere 0,1-5 Gew -%,Complexing agents, for example sodium citrate, sodium phosphonate, preferably in amounts of 0-10% by weight, in particular 0.1-5% by weight,
Füllstoffe, z B Natriumsulfat, vorzugsweise in Mengen von 0-60 Gew -%, insbesondere 0,1-30 Gew -%,Fillers, for example sodium sulphate, preferably in amounts of 0-60% by weight, in particular 0.1-30% by weight,
Farbstoff, vorzugsweise <1 Gew -%Dye, preferably <1% by weight
Riechstoff, vorzugsweise 0,01-10 Gew -%, insbesondere 0,05-5 Gew -% Oxidationsmittel, vorzugsweise 0,01-25 Gew -%, insbesondere 0,1-20 Gew -%, wobei die Gew -%-Angabe jeweils auf das gesamte Mittel bezogen istPerfume, preferably 0.01-10% by weight, in particular 0.05-5% by weight of oxidizing agent, preferably 0.01-25% by weight, in particular 0.1-20% by weight, the percent by weight indicating in each case based on the total mean
Typische Bestandteile eines Spulreinigers (flussig) zum Einhangen in das WC-Becken oder denTypical components of a rinsing cleaner (liquid) for hanging in the toilet bowl or the
Spulkasten können vorzugsweise aus folgenden ausgewählt seinWinding boxes may preferably be selected from the following
Tenside, z B APG, Fettalkoholethoxylate, Fettalkylsulfate, Fettalkylethersulfate, lineare Alkyl- benzolsulfonate, Alkansulfonate usw , vorzugsweise in Mengen von 0-30 Gew -%, insbesondere 5-20 Gew -%,Surfactants, for example APG, fatty alcohol ethoxylates, fatty alkyl sulfates, fatty alkyl ether sulfates, linear alkylbenzenesulfonates, alkanesulfonates etc., preferably in amounts of 0-30% by weight, in particular 5-20% by weight,
Säuren bzw saure Salze, z B Ameisensäure, Essigsaure, Zitronensäure, Amidosulfonsaure, Natriumhydrogensulfat, Kokosfettsäuren usw , vorzugsweise in Mengen von 0-10 Gew -%, insbesondere 0,1-5 Gew -%,Acids or acidic salts, for example formic acid, acetic acid, citric acid, amidosulfonic acid, sodium hydrogensulfate, coconut fatty acids, etc., preferably in amounts of 0-10% by weight, in particular 0.1-5% by weight,
Komplexbildner, z B Natπumcitrat, Natπumphosphonat, vorzugsweise in Mengen von 0-10 Gew -%, insbesondere 0,1-5 Gew -%, Wasser, Lösungsmittel, vorzugsweise 0-99 Gew -%, Farbstoff, vorzugsweise <1 Gew -% Riechstoff, vorzugsweise 0,01-10 Gew -% Oxidationsmittel, vorzugsweise 0,01-25 Gew -%, insbesondere 0,1-20 Gew -%, wobei die Gew -%-Angabe jeweils auf das gesamte Mittel bezogen istComplexing agent, for example sodium citrate, sodium phosphonate, preferably in amounts of 0-10% by weight, in particular 0.1-5% by weight, water, solvent, preferably 0-99% by weight, dye, preferably <1% by weight fragrance , preferably 0.01-10% by weight of oxidizing agent, preferably 0.01-25% by weight, in particular 0.1-20% by weight, the percentage by weight in each case being based on the total agent
Zu den bevorzugten Reinigungsmitteln zählen u a auch die Rohrreinigungsmittel bzw Abflußremi- ger Dies sind vorzugsweise stark alkalische Präparate, welche in der Regel der Beseitigung von Rohr-Verstopfungen aus organischen Materialien - wie Haare, Fett, Nahrungsmittel-Reste, Seifen- Ablagerungen etc - dienen Zur Bildung von H2-GaS mit Sprudel-Effekt können z B Zusätze von AI- oder Zn-Pulver dienen Mögliche Inhaltsstoffe, neben Oxidationsmittel und Riechstoffen, sind vorzugsweise Alkalien, alkalische Salze und Neutralsalze In pulverförmigen Anbietungsformen sind vorzugsweise auch Natriumnitrat und Natriumchlorid enthalten Rohrreinigungsmittel in flussi- ger Form können vorzugsweise auch Hypochlorit enthalten. Daneben gibt es auch Abflußreiniger auf Enzymbasis. Saure Präparate sind ebenfalls möglich. Oxidationsmittel ist vorzugsweise in Mengen von 0,01 bis 60 Gew.-%, insbesondere in Mengen bis 40 Gew.-% enthalten, Riechstoffe vorzugsweise in Mengen von 0,01-10 Gew.-%, wobei die Gew.-%-Angabe jeweils auf das gesamte Mittel bezogen ist.The preferred cleaning agents include, inter alia, the pipe cleaning agents or Abflußremi- ger These are preferably strong alkaline preparations, which are usually the elimination of pipe blockages of organic materials - such as hair, fat, food residues, soaps deposits etc - serve Zur Formation of H 2 -GaS with a sparkling effect can serve as additives of AI or Zn powder. Possible ingredients, in addition to oxidizing agents and fragrances, are preferably alkalis, alkaline salts and neutral salts. In powdered formulations, preferably sodium nitrate and sodium chloride are also contained in pipe cleaners flussi- ger form may preferably contain hypochlorite. In addition, there are also drain cleaner on Enzymbasis. Acid preparations are also possible. Oxidizing agent is preferably present in amounts of 0.01 to 60 wt .-%, in particular in amounts up to 40 wt .-%, fragrances preferably in amounts of 0.01-10 wt .-%, wherein the wt .-% statement in each case based on the total mean.
Zu den bevorzugten Reinigungsmitteln zahlen u.a. auch die Universal- oder Allzweckreiniger bzw. Allesreiniger. Dies sind universell einsetzbare Reiniger für alle harten Oberflächen in Haushalt und Gewerbe, welche nass oder feucht abwischbar sind. In der Regel handelt es sich um neutrale oder schwach alkalische bzw. schwach saure Produkte, insbesondere Flüssigprodukte. Insbesondere Allzweckreiniger bzw. Allesreiniger können Inhaltsstoffe, ausgewählt aus den folgenden enthalten: Tenside [z.B. Alkansulfonate (SAS), Alkylbenzolsulfonate (LAS), Alkylpolyglucoside (APG), Fettalkoholpolyglycolethersulfate (FAES), Fettalkoholpolyglycolether (FAE, FAEO], vorzugsweise 0-25 Gew.-%, insbesondere 0,1 bis 20 Gew.-%Among the preferred cleaning agents pay u.a. also the universal or all-purpose cleaner or all-purpose cleaner. These are universally applicable cleaners for all hard surfaces in household and commercial, which are wet or damp wipeable. As a rule, these are neutral or weakly alkaline or weakly acidic products, in particular liquid products. In particular, all-purpose cleaners may contain ingredients selected from the following: surfactants [e.g. Alkanesulfonates (SAS), alkylbenzenesulfonates (LAS), alkylpolyglucosides (APG), fatty alcohol polyglycol ether sulfates (FAES), fatty alcohol polyglycol ethers (FAE, FAEO), preferably 0-25% by weight, in particular 0.1 to 20% by weight
Gerüststoffe [z.B. Trinatriumcitrat, Natriumsalz der Nitrilotriessigsäure, Natriumphosphonat, Pentanatriumtriphosphat ] vorzugsweise 0-10 Gew.-%, insbesondere 0,1 bis 5 Gew.-% Lösemittel und Hydrotrope [z.B. Ethanol, Propylenglycolether, Natriumtoluol- oder -cumolsulfo- nat], vorzugsweise 0-10 Gew.-%, insbesondere 0,1 bis 5 Gew.-% Farbstoffe, vorzugsweise <1 Gew.-%Builders [e.g. Trisodium citrate, sodium nitrilotriacetic acid salt, sodium phosphonate, pentasodium triphosphate] preferably 0-10% by weight, especially 0.1 to 5% by weight, of solvent and hydrotrope [e.g. Ethanol, propylene glycol ether, sodium toluene or cumene sulfonate], preferably 0-10% by weight, in particular 0.1 to 5% by weight of dyes, preferably <1% by weight
Riechstoff, vorzugsweise 0,01-10 Gew.-%, insbesondere 0,05-5 Gew.-% Konservierungsmittel,Perfume, preferably 0.01-10% by weight, in particular 0.05-5% by weight preservative,
Oxidationsmittel, vorzugsweise 0,01-30 Gew.-%, insbesondere 0,1-20 Gew.-% Säuren, wie z.B. Essigsäure, Citronensäure, Maleinsäure, vorzugsweise 0,1-10 Gew.-%, insbesondere 0,1-5 Gew.-% im Falle schwach alkalisch eingestellte Allzweckreiniger auch Alkalien, z.B. Natronlauge, Soda, vorzugsweise 0-5 Gew.-% Wasser, vorzugsweise 0-99 Gew.-%, wobei die Gew. -%-Angabe jeweils auf das gesamte Mittel bezogen ist.Oxidizing agent, preferably 0.01-30% by weight, especially 0.1-20% by weight of acids, e.g. Acetic acid, citric acid, maleic acid, preferably 0.1-10% by weight, in particular 0.1-5% by weight in the case of weakly alkaline all-purpose cleaners, also alkalis, e.g. Sodium hydroxide solution, soda, preferably 0-5 wt .-% water, preferably 0-99 wt .-%, wherein the wt .-% - in each case based on the total mean.
Es gibt auch speziell desinfizierende Allzweckreiniger. Diese enthalten zusätzlich antimikrobielle Wirkstoffe (z.B. Alkohole, quartäre Ammonium-Verbindungen, Amphotenside, Triclosan) oder vermehrt Oxidationsmittel, z.B. vorzugsweise >1 Gew.-%, wobei die Gew.-%-Angabe auf das gesamte Mittel bezogen ist.There are also special disinfecting all-purpose cleaners. These additionally contain antimicrobial agents (e.g., alcohols, quaternary ammonium compounds, amphoteric surfactants, triclosan) or more oxidizing agents, e.g. preferably> 1% by weight, the percentage by weight being based on the total agent.
Zu den bevorzugten Reinigungsmitteln zählen u.a. auch die Sanitärreiniger. Hierbei handelt es sich um Produkte zur Reinigung in Bad und Toilette. Die alkalischen Sanitärreiniger werden vorzugsweise zur Entfernung von Fettschmutz eingesetzt, während die sauren Sanitärreiniger vor allem zur Entfernung von Kalkablagerungen herangezogen werden. Sanitärreiniger haben vorteilhafter- weise auch eine erhebliche desinfizierende Wirkung, insbesondere die stark alkalischen, Chlorhaltigen Sanitärreiniger.The preferred cleaning agents include, among others, the sanitary cleaners. These are products for cleaning in the bathroom and toilet. The alkaline sanitary cleaners are preferably used to remove grease, while the acidic sanitary cleaners are used primarily for the removal of limescale. Sanitary cleaners have advantageous wise also a significant disinfecting effect, especially the strong alkaline, chlorine-containing sanitary cleaner.
Insbesondere die Bestandteile alkalischer Sanitärreiniger können Inhaltsstoffe enthalten, auswählbar aus folgenden: anionische Tenside, vorzugsweise 0-10 Gew.-%, insbesondere 1-5 Gew.-% nichtionische Tenside, vorzugsweise 0-5 Gew.-%, insbesondere 1-3 Gew.-% Natriumhydroxid, vorzugsweise 0-10 Gew.-%, insbesondere 1-5 Gew.-% Oxidationsmittel, z.B. Natriumhypochlorit bzw. Calciumhypochlorit oder Wasserstoffperoxid, vorzugsweise 0,01-10 Gew.-%, insbesondere 1-5 Gew.-% Riechstoff vorzugsweise 0,01-10 Gew.-%, insbesondere 0,05-5Gew.-%, Wasser, vorzugsweise 0-99 Gew.-%, wobei die Gew. -%-Angabe jeweils auf das gesamte Mittel bezogen ist.In particular, the components of alkaline sanitary cleaners may contain ingredients, selectable from the following: anionic surfactants, preferably 0-10 wt .-%, in particular 1-5 wt .-% of nonionic surfactants, preferably 0-5 wt .-%, in particular 1-3 wt .-% sodium hydroxide, preferably 0-10 wt .-%, in particular 1-5 wt .-% oxidizing agent, for example Sodium hypochlorite or calcium hypochlorite or hydrogen peroxide, preferably 0.01-10% by weight, in particular 1-5% by weight of perfume, preferably 0.01-10% by weight, in particular 0.05-5% by weight, of water, preferably 0-99 wt .-%, wherein the wt .-% - is in each case based on the total average.
Sauere Sanitärreiniger enthalten vorzugsweise keine Alkalien, dafür Säure oder saure Salze, vorzugsweise in Mengen von 0.01-30 Gew.-%, wobei die Gew.-%-Angabe auf das gesamte Mittel bezogen ist.Acid sanitary cleaners preferably contain no alkalis, but acid or acid salts, preferably in amounts of 0.01-30 wt .-%, wherein the wt .-% - refers to the total average.
Zu den bevorzugten Reinigungsmitteln zählen u.a. auch die Backofenreiniger bzw. Grillreiniger, welche vorteilhafterweise in Form von Gelen oder Schaumsprays angeboten werden. Diese dienen in der Regel zur Entfernung angebrannter oder verkohlter Speisereste. Vorzugsweise sind Backofenreiniger z.B. mit Natriumhydroxid, Natriummetasilicat, 2-Aminoethanol stark alkalisch eingestellt. In der Regel enthalten sie außerdem vorzugsweise anionische und/oder nichtionische Tenside, vorzugsweise wasserlösliche Lösemittel und vorzugsweise Verdickungsmittel wie Polycar- boxylate, Carboxymethylcellulose, sowie Oxidationsmittel und Riechstoffe.Among the preferred cleaning agents include i.a. also the oven cleaner or grill cleaner, which are advantageously offered in the form of gels or foam sprays. These are usually used to remove burnt or charred food particles. Preferably, oven cleaners are e.g. strongly alkaline with sodium hydroxide, sodium metasilicate, 2-aminoethanol. In general, they also preferably contain anionic and / or nonionic surfactants, preferably water-soluble solvents and preferably thickeners such as polycarboxylates, carboxymethylcellulose, as well as oxidizing agents and fragrances.
Zu den bevorzugten Reinigungsmitteln zählen u. a. auch die Metallputzmittel. Das sind Reiniger für bestimmte Metalltypen wie Edelstahl oder Silber. Edelstahlreiniger enthalten vorzugsweise neben Säuren (vorzugsweise bis 3 Gew.-%, z.B. Citronensäure, Milchsäure), Tensiden (insbesondere bis 5% Gew.-%, vorzugsweise nichtionische und/oder anionische Tenside), Wasser auch Lösemittel (vorzugsweise bis 15 Gew.-%) zur Beseitigung fetthaltiger Verschmutzungen sowie weitere Stoffe wie z. B. Verdicker und Konservierungsmittel. Sehr feine Polierkörper sind zudem in Produkten für vorzugsweise glänzende Edelstahloberflächen enthalten. Silberputzmittel wiederum sind vorzugsweise sauer eingestellt. Sie enthalten insbesondere zur Entfernung schwarzer Beläge von Silbersulfid vorzugsweise Komplexbildner (z.B. Thioharnstoff, Natriumthiosulfat). Typische Angebotsformen sind Putztücher, Tauchbäder, Pasten, Flüssigkeiten. Zur Beseitigung dunkler Verfärbungen (Oxidschichten) dienen Kupfer- und Buntmetallreiniger (z.B. für Messing und Bronze). Diese sind in der Regel schwach alkalisch (vorzugsweise mit Ammoniak) eingestellt und enthalten in der Regel Poliermittel sowie vorzugsweise auch Ammoniumseifen und/oder Komplexbildner. Zu den bevorzugten Reinigungsmitteln zählen u.a. auch die Glasreiniger bzw. Fensterreiniger. Diese dienen vorzugsweise zur Beseitigung insbesondere von fetthaltigem Schmutz von Glasoberflachen. Sie beinhalten vorzugsweise Stoffe, welche vorteilhafterweise aus den folgenden auswählbar sind: anionische und/oder nichtionische Tenside (insbesondere bis 5 Gew.-%),The preferred cleaning agents include, inter alia, the metal cleaning agents. These are cleaners for certain metal types such as stainless steel or silver. Stainless steel cleaners preferably contain not only acids (preferably up to 3% by weight, eg citric acid, lactic acid), surfactants (in particular up to 5% by weight, preferably nonionic and / or anionic surfactants), water also solvents (preferably up to 15% by weight). %) to eliminate greasy soiling and other substances such. As thickeners and preservatives. Very fine polishing bodies are also contained in products for preferably glossy stainless steel surfaces. Silver cleaning agents, in turn, are preferably acidified. They contain, in particular for removing black deposits of silver sulfide, preferably complexing agents (eg thiourea, sodium thiosulfate). Typical offer forms are cleaning cloths, dip baths, pastes, liquids. To remove dark discolorations (oxide layers), copper and non-ferrous metal cleaners (eg for brass and bronze) are used. These are usually adjusted to weakly alkaline (preferably with ammonia) and usually contain polishing agents and preferably also ammonium soaps and / or complexing agents. Among the preferred cleaning agents include the glass cleaner or window cleaner. These are preferably used to eliminate in particular fatty greasy soil from glass surfaces. They preferably contain substances which are advantageously selectable from the following: anionic and / or nonionic surfactants (in particular up to 5% by weight),
Ammoniak und/oder Ethanolamin (insbesondere bis 1 Gew.-%),Ammonia and / or ethanolamine (in particular up to 1% by weight),
Ethanol und/oder 2-Pro-panol, Glykolether ( insbesondere 10-30 Gew.-%),Ethanol and / or 2-propanol, glycol ether (in particular 10-30% by weight),
Wasser,Water,
Konservierungsstoffe,Preservatives,
Farbstoffe,dyes,
Riechstoffe,fragrances,
Oxidationsmittel,Oxidant
Beschlagverhinderungsmittel etc, wobei die Gew.-%-Angabe jeweils auf das gesamte Mittel bezogen ist.Anti-fogging agent etc, wherein the wt .-% indication in each case based on the total mean.
Zu den bevorzugten Reinigungsmitteln zählen u.a. auch alle Spezialreinigungsmittel, z.B. solche für Kochfelder aus Glaskeramik, sowie Teppich- und Polsterreiniger und Fleckentfernungsmittel.Among the preferred cleaning agents include i.a. also all special cleaning agents, e.g. such as ceramic hobs, as well as carpet and upholstery cleaners and stain removers.
Erfindungsgemäß bevorzugte Produkte sind auch Autopflegemittel. Zu den bevorzugten Autopflegemitteln zählen u.a. Lackkonservierer, Lackpolituren, Lackreiniger, Waschkonservierer, Shampoos zur Autowäsche, Autowasch- und Wachsprodukte, Polituren für Ziermetalle, Schutzfilme für Ziermetalle, Kunststoff-Reiniger, Teerentferner, Scheibenreiniger, Motorreiniger etc.Products preferred according to the invention are also car care products. Among the preferred car care products include u.a. Paint preservatives, paint polishes, paint cleaners, washing preservatives, shampoos for car wash, car wash and wax products, polishes for decorative metals, protective films for decorative metals, plastic cleaner, tar remover, window cleaner, engine cleaner etc.
Die erfindungsgemäßen Reiniger können ganz allgemein zur Reinigung von Oberflächen wie Glas, Porzellan, Kunststoff, Textilien, Leder, Lacken oder Holz verwendet werden.The cleaners of the invention can be used in general for cleaning surfaces such as glass, porcelain, plastic, textiles, leather, paints or wood.
Die institutionellen bzw. gewerblichen Reiniger, welche in der Regel in Form von Großgebinden verfügbar gemacht werden, sind vorzugsweise für die betriebliche Reinigung und Hygiene z.B. in öffentlichen Gebäuden, Schulen, Bürogebäuden, Hotels, Gaststätten und Krankenhäusern konzipiert, wobei solche Produkte vorzugsweise so ausgestaltet sind, dass vorzugsweise eine sichere Flächendesinfektion gewährleistet werden kann. So können z.B. größere Mengen an Oxidationsmittel enthalten sein, z.B. >1 Gew.-% oder >3 Gew.-% oder >5 Gew.-%, wobei die Gew.-%-Angabe jeweils auf das gesamte Mittel bezogen ist.The institutional or commercial cleaners, which are usually made available in the form of large containers, are preferably for the operational cleaning and hygiene, e.g. designed in public buildings, schools, office buildings, hotels, restaurants and hospitals, such products are preferably designed so that preferably a safe surface disinfection can be guaranteed. Thus, e.g. greater amounts of oxidizing agent, e.g. > 1 wt .-% or> 3 wt .-% or> 5 wt .-%, wherein the wt .-% indication in each case based on the total mean.
Technische Reiniger gelangen im allgemeinen in der Industrie, nämlich insbesondere in der Getränke-, Metall-, Nahrungsgüter-, kosmetischen und pharmazeutischen Industrie zum Einsatz, z.B. als Reiniger für Kfz-Waschanlagen, Tankwagen- u. Flugzeug-Reiniger. Vorteilhafterweise können insbesondere technische Reiniger mit besonders schaumarmen Tensi- den (z B spezielle nichtionische Tenside, wie Ethylenoxid-Propylenoxid-Blockcopolymere und so genannte endgruppenverschlossene Alkylethoxylate) formuliert sein, um eine ggf erforderliche Produktivität zu erreichenTechnical cleaners are generally used in industry, namely in particular in the beverage, metal, food, cosmetic and pharmaceutical industries used, for example as a cleaner for car washes, Tankwagen- u. Aircraft cleaner. Advantageously, in particular technical cleaners with particularly low-foaming surfactants (for example special nonionic surfactants, such as ethylene oxide-propylene oxide block copolymers and so-called end-capped alkyl ethoxylates) may be formulated in order to achieve a possibly required productivity
Hier können z B größere Mengen an Oxidationsmittel enthalten sein, z B >1 Gew -% oder >3 Gew -% oder >5 Gew -%, wobei die Gew -%-Angabe jeweils auf das gesamte Mittel bezogen istHere, for example, larger amounts of oxidizing agent may be contained, for example,> 1% by weight or> 3% by weight or> 5% by weight, the weight percentage being based in each case on the total agent
Zu den erfindungsgemäß bevorzugten kosmetischen Mitteln zählen insbesondereThe inventively preferred cosmetic agents include in particular
(a) solche zur Hautpflege, wie vorzugsweise Badepraparate, Hautwasch- u -reinigungsmittel, Hautpflegemittel, Augenkosmetika, Lippenpflegemittel, Nagelpflegemittel, Intimpflegemittel, Fußpflegemittel(a) those for skin care, such as, preferably, bath preparations, skin cleansers, skin care products, ocular cosmetics, lip care products, nail care products, personal care products, foot care products
(b) solche mit spezieller Wirkung, wie vorzugsweise Depigmentierungsmittel, Desodorantien, Anti- hidrotika, Haarentfernungsmittel, Rasiermittel, Duftmittel(b) those having a specific action, such as, preferably, depigmenting agents, deodorants, antihidrotic agents, hair removing agents, shaving agents, fragrances
(c) solche zur Zahn- und Mundpflege, wie vorzugsweise Zahn- und Mundpflegemittel, Gebißpflegemittel, Zahnprothesenreinigungsmittel, Zahnprothesenhaftmittel(c) dentifrice and oral care such as, preferably, oral and oral care products, dentifrices, denture cleaners, denture adhesives
(d) solche zur Haarpflege, wie vorzugsweise Haarwaschmittel, Haarpflegemittel, Haarverfesti- gungsmittel, Haarbehandlungsmittel, Haarwasser, Haarverformungsmittel, Haarfärbemittel, Blondiermittel(D) those for hair care, such as, preferably, shampoos, hair care preparations, hair hardening agents, hair treatment agents, hair lotions, hair styling agents, hair dyes, bleaching agents
Bevorzugte Inhaltsstoffe der erfindungsgemäßen Verbrauchsprodukte, insbesondere der kosmetischen Mittel, können über ihre Funktion definiert werden Naturlich können manche Inhaltsstoffe auch multifunktionell seinPreferred ingredients of the consumer products according to the invention, in particular of the cosmetic agents, can be defined by their function. Of course, some ingredients may also be multifunctional
Bevorzugte Inhaltsstoffe der erfindungsgemäßen Verbrauchsprodukte, vorzugsweise Kosmetikprodukte können aus folgenden ausgewählt sein a) AbsorptionsmittelPreferred ingredients of the consumer products of the invention, preferably cosmetic products, may be selected from the following: a) Absorbents
Diese haben vorzugsweise die Aufgabe, wasser- und/oder öllösliche aufgelöste oder feinverteilte Substanzen aufzunehmen b) Antimikrobielle StoffeThese preferably have the task of absorbing water and / or oil-soluble dissolved or finely divided substances b) antimicrobial substances
Diese können den Produkten zugesetzt werden, um ganz allgemein die Aktivitäten von Mikroorganismen, z B auf der Haut und in der Mundhöhle zu verringern c) Antioxidantien, vorzugsweise durch eine spezielle Konfektionierung vom Oxidationsmittel getrennt vorliegendThese may be added to the products to generally reduce the activities of microorganisms, eg on the skin and in the oral cavity. C) Antioxidants, preferably present in a separate form from the oxidizing agent
Diese sollen dazu dienen, durch Sauerstoff ausgeloste Reaktionen wie Oxidation zu verhindern und somit die Haltbarkeit der Produkte verlängern, d h die Qualität der Produkte erhalten d) AntiperspirantienThese are intended to prevent oxygen-triggered reactions such as oxidation and thus extend the shelf life of the products, ie the quality of the products obtained d) antiperspirants
Diese werden vorzugsweise in Kosmetika eingesetzt und verringern die Schweißabgabe e) Antischaummittel Diese können zugesetzt werden, z.B. um Schaum während der Herstellung zu beseitigen oder um die Neigung von Fertigprodukten zur überschießenden Schaumbildung zu verringern, f) AntischuppenwirkstoffeThese are preferably used in cosmetics and reduce the sweat e) antifoam These may be added, for example, to remove foam during manufacture or to reduce the tendency of finished products to over foam, f) anti-dandruff actives
Diese werden in erster Linie in Haarpflegeprodukten eingesetzt, da sie der Schuppenbildung entgegenwirken können. g)AntistatikaThese are used primarily in hair care products because they can counteract dandruff. g) antistatics
Das sind z.B. Kämmbarkeitshilfen in Haarpflegeprodukten. Sie verringern allgemein die elektrostatische Aufladung von Objekten, beispielsweise der Haaroberfläche. Haare lassen sich so deutlich leichter kämmen, h) BindemittelThese are e.g. Combability aids in hair care products. They generally reduce the electrostatic charge on objects, such as the hair surface. Hair can be combed much easier, h) binders
Sie gewährleisten z.B. den Zusammenhalt pulver- und puderhaltiger Produkte, wie z.B. kosmetischer Zubereitungen, i) Stoffe biologischen UrsprungsThey ensure e.g. the cohesion of powdered and powdered products, e.g. cosmetic preparations, (i) substances of biological origin
Das sind z.B. bestimmte Pflanzeninhaltsstoffe, z.B. Grüner-Tee-Extrakt. Sie sollen einem Produkt bestimmte, gewünschte Eigenschaften verleihen, die mit dem entsprechenden biologischen Mate- rialen in Zusammenhang stehen, oder aber bereits bestehende Eigenschaften weiter verbessern oder unerwünschte Eigenschaften unterdrücken bzw. sie soweit wie möglich verringern, k) ChelatbildnerThese are e.g. certain plant ingredients, e.g. Green tea extract. They are intended to give certain desired properties to a product, which are related to the corresponding biological material, or to further improve existing properties or to suppress undesirable properties or reduce them as much as possible, k) chelating agents
Diese werden z.B. kosmetischen Mitteln zugesetzt, damit sie Komplexe mit Metallionen bilden, um so beispielsweise die Stabilität und/oder das Aussehen der Mittel zu manipulieren I) Desodorierungsmittel/AntitranspirantienThese are e.g. added to cosmetic agents to form complexes with metal ions, for example, to manipulate the stability and / or the appearance of the agents. I) Deodorants / antiperspirants
Diese können dazu beitragen, dass das Entstehen unangenehmer Körpergerüche verhindert oder verringert wird. Sie können solche Gerüche überdecken und ggf. die Schweißbildung. Reduzieren m) EmollentienThese can help to prevent or reduce the development of unpleasant body odors. You can cover such odors and possibly the formation of perspiration. Reduce m) emollients
Diese haben z.B. im kosmetischen Bereich die Aufgabe, die Haut geschmeidig zu machen und zu glätten. n) EmulgatorenThese have e.g. In the cosmetic field, the task of making the skin supple and smooth. n) emulsifiers
Hierbei handelt es sich um oberflächenaktive Substanzen, die vorzugsweise im Stande sind, nicht mischbare Flüssigkeiten wie öl und Wasser stabil ineinander zu verteilen, o) EmulsionsstabilisatorenThese are surface-active substances which are preferably capable of stably dispersing immiscible liquids such as oil and water, o) emulsion stabilizers
Diese können den Prozess der Emulgierung (vgl. Emulgatoren) noch weiter unterstützen und auf diese Weise die Stabilität und Haltbarkeit des Produktes weiter verbessern, p) EnthaarungsmittelThese can further support the process of emulsification (see emulsifiers) and thus further improve the stability and shelf life of the product, p) depilatories
Diese dienen der vorzugsweise selektiven Entfernung von Körperbehaarung, q) FeuchtigkeitsspenderThese are used for preferably selective removal of body hair, q) moisturizers
Diese können einen Beitrag zur Erhaltung oder Wiederherstellung der Hautfeuchtigkeit leisten und dem Austrocknen der Haut entgegenwirken, r) Filmbildner Diese sind dazu im Stande, beispielsweise in kosmetischen Mitteln einen schutzenden, stabilisierenden Film auf Oberflächen Vorzugsweise Haut, Haar oder Nägeln zu erzeugen s) FarbstoffeThese can contribute to the maintenance or restoration of the skin moisture and counteract the drying out of the skin, r) film former These are capable of producing, for example, in cosmetics, a protective, stabilizing film on surfaces, preferably skin, hair or nails
Diese werden z B auch kosmetischen Produkten zugesetzt, um eine Produktfärbung zu erzeugen oder aber auch um eine mittelbare Objektfärbung zu bewirken, z B Haarfärbung t) KonservierungsstoffeThese are, for example, also added to cosmetic products in order to produce a product coloration or else to bring about an indirect object coloration, for example hair colorant t) preservatives
Diese werden z B kosmetischen Mitteln zugesetzt, um sie vor der schadhaften Einwirkung von Mikroorganismen (Bakterien, Pilze, Hefen) zu bewahren und damit ihren Verderb zu vermeiden u) KorrosionsschutzmittelThese are added, for example, to cosmetic products in order to protect them from the harmful action of microorganisms (bacteria, fungi, yeasts) and thus to prevent their spoilage u) anticorrosive agents
Diese können z B dazu dienen, die Korrosion der Verpackung z B eines kosmetischen Mittels zu verhindern oder aber auch die Korrosion von Teilen die mit dem Mittel ansonsten in Kontakt treten v) LosungsmittelThese can serve, for example, to prevent the corrosion of the packaging, for example of a cosmetic agent, or else the corrosion of parts which otherwise come into contact with the agent. V) Solvent
Sie können z B die Grundlage für beispielsweise flussige kosmetische Zubereitungen sein oder aber Bestandteil fester Produkte verwendet werden w) MundpflegestoffeThey may, for example, be the basis for, for example, liquid cosmetic preparations or else be part of solid products w) oral care substances
Diese können der Pflege von Zähnen und Zahnfleisch dienen y) pH-Wert-Regler/PuffersubstanzenThese can serve the care of teeth and gums y) pH regulator / buffer substances
Diese können z B in Kosmetika dazu dienen, um einen gewünschten pH-Wert einzustellen bzw zu stabilisieren z) Reduktionsmittel, vorzugsweise durch eine spezielle Konfektionierung vom Oxidationsmittel getrennt vorliegendThese can be used, for example, in cosmetics to adjust or stabilize a desired pH. Z) Reducing agent, preferably present in a separate form from the oxidizing agent
Diese sind im Stande, die chemische Beschaffenheit einer anderen Substanz durch Redoxpro- zesse zu ändern aa) SchleifmittelThese are able to change the chemical composition of another substance by redox processes aa) abrasives
Diese können dazu dienen, um Materialien von verschiedenen (Korper-)Oberflächen zu entfernen, beispielsweise um die mechanische Zahnreinigung zu unterstutzen oder um den Zahnglanz zu verbessern bb) Tenside/Waschaktive SubstanzenThese can be used to remove materials from various (body) surfaces, for example, to assist the mechanical cleaning of the teeth or to improve tooth gloss. B) Surfactants / wash-active substances
Dies sind grenzflächenaktive Verbindungen, die Reinigungszwecken dienen cc) TreibgaseThese are surface-active compounds used for cleaning purposes cc) propellants
Dies sind gasförmige Substanzen, mit denen Produkte, z B kosmetischen Mittel unter Druck in druckbeständigen Behältern gesetzt werden können, um den Inhalt dann bei Druckentlastung hervorzubringen dd) TrubungsmittelThese are gaseous substances with which products, for example cosmetic agents, can be placed under pressure in pressure-resistant containers in order to produce the contents when pressure is released dd) turbidity agent
Diese kann man vorzugsweise durchsichtigen oder durchscheinenden Produkten beigeben, um sie undurchdringlicher für sichtbares Licht oder hchtnahe Strahlung zu machen ee) UV-Absorber/Lichtfiltersubstanzen Sie sind im Stande, bestimmte UV-Strahlen zu filtern und können auf diese Weise z.B. die Haut vor vorzeitiger, lichtbedingter Alterung sowie vor Sonnenbrand schützen. ff) VergällungsmittelThese can be added preferably transparent or translucent products to make them more impenetrable to visible light or near-light radiation ee) UV absorber / light filter substances They are able to filter certain UV rays and can thus protect the skin, for example, from premature light-induced aging as well as from sunburn. ff) denaturant
Diese werden beispielsweise kosmetischen Mitteln, die Ethanol enthalten, zugesetzt, um sie ungenießbar zu machen. gg) ViskositätsreglerFor example, these are added to cosmetics containing ethanol to render them inedible. gg) viscosity regulator
Diese sind im Stande, die Zähflüssigkeit eines Produkts zu erhöhen oder auch zu verringern.These are able to increase or decrease the viscosity of a product.
Vorgenannte Inhaltsstoffe können gemäß einer bevorzugten Ausführungsformen in den erfindungsgemäßen Produkten, vorzugsweise kosmetischen Mitteln, enthalten sein.The aforementioned ingredients can be contained according to a preferred embodiment in the products according to the invention, preferably cosmetic agents.
Als Konfektionierung der Produkte, insbesondere der Kosmetika, aber auch aller anderen, sind beispielsweise unter anderem auch Cremes, Pasten, Tinkturen, Lotionen, Lösungen, Wässer, Emulsionen wie W/O-, O/W-, PIT-Emulsionen (Emulsionen nach der Lehre der Phaseninversion, PIT genannt), Mikroemulsionen und multiple Emulsionen, grobe, instabile, ein oder mehrphasige Schüttelmixturen, Gele, Sprays, Pouches, Aerosole und Schaumaerosole geeignet.For example, creams, pastes, tinctures, lotions, solutions, waters, emulsions such as W / O, O / W, PIT emulsions (emulsions according to US Pat Phase inversion theory called PIT), microemulsions and multiple emulsions, coarse, unstable, single or multi-phase shaking mixtures, gels, sprays, pouches, aerosols and foam aerosols.
Die erfindungsgemäßen Produkte, wie vorzugsweise Wasch- oder Reinigungsmittel, sind vorteilhafterweise im Stande, insbesondere im Vergleich zu oxidationsmittelfreien Mitteln, verbesserte Leistungen, insbesondere Reinigungsleistungen, z.B. im Hinblick auf die Entfernung von Anschmutzungen, insbesondere von farbigen Anschmutzungen, zu erbringen. Weiter sind sie vorteilhafterweise im Stande, insbesondere im Vergleich zu oxidationsmittelfreien Mitteln, durch eine Verbesserung der Vernichtung von Bakterien und anderen Mikroorganismen zu wirksameren Hygieneleistungen beim zu behandelnde Gut (z.B. Textilien, Geschirr, harte Oberflächen etc.) zu kommen, insbesondere mit Blick auf eine deutliche Verminderung der Keimzahl. Ferner trägt die erfindungsgemäße Riechstoffzusammensetzung zu einem Wohlgeruch des gesamten Mittels, insbesondere Wasch- oder Reinigungsmittels oder Kosmetikums bei und steigert so dessen Akzeptanz beim Verbraucher.The products according to the invention, such as preferably detergents or cleaners, are advantageously able, in particular in comparison with oxidant-free compositions, improved performances, in particular cleaning performances, e.g. with regard to the removal of stains, in particular colored stains. Furthermore, they are advantageously able to achieve more effective hygiene performance in the material to be treated (eg textiles, dishes, hard surfaces, etc.), in particular in comparison with oxidant-free compositions, by improving the destruction of bacteria and other microorganisms, in particular with regard to one significant reduction in germ count. Furthermore, the fragrance composition according to the invention contributes to a pleasant odor of the entire composition, in particular washing or cleaning agent or cosmetic and thus increases its acceptance by the consumer.
Ein weiterer Vorteil der Erfindung liegt darin, dass ein solches Produkt lagerstabil ist, insbesondere was die Stabilität des Oxidationsmittels als auch was die Parfümierung des Produktes betrifft. Der Dufteindruck des erfindungsgemäßen, parfümierten Mittels verändert sich vorteilhafterweise auch bei längerer Lagerung über mehrere Wochen nicht. Ebenso lässt die Aktivität des Oxidationsmittels vorteilhafterweise auch bei längerer Lagerung über mehrere Wochen nicht wesentlich stärker als in Abwesenheit der Parfümierung nach. Beides gilt vorteilhafterweise auch für flüssige Mittel.Another advantage of the invention is that such a product is stable on storage, in particular as regards the stability of the oxidizing agent as well as the perfuming of the product. The scent impression of the perfumed composition according to the invention advantageously does not change even during prolonged storage over several weeks. Likewise, the activity of the oxidizing agent advantageously does not diminish significantly more than in the absence of perfuming even after prolonged storage for several weeks. Both advantageously also apply to liquid funds.
Nach einer bevorzugten Ausführungsform enthält die im erfindungsgemäßen Mittel enthaltene Riechstoffzusammensetzung zumindest 91 Gew.-%, vorzugsweise zumindest 92 Gew.-%, vorteil- hafterweise zumindest 94 Gew -%, in vorteilhafterer Weise zumindest 96 Gew -%, in noch vorteilhafterer Weise zumindest 98 Gew -%, in weiter vorteilhafter Weise zumindest 99 Gew -%, insbesondere sogar 100 Gew -% an solchen Riechstoffen, welche zumindest einer der folgenden Stoffklassen zuordbar sind gesättigte Alkohole, vorzugsweise primäre, sekundäre, und/oder tertiäre gesättigte, ggf verzweigte oder ggf zyklische Alkohole, gesättigte Ester, ggf verzweigte oder zyklische gesättigte Ester gesättigte Ether, ggf verzweigte oder zyklische gesättigte Ether - Aromaten mit gesättigten Substituenten, ggf mit verzweigten, gesättigten SubstituentenAccording to a preferred embodiment, the perfume composition contained in the agent according to the invention contains at least 91% by weight, preferably at least 92% by weight, advantageously at least 94% by weight, more preferably at least 96% by weight, even more preferably at least 98% by weight, more preferably at least 99% by weight, in particular even 100% by weight of such fragrances, which at least one of saturated alcohols, preferably primary, secondary, and / or tertiary saturated, optionally branched or optionally cyclic alcohols, saturated esters, optionally branched or cyclic saturated esters saturated ethers, optionally branched or cyclic saturated ether - aromatics with saturated substituents, if necessary with branched, saturated substituents
Nitπle, ggf ungesättigt in Konjugation mit der Nitnlgruppe gesättigte Acetale, ggf verzweigte oder zyklische gesättigte Acetale gesättigte Halbacetale, wobei die Gew -%-Angabe auf die gesamte Riechstoffmenge bezogen istNitriles, optionally unsaturated in conjugation with the nitrile group, saturated acetals, optionally branched or cyclic saturated acetals, saturated hemiacetals, the percentages by weight being based on the total amount of fragrance
Nach einer weiteren bevorzugten Ausfuhrungsform enthält die im erfindungsgemaßen Mittel enthaltene Riechstoffzusammensetzung zumindest 50 Gew -%, zumindest 60 Gew -%, zumindest 70 Gew -%, zumindest 80 Gew -%, zumindest 90 Gew -% oder zumindest 91 Gew -%, vorzugsweise zumindest 92 Gew -%, vorteilhafterweise zumindest 94 Gew -%, in vorteilhafterer Weise zumindest 96 Gew -%, in noch vorteilhafterer Weise zumindest 98 Gew -%, in weiter vorteilhafter Weise zumindest 99 Gew -%, insbesondere sogar 100 Gew -% an Riechstoffen, ausgewählt aus Citronitπl, Ortho-tert -butylcyclohexylacetat, Cyclohexylsahcylat, (+)-(1lR,3S,6'S)-1-(2l,2l,6'-trιmethyl-1'-cydo- hexyl)-3-hexanol, (-)-(11S1SR^1R)-I -(2\2\6'-trιmethyl-r-cydohexyl)-3-hexanol, (+)-(rR,3R,6'S)-1- (2l,2l,6l-trιmethyl-1l-cyclohexyl)-3-hexanol, (-)-(1'S,3S,6lR)-1-(2l,2l I6l-trιmethyl-1'-cyclohexyl)-3-he- xanol, Phenylethylalkohol, 2-Cyclohexylιdene-2-phenylacetonιtrιle, Decahydro-b-naphtolacetat, Kresylacetat (para), Methylphenylacetat, Allylamylglycolat, Benzylacetat, Cyclohexylethylacetat, Ethyl-2-cyclohexyl-propιonat, Phenylethylacetat, Cyclopentyliden-Essigsäuremethylester [CAS-Nr 0040203-73-4), Allyl-(cyclohexyloxy)acetat, 2,4-Dιmethyl-1 ,3-dιoxolan-2-essιgsäureethylester, 3,12-Trιdecadιen-nιtπl, Amylacetat, Isoamylacetat, Ethylphenylacetat, 2-Propenylphenoxyacetat, Isobornylacetat, Dimethylbenzylcarbinylacetat, Hexylacetat, Kresylacetat (para), Isobutylphenyl- acetat, Butylcyclohexylacetat- cis-para-tert , Butylcyclohexylacetat- trans-para-tert , Hydrozimtalko- hol, 2,6-Dιmethylheptan-2-ol, Decanol, Octanol, 2,6-Dιmethylbιcyclo-[4 4 0]decan-1-ol (0 1 % in Di- propylenglykol), Tetrahydromuguol [= Tetrahydrohnalool (3,7-Dιmethyloctan-3-ol)/Tetrahydromyrce- nol (2-Octanol, 2,6-dιmethyl) Gemisch (1 1)], Dihydroterpmeol, alpha 3,3 - tπmethylcyclohexylme- thylformat, Octanol-3, Hexanol, 2,2,6-Trιmethy!-alpha-propylcyc(ohexanpropanol, Decahydro-b- naphtolformiat, (11S, 1"S,2'S,3"R, 511R)-[I -Methyl-2-(1 ,2,2-trιmethyl-bιcyclo[3 1 0]hex-3-ylmethyl)-cy- clopropylj-methanol, (1lR,1"R,2'R,3"S,5"S)-[1-Methyl-2-(1 ,2,2-tπmethyl- bιcyclo[3 1 0]hex-3-ylme- thyl)-cyclopropyl]-methanol, (1lR,1"S,2lR,3"R,5"R)-[1-Methyl-2-(1 ,2,2-tπmethyl-bιcyclo[3 1 0]hex-3- ylmethyl)-cyclopropyl]-methanol, (1'S,1"R,2'S,3"S,5"S)-[1-Methyl-2-(1 ,2,2-trιmethyl-bιcyclo- [3 1 Olhex-S-ylmethyO-cyclopropyll-methanol, Borneol, Dipropylenglycol, Tetrahydrogeraniol, Tetra- hydrolinalool, 2,2,6-Trιmethyl-alpha-propylcyclohexanepropanol (Timberol forte), alpha-Methyl-4- (1 -methylethyOcyclohexanemethanol, Isocyclogeraniol, Fenchylalkohol, (-)-(2R,4S)-2-ιsobutyl-4- methyltetrahydro-2H-pyran-4-ol, (+)-(2S,4R)-2-ιsobutyl-4-methyltetrahydro-2H-pyran-4-ol, (+)- (2S,4S)-2-ιsobutyl-4-methyltetrahydro-2H-pyran-4-ol, (-)-(2R,4R)-2-ιsobutyl-4-methyltetrahydro-2H- pyran-4-ol, Methylbenzoat, Ethylbenzoat, Methylsalicylat, Amylpropionat, 2,6,6-Tπmethyl-1 ,3- cyclohexadιen-1-carbonsäureethylester, Benzylpropionat, Ethylsalicylat, 2-Methoxy-4-formylphe- nylisobutyrat (Isobutavan), Ethylcaprylat, Allylcapronat, 2-Methyl-2-butensäure-2-methylpropyl- ester, 2-Ethyl-Ethylhexanoat (Irotyl), 2-Methylpentansaure-2-methylpentylester, Jasmacyclat, 2,5- Dιmethyl-4,6-dιhydroxybenzoesäuremethylester, Ethyl-2-methylvalerat, Heptansäure-2-propenyl- ester (Allylheptanoat - allyloenanthat), Methylanthranilat, Phenylessigsaeure, Allylcyclohexylpro- pionat, 2-Nonιnsäuremethylester, Cyclohexylsalicylat, 2-tert-Butylcyclohexylethylcarbonat, 2,2,4- Tπmethylcapronsäureethylester, Ethylester Labdanum Extract (Ambrarome), Styrolylacetat, Hydro- chinondimethylaether, Diphenylether, Kresylmethylether (para), Cymol (para), Phenylethylisoamyl- ether, Phenylethylmethylether, 4-lsopropyl-5,5-dιmethyl-1 ,3-dιoxan, 2,2,5,5-Tetramethyl-4-ιsopro- pyl-1 ,3-dιoxan, 5-Methyl-5-propyl-2(1-methylbutyl)-1 ,3-dιoxan, Anethol, 2-Phenylpropιonaldehyde- dimethyl acetal, Frambmonmethylether, Cumarin, Isocumaπn, Acetophenon, 1 , 1 ,2,3, 3-Pentame- thyl-6,7-dιhydro-4(5H)-ιndanon, Octalacton gamma, Ethylamylketon, Campher synth , Oxacyclo- heptadec-8-en-2-on, 2-Heptylcyclopentanon, 2-(1-methylpropyl)-Cyclohexanon, 4-tert-Butyl-2,6-dι- methylacetophenon, Cyclopentadecanolide, 3-Methyl-cyclopentadecanon, Dihydrojasmon, Dihy- dro-iso-jasmon, Decalacton gamma, Methyloctalacton, 1 ,4-Dιoxacyclohexadecan-5,16-dιon, 4-(2- Butenyliden)-3,5,5-trimethyl-2-cyclohexen-1-on, Ethyl^^.δ.-tnmethylcyclohexancarboxylat, Zimt- säurenitnl, Launnsäurenitril, Hydrocitronitπl, 2-Benzyl-2-methyl-3-butennιtrιl, 3-Methyldodecanonι- tπl, Citronitπl, Trιdecen-2-nιtrιl, *3(4,7,7-Trιmethylbιcyclo<4 1 0>hept-3-yl)-2-propenylnιtrιl, Irolene p, 8-alpha-12-Oxιdo-13,14,15,16-tetranorlabdan, 3,3,5-Trιmethylcyclohexylethylether, Inval (70% 4- tert-Pentylcyclohexanon, 10% Weißes Mineralöl, 10% Non-2-enenιtrιl, 10% Dibutylsebacat), Iso- butylchinolin, 5-Ethylιdenbιcyclo[2 2 1]-2-hepten-2-Methoxyphenol-Addukt, Methylbutyl-2 propionat, lndeno[1 ,2-d]-tetrahydro-1,3-dιoxan, Dodecahydro-3a,6,6,9a-tetramethyl-Naphtrio(2,1-b)furan, 2,4- Dιmethyl-4-phenyl-tetrahydrofuran, Spiroti .S-dioxolan^.S'^'^'.δ'.δ'-tetramethyl-hexahydro-S'.θ'- methanonaphthalen)], Methyldihydrojasmonat, Methyl S-oxo^-pentylcyclopentaneacetat, 0-(AlIyI- oxy)anιsol, Dihydromyrcenol, 9-Decen-1-ol, Tetrahydromyrcenol, Hexahydro-4,7-methanoιnden-6- yl acetat, 2-Phenoxyethylιsobutyrat, 2-Methylpropensaure-1 ,3-dιmethyl-3-butenylester, Methylace- tophenon para, 4-Phenyl-2-butanon, Hδ.δ-Dimethyl-i-Cyclohexen-i-ylM-Penten-i-one, 3-Hy- droxy-1-methyl-4-ιsopropylbenzol [CAS Nr 89-83-8], wobei sich die Gew -Angabe auf die Gesamtmenge der Riechstoffe beziehtAccording to a further preferred embodiment, the perfume composition contained in the agent according to the invention contains at least 50% by weight, at least 60% by weight, at least 70% by weight, at least 80% by weight, at least 90% by weight or at least 91% by weight, preferably at least 92% by weight, advantageously at least 94% by weight, more preferably at least 96% by weight, even more preferably at least 98% by weight, more preferably at least 99% by weight, in particular even 100% by weight of fragrances, selected from citronitrile, ortho-tert-butylcyclohexyl acetate, cyclohexylsahcylate, (+) - (1 l R, 3S, 6S) -1- (2 l , 2 l , 6'-tri-methyl-1'-cyclohexyl) -3- hexanol, (-) - (1 1 S 1 SR 1 R) -I - (2 \ 2 \ 6'-tri-methyl-r-cyclohexyl) -3-hexanol, (+) - (r R, 3 R, 6'S) - 1- (2 l , 2 l , 6 l -trimethyl-1 l -cyclohexyl) -3-hexanol, (-) - (1'S, 3S, 6 l R) -1- (2 l , 2 l of I 6 l - trimethyl-1'-cyclohexyl) -3-hexanol, phenylethyl alcohol, 2-cyclohexyl-2-phenylacetone, decahydro-b-naphthol acetate, kresylac eta (para), methyl phenylacetate, allylamyl glycolate, benzyl acetate, cyclohexyl ethyl acetate, ethyl 2-cyclohexyl propionate, phenylethyl acetate, cyclopentylidene-acetic acid methyl ester [CAS No. 0040203-73-4), allyl (cyclohexyloxy) acetate, 2,4-dimethylethyl 1, 3-dιoxolan-2-ethyl acetate, 3,12-Trιdecadιen-nιtπl, amyl acetate, isoamyl acetate, ethyl phenylacetate, 2-Propenylphenoxyacetat, Isobornylacetat, Dimethylbenzylcarbinylacetat, hexyl acetate, cresyl acetate (para), Isobutylphenyl- acetate, Butylcyclohexylacetat- cis-para-tert , Butylcyclohexylacetate trans-para-tert, hydroxymethyl alcohol, 2,6-dimethylheptan-2-ol, decanol, octanol, 2,6-dimethylcyclo [4 4 0] decan-1-ol (0 1% in di- propylene glycol), tetrahydrouguol [= tetrahydro-naph- ol (3,7-dimethyl-octan-3-ol) / tetrahydromyr- nol (2-octanol, 2,6-dimethyl) mixture (11)], dihydroterpmeol, alpha 3,3-t-methylcyclohexylmethyl format , Octanol-3, hexanol, 2,2,6-Trιmethy! -Alpha-propylcyc (ohexanpropanol, Decahydro-b-naphtolformiat, (1 1 S , 1 "S, 2'S, 3" R, 5 11 R) - [I-methyl-2- (1,2,2-tri-methyl-bicyclic [3 1 0] hex-3-ylmethyl) -cyclopropyl-1-methanol , (1 L R, 1 "R, 2'R, 3" S, 5 "S) - [1-methyl-2- (1,2,2-t-methyl-bicyclic [3 1 0] hex-3-ylme - methyl) -cyclopropyl] -methanol, (1 l of R, 1 "S, 2 l of R, 3" R, 5 "R) - [1-methyl-2- (1, 2,2-tπmethyl-bιcyclo [3 1 0] hex-3-ylmethyl) -cyclopropyl] -methanol, (1'S, 1 "R, 2'S, 3" S, 5 "S) - [1-methyl-2- (1,2,2-tri-methyl-bicycl - [3 l] Olhex-S-ylmethoxy-cyclopropyl-methanol, borneol, dipropylene glycol, tetrahydrogeraniol, tetrahydrolyn-olool, 2,2,6-tri-methyl-alpha-propylcyclohexanepropanol (Timberolforte), alpha-methyl-4- (1-methylethylcyclohexanemethanol, Isocyclogeraniol, fenchyl alcohol, (-) - (2R, 4S) -2-isobutyl-4-methyltetrahydro-2H-pyran-4-ol, (+) - (2S, 4R) -2-isobutyl-4-methyltetrahydro-2H- pyran-4-ol, (+) - (2S, 4S) -2-isobutyl-4-methyltetrahydro-2H-pyran-4-ol, (-) - (2R, 4R) -2-isobutyl-4-methyltetrahydro- 2H-pyran-4-ol, methyl benzoate, ethyl benzoate, methyl salicylate, amyl propionate, ethyl 2,6,6-tri-methyl-1,3-cyclohexadiene-1-carboxylate, benzyl propionate, ethyl salicylate, 2-methoxy-4-formyl-phenyl isobutyrate (isobutane) , Ethyl caprylate, allyl caproate, 2-methyl-2-butenoic acid 2-methylpropyl ester, 2-ethyl-ethylhexanoate (Irotyl), 2-methylpentanoic acid 2-methylpentyl ester, jasmacycate, 2,5-dimethyl-4,6-dihydroxybenzoic acid methyl ester, Ethyl 2-methylvalerate, heptanoic acid 2-propenyl ester (allylheptanoate - al lyloenanthate), methyl anthranilate, phenylacetic acid, allylcyclohexyl propionate, 2-nonynoic acid methyl ester, cyclohexyl salicylate, 2-tert-butylcyclohexylethyl carbonate, 2,2,4-trimethylcaproic acid ethyl ester, ethyl ester labdanum extract (ambrarome), styrolyl acetate, hydroquinone dimethyl ether, diphenyl ether, cresyl methyl ether (para) , Cymene (para), phenylethyl isoamyl ether, phenylethyl methyl ether, 4-isopropyl-5,5-dimethyl-1,3-dicanoan, 2,2,5,5-tetramethyl-4-isopropyl-1,3-dicoxan, 5-methyl-5-propyl-2 (1-methylbutyl) -1,3-dinoxane, anethole, 2-phenylpropionaldehyde dimethyl acetal, frambomethyl ether, coumarin, isocumarin, acetophenone, 1,1,3,3-pentamethylene ethyl 6,7-dihydro-4 (5H) -indanone, octalactone gamma, ethylamyl ketone, camphor synth, oxacycloheptadec-8-en-2-one, 2-heptylcyclopentanone, 2- (1-methylpropyl) cyclohexanone, 4 tert-butyl-2,6-dimethylacetophenone, cyclopentadecanolides, 3-methylcyclopentadecanone, dihydrojasmon, dihydro-iso-jasmon, decalactone gamma, methyl octalactone, 1,4-Dicoxacyclohexadecane-5,16-dιone, 4- (2-butenylidene) -3,5,5-trimethyl-2-cyclohexen-1-one, ethyl ^^, δ-methylcyclohexanecarboxylate, cinnamic acid nitrate, lactonitrile , Hydrocitronitπl, 2-benzyl-2-methyl-3-butennιtrιl, 3-Methyldodecanonι- tπl, Citronitπl, Trιdecen-2-nιtrιl, * 3 (4,7,7-Trιmethylbιcyclo <4 1 0> hept-3-yl) -2-propenylnιtrιl, Irolene p, 8-alpha-12-Oxιdo-13,14,15,16-tetranorlabdane, 3,3,5-Trιmethylcyclohexylethylether, Inval (70% 4-tert-pentylcyclohexanone, 10% white mineral oil, 10 % Non-2-enenetrile, 10% dibutyl sebacate), isobutylquinoline, 5-ethylbendenebicyclo [2 2 1] -2-heptene-2-methoxyphenol adduct, methylbutyl-2-propionate, indeno [1,2-d] -tetrahydro 1,3-dioxan, dodecahydro-3a, 6,6,9a-tetramethyl-naphthio (2,1-b) furan, 2,4-dimethyl-4-phenyl-tetrahydrofuran, spiroti .s-dioxolane ^ .S ' ^ '^'. δ'.δ'-tetramethyl-hexahydro-S'.'-methanonaphthalene)], methyl dihydrojasmonate, methyl S-oxo-pentylcyclopentane acetate, O- (allyloxy) anil sol, dihydromyrcenol, 9-decene 1-ol, Tetrahydromyrcenol, hexahydro-4,7-methyl-6-yl acetate, 2-Phenoxyethylιsobutyrat, 2-Methylpropensaure-1, 3-dιmethyl-3-butenylester, methylace- tophenone para, 4-phenyl-2-butanone, Hδ.δ- Dimethyl-i-cyclohexen-i-ylM-pentene-i-one, 3-hydroxy-1-methyl-4-isopropylbenzene [CAS No. 89-83-8], wherein the Gew -Ngabe on the total amount of the fragrances refers
Diese vorgenannten Riechstoffe sind insbesondere in flussigen Mitteln mit großem Erfolg im erfindungsgemäßen Sinne einsetzbar Entsprechende Riechstoffzusammensetzungen gewährleisten selbst bei hochreaktiven Oxidations- mitteln wie Peroxycarbonsäuren, wobei diese vorteilhafterweise aus Mono- und Diperoxycarbon- säuren, insbesondere Dodekandiperoxysäure oder vorzugsweise Imidoperoxycarbonsäuren, besonders bevorzugt 6-Phthalimidoperoxycapronsäure (6-Phthalimidoperoxyhexansäure, PAP) ausgewählt sein können, außergewöhnliche Stabilitätsergebnisse, insbesondere mit Blick auf PAP. Die Potenz des Oxidationsmittels bleibt auch nach längerer Lagerung sehr gut gewahrt, vorteilhafterweise auch in flüssigen Mitteln. Der Wohlgeruch der Riechstoffzusammensetzung bleibt auch nach längerer Lagerung sehr gut gewahrt, vorteilhafterweise auch in flüssigen Mitteln.These aforementioned fragrances can be used in particular in liquid agents with great success in the context of the invention Corresponding fragrance compositions, even with highly reactive oxidizing agents such as peroxycarboxylic acids, which may advantageously be selected from mono- and diperoxycarboxylic acids, in particular dodecanediperoxyacid or preferably imidoperoxycarboxylic acids, more preferably 6-phthalimidoperoxycaproic acid (6-phthalimidoperoxyhexanoic acid, PAP), provide exceptional stability results, in particular Look at PAP. The potency of the oxidizing agent remains very well preserved even after prolonged storage, advantageously also in liquid agents. The fragrance of the fragrance composition remains very well preserved even after prolonged storage, advantageously also in liquid agents.
In einer bevorzugten Ausführungsform enthält das Produkt bestimmte Minimalwerte an Riechstoffen, nämlich zumindest 0,01 Gew.-% oder 0,05 Gew.-%, vorteilhafterweise zumindest 0,1 Gew.-%, in beträchtlich vorteilhafter Weise zumindest 0,15 Gew.-%, in vorteilhafterer Weise zumindest 0,2 Gew.-%, in weiter vorteilhafter Weise zumindest 0,25 Gew.-%, in noch weiter vorteilhafter Weise zumindest 0,3 Gew.-%, in sehr vorteilhafter Weise zumindest 0,35 Gew.-%, in besonders vorteilhafter Weise zumindest 0,4 Gew.-%, in ganz besonders vorteilhafter Weise zumindest 0,45 Gew.- %, in erheblich vorteilhafter Weise zumindest 0,5 Gew.-%, in ganz erheblich vorteilhafter Weise zumindest 0,55 Gew.-%, in äußerst vorteilhafter weise zumindest 0,6 Gew.-%, in höchst vorteilhafterweise zumindest 0,65 Gew.-%, in überaus vorteilhafterweise zumindest 0,7 Gew.-%, in ausnehmend vorteilhafter Weise zumindest 0,75 Gew.-%, in außergewöhnlich vorteilhafter Weise zumindest 0,8 Gew.-%, in außerordentlich vorteilhafter Weise zumindest 0,85 Gew.-%, insbesondere zumindest 0,9 Gew.-% an Riechstoffen, bezogen auf das gesamte Produkt.In a preferred embodiment, the product contains certain minimum values of fragrances, namely at least 0.01% by weight or 0.05% by weight, advantageously at least 0.1% by weight, in a considerably advantageous manner at least 0.15% by weight. -%, more preferably at least 0.2 wt .-%, in a further advantageous manner at least 0.25 wt .-%, more preferably at least 0.3 wt .-%, in a very advantageous manner at least 0.35 Wt .-%, in a particularly advantageous manner at least 0.4 wt .-%, in a particularly advantageous manner at least 0.45 wt .-%, in a significantly advantageous manner at least 0.5 wt .-%, in a very significantly advantageous manner at least 0.55 wt .-%, in an extremely advantageous manner at least 0.6 wt .-%, most advantageously at least 0.65 wt .-%, in an extremely advantageous manner at least 0.7 wt .-%, in exceptionally advantageous manner at least 0.75 wt .-%, in an exceptionally advantageous manner at least 0.8 wt .-%, in extremely vorteilha at least 0.85 wt .-%, in particular at least 0.9 wt .-% of fragrances, based on the total product.
In einer bevorzugten Ausführungsform enthält das Produkt allerdings größere Mengen an Riechstoffen, nämlich zumindest 1 Gew.-%, vorteilhafterweise zumindest 2 Gew.-%, in beträchtlich vorteilhafter Weise zumindest 5 Gew.-%, in vorteilhafterer Weise zumindest 10 Gew.-%, in weiter vorteilhafter Weise zumindest 13 Gew.-%, in noch weiter vorteilhafter weise zumindest 14 Gew.-%, in sehr vorteilhafter Weise zumindest 15 Gew.-%, in besonders vorteilhafter Weise zumindest 16 Gew.-%, in ganz besonders vorteilhafter Weise zumindest 17 Gew.-%, in erheblich vorteilhafter Weise zumindest 18 Gew.-%, in ganz erheblich vorteilhafter Weise zumindest 19 Gew.-%, insbesondere zumindest 20 Gew.-% an Riechstoffen, bezogen auf das gesamte Produkt.In a preferred embodiment, however, the product contains larger amounts of fragrances, namely at least 1 wt .-%, advantageously at least 2 wt .-%, in a considerably advantageous manner at least 5 wt .-%, more preferably at least 10 wt .-%, in a further advantageous manner at least 13 wt .-%, more preferably at least 14 wt .-%, in a very advantageous manner at least 15 wt .-%, in a particularly advantageous manner at least 16 wt .-%, in a particularly advantageous manner at least 17% by weight, in a significantly advantageous manner at least 18% by weight, in a very advantageous manner at least 19% by weight, in particular at least 20% by weight, of perfumes, based on the total product.
Es ist aber eher ungewöhnlich in Verbrauchsprodukten sehr hohe Riechstoffgehalte zu verwirklichen, um zu verhindern, dass das Produkt zu aufdringlich riecht. Vielmehr ist es oftmals erwünscht, dass die enthaltene Menge an Riechstoffen begrenzt ist. In einer bevorzugten Ausführungsform enthält das Produkt daher bestimmte Maximalwerte an Parfümöl, nämlich z.B. nicht mehr als 30 Gew.-%, 25 Gew.-%, 20 Gew.-% oder 15 Gew.-%, vorteilhafterweise nicht mehr als 10 Gew.-%, in beträchtlich vorteilhafter Weise nicht mehr als 9 Gew.-%, in vorteilhafterer Weise nicht mehr als 8 Gew.-%, in weiter vorteilhafter Weise nicht mehr als 7 Gew.-%, in noch weiter vorteilhafter Weise nicht mehr als 6 Gew.-%, in sehr vorteilhafter Weise nicht mehr als 5 Gew.-%, in beson- ders vorteilhafter Weise nicht mehr als 4,5 Gew.-%, in ganz besonders vorteilhafter Weise nicht mehr als 4 Gew.-%, in erheblich vorteilhafter Weise nicht mehr als 3,5 Gew.-%, in insbesondere nicht mehr als 3 Gew.-% oder 2 Gew.-% an Riechstoffen, bezogen auf das gesamte Produkt. Es sei an dieser Stelle einmal für den gesamten Text angemerkt, dass sich die Angabe Gew.-% jeweils auf das gesamte Produkt bezieht, es sei denn, es ist konkret etwas anderes angegeben oder es ergibt sich aus dem konkreten Kontext in eindeutiger Weise ein anderer Bezug.However, it is rather uncommon in consumer products to achieve very high fragrance levels in order to prevent the product from smelling too intrusive. Rather, it is often desirable that the amount of fragrance contained is limited. In a preferred embodiment, the product therefore contains certain maximum values of perfume oil, namely, for example, not more than 30% by weight, 25% by weight, 20% by weight or 15% by weight, advantageously not more than 10% by weight. %, in a considerably advantageous manner not more than 9% by weight, more advantageously not more than 8% by weight, more advantageously not more than 7% by weight, even more advantageously not more than 6% by weight %, most preferably not more than 5% by weight, in particular Advantageously, not more than 4.5 wt .-%, in a particularly advantageous manner not more than 4 wt .-%, in a significantly advantageous manner not more than 3.5 wt .-%, in particular not more than 3 wt .-% or 2 wt .-% of fragrances, based on the total product. It should be noted at this point for the entire text that the statement Gew .-% refers in each case to the entire product, unless it is concretely stated otherwise, or it emerges from the concrete context in a clear way another Reference.
Der allgemeine Begriff des Riechstoffes im Sinne der Erfindung steht im Einklang mit der üblichen Definition, d.h. es handelt sich üblicherweise um Stoffe, die durch ihren Geruch, insbesondere angenehmen Geruch wahrnehmbar sind. Hierzu zählen vorzugsweise auch die Aromastoffe. Als Riechstoffe werden heute vor allem ätherische öle, Blütenöle, Extrakte aus pflanzlichen und animalischen Drogen, aus Naturprodukten, isolierte Komponenten (Isolate) sowie halbsynthetische und vollsynthetische einheitliche Riechstoffe verwendet.The general concept of the fragrance within the meaning of the invention is in accordance with the usual definition, i. they are usually substances that are perceptible by their smell, especially pleasant smell. These preferably also include the flavorings. The fragrances used today are above all essential oils, flower oils, extracts from plant and animal drugs, from natural products, isolated components (isolates) as well as semi-synthetic and fully synthetic uniform fragrances.
Als Oxidationsmittel können alle denkbaren Oxidationsmittel eingesetzt werden, z.B. Perborate, Percarbonate, Wasserstoffperoxid, Natriumhypochlorit, Dichromat, Dithionit, Permanganat, Chlor, konzentrierte Schwefelsäure, organische Persäuren, Chlor, Hypochlorit, Chlordioxid, Peroxide, usw. Eine Reihe von vorteilhafterweise einsetzbaren Bleichmitteln wird weiter unten genannt.As the oxidizing agent, any conceivable oxidizing agent may be used, e.g. Perborates, percarbonates, hydrogen peroxide, sodium hypochlorite, dichromate, dithionite, permanganate, chlorine, concentrated sulfuric acid, organic peracids, chlorine, hypochlorite, chlorine dioxide, peroxides, etc. A number of advantageously usable bleaching agents are mentioned below.
Die Oxidationsmittel, vorzugsweise Bleichmittel können vorzugsweise gecoatet sein. Das Coating kann dazu dienen, die Wechselwirkung mit anderen Inhaltsstoffen zu verringern, was aber nicht vollständig gelingt.The oxidizing agents, preferably bleaching agents, may preferably be coated. The coating can serve to reduce the interaction with other ingredients, but this is not completely successful.
Nach einer weiteren bevorzugten Ausführungsform handelt es sich bei dem Oxidationsmittel um ein oxidatives Bleichmittel, vorzugsweise auf Sauerstoffbasis, wobei insbesondere Peroxycarbon- säuren bevorzugt sind.According to a further preferred embodiment, the oxidizing agent is an oxidative bleaching agent, preferably based on oxygen, with particular preference being given to peroxycarboxylic acids.
Nach einer weiteren bevorzugten Ausführungsform ist in dem erfindungsgemäßen Mittel eine Per- oxycarbonsäure enthalten, wobei diese vorteilhafterweise aus Mono- und Diperoxycarbonsäuren, insbesondere Dodekandiperoxysäure oder vorzugsweise Imidoperoxycarbonsäuren, besonders bevorzugt 6-Phthalimidoperoxycapronsäure (6-Phthalimidoperoxyhexansäure, PAP) ausgewählt ist und/oder wobei die Peroxycarbonsäure bei Atmosphärendruck einen Schmelzpunkt oberhalb von 25°C, insbesondere oberhalb von 35°C, vorzugsweise oberhalb von 450C, bevorzugt oberhalb von 50°C, besonders bevorzugt oberhalb von 1000C, aufweist.According to a further preferred embodiment, the agent according to the invention contains a peroxycarboxylic acid, which is advantageously selected from mono- and diperoxycarboxylic acids, in particular dodecanediperoxyacid or preferably imidoperoxycarboxylic acids, more preferably 6-phthalimidoperoxycaproic acid (6-phthalimidoperoxyhexanoic acid, PAP) and / or wherein the Peroxycarboxylic acid at atmospheric pressure has a melting point above 25 ° C, in particular above 35 ° C, preferably above 45 0 C, preferably above 50 ° C, more preferably above 100 0 C.
Nach einer weiteren bevorzugten Ausführungsform liegt das Oxidationsmittel, insbesondere die Peroxycarbonsäure, im wesentlichen in granulärer Form vor, vorzugsweise gecoatet, wobei die Masse des Coatings vorteilhafterweise 0,1 bis 30 Gew.-% beträgt, bezogen auf das gesamte das Oxidationsmittel enthaltende Teilchen, vorzugsweise Granulat. „Im wesentlichen" bedeutet hier, dass, vorzugsweise bei einem frisch hergestelltem Produkt, vorteilhafterweise zumindest 50, 55, 60, 65, 70, 75 Gew -% des Oxidationsmittels in granulärer Form vorliegen, wobei sich die Angabe Gew -% hier auf die Gesamtmenge Oxidationsmittel bezieht Z B kann in einem flussigen Mittel, insbesondere nach einer Lagerzeit, auch ein Anteil des Oxidationsmittels in gelöster Form vorliegenAccording to a further preferred embodiment, the oxidizing agent, in particular the peroxycarboxylic acid, is present in granular form, preferably coated, the mass of the coating advantageously being from 0.1 to 30% by weight, based on the total of the particles containing the oxidizing agent, preferably Granules. "Essentially" means here that, preferably in the case of a freshly prepared product, advantageously at least 50, 55, 60, 65, 70, 75% by weight of the oxidizing agent are present in granular form, the statement wt% here referring to the total amount of oxidizing agent Means, in particular after a storage period, also present a proportion of the oxidizing agent in dissolved form
Nach einer bevorzugten Ausfuhrungsform enthält das erfindungsgemäße Mittel zumindest 0,01 Gew -% TensideAccording to a preferred embodiment, the agent according to the invention contains at least 0.01% by weight of surfactants
Dabei kann der Tensidgehalt des gesamten Mittels z B 0,1-60 Gew -%, vorzugsweise 1-50 Gew - %, vorteilhafterweise 5-45 Gew -%, noch vorteilhafter 10-40 Gew -%, insbesondere 15-30 Gew -%, bezogen auf das gesamte Mittel betragen Nach einer anderen bevorzugten Ausfuhrungsform kann die Untergrenze des Tensidgehaltes aber auch bei einem Wert von vorzugsweise 1 Gew -%, 2 Gew -%, 3 Gew -%, 4 Gew -%, 5 Gew -%, 6 Gew -%, 7 Gew -%, 8 Gew -%, 9 Gew -%, 10 Gew - %, 11 Gew -%, 12 Gew -%, 13 Gew -%, 14 Gew -%, 15 Gew -%, 16 Gew -%, 17 Gew -%, 18 Gew -%, 19 Gew -%, 20 Gew -%, 21 Gew -%, 22 Gew -%, 23 Gew -%, 24 Gew -%, 25 Gew -%, 26 Gew -%, 27 Gew -%, 28 Gew -%, 29 Gew -% oder 30 Gew -% hegen, bezogen auf das gesamte Mittel Die Untergrenze an Tensid kann insbesondere sogar bei noch höheren Werten liegen, z B bei einem Wert von vorzugsweise 35 Gew -%, 40 Gew -%, 45 Gew -%, 50 Gew -%, 55 Gew -% oder 60 Gew -%, bezogen auf das gesamte MittelIn this case, the surfactant content of the entire composition z B is 0.1-60% by weight, preferably 1-50% by weight, advantageously 5-45% by weight, more preferably 10-40% by weight, in particular 15-30% by weight However, according to another preferred embodiment, the lower limit of the surfactant content may also be at a value of preferably 1% by weight, 2% by weight, 3% by weight, 4% by weight, 5% by weight, 6 % By weight, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, % By weight, 17% by weight, 18% by weight, 19% by weight, 20% by weight, 21% by weight, 22% by weight, 23% by weight, 24% by weight, 25% by weight, 26 % By weight, 27% by weight, 28% by weight, 29% by weight or 30% by weight, based on the total agent The lower limit of surfactant may in particular even be even higher values, for example at a value of preferably 35% by weight, 40% by weight, 45% by weight, 50% by weight, 55% by weight or 60% by weight, based on the total agent
Die Obergrenze an Tensid kann beispielsweise auch bei einem Wert von vorzugsweise 65 Gew - %, 60 Gew -%, 55 Gew -%, 50 Gew -%, 45 Gew -%, 40 Gew -%, 35 Gew -%, 30 Gew -% oder 25 Gew -% oder sogar nur bei Werten wie 20 Gew -%,19 Gew -%, 18 Gew -%, 17 Gew -%, 16 Gew - %, 15 Gew -%, 14 Gew -%, 13 Gew -%, 12 Gew -%, 11 Gew -% oder 10 Gew -% liegen Es ist z B auch möglich die genannten Untergrenze und Obergrenzen aus den vorgenannten Angaben geeignet zu kombinieren, z B um zu einem Tensidgehalt von 4-18 Gew -% darzustellen Es ist auch möglich, dass 0 Gew -% Tensid enthalten istThe upper limit of surfactant can also be used, for example, at a value of preferably 65% by weight, 60% by weight, 55% by weight, 50% by weight, 45% by weight, 40% by weight, 35% by weight, 30% by weight. % or 25% by weight or even only at values such as 20% by weight, 19% by weight, 18% by weight, 17% by weight, 16% by weight, 15% by weight, 14% by weight, 13% by weight %, 12% by weight, 11% by weight or 10% by weight It is, for example, also possible to suitably combine the stated lower limit and upper limits from the abovementioned data, for example to represent a surfactant content of 4-18% by weight It is also possible that 0% by weight of surfactant is included
Erfindungsgemäß bevorzugt sind dabei insbesondere anionische Tenside, wie z B (lineare) Alkyl- benzolsulfonate, Fettalkoholsulfate oder Alkansulfonate usw , vorzugsweise in Mengen von z B 0,1 bis 30 Gew -%, und/oder nichtionische Tenside, wie z B Alkylpolyglykolether, Alkylpolygluco- side oder Aminoxide usw , vorzugsweise in Mengen von z B 0,1 bis 30 Gew -%, jeweils bezogen auf das gesamte MittelParticularly preferred according to the invention are anionic surfactants, such as, for example, (linear) alkylbenzenesulfonates, fatty alcohol sulfates or alkanesulfonates etc., preferably in amounts of from 0.1 to 30% by weight, and / or nonionic surfactants, for example alkylpolyglycol ethers, alkylpolygluco - side or amine oxides, etc., preferably in amounts of, for example, from 0.1 to 30% by weight, in each case based on the total agent
Das erfindungsgemaße Mittel kann auch kationische Tenside enthalten, z B in Mengen von 0,01 Gew -% oder 0,05 Gew -% bis 30 Gew -% Es entspricht aber einer bevorzugten Ausfuhrungsform, wenn das erfindungsgemäße Mittel kationtensidfrei ist, was hier bedeutet, dass das Mittel weniger als 10 Gew -%, vorzugsweise weniger als 5 Gew -%, vorteilhafterweise weniger als 3 Gew -%, in vorteilhafterer Weise weniger als 1 Gew -%, in noch vorteilhafter Weise weniger als 0,5 Gew -%, insbesondere 0 Gew -% Kationtensid enthält Nach einer bevorzugten Ausführungsform enthält das erfindungsgemäße Mittel Elektrolyte, insbesondere anorganische und/oder organische Salze, insbesondere Phosphat, Citrat und/oder Sulfat, besonders bevorzugt Natriumsulfat, vorzugsweise in Mengen von zumindest 0,1 Gew.-%, vorteilhafterweise zumindest 3 Gew.-%, insbesondere in Mengen von 5 bis 30 Gew.-%, jeweils bezogen auf das gesamte Mittel. Es ist auch möglich, dass 0 Gew.-% Elektrolyt enthalten ist.The agent according to the invention may also contain cationic surfactants, for example in amounts of 0.01% by weight or 0.05% by weight to 30% by weight. However, it corresponds to a preferred embodiment if the agent according to the invention is cationic surfactant-free, which means the agent is less than 10% by weight, preferably less than 5% by weight, advantageously less than 3% by weight, more preferably less than 1% by weight, even more preferably less than 0.5% by weight, in particular 0% by weight of cationic surfactant According to a preferred embodiment, the agent according to the invention contains electrolytes, in particular inorganic and / or organic salts, in particular phosphate, citrate and / or sulfate, more preferably sodium sulfate, preferably in amounts of at least 0.1% by weight, advantageously at least 3% by weight. %, in particular in amounts of 5 to 30 wt .-%, each based on the total agent. It is also possible that 0 wt .-% electrolyte is included.
Wenn das erfindungsgemäße Mittel Komplexbildner enthält, wie z.B. Nitrilotriessigsäure, Ethylendi- amintetraessigsäure oder Phsophonat usw., vorzugsweise in Mengen von bis zu 30 Gew.-% oder bis zu 20 Gew.-%, insbesondere 0 bis 10 Gew.-%, vorteilhafterweise von 0,1 bis 5 Gew.-%, bezogen auf das gesamte Mittel, so liegt eine weitere bevorzugten Ausführungsform der Erfindung vor. Besonders vorteilhaft sind dabeiWhen the agent of the invention contains complexing agents, e.g. Nitrilotriacetic acid, ethylenediaminetetraacetic acid or phosphonate etc., preferably in amounts of up to 30% by weight or up to 20% by weight, in particular 0 to 10% by weight, advantageously from 0.1 to 5% by weight , based on the total agent, so is a further preferred embodiment of the invention. Particularly advantageous are
(a) stickstoffreie Komplexbildner wie z.B. vorzugsweise Alkalimetallpolyphosphonate, Mono- oder Polyphosphonsäuren, insbesondere 1-Hydroxyethyliden-1,1-diphosphonsäure (HEDP), Citrat und/ oder kurzkettige Dicarbonsäuren. und/oder(a) nitrogen-free chelating agents such as e.g. preferably alkali metal polyphosphonates, mono- or polyphosphonic acids, in particular 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP), citrate and / or short-chain dicarboxylic acids. and or
(b) Komplexbildner aus der Gruppe Chinolin und/oder seine Salze, Picolinsäure und Dipicolinsäure (Ethylendiamintetraessigsäure (EDTA), Diethylentriaminpenta(methylenphosphonsäure) (DTPMP), Azacycloheptandiphosphonat (AHP), Nitrilotriessigsäure (NTA), Aminopolycarbonsäuren, Aminohy- droxypolycarbonsäuren, Polyphosphonsäuren und Aminopolyphosphonsäuren.(b) complexing agents from the group quinoline and / or its salts, picolinic acid and dipicolinic acid (ethylenediaminetetraacetic acid (EDTA), diethylenetriamine penta (methylenephosphonic acid) (DTPMP), azacycloheptane diphosphonate (AHP), nitrilotriacetic acid (NTA), aminopolycarboxylic acids, aminohydroxypolycarboxylic acids, polyphosphonic acids and aminopolyphosphonic acids ,
Dabei ist 1-Hydroxyethyliden-1 ,1-diphosphonsäure am meisten bevorzugt. Es ist auch möglich, dass 0 Gew.-% Komplexbildner enthalten ist.Here, 1-hydroxyethylidene-1, 1-diphosphonic acid is most preferred. It is also possible that 0 wt .-% complexing agent is included.
Diese Komplexbildner können erfindungsgemäß eingesetzt werden, um vorzugsweise Schwermetallionen zu inaktivieren bzw. zu binden, die insbesondere als Katalysatoren von Oxidationsprozes- sen fungieren können und somit zu einem Abbau von Oxidationsmittel z.B. Peroxycarbonsäuren, wie PAP, führen können und die beispielsweise über Wasserleitungen oder metallische Bauteile der Produktionsanlagen oder über Roh- bzw. Inhaltsstoffe in das erfindungsgemäße Mittel, z.B. Wasch- oder Reinigungsmittel, eingetragen werden können.These complexing agents can be used according to the invention to preferably inactivate or bind heavy metal ions, which in particular can act as catalysts of oxidation processes and thus lead to degradation of oxidizing agent, e.g. Peroxycarboxylic acids, such as PAP, and which, for example, via water pipes or metallic components of the production plants or via raw materials or ingredients in the agent according to the invention, e.g. Detergents or cleaners, can be registered.
Nach einer bevorzugten Ausführungsform der Erfindung enthält das erfindungsgemäße Mittel außerdem Enzyme, wie insbesondere z.B. Proteasen, Amylasen, Katalasen, Peroxidasen, CeIIuIa- sen und/oder Lipasen, und/oder Enzymstabilisatoren, vorzugsweise in Mengen von 0 bis 10 Gew.- % jeweils bezogen auf das gesamte Mittel. Es ist auch möglich, dass 0 Gew.-% Enzym enthalten ist.According to a preferred embodiment of the invention, the agent according to the invention also contains enzymes, in particular e.g. Proteases, amylases, catalases, peroxidases, cellulases and / or lipases, and / or enzyme stabilizers, preferably in amounts of from 0 to 10% by weight, based in each case on the total agent. It is also possible that 0 wt .-% enzyme is included.
Nach einer bevorzugten Ausführungsform enthält das erfindungsgemäße Mittel Builder (Gerüststoffe). Gemäß einer weiteren bevorzugten Ausführungsform der Erfindung beträgt der Builderge- halt des Mittels z.B. 0-99 Gew.-%, vorzugsweise 1-60 Gew.-%, vorteilhafterweise 2-50 Gew.-%. noch vorteilhafter 3-60 Gew.-%, weiter vorteilhaft 5-50 Gew.-%., insbesondere 6-40 Gew.-%. Nach einer anderen bevorzugten Ausführungsform kann die Untergrenze des Buildergehaltes aber auch bei einem Wert von vorzugsweise 7 Gew.-%, 8 Gew.-%, 9 Gew.-%, 10 Gew.-%, 11 Gew.-%, 12 Gew.-%, 13 Gew.-%, 14 Gew.-%, 15 Gew.-%, 16 Gew.-%, 17 Gew.-%, 18 Gew.-%, 19 Gew.-%, 20 Gew.-%, 21 Gew.-%, 22 Gew.-%, 23 Gew.-%, 24 Gew.-%, 25 Gew.-%, 26 Gew.-%, 27 Gew.-%, 28 Gew.-%, 29 Gew.-% oder 30 Gew.-% liegen. Die Untergrenze kann insbesondere sogar bei noch höheren Werten liegen, z.B. bei einem Wert von vorzugsweise 35 Gew.-%, 40 Gew.-%, 45 Gew.- %, 50 Gew.-%, 55 Gew.-% oder 60 Gew.-%.According to a preferred embodiment, the agent according to the invention contains builders (builders). According to a further preferred embodiment of the invention, the builder content of the agent is, for example, 0-99% by weight, preferably 1-60% by weight, advantageously 2-50% by weight. even more advantageously 3-60% by weight, more preferably 5-50% by weight, in particular 6-40% by weight. According to another preferred embodiment, the lower limit of the builder content but also at a value of preferably 7 wt .-%, 8 wt .-%, 9 wt .-%, 10 wt .-%, 11 wt .-%, 12 wt. %, 13 wt%, 14 wt%, 15 wt%, 16 wt%, 17 wt%, 18 wt%, 19 wt%, 20 wt% , 21 wt%, 22 wt%, 23 wt%, 24 wt%, 25 wt%, 26 wt%, 27 wt%, 28 wt%, 29 Wt .-% or 30 wt .-% are. The lower limit may in particular even be at even higher values, for example at a value of preferably 35% by weight, 40% by weight, 45% by weight, 50% by weight, 55% by weight or 60% by weight. -%.
Nach einer weiteren bevorzugten Ausführungsform kann die Obergrenze des Buildergehaltes auch bei einem Wert von vorzugsweise 70 Gew.-%, 71 Gew.-%, 72 Gew.-%, 73 Gew.-%, 74 Gew.-%, 75 Gew.-%, 76 Gew.-%, 77 Gew.-%, 78 Gew.-%, 79 Gew.-%, 80 Gew.-%, 81 Gew.-%, 82 Gew.-%, 83 Gew.-%, 84 Gew.-%, 85 Gew.-%, 86 Gew.-%, 87 Gew.-%, 88 Gew.-%, 89 Gew.-%, 90 Gew.-%, 91 Gew.-%, 92 Gew.-%, 93 Gew.-%, 94 Gew.-% oder 95 Gew.-% liegen. Die Obergrenze kann insbesondere auch bei tieferen Werten liegen, z.B. bei einem Wert von vorzugsweise 65 Gew.-%, 45 Gew.-%, 35 Gew.-%, 30 Gew.-%, 25 Gew.-%, 20 Gew.-%, 15 Gew.-%, 10 Gew.-% oder 5 Gew.-%. Es kann im Sinne einer wiederum anderen Ausführungsform auch möglich sein, dass kein Builder, also 0 Gew.-%, enthalten ist.According to a further preferred embodiment, the upper limit of the builder content may also be at a value of preferably 70% by weight, 71% by weight, 72% by weight, 73% by weight, 74% by weight, 75% by weight. %, 76 wt%, 77 wt%, 78 wt%, 79 wt%, 80 wt%, 81 wt%, 82 wt%, 83 wt%, 84 wt.%, 85 wt.%, 86 wt.%, 87 wt.%, 88 wt.%, 89 wt.%, 90 wt.%, 91 wt.%, 92 wt .-%, 93 wt .-%, 94 wt .-% or 95 wt .-% are. In particular, the upper limit can also be at lower values, e.g. at a value of preferably 65 wt .-%, 45 wt .-%, 35 wt .-%, 30 wt .-%, 25 wt .-%, 20 wt .-%, 15 wt .-%, 10 wt. -% or 5 wt .-%. It may also be possible within the meaning of another embodiment that no builder, ie 0% by weight, is contained.
Insbesondere im Falle der Flüssigwaschmittel kann nach einer bevorzugten Ausführungsform vorzugsweise auch nur sehr wenig Builder enthalten sein, z.B. mehr als 0,1 Gew.-%, mehr als 0,5 Gew.-% oder mehr als 1 Gew.-%, vorteilhafterweise aber weniger als 30Gew.-%, vorzugsweise weniger als 20 Gew.-%, insbesondere weniger als 10 Gew.-%.In particular, in the case of liquid detergents, according to a preferred embodiment, preferably also very little builder may be present, e.g. more than 0.1 wt .-%, more than 0.5 wt .-% or more than 1 wt .-%, but advantageously less than 30 wt .-%, preferably less than 20 wt .-%, in particular less than 10 wt .-%.
Nach einer weiteren bevorzugten Ausführungsform enthält das erfindungsgemäße Mittel als Builder insbesondere Fettsäuren, vorzugsweise gesättigte und/oder verzweigte Fettsäuren, insbesondere mit einem Schmelzpunkt unterhalb von 4O0C1 bevorzugt unterhalb von 300C, und/oder Citro- nensäure und/oder Citrat, vorzugsweise in Mengen von z.B. 0 bis 15 Gew.-%, und/oder Polyacry- late, vorzugsweise in Mengen von z.B. 0 bis 15 Gew.-% , und/oder Phosphonate, wobei sich die Angabe Gew.-% jeweils auf das gesamte Mittel bezieht.According to a further preferred embodiment, the inventive composition contains as builder in particular fatty acids, preferably saturated and / or branched fatty acids, especially having a melting point below 4O 0 C 1 is preferably less than 30 0 C, and / or citric nensäure and / or citrate, preferably in amounts of, for example, from 0 to 15% by weight, and / or polyacrylates, preferably in amounts of, for example, from 0 to 15% by weight, and / or phosphonates, where the term% by weight refers in each case to the total Means relates.
Wenn das erfindungsgemäße Mittel zumindest im wesentlichen keine Halogenidionen, insbesondere keine Chloridionen, aufweist, wobei die Menge an Halogenidionen, insbesondere Chloridionen, vorteilhafterweise höchstens 500 ppm, vorzugsweise höchstens 100 ppm, insbesondere höchstens 30 ppm, beträgt, so liegt eine bevorzugte Ausführungsform vor. Denn die Anmelderin hat überraschenderweise herausgefunden, dass eine hohe Halogenid-, insbesondere Chloridionenkonzentration, wie sie beispielsweise in herkömmlichen Wasch- und Reinigungsmitteln infolge von Verunreinigungen mancher Roh- bzw. Inhaltsstoffe üblich sein kann, insbesondere bei flüssigen Mitteln zu einem verstärktem Abbau von Oxidationsmittel, wie z.B. Peroxycarbonsäuren führen kann. Somit kann eine Verringerung der Halogenidkonzentration, insbesondere der Chloridionen- konzentration, zu einem verminderten Abbau des Oxidationsmittels, z.B. der Peroxycarbonsäure führen. Eine geringe Chloridionenkonzentration kann erfindungsgemäß beispielsweise durch den Einsatz von Methylsulfat-, Phosphat-, Tosylat- oder Cumolsulfonatverbindungen bzw. durch die Verwendung chloridarmer Roh- bzw. Inhaltsstoffe erreicht werden (z.B. Verwendung von im wesentlichen halogenidfreien Komponenten, so z.B. halogenidfreien Tensiden, halogenidfreien Phos- phonaten etc.).If the agent according to the invention has at least substantially no halide ions, in particular no chloride ions, the amount of halide ions, in particular chloride ions, advantageously being at most 500 ppm, preferably at most 100 ppm, in particular at most 30 ppm, then a preferred embodiment is present. Because the Applicant has surprisingly found that a high halide, in particular chloride ion concentration, as may be common in conventional detergents and cleaners due to contamination of some raw materials or ingredients, especially in liquid agents to increased degradation of oxidizing agents, such as For example, peroxycarboxylic acids can lead. Thus, a reduction of the halide concentration, in particular the chloride ion concentration, lead to a reduced degradation of the oxidizing agent, for example the peroxycarboxylic acid. A low chloride ion concentration can be achieved according to the invention, for example, by the use of methylsulfate, phosphate, tosylate or cumene sulfonate compounds or by the use of low-chloride raw materials or ingredients (eg use of essentially halide-free components, eg halide-free surfactants, halide-free phosphates). phonates etc.).
Nach einer weiteren bevorzugten Ausführungsform sind weniger als 30 Gew.-%, vorzugsweise weniger als 20 Gew.-%, vorteilhafterweise weniger als 15 Gew.-%, in vorteilhafterer Weise weniger als 10 Gew.-%, in noch vorteilhafterer Weise weniger als 5 Gew.-%, in wiederum vorteilhafterer Weise weniger als 3 Gew.-%, in weiter vorteilhafter Weise weniger als 2 Gew.-%, in noch weiter vorteilhafter Weise weniger als 1 Gew.-%, in besonders vorteilhafter Weise weniger als 0,5 Gew.- % insbesondere 0 Gew.-% der enthaltenen Riechstoffe aus solchen Riechstoffen ausgewählt, welche eine Aldehydfunktion (RCH=O) und/oder eine Keto-Gruppe ( RR1C=O ) tragen, wobei sich die Angabe Gew.-% auf die Gesamtmenge der im Mittel enthaltenen Riechstoffe bezieht.In a further preferred embodiment less than 30% by weight, preferably less than 20% by weight, advantageously less than 15% by weight, more preferably less than 10% by weight, more preferably less than 5% % By weight, more preferably less than 3% by weight, more preferably less than 2% by weight, even more advantageously less than 1% by weight, most preferably less than 0, 5% by weight, in particular 0% by weight, of the fragrance substances contained are selected from those fragrances which have an aldehyde function (RCH = O) and / or a keto group (RR 1 C = O), the wording Gew.- % refers to the total amount of fragrances contained in the middle.
Wenn das Mittel in flüssiger Form, vorzugsweise in wässriger oder nichtwässriger Form, vorliegt, wobei es sich vorteilhafterweise um eine Dispersion, vorzugsweise um eine Emulsion oder Suspension, handelt, so liegt eine bevorzugte Ausführungsform vor. Dabei kann das Mittel auch als Pouch vorliegen.If the agent is in liquid form, preferably in aqueous or nonaqueous form, which is advantageously a dispersion, preferably an emulsion or suspension, then a preferred embodiment is present. The agent may also be present as a pouch.
Es lassen sich durch die Erfindung z.B. flüssige Vollwaschmittel mit hervorragender Waschleistung insbesondere im Bereich der bleichbaren Anschmutzungen in Verbindung mit einer sehr ansprechenden Parfümierung sowohl im Produkt als auch auf der Wäsche realisieren. Der Dufteindruck im Produkt unterliegt dabei auch bei längerer Lagerung keiner Veränderung und die Parfümierung zeigt keine destabilisierende Wirkung auf das Bleichmittel.The invention can be e.g. liquid heavy-duty detergents with outstanding washing performance, especially in the area of bleachable stains in connection with a very appealing perfuming both in the product and on the laundry realize. The fragrance impression in the product is subject to no change even during prolonged storage and the perfuming does not show a destabilizing effect on the bleaching agent.
Das Mittel, welches insbesondere in flüssiger Form vorliegt, weist nach einer weiteren bevorzugten Ausführungsform einen pH-Wert von vorteilhafterweise höchstens 7, insbesondere einen pH-Wert von 3,5 bis 7, vorzugsweise von 4,0 bis 6,5, besonders bevorzugt von 4,5 bis 6, ganz besonders bevorzugt von etwa 5, auf, und/oder, sofern es sich um ein flüssiges Mittel handelt, kann es vorzugsweise mindestens ein wassermischbares Lösemittel mit einem für die Peroxycarbonsäure, insbesondere Imidoperoxycarbonsäure, geringen Lösungsvermögen, vorzugsweise Glycerin, enthalten.The agent, which is present in particular in liquid form, according to a further preferred embodiment has a pH of advantageously at most 7, in particular a pH of 3.5 to 7, preferably from 4.0 to 6.5, particularly preferably from From 4.5 to 6, very particularly preferably from about 5 to, and / or, if it is a liquid agent, it may preferably be at least one water-miscible solvent having a low dissolving power, preferably glycerol, for the peroxycarboxylic acid, in particular imidoperoxycarboxylic acid. contain.
Bleichmittel, insbesondere auf Basis von Peroxycarbonsäuren, wie PAP, können in einer sauren Umgebung, insbesondere bei einem pH-Wert um 6 relativ wirkungsvoll stabilisiert werden. Die nach einer bevorzugten Ausfuhrungsform mögliche Herabsetzung des pH-Wertes in den erfin- dungsgemaßen Mitteln, vorzugsweise flussige Mittel, insbesondere flussige Wasch- und Reinigungsmitteln kann beispielsweise durch Zugabe von Säuren oder sauren Salzen erfolgen Erfindungsgemäß bevorzugt sind Bisulfate, Bicarbonate und organische Polycarbonsäuren, die zum Beispiel gleichzeitig auch als Buildersubstanzen eingesetzt werden können Ferner können die als Komplexbildner einsetzbaren Phosphonate oder Citrate als Phosphonsäuren bzw Zitronensäure eingearbeitet werden und anschließend der gewünschte pH-Wert durch Zugabe von Alkalien eingestellt werden Auch die Zugabe von ionogenem Tensid, z B LAS, ist als Säure möglich, wobei der pH-Wert durch anschließende Zugabe von Natronlauge eingestellt werden kannBleaching agents, in particular those based on peroxycarboxylic acids, such as PAP, can be stabilized relatively effectively in an acid environment, in particular at a pH of around 6. The According to a preferred embodiment possible reduction of the pH in the inventive dungsgemaßen means, preferably liquid agents, in particular liquid detergents and cleaners can be carried out for example by adding acids or acidic salts According to the invention are preferred bisulfates, bicarbonates and organic polycarboxylic acids, for example It is also possible to use the phosphonates or citrates which can be used as complexing agents as phosphonic acids or citric acid and then to adjust the desired pH by adding alkalis. The addition of ionic surfactant, for example LAS, is also possible as acid , wherein the pH can be adjusted by subsequent addition of sodium hydroxide solution
Die erfindungsgemäßen Mittel, vorzugsweise (flussige) Wasch- oder Reinigungsmittel, können nach einer bevorzugten Ausfuhrungsform mindestens eine Fettsaure enthalten Dabei sind gesättigte und/oder verzweigte Fettsäuren, insbesondere mit einem Schmelzpunkt unterhalb von 3O0C, erfindungsgemäß bevorzugt Im Rahmen der vorliegenden Erfindung kann beispielsweise Isocarb- 16® der Firma Sasol in den erfindungsgemäßen Wasch- oder Reinigungsmitteln eingesetzt werdenThe agents of the invention, preferably (LIQUID) washing or cleaning agent, can, in a preferred embodiment contain at least one fatty acid this case are saturated and / or branched fatty acids, especially having a melting point below 3O 0 C, preferable in the invention In the present invention, for example Isocarb- 16 ® Sasol be used in the inventive washing or cleaning agents
Die erfindungsgemäßen Mittel, vorzugsweise (flussige) Wasch- oder Reinigungsmittel, können vor- teilhafterweise einen Citronensäure- bzw Citratgehalt aufweisen Zwar kann Citronensäure bzw Citrat beispielsweise zu einem Abbau von Peroxycarbonsäuren, insbesondere PAP, fuhren Dennoch kann es gegebenenfalls vorteilhaft sein, Citronensäure bzw Citrate in dem erfindungsgemäßen Mittel, z B dem Wasch- oder Reinigungsmittel einzusetzen (zum Beispiel als Builder und/oder als Komplexbildner)The agents according to the invention, preferably (liquid) washing or cleaning agents, may advantageously have a citric acid or citrate content. Citric acid or citrate may, for example, lead to a degradation of peroxycarboxylic acids, especially PAP. Nevertheless, it may be advantageous to use citric acid or citrates in the agent according to the invention, for example the detergent or cleaning agent (for example as builder and / or as complexing agent)
Das erfindungsgemaße Mittel kann auch von gelformiger oder pastenformiger Konsistenz sein Nach einer bevorzugten Ausfuhrungsform ist das mittel gießfähig, vorzugsweise weist es eine Viskosität zwischen 100 und 10000 mPas bei einer Scherrate von 30 s'1 und einer Temperatur von 25°C aufThe composition according to the invention may also be of gel-like or paste-like consistency. According to a preferred embodiment, the agent is pourable, preferably it has a viscosity between 100 and 10000 mPas at a shear rate of 30 s -1 and a temperature of 25 ° C.
Nach einer anderen bevorzugten Ausfuhrungsform hegt das Mittel in fester Form vor, vorzugsweise als PulverAccording to another preferred embodiment, the agent is present in solid form, preferably as a powder
Gemäß einer bevorzugten Ausfuhrungsform der Erfindung ist das Pulver mehrheitlich (z B in Mengen >50 Gew -%, >60 Gew -%, >70 Gew -%, >80 Gew -%, >90 Gew -% oder >95 Gew -% bezogen auf das gesamte Pulver) aus gleichmäßigen, vorzugsweise nahezu kugelförmigen oder ellip- soiden Partikeln ausgebildet Das Ellipsoid ist ähnlich der Kugel, jedoch Längsachse und Quer- achse sind unterschiedlich. Das Pulver kann aber auch nach anderen Ausführungsformen aus Partikeln bestehen, die ebenso mehrheitlichAccording to a preferred embodiment of the invention, the powder is predominantly (for example, in amounts of> 50% by weight,> 60% by weight,> 70% by weight,> 80% by weight,> 90% by weight or> 95% by weight). based on the total powder) of uniform, preferably almost spherical or elliptical particles formed. The ellipsoid is similar to the ball, but longitudinal axis and transverse Axes are different. However, the powder can also consist of other embodiments of particles, the majority as well
(a) kubisch geformt (würfelförmig) oder zumindest annähernd kubisch geformt oder(a) cubic (cube-shaped) or at least approximately cubic-shaped or
(b) parallelepiped geformt (z.B. quaderförmig) oder zumindest annähernd parallelepiped geformt oder(b) shaped parallelepiped (e.g., cuboid) or at least approximately parallelepiped shaped or
(c) lamellar geformt (plättchenförmig und ähnliches) oder zumindest annähernd lamellar geformt oder(c) lamellar (platy and the like) or at least approximately lamellar or
(d) nadelartig oder faserartig geformt oder zumindest annähernd nadelartig oder faserartig oder(d) needle-like or fibrous-shaped, or at least approximately needle-like or fibrous, or
(e) zylindrisch geformt oder(e) cylindrically shaped or
(f) strangartig oder zumindest annähernd strangartig geformt sind.(f) are strand-like or at least approximately strand-like.
Gemäß einer anderen bevorzugten Ausführungsform der Erfindung weisen die erfindungsgemäßenAccording to another preferred embodiment of the invention, the inventive
Mittel, wenn es sich um feste Mittel handelt, Schüttgewichte im Bereich von 200-1500 g/L auf.In the case of solid compositions, bulk densities in the range of 200-1500 g / L.
Die untere Grenze für das Schüttgewicht kann auch bei einem Wert von vorzugsweise 250, 300,The lower limit for the bulk density can also be set at a value of preferably 250, 300,
350, 400, 450, 500, 550, 600, 650, 700 oder sogar bei 750 g/L liegen. Es ist auch möglich, dass die untere Grenze noch höher liegt, z.B. bei 800g/L.350, 400, 450, 500, 550, 600, 650, 700 or even 750 g / L. It is also possible that the lower limit is even higher, e.g. at 800g / L.
Die obere Grenze für das Schüttgewicht kann bei einem Wert von vorzugsweise 1450, 1400, 1350,The upper limit for the bulk density may be at a value of preferably 1450, 1400, 1350,
1300, 1250, 1200, 1150, 1100, 1050, 1000, 950, 900, 850, 800 oder 750 g/L liegen.1300, 1250, 1200, 1150, 1100, 1050, 1000, 950, 900, 850, 800 or 750 g / L.
Es ist auch möglich, dass die obere Grenze noch tiefer liegt, z.B. bei einem Wert von vorzugsweise 700, 650, 600, 550 oder 500 g/L.It is also possible that the upper limit is even lower, e.g. at a value of preferably 700, 650, 600, 550 or 500 g / L.
Wenn es sich bei dem festen Mittel um ein Kompaktat handelt, erhältlich z.B. durch Vorgänge wie Pressen, Walzen, Brikettieren, Pelleti(si)eren, Extrudieren, Agglomerieren oder verwandte verdichtende Verfahren, so handelt es sich dabei um eine weiter bevorzugte Ausführungsform.When the solid agent is a compactate, available e.g. by operations such as pressing, rolling, briquetting, pelletizing, extruding, agglomerating or related compaction processes, this is a further preferred embodiment.
Nach einer weiteren bevorzugten Ausführungsform handelt es sich bei dem Mittel in fester Form um einen Formkörper, vorzugsweise um eine Tablette oder um einen Block oder um einen Strang. Dabei können mehrphasige bzw. mehrschichtige Formkörper bevorzugt sein. Möglich sind auch Festkörperpouches, also z.B. Pulver im Pouch.According to a further preferred embodiment, the agent in solid form is a shaped body, preferably a tablet or a block or a strand. In this case, multiphase or multilayer shaped bodies may be preferred. Also possible are solid pouches, e.g. Powder in the pouch.
Bei den flüssigen Mitteln, insbesondere flüssigen Wasch- bzw. Reinigungsmitteln, kann nach einer bevorzugten Ausführungsform der Gehalt an anorganischem Salz, besonders bevorzugt Natriumsulfat, in der Dispersion (des flüssigen Mittels) derart gewählt werden, dass bei einer Temperatur, welche um 50C, insbesondere um 1O0C, vorzugsweise um 15°C, geringer ist als die Lager- oder Aufbewahrungstemperatur (etwa 2O0C) der Dispersion, im wesentlichen eine Dispersion vorliegt, deren wässrige Phase mit dem anorganischen Salz gesättigt ist. In dieser Ausführungsform kann der Gehalt an organischem Salz, besonders bevorzugt Natriumsulfat, derart gewählt werden, dass bei etwa O0C bis 150C, insbesondere O0C bis 100C, bevorzugt O0C bis 50C, im wesentlichen eine mit dem anorganischen Salz gesättigte Dispersion erhalten wird. Dabei kann der Gehalt an anorganischem Salz, besonders bevorzugt Natriumsulfat, in der Dispersion, 5 bis 30 Gew.-%, insbesondere 10 bis 30 Gew.-%, vorzugsweise 15 bis 30 Gew.-%, bezogen auf die gesamte Formulierung betragen.In the case of the liquid agents, in particular liquid detergents or cleaners, according to a preferred embodiment, the content of inorganic salt, particularly preferably sodium sulfate, in the dispersion (of the liquid agent) can be selected such that at a temperature which is around 5 ° C. , in particular to 1O 0 C, preferably around 15 ° C, is less than the warehouse or storage temperature (about 2O 0 C) of the dispersion, substantially there is a dispersion in which the aqueous phase is saturated with the inorganic salt. In this embodiment can the content of organic salt, particularly preferably sodium sulfate, are chosen such that at about O 0 C to 15 0 C, in particular O 0 C to 10 0 C, preferably 0 0 C to 5 0 C, essentially one with the inorganic salt saturated dispersion is obtained. In this case, the content of inorganic salt, particularly preferably sodium sulfate, in the dispersion, 5 to 30 wt .-%, in particular 10 to 30 wt .-%, preferably 15 to 30 wt .-%, based on the total formulation.
Weiterhin kann nach einer weiteren bevorzugten Ausführungsform der Gehalt an anorganischem Salz, besonders bevorzugt Natriumsulfat, in dem erfindungsgemäßen Mittel, vorzugsweise flüssigem Mittel, insbesondere flüssigem Wasch- oder Reinigungsmittel, derart gewählt sein, dass die Tenside in dem Mittel zumindest im wesentlichen inaktiviert sind, insbesondere durch Aussalzen, d.h. Induzierung einer Phasentrennung in eine tensidarme, kontinuierliche Phase und eine vorzugsweise lamellare, im allgemeinen hochviskose, kristalline oder flüssigkristalline tensidreiche Phase, vorzugsweise durch Einbringen mindestens einer Sulfatverbindung, besonders bevorzugt Natriumsulfat. Bei solch einer Ausführungsform wird in der Formulierung, vorzugsweise Waschoder Reinigungsmittelformulierung, insbesondere ein Auflösen der organischen Peroxycarbon- säure zumindest im wesentlichen verhindert oder zumindest verringert. Erfindungsgemäß wird unter dem Begriff "kontinuierliche Phase" das Dispersionsmittel mit den darin gelösten Bestandteilen oder Inhaltstoffen (z.B. Salze, Tenside etc.) verstanden. Erfindungsgemäß bevorzugt ist das Dispersionsmittel Wasser.Furthermore, according to a further preferred embodiment, the content of inorganic salt, more preferably sodium sulfate, in the agent according to the invention, preferably liquid agent, in particular liquid detergent or cleaning agent, be chosen such that the surfactants are at least substantially inactivated in the agent, in particular by salting out, ie Inducing a phase separation in a low-surfactant, continuous phase and a preferably lamellar, generally highly viscous, crystalline or liquid-crystalline surfactant-rich phase, preferably by introducing at least one sulfate compound, particularly preferably sodium sulfate. In such an embodiment, in the formulation, preferably washing or cleaning agent formulation, in particular dissolution of the organic peroxycarboxylic acid is at least substantially prevented or at least reduced. According to the invention, the term "continuous phase" is understood to mean the dispersant with the constituents or ingredients dissolved therein (for example salts, surfactants, etc.). According to the invention, the dispersant is preferably water.
Durch die Zugabe von z.B. Sulfat gemäß einer bevorzugten Ausführungsform können - ohne sich auf eine Theorie festlegen zu wollen - die Tenside, welche womöglich zu einer Deaktivierung des Oxidationsmittels führen können, zumindest teilweise inaktiviert werden, was insbesondere durch Aussalzen geschehen kann, wobei die Tenside aus der insbesondere micellaren, aktiven Form in eine vorzugsweise lamellare, kristalline oder flüssigkristalline Form (Kristall- oder Flüssigkristallbildung) überführt werden können, die in einer nahezu tensidfreien kontinuierlichen Phase dispergiert ist. Der dispergierte Flüssigkristall selbst, der beispielsweise durch Zentrifugation abgetrennt werden kann, sollte dabei möglichst hochviskos sein. Der Gehalt an freien bzw. aktiven Tensiden, d.h. in mizellarer Form vorliegenden in den flüssigen Mitteln, vorzugsweise flüssigen Wasch- und Reinigungsmittelformulierungen bzw. in der kontinuierlichen Phase der erfindungsgemäßen flüssigen Wasch- und Reinigungsmittelformulierungen kann daher nach einer bevorzugten Ausführungsform vorzugsweise sehr gering sein, vorteilhafterweise nicht mehr als 1% betragen. Nach einer bevorzugten Ausführungsform sollte die Konzentration eines anorganischen Salzes, besonders bevorzugt Natriumsulfat, in dem erfindungsgemäßen Mittel, vorzugsweise flüssiges Mittel, insbesondere flüssiges Wasch- oder Reinigungsmittel, so gewählt sein, dass in der kontinuierlichen Phase des nichtverdünnten Wasch- oder Reinigungsmittels vorteilhafterweise weniger als 1% gelöstes Tensid vorliegt und bei Temperaturabsenkung, insbesondere bei Temperaturabsenkungen bis auf O0C, keine Auskristallisation des Salzes, vorzugsweise Sulfats, stattfindet.The addition of, for example, sulfate according to a preferred embodiment, the surfactants, which may possibly lead to a deactivation of the oxidizing agent, are at least partially inactivated, which can be done in particular by salting out, the surfactants from the particular micellar, active form can be converted into a preferably lamellar, crystalline or liquid-crystalline form (crystal or liquid crystal formation), which is dispersed in a nearly surfactant-free continuous phase. The dispersed liquid crystal itself, which can be separated, for example, by centrifugation, should be as highly viscous as possible. The content of free or active surfactants, ie present in micellar form in the liquid agents, preferably liquid detergents and cleaners formulations or in the continuous phase of the liquid detergent formulations according to the invention may therefore according to a preferred embodiment preferably be very low, advantageously not more than 1%. According to a preferred embodiment, the concentration of an inorganic salt, particularly preferably sodium sulfate, in the agent according to the invention, preferably liquid agent, in particular liquid detergent or cleaning agent should be chosen so that in the continuous phase of the undiluted washing or cleaning agent advantageously less than 1% dissolved surfactant is present and when the temperature is lowered, especially at temperature drops to 0 0 C, no crystallization of the salt, preferably sulfate, takes place.
Da insbesondere nichtionische Tenside hinsichtlich der Stabilität von Peroxycarbonsäure in dem erfindungsgemäßen Mittel, vorzugsweise flüssigem Mittel, insbesondere flüssigem Wasch- oder Reinigungsmittel problematisch sein können, können die erfindungsgemäßen Mittel vorzugsweise ein entsprechend angepasstes bzw. optimiertes Tensidverhältnis aufweisen. Dabei kann der Gehalt an Alkylpolyglykolethern vorzugsweise möglichst gering sein. In einer bevorzugten Ausführungsform geht der Gehalt an nichtionischen Tenside sogar gegen null. Entsprechende Formulierungen können als Tenside z.B. ausschließlich (lineare) Alkylbenzolsulfonate und/oder (sekundäre) Alkansulfonate enthalten und können eine hervorragende Stabilität des Bleichmittels zeigen. Nach einer weiteren bevorzugten Ausführungsform weist das erfindungsgemäße Produkt, wie insbesondere Wasch, Pflege- oder Reinigungsmittel, wenigstens eine, vorzugsweise mehrere, aktive Komponenten, insbesondere wasch-, pflege- und/oder reinigungsaktive Komponenten auf, vorteilhafterweise ausgewählt aus der Gruppe umfassend anionische Tenside, kationische Tenside, am- photere Tenside, nichtionische Tenside, Acidifizierungsmittel, Alkalisierungsmittel, Anti-Knitter-Verbindungen, antibakterielle Stoffe, Antioxidantien, Antiredepositionsmittel, Antistatika, Buildersub- stanzen, Bleichmittel, Bleichaktivatoren, Bleichstabilisatoren, Bleichkatalysatoren, Bügelhilfsmittel, Cobuilder, Einlaufverhinderer, Elektrolyte, Enzyme, Farbschutzstoffe, Färbemittel, Farbstoffe, Farb- übertragungsinhibitoren, Fluoreszensmittel, Fungizide, Germizide, geruchskomplexierende Substanzen, Hilfsmittel, Hydrotrope, Klarspüler, Komplexbildner, Konservierungsmittel, Korrosionsinhibitoren, optische Aufheller, Parfümträger, Perlglanzgeber, pH-Stellmittel, Phobier- und Imprägniermittel, Polymere, Quell- und Schiebefestmittel, Schauminhibitoren, Schichtsilikate, schmutzabweisende Stoffe, Silberschutzmittel, Silikonöle, UV-Schutz-Substanzen, Viskositätsregulatoren, Verdickungsmittel, Verfärbungsinhibitoren, Vergrauungsinhibitoren, Vitamine und/oder Weichspü- ler. In einer weiteren bevorzugten Ausführungsform enthält das erfindungsgemäße Mittel ein oder mehrere hautpflegende und/oder hautschützende und/oder hautheilende Aktivstoffe.Since, in particular, nonionic surfactants can be problematic with regard to the stability of peroxycarboxylic acid in the agent according to the invention, preferably liquid agent, in particular liquid detergent or cleaning agent, the agents according to the invention may preferably have a correspondingly adapted or optimized surfactant ratio. The content of alkyl polyglycol ethers may preferably be as low as possible. In a preferred embodiment, the content of nonionic surfactants even approaches zero. Corresponding formulations may be used as surfactants, e.g. contain only (linear) alkylbenzenesulfonates and / or (secondary) alkanesulfonates and can show excellent stability of the bleaching agent. According to a further preferred embodiment, the product according to the invention, in particular washing, care or cleaning agent, at least one, preferably more, active components, in particular washing, care and / or cleaning active components, advantageously selected from the group comprising anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, acidifiers, alkalizing agents, anti-wrinkle compounds, antibacterial agents, antioxidants, anti redeposition agents, antistatics, builders, bleaches, bleach activators, bleach stabilizers, bleach catalysts, ironing aids, cobuilders, anti-shrinkage agents, electrolytes, Enzymes, colorants, colorants, dyes, color transfer inhibitors, fluorescers, fungicides, germicides, odor-complexing substances, adjuvants, hydrotropes, rinse aids, complexing agents, preservatives, corrosion inhibitors, optical brighteners , Perfume carriers, pearlescers, pH adjusters, repellents and impregnating agents, polymers, swelling and anti-slip agents, foam inhibitors, phyllosilicates, dirt repellents, silver protectants, silicone oils, UV protectants, viscosity regulators, thickeners, discoloration inhibitors, grayness inhibitors, vitamins and / or Fabric softener. In a further preferred embodiment, the agent according to the invention contains one or more skin-care and / or skin-protecting and / or skin-healing active substances.
Hautpflegende Aktivstoffe sind alle solchen Aktivstoffe die der Haut einen sensorischen und/oder kosmetischen Vorteil verleihen. Hautpflegende Aktivstoffe sind bevorzugt ausgewählt aus den nachfolgenden Substanzen: a) Wachse wie beispielsweise Carnauba, Spermaceti, Bienenwachs, Lanolin und/oder Derivate derselben und andere. b) Hydrophobe Pflanzenextrakte c) Kohlenwasserstoffe wie beispielsweise Squalene und/oder Squalane d) Höhere Fettsäuren, vorzugsweise solche mit wenigstens 12 Kohlenstoffatomen, beispielsweise Laurinsäure, Stearinsäure, Behensäure, Myristinsäure, Palmitinsäure, Ölsäure, Linol- säure, Linolensäure, Isostearinsäure und/oder mehrfach ungesättigte Fettsäuren und andere. e) Höhere Fettalkohole, vorzugsweise solche mit wenigstens 12 Kohlenstoffatomen, beispielsweise Laurylalkohol, Cetylalkohol, Stearylalkohol, Oleylalkohol, Behenylalkohol, Cholesterol und/oder 2-Hexadecanaol und andere f) Ester, vorzugsweise solche wie Cetyloctanoat, Lauryllactat, Myπstyllactat, Cetyllactat, Isopro- pylmynstat, Myπstylmyristat, Isopropylpalmitat, Isopropyladipat, Butylstearat, Decyloleat, Chol- esterolisostearat, Glycerolmonostearat, Glyceroldistearat, Glyceroltnstearat, Alkyllactat, Alkyl- citrat und/oder Alkyltartrat und andere g) Lipide wie beispielsweise Cholesterol, Ceramide und/oder Saccharoseester und andere h) Vitamine wie beispielsweise die Vitamine A und E, Vitammalkylester, einschließlich Vitamin CSkin-care active substances are all those active substances which give the skin a sensory and / or cosmetic advantage. Skin-care active substances are preferably selected from the following substances: a) waxes such as, for example, carnauba, spermaceti, beeswax, lanolin and / or derivatives thereof and others. b) Hydrophobic plant extracts c) Hydrocarbons such as squalene and / or squalane d) Higher fatty acids, preferably those having at least 12 carbon atoms, for example lauric acid, stearic acid, behenic acid, myristic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid, isostearic acid and / or multiple times unsaturated fatty acids and others. e) Higher fatty alcohols, preferably those having at least 12 carbon atoms, for example lauryl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, behenyl alcohol, cholesterol and / or 2-hexadecanol and other f) esters, preferably such as Cetyloctanoat, lauryl lactate, Myπstyllactat, Cetyllactat, Isopropylmynstat , Myπstyl myristate, isopropyl palmitate, isopropyl adipate, butyl stearate, decyl oleate, cholesterol isoleostearate, glycerol monostearate, glyceryl distearate, glycerol stearate, alkyl lactate, alkyl citrate and / or alkyl tartrate and other g) lipids such as cholesterol, ceramides and / or sucrose esters and other h) vitamins such as for example, vitamins A and E, vitamin VI esters, including vitamin C.
Alkylester und andere ι) Sonnenschutzmittel j) Phospholipide k) Derivate von alpha-Hydroxysäuren I) Riechstoffe m) Germizide für den kosmetischen Gebrauch, sowohl synthetische wie beispielsweise Salicyl- säure und/oder andere als auch natürliche wie beispielsweise Neemöl und/oder andere n) Silikone o) sowie Mischungen jeglicher vorgenannter KomponentenAlkyl esters and other ι) sunscreens j) phospholipids k) derivatives of alpha-hydroxy acids I) fragrances m) germicides for cosmetic use, both synthetic and, for example, salicylic acid and / or other as well as natural ones such as neem oil and / or other n) Silicones o) and mixtures of any of the aforementioned components
Im folgenden werden bevorzugte Inhaltsstoffe der erfindungsgemaßen Mittel näher beschrieben Anionische Tenside sind bevorzugt in den erfindungsgemaßen Produkten enthalten Als anionische Tenside werden beispielsweise solche vom Typ der Sulfonate und Sulfate eingesetzt Als Tenside vom Sulfonat-Typ kommen dabei vorzugsweise C9.13-Alkylbenzolsulfonate, Olefinsulfonate, d h Gemische aus Alken- und Hydroxyalkansulfonaten sowie Disulfonaten, wie man sie beispielsweise aus C12-i8-Monoolefιnen mit end- oder innenständiger Doppelbindung durch Sulfonieren mit gasförmigem Schwefeltrioxid und anschließende alkalische oder saure Hydrolyse der Sulfonierungs- produkte erhält, in Betracht Geeignet sind auch Alkansulfonate, die aus C12.i8-Alkanen beispielsweise durch Sulfochloπerung oder Sulfoxidation mit anschließender Hydrolyse bzw Neutralisation gewonnen werden Ebenso sind auch die Ester von α-Sulfofettsäuren (Estersulfonate), z B die α- sulfonierten Methylester der hydrierten Kokos-, Palmkern- oder Taigfettsäuren geeignetPreferred ingredients of the compositions according to the invention are described in more detail below. Anionic surfactants are preferably present in the products according to the invention. Suitable anionic surfactants are, for example, those of the sulfonate and sulfates type. The surfactants of the sulfonate type are preferably C 9 . 13- Alkylbenzolsulfonate, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as obtained for example from C 12 -i 8 -Monoolefιnen with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation Also suitable are alkanesulfonates which are obtained from C 12 .i 8 -alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Likewise, the esters of α-sulfofatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or Taigfettsäuren suitable
Weitere geeignete Aniontenside sind sulfierte Fettsäureglyceπnester Unter Fettsäureglycenn- estern sind die Mono-, Di- und Tnester sowie deren Gemische zu verstehen, wie sie bei der Herstellung durch Veresterung von einem Monoglyceπn mit 1 bis 3 Mol Fettsäure oder bei der Um- esterung von Triglyceriden mit 0,3 bis 2 Mol Glycenn erhalten werden Bevorzugte sulfierte Fett- säureglyceπnester sind dabei die Sulfierprodukte von gesättigten Fettsäuren mit 6 bis 22 Kohlenstoffatomen, beispielsweise der Capronsäure, Caprylsäure, Capnnsäure, Myπstinsäure, Launn- säure, Palmitinsäure, Stearinsäure oder Behensaure Als Alk(en)ylsulfate werden die Alkali- und insbesondere die Natriumsalze der Schwefelsaurehalb- ester der C12-C18-Fettalkohole, beispielsweise aus Kokosfettalkohol, Taigfettalkohol, Lauryl-, Myπstyl-, Cetyl- oder Stearylalkohol oder der C10-C20-Oxoalkohole und diejenigen Halbester sekundärer Alkohole dieser Kettenlängen bevorzugt Weiterhin bevorzugt sind Alk(en)ylsulfate der genannten Kettenlange, welche einen synthetischen, auf petrochemischer Basis hergestellten gerad- kettigen Alkylrest enthalten, die ein analoges Abbauverhalten besitzen wie die adäquaten Verbindungen auf der Basis von fettchemischen Rohstoffen Aus waschtechnischem Interesse sind die C12-C16-Alkylsulfate und C12-C15-Alkylsulfate sowie Ci4-C1s-Alkylsulfate bevorzugt Auch 2,3-Alkyl- sulfate, als Handelsprodukte der Shell Oil Company unter dem Namen DAN® erhalten werden können, sind geeignete AniontensideOther suitable anionic surfactants are sulfonated fatty acid glycine esters. Fatty acid glycylesters are understood as meaning the mono-, di- and diesters and mixtures thereof, as in the preparation by esterification of a monoglycerine with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 mol of glycene are obtained. Preferred sulfated fatty acid glycine esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capnic acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid Alk (en) ylsulfates are the alkali metal salts and in particular the sodium salts of the sulfuric monoesters of C 12 -C 18 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myriphenyl, cetyl or stearyl alcohol or the C 10 -C 20 Oxyalcohols and those half-esters of secondary alcohols of these chain lengths are also preferred. Alk (en) ylsulfates of said chain length which contain a synthetic, petrochemical-based straight-chain alkyl radical which has an analogous degradation behavior as the adequate compounds based on oleochemicals Raw Materials Of washing technology interest, the C 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates and C 4 -C 1 s alkyl sulfates are preferred. Also 2,3-alkyl sulfates, as commercial products of the Shell Oil Company under the name DAN ® can be obtained, are suitable anionic surfactants
Auch die Schwefelsäuremonoester der mit 1 bis 6 Mol Ethylenoxid ethoxylierten geradkettigen oder verzweigten C7.21-Alkohole, wie 2-Methyl-verzweιgte C9 11-Alkohole mit im Durchschnitt 3,5 Mol Ethylenoxid (EO) oder C12.18-Fettalkohole mit 1 bis 4 EO, sind geeignet Sie werden insbesondere in Reinigungsmitteln aufgrund ihres hohen Schaumverhaltens vorzugsweise nur in relativ geringen Mengen, beispielsweise in Mengen von 1 bis 5 Gew -%, eingesetztAlso, the sulfuric acid monoesters of straight-chain or branched C 7 ethoxylated with 1 to 6 moles of ethylene oxide. 21 -alcohols, such as 2-methyl-branched C 9 11 alcohols having an average of 3.5 moles of ethylene oxide (EO) or C 12 . 18- fatty alcohols with 1 to 4 EO, are suitable They are particularly in detergents due to their high foaming behavior preferably only in relatively small amounts, for example in amounts of 1 to 5 wt -%, used
Eine weitere Klasse von Aniontensiden ist die durch Umsetzung von Fettalkoholethoxylaten mit Natnumchloracetat in Gegenwart basischer Katalysatoren zugängliche Klasse der Ethercarbonsäu- ren Sie haben die allgemeine Formel R10 O-(CH2-CH2-O)P-CH2-COOH mit R10 = Ci-C18 und p = 0,1 bis 20 Ethercarbonsäuren sind wasserhärteunempfindhch und weisen ausgezeichnete Tensideigenschaften aufAnother class of anionic surfactants is the class of ether carboxylic acids obtainable by reaction of fatty alcohol ethoxylates with sodium chloroacetate in the presence of basic catalysts. They have the general formula R 10 O- (CH 2 -CH 2 -O) P -CH 2 -COOH with R 10 = C 1 -C 18 and p = 0.1 to 20 ether carboxylic acids are water hardness insensitive and have excellent surfactant properties
Geeignete anionische Tenside sind beispielsweise auch die Partialester von Di- oder Polyhydroxy- alkanen, Mono- und Disacchaπden, Polyethylenglykolen mit den En-Addukten von Maleinsäurean- hydπd an mindestens einfach ungesättigte Carbonsäuren mit einer Kettenlänge von 10 bis 25 Kohlenstoffatomen mit einer Säurezahl von 10 bis 140Suitable anionic surfactants are, for example, the partial esters of di- or polyhydroxyalkanes, mono- and disaccharides, polyethylene glycols with the ene adducts of maleic anhydride and at least monounsaturated carboxylic acids having a chain length of from 10 to 25 carbon atoms with an acid number of from 10 to 140
Bevorzugte anionische Tenside weisen neben einem unverzweigten oder verzweigten, gesättigten oder ungesättigten, aliphatischen oder aromatischen, acychschen oder cychschen, optional alkoxy- lierten Alkylrest mit 4 bis 28, vorzugsweise 6 bis 20, insbesondere 8 bis 18, besonders bevorzugt 10 bis 16, äußerst bevorzugt 12 bis 14 Kohlenstoffatomen, zwei oder mehr anionische, insbesondere zwei, Säuregruppen, vorzugsweise Carboxylat-, Sulfonat- und/oder Sulfatgruppen, insbesondere eine Carboxylat- und eine Sulfatgruppe, auf Beispiele dieser Verbindungen sind die α-Sulfo- fettsäuresalze, die Acylglutamate, die Monoglycenddisulfate und die Alkylether des Glycenndisul- fats sowie insbesondere die nachfolgend beschriebenen monoveresterten Sulfosuccinate Besonders bevorzugte anionische Tenside sind die Sulfosuccinate, Sulfosuccinamate und Sulfo- succinamide, insbesondere Sulfosuccinate und Sulfosuccinamate, äußerst bevorzugt Sulfosuccinate. Bei den Sulfosuccinaten handelt es sich um die Salze der Mono- und Di-ester der Sulfobern- steinsäure HOOCCH(SO3H)CH2COOH , wahrend man unter den Sulfosuccinamaten die Salze der Monoamide der Sulfobernsteinsäure und unter den Sulfosuccinamiden die Salze der Diamide der Sulfobemsteinsäure versteht.Preferred anionic surfactants have, in addition to an unbranched or branched, saturated or unsaturated, aliphatic or aromatic, acyclic or cyan, optionally alkoxylated alkyl radical having 4 to 28, preferably 6 to 20, especially 8 to 18, particularly preferably 10 to 16, extremely preferred 12 to 14 carbon atoms, two or more anionic, especially two, acid groups, preferably carboxylate, sulfonate and / or sulfate groups, in particular a carboxylate and a sulfate group, examples of these compounds are the α-sulfo fatty acid salts, the acylglutamates, the Monoglycene disulfates and the alkyl ethers of Glycenndisul- fats and in particular the below-described monoester sulfosuccinates Particularly preferred anionic surfactants are the sulfosuccinates, sulfosuccinamates and sulfosuccinamides, especially sulfosuccinates and sulfosuccinamates, most preferably sulfosuccinates. The sulfosuccinates are the salts of the mono- and di-esters of sulfosuccinic acid HOOCCH (SO 3 H) CH 2 COOH, while the sulfosuccinamates include the salts of the monoamides of sulfosuccinic acid and the sulfosuccinamides the salts of the diamides of Sulfosuccinic acid understands.
Bei den Salzen handelt es sich bevorzugt um Alkalimetallsalze, Ammoniumsalze sowie Mono-, Di- bzw. Trialkanolammoniumsalze, beispielsweise Mono-, Di- bzw. Triethanolammoniumsalze, insbesondere um Lithium-, Natrium-, Kalium- oder Ammoniumsalze, besonders bevorzugt Natrium- oder Ammoniumsalze, äußerst bevorzugt Natriumsalze.The salts are preferably alkali metal salts, ammonium salts and mono-, di- or trialkanolammonium salts, for example mono-, di- or triethanolammonium salts, in particular lithium, sodium, potassium or ammonium salts, particularly preferably sodium or ammonium salts , most preferably sodium salts.
In den Sulfosuccinaten ist eine bzw. sind beide Carboxylgruppen der Sulfobernsteinsäure vorzugsweise mit einem bzw. zwei gleichen oder verschiedenen unverzweigten oder verzweigten, gesättigten oder ungesättigten, acyclischen oder cyclischen, optional alkoxylierten Alkoholen mit 4 bis 22, vorzugsweise 6 bis 20, insbesondere 8 bis 18, besonders bevorzugt 10 bis 16, äußerst bevorzugt 12 bis 14 Kohlenstoffatomen verestert. Besonders bevorzugt sind die Ester unverzweigter und/oder gesättigter und/oder acyclischer und/oder alkoxylierter Alkohole, insbesondere unverzweigter, gesättigter Fettalkohole und/oder unverzweigter, gesättigter, mit Ethylen- und/oder Propylenoxid, vorzugsweise Ethylenoxid, alkoxylierter Fettalkohole mit einem Alkoxylierungsgrad von 1 bis 20, vorzugsweise 1 bis 15, insbesondere 1 bis 10, besonders bevorzugt 1 bis 6, äußerst bevorzugt 1 bis 4. Die Monoester werden im Rahmen der vorliegenden Erfindung gegenüber den Diestern bevorzugt. Ein besonders bevorzugtes Sulfosuccinat ist Sulfobernsteinsäurelaurylpolyglykolester-di-Na- trium-Salz (Lauryl-EO-sulfosuccinat, Di-Na-SaIz; INCI Disodium Laureth Sulfosuccinate), das beispielsweise als Tego® Sulfosuccinat F 30 (Goldschmidt) mit einem Sulfosuccinatgehalt von 30 Gew.-% kommerziell erhältlich ist.In the sulfosuccinates, one or both carboxyl groups of the sulfosuccinic acid is preferably with one or two identical or different unbranched or branched, saturated or unsaturated, acyclic or cyclic, optionally alkoxylated alcohols having 4 to 22, preferably 6 to 20, in particular 8 to 18 , more preferably 10 to 16, most preferably 12 to 14 carbon atoms esterified. Particularly preferred are the esters of unbranched and / or saturated and / or acyclic and / or alkoxylated alcohols, in particular unbranched, saturated fatty alcohols and / or unbranched, saturated, with ethylene and / or propylene oxide, preferably ethylene oxide, alkoxylated fatty alcohols having a degree of alkoxylation of 1 to 20, preferably 1 to 15, in particular 1 to 10, more preferably 1 to 6, most preferably 1 to 4. The monoesters are preferred in the context of the present invention over the diesters. A particularly preferred sulfosuccinate is Sulfobernsteinsäurelaurylpolyglykolester-di-Na- trium salt (lauryl EO sulfosuccinate, di-sodium salt; INCI Disodium Laureth Sulfosuccinate), for example, as Tego ® sulfosuccinate F 30 (Goldschmidt) with a sulfosuccinate of 30 weight .-% is commercially available.
In den Sulfosuccinamaten bzw. Sulfosuccinamiden bildet eine bzw. bilden beide Carboxylgruppen der Sulfobernsteinsäure vorzugsweise mit einem primären oder sekundären Amin, das einen oder zwei gleiche oder verschiedene, unverzweigte oder verzweigte, gesättigte oder ungesättigte, acy- clische oder cyclische, optional alkoxylierte Alkylreste mit 4 bis 22, vorzugsweise 6 bis 20, insbesondere 8 bis 18, besonders bevorzugt 10 bis 16, äußerst bevorzugt 12 bis 14 Kohlenstoffatomen trägt, ein Carbonsäureamid. Besonders bevorzugt sind unverzweigte und/oder gesättigte und/oder acyclische Alkylreste, insbesondere unverzweigte, gesättigte Fettalkylreste.In the sulfosuccinamates or sulfosuccinamides, one or both carboxyl groups of the sulfosuccinic acid forms preferably with a primary or secondary amine having one or two identical or different, unbranched or branched, saturated or unsaturated, acyclic or cyclic, optionally alkoxylated alkyl radicals with 4 to 22, preferably 6 to 20, in particular 8 to 18, more preferably 10 to 16, most preferably 12 to 14 carbon atoms carries, a carboxylic acid amide. Particular preference is given to unbranched and / or saturated and / or acyclic alkyl radicals, in particular unbranched, saturated fatty alkyl radicals.
Weiterhin geeignet sind beispielsweise die folgenden gemäß INCI bezeichneten Sulfosuccinate und Sulfosuccinamate, die im International Cosmetic Ingredient Dictionary and Handbook näher beschrieben sind: Ammonium Dinonyl Sulfosuccinate, Ammonium Lauryl Sulfosuccinate, Diammo- nium Dimethicone Copolyol Sulfosuccinate, Diammonium Lauramido-MEA Sulfosuccinate, Diam- monium Lauryl Sulfosuccinate, Diammonium Oleamido PEG-2 Sulfosuccinate, Diamyl Sodium Sulfosuccinate, Dicapryl Sodium Sulfosuccinate, Dicyclohexyl Sodium Sulfosuccinate, Diheptyl Sodium Sulfosuccinate, Dihexyl Sodium Sulfosuccinate, Diisobutyl Sodium Sulfosuccinate, Dioctyl Sodium Sulfosuccinate, Disodium Cetearyl Sulfosuccinate, Disodium Cocamido MEA-Sulfosucci- nate, Disodium CocamidoGlucoside Sulfosuccinate, Disodium Cocoyl Butyl Gluceth-10 Sulfosuccinate, Disodium C 12-15 Pareth Sulfosuccinate, Disodium Deceth-5 Sulfosuccinate, Disodium De- ceth-6 Sulfosuccinate, Disodium Dihydroxyethyl Sulfosuccinylundecylenate, Disodium Dimethicone Copolyol Sulfosuccinate, Disodium Hydrogenated Cottonseed Glyceride Sulfosuccinate, Disodium Isodecyl Sulfosuccinate, Disodium Isostearamido MEA-Sulfosuccinate, Disodium Isostearamido MIPA-Sulfosuccinate, Disodium Isostearyl Sulfosuccinate, Disodium Laneth-5 Sulfosuccinate, Disodium Lauramido MEA-Sulfosuccinate, Disodium Lauramido PEG-2 Sulfosuccinate, Disodium Lauramido PEG-5 Sulfosuccinate, Disodium Laureth-6 Sulfosuccinate, Disodium Laureth-9 Sulfosuccinate, Disodium Laureth-12 Sulfosuccinate, Disodium Lauryl Sulfosuccinate, Disodium Myrist- amido MEA-Sulfosuccinate, Disodium Nonoxynol-10 Sulfosuccinate, Disodium Oleamido MEA- Sulfosuccinate, Disodium Oleamido MIPA-Sulfosuccinate, Disodium Oleamido PEG-2 Sulfosuccinate, Disodium Oleth-3 Sulfosuccinate, Disodium Oleyl Sulfosuccinate, Disodium Palmitamido PEG-2 Sulfosuccinate, Disodium Palmitoleamido PEG-2 Sulfosuccinate, Disodium PEG-4 Cocamido MIPA-Sulfosuccinate, Disodium PEG-5 Laurylcitrate Sulfosuccinate, Disodium PEG-8 Palm Glycerides Sulfosuccinate, Disodium Ricinoleamido MEA-Sulfosuccinate, Disodium Sitostereth-14 Sulfosuccinate, Disodium Stearamido MEA-Sulfosuccinate, Disodium Stearyl Sulfosuccinamate, Disodium Stearyl Sulfosuccinate, Disodium Tallamido MEA-Sulfosuccinate, Disodium Tallowamido MEA-Sulfosuccinate, Disodium Tallow Sulfosuccinamate, Disodium Tridecylsulfosuccinate, Disodium Undecylenamido MEA-Sulfosucci-nate, Disodium Undecylenamido PEG-2 Sulfosuccinate, Disodium Wheat Germamido MEA-Sulfosuccinate, Disodium Wheat Germamido PEG-2 Sulfosuccinate, Di-TEA-Ole-amido PEG-2 Sulfosuccinate, Ditridecyl Sodium Sulfosuccinate, Sodium Bisgly- col Ricinosulfosuccinate, Sodium/MEA Laureth-2 Sulfosuccinate und Tetrasodium Dicarboxyethyl Stearyl Sulfosuccinamate. Noch ein weiteres geeignetes Sulfosuccinamat ist Dinatrium-C16-i8- alkoxypropylensulfosuccinamat.Also suitable are, for example, the following sulfosuccinates and sulfosuccinamates designated according to INCI, which are described in more detail in the International Cosmetic Ingredient Dictionary and Handbook: Ammonium Dinonyl Sulfosuccinates, Ammonium Lauryl Sulfosuccinates, Diammo- Dimethicone Copolyol Sulfosuccinate, Diammonium Lauramido-MEA Sulfosuccinate, Diamonium Lauryl Sulfosuccinate, Diammonium Oleamido PEG-2 Sulfosuccinate, Diamyl Sodium Sulfosuccinate, Dicapryl Sodium Sulfosuccinate, Dicyclohexyl Sodium Sulfosuccinate, Diheptyl Sodium Sulfosuccinate, Dihexyl Sodium Sulfosuccinate, Diisobutyl Sodium Sulfosuccinate, Dioctyl Sodium Sulfosuccinates, disodium cetearyl sulfosuccinates, disodium cocamido MEA sulfosuccinates, disodium cocamido glucosides sulfosuccinates, disodium cocoyl butyl gluceth-10 sulfosuccinates, disodium C 12-15 pareth sulfosuccinates, disodium deceth-5 sulfosuccinates, disodium deceth-6 sulfosuccinates, disodium dihydroxyethyl Sulfosuccinyl undecylenates, disodium dimethicone copolyol sulfosuccinates, disodium hydrogenated cottonseed glycerides sulfosuccinates, disodium isodecyl sulfosuccinates, disodium isostearamido MEA sulfosuccinates, disodium isostearamido MIPA sulfosuccinates, disodium isostearyl sulfosuccinates, disodium laneth-5 sulfos uccinate, disodium lauramido MEA sulfosuccinates, disodium lauramido PEG-2 sulfosuccinates, disodium lauramido PEG-5 sulfosuccinates, disodium laureth-6 sulfosuccinates, disodium laureth-9 sulfosuccinates, disodium laureth-12 sulfosuccinates, disodium lauryl sulfosuccinates, disodium myristic amido MEA- Sulfosuccinates, disodium nonoxynol-10 sulfosuccinates, disodium oleamido MEA sulfosuccinates, disodium oleamido MIPA sulfosuccinates, disodium oleamido PEG-2 sulfosuccinates, disodium oleth-3 sulfosuccinates, disodium oleyl sulfosuccinates, disodium palmitamido PEG-2 sulfosuccinates, disodium palmitoleamido PEG-2 sulfosuccinates , Disodium PEG-4 Cocamido MIPA Sulfosuccinate, Disodium PEG-5 Lauryl Citrate Sulfosuccinate, Disodium PEG-8 Palm Glycerides Sulfosuccinate, Disodium Ricinoleamido MEA Sulfosuccinate, Disodium Sitostereth-14 Sulfosuccinate, Disodium Stearamido MEA Sulfosuccinate, Disodium Stearyl Sulfosuccinamate, Disodium Stearyl Sulfosuccinate , Disodium Tallamido MEA Sulfosuccinate, Disodium Valley lowamido MEA sulfosuccinates, disodium tallow sulfosuccinamates, disodium tridecyl sulfosuccinates, disodium undecylenamido MEA sulfosuccinates, disodium undecylenamido PEG-2 sulfosuccinates, disodium wheat germamido MEA sulfosuccinates, disodium wheat germamido PEG-2 sulfosuccinates, di-TEA-Ole-amido PEG -2 Sulfosuccinates, Ditridecyl Sodium Sulfosuccinate, Sodium Bisglycol Ricinosulfosuccinate, Sodium / MEA Laureth-2 Sulfosuccinate and Tetrasodium Dicarboxyethyl Stearyl Sulfosuccinamate. Yet another suitable sulfosuccinamate is disodium C 16 -i 8 -alkoxy-propylene sulfosuccinamate.
Der Gehalt des erfindungsgemäßen Mittels an anionischen Tensiden, vorzugsweise an den genannten anionischen Tensiden, kann in weiten Bereichen variieren, je nachdem welchem Zweck das betreffende Mittel dient. So kann ein erfindungsgemäßes Mittel sehr große Mengen Anion- tensid enthalten, vorzugsweise bis zu einer Größenordnung von bis zu 40, 50 oder 60 Gew.-% oder mehr. Ebenso kann ein erfindungsgemäßes Mittel nur sehr geringe Mengen Aniontensid enthalten, beispielsweise weniger als 15 oder 10 Gew.-% oder weniger als 5 Gew.-% oder noch weniger. Vorteilhafterweise können in den erfindungsgemäßen Mitteln jedoch Aniontenside in Mengen von 2 bis 35 Gew.-% und insbesondere 5 bis 30 Gew.-% enthalten sein, wobei Konzentrationen oberhalb von 10 Gew.-% und sogar oberhalb von 15 Gew.-% besondere Bevorzugung finden können. Nach einer bevorzugten Ausführungsform enthält das erfindungsgemäße Produkt anionische Tenside, vorzugsweise in Mengen von zumindest 0,1 Gew.-%.The content of anionic surfactants in the composition according to the invention, preferably of the anionic surfactants mentioned, can vary within wide ranges, depending on the purpose of the agent in question. Thus, an agent according to the invention may contain very large amounts of anionic surfactant, preferably up to an order of magnitude of up to 40, 50 or 60% by weight or more. Likewise, an agent according to the invention may contain only very small amounts of anionic surfactant, for example less than 15 or 10% by weight or less than 5% by weight or even less. However, anionic surfactants may advantageously be present in the compositions according to the invention in amounts of from 2 to 35% by weight and in particular from 5 to 30% by weight, with concentrations above 10% by weight and even above 15% by weight may find particular preference. According to a preferred embodiment, the product according to the invention contains anionic surfactants, preferably in amounts of at least 0.1% by weight.
Zusätzlich zu den genannten anionischen Tensiden, aber auch unabhängig von diesen, können in den erfindungsgemäßen Mitteln Seifen enthalten sein. Geeignet sind insbesondere gesättigte Fettsäureseifen, wie die Salze der Laurinsäure, Myristinsäure, Palmitinsäure, Stearinsäure, hydrierte Erucasäure und Behensäure sowie insbesondere aus natürlichen Fettsäuren, z.B. Kokos-, Palmkern- oder Taigfettsäuren, abgeleitete Seifengemische. Der Gehalt des Mittels an Seifen beträgt, unabhängig von anderen Aniontensiden, vorzugsweise nicht mehr als 3 Gew.-% und insbesondere 0,5 bis 2,5 Gew.-%.In addition to the anionic surfactants mentioned, but also independently of these, soaps may be present in the compositions according to the invention. Particularly suitable are saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular of natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures. The content of the soap soaps, independently of other anionic surfactants, is preferably not more than 3% by weight, and more preferably 0.5 to 2.5% by weight.
Die anionischen Tenside und Seifen können in Form ihrer Natrium-, Kalium- oder Ammoniumsalze sowie als lösliche Salze organischer Basen, wie Mono-, Di- oder Triethanol-amin, vorliegen. Vorzugsweise liegen sie in Form ihrer Natrium- oder Kaliumsalze, insbesondere in Form der Natriumsalze vor. Anionische Tenside und Seifen können auch in situ hergestellt werden, indem in die sprühzutrocknende Zusammensetzung die Aniontensidsäuren und gegebenenfalls Fettsäuren eingebracht werden, welche dann durch die Alkaliträger in der sprühzutrocknenden Zusammensetzung neutralisiert werden.The anionic surfactants and soaps may be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine. Preferably, they are in the form of their sodium or potassium salts, especially in the form of the sodium salts. Anionic surfactants and soaps may also be prepared in situ by incorporating into the spray-dried composition the anionic surfactant acids and optionally fatty acids which are then neutralized by the alkali carriers in the spray-dried composition.
Vorteilhafterweise können nichtionische Tenside in den erfindungsgemäßen Mitteln ebenfalls enthalten sein, sowohl in festen wie in flüssigen Mitteln. Beispielsweise kann ihr Gehalt bis zu 2 oder 3 oder 5 Gew.-% betragen. Es können auch größere Mengen an nichtionischem Tensid enthalten sein, beispielsweise bis zu 5 Gew.-% oder 10 Gew.-% oder 15 Gew.-% oder 20 Gew.-% oder 30 Gew.-% oder sogar darüber hinaus, falls es zweckmäßig ist. Sinnvolle Untergrenzen können bei Werten von 1 , 2, 3 oder 4 Gew.-% liegen.Advantageously, nonionic surfactants may also be included in the compositions of the invention, both in solid and in liquid compositions. For example, their content may be up to 2 or 3 or 5 wt .-%. It may also contain greater amounts of nonionic surfactant, for example, up to 5 wt% or 10 wt% or 15 wt% or 20 wt% or 30 wt% or even more if it is is appropriate. Useful lower limits may be at values of 1, 2, 3 or 4 wt .-%.
Vorzugsweise sind die nichtionischen Tenside aber in größeren Mengen, also bis zu 50 Gew.-%, vorteilhafterweise von 0,1 bis 40 Gew.-%, besonders bevorzugt von 0,5 bis 30 und insbesondere von 2 bis 25 Gew.-%, jeweils bezogen auf das gesamte Mittel, enthalten. Nach einer bevorzugten Ausführungsform enthält das erfindungsgemäße Produkt nichtionische Tenside, vorzugsweise in Mengen von zumindest 0,1 Gew.-%.Preferably, however, the nonionic surfactants are in relatively large amounts, ie up to 50% by weight, advantageously from 0.1 to 40% by weight, particularly preferably from 0.5 to 30 and in particular from 2 to 25% by weight, in each case based on the total agent included. According to a preferred embodiment, the product according to the invention contains nonionic surfactants, preferably in amounts of at least 0.1% by weight.
Vorteilhafterweise können alle aus dem Stand der Technik bekannten nichtionischen Tenside in den erfindungsgemäßen Mitteln enthalten sein. Bevorzugte Niotenside werden weiter unten vorgestellt.Advantageously, all known from the prior art nonionic surfactants may be included in the inventive compositions. Preferred nonionic surfactants are presented below.
Die erfindungsgemäßen Mittel, wie insbesondere Reinigungs-, Pflege- und Waschmittel, können vorzugsweise auch kationische Tenside enthalten. Geeignete Kationtenside sind beispielsweise oberflächenaktive quaternäre Verbindungen, insbesondere mit einer Ammonium-.Sulfonium-, Phosphonium-, Jodonium- oder Arsoniumgruppe. Durch den Einsatz von quaternären oberflächenaktiven Verbindungen mit antimikrobieller Wirkung kann das Mittel mit einer antimikrobiellen Wirkung ausgestaltet werden bzw. dessen gegebenenfalls aufgrund anderer Inhaltsstoffe bereits vorhandene antimikrobielle Wirkung verbessert werden.The agents according to the invention, in particular cleaning, care and washing agents, can preferably also contain cationic surfactants. Suitable cationic surfactants are, for example, surface-active quaternary compounds, in particular having an ammonium, sulfonium, phosphonium, iodonium or arsonium group. Through the use of quaternary surface-active compounds with antimicrobial action, the agent can be designed with an antimicrobial effect or its possibly existing antimicrobial effect due to other ingredients can be improved.
Besonders bevorzugte kationische Tenside sind die quaternären, z.T. antimikrobiell wirkenden Ammoniumverbindungen (QAV; INCI Quaternary Ammonium Compounds) gemäß der allgemeinen Formel (R')(R")(R"')(RIV)N+ X", in der R1 bis Rιv gleiche oder verschiedene d.z-Alkylreste1 C7-28- Aralkyl-reste oder heterozyklische Reste, wobei zwei oder im Falle einer aromatischen Einbindung wie im Pyridin sogar drei Reste gemeinsam mit dem Stickstoffatom den Heterozyklus, z.B. eine Pyridinium- oder Imidazoliniumverbindung, bilden, darstellen und X" Halogenidionen, Sulfationen, Hydroxidionen oder ähnliche Anionen sind. Für eine optimale antimikrobielle Wirkung weist vorzugsweise wenigstens einer der Reste eine Kettenlänge von 8 bis 18, insbesondere12 bis 16, C- Atomen auf.Particularly preferred cationic surfactants are the quaternary, partially antimicrobial ammonium compounds (QAV, INCI quaternary ammonium compounds) according to the general formula (R ') (R ") (R"') (R IV ) N + X " , in which R 1 to R ιv identical or different dz Σ- alkyl radicals 1 C 7-28 - aralkyl radicals or heterocyclic radicals, wherein two or in the case of an aromatic inclusion as in pyridine even three radicals together with the nitrogen atom, the heterocycle, for example a pyridinium or Imidazoliniumverbindung , form, represent and X "are halide ions, sulfate ions, hydroxide ions or similar anions. For optimum antimicrobial activity, preferably at least one of the radicals has a chain length of 8 to 18, in particular 12 to 16, carbon atoms.
QAV sind durch Umsetzung tertiärer Amine mit Alkylierungsmitteln, wie z.B. Methylchlorid, Benzyl- chlorid, Dimethylsulfat, Dodecylbromid, aber auch Ethylenoxid herstellbar. Die Alkylierung von tertiären Aminen mit einem langen Alkyl-Rest und zwei Methyl-Gruppen gelingt besonders leicht, auch die Quaternierung von tertiären Aminen mit zwei langen Resten und einer Methyl-Gruppe kann mit Hilfe von Methylchlorid unter milden Bedingungen durchgeführt werden. Amine, die über drei lange Alkyl-Reste oder Hydroxy-substi-tuierte Alkyl-Reste verfügen, sind wenig reaktiv und werden bevorzugt mit Dimethylsulfat quaterniert.QACs are prepared by reacting tertiary amines with alkylating agents, e.g. Methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethylene oxide produced. The alkylation of tertiary amines with a long alkyl radical and two methyl groups succeeds particularly easily, and the quaternization of tertiary amines with two long radicals and one methyl group can be carried out with the aid of methyl chloride under mild conditions. Amines which have three long alkyl radicals or hydroxy-substituted alkyl radicals are less reactive and are preferably quaternized with dimethyl sulfate.
Geeignete QAV sind beispielweise Benzalkoniumchlorid (N-Alkyl-N,N-dimethyl-benzylammonium- chlorid, CAS No. 8001-54-5), Benzalkon B (m.p-Dichlorbenzyl-dimethyl-C^-alkylammoniumchlorid, CAS No. 58390-78-6), Benzoxoniumchlorid (Benzyl-dodecyl-bis-(2-hydroxyethyl)-ammoniumchlo- rid), Cetrimoniumbromid (N-Hexadecyl-N,N-trimethyl-ammoniumbromid, CAS No. 57-09-0), Benze- toniumchlorid (N,N-Dimethyl-N-[2-[2-[p-(1 ,1 ,3,3-tetramethylbutyl)phenoxy]ethoxy]ethyl]-benzylam- moniumchlorid, CAS No. 121-54-0), Dialkyldimethylammoniumchloride wie Di-n-decyl-dimethyl-am- moniumchlorid (CAS No. 7173-51-5-5), Didecyldimethylammoniumbromid (CAS No. 2390-68-3), Dioctyl-dimethyl-ammoniumchloric, 1-Cetylpyridiniumchlorid (CAS No. 123-03-5) und Thiazolinjodid (CAS No. 15764-48-1) sowie deren Mischungen. Bevorzugte QAV sind die Benzalkoniumchloride mit C8-C18-Alkylresten, insbesondere C^-Cu-Aklyl-benzyl-dimethylammo-niumchlorid. Eine besonders bevorzugte QAV Kokospentaethoxymethylammoniummethosulfat (INCI PEG-5 Cocomonium Methosulfate; Rewoquat® CPEM). Zur Vermeidung möglicher Inkompatibilitäten der antimikrobiellen kationischen Tenside mit in dem erfindungsgemäßen Mittel ggf enthaltenen anionischen Tensiden werden möglichst aniontensid- verträghches und/oder ggf möglichst wenig kationisches Tensid eingesetzt oder in einer besonderen Ausfuhrungsform der Erfindung gänzlich auf kationische Tenside verzichtetSuitable QACs are, for example, benzalkonium chloride (N-alkyl-N, N-dimethylbenzylammonium chloride, CAS No. 8001-54-5), benzalkone B (mp-dichlorobenzyl-dimethyl-C 1-4 -alkylammonium chloride, CAS No. 58390-78 -6), benzoxonium chloride (benzyldodecyl-bis- (2-hydroxyethyl) -ammonium chloride), cetrimonium bromide (N-hexadecyl-N, N-trimethyl-ammonium bromide, CAS No. 57-09-0), benzotrium chloride (N, N-dimethyl-N- [2- [2- [p- (1,1,3,3-tetramethylbutyl) phenoxy] ethoxy] ethyl] benzylammonium chloride, CAS No. 121-54-0), Dialkyldimethylammonium chlorides such as di-n-decyldimethylammonium chloride (CAS No. 7173-51-5-5), didecyldimethylammonium bromide (CAS No. 2390-68-3), dioctyldimethylammoniumchloric, 1-cetylpyridinium chloride (CAS No 123-03-5) and thiazoline iodide (CAS No. 15764-48-1) and mixtures thereof. Preferred QACs are the benzalkonium chlorides having C 8 -C 18 -alkyl radicals, in particular C 1 -C -acyl-benzyl-dimethylammonium chloride. A particularly preferred QAC Kokospentaethoxymethylammoniummethosulfat (INCI PEG-5 Cocomonium Methosulfate; Rewoquat CPEM ®). In order to avoid possible incompatibilities of the antimicrobial cationic surfactants with anionic surfactants optionally present in the composition according to the invention, as far as possible anionic surfactant-compatible and / or optionally cationic surfactant are used or, in a particular embodiment of the invention, cationic surfactants are completely dispensed with
Weiter unten werden insbesondere im Zusammenhang mit Konditioniermitteln und Weichmachern weitere kationische Tenside, so auch quartare Ammoniumverbindungen beschrieben Auch diese können vorzugsweise in den erfindungsgemaßen Mitteln enthalten seinFurther below, in particular in connection with conditioning agents and plasticizers, further cationic surfactants, including quaternary ammonium compounds, are described. These too may preferably be present in the compositions according to the invention
Die erfindungsgemaßen Mittel, wie vorzugsweise Reinigungs-, Pflege- und Waschmittel, können ein oder mehrere kationische Tenside enthalten, vorteilhafterweise in Mengen, bezogen auf die Gesamtzusammensetzung, von 0 bis 30 Gew -%, noch vorteilhafter großer 0 bis 20 Gew -%, vorzugsweise 0,01 bis 10 Gew -%, insbesondere 0,1 bis 5 Gew -% Geeignete Mindestwerte können auch bei 0,5, 1 , 2 oder 3 Gew -% hegen Nach einer bevorzugten Ausfuhrungsform enthält das erfindungsgemäße Produkt kationische Tenside, vorzugsweise in Mengen von zumindest 0,1 Gew - %The compositions according to the invention, such as preferably cleaning, care and washing agents, may contain one or more cationic surfactants, advantageously in amounts, based on the total composition, of from 0 to 30% by weight, more preferably from 0 to 20% by weight, preferably 0.01 to 10% by weight, in particular 0.1 to 5% by weight Suitable minimum values may also be present at 0.5, 1, 2 or 3% by weight. According to a preferred embodiment, the product according to the invention contains cationic surfactants, preferably in quantities of at least 0.1% by weight
Ebenso können die erfindungsgemaßen Mittel, wie vorzugsweise Reinigungs-, Pflege- und Waschmittel, auch amphotere Tenside enthalten Diese werden weiter unten insbesondere im Zusammenhang mit Konditioniermitteln und Weichmachern noch näher beschriebenLikewise, the agents according to the invention, such as, preferably, cleaning agents, care agents and detergents, may also contain amphoteric surfactants. These will be described in more detail below, in particular in connection with conditioning agents and plasticizers
Die erfindungsgemäßen Mittel, wie Reinigungs-, Pflege- und Waschmittel, können ein oder mehrere amphotere Tenside enthalten, vorteilhafterweise in Mengen, bezogen auf die Gesamtzusammensetzung, von 0 bis 30 Gew -%, noch vorteilhafter größer 0 bis 20 Gew -%, vorzugsweise 0,01 bis 10 Gew -%, insbesondere 0,1 bis 5 Gew -%The agents according to the invention, such as cleansing, care and washing agents, may contain one or more amphoteric surfactants, advantageously in amounts, based on the total composition, of from 0 to 30% by weight, more preferably greater than 0 to 20% by weight, preferably 0 , 01 to 10% by weight, in particular 0.1 to 5% by weight
Weitere Inhaltsstoffe der erfindungsgemäßen Mittel können anorganische und organische Buil- dersubstanzen sein Zu den anorganischen Buildersubstanzen gehören wasserunlösliche oder nicht wasserlösliche Inhaltsstoffe, wie Aluminosilikate und insbesondere ZeohtheFurther ingredients of the compositions according to the invention may be inorganic and organic builders. The inorganic builders include water-insoluble or non-water-soluble ingredients, such as aluminosilicates and, in particular, zeolites
In einer bevorzugten Ausfuhrungsform enthält das erfindungsgemäße Mittel kein Phosphat und/oder kein Zeolith Es ist aber auch möglich, dass das Mittel Zeohth enthält Bevorzugt kann es dann sein, dass dieser Zeohthanteil, bezogen auf das Gesamtgewicht des Mittel, weniger als 5 Gew -%, vorzugsweise maximal 4 Gew -%, maximal 3 Gew -% oder maximal 2 Gew -% beträgtIn a preferred embodiment, the agent according to the invention contains no phosphate and / or no zeolite. However, it is also possible for the agent to comprise Zeohth. It may then be preferred that this zeohth content, based on the total weight of the agent, is less than 5% by weight, preferably not more than 4% by weight, not more than 3% by weight or not more than 2% by weight
Es kann aber vorteilhafterweise auch vorgesehen sein, dass das erfindungsgemäße Mittel einen Zeohthgehalt von mindestens 10 Gew -%, z B mindestens 15 Gew -% oder mindestens 20 Gew - % oder mindestens 30 Gew -% oder auch darüber hinaus, beispielsweise mindestens 50 Gew -% aufweist.However, it can also advantageously be provided that the agent according to the invention has a zeolite content of at least 10% by weight, for example at least 15% by weight or at least 20% by weight or at least 30% by weight or even beyond, for example at least 50% by weight. % having.
Lösliche Builder kann das erfindungsgemäße Mittel vorzugsweise in Mengen von 10 Gew.-% bis 30 Gew.-%, bevorzugt 15 Gew.-% bis 25 Gew.-% und besonders bevorzugt 18 Gew.-% bis 20 Gew.-%, bezogen auf das Gesamtgewicht des Mittel, enthalten, wobei Natriumcarbonat als löslicher Builder besonders bevorzugt ist. Es kann aber vorteilhafterweise auch vorgesehen sein, dass das erfindungsgemäße Mittel weniger als 10 Gew.-%, beispielsweise weniger als 5 Gew.-% lösliche Builder enthält.Soluble builders may preferably contain the agent according to the invention in amounts of 10% by weight to 30% by weight, preferably 15% by weight to 25% by weight and particularly preferably 18% by weight to 20% by weight on the total weight of the agent, with sodium carbonate as the soluble builder being particularly preferred. However, it can also be advantageously provided that the agent according to the invention contains less than 10% by weight, for example less than 5% by weight, of soluble builder.
Einsetzbarer feinkristalliner, synthetischer und gebundenes Wasser enthaltender Zeolith ist vorzugsweise Zeolith A und/oder P. Als Zeolith P wird beispielsweise Zeolith MAP(R) (Handelsprodukt der Firma Crosfield) besonders bevorzugt. Geeignet sind jedoch auch Zeolith X sowie Mischungen aus A, X und/oder P. Von besonderem Interesse ist auch ein cokristallisiertes Natrium/Kalium-Aluminiumsilikat aus Zeolith A und Zeolith X, welches als VEGOBOND AX® (Handelsprodukt der Firma Condea Augusta S.p.A.) im Handel erhältlich ist. Dieses Produkt wird unten näher beschrieben. Der Zeolith kann als sprühgetrocknetes Pulver oder auch als ungetrocknete, von ihrer Herstellung noch feuchte, stabilisierte Suspension zum Einsatz kommen. Für den Fall, dass der Zeolith als Suspension eingesetzt wird, kann diese geringe Zusätze an nichtionischen Tensiden als Stabilisatoren enthalten, beispielsweise 1 bis 3 Gew.-%, bezogen auf Zeolith, an ethoxylierten C12-C18-FeK- alkoholen mit 2 bis 5 Ethylenoxidgruppen, C12-C14-Fettalkoholen mit 4 bis 5 Ethylenoxidgruppen oder ethoxylierten Isotridecanolen. Geeignete Zeolithe weisen eine mittlere Teilchengröße von vorzugsweise weniger als 10 μm (Volumenverteilung; Meßmethode: Coulter Counter) auf und enthalten vorzugsweise 18 bis 22 Gew.-%, insbesondere 20 bis 22 Gew.-% an gebundenem Wasser.Useful finely crystalline, synthetic and bound water-containing zeolite is preferably zeolite A and / or P. As zeolite P, for example, zeolite MAP (R) (commercial product of Crosfield) is particularly preferred. Also suitable however are zeolite X and mixtures of A, X and / or P. Of particular interest is a co-crystallized sodium / potassium aluminum silicate of zeolite A and zeolite X, which as VEGOBOND AX ® (a product of Condea Augusta SpA) Trade is available. This product is described below. The zeolite can be used as a spray-dried powder or else as undried, still moist, stabilized suspension of its preparation. In the event that the zeolite is used as a suspension, it may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3 wt .-%, based on zeolite, of ethoxylated C 12 -C 18 -FeK- alcohols with 2 to 5 ethylene oxide groups, C 12 -C 14 fatty alcohols having 4 to 5 ethylene oxide groups or ethoxylated isotridecanols. Suitable zeolites have an average particle size of preferably less than 10 μm (volume distribution, measuring method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
Als weitere besonders geeignete Zeolithe sind Zeolithe vom Faujasit-Typ zu nennen. Zusammen mit den Zeolithen X und Y gehört das Mineral Faujasit zu den Faujasit-Typen innerhalb der Zeolith- Strukturgruppe 4, die durch die Doppelsechsring-Untereinheit D6R gekennzeichnet sind. Zur Zeo- lith-Strukturgruppe 4 zählen neben den genannten Faujasit-Typen noch die Mineralien Chabazit und Gmelinit sowie die synthetischen Zeolithe R (Chabazit-Typ), S (Gmelinit-Typ), L und ZK-5. Die beiden letztgenannten synthetischen Zeolithe haben keine mineralischen Analoga.Other particularly suitable zeolites are faujasite-type zeolites. Together with the zeolites X and Y, the mineral faujasite belongs to the faujasite types within the zeolite structure group 4, which are characterized by the double-six-membered subunit D6R. In addition to the faujasite types mentioned, the zeolite structural group 4 also includes the minerals chabazite and gmelinite as well as the synthetic zeolites R (chabazite type), S (gmelinite type), L and ZK-5. The latter two synthetic zeolites have no mineral analogs.
Zeolithe vom Faujasit-Typ sind aus ß-Käfigen aufgebaut, die tetrahedral über D6R-Unter-einheiten verknüpft sind, wobei die ß-Käfige ähnlich den Kohlenstoffatomen im Diamanten angeordnet sind. Das dreidimensionale Netzwerk der erfindungsgemäß geeigneten Zeolithe vom Faujasit-Typ weist Poren von 2,2 und 7,4 A auf, die Elementarzelle enthält darüber hinaus 8 Kavitäten mit ca. 13 A Durchmesser und lässt sich durch die Formel Na86[(AI02)86(Siθ2)1o6] 264 H2O beschreiben. Das Netzwerk des Zeolith X enthält dabei ein Hohlraumvolumen von ungefähr 50%, bezogen auf den dehydratisierten Kristall, was den größten Leerraum aller bekannten Zeolithe darstellt (Zeolith Y: ca. 48% Hohlraumvolumen, Faujasit: ca. 47% Hohlraumvolumen).Faujasite-type zeolites are composed of β-cages linked by tetrahedral D6R subunits, with the β-cages resembling the carbon atoms in the diamond. The three-dimensional network of the faujasite-type zeolites suitable according to the invention has pores of 2.2 and 7.4 Å, and the unit cell also contains 8 cavities with a diameter of approximately 13 A and can be represented by the formula Na 86 [(Al 2 O) 86 (SiO 2) 1 o6] 264 H 2 O describe. The network of zeolite X contains a void volume of about 50%, based on the dehydrated crystal, which represents the largest void space of all known zeolites (zeolite Y: approx. 48% void volume, faujasite: approx. 47% void volume).
Im Rahmen der vorliegenden Erfindung kennzeichnet der Begriff "Zeolith vom Faujasit-Typ" alle drei Zeolithe, die die Faujasit-Untergruppe der Zeolith-Strukturgruppe 4 bilden. Neben dem Zeolith X sind erfindungsgemäß also auch Zeolith Y und Faujasit sowie Mischungen dieser Verbindungen geeignet, wobei der reine Zeolith X bevorzugt ist.In the context of the present invention, the term "faujasite type zeolite" denotes all three zeolites which form the faujasite subgroup of the zeolite structure group 4. In addition to zeolite X, zeolite Y and faujasite and mixtures of these compounds are also suitable according to the invention, with pure zeolite X being preferred.
Auch Mischungen oder Cokristallisate von Zeolithen des Faujasit-Typs mit anderen Zeolithen, die nicht zwingend der Zeolith-Strukturgruppe 4 angehören müssen, sind erfindungsgemäß geeignet, wobei vorzugsweise mindestens 50 Gew.-% der Zeolithe vom Faujasit-Typ sind.Mixtures or cocrystallizates of faujasite-type zeolites with other zeolites, which need not necessarily belong to the zeolite structure group 4, are also suitable according to the invention, with preferably at least 50% by weight of the faujasite-type zeolites being suitable.
Die geeigneten Aluminiumsilikate sind kommerziell erhältlich, und die Methoden zu ihrer Darstellung sind in Standardmonographien beschrieben.The suitable aluminum silicates are commercially available and the methods for their preparation are described in standard monographs.
Beispiele für kommerziell erhältliche Zeolithe vom X-Typ können durch die folgenden Formeln beschrieben werden:Examples of commercially available X-type zeolites can be described by the following formulas:
Na86[(AIO2)86(SiO2)i06] " x H2O, Kββl(Alθ2)Bβ(SiO2)10β] ' x H2O, Ca4oNa6[(AI02)86(Si02)106] x H2O, Sr21Ba22[(AIO2)86(SiO2)106] ' x H2O, in denen x Werte von größer O bis 276 annehmen kann. Diese Zeolithe weisen Porengrößen von 8,0 bis 8,4 A auf.Na 86 [(AIO 2 ) 86 (SiO 2 ) i06] " x H 2 O, Kββ1 (Alθ2) Bβ (SiO 2 ) 10 β] ' x H 2 O, Ca 4oNa 6 [(AlO 2 ) 8 6 (SiO 2 ) 10 6] x H 2 O, Sr 21 Ba 22 [(AIO 2 ) 86 (SiO 2 ) 10 6] ' x H 2 O, in which x can assume values of greater than 0 to 276. These zeolites have pore sizes of 8, 0 to 8.4 A on.
Geeignet ist beispielsweise auch Zeolith A-LSX, der einem Co-Kristallisat aus Zeolith X und Zeotith A entspricht und in seiner wasserfreien Form die Formel (M2/nO + M'2/nO) AI2O3 zSiO2 besitzt, wobei M und M' Alkali- oder Erdalkalimetalle sein können und z eine Zahl von 2,1 bis 2,6 ist. Kommerziell erhältlich ist dieses Produkt unter dem Markennamen VEGOBOND AX von der Firma CONDEA Augusta S.p.A.Also suitable, for example, is zeolite A-LSX, which corresponds to a cocrystal of zeolite X and zeolite A and in its anhydrous form has the formula (M 2 / n O + M'2 / n O) Al 2 O 3 zSiO 2 , wherein M and M 'may be alkali or alkaline earth metals and z is a number from 2.1 to 2.6. Commercially available this product is under the brand name VEGOBOND AX by the company CONDEA Augusta SpA
Auch Zeolithe vom Y-Typ sind kommerziell erhältlich und lassen sich beispielsweise durch die FormelnY-type zeolites are also commercially available and can be obtained, for example, by the formulas
Na56[(AIO2)56(SiO2)136] x H2O, K56[(AIO2)56(SiO2)136] x H2O, in denen x für Zahlen von größer O bis 276 steht, beschreiben. Diese Zeolithe weisen Porengrößen von 8,0 A auf.Na 56 [(AIO 2 ) 56 (SiO 2 ) 136 ] x H 2 O, K 56 [(AIO 2 ) 56 (SiO 2 ) 136 ] x H 2 O, where x is numbers greater than 0 to 276 stands, describe. These zeolites have pore sizes of 8.0 Å.
Die Teilchengrößen der geeigneten Zeolithe liegt dabei vorteilhafterweise im Bereich von 0,1 μm bis zu 100 μm, vorzugsweise von 0,5 μm bis 50 μm und insbesondere von 1 μm bis 30 μm, jeweils mit Standard-Teilchengrößenbestimmungsmethoden gemessen. In einer bevorzugten Ausführungsform der Erfindung sollen alle enthaltenen anorganischen Bestandteile vorzugsweise wasserlöslich sein. In diesen Ausführungsformen werden deshalb andere Buildersubstanzen als die genannten Zeolithe eingesetzt.The particle sizes of the suitable zeolites are advantageously in the range from 0.1 μm to 100 μm, preferably from 0.5 μm to 50 μm and in particular from 1 μm to 30 μm, in each case measured by standard particle size determination methods. In a preferred embodiment of the invention, all of the inorganic constituents contained should preferably be water-soluble. Therefore, builders other than the zeolites mentioned are used in these embodiments.
Weitere geeignete Buildersubstanzen sind Polyacetale, welche durch Umsetzung von Dialdehyden mit Polyolcarbonsäuren, welche 5 bis 7 C-Atome und mindestens 3 Hydroxylgruppen aufweisen, erhalten werden können. Bevorzugte Polyacetale werden aus Dialdehyden wie Glyoxal, Glutaral- dehyd, Terephthalaldehyd sowie deren Gemischen und aus Polyolcarbonsäuren wie Gluconsäure und/oder Glucoheptonsäure erhalten.Further suitable builder substances are polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 C atoms and at least 3 hydroxyl groups. Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
Weitere geeignete organische Buildersubstanzen sind Dextrine, beispielsweise Oligomere bzw. Polymere von Kohlenhydraten, die durch partielle Hydrolyse von Stärken erhalten werden können. Die Hydrolyse kann nach üblichen, beispielsweise säure- oder enzymkatalysierten Verfahren durchgeführt werden. Vorzugsweise handelt es sich um Hydrolyseprodukte mit mittleren Molmassen im Bereich von 400 bis 500000 g/mol. Dabei ist ein Polysaccharid mit einem Dextrose-Äquivalent (DE) im Bereich von 0,5 bis 40, insbesondere von 2 bis 30 bevorzugt, wobei DE ein gebräuchliches Maß für die reduzierende Wirkung eines Polysaccharids im Vergleich zu Dextrose, welche ein DE von 100 besitzt, ist. Brauchbar sind sowohl Maltodextrine mit einem DE zwischen 3 und 20 und Trockenglucosesirupe mit einem DE zwischen 20 und 37 als auch sogenannte Gelbdextrine und Weißdextrine mit höheren Molmassen im Bereich von 2000 bis 30000 g/mol. Ein bevorzugtes Dextrin ist in der britischen Patentanmeldung 94 19 091 beschrieben. Bei den oxidierten Derivaten derartiger Dextrine handelt es sich um deren Umsetzungsprodukte mit Oxidationsmitteln, welche in der Lage sind, mindestens eine Alkoholfunktion des Saccharidrings zur Carbonsäurefunktion zu oxidieren.Further suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary, for example acid or enzyme catalyzed processes. Preferably, it is hydrolysis products having average molecular weights in the range of 400 to 500,000 g / mol. In this case, a polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30 is preferred, DE being a common measure of the reducing action of a polysaccharide compared to dextrose, which has a DE of 100 , is. Usable are both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 and so-called yellow dextrins and white dextrins with higher molecular weights in the range from 2000 to 30,000 g / mol. A preferred dextrin is described in British Patent Application 94 19 091. 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.
Auch Oxydisuccinate und andere Derivate von Disuccinaten, vorzugsweise Ethylendiamindisucci- nat, sind weitere geeignete Cobuilder. Dabei wird Ethylendiamin-N,N'-di-succinat (EDDS) bevorzugt in Form seiner Natrium- oder Magnesiumsalze verwendet. Weiterhin bevorzugt sind in diesem Zusammenhang auch Glycerindisuccinate und Glycerintrisuccinate. Geeignete Einsatzmengen liegen beispielsweise bei 3 bis 15 Gew.-%, bezogen auf das gesamte Mittel.Oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate, are further suitable co-builders. Ethylenediamine-N, N '-di-succinate (EDDS) is preferably in the form of its sodium or magnesium salts. Also preferred in this context are glycerol disuccinates and glycerol trisuccinates. Suitable amounts are, for example, 3 to 15 wt .-%, based on the total agent.
Weitere brauchbare organische Cobuilder sind beispielsweise acetylierte Hydroxycarbonsäuren bzw. deren Salze, welche gegebenenfalls auch in Lactonform vorliegen können und welche mindestens 4 Kohlenstoffatome und mindestens eine Hydroxygruppe sowie maximal zwei Säuregruppen enthalten.Other useful organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be present in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.
Eine weitere Substanzklasse mit Cobuildereigenschaften stellen die Phosphonate dar. Dabei han- delt es sich insbesondere um Hydroxyalkan- bzw. Aminoalkanphosphonate. Unter den Hydroxyal- kanphosphonaten ist das 1-Hydroxyethan-1 ,1-diphosphonat (HEDP) von besonderer Bedeutung als Cobuilder. Es wird vorzugsweise als Natriumsalz eingesetzt, wobei das Dinatriumsalz neutral und das Tetranatriumsalz alkalisch (pH 9) reagiert. Als Aminoalkanphosphonate kommen vorzugsweise Ethylendiamintetramethylenphos-phonat (EDTMP), Diethylentriaminpentamethylenphospho- nat (DTPMP) sowie deren höhere Homologe in Frage. Sie werden vorzugsweise in Form der neutral reagierenden Natriumsalze, z.B. als Hexanatriumsalz der EDTMP bzw. als Hepta- und Octa-Natriumsalz der DTPMP, eingesetzt. Als Builder wird dabei aus der Klasse der Phosphonate bevorzugt HEDP verwendet. Die Aminoalkanphosphonate besitzen zudem ein ausgeprägtes Schwermetallbindevermögen. Dementsprechend kann es, insbesondere wenn die Mittel auch Bleiche enthalten, bevorzugt sein, Aminoalkanphosphonate, insbesondere DTPMP, einzusetzen, oder Mischungen aus den genannten Phosphonaten zu verwenden.Another substance class with co-builder properties are the phosphonates. these are in particular hydroxyalkane or aminoalkanephosphonates. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a co-builder. It is preferably used as the sodium salt, the disodium salt neutral and the tetrasodium salt alkaline (pH 9). Preferred aminoalkane phosphonates are ethylenediamine tetramethylene phosphonate (EDTMP), diethylene triamine pentamethylene phosphonate (DTPMP) and their higher homologs. They are preferably used in the form of the neutral-reacting sodium salts, for example as the hexasodium salt of EDTMP or as the hepta- and octa-sodium salt of DTPMP. The builder used here is preferably HEDP from the class of phosphonates. The aminoalkanephosphonates also have a pronounced heavy metal binding capacity. Accordingly, in particular if the agents also contain bleach, it may be preferable to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.
In Fällen, in denen ein Phosphat-Gehalt toleriert wird, können auch Phosphate mitverwendet werden, insbesondere Pentanatriumtriphosphat, gegebenenfalls auch Pyrophosphate sowie Ortho- phosphate, die in erster Linie als Fällungsmittel für Kalksalze wirken. Phosphate werden überwiegend in maschinellen Geschirrspülmitteln, teilweise aber auch noch in Waschmitteln eingesetzt. Alkalimetallphosphate ist dabei die summarische Bezeichnung für die Alkalimetall- (insbesondere Natrium- und Kalium-) -Salze der verschiedenen Phosphorsäuren, bei denen man Metaphosphor- säuren (HPO3),, und Orthophosphorsäure H3PO4 neben höhermolekularen Vertretern unterscheiden kann. Die Phosphate vereinen dabei mehrere Vorteile in sich: Sie wirken als Alkaliträger, verhindern Kalkbeläge auf Maschinenteilen bzw. Kalkinkrustationen in Geweben und tragen überdies zur Reinigungsleistung bei.In cases in which a phosphate content is tolerated, it is also possible to use phosphates, in particular pentasodium triphosphate, optionally also pyrophosphates and orthophosphates, which act primarily as precipitants for calcium salts. Phosphates are predominantly used in automatic dishwasher detergents, but in some cases also in detergents. Alkali metal phosphates is the summary term for the alkali metal (especially sodium and potassium) salts of various phosphoric acids, in which one can distinguish metaphosphoric acids (HPO 3 ), and orthophosphoric H 3 PO 4 in addition to high molecular weight representatives. The phosphates combine several advantages: they act as alkali carriers, prevent lime deposits on machine parts or lime incrustations in fabrics and also contribute to the cleaning performance.
Natriumdihydrogenphosphat, NaH2PO4, existiert als Dihydrat (Dichte 1 ,91 gern'3, Schmelzpunkt 60°) und als Monohydrat (Dichte 2,04 gern'3). Beide Salze sind weiße, in Wasser sehr leicht lösliche Pulver, die beim Erhitzen das Kristallwasser verlieren und bei 200°C in das schwach saure Diphosphat (Dinatriumhydrogendiphosphat, Na2H2PaO7), bei höherer Temperatur in Natiumtrimeta- phosphat (Na3P3O9) und Maddrellsches Salz (siehe unten), übergehen. NaH2PO4 reagiert sauer; es entsteht, wenn Phosphorsäure mit Natronlauge auf einen pH-Wert von 4,5 eingestellt und die Maische versprüht wird. Kaliumdihydrogenphosphat (primäres oder einbasiges Kaliumphosphat, Kaliumbiphos-phat, KDP), KH2PO4, ist ein weißes Salz der Dichte 2,33 gern"3, hat einen Schmelzpunkt 253° [Zersetzung unter Bildung von Kaliumpolyphosphat (KPO3)X] und ist leicht löslich in Wasser.Sodium dihydrogen phosphate, NaH 2 PO 4 , exists as a dihydrate (density 1, 91 like '3 , melting point 60 °) and monohydrate (density 2.04 like ' 3 ). Both salts are white powders which are very soluble in water and which lose the water of crystallization on heating and at 200 ° C into the weak acid diphosphate (disodium hydrogen diphosphate, Na 2 H 2 PaO 7 ), at higher temperature in sodium trimetaphosphate (Na 3 P 3 O 9 ) and Maddrell's salt (see below). NaH 2 PO 4 is acidic; It arises when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed. Potassium dihydrogen phosphate (potassium phosphate primary or monobasic, potassium bisphosphate, KDP), KH 2 PO 4 , is a white salt of density 2.33 "3 , has a melting point of 253 ° [decomposition to form potassium polyphosphate (KPO 3 ) X ] and is easily soluble in water.
Dinatriumhydrogenphosphat (sekundäres Natriumphosphat), Na2HPO4, ist ein farbloses, sehr leicht wasserlösliches kristallines Salz. Es existiert wasserfrei und mit 2 Mol. (Dichte 2,066 gern"3, Wasserverlust bei 95°), 7 Mol. (Dichte 1 ,68 gern'3, Schmelzpunkt 48° unter Verlust von 5 H2O) und 12 Mol. Wasser (Dichte 1 ,52 gern'3, Schmelzpunkt 35° unter Verlust von 5 H2O), wird bei 100° wasserfrei und geht bei stärkerem Erhitzen in das Diphosphat Na4P2O7 über. Dinatriumhydrogenphos- phat wird durch Neutralisation von Phosphorsäure mit Sodalösung unter Verwendung von Phenolphthalein als Indikator hergestellt. Di-kaliumhydrogenphosphat (sekundäres od. zweibasiges Kaliumphosphat), K2HPO4, ist ein amorphes, weißes Salz, das in Wasser leicht löslich ist.Disodium hydrogen phosphate (secondary sodium phosphate), Na 2 HPO 4 , is a colorless, very slightly water-soluble crystalline salt. It exists anhydrous and with 2 mol. (Density 2.066 like "3 , water loss at 95 °), 7 mol. (Density 1, 68 like '3 , melting point 48 ° with loss of 5 H 2 O) and 12 mol. Water (density 1, 52 like '3 , melting point 35 ° with loss of 5 H 2 O), becomes anhydrous at 100 ° and on more intense heating in the diphosphate Na 4 P 2 O 7 over. Disodium hydrogen phos- phate is prepared by neutralization of phosphoric acid with soda solution using phenolphthalein as an indicator. Di-potassium hydrogen phosphate (secondary or dibasic potassium phosphate), K 2 HPO 4 , is an amorphous, white salt that is readily soluble in water.
Trinatriumphosphat, tertiäres Natriumphosphat, Na3PO4, sind farblose Kristalle, die als Dodecahy- drat eine Dichte von 1,62 gern"3 und einen Schmelzpunkt von 73-760C (Zersetzung), als Decahy- drat (entsprechend 19-20% P2O5) einen Schmelzpunkt von 10O0C und in wasserfreier Form (entsprechend 39-40% P2O5) eine Dichte von 2,536 gern"3 aufweisen. Trinatriumphosphat ist in Wasser unter alkalischer Reaktion leicht löslich und wird durch Eindampfen einer Lösung aus genau 1 Mol Dinatrium-phosphat und 1 Mol NaOH hergestellt. Trikaliumphosphat (tertiäres oder dreibasi- ges Kaliumphosphat), K3PO4, ist ein weißes, zerfließliches, körniges Pulver der Dichte 2,56 gern'3, hat einen Schmelzpunkt von 1340° und ist in Wasser mit alkalischer Reaktion leicht löslich. Es entsteht z.B. beim Erhitzen von Thomasschlacke mit Kohle und Kaliumsulfat. Trotz des höheren Preises werden in der Reinigungsmittel-Industrie die leichter löslichen, daher hochwirksamen Kaliumphosphate gegenüber entsprechenden Natrium-Verbindungen vielfach bevorzugt.Trisodium phosphate, tertiary sodium phosphate, Na 3 PO 4, colorless crystals, as a hydrate Dodecahy- a density of 1.62 liked "3 and a melting point of 73-76 0 C (decomposition), Decahy- hydrate (corresponding to 19-20 % P 2 O 5 ) has a melting point of 10O 0 C and in anhydrous form (corresponding to 39-40% P 2 O 5 ) has a density of 2.536 like "3 . Trisodium phosphate is readily soluble in water under alkaline reaction and is prepared by evaporation of a solution of exactly 1 mole of disodium phosphate and 1 mole of NaOH. Tripotassium phosphate (tertiary or tribasic potassium phosphate), K 3 PO 4 , is a white, deliquescent, granular powder with a density of 2.56 '3 , has a melting point of 1340 ° and is readily soluble in water with an alkaline reaction. It arises, for example, when heating Thomasschlacke with coal and potassium sulfate. Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred over the corresponding sodium compounds in the detergent industry.
Tetranatriumdiphosphat (Natriumpyrophosphat), Na4P2O7, existiert in wasserfreier Form (Dichte 2,534 gern'3, Schmelzpunkt 988°, auch 880° angegeben) und als Decahydrat (Dichte 1 ,815-1 ,836 gern'3, Schmelzpunkt 94° unter Wasserverlust). Beide Substanzen sind farblose, in Wasser mit alkalischer Reaktion lösliche Kristalle. Na4P2O7 entsteht beim Erhitzen von Dinatriumphosphat auf >200° oder indem man Phosphorsäure mit Soda im stöchiometrischem Verhältnis umsetzt und die Lösung durch Versprühen entwässert. Das Decahydrat komplexiert Schwermetall-Salze und Härtebildner und verringert daher die Härte des Wassers. Kaliumdiphosphat (Kaliumpyrophosphat), K4P2O7, existiert in Form des Trihydrats und stellt ein farbloses, hygroskopisches Pulver mit der Dichte 2,33 gern'3 dar, das in Wasser löslich ist, wobei der pH-Wert der 1%igen Lösung bei 25° 10,4 beträgt.Tetrasodium diphosphate (sodium pyrophosphate), Na 4 P 2 O 7 , exists in anhydrous form (density 2.534 '3 , melting point 988 °, also indicated 880 °) and as decahydrate (density 1, 815-1, 836 like ' 3 , melting point 94 ° with loss of water). Both substances are colorless crystals which are soluble in water with an alkaline reaction. Na 4 P 2 O 7 is formed on heating of disodium phosphate to> 200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dewatering the solution by spraying. The decahydrate complexes heavy metal salts and hardness agents and therefore reduces the hardness of the water. Potassium diphosphate (potassium pyrophosphate), K 4 P 2 O 7 , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33% '3 , which is soluble in water, the pH being 1% Solution at 25 ° 10.4.
Durch Kondensation des NaH2PO4 bzw. des KH2PO4 entstehen höhermolekulare Natrium- und Kaliumphosphate, bei denen man cyclische Vertreter, die Natrium- bzw. Kaliummetaphos-phate und kettenförmige Typen, die Natrium- bzw. Kaliumpolyphosphate, unterscheiden kann. Insbesondere für letztere sind eine Vielzahl von Bezeichnungen in Gebrauch: Schmelz- oder Glühphosphate, Grahamsches Salz, Kurrolsches und Maddrellsches Salz. Alle höheren Natrium- und Kaliumphosphate werden gemeinsam als kondensierte Phosphate bezeichnet.Condensation of the NaH 2 PO 4 or of the KH 2 PO 4 gives rise to relatively high molecular weight sodium and potassium phosphates, in which cyclic representatives, the sodium or potassium metaphosphates and chain-type, the sodium or potassium polyphosphates, can be distinguished. In particular, for the latter are a variety of names in use: melting or annealing phosphates, Graham's salt, Kurrolsches and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.
Das technisch wichtige Pentanatriumtriphosphat, Na5P3Oi0 (Natriumtripolyphosphat), ist ein wasserfrei oder mit 6 H2O kristallisierendes, nicht hygroskopisches, weißes, wasserlösliches Salz der allgemeinen Formel NaO-[P(O)(ONa)-O]n-Na mit n=3. In 10O g Wasser lösen sich bei Zimmertemperatur etwa 17 g, bei 60° ca. 20 g, bei 100° rund 32 g des kristallwasserfreien Salzes; nach zweistündigem Erhitzen der Lösung auf 100° entstehen durch Hydrolyse etwa 8% Orthophosphat und 15% Diphosphat. Bei der Herstellung von Pentanatriumtriphosphat wird Phosphorsäure mit Sodalösung oder Natronlauge im stöchiometrischen Verhältnis zur Reaktion gebracht und die Lösung durch Versprühen entwässert. Ähnlich wie Grahamsches Salz und Natriumdiphosphat löst Pentanatriumtriphos-phat viele unlösliche Metall-Verbindungen (auch Kalkseifen usw.). Pentaka- liumtriphos-phat, K5P3O10 (Kaliumtripolyphosphat), kommt beispielsweise in Form einer 50 Gew.- %-igen Lösung (> 23% P2O5, 25% K2O) in den Handel. Die Kaliumpolyphosphate finden in der Wasch- und Reinigungsmittel-Industrie breite Verwendung. Weiter existieren auch Natriumkalium- tripolyphosphate, welche ebenfalls im Rahmen der vorliegenden Erfindung einsetzbar sind. Diese entstehen beispielsweise, wenn man Natriumtrimetaphosphat mit KOH hydrolysiert:The technically important pentasodium triphosphate, Na 5 P 3 Oi 0 (sodium tripolyphosphate), is an anhydrous or with 6 H 2 O crystallizing, non-hygroscopic, white, water-soluble salt of general formula NaO- [P (O) (ONa) -O] n -Na where n = 3. In 10O g of water dissolve at room temperature about 17 g, at 60 ° about 20 g, at 100 ° about 32 g of the salt water-free salt; after two hours of heating the solution to 100 ° caused by hydrolysis about 8% orthophosphate and 15% diphosphate. In the preparation of pentasodium triphosphate, phosphoric acid is reacted with soda solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dehydrated by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentakaliumtriphos-phat, K 5 P 3 O 10 (potassium tripolyphosphate), for example, in the form of a 50% by weight solution (> 23% P 2 O 5 , 25% K 2 O) in the trade. The potassium polyphosphates are widely used in the washing and cleaning industry. Furthermore, there are also sodium potassium tripolyphosphates, which can also be used in the context of the present invention. These arise, for example, when hydrolyzed sodium trimetaphosphate with KOH:
(NaPO3)3 + 2 KOH -> Na3K2P3O10 + H2O(NaPO 3 ) 3 + 2 KOH -> Na 3 K 2 P 3 O 10 + H 2 O
Diese sind erfindungsgemäß genau wie Natriumtripolyphosphat, Kaliumtripolyphosphat oder Mischungen aus diesen beiden einsetzbar; auch Mischungen aus Natriumtripoly-phosphat und Na- triumkaliumtripolyphosphat oder Mischungen aus Kaliumtripolyphosphat und Natriumkaliumtripoly- phosphat oder Gemische aus Natriumtripolyphosphat und Kaliumtripolyphosphat und Natriumkali- umtripolyphos-phat sind erfindungsgemäß einsetzbar.These are used according to the invention exactly as sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these two; Mixtures of sodium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium tripolyphosphate can also be used according to the invention.
In einer bevorzugten Ausführungsform der Erfindung werden als anorganischen Buildersubstanzen insbesondere Carbonate und Silicate eingesetzt.In a preferred embodiment of the invention, in particular carbonates and silicates are used as inorganic builder substances.
Zu nennen sind hier insbesondere kristalline, schichtförmige Natriumsilicate der allgemeinen Formel NaMSix02x+1 yH20, wobei M Natrium oder Wasserstoff bedeutet, x eine Zahl von 1 ,6 bis 4, vorzugsweise 1 ,9 bis 4,0 und y eine Zahl von 0 bis 20 ist und bevorzugte Werte für x 2, 3 oder 4 sind. Da derartige kristalline Silicate aber in einem Sprühtrocknungsverfahren mindestens teilweise ihre kristalline Struktur verlieren, werden kristalline Silicate vorzugsweise nachträglich zu dem direkten oder nachbehandelten Sprühtrocknungsprodukt zugemischt. Bevorzugte kristalline Schicht- silicate der angegebenen Formel sind solche, in denen M für Natrium steht und x die Werte 2 oderParticularly noteworthy here are crystalline, layered sodium silicates of the general formula NaMSi x 0 2x + 1 yH 2 O, where M is sodium or hydrogen, x is a number from 1, 6 to 4, preferably 1, 9 to 4.0 and y is one Number is from 0 to 20 and preferred values for x are 2, 3 or 4. However, since such crystalline silicates at least partially lose their crystalline structure in a spray-drying process, crystalline silicates are preferably subsequently added to the direct or post-treated spray-drying product. Preferred crystalline layer silicates of the formula given are those in which M is sodium and x is 2 or
3 annimmt. Insbesondere sind sowohl ß- als auch δ-Natriumdisilicate Na2Si205 yH20 bevorzugt. Im Handel befinden sich derartige Verbindungen beispielsweise unter der Bezeichnung SKS® (Fa. Clariant). So handelt es sich bei SKS-6® vorwiegend um ein δ-Natriumdi-silicat mit der Formel3 accepts. In particular, both β- and δ-sodium disilicates Na 2 Si 2 O 5 yH 2 O are preferred. Such compounds are commercially available, for example, under the name SKS® (from Clariant). Thus, it is mainly SKS-6 ® is a δ-sodium di-silicate having the formula
Na2Si2OS yH2O, bei SKS-7® vorwiegend um das ß-Natriumdisilicat. Durch Reaktion mit Säuren (z.B. Citronensäure oder Kohlensäure) entsteht aus dem δ-Natriumdisilicat KanemitNa 2 Si 2 O S yH 2 O, SKS-7 ® is predominantly a beta-sodium disilicate. Reaction with acids (eg citric acid or carbonic acid) produces kanemite from the δ-sodium disilicate
NaHSi2O5 yH2O, im Handel unter den Bezeichnungen SKS-9® bzw. SKS-10® (Fa. Clariant). Von Vorteil kann es auch sein, chemische Modifikationen dieser Schichtsilicate einzusetzen. So kann beispielsweise die Alkalitat der Schichtsilicate geeignet beeinflusst werden. Mit Phosphat bzw. mit Carbonat dotierte Schichtsilicate weisen im Vergleich zu dem δ-Natriumdisilicat veränderte Kristallmorphologien auf, lösen sich schneller und zeigen im Vergleich zu δ-Natriumdisilicat ein erhöhtes Calciubindevermögen. So sind Schichtsilicate der allgemeinen Summenformel x Na2O • y SiO2 • z P2O5 in der das Verhältnis x zu y einer Zahl 0,35 bis 0,6, das Verhältnis x zu z einer Zahl von 1 ,75 bis 1200 und das Verhältnis y zu z einer Zahl von 4 bis 2800 entspricht bekannt. Die Löslichkeit der Schichtsilicate kann auch erhöht werden, indem besonders feinteilige Schichtsilicate eingesetzt werden. Auch Compounds aus den kristallinen Schichtsilicaten mit anderen Inhaltsstoffen können eingesetzt werden. Dabei sind insbesondere Compounds mit Cellulose- derivaten, die Vorteile in der desintegrierenden Wirkung aufweisen, sowie Compounds mit Polycar- boxylaten, z.B. Citronensäure, bzw. polymeren Polycarboxylaten, z.B. Copolymeren der Acryl- säure, zu nennen.NaHSi 2 O 5 yH 2 O, commercially available under the names SKS- or SKS- 10® (from Clariant). It may also be advantageous to use chemical modifications of these phyllosilicates. So can For example, the alkalinity of the layered silicates are suitably influenced. Phyllosilicates doped with phosphate or with carbonate have altered crystal morphologies in comparison with the δ-sodium disilicate, dissolve more rapidly and show an increased calcium binding capacity in comparison to δ-sodium disilicate. Thus, phyllosilicates of the general empirical formula x Na 2 O • y SiO 2 • z P 2 O 5 in which the ratio x to y is a number 0.35 to 0.6, the ratio x to z a number of 1.75 to 1200 and the ratio y to z of a number of 4 to 2800 is known. The solubility of the layered silicates can also be increased by using particularly finely divided layered silicates. Also compounds from the crystalline layer silicates with other ingredients can be used. In particular, compounds with cellulose derivatives which have advantages in the disintegrating action, as well as compounds with polycarboxylates, for example citric acid, or polymeric polycarboxylates, for example copolymers of acrylic acid, may be mentioned.
Zu den bevorzugten Buildersubstanzen gehören auch amorphe Natriumsilikate mit einem Modul Na2O : SiO2 von 1 :2 bis 1 :3,3, vorzugsweise von 1 :2 bis 1 :2,8 und insbesondere von 1 :2 bis 1 :2,6, welche Sekundärwascheigenschaften aufweisen. Im Rahmen dieser Erfindung wird unter dem Begriff "amorph" auch "röntgenamorph" verstanden. Dies heißt, dass die Silikate bei Röntgenbeu- gungsexperimenten keine scharfen Röntgen reflexe liefern, wie sie für kristalline Substanzen typisch sind, sondern allenfalls ein oder mehrere Maxima der gestreuten Röntgenstrahlung, die eine Breite von mehreren Gradeinheiten des Beugungswinkels aufweisen. Es kann jedoch sehr wohl sogar zu besonders guten Buildereigenschaften führen, wenn die Silikatpartikel bei Elektronenbeugungsexperimenten verwaschene oder sogar scharfe Beugungsmaxima liefern. Dies ist so zu interpretieren, dass die Produkte mikrokristalline Bereiche der Größe 10 bis einige Hundert nm aufweisen, wobei Werte bis max. 50 nm und insbesondere bis max. 20 nm bevorzugt sind. Derartige so genannte röntgenamorphe Silikate, welche ebenfalls eine Löseverzögerung gegenüber den herkömmlichen Wassergläsern aufweisen, sind bekannt. Insbesondere bevorzugt sind verdich- tete/kom paktierte amorphe Silikate, compoundierte amorphe Silikate und übertrocknete röntgenamorphe Silikate. Der Gehalt der (röntgen-)amorphen Silicate in insbesondere zeolithfreien Mitteln beträgt vorzugsweise 1 bis 10 Gew.-%, was einer bevorzugten Ausführungsform der Erfindung entspricht.The preferred builder substances also include amorphous sodium silicates having a modulus Na 2 O: SiO 2 of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2, 6, which have secondary washing properties. 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 give sharp X-ray reflections typical of crystalline substances, but at best one or more maxima of the scattered X-radiation, which have a width of several degrees of diffraction angle. However, it may well even lead to particularly good builder properties if the silicate particles provide blurred or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of size 10 to a few hundred nm, with values of up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray amorphous silicates, which also have a dissolution delay compared with conventional water glasses, are known. Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates. The content of the (X-ray) amorphous silicates in particular zeolite-free compositions is preferably 1 to 10 wt .-%, which corresponds to a preferred embodiment of the invention.
Besonders bevorzugte anorganische wasserlösliche Builder sind Alkalimetallcarbonate und Alkali- metallbicarbonate, wobei Natrium- und Kaliumcarbonat und insbesondere Natriumcarbonat zu den bevorzugten Ausführungsformen zählen. Der Gehalt der Alkalimetallcarbonate in insbesondere zeolithfreien Mitteln kann in einem sehr breiten Rahmen variieren und beträgt vorzugsweise 5 bis 40 Gew.-%, insbesondere 8 bis 30 Gew.-%, wobei üblicherweise der Gehalt an Alkalimetallcarbo- naten höher ist als an (röntgen-)amorphen Silicaten. Brauchbare organische Gerüstsubstanzen sind beispielsweise die in Form ihrer Alkali- und insbesondere Natriumsalze einsetzbaren Polycarbonsäuren, wie Citronensäure, Adipinsäure, Bernstein- säure, Glutarsäure, Weinsäure, Zuckersäuren, Aminocarbonsäuren, Nitrilotriessigsäure (NTA), sofern ein derartiger Einsatz aus ökologischen Gründen nicht zu beanstanden ist, sowie Mischungen aus diesen. Bevorzugte Salze sind die Salze der Polycarbonsäuren wie Citronensäure, Adipinsäure, Bernsteinsäure, Glutarsäure, Weinsäure, Zuckersäuren und Mischungen aus diesen. Auch die Säuren an sich können eingesetzt werden. Die Säuren besitzen neben ihrer Builderwirkung typischerweise auch die Eigenschaft einer Säuerungskomponente und dienen somit, wie beispielsweise in den erfindungsgemäßen Granulaten, auch zur Einstellung eines niedrigeren und milderen pH-Wertes von Wasch- und Reinigungsmitteln. Insbesondere sind hierbei Citronensäure, Bernsteinsäure, Glutarsäure, Adipinsäure, Gluconsäure und beliebige Mischungen aus diesen zu nennen.Particularly preferred inorganic water-soluble builders are alkali metal carbonates and alkali metal bicarbonates, with sodium and potassium carbonate and especially sodium carbonate being among the preferred embodiments. The content of alkali metal carbonates in particular zeolite-free compositions can vary within a very broad range and is preferably from 5 to 40% by weight, in particular from 8 to 30% by weight, the content of alkali metal carbonates usually being higher than (X-ray). ) amorphous silicates. Useful organic builders are, for example, usable in the form of their alkali and especially sodium polycarboxylic acids, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for environmental reasons , as well as 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 thereof. The acids themselves can also be used. In addition to their builder action, the acids typically also have the property of an acidifying component and thus also serve, for example in the granules according to the invention, for setting a lower and milder pH of detergents and cleaners. In particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.
Als organische Builder sind weiter polymere Polycarboxylate geeignet, dies sind beispielsweise die Alkalimetallsalze der Polyacrylsäure oder der Polymethacrylsäure, beispielsweise solche mit einer relativen Molekülmasse von 500 bis 70000 g/mol. Bei den für polymere Polycarboxylate angegebenen Molmassen handelt es sich im Sinne dieser Schrift um gewichtsmittlere Molmassen Mw der jeweiligen Säureform, die grundsätzlich mittels Gelpermeationschromatographie (GPC) bestimmt wurden, wobei ein UV-Detektor eingesetzt wurde. Die Messung erfolgte dabei gegen einen externen Polyacrylsäure-Standard, der aufgrund seiner strukturellen Verwandtschaft mit den untersuchten Polymeren realistische Molgewichtswerte liefert. Diese Angaben weichen deutlich von den Molgewichtsangaben ab, bei denen Polystyrolsulfonsäuren als Standard eingesetzt werden. Die gegen Polystyrolsulfonsäuren gemessenen Molmassen sind in der Regel deutlich höher als die in dieser Schrift angegebenen Molmassen.Further suitable organic builders are polymeric polycarboxylates, for example the alkali metal salts of polyacrylic acid or of polymethacrylic acid, for example those having a relative molecular mass of 500 to 70,000 g / mol. For the purposes of this document, the molecular weights stated for polymeric polycarboxylates are weight-average molar masses M w of the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the polymers investigated. These data differ significantly from the molecular weight data, in which polystyrene sulfonic acids are used as standard. The molar masses measured against polystyrenesulfonic acids are generally significantly higher than the molecular weights specified in this document.
Die erfindungsgemäßen Mittel können auch Polymere enthalten, insbesondere als Träger für die Parfümöle (Riechstoffe). Geeignete Polymere, die auch als Trägerstoffe in Verbindung mit Riechstoff einsetzbar sind, umfassen insbesondere Polyacrylate, die bevorzugt eine Molekülmasse von 2000 bis 20000 g/mol aufweisen. Aufgrund ihrer überlegenen Löslichkeit können aus dieser Gruppe wiederum die kurzkettigen Polyacrylate, die Molmassen von 2000 bis 10000 g/mol, und besonders bevorzugt von 3000 bis 5000 g/mol, aufweisen, bevorzugt sein.The compositions according to the invention may also contain polymers, in particular as carriers for the perfume oils (fragrances). Suitable polymers which can also be used as carriers in combination with perfume include, in particular, polyacrylates which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molar masses of from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, may again be preferred from this group.
Geeignet sind weiterhin copolymere Polycarboxylate, insbesondere solche der Acrylsäure mit Methacrylsäure und der Acrylsäure oder Methacrylsäure mit Maleinsäure. Als besonders geeignet haben sich Copolymere der Acrylsäure mit Maleinsäure erwiesen, die 50 bis 90 Gew.-% Acrylsäure und 50 bis 10 Gew.-% Maleinsäure enthalten. Ihre relative Molekülmasse, bezogen auf freie Säuren, beträgt im allgemeinen 2000 bis 70000 g/mol, vorzugsweise 20000 bis 50000 g/mol und insbesondere 30000 bis 40000 g/mol. Der Gehalt der Mittel an organischen Buildersubstanzen kann in einem breiten Rahmen variieren Bevorzugt sind Gehalte von 2 bis 20 Gew -%, wobei insbesondere Gehalte von maximal 10 Gew - % besonderen Anklang findenAlso suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable. Their relative molecular weight, based on free acids, is generally from 2000 to 70000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol. The content of the organic builder substances may vary within a broad range. Preference is given to contents of from 2 to 20% by weight, in particular contents of not more than 10% by weight being particularly preferred
Die erfindungsgemaßen Mittel können Komponenten aus den Klassen der Vergrauungsinhibitoren (Schmutzträger), der Neutralsalze und/oder der textilweichmachenden Hilfsmittel (beispielsweise Kationtenside) aufweisen, was bevorzugt istThe agents according to the invention may contain components from the classes of the grayness inhibitors (soil carriers), the neutral salts and / or the fabric softening auxiliaries (for example cationic surfactants), which is preferred
Vergrauungsinhibitoren haben die Aufgabe, den von der Faser abgelösten Schmutz in der Flotte suspendiert zu halten und so das Wiederaufziehen des Schmutzes zu verhindern Hierzu sind wasserlösliche Kolloide meist organischer Natur geeignet, beispielsweise die wasserlöslichen Salze polymerer Carbonsäuren, Leim, Gelatine, Salze von Ethercarbon-säuren oder Ethersulfonsäuren der Stärke oder der Cellulose oder Salze von sauren Schwefelsäureestern der Cellulose oder der Stärke Auch wasserlösliche, saure Gruppen enthaltende Polyamide sind für diesen Zweck geeignet Weiterhin lassen sich lösliche Stärkepräparate und andere als die oben genannten Stärkeprodukte verwenden, z B abgebaute Stärke, Aldehydstärken usw Auch Polyvinylpyrrolidon ist brauchbar Bevorzugt werden jedoch Celluloseether, wie Carboxymethylcellulose (Na-SaIz)1 Me- thylcellulose, Hydroxyalkylcellulose und Mischether, wie Methylhydroxyethylcellulose, Methylhydro- xypropylcellulose, Methylcarboxy-methylcellulose und deren Gemische, sowie Polyvinyl-pyrrolidon beispielsweise in Mengen von vorzugsweise 0,1 bis 5 Gew -%, bezogen auf die Mittel, eingesetztGraying inhibitors have the task to keep suspended from the fiber debris suspended in the fleet and so prevent the re-accumulation of dirt For this purpose, water-soluble colloids are mostly organic nature suitable, for example, the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Also water-soluble polyamides containing acidic groups are suitable for this purpose. Furthermore, soluble starch preparations and starch products other than those mentioned above can be used, eg degraded starch, aldehyde starches, etc Polyvinylpyrrolidone is also useful. However, preference is given to cellulose ethers, such as carboxymethylcellulose (Na salt), 1 -methylcellulose, hydroxyalkylcellulose and mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and the like d their mixtures, and polyvinylpyrrolidone, for example, in amounts of preferably 0.1 to 5% by weight, based on the means used
Als typisches Beispiel für einen geeigneten Vertreter der Neutralsalze ist das Natriumsulfat zu nennen Es kann in Mengen von beispielsweise 0 bis 60 Gew -%, vorzugsweise 2 bis 45 Gew -% eingesetzt werdenA typical example of a suitable representative of the neutral salts is sodium sulfate. It can be used in amounts of, for example, from 0 to 60% by weight, preferably from 2 to 45% by weight
Geeignete Weichmacher, welche weiter unten ausführlicher beschrieben werden, sind beispielsweise quellfähige Schichtsilikate von der Art entsprechender Montmorillonite, beispielsweise Bentonit, ebenso kationische TensideSuitable plasticizers, which are described in more detail below, are, for example, swellable phyllosilicates of the type of corresponding montmorillonites, for example bentonite, as well as cationic surfactants
Der Gehalt an Wasser im Mittel richtet sich u a danach, ob das Mittel in flussiger oder fester Form vorliegt, beträgt daher vorzugsweise 0 bis weniger als 100 Gew -% und insbesondere 0,5 bis 95 Gew -%, wobei Werte von maximal 5 Gew -% insbesondere bei festen oder nichtwässngen flussigen Mitteln besondere Bevorzugung finden Nicht miteingerechnet wurde hierbei im Falle der festen Mittel das an gegebenenfalls vorhandene Alummosilikate wie Zeolith anhaftende WasserThe content of water on average depends, inter alia, on whether the composition is in liquid or solid form, and is therefore preferably 0 to less than 100% by weight and in particular 0.5 to 95% by weight, with values of not more than 5% by weight. Particular preference is given in particular to solid or non-aqueous liquid agents Not included in the case of the solid compositions is the water adhering to any aluminosilicates such as zeolite
Im Falle flussiger Mittel enthält das erfindungsgemäße Mittel nach einer bevorzugten Ausfuhrungsform Wasser in einer Menge von mehr als 20 Gew -%, vorteilhafterweise mehr als 30 Gew -%, in weiter vorteilhafter Weise mehr als 40 Gew.-%, noch vorteilhafter mehr als 50 Gew.-%, insbesondere 60 bis 95 Gew.-%, besonders bevorzugt 70 bis 93 Gew.-% und äußerst bevorzugt 80 bis 90 Gew.-%.In the case of liquid agents, the composition according to the invention according to a preferred embodiment contains water in an amount of more than 20% by weight, advantageously more than 30% by weight, in more advantageously more than 40 wt .-%, more preferably more than 50 wt .-%, in particular 60 to 95 wt .-%, particularly preferably 70 to 93 wt .-% and most preferably 80 to 90 wt .-%.
Das erfindungsgemäße Mittel kann, so es ein Feststoff ist, ein hervorragendes Rieselverhalten aufweisen. Nach einer bevorzugten Ausführungsform ist das erfindungsgemäße Mittel im wesentlichen festförmig, liegt vorzugsweise in pulvriger, gepresster oder granulärer Form vor.The agent according to the invention can, if it is a solid, have an excellent trickling behavior. According to a preferred embodiment, the agent according to the invention is substantially solid, preferably in powdery, pressed or granular form.
Liegt das Mittel in partikulärer Form vor, so können die Partikel nachbehandelt werden, beispielsweise indem man die Partikel des Mittels verrundet. Die Verrundung kann in einem üblichen Verrunder erfolgen. Vorzugsweise beträgt die Verrundungszeit dabei nicht länger als 4 Minuten, insbesondere nicht länger als 3,5 Minuten. Verrundungszeiten von maximal 1 ,5 Minute oder darunter sind insbesondere bevorzugt. Durch die Verrundung wird eine weitere Vereinheitlichung des Kornspektrums erreicht, da gegebenenfalls entstandene Agglomerate zerkleinert werden.If the agent is in particulate form, the particles can be post-treated, for example, by rounding the particles of the agent. The rounding can be done in a standard roundabout. Preferably, the rounding time is not longer than 4 minutes, especially not longer than 3.5 minutes. Rounding times of a maximum of 1.5 minutes or less are particularly preferred. By rounding a further standardization of the grain spectrum is achieved as any resulting agglomerates are crushed.
Ein erfindungsgemäßes Mittel in Partikelform kann man insbesondere mit nichtionischen Tensiden, Parfümöl (Riechstoffe) und/oder Schauminhibitoren bzw. Zubereitungsformen, welche diese Inhaltsstoffe enthalten, vorzugsweise mit Mengen bis zu 20 Gew.-% Aktivsubstanz, insbesondere mit Mengen von 2 bis 18 Gew.-% Aktivsubstanz, jeweils bezogen auf das nachbehandelte Produkt, in an sich üblicher Weise, vorzugsweise in einem Mischer oder ggf. einer Wirbelschicht, nachbehandeln.An inventive agent in particulate form can in particular with nonionic surfactants, perfume oil (fragrances) and / or foam inhibitors or formulations containing these ingredients, preferably with amounts up to 20 wt .-% of active ingredient, in particular with amounts of 2 to 18 wt. -% active substance, in each case based on the aftertreated product, in a conventional manner, preferably in a mixer or optionally a fluidized bed, post-treatment.
Insbesondere kann ein erfindungsgemäßes Mittel ebenfalls mit Feststoffen, vorzugsweise in Mengen bis zu 15 Gew.-%, insbesondere in Mengen von 2 bis 15 Gew.-%, jeweils bezogen auf das Gesamtgewicht des nachbehandelten Mittels, nachbehandelt bzw. abgepudert werden.In particular, an agent according to the invention may also be post-treated or powdered with solids, preferably in amounts of up to 15% by weight, in particular in amounts of from 2 to 15% by weight, based in each case on the total weight of the post-treated agent.
Als Feststoffe zur Nachbehandlung lassen sich vorzugsweise Bicarbonat, Carbonat, Zeolith, Kieselsäure, Citrat, Harnstoff oder Mischungen aus diesen, insbesondere in Mengen von 2 bis 15 Gew.-%, bezogen auf das Gesamtgewicht des nachbehandelten Produkts, verwenden. Die Nachbehandlung lässt sich in vorteilhafter Weise in einem Mischer und/oder mittels Verrunder durchführen.Bicarbonate, carbonate, zeolite, silica, citrate, urea or mixtures thereof, in particular in amounts of from 2 to 15% by weight, based on the total weight of the aftertreated product, can preferably be used as solids for the aftertreatment. The aftertreatment can be carried out in an advantageous manner in a mixer and / or by means of Verrunder.
In einer bevorzugten Ausführungsform der Erfindung ist ein erfindungsgemäßes Mittel nachbehandelt mit nichtionischen Tensiden, die beispielsweise auch optische Aufheller und/oder Hydrotrope enthalten können, Parfüm(Riechstoffe), und/oder einer Lösung von optischem Aufheller und/oder Schauminhibitoren bzw. Zubereitungsformen, welche diese Inhaltsstoffe enthalten können. Vorzugsweise werden diese Inhaltsstoffe oder Zubereitungsformen, welche diese Inhaltsstoffe enthalten, in flüssiger, geschmolzener oder pastöser Form auf das partikuläre Mittel, welches nachbe- handelt werden soll, aufgebracht.In a preferred embodiment of the invention, an agent according to the invention is aftertreated with nonionic surfactants, which may also contain, for example, optical brighteners and / or hydrotropes, perfume (fragrances), and / or a solution of optical brightener and / or foam inhibitors or preparation forms containing same May contain ingredients. These ingredients or preparation forms containing these ingredients are preferably applied in liquid, molten or pasty form to the particulate agent, which is to be acted upon.
Dabei ist es bevorzugt, dass die Nachbehandlung mit den hier genannten Substanzen in einem üblicher Mischer, lediglich beispielsweise in einem 2-Wellen-Mischer innerhalb von maximal 1 Minute, vorzugsweise innerhalb von 30 Sekunden und beispielsweise innerhalb von 20 Sekunden, wobei die Zeitangaben gleichzeitig für Zugabe- und Mischzeit steht, erfolgen.It is preferred that the aftertreatment with the substances mentioned here in a conventional mixer, only for example in a 2-wave mixer within a maximum of 1 minute, preferably within 30 seconds and for example within 20 seconds, the time information for Addition and mixing time is done.
Im folgenden werden die nichtionischen Tenside naher beschrieben. Diese nichtionischen Tenside können in einem Nachbehandlungsschritt auf die partikulären Mittel aufgebracht werden. Selbstverständlich können alle nichtionischen Tenside aber vorteilhafterweise direkt im erfindungsgemäßen Mittel, flüssig oder fest, schäum- oder gelförmig sein kann, enthalten sein.In the following, the nonionic surfactants are described in more detail. These nonionic surfactants can be applied to the particulate agents in an aftertreatment step. Of course, all nonionic surfactants but can advantageously be directly in the composition according to the invention, liquid or solid, foaming or gel may be included.
Als nichtionische Tenside werden vorzugsweise alkoxylierte, vorteilhafterweise ethoxylierte, insbesondere primäre Alkohole mit vorzugsweise 8 bis 18 C-Atomen und durchschnittlich 1 bis 12 Mol Ethylenoxid (EO) pro Mol Alkohol eingesetzt, in denen der Alkoholrest linear oder bevorzugt in 2- Stellung methylverzweigt sein kann bzw. lineare und methyl-verzweigte Reste im Gemisch enthalten kann, so wie sie üblicherweise in Oxoalkoholresten vorliegen. Insbesondere sind jedoch Alko- holethoxylate mit linearen Resten aus Alkoholen nativen Ursprungs mit 12 bis 18 C-Atomen, z.B. aus Kokos-, Palm-, Palmkern-, Taigfett- oder Oleylalkohol, und durchschnittlich 2 bis 8 EO pro Mol Alkohol bevorzugt. Zu den bevorzugten ethoxylierten Alkoholen gehören beispielsweise C12-C14-Al- kohole mit 3 EO oder 4 EO, C9-C11-AIkOhOIe mit 7 EO, C13-C15-Alkohole mit 3 EO, 5 EO, 7 EO oder 8 EO, C12-C18-Alkohole mit 3 EO, 5 EO oder 7 EO und Mischungen aus diesen, wie Mischungen aus C12-C14-AIkOhOl mit 3 EO und C12-C18-Alkohol mit 7 EO. Die angegebenen Ethoxylierungs- grade stellen statistische Mittelwerte dar, die für ein spezielles Produkt eine ganze oder eine gebrochene Zahl sein können.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 residue can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture may contain, as they are usually present in Oxoalkoholresten. In particular, however, alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, palm kernel, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred. The preferred ethoxylated alcohols include, for example, C 12 -C 14 -alcohols with 3 EO or 4 EO, C 9 -C 11 -alkyl with 7 EO, C 13 -C 15 -alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12 -C 18 -alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12 -C 14 -AlkOhOl with 3 EO and C 12 -C 18 -alcohol with 7 EO. The stated degrees of ethoxylation represent statistical averages, which may be an integer or a fractional number for a particular product.
Bevorzugte Alkoholethoxylate weisen eine eingeengte Homologenverteilung auf (narrow ränge ethoxylates, NRE). Zusätzlich zu diesen nichtionischen Tensiden können auch Fettalkohole mit mehr als 12 EO eingesetzt werden. Beispiele hierfür sind (TaIg-) Fettalkohole mit 14 EO1 16 EO, 20 EO, 25 EO, 30 EO oder 40 EO.Preferred alcohol ethoxylates have a narrow homolog distribution (narrow rank ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples of these are (TaIg) fatty alcohols with 14 EO 1 16 EO, 20 EO, 25 EO, 30 EO or 40 EO.
Bevorzugte nichtionische Tenside sind ein oder mehrere mit Ethylen- (EO) und/oder Propylenoxid (PO) alkoxylierte, unverzweigte oder verzweigte, gesättigte oder ungesättigte C10.22-Alkohole mit einem Alkoxylierungsgrad bis zu 30, vorzugsweise ethoxylierte C10-18-Fettalkohole mit einem Etho- xylierungsgrad von weniger als 30, bevorzugt 1 bis 20, insbesondere 1 bis 12, besonders bevorzugt 1 bis 8, äußerst bevorzugt 2 bis 5, beispielsweise C12.14-Fettalkoholethoxylate mit 2, 3 oder 4 EO oder eine Mischung von der C12-14-Fettalkoholethoxylate mit 3 und 4 EO im Gewichtsverhältnis von 1 zu 1 oder Isotridecylalkoholethoxylat mit 5, 8 oder 12 EO. Außerdem können als weitere nichtionische Tenside auch Alkylglykoside der allgemeinen Formel RO(G)x eingesetzt werden, in der R einen primären geradkettigen oder methylverzweigten, insbesondere in 2-Stellung methylverzweigten aliphatischen Rest mit 8 bis 22, vorzugsweise 12 bis 18 C-Atomen bedeutet und G das Symbol ist, das für eine Glykoseeinheit mit 5 oder 6 C-Atomen, vorzugsweise für Glucose, steht. Der Oligomerisierungsgrad x, der die Verteilung von Monoglykosiden und Oligoglykosiden angibt, ist eine beliebige Zahl von 1 bis 10; vorzugsweise liegt x bei 1 ,1 bis 1 ,4.Preferred nonionic surfactants are one or more ethylene oxide (EO) and / or propylene oxide (PO) alkoxylated, unbranched or branched, saturated or unsaturated C 10 . 22 alcohols having a degree of alkoxylation of up to 30, preferably ethoxylated C 10-18 fatty alcohols having an ethoxylation degree of less than 30, preferably 1 to 20, in particular 1 to 12, more preferably 1 to 8, most preferably 2 to 5, for example C 12 . 14 fatty alcohol ethoxylates with 2, 3 or 4 EO or a mixture of the C 12-14 fatty alcohol ethoxylates with 3 and 4 EO in a weight ratio of 1 to 1 or isotridecyl alcohol ethoxylate with 5, 8 or 12 EO. In addition, as further nonionic surfactants and alkyl glycosides of the general formula RO (G) x can be used in which R is a primary straight-chain or methyl-branched, especially in the 2-position methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which 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 from 1 to 10; preferably x is 1, 1 to 1, 4.
Eine weitere Klasse bevorzugt eingesetzter nichtionischer Tenside, die entweder als alleiniges nichtionisches Tensid oder in Kombination mit anderen nichtionischen Tensiden, insbesondere zusammen mit alkoxylierten Fettalkoholen und/oder Alkylglykosiden, eingesetzt werden, sind alkoxy- lierte, vorzugsweise ethoxylierte oder ethoxylierte und propoxylierte Fettsäurealkylester, vorzugsweise mit 1 bis 4 Kohlenstoffatomen in der Alkylkette, insbesondere Fettsäuremethylester, wie sie beispielsweise in der japanischen Patentanmeldung JP 58/217598 beschrieben sind oder die vorzugsweise nach dem in der internationalen Patentanmeldung WO-A-90/13533 beschriebenen Verfahren hergestellt werden. Besonders bevorzugt sind C12-Ci8-Fettsäuremethylester mit durchschnittlich 3 bis 15 EO, insbesondere mit durchschnittlich 5 bis 12 EO.Another class of preferred nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants, in particular together with alkoxylated fatty alcohols and / or alkyl glycosides, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, as described for example in Japanese Patent Application JP 58/217598 or which are preferably prepared according to the method described in International Patent Application WO-A-90/13533. Particularly preferred are C 12 -C 8 fatty acid methyl esters with an average of 3 to 15 EO, in particular with an average of 5 to 12 EO.
Auch nichtionische Tenside vom Typ der Aminoxide, beispielsweise N-Kokosalkyl-N,N-dimethyl- aminoxid und N-Talgalkyl-N,N-dihydroxyethylaminoxid, und der Fettsäurealkanolamide können geeignet sein. Die Menge dieser nichtionischen Tenside beträgt vorzugsweise nicht mehr als die der ethoxylierten Fettalkohole, insbesondere nicht mehr als die Hälfte davon.Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.
Weiterhin geeignet sind alkoxylierte Amine, vorteilhafterweise ethoxylierte und/oder propoxylierte, insbesondere primäre und sekundäre Amine mit vorzugsweise 1 bis 18 C-Atomen pro Alkylkette und durchschnittlich 1 bis 12 MoI Ethylenoxid (EO) und/oder 1 bis 1O MoI Propylenoxid (PO) pro Mol Amin.Also suitable are alkoxylated amines, advantageously ethoxylated and / or propoxylated, in particular primary and secondary amines having preferably 1 to 18 carbon atoms per alkyl chain and an average of 1 to 12 MoI ethylene oxide (EO) and / or 1 to 10 MoI propylene oxide (PO) per Mole of amine.
Bei erfindungsgemäßen Mitteln die besonders für das maschinelle Geschirrspülen geeignet sind, insbesondere Geschirrspülmittel in Form von Tablettenformkörpern, wie Tabs, kommen als Tenside prinzipiell zwar alle Tenside in Frage. Bevorzugt sind für diesen Anwendungszweck aber gerade die vorstehend beschriebenen nichtionischen Tenside und hier vor allem die schwachschäumenden nichtionischen Tenside. Besonders bevorzugt sind die alkoxylierten Alkohole, besonders die ethoxylierten und/oder propoxylierten Alkohole. Dabei versteht der Fachmann allgemein unter alkoxylierten Alkoholen die Reaktionsprodukte von Alkylenoxid, bevorzugt Ethylenoxid, mit Alkoholen, bevorzugt im Sinne der vorliegenden Erfindung die längerkettigen Alkohole C10 bis C18, bevorzugt von C12 bis C16, wie C11-, C12-, C13-, C14-, C15-, C16- ,C17- und C18-Alkohole. In der Regel entstehen aus n Molen Ethylenoxid und einem Mol Alkohol, abhängig von den Reaktionsbedingungen ein komplexes Gemisch von Additionsprodukten unterschiedlichen Ethoxylie- rungsgrades. Eine weitere Ausführungsform besteht im Einsatz von Gemischen der Alkylenoxide bevorzugt des Gemisches von Ethylenoxid und Propylenoxid. Auch kann man gewünschtenfalls durch eine abschließende Veretherung mit kurzkettigen Alkylgruppen, wie bevorzugt der Butyl- gruppe, zur Substanzklasse der "verschlossenen" AI koholethoxy taten gelangen, die ebenfalls im Sinne der Erfindung eingesetzt werden kann. Ganz besonders bevorzugt im Sinne der vorliegenden Erfindung sind dabei hochethoxylierte Fettalkohole oder deren Gemische mit endgruppenver- schlossenen Fettalkoholethoxylaten.In the case of compositions according to the invention which are particularly suitable for automatic dishwashing, in particular dishwashing compositions in the form of tablet tablets, such as tabs, all surfactants are suitable in principle as surfactants. However, the nonionic surfactants described above and especially the low-foaming nonionic surfactants are particularly preferred for this purpose. Particularly preferred are the alkoxylated alcohols, especially the ethoxylated and / or propoxylated alcohols. The person skilled in the art generally means, under alkoxylated alcohols, the reaction products of alkylene oxide, preferably ethylene oxide, with alcohols, preferably in the context of the present invention, the longer-chain alcohols C 10 to C 18 , preferably C 12 to C 16 , such as C 11 -, C 12 - , C 13 , C 14 , C 15 , C 16 , C 17 and C 18 alcohols. In As a rule, n moles of ethylene oxide and one mole of alcohol give rise to a complex mixture of addition products of varying degrees of ethoxylation, depending on the reaction conditions. A further embodiment consists in the use of mixtures of the alkylene oxides, preferably the mixture of ethylene oxide and propylene oxide. If desired, it is also possible, by a conclusive etherification with short-chain alkyl groups, such as preferably the butyl group, to obtain the class of "closed" Al koholethoxy, which can likewise be used in the context of the invention. Very particularly preferred for the purposes of the present invention are highly ethoxylated fatty alcohols or mixtures thereof with end-group-capped fatty alcohol ethoxylates.
Vorteilhafterweise können die erfindungsgemäßen Mittel auch Schauminhibitoren enthalten, beispielsweise schauminhibierendes Paraffinöl oder schauminhibierendes Silikon-öl, beispielsweise Dimethylpolysiloxan. Auch der Einsatz von Mischungen dieser Wirkstoffe ist möglich. Als bei Raumtemperatur feste Zusatzstoffe kommen, insbesondere bei den genannten schauminhibierenden Wirkstoffen, Paraffinwachse, Kieselsäuren, die auch in bekannter Weise hydrophobiert sein können, und von C2.7-Diaminen und C12.22-Carbon-säuren abgeleitete Bisamide in Frage.Advantageously, the compositions according to the invention may also contain foam inhibitors, for example foam-inhibiting paraffin oil or foam-inhibiting silicone oil, for example dimethylpolysiloxane. The use of mixtures of these agents is possible. As additives which are solid at room temperature, paraffin waxes, silicic acids, which may also be rendered hydrophobic in a known manner, and of C 2 , in particular in the case of the abovementioned foam-inhibiting active ingredients. 7 diamines and C 12 . 22 -carboxylic acids derived bisamides in question.
Für den Einsatz bevorzugt in Frage kommende schauminhibierende Paraffinöle, die auch in Ab- mischung mit Paraffinwachsen vorliegen können, sind im allgemeinen komplexe Stoffgemische ohne scharfen Schmelzpunkt. Zur Charakterisierung bestimmt man üblicherweise den Schmelzbereich durch Differential-Thermo-Analyse (DTA) und/oder den Erstarrungspunkt. Darunter versteht man die Temperatur, bei der das Paraffin durch langsames Abkühlen aus dem flüssigen in den festen Zustand übergeht. Paraffine mit weniger als 17 C-Atomen sind erfindungsgemäß nicht brauchbar, ihr Anteil im Paraffinölgemisch sollte daher so gering wie möglich sein und liegt vorzugsweise unterhalb der mit üblichen analytischen Methoden, zum Beispiel Gaschromatographie, signifikant messbaren Grenze. Vorzugsweise werden Paraffine verwendet, die im Bereich von 2O0C bis 700C erstarren. Dabei ist zu beachten, dass auch bei Raumtemperatur fest erscheinende Paraffinwachsgemische unterschiedliche Anteile an flüssigen Paraffinölen enthalten können. Bei den erfindungsgemäß brauchbaren Paraffinwachsen liegt der Flüssiganteil bei 400C möglichst hoch, ohne bei dieser Temperatur schon 100% zu betragen. Bevorzugte Paraffinwachsgemische weisen bei 4O0C einen Flüssiganteil von mindestens 50 Gew.-%, insbesondere von 55 Gew.-% bis 80 Gew.-%, und bei 6O0C einen Flüssiganteil von mindestens 90 Gew.-% auf. Dies hat zur Folge, dass die Paraffine bei Temperaturen bis hinunter zu mindestens 7O0C, vorzugsweise bis hinunter zu mindestens 600C fließfähig und pumpbar sind. Außerdem ist darauf zu achten, dass die Paraffine möglichst keine flüchtigen Anteile enthalten. Bevorzugte Paraffinwachse enthalten weniger als 1 Gew.-%, insbesondere weniger als 0,5 Gew.-% bei 11O0C und Normaldruck verdampfbare Anteile. Erfindungsgemäß brauchbare Paraffine können beispielsweise unter den Handelsbezeichnungen Lunaflex® der Firma Füller sowie Deawax® der DEA Mineralöl AG bezogen werden. Die Paraffinöle können bei Raumtemperatur feste Bisamide, die sich von gesättigten Fettsäuren mit 12 bis 22, vorzugsweise 14 bis 18 C-Atomen sowie von Alkylendiaminen mit 2 bis 7 C-Atomen ableiten, enthalten. Geeignete Fettsäuren sind Laurin-, Myristin-, Stearin-, Arachin- und Behen- säure sowie deren Gemische, wie sie aus natürlichen Fetten beziehungsweise gehärteten ölen, wie Talg oder hydriertem Palmöl, erhältlich sind. Geeignete Diamine sind beispielsweise Ethylendi- amin 1 ,3-Propy-lendiamin, Tetramethylendiamin, Pentamethylendiamin, Hexamethylendiamin, p- Phenylendi-amin und Toluylendiamin. Bevorzugte Diamine sind Ethylendiamin und Hexamethylendiamin. Besonders bevorzugte Bisamide sind Bis-myristoyl-ethylendiamin, Bispalmitoyl-ethylendi- amin, Bis-stearoyl-ethylendi-amin und deren Gemische sowie die entsprechenden Derivate des Hexamethylendiamins.Foam-inhibiting paraffin oils which are suitable for use and which may also be present in admixture with paraffin waxes are generally complex mixtures without a sharp melting point. For characterization, the melting range is usually determined by differential thermal analysis (DTA) and / or the solidification point. This is the temperature at which the paraffin passes from the liquid to the solid state by slow cooling. Paraffins with less than 17 carbon atoms are not useful according to the invention, their proportion in the paraffin oil mixture should therefore be as low as possible and is preferably below the limit significantly measurable by conventional analytical methods, for example gas chromatography. Preferably, paraffins are used, which solidify in the range of 2O 0 C to 70 0 C. It should be noted that even at room temperature appearing paraffin wax mixtures may contain different proportions of liquid paraffin oils. In the case of the paraffin waxes which can be used according to the invention, the liquid fraction at 40 ° C. is as high as possible, even without being 100% at this temperature. Preferred paraffin wax mixtures have at 4O 0 C a liquid content of at least 50 wt .-%, in particular from 55 wt .-% to 80 wt .-%, and at 6O 0 C, a liquid content of at least 90 wt .-%. This has the consequence that the paraffins at temperatures down to at least 7O 0 C, preferably down to at least 60 0 C are flowable and pumpable. It should also be ensured that the paraffins contain as far as possible no volatile components. Preferred paraffin waxes contain less than 1 wt .-%, in particular less than 0.5 wt .-% at 11O 0 C and atmospheric pressure vaporizable fractions. Paraffins which can be used according to the invention can be obtained, for example, under the trade names Lunaflex® from Füller and Deawax® from DEA Mineralöl AG. The paraffin oils may contain at room temperature solid bisamides derived from saturated fatty acids containing 12 to 22, preferably 14 to 18, carbon atoms and alkylenediamines having 2 to 7 carbon atoms. Suitable fatty acids are lauric, myristic, stearic, arachic and behenic acids and mixtures thereof, such as are obtainable from natural fats or hardened oils, such as tallow or hydrogenated palm oil. Suitable diamines are, for example, ethylenediamine 1, 3-propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, p-phenylenediamine and toluenediamine. Preferred diamines are ethylenediamine and hexamethylenediamine. Particularly preferred bisamides are bis-myristoyl-ethylenediamine, bispalmitoyl-ethylenediamine, bis-stearoyl-ethylenediamine and mixtures thereof and the corresponding derivatives of hexamethylenediamine.
Die erfindungsgemäßen Produkte können vorzugsweise mit weiteren Bestandteile, insbesondere von Wasch-, Pflege-, und/oder Reinigungsmitteln oder kosmetischen Inhaltsstoffen, vermischt werden. Aus dem breiten Stand der Technik ist allgemein bekannt, welche Inhaltsstoffe von Wasch- und Reinigungsmitteln und welche Rohstoffe üblicherweise noch zugemischt werden können. Es handelt sich hierbei beispielsweise um Stoffe wie Bleichmittel, Bleichaktivatoren und/oder Bleichkatalysatoren, Enzyme, temperaturempfindliche Farbstoffe usw., welche natürlich auch direkt im Mittel enthalten sein können.The products according to the invention can preferably be mixed with further constituents, in particular detergents, care and / or cleaning agents or cosmetic ingredients. From the broad state of the art is generally known which ingredients of detergents and cleaners and which raw materials can usually be added. These are, for example, substances such as bleaching agents, bleach activators and / or bleach catalysts, enzymes, temperature-sensitive dyes, etc., which of course may also be contained directly in the composition.
Vorzugsweise kann das Mittel UV-Absorber, die vorteilhafterweise auf die behandelten Textilien aufziehen und die Lichtbeständigkeit der Fasern und/oder die Lichtbeständigkeit sonstiger Rezepturbestandteile verbessern, aufweisen. Unter UV-Absorber sind organische Substanzen (Lichtschutzfilter) zu verstehen, die in der Lage sind, ultraviolette Strahlen zu absorbieren und die aufgenommene Energie in Form längerwelliger Strahlung, z.B. Wärme wieder abzugeben. Verbindungen, die diese gewünschten Eigenschaften aufweisen, sind beispielsweise die durch strahlungslose Desaktivierung wirksamen Verbindungen und Derivate des Benzophenons mit Substituenten in 2- und/oder 4-Stellung. Weiterhin sind auch substituierte Benzotriazole, in 3-Stellung Phenylsub- stituierte Acrylate (Zimtsäurederivate), gegebenenfalls mit Cyanogruppen in 2-Stellung, Salicylate, organische Ni-Komplexe sowie Naturstoffe wie Umbelliferon und die körpereigene Urocansäure geeignet. Besondere Bedeutung haben Biphenyl- und vor allem Stilbenderivate, kommerziell als Tinosorb® FD oder Tinosorb® FR ex Ciba erhältlich. Als UV-B-Absorber sind zu nennen 3-Benzyli- dencampher bzw. 3-Benzylidennorcampher und dessen Derivate, z.B. 3-(4-Methylbenzyliden)cam- pher; 4-Aminobenzoesäure-derivate, vorzugsweise 4-(Di-methylamino)benzoesäure-2-ethylhexyl- ester, 4-(Dimethylamino)benzoe-säure-2-octylester und 4-(Dimethylamino)benzoesäureamylester; Ester der Zimtsäure, vorzugsweise 4-Meth-oxyzimtsäure-2-ethylhexylester, 4-Methoxyzimtsäure- propylester, 4-Methoxyzimtsäureiso-amyl-ester, 2-Cyano-3,3-phenylzimtsäure-2-ethylhexylester (Octocrylene); Ester der Salicylsäure, vorzugsweise Salicylsäure-2-ethylhexylester, Salicylsäure-4- isopropylbenzyl-ester, Salicylsäurehomomenthylester; Derivate des Benzophenons, vorzugsweise 2-Hy-droxy-4-methoxybenzophenon, 2-Hydroxy-4-methoxy-4'-methylbenzophenon, 2,2'-Dihy- droxy-4-methoxybenzophenon; Ester der Benzalmalonsäure, vorzugsweise 4-Methoxy-benzmalon- säuredi-2-ethylhexylester; Triazinderivate, wie z.B. 2,4,6-Trianilino-(p-carbo-2'-ethyl-1'-hexyloxy)- 1 ,3,5-triazin und Octyl Triazon, oder Dioctyl Butamido Triazone (Uvasorb® HEB); Propan-1 ,3- dione, wie z.B. 1-(4-tert.Butylphenyl)-3-(4'methoxyphenyl)propan-1 ,3-dion; Ketotricy- clo(5.2.1.0)decan-Derivate. Weiterhin geeignet sind 2-Phenylbenzimidazol-5-sul-fonsäure und deren Alkali-, Erdalkali-, Ammonium-, Alkylammonium-, Alkanolammonium- und Glucammonium- salze; Sulfonsäurederivate von Benzophenonen, vorzugsweise 2-Hy-droxy-4-methoxybenzophe- non-5-sulfon-säure und ihre Salze; Sulfonsäurederivate des 3-Benzylidencamphers, wie z.B. 4-(2- Oxo-3-bor-nylidenmethyl)benzol-sulfonsäure und 2-Methyl-5-(2-oxo-3-bornyliden)sulfonsäure und deren Salze.Preferably, the agent may comprise UV absorbers, which are advantageously applied to the treated fabrics and improve the lightfastness of the fibers and / or the lightfastness of other formulation ingredients. Under UV absorber are organic substances (sunscreen) to understand, which are able to absorb ultraviolet rays and the absorbed energy in the form of longer-wave radiation, eg heat to give back. Compounds having these desired properties include, for example, the non-radiative deactivating compounds and derivatives of benzophenone having substituents in the 2- and / or 4-position. Also suitable are substituted benzotriazoles, phenyl-substituted acrylates (cinnamic acid derivatives) in the 3-position, optionally with cyano groups in the 2-position, salicylates, organic Ni complexes and natural substances such as umbelliferone and the endogenous urocanic acid. The biphenyl and especially stilbene derivatives, commercially available as Tinosorb ® FD or Tinosorb ® FR ex Ciba. As UV-B absorbers there may be mentioned 3-benzylidene camphor or 3-benzylidene norcamphor and its derivatives, eg 3- (4-methylbenzylidene) camphor; 4-aminobenzoic acid derivatives, preferably 2-ethylhexyl 4- (dimethylamino) benzoate, 2-octyl 4- (dimethylamino) benzoate and 4-dimethylaminobenzoic acid amide; Esters of cinnamic acid, preferably 2-ethylhexyl 4-methoxycinnamate, 4-methoxycinnamic acid propyl ester, 4-methoxycinnamic acid iso-amyl ester, 2-cyano-3,3-phenylcinnamic acid 2-ethylhexyl ester (octocrylene); Esters of salicylic acid, preferably 2-ethylhexyl salicylate, 4-salicylic acid isopropylbenzyl ester, salicylic acid homomenthyl ester; Derivatives of benzophenone, preferably 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone; Esters of benzalmalonic acid, preferably di-2-ethylhexyl 4-methoxybenzmalonate; Triazine derivatives such as 2,4,6-trianilino (p-carbo-2'-ethyl-1'-hexyloxy) -1,3,5-triazine and octyl triazone, or dioctyl butamido triazone (Uvasorb® HEB); Propane-1,3-diones such as 1- (4-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1,3-dione; Ketotricyclo (5.2.1.0) decane derivatives. Also suitable are 2-phenylbenzimidazole-5-sulfonic acid and its alkali metal, alkaline earth metal, ammonium, alkylammonium, alkanolammonium and glucammonium salts; Sulfonic acid derivatives of benzophenones, preferably 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its salts; Sulfonic acid derivatives of 3-Benzylidencamphers, such as 4- (2-oxo-3-boryl-nylidenemethyl) benzenesulfonic acid and 2-methyl-5- (2-oxo-3-bomylidene) sulfonic acid and salts thereof.
Als typische UV-A-Filter kommen insbesondere Derivate des Benzoylmethans in Frage, wie beispielsweise 1-(4'-tert.Butylphenyl)-3-(4'-methoxyphenyl)propan-1 ,3-dion, 4-tert.-Butyl-4'-methoxydi- benzoylmethan (Parsol 1789), 1-Phenyl-3-(4'-isopropylphenyl)-propan-1,3-dion sowie Enaminver- bindungen. Die UV-A und UV-B-Filter können selbstverständlich auch in Mischungen eingesetzt werden. Neben den genannten löslichen Stoffen kommen für diesen Zweck auch unlösliche Lichtschutzpigmente, nämlich feindisperse, vorzugsweise nanoisierte Metalloxide bzw. Salze in Frage. Beispiele für geeignete Metalloxide sind insbesondere Zinkoxid und Titandioxid und daneben Oxide des Eisens, Zirkoniums, Siliciums, Mangans, Aluminiums und Cers sowie deren Gemische. Als Salze können Silicate (Talk), Bariumsulfat oder Zinkstearat eingesetzt werden. Die Oxide und Salze werden in Form der Pigmente bereits für hautpflegende und hautschützende Emulsionen und dekorative Kosmetik verwendet. Die Partikel sollten dabei einen mittleren Durchmesser von weniger als 100 nm, vorzugsweise von 5 bis 50 nm und insbesondere von 15 bis 30 nm aufweisen. Sie können eine sphärische Form aufweisen, es können jedoch auch solche Partikel zum Einsatz kommen, die eine ellipsoide oder in sonstiger Weise von der sphärischen Gestalt abweichende Form besitzen. Die Pigmente können auch oberflächenbehandelt, d.h. hydrophilisiert oder hydro- phobiert vorliegen. Typische Beispiele sind gecoatete Titandioxide, wie z.B. Titandioxid T 805 (Degussa) oder Eusolex® T2000 (Merck). Als hydrophobe Coatingmittel kommen dabei vor allem Silicone und dabei speziell Trialkoxyoctylsilane oder Simethicone in Frage Vorzugsweise wird mikronisiertes Zinkoxid verwendet. Weitere geeignete UV-Lichtschutzfilter sind dem einschlägigen Stand der Technik zu entnehmen zu entnehmen.As a typical UV-A filter, in particular derivatives of benzoylmethane come into question, such as 1- (4'-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1, 3-dione, 4-tert-butyl 4'-methoxydibenzoylmethane (Parsol 1789), 1-phenyl-3- (4'-isopropylphenyl) -propane-1,3-dione and enamine compounds. Of course, the UV-A and UV-B filters can also be used in mixtures. In addition to the soluble substances mentioned, insoluble photoprotective pigments, namely finely dispersed, preferably nano-metal oxides or salts, are also suitable for this purpose. Examples of suitable metal oxides are in particular zinc oxide and titanium dioxide and, in addition, oxides of iron, zirconium, silicon, manganese, aluminum and cerium and mixtures thereof. As salts silicates (talc), barium sulfate or zinc stearate can be used. The oxides and salts are already used in the form of the pigments for skin-care and skin-protecting emulsions and decorative cosmetics. The particles should have an average diameter of less than 100 nm, preferably from 5 to 50 nm and in particular from 15 to 30 nm. They may have a spherical shape, but it is also possible to use those particles which have an ellipsoidal or otherwise deviating shape from the spherical shape. The pigments can also be surface treated, i. hydrophilized or hydrophobized. Typical examples are coated titanium dioxides, e.g. Titanium dioxide T 805 (Degussa) or Eusolex® T2000 (Merck). Suitable hydrophobic coating agents are in particular silicones and in particular trialkoxyoctylsilanes or simethicones. Micronized zinc oxide is preferably used. Further suitable UV light protection filters can be found in the relevant prior art.
Die UV-Absorber sind vorteilhafterweise in Mengen von 0,01 Gew.-% bis 5 Gew.-%, vorzugsweise von 0,03 Gew.-% bis 1 Gew.-%, in dem Mittel enthalten. Sie können dem Mittel auch nachträglich, beispielsweise zusammen mit anderen Stoffen, zugemischt werden. Vorzugsweise können die erfindungsgemäßen Mittel, so sie denn fest sind, auch als Tablette oder Formkörper vorliegen, wie schon gezeigt wurde. Als "Tablette" oder "Formkörper" werden im Rahmen der vorliegenden Anmeldung unabhängig von der Art ihrer Herstellung formstabile, feste Körper bezeichnet. Derartige Körper lassen sich beispielsweise durch Kristallisation, Formguss, Spritz- guss, reaktive oder thermische Sinterung, (Co)Extrusion, Verprillung, Pastillierung, oder Kompak- tierungsverfahren wie die Kalandrierung oder Tablettierung herstellen. Die Herstellung der "Tabletten" oder "Formkörper" durch Tablettierung ist im Rahmen der vorliegenden Anmeldung besonders bevorzugt. Die Tablette besteht also vorzugsweise aus verpresstem, teilchenförmigen Material.The UV absorbers are advantageously contained in amounts of from 0.01% to 5% by weight, preferably from 0.03% to 1% by weight, in the composition. They can also be added to the product later, for example together with other substances. Preferably, the agents according to the invention, if they are solid, can also be in the form of a tablet or shaped article, as has already been shown. For the purposes of the present application, "tablet" or "shaped bodies" are dimensionally stable, solid bodies, irrespective of the manner of their preparation. Such bodies can be produced, for example, by crystallization, molding, injection molding, reactive or thermal sintering, (co) extrusion, powdering, pastillation or compacting processes such as calendering or tableting. The preparation of the "tablets" or "shaped bodies" by tabletting is particularly preferred in the context of the present application. The tablet is thus preferably made of compressed, particulate material.
Erfindungsgemäßen Mittel in fester Form, vorzugsweise als Tablette oder Formkörper vorliegend, können vorzugsweise Desintegrationshilfsmittel enthalten. Als quellfähige Desintegrationshilfsmittel kommen beispielsweise Bentonite oder andere quellbare Silikate in Betracht. Auch synthetische Polymere, insbesondere die im Hygienebereich eingesetzten Superabsorber oder quervernetztes Polyvinylpyrrolidon, lassen sich einsetzen.Solid compositions according to the invention, preferably in the form of tablets or moldings, may preferably contain disintegration aids. Suitable swellable disintegration aids are, for example, bentonites or other swellable silicates. It is also possible to use synthetic polymers, in particular the superabsorbents or cross-linked polyvinylpyrrolidone used in the hygiene sector.
Mit besonderem Vorteil werden als quellfähige Desintegrationshilfsmittel Polymere auf der Basis von Stärke und/oder Cellulose eingesetzt. Diese Basis-Substanzen können allein oder in Mischung mit weiteren natürlichen und/oder synthetischen Polymeren zu quellfähigen Desintegrationsmitteln verarbeitet werden. Im einfachsten Fall kann ein cellulosehaltiges Material oder reine Cellulose durch Granulierung, Kompaktierung oder andere Anwendung von Druck in Sekundärpartikel überführt werden, welche bei Kontakt mit Wasser quellen und so als Sprengmittel dienen. Als cellulosehaltiges Material hat sich Holzstoff bewährt, der durch thermische oder chemisch-thermische Verfahren aus Hölzern bzw. Holzspänen (Sägespäne, Sägereiabfälle) zugänglich ist. Dieses CeIIuIo- sematerial aus dem TMP-Verfahren (thermo mechanical pulp) oder dem CTMP-Verfahren (chemo- thermo mechanical pulp) kann dann durch Anwendung von Druck konnpaktiert werden, vorzugsweise Walzenkompaktiert und in Partikelform überführt werden. Selbstverständlich lässt sich völlig analog auch reine Cellulose einsetzen, die allerdings von der Rohstoffbasis her teurer ist. Hier können sowohl mikrokristalline als auch amorphe feinteilige Cellulose und Mischungen derselben verwendet werden.With particular advantage, polymers based on starch and / or cellulose are used as swellable disintegration aids. These base substances can be processed alone or in mixture with other natural and / or synthetic polymers to swellable disintegrating agents. In the simplest case, a cellulosic material or pure cellulose can be converted by pressure transfer into secondary particles by granulation, compaction or other application, which swell on contact with water and thus serve as a disintegrant. Wood pulp which has been obtained by thermal or chemical-thermal processes from wood or wood chips (sawdust, sawmill waste) has proven to be suitable as a cellulosic material. This cellulose material from the TMP process (thermomechanical pulp) or the CTMP process (chemothermomechanical pulp) can then be compacted by application of pressure, preferably roller compacted and converted into particle form. Of course, pure cellulose can also be used in a completely analogous manner, although it is more expensive from the raw material base. Here, both microcrystalline and amorphous finely divided cellulose and mixtures thereof can be used.
Ein anderer Weg besteht darin, das cellulosehaltige Material unter Zusatz von Granulierhilfsmitteln zu granulieren. Als Granulierhilfsmittel haben sich beispielsweise Lösungen synthetischer Polymere oder nichtionische Tenside bewährt. Um Rückstände auf mit den erfindungsgemäßen Mitteln gewaschenen Textilien zu vermeiden, sollte die Primärfaserlänge der eingesetzten Cellulose bzw. der Cellulose im cellulosehaltigen Material unter 200 μm liegen, wobei Primärfaserlängen unter 100 μm, insbesondere unterhalb von 50μm bevorzugt sind. Die Sekundärpartikel besitzen idealerweise eine Partikelgrößenverteilung, bei der vorzugsweise mehr als 90 Gew.-% der Partikel Größen oberhalb von 200 μm haben. Ein gewisser Staubanteil kann zu einer verbesserten Lagerstabilität der damit hergestellten Tabletten beitragen. Anteile eines Feinstaubanteils von kleiner 0,1 mm bis zu 10 Gew.-%, vorzugsweise bis zu 8 Gew.-% können in den erfindungsgemäß eingesetzten Mitteln mit Sprengmittelgranulaten vorhanden sein.Another way is to granulate the cellulose-containing material with the addition of granulation aids. For example, solutions of synthetic polymers or nonionic surfactants have proven useful as granulating aids. In order to avoid residues on textiles washed with the agents according to the invention, the primary fiber length of the cellulose or cellulose used in the cellulosic material should be less than 200 .mu.m, preference being given to primary fiber lengths of less than 100 .mu.m, in particular less than 50 .mu.m. The secondary particles ideally have a particle size distribution in which preferably more than 90 wt .-% of the particles have sizes above 200 microns. A certain proportion of dust can contribute to an improved storage stability of the tablets produced therewith. Shares of a fine dust content of less than 0.1 mm up to 10 wt .-%, preferably up to 8 wt .-% may be present in the agents used in the invention with disintegrant granules.
Weiterhin können die erfindungsgemäßen Mittel in Form eines Konditioniermittels und/oder Kondi- tioniersubstrats vorliegen und dem gemäße Komponenten enthalten. Unter dem Begriff Konditionierung ist im Sinne dieser Erfindung vorzugsweise die avivierende Behandlung von Textilien, Stoffen und Geweben zu verstehen. Durch die Konditionierung werden den Textilien positive Eigenschaften verliehen, wie beispielsweise ein verbesserter Weichgriff, eine erhöhte Glanz- und Farbbrillanz, ein verbesserter Dufteindruck, Verringerung der Filzbildung, Bügelerleichterung durch Verringerung der Gleiteigenschaften, Verringerung des Knitterverhaltens und der statischen Aufladung sowie eine Farbübertragungsinhibierung bei gefärbten Textilien.Furthermore, the agents according to the invention can be present in the form of a conditioning agent and / or conditioner substrate and contain the appropriate components. For the purposes of this invention, the term conditioning is preferably to be understood as meaning the avivating treatment of textiles, fabrics and fabrics. Conditioning gives the textiles positive properties, such as improved softness, increased gloss and color brilliance, improved fragrance impression, reduction of felting, ironing relief by reducing the sliding properties, reducing the creasing behavior and the static charge and a color transfer inhibition in dyed textiles ,
Zur Verbesserung des Weichgriffs und der avivierenden Eigenschaften können die erfindungsgemäßen Mittel Weichmacherkomponenten aufweisen. Beispiele für solche Verbindungen sind quar- täre Ammoniumverbindungen, kationische Polymere und Emulgatoren, wie sie in Haarpflegemitteln und auch in Mitteln zur Textilavivage eingesetzt werden. Diese weichmachenden Verbindungen, welche auch nachfolgend näher beschreiben werden, können in allen erfindungsgemäßen Mitteln, insbesondere aber in den Konditioniermitteln bzw. in Mitteln mit angestrebter weichmachender Wirkung, enthalten sein.To improve the softness and the reviving properties, the compositions according to the invention may comprise plasticizer components. Examples of such compounds are quaternary ammonium compounds, cationic polymers and emulsifiers, as are used in hair care products and also in agents for Textilavivage. These softening compounds, which will also be described in more detail below, can be present in all inventive compositions, but especially in the conditioners or in compositions with the desired softening effect.
Geeignete Beispiele sind quartäre Ammoniumverbindungen der Formeln (III) und (IV),Suitable examples are quaternary ammonium compounds of the formulas (III) and (IV),
wobei in (III) R und R1 für einen acyclischen Alkylrest mit 12 bis 24 Kohlenstoffatomen, R2 für einen gesättigten C1-C4 Alkyl- oder Hydroxyalkylrest steht, R3 entweder gleich R, R1 oder R2 ist oder für einen aromatischen Rest steht. X" steht entweder für ein Halogenid-, Methosulfat-, Methophos- phat- oder Phosphation sowie Mischungen aus diesen. Beispiele für kationische Verbindungen der Formel (III) sind Didecyldimethylammoniumchlorid, Ditalgdimethylammoniumchlorid oder Dihexa- decylammoniumchlorid. wherein in (III) R and R 1 is an acyclic alkyl radical having 12 to 24 carbon atoms, R 2 is a saturated C 1 -C 4 alkyl or hydroxyalkyl radical, R 3 is either R, R 1 or R 2 or is a aromatic residue stands. X " represents either a halide, methosulfate, methophosphate or phosphate ion and mixtures of these Examples of cationic compounds of the formula (III) are didecyldimethylammonium chloride, ditallowdimethylammonium chloride or dihexadecylammonium chloride.
Verbindungen der Formel (IV) sind so genannte Esterquats. Esterquats zeichnen sich durch eine hervorragende biologische Abbaubarkeit aus. Hierbei steht R4 für einen aliphatischen Alkylrest mit 12 bis 22 Kohlenstoffatomen mit 0, 1 , 2 oder 3 Doppelbindungen; R5 steht für H, OH oder 0(CO)R7, R6 steht unabhängig von R5 für H, OH oder 0(CO)R8, wobei R7 und R8 unabhängig von- einander jeweils für einen aliphatischen Alk(en)ylrest mit 12 bis 22 Kohlenstoffatomen mit 0, 1 , 2 oder 3 Doppelbindungen steht, m, n und p können jeweils unabhängig voneinander den Wert 1 , 2 oder 3 haben. X" kann entweder ein Halogenid-, Methosulfat-, Methophosphat- oder Phosphation sowie Mischungen aus diesen sein. Bevorzugt sind Verbindungen, die für R5 die Gruppe 0(CO)R7 und für R4 und R7 Alkylreste mit 16 bis 18 Kohlenstoffatomen enthalten. Besonders bevorzugt sind Verbindungen, bei denen R6 zudem für OH steht. Beispiele für Verbindungen der Formel (IV) sind Methyl-N-(2-hydroxyethyl)-N,N-di(talg-acyl-oxyethyl)ammonium-methosulfat, Bis-(palmitoyl)-ethyl- hydroxyethyl-methyl-ammonium-metho-sulfat oder Methyl-N,N-bis(acyl-oxyethyl)-N-(2-hydroxy- ethyl)ammonium-methosulfat. Werden quarternierte Verbindungen der Formel (IV) eingesetzt, die ungesättigte Alkylketten aufweisen, sind die Acylgruppen bevorzugt, deren korrespondierenden Fettsäuren eine Jodzahl zwischen 5 und 80, vorzugsweise zwischen 10 und 60 und insbesondere zwischen 15 und 45 aufweisen und die ein cis/trans-lsomerenverhältnis (in Gew.-%) von größer als 30 : 70, vorzugsweise größer als 50 : 50 und insbesondere größer als 70 : 30 haben. Handelsübliche Beispiele sind die von Stepan unter dem Warenzeichen Stepantex® vertriebenen Methylhy- droxyalkyldi-alkoyloxyalkylammoniummethosulfate oder die unter Dehyquart® bekannten Produkte von Cognis bzw. die unter Rewoquat® bekannten Produkte von Goldschmidt-Witco. Weitere bevorzugte Verbindungen sind die Diesterquats der Formel (V)1 die unter dem Namen Rewoquat® W 222 LM bzw. CR 3099 erhältlich sind und neben der Weichheit auch für Stabilität und Farbschutz sorgen.Compounds of formula (IV) are so-called ester quats. Esterquats are characterized by excellent biodegradability. Here, R 4 is an aliphatic alkyl radical having 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds; R 5 is H, OH or O (CO) R 7 , R 6 is, independently of R 5, H, OH or O (CO) R 8 , where R 7 and R 8 are independently of each represents an aliphatic alk (en) yl radical having 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds, m, n and p can each independently of one another have the value 1, 2 or 3. X " can be either a halide, methosulfate, methophosphate or phosphate ion and mixtures thereof Preferred compounds are those for R 5, the group 0 (CO) R 7 and for R 4 and R 7 are alkyl radicals having 16 to 18 carbon atoms included. Especially preferred are compounds in which R 6 is also OH. Examples of compounds of 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 (acyl-oxy-ethyl) -N- (2-hydroxy-ethyl) -ammonium-methosulphate are quaternized compounds of the formula (IV) having unsaturated alkyl chains, the acyl groups are preferred whose corresponding fatty acids have an iodine value between 5 and 80, preferably between 10 and 60 and in particular between 15 and 45 and which have a cis / trans isomer ratio (in parts by weight). %) of greater than 30: 70, preferably greater than 50: 50 and in particular re greater than 70: 30. Commercial examples are sold by Stepan under the tradename Stepantex ® Methylhy- droxyalkyldi-alkoyloxyalkylammoniummethosulfate or those known under Dehyquart ® Cognis products known under or Rewoquat ® manufactured by Goldschmidt-Witco. Further preferred compounds are the diester quats of the formula (V) 1 which are obtainable under the name Rewoquat® W 222 LM or CR 3099 and, in addition to the softness, also provide stability and color protection.
R21 und R22 stehen dabei unabhängig voneinander jeweils für einen aliphatischen Rest mit 12 bis 22 Kohlenstoffatomen mit 0, 1 , 2 oder 3 Doppelbindungen.R 21 and R 22 are each independently an aliphatic radical having 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds.
Neben den oben beschriebenen quartären Verbindungen können auch andere bekannte Verbin- dun. gen eingesetzt werden, wie beispielsweise quartäre Imidazoliniumverbindungen der Formel (VI),In addition to the quaternary compounds described above, other known compounds may also be used. are used, such as, for example, quaternary imidazolinium compounds of the formula (VI),
wobei Rs für H oder einen gesättigten Alkylrest mit 1 bis 4 Kohlenstoffatomen, R'υ und R" unabhängig voneinander jeweils für einen aliphatischen, gesättigten oder ungesättigten Alkylrest mit 12 bis 18 Kohlenstoffatomen, R10 alternativ auch für O(CO)R20 stehen kann, wobei R20 einen aliphatischen, gesättigten oder ungesättigten Alkylrest mit 12 bis 18 Kohlenstoffatomen bedeutet, und Z eine NH-Gruppe oder Sauerstoff bedeutet und X" ein Anion ist. q kann ganzzahlige Werte zwischen 1 und 4 annehmen. Weitere geeignete quartäre Verbindungen sind durch Formel (VII) beschrieben, where R s is H or a saturated alkyl radical having 1 to 4 carbon atoms, R ' υ and R "are each independently an aliphatic, saturated or unsaturated alkyl radical having 12 to 18 carbon atoms, R 10 alternatively also O (CO) R 20 wherein R 20 is an aliphatic, saturated or unsaturated alkyl radical having 12 to 18 carbon atoms, and Z is an NH group or oxygen and X "is an anion. q can take integer values between 1 and 4. Further suitable quaternary compounds are described by formula (VII)
R13 HR13 H
R12 — N— (CH2)r — C— O(CO)R15 X" (VII);R12 - N- (CH 2) r - CO (CO) R15 X '(VII);
R14 CH2 — O(CO)R16 wobei R12, R13 und R14 unabhängig voneinander für eine d-4-Atkyl-, Alkenyl- oder Hydroxyalkyl- gruppe steht, R15 und R16 jeweils unabhängig ausgewählt eine C8_28-Alkylgruppe darstellt und r eine Zahl zwischen 0 und 5 ist.R14 CH 2 - O (CO) R 16 wherein R 12, R 13 and R 14 independently are a C 4 -Atkyl-, alkenyl or hydroxyalkyl group is of one another, R 15 and R 16 are each independently selected a C 8 _2 8 -Alkyl group and r is a number between 0 and 5.
Neben den Verbindungen der Formeln (III) und (IV) können auch kurzkettige, wasserlösliche, quartäre Ammoniumverbindungen eingesetzt werden, wie Trihydroxyethylmethylammonium-methosul- fat oder die Alkyltrimethylammoniumchloride, Dialkyldimethylammo-niumchloride und Trialkylme- thylammoniumchloride, z.B. Cetyltrimethylammoniumchlorid, Stearyltrimethylammoniumchlorid, Di- stearyldi-methylammoniumchlorid, Lauryldimethylammoniumchlorid, Lauryldimethylbenzylammoni- umchlorid und Tricetylmethylammonium-chlorid.In addition to the compounds of the formulas (III) and (IV) it is also possible to use short-chain, water-soluble, quaternary ammonium compounds, such as trihydroxyethylmethylammonium methosulfate or the alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, e.g. Cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride.
Auch protonierte Alkylaminverbindungen, die weichmachende Wirkung aufweisen, sowie die nicht quaternierten, protonierten Vorstufen der kationischen Emulgatoren sind geeignet.Also protonated alkylamine compounds which have plasticizing effect, as well as the non-quaternized, protonated precursors of cationic emulsifiers are suitable.
Weitere erfindungsgemäß verwendbare kationische Verbindungen stellen die quatemisierten Proteinhydrolysate dar.Further cationic compounds which can be used according to the invention are the quaternized protein hydrolysates.
Zu den geeigneten kationischen Polymeren zählen die Polyquaternium-Polymere, wie sie im CTFA Cosmetic Ingredient Dictionary (The Cosmetic, Toiletry und Fragrance, Inc., 1997) genannt werden, insbesondere die auch als Merquats bezeichneten Polyquaternium-6-, Polyquaternium-7-, Po- lyquaternium-10-Polymere (Ucare Polymer IR 400; Amerchol), Polyquaternium-4-Copolymere, wie Pfropf-copolymere mit einen Cellulosegerüst und quartären Ammoniumgruppen, die über Allyldi- methylammoniumchlorid gebunden sind, kationische Cellulosederivate, wie kationisches Guar, wie Guar-hydroxypropyltriammoniumchlorid, und ähnliche quaternierte Guar-Derivate (z.B. Cosmedia Guar, Hersteller: Cognis GmbH), kationische quartäre Zuckerderivate (kationische Alkylpolyglu- coside), z. B. das Handelsprodukt Glucquat®100, gemäß CTFA-Nomenklatur ein "Lauryl Methyl Gluceth-10 Hydroxypropyl Dimonium Chloride", Copolymere von PVP und Dimethylaminometh- acrylat, Copolymere von Vinylimidazol und Vinylpyrrolidon, Aminosilicon-polymere und Copolymere.Suitable cationic polymers include the polyquaternium polymers as referred to in the CTFA Cosmetic Ingredient Dictionary (The Cosmetic, Toiletry and Fragrance, Inc., 1997), in particular the Polyquaternium-6, Polyquaternium-7, also referred to as Merquats, Polyquaternium-10 polymers (Ucare Polymer IR 400, Amerchol), polyquaternium-4 copolymers such as graft copolymers having a cellulose backbone and quaternary ammonium groups attached via allyldimethylammonium chloride, cationic cellulose derivatives such as cationic guar such as guar hydroxypropyl triammonium chloride, and similar quaternized guar derivatives (eg Cosmedia Guar, manufacturer: Cognis GmbH), cationic quaternary sugar derivatives (cationic alkyl polyglucosides), eg. , The commercial product Glucquat ® 100, a "Lauryl Methyl Gluceth-10 Hydroxypropyl Dimonium Chloride", copolymers of PVP and Dimethylaminometh- acrylate according to CTFA nomenclature, copolymers of vinylimidazole and vinylpyrrolidone, aminosilicone polymers and copolymers.
Ebenfalls einsetzbar sind polyquaternierte Polymere (z.B. Luviquat Care von BASF) und auch kationische Biopolymere auf Chitinbasis und deren Derivate, beispielsweise das unter der Handelsbezeichnung Chitosan® (Hersteller: Cognis) erhältliche Polymer. Erfindungsgemäß ebenfalls verwendbar sind kationische Silikonöle wie beispielsweise die im Handel erhältlichen Produkte Q2-7224 (Hersteller: Dow Corning; ein stabilisiertes Trimethylsilyla- modimeth-icon), Dow Corning 929 Emulsion (enthaltend ein hydroxyl-amino-modifiziertes Silicon, das auch als Amodimethicone bezeichnet wird), SM-2059 (Hersteller: General Electric), SLM- 55067 (Hersteller: Wacker) Abil®-Quat 3270 und 3272 (Hersteller: Goldschmidt-Rewo; diquartäre Polydimethylsiloxane, Quaternium-80), sowie Siliconquat Rewoquat® SQ 1 (Tegopren® 6922, Hersteller: Goldschmidt-Rewo).Polyquaternized polymers (for example Luviquat Care from BASF) and also cationic biopolymers based on chitin and derivatives thereof, for example, under the trade designation chitosan ® (manufacturer: Cognis) polymer obtainable. Also useful in the present invention are cationic silicone oils such as the commercially available products Q2-7224 (manufactured by Dow Corning, a stabilized trimethylsilyl-modimeth-icon), Dow Corning 929 emulsion (containing a hydroxylamino-modified silicone, also referred to as amodimethicones is SM-2059 (manufacturer): General Electric), SLM-55067 (manufacturer: Wacker) Abil ® -Quat 3270 and 3272 (manufacturer: Goldschmidt-Rewo; diquaternary polydimethylsiloxanes, quaternium-80), and Silicone quat Rewoquat ® SQ 1 ( Tegopren® ® 6922, manufacturer: Goldschmidt-Rewo).
Ebenfalls einsetzbar sind Verbindungen der Formel (VIII),It is likewise possible to use compounds of the formula (VIII)
die Alkylamidoamine in ihrer nicht quaternierten oder, wie dargestellt, ihrer quaternierten Form, sein können. R17 kann ein aliphatischer Alk(en)ylrest mit 12 bis 22 Kohlenstoffatomen mit 0, 1 , 2 oder 3 Doppelbindungen sein, s kann Werte zwischen 0 und 5 annehmen. R18 und R19 stehen unabhängig voneinander jeweils für H1 C^-Alkyl oder Hydroxyalkyl. Bevorzugte Verbindungen sind Fettsäureamidoamine wie das unter der Bezeichnung Tego Amid®S 18 erhältliche Stearylamido- propyldimethylamin oder das unter der Bezeichnung Stepantex® X 9124 erhältliche 3-Talgamido- propyl-trimethylammo-nium-methosulfat, die sich neben einer guten konditionierenden Wirkung auch durch farbübertragungsinhibierende Wirkung sowie speziell durch ihre gute biologische Ab- baubarkeit auszeichnen. the alkylamidoamines may be in their quaternized or, as shown, their quaternized form. R 17 can be an aliphatic alk (en) yl radical having 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds, s can assume values between 0 and 5. R 18 and R 19 are each independently H 1 C 1-4 alkyl or hydroxyalkyl. Preferred compounds are fatty acid amidoamines, such as the propyldimethylamine Stearylamido- obtainable under the name Tego Amid ® S 18 or the 3-9124 available Talgamido- propyl-trimethylammo-nium methosulfate under the name Stepantex ® X, which is a good conditioning effect by dye transfer-inhibiting Effect and especially characterized by their good biodegradability.
Besonders bevorzugt sind alkylierte quatemäre Ammoniumverbindungen, von denen mindestens eine Alkylkette durch eine Estergruppe und/oder Amidogruppe unterbrochen ist, insbesondere N- Methyl-N(2-hydroxyethyl)-N,N-(ditalgacyloxyethyl)ammonium-methosulfat.Particularly preferred are alkylated quaternary ammonium compounds, of which at least one alkyl chain is interrupted by an ester group and / or amido group, in particular N-methyl-N (2-hydroxyethyl) -N, N- (ditalgacyloxyethyl) ammonium methosulfate.
Als nichtionische Weichmacher kommen vor allem Polyoxyalkylenglycerolalkanoate, Polybutylene, langkettige Fettsäuren, ethoxylierte Fettsäureethanolamide, Alkylpolyglycoside, insbesondere Sorbitan- mono,-di- und triester und Fettsäureester von Polycarbonsäuren in Betracht.Suitable nonionic plasticizers are, in particular, polyoxyalkylene glycol alkanoates, polybutylenes, long-chain fatty acids, ethoxylated fatty acid ethanolamides, alkyl polyglycosides, in particular sorbitan mono-, di- and triester and fatty acid esters of polycarboxylic acids.
In einem erfindungsgemäßen Mittel, vorzugsweise Konditionierungsmittel können Weichmacher in Mengen von 0,1 bis 80 Gew.-%, üblicherweise 0,1 bis 70 Gew.-%, vorzugsweise 0,2 bis 60 Gew.- % und insbesondere 0,5 bis 40 Gew.-%, jeweils bezogen auf das gesamte Mittel, enthalten sein.In an agent according to the invention, preferably conditioning agents, plasticizers may be used in amounts of from 0.1 to 80% by weight, usually from 0.1 to 70% by weight, preferably from 0.2 to 60% by weight and in particular from 0.5 to 40 Wt .-%, in each case based on the total agent to be included.
Erfindungsgemäße Konditioniermittel können vorzugsweise ein oder mehrere Aniontenside enthalten, insbesondere jene, welche weiter oben schon beschrieben wurden. Erfindungsgemäße Konditioniermittel können vorzugsweise ein oder mehrere nichtionische Ten- side enthalten, insbesondere solche, welche weiter oben schon beschrieben wurden.Conditioners according to the invention may preferably contain one or more anionic surfactants, in particular those which have already been described above. Conditioners according to the invention may preferably contain one or more nonionic surfactants, in particular those which have already been described above.
Als weitere Tenside für alle erfindungsgemäßen Mittel, insbesondere für die Konditioniermittel, kommen so genannte Gemini-Tenside in Betracht. Hierunter werden im allgemeinen solche Verbindungen verstanden, die zwei hydrophile Gruppen und zwei hydrophobe Gruppen pro Molekül besitzen. Diese Gruppen sind in der Regel durch einen sogenannten "Spacer" voneinander getrennt. Dieser Spacer ist in der Regel eine Kohlenstoffkette, die lang genug sein sollte, dass die hydrophilen Gruppen einen ausreichenden Abstand haben, damit sie unabhängig voneinander agieren können. Derartige Tenside zeichnen sich im allgemeinen durch eine ungewöhnlich geringe kritische Micellkonzentration und die Fähigkeit, die Oberflächenspannung des Wassers stark zu reduzieren, aus. In Ausnahmefällen werden jedoch unter dem Ausdruck Gemini-Tenside nicht nur dimere, sondern auch trimere Tenside verstanden.As further surfactants for all agents according to the invention, in particular for the conditioning agents, so-called gemini surfactants come into consideration. These are generally understood as meaning those compounds which have two hydrophilic groups and two hydrophobic groups per molecule. These groups are usually separated by a so-called "spacer". This spacer is typically a carbon chain that should be long enough for the hydrophilic groups to be spaced sufficiently apart for them to act independently of each other. Such surfactants are generally characterized by an unusually low critical micelle concentration and the ability to greatly reduce the surface tension of the water. In exceptional cases, however, the term gemini surfactants is understood to mean not only dimeric but also trimeric surfactants.
Geeignete Gemini-Tenside sind beispielsweise sulfatierte Hydroxymischether oder Dimeralkohol- bis- und Trimeralkohol-tris-sulfate und -ether-sulfate. Endgruppenverschlossene dimere und trimere Mischether zeichnen sich insbesondere durch ihre Bi- und Multifunktionalität aus. So besitzen die genannten endgruppenverschlossenen Tenside gute Netzeigenschaften und sind dabei schaumarm, so dass sie sich insbesondere für den Einsatz in maschinellen Wasch- oder Reinigungsverfahren eignen.Suitable gemini surfactants are, for example, sulfated hydroxy mixed ethers or dimer alcohol bis- and trimer tris sulfates and ether sulfates. End-capped dimeric and trimeric mixed ethers are characterized in particular by their bi- and multi-functionality. Thus, the end-capped surfactants mentioned have good wetting properties and are low foaming, so that they are particularly suitable for use in machine washing or cleaning processes.
Eingesetzt werden können aber auch Gemini-Polyhydroxyfettsäureamide oder Poly-Polyhydroxy- fett-säureamide, wie sie im einschlägigen Stand der Technik beschrieben werden.However, it is also possible to use gemini-polyhydroxy fatty acid amides or poly-polyhydroxy fatty acid amides, as described in the relevant prior art.
Weitere geeignete Tenside sind Polyhydroxyfettsäureamide der folgenden Formel,Further suitable surfactants are polyhydroxy fatty acid amides of the following formula
R23 R 23
I R-CO-N-[Z] in der RCO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen, R23 für Wasserstoff, einen Alkyl- oder Hydroxyalkylrest mit 1 bis 4 Kohlenstoffatomen und [Z] für einen linearen oder verzweigten Polyhydroxyalkylrest mit 3 bis 10 Kohlenstoffatomen und 3 bis 10 Hydroxylgruppen steht. Bei den Polyhydroxyfettsäureamiden handelt es sich um bekannte Stoffe, die üblicherweise durch reduktive Aminierung eines reduzierenden Zuckers mit Ammoniak, einem Alkylamin oder einem Alkanolamin und nachfolgende Acylierung mit einer Fettsäure, einem Fettsäurealkylester oder einem Fettsäurechlorid erhalten werden können.I R-CO-N- [Z] in the RCO for an aliphatic acyl radical having 6 to 22 carbon atoms, R 23 for hydrogen, an alkyl or hydroxyalkyl radical having 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. 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.
Zur Gruppe der Polyhydroxyfettsäureamide gehören auch Verbindungen der folgenden Formel, R24-O-R25 The group of polyhydroxy fatty acid amides also includes compounds of the following formula R 24 -OR 25
I R-CO-N-[Z] in der R für einen linearen oder verzweigten Alkyl- oder Alkenylrest mit 7 bis 12 Kohlenstoffatomen, R24 für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest mit 2 bis 8 Kohlenstoffatomen und R25 für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest oder einen Oxy-Alkylrest mit 1 bis 8 Kohlenstoffatomen steht, wobei C1-4-Alkyl- oder Phenylreste bevorzugt sind und [Z] für einen linearen Polyhydroxyalkylrest steht, dessen Alkylkette mit mindestens zwei Hydroxylgruppen substituiert ist, oder alkoxylierte, vorzugsweise ethoxylierte oder propoxylierte Derivate dieses Restes.I R-CO-N- [Z] in the R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R 24 is a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R 25 is a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, wherein C 1-4 alkyl or phenyl radicals are preferred and [Z] is a linear polyhydroxyalkyl radical whose alkyl chain having at least two hydroxyl groups substituted, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this radical.
[Z] wird vorzugsweise durch reduktive Aminierung eines reduzierten Zuckers erhalten, beispielsweise Glucose, Fructose, Maltose, Lactose, Galactose, Mannose oder Xylose. Die N-Alkoxy- oder N-Aryloxy-substituierten Verbindungen können dann beispielsweise durch Umsetzung mit Fettsäuremethylestern in Gegenwart eines Alkoxids als Katalysator in die gewünschten Polyhydroxy- fettsäureamide überführt werden.[Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds can then be converted into the desired polyhydroxy fatty acid amides, for example, by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
Die erfindungsgemäßen Mittel enthalten vorzugsweise auch amphoterische Tenside. Neben zahlreichen ein- bis dreifach alkylierten Aminoxiden stellen die Betaine eine bedeutende Klasse dar.The agents according to the invention preferably also contain amphoteric surfactants. In addition to numerous mono- to tri-alkylated amine oxides, the betaines represent an important class.
Betaine stellen bekannte Tenside dar, die überwiegend durch Carboxyalkylierung, vorzugsweise Carboxymethylierung von aminischen Verbindungen hergestellt werden. Vorzugsweise werden die Ausgangsstoffe mit Halogencarbonsäuren oder deren Salzen, insbesondere mit Natriumchloracetat kondensiert, wobei pro Mol Betain ein Mol Salz gebildet wird. Ferner ist auch die Anlagerung von unge-sättigten Carbonsäuren, wie beispielsweise Acrylsäure möglich. Zur Nomenklatur und insbesondere zur Unterscheidung zwischen Betainen und "echten" Amphotensiden sei auf die einschlägige Fachliteratur hingewiesen. Beispiele für geeignete Betaine stellen die Carboxyalkylierungspro- dukte von sekundären und insbesondere tertiären Aminen dar, die der Formel (IX) folgen,Betaines are known surfactants which are predominantly produced by carboxyalkylation, preferably carboxymethylation of aminic compounds. Preferably, the starting materials are condensed with halocarboxylic acids or their salts, in particular with sodium chloroacetate, wherein one mole of salt is formed per mole of betaine. Furthermore, the addition of unsaturated carboxylic acids, such as acrylic acid is possible. As regards the nomenclature and, in particular, the distinction between betaines and 'true' amphoteric surfactants, reference should be made to the relevant literature. Examples of suitable betaines are the carboxyalkylation products of secondary and in particular tertiary amines which follow the formula (IX),
R27 R 27
R26-N-(CH2)nCOOX1 (IX)R 26 -N- (CH 2 ) n COOX 1 (IX)
R28 in der R26 für Alkyl- und/oder Alkenylreste mit 6 bis 22 Kohlenstoffatomen, R27 für Wasserstoff oder Alkylreste mit 1 bis 4 Kohlenstoffatomen, R28 für Alkylreste mit 1 bis 4 Kohlen-stoffatomen, n für Zahlen von 1 bis 6 und X1 für ein Alkali- und/oder Erdalkalimetall oder Ammonium steht. Typische Beispiele sind die Carboxymethylierungsprodukte von Hexylmethylamin, Hexyldimethylamin, Octyl- dimethylamin, Decyldimethylamin, Dodecylmethylamin, Dodecyldimethylamin, Dodecylethylmethyl- amin, C^m-Kokosalkyldimethylamin, Myristyldimethylamin, Cetyldimethylamin, Stearyldimethyl- amin, Stearylethyl-methylamin, Oleyldimethylamin, C16/i8-Talgalkyldimethylamin sowie deren technische Gemische.R 28 in the R 26 is alkyl and / or alkenyl radicals having 6 to 22 carbon atoms, R 27 is hydrogen or alkyl radicals having 1 to 4 carbon atoms, R 28 is alkyl radicals having 1 to 4 carbon atoms, n is from 1 to 6 and X 1 is an alkali and / or alkaline earth metal or ammonium. Typical examples are the carboxymethylation products of hexylmethylamine, hexyldimethylamine, octyldimethylamine, decyldimethylamine, dodecylmethylamine, dodecyldimethylamine, dodecylethylmethylamine amine, C ^ m cocoalkyldimethylamine, myristyldimethylamine, cetyldimethylamine, stearyldimethylamine, stearylethyl-methylamine, oleyldimethylamine, C 16/ 8- tallowalkyldimethylamine and technical mixtures thereof.
Weiterhin kommen auch Carboxyalkylierungsprodukte von Amidoaminen in Betracht, die der Formel (X) folgen,Also suitable are carboxyalkylation products of amidoamines which follow the formula (X),
R29 R31CO-NH-(CH2)m-N-(CH2)nCOOX2 (X)R 29 R 31 CO-NH- (CH 2 ) m -N- (CH 2 ) n COOX 2 (X)
A- in der R31CO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen und 0 oder 1 bis 3 Doppelbindungen, m für Zahlen von 1 bis 3 steht und R29, R30, n und X2 die oben angegebenen Bedeutungen haben. Typische Beispiele sind Umsetzungsprodukte von Fettsäuren mit 6 bis 22 Kohlenstoffatomen, namentlich Capronsäure, Caprylsäure, Caprin-säure, Laurinsäure, Myristin- säure, Palmitinsäure, Palmoleinsäure, Stearinsäure, Isostearinsäure, Ölsäure, Elaidinsäure, Petro- selinsäure, Linolsäure, Linolensäure, Elaeostearin-säure, Arachinsäure, Gadoleinsäure, Behen- säure und Erucasäure sowie deren technische Gemische, mit N,N-Dimethylaminoethylamin, N1N- Dimethylaminopropylamin, N,N-Diethylaminoethylamin und N,N-Diethylaminopropylamin, die mit Natriumchloracetat kondensiert werden. Bevorzugt ist der Einsatz eines Kondensationsproduktes von C8/i8-Kokosfettsäure-N,N-dimethylaminopropylamid mit Natriumchloracetat.A- in which R 31 is CO for an aliphatic acyl radical having 6 to 22 carbon atoms and 0 or 1 to 3 double bonds, m is a number from 1 to 3 and R 29 , R 30 , n and X 2 are as defined above. Typical examples are reaction products of fatty acids having 6 to 22 carbon atoms, namely caproic, caprylic, capric, lauric, myristic, palmitic, palmitic, stearic, isostearic, oleic, elaidic, petro-, linoleic acid gadoleic, behenic, and, which are condensed with sodium chloroacetate erucic acid and technical mixtures with N, N-dimethylaminoethylamine, N 1 N- dimethylaminopropylamine, N, N-diethylaminoethylamine and N, N-diethylaminopropylamine. Preference is given to the use of a condensation product of C 8 / i 8 coconut fatty acid N, N-dimethylaminopropylamide with sodium chloroacetate.
Weiterhin kommen als geeignete Ausgangsstoffe für die im Sinne der Erfindung einsetzbaren Betaine auch Imidazoline in Betracht, die der Formel (Xl) folgen,Furthermore, suitable starting materials for the betaines usable in the context of the invention are imidazolines which follow the formula (XI),
in der R32 für einen Alkylrest mit 5 bis 21 Kohlenstoffatomen, R33 für eine Hydroxylgruppe, einen OCOR32- oder NHCOR32-Rest und m für 2 oder 3 steht. Auch bei diesen Substanzen handelt es sich um bekannte Stoffe, die beispielsweise durch cyclisierende Kondensation von 1 oder 2 Mol Fettsäure mit mehrwertigen Aminen, wie beispielsweise Aminoethyl-ethanolamin (AEEA) oder Di- ethylentriamin erhalten werden können. Die entsprechenden Carboxyalkylierungsprodukte stellen Gemische unterschiedlicher offenkettiger Betaine dar. Typische Beispiele sind Kondensationsprodukte der oben genannten Fettsäuren mit AEEA, vorzugsweise Imidazoline auf Basis von Laurinsäure oder wiederum C12/i4-Kokosfettsäure, die anschließend mit Natriumchloracetat betainisiert werden. In einer bevorzugten Ausführungsform liegen die erfindungsgemäßen Mittel, wie bereits gezeigt wurde, in flüssiger Form vor, beispielsweise in Form von Konditioniermittel oder Flüssigwaschmittel usw. Zum Erreichen einer flüssigen Konsistenz kann der Einsatz sowohl flüssiger organischer Lösungsmittel, wie auch der von Wasser angezeigt sein. Die erfindungsgemäßen Mittel enthalten daher gegebenenfalls Lösungsmittel.in which R 32 is an alkyl radical having 5 to 21 carbon atoms, R 33 is a hydroxyl group, an OCOR 32 or NHCOR 32 radical and m is 2 or 3. These substances are also known substances which can be obtained, for example, by cyclizing condensation of 1 or 2 moles of fatty acid with polyfunctional amines, such as, for example, aminoethyl-ethanolamine (AEEA) or diethylenetriamine. The corresponding carboxyalkylation products are mixtures of different open-chain betaines. Typical examples are condensation products of the above mentioned fatty acids with AEEA, preferably imidazolines based on lauric acid or C, in turn, 12 /, which are then betainized with sodium coconut oil fatty acid 4 i. In a preferred embodiment, as already shown, the compositions according to the invention are in liquid form, for example in the form of conditioning agents or liquid detergents etc. To achieve a liquid consistency, the use of both liquid organic solvents and water can be indicated. The agents according to the invention therefore optionally contain solvents.
Lösungsmittel, die in den erfindungsgemäßen Mitteln eingesetzt werden können, stammen beispielsweise aus der Gruppe ein- oder mehrwertigen Alkohole, Alkanolamine oder Glycolether, sofern sie im angegebenen Konzentrationsbereich mit Wasser mischbar sind. Vorzugsweise werden die Lösungsmittel ausgewählt aus Ethanol, n- oder i-Propanol, Butanolen, Glykol, Propan- oder Butandiol, Glycerin, Diglykol, Propyl- oder Butyldiglykol, Hexylenglycol, Ethylenglykolmethylether, Ethylenglykolethylether, Ethylenglykolpropylether, Ethylenglykolmono-n-butylether, Diethylenglykol- methylether, Diethylenglykolethylether, Propylenglykolmethyl-, -ethyl- oder -propyl-ether, Butoxy- propoxy-propanol (BPP), Dipropylenglykolmonomethyl-, oder -ethylether, Di-isopropylenglykol-mo- nomethyl-, oder -ethylether, Methoxy-, Ethoxy- oder Butoxytriglykol, 1-Butoxyethoxy-2-propanol, 3- Methyl-3-methoxybutanol, Propylen-glykol-t-butylether sowie Mischungen dieser Lösungsmittel.Solvents that can be used in the compositions according to the invention originate, for example, from the group of monohydric or polyhydric alcohols, alkanolamines or glycol ethers, provided they are miscible with water in the concentration range indicated. The solvents are preferably selected from ethanol, n- or i-propanol, butanols, glycol, propane- or butanediol, glycerol, diglycol, propyl- or butyldiglycol, hexylene glycol, 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 ether, butoxy propoxy-propanol (BPP), dipropylene glycol monomethyl, or ethyl ether, di-isopropylene glycol monomethyl, or ethyl ether, methoxy, ethoxy or Butoxytriglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol t-butyl ether and mixtures of these solvents.
Einige Glykolether sind unter den Handelsnamen Arcosolv® (Arco Chemical Co.) oder Cellosolve®, Carbitol® oder Propasol® (Union Carbide Corp.) erhältlich; dazu gehören auch z.B. ButylCarbitol®, HexylCarbitol®, MethylCarbitol®, und Carbitol® selbst, (2-(2-Ethoxy)ethoxy)ethanol. Die Wahl des Glykolethers kann vom Fachmann leicht auf der Basis seiner Flüchtigkeit, Wasserlöslichkeit, seines Gewichtsprozentanteils an der gesamten Dispersion und dergleichen getroffen werden. Pyr- rolidon-Lösungsmittel, wie N-Alkyl-pyrrolidone, beispielsweise N-Methyl-2-pyrrolidon oder N-C8- C12-Alkyl-pyrrolidon, oder 2-Pyrrolidon, können ebenfalls eingesetzt werden. Weiterhin bevorzugt als alleinige Lösungsmittel oder als Bestandteil eines Lösungsmittelgemisches sind Glycerinderi- vate, insbesondere Glycerincarbonat.Some glycol ethers are available under the trade names Arcosolv ® (Arco Chemical Co.) or Cellosolve ®, carbitol ® or Propasol ® (Union Carbide Corp.); this includes for example ButylCarbitol® ®, hexyl carbitol ®, MethylCarbitol® ®, and carbitol ® itself, (2- (2-ethoxy) ethoxy) ethanol. The choice of glycol ether can be readily made by one skilled in the art on the basis of its volatility, water solubility, weight percent of total dispersion, and the like. Pyrrolidone solvents, such as N-alkyl-pyrrolidones, for example N-methyl-2-pyrrolidone or NC 8 - C 12 -alkyl-pyrrolidone, or 2-pyrrolidone, can also be used. Also preferred as the sole solvent or as a component of a solvent mixture are glycerol derivatives, in particular glycerol carbonate.
Zu den Alkoholen, die in der vorliegenden Erfindung vorzugsweise als Cosolvention eingesetzt werden können, gehören flüssige Polyethylenglykole, mit niederem Molekulargewicht, beispielsweise Polyethylenglykole mit einem Molekulargewicht von 200, 300, 400 oder 600. Weitere geeignete Cosolventien sind andere Alkohole, zum Beispiel (a) niedere Alkohole wie Ethanol, Propanol, Isopropanol und n-Butanol, (b) Ketone wie Aceton und Methylethylketon, (c) C2-C4-PoIyOIe wie ein Diol oder ein Triol, beispielsweise Ethylenglykol, Propylenglykol, Glycerin oder Gemische davon. Insbesondere bevorzugt ist aus der Klasse der Diole 1 ,2-Octandiol.Alcohols which may be preferably used as cosolvents in the present invention include low molecular weight liquid polyethylene glycols, for example, polyethylene glycols having a molecular weight of 200, 300, 400 or 600. Further suitable cosolvents are other alcohols, for example (a) lower alcohols such as ethanol, propanol, isopropanol and n-butanol, (b) ketones such as acetone and methyl ethyl ketone, (c) C 2 -C 4 polyols such as a diol or a triol, for example ethylene glycol, propylene glycol, glycerol or mixtures thereof. Particularly preferred is from the class of diols 1, 2-octanediol.
In einer bevorzugten Ausführungsform enthält das erfindungsgemäße Mittel ein oder mehrere Lösungsmittel aus der Gruppe, umfassend C1- bis C4-Monoalko-hole, C2- bis C6-Glykole, C3- bis Ci2-Glykolether und Glycerin, insbesondere Ethanol. Die erfindungsgemäßen C3- bis C12-Glykol- ether enthalten Alkyl- bzw. Alkenylgruppen mit weniger als 10 Kohlenstoffatomen, vorzugsweise bis zu 8, insbesondere bis zu 6, besonders bevorzugt 1 bis 4 und äußerst bevorzugt 2 bis 3 Kohlenstoffatomen.In a preferred embodiment, the inventive composition contains one or more solvents from the group comprising C 1 - to C 4 -Monoalko-hole, C 2 - to C 6 glycols, C 3 - to C 2 glycol ethers and glycerol, in particular ethanol , The inventive C 3 - to C 12 glycol ethers contain alkyl or alkenyl groups having less than 10 carbon atoms, preferably up to 8, especially up to 6, more preferably 1 to 4 and most preferably 2 to 3 carbon atoms.
Bevorzugte Ci- bis C4-Monoalkohole sind Ethanol, n-Propanol, iso-Propanol und tert-Butanol. Bevorzugte C2- bis C6-Glykole sind Ethylenglykol, 1,2-Propylenglykol, 1 ,3-Propylenglykol, 1 ,5-Pentan- diol, Neopentylglykol und 1 ,6-Hexandiol, insbesondere Ethylenglykol und 1 ,2-Propylenglykol. Bevorzugte C3- bis Ci2-Glykolether sind Di-, Tri-, Tetra- und Pentaethylenglykol, Di-, Tri-und Tetrapro- pylenglykol, Propylenglykolmonotertiärbutylether und Propylenglykolmonoethylether sowie die gemäß INCI bezeichneten Lösungsmittel Butoxydiglycol, Butoxyethanol, Butoxyisopropanol, Butoxy- propanol, Butyloctanol, Ethoxydiglycol, Ethoxyethanol, Ethyl Hexanediol, Isobutoxypropanol, Iso- pentyldiol, 3-Methoxybutanol, Methoxyethanol, Methoxyisopropanol und Methoxymethylbutanol.Preferred C 1 to C 4 monoalcohols are ethanol, n-propanol, isopropanol and tert-butanol. Preferred C 2 -C 6 -glycols are ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,5-pentanediol, neopentyl glycol and 1,6-hexanediol, in particular ethylene glycol and 1,2-propylene glycol. Preferred C 3 - to C 2 glycol ethers are di-, tri-, tetra- and pentaethylene glycol, di-, tri- and tetrapropylammonium pylenglykol, Propylenglykolmonotertiärbutylether and propylene glycol monoethyl ether as well as pursuant propanol INCI designated solvent Butoxydiglycol, butoxyethanol, butoxyisopropanol, butoxy, Butyloctanol, ethoxydiglycol, ethoxyethanol, ethyl hexanediol, isobutoxypropanol, isopentyldiol, 3-methoxybutanol, methoxyethanol, methoxyisopropanol and methoxymethylbutanol.
Das erfindungsgemäße Mittel, vorzugsweise Konditioniermittel oder Flüssigwaschmittel, kann ein oder mehrere Lösungsmittel in einer Menge von üblicherweise bis zu 40 Gew.-%, vorzugsweise 0,1 bis 30 Gew.-%, insbesondere 2 bis 20 Gew.-%, besonders bevorzugt 3 bis 15 Gew.-%, äußerst bevorzugt 5 bis 12 Gew.-%, beispielsweise 5,3 oder 10,6 Gew.-%, jeweils bezogen auf das gesamte Mittel, enthalten.The agent according to the invention, preferably conditioning agent or liquid detergent, may contain one or more solvents in an amount of usually up to 40% by weight, preferably 0.1 to 30% by weight, in particular 2 to 20% by weight, more preferably 3 to 15 wt .-%, most preferably 5 to 12 wt .-%, for example, 5.3 or 10.6 wt .-%, each based on the total agent included.
In einer bevorzugten Ausführungsform kann das erfindungsgemäße Mittel, wie insbesondere das Konditioniermittel gegebenenfalls ein oder mehrere Komplexbildner enthalten.In a preferred embodiment, the agent according to the invention, in particular the conditioning agent, may optionally contain one or more complexing agents.
Komplexbildner (INCI Chelating Agents), auch Sequestriermittel genannt, sind Inhaltsstoffe, die Metallionen zu komplexieren und inaktivieren vermögen, beispielsweise um ihre nachteiligen Wirkungen auf die Stabilität oder das Aussehen der Mittel, beispielsweise Trübungen, zu verhindern. Einerseits ist es dabei wichtig, die mit zahlreichen Inhaltsstoffen inkompatiblen Calcium- und Magnesiumionen der Wasserhärte zu komplexieren. Die Komplexierung der Ionen von Schwermetallen wie Eisen oder Kupfer verzögert die oxidative Zersetzung der fertigen Mittel.Chelating agents (INCI), also called sequestering agents, are ingredients that are capable of complexing and inactivating metal ions, for example, to prevent their adverse effects on the stability or appearance of the agents, for example clouding. On the one hand, it is important to complex the incompatible with numerous ingredients calcium and magnesium ions of water hardness. The complexation of the ions of heavy metals such as iron or copper retards the oxidative decomposition of the finished agents.
Geeignet sind beispielsweise die folgenden gemäß INCI bezeichneten Komplexbildner, die beispielsweise im International Cosmetic Ingredient Dictionary and Handbook näher beschrieben sind: Aminotrimethylene Phosphonic Acid, Beta-Alanine Diacetic Acid, Calcium Disodium EDTA, Citric Acid, Cyclodextrin, Cyclohexanediamine Tetraacetic Acid, Diammonium Citrate, Diammonium EDTA, Diethylenetriamine Pentamethylene Phosphonic Acid, Dipotassium EDTA, Disodium Azacy- cloheptane Diphosphonate, Disodium EDTA, Disodium Pyrophosphate, EDTA, Etidronic Acid, Ga- lactaric Acid, Gluconic Acid, Glucuronic Acid, HEDTA1 Hydroxypropyl Cyclodextrin, Methyl Cyclodextrin, Pentapotassium Triphosphate, Pentasodium Aminotrimethylene Phosphonate, Pentaso- dium Ethylenediamine Tetramethylene Phosphonate, Pentasodium Pentetate, Pentasodium Tri- phosphate, Pentetic Acid, Phytic Acid, Potassium Citrate, Potassium EDTMP, Potassium Gluco- nate, Potassium Polyphosphate, Potassium Trisphosphonomethylamine Oxide, Ribonic Acid, So- dium Chitosan Methylene Phosphonate, Sodium Citrate, Sodium Diethylenetriamine Pentamethy- lene Phosphonate, Sodium Dihydroxyethylglycinate, Sodium EDTMP, Sodium Gluceptate, Sodium Gluconate, Sodium Glycereth-1 Polyphosphate, Sodium Hexametaphos-phate, Sodium Metaphos- phate, Sodium Metasilicate, Sodium Phytate, Sodium Polydimethylglycinophenolsulfonate, Sodium Trimetaphosphate, TEA-EDTA, TEA-Polyphos-phate, Tetrahydroxyethyl Ethylenediamine, Tetrahy- droxypropyl Ethylenediamine, Tetrapotassium Etidronate, Tetrapotassium Pyrophosphate, Tetrasodium EDTA, Tetrasodium Etidronate, Tetrasodium Pyrophosphate, Tripotassium EDTA, Triso- dium Dicarboxymethyl Alaninate, Trisodium EDTA1 Trisodium HEDTA, Trisodium NTA und Triso- dium Phosphate.For example, the following complexing agents designated according to INCI are suitable: Aminotrimethylene Phosphonic Acid, Beta-Alanine Diacetic Acid, Calcium Disodium EDTA, Citric Acid, Cyclodextrin, Cyclohexanediamine Tetraacetic Acid, Diammonium Citrate, Diammonium EDTA, Diethylenetriamine Pentamethylene Phosphonic Acid, Dipotassium EDTA, Disodium Azacyloheptane Diphosphonate, Disodium EDTA, Disodium Pyrophosphate, EDTA, Etidronic Acid, Galactic Acid, Gluconic Acid, Glucuronic Acid, HEDTA 1 Hydroxypropyl Cyclodextrin, Methyl Cyclodextrin, Pentapotassium Triphosphate, Pentasodium Aminotrimethylene Phosphonates, Pentasodiene, Ethylenediamines, Tetramethylene Phosphonates, Pentasodium Pentetates, Pentasodium Tri- Phosphates, Pentetic Acid, Phytic Acid, Potassium Citrate, Potassium EDTMP, Potassium Gluconate, Potassium Polyphosphate, Potassium Trisphosphonomethylamine Oxides, Ribonic Acid, So- dium Chitosan Methylene Phosphonates, Sodium Citrate, Sodium Diethylenetriamine, Penta- methylene Phosphonates, Sodium Dihydroxyethyl Glycinate, Sodium EDTMP, Sodium Gluceptate, Sodium Gluconate, Sodium Glycereth-1 Polyphosphate, Sodium Hexametaphosphate, Sodium Metaphosphate, Sodium Metasilicate, Sodium Phytate, Sodium Polydimethylglycinophenolsulfonate, Sodium Trimetaphosphate, TEA-EDTA, TEA Polyphosphate, Tetrahydroxyethyl Ethylenediamine, Tetrahy - droxypropyl Ethylenediamine, Tetrapotassium Etidronate, Tetrapotassium Pyrophosphate, Tetrasodium EDTA, Tetrasodium Etidronate, Tetrasodium Pyrophosphate, Tripotassium EDTA, Trisodium Dicarboxymethyl Alaninate, Trisodium EDTA 1 Trisodium HEDTA, Trisodium NTA and Trisodium Phosphate.
Bevorzugte Komplexbildner sind tertiäre Amine, insbesondere tertiäre Alkanolamine (Ami-noalko- hole). Die Alkanolamine besitzen sowohl Amino- als auch Hydroxy- und/oder Ether-gruppen als funktionelle Gruppen. Besonders bevorzugte tertiäre Alkanolamine sind Tri-ethanolamin und Tetra- 2-hydroxypro-pylethylendiamin (N,N,N',N'-Tetrakis-(2-hydroxy-pro-pyl)ethylendiamin). Besonders bevorzugte Kombinationen tertiärer Amine mit Zinkricinoleat und einem oder mehreren ethoxy- lierten Fettalkoholen als nichtionische Lösungsvermittler sowie ggf. Lösungsmittel sind im Stand der Technik beschrieben.Preferred complexing agents are tertiary amines, in particular tertiary alkanolamines (aminoalkanol). The alkanolamines have both amino and hydroxy and / or ether groups as functional groups. Particularly preferred tertiary alkanolamines are tri-ethanolamine and tetra-2-hydroxypropyl-ethylenediamine (N, N, N ', N'-tetrakis (2-hydroxy-propyl) ethylenediamine). Particularly preferred combinations of tertiary amines with Zinkricinoleat and one or more ethoxylated fatty alcohols as nonionic solubilizers and optionally solvents are described in the prior art.
Ein besonders bevorzugter Komplexbildner ist die Etidronsäure (1-Hydroxyethyliden-1 ,1-diphos- phon-säure, 1-Hydroxyethyan-1 ,1-diphosphonsäure, HEDP, Acetophosphonsäure, INCI Etidronic Acid) einschließlich ihrer Salze. In einer bevorzugten Ausführungsform enthält das erfindungsgemäße Mittel demgemäß als Komplexbildner Etidronsäure und/oder eines oder mehrere ihrer Salze.A particularly preferred complexing agent is etidronic acid (1-hydroxyethylidene-1, 1-diphosphonous acid, 1-hydroxyethyl-1, 1-diphosphonic acid, HEDP, acetophosphonic acid, INCI Etidronic Acid) including their salts. In a preferred embodiment, the agent according to the invention accordingly contains etidronic acid and / or one or more of its salts as complexing agent.
In einer besonderen Ausführungsform enthält das erfindungsgemäße Mittel eine Komplexbildnerkombination aus einem oder mehreren tertiären Aminen und einer oder mehreren weiteren Kom- blexbildnern, vorzugsweise einer oder mehreren Komplexbildnersäuren oder deren Salzen, insbesondere aus Triethanolamin und/oder Tetra-2-hydroxypropylethylendiamin und Etidronsäure und/oder einem oder mehrerer ihrer Salze.In a particular embodiment, the agent according to the invention contains a complexing agent combination of one or more tertiary amines and one or more other complexing agents, preferably one or more complexing acids or their salts, in particular triethanolamine and / or tetra-2-hydroxypropylethylenediamine and etidronic acid and / or one or more of their salts.
In einer weiteren Ausführungsform enthält das erfindungsgemäße Mittel, wie insbesondere Kondi- tioniermittel, gegebenenfalls ein oder mehrere Viskositätsregulatoren, die vorzugsweise als Verdicker fungieren.In a further embodiment, the agent according to the invention, in particular conditioner, optionally contains one or more viscosity regulators, which preferably act as thickener.
Die Viskosität der Mittel kann mit üblichen Standardmethoden (beispielsweise Brookfield-Viskosi- meter RVD-VII bei 20 U/min und 2O0C1 Spindel 3) gemessen werden. Bevorzugte flüssige bis gel- förmige Mittel können Viskositäten von 20 bis 4000 mPas aufweisen, wobei Werte zwischen 40 und 2000 mPas besonders bevorzugt sein können.The viscosity of the agent may be measured using standard methods (e.g., Brookfield viscometer RVD-VII at 20 U / min and 2O 0 C 1 spindle 3) are measured. Preferred liquid to gel compositions may have viscosities of 20 to 4000 mPas, with values between 40 and 40 mPas and 2000 mPas may be particularly preferred.
Geeignete Verdicker sind anorganische oder polymere organische Verbindungen. Es können auch Gemische aus mehreren Verdickern eingesetzt werden.Suitable thickeners are inorganic or polymeric organic compounds. It is also possible to use mixtures of several thickeners.
Zu den anorganischen Verdickern zählen beispielsweise Polykieselsauren, Tonmineralien wie Montmorillonite, Zeolithe, Kieselsäuern, Aluminiumsilikate, Schichtsilikate und Bentonite.The inorganic thickeners include, for example, polysilicic acids, clay minerals such as montmorillonites, zeolites, silicas, aluminum silicates, phyllosilicates and bentonites.
Die organischen Verdicker stammen aus den Gruppen der natürlichen Polymere, der abgewandelten natürlichen Polymere und der vollsynthetischen Polymere.The organic thickeners are derived from the groups of natural polymers, modified natural polymers and fully synthetic polymers.
Aus der Natur stammende Polymere, die als Verdicker Verwendung finden, sind beispiels-weise Xanthan, Agar-Agar, Carrageen, Tragant, Gummi arabicum, Alginate, Pektine, Polyosen, Guar- Mehl, Gellan-Gum, Johannisbrotbaumkernmehl, Stärke, Dextrine, Gelatine und Casein.Naturally derived polymers which are used as thickeners are, for example, xanthan gum, agar agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, guar gum, gellan gum, locust bean gum, starch, dextrins, gelatin and casein.
Abgewandelte Naturstoffe stammen vor allem aus der Gruppe der modifizierten Stärken und CeIIu- losen, beispielhaft seien hier Carboxymethylcellulose und andere Celluloseether, Hydroxyethyl- und -propylcellulose, hochveretherte Methylhydroxyethylcellulose sowie Kernmehlether genannt.Modified natural substances are derived primarily from the group of modified starches and celluloses, examples being carboxymethylcellulose and other cellulose ethers, hydroxyethyl and propylcellulose, highly etherified methylhydroxyethylcellulose and core flour ethers.
Eine große Gruppe von Verdickern, die breite Verwendung in den unterschiedlichsten Anwendungs-gebieten finden, sind die vollsynthetischen Polymere wie Polyacryl- und Polymethacryl-Ver- bindungen, die vernetzt oder unvernetzt und ggf. kationisch modifiziert sein können, Vinylpolymere, Polycarbonsäuren, Polyether, aktivierte Polyamidderivate, Rizinusölderivate, Polyimine, Polyamide und Polyurethane. Beispiele für derartige Polymer sind Acrylharze, Ethylacrylat-Acrylamid-Copoly- mere, Acrylsäureester-Methacrylsäure-ester-Copolymere, Ethylacrylat-Acrylsäure-Methacrylsäure- Copolymere, N-Methylolmeth-acrylamid, Maleinsäureanhydrid-Methylvinylether-Copolymere, PoIy- ether-Polyol-Copoly-mere sowie Butadien-Styrol-Copolymere.A large group of thickeners, which find wide use in a variety of applications, are the fully synthetic polymers such as polyacrylic and polymethacrylic compounds, which may be crosslinked or uncrosslinked and optionally cationically modified, vinyl polymers, polycarboxylic acids, polyethers, activated Polyamide derivatives, castor oil derivatives, polyimines, polyamides and polyurethanes. Examples of such polymers are acrylic resins, ethyl acrylate-acrylamide copolymers, acrylic ester-methacrylic acid-ester copolymers, ethyl acrylate-acrylic acid-methacrylic acid copolymers, N-methylolmeth-acrylamide, maleic anhydride-methyl vinyl ether copolymers, polyether-polyol copoly -mere as well as butadiene-styrene copolymers.
Weitere geeignete Verdicker sind Derivate organischer Säuren sowie deren Alkoxid-Addukte, beispielsweise Arylpolyglykolether, carboxylierte Nonylphenolethoxylatderivate, Natriumalginat, Digly- cerinmonoisostearat, Nichtionogene Ethylenoxid-Addukte, Kokosfettsäurediethanolamid, Isodode- cenylbemsteinsäureanhydrid sowie Galactomannan. Verdicker aus den genannten Substanzklassen sind kommerziell erhältlich und werden beispielsweise unter den Handelsnamen Acusol®-820 (Methacrylsäure(stearylalkohol-20-EO)ester-Acrylsäure-Copolymer, 30%ig in Wasser, Rohm & Haas), Da-pral®-GT-282-S (Alkylpolyglykolether, Akzo), Deuterol®-Polymer-11 (Dicarbon- säure-Co-polymer, Schöner GmbH), Deuteron®-XG (anionisches Heteropolysaccharid auf Basis von ß-D-Glucose, D-Manose, D-Glucuronsäure, Schöner GmbH), Deuteron®-XN (nicht-ionogenes Polysaccharid, Schöner GmbH), Dicrylan®-Verdicker-0 (Ethylenoxid-Addukt, 50%ig in Was- ser/lsopropanol, Pfersse Chemie), EMA®-81 und EMA®-91 (Ethylen-Ma-Ieinsäureanhydrid- Copolymer, Monsanto), Verdicker-QR-1001 (Polyurethan-Emulsion, 19-21%ig in Wasser/Diglykol- ether, Rohm & Haas), Mirox®-AM (anionische Acrylsäure-Acrylsäureester-Copolymer-Dispersion, 25%ig in Wasser, Stockhausen), SER-AD-FX-1100 (hydrophobes Urethanpolymer, Servo Delden), Shellflo®-S (hoch-molekulares Polysaccharid, mit Formaldehyd stabilisiert, Shell), Shellflo®-XA (Xanthan-Biopolymer, mit Formaldehyd stabilisiert, Shell), Kelzan, Keltrol T (Kelco) angeboten.Further suitable thickeners are derivatives of organic acids and their alkoxide adducts, for example aryl polyglycol ethers, carboxylated nonylphenol ethoxylate derivatives, sodium alginate, diglycerol monoisostearate, nonionic ethylene oxide adducts, coconut fatty acid diethanolamide, isododecenemene succinic anhydride and galactomannan. Thickeners from the mentioned classes of substances are commercially available and are described, for example, under the trade names Acusol®-820 (methacrylic acid (stearyl alcohol-20-EO) ester-acrylic acid copolymer, 30% in water, Rohm & Haas), Da-pral®-GT -282-S (alkyl polyglycol ether, Akzo), Deuterol® polymer-11 (dicarboxylic acid co-polymer, Schöner GmbH), Deuteron®-XG (anionic heteropolysaccharide based on β-D-glucose, D-manose, D -Glucuronic acid, Schöner GmbH), Deuteron®-XN (nonionic polysaccharide, Schöner GmbH), Dicrylan®-thickener-0 (ethylene oxide adduct, 50% in water). ser / isopropanol, Pfersse Chemie), EMA®-81 and EMA®-91 (ethylene-maleic anhydride copolymer, Monsanto), thickener QR-1001 (polyurethane emulsion, 19-21% in water / diglycol ether , Rohm & Haas), Mirox® AM (anionic acrylic acid-acrylic acid ester copolymer dispersion, 25% in water, Stockhausen), SER-AD-FX-1100 (hydrophobic urethane polymer, Servo Delden), Shellflo®-S (high Molecular polysaccharide stabilized with formaldehyde, Shell), Shellflo®-XA (xanthan biopolymer stabilized with formaldehyde, Shell), Kelzan, Keltrol T (Kelco).
In einer weiteren bevorzugten Ausführungsform enthalt das erfindungsgemäße Mittel, wie insbesondere Konditioniermittel, gegebenenfalls ein oder mehrere Enzyme.In a further preferred embodiment, the agent according to the invention, in particular conditioning agent, optionally contains one or more enzymes.
Als Enzyme kommen insbesondere solche aus der Klassen der Hydrolasen wie der Proteasen, Esterasen, Lipasen bzw. lipolytisch wirkende Enzyme, Amylasen, Cellulasen bzw. andere Glyko- sylhydrolasen und Gemische der genannten Enzyme in Frage. Alle diese Hydrolasen tragen in der Wäsche zur Entfernung von Verfleckungen wie protein-, fett- oder stärkehaltigen Verfleckungen und Vergrauungen bei. Cellulasen und andere Glykosylhydrolasen können darüber hinaus durch das Entfernen von Pilling und Mikrofibrillen zur Farberhaltung und zur Erhöhung der Weichheit des Textils beitragen. Zur Bleiche bzw. zur Hemmung der Farbübertragung können auch Oxiredukta- sen eingesetzt werden.Suitable enzymes are, in particular, those from the classes of the hydrolases, such as the proteases, esterases, lipases or lipolytic enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of said enzymes. All of these hydrolases in the wash contribute to the removal of stains such as proteinaceous, greasy or starchy stains and graying. In addition, cellulases and other glycosyl hydrolases may contribute to color retention and to enhancing the softness of the fabric by removing pilling and microfibrils. Oxireductases can also be used for bleaching or inhibiting color transfer.
Besonders gut geeignet sind aus Bakterienstämmen oder Pilzen wie Bacillus subtilis, Bacillus Ii- cheniformis, Streptomyceus griseus und Humicola insolens gewonnene enzymatische Wirkstoffe. Vorzugsweise werden Proteasen vom Subtilisin-Typ und insbesondere Proteasen, die aus Bacillus lentus gewonnen werden, eingesetzt. Dabei sind Enzymmischungen, beispielsweise aus Protease und Amylase oder Protease und Lipase bzw. lipolytisch wirkenden Enzymen oder Protease und Cellulase oder aus Cellulase und Lipasebzw. lipolytisch wirkenden Enzymen oder aus Protease, Amylase und Lipase bzw. lipolytisch wirkenden Enzymen oder Protease, Lipase bzw. lipolytisch wirkenden Enzymen und Cellulase, insbesondere jedoch Protease und/oder Lipase-haltige Mischungen bzw. Mischungen mit lipolytisch wirkenden Enzymen von besonderem Interesse. Beispiele für derartige lipolytisch wirkende Enzyme sind die bekannten Cutinasen. Auch Peroxidasen oder Oxidasen haben sich in einigen Fällen als geeignet erwiesen. Zu den geeigneten Amylasen zählen insbesondere α-Amylasen, Iso-Amylasen, Pullulanasen und Pektinasen. Als Cellulasen werden vorzugsweise Cellobiohydrolasen, Endoglucanasen und ß-Glucosi-dasen, die auch Cellobiasen genannt werden, bzw. Mischungen aus diesen eingesetzt. Da sich verschiedene Cellulase-Typen durch ihre CMCase- und Avicelase-Aktivitäten unterscheiden, können durch gezielte Mischungen der Cellulasen die gewünschten Aktivitäten eingestellt werden.Particularly suitable are enzymatic agents obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus ichicheniformis, Streptomyceus griseus and Humicola insolens. Preferably, subtilisin-type proteases and in particular proteases derived from Bacillus lentus are used. Enzyme mixtures, for example from protease and amylase or protease and lipase or lipolytic enzymes or protease and cellulase or from cellulase and Lipasebzw. lipolytic enzymes or from protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic enzymes and cellulase, but in particular protease and / or lipase-containing mixtures or mixtures with lipolytic enzymes of particular interest. Examples of such lipolytic enzymes are the known cutinases. Peroxidases or oxidases have also proved suitable in some cases. Suitable amylases include in particular α-amylases, iso-amylases, pullulanases and pectinases. As cellulases are preferably cellobiohydrolases, endoglucanases and ß-Glucosi-denen, which are also called cellobiases, or mixtures thereof used. Since different cellulase types differ by their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases.
Die Enzyme können als Formkörper an Trägerstoffe adsorbiert oder gecoated eingebettet sein, um sie gegen vorzeitige Zersetzung zu schützen. Der Anteil der Enzyme, Enzymmischungen oder En- zymgranulate kann beispielsweise etwa 0,1 bis 5 Gew.-%, vorzugsweise 0,12 bis etwa 2 Gew.-% betragen, bezogen auf das gesamte Mittel.The enzymes may be adsorbed as a shaped body to carriers or embedded coated to protect against premature decomposition. The proportion of enzymes, enzyme mixtures or enzymes For example, zymgranulate may be about 0.1 to 5% by weight, preferably 0.12 to about 2% by weight, based on the total agent.
Die erfindungsgemäßen Mittel, wie insbesondere Wasch- und Reinigungsmittel, Pflegemittel oder Konditioniermittel, können Bleichmittel enthalten. Unter den als Bleichmittel dienenden, in Wasser H2O2 liefernden Verbindungen haben das Natriumpercarbonat, das Natriumperborattetrahydrat und das Natriumperboratmonohydrat besondere Bedeutung. Weitere brauchbare Bleichmittel sind beispielsweise Peroxopyrophosphate, Citratperhydrate sowie H2O2 liefernde persaure Salze oder Persäuren, wie Persulfate beziehungsweise Perschwefelsäure. Brauchbar ist auch das Hamstoffper- oxohydrat Percarbamid, das durch die Formel H2N-CO-NH2 H2O2 beschrieben werden kann. Insbesondere beim Einsatz der Mittel für das Reinigen harter Oberflächen, zum Beispiel beim maschinellen Geschirrspülen, können sie gewünschtenfalls auch Bleichmittel aus der Gruppe der organischen Bleichmittel enthalten, obwohl deren Einsatz prinzipiell auch bei Mitteln für die Textil- wäsche möglich ist. Typische organische Bleichmittel sind die Diacylperoxide, wie zum Beispiel Di- benzoylperoxid. Weitere typische organische Bleichmittel sind die Peroxysäuren, wobei als Beispiele besonders die Alkylperoxysäuren und die Arylperoxysäuren genannt werden. Bevorzugte Vertreter sind die Peroxybenzoesäure und ihre ringsubstituierten Derivate, wie Alkylperoxybenzoe- säuren, aber auch Peroxy-α-Naphtoesäure und Magnesium-monoperphthalat, die aliphatischen oder substituiert aliphatischen Peroxysäuren, wie Peroxylaurinsäure, Peroxystearinsäure, ε-Phthal- imidoperoxycapronsäure (Phthalimidoperoxyhexansäure, PAP), o-Carboxybenzamidoperoxyca- pronsäure, N-No-nenylamidoperadipinsäure und N-Nonenylamidopersuccinate, und aliphatische und araliphatische Peroxydicarbonsäuren, wie 1 ,12-Diperoxycarbonsäure, 1 ,9-Diperoxyazelain- säure, Diperoxysebacinsäure, Diperoxybrassylsäure, die Diperoxyphthalsäuren, 2-Decyl-diperoxy- butan-1 ,4-disäure, N,N-Terephthaloyl-di(6-aminopercapronsäure) können eingesetzt werden.The agents according to the invention, in particular washing and cleaning agents, conditioners or conditioning agents, may contain bleaching agents. Among the compounds serving as bleaches in water H 2 O 2 , sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Other useful bleaching agents are, for example, peroxopyrophosphates, citrate perhydrates and H 2 O 2 -producing peracidic salts or peracids, such as persulfates or persulfuric acid. The urea peroxohydrate percarbamide, which can be described by the formula H 2 N-CO-NH 2 H 2 O 2 , is also useful. In particular, when using the means for cleaning hard surfaces, for example in automatic dishwashing, they can, if desired, also contain bleaching agents from the group of organic bleaches, although their use is in principle also possible with detergents for textile laundry. Typical organic bleaching agents are the diacyl peroxides, such as, for example, dibenzoyl peroxide. Other typical organic bleaches are the peroxyacids, examples of which include the alkyl peroxyacids and the aryl peroxyacids. Preferred representatives are the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monoperphthalate, the aliphatic or substituted aliphatic peroxy acids, such as peroxylauric acid, peroxystearic acid, ε-phthalimidoperacycaproic acid (phthalimidoperoxyhexanoic acid, PAP), O-carboxybenzamidoperoxycaproic acid, N -nonylamidoperadipic acid and N-nonenylamidopersuccinates, and aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelic acid, diperoxysebacic acid, diperoxybrassic acid, the diperoxyphthalic acids, 2-decyldiperoxy- butane-1,4-diacid, N, N-terephthaloyl-di (6-aminopercaproic acid) can be used.
Farbstoffe können im erfindungsgemäßen Mittel eingesetzt werden, wobei die Menge an einem oder mehreren Farbstoffen so gering zu wählen ist, dass nach der Anwendung des Mittels keine sichtbaren Rückstände verbleiben. Vorzugsweise ist das erfindungsgemäße Mittel frei von Farbstoffen.Dyes can be used in the composition according to the invention, wherein the amount of one or more dyes is to be chosen so low that remain after application of the agent no visible residues. Preferably, the agent according to the invention is free of dyes.
Das erfindungsgemäße Mittel kann vorzugsweise einen oder mehrere antimikrobielle Wirkstoffe bzw. Konservierungsmittel in einer Menge von üblicherweise 0,0001 bis 3 Gew.-%, vorzugsweise 0,0001 bis 2 Gew.-%, insbesondere 0,0002 bis 1 Gew.-%, besonders bevorzugt 0,0002 bis 0,2 Gew.-%, äußerst bevorzugt 0,0003 bis 0,1 Gew.-%, enthalten.The agent according to the invention may preferably contain one or more antimicrobial agents or preservatives in an amount of usually 0.0001 to 3 wt.%, Preferably 0.0001 to 2 wt.%, In particular 0.0002 to 1 wt. more preferably 0.0002 to 0.2% by weight, most preferably 0.0003 to 0.1% by weight.
Antimikrobielle Wirkstoffe bzw. Konservierungsmittel unterscheidet man je nach antimikro-biellem Spektrum und Wirkungsmechanismus zwischen Bakteriostatika und Bakteriziden, Fungistatika und Fungiziden usw. Wichtige Stoffe aus diesen Gruppen sind beispielsweise Benzalkoniumchloride, Alkylarylsulfonate, Halogenphenole und Phenolmercuriacetat. Die Begriffe antimikrobielle Wirkung und antimikrobieller Wirkstoff haben im Rahmen der erfindungsgemäßen Lehre die fachübliche Bedeutung. Geeignete antimikrobielle Wirkstoffe sind vorzugsweise ausgewählt aus den Gruppen der Alkohole, Amine, Aldehyde, antimikrobiellen Säuren bzw. deren Salze, Carbonsäureester, Säure- amide, Phenole, Phenolderivate, Diphenyle, Diphenylalkane, Harnstoffderivate, Sauerstoff-, Stick- stoff-acetale sowie -formale, Benzamidine, Isothiazoline, Phthalimidderivate, Pyridinderivate, antimikrobiellen oberflächenaktiven Verbindungen, Guanidine, antimikrobiellen amphoteren Verbindungen, Chinoline, 1 ,2-Dibrom-2,4-di-cyanobutan, lodo-2-propyl-butyl-carbamat, lod, lodophore, Per- oxoverbindungen, Halogenverbindungen sowie beliebigen Gemischen der voranstehenden.Antimicrobial agents or preservatives are distinguished depending on the antimicrobial spectrum and mechanism of action between bacteriostats and bactericides, fungistats and fungicides, etc. Important substances from these groups are, for example, benzalkonium chlorides, alkylarylsulfonates, halophenols and phenol mercuriacetate. The terms antimicrobial effect and antimicrobial agent in the context of the teaching of the invention have the usual meaning. Suitable antimicrobial agents are preferably selected from the groups of the alcohols, amines, aldehydes, antimicrobial acids or their salts, carboxylic acid esters, acid amides, phenols, phenol derivatives, diphenyls, diphenylalkanes, urea derivatives, oxygen, nitrogen acetals and formals , Benzamidines, isothiazolines, phthalimide derivatives, pyridine derivatives, antimicrobial surface-active compounds, guanidines, antimicrobial amphoteric compounds, quinolines, 1,2-dibromo-2,4-di-cyanobutane, iodo-2-propyl-butyl-carbamate, iodine, iodophores, Per - oxo compounds, halogen compounds and any mixtures of the above.
Der antimikrobielle Wirkstoff kann dabei ausgewählt sein aus Ethanol, n-Propanol, i-Pro-panol, 1 ,3- Butandiol, Phenoxyethanol, 1 ,2-Propylenglykol, Glycerin, Undecylensäure, Benzoesäure, Salicyl- säure, Dihydracetsäure, o-Phenylphenol, N-Methylmorpholin-aceto-nitril (MMA), 2-Benzyl-4-chlor- phenol, 2,2'-Methylen-bis-(6-brom-4-chlorphenol), 4,4'-Di-chlor-2'-hydroxydiphenylether (Dichlo- san), 2,4,4'-Trichlor-2'-hydroxydiphenylether (Trichlosan), Chlorhexidin, N-(4-Chlorphenyl)-N-(3,4- dichlorphenyl)-harnstoff, N,N'-(1 ,10-decan-diyldi-1-pyridinyl-4-yliden)-bis-(1-octanamin)-dihydro- chlorid, N,N'-Bis-(4-chlorphenyl)-3,12-diimino-2,4,11 ,13-tetraaza-tetradecandiimidamid, Glucopro- taminen, antimikrobiellen oberflächenaktiven quaternären Verbindungen, Guanidinen einschl. den Bi- und Polyguani-dinen, wie beispielsweise 1 ,6-Bis-(2-ethylhexyl-biguanido-hexan)-dihydrochlorid, 1 , 6-Di-(N1, N1'-phenyldiguanido-N5,N5')-hexan-tetrahydochlorid, 1 ,6-Di-(N1 lN1'-phenyl-N1,N1- me- thyldiguanido-N5,N5')-hexan-dihydro-chlorid, 1 , 6-Di-(N1, N^-o-chlorophenyldiguanido- N5,N5')-he- xan-dihydrochlorid, 1 , 6-Di-(N1, N^.e-dichlorophenyldiguanido-Ns.Ns'Jhexaπ-dihydrochlorid, 1 ,6-Di- [N^N^-beta^p-methoxyphenyl) diguanido-N5,N5']-hexane-dihy-drochlorid, 1, 6-Di-(N1, N^-alpha-me- thyl-.beta.-phenyldiguanido-N5,N5')-hexan-dihydro-chlorid, 1 , 6-Di-(N1, N^-p-nitrophenyldiguanido- N5,N5')hexan-dihydrochlorid, omega:omega-Di-( NLN^-phenyldiguanido-Ns.Ns^-di-n-propylether- dihydrochlorid, omega.omega'-Di-^.NT'-p-chlorophe-nyldiguanido-Ns.Ns'J-di-n-propylether-tetra- hydrochlorid, 1 , 6-Di-(N1, N/-2, 4- dichlorophenyldiguanido-N5,N5')hexan-tetrahydrochlorid, 1 ,6-Di- (NLN^-p-methylphe-nyldiguanido-Ns.Ns'Jhexan-dihydrochlorid, i ^-DKN^N^AS-trichlorophe- nyldi-guanido-N5,N5')hexan-tetrahydrochlorid, 1 , 6-Di-[N1, N1'-alpha-(p-chlorophenyl) ethyldiguanido- N51N5'] hexan-dihydrochlorid, OmBgBiOmBgS-Di-(N1, N1 '-p-chlorophe-nyldiguanido-N5,N5')m-xylene- dihydrochlorid, 1 , 12-Di-(N1, N^-p-chlorophenyldiguanido-Ns, N5') dodecan-dihydro-chlorid, 1 ,10-Di- (N^N^-phenyldiguanido- N5,N5')-decan-tetrahydrochlorid, 1 ,12-Di-(N1, N^-phenyldiguanido- N51N5') dodecan-tetrahydrochlorid, 1 , 6-Di-(N1, N^-o-chlorophenyldi-guanido- N51N5') hexan-dihydrochlorid, 1 , 6-Di-(N1, N^-o-chlorophenyldiguanido- N51N5') hexan-tetrahydrochlorid, Ethylen-bis-(1-tolyl bigua- nid), Ethylen-bis-(p-tolyl biguanide), Ethylen-bis-(3,5-dimethylphenylbiguanid), Ethylen-bis-(p-tert- amylphenylbiguanid), Ethylen-bis-(nonylphenylbiguanid), Ethylen-bis-(phenylbi-guanid), Ethylen- bis-(N-butylphenylbi-guanid), Ethylen-bis (2,5-diethoxyphenylbiguanid), Ethylen-bis (2,4-dimethyl- phenyl biguanid), Ethylen-bis (o-diphenylbiguanid), Ethylen-bis (mixed amyl naphthylbiguanid), N- Butyl-ethylen-bis-(phenylbiguanid), Trimethylen bis (o-tolylbiguanid), N-Butyl-trimethyle- bis-(phenyl biguaπide) und die entsprechenden Salze wie Acetate, Gluconate, Hydrochloride, Hydrobromide, Citrate, Bisulfite, Fluoride, Polymaleate, N-Cocosalkylsarcosinate, Phosphite, Hypophosphite, Per- fluorooctanoate, Silicate, Sorbate, Salicylate, Maleate, Tartrate, Fumarate, Ethylendiamintetraace- tate, Iminodiacetate, Cinnamate, Thiocyanate, Arginate, Pyromellitate, Tetracarboxybutyrate, Ben- zoate, Glutarate, Monofluorphosphate, Perfluorpropionate sowie beliebige Mischungen davon. Weiterhin eignen sich halogenierte XyIoI- und Kresolderivate, wie p-Chlormetakresol oder p-Chlor- meta-xylol, sowie natürliche antimikrobielle Wirkstoffe pflanzlicher Herkunft (z.B. aus Gewürzen oder Kräutern), tierischer sowie mikrobieller Herkunft. Vorzugsweise können antimikrobiell wirkende oberflächenaktive quaternäre Verbindungen, ein natürlicher antimikrobieller Wirkstoff pflanzlicher Herkunft und/oder ein natürlicher antimikrobieller Wirkstoff tierischer Herkunft, äußerst bevorzugt mindestens ein natürlicher antimikrobieller Wirkstoff pflanzlicher Herkunft aus der Gruppe, umfassend Coffein, Theobromin und Theophyllin sowie etherische öle wie Eugenol, Thymol und Geraniol, und/ oder mindestens ein natürlicher antimikrobieller Wirkstoff tierischer Herkunft aus der Gruppe, umfassend Enzyme wie Eiweiß aus Milch, Lysozym und Lactoperoxidase, und/ oder mindestens eine antimikrobiell wirkende oberflächenaktive quaternäre Verbindung mit einer Ammonium-, Sulfonium-, Phosphonium-, lodonium- oder Arsoniumgruppe, Peroxoverbindungen und Chlorverbindungen eingesetzt werden. Auch Stoffe mikrobieller Herkunft, sogenannte Bakter- iozine, können eingesetzt werden. Vorzugsweise finden Glycin, Glycinderivate, Formaldehyd, Verbindungen, die leicht Formaldehyd abspalten, Ameisensäure und Peroxide Verwendung.The antimicrobial agent may be selected from ethanol, n-propanol, i-propanol, 1,3-butanediol, phenoxyethanol, 1,2-propylene glycol, glycerol, undecylenic acid, benzoic acid, salicylic acid, dihydracetic acid, o-phenylphenol, N-methylmorpholine-acetonitrile (MMA), 2-benzyl-4-chlorophenol, 2,2'-methylenebis (6-bromo-4-chlorophenol), 4,4'-di-chloro-2 'hydroxydiphenyl ether (dichlorosilane), 2,4,4'-trichloro-2'-hydroxydiphenyl ether (trichlosan), chlorhexidine, N- (4-chlorophenyl) -N- (3,4-dichlorophenyl) -urea, N, N '- (1, 10-decanediyldi-1-pyridinyl-4-ylidene) bis (1-octanamine) dihydrochloride, N, N'-bis (4-chlorophenyl) -3,12- diimino-2,4,11,13-tetraaza-tetradecandiimidamide, glucopro- tamines, antimicrobial quaternary surface active compounds, guanidines including the bi- and polyguanidine, such as 1,6-bis- (2-ethylhexyl-biguanido-hexane ) -dihydrochloride, 1,6-di- (N 1 , N 1 '-phenyldiguanido-N 5 , N 5 ') -hexane-tetrahydrochloride, 1,6-di- (N 1 l N 1 '-phenyl-N 1 , N 1 -methyldiguanido-N 5 , N 5 ') -hexane dihydrochloride, 1,6-di- (N 1 , N 2 -o-chlorophenyl-diguanido- N 5 , N 5 ') -hexane dihydrochloride , 1, 6-di- (N 1 , N ^ .e-dichlorophenyldiguanido-Ns.Ns'Jhexaπ dihydrochloride, 1, 6-di- [N ^ N ^ -beta ^ p-methoxyphenyl) diguanido-N 5 , N 5 '] -hexane-dihydrochloride, 1,6-di- (N 1 , N 1 -α-alpha-methyl-beta-phenyldiguanido-N 5 , N 5 ') -hexane dihydrochloride, 1 , 6-di- (N 1 , N 2 -p-nitrophenyl-diguanido- N 5 , N 5 ') hexane-dihydrochloride, omega: omega-di- (N L N 1 -phenyl-diguanido-N s, N s ^ -di-n- propylether- dihydrochloride, omega.omega'-di -. ^ N T '-p-chlorophe-nyldiguanido-Ns.Ns'J-di-n-propyl-tetra hydrochloride, 1, 6-di- (N 1, N / -2, 4-dichlorophenyldiguanido-N 5, N 5 ') hexane tetrahydrochloride, 1, 6-di- (N L N ^ -p-methylphe-nyldiguanido-Ns.Ns'Jhexan dihydrochloride, i ^ ^ -DKN N, 1-AS-trichlorophenyl-di-guanido-N 5 , N 5 ') hexane-tetrahydrochloride, 1,6-di- [N 1 , N 1 ' -alpha- (p-chlorophenyl) ethyl-diguanido- N 51 N 5 '] hexane dihydrochloride, OmBgBiOmBgS-di- (N 1, N 1 '-p-chlo rophe-nyldiguanido-N 5 , N 5 ') m-xylenedihydrochloride, 1, 12-di- (N 1 , N 1 -p-chlorophenyldiguanido-N, N 5 ') dodecane dihydrochloride, 1, 10 Di- (N, N'-phenyldiguanido- N 5 , N 5 ') -decane-tetrahydrochloride, 1, 12-di (N 1 , N 1 -phenyl-diguanido- N 51 N 5 ') dodecane-tetrahydrochloride, 1, 6 Di- (N 1 , N 1 -o-chlorophenyl-guanido- N 51 N 5 ') hexane dihydrochloride, 1,6-di- (N 1 , N 1 -o-chloro-phenyldiguanido-N 51 N 5 ') hexane tetrahydrochloride, ethylene bis (1-tolyl biguanide), ethylene bis (p-tolyl biguanide), ethylene bis (3,5-dimethylphenyl biguanide), ethylene bis (p-tert-amylphenyl biguanide) , Ethylene-bis- (nonylphenylbiguanide), ethylene-bis (phenylbi-guanide), ethylene-bis- (N-butylphenyl-biurid), ethylene-bis (2,5-diethoxyphenylbiguanide), ethylene-bis (2,4-) dimethylphenyl biguanide), ethylene bis (o-diphenylbiguanide), ethylene bis (mixed amyl naphthyl biguanide), N-butyl ethylene bis (phenylbiguanide), trimethylene bis (o-tolylbiguanide), N-butyl trimethyl bis- (phenyl biguanides) and the corresponding salts, such as acetates, gluconates, hydrochlorides, hydrobromides, citrates, bisulfites, fluorides, polymaleates, N-cocoalkyl sarcosinates, phosphites, hypophosphites, perfluorooctanoates, silicates, sorbates, salicylates, maleates, tartrates, fumarates, ethylenediamine tetraacetates , Iminodiacetates, cinnamates, thiocyanates, arginates, pyromellitates, tetracarboxybutyrates, benzoates, glutarates, monofluorophosphates, perfluoropropionates and any mixtures thereof. Also suitable are halogenated xylene and cresol derivatives, such as p-chlorometacresol or p-chloro-meta-xylene, and natural antimicrobial agents of plant origin (for example, from spices or herbs), of animal and microbial origin. Preferably, antimicrobial surface-active quaternary compounds, a natural antimicrobial agent of plant origin and / or a natural antimicrobial agent of animal origin, most preferably at least one natural antimicrobial agent of plant origin from the group comprising caffeine, theobromine and theophylline and essential oils such as eugenol, thymol and geraniol, and / or at least one natural antimicrobial agent of animal origin from the group, comprising enzymes such as protein from milk, lysozyme and lactoperoxidase, and / or at least one antimicrobial surface-active quaternary compound with an ammonium, sulfonium, phosphonium, iodonium - or Arsoniumgruppe, peroxo compounds and chlorine compounds are used. Substances of microbial origin, so-called bacteriocins, can also be used. Glycine, glycine derivatives, formaldehyde, compounds which readily split off formaldehyde, formic acid and peroxides are preferably used.
Die als antimikrobielle Wirkstoffe geeigneten quaternären Ammoniumverbindungen (QAV) sind oben schon beschrieben worden. Besonders geeignet ist beispielsweise Benzalkoniumchlorid etc. Benzalkoniumhalogenide und/oder substituierte Benzalkoniumhalogenide sind beispielsweise kommerziell erhältlich als Barquat® ex Lonza, Marquat® ex Mason, Variquat® ex Witco/ Sherex und Hyamine® ex Lonza, sowie Bardac® ex Lonza. Weitere kommerziell erhältliche antimikrobielle Wirkstoffe sind N-(3-Chlorallyl)-hexaminiumchlorid wie Dowicide® und Dowicil® ex Dow, Benzethonium- chlorid wie Hyamine® 1622 ex Rohm & Haas, Methylbenzethoniumchlorid wie Hyamine® 1OX ex Rohm & Haas, Cetylpyridiniumchlorid wie Cepacolchlorid ex Merrell Labs.The suitable as antimicrobial agents quaternary ammonium compounds (QAV) have been described above. Particularly suitable is, for example, benzalkonium chloride, etc. Benzalkonium halides and / or substituted benzalkonium halides are for example commercially available as Barquat ® ex Lonza, Marquat® ® ex Mason Variquat ® ex Witco / Sherex and Hyamine, ® ex Lonza and as Bardac ® ex Lonza. Other commercially obtainable antimicrobial agents are N- (3-chloroallyl) hexaminium chloride such as Dowicide and Dowicil ® ® ex Dow, Benzethonium- chloride such as Hyamine ® 1622 ex Rohm & Haas, methylbenzethonium as Hyamine ® 1ox ex Rohm & Haas, cetylpyridinium chloride such as Cepacol ex Merrell Labs.
Weiterhin können die erfindungsgemäßen Mittel, wie insbesondere Wasch- und Reinigungsmittel, Pflegemittel oder Konditioniermittel, gegebenenfalls Bügelhilfsstoffe zur Verbesserung des Wasserabsorptionsvermögens, der Wiederbenetzbarkeit der behandelten Textilien und zur Erleichterung des Bügeins der behandelten Textilien enthalten. Es können in den Formulierungen beispielsweise Silikonderivate eingesetzt werden. Diese verbessern zusätzlich das Ausspülverhalten der waschaktiven Formulierungen durch ihre schauminhibierenden Eigenschaften. Bevorzugte Silikonderivate sind beispielsweise Polydialkyl- oder Alkylarylsiloxane, bei denen die Alkylgruppen ein bis fünf C-Atome aufweisen und ganz oder teilweise fluoriert sind. Bevorzugte Silikone sind Polydimethyl- siloxane, die gegebenenfalls derivatisiert sein können und dann aminofunktionell oder quatemiert sind bzw. Si-OH-, Si-H- und/oder Si-Cl-Bindungen aufweisen. Die Viskositäten der bevorzugten Silikone liegen bei 250C im Bereich zwischen 100 und 100.000 mPas, wobei die Silikone in Mengen zwischen 0,2 und 5 Gew.-%, bezogen auf das gesamte Mittel eingesetzt werden können.Furthermore, the agents according to the invention, in particular detergents and cleaners, conditioners or conditioners, may optionally contain ironing aids for improving the water absorbency, the rewettability of the treated textiles and for ease of ironing the treated textiles. For example, silicone derivatives can be used in the formulations. These additionally improve the rinsing out of the wash-active formulations by their foam-inhibiting properties. Preferred silicone derivatives are, for example, polydialkyl or alkylaryl siloxanes in which the alkyl groups have one to five carbon atoms and are completely or partially fluorinated. Preferred silicones are polydimethylsiloxanes, which may optionally be derivatized and then amino-functional or quaternized or Si-OH, Si-H and / or Si-Cl bonds. The viscosities of the preferred silicones at 25 0 C in the range between 100 and 100,000 mPas, wherein the silicones in amounts between 0.2 and 5 wt .-%, based on the total composition can be used.
Die erfindungsgemäßen Mittel, insbesondere Konditioniermittel, können nach allen bekannten, dem Fachmann geläufigen Techniken erhalten werden. Die Mittel können beispielsweise durch Aufmischen unmittelbar aus ihren Rohstoffen, gegebenenfalls unter Einsatz von hochscherenden Mischapparaturen erhalten werden. Für flüssige Formulierungen, insbesondere Konditioniermittel, empfiehlt sich ein Aufschmelzen, gegebenenfalls vorhandener Weichmacherkomponenten und ein nachfolgendes Dispergieren der Schmelze in einem Lösungsmittel, vorzugsweise Wasser. Die erfindungsgemäß einsetzbaren polymerisierbaren Betainester der Formel (I) oder erfindungsgemäß daraus herstellbare Polymere können durch einfaches Zumischen in die Konditioniermittel integriert werden.The agents according to the invention, in particular conditioning agents, can be obtained by all known techniques known to the person skilled in the art. The agents can be obtained, for example, by mixing directly from their raw materials, optionally with the use of high-shear mixing equipment. For liquid formulations, in particular conditioning agents, it is recommended to melt, where appropriate, any plasticizer components present and to subsequently disperse the melt in a solvent, preferably water. The polymerizable betaine esters of the formula (I) which can be used according to the invention or polymers which can be prepared from them according to the invention can be incorporated into the conditioning agents by simple admixing.
Vorzugsweise liegen die Konditioniermittel als Weichspülmittel vor. Sie werden dabei üblicherweise in den Nachspülgang einer automatischen Waschmaschine eingebracht.The conditioning agents are preferably present as fabric softeners. They are usually introduced into the rinse cycle of an automatic washing machine.
Ein weiterer Gegenstand der Erfindung ist ein Substrat, insbesondere Konditioniersubstrat, welches mit einem erfindungsgemäßen Mittel, welches also die erfindungsgemäße Riechstoffzusammensetzung und Oxidationsmittel enthält, imprägniert und/oder beschichtet ist.Another object of the invention is a substrate, in particular conditioning substrate, which is impregnated and / or coated with an agent according to the invention, which thus contains the fragrance composition according to the invention and oxidizing agent.
Erfindungsgemäße Konditioniersubstrate finden ihren Einsatz vor allem in der Textilbehandlung und insbesondere in Textiltrocknungsverfahren. Das Substratmaterial besteht vorzugsweise aus porösen flächigen Tüchern. Sie können aus einem faserigen oder zellulären flexiblen Material bestehen, das ausreichend thermische Stabilität zur Verwendung im Trockner aufweist und das ausreichende Mengen eines Imprägnierungs- bzw. Beschichtungsmittels zurückhalten kann, um Stoffe effektiv zu konditionieren, ohne dass während der Lagerung ein nennenswertes Auslaufen oder Ausbluten des Mittels erfolgt. Zu diesen Tüchern gehören Tücher aus gewebtem und ungewebtem synthetischen und natürlichen Fasern, Filz, Papier oder Schaumstoff, wie hydrophilem Polyurethanschaum.Conditioning substrates according to the invention are mainly used in textile treatment and in particular in textile drying processes. The substrate material is preferably made of porous sheet-like cloths. They may consist of a fibrous or cellular flexible material which has sufficient thermal stability for use in the dryer and which can retain sufficient quantities of impregnating or coating agent to effectively condition fabrics without significant bleeding or bleeding during storage By means of done. These wipes include cloths of woven and non-woven synthetic and natural fibers, felt, paper or foam, such as hydrophilic polyurethane foam.
Vorzugsweise werden hier herkömmliche Tücher aus ungewebtem Material (Vliese) verwendet. Vliese sind im allgemeinen als adhesiv gebondete faserige Produkte definiert, die eine Matte oder geschichtete Faserstruktur aufweisen, oder solche, die Fasermatten umfassen, bei denen die Fasern zufällig oder in statistischer Anordnung verteilt sind. Die Fasern können natürlich sein, wie Wolle, Seide, Jute, Hanf, Baumwolle, Lein, Sisal oder Ramie; oder synthetisch, wie Rayon, CeIIu- loseester, Polyvinylderivate, Polyolefine, Polyamide oder Polyester. Im Allgemeinen ist jeder Faserdurchmesser bzw. -titer für die vorliegende Erfindung geeignet. Die hier eingesetzten ungewebten Stoffe neigen aufgrund der zufälligen oder statistischen Anordnung von Fasern in dem ungewebten Material, die ausgezeichnete Festigkeit in allen Richtungen verleihen, nicht zum Zerreißen oder Zerfallen, wenn sie zum Beispiel in einem haushaltsüblichen Wäschetrockner eingesetzt werden. Beispiele für ungewebte Stoffe, die sich als Substrate in der vorliegenden Erfindung eignen, sind beispielsweise aus WO 93/23603 bekannt. Bevorzugte poröse und flächige Reinigungstücher bestehen aus einem oder verschiedenen Fasermaterialien, insbesondere aus Baumwolle, veredelter Baumwolle, Polyamid, Polyester oder Mischungen aus diesen. Vorzugsweise weisen die Reinigungssubstrate in Tuchform eine Fläche von 10 bis 5000 cm2, vorzugsweise von 50 bis 2000 cm2, insbesondere von 100 bis 1500 cm2 und besonders bevorzugt von 200 bis 1000 cm2 auf. Die Grammatur des Materials beträgt dabei üblicherweise zwischen 20 und 1000 g/m2, vorzugsweise von 30 bis 500 g/m2 und insbesondere von 50 bis 150 g/m2. Konditioniersubstrate können durch Tränken oder Imprägnierung oder auch durch Aufschmelzen der erfindungsgemäßen Mittel oder Konditioniermittel auf ein Substrat erhalten werden.Preferably, conventional cloths of nonwoven material (nonwovens) are used here. Nonwovens are generally defined as adhesively bonded fibrous products having a mat or layered fibrous structure, or those comprising fibrous mats in which the fibers are randomly or randomly distributed. The fibers may be natural such as wool, silk, jute, hemp, cotton, flax, sisal or ramie; or synthetically, such as rayon, cellulose esters, polyvinyl derivatives, polyolefins, polyamides or polyesters. In general, any fiber diameter or titer is suitable for the present invention. The non-woven used here Fabrics do not tend to rupture or disintegrate due to the random or random arrangement of fibers in the nonwoven material that impart excellent strength in all directions, for example, when used in a household tumble dryer. Examples of nonwoven fabrics suitable as substrates in the present invention are known, for example, from WO 93/23603. Preferred porous and flat cleaning cloths consist of one or different fiber materials, in particular of cotton, refined cotton, polyamide, polyester or mixtures of these. The cleaning substrates in fabric form preferably have an area of from 10 to 5000 cm 2 , preferably from 50 to 2000 cm 2 , in particular from 100 to 1500 cm 2 and particularly preferably from 200 to 1000 cm 2 . The grammage of the material is usually between 20 and 1000 g / m 2 , preferably from 30 to 500 g / m 2 and in particular from 50 to 150 g / m 2 . Conditioning substrates can be obtained by impregnation or impregnation or else by melting the agents or conditioners according to the invention onto a substrate.
Ein weiterer Gegenstand der Erfindung ist die Verwendung eines erfindungsgemäßen Konditionier- mittels oder eines erfindungsgemäßen Konditioniersubstrats in einem Textilkonditionierverfahren, wie beispielsweise einem Nachspülgang, einem Textiltrocknungsverfahren und einem Textil- trockenreiritgυngs- oder Textilaυffrischungsverfahren.The invention further provides for the use of a conditioning agent or a conditioning substrate according to the invention in a textile conditioning process, such as, for example, a final rinse, a textile drying process and a textile drying process or textile drying process.
Bevorzugte erfindungsgemäße Mittel sind Flüssigwaschmittel, vorzugsweise enthaltend Tensid(e) sowie weitere übliche Inhaltsstoffe von Wasch- und Reinigungsmitteln. Beispielsweise können erfindungsgemäß geeignete Flüssigwaschmittel als Verdickungssystem, jeweils bezogen auf das gesamte Mittel a) 0, 1 bis 5 Gew.-% eines polymeren Verdickungsmittels, b) 0,5 bis 7 Gew.-% einer Borverbindung sowie c) 1 bis 8 Gew.-% eines Komplexbildners, enthalten.Preferred agents according to the invention are liquid detergents, preferably containing surfactant (s) and other customary ingredients of detergents and cleaners. For example, according to the invention suitable liquid detergent as a thickening system, based in each case on the total agent a) 0, 1 to 5 wt .-% of a polymeric thickener, b) 0.5 to 7 wt .-% of a boron compound and c) 1 to 8 wt. -% of a complexing agent, included.
Im Rahmen der vorliegenden Erfindung sind wässrige, höherviskose Flüssigwaschmittel bevorzugt, deren Gehalt an Tensid(en) über 35 Gew.-% liegt.In the context of the present invention, preference is given to aqueous, higher-viscosity liquid detergents whose content of surfactant (s) is above 35% by weight.
Geeignete Verdickungsmittel, auch Quell(ungs)mittel genannt, wie z.B. Alginate oder Agar-Agar wurden schon weiter oben beschrieben. Bevorzugte wässrige Flüssigwaschmittel enthalten als Verdickungssystem 0,2 bis 4 Gew.-%, vorzugsweise 0,3 bis 3 Gew.-% und insbesondere 0, 4 bis 1 ,5 Gew.-%, eines Polysaccharids.Suitable thickening agents, also called swelling agents, e.g. Alginates or agar-agar have been described above. Preferred aqueous liquid detergents contain as thickening system 0.2 to 4 wt .-%, preferably 0.3 to 3 wt .-% and in particular 0, 4 to 1, 5 wt .-%, of a polysaccharide.
Ein bevorzugt einzusetzendes polymeres Verdickungsmittel ist Xanthan, ein mikrobielles anionisches Heteropolysaccharid, das von Xanthomonas campestris und einigen anderen Species unter aeroben Bedingungen produziert wird und eine Molmasse von 2 bis 15 Millionen Dalton aufweist. Xanthan wird aus einer Kette mit ß-1 ,4-gebundener Glucose (Cellulose) mit Seitenketten gebildet. Die Struktur der Untergruppen besteht aus Glucose, Mannose, Glucu- ronsäure, Acetat und Pyruvat, wobei die Anzahl der Pyruvat-Einheiten die Viskosität des Xanthan bestimmt.A preferred polymeric thickener is xanthan gum, a microbial anionic heteropolysaccharide produced by Xanthomonas campestris and some other species under aerobic conditions and having a molecular weight of from 2 to 15 million daltons. Xanthan is formed from a chain of β-1,4-linked glucose (cellulose) with side chains. The structure of the subgroups consists of glucose, mannose, glucuronic acid, acetate and Pyruvate, where the number of pyruvate units determines the viscosity of xanthan gum.
Erfindungsgemäße Flüssigwaschmittel können vorzugsweise eine Borverbindung enthalten, die in Mengen von 0,5 bis 7 Gew.-% eingesetzt wird, enthalten. Beispiele für Borverbindungen, die im Rahmen der vorliegenden Erfindung einsetzbar sind, sind Borsäure, Boroxid, Alkaliborate wie Ammonium-, Natrium- und Kalium-ortho-, -meta- und- pyroborate, Borax in seinen verschiedenen Hydratationsstufen und Polyborate wie beispielsweise Alkalimetallpentaborate.Liquid detergents of the invention may preferably contain a boron compound which is used in amounts of from 0.5 to 7% by weight. Examples of boron compounds useful in the present invention are boric acid, boric oxide, alkali borates such as ammonium, sodium and potassium ortho-, meta- and pyroborates, borax in its various stages of hydration and polyborates such as alkali metal pentaborates.
Auch organische Borverbindungen wie Ester der Borsäure sind einsetzbar.Organic boron compounds such as esters of boric acid can also be used.
Bevorzugte Flüssigwaschmittel enthalten 0,5 bis 4 Gew.-%, vorzugsweise 0,75 bis 3 Gew.-% und insbesondere 1 bis 2 Gew.-% Borsäure und/oder Natriumtetraborat.Preferred liquid detergents contain 0.5 to 4 wt .-%, preferably 0.75 to 3 wt .-% and in particular 1 to 2 wt .-% boric acid and / or sodium tetraborate.
Weiterhin können erfindungsgemäße Flüssigwaschmittel 1 bis 8 Gew.-% eines Komplexbildners enthalten. Besonders bevorzugte Flüssigwaschmittel enthalten dabei Citronensäure oder Natrium- citrat, wobei Flüssigwaschmittel bevorzugt sind, die 2,0 bis 7,5 Gew.-%, vorzugsweise 3,0 bis 6,0 Gew.-% und insbesondere 4,0 bis 5,0 Gew.-% Natriumeitrat enthalten.Furthermore, liquid detergents according to the invention may contain 1 to 8% by weight of a complexing agent. Particularly preferred liquid detergents contain citric acid or sodium citrate, preference being given to liquid detergents which contain from 2.0 to 7.5% by weight, preferably from 3.0 to 6.0% by weight and in particular from 4.0 to 5.0 Wt .-% sodium citrate.
Neben anderen Bestandteilen enthalten die erfindungsgemäßen Flüssigwaschmittel vorzugsweise Tensid(e), wobei anionische, nichtionische, kationische und/oder amphotere Tenside eingesetzt werden. Bevorzugt sind aus anwendungstechnischer Sicht Mischungen aus anionischen und nichtionischen Tensiden, wobei der Anteil der nichtionischen Tenside vorzugsweise größer sein kann als der Anteil an anionischen Tensiden. Der Einsatz von Zuckern und/oder Zuckerderivaten wie beispielsweise Alkylpolyglucoside oder Cyclodextrine kann ebenfalls erfolgen.Among other constituents, the liquid detergents according to the invention preferably contain surfactant (s), wherein anionic, nonionic, cationic and / or amphoteric surfactants are used. From an application point of view, preference is given to mixtures of anionic and nonionic surfactants, wherein the proportion of nonionic surfactants may preferably be greater than the proportion of anionic surfactants. The use of sugars and / or sugar derivatives such as alkyl polyglucosides or cyclodextrins can also be done.
Selbstverständlich enthalten die erfindungsgemäßen Flüssigwaschmittel Oxidationsmittel und Riechstoffe in erfindungsgemäßer Weise. Dies trifft auf alle Mittel zu, die im Rahmen dieser Beschreibung als erfindungsgemäß bezeichnet wurden. Of course, liquid detergents according to the invention contain oxidizing agents and fragrances in accordance with the invention. This applies to all means which have been designated as being according to the invention in the context of this description.
BeispieleExamples
Beispiel 1 :Example 1 :
Es wurde ein flüssiges Waschmittel folgender Zusammensetzung hergestellt, Gew.-% jeweils bezogen auf das gesamte Mittel 16,5 Gew.-% lineares Alkylbenzolsulfonat 10 Gew.-% C12-18-Fettalkohol+7-Ethoxyeinheiten 1 Gew.-% 1-Hydroxyethan-1 ,1-diphosphonsäure 3 Gew.-% Natriumeitrat 8 Gew.-% NatriumsulfatThere was prepared a liquid detergent of the following composition, wt .-% each based on the total average 16.5 wt .-% linear alkylbenzenesulfonate 10 wt .-% C12-18-fatty alcohol + 7-ethoxy units 1 wt .-% 1-hydroxyethane -1, 1-diphosphonic acid 3 wt .-% sodium citrate 8 wt .-% sodium sulfate
3 Gew.-% PAP-Granulat bezogen auf die Aktivsubstanz 0,25 Gew.-% Xanthan Gum3 wt .-% PAP granules based on the active substance 0.25 wt .-% xanthan gum
1 ,3 Gew.-% Riechstoffmischung (siehe Beispiel 2 bzw. 3) ad 100 Gew.-%: Wasser Der pH-Wert wurde durch Zugabe von 50%-iger NaOH auf 5,0 eingestellt.1, 3 wt .-% fragrance mixture (see Example 2 or 3) ad 100 wt .-%: water The pH was adjusted to 5.0 by addition of 50% NaOH.
Beispiel 2 (erfindunqsqemäß):Example 2 (according to the invention):
Die Rezeptur aus Beispiel 1 wurde mit einem Parfümöl I parfümiert, welches Riechstoffe in erfindungsgemäßer Weise umfasste, so dass mehr als 50 Gew.-% der enthaltenen Riechstoffe aus solchen Riechstoffen ausgewählt waren, welche zumindest einer der folgenden Stoffklassen zuordenbar waren gesättigte Alkohole gesättigte Ester gesättigte EtherThe formulation of Example 1 was perfumed with a perfume oil I, which included fragrances according to the invention, so that more than 50 wt .-% of the fragrances contained were selected from such fragrances, which at least one of the following classes were attributable saturated alcohols saturated saturated esters ether
Aromaten mit gesättigten Substituenten - Nitrile gesättigte Acetale gesättigte Halbacetale, wobei die Gew.-%-Angabe auf die gesamte Riechstoffmenge bezogen ist.Aromatics with saturated substituents - Nitriles saturated acetals saturated hemiacetals, wherein the wt .-% - refers to the total amount of fragrance.
Beispiel 3 (VerqleichsbeispieP:Example 3 (Comparative Example)
Die Rezeptur aus Beispiel 1 wurde mit einem herkömmlichen waschmitteltypischen Parfümöl Il parfümiert, u.a. enthaltend:The formulation of Example 1 was perfumed with a conventional perfume oil II typical for washing-things, i.a. including:
14,7 Gew.-% Iso E Super (2-Acetyl-1 , 2,3,4,6,7, 8,8A-octahydro-2,3,8,8-tetramethyl- naphthalin)14.7% by weight of Iso E Super (2-acetyl-1,2,3,4,6,7,8,8A-octahydro-2,3,8,8-tetramethylnaphthalene)
12,5 Gew.-% PTBCA 25 eis (68% trans-4-tert-Butylcyclohexylacetat / 32% cis-4-tert-12.5% by weight PTBCA 25 ice (68% trans-4-tert-butylcyclohexyl acetate / 32% cis-4-tert-butyl)
Butylcyclohexylacetat)butylcyclohexyl)
8,0 Gew.-% Dihydromyrcenol8.0% by weight of dihydromyrcenol
6,0 Gew.-% Habanolide (Oxacyclohexadecen-2-on) 5,0 Gew.-% Phenylethylalkohol6.0% by weight of habanolide (oxacyclohexadecen-2-one) 5.0% by weight of phenylethyl alcohol
3,0 Gew.-% OTBCA (85% cis-2-tert-Butylcyclohexylacetat/15% trans-2-tert-Butylcyclohexy lacetat)3.0% by weight OTBCA (85% cis-2-tert-butylcyclohexyl acetate / 15% trans-2-tert-butylcyclohexyl acetate)
2,0 Gew.-% Vertofix Coeur (Wacholder, Juniperus mexicana, Extrakt, acetyliert, [3R-2.0% by weight of Vertofix Coeur (juniper, Juniperus mexicana, extract, acetylated, [3R]
(3.alpha.,3a.beta.,7.beta.,8a.alpha.)]-1-(2,3,4,7,8,8a-Hexahydro-3,6,8,8-tetramethyl- 1H-3a,7-meth- anoazulen-5-yl)ethan-1-on)(. 3.alpha, 3a.beta, 7.beta, 8a.alpha...)] - 1- (2,3,4,7,8,8a-hexahydro-3,6,8,8-tetramethyl- 1H-3a, 7-methano-azulene-5-yl) ethan-1-one)
1 ,5 Gew.-% Citronitril1, 5 wt .-% citronitrile
4.0 Gew.-% Aldehyd C14 sog. (gamma-Undecalacton ) 16,8 Gew.-% Dipropylenglykol4.0% by weight of aldehyde C14 so-called (gamma undecalactone) 16.8% by weight of dipropylene glycol
12,4 Gew.-% Lilial (2-Methyl-3(4-tert-butylphenyl)propionaldehyd )12.4% by weight of Lilial (2-methyl-3 (4-tert-butylphenyl) propionaldehyde)
4,3 Gew.-% Hexylzimtaldehyd4.3% by weight hexyl cinnamaldehyde
2,3 Gew.-% Bacdanol (2- Ethyl-4(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol)2.3% by weight of bacdanol (2-ethyl-4 (2,2,3-trimethyl-3-cyclopenten-1-yl) -2-buten-1-ol)
2.1 Gew.-% Lyral (4(4-Methyl-4-hydroxypentyl)cyclohexen-1-carbaldehyd ) 1 ,9 Gew.-% Isoeugenol (2-Methoxy-4-propenylphenol)2.1% by weight of lyral (4 (4-methyl-4-hydroxypentyl) cyclohexene-1-carbaldehyde) 1, 9% by weight of isoeugenol (2-methoxy-4-propenylphenol)
0,5 Gew.-% Aldehyd C08 (Octanal)0.5% by weight of aldehyde C08 (octanal)
Gew.-%-Angabe jeweils bezogen auf das gesamte Parfümöl Il% By weight, in each case based on the total perfume oil II
Beispiel 4 (Beurteilung der zeitlichen Entwicklung des Dufteindruckes):Example 4 (Evaluation of the temporal evolution of the fragrance impression):
Die zeitliche Entwicklung des Dufteindruckes wurde über 4 Wochen hinweg bei 250C durch Abriechen durch drei Parfümeure beurteilt. Hierbei stellte sich heraus, dass die erfindungsgemäße Zusammensetzung, also das flüssige Waschmittel gemäß Beispiel 1 mit dem Parfüm aus Beispiel 2, sich über diesen Zeitraum geruchlich nicht verändert. Die Vergleichszusammensetzung, also das flüssige Waschmittel gemäß Beispiel 1 mit dem herkömmlichen Waschmittelparfüm aus Beispiel 3, nahm jedoch einen so sehr unangenehmen Geruch an, so dass es alleine aus geruchlichen Gründen keinesfalls mehr zum Wäschewaschen oder Verkauf geeignet gewesen wäre.The development over time of the fragrance impression was evaluated over 4 weeks at 25 0 C by abrasion by three perfumers. It turned out that the composition according to the invention, ie the liquid detergent according to Example 1 with the perfume from Example 2, does not change in odor over this period. However, the comparative composition, ie the liquid detergent according to Example 1 with the conventional detergent perfume from Example 3, however, assumed such a very unpleasant odor, so that it would have been no longer suitable for laundry washing or sale solely for reasons of odor.
Beispiel 5 (Ermittlung der Stabilität des Bleichmittels):Example 5 (determination of bleach stability):
Der Erhaltungsgrad des Bleichmittels PAP wurde im Wochenabstand bei einer Lagerung bei 25°C über einen Zeitraum von 4 Wochen hinweg für die erfindungsgemäße Zusammensetzung, also das Flüssigwaschmittel gemäß Beispiel 1 mit dem Parfüm aus Beispiel 2 (entspricht „Waschmittel A erfindungsgemäß"), und für die Vergleichszusammensetzung also das flüssige Waschmittel gemäß Beispiel 1 mit dem mit dem herkömmlichen Waschmittelparfüm aus Beispiel 3 (entspricht Vergleichswaschmittel B) beurteilt.The degree of preservation of the bleach PAP was at weekly intervals during storage at 25 ° C over a period of 4 weeks for the composition of the invention, ie the liquid detergent according to Example 1 with the perfume of Example 2 (corresponds to "detergent A according to the invention"), and the comparative composition thus the liquid detergent according to Example 1 with that with the conventional detergent perfume from Example 3 (equivalent to Comparative detergent B) assessed.
Dazu wurde der Gehalt an Bleichmittel durch iodometrische Titration bestimmt. Der Ausgangsgehalt (3% absolut) wurde dabei als 100% gesetzt. In der folgenden Tabelle sind die Bleichmittelgehalte (in %) nach den jeweiligen Lagerzeiten (in Wochen) bei 25°C angegeben:For this purpose, the content of bleach was determined by iodometric titration. The initial content (3% absolute) was set as 100%. The following table shows the bleach contents (in%) after the respective storage times (in weeks) at 25 ° C:
Lagerzeit 0 1 2 3 4Storage time 0 1 2 3 4
Waschmittel A (erfindungsgemäß) 100 99 96 93 89Detergent A (according to the invention) 100 99 96 93 89
Vergleichswaschmittel B 100 90 75 55 30 Man beobachtete somit bei dem Vergleichswaschmittel B einen drastischen Verlust des Bleichmittels in Gegenwart des herkömmlichen Parfüms aus Beispiel 3. Beim Waschmittel A (erfindungsgemäß), enthaltend das erfindungsgemäße Parfüm, fand man eine unerwartet gute Stabilität. Comparative detergent B 100 90 75 55 30 It was thus observed in the comparison detergent B a drastic loss of the bleaching agent in the presence of the conventional perfume of Example 3. In the detergent A (according to the invention) containing the perfume of the invention, found an unexpectedly good stability.

Claims

Patentansprüche claims
1. Oxidationsmittel enthaltendes Verbrauchsprodukt, umfassend eine Riechstoffzusammensetzung, dadurch gekennzeichnet, dass zumindest 50 Gew.-% der enthaltenen Riechstoffe aus solchen Riechstoffen ausgewählt sind, welche zumindest einer der folgenden Stoffklassen zuordenbar sind gesättigte Alkohole gesättigte Ester gesättigte Ether1. A consumable product containing oxidizing agent, comprising a fragrance composition, characterized in that at least 50 wt .-% of the fragrances contained are selected from such fragrances, which are attributable to at least one of the following classes saturated alcohols saturated esters saturated ethers
Aromaten mit gesättigten Substituenten - Nitrile gesättigte Acetale gesättigte Halbacetale, wobei die Gew.-%-Angabe auf die gesamte Riechstoffmenge bezogen ist.Aromatics with saturated substituents - Nitriles saturated acetals saturated hemiacetals, wherein the wt .-% - refers to the total amount of fragrance.
2. Mittel nach Anspruch 1, dadurch gekennzeichnet, dass es sich bei dem Oxidationsmittel um ein oxidatives Bleichmittel handelt, vorzugsweise auf Sauerstoffbasis wobei insbesondere Peroxycar- bonsäuren bevorzugt sind.2. Composition according to claim 1, characterized in that it is the oxidizing agent is an oxidative bleaching agent, preferably based on oxygen, in particular Peroxycar- bonsäuren are preferred.
3. Mittel nach Anspruch 2, dadurch gekennzeichnet, dass eine Peroxycarbonsäure enthalten ist, wobei die Peroxycarbonsäure vorteilhafterweise ausgewählt ist aus Mono- und Diperoxycarbon- säuren, insbesondere Dodekandiperoxysäure oder vorzugsweise Imidoperoxycarbonsäuren, besonders bevorzugt 6-Phthalimidoperoxycapronsäure (6-Phthalimidoperoxyhexansäure, PAP), und/oder wobei die Peroxycarbonsäure bei Atmosphärendruck einen Schmelzpunkt oberhalb von 250C, insbesondere oberhalb von 35°C, vorzugsweise oberhalb von 45°C, bevorzugt oberhalb von 500C, besonders bevorzugt oberhalb von 1000C, aufweist.3. Composition according to claim 2, characterized in that a peroxycarboxylic acid is contained, wherein the peroxycarboxylic acid is advantageously selected from mono- and diperoxycarboxylic acids, in particular dodecanediperoxyacid or preferably imidoperoxycarboxylic acids, more preferably 6-phthalimidoperoxycaproic acid (6-phthalimidoperoxyhexanoic acid, PAP), and / or wherein the peroxycarboxylic acid at atmospheric pressure has a melting point above 25 0 C, in particular above 35 ° C, preferably above 45 ° C, preferably above 50 0 C, particularly preferably above 100 0 C.
4. Mittel nach Anspruch 1 bis 3, dadurch gekennzeichnet, dass das Oxidationsmittel, insbesondere die Peroxycarbonsäure, im wesentlichen in granulärer Form vorliegt sowie vorzugsweise gecoatet ist, wobei die Masse des Coatings vorteilhafterweise 0,1 bis 30 Gew.-% beträgt, bezogen auf das gesamte das Oxidationsmittel enthaltende Teilchen, vorzugsweise Granulat.4. Composition according to claim 1 to 3, characterized in that the oxidizing agent, in particular the peroxycarboxylic acid, is present in granular form and is preferably coated, wherein the mass of the coating is advantageously 0.1 to 30 wt .-%, based on the whole of the oxidant-containing particles, preferably granules.
5. Mittel nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass es zumindest 0,01 Gew.-% Tenside enthält, insbesondere anionische Tenside, vorzugsweise in Mengen von 0,1 bis 30 Gew.-%, und/oder nichtionische Tenside, vorzugsweise in Mengen von 0,1 bis 30 Gew.-%, jeweils bezogen auf das gesamte Mittel.5. Composition according to one of claims 1 to 4, characterized in that it contains at least 0.01 wt .-% surfactants, in particular anionic surfactants, preferably in amounts of 0.1 to 30 wt .-%, and / or nonionic surfactants , preferably in amounts of 0.1 to 30 wt .-%, each based on the total agent.
6. Mittel nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass es Elektrolyte enthält, insbesondere anorganische und/oder organische Salze, insbesondere Phosphat, Citrat und/oder Sulfat, besonders bevorzugt Natriumsulfat, vorzugsweise in Mengen von zumindest 0,1 Gew.-%, vorteilhafterweise zumindest 3 Gew.-%, insbesondere in Mengen von 5 bis 30 Gew.-%, jeweils bezogen auf das gesamte Mittel.6. Composition according to one of claims 1 to 5, characterized in that it contains electrolytes, in particular inorganic and / or organic salts, in particular phosphate, citrate and / or sulfate, more preferably sodium sulfate, preferably in amounts of at least 0.1 wt. -% advantageously at least 3 wt .-%, in particular in amounts of 5 to 30 wt .-%, each based on the total agent.
7. Mittel nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass es Komplexbildner enthält, vorzugsweise in Mengen von bis zu 30 Gew.-%, insbesondere 0 bis 10 Gew.-%, bezogen auf das gesamte Mittel, wobei insbesondere7. Composition according to one of claims 1 to 6, characterized in that it contains complexing agents, preferably in amounts of up to 30 wt .-%, in particular 0 to 10 wt .-%, based on the total agent, in particular
(a) stickstofffreie Komplexbildner wie z.B. vorzugsweise Alkalimetallpolyphosphonate, Mono- oder Polyphosphonsäuren, insbesondere 1-Hydroxyethyliden-1 ,1-diphosphonsäure(HEDP), Citrat und/ oder kurzkettige Dicarbonsäuren und/oder(a) nitrogen-free chelating agents such as e.g. preferably alkali metal polyphosphonates, mono- or polyphosphonic acids, in particular 1-hydroxyethylidene-1, 1-diphosphonic acid (HEDP), citrate and / or short-chain dicarboxylic acids and / or
(b) Komplexbildner aus der Gruppe Chinolin und/oder seine Salze, Picolinsäure und Dipicolin- säure, Ethylendiamintetraessigsäure (EDTA), Diethylentriaminpenta(methylenphosphonsäure) (DTPMP), Azacycloheptandiphosphonat (AHP), Nitrilotriessigsäure (NTA), Aminopolycarbon- säuren, Aminohydroxypolycarbonsäuren, Polyphosphonsäuren und Aminopolyphosphon- säuren, enthalten sein können.(b) complexing agents from the group quinoline and / or its salts, picolinic acid and dipicolinic acid, ethylenediaminetetraacetic acid (EDTA), diethylenetriamine penta (methylenephosphonic acid) (DTPMP), azacycloheptane diphosphonate (AHP), nitrilotriacetic acid (NTA), aminopolycarboxylic acids, aminohydroxypolycarboxylic acids, polyphosphonic acids and aminopolyphosphonic acids.
8. Mittel nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass es Enzyme, vorzugsweise in Mengen von 0 bis 10 Gew.-% enthält, jeweils bezogen auf das gesamte Mittel.8. Composition according to one of claims 1 to 7, characterized in that it contains enzymes, preferably in amounts of 0 to 10 wt .-%, each based on the total agent.
9. Mittel nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass es Builder enthält, insbesondere Fettsäuren, vorzugsweise gesättigte und/oder verzweigte Fettsäuren, insbesondere mit einem Schmelzpunkt unterhalb von 30 0C, und/oder Citronensäure und/oder Citrat, vorzugsweise in Mengen von 0 bis 15 Gew.-%, und/oder Polyacrylate, vorzugsweise in Mengen von 0 bis 15 Gew.-%, und/oder Phosphonate, wobei sich die Angabe Gew.-% jeweils auf das gesamte Mittel bezieht.9. Composition according to one of claims 1 to 8, characterized in that it contains builders, in particular fatty acids, preferably saturated and / or branched fatty acids, in particular having a melting point below 30 0 C, and / or citric acid and / or citrate, preferably in amounts of from 0 to 15% by weight, and / or polyacrylates, preferably in amounts of from 0 to 15% by weight, and / or phosphonates, the percentage by weight being based on the total agent.
10. Mittel nach einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, dass es zumindest im wesentlichen keine Halogenidionen, insbesondere keine Chloridionen, aufweist, wobei die Menge an Halogenidionen, insbesondere Chloridionen, vorteilhafterweise höchstens 500 ppm, vorzugsweise höchstens 100 ppm, insbesondere höchstens 30 ppm, beträgt.10. Composition according to one of claims 1 to 9, characterized in that it comprises at least substantially no halide ions, in particular no chloride ions, wherein the amount of halide ions, in particular chloride ions, advantageously at most 500 ppm, preferably at most 100 ppm, in particular at most 30 ppm, is.
11. Mittel nach einem der Ansprüche 1-10, dadurch gekennzeichnet, dass weniger als 30 Gew.-%, vorzugsweise weniger als 20 Gew.-%, vorteilhafterweise weniger als 15 Gew.-%, in vorteilhafterer Weise weniger als 10 Gew.-%, in noch vorteilhafterer Weise weniger als 5 Gew.-%, in wiederum vorteilhafterer Weise weniger als 3 Gew.-%, in weiter vorteilhafter Weise weniger als 2 Gew.-%, in noch weiter vorteilhafter Weise weniger als 1 Gew.-%, in besonders vorteilhafter Weise weniger als 0,5 Gew.-% insbesondere 0 Gew.-% der enthaltenen Riechstoffe aus solchen Riechstoffen ausgewählt sind, welche eine Aldehydfunktion ( RCH=O) und/oder eine Keto-Gruppe ( RR1C=O ) tragen, wobei sich die Angabe Gew.-% auf die Gesamtmenge der im Mittel enthaltenen Riechstoffe bezieht.11. Composition according to one of claims 1-10, characterized in that less than 30 wt .-%, preferably less than 20 wt .-%, advantageously less than 15 wt .-%, more preferably less than 10 wt. %, more preferably less than 5% by weight, more preferably less than 3% by weight, more preferably less than 2% by weight, even more advantageously less than 1% by weight. , in a particularly advantageous manner less than 0.5 wt .-%, in particular 0 wt .-% of the fragrances contained in such fragrances are selected which an aldehyde function (RCH = O) and / or a keto group (RR 1 C = O ) wear, wherein the indication Gew .-% refers to the total amount of fragrances contained in the middle.
12. Mittel nach einem der Ansprüche 1-11 , dass dadurch gekennzeichnet, dass das Mittel in flüssiger Form, vorzugsweise in wässriger oder nichtwässriger Form, vorliegt, wobei es sich vorteilhafterweise um eine Dispersion, vorzugsweise um eine Emulsion oder Suspension, handelt.12. Composition according to one of claims 1-11, characterized in that the agent is in liquid form, preferably in aqueous or non-aqueous form, which is advantageously a dispersion, preferably an emulsion or suspension.
13. Mittel nach Anspruch 12, dadurch gekennzeichnet, dass es gießfähig ist, vorzugsweise eine Viskosität zwischen 100 und 10000 mPas aufweist bei einer Scherrate von 30s'1 und einer Temperatur von 250C.13. Composition according to claim 12, characterized in that it is pourable, preferably has a viscosity between 100 and 10,000 mPas at a shear rate of 30 s ' 1 and a temperature of 25 0 C.
14. Mittel nach einem der Ansprüche 1 bis 13, dadurch gekennzeichnet, dass einen pH-Wert von höchstens 7, insbesondere einen pH-Wert von 3,5 bis 7, vorzugsweise von 4,0 bis 6,5, besonders bevorzugt von 4,5 bis 6, ganz besonders bevorzugt von etwa 5, aufweist.14. Composition according to one of claims 1 to 13, characterized in that a pH of at most 7, in particular a pH of 3.5 to 7, preferably from 4.0 to 6.5, particularly preferably from 4, 5 to 6, most preferably from about 5, has.
15. Mittel nach einem der Ansprüche 1-11 , dadurch gekennzeichnet, dass das Mittel in fester Form vorliegt, vorzugsweise als Pulver.15. Composition according to one of claims 1-11, characterized in that the agent is in solid form, preferably as a powder.
16. Mittel nach Anspruch 15, dadurch gekennzeichnet, dass es sich um ein Kompaktat handelt, erhältlich z.B. durch Vorgänge wie Pressen, Walzen, Brikettieren, Pelleti(si)eren, Extrudieren, Agglomerieren oder verwandte verdichtende Verfahren,.16. Composition according to claim 15, characterized in that it is a Kompaktat, available for. by processes such as pressing, rolling, briquetting, pelletizing, extruding, agglomerating or related compacting processes.
17. Mittel nach einem der Ansprüche 15 oder 16, dadurch gekennzeichnet, dass es sich um einen Formkörper handelt, vorzugsweise um eine Tablette oder um einen Block oder um einen Strang.17. Composition according to one of claims 15 or 16, characterized in that it is a molding, preferably a tablet or a block or a strand.
18. Mittel nach einem der Ansprüche 1 bis 17, dadurch gekennzeichnet, dass die im erfindungsgemäßen Mittel enthaltene Riechstoffzusammensetzung zumindest 50 Gew.-%, zumindest 60 Gew.- % oder zumindest 70 Gew.-% oder zumindest 80 Gew.-% oder zumindest 90 Gew.-% oder zumindest 91 Gew.-%, vorzugsweise zumindest 92 Gew.-%, vorteilhafterweise zumindest 94 Gew.-%, in vorteilhafterer Weise zumindest 96 Gew.-%, in noch vorteilhafterer Weise zumindest 98 Gew.-%, in weiter vorteilhafter Weise zumindest 99 Gew.-%, insbesondere sogar 100 Gew.-% an Riechstoffen, ausgewählt aus Citronitril, Ortho-tert.-butylcyclohexylacetat, Cyclohexylsalicylat, (+)-(1'R,3S,6'S)-1- (2',2l,6l-trimethyl-1'-cydohexyl)-3-hexanol, (-)-(1lS,3R,6'R)-1-(2',2l,6'-trimethyl-1l-cydohexyl)-3-hexa- nol, (+)-(1lR,3R,6'S)-1-(2l,2',6'-trimethyl-1l-cyclohexyl)-3-hexanol, (-)-(1'S,3S,6'R)-1-(2l,2l,6l-trime- thyl-1 '-cyclohexyl)-3-hexanol, Phenylethylalkohol, 2-Cyclohexylidene-2-phenylacetonitrile, Decahy- dro-b-naphtolacetat, Kresylacetat (para), Methylphenylacetat, Allylamylglycolat, Benzylacetat, Cyclohexylethylacetat, Ethyl-2-cyclohexyl-propionat, Phenylethylacetat, Cyclopentyliden-Essig- säuremethylester [CAS-Nr. 0040203-73-4), Allyl-(cyclohexyloxy)acetat, 2,4-Dimethyl-1 ,3-dioxolan- 2-essigsäureethylester, 3,12-Tridecadien-nitril, Amylacetat, Isoamylacetat, Ethylphenylacetat, 2- Propenylphenoxyacetat, Isobornylacetat, Dimethylbenzylcarbinylacetat, Hexylacetat, Kresylacetat (para), Isobutylphenylacetat, Butylcyclohexylacetat- cis-para-tert., Butylcyclohexylacetat-trans- para-tert, Hydrozimtalkohol, 2,6-Dimethylheptan-2-ol, Decanol, Octanol, 2,6-Dimethylbicyclo- [4.4.0]decan-1-ol (0.1% in Dipropylenglykol), Tetrahydromuguol [= Tetrahydrolinalool (3,7-Dime- thyloctan-3-ol) / Tetrahydromyrcenol (2-Octanol, 2,6-dimethyl) Gemisch (1 :1)], Dihydroterpineol, alpha 3,3-trimethylcyclohexylmethylformat, Octanol-3, Hexanol, 2,2,6-Trimethyl-alpha-propylcyclo- hexanpropanol, Decahydro-b-naphtolformiat, (1'S,1"S,2'S,3"R,5"R)-[1-Methyl-2-(1 ,2,2-trimethyl-bi- cyclo[3.1.0]hex-3-ylmethyl)-cyclopropyl]-methanol, (1'R,1"R,2'R,3"S,5"S)-[1-Methyl-2-(1 ,2,2-trime- thyl-bicyclo[3.1.0]hex-3-ylmethyl)-cyclopropyl]-methanol, (1'R,1"S,2'R,3"R,5"R)-[1-Methyl-2-(1 ,2,2- trimethyl-bicyclo[3.1.0]hex-3-ylmethyl)-cyclopropyl]-methanol, (1'S,1"R,2'S,3"S,5"S)-[1-Methyl-2- (1 ,2,2-trimethyl-bicyclo[3.1.0]hex-3-ylmethyl)-cyclopropyl]-methanol, Borneol, Dipropylenglycol, Tetrahydrogeraniol, Tetrahydrolinalool, 2,2,6-Trimethyl-alpha-propylcyclohexanepropanol (Timberol forte), alpha- Methyl-4-(1-methylethyl)cyclohexanemethanol, Isocyclogeraniol, Fenchylalkohol, (-)- (2R,4S)-2-isobutyl-4-methyltetrahydro-2H-pyran-4-ol, (+)-(2S,4R)-2-isobutyl-4-methyltetrahydro- 2H-pyran-4-ol, (+)-(2S,4S)-2-isobutyl-4-methyltetrahydro-2H-pyran-4-ol, (-)-(2R,4R)-2-isobutyl-4- methyltetrahydro-2H-pyran-4-ol, Methylbenzoat, Ethylbenzoat, Methylsalicylat, Amylpropionat, 2,6,6-Trimethyl-1.S-cyclohexadien-i-carbonsäureethylester, Benzylpropionat, Ethylsalicylat, 2- Methoxy-4-formylphenylisobutyrat (Isobutavan), Ethylcaprylat, Allylcapronat, 2-Methyl-2-buten- säure-2-methylpropylester, 2-Ethyl-Ethylhexanoat (Irotyl), 2-Methylpentansäure-2-methylpentyl- ester, Jasmacyclat, 2,5-Dimethyl-4,6-dihydroxybenzoesäuremethylester, Ethyl-2-methylvalerat, Heptansäure-2-propenylester (Allylheptanoat - allyloenanthat), Methylanthranilat, Phenylessig- säure, Allylcyclohexylpropionat, 2-Noninsäuremethylester, Cyclohexylsalicylat, 2-tert-Butylcyclohe- xylethylcarbonat, 2,2,4-Trimethylcapronsaureethylester, Ethylester Labdanum Extract (Ambra- rome), Styrolylacetat, Hydrochinondimethylaether, Diphenylether, Kresylmethylether (para), Cymol (para), Phenylethylisoamylether, Phenylethylmethylether, 4-lsopropyl-5,5-dimethyl-1,3-dioxan, 2,2,5,5-Tetramethyl-4-isopropyl-1 ,3-dioxan, 5-Methyl-5-propyl-2(1-methylbutyl)-1 ,3-dioxan, Ane- thol, 2-Phenylpropionaldehyde-dimethyl acetal, Frambinonmethylether, Cumarin, Isocumarin, Ace- tophenon, 1,1,2,3,3-Pentamethyl-6I7-dihydro-4(5H)-indanon, Octalacton gamma, Ethylamylketon, Campher synth., Oxacycloheptadec-δ-en-2-on, 2-Heptylcyclopentanon, 2-(1-methylpropyl)-Cyclo- hexanon, 4-tert-Butyl-2,6-dimethylacetophenon, Cyclopentadecanolide, 3-Methyl-cyclopentadeca- non, Dihydrojasmon, Dihydro-iso-jasmon, Decalacton gamma, Methyloctalacton, 1 ,4-Dioxacyclo- hexadecan-5, 16-dion, 4-(2-Butenyliden)-3,5,5-trimethyl-2-cyclohexen-1-on, Ethyl-2,2,6,-trimethylcy- clohexancarboxylat, Zimtsäurenitril, Laurinsäurenitril, Hydrocitronitril, 2-Benzyl-2-methyl-3-buten- nitril, 3-Methyldodecanonitril, Citronitril, Tridecen-2-nitril, *3(4,7,7-Trimethylbicyclo<4.1.0>hept-3- yl)-2-propenylnitril, Irolene p, 8-alpha-12-Oxido-13,14,15,16-tetranorlabdan, 3,3,5-Trimethylcyclo- hexylethylether, Irival (70% 4-tert-Pentvlcyclohexanon, 10% Weißes Mineralöl, 10% Non-2-eneni- tril, 10% Dibutylsebacat), Isobutylchinolin, 5-Ethylidenbicyclo[2.2.1]-2-hepten-2-Methoxyphenol-Ad- dukt, Methylbutyl-2 propionat, lndeno[1 ,2-d]-tetrahydro-1 ,3-dioxan, Dodecahydro-3a,6,6,9a-tetra- methyl-Naphtho(2,1-b)furan, 2,4-Dimethyl-4-phenyl-tetrahydrofuran, Spiro[1 ,3-dioxolan-2,5'- (4',4',8',8'-tetramethyl-hexahydro-3',9'-methanonaphthalen)], Methyldihydrojasmonat, Methyl 3-oxo- 2-pentylcyclopentaneacetat, o-(Allyloxy)anisol, Dihydromyrcenol, 9-Decen-1-ol, Tetrahydromyrce- nol, Hexahydro-4,7-methanoinden-6-yl acetat, 2-Phenoxyethylisobutyrat, 2-Methylpropensäure-1 ,3- dimethyl-3-butenylester, Methylacetophenon para, 4-Phenyl-2-butanon, 1-(5,5-Dimethyl-1-Cyclohe- xen-1-yl)-4-Penten-1-one, 3-Hydroxy-1-methyl-4-isopropylbenzol [CAS Nr.: 89-83-8] enthält, wobei sich die Gew.-Angabe auf die Gesamtmenge der Riechstoffe bezieht. 18. Composition according to one of claims 1 to 17, characterized in that the perfume composition contained in the agent according to the invention at least 50 wt .-%, at least 60% by weight or at least 70 wt .-% or at least 80 wt .-% or at least 90% by weight or at least 91% by weight, preferably at least 92% by weight, advantageously at least 94% by weight, more preferably at least 96% by weight, more preferably at least 98% by weight, in a further advantageous manner, at least 99% by weight, in particular even 100% by weight, of odorants selected from citronitrile, ortho-tert-butylcyclohexyl acetate, cyclohexyl salicylate, (+) - (1'R, 3S, 6'S) -1- (2 ', 2 l , 6 l -trimethyl-1'-cyclohexyl) -3-hexanol, (-) - (1 l S, 3R, 6'R) -1- (2', 2 l , 6 ') trimethyl-1 l -hydroxyl) -3-hexanol, (+) - (1 l R, 3R, 6'S) -1- (2 l , 2 ', 6'-trimethyl-1 l -cyclohexyl) -3- hexanol, (-) - (1'S, 3S, 6'R) -1- (2 L , 2 L , 6 L -trimethyl-1'-cyclohexyl) -3-hexanol, phenylethyl alcohol, 2-cyclohexylidenes-2- phenylacetonitrile, decahydr o-b-naphthol acetate, cresyl acetate (para), methyl phenylacetate, allylamyl glycolate, benzyl acetate, cyclohexyl ethyl acetate, ethyl 2-cyclohexyl-propionate, phenylethyl acetate, cyclopentylidene-acetic acid methyl ester [CAS-No. 0040203-73-4), allyl (cyclohexyloxy) acetate, 2,4-dimethyl-1,3-dioxolane-2-acetic acid ethyl ester, 3,12-tridecadienitrile, amyl acetate, isoamyl acetate, ethyl phenylacetate, 2-propenylphenoxyacetate, isobornyl acetate, Dimethylbenzylcarbinylacetate, hexylacetate, cresylacetate (para), isobutylphenylacetate, butylcyclohexylacetate-cis-para-tert., Butylcyclohexylacetate-trans. para-tert, hydrocinnamyl alcohol, 2,6-dimethylheptan-2-ol, decanol, octanol, 2,6-dimethylbicyclo [4.4.0] decan-1-ol (0.1% in dipropylene glycol), tetrahydrouguol [= tetrahydrolinalool (3, 7-dimethyl-octan-3-ol) / tetrahydromyrcenol (2-octanol, 2,6-dimethyl) mixture (1: 1)], dihydroterpineol, alpha 3,3-trimethylcyclohexylmethyl formate, octanol-3, hexanol, 2,2, 6-trimethyl-alpha-propylcyclohexanopropanol, decahydro-b-naphtholformate, (1'S, 1 "S, 2'S, 3" R, 5 "R) - [1-methyl-2- (1,2,2-trimethyl- bicyclo [3.1.0] hex-3-ylmethyl) -cyclopropyl] -methanol, (1'R, 1 "R, 2'R, 3" S, 5 "S) - [1-methyl-2 ( 1, 2,2-trimethyl-bicyclo [3.1.0] hex-3-ylmethyl) -cyclopropyl] -methanol, (1'R, 1 "S, 2'R, 3" R, 5 "R) - [1-Methyl-2- (1,2,2-trimethyl-bicyclo [3.1.0] hex-3-ylmethyl) -cyclopropyl] -methanol, (1'S, 1 "R, 2'S, 3" S, 5 "S ) - [1-Methyl-2- (1,2,2-trimethyl-bicyclo [3.1.0] hex-3-ylmethyl) -cyclopropyl] -methanol, borneol, dipropylene glycol, tetrahydrogeraniol, tetrahydrolinalool, 2,2,6- Trimethyl-alpha-propylcyclohexanepropanol (Timberol forte), alpha-methyl -4- (1-methylethyl) cyclohexanemethanol, isocyclogeraniol, fenchyl alcohol, (-) - (2R, 4S) -2-isobutyl-4-methyltetrahydro-2H-pyran-4-ol, (+) - (2S, 4R) - 2-isobutyl-4-methyltetrahydro-2H-pyran-4-ol, (+) - (2S, 4S) -2-isobutyl-4-methyltetrahydro-2H-pyran-4-ol, (-) - (2R, 4R ) -2-isobutyl-4-methyltetrahydro-2H-pyran-4-ol, methyl benzoate, ethyl benzoate, methyl salicylate, amyl propionate, ethyl 2,6,6-trimethyl-1S-cyclohexadiene-i-carboxylate, benzyl propionate, ethyl salicylate, 2- Methoxy-4-formylphenyl isobutyrate (isobutane), ethyl caprylate, allyl caproate, 2-methyl-2-butenoic acid 2-methylpropyl ester, 2-ethyl-ethylhexanoate (irotyl), 2-methylpentanoic acid 2-methylpentyl ester, jasmacycline, 2, Methyl 5-dimethyl-4,6-dihydroxybenzoate, ethyl 2-methylvalerate, heptanoic acid 2-propenyl ester (allylheptanoate-allyloenanthat), methyl anthranilate, phenylacetic acid, allylcyclohexylpropionate, 2-nonynoic acid methyl ester, cyclohexyl salicylate, 2-tert-butylcyclohexylethyl carbonate, 2 , 2,4-Trimethylcapronsaureethylester, Ethyl ester Labdanum Extract (Ambra- rome), styrolyl acetate, hydroquinone dimethyl ether, diphenyl ether, cresyl methyl ether (para), cymene (para), phenylethyl isoamyl ether, phenylethyl methyl ether, 4-isopropyl-5,5-dimethyl-1,3-dioxane, 2,2,5 , 5-Tetramethyl-4-isopropyl-1,3-dioxane, 5-methyl-5-propyl-2 (1-methylbutyl) -1,3-dioxane, anethole, 2-phenylpropionaldehyde dimethyl acetal, frambinone methyl ether, coumarin , isocoumarin, acetophenone, 1,1,2,3,3-pentamethyl-6 I 7-dihydro-4 (5H) -indanon, octalactone gamma, ethyl amyl ketone, camphor synth., -oxacycloheptadec-δ-en-2-on , 2-heptylcyclopentanone, 2- (1-methylpropyl) -cyclohexanone, 4-tert-butyl-2,6-dimethylacetophenone, cyclopentadecanolides, 3-methyl-cyclopentadecane, dihydrojasmon, dihydro-iso-jasmon, decalactone gamma, Methyloctalactone, 1,4-dioxacyclohexadecane-5,16-dione, 4- (2-butenylidene) -3,5,5-trimethyl-2-cyclohexen-1-one, ethyl-2,2,6, -trimethylcy - clohexanecarboxylate, cinnamonitrile, lauric acid nitrile, hydrocitronitrile, 2-benzyl-2-methyl-3-butene nitrile, 3-methyldodecanonitrile, citronitrile, tridecen-2-nitrile, * 3 (4,7,7-trimethylbicyclo <4.1.0> hept-3-yl) -2-propenylnitrile, Irolene p, 8-alpha-12-oxido -13,14,15,16-tetranorlabdane, 3,3,5-trimethylcyclohexylethyl ether, Irival (70% 4-tert-pentylcyclohexanone, 10% white mineral oil, 10% non-2-enenetrile, 10% dibutyl sebacate) , Isobutylquinoline, 5-ethylidenebicyclo [2.2.1] -2-heptene-2-methoxyphenol adduct, methylbutyl 2-propionate, indeno [1,2-d] -tetrahydro-1,3-dioxane, dodecahydro-3a, 6,6,9a-tetra- methyl-naphtho (2,1-b) furan, 2,4-dimethyl-4-phenyl-tetrahydrofuran, spiro [1,3-dioxolane-2,5'- (4 ', 4'')',8',8'-tetramethyl-hexahydro-3',9'-methanonaphthalene)], methyl dihydrojasmonate, methyl 3-oxo 2-pentylcyclopentane acetate, o- (allyloxy) anisole, dihydromyrcenol, 9-decen-1-ol, tetrahydromyrocene, hexahydro-4,7-methanoinden-6-yl acetate, 2-phenoxyethyl isobutyrate, 2-methylpropenoic acid 1, 3 dimethyl 3-butenyl ester, methylacetophenone para, 4-phenyl-2-butanone, 1- (5,5-dimethyl-1-cyclohexyl-1-yl) -4-penten-1-one, 3-hydroxy-1 Methyl-4-isopropylbenzene [CAS No .: 89-83-8] contains, wherein the Gew.-indication refers to the total amount of the fragrances.
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