EP3118297B1 - Washing and cleaning agent containing compounds containing boron and preservatives - Google Patents

Description

The present invention relates to the use of boron-containing compounds, in particular boric acid, boronic acids and compounds derived therefrom, and salts thereof, for enhancing the effect of the preservative 2-phenoxyethanol in detergents and cleaners.

Liquid detergents are becoming increasingly important in the marketplace. Unlike solid detergents, liquid detergents often contain preservatives to kill existing microorganisms in the detergent. Otherwise, it may be due to existing microorganisms, for example, mold or phase separation, whereby the detergent would no longer be used by the consumer. Since preservatives are antimicrobial biocides, the aim is to use them in the smallest possible amounts. High concentrations of this are usually associated with low ecological compatibility.

Although great progress has been made in recent decades in that ecologically harmful ingredients, such as phosphate, are no longer used in detergents, it is still necessary to improve the environmental performance of detergents, especially liquid detergents. In this case, of course, substances which have a double effect effect, particularly interesting, since thus an overall smaller amount of raw materials must be used.

The publication WO 2012/055775 A1 relates to detergents and cleaners, comprising biocidal quaternary ammonium compounds and preferably boric acid and / or boron salt for improving performance.

It has now surprisingly been found that the boron-containing compounds according to the invention, in particular boric acid, boronic acids and compounds derived therefrom and salts thereof, can enhance the effect of preservatives and therefore make it possible to reduce their amount in the compositions without fear of loss of activity have to.

wobei
R¹ und R² jeweils unabhängig voneinander ausgewählt sind aus -OH, -Cl, -F, -Br, substituierten oder unsubstituierten C_1-8 Alkyl- oder Alkenylgruppen, substituierten oder unsubstituierten C_1-8 Heteroalkyl- oder Heteroalkenylgruppen, substituierten oder unsubstituierten Arylgruppen und substituierten oder unsubstituierten Heteroarylgruppen,
zur Verstärkung der Wirkung eines Konservierungsmittels in Wasch- und Reinigungsmitteln, wobei mindestens 2-Phenoxyethanol als ein Konservierungsmittel ausgewählt wird.In a first aspect, the present invention is therefore directed to the use of a compound of the formula (I)

in which
R ¹ and R ^{2 are} each independently selected from -OH, -Cl, -F, -Br, substituted or unsubstituted C _1-8 alkyl or alkenyl groups, substituted or unsubstituted C _1-8 heteroalkyl or heteroalkenyl groups, substituted or unsubstituted Aryl groups and substituted or unsubstituted heteroaryl groups,
for enhancing the effect of a preservative in detergents and cleaners, wherein at least 2-phenoxyethanol is selected as a preservative.

In a further aspect, the present invention is directed to a laundry or cleaning composition containing at least one of the above-described boron-containing compounds of formula (I) and at least 2-phenoxyethanol as a preservative.

In yet another aspect, the present invention is further directed to the use of such a laundry or cleaning composition for laundering textiles or cleaning solid surfaces.

In a final aspect, the present invention is directed to a process for cleaning textiles or hard surfaces, characterized in that in at least one process step, a washing or cleaning agent as described herein is used.

These and other aspects, features, and advantages of the invention will become apparent to those skilled in the art from a study of the following detailed description and claims. Any feature of one aspect of the invention may be employed in any other aspect of the invention. Further, it is to be understood that the examples contained herein are intended to describe and illustrate the invention, but not to limit it, and in particular that the invention is not limited to these examples.

The compositions described herein include all conceivable types of detergents or cleaners, both concentrates and neat agents, for use on a commercial scale, in the washing machine or in hand washing or cleaning. These include detergents for textiles, carpets, or natural fibers, for which the term detergent is used. These include, for example, dishwashing detergents for dishwashers or manual dishwashing detergents or cleaners for hard surfaces such as metal, glass, porcelain, ceramics, tiles, stone, painted surfaces, plastics, wood or leather, for which the term detergent is used, ie in addition to manual and machine Dishwashing agents, for example, scouring agents, glass cleaners, toilet scenters, etc. The washing and cleaning agents in the invention also include washing aids which are added to the actual detergent in the manual or machine textile laundry to achieve a further effect. Furthermore, laundry detergents and cleaners in the context of the invention also include textile pre-treatment and post-treatment agents, ie those agents with which the laundry item is brought into contact before the actual laundry, for example for Solving stubborn soiling, and also means that in a the actual textile laundry downstream step give the laundry further desirable properties such as comfortable grip, crease resistance or low static charge. Amongst others, the fabric softeners are calculated.

All percentages are by weight unless otherwise specified. Numeric ranges indicated in the format "from x to y" include the above values. If multiple preferred numeric ranges are specified in this format, it is understood that all ranges resulting from the combination of the various endpoints are also captured.

"At least one" as used herein refers to 1 or more, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9 or more.

The present invention is directed to the use of compounds derived from boric acid or boronic acid as boosters of the effect of the preservative 2-phenoxyethanol in detergents and cleaners.

wobei
R¹ und R² jeweils unabhängig voneinander ausgewählt sind aus -OH, -Cl, -F, -Br, substituierten oder unsubstituierten C_1-8 Alkyl- oder Alkenylgruppen, substituierten oder unsubstituierten C_1-8 Heteroalkyl- oder Heteroalkenylgruppen, substituierten oder unsubstituierten Arylgruppen und substituierten oder unsubstituierten Heteroarylgruppen.These compounds are compounds of the formula (I), or salts or esters thereof:

in which
R ¹ and R ^{2 are} each independently selected from -OH, -Cl, -F, -Br, substituted or unsubstituted C _1-8 alkyl or alkenyl groups, substituted or unsubstituted C _1-8 heteroalkyl or heteroalkenyl groups, substituted or unsubstituted Aryl groups and substituted or unsubstituted heteroaryl groups.

"Substituted," as used in connection with alkyl, alkenyl, heteroalkyl, heteroalkenyl, aryl, and heteroaryl groups, for which R ¹ and R ^{2 may} each be independently, means that the corresponding group contains one or more Substituents are substituted, each independently selected from the group consisting of -OR ', -COOR', -NR'R ", -CONR'R", -NR "COR ', -NO ₂ , -CN, halogen, C _6-14 aryl, C _2-14 heteroaryl containing 1 to 5 heteroatoms selected from O, N and S, C _3-10 cycloalkyl and C _2-10 heteroalicyclyl containing 1 to 5 heteroatoms selected from O, N and S. The Aryl, heteroaryl, containing 1 to 5 heteroatoms selected from O, N and S. The aryl, heteroaryl, cycloalkyl and heteroalicyclyl groups in turn may also be selected with one or more substituents selected from the group consisting of -OR ', -COOR', -NR ' R ", -NO ₂ , -CN, halogen, unsubstituted C _1-10 alkyl, unsubstituted C _2-10 alkenyl and unsubstituted C _2-10 alkynyl R 'and R" are each independently selected from H, unsubstituted C _1-10 alkyl, unsubstituted C _2-10 alkenyl, unsubstituted C _2-10 alkynyl, unsubstituted C _6-14 aryl, unsubstituted C _2-14 heteroaryl, unsubstituted C _3-10 cycloalkyl, unsubstituted C _2-10 heteroalicyclyl, alkylaryl, arylalkyl , Heteroarylalkyl and alkylheteroaryl.

"Alkyl" as used herein refers to linear or branched alkyl groups such as methyl, ethyl, n -propyl, iso -propyl, n -butyl, n -pentyl, n -hexyl, n -heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl and n-dodecyl and the linear C ₁₄ , C ₁₆ and C ₁₈ alkyl radicals. In various embodiments, the alkyl radicals are short chain C _1-8 alkyl radicals, especially unsubstituted, linear C _1-8 alkyl radicals. The alkyl radicals may be substituted or unsubstituted, but are preferably unsubstituted. In particular, when substituted, the substituents are selected from the group of substituents described above.

"Heteroalkyl" as used herein refers to alkyl radicals as defined above in which at least one carbon atom is replaced by a heteroatom, especially N or O, more preferably O.

"Alkenyl" as used herein refers to linear or branched alkenyl groups containing at least one C = C double bond, such as ethenyl, n-propenyl, iso-propenyl and n-butenyl, and the linear C ₆ , C ₈ , C ₁₀ , C ₁₂ , C ₁₄ , C ₁₆ and C ₁₈ alkenyl radicals. The alkenyl radicals may be substituted or unsubstituted, but are preferably unsubstituted. In particular, when substituted, the substituents are selected from the group of substituents described above.

"Heteroalkenyl" as used herein refers to alkenyl radicals as defined above in which at least one carbon atom is replaced by a heteroatom, especially N or O, more preferably O.

"Alkynyl" as used herein refers to linear or branched alkynyl groups containing at least one C≡C triple bond, such as ethynyl, propynyl, and butynyl, and the linear C ₆ , C ₈ , C ₁₀ , C ₁₂ , C ₁₄ , C ₁₆ and C ₁₈ alkynyl radicals.

"Aryl" as used herein refers to aromatic groups which may have at least one aromatic ring, but also multiple condensed rings, such as phenyl, naphthyl, anthracenyl, and the like. The aryl radicals can be substituted or unsubstituted his. When substituted, the substituents are selected from the group described above.

"Heteroaryl" as used herein refers to aryl radicals as defined above in which at least one carbon atom is replaced by a heteroatom, in particular N, S or O, more preferably O.

"Halogen" as used herein refers to fluorine, chlorine, bromine and iodine.

"Cycloalkyl" as used herein refers to non-aromatic, cyclic hydrocarbons, especially cyclic alkyl or alkenyl radicals as defined above, e.g. Cyclopentyl, cyclohexyl and cyclohexenyl radicals. When substituted, the substituents are selected from the group described above.

"Heteroalicyclyl" as used herein refers to cycloalkyl radicals as defined above in which at least one carbon atom is replaced by a heteroatom, especially N, S or O, more preferably O.

In various embodiments, in the compounds of formula (I), R ^{1 is} -OH and R ² is selected from substituted or unsubstituted C _1-8 alkyl groups, preferably C _1-4 alkyl groups. Most preferred are compounds in which R ^{2 is} a 2-aminoethoxy group.

In various embodiments, in the compounds of formula (I), R ^{1 is} -OH and R ² is selected from substituted or unsubstituted aryl groups and substituted or unsubstituted heteroaryl groups, preferably from substituted or unsubstituted phenyl groups or substituted or unsubstituted naphthyl groups or substituted or unsubstituted thienyl groups.

Particularly preferred examples of compounds of the formula (I) are ortho, meta or para-substituted phenylboronic acids and their salts and esters. Particular mention may be made of: 2-thienylboronic acid, 3-thienylboronic acid, (2-acetamidophenyl) boronic acid, 2-benzofuranylboronic acid, 1-naphthylboronic acid, 2-naphthylboronic acid, 2-formylphenylboronic acid, 3-formylphenylboronic acid, 4-formylphenylboronic acid, 4-dibenzofuranylboronic acid, 5-methyl 2 -thienylboronic acid, 2-furanylboronic acid, 3-furanylboronic acid, 4,4'-biphenyldiboronic acid, 6-hydroxy-2-naphthylboronic acid, 4- (methylthio) phenylboronic acid, 4- (trimethylsilyl) phenylboronic acid, 3-bromo-2-thienylboronic acid, 4- Methyl 2-thienylboronic acid, 5-bromo-2-thienylboronic acid, 5-chloro-2-thienylboronic acid, dimethylthienylboronic acid, 2-bromophenylboronic acid, 3-chlorophenylboronic acid, 3-methoxy-2-thienylboronic acid, p-methylphenylethylboronic acid, 2-Thianthrenylboronic acid, dibenzothienylboronic acid, 4-carboxyphenylboronic acid, 9-anthrylboronic acid, 3,5-dichlorophenylboronic acid o-chlorophenylboronic acid, p-chlorophenylboronic acid, m-bromophenylboronic acid, p-bromophenylboronic acid, p-fluorophenylboronic acid, p-tolylboronic acid, o-tolylboronic acid, cctylboronic acid, 1 , 3,5-trimethylphenylboronic acid, 3-chloro-4-fluorophenylboronic acid, 3-aminophenylboronic acid, 2,4-dichlorophenylboronic acid, 4-methoxyphenylboronic acid, as well as salts and esters of the abovementioned.

According to the present invention, the boron-containing compounds described above are used in an amount of 0.01-5% by weight, preferably 0.01-2% by weight, in detergent formulations, based on the total weight of the respective formulation.

In one embodiment, the present invention is further directed to a laundry or cleaning composition containing at least one boric acid or boronic acid compound of the formula (I) as defined herein and at least 2-phenoxyethanol as a preservative.

According to the present invention, the preservatives described above are used in an amount of 0.0001-2% by weight, preferably in an amount of 0.001-1% by weight in detergent formulations, based on the total weight of the respective formulation. Since the combination of the boron-containing compound of formula (I) the effect strengthened said preservative, the amount of preservatives compared to conventional formulations can be reduced without negatively affecting the preserving properties.

In addition to the boron-containing compounds described herein and 2-phenoxyethanol as at least one preservative, the washing or cleaning agent may also contain other ingredients that further improve the performance and / or aesthetic properties of the detergent or cleaning agent. In the context of the present invention, the washing or cleaning agent contains at least one or preferably several substances from the group of enzymes, surfactants, bleaching agents, complexing agents, builders, electrolytes, nonaqueous solvents, pH adjusters, perfumes, perfume carriers, fluorescers, dyes, hydrotropes, Foam inhibitors, silicone oils, anti-redeposition agents, graying inhibitors, anti-shrinkage agents, anti-crease agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, corrosion inhibitors, antistatic agents, bittering agents, ironing aids, repellents and impregnating agents, swelling and anti-slip agents, plasticizing components and UV absorbers.

The washing or cleaning agent preferably contains at least one surfactant. Suitable surfactants are, in particular, anionic surfactants, nonionic surfactants and mixtures thereof, but also cationic, zwitterionic and amphoteric surfactants.

in der R' und R" unabhängig H oder Alkyl sind und zusammen 9 bis 19, vorzugsweise 9 bis 15 und insbesondere 9 bis 13 C-Atome enthalten. Ein ganz besonders bevorzugter Vertreter ist Natriumdodecylbenzylsulfonat.In various embodiments, the agent comprises at least one alkylbenzenesulfonate. Such alkylbenzenesulfonates are preferably selected from linear or branched alkylbenzenesulfonates of the formula

in which R 'and R "are independently H or alkyl and together contain 9 to 19, preferably 9 to 15 and in particular 9 to 13 C atoms A particularly preferred representative is sodium dodecylbenzylsulfonate.

Further, the agents may comprise at least one alkyl ether sulfate. Preferred alkyl ether sulfates are those of the formula

R ^{1 is} -O- (AO) _n -SO ₃ ^- X ⁺ (III).

In this formula (III), R ^{1 is} a linear or branched, substituted or unsubstituted alkyl radical, preferably a linear, unsubstituted alkyl radical, more preferably a fatty alcohol radical. Preferred radicals R ¹ are selected from decyl, undecyl, dodecyl, tridecyl, Tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl and mixtures thereof, wherein the even number of C atoms are preferred. Particularly preferred radicals R ¹ are derived from C ₁₂ -C ₁₈ fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or C ₁₀ -C ₂₀ oxo alcohols.

AO represents an ethylene oxide (EO) or propylene oxide (PO) moiety, preferably an ethylene oxide moiety. The index n stands for an integer from 1 to 50, preferably from 1 to 20 and especially from 2 to 10. Most preferably, n stands for the numbers 2, 3, 4, 5, 6, 7 or 8. X stands for a monovalent cation or the nth part of an n-valent cation, the alkali metal ions are preferred, and Na ⁺ or K ⁺ including Na, with Na ^{+ being} extremely preferred. Other cations X + may be selected from NH ₄ ⁺ , ½Zn ²⁺ , ½Mg ²⁺ , ½Ca ²⁺ , ½Mn ²⁺ , and mixtures thereof.

mit k = 11 bis 19, n = 2, 3, 4, 5, 6, 7 oder 8. Ganz besonders bevorzugte Vertreter sind C_12-14 Fettalkoholethersulfate mit 2 EO (k = 11-13, n = 2) und dabei insbesondere deren Na-Salze. Der angegebenen Ethoxylierungsgrad stellt einen statistischen Mittelwert dar, der für ein spezielles Produkt eine ganze oder eine gebrochene Zahl sein kann.Particularly preferred agents may further comprise an alkyl ether sulfate selected, in particular, from fatty alcohol ether sulfates of the formula

with k = 11 to 19, n = 2, 3, 4, 5, 6, 7 or 8. Very particularly preferred representatives are C _12-14 fatty alcohol _ether sulfates with 2 EO (k = 11-13, n = 2) and in particular their Na salts. The stated degree of ethoxylation represents a statistical average that may be an integer or a fractional number for a particular product.

R²

für einen linearen oder verzweigten, substituierten oder unsubstituierten Alkylrest,

AO

für eine Ethylenoxid- (EO) oder Propylenoxid- (PO) Gruppierung,

m

für ganze Zahlen von 1 bis 50 stehen.

In various embodiments, the agents comprise at least one nonionic surfactant, in particular at least one fatty alcohol alkoxylate. Preferred agents therefore contain at least one nonionic surfactant of the formula

R ^{2 is} -O- (AO) _m -H (V),

in the

R ²

a linear or branched, substituted or unsubstituted alkyl radical,

AO

for an ethylene oxide (EO) or propylene oxide (PO) grouping,

m

stand for integers from 1 to 50.

In the abovementioned formula (V), R ^{2 is} a linear or branched, substituted or unsubstituted alkyl radical, preferably a linear, unsubstituted alkyl radical, particularly preferably a fatty alcohol radical. Preferred radicals R ² are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, Nonadecyl, eicosyl and mixtures thereof, wherein the even number of C atoms are preferred. Particularly preferred radicals R ² are derived from C ₁₂ -C ₁₈ -fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or C ₁₀ -C ₂₀ -oxo alcohols.

AO represents an ethylene oxide (EO) or propylene oxide (PO) moiety, preferably an ethylene oxide moiety. The subscript m is an integer from 1 to 50, preferably from 1 to 20 and especially from 2 to 10. Most preferably, m is the numbers 2, 3, 4, 5, 6, 7 or 8.

mit k = 11 bis 19, m = 2, 3, 4, 5, 6, 7 oder 8. Ganz besonders bevorzugte Vertreter sind C_12-18 Fettalkohole mit 7 EO (k = 11-17, m = 7 in Formel (VI)).In summary, particularly preferred fatty alcohol alkoxylates are those of the formula

with k = 11 to 19, m = 2, 3, 4, 5, 6, 7 or 8. Very particularly preferred representatives are C _12-18 fatty alcohols with 7 EO (k = 11-17, m = 7 in formula (VI )).

Other nonionic surfactants which may be included in the described compositions within the meaning of the present invention include, but are not limited to, alkyl glycosides, alkoxylated fatty acid alkyl esters, amine oxides, fatty acid alkanolamides, hydroxy mixed ethers, sorbitan fatty acid esters, polyhydroxy fatty acid amides, and alkoxylated alcohols.

In various embodiments, the amount of surfactants based on the weight of the agent is 1 to 40 wt.%, Preferably 2 to 30 wt.%, More preferably 5 to 30 wt.%, Most preferably 12 to 27 wt. ,

It may be advantageous in particular for the cold washing performance of detergents if the agents additionally contain soap (s). Preferred detergents are therefore characterized in that they contain, based on their weight, from 0.25 to 15% by weight, preferably from 0.5 to 12.5% by weight, more preferably from 1 to 10% by weight, still further preferably from 1.5 to 7.5% by weight and in particular from 2 to 6% by weight of soap (s). Particularly preferred are soaps of C ₁₂ -C ₁₈ fatty acids.

The agent preferably contains at least one enzyme. In principle, all the enzymes established in the prior art for this purpose can be used in this regard. Preferably, it is one or more enzymes that can develop a catalytic activity in a detergent, in particular an amylase, lipase, cellulase, hemicellulase, mannanase, pectin-splitting enzyme, tannase, xylanase, xanthanase, ß-glucosidase, carrageenase, perhydrolase , Oxidase, oxidoreductase and their mixtures. Preferred hydrolytic enzymes include in particular Amylases, in particular α-amylases, cellulases, lipases, hemicellulases, in particular pectinases, mannanases, β-glucanases, and mixtures thereof. Particularly preferred are amylases and / or lipases and mixtures thereof. These enzymes are basically of natural origin; Starting from the natural molecules, improved variants are available for use in detergents or cleaning agents, which are preferably used accordingly.

The enzymes to be used may also be formulated together with accompanying substances, for example from the fermentation, or with stabilizers.

Suitable builders which may be present in the composition are, in particular, silicates, aluminum silicates (in particular zeolites), carbonates, salts of organic di- and polycarboxylic acids and mixtures of these substances.

Organic builders which may be present in the composition are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. For example, these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, and mixtures of these. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof.

As builders further polymeric polycarboxylates are suitable. These are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example, those having a molecular weight of 600 to 750,000 g / mol.

Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of from 1,000 to 15,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molecular weights of from 1,000 to 10,000 g / mol, and particularly preferably from 1,000 to 5,000 g / mol, may again be preferred from this group.

Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. To improve the water solubility, the polymers may also contain allylsulfonic acids, such as allyloxybenzenesulfonic acid and methallylsulfonic acid, as a monomer.

In liquid detergents, in particular washing or dishwashing detergents, soluble builders, such as, for example, citric acid, or acrylic polymers having a molar mass of from 1,000 to 5,000 g / mol are preferably used.

Liquid or gelled agents preferably contain water as the main solvent. It is preferred that the agent more than 5 wt .-%, preferably more than 15 wt .-% and particularly preferably more than 25 wt .-%, each based on the total amount of detergent, water. Particularly preferred liquid agents contain - based on their weight - 5 to 90 wt .-%, preferably 10 to 85 wt .-%, particularly preferably 25 to 75 wt .-% and in particular 35 to 65 wt .-% water. Alternatively, the agents may be low to anhydrous, the level of water in a preferred embodiment being less than 10% by weight, and more preferably less than 8% by weight, based on the total liquid agent ,

In addition, non-aqueous solvents may be added to the composition. Suitable non-aqueous solvents include mono- or polyhydric alcohols, alkanolamines or glycol ethers, provided that they are miscible with water in the specified concentration range. Preferably, the solvents are selected from ethanol, n-propanol, i-propanol, butanols, glycol, propanediol, butanediol, methylpropanediol, glycerol, diglycol, propyldiglycol, 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 ether, propylene glycol ethyl ether, propylene glycol propyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, methoxytriglycol, ethoxytriglycol, butoxytriglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol t-butyl ether, di-n-octyl ether and mixtures thereof Solvent.

The liquid agents described herein may be filled into a water-soluble wrapper and thus be part of a water-soluble wrapper. When the liquid agent is packaged in a water-soluble casing, it is preferred that the content of water is less than 10% by weight based on the total liquid agent and that anionic surfactants, if present, are in the form of their ammonium salts.

The neutralization with amines, unlike bases such as NaOH or KOH, does not lead to the formation of water. Thus, low-water liquid agents can be prepared which are directly suitable for use in water-soluble coatings.

A water-soluble packaging contains, in addition to the liquid agent, a water-soluble coating. The water-soluble coating is preferably formed by a water-soluble film material.

Such water-soluble packages can be made by either vertical fill-seal (VFFS) or thermoforming techniques.

The thermoforming process generally includes forming a first layer of water-soluble sheet material to form protrusions for receiving a composition therein, filling the composition into the protrusions, covering the composition-filled protrusions with a second layer of water-soluble sheet material, and sealing the first and second layers at least around the bulges.

The water-soluble coating is preferably formed from a water-soluble film material selected from the group consisting of polymers or polymer blends. The wrapper may be formed of one or two or more layers of the water-soluble film material. The water-soluble film material of the first layer and the further layers, if present, may be the same or different.

The water-soluble package comprising the liquid agent and the water-soluble envelope may have one or more chambers. The liquid agent may be contained in one or more chambers, if present, of the water-soluble coating. The amount of liquid agent preferably corresponds to the full or half dose needed for a wash or rinse cycle.

It is preferable that the water-soluble coating contains polyvinyl alcohol or a polyvinyl alcohol copolymer.

Suitable water-soluble films for producing the water-soluble coating are preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer whose molecular weight is in the range of 10,000 to 1,000,000 gmol ^-1 , preferably 20,000 to 500,000 gmol ^-1 , more preferably 30,000 to 100,000 gmol ^-1 and especially from 40,000 to 80,000 gmol ^-1 .

A suitable for preparing the water-soluble coating sheet material may additionally polymers, selected from the group comprising acrylic acid-containing polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters, polyether polylactic acid, and / or mixtures of the above polymers may be added.

Preferred polyvinyl alcohol copolymers include, in addition to vinyl alcohol, dicarboxylic acids as further monomers. Suitable dicarboxylic acids are itaconic acid, malonic acid, succinic acid and mixtures thereof, with itaconic acid being preferred.

Likewise preferred polyvinyl alcohol copolymers include, in addition to vinyl alcohol, an ethylenically unsaturated carboxylic acid, its salt or its esters. Particularly preferably contain such Polyvinyl alcohol copolymers in addition to vinyl alcohol, acrylic acid, methacrylic acid, acrylic acid esters, methacrylic acid esters or mixtures thereof.

Suitable water-soluble films for use in the casings of the water-soluble packaging according to the invention are films sold by the company MonoSol LLC, for example under the designation M8630, C8400 or M8900. Other suitable films include films named Solublon® PT, Solublon® GA, Solublon® KC or Solublon® KL from Aicello Chemical Europe GmbH or the films VF-HP from Kuraray.

The water-soluble packages may have a substantially dimensionally stable spherical and pillow-shaped configuration with a circular, elliptical, square or rectangular basic shape.

The water soluble package may include one or more chambers for storing one or more agents. If the water-soluble package has two or more chambers, at least one chamber contains the liquid agent. The further chambers may each contain a solid or a liquid agent.

Another subject of the invention is the use of an agent described herein for cleaning or washing textiles or for cleaning hard surfaces.

A further subject of the invention is a method for the cleaning of textiles or hard surfaces, which is characterized in that in at least one method step a means described herein is used.

These include both manual and mechanical processes, with mechanical processes being preferred. Methods for cleaning textiles are generally distinguished by the fact that various cleaning-active substances are applied to the items to be cleaned and washed off after the contact time, or that the items to be cleaned are otherwise treated with a detergent or a solution or dilution of this product. The same applies to processes for cleaning all other materials than textiles, especially hard surfaces. All conceivable washing or cleaning methods can be enriched in at least one of the method steps by the use of a washing or cleaning agent described herein and then represent embodiments of the present invention.

All aspects, objects, and embodiments described for means described herein are also applicable to the aforementioned methods and uses. Therefore, at this point, the disclosure in the appropriate place with the reference that this disclosure also applies to the above described methods and uses.

Examples Example 1:

Table 1: Detergent formulation connection basic formulation Active substance [ % by weight ] water rest surfactants 20.1 Builder (citric acid, phosphonates) 4.06 preservative according to column C of Tables 2 & 3 propanediol 3.0 enzymes 0.085

The results of the challenge test method as preservation test are shown in Tables 2 and 3: <b> Table 2: Freshly prepared compositions </ b> Sample no. * preservative preservation test Surname C [ % by weight ] pH B F Res. Cat. V1 2-phenoxyethanol 0.7 8.6 7 > 27 nb / E1 MEA-Borate 1.64 8.8 7 7 b. A 2-phenoxyethanol 0.7 E2 MEA-Borate 2.46 8.7 7 7 b. A 2-phenoxyethanol 0.7 E3 MEA-Borate 3.28 8.7 7 7 b. A 2-phenoxyethanol 0.7 Sample no. * preservative preservation test Surname C [ % by weight ] pH B F Res. Cat. V2 2-phenoxyethanol 0.7 8.6 7 > 28 nb / E4 MEA-Borate 1.64 8.3 14 7 b. A 2-phenoxyethanol 0.7 E5 MEA-Borate 2.46 8.3 7 7 b. A 2-phenoxyethanol 0.7 E6 MEA-Borate 3.28 8.4 7 7 b. A 2-phenoxyethanol 0.7 * Samples V1, V2 = comparative sample 1, comparison sample 2; Samples E1, E2, E3, E4, E5 and E6 = samples 1, 2, 3, 4, 5, and 6 according to the invention.
B = bacteria
F = mushrooms
Res. = Result b. = passed nb = failed
Cat. = Criterion A, B or C of the challenge test

Principle of the Challenge Test Method

The method is used to test the stability of raw materials, premixes and end products against microbial spoilage.

Basically, for the test method freshly prepared detergent formulations and stored detergent formulations (usually 12 weeks storage) can be examined in a so-called challenge test. Similar results were also obtained with corresponding stored samples (4 weeks for 40 ° C).

The sample to be examined was artificially inoculated with representative bacteria and fungi (contaminated). The death of the microorganisms was monitored quantitatively at defined test times.

specification

Conservation of the samples is considered sufficient if in the Standard Challenge Test the vaccine colonies (bacteria and fungi) are killed within 35 days at <10 cfu / g.

The microbial cells from the vaccinated formulation were measured at defined intervals for a period of 4 weeks. Each time viable cell counts were calculated and compared to the minimum requirements of the test series. This evaluation of the standard challenge test and the categorization was carried out schematically illustration 1

All ABC criteria according to illustration 1 basically show the effectiveness of the preservative as a function of time. All products with an ABC level are sufficiently conserved and pass the test. Category C means that the preservative must be used in high concentrations to ensure appropriate activity and product stability. However, high concentrations are usually associated with lower ecological compatibility.

It turns out that the sample without MEA borate (monoethanolamine borate) with only 0.7% phenoxyethanol as a preservative fresh and after storage does not pass the challenge test. Only with the addition of MEA borate can a sufficient microbiological result be achieved.

Claims (10)

1. The use of a compound of formula (I)

   

   wherein
   R¹ and R², independently of one another, are selected from -OH, -Ci, -F, -Br, substituted or unsubstituted C_1-8 alkyl or alkenyl groups, substituted or unsubstituted C_1-8 heteroalkyl or heteroalkenyl groups, substituted or unsubstituted aryl groups and substituted or unsubstituted heteroaryl groups, for increasing the effect of a preservative in washing and cleaning agents, wherein at least 2-phenoxyethanol is selected as a preservative.
2. The use according to claim 1, wherein R¹ is -OH and R² is selected from substituted or unsubstituted C_1-8 alkyl groups, preferably substituted or unsubstituted C_1-4 alkyl groups.
3. The use according to one of claims 1 or 2, wherein R¹ is -OH and R² is a 2-aminoethoxy group.
4. The use according to claim 1, wherein R¹ is -OH and R² is selected from substituted or unsubstituted aryl groups and substituted or unsubstituted heteroaryl groups.
5. The use according to claim 4, wherein R¹ is -OH and R² is selected from substituted or unsubstituted phenyl groups, substituted or unsubstituted naphthyl groups and substituted or unsubstituted thienyl groups.
6. The use of a compound according to one of claims 1 to 5, wherein the compound is used in an amount of from 0.01 to 5 wt.%, preferably from 0.01 to 2 wt.%.
7. A washing or cleaning agent containing at least one compound of formula (I) as defined in claim 1 and at least 2-phenoxyethanol as a preservative.
8. The washing or cleaning agent according to claim 7, further containing at least one substance, preferably a plurality of substances, from the group of enzymes, surfactants, bleaching agents, complexing agents, builders, electrolytes, non-aqueous solvents, pH adjusters, perfumes, perfume carriers, fluorescing agents, dyes, hydrotropic substances, suds suppressors, silicone oils, anti-redeposition agents, graying inhibitors, anti-shrink agents, anti-crease agents, dye transfer inhibitors, antimicrobial active ingredients, germicides, fungicides, antioxidants, corrosion inhibitors, antistatic agents, bittering agents, ironing aids, repellents and impregnating agents, anti-swelling and anti-slip agents, softening components and UV absorbers.
9. The use of a washing or cleaning agent according to one of claims 7 or 8 for washing textiles or cleaning hard surfaces.
10. A method for cleaning textiles or hard surfaces, characterized in that a washing or cleaning agent according to one of claims 7 or 8 is used in at least one method step.

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