EP2430137A1 - Color-protecting washing or cleaning agent - Google Patents
Color-protecting washing or cleaning agentInfo
- Publication number
- EP2430137A1 EP2430137A1 EP10716362A EP10716362A EP2430137A1 EP 2430137 A1 EP2430137 A1 EP 2430137A1 EP 10716362 A EP10716362 A EP 10716362A EP 10716362 A EP10716362 A EP 10716362A EP 2430137 A1 EP2430137 A1 EP 2430137A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- benzoxazine
- compounds
- polymer
- general formula
- formula
- 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
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Classifications
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0021—Dye-stain or dye-transfer inhibiting compositions
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
- C11D3/3776—Heterocyclic compounds, e.g. lactam
Definitions
- the present invention relates to the use of polymers which are accessible by polymerization of benzoxazines, as dye transfer inhibiting agents in the washing and / or cleaning of textiles and detergents or cleaners containing such color transfer inhibiting polymers.
- Detergents and cleaners in addition to the indispensable for the washing or cleaning process ingredients such as surfactants and builders usually other ingredients that can be summarized under the term washing aids and the different drug classes such as foam regulators, grayness inhibitors, bleach, bleach activators and enzymes include.
- auxiliaries also include substances which are intended to prevent dyed textile fabrics from causing a changed color impression after washing. This color impression change washed, i. Cleaner, textiles can be based on the fact that dye components are removed by the washing or cleaning process from the textile ("fading"), on the other hand can be deposited by differently colored textiles dyes on the textile ("discoloration"). The discoloration aspect may also play a role in undyed laundry items when washed together with colored laundry items.
- detergents In order to avoid these unwanted side effects of removing dirt from textiles by treatment with usually surfactant-containing aqueous systems, detergents, especially if they are provided as so-called color or colored laundry detergents for colored textiles, contain active ingredients that prevent the detachment of dyes from the textile or At least the deposition of detached, located in the wash liquor to avoid dyes on textiles.
- many of the commonly used polymers have such a high affinity for dyes that they draw more of them from the dyed fiber, resulting in loss of color when used. The same applies to cleaning hard surfaces.
- benzoxazine (co) polymers lead to unexpectedly high color transfer inhibition when used in detergents or cleaners. Particularly pronounced is the prevention of dyeing of white or other colored fabrics by washed out of textiles dyes. It is conceivable that the benzoxazine (co) polymers defined below are applied to the textiles during washing and thereby effectively prevent the dyes from being removed from the textiles and, secondly, they have a repellent effect on dye molecules already present in the liquor.
- the invention relates to the use of polymers which are obtainable by polymerization of benzoxazine monomers, to avoid the transfer of textile dyes of dyed textiles to undyed or differently colored textiles in their common washing in particular surfactant-containing aqueous solutions.
- the benzoxazine (co) polymers used according to the invention can be obtained in a basically known manner by polymerization of benzoxazines.
- the benzoxazine compounds which can be used to prepare the benzoxazine (co) polymers used in the present invention are polymerizable monomers comprising at least one benzoxazine group.
- Preferred monomers may preferably comprise up to four benzoxazine groups, it being possible to use both individual monomers and mixtures of two or more monomers for the preparation of benzoxazine (co) polymers used according to the invention.
- Polymerization of the polymerizable benzoxazine compound (to the benzoxazine polymer) or mixture of various polymerizable benzoxazine compounds (to the benzoxazine copolymer) can be accomplished by methods known in the art, for example, at elevated temperatures according to a self-initiating mechanism (thermal polymerization) or by addition of cationic initiators .
- Suitable cationic initiators are, for example, Lewis acids or other cationic initiators, for example metal halides, organometallic reagents, such as metalloporphyrins, methyl tosylates, methyltriflates or trifluorosulphonic acids.
- basic reagents can be used to initiate the polymerization of the polymerizable benzoxazine compound or the mixture of various polymerizable benzoxazine compounds.
- Suitable basic reagents may for example be selected from imidazole or imidazole derivatives.
- the thermal polymerization is carried out usually at temperatures of 150 0 C to 300 0 C, in particular at temperatures of 160 0 C to 220 0 C. By using the above-mentioned initiators and / or other reagents, the polymerization temperature may also be lower.
- the polymerization process is based essentially on the thermally-induced ring opening of the oxazine ring of a benzoxazine system
- the polymerizable benzoxazine compound is selected from compounds of the general formula (I) or from compounds of the general formula (II) or mixtures of these, q formula (I),
- n is a number from 2 to 20,000, preferably from 3 to 10,000, particularly preferably from 4 to 8,000 and in particular from 5 to 7,000,
- R in each repeating unit is independently selected from hydrogen or linear or branched, optionally substituted alkyl groups comprising from 1 to 8 carbon atoms,
- R 1 is a covalent bond or is a divalent linking group comprising 1 to 100 carbon atoms
- R 2 is selected from hydrogen, halogen, alkyl and alkenyl, or R 2 is a divalent radical which renders the benzoxazine structure a corresponding naphthoxazine structure;
- R 5 is selected from hydrogen, halogen, alkyl and alkenyl, or R 5 is a divalent radical which makes a corresponding naphthoxazine structure from the benzoxazine structure and R 6 is a covalent bond or is a divalent linking group containing 1 to 100 Carbon atoms.
- R in each repeating unit is independently selected from hydrogen and methyl.
- the divalent organic compound groups R 1 in formula (I) and / or R 6 in formula (II) preferably comprise 2 to 50, particularly preferably 2 to 25 and in particular 2 to 20 carbon atoms. Furthermore, the divalent organic compound groups R 1 and R 6 may each be selected from linear or branched, optionally substituted alkylene groups comprising 1 to 15 carbon atoms, wherein the alkylene groups are optionally interrupted by at least one heteroatom selected from oxygen, sulfur or nitrogen.
- the term "interrupted" means that in a divalent alkylene group at least one non-terminal carbon atom of said group is replaced by a heteroatom, the heteroatom preferably being selected from -S- (sulfur), -O - (oxygen), and -NR a - (nitrogen), wherein R a is in particular hydrogen or a linear or branched, optionally substituted alkyl groups having 1 to 15 carbon atoms.
- the divalent organic linking groups R 1 and / or R 6 are selected from alkylene groups comprising 2 to 8 C atoms.
- R 1 and / or R 6 is selected from linear alkylene groups comprising from 2 to 6, especially 2 or 3, carbon atoms, such as ethylene, propylene, butylene, pentylene and hexylene groups.
- R 1 in formula (I) and / or R 6 in formula (II) may be a covalent bond.
- the divalent organic linking groups R 1 and / or R 6 may comprise at least one arylene group and / or at least one biphenylene group, each preferably containing from 6 to 12 carbon atoms.
- the arylene groups and biphenylene groups may be substituted or unsubstituted, suitable substituents being selected, for example, from alkyl, alkenyl, halogen, amine, thiol, carboxyl and hydroxyl groups.
- at least one carbon atom of the aromatic ring system of said groups can be replaced by a heteroatom, wherein the heteroatom is preferably selected from oxygen, nitrogen and sulfur.
- the radicals R 2 and R 5 in formula (I) and formula (II) are preferably each hydrogen and methyl.
- the radical A in formula (II) represents a hydroxyl group or a nitrogen-containing heterocycle.
- nitrogen-containing heterocycle is understood in particular to mean those ring systems which contain 3 to 8 ring atoms, preferably 5 to 6 ring atoms, where the ring system comprises at least one nitrogen atom and at least two carbon atoms.
- Said nitrogen-containing heterocycle can have a saturated, unsaturated or aromatic structure and, in addition to the abovementioned atoms, also comprise further heteroatoms, for example sulfur and / or oxygen atoms.
- the nitrogen-containing heterocycle is connected according to formula (II) via the divalent compound group R 6 with the nitrogen atom of the oxazine ring of the benzoxazine structure.
- the divalent linking group R 6 may be linked to any nitrogen or carbon ring atom of the nitrogen-containing heterocycle by R 6 formally replacing a hydrogen atom covalently linked to a nitrogen or carbon ring atom.
- nitrogen-containing heterocycles are selected, for example, from 5-membered nitrogen-containing heterocycles such as imidazoles, imidazolidones, tetrazoles, oxazoles, pyrroles, pyrrolidines and pyrazoles or 6-membered nitrogen-containing heterocycles such as piperidines, piperidones, piperazines, pyridines, diazines and morpholines.
- 5-membered nitrogen-containing heterocycles such as imidazoles, imidazolidones, tetrazoles, oxazoles, pyrroles, pyrrolidines and pyrazoles
- 6-membered nitrogen-containing heterocycles such as piperidines, piperidones, piperazines, pyridines, diazines and morpholines.
- the polymerizable benzoxazine compounds of the general formula (I) are selected from compounds of the general formula (III)
- x is a number between 0 and 1000 and y is a number between 0 and 1000, with the proviso that x + y> 2, where Z, R 2 , Y and q are each as defined above in formula (I).
- n and / or x + y therefore takes as the lower limit a value of at least 3, 4, 6, 10, 12, 14, 16, 18, 20, 25, 30, 35, 40, 50, 60, 80, 100, 150 or 200.
- a useful upper limit for n and / or x + y in the benzoxazine compounds of the general formula (I) or (III) according to the invention is preferably at a value of at most 10,000, 2000, 1800, 1600, 1400, 1200, 1000, 800, 600 or 400.
- benzoxazine compounds of the general formula (II) are selected from compounds of the general formula (IV) and / or from compounds of the general formula (V)
- R 7 and R 8 are each independently selected from hydrogen, halogen, linear or branched, optionally substituted alkyl groups, alkenyl groups and aryl groups, wherein c, B, R 5 and R 6 are each as defined above in formula (II).
- R 7 and R 8 in formula (IV) are independently selected from hydrogen, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl and iso-butyl, where R 7 and R 8 are in particular hydrogen or methyl.
- Particularly preferred benzoxazine compounds of the general formula (IV) are selected from the following benzoxazine compounds:
- the illustrated benzoxazine compounds bearing an imidazole ring as a nitrogen-containing heterocycle can be obtained, for example, by the reaction of a phenolic compound with an aldehyde such as formaldehyde and an aminoalkylimidazole compound.
- Suitable phenolic compounds can be selected, for example, from mono- or biphenolic compounds such as phenol, bisphenol A, bisphenol F, bisphenol S or thiodiphenol.
- aldehyde in addition to formaldehyde and paraformaldehyde trioxane or polyoxymethylene or any mixtures thereof may be used.
- preferred aminoalkylimidazole compounds have a primary amino group and can be selected, for example, from compounds of general formula (VI)
- R 6 , R 7 and R 8 are as defined above.
- Suitable 1-aminoalkylimidazole compounds of general formula (VII) are known in the art and are commercially available. Examples are about 1- (3-aminopropyl) imidazole, available under the tradename Lupragen® API from BASF SE, 3-imidazol-1-yl-2-methylpropylamine (Chem Pacific), 2-methyl-1H-imidazole-1-propanannine, (3B Scientific Corporation), 3 - imidazol-1-yl-2-hydroxypropylannin (Ambinter, Paris Collection), 1- (4-aminobutyl) innidazole (Ambinter, Paris), 2-ethyl-1H-imidazole-1-propanannine (ChemBridge Corp.).
- 2-Aminoalkylimidazole compounds of the general formula (VIII) are also known from the prior art.
- the preparation can be carried out by means of common organic synthesis methods.
- a workable synthesis is described, for example, in Tetrahedron 2005, Vol. 61, at pages 11148-11155.
- the illustrated benzoxazine compounds bearing a free hydroxyl group can be prepared by reacting a phenolic compound with an aldehyde such as formaldehyde and an aminoalcohol.
- the reaction time can vary from a few minutes to a few hours.
- Suitable amino alcohols such as 2-aminoethanol, 3-amino-1-propanol, amino-2-propanol, 4-amino-1-butanol, 2-amino-1-butanol, 4-amino-2-butanol, 5-amino 1-pentanol, 6-amino-1-hexanol, 7-amino-1-heptanol, 3-amino-1,2-propanediol, 2- (2-aminoethoxy) ethanol and 2-amino-1,3-propanediol are commercially available and can be obtained, for example, from Sigma-Aldrich or Tokyo Chemical Industry.
- the polymerizable benzoxazine compounds can be used either alone or in any possible combination for the preparation of the benzoxazine (co) polymer used according to the invention.
- the weight ratio of the at least one polymerizable benzoxazine compound of the general formula (I) to the at least one polymerizable benzoxazine compound of the general formula (II) is preferably between 10: 1 and 1:10, particularly preferably between 5: 1 and 1: 5 and in particular between 2: 1 and 1: 2, wherein a weight ratio of 1: 1 may be particularly useful.
- a mixture is prepared for the preparation of the benzoxazine (co) polymer used in accordance with the invention
- the weight ratio of the at least one polymerizable benzoxazine compound of the general formula (I) to the at least one polymerizable benzoxazine compound of the general formula (IV) is preferably between 10: 1 and 1:10, particularly preferably between 5: 1 and 1: 5 and in particular between 2: 1 and 1: 2, wherein a weight ratio of 1: 1 may be particularly useful.
- At least one polymerizable benzoxazine compound of the general formula (V) comprises.
- the weight ratio of the at least one polymerizable benzoxazine compound of the general formula (I) to the at least one polymerizable benzoxazine compound of the general formula (V) is preferably between 10: 1 and 1:10, more preferably between 5: 1 and 1: 5 and in particular between 2: 1 and 1: 2, wherein a weight ratio of 1: 1 may be particularly useful.
- the proportion of the polymerizable benzoxazine compound of the general formula (I) in the total amount of the polymerizable benzoxazine compounds is preferably from 5 to 90% by weight, particularly preferably from 10 to 80% by weight and very particularly preferably from 25 to 50% by weight.
- the proportion of the polymerizable benzoxazine compound of the general formula (IV) is preferably 5 to 90 wt .-%, particularly preferably 10 to 80 wt .-% and very particularly preferably 25 to 50 wt .-% and the proportion of the polymerizable benzoxazine compound of the general formula (IV) is preferably 5 to 90 wt .-%, particularly preferably 10 to 80 wt .-% and most preferably 25 to 50 wt. -%, in each case based on the total amount of polymerizable benzoxazine compounds.
- Suitable benzoxazine compounds are preferably described by formula (B-XVIII),
- R 1 is selected from the group consisting of hydrogen, alkyl, alkenyl and aryl and R 4 is selected from the group consisting of hydrogen, halogen, alkyl and alkenyl, or R 4 is a divalent radical selected from the benzoxazine Structure makes a corresponding naphthoxazine structure.
- Preferred benzoxazine compounds are furthermore compounds of the general formula (B-IXX),
- benzoxazine compounds are furthermore compounds of the general formula (B-XX) to (B-XXII),
- R 1 and R 4 are as defined above and R 3 and R 2 ' are defined as R 1 .
- the benzoxazine compounds shown are commercially available and are described i.a. by Huntsman Advanced Materials; Georgia-Pacific Resins, Inc. and Shikoku Chemicals Corporation, Chiba, Japan. Regardless, the benzoxazine compounds may also be obtained by reacting a phenolic compound such as bisphenol A, bisphenol F, bisphenol S or thiophenol with an aldehyde such as formaldehyde in the presence of a primary amine. Suitable preparation processes are disclosed, for example, in US Pat. No. 5,543,516, in particular in Examples 1 to 19 in Columns 10 to 14, where the reaction time of the corresponding reaction may take from a few minutes to a few hours, depending on the concentration, reactivity and reaction temperature.
- a phenolic compound such as bisphenol A, bisphenol F, bisphenol S or thiophenol
- aldehyde such as formaldehyde
- the benzoxazine (co) polymer used according to the invention has a linear or branched structure. Linear structures are preferred for their high water solubility and good interaction with a variety of surfaces.
- the weight-average molecular weight "M w " of the benzoxazine (co) polymers used according to the invention is preferably between 500 and 100,000 g / mol, particularly preferably between 1,000 and 100,000 g / mol and very particularly preferably between 3,000 and 50,000 g / mol.
- the weight-average molecular weight can be determined by gel permeation chromatography (GPC) using polystyrene as standard.
- the benzoxazine (co) polymers obtainable by polymerization from the benzoxazine compounds are used as such according to the invention as color transfer inhibitors.
- the alkylation can be carried out in a manner known per se.
- the benzoxazine (co) polymer is introduced either as a pure substance or as a solution or as a dispersion or emulsion and mixed with the respective alkylating agent or a mixture of different alkylating agents.
- the reaction can be carried out in alcoholic solution, for example in ethanol or isopropanol, it also being possible to work in the presence of inert emulsifiers or dispersants.
- the particular reaction conditions and the amount of alkylating agent are preferably chosen so that at least 5% of all nitrogen atoms, based on the total number of nitrogen atoms in the benzoxazine (co) polymer, are converted into permanently quaternary nitrogen atoms.
- Suitable alkylating agents in this context are preferably alkyl halides, dialkyl sulfates, dialkyl carbonates and alkylene oxides, such as, for example, ethylene oxide - the latter in the presence of dialkyl phosphates.
- the alkylation is carried out with methyl iodide and / or dialkyl sulfates.
- Benzoxazine (co) polymer with permanently quaternary nitrogen atoms are referred to in the context of the present invention as cationic benzoxazine (co) polymers.
- the desired color transfer inhibiting effect occurs except in the washing process in the narrower sense, if one brings the above-defined polymers which are accessible by polymerization of benzoxazines in a Wambasenach aspects Kunststoff, for example as part of a fabric softener, in contact with the textile and the textile thus treated in the next washing process, which can be carried out with a polymer containing the polymer used according to the invention or one which is free of it, in the presence of different colored laundry washes.
- Another object of the invention is therefore a color-protective cleaning, washing or laundry aftertreatment agent containing a dye transfer inhibitor in the form of a polymer as defined above.
- An agent according to the invention preferably contains from 0.01% by weight to 10% by weight, in particular from 0.1% by weight to 1% by weight, of said polymer.
- the polymers used in the present invention contribute to both of the above-mentioned aspects of color constancy, that is, they reduce both discoloration and fading, although the effect of preventing staining, especially when washing white textiles, is most pronounced.
- Another object of the invention is therefore the use of a corresponding polymer to prevent the change in the color impression of textiles in their washing in particular surfactant-containing aqueous solutions. By changing the color impression is by no means the difference between dirty and clean textile to understand, but the color difference between each clean textile before and after the washing process.
- Another object of the invention is a process for washing dyed textiles in surfactant-containing aqueous solutions, which is characterized in that one uses a surfactant-containing aqueous solution containing a polymer as defined above.
- a surfactant-containing aqueous solution containing a polymer as defined above.
- the color transfer inhibiting effect of polymers used according to the invention in the washing of textiles made of cotton, wherein the type of textile refers to the white or undyed textile.
- the color transfer inhibiting effect of polymers used according to the invention is particularly pronounced in the washing of textiles dyed with direct, reactive or acid dyeings.
- An inventive composition can, in addition to the polymer, which is accessible by polymerization of benzoxazines, if desired, additionally a known color transfer inhibitor, this then preferably in amounts of 0.01 wt .-% to 5 wt .-%, in particular 0.1 wt % to 1% by weight, which in a preferred embodiment of the invention is a polymer of vinylpyrrolidone, vinylimidazole, vinylpyridine-N-oxide or a copolymer thereof.
- N-polyvinylpyrrolidones N-vinylimidazole / N-vinylpyrrolidone copolymers
- polyvinyl oxazolidones copolymers based on vinyl monomers and carboxylic acid amides
- polyesters containing polyesters containing pyrrolidone groups and polyamides grafted polyamidoamines and polyethyleneimines, polymers containing amide groups from secondary amines, polyamine-N-oxide polymers , Polyvinyl alcohols and copolymers based on acrylamidoalkenylsulfonic acids.
- enzymatic systems comprising a peroxidase and hydrogen peroxide or a substance which gives off hydrogen peroxide in water.
- a mediator compound for the peroxidase for example an acetosyringone, a phenol derivative or a phenotiazine or phenoxazine, is preferred in this case, with the above-mentioned polymeric color transfer inhibiting agents being additionally used can.
- the copolymers useful as additional color transfer inhibiting agents those of vinylpyrrolidone and vinylimidazole in the molar ratio of 5: 1 to 1: 1 are preferred.
- the detergents according to the invention may in principle contain, in addition to the active ingredient used in accordance with the invention, all known ingredients customary in such agents.
- the agents according to the invention may in particular contain reducing substances, surface-active surfactants, bleaches based on organic and / or inorganic peroxygen compounds, bleach activators, water-miscible organic solvents, enzymes, sequestering agents, electrolytes, pH regulators and other auxiliaries, such as optical brighteners, grayness inhibitors, foam regulators and dyes and fragrances.
- compositions according to the invention may comprise one or more surfactants, in particular anionic surfactants, nonionic surfactants and mixtures thereof, but also cationic, zwitterionic and amphoteric surfactants.
- Suitable nonionic surfactants are in particular alkyl glycosides and ethoxylation and / or propoxylation of alkyl glycosides or linear or branched alcohols each having 12 to 18 carbon atoms in the alkyl moiety and 3 to 20, preferably 4 to 10 alkyl ether groups. Also suitable are ethoxylation and / or propoxylation products of N-alkylamines, vicinal diols, fatty acid esters and fatty acid amides which correspond to the said long-chain alcohol derivatives with respect to the alkyl moiety and alkylphenols having from 5 to 12 carbon atoms in the alkyl radical.
- the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as they are usually present in Oxoalkoholresten.
- EO ethylene oxide
- alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred.
- Preferred ethoxylated alcohols include, for example, C 12 - C 4 alcohols containing 3 EO or 4 EO, C 9 -C i-alcohols containing 7 EO, C 3 -C 5 alcohols containing 3 EO, 5 EO, 7 EO or 8 EO, C 12 -C 18 -AlkOhOIe with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12 -C 14 alcohol with 3 EO and C 12 -C 18 alcohol with 7 EO.
- the degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number.
- Preferred alcohol ethoxylates have a narrowed 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, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO.
- agents for use in mechanical processes usually extremely low-foam compounds are used. These preferably include Ci 2 -C 8 -Alkylpolyethylenglykol- polypropylene glycol ethers containing up to 8 moles of ethylene oxide and propylene oxide units in the molecule.
- the nonionic surfactants also include alkyl glycosides of the general formula RO (G) x , in which R is a primary straight-chain or methyl-branched, in particular 2-methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is a Glykoseiki with 5 or 6 C-atoms, preferably for glucose.
- the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is an arbitrary number - which, as a variable to be determined analytically, may also assume fractional values - between 1 and 10; preferably x is 1, 2 to 1, 4.
- R 11 is CO for an aliphatic acyl radical having 6 to 22 carbon atoms
- R 12 is hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms
- [Z] is a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups stands.
- the polyhydroxy fatty acid amides are preferably derived from reducing sugars having 5 or 6 carbon atoms, in particular from glucose.
- the group of polyhydroxy fatty acid amides also includes compounds of the formula
- R 13 is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
- R 14 is a linear, branched or cyclic alkylene radical or an arylene radical having 2 to 8 carbon atoms
- R 15 is a linear, branched or cyclic alkyl radical or a Aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, wherein C- ⁇ -C 4 alkyl or phenyl radicals are preferred
- [Z] is a linear polyhydroxyalkyl radical whose alkyl chain is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this group.
- [Z] is also obtained here preferably by reductive amination of a sugar such as glucose, fructose, maltose, lactose, galactose, mannose or xylose.
- a sugar such as 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.
- 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 from 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl ester.
- 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.
- nonionic surfactants are so-called gemini surfactants. These are generally understood as meaning those compounds which have two hydrophilic 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, the term gemini surfactants not only such "dimer”, but also corresponding to "trimeric” surfactants understood.
- Suitable gemini surfactants are, for example, sulfated hydroxy mixed ethers or dimer alcohol bis and trimer alcohol tris sulfates and ether sulfates. End-capped dimeric and trimeric mixed ethers are characterized in particular by their antibiotic activity. The end-capped surfactants mentioned have good wetting properties and are low-foaming, making them particularly suitable for use in machine washing or cleaning processes. However, it is also possible to use gemini-polyhydroxy fatty acid amides or poly-polyhydroxy fatty acid amides.
- sulfuric acid monoesters of the straight-chain or branched C 7 -C 2 -substituted alcohols ethoxylated with from 1 to 6 mol of ethylene oxide such as 2-methyl-branched C 9 -C 11 -alcohols having on average 3.5 mol of ethylene oxide (EO) or C 12 C 18 fatty alcohols with 1 to 4 EO.
- EO ethylene oxide
- the preferred anionic surfactants also include the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters, and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
- alcohols preferably fatty alcohols and in particular ethoxylated fatty alcohols.
- Preferred sulfosuccinates contain C 8 - to C 18 - fatty alcohol residues or mixtures of these.
- Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which are by themselves nonionic surfactants.
- Sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred.
- alk (en) ylsuccinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
- Suitable further anionic surfactants are fatty acid derivatives of amino acids, for example N-methyltaurine (Tauride) and / or N-methylglycine (sarcosides).
- sarcosides or the sarcosinates and here especially sarcosinates of higher and optionally monounsaturated or polyunsaturated fatty acids such as oleyl sarcosinate.
- anionic surfactants are particularly soaps into consideration.
- 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, soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids. Together with these soaps or as a substitute for soaps, it is also possible to use the known alkenylsuccinic acid salts.
- the anionic surfactants 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.
- the anionic surfactants are preferably present in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
- Cationic surfactants which are used in particular in laundry after-treatment compositions according to the invention, are preferably selected from esterquats and / or quaternary ammonium compounds (QAV) according to the general formula (R 1 XR 11 XR 111 XR 1) N + X " in which R 1 to R IV are identical or different CI_ 22 -alkyl radicals, C 7.
- QAV quaternary ammonium compounds
- arylalkyl radicals or heterocyclic radicals wherein two or in the case of an aromatic compound such as pyridine-even three groups together with the nitrogen atom forming the heterocycle, for example a pyridinium or imidazolinium, and X "represents halide ions, sulfate ions, hydroxide ions or similar anions.
- QACs can be prepared by reacting tertiary amines with alkylating agents, such as, for example, methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethylene oxide.
- 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 quaternized, for example, with dimethyl sulfate.
- Suitable QACs are benzalkonium chloride (N-alkyl-N, N-dimethylbenzylammonium chloride), benzalkone B (m, p-dichlorobenzyl-dimethyl-C 2 -alkylammonium chloride, benzoxonium chloride (benzyldodecyl-bis (2-hydroxyethyl) - ammonium chloride), cetrimonium bromide (N-hexadecyl-N, N-trimethyl-ammonium bromide), benzetonium chloride (N, N-dimethyl-N [2- [2- [2- [p- (1,1,3,3-tetramethyl-butyl) -phenoxy] - ethoxy] ethyl] benzylammonium chloride), dialkyldimethylammonium chlorides such as di-n-decyldimethylammonium chloride, didecyldimethylammonium chloride,
- Esterquats are here compounds of the general formula,
- R 6 is an alkyl or alkenyl radical having 12 to 22 carbon atoms and 0, 1, 2 or 3 double bonds
- R 7 and R 8 are independently H, OH or O (CO)
- R 6 , s, t and u each independently is 1, 2 or 3
- R 7 the group 0 (CO)
- R 6 and R 6 represent an alkyl radical having 16 to 18 carbon atoms, particular preference is given to compounds in which R 8 additionally represents OH.
- Examples of compounds of the abovementioned formula are methyl N- (2-hydroxyethyl) -N, N-di (tallowacyl oxyethyl) ammonium methosulfate, bis (palmitoyl) ethyl hydroxyethyl methyl ammonium methosulfate or methyl N, N bis (acyloxyethyl) -N- (2-hydroxyethyl) ammonium methosulfate are quaternized compounds used, which have unsaturated groups, the acyl groups are preferred, the corresponding End fatty acids have an iodine value between 5 and 80, preferably between 10 and 60 and in particular between 15 and 45 and / or a cis / trans isomer ratio (in mol%) of greater than 30: 70, preferably greater than 50: 50 and in particular greater than 70:30.
- Stepan methosulfate marketed by Stepan under the trade name Stepantex® ® Methylhydroxyalkyldialkoyloxyalkylammonium- or those known under the trade name Dehyquart® ® products from Cognis Germany GmbH or the known under the name Rewoquat ® products by manufacturer Goldschmidt-Witco.
- Surfactants are present in inventive compositions in proportions of preferably 5 wt .-% to 50 wt .-%, in particular from 8 wt .-% to 30 wt .-%.
- An agent according to the invention preferably contains at least one water-soluble and / or water-insoluble, organic and / or inorganic builder.
- the water-soluble organic builder substances include polycarboxylic acids, in particular citric acid and sugar acids, monomeric and polymeric aminopolycarboxylic acids, in particular methylglycine diacetic acid, nitrilotriacetic acid and ethylenediaminetetraacetic acid and polyaspartic acid, polyphosphonic acids, in particular aminotris (methylenephosphonic acid), ethylenediaminetetrakis (methylenephosphonic acid) and 1-hydroxyethane-1, 1-diphosphonic acid, polymeric hydroxy compounds such as dextrin and polymeric (poly) carboxylic acids, in particular the accessible by oxidation of polysaccharides or dextrins polycarboxylates, polymeric acrylic acids, methacrylic acids, maleic acids and copolymers thereof, which also small amounts of polymerizable substances without carboxylic acid functionality may contain polymerized.
- polycarboxylic acids in particular citric acid and sugar acids
- monomeric and polymeric aminopolycarboxylic acids
- the molecular weight of the homopolymers of unsaturated carboxylic acids is generally between 3,000 and 200,000, of the copolymers between 2,000 and 200,000, preferably 30,000 to 120,000, each based on the free acid.
- a particularly preferred acrylic acid-maleic acid copolymer has a molecular weight of from 30,000 to 100,000.
- Commercially available products are, for example, Sokalan® CP 5, CP 10 and PA 30 from BASF.
- Suitable, although less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinylmethyl ethers, vinyl esters, ethylene, propylene and styrene, in which the proportion of the acid is at least 50% by weight.
- the first acidic monomer or its salt is derived from a monoethylenically unsaturated C 3 -C 8 -carboxylic acid and preferably from a C 3 -C 4 -monocarboxylic acid, in particular from (meth) -acrylic acid.
- the second acidic monomer or its salt may be a derivative of a C 4 -C 8 -dicarboxylic acid, with maleic acid being particularly preferred, and / or a derivative of an allylsulfonic acid substituted in the 2-position with an alkyl or aryl radical.
- Such polymers generally have a molecular weight between 1,000 and 200,000.
- Further preferred copolymers are those which preferably have as monomers acrolein and acrylic acid / acrylic acid salts or vinyl acetate.
- the organic builder substances can be used, in particular for the preparation of liquid agents, in the form of aqueous solutions, preferably in the form of 30 to 50 percent by weight aqueous solutions. All of the acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali metal salts.
- organic builder substances may be present in amounts of up to 40% by weight, in particular up to 25% by weight and preferably from 1% by weight to 8% by weight. Quantities close to the stated upper limit are preferably used in paste-form or liquid, in particular water-containing, agents according to the invention.
- Suitable water-soluble inorganic builder materials are, in particular, alkali metal silicates, alkali metal carbonates and alkali metal phosphates, which may be in the form of their alkaline, neutral or acidic sodium or potassium salts.
- crystalline or amorphous alkali metal aluminosilicates in amounts of up to 50% by weight, preferably not more than 40% by weight, and in liquid agents, in particular from 1% by weight to 5% by weight, are particularly suitable as water-insoluble, water-dispersible inorganic builder materials. used.
- detergent grade crystalline sodium aluminosilicates particularly zeolite A, P and optionally X, alone or in mixtures, for example in the form of a cocrystal of zeolites A and X (Vegobond® AX, a commercial product of Condea Augusta SpA)
- zeolites A and X a cocrystal of zeolites A and X
- Amounts near the above upper limit are preferably used in solid, particulate agents.
- suitable aluminosilicates have no particles with a particle size greater than 30 .mu.m and preferably consist of at least 80% by weight of particles having a size of less than 10 .mu.m.
- Their calcium binding capacity which can be determined according to the specifications of the German patent DE 24 12 837, is generally in the range of 100 to 200 mg CaO per gram.
- Suitable substitutes or partial substitutes for the said aluminosilicate are crystalline alkali silicates which may be present alone or in a mixture with amorphous silicates.
- the alkali metal silicates useful as builders in the compositions according to the invention preferably have a molar ratio of alkali metal oxide to SiO 2 of less than 0.95, in particular of 1: 1, 1 to 1: 12, and may be amorphous or crystalline.
- Preferred alkali metal silicates are the sodium silicates, in particular the amorphous sodium silicates, with a molar ratio of Na 2 O: SiO 2 of 1: 2 to 1: 2.8.
- the crystalline silicates which may be present alone or in admixture with amorphous silicates, are crystalline layer silicates with the general formula Na 2 Si x O y are used 2x + 1 H 2 O, in which x, known as the modulus, an integer of 1, 9 to 22, in particular 1, 9 to 4 and y is a number from 0 to 33 and preferred values for x are 2, 3 or 4.
- Preferred crystalline phyllosilicates are those in which x in the abovementioned general formula assumes the values 2 or 3. In particular, both ⁇ - and ⁇ -sodium disilicates (Na 2 Si 2 O 5 y H 2 O) are preferred.
- compositions according to the invention are also prepared from amorphous alkali metal silicates, practically anhydrous crystalline alkali silicates of the abovementioned general formula in which x is a number from 1, 9 to 2, 1, can be used in inventive compositions.
- a crystalline sodium layer silicate with a modulus of 2 to 3 is used, as can be prepared from sand and soda. Crystalline sodium silicates with a modulus in the range of 1.9 to 3.5 are used in a further preferred embodiment of compositions according to the invention.
- Crystalline layered silicates of the above Formula (I) are marketed by Clariant GmbH under the trade name Na-SKS, eg Na-SKS-1 (Na 2 Si 22 O 45 XH 2 O, Kenyaite), Na-SKS-2 (Na 2 Si 14 O 29 XH 2 O, magadiite), Na-SKS-3 (Na 2 Si 8 O 17 XH 2 O) or Na-SKS-4 (Na 2 Si 4 O 9 XH 2 O, makatite).
- Na-SKS eg Na-SKS-1 (Na 2 Si 22 O 45 XH 2 O, Kenyaite)
- Na-SKS-2 Na 2 Si 14 O 29 XH 2 O, magadiite
- Na-SKS-3 Na 2 Si 8 O 17 XH 2 O
- Na-SKS-4 Na 2 Si 4 O 9 XH 2 O, makatite
- Na SKS-5 (Na-X are 2 Si 2 O 5), Na-SKS-7 (.beta.-Na 2 Si 2 0 5, natrosilite), Na-SKS-9 (NaHSi 2 O 5 3H 2 O), Na-SKS-10 (NaHSi 2 O 5 3H 2 O, kanemite), Na-SKS-11 (t-Na 2 Si 2 0 5) and Na-SKS-13 (NaHSi 2 O 5) , but in particular Na-SKS-6 (5-Na 2 Si 2 O 5).
- Builder substances are preferably present in the compositions according to the invention in amounts of up to 75% by weight, in particular 5% by weight to 50.
- suitable peroxygen compounds are in particular organic peracids or pers acid salts of organic acids, such as phthalimidopercaproic acid, perbenzoic acid or salts of diperdodecanedioic acid, hydrogen peroxide and under the washing conditions hydrogen peroxide donating inorganic salts, which include perborate, percarbonate, persilicate and / or persulfate Caroat belong into consideration.
- organic peracids or pers acid salts of organic acids such as phthalimidopercaproic acid, perbenzoic acid or salts of diperdodecanedioic acid, hydrogen peroxide and under the washing conditions hydrogen peroxide donating inorganic salts, which include perborate, percarbonate, persilicate and / or persulfate Caroat belong into consideration.
- solid peroxygen compounds are to be used, they can be used in the form of powders or granules, which can also be enveloped in a manner known in principle.
- an agent according to the invention contains peroxygen compounds, they are present in amounts of preferably up to 50% by weight, in particular from 5% by weight to 30% by weight.
- bleach stabilizers such as phosphonates, borates or metaborates and metasilicates and magnesium salts such as magnesium sulfate may be useful.
- bleach activators it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid.
- Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups.
- polyacylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate, 2,5-diacetoxy- 2,5-dihydrofuran and enol ester
- hydrophilic substituted acyl acetals and the acyl lactams are also preferably used.
- Combinations of conventional bleach activators can also be used.
- Such bleach activators can, in particular in the presence of the abovementioned hydrogen peroxide-supplied bleach, in the usual amount range, preferably in amounts of from 0.5 wt .-% to 10 wt .-%, in particular 1 wt .-% to 8 wt .-%, based on However, total agent, be included, missing when using percarboxylic acid as the sole bleach, preferably completely.
- sulfone imines and / or bleach-enhancing transition metal salts or transition metal complexes may also be present as so-called bleach catalysts.
- Suitable enzymes which can be used in the compositions are those from the class of amylases, proteases, lipases, cutinases, pullulanases, hemicellulases, cellulases, oxidases, laccases and peroxidases and mixtures thereof. Particularly suitable are from fungi or bacteria, such as Bacillus subtilis, Bacillus licheniformis, Bacillus lentus, Streptomyces griseus, Humicola lanuginosa, Humicola insolens, Pseudomonas pseudoalcaligenes, Pseudomonas cepacia or Coprinus cinereus derived enzymatic agents.
- the enzymes may be adsorbed to carriers and / or embedded in encapsulants to protect against premature inactivation. They are preferably present in the detergents or cleaners according to the invention in amounts of up to 5% by weight, in particular from 0.2% by weight to 4% by weight. If the agent of the invention contains protease, it preferably has a proteolytic activity in the range of about 100 PE / g to about 10,000 PE / g, in particular 300 PE / g to 8000 PE / g. If several enzymes are to be used in the agent according to the invention, this can be carried out by incorporation of the two or more separate or in a known manner separately prepared enzymes or by two or more enzymes formulated together in a granule.
- organic solvents which can be used in addition to water include alcohols having 1 to 4 C atoms, in particular methanol, ethanol, isopropanol and tert-butanol, diols having 2 to 4 C -Ato- men, in particular ethylene glycol and propylene glycol, and mixtures thereof and derived from the said classes of compounds ethers.
- Such water-miscible solvents are preferably present in the compositions according to the invention in amounts of not more than 30% by weight, in particular from 6% by weight to 20% by weight.
- the compositions according to the invention may contain system and environmentally acceptable acids, in particular citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and / or adipic acid, but also mineral acids, in particular sulfuric acid, or bases, in particular ammonium or alkali metal hydroxides.
- Such pH regulators are present in the compositions according to the invention in amounts of preferably not more than 20% by weight, in particular from 1.2% by weight to 17% by weight.
- Graying inhibitors have the task of keeping suspended from the textile fiber dirt suspended in the fleet.
- Water-soluble colloids of mostly organic nature are suitable for this purpose, for example starch, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or of cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
- water-soluble polyamides containing acidic groups are suitable for this purpose.
- starch derivatives can be used, for example aldehyde starches.
- cellulose ethers such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose and mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof, for example in amounts of from 0.1 to 5% by weight, based on the compositions ,
- Detergents according to the invention may contain, for example, derivatives of diaminostilbenedisulfonic acid or their alkali metal salts as optical brighteners, although they are preferably free of optical brighteners for use as color detergents.
- optical brighteners for use as color detergents.
- salts of 4,4'-bis (2-anilino-4-morpholino-1, 3,5-triazinyl-6-amino) stilbene-2,2'-disulphonic acid or compounds of similar construction which are used instead of the morpholino Group carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group.
- brighteners of the substituted diphenylstyrene type may be present, for example, the alkali salts of 4,4'-bis (2-sulfostyryl) -diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) -diphenyl, or 4 - (4-chlorostyryl) -4 '- (2-sulfostyryl).
- Mixtures of the aforementioned optical brightener can be used.
- foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of Ci 8 -C 24 fatty acids.
- Suitable non-surfactant foam inhibitors are, for example, organopolysiloxanes and mixtures thereof with microfine, optionally signed silica and paraffins, waxes, microcrystalline waxes and mixtures thereof with signed silica or bis-fatty acid alkylenediamides.
- mixtures of various foam inhibitors for example those of silicones, paraffins or waxes.
- the foam inhibitors in particular silicone and / or paraffin-containing foam inhibitors, are bound to a granular, water-soluble or dispersible carrier substance.
- mixtures of paraffins and bistrearylethylenediamide are preferred.
- compositions according to the invention presents no difficulties and can be carried out in a known manner, for example by spray-drying or granulation, enzymes and possibly other thermally sensitive ingredients such as, for example, bleaching agents optionally being added separately later.
- inventive compositions having an increased bulk density in particular in the range from 650 g / l to 950 g / l, a process comprising an extrusion step is preferred.
- compositions according to the invention in tablet form, which may be monophasic or multiphase, monochromatic or multicolor and in particular consist of one or more layers, in particular two layers
- the procedure is preferably such that all constituents - if appropriate one per layer - in one Mixer mixed together and the mixture by means of conventional tablet presses, such as eccentric or rotary presses, pressed with compressive forces in the range of about 50 to 100 kN, preferably at 60 to 70 kN.
- a tablet produced in this way has a weight of 10 g to 50 g, in particular 15 g up to 40 g.
- the spatial form of the tablets is arbitrary and can be round, oval or angular, with intermediate forms are also possible. Corners and edges are advantageously rounded. Round tablets preferably have a diameter of 30 mm to 40 mm.
- the size of rectangular or cuboid-shaped tablets, which are introduced predominantly via the metering device, for example the dishwasher, is dependent on the geometry and the volume of this metering device.
- Exemplary preferred embodiments have a base area of (20 to 30 mm) x (34 to 40 mm), in particular of 26x36 mm or 24x38 mm.
- Liquid or pasty compositions according to the invention in the form of customary solvent-containing solutions are generally prepared by simply mixing the ingredients, which can be added in bulk or as a solution in an automatic mixer. Examples
- Paraformaldehyde was introduced into ethyl acetate and the p-cresol, likewise dissolved in ethyl acetate, was added dropwise within 10 minutes. The mixture was then added within 30 minutes of Jeffamine M 2070 wherein the temperature was kept below 10 0 C. After 10 minutes of stirring, the reaction mixture was refluxed for 6 hours. After cooling, the reaction mixture was filtered and the solvent and water formed were removed in vacuo. 318.90 g of the corresponding polymerizable benzoxazine compound B-Box-l-1.1 were obtained.
- Example 1.1 Under the conditions described in Example 1.1, paraformaldehyde, p-cresol and ethanolamine were reacted. 328.6 g of the corresponding polymerizable benzoxazine compound B-Box-III were obtained.
- benzoxazine (co) polymers were prepared in the composition shown in Table 1.
- Example 3 Alkylation of benzoxazine (co) polymers for the preparation of cationic benzoxazine (co) polymers
- NMR spectroscopic methods have shown that at least 5% of all nitrogen atoms, based on the total number of nitrogen atoms in the cationic benzoxazine (co) polymer mentioned above, are in the form of permanent quaternary nitrogen atoms.
- NMR spectroscopic methods have shown that at least 5% of all nitrogen atoms, based on the total number of nitrogen atoms in the cationic benzoxazine (co) polymer mentioned above, are in the form of permanent quaternary nitrogen atoms.
- compositions E according to the invention and those of a comparative example C 1:
- compositions E according to the invention which contained a benzoxazine (co) polymer prepared in Examples 2 and 3, showed better ink transfer-inhibiting properties in washing experiments than the comparative formulation V1.
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Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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DE102009003034A DE102009003034A1 (en) | 2009-05-12 | 2009-05-12 | Color protecting detergent or cleaner |
PCT/EP2010/056175 WO2010130624A1 (en) | 2009-05-12 | 2010-05-06 | Color-protecting washing or cleaning agent |
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EP2430137A1 true EP2430137A1 (en) | 2012-03-21 |
EP2430137B1 EP2430137B1 (en) | 2014-11-12 |
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EP10716362.8A Not-in-force EP2430137B1 (en) | 2009-05-12 | 2010-05-06 | Color-protecting washing or cleaning agent |
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US (1) | US8580726B2 (en) |
EP (1) | EP2430137B1 (en) |
DE (1) | DE102009003034A1 (en) |
WO (1) | WO2010130624A1 (en) |
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US20130139327A1 (en) * | 2010-08-03 | 2013-06-06 | Henkel Ag & Co. Kgaa | Textile treatment composition for removal of deodorant stains |
US20130111675A1 (en) | 2011-11-03 | 2013-05-09 | Ecolab Usa Inc. | Sustainable laundry sour compositions with iron control |
WO2015112341A1 (en) | 2014-01-22 | 2015-07-30 | The Procter & Gamble Company | Fabric treatment composition |
WO2015112338A1 (en) | 2014-01-22 | 2015-07-30 | The Procter & Gamble Company | Method of treating textile fabrics |
WO2015112340A1 (en) | 2014-01-22 | 2015-07-30 | The Procter & Gamble Company | Method of treating textile fabrics |
WO2015112339A1 (en) | 2014-01-22 | 2015-07-30 | The Procter & Gamble Company | Fabric treatment composition |
JP2018501331A (en) | 2014-11-17 | 2018-01-18 | ザ プロクター アンド ギャンブル カンパニー | Beneficial agent delivery composition |
CN107548415A (en) | 2015-04-29 | 2018-01-05 | 宝洁公司 | The method of laundering of textile fabrics |
JP6545822B2 (en) | 2015-04-29 | 2019-07-17 | ザ プロクター アンド ギャンブル カンパニーThe Procter & Gamble Company | Cloth processing method |
DK3088503T3 (en) | 2015-04-29 | 2018-08-20 | Procter & Gamble | PROCEDURE FOR TREATING A TEXTILE SUBSTANCE |
ES2682178T3 (en) | 2015-04-29 | 2018-09-19 | The Procter & Gamble Company | Detergent composition |
WO2016176240A1 (en) | 2015-04-29 | 2016-11-03 | The Procter & Gamble Company | Method of treating a fabric |
MX2018006475A (en) | 2015-11-26 | 2018-09-28 | Procter & Gamble | Liquid detergent compositions comprising protease and encapsulated lipase. |
EP4112707A1 (en) | 2021-06-30 | 2023-01-04 | The Procter & Gamble Company | Fabric treatment |
WO2024011343A1 (en) | 2022-07-11 | 2024-01-18 | The Procter & Gamble Company | Laundry detergent composition containing polyalkylene oxide graft copolymer and dye transfer inhibitor polymer |
EP4306628A1 (en) | 2022-07-11 | 2024-01-17 | The Procter & Gamble Company | Laundry detergent composition containing two graft copolymer |
WO2024011345A1 (en) | 2022-07-11 | 2024-01-18 | The Procter & Gamble Company | Laundry detergent composition containing graft copolymer and benefit agent |
WO2022214113A2 (en) | 2022-07-11 | 2022-10-13 | The Procter & Gamble Company | Laundry detergent composition containing graft copolymer and dye transfer inhibitor polymer |
CA3234192A1 (en) | 2022-07-11 | 2024-01-18 | Ming Tang | Laundry detergent composition containing graft copolymer and perfume raw material |
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AT330930B (en) | 1973-04-13 | 1976-07-26 | Henkel & Cie Gmbh | PROCESS FOR THE PRODUCTION OF SOLID, SPILLABLE DETERGENTS OR CLEANING AGENTS WITH A CONTENT OF CALCIUM BINDING SUBSTANCES |
DE3434820A1 (en) | 1984-09-22 | 1986-04-03 | Bayer Ag, 5090 Leverkusen | AGING-RESISTANT POLYAMIDE ALLOYS |
CN1066194C (en) * | 1994-04-07 | 2001-05-23 | 普罗格特-甘布尔公司 | Bleach compositions comprising bleach activators and bleach catalysts |
US5755992A (en) * | 1994-04-13 | 1998-05-26 | The Procter & Gamble Company | Detergents containing a surfactant and a delayed release peroxyacid bleach system |
US5543516A (en) | 1994-05-18 | 1996-08-06 | Edison Polymer Innovation Corporation | Process for preparation of benzoxazine compounds in solventless systems |
EP1760110B1 (en) * | 2005-09-03 | 2011-11-02 | Samsung SDI Co., Ltd. | Polybenzoxazine-based compound, electrolyte membrane including the same, and fuel cell employing the electrolyte membrane |
DE102009003032A1 (en) * | 2009-05-12 | 2010-11-18 | Henkel Ag & Co. Kgaa | Cationic benzoxazine (co) polymers |
-
2009
- 2009-05-12 DE DE102009003034A patent/DE102009003034A1/en not_active Withdrawn
-
2010
- 2010-05-06 WO PCT/EP2010/056175 patent/WO2010130624A1/en active Application Filing
- 2010-05-06 EP EP10716362.8A patent/EP2430137B1/en not_active Not-in-force
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2011
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US20120047664A1 (en) | 2012-03-01 |
WO2010130624A1 (en) | 2010-11-18 |
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