Cleaning compositions with amphiphilic graft polymers based on polyalkylene oxides and vinyl esters

FIELD: chemistry.

SUBSTANCE: invention can be used for laundry, cleaning solid surfaces and washing dishes. The composition contains a surface-active system and an amphiphilic graft polymer based on water-soluble polyalkylene oxides (A) which are the base of graft polymers, as well as side chains formed from polymerisation of a vinyl ester (B). The graft polymer has ≤1 branching places on 50 alkylene oxide fragments and is characterised by average molar mass Mw between 3000 and 100000.

EFFECT: high efficiency of removing hydrophobic contaminants from textile articles and solid surfaces.

12 cl, 11 ex, 1 dwg

 

Reference to related application

This application claims priority to EPO application No. 06114756, filed may 31, 2006

The technical field to which the invention relates.

The present invention is directed to compositions for washing and cleaning compositions comprising amphiphilic graft polymers based on water-soluble polyalkyleneglycol, which is the basis of the grafted polymers, as well as the side chains of esters of vinyl alcohol.

The invention

The present invention relates to new detergents for washing and cleaning compositions, including new amphiphilic graft polymers based on water-soluble polyalkyleneglycol (A), which is the basis of the grafted polymers, and side chains formed by polymerization of ester of vinyl alcohol (B), and the above-mentioned polymers have ≤1 points of divergence at 50 fragments accelerated and are characterized by an average molar mass Mwfrom 3000 to 100,000. In addition, the present invention relates to the use of the above amphiphilic graft polymers as additives for facilitating the separation of dirt, detergents for washing and cleaning compositions.

Detailed description of the invention

In compositions intended for washing and cleaning, in addition to the surface is about-active substances are also used polymers, which facilitate the separation of impurities and additives. Known polymers are ideal, for example, as a dispersing agent for impurities such as clay or carbon black, as well as additives that prevent the re-accumulation of separated contaminants. At the same time, such dispersing agents, especially at low temperatures, are largely ineffective in the removal of hydrophobic contaminants from textiles and hard surfaces.

The aim of the present invention was the creation of polymers suitable for use as additives to compositions used for washing and cleaning, in particular for the removal of hydrophobic contaminants from textiles and hard surfaces.

Accordingly, we found amphiphilic graft polymers based on water-soluble polyalkyleneglycol (A), which is the basis of the grafted polymers, and side chains formed by polymerization of ester of vinyl alcohol, and the above-mentioned polymers have an average ≤ a single location branch at 50 fragments accelerated and are characterized by an average molar mass Mwfrom 3000 to 100,000.

In addition, we found the process of making a grafted polymer comprising a polymerization component, which is a complex ester in delovogo alcohol (In), consisting of vinyl acetate and / or finalproject (B1) and, if desired, additional unsaturated ethylene monomer (B2)in the presence of water-soluble polyalkylene (A)forming a free radical initiator (C), and optionally up to 40 wt.% organic solvent (D), counting on the sum of components a, b and C. While the average temperature of polymerization is chosen so that the time half-life of the initiator (S) ranged from 40 to 500 minutes the Process is carried out so that the content of unreacted grafted monomer (b) and initiator (C) in the reaction mixture was constantly in quantitative disadvantage in relation to polyalkyleneglycol (A).

Grafted polymers of the present invention are characterized by a low degree of branching (degree of previtali). On average, depending on the parameters of the obtained reaction mixture, they are characterized by not more than 1 fork, mostly not more than 0.6 branching, more preferably not more than 0.5 branching and most preferably not more than 0.4 branching 50 alkalinising fragments. They contain, on average, depending on the parameters of the obtained reaction mixture, mainly of not less than 0.05, in particular not less than 0.1, branching 50 alkalinising fragments. The degree of branching can is predelete, for example, by NMR spectroscopy on nuclei13With integrated intensity of signals from the branching of the carbon chain and CH2groups polyalkylated.

In accordance with their low degree of branching, the molar ratio of grafted alkalinising fragments to unvaccinated in the grafted polymers of the present invention has a value of from 0.002 to 0.05, preferably from 0.002 to 0,035, more preferably from 0.003 to 0.025, and most preferably from 0.004 to 0.02.

Preferred embodiments of the grafted polymers of the present invention differ in that they have a narrow distribution of molar masses and, therefore, the polydispersity Mw/Mnis usually ≤3, preferably ≤2.5 and more preferably ≤2,3. Most preferably, the polydispersity Mw/Mnranged from 1.5 to 2.2. The polydispersity of the grafted polymers can be defined, for example, by the method of gel chromatography, using as a standard polymetylmetacrylate with a narrow distribution.

The average weight molar mass Mwthe grafted polymers of the present invention is in the range from 3000 to 100,000, preferably in the range from 6000 to 45,000 units, and more preferably in the range from 8000 to 30,000.

Due to their low degree of RA is wetlanet and low polydispersity especially clearly manifested amphiphilic character and block polymer structure of the grafted polymers of the present invention.

Other preferred embodiments of the grafted polymers of the present invention also have a small number of unvaccinated complex ester of polyvinyl alcohol (In). In General they contain ≤10 wt.%, preferably ≤7.5 wt.% and more preferably ≤5 wt.% unvaccinated complex ester of polyvinyl alcohol (C).

The low percentage of unvaccinated complex ester of polyvinyl alcohol and a selected ratio of components (a) and (b) grafted polymers of the present invention are soluble in water or hydroalcoholic mixtures (for example, in an aqueous solution containing 25 wt.% monobutyl ether of diethylene glycol). They are characterized by low temperature values of turbidity, which for grafted polymers, soluble in water at a temperature not exceeding 50°C is ≤95°C, preferably ≤85°C, and more preferably ≤75°C, and for other grafted polymers in a 25 wt.% the solution monobutyl ether of diethylene glycol, predominantly in General ≤90°C, preferably from 45 to 85°C.

Amphiphilic graft polymers according to the present invention preferably contain:

(A) from 20 to 70 wt.% water-soluble polyalkylene, which is the basis of the grafted polymer, and

(B) side chains formed by free radical polymerization of 30-80 wt.% SL is mportant ester of vinyl alcohol, consisting of:

(B1) from 70 to 100 wt.% vinyl acetate and / or finalproject and

(B2) from 0 to 30 wt.% additional unsaturated ethylene monomer, in the presence of (A).

More preferably they comprise from 25 to 60 wt.% fundamentals of grafted polymer (a) and from 40 to 75 wt.% complex ester of polyvinyl alcohol (C).

Water-soluble polyalkyleneglycol suitable to form the basis of grafted polymer (A)are, in principle, any polymer based on C2-C4accelerated and comprising at least 50 wt.%, preferably at least 60 wt.%, more preferably at least 75 wt.% of ethylene oxide in copolymerization.

Polyalkyloxy (A) preferably have low polydispersity Mw/Mn. Their polydispersity is preferably ≤1,5.

Polyalkyloxy (A) may be appropriate polyalkylene glycols in unbound form, i.e. with the terminal HE-groups, but also on one or both ends of the terminal Oh-group can be closed. Suitable groups that covers the ends of the chain are, for example, With1-C25alkyl, phenyl, and C1-C14alkylphenyl group.

Specific examples of particularly suitable polyalkyleneglycol (A) include:

(A1) glycols, which may contain the nominal group at one or both ends of the chain, especially With1-C25alkyl terminal groups, but which preferably are not esterified and have average molar mass Mn, preferably in the range from 1500 to 20,000, more preferably in the range from 2500 to 15,000,

(A2) copolymers of ethylene oxide and of propylene oxide and (or) butilenica, the content in which ethylene oxide is not less than 50 wt.%, which may also contain terminal groups at one or both ends of the chain, especially With1-C25alkyl terminal groups, but which preferably are not esterified and have average molar mass Mn, preferably in the range from 1500 to 20,000, more preferably in the range from 2500 to 15,000,

(A3) products with an elongated chain, the average molar masses which are, in particular, in the range from 2500 to 20000, which can be obtained by reacting polyethylene glycol (A1)having average molar mass Mnlocated in the interval from 200 to 5000, or a copolymer (A2)having average molar mass Mnlocated in the interval from 200 to 5000, C2-C12-dicarboxylic acids or dicarboxylic esters or6-C18-diisocyanate.

Preferred as the basis of the grafted polymers (A) are polietilenglikol and (A1).

Side chains of the grafted polymers of the present invention are formed by polymerization of ester of vinyl alcohol (B) in the presence of bases of grafted polymer (A).

An ester of vinyl alcohol (b) may be preferably from (B1) vinyl acetate or finalproject or mixtures of vinyl acetate and finalproject, particularly preferred is the use of vinyl acetate as a complex ester of vinyl alcohol (B).

In addition, side chains grafted polymer can also be formed by copolymerization of vinyl acetate and / or finalproject (B1) with additional monomer containing ethylene unsaturated group (B2). The proportion of monomer (B2) in a complex ester of vinyl alcohol (B) can reach 30 wt.%, that corresponds to a content of (B2) in the grafted polymer equal to 24 wt.%.

Suitable comonomers (B2) are, for example, unsaturated carboxylic acids containing one ethylene linkage, and dicarboxylic acids and their derivatives, for example esters, amides and anhydrides, as well as styrene. In addition, it is also allowed to use mixtures of different comonomers.

Specific examples include (meth)acrylic acid, complex1-C5alkyl, hydroxy-C2-C12alkyl esters of (meth)acrylic acid, (meth)acrylamide, N-C1-C12/sub> the alkyl(meth)acrylamide, N,N-di(C1-C6alkyl)(meth)acrylamide, maleic acid, maleic anhydride and monosubstituted With1-C12alkyl esters of maleic acid.

Preferred monomers (B2) are complex, C1-C8alkyl esters of (meth)acrylic acid and hydroxyethylacrylate, particularly preferred are C1-C4alkyl esters of (meth)acrylic acid.

Particularly preferred monomers (B2) are methyl acrylate, acrylate, in particular n-butyl acrylate.

When grafted polymers of the present invention contain the monomers (B2) as an integral part of a complex ester of vinyl alcohol (B), the content of grafted polymer (B2) is preferably from 0.5 to 20 wt.%, more preferably from 1 to 15 wt.% and most preferably from 2 to 10 wt.%.

Grafted polymers of the present invention is preferably obtained in the course of the process, in accordance with the present invention by the polymerization of ester of vinyl alcohol (b)consisting of vinyl acetate and / or finalproject (B1) and optionally additional monomer containing ethylene unsaturated group (B2), in the presence of water-soluble polyalkylene (A)forming a free radical initiator (C), and, when gelan and, up to 40 wt.% organic solvent (D), counting on the sum of components a, b and C. the average temperature of polymerization is such that the time half-life of the initiator (S) ranged from 40 to 500 minutes the Process is carried out so that the content of unreacted grafted monomer (b) and initiator (C) in the reaction mixture was constantly in quantitative disadvantage in relation to polyalkyleneglycol (A).

In this process, the content of ester of vinyl alcohol (B) is preferably from 30 to 80 wt.%. An ester of vinyl alcohol (In) includes:

(B1) from 70 to 100 wt.% vinyl acetate and / or finalproject and

(B2) from 0 to 30 wt.% additional unsaturated ethylene monomer,

and from 20 to 70 wt.% water-soluble polyalkylene (A)having an average molar mass Mnfrom 1500 to 20,000.

The amount of initiator (C) is preferably from 0.2 to 5 wt.%, in particular from 0.5 to 3.5 wt.%, in each case, in relation to the component (B).

For a process in accordance with the present invention it is necessary that the stationary concentration of radicals at an average temperature of polymerization was almost constant, while the concentration of grafted monomer (C) in the reaction mixture constant only at a low concentration (for example, not more than 5 wt.%). This provides the reaction to proceed in a controlled manner, and grafted polymers can be obtained in a controlled way and to have the desired low degree of branching and the desired low degree of polydispersity.

The term "average temperature of polymerization" means here that although the process is practically isothermal, due to the exothermic effect of the reaction may vary with temperature, which is preferably maintained within the range of ±10°C, more preferably in the range of ±5°C.

In accordance with the present invention forming a free radical initiator (S) at an average temperature of polymerization should be characterized by the time half-life of from 40 to 500 rpm, preferably from 50 to 400 rpm, and more preferably from 60 to 300 minutes

In accordance with the present invention, the initiator (S) and grafted monomer (C) is preferably added in such a way that the reaction mixture was low and almost constant concentration of undecomposed initiator and grafted monomer (B). The content of undecomposed initiator in the reaction mixture should be preferably ≤15 wt.%, in particular ≤10 wt.%, calculated on the total amount of initiator, measured during the addition of the monomer.

The appropriate value of the average temperature of polymerization is in the range from 50 to 140°C, predpochtitel is but from 60 to 120°C, and more preferably from 65 to 110°C.

Examples of suitable initiators (C), for which the half-life time in the temperature range from 50 to 140°C. is from 20 to 500 rpm, are:

- O-C2-C12acylated derivatives of tert-C4-C12alkyl hydroperoxides and tert-(C9-C12-aralkyl of hydroperoxides, such as tert-butyl peroxyacetate, tert-butyl monoperoxyphthalate, tert-butyl peroxyisobutyrate, tert-butyl peroxypivalate, tert-butyl, peroxyneoheptanoate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxy-3,5,5-trimethylhexanoate, tert-butyl, peroxyneodecanoate, tert-AMYLPEROXY, tert-AMYLPEROXY-2-ethylhexanoate, tert-anilinoquinazolines, 1,1,3,3-TETRAMETHYLBUTYL peroxyneodecanoate, semiproletariat, tert-butyl peroxybenzoate, tert-AMYLPEROXY and di-tert-butylperoxide;

di-O-C4-C12acylated derivatives of tert-C8-C14-alkalinisation, such as 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane and 1,3-di(2-neodecanoic phenoxyisopropyl)benzene;

di(C2-C12-alkanoyl)and dibenzoylperoxide, such as diacetyltartaric, di-propionyl peroxide, disuccinic peroxide, decapryloyl peroxide, di(3,5,5-trimethylhexanoyl)peroxide, didecanoyl peroxide, Dilauroyl lane is xed, Dibenzoyl peroxide, di(4-methylbenzoyl)peroxide, di(4-chlorobenzoyl)peroxide and di(2,4-dichlorobenzoyl)peroxide;

- tert-C4-C5alkylperoxy(C4-C12alkyl)carbonates, such as tert-AMYLPEROXY(2-ethylhexyl)carbonate;

di(C2-C12alkyl)PEROXYDICARBONATE, such as di(n-butyl) PEROXYDICARBONATE and di(2-ethylhexyl) PEROXYDICARBONATE.

Depending on the values of the average temperature of polymerization, examples of particularly suitable initiators (C) are:

- when the average temperature of polymerization in the range from 50 to 60°C: tert-butyl peroxyneoheptanoate, tert-butyl, peroxyneodecanoate, tert-amyl peroxypivalate, tert-amyl peroxyneodecanoate, 1,1,3,3-TETRAMETHYLBUTYL peroxyneodecanoate, Cumyl peroxyneodecanoate, 1,3-di(2-neodecanoylperoxyisopropyl) benzene, di(n-butyl) PEROXYDICARBONATE and di(2-ethylhexyl) PEROXYDICARBONATE;

- when the average temperature of polymerization in the range from 60 to 70°C: tert-butyl peroxypivalate, tert-butyl, peroxyneoheptanoate, tert-butyl, peroxyneodecanoate, tert-amyl peroxypivalate and di(2,4-dichlorobenzoyl) peroxide;

- when the average temperature of polymerization in the range from 70 to 80°C: tert-butyl peroxypivalate, tert-butyl, peroxyneoheptanoate, tert-amyl peroxypivalate, dipropionyl of Perak the ID, decapryloyl peroxide, didecanoyl peroxide, di-lauroyl peroxide, di(2,4-dichlorobenzoyl) peroxide and 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane;

- when the average temperature of polymerization in the range from 80 to 90°C: tert-butyl peroxyisobutyrate, tert-butyl peroxy-2-ethylhexanoate, tert-AMYLPEROXY-2-ethylhexanoate, dipropionyl peroxide, decapryloyl peroxide, didecanoyl peroxide, Dilauroyl peroxide, di(3,5,5-trimethylhexanoyl) peroxide, Dibenzoyl peroxide, di(4-methylbenzoyl) peroxide;

- when the average temperature of polymerization in the range from 90 to 100°C: tert-butyl peroxyisobutyrate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl monoperoxyphthalate, tert-amyl peroxy-2-ethylhexanoate, Dibenzoyl peroxide and di(4-methylbenzoyl) peroxide;

- when the average temperature of polymerization in the range from 100 to 110°C: tert-butyl monoperoxyphthalate, tert-butyl peroxyisobutyrate and tert-amyl peroxy(2-ethylhexyl)carbonate;

- when the average temperature of polymerization in the range from 110 to 120°C: tert-butyl monoperoxyphthalate, tert-butyl peroxy-3,5,5-trimethyl of hexanoate and tert-AMYLPEROXY(2-ethylhexyl)carbonate.

The preferred initiators (C) are O-C4-C12acylated derivatives of tert-C4-C5alkylamide is peroxides, particularly preferred are tert-butyl peroxypivalate and tert-butyl peroxy-2-ethylhexanoate.

Especially preferred conditions for the polymerization reaction can be easily installed by precisely varying the reaction temperature and initiator (S). For example, the preferred temperature of polymerization in the case of tert-butyl peroxypivalate is in the range from 60 to 80°C, and in the case of tert-butyl peroxy-2-ethylhexanoate is in the range from 80 to 100°C.

The polymerization reaction of the present invention can be carried out in the presence of a small amount of organic solvent (D). It is also possible to use mixtures of different organic solvents (D). Preferred solvents are soluble in water or miscible with water.

When using the solvent (D) as a diluent for the content, in each case based on the sum of components (A), (b) and (C) is in General from 1 to 40 wt.%, preferably from 1 to 35 wt.%, more preferably from 1.5 to 30 wt.%, most preferably from 2 to 25 wt.%.

Examples of suitable solvent (D) include:

- monohydroxy alcohols, preferably aliphatic alcohols C1-C16more preferably alcohols With2-C12most preferably alcohols With2-C such as ethanol, propanol, isopropanol, butanol, sec-butanol, tert-butanol;

- polyhydric alcohols, preferably diols With2-C10more preferably diols With2-C6most preferably alkalophile2-C4such as ethylene glycol and propylene glycol;

- ethers of alkalophile, preferably mono(C1-C12) alkyl ethers of alkalophile and di(C1-C6) alkyl ethers of alkalophile, more preferably mono - and di(C1-C2) alkyl ethers of alkalophile, most preferably mono(C1-C2) alkyl ethers of alkalophile, such as onomatology or monotropy ether of ethylene glycol and onomatology or monotropy ether of propylene glycol;

the polyalkylene glycols, preferably poly(C2-C4alkylene) glycols comprising from 2 to 20 fragments With2-C4alkalophile, more preferably glycols comprising from 2 to 20 fragments of ethylene glycol, and polypropylenglycol comprising 2-10 fragments of propylene glycol, most preferably polyethylene glycols, comprising 2-15 fragments of ethylene glycol, and polypropylenglycol, including 2-4 fragment of propylene glycol, such as diethylene glycol, threateningly is l, dipropyleneglycol and dipropyleneglycol;

- simple monetary of polyalkylene glycols, preferably mono(C1-C25alkyl) ethers, poly(C2-C4alkylene) glycols comprising from 2 to 20 fragments alkalophile, more preferably mono(C1-C20alkyl) ethers, poly(C2-C4alkylene) glycols comprising from 2 to 20 fragments alkalophile, most preferably mono(C1-C16alkyl) ethers, poly(C2-C3alkylene) glycols comprising 3-20 fragments alkalophile;

- esters of carboxylic acids, preferably1-C8alkyl esters of C1-C6-carboxylic acids, more preferably1-C4alkyl esters of C1-C3-carboxylic acids, most preferably2-C4alkyl esters With2-C3carboxylic acids, such as ethyl acetate and ethylpropane;

- aliphatic ketones, preferably comprising from 3 to 10 carbon atoms, such as acetone, methyl ethyl ketone, diethylketone and cyclohexanone;

cyclic ethers, in particular tetrahydrofuran and dioxane.

The solvents (D) preferably represent such solvents, which are also used in the synthesis of grafted on is Kerov of the present invention (for example, in compositions for cleaning and washing) and, thus, may remain in the composition of the polymeric product.

Preferred examples of such solvents are glycols, comprising 2-15 fragments glycol, polypropyleneglycol, including 2-6 fragments of propylene glycol, and in particular the products alkoxysilane alcohols With6-C8(monoalkyl ethers of alkalophile and monoalkyl ethers of polyalkylene glycols).

Particularly preferred here are the products alkoxysilane alcohols With8-C16with a high degree of branching, which allows to obtain a mixture of polymers, freely flowable at temperatures of 40-70°C and with a very low content of polymers with a relatively low viscosity. Branching can take place in the alkyl chain of the alcohol and (or) in polyalkoxyalkyl parts (copolymerization of at least one fragment of propylene oxide, butilenica or isobutyramide). Particularly suitable examples of such products alkoxysilane are 2-ethylhexanol or 2-propylheptanol, alkoxycarbonyl using 1-15 moles of ethylene oxide, With13/S15oxo-Peart or12/S14or16/S18fatty alcohol, alkoxycarbonyl using 1-15 moles of ethylene oxide and 1 to 3 moles of propylene oxide. However predpochteni is give 2-propylheptanol, alkoxysilanes using 1-15 moles of ethylene oxide and 1 to 3 moles of propylene oxide.

During the process of the present invention polyalkylene (A)let monomer (B1) and optionally, (B2), initiator (S) and, if necessary, the solvent (D) is heated in the reactor to a selected average temperature of polymerization.

In accordance with the present invention the polymerization is conducted in such a way that the reactor was constantly attended by an excess of polymer (polyalkylated (a) and the resulting grafted polymer). The quantitative content of the polymer to the content of the grafting monomer and initiator, as a rule, is ≥10:1, preferably ≥15:1 and more preferably ≥20:1.

The polymerization process in accordance with the present invention can, in principle, be carried out in reactors of various types.

Used reactor preferably is a container with stirring, which initially entered polyalkylene (A), optionally fully or partially mixed with a certain amount, generally up to 15 wt.% from the total number of grafted monomers (B), initiator (S) and solvent (D). The reactor is heated to the polymerization temperature, while preferably independently measure the amount remaining in the reaction mixture of components (B), (C) and optionally (d The number remaining in the reaction mixture of components (B), (C) and optionally (D) is preferably measured for ≥2 hours, more preferably ≥4 hours and most preferably ≥5 hours.

In the case of a particularly preferred variant of the process, which is almost never used solvent, first in the form of melt enter the total number of polyalkylated (A)and grafted monomers (B1) and optionally, (B2)and initiator (C) are preferably in the form of a solution in one of the solvents (D) with a concentration of from 10 to 50 wt.%, their content is measured, and the temperature of the support so that on average during the polymerization of the selected polymerization temperature was maintained in the range mainly ±10°C, in particular in the range of ±5°C.

The following are particularly preferred process variant, which uses a small amount of solvent, the method described above, except that during polymerization measure the content of the solvent (D). This is done in order to limit the viscosity of the reaction mixture. You can also start the process, gradually adding the solvent only after a certain period of time when the polymerization process is already to a certain extent passed, or add it in portions.

PR is the process of polymerization can be conducted under standard pressure or under reduced or increased pressure. If the temperature exceeds the boiling point of the used monomers (B) or any of the diluents (D) when the selected pressure, the polymerization is performed using a reverse refrigerator.

Grafted polymers of the present invention due to its pronounced amphiphilic properties are particularly attractive properties at the interface. They can be preferably used in the composition of detergents and cleaning compositions, where they facilitate the removal of surfactants hydrophobic contaminants with textiles and hard surfaces and thereby improve detergents and cleaning data quality compositions. In addition, they provide the best dispersion remote dirt in the washing or cleaning fluid and prevent re-accumulation of contaminants on the surface of the cleaned and washed materials.

Detergents for washing and cleaning compositions

Detergents and cleaning compositions according to the present invention include amphiphilic graft polymers according to the present invention in the General case, the number depending on the particular overall composition, from 0.05 to 10 wt.%, preferably from 0.1 to 5 wt.% and more preferably from 0.25 to 2.5 wt.%.

In addition, detergents for washing and cleaning compositions in the General case, including the indicate in itself surfactants and optionally other polymers as washing substances, fillers and other commonly used components, such as conpanies, complexing agents, bleaching agents, conditioners, inhibitors darkening, inhibitors transfer of dyes, enzymes and perfumes.

Amphiphilic graft polymers according to the present invention can be used in the composition of detergents for washing or cleaning compositions comprising surfactant system containing10-C15alkylbenzenesulfonate (LAS), and one or more auxiliary surfactants selected from nonionic, cationic, anionic or mixtures thereof. The choice of auxiliary surfactants can be determined what effect you want to achieve. In one embodiment of the invention as an auxiliary surfactant selected non-ionic surfactant, preferably12-C18alkylalkoxysilane. In another example embodiment of the invention as an auxiliary surfactant selected anionic surfactant, preferably10-C18alkylalkoxysilane (AEXS), where x is from 1 to 30. In another example embodiment of the invention as auxiliary surfactants SEL is extended cationic surfactant, preferably dimethylhydroxylamine chloride. If the system surface-active substances include10-C15alkylbenzenesulfonate (LAS), the number of LAS is a value in the range from about 9% to about 25%, or from about 13% to about 25%, or from about 15% to about 23% by weight of the composition.

The system of surface-active substances may include auxiliary surfactant selected from nonionic auxiliary surface substances, cationic auxiliary surfactants, anionic auxiliary surfactants and any mixtures thereof, in an amount of from 0% to about 7%, or from about 0.1% to about 5%, or from about 1% to about 4% based on the weight of the composition.

Non-limiting examples of non-ionic auxiliary surfactants include12-C18alkylalkoxysilane, such as non-ionic surfactant NEODOL® Shell; C6-C12alkylphenolethoxylate where alkoxylate fragments are a mixture of ethyleneoxy and PROPYLENEIMINE; alcohols With12-C18and condensation products6-C12of alkyl phenols with ethylene oxide/propylene oxide block acylpolyamines what xylotomy, such as PLURONIC® from BASF; C14-C22branched in the center of the chain alcohols, WA, for U.S. patent No. 6.150.322; C14-C22branched in the center of the chain alkylalkoxysilane, BAExwhere the value x is in the range from 1 to 30, under U.S. patent No. 6.153.577, 6.020.303 and 6.093.856; alkylpolyglucoside for U.S. patent No. 4.565.647 name Llenado, issued January 26, 1986; more precisely alkylpolyglucoside under U.S. patent No. 4.483.780 and 4.483.779; amides polygalacturonic acids for U.S. patent No. 5.332.528; and poly(oxyalkylene) alcohols containing terminal ether groups and which surfactants for U.S. patent No. 6482994 and publication of the international application WO 01/42408.

Non-limiting examples polupryamykh nonionic auxiliary surfactants include water-soluble aminoxide comprising one alkyl fragment from about 10 to about 18 carbon atoms and 2 fragment selected from the group consisting of alkyl fragments and hydroxyalkyl fragments containing from about 1 to about 3 carbon atoms; water-soluble phosphine oxides comprising one alkyl fragment from about 10 to about 18 carbon atoms and 2 fragment selected from the group consisting of alkyl fragments and hydroxyalkyl fragments provided is from about 1 to about 3 carbon atoms; and water-soluble sulfoxidov comprising one alkyl fragment from about 10 to about 18 carbon atoms, and a fragment selected from the group consisting of alkyl fragments and hydroxyalkyl fragments containing from about 1 to about 3 carbon atoms. Cm. a publication of the international application WO 01/32816, U.S. patent No. 4.681.704 and 4.133.779.

Non-limiting examples of cationic auxiliary surfactants include: surface-active Quaternary ammonium base, which can include up to 26 carbon atoms, including: surface-active CNS Quaternary ammonium base (AQA) for US 6136769, Quaternary dimethylhydroxylamine on 6004922; dimethyldiallylammonium chloride; polianinova cationic surfactants on the publication of international applications WO 98/35002, WO 98/35003, WO 98/35004, WO 98/35005 and WO 98/35006; cationic ester surfactants in U.S. patent No. 4.228.042, 4.239.660, 4.260.529 and 6.022.844; and amine surface active substances for U.S. patent No. 6.221.825 and publication of the international application WO 00/47708, more specifically aminopropyldimethylamine (ARA).

Non-limiting examples of anionic auxiliary surfactants that can be used here include:10-C20pervi the data, extensive and random alkyl sulphates (AS); C10-C18secondary (2,3) alkyl sulphates; C10-C18alkylalkoxysilane (AExS), where the value x is in the range from 1 to 30; C10-C18alkylalkoxysilane comprising from 1 to 5 ethoxyline groups; branched in the centre chain alkyl sulphates under U.S. patent No. 6.020.303 and 6.060.443; branched in the center of the chain alkylalkoxysilane under U.S. patent No. 6.008.181 and 6.020.303; modified Las (MLAS) on the publication of international applications WO 99/05243, WO 99/05242 and WO 99/05244; methylsulfonyl ether (MES); and alpha-reincorporate (AOS).

The present invention may also relate to compositions containing amphiphilic graft polymers according to the present invention and a surfactant system comprising C8-C18linear alkylsulfonate as surfactants and auxiliary surfactant. The composition may be in any form, namely in the form of liquids, solids such as powder, granules, pieces, pastes, tablets, bags, bars, gel, emulsion; forms supplied in containers with two departments; detergent in the form of a spray or foam; pre-moistened with devices for cleaning (i.e. cleaning composition in combination with non-woven material is m, such as described in U.S. patent No. 6.121.165 in the name of Mackey et al.); dry fit to clean (i.e. cleaning composition in combination with non-woven material, such as described in U.S. patent No. 5.980.931 in the name of Fowler et al.), which the consumer results in a condition suitable for operation with water; as well as other homogeneous or multiphase forms of consumer cleaning products.

In one embodiment of the invention the cleaning composition of the present invention is a liquid or solid washing composition for washing. In another example embodiment of the invention the cleaning composition of the present invention is a cleaning composition for hard surfaces, where preferably non-woven material impregnated with a cleaning composition for hard surfaces. Used herein, the term "saturated" means that the cleaning composition for hard surfaces is introduced into contact with the nonwoven substrate so that a cleaning composition for hard surfaces penetrated at least in part non-woven substrate and preferably to non-woven substrate was completely saturated with a cleaning composition for hard surfaces. The cleaning composition can also be used in compositions for car care products for cleaning various surfaces, such as the solid wood, ceramic, plastic, leather, metal, glass. This cleaning composition may be intended for use in compositions for personal hygiene and care of animals, such as shampoos, body washes, liquid or solid soap, and other cleaning compositions, in which the surface-active substance comes into contact with a free solid surface, and in all compositions which require the use of the system of surfactants, neutral to solid surfaces, such as oil drilling compositions.

In another example embodiment of the invention the cleaning composition is a detergent composition for household utensils, such as a liquid composition for hand washing, the solid composition for washing dishes in an automatic dishwasher liquid composition for washing dishes in an automatic dishwasher, as well as composition for automatic dishwashing machines, located in unit dose form.

Fairly typical is the fact that mentioned here cleaning compositions, such as surfactants for washing, Supplement surface-active substances for Laundry, cleaners for hard surfaces, tile Laundry made of synthetic materials with soap base, softeners tissue, liquid and solid the courthouse square, as well as all other drugs for the treatment of fabrics, require the use of several auxiliary substances, although some products simple composition, such as bleaching additives, may only require, for example, oxygen bleaching agent and a surfactant, as described herein. A complete list of suitable supporting materials for washing and cleaning can be found in the description of the published international application WO 99/05242.

Conventional auxiliary substances for cleaning include fillers, enzymes that are not described above polymers, bleaches and bleach activators, catalytic materials and the like, to the exclusion of all the materials already described here above. Other auxiliary substances for cleaning here may include activators of foaming, foam suppressors (defoamers), and the like, other active ingredients or specialized materials, such as dispersant polymers (e.g., BASF Corp. or Rohm & Haas, other than those described above, colored granules, means to care for silver, drugs, preventing discoloration and / or corrosion protection additives, colorants, fillers, antibacterial agents, alkalizing agents, girotropnye substances, antioxidants, fermentability agents, proot the ears, perfumes, solubilizing agents, carriers, processing AIDS, pigments, and, for liquid formulations - solvents, chelating agents, inhibitors transfer dyes, dispersing agents, brighteners, foam suppressors, dyes, substances that increase the elasticity of the finest fabrics, antiwear agents, hydrotropes, processing AIDS, and other agents to care for fabrics, surfaces and skin. Suitable examples of such other auxiliary substances for cleaning and levels of use are described in U.S. patent No. 5.576.282, 6.306.812 and 6.326.348.

Method of use

The present invention includes a method of cleaning a target surface. The term "target surface", as used here, may include surfaces such as fabric, dishes, glassware and other items for cooking, hard surfaces, hair or skin. The term "hard surface", as used here, includes solid surface, which are found in a typical home, such as hardwood, tiles, ceramics, plastic, leather, metal, glass. This method includes a procedure in which a composition comprising a modified polyol in pure form or diluted washing liquid is brought into contact with at least one area of the target surface is resti, then optionally the target surface is washed. Preferably, the target surface is subjected to the cleaning procedure before the above-mentioned optional washing procedure. For the purposes of the present invention, the cleaning includes but is not limited to, cleaning brush, wiping and mechanical movement.

Specialist in the art will appreciate that the cleaning compositions of the present invention is ideal for household use (cleaning compositions for solid surfaces) and / or applications associated with the Laundry.

the pH of the solution composition is chosen to provide the best fit to purify the target surface, and cover a wide range of values from about 5 to about 11. The pH value of the compositions intended for personal hygiene, for example washing the skin and hair, preferably is in the range from about 5 to about 8, and the pH value of the compositions intended for washing, is in the range from about 8 to about 10. The compositions are preferably used at concentrations in the solution is from about 200 parts per million (h/m) to about 10.000 hours/million water Temperature is preferably from about 5 to about 100°C.

When using the compositions as compositions for washing their concentration in the solution (or the scrubbing of the LM the bone) is preferably from about 200 h/m to approximately 10,000 hours/million The water temperature is preferably from about 5 to about 60°C. the ratio of the quantities of water and tissue is preferably from 1:1 to 20:1.

The method may include the step, which is the contact nonwoven substrate impregnated with an embodiment of the composition according to the present invention. Used herein, the term "non-woven substrate" may include a sheet or woven substrate of any conventional form, characterized by appropriate values of density, thickness, absorbency and strength. Examples of suitable commercially available non-woven substrates include those available under the trade names SONTARA® DuPont and POLYWEB® company James River Corp.

Specialist in the art will appreciate that the cleaning compositions of the present invention are ideally suited for liquid compositions intended for washing dishes. The method of using liquid compositions for washing according to the present invention includes injection into contact with contaminated utensils with an effective amount, typically from about 0.5 ml to about 20 ml (25 machined plates), liquid compositions for washing according to the present invention, diluted with water.

Examples of polymers

Amphiphilic graft polymers according to the present invented the Yu can be prepared as follows. Values can be measured at 23°C in 3 wt.% aqueous NaCl solution in which the polymer concentration is 1 wt.%. Average molar masses and polydispersity determined by the method of gel chromatography using 0.5 wt.% the LiBr solution in dimethylacetamide as solvent and polymethylmethacrylate (emission spectra obtained for pure) as a standard. The degree of branching can be determined by NMR spectroscopy on nuclei13With in deuterated dimethyl sulfoxide on the integrated intensity of the signals from the branching of the carbon chain and CH2- groups of the glycol. These values characterize the entire glycol present in the product, i.e. including grafting polyethylene glycol, and corresponds to the number of side chains, the average per one molecule of polyethylene glycol.

Grafted polymer 1

In the reactor for polymerization, equipped with a stirrer and a refrigerator backflow first place 480 g of polyethylene glycol (Mn12000) and melted at a temperature of 70°C. in a nitrogen atmosphere.

After you have added 16.0 g of vinyl acetate and 0.2 g of tert-butyl peroxypivalate in a solution of 9.0 g of dipropyleneglycol, and further mixing for 5 min, parallel to continuously measure 304 g of vinyl acetate for 6 h (load 1) and 4.0 g of tert-butyl peroxypivalate in Rast is the EOS 18 g dipropyleneglycol within 7 h (loading 2) at constant flow rates, under stirring, and the internal temperature is 70°C.

After the end of the boot 2 and after further stirring the mixture at 70°C for one hour, three portions over two hours in each case at a temperature of 70°C. and further stirring, 4.8 g of tert-butyl peroxypivalate dissolved in 9.0 g of dipropyleneglycol. In addition, to reduce the viscosity added 73 g dipropyleneglycol.

Unreacted residues of vinyl acetate is removed by distillation under vacuum at 70°C. In further addition of water was adjusted to a solids content of 24.3%.

The resulting grafted polymer is characterized by the value To equal 28,4, a polydispersity of 1.8 (average molecular mass Mw36.900, Brednikova molecular mass Mn21.000) and degree of branching of 0.8% (corresponding to 0.15 places vaccinations 50 fragments of ethylene oxide).

Grafted polymer 2

In the reactor for polymerization, equipped with a stirrer and a fridge, a counter-flow initially placed 400 g of polyethylene glycol (Mn9000) and melted at a temperature of 85°C. in a nitrogen atmosphere.

After the addition of 20.0 g of vinyl acetate and 0.25 g of tert-butyl peroxy-2-ethylhexanoate in a solution of 0.9 g of dipropyleneglycol, and further mixing for 5 min, parallel to continuously measure 380 g of vinyl acetate for 6 h (the recalls 1) and 5.0 g of tert-butyl peroxy-2-ethylhexanoate in a solution of 18 g of dipropyleneglycol within 7 h (loading 2) at constant flow rates, under stirring at an internal temperature of 85°C.

After the end of the boot 2 and after further stirring the mixture at 85°C for one hour, three portions over two hours in each case at a temperature of 85°C. with further stirring, 6.0 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 9.0 g of dipropyleneglycol. In addition, to reduce the viscosity added 73 g dipropyleneglycol.

Unreacted residues of vinyl acetate is removed by distillation under vacuum at a temperature of 85°C. further addition of water was adjusted to a solids content of 23.2%.

The resulting grafted polymer is characterized by the value To equal 24,0, a polydispersity of 1.9 (Mw37000, Mn19500) and degree of branching of 0.8% (corresponds to 0.2 places vaccinations 50 fragments of ethylene oxide).

Grafted polymer 3

In the reactor for polymerization, equipped with a stirrer and a fridge, a counter-flow initially placed 1000 g of polyethylene glycol (Mn6000) and melted at a temperature of 90°C. in a nitrogen atmosphere.

In parallel continuously measure 1500 g of vinyl acetate for 6 h (load 1) and 14.5 g of tert-butyl peroxy-2-ethylhexanoate in a solution of 60.5 g tripropyleneglycol within 7 h (loading 2) at constant flow rates, under stirring at an internal temperature of 90°C.

After the end the of the boot 2 and after further stirring the mixture at 90°C for one hour, three portions over two hours in each case at a temperature of 90°C. and further stirring 17.1 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 22,6 g tripropyleneglycol. In addition, to reduce the viscosity added 73 g dipropyleneglycol.

Unreacted residues of vinyl acetate is removed by distillation under vacuum at a temperature of 90°C. further addition of water was adjusted to a solids content of 22.8%.

The resulting grafted polymer is characterized by the value To equal 19,6, a polydispersity of 1.9 (Mw35.700, Mn18.800) and degree of branching of 0.9% (corresponding to 0.33 places vaccinations 50 fragments of ethylene oxide).

Grafted polymer 4

In the reactor for polymerization, equipped with a stirrer and a refrigerator backflow first place 480 g of polyethylene glycol (Mn12.000) and melted at a temperature of 70°C. in a nitrogen atmosphere.

After addition of 14.0 g of vinyl acetate, 1.6 g of butyl acrylate and 0.3 g of tert-butyl peroxypivalate in a solution of 0.9 g of dipropyleneglycol, and further mixing for 5 min, parallel to continuously measure 274 g of vinyl acetate for 6 h (loading 1), a 30.4 g of butyl acrylate for 6 h (loading 2) and 6.0 g of tert-butyl peroxypivalate in a solution of 18 g of dipropyleneglycol within 7 h (loading 3) at constant flow rates, with stirring and within Enna temperature, equal to 70°C.

After downloading 3 and after further stirring the mixture at 70°C for one hour, three portions over two hours in each case at a temperature of 70°C. and further stirring 7.2 g of tert-butyl peroxypivalate dissolved in 9.0 g of dipropyleneglycol. In addition, to reduce the viscosity added 73 g dipropyleneglycol.

Unreacted residues of vinyl acetate is removed by distillation under vacuum at 70°C. In further addition of water was adjusted to a solids content of 19.8%.

The resulting grafted polymer is characterized by the value To equal 29,1, a polydispersity of 1.9 (Mw35.500, Mn18.400) and degree of branching of 0.7% (corresponding to 0.13 places vaccinations 50 fragments of ethylene oxide).

Grafted polymer 5

In the reactor for polymerization, equipped with a stirrer and a refrigerator backflow first place 1175 g of polyethylene glycol (Mn4.000) and melted at a temperature of 90°C. in a nitrogen atmosphere.

After adding 88.0 g of vinyl acetate and of 0.85 g of tert-butyl peroxy-2-ethylhexanoate in a solution of 3.5 g of tripropyleneglycol, and further mixing for 5 min, parallel to continuously measure 1674 vinyl acetate for 6 h (load 1) and 17.0 g of tert-butyl peroxy-2-ethylhexanoate in a solution of 71 g of tripropyleneglycol within 7 h (loading 2) at constant when arasteh thread under stirring at an internal temperature of 90°C.

After the end of the boot 2 and after further stirring the mixture at 90°C for one hour, three portions over two hours in each case at a temperature of 70°C. and further stirring of 39.0 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 21,0 g tripropyleneglycol. In addition, to reduce the viscosity added 73 g dipropyleneglycol.

Unreacted residues of vinyl acetate is removed by distillation under vacuum at a temperature of 90°C. further addition of water was adjusted to a solids content of 23.4%.

The resulting grafted polymer is characterized by the value of K, equal to 17.9, a polydispersity of 2.3 (Mw26.800, Mn11.700) and degree of branching of 0.6% (equivalent to 0.33 places vaccinations 50 fragments of ethylene oxide).

Grafted polymer 6

In the reactor for polymerization, equipped with a stirrer and a refrigerator backflow first place 444 g of polyethylene glycol (Mn6000) and melted at a temperature of 90°C. in a nitrogen atmosphere.

After adding 0,55 tert-butyl peroxy-2-ethylhexanoate dissolved 1.7 g of tripropyleneglycol, and subsequent stirring for 15 min, parallel to continuously measure 666 g of vinyl acetate for 6 h (load 1) and 7,22 g tert-butyl peroxy-2-ethylhexanoate dissolved in 21.6 g t is propilenglikola, within 6.5 h (loading 2) and also after 3 h after the beginning of the boot 1,233 g alkoxysilanes 2-propylheptanol (1 mol of propylene oxide and 10 mol of ethylene oxide/mol) for 3.5 h (loading 3) at constant flow rates, under stirring at an internal temperature of 90°C.

After download 2 and 3, and after further stirring the mixture at a temperature of 90°C for one hour, three portions over two hours in each case at a temperature of 90°C. and further stirring of 6.1 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 18,25 g tripropyleneglycol.

Unreacted residues of vinyl acetate is removed by distillation under vacuum at 90°C. further addition of water was adjusted to a solids content of at 86.9 per cent.

The resulting grafted polymer is characterized by a value of K equal to 17.6, a polydispersity of 1.8 (Mw35.700, Mn20.000) and degree of branching of 0.9% (corresponding to 0.33 places vaccinations 50 fragments of ethylene oxide).

The compositions

Example 7 - Granular detergent for washing

0-10
AndInDE
wt.%wt.%wt.%wt.%wt.%
With11-12line Las13-2513-2513-2513-259-25
With12-18ethoxyacrylate--0-3-0-1
With14-15alkylators (EO=7)0-30-3-0-50-3
Dimethylhydroxylamine chloride--0-20-20-2
Sodium tripolyphosphate20-40-18-3312-220-15
Zeolite0-1020-40 0-3--
Silicate filler0-100-100-100-100-10
Carbonate0-300-300-305-250-20
Diethylenetriaminepentaacetate0-10-10-10-10-1
Polyacrylate0-30-30-30-30-3
Carboxymethylcellulose0,2-0,80,2-0,80,2-0,80,2-0,80,2-0,8
Polymer1of 0.05-10of 0.05-105,02,51,0
PENTACARBONYL0-100-100-100-10
Nonanoyloxybenzenesulfonate--0-20-20-2
Tetraacetylethylenediamine--0-0,60-0,60-0,6
Zinc phthalocyanine tetrasulfonic--0-0,0050-0,0050-0,005
Dodgeof 0.05-0.2of 0.05-0.2of 0.05-0.2of 0.05-0.2of 0.05-0.2
MgSO4----0-0,50-0,50-0,5
Enzymes0-0,50-0,50-0,50-0,5 0-0,5
Minor additives (flavors, colors, foam stabilizers)restrestrestrestrest
1Amphiphilic graft polymer or any mixture of polymers according to any of Examples 1, 2, 3, 4, 5 or 6.

Example 8 - Granular detergent for washing

Waterborne composition

ComponentThe content in the aqueous slurry, wt.%
The compound having the following General structure: bis((C2H5O)(C2H4O)n)(CH3)-N+-CxH2x-N+-(CH3)-bis((C2H5O)(C2H4O)n), where n = from 20 to 30, and x = from 3 to 8, or sulfated or sulfonated options1,23
Ethylenediaminetetra acid0,35
Dodge0,12
Magnesium sulfate0,72
Acrylate/ malaty copolymer6,45
Polymer11,60
Line Las11,92
Hydroxyethane(methylenephosphonate acid)0,32
Sodium carbonate4,32
The sodium sulfate47,49
Soap0,78
Water24,29
Other substances0,42
Only100,00
1Amphiphilic graft polymer or any mixture of polymers according to any of Examples 1,2, 3,4, 5 or 6.

Preparation of powder using spray drying

Prepare a water suspension having the above composition and containing 25,89% moisture. The aqueous suspension is heated to 72°C and pumped under high pressure (from 5.5×106N/m2to 6.0×106N/m2in countercurrent column for the spray drying temperature of the input air from 270 to 300°C. In the bacterial suspension is sprayed and itemizedoverlay suspension is dried, receiving a dry mixture, which is subsequently cooled and sieved in order to separate too large lumps (>1.8 mm). The result is a free flowing powder obtained by spray drying. Small particles (<0.15 mm) otmuchivajut exhaust air in the column for spray drying and collect in a protective system after the column. The powder obtained by spray drying, characterized by a moisture content of 1.0 wt.%, bulk density 427 g/l and the parameters of the distribution of particle size that is 95.2 wt.% the powder particles have a size of from 150 to 710 μm. The powder obtained by spray drying below.

The powder obtained by spray drying

ComponentThe content in the powder obtained by spray drying, wt.%
The compound having the following General structure: bis((C2H5O)(C2H4O)n)(CH3)-N+-CxH2x-N+-(CH3)-bis((C2H5O)(C2H4O)n), where n = from 20 to 30, and x = from 3 to 8, or sulfated or sulfonated options1,65
Atlantium nayantara acid 0,47
Dodge0,16
Magnesium sulfate0,96
Acrylate/malaty copolymer8,62
Line Las15,92
Hydroxyethane(methylenephosphonate acid)0,43
Sodium carbonate5,77
The sodium sulfate63,43
Soap1,04
Water1,00
Other substances0,55
Only100,00

Preparation of fraction 1 anionic surfactants

Fraction 1 anionic detergent surfactants are obtained from mixtures of a total weight of 520 g using a mixing device Tilt-A-Pen, and then the device Tilt-A-Flow (both devices are manufactured by the company Processall). 108 g of sodium sulfate is introduced into a mixing device Tilt-A-Pen together with 244 g of sodium carbonate. 168 g PA who you are C 25E3S (alexisoliviat sodium-based alcohol12/15and of ethylene oxide)containing 70% of the active substance added to a mixing device Tilt-A-Pen. After this, the components are stirred at 1200 rpm for 10 C. the resulting powder is transferred into a mixing device Tilt-A-Flow and mixed at 200 rpm for 2 min to form granules. The pellets are dried in a fluidized bed dryer at a flow of 2500 l/min at a temperature of 120°C until equilibrium relative humidity of the granules will not be less than 15%. After that, the dried granules are sieved and retain the fraction that has passed through the sieve 1180 μm and remaining on a sieve of 250 μm. Composition of fraction 1 anionic detergent surfactants is as follows:

to 25.0 wt.% ethoxysulfuron sodium C25E3S,

18.0 wt.% sodium sulfate

to 57.0 wt.% sodium carbonate.

Preparation of fraction 1 cationic detergent surfactants

Fraction 1 cationic surfactants derived from mixtures of a total weight of 14.6 kg using a mixing device Morton FM-50 Loedige. 4.5 kg of finely ground sodium sulfate and 4.5 kg of finely ground sodium carbonate mixed in a mixing device Morton FM-50 Loedige. 4.6 kg of an aqueous solution of mono12/14alkyla gidroxiatilzelllozu chloride (cationic surfactant), containing 40% of active substance added in the mixing device Morton FM-50 Loedige running the main drive and the chopper. After about 2 min of mixing in the mixing device added to 1.0 kg of a mixture 1:1 by weight of finely ground sodium sulfate and finely ground potassium carbonate. The obtained granulate is collected and dried in a fluidized bed dryer with air flow 2500 l/min at a temperature of 100-140°C for 30 minutes the resulting powder was sieved and as a fraction of 1 cationic detergent surfactant selected fraction that has passed through the sieve 1400 μm. Composition of fraction 1 of cationic surfactants is as follows:

40,76 wt.% sodium carbonate,

40,76 wt.% sodium sulfate

3,48 wt.% moisture and other substances.

Preparation of a granular surfactant composition for washing

10,84 kg powder obtained by the method of spray drying as in example 1, 4,76 kg fraction 1 anionic surfactants, 1.57 kg of fraction 1 cationic detergent surfactants and 7,83 kg (total number) of other individually dosed materials in dry form is dosed into the concrete mixing device with a diameter of 1 m, operating at a speed of 24 rpm After the batching of all materials in the concrete mixing condition the device, for the formation of the granular surfactant composition for washing the mixture is stirred for 5 minutes, the Composition of the granular surfactant composition for washing described below.

Granular surfactant composition for washing

ComponentThe content in the granular surfactant composition for washing, wt.%
The powder obtained by spray drying, for example 143,34
Line Las containing of 91.6 wt.% the active substance in the form of flakes supplied by the Stephan company under trade name Nacconol 90G®0,22
Citric acid5,00
Percarbonate sodium (the active substance ranges from 12% to 15% AvOx)14,7
Potootvedeniya particles0,01
Lipase (11,00 mg active substance/g)0,70
Amylase (21,55 mg active substance/g)0,33
Protease (56,00 mg active substance/g)0,43
Granulated tetraacetylethylenediamine (92 wt.% active substances)4,35
Granulated antifoam (11.5 wt.% active substances)0,87
Granulated acrylate-malaty copolymer (95,7 wt.% active substances)0,29
Green/blue carbonate granules0,50
Fraction 1 anionic detergent surfactants19,04
Fraction 1 cationic detergent surfactants6,27
The sodium sulfate3,32
Granulated perfume0,63
Only100,00

Example 9 Liquid detergent for washing

1,9
IngredientAndInD EF5
wt.%wt.%wt.%wt.%wt.%wt.%
Alkylsulfate sodium14.4V14.4V9,2of 5.4
Linear alkylbenzenesulfonate acid4,44,412,2the 5.71,3
Alkalitolerant2,22,28,88,13,4
Aminexil0,70,71,5
Citric acid2,02,03,41,01,6
Fatty acid3,03,08,316,0
Protease1,01,00,71,02,5
Amylase0,20,20,20,3
Lipase0,2
Borax1,51,52,42,9
The calcium formate and sodium0,20,2
Formic acid1,1
Polymer11,81,82,13,2
Polyacrylate sodium0,2
A copolymer of sodium polyacrylate0,6
DTPA20,10,10,9
DTPMP30,3
EDTA40,1
Fluorescent brightening agent0,150,150,20,120,120,2
Ethanol2,52,51,41,5
Propandiol6,66,6a 4.94,015,7
Sorbitol4,0
Ethanolamine1,51,50,80,1/td> 11,0
Sodium hydroxide3,03,0a 4.91,91,0
Coolcullen sodium2,0
Silicone antifoam0,01
Perfume0,30,30,70,30,40,6
Cloud50,300,200,50
Waterrestrestrest restrestrest
100,0100,0100,0100,0100,0100,0
1Amphiphilic graft polymer or any mixture of polymers according to any of Examples 1, 2, 3,4, 5 or 6.
2Diethylenetriaminepentaacetic acid sodium salt
3Diethylenetriaminepentaacetate acid sodium salt
4Ethylenediaminetetraacetic acid sodium salt
5Acusol OP 301

Example 10 is a Liquid detergent for washing dishes

td align="center"> 1,0
TrackAndIn
With12-13natural AE0,6S29,029,0
With10-14srednerazmernyj aminexil-6,0
C12-14linear aminexil6,0-
SAFOL® 23 aminexil1,0
With11E9non-ionic surfactants22,02,0
Ethanol4,54,5
Polymer15,02,0
Coolcullen sodium1,61,6
Polypropylenglycol 20000,80,8
NaCl0,80,8
1,3 BANG diamine30,50,5
Polymeric activator foam40,20,2
Waterrestrest
1Amphiphilic graft polymer or any mixture of polymers according to any of
from Examples 1, 2, 3, 4, 5 or 6.
2Nonionic surfactants can be any of the C11alkylalkoxysilane surfactant ve the EU ETS, containing 9 ethoxyline fragments
31,3 BANG - 1,3-bis(methylamine)cyclohexane
4(N,N-dimethylamino)atheletically a homopolymer

Example 11 - Detergent for automatic dishwashers

AndInDE
Polymer dispersant0,55655
Carbonate35404035-4035-40
Sodium tripolyphosphate06100-100-10
Solid silicates66666
Bleach and bleach activators 4444
Polymer1of 0.05-1012,5510
Enzymes0,3-0,60,3-0,60,3-0,60,3-0,60,3-0,6
Dehydrate twosemester of citrate0002-200
Nonionic surfactant300000,8-5
Water, sulfate, fragrance, dyes and other additivesthe rest is up to 100the rest is up to 100the rest is up to 100the rest is up to 100the rest is up to 100
1Amphiphilic grafted floor is taken or any mixture of polymers according to any of Examples 1, 2, 3, 4, 5 or 6.
2Such as ACUSOL® 445N, supplied by Rohm & Haas, or ALCOSPERSE® company Alco.
3Such as SLF-18 POLY TERGENT company Olin Corporation.

Unless otherwise stated, all grades of components or compositions are given in relation to active gradation of this component or composition, and eliminate impurities such as residues of solvents or by-products that may be present in commercially available sources.

All values are percentage of the contents and relations are calculated by weight, unless otherwise indicated. All values are percentage of the contents and relations are calculated based on the total composition, unless otherwise indicated.

You must understand that every maximum numerical limit given in this description, includes each of the minimum numeric limit, if the data is the minimum numeric limits were explicitly specified here in writing. Each minimum numeric limit given in this description, includes every maximum numerical limit, if the data is the maximum numerical limit has been explicitly stated here in writing. Each numerical range given in this description, includes every narrower numerical range that is located within such broader numerical range, if such narrower numerical range is asony were all explicitly specified here in writing.

All documents cited in the description of the invention, includes, in its relevant part, by reference; the citation of any document is not to be construed as a recognition of his prior art against the present invention.

Although described and illustrated private embodiments of the invention, those skilled in the art should be obvious that various other changes and modifications may be made without departing beyond being and scope of the invention. Therefore, the attached claims means cover all such changes and modifications that are within the scope of the present invention.

1. Examples of the polymers in accordance with the present invention

PEG-PVA 101 polymer has a structure that is highly similar to the structure of the polymer Sokalan HP22 (as shown in the table below), the main difference is the lower previtali (from 0.7±0.1 to 0.3±0.1 to 50 fragments accelerated).

To evaluate the effectiveness of the polymers when removing stains, grease and dirt from the fabric were carried out the following tests in standardized Mexican conditions of the washing using the Mexican double-drum washing machines.

The concentration of detergent2414 ppmPre-rinseno
The volume of water33 lPreliminary dissolution3 min
Water hardness12 gpg (Grand Prix in gallons) (Ca:Mg=2:1)Steeping time0 min
Water temperature20-25°CThe wash20 min
1th/2thtime rinse5 min
Download size1.3 kg, a typical Mexican pollutionMethod of evaluationVisual analysis and image analysis (SRI)

The following detergents were obtained with Neal polymer, Sokalan HP22 (B), and PEG-PVA(S):

To determine the effectiveness of detergent compositions during washing the level of each of contamination was evaluated before and after washing with SIP the soup photometer Elrepho 2000 (Datacolor). The reaction was measured at 460 nm and used to calculate the Delta mud removal in % (ΔSR) in accordance with formula 1. The results are shown below.

Formula 1: calculation of Delta contaminant removal in % (ΔSR)

= Remission before washing,

Rafter= Remission after washing,

Rnet= Remission pure white cotton.

Were applied following the model of the spot and the results were averaged: contaminated cooking oil, bacon, lard, olive oil, margarine, butter, beef.

2. Results: the Cumulative value of the Delta-SRI (index remove dirt) compared to the benchmark (Nile-polymer) for all spots of fat

From the following data can clearly be observed beneficial effect of the polymer in accordance with the present invention for removing stains. Additionally, data demonstrate that the effect increases with decreasing level of previtali, from an average of 0.7 to 0.3 50 fragments accelerated:

ΔSR
Neil polymer0,0 (=standard)
Sokalan HP229,4
PEG-PVA3,6

1. A cleaning composition containing an amphiphilic graft polymer based on water-soluble polyalkyleneglycol (A), which is the basis of the grafted polymers, and side chains formed by polymerization of ester of vinyl alcohol (B), with the said polymer has an average ≤1 place fork 50 fragments accelerated and is the average molar mass Mwfrom 3000 to 100000 and surfactant system.

2. The cleaning composition according to claim 1, characterized in that the cleaning composition is selected from the group consisting of liquid detergent compositions for washing, solid detergent compositions for washing, cleaning compositions for solid surfaces, liquid compositions for washing dishes manually, solid compositions for automatic dishwashing machines, liquid products for automatic dishwashers and compositions for automatic dishwashing machines, located in unit dose form.

3. The cleaning composition according to claim 1 or 2, characterized in that the cleaning composition comprises an amphiphilic graft polymer in an amount of from 0.05 to 10 wt.% the cleaning composition.

4. The cleaning composition according to claim 1 or 2, characterized in that the amphiphilic graft polymer has a polydispersity of less than or equal to 3.

5. The cleaning composition according to claim 1 or 2, characterized in that the amphiphilic graft polymer contains less than or equal to 10 wt.% unvaccinated complex ester of polyvinyl alcohol.

6. The cleaning composition according to claim 1 or 2, characterized in that the amphiphilic graft polymer contains:
(A) from 20 to 70 wt.% water-soluble polyalkylene as the basis of the grafted polymer and
(B) side chains formed by free radical polymerization of from 30 to 80 wt.% complex ester of vinyl alcohol, consisting of:
(B1) from 70 to 100 wt.% vinyl acetate and / or finalproject and
(B2) from 0 to 30 wt.% additional unsaturated ethylene monomer
in the presence of (A).

7. The cleaning composition according to claim 1 or 2, characterized in that the amphiphilic graft polymer obtained by free radical polymerization:
(B) from 30 to 80 wt.% complex ester of vinyl alcohol, consisting of
(B1) from 70 to 100 wt.% vinyl acetate and / or finalproject and
(B2) from 0 to 30 wt.% additional unsaturated ethylene monomer, in the presence of
(A) from 20 to 70 wt.% water-soluble polyalkylene with an average molar mass Mnfrom 1500 to 20000,
(C) from 0.25 to 5 wt.%, in the calculation of the component (B), initiator forming free radicals, and
(D) from 0 to 40 wt.%, based on the sum of components (A), (b) and (C)an organic solvent
at an average temperature of polymerization, at which time half-life of the initiator (C) is from 40 to 500 rpm, polymerized so that the proportion of unreacted teach monomial is RA (b) and initiator (C) in the reaction mixture is maintained in a quantitative deficiency in relation to polyalkyleneglycol (A).

8. The cleaning composition according to claim 1, characterized in that the surfactant system contains a C10-C15alkylbenzenesulfonate.

9. The cleaning composition according to claim 1, characterized in that the surfactant system contains a C8-C18linear alkylsulfonate surfactant.

10. The cleaning composition of claim 8 or 9, wherein the surfactant system further comprises one or more auxiliary surfactant selected from the group consisting of nonionic surfactants, cationic surfactants, anionic surfactants and mixtures thereof.

11. The cleaning composition according to any one of claims 1, 2 or 8, wherein the cleaning composition further comprises an auxiliary cleansing supplements.

12. The cleaning fixture containing non-woven substrate and a cleaning composition according to any one of the preceding paragraphs.



 

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19 cl, 7 tbl, 6 ex

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21 cl, 5 tbl

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10 cl, 6 tbl, 6 ex

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22 cl, 6 ex

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10 cl, 7 tbl, 5 ex

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19 cl, 2 tbl, 11 ex

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11 cl, 1 tbl, 6 ex

FIELD: cosmetology.

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15 cl, 3 ex, 1 dwg

FIELD: medicine.

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1 ex

FIELD: textile industry.

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20 cl, 17 dwg, 11 ex

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1 tbl, 6 ex

FIELD: household chemical goods.

SUBSTANCE: invention relates to solid molded detergent compositions for cleaning hard surfaces, washing of textiles, or for personal hygiene. Cleaning agent contains 5 to 95% active detergent, 0 to 90% inorganic substance particles or other common ingredients, and at least 5% water. Outside surface of cleaning agent is covered by at least one polymer film formed by radiation hardening of polymer composition capable of being hardened under irradiation.

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22 cl, 6 tbl, 6 ex

FIELD: chemistry of polymers.

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EFFECT: improved preparing method, improved and valuable properties of composition.

55 cl, 11 tbl, 14 ex

FIELD: chemistry.

SUBSTANCE: composition, which contains one or several surface active substances (5-95 wt.%), 40 wt.% or more of all surface active substances being non-ionic, and one or several water-swellable polymers, which absorb water in amount exceeding their own weight (5-95 wt.%), is suggested. Weight ratio of surface active substances to water-swellable polymers is within 1:0.4 to 0.4:1. Water-swellable polymer is selected from the following compounds: polyacrylic acids, polyacrylates, cross-linked acrylates, guar gum and derivatives thereof, starch acrylic grafted copolymers, hydrolysates of starch acrylic grafted copolymers, cross-linked polyoxyethylene, cross-linked carboxymethyl cellulose, partially cross-linked water-swellable polymers, such as polyethylenoxide and polyacrylamide, isobutylene/maleic acid copolymers.

EFFECT: concentrates composition can be converted to an easy-to-use product by adding water prior to use.

15 cl, 2 tbl, 2 ex

FIELD: chemistry.

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EFFECT: higher efficiency of bleaching detergent, all type decontamination with additional softening of fabric and without irritation of hand skin during manual washing, lower temperature modes of washing, reduced damage effect on metal parts of washing machines.

10 cl, 2 tbl, 5 ex

FIELD: chemistry.

SUBSTANCE: detergent contains, wt %: sodium alkylbenzolsulphonate 5-10, synthanol ALM-7 1-2, polyethylene glycol 1-2, trisodphium phosphate 4-16, caustic soda 1-2, and water - the rest.

EFFECT: higher detergent power in solid surface cleaning.

2 tbl, 3 ex

FIELD: medicine.

SUBSTANCE: first, waterproof layer of absorbing tissue is placed on victim's body surface under blood-stained section of clothes, then the section is continuously flushed and rubbed with a sponge soaked in aqueous flushing fluid with pH over 7.0 and hypoosmolarity under 140 milliosmol per litre of water at +26 to +42°C till the stain changes colour from red to yellow. Afterwards the tissue is replaced with a new one, stained clothe sector is soaked for up to 2 seconds in bleach fluid with pH over 7.0, and is soaked twice in 2 seconds by sponge with flushing fluid. Further the tissue is removed, wet fabric is dried by drying tissues and warm dry air flow.

EFFECT: enhanced efficiency, safety and expediency of stain removal.

1 ex

FIELD: cosmetology.

SUBSTANCE: invention relates to cosmetology and is represented by a cleansing compound consisting from approximately 2.6% to approximately 3% (weight) of an aqueous emulsion of an acrylate copolymer, from approximately 7.7% to approximately 10.2% (weight) of an anionic surfactant and from approximately 1.4% to approximately 1.7% (weight) of an amphoteric surfactant, an effective quantity of balls of shea butter and seeds, the diametre of each ball varying within the range from 100 to 1200 micron; and additional ingredients required to bring the compound composition to 100%.

EFFECT: invention enables improvement of cleansing properties, is characterised by high translucency and improved stability.

15 cl, 3 ex, 1 dwg

FIELD: chemistry.

SUBSTANCE: detergent composition for hand washing linen contains a polymer in which 90 wt % or more of monomer units consists ethylene oxide. The polymer has average molecular weight ranging from 1500000 or more to 4500000 or less and is contained in amount ranging from over 0.03 wt % to 5 wt % of the detergent composition. The composition also contains 10-40 wt % alkyl benzene sulphonate and 7-40 wt % alkalising agent.

EFFECT: improved smoothness when washing with mechanical friction.

11 cl, 1 tbl, 6 ex

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