Patent Application
20120015860
The present invention generally relates to the use of carboxy group-carrying saccharidic polymer to reduce the damage of bleach-activating transition metal complexes in the treatment of material containing cellulose in particular in washing textiles, a gentle method for treating material containing cellulose in the presence of a peroxygen-containing bleaching agent and a bleach-activating transition metal complex as well as agents containing peroxygen-containing bleaching agent, bleach-activating transition metal complex and carboxyl group-carrying saccharidic polymer.
Inorganic peroxygen compounds, in particular hydrogen peroxide and solid peroxygen compounds which dissolved in water, releasing hydrogen peroxide such as sodium perborate and sodium carbonate perhydrate, have long been used as oxidizing agents for disinfection and bleaching purposes. The oxidizing effect of these substances in dilute solutions depends greatly on the temperature. For example, with H2O2 or perborate in alkaline bleaching solutions, a sufficiently rapid bleaching of soiled textiles is achieved only at temperatures above approx. 80° C. At lower temperatures the oxidation effect of the inorganic peroxygen compounds can be improved by adding so-called bleach activators for which numerous proposals have become known in the literature, especially from the substance classes of N- or O-acyl compounds, for example, polyacylated alkylene diamines, in particular tetraacetylethylene diamine, acylated glycol urils, in particular tetraacetylglycol uril, N-acylated hydantoins, hydrazides, triazoles, hydrotriazines, urazoles, diketopiperazines, sulfurylamides and cyanurate, also carboxylic anhydrides, in particular phthalic anhydride, carboxylic acid esters, in particular sodium nonanoyloxybenzene sulfonate, sodium isononanoyloxybenzene sulfonate and acylated sugar derivatives such as pentaacetylglucose. By adding these substances, the bleaching effect of aqueous peroxide solutions can be increased to such an extent that essentially the same effects occur even at temperatures around 60° C. as with the peroxide bath alone at 95° C. Damage to the tissue remains within an acceptable framework for the user.
In an effort to develop energy-saving washing and bleaching methods, use temperatures definitely below 60° C. in particular less than 45° C. down to cold water temperature have become increasingly important in the recent years.
At these low temperatures, the effect of the activator compounds known in the past usually declines perceptibly. Therefore there has been no lack of attempts to develop more effective bleach systems for this temperature range. One approach is obtained by using hydrogen peroxide-supplying compounds together with transition metal salts and complexes as so-called bleaching catalysts. With these catalysts, however, there is the risk of oxidative damage to the textile presumably because of the high reactivity of the oxidizing intermediates formed from them and the peroxygen compound. The use of such transition metal catalysts in washing agents has previously been made difficult in practice because then the damage to the tissue is much higher than that with a conventional peracid-forming system of bleaching agent and bleach activator. The same thing is logically also true of bleaching processes performed in the production of materials containing cellulose such as pulp or paper.
Furthermore, other desirable features and characteristics of the present invention will become apparent from the subsequent detailed description of the invention and the appended claims, taken in conjunction with this background of the invention.
Accordingly, it is desirable to reduce the damage to the material containing cellulose, for example, a textile containing cotton with the use of bleaching catalysts in bleaching treatment of material containing cellulose, for example, in washing textiles containing cotton, without significantly influencing the bleaching performance.
The present invention relates to a method for bleaching treatment of material containing cellulose in particular the production of pulp or paper or in washing textiles containing cotton in the presence of a peroxygen-containing bleaching agent and a bleach-activating transition metal complex which is characterized in that it is performed in the presence of carboxyl group-carrying saccharidic polymer.
The following detailed description of the invention is merely exemplary in nature and is not intended to limit the invention or the application and uses of the invention. Furthermore, there is no intention to be bound by any theory presented in the preceding background of the invention or the following detailed description of the invention.
The carboxyl group-carrying saccharidic polymer of the present invention is preferably selected from alginate, pectin, pectinate and mixtures of at least two of these.
Alginic acid and/or its salts are naturally occurring ingredients of brown algae (Phaeophycea) in which they are present as cell wall constituents. Alginic acids are acidic carboxyl group-containing polysaccharides with a relative molecular weight MR of approx. 200,000 consisting of d-mannuronic acid and 1 guluronic acid in different ratios which are linked by 1,4-glycosidic bonds. Alginates that may be used according to the invention include in particular the alkali and alkaline earth salts of alginic acid, but not all carboxyl groups of the alginic acid must be present in salt form. The sodium, potassium, ammonium and magnesium alginates are readily water soluble. The viscosity of alginate solutions depends on the molecular weight and the counterion among other things. Calcium alginates form thermoirreversible gels, for example, at certain quantity ratios. Sodium alginates yield more or less highly viscous solutions in water.
Pectins are naturally occurring polysaccharides whose main constituent (normally at least 65 wt %) is α-D-galacturonic acid. The galacturonic acid monomers are linked together by α-1,4-glycosidic bonds, and to a small extent also by β-1,4-glycosidic bonds and thus form the backbone of the pectin molecule. The linear backbone is interrupted periodically by 1,2-bonds with α L rhamnose. The rhamnose units in natural pectins have oligomeric side chains from the sugars arabinose, galactose and/or xylose. The neutral sugar side chains may in turn be subdivided into arabinans, galactans and arabinogalactan-1 and arabinogalactan-II, which are linked to proteins. The lengths of the side chains are usually between 1 and 50 sugar units. Industrially production of pectins, these side chains are mostly lost. The hydroxyl groups at C2 and/or C3 of the galacturonic acid units are acetylated to a small extent or are substituted by other neutral sugars such as D-galactose, D-xylose, L arabinose, L-rhamnose. Some of the carboxyl groups of polygalacturonic acid are usually esterified with methanol. The degree of esterification and acetylation varies with the origin of the pectin. On action of aqueous alkaline solutions or pectinase on pectin, pectosinic acid is formed and then pectinic acid. Pectinic acid forms a colorless mass which is hardly soluble in cold water, sparingly soluble in hot water, insoluble in alcohol but readily soluble in the solutions of neutral salts; it reacts and tastes acidic and forms soluble gelatinous salts with the alkalis, insoluble gelatinous salts with other metals. By addition of calcium ions onto the galacturonic acid units, the largely water-insoluble calcium pectinate is formed. Pectinates that may be used according to the invention include in particular the alkali and alkaline earth salts of pectinic acid, where the alkali salts are especially preferred and not all carboxyl groups of the pectinic acid must be present in salt form.
Bleach-activating transition metal complex compounds that may be used include in particular those of the metals Fe, Mn, Co, V. Ru, Ti, Mo, W, Cu and/or Cr, for example, manganese, iron, cobalt, ruthenium or molybdenum-saline complexes, manganese, iron, cobalt, ruthenium or molybdenum-carbonyl complexes, manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes with nitrogen-containing tripod ligands, cobalt, iron, copper and ruthenium-ammine complexes and iron or manganese complexes with polyazacycloalkane ligands such as TACN.
The preferred bleach-activating transition metal complex compounds include metal complexes of the formula (I)
[LnMmXp]z Yq (I)
where M denotes manganese or iron or mixtures of these metals, which may be present in oxidation states II, III, IV or V, or mixtures of same, n and m independently of one another are integers with a value of 1 to 4, X is a coordinating or bridging species, p is an integer with a value of 0 to 12, Y is a counterion whose type depends on the charge z of the complex, which may be positive, zero or negative, q=z/[charge Y] and L is a ligand which is a macrocyclic organic molecule of the general formula (II)
in which each of the radicals are R1 and R2 is zero, H, alkyl or aryl, optionally substituted; t and t′ independently of one another are 2 or 3; D and D1 independently of one another are N, NR, PR, O or S wherein R is H, alkyl or aryl, optionally substituted and S is an integer with a value of 2 to 5, wherein if D=N, then a heterocarbon bond bound thereto is unsaturated, which leads to the creation of an N═CR1 fragment. The preferred metal M is manganese. The coordinating or bridging species X is preferably a small coordinating ion or bridging molecule or a mixture of same, for example, water, OH−, O2−, S2−, S(═O), N3, HOO, O22−, O2−, amine, Cl−, SCN−, N3−, and carboxylate, for example, acetate or mixtures thereof. If the charge z is positive, then Y is an anion, for example, chloride, bromide, iodide, nitrate, perchlorate, rhodanide, hexafluorophosphate, sulfate, alkyl sulfate, alkyl sulfonate or acetate; if the charge z is negative, Y is a cation, for example, an alkali ion, ammonium, ion or alkaline earth ion. The preferred ligands L include 1,4,7-triazacyclononane, 1,4,7-trimethyl-1,4,7-triazacyclononane, 1,5,9-trimethyl-1,5,9-triazacyclododecane and 1,2,4,7-tetramethyl-1,4,7-triazacyclononane.
In another preferred embodiment the bleach-activating transition metal complex compound corresponds to general formula (III)
in which R10 and R11 independently of one another stand for hydrogen, a C1-18 alkyl group, a group NR13R14, a group N+R13R14R15 or a group
R12 stands for hydrogen, OH or a C1-18 alkyl group, R13, R14 and R15 independently of one another stand for hydrogen, a C1-4 alkyl or hydroxyalkyl group and X stands for halogen and A stands for a charge equalizing anion ligand which depending on its charge and the type and number of other charges in particular the charge of the manganese central atom may also be absent or may be present several times. Manganese may have oxidation stages II, III, IV or V therein as well as in the complexes according to formula (I). If desired, although less preferred, other transition metals, for example, Fe, Co, Ni, V, Ru, Ti, Mo, W, Cu and/or Cr may also be present instead of the Mn central atom in such complex compounds.
The inventive method may if desired be carried out at temperatures in the range of 10° C. to 95° C. The temperature is preferably in the range of 20° C. to 40° C.
The inventive method may if desired be performed at a pH in the weakly acidic to alkaline range in particular in the range of pH 5 to pH 12, preferably pH 8 to pH 11.
In an inventive method, concentrations of 0.0001 g/L to 2 g/L in particular 0.01 g/L to 1 g/L carboxyl group-carrying saccharidic polymer is used in the aqueous treatment solution.
In an inventive textile washing method preferred per oxygen concentrations (calculated as H2O2) in the wash solution are in the range of 0.001 g/L to 10 g/L, in particular 0.1 g/L to 1 g/L. The concentration of bleach-activating transition metal complex in the wash solution is preferably in the range of 0.1 μmol to 100 μmol/L in particular 0.5 μmol/L to 25 μmol/L.
The inventive method can be implemented, for example, by adding peroxygen-containing bleaching agent, bleach-activating transition metal complex and the carboxyl group-carrying saccharidic polymer each separately to a treatment solution for material containing cellulose, for example, a washing solution which may contain a conventional washing agent. It is also possible not to use the finished bleach-activating transition metal complex but instead to use separately one or more ligands which may form a bleach-activating transition metal complex in the process with a transition in situ; the transition metal may then also be added separately in the form of a salt or non-bleach-activating complex or it is added as a component of the process water used for the process or introduce into the process via the material containing cellulose to be treated in the case of textiles to be cleaned, for example, as a component of the soiling to be removed. It is possible or preferable here to introduce the bleach-activating transition metal complex and the carboxyl group-carrying saccharidic polymer simultaneously in particular as a premix preferably containing water and/or present in the form of an aqueous solution.
A second subject matter of the invention is the use of carboxyl group-carrying saccharidic polymer to prevent damage to material containing cellulose, for example, textiles containing cotton due to the presence of bleach-activating transition metal complexes in the bleaching treatment of material containing cellulose, for example, in washing textiles containing cotton.
It has surprisingly been found that by using carboxyl group-carrying saccharidic polymer, not only is damage to the material containing cellulose reduced but also the bleaching performance of the system of peroxygen-containing bleaching agent and bleach-activating transition metal complex is improved. Another subject matter of the invention is therefore the use of carboxyl group-carrying saccharidic polymer to improve the bleaching performance of bleach-activating transition metal complex and aqueous solutions containing peroxygen-containing bleaching agent.
In another preferred embodiment of the invention, an agent containing a peroxygen-containing bleaching agent, bleach-activating transition metal complex or a ligand which may form a bleach-activating transition metal complex in situ with a transition metal in the process and carboxyl group-carrying saccharidic polymer. Such a washing agent which is gentle to textiles is another subject matter of the invention.
Inventive washing agents which are present in solid form or as liquids or pastes may be used as such in machine or manual washing processes but may also be used as washing agent additives and/or as washing and/or textile pretreatment agents.
Inventive agents together with a conventional washing agent are used as the washing agent additive. This is appropriate in particular when the user wants to improve the bleaching performance of the usual washing agent. In the wash pretreatment the inventive agents are used to improve the removal of encrusted dirt or spots in particular “problem spots,” such as coffee, tea, red wine, grass or fruit juice which are difficult to remove by washing with usual textile washing agents but are accessible to an oxidative attack. Another area for use of such agents is to remove local soiling from otherwise clean surfaces so that a more complex washing or cleaning process of the corresponding overall structure, whether a clothing item or a carpet or a furniture upholstery part can be avoided. To do so, one may apply an inventive agent optionally together with an amount of water which is not sufficient to completely dissolve the agent to the textile surface and/or to the part to be cleaned in a simple manner, optionally applying mechanical energy, for example, by rubbing with a cloth or a sponge, and then removing the agent and the oxidatively attacked soil by washing out with water, for example, with the help of a moistened cloth or sponge after a period of time to be determined by the user.
The inventive agents preferably contain 0.01 wt % to 0.5 wt %, in particular 0.02 wt % to 0.3 wt % of bleach-activating transition metal complex. Alternatively or optionally also additionally the inventive agent may also contain only one or several ligands which can form a bleach-activating transition metal complex in situ with a transition metal in the washing process. The transition metal may also be present in the washing agent in the form of a salt or a non-bleach-activating complex or it is introduced into the washing process as a component of the process water used for it or via the textile to be cleaned, for example, as a component of the soil to be removed.
The inventive washing agent and cleaning agents may in principle contain all the known ingredients conventionally used in such agents, in addition to the peroxygen-containing bleach agent, the bleach-activating transition metal complex and/or the ligand, which may form the bleach-activating transition metal complex in situ, and carboxyl group-carrying saccharidic polymer. The inventive washing agents and cleaning agents may in particular contain builder substances, surface-active surfactants, enzymes, sequestering agents, electrolytes, pH regulators, polymers with special effects such as soil-release polymers, dye transfer inhibitors, graying inhibitors, wrinkle-reducing active ingredients and shape-retaining active ingredients and additional auxiliary substances such as optical brighteners, foam regulators, additional peroxygen activators, dyes and perfumes.
In particular organic peracids and/or peracidic salts of organic acids may be considered as peroxygen compounds suitable for use in the inventive method, in the inventive use and in the inventive agents, such as phthalimidopercaproic acid, perbenzoic acid or salts of diperdodecanedioic acid, hydrogen peroxide and inorganic salts that release hydrogen peroxide under the washing conditions, including alkali perborate, alkali percarbonate, alkali persilicate and/or alkali persulfate such as caroate. If solid peroxygen compounds are to be used, they may be used in the form of powders or granules which may also be coated in a manner which is known in principle. The addition of small amounts of known bleach agent stabilizers, for example, phosphonates, borates and/or metaborates and metasilicates as well as magnesium salts such as magnesium sulfate may be expedient. An inventive agent preferably contains 15 wt % to 50 wt %, in particular 18 wt % to 35 wt % peroxygen-containing bleaching agent in particular alkali percarbonate. Alternatively or optionally additionally, hydrogen peroxide may also be produced in the inventive process by an enzymatic system namely an oxidase in combination with its substrate which in a preferred embodiment of the invention is a component of the inventive agent and may partially or preferably completely replace the peroxygen-containing bleach agent in this inventive agent.
In addition to the bleach-activating transition metal complex compound, additional compounds known as bleach activating active ingredients may, if desired, also be used in the inventive agents, in particular conventional bleach activators, i.e., compounds which yield optionally substituted perbenzoic acid and/or peroxocarboxylic acids with 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms under perhydrolysis conditions. Conventional bleach activators which have O- and/or N-acyl groups of the aforementioned number of carbon atoms and/or optionally substituted benzoyl groups are suitable. Polyacylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated glycolurils in particular tetraacetylglycoluril (TAGU), acylated triazine derivatives in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-trizine (DADHT), acylated phenyl sulfonates in particular nonanoyloxy- or isononanoyloxybenzene sulfonate, N-acylated caprolactams or valerolactams, in particular N-acetylcaprolactam, acylated polyvalent alcohols in particular triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran as well as acetylated sorbitol and mannitol and acylated sugar derivatives in particular pentaacetyl glucose (PAG), pentaacetyl fructose, tetraacetyl xylose and octaacetyl lactose as well as acetylated optionally N-alkylated glucamine and gluconolactone. Nitriles which form perimidic acids under perhydrolysis conditions such as 4-morpholine carbonitrile or ammonium group-carrying acetonitriles may also be used. However, the inventive agents are preferably free of such conventional bleach activators.
The inventive agents may contain one or more surfactants, and in particular anionic surfactants, nonionic surfactants and mixtures of those may be considered. Suitable nonionic surfactants include in particular alkyl glycosides and ethoxylation and/or propoxylation products of alkyl glycosides or linear or branched alcohols each with 12 to 18 carbon atoms in the alkyl part and 3 to 20, preferably 4 to 10 alkyl ether groups. In addition corresponding ethoxylation and/or propoxylation products of N-alkylamines, vicinal diols, fatty acid esters and fatty acid amides which correspond to the aforementioned long-chain alcohol derivatives with regard to the alkyl part as well as alkyl phenols with 5 to 12 carbon atoms in the alkyl part may also be used.
Suitable anionic surfactants include in particular soaps and those containing sulfate or sulfonate groups with preferable alkali ions as cations. Soaps that may be used are preferable the alkali salts of saturated or unsaturated fatty acids with 12 to 18 carbon atoms. Such fatty acids may also be used in incompletely neutralized form. The usable surfactants of the sulfate type include the salts of sulfuric acid hemiesters of fatty alcohols with 12 to 18 carbon atoms and the sulfation products of the aforementioned nonionic surfactants with a low degree of ethoxylation. The usable surfactants of the sulfonate type include linear alkylbenzene sulfonates with 9 to 14 carbon atoms in the alkyl part, alkane sulfonates with 12 to 18 carbon atoms and olefin sulfonates with 12 to 18 carbon atoms which are formed by the reaction of corresponding monoolefins with sulfur trioxide as well as α-sulfofatty acid esters which are formed in sulfonation of fatty acid methyl or ethyl esters.
Such surfactants are present in the inventive cleaning agents or washing agents in amounts of preferably 5 wt % to 50 wt %, in particular 8 wt % to 30 wt %.
An inventive agent 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 methyl glycine diacetic acid, nitrolotriacetic acid, ethylenediamine-N,N′-disuccinic acid and ethylenediamine tetraacetic acid as well as polyaspartic acid, polyphosphonic acids in particular aminotris(methylenephosphonic acid), ethylenediamine tetrakis(methylenephosphonic acid) and 1 hydroxyethane-1,1-diphosphonic acid, polymeric hydroxyl compounds such as dextrin and polymeric (poly)carboxylic acids in particular the polycarboxylates accessible by oxidation of polysaccharides and/or dextrins, polymeric acrylic acids, methacrylic acids, maleic acids and copolymers thereof which may also contain small amounts of polymerizable substances without any carboxylic acid functionality polymerized into them. The relative molecular weight of the homopolymers of unsaturated carboxylic acids is generally between 5000 and 200,000 while that of the copolymers is between 2000 and 200,000 preferably from 50,000 to 120,000 each based on free acid. An especially preferred acrylic acid-maleic acid copolymer has a relative molecular weight of 50,000 to 100,000. Suitable although less preferred compounds of this class include copolymers of acrylic acid or methacrylic acid with vinyl ethers such as vinyl methyl ethers, vinyl esters, ethylene, propylene and styrene in which the amount of acid is at least 50 wt %. The water-soluble organic builder substances may also be terpolymers which contain as monomers two unsaturated acids and/or their salts and as the third monomer vinyl alcohol and/or an esterified vinyl alcohol or a carbohydrate. The first acetic monomer and/or its salt is derived from a monoethylenically unsaturated C3-C8 carboxylic acid and preferably from a C3-C4 monocarboxylic acid in particular (meth)acrylic acid. The second acidic monomer and/or its salt may be a derivative of a C4-C8 dicarboxylic acid, where maleic acid is especially preferred, and/or a derivative of an alkylsulfonic acid which is substituted in position 2 with an alkyl or aryl radical. Such polymers usually have a relative molecular weight between 1000 and 200,000. Additional preferred copolymers include those having preferably acrolein and acrylic acid/acrylic acid salt and/or vinyl acetate as monomers. All the aforementioned acids are usually used in the form of their water-soluble salts in particular their alkali salts.
Such organic builder substances may if desired be present in amounts of up to 40 wt %, in particular up to 25 wt % and preferably from 1 wt % to 8 wt %.
Water-soluble inorganic builder materials that may be considered include in particular polymeric alkali phosphates which may be present in the form of their alkaline, neutral or acidic sodium or potassium salts. Examples include tetrasodium diphosphate, disodium dihydrogen diphosphate, pentasodium triphosphate, so-called sodium hexametaphosphate and the corresponding potassium salts and/or mixtures of sodium and potassium salts. Water-insoluble, water-dispersible inorganic builder materials used include in particular crystalline or amorphous alkali aluminosilicates in amounts of up to 50 wt %, preferably no more than 40 wt % and in liquid agents in particular from 1 wt % to 5 wt %. Of these, the crystalline sodium aluminosilicates in washing agent quality, in particular zeolite A, P and optionally X are preferred. Quantities near the aforementioned upper limit are preferably used in solid particulate agents. Suitable aluminosilicates in particular do not have any particles with a grain size of greater than 30 μm and preferably consist of at least 80 wt % particles less than 10 μm in size. Their calcium binding capacity, which can be determined according to the specifications of German Patent DE 24 12 837, is usually in the range of 100 to 200 mg CaO per gram.
Suitable substitutes and/or partial substitutes for the aforementioned aluminosilicate include crystalline alkali silicates which may be present alone or in mixture with amorphous silicates. The alkali silicates which can be used as builders in the inventive agents preferably have a molar ratio of alkali oxide to SiO2 of less than 0.95 in particular 1:1.1 to 1:12 and may be in amorphous or crystalline form. Preferred alkali silicates include the sodium silicates in particular the amorphous sodium silicates with a molar ratio of Na2O:SiO2 of 1:2 to 1:2.8. Crystalline layered silicates of the general formula Na2SixO2x+1≅yH2O, where x, the so-called modulus, is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4, are preferably used as crystalline silicates, which may be present alone or in mixture with amorphous silicates. Preferred crystalline layered silicates include those in which x in the aforementioned general formula assumes the values of 2 or 3. In particular both β- and δ-sodium disilicates (Na2Si2O5≅yH2O) are preferred. Practically anhydrous crystalline alkali silicates of the aforementioned general formula produced from amorphous alkali silicates, where x is a number from 1.9 to 2.1, may be used in the inventive agents. In another preferred embodiment of inventive agents, a crystalline sodium layered silicate with a modulus of 2 to 3 is used such as that which can be produced from sand and sodium carbonate. Crystalline sodium silicates with a modulus in the range of 1.9 to 3.5 are used in another preferred embodiment of the inventive agents. In a preferred embodiment of inventive agents, a granular compound of alkali silicate and alkali carbonate is used such as that available commercially under the brand name Nabion® 15. If alkali aluminosilicates in particular a zeolite is also present as an additional builder substance, then the weight ratio of aluminosilicate to silicate, each based on anhydrous active substances, is preferably 1:10 to 10:1. The weight ratio of amorphous alkali silicate to crystalline alkali silicate in agents containing both amorphous and crystalline alkali silicates is preferably 1:2 to 2:1 and in particular 1:1 to 2:1.
Builder substances are preferably present in the inventive washing agents or cleaning agents in amounts of up to 60 wt %, in particular from 5 wt % to 40 wt %, while the inventive disinfectants are preferably free of the builder substances which complex only the components of water hardness and preferably contain no more than 20 wt %, in particular 0.1 to 5 wt % heavy metal complexing substances, preferably from the group comprising aminopolycarboxylic acids, aminopolyphosphonic acids and hydroxypolyphosphonic acids and their water-soluble salts and mixtures thereof.
In a preferred embodiment of the invention, an inventive agent contains a water-soluble builder block. By using the term “builder block” this should express the fact that the agent does not contain any other builder substances than those which are water soluble, i.e., all the builder substances present in the agent are combined in what is characterized as a “block” but at any rate the quantities of substances excluding those stabilizing additives and/or impurities may be present in small amount in the other ingredients of the agents. The term “water soluble” should be understood to mean that the builder block dissolves without leaving a residue at the concentration which results from the use quantity of the agent containing it under the usual conditions. Preferably at least 15 wt % and up to 55 wt %, in particular 25 wt % to 50 wt % water-soluble builder block is present in the inventive agents. This is preferably composed together of the components
a) 5 wt % to 35 wt % citric acid, alkali citrate and/or alkali carbonate, which may be replaced at least proportionally by alkali bicarbonate,
b) up to 10 wt % alkali silicate with a modulus in the range of 1.8 to 2.5,
c) up to 2 wt % phosphonic acid and/or alkali phosphonate,
d) up to 50 wt % alkali phosphate and
e) up to 10 wt % polymeric polycarboxylate,
where the quantities given are also based on the total washing agent and/or cleaning agent. This is also true of all the other quantity information unless explicitly stated otherwise.
In a preferred embodiment of inventive agents the water-soluble builder block contains at least two of the components b), c), d) and e) in amounts greater than 0 wt %.
With regard to component a), in a preferred embodiment of inventive agents, 15 wt % to 25 wt % alkali carbonate, which may be replaced at least proportionately by alkali bicarbonate, and up to 5 wt %, in particular 0.5 wt % to 2.5 wt % citric acid and/or alkali citrate are contained in it. In an alternative embodiment of the inventive agents, 5 wt % to 25 wt %, in particular 5 wt % to 15 wt % citric acid and/or alkali citrate and up to 5 wt %, in particular 1 wt % to 5 wt % alkali carbonate which may be replaced at least proportionally by alkali bicarbonate are present as component a). If both alkali carbonate and alkali bicarbonate are present, then component a) contains alkali carbonate and alkali bicarbonate preferably in a weight ratio of 10:1 to 1:1.
With regard to component b), in a preferred embodiment of the inventive agents, 1 wt % to 5 wt % alkali silicate with a modulus in the range of 1.8 to 2.5 may be present.
With regard to component c) in a preferred embodiment of inventive agents 0.05 wt % to 1 wt % phosphonic acids and/or alkali phosphonate are present. Of the phosphonic acids, optionally substituted alkyl and aryl phosphonic acids such as, for example, phenyl phosphonic acid are understood which may also contain several phosphonic acid groupings (so-called polyphosphonic acids). They are preferably selected from the hydroxy and/or aminoalkylphosphonic acids and/or their alkali salts, for example, dimethylaminomethane diphosphonic acid, 3-aminopropane-1-hydroxy-1,1
diphosphonic acid, 1-amino-1-phenylmethanediphosphonic acid, 1-hydroxy
ethane-1,1-diphosphonic acid (HEDP), amino-tris(methylenephosphonic acid), and acylated derivatives of phosphorous acid which may also be used in any mixtures.
With regard to component d) in a preferred embodiment of the inventive agents 15 wt % to 35 wt % alkali phosphate in particular trisodium polyphosphate is present. Alkali phosphate is the umbrella term for the alkali metal salts (in particular sodium and potassium salts) of the various phosphoric acids, and a distinction can be made between metaphosphoric acids (HPO3)n and orthophosphoric acid H3PO4 in addition to higher molecular representatives. The phosphates combine several advantages: they act as alkali carriers, prevent lime deposits on machine parts and/or lime encrustations in fabrics and also contribute toward the cleaning performance. Sodium dihydrogen phosphate NaH2PO4 exists as a dihydrate (density 1.91 gcm−3, melting point 60° C.) and as a monohydrate (density 2.04 gcm−3). Both salts are white powders which are very highly soluble in water, lose their water of crystallization on heating and are converted at 200° C. into the weakly acidic diphosphate (disodium hydrogen diphosphate Na2H2P2O7), at a higher temperature into sodium trimetaphosphate (Na3P3O9) and Madrell's salt. NaH2PO4 gives an acidic reaction and is formed when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the slurry is sprayed. Potassium dihydrogen phosphate (primary or monobasic potassium phosphate, potassium biphosphate KDP), KH2PO4 is a white salt of the density 2.33 gcm−3 has a melting point of 253° C. (decomposes, forming (KPO3)x, potassium polyphosphate and is readily soluble in water. Disodium hydrogen phosphate (secondary sodium phosphate) Na2HPO4 is a colorless very readily water-soluble crystalline salt. It exists in an anhydrous form and with 2 mol water (density 2.066 gcm−3, water loss at 95° C.), 7 mol water (density 1.68 gcm−3, melting point 48° C. with the loss of 5H2O) and 12 mol water (density 1.52 gcm−3, melting point 35° C. with a loss of 5H2O), becoming anhydrous at 100° C. and, when heated to an even greater extent, developing into the diphosphate Na4P2O7. Disodium hydrogen phosphate is synthesized by neutralizing phosphoric acid with sodium carbonate solution using phenolphthalein as an indicator. Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate) K2HPO4 is an amorphous white salt which is readily soluble in water. Trisodium phosphate, tertiary sodium phosphate, Na3PO4 forms colorless crystals which have a density of 1.62 gcm−3 as the dodecahydrate and has a melting point of 73-76° C. (decomp), as the decahydrate (corresponding to 19-20% P2O5) has a melting point of 100° C. and in anhydrous form (corresponding to 39-40% P2O5) has a density of 2.536 gcm−3. Trisodium phosphate is readily soluble in water giving an alkaline reaction and is synthesized by evaporating a solution of exactly 1 mol disodium phosphate and 1 mol NaOH. Tripotassium phosphate (tertiary or tribasic potassium phosphate), K3PO4 is a white deliquescing granular powder with a density of 2.5 gcm−3, a melting point of 1340° C. and is readily soluble in water and gives an alkaline reaction. It is formed, for example, on heating Thomas slag with coal and potassium sulfate. Despite the higher price, the more readily soluble and therefore highly effective potassium phosphates are often preferred in the cleaning agent industry in comparison with the corresponding sodium compounds. Tetrasodium diphosphate (sodium pyrophosphate), Na4P2O7 exists in an anhydrous form (density 2.534 gcm−3, melting point 988° C. also reported as 880° C.) and as a decahydrate (density 1.815-1.836 gcm−3, melting point 94° with loss of water). With these substances there are colorless crystals which are soluble in water with an alkaline reaction. Na4P2O7 is formed on heating disodium phosphate to >200° or by reacting phosphoric acid with sodium carbonate in a stoichiometric ratio and dehydrating the solution by spraying. The decahydrate forms complexes with heavy metal salts and substances that make water hard and thereby reduces the hardness of the water. Potassium diphosphate (potassium pyrophosphate) K4P2O7 exists in the form of trihydrate and is a colorless hygroscopic powder with a density of 2.33 gcm−3 which is soluble in water in which a 1% solution at 25° C. has a pH of 10.4. By condensation of NaH2PO4 and/or KH2PO4 higher molecular sodium and potassium phosphate are formed in which cyclic representatives, the sodium and/or potassium metaphosphates and chain type compounds the sodium and/or potassium polyphosphates can be differentiated. A variety of terms are customarily used for the latter in particular: melt or calcinations phosphates, Graham's salt, Kurrol's salt and Madrell's salt. All higher sodium and potassium phosphates are referred to jointly as condensed phosphates. Pentasodium triphosphate Na5P3O10 (sodium tripolyphosphate), which is important industrially is a white, nonhygroscopic, water-soluble salt of the general formula NaO—[P(O)(ONa)—O]n—Na where n=3, which is anhydrous or crystallizes with 6H2O. At room temperature, approx. 17 g will dissolve in 100 g water, at 60° approx. 20 g will dissolve and at 100° approx. 32 g of the salt which is free of water of crystallization will dissolve. After heating the solution at 100° C. for 2 hours, approx. 8% orthophosphate and 15% diphosphate are formed by hydrolysis. In the synthesis of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dehydrated by spraying. Like Graham's salt and sodium diphosphate, pentasodium triphosphate will dissolve many insoluble metal compounds (including lime soaps, etc.). Pentapotassium triphosphate K5P3O10 (potassium tripolyphosphate) is marketed, for example, in the form of a 50 wt % solution (>23% P2O5, 25% K2O). The potassium polyphosphates are used widely in the washing agent and cleaning agent industry. In addition there are also sodium potassium tripolyphosphates which can also be used within the scope of the present invention. These are formed, for example, when sodium trimetaphosphate is hydrolyzed with KOH:
(NaPO3)3+2KOH→Na3K2P3O10+H2O
These can be used exactly the same according to the invention as sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these two; mixtures of sodium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium tripolyphosphate can also be used according to the invention.
With regard to component e), in a preferred embodiment of inventive agents 1.5 wt % to 5 wt % polymeric polycarboxylate, selected in particular from the polymerization products and/or copolymerization products of acrylic acid, methacrylic acid and/or maleic acid is present. Of these, the homopolymers of acrylic acid are preferred, and of these in turn those having an average molecular weight in the range of 5000 D to 15,000 D (PA standard) are particularly preferred.
In addition to the above mentioned oxidase, enzymes that may be used in these agents also include those from the class of proteases, lipases, cutinases, amylases, pullulanases, mannanases, cellulases, hemicellulases, xylanases and peroxidases as well as mixtures thereof, for example, proteases such as BLAP®, Optimase®, Opticlean®, Maxacal®, Maxapem®, Alcalase®, Esperase®, Savinase®, Durazym® and/or Purafect® OxP, amylases such as Termamyl®, Amylase-LT®, Maxamyl®, Duramyl® and/or Purafect® OxAm, lipases such as Lipolase®, Lipomax®, Lumafast® and/or Lipozym®, cellulases such as Celluzyme® and/or Carezyme®. Enzymatic active ingredients obtained from fungi or bacteria are especially suitable such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus, Humicola lanuginose, Humicola insolens, Pseudomonas pseudoalcaligenes or Pseudomonas cepacia. The enzymes which may optionally be used may be adsorbed onto carrier substances and/or embedded into coating substances to protect them from premature inactivation. They are present in the inventive washing agents, cleaning agents and disinfectants preferably in amounts up to 10 wt %, in particular from 0.2 wt % to 2 wt %, whereby enzymes stabilized against oxidative degradation are especially preferred for use here.
In a preferred embodiment of the invention the agent contains 5 wt % to 50 wt %, in particular 8-30 wt % anionic and/or nonionic surfactant, up to 60 wt %, in particular 5-40 wt % builder substance and 0.2 wt % to 2 wt % enzymes selected from the proteases, lipases, cutinases, amylases, pullulanases, mannanases, cellulases, oxidases and peroxidases as well as mixtures thereof.
To adjust a desired pH which does not result automatically from mixing the other components when adding water, the inventive agents may also acids which are compatible with the system and are environmentally friendly, 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 hydroxides. Such pH regulators are preferably present in the inventive agents in amounts of no more than 20 wt %, in particular 1.2 wt % to 17 wt %.
Soil release-enabling polymers, often referred to as “soil release” active ingredients or as “soil repellents” because of their ability to finish the treated surface, for example, the fiber, to make it dirt repellant include, for example, nonionic or cationic cellulose derivatives. The soil release polymers which are polyester active in particular include copolyesters of dicarboxylic acids, for example, adipic acid, phthalic acid or terephthalic acid, diols, for example, ethylene glycol or propylene glycol and polydiols, for example, polyethylene glycol or polypropylene glycol. The preferred soil release polyesters for use here include those compounds which are formally accessible by esterification of two monomer parts, where the first monomer is a dicarboxylic acid HOOC-Ph-COOH and the second monomer is a diol HO—(CHR21)aOH which may also be present as a polymeric diol H—(O—(CHR21)a)bOH, where Ph denotes an o-, m- or p-phenylene radical which may have 1 to 4 substituents selected from alkyl radicals with 1 to 22 carbon atoms, sulfonic acid groups, carboxyl groups and mixtures thereof, R21 is hydrogen, an alkyl radical with 1 to 22 carbon atoms and mixtures thereof, a is a number from 2 to 6 and b is a number from 1 to 300. Preferably the polyesters obtainable from these contain both monomer diol units O—(CHR21)aO as well as polymer diol units (O—(CHR21)a)bO. The molar ratio of monomer diol units to polymer diol units is preferably 100:1 to 1:100 in particular 10:1 to 1:10. In the polymer diol units the degree of polymerization b is preferably in the range of 4 to 200 in particular 12 to 140. The molecular weight and/or the average molecular weight or the maximum of the molecular weight distribution of preferred soil release polyesters is in the range of 250 to 100,000, in particular from 500 to 50,000. The acid on which the Ph radical is based is preferably selected from terephthalic acid, isophthalic acid, phthalic acid, trimellitic acid, mellitic acid, the isomers of sulfophthalic acid, sulfoisophthalic acid and sulfoterephthalic acid as well as mixtures thereof. If their acid groups are not part of the ester bonds in the polymer, they are preferably in salt form, in particular as the alkali or ammonium salt. Of these the sodium and potassium salts are especially preferred. If desired, instead of the monomer HOOC-Ph-COOH, small amounts in particular no more than 10 mol % based on the amount of Ph with the meaning given above, other acids having at least two carboxyl groups may also be present in the soil release polyester. These include, for example, alkylene and alkenylene dicarboxylic acids such as malonic acid, succinic acid, fumaric acid, maleic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid. The most preferred diols HO—(CHR21)aOH include those in which R21 is hydrogen and a is a number from 2 to 6 and those in which a has the value 2 and R11 is selected from hydrogen and the alkyl radicals with 1 to 10 in particular 1 to 3 carbon atoms. Of the diols mentioned last, those of the formula HO—CH2—CHR11—OH in which R11 has the meaning given above are especially preferred. Examples of diol components include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,2-decanediol, 1,2-dodecanediol and neopentyl glycol. Of the polymeric diols, polyethylene glycol with an average molecular weight in the range of 1000 to 6000 is especially preferred. If desired, these polyesters may also be end group capped, whereby alkyl groups with 1 to 22 carbon atoms and esters of monocarboxylic acids may be considered as end groups. The end groups bound by ester bonds may be based on alkyl, alkenyl and aryl monocarboxylic acids with 5 to 32 carbon atoms, in particular 5 to 18 carbon atoms. These include valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, undecenoic acid, lauric acid, lauroleic acid, tridecanoic acid, myristic acid, myristoleic acid, pentadecanoic acid, palmitic acid, stearic acid, petroselinic acid, petroselaidic acid, oleic acid, linoleic acid, linolaideic acid, linolenic acid, elaostearic acid, arachic acid, gadoleic acid, arachidonic acid, behenic acid, erucaic acid, brassidic acid, clupanodonic acid, lignoceric acid, cerotinic acid, melissic acid, benzoic acid which may have 1 to 5 substituents with a total of up to 25 carbon atoms, in particular 1 to 12 carbon atoms, for example, tert-butyl benzoic acid. The end groups may also be based on hydroxymonocarboxylic acids with 5 to 22 carbon atoms including, for example, hydroxyvaleric acid, hydroxycaproic acid, ricinoleic acid, their hydrogenation product hydroxystearic acid as well as o-, m- and p-hydroxybenzoic acid. The hydromonocarboxylic acids may in turn be linked together by their hydroxyl group and their carboxyl group and may thus be present several times in one end group. The number of hydroxymonocarboxylic acid units per end group, i.e., their degree of oligomerization is preferably in the range of 1 to 50 in particular 1 to 10. In a preferred embodiment of the invention, polymers of ethylene terephthalate and polyethylene oxide terephthalate in which the polyethylene glycol units have molecular weights of 750 to 5000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate is 50:50 to 90:10 may be used alone or in combination with cellulose derivatives.
The dye transfer inhibitors which may be considered for use in the inventive agents for washing textiles include in particular polyvinylpyrrolidones, polyvinylimidazoles, polymeric N-oxides such as poly(vinylpyridine-N-oxide) and copolymers of vinylpyrrolidone with vinylimidazole and optionally other monomers.
The inventive agents for use in washing textiles may contain antiwrinkle agents because textile sheeting in particular of rayon, wool, cotton and blends thereof may tend to wrinkle because the individual fibers are sensitive to bending, folding, pressing and squeezing across the direction of the fiber. These include, for example, synthetic products based on fatty acids, fatty acid esters, fatty acid amides, alkylol esters, alkylol amides or fatty alcohols, mostly reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid esters.
Graying inhibitors have the function of keeping the soil released from the hard surface and in particular from the textile fiber suspended in the solution. Water soluble colloids usually of an organic nature are suitable for this purpose, for example, starch, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or of starch. Polyamides containing water-soluble acidic groups are also suitable for this purpose. In addition, starch derivatives other than those mentioned above may also be used, for example, aldehyde starches. Cellulose ethers such as carboxymethyl cellulose (Na salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methylhydroxyethyl cellulose, methylhydroxypropyl cellulose, methylcarboxymethyl cellulose and mixtures thereof, for example, in amounts of 0.1 to 5 wt %, based on the agent, are preferred.
The agents may contain optical brighteners, in particular derivatives of diaminostilbene disulfonic acid and/or their alkali metal salts. For example, salts of 4,4′-bis(2-anilino-4-morpholino-1,3,5-triazinyl-6-amino)stilbene-2,2′-disulfonic acid or compounds of similar structure containing instead of the morpholino group a diethanolamine group, a methylamino group, an anilino group or a 2 methoxyethylamino group are also suitable. In addition, brighteners of the substituted diphenylstyryl type may also be present, for example, the alkali salts of 4,4′-bis(2-sulfostyryl)diphenyls, 4,4′-bis(4-chloro-3-sulfostyryl)diphenyls or 4(4 chlorostyryl)-4′-(2-sulfostyryl)diphenyls. Mixtures of the aforementioned optical brighteners may also be used.
In particular for use in machine washing and cleaning processes it may be advantageous to add the usual foam inhibitors to these agents. Suitable foam inhibitors include, for example, soaps of natural or synthetic origin containing a large amount of C18-C24 fatty acids. Suitable nonsurfactant foam inhibitors include, for example, organopolysiloxanes and mixtures thereof with microfine optionally silanized silicic acid as well as paraffins, waxes, microcrystalline waxes and mixtures thereof with silanized silicic acid or bis-fatty acid alkylenediamides. Mixtures of various foam inhibitors may also be used to advantage, for example, those of silicones, paraffins or waxes. The foam inhibitors in particular foam inhibitors containing silicone and/or paraffin are preferably ground to a granular carrier substance which is soluble and/or dispersible in water. In particular mixtures of paraffins and bistearylethylenediamide are preferred.
In the inventive agents active ingredients to prevent tarnishing of objects made of silver, so-called silver corrosion inhibitors may also be used. Preferred silver corrosion inhibitors include organic disulfides, divalent phenols, trivalent phenols, optionally alkyl- or aminoalkyl-substituted triazoles such as benzotriazole as well as cobalt, manganese, titanium, zirconium, hafnium, vanadium or cerium salts and/or complexes in which the aforementioned metals are present in one of the oxidation stages II, III, IV, V or VI.
An inventive agent may also contain the usual antimicrobial active ingredients to potentiate the disinfectant effect with respect to special microbes in addition to containing the aforementioned ingredients. Such antimicrobial additives are preferably contained in the inventive agents in amounts of no more than 10 wt %, in particular from 0.1 wt % to 5 wt %.
An inventive cleaning agent for hard surfaces may also contain abrasive active ingredients in particular from the group comprising powdered quartz, wood dust, plastic powder, chalk and microglass beads as well as mixtures thereof. Abrasive substances are preferably present in the inventive cleaning agents in amounts of no more 20 wt %, in particular 5 wt % to 15 wt %.
Primary detergency and loss of wet tensile strength were tested in a miniaturized washing test. The test was conducted using a simplified washing solution consisting of H2O2 and catalyst (1,4,7-trimethyl-1,4,7-triazacyclononane-manganese complex, Mn-Me3TACN). Solutions of 0.35 g/L H2O2 and 5 μmol/L Mn-Me3TACN and 0 g/L (V1) o 0.11 g/L (M1) Na alginate and/or 0.11 g/L (M2) pectin in water (3° dH) were used, the pH of the solution having been adjusted by NaOH to pH 10.5.
For measurement of the primary detergency, cotton substrates which had been provided with a standardized tea soil were treated for 30 minutes at 30° C. in the respective solutions. The treated fabric substrate was washed out under running water and then dried and the color was measured. The following table shows the brightness value of the cotton test pieces.
For measurement of the loss of wet tensile strength, cotton strips of a defined width (number of threads) were treated 20 times over 45 minutes each at 60° C. in the respective solutions. The strips were dried and immersed in a wetting solution before being torn using a tensile testing machine at a constant tensile test speed. The tear strength of the treated cotton was compared with the tear strength of the untreated cotton and the results were calculated in loss of wet tensile strength in percentage.
Five determinations were performed for each of the primary detergency and the loss of wet tensile strength. The averages are given in the following table.
While at least one exemplary embodiment has been presented in the foregoing detailed description of the invention, it should be appreciated that a vast number of variations exist. It should also be appreciated that the exemplary embodiment or exemplary embodiments are only examples, and are not intended to limit the scope, applicability, or configuration of the invention in any way. Rather, the foregoing detailed description will provide those skilled in the art with a convenient road map for implementing an exemplary embodiment of the invention, it being understood that various changes may be made in the function and arrangement of elements described in an exemplary embodiment without departing from the scope of the invention as set forth in the appended claims and their legal equivalents.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10 2009 001 786.0 | Mar 2009 | DE | national |
This application is a continuation of PCT/EP2010/053079, filed on Mar. 11, 2010, which claims priority under 35 U.S.C. §119 to DE 10 2009 001 786.0 filed on Mar. 24, 2009.
| Number | Date | Country | |
|---|---|---|---|
| Parent | PCT/EP2010/053079 | Mar 2010 | US |
| Child | 13239588 | US |
