BLEACHING AGENT

Abstract: The present invention relates to a photo-bleaching agent which comprises a photo-bleaching compound and a polymeric compound, which has an improved photo-bleaching performance. The agent can be used in any application where bleaching is required, such as cleaning compositions. The invention also relates to a process for making the photo-bleaching agent.

Description: Bleaching Agent Technical Field The present invention relates to a photo-bleaching agent which comprises a photo- bleaching compound and a polymeric compound, which has an improved photo- bleaching performance. The agent can be used in any application where bleaching is required, such as cleaning compositions. The invention also relates to a process for making the photo-bleaching agent. Background to the Invention Various compounds are known in the art which, upon exposure to light, can be photo-activated, to become an active species for chemical or further photo-chemical reactions. Two general examples thereof are porphyrin and phthalocyanine photo-bleaching compounds. These compounds, unmetallated and especially when combined with a suitable cation, can undergo a series of reactions, starting with a photochemical reaction step which transforms the compound into an excited state. The excited state of the molecule can react with stains to bleach them or alternatively after subsequent reaction steps in conjunction with molecular oxygen can produce "active oxygen". Active oxygen includes molecules of "singlet oxygen" or superoxide. Superoxide can subsequently be converted to hydrogen peroxide. "Singlet oxygen" , superoxide or hydrogen peroxide, formed in this series of reactions, are oxidative species capable of reacting with stains to chemically bleach them to a colourless and usually water-soluble state, thereby resulting in what is called photochemical bleaching. Examples of porphyrins or porphyrin-like compounds include haematoporphyrin, chlorophyll, chlorin, oxo-chlorins, pheophorbide, pyropheophorbide, benzoporphyrins, tetra-arylporphyrin, zinc tetraphenylporphyrin, tripyrroledimethane-derived expanded porphyrins, . Examples of phthalocyanines and naphthalocyanines include zinc, aluminum, indium, silicon, and gallium phthalocyanines and naphthalocyanines, the most common being the zinc and aluminium phthalocyanines. Other examples of photobleaches are xanthene dyes such as rose bengal, eosin, and fluorescein. Additional photobleach examples include metachromic dyes such as thionine, methylene blue, benzo[a]phenoxazinium (Nile Blue A), and benzo[a]phenothiazinium. A limitation to the use of some of these more water- soluble photo-bleaches can be their poor surface-activity. 0 One problem associated with the use of phthalocyanine, naphthalocyanines, and porphyrin photo-bleaching compounds arises from the fact that these are not water soluble, in particular when the parent rings are substituted solely with hydrogen. It has been a task for the formulators of photo-bleaching compounds and cleaning 5 products to prepare photo-bleaching agents which are soluble in water. In an effort to do so, various patent documents relate to photo-bleaching with phthalocyanine derivatives, having various solubilising substituents, such as EP-119746, EP- 379312, EP-553608, EP-596187 and EP-692947. These documents teach selected substituent units that are hydrophilic and which are bonded to the photo-sensitive o ring units to enhance the solubility or photochemical properties of the molecule. In general, three or more substituents are needed to obtain the required solubility. However, a problem relating to the introduction of (high numbers of) substituent groups to the photo-bleaching compound (to ensure a certain level of water 5 solubility) is that the photo-bleaching properties of the ring system are often affected. For example, a change which increases solubility may reduce the quantum efficiency of the molecule. This can render the derivative compound without sufficient photo-bleaching properties. Firstly, this can lead to less formation of singlet oxygen and thus less bleaching. Secondly, the absorption spectrum may o change, leading to an undesirable colouring of the photo-bleaching compounds in use, which is in particular a problem when used for photo-bleaching of fabrics. It is known in the art how to prepare these derivative photo-bleaching agents. However, the preparation of these derivative photo-bleaching agents can proceed in 5 low yield which introduces impurities and increases cost. These impurities may also introduce undesirable colouring which produces staining, in particular when used on fabric. Another major limitation to the use of most photo-bleaching compounds known in the art is that they are highly coloured materials (having an absorption in the range of 600-800 nanometres). For example, high concentrations of these compounds on the fabric will thus lead to staining of the fabric. Therefore, deposition of the photo- bleaching compounds in high quantities on the fabric in the wash should be avoided. Furthermore, build up of these compounds on fabric surface should be avoided. Yet another limitation of most photo-bleaching compounds known in the art is that 0 introduction of solubilising groups tends to destabilise the compounds so that they tend to decompose once exposed to light, in particular sunlight, which deactivates them as photo-bleaching compound, thus leading to a lesser bleaching performance. Furthermore, in cleaning compositions containing the photo-bleaching compounds it is often required that additional bleaching agents are present. However, these s bleaching agents can also cause decomposition and inactivation of the photo- bleaching agents. Thus, there is a need for improved photo-bleaching compounds which are water- soluble, which have optimum photo-bleaching properties, and will overcome the o decomposition and build up problems. In accordance with the invention, improved photo-bleaching agents are provided. The present inventors have found that when a photo-bleaching compound which is insoluble in water or slightly water-soluble is integrated with a specific polymeric 5 compound, a photo-bleaching agent is formed which is water-soluble. Furthermore, the inventors have found that when (soluble) photo-bleaching compounds, which have a poor surface-activity, are integrated with these polymeric compounds, a (water-soluble) bleaching agent with improved surface-activity is obtained. While not being bound by theory, the improvement inphotobleaching results from photo- o bleaching agents which have an improved affinity for the soils present on fabric for laundering. Thus, more specific and effective bleaching of these soils is achieved. In addition, the photo-bleaching agents included in the invention may provide more efficient photo-bleaching performance because they are more stable when exposed to light or bleach. Thus for a given amount of photobleaching agent deposited on a 5 surface, a higher amount of singlet oxygen or other bleaching species can be generated before the photobleaching agent decomposes. Also, the photo-bleaching agent has an absorption spectrum which results in a desired colour, in particular blue, of the agent and of the fabric comprising the agent. Furthermore, they have found that the photo-bleaching agent migrates evenly to the fabric surface. Thus localised high quantities of photo-bleaching agent, leading to staining, can be avoided. They also have found that the agent accumulates to a lesser extent on the fabric in subsequent washings. Also staining of the fabric by highly coloured, inactive agents can be avoided because the photo-bleaching agent of the invention can be prepared without introduction of impurities. Additionally, the photobleaching agent can provide a desired hueing on the fabric, leading to an improved fabric appearance. Thus, overall an improved photo-bleaching performance is achieved with additional benefits. All documents cited in the present description are, in relevant part, incorporated herein by reference. Summary of the Invention The invention comprises a photo-bleaching agent comprising a) a polymeric component; and b) a photo-bleaching component, integrated with one another, whereby the weight ratio of a) to b) is from 1 : 1 to 1000:1. The invention also relates to a photo-bleaching agent a photo bleaching component and a polymeric component, integrated with one another, whereby the weight ratio of a) to b) is from 1 : 1 to 1000: 1 , obtainable by a process comprising the steps of: a) forming a melt or a solution, comprising a photo-bleaching compound and a polymeric compound; b) in a further step, forming and separating the photo-bleaching agent. The invention also comprises the use of specific polymeric compounds preferably having monomeric units with dipolar, aprotic groups for improving the water- solubility and/or improving the surface-activity of compounds. Detailed Description of the Invention Photo-Bleaching Agent The photo-bleaching agent of the invention comprises one or more specific polymeric components and one or more photo-bleaching components integrated with one another, as described herein. 'Integrated with one another' when used herein refers to the integration between the components of the agent, which is obtainable by a process comprising the steps of a) forming a melt of or a solution, comprising a photo-bleaching compound and a polymeric compound; b) in a further step, forming and separating the photo-bleaching agent. This may mean that the photo-bleaching component is adsorbed onto or absorbed in the polymeric component, or that the polymeric component and the photo-bleaching component form an associative complex-structure or coacervate complex-structure. The weight ratio of the polymeric component to the photo-bleaching component in the photo-bleaching agent is from 1:1 to 1000:1, more preferably from 5:1 to 1000:1, more preferably 20:1 to 100:1, most preferably from 20:1 to 60:1 The photo-bleaching agent of the invention preferably comprises from 50% to 99.9%o by weight, more preferably from 90%> to 99.9%> by weight, more preferably from 92% to 99% by weight, most preferably from 95% to 98% by weight the polymeric component. The photo-bleaching agent of the invention preferably comprises from 0.1% to 50 % by weight, more preferably from 0.1%) to 10%> by weight, more preferably from 1% to 8%> by weight most preferably from 2%> to 5%> by weight the photo-bleaching component. When the agent is used on fabrics, the higher levels of the photo- bleaching component can be preferred when a hueing effect on the fabrics is desirable. Polymeric Compounds The polymeric compounds for integration with a photo-bleaching compound to form the polymeric component of the photo-bleaching agent of the invention, preferably comprises polymerised monomeric units which comprise di-polar, aprotic groups. 0 Preferably, at least 50%>, more preferably at least 75%>, more preferably at least 90%>, even more preferably at least 95 %> of the polymerised monomeric units comprise a di-polar, aprotic group. The polymeric compounds of the invention can be homo-polymers, comprising a 5 backbone having one type of polymerised monomeric units, or co-polymers comprising a backbone having different polymerised monomeric units. The polymeric compounds preferably have a number average molecular weight of from 500 to 1,000,000, more preferably from 1,000 to 100,000, more preferably o from 2000 to 80,000, most preferably from 5000 to 60,000. Highly preferred monomeric units include vinylamides such as N-vinylpyrrolidone and N-vinylacetamide as well as vinylheterocycles such as N-vinylimidazole, N- vinyloxazolidone, N-vinyltriazole, 4-vinylpyridine, and 4-vinylpyridine-N-oxide. 5 These dipolar, aprotic group-containing monomeric units are particularly effective for solubilising the photo-bleaching component. Co-monomers can be used to confer additional properties to the polymer such as charge, hydrophilicity and hydrophobicity. Suitable comonomers include acrylic o acid or methacrylic acid, their salts, and their esters including methyl, ethyl, hydroxyethyl, propyl, hydroxypropyl, butyl, ethylhexyl, decyl, lauryl, i-bornyl, cetyl, palmityl, phenoxyethyl, stearylacrylate. Also included are diethylaminoethylacrylate, dimethylaminoethylacrylate, dimethylaminopropylacrylate, andcholine esters of acrylic or methacrylic acid. Also 5 included are acrylamide or methacrylamide and their various N-substituted derivatives including N-methylol-acrylamide, N,N-dimethylaminopropylacrylamide, N,N,N-trimethylammoniumpropylacrylamide,N,N-diethylaminopropylacrylamide, N-tert-butylacrylamide, N-tert-octylacrylamide, N-undecylacrylamide, 2-acrylamido- 2-methylpropanesulfonic acid. Also included are vinyl esters such as vinyl acetate, vinyl propionate, vinyllaurate, neooctanoic acid vinylester, neononanoic acid vinylester, neodecanoic acid vinylester. Also included are other vinyl monomers such as styrene, vinyltoluene, α-methylstyrene. Also included are unsaturated acids such as crotonic acid, maleic acid, fumaric acid, itaconic acid or their respective anhydride or esters. Most preferred polymeric compounds in accordance with this invention are polyvinylimidazole (PVI), or a copolymer of polyvinylpyrrolidinone and polyvinylimidazole (PVPVI), most preferably polyvinylpyrrolidinone (PVP). Preferably, these highly preferred polymeric compounds have an average molecular weight of from 20,000 to 60,000. Also, mixtures of two or more polymeric compounds, descibed herein can be used for integration with a photo-bleaching compound to form the polymeric component of the photo-bleaching agent of the invention. Photo-Bleaching Compound The photo-bleaching compound for integration with a polymeric compound to form the photo-bleaching component of the photo-bleaching agent of the invention can be any compound known in the art which can undergo a reaction or a series of reactions, starting with a photochemical reaction in conjunction with molecular oxygen to produce molecules of "active oxygen". Active oxygen includes molecules of "singlet oxygen" or superoxide. Superoxide can subsequently be converted to hydrogen peroxide. "Singlet oxygen" , superoxide or hydrogen peroxide, formed in this series of reactions, are oxidative species capable of reacting with stains to chemically bleach them to a colourless and usually water-soluble state, thereby resulting in what is called photochemical bleaching. Preferred photo-bleaching compounds are compounds having a porphin or porphyrin structure. Porphin and porphyrin, in the literature, are used as synonyms, but conventionally porphin stands for the simplest porphyrin without any substituents; wherein porphyrin is a sub-class of porphin. The references to porphin in this application will include porphyrin. The porphin structures preferably comprise a metal element or cation, preferably Ca, Mg, P, Ti, Cr, Zr, In, Sn or Hf, more preferably Ge, Si or Ga, or more preferably Al , most preferably Zn. It can be preferred that the photo-bleaching compound or component is substituted with substituents selected from alkyl groups such as methyl, ethyl, propyl, t-butyl group and aromatic ring systems such as pyridyl, pyridyl-N-oxide, phenyl, naphthyl and anthracyl moieties. The photo-bleaching compound or component can have solubihsing groups as substituents, however, for the present invention it is preferred that the photo- bleaching compound or component has only 2 or less solubihsing substituent groups. Even more preferably the photo-bleaching compound or component has no solubihsing substituent groups, or most preferably is unsubstituted. Highly preferred photo-bleaching compounds are compounds having a phthalocyanine structure, which preferably have the metal elements or cations described above. Metal phthalocyanines and their derivatives have the structure indicated in Figure 1 and/or Figure 2, wherein the atom positions of the phthalocyanine structure are numbered conventionally. The phthalocyanines can be substituted for example the phthalocyanine structures which are substituted at one or more of the 1-4, 6, 8-11, 13, 15-18, 20, 22-25, 27 atom positions of Figure 1 and/or Figure 2. A highly preferred transition metal phthalocyanine however is non-substituted phthalocyanine. For oxidation state of the metal element or cation greater than (II), the symbol X4 of Figure 2 represents an anion, preferably OH- or Cl- when the oxidation state is (III). FIGURE 1 FIGURE 2 Process for Preparation of the Photo-Bleaching Agent The photo-bleaching agent of the invention is obtainable by a process comprising the steps of a) forming a melt of or a solution comprising a photo-bleaching compound and a polymeric compound; b) in a further step, separating the photo-bleaching agent. Preferably, when a solution is obtained in step a), any solid photo-bleaching compound, which is not dissolved in the solution, is removed in an optional step for example, by filtration or centrifugation. In the situation that a solution is obtained in step a), which is optionally filtered to remove any undissolved photo-bleaching compound the further step preferably comprises a precipitation step, whereby the photo-bleaching agent precipitates out of the solution, preferably by addition to a second solvent and/or solution. The precipitate is preferably a clearly visible precipitate. The photo-bleaching agent can then be collected as the precipitate by, for example, filtration or centrifugation of the solution (s). In the situation that a melt is obtained in step a), the separation step c) preferably comprises the step of cooling the melt to obtain the photo-bleaching agent preferably, as a solid. The process is preferably such that a minimum of process steps is required and a high yield of photo-bleaching agent (final product) is achieved, and thus a minimum of the starting materials, being the polymeric compound and the photo-bleaching compound, is lost during the process. In one alternative process, the process conditions are preferably such that the starting materials dissolve in a specific solvent and react to form the final product. Preferably, the process conditions are such that the final product is easily obtainable by precipitation from the solvent(s). Thereby it is preferred that the process conditions are such that possible unreacted starting material does not precipitate, but stays in solution. A preferred process for preparation of the photo-bleaching agent of the invention comprises the steps of: a) forming a solution of a photo-bleaching compound and a polymeric compound in a solvent; b) removing any undissolved photo-bleaching agent by filtration or centrifugation; c) a further step comprising: 1) addition of the solution of step a), to a second solvent whereby a precipitate is formed in the solvent-mixture comprising the solvent of step a) and the second solvent; 2) separation of the precipitate, comprising the bleaching agent comprising the polymeric compound and the photo-bleaching compound (in the form of a polymeric component and a photo-bleaching component, integrated with one another) from the solvent-mixture. Preferably, the separation step c) 2) comprises the steps of filtration of the solvent- mixture and subsequently washing of the precipitate and drying of the precipitate. Preferably, the solvent used in step a); as described herein, comprises in its structure a group, which is similar to the structure of one or more of the polymerised monomeric units comprised in the polymeric compound of the invention. Highly preferred is that the solvent is a N-alkyl pyrrolidinone, preferably N-methyl pyrrolidinone or N-octyl pyrrolidinone Other preferred solvents are pyridine, pyridine N-oxide, N-methylmorpholine N- oxide. The solvent can also be a mixture of the solvents described herein, or a mixture of water and one or more solvents described herein. The second solvent preferably is an ether, preferably diethyl ether or t-butylmethyl ether. The temperature where at the process is done, should be such that the starting materials dissolve, and a precipitate of the final product, the photo-bleaching agent, can be formed and preferably such that the unreacted starting materials stay in solution. Preferably the process is such that the temperature can be from 0 °C to 100 °C, preferably around 25 °C. Optionally, other compounds or components can be present or added to the solution of step a) above or in the solvents preferably used therein, for example to improve the process for preparation or the performance of the photo-bleaching agent. Alternatively, the process for preparation of the photo-bleaching agent of the invention can comprise the step of: a) formation of a melt comprising the polymeric compound and the photobleaching compound; b) separation of the photo-bleaching agent by cooling of the melt. Preferably, step a) comprises the steps of melting the polymeric compound and adding the photo-bleaching compound to the molten polymeric compound. A highly preferred polymeric compound comprised in a melt formed in step a) is N- methylmorpholine-N-oxide. It can be preferred that the melt comprises additional compounds or components. For example, other components or compounds greatly used in cleaning compositions such as surfactants. Examples of Preparation During all the preparations described herein precautions are to be taken to exclude light from all solutions and solids of the photo-bleach compounds or components, also during subsequent storage. The photo-bleaching agents obtained in the processes of the following examples are analysed by a IPC analysis method. In this method a specific amount of the obtained photo-bleaching agent is weighed in a grade A volumetric flask, whereafter a specific amount of distilled water from a Pyrex/ Quartz still is added. The analysis is performed with a Unicam 701 ICP-OES instrument, which is peaked on a solution of manganese and calibrated on commercial ICP standards for the elements of interest and in the concentration range of interest. A minimum of three calibration points is used, with each point being the mean of three measurements at that point. Each sample is then measured three times for each element of interest and the mean of the measurements is reported (together with the three measurements used to calibrate that mean). 0 In the following examples "parts by weight" and "parts by volume" refer to the corresponding SI units, i.e. if "one part by weight" corresponds to one gram, then "one part by volume" corresponds to one millilitre and if "one part by weight" corresponds to one kilogram, then "one part by volume" corresponds to one litre. 5 Example 1 1 part by weight of polyvinylpyrrolidone (ex Aldrich, M w approx. 10,000) is dissolved at room temperature in 4.5 parts by volume of l-methyl-2-pyrrolidone (ex o Aldrich). To this solution is added 0.046 parts by weight of zinc phthalocyanine (ex Aldrich) at 97%> activity and the resultant mix is stirred at room temperature overnight. The solution is then filtered, under argon to exclude moisture, before adding it 5 under argon to 60 parts by volume of diethyl ether (ex Merck) with vigorous agitation. A turquoise-blue solid precipitates, which is then collected by filtration, washed with diethyl ether and dried in vacuo over calcium chloride giving 1.03 parts by weight of o photo-bleaching agent. The thus obtained photo-bleaching agent is submitted for analysis. Analysis by ICP- OES indicates a zinc phthalocyanine content of 3.8%> by weight. 5 Example 2 1 part by weight of polyvinylpyrrolidone (ex Aldrich, M w approx. 10,000) is dissolved at room temperature in 4.5 parts by volume of l-methyl-2-pyrrolidone (ex Aldrich). To this solution is added 0.053 parts by weight of aluminium phthalocyanine chloride (ex Aldrich) at 85% activity and the resultant mix is stirred at room temperature overnight. The solution is then filtered, under argon to exclude moisture, before adding it under argon to 60 parts by volume of diethyl ether (ex Merck) with vigorous agitation. A turquoise-blue solid precipitates which is then collected by filtration, washed with diethyl ether and dried in vacuo over calcium chloride giving 1.07 parts by weight of 0 photo-bleaching agent. The thus obtained photo-bleaching agent is submitted to analysis. Analysis by ICP- OES indicates an aluminium phthalocyanine chloride content of 3.9%> by weight. 5 Example 3 1 part by weight of polyvinylpyrrolidone (ex Aldrich, M w approx. 40,000) is dissolved at room temperature in 4.5 parts by volume of l-methyl-2-pyrrolidone (ex Aldrich). To this solution is added 0.091 parts by weight of zinc phthalocyanine (ex o Aldrich) at 97% activity and the resultant mix stirred at 95 °C overnight. The solution is then cooled to room temperature, filtered, under argon to exclude moisture, before adding it under argon to 60 parts by volume of diethyl ether (ex Merck) with vigorous agitation. 5 A turquoise-blue solid precipitates which is then collected by filtration, washed with diethyl ether and dried in vacuo over calcium chloride giving 0.83 parts by weight of photo-bleaching agent. The thus obtained photo-bleaching agent is submitted to analysis. Analysis by ICP- o OES indicates a zinc phthalocyanine content of 4.2%> by weight. Example 4 1 part by weight of polyvinylpyrrolidone (ex Polysciences, M w approx. 2,500) is 5 dissolved at room temperature in 4.5 parts by volume of 1 -methyl-2-pyrrolidone (ex Aldrich). To this solution is added 0.091 parts by weight of zinc phthalocyanine (ex Aldrich) at 97%> activity and the resultant mix stirred at 95°C overnight. The solution is then cooled to room temperature, filtered, under argon to exclude moisture, before adding it under argon to 60 parts by volume of diethyl ether (ex Merck) with vigorous agitation. A turquoise-blue solid precipitates, which is then collected by filtration, washed with diethyl ether and dried in vacuo over calcium chloride giving 0.77 parts by weight of photo-bleaching agent. The thus obtained photo-bleaching agent is submitted to analysis. Analysis by ICP- OES indicates a zinc phthalocyanine content of 3.9%> by weight. Example 5 1 part by weight of poly[vinylpyrrolidone-co-acrylic acid] (ex Aldrich, M w approx. 96,000, acrylic acid content 25%>) is dissolved at room temperature in 4.5 parts by volume of l-methyl-2-pyrrolidone (ex Aldrich). To this solution is added 0.205 parts by weight of zinc phthalocyanine (ex Aldrich) at 97%> activity and the resultant mix stirred at 95°C overnight. The photo-bleach solution is then cooled to room temperature, filtered, under argon to exclude moisture, before adding it under argon to 60 parts by volume of diethyl ether (ex Merck) with vigorous agitation. A turquoise-blue solid precipitates which is then collected by filtration, washed with diethyl ether and dried in vacuo over calcium chloride. The thus obtained photo-bleaching agent is submitted to analysis. Analysis by ICP- OES indicates a zinc phthalocyanine content of 1.4% by weight. Example 6 1 part by weight of poly[vinylpyrrolidone-co-vinylimidazole] (K 20 ex BASF) is dissolved at room temperature in 4.5 parts by volume of l-methyl-2-pyrrolidone (ex Aldrich). To this solution is added 0.091 parts by weight of aluminium phthalocyanine chloride (ex Aldrich) at 85%> activity and the resultant mix is stirred at 95 °C overnight. The solution is then cooled to room temperature, filtered, under argon to exclude moisture, before adding it under argon to 60 parts by volume of diethyl ether (ex Merck) with vigorous agitation. A turquoise-blue solid precipitates which is then collected by filtration, washed with diethyl ether and dried in vacuo over calcium chloride. The thus obtained photo-bleaching agent is submitted to analysis. Analysis by ICP- OES indicates an aluminium phthalocyanine chloride content of approximately 7.4%> by weight. Example 7 1 part by weight of poly[vinylpyπolidone-co-dimethylaminoethyl methacrylate] dimethyl sulphate quaternary (obtained by rotary evaporating a 50%> solution in ethanol ex Polysciences) is dissolved at room temperature in 4.5 parts by volume of l-methyl-2-pyrrolidone (ex Aldrich). To this solution is added 0.091 parts by weight of aluminium phthalocyanine chloride (ex Aldrich) at 85%> activity and the resultant mix is stπxed at 95 °C overnight. The solution is then cooled to room temperature, filtered, under argon to exclude moisture, before adding it under argon to 60 parts by volume of diethyl ether (ex Merck) with vigorous agitation. A sticky dark blue solid precipitates which is then re-slurried in diethyl ether, then filtered, washed with diethyl ether and dried in vacuo over calcium chloride. The thus obtained photo-bleaching agent is submitted to analysis. Analysis by ICP- OES indicated an aluminium phthalocyanine chloride content of 5.0%> by weight. Example 8 1 part by weight of polyvinylpyπolidone (ex Aldrich, M w approx. 10,000) was dissolved at room temperature in 4.5 parts by volume of l-methyl-2-pyrrolidone (ex Aldrich). To this solution is added 0.236 parts by weight of aluminium phthalocyanine hydroxide (ex Aldrich) at 85% activity and the resultant mix is stirred at 95 °C overnight. The solution is then cooled to room temperature, filtered, under argon to exclude moisture, before adding it under argon to 60 parts by volume of diethyl ether (ex Merck) with vigorous agitation. A turquoise-blue solid precipitates, which is then collected by filtration, washed with diethyl ether and dried in vacuo over calcium chloride. The thus obtained photo-bleaching agent is submitted to analysis. Analysis by ICP- OES nmr indicates an aluminium phthalocyanine hydroxide content of 4.6%» by weight. Example 9 1 part by weight of polyvinylpyrrolidone (ex Aldrich, M w approx. 10,000) is dissolved at room temperature in 4.5 parts by volume of l-methyl-2-pyrrolidone (ex Aldrich). To this solution is added 0.100 parts by weight of aluminium phthalocyanine chloride (ex Aldrich) at 85% activity and the resultant mix stirred at 95°C overnight. The solution is then cooled to room temperature, filtered, under argon to exclude moisture, before adding it under argon to 60 parts by volume of t-butyl methyl ether (ex Merck) with vigorous agitation. A turquoise-blue solid precipitates and is then collected by filtration, washed with t- butyl methyl ether and dried in vacuo over calcium chloride giving 0.99 parts by weight of photo-bleaching agent. The thus obtained photo-bleaching agent is submitted to analysis. Analysis by ICP- OES indicated an aluminium phthalocyanine chloride content of 4.2%> by weight. Example 10 1 part by weight of polyvinylpyrrolidone (ex Aldrich, M w approx. 10,000) is dissolved at room temperature in 4.5 parts by volume of l-methyl-2-pyrrolidone (ex Aldrich). To this solution is added 0.205 parts by weight of zinc phthalocyanine (ex Aldrich) at 97% activity and 0.055 parts by weight of pyridine (ex Merck), i.e. 2 moles pyridine er mole zinc phthalocyanine. The resultant mix is strrred at 95°C overnight. The solution is then cooled to room temperature, filtered, under argon to exclude moisture, before adding it under argon to 60 parts by volume of diethyl ether (ex Merck) with vigorous agitation. 0 The turquoise-green solid precipitates and is then collected by filtration, washed with diethyl ether and dried in vacuo over calcium chloride giving 0.97 parts by weight of photo-bleaching agent. The thus obtained photo-bleaching agent is submitted to analysis. Analysis by ICP- 5 OES indicated a zinc phthalocyanine content of 4.4%> by weight. Example 11 1 part by weight of polyvinylpyrrolidone (ex Aldrich, M w approx. 10,000) is o dissolved at room temperature in 4.5 parts by volume of NN-dimethylformamide (ex Merck). To this solution is added 0.205 parts by weight of zinc phthalocyanine (ex Aldrich) at 97%> activity and the resultant mix was stirred at 95°C overnight. The solution is then cooled to room temperature, filtered, under argon to exclude 5 moisture, before adding it under argon to 60 parts by volume of diethyl ether (ex Merck) with vigorous agitation. A turquoise-green solid precipitates and is then collected by filtration, washed with diethyl ether and dried in vacuo over calcium chloride giving 0.83 parts by weight of o photo-bleaching agent. The thus obtained photo-bleaching agent is submitted to analysis.. Analysis by ICP- OES indicated a zinc phthalocyanine content of 1.9%> by weight. 5 Example 12 1 part by weight of polyvinylpyrrolidone (ex Aldrich, M w approx. 10,000) is dissolved at room temperature in 4.5 parts by volume of l-methyl-2-pyrrolidone (ex Aldrich). To this solution is added 0.110 parts by weight of aluminium phthalocyanine chloride (ex Aldrich) at 85%> activity and the resultant mix is stirred at 95°C for 30 minutes. The solution is then filtered, under argon to exclude moisture, before adding it under argon to 60 parts by volume of diethyl ether (ex Merck) with vigorous agitation. A turquoise-blue solid precipitates, which is then collected by filtration, washed with diethyl ether and dried in vacuo over calcium chloride. The thus obtained photo-bleaching agent is submitted for analysis. Analysis by ICP- OES indicates a aluminium phthalocyanine content of 6.7%> by weight. Example 13 1 part by weight of polyvinylpyrrolidone (ex Aldrich, M w approx. 10,000) and 0.5 parts by weight 4-methylmorpholine N-oxide monohydrate (ex Fluka) are heated to 95°C when the solids melt to form a viscous liquid. To this is added 0.02 parts by weight of zinc phthalocyanine (ex Aldrich) at 97%> activity and the mix is agitated at 95 °C overnight. On cooling to room temperature the mix solidifies to a hard, dark blue solid, the photo-bleaching agent, which was soluble in aqueous solutions such as detergent solutions. Example 14 1 part by weight of polyvinylpyrrolidone (ex Aldrich, M w approx. 10,000) and an equal part by weight 4-methylmorpholine N-oxide monohydrate (ex Fluka) are heated to 95°C when the solids melts to form a viscous liquid. To this is added 0.04 parts by weight of zinc phthalocyanine (ex Aldrich) at 97%> activity and the mix is agitated at 95°C overnight. On cooling to room temperature the mix solidifies to a hard, dark blue solid, the photo-bleaching agent, which is soluble in aqueous solutions such as cleaning solutions. Use of the Polymeric Compounds The invention also relates to the use of the polymeric compounds for (or a method for) improving or increasing of compounds. Preferably, the polymeric compounds have an average number molecular weight of from 500 to 1,000,000 and preferably comprise polymerised monomeric units whereof at least 50%> of the units comprise a di-polar, aprotic group. Alternatively or additionally, the invention also relates to the use of the polymeric compounds for (or a method for) improving or increasing of compounds. Preferably, the polymeric compounds has an average number molecular weight of from 500 to 1,000,000 and preferably comprises polymerised monomeric units whereof at least 50%) of the units comprise a di-polar, aprotic group. Cleaning Compositions The photo-bleaching agent of the invention can be used in any cleaning composition which requires bleaching performance, such as for example granular or liquid detergent compositions, hard-surface cleaning composition or hair-care products. In particular the photo-bleaching agents can be useful in compositions which are used for cleaning of fabrics or surfaces which will be exposed to light, in particular sunlight after the cleaning or washing process. Preferred cleaning compositions, which comprise the photo-bleaching agent according to the invention, comprise additionally an oxygen-based or chlorine-based bleaching agent. The level of photo-bleaching agent present in such compositions will depend on the nature of these compositions and their application. Preferably, the cleaning compositions comprise the photo-bleaching agent at a level of from 0.01 ppm to 10%, more preferably from 0.05 ppm to 5%>, most preferably from 15 ppm to 1% by weight of the composition. Preferred cleaning compositions wherein the photo-bleaching agent of the invention can be used are detergent compositions, preferably laundry detergent compositions. Detergent Compositions and Components Thereof The photo-bleaching agent of the present invention may be used in any detergent composition wherein bleaching is required. The detergent compositions or components thereof can contain any of the traditionally known and used detergent ingredients or components. The precise nature of these components, and levels of incorporation thereof will depend on the physical form of the composition, and the precise nature of the washing operation for which it is to be used. The detergent compositions or components thereof preferably contain one or more detergent components selected from additional surfactants, bleaches, such as oxygen-based and chlorine- based, and/ or bleach catalysts, and/ or bleach precursors, water-soluble and insoluble builders, chelants, organic polymeric compounds, enzymes, suds suppressors, lime soap dispersants, soil suspension and anti-redeposition agents, perfumes and corrosion inhibitors. The surfactants can be selected from anionic, nonionic, cationic, ampholytic, amphoteric and zwitterionic surfactants and mixtures thereof. The detergent compositions preferably have a pH measured as a 1% solution in distilled water of at least 8.5, preferably from 9.0 to 12.5, most preferably from 9.5 to 11.0. Form of the Compositions The cleaning compositions, comprising the photo-bleaching agent of the present invention, can take a variety of physical forms including solid forms, such as granular, tablet, bar and liquid forms. Granular detergent compositions in accordance with the present invention can be made via a variety of methods including dry mixing, spray drying, agglomeration and granulation.

Claims: WHAT IS CLAIMED IS: 1. A photo-bleaching agent comprising: a) a polymeric component; and b) a photo-bleaching component, integrated with one another, whereby the weight ratio of a) to b) is from 1 :1 to 1000: 1, preferably from 20:1 to 100:1. 2. A photo-bleaching agent comprising a photo bleaching component and a polymeric component, integrated with one another, whereby the weight ratio of a) to b) is from 1 :1 to 1000:1, preferably from 20:1 to 100:1, obtainable by a process comprising the steps of: a) forming a melt of or a solution comprising a photo-bleaching compound and a polymeric compound; c) in a further step, forming and separating the photo-bleaching agent. 3. A photo-bleaching agent according to claim 2, wherein the polymeric compound has an average number molecular weight of from 500 to 1,000,000 and comprises polymerised monomeric units whereof at least 50%> of the units comprise a di-polar, aprotic group. 4. A photo bleaching agent obtainable by a process according to claim 2 or 3 wherein the solvent in step a) is N-alkyl pyrrolidinone, preferably N methyl or octyl pyrrolidinone. 5. A photo bleaching agent obtainable by a process according to claim 2, 3 or 4 wherein the further step b) comprises addition of the solution of step a) to an ether, preferably a diethyl ether or t-buthylmethyl ether. 6. A photo-bleaching agent according to any preceding claim which comprises from 90%) to 99.9%o by weight of the agent of the polymeric component and from 0.1% to 10%) by weight of the agent of the photo-bleaching component. 7. A photo-bleaching agent according to any preceding claim whereby the polymeric compound comprises at least 95%> by weight of the component or compound polymerised monomeric units comprising a di-polar, aprotic group. 8. A photo-bleaching agent according to any preceding claim, wherein the polymeric compound comprises one or more monomeric units selected from the group of N-vinylpyπolidone, N-vinylacetamide, N-vinylimidazole, N- vinyloxazolidone, N-vinyltriazole, 4-vinylpyridine, and 4-vinylpyridine-N- oxide. 9. A photo-bleaching agent according to any preceding claim, wherein the photo bleaching compound is a metallo phthalocyanine, preferably zinc or aluminium metallo phthalocyanine. 10. A photo-bleaching agent according to any preceding claim, wherein the photo bleaching compound does not comprise solubihsing substituent groups. 11. A photo-bleaching agent according to any preceding claim comprising from 92%o to 99 %> by weight the polymeric component. 12. A photo-bleaching agent according to any preceding claim comprising from 1% to 8% by weight the photo-bleaching component. 13. A process for formation of a photo-bleaching agent according to any of the preceding claims comprising the steps of: a) forming a melt of or a solution comprising a photo-bleaching compound and a polymeric compound; b) in a further step, separating the photo-bleaching agent. 14. A process according to claim 13 comprising the steps of a) forming a solution comprising a photo-bleaching compound and a polymeric compound in a solvent; b) removing the undissolved photo-bleaching agent by filtration or centrifugation; c) a further step comprising: 1) addition of the solution of step a), to a second solvent whereby a precipitate is formed in the solvent-mixture comprising the solvent of step a) and the second solvent; 2) separation of the precipitate comprising the photobleaching agent, comprising the polymeric compound and the compound, being in the form of a polymeric component and the photo-bleaching component, integrated with one another from the solvent-mixture. 15. A process according to claim 14 wherein the solvent of step a) is N-methyl pyπolidinone and the second solvent is an ether. 16. A process according to claim 13 wherein in step a) a melt is formed which comprises N-methylmorpholine-N-oxide. 17. Use of a polymeric compound for increasing the water-solubility and/ or the surface-activity of a compound. 18. Use according to claim 17, of a polymeric compound, having an average number molecular weight of from 500 to 1 , 000,000 and comprising polymerised monomeric units whereof at least 50%> of the units comprise a dipolar, aprotic group, for increasing the water-solubility and/ or the surface- activity of a compound. 19. A cleaning composition comprising the photo-bleaching agent according to any preceding claim, which comprises additionally an oxygen-based or chlorine- based bleaching agent. 20. A cleaning composition comprising the photo-bleaching agent according to any preceding claim, which is present at a level of from 0.05 ppm to 5%> by weight of the composition. 21. A cleaning composition according to claim 19 or 20 in the form of a laundry detergent composition.

Inventors: HEINZMAN STEPHEN WAYNE, OUBRAHIM YOUSSAF, ROWLAND GEOFFREY WILLIAM, HEINZMAN, STEPHEN, WAYNE, OUBRAHIM, YOUSSAF, ROWLAND, GEOFFREY, WILLIAM
Applicants: HEINZMAN STEPHEN WAYNE, OUBRAHIM YOUSSAF, PROCTER & GAMBLE, ROWLAND GEOFFREY WILLIAM, HEINZMAN, STEPHEN, WAYNE, OUBRAHIM, YOUSSAF, ROWLAND, GEOFFREY, WILLIAM, THE PROCTER & GAMBLE COMPANY
Application year: 1998
Main classification: C11D3
IPC codes: C11D1, C11D3, C11D11, D06L3