Title of Invention

A SKIN-PROTECTING ALKALINITY-CONTROLLING COMPOSITION

Abstract

A skin-protecting alkalinity-controlling composition comprises one or more carboxylic acid polysaccharides. Said compositions are capable of providing buffering, and thus avoiding a major increase in the pH of an aqueous system and/or are capable of reducing the pH of aqueous systems, in which alkalinity is formed as a result of chemical and/or biological reactions. The compositions may be used in personal care products, such as skin creams and lotions, hygiene products, wound care products, fabric treating products etc.

Full Text

WO 2005/102262 PCT/DK2005/000285 Title: Sldn-protecting.alkalinitv-controlliiig composition and the use thereof-Technical Field The present invention relates to a skin-protecting alkalinity-controlling composition as well as the use of a composition comprising at least one carboxylic acid polysac-charide for skin protection and/or alkalinity control. Background Art Pectin is a complex polysaccharide associated with plant cell walls. It consists of an alpha 1-4 linked polygalacturonic acid backbone intervened by rhamnose residues and modified with neutral sugar side chains and non-sugar components such as ace-tyl, methyl, and ferulic acid groups. The neutral sugar side chains, which include arabman and arabinogalactans, are attached to the rhamnose residues in the backbone. The rhamnose residues tend to cluster together on the backbone. So, with the side chains attached, this region is referred to as the hairy region and the rest of the backbone is hence named the smooth region. In US 5,929,051, Ni, et al. pectin is described as a plant cell wall component. The cell wall is divided into three layers, middle lamella, primary, and secondary cell wall. The middle lamella is the richest in pectin. Pectins are produced and deposited during cell wall growth. Pectins are particularly abundant in soft plant tissues under conditions of fast growth and high moisture content. In cell walls, pectins are present in the form of a calcium complex. The involvement of calcium cross-linking is substantiated by the fact that chelating agents facilitate the release of pectin from cell walls as disclosed by Nanji (US 1,634,879) and Maclay (US 2,375,376). WO 2005/102262 PCT/DK2005/000285 2 According to Dumitriu, S.: Polysaccharides, Structural diversity and functional ver-satility, Marcel Delcker, Inc., New York, 1998, 416 - 419, pectin is used in a range of food products. Historically, pectin has mainly been used as a gelling agent for jam or similar, fruit-containing, or fruit-flavoured, sugar-rich systems. Examples are traditional jams, jams with reduced sugar content, clear jellies, fruit-flavoured confectionery gels, non-fruit-flavoured confectionery gels, heat-reversible glazing for the bakery industry, heat-resistant jams for the bakery industry, ripples for use in ice cream, and fruit preparations for yoghurt. A substantial portion of pectin is used today for stabilization of low-pH milk drinks, including fermented drinks and mixtures of fruit juice and milk. The galacturonic acid residues in pectin are partly esterified and present as the it methyl ester. The degree of esterification is defined as the percentage of carboxyl groups esterified. Pectin with a degree of esterification ("DE") above 50% is named high methyl ester ("HM") pectin or high ester pectin and one with a DE lower than 50% is referred to as low methyl ester ("LM") pectin or low ester pectin. Most pectins found in plant material such as fruits, vegetables and eelgrass are HM pectins. Pectins are soluble in water and insoluble in most organic solvents. Pectins with a very low level of methyl-esterification and pectic acids are for practical purposes only soluble as the potassium or sodium salts. Pectins are most stable at pH 3-4. Below pH 3, methoxyl and acetyl groups and neutral sugar side chains are removed. At elevated temperatures, these reactions are accelerated and cleavage of glycosidic bonds in the galacturonan backbone occurs. Under neutral and alkaline conditions, methyl ester groups are saponified and the polygalacturonan backbone breaks through beta-elimination-cleavage of glycosidic WO 2005/102262 PCT/DK2005/000285 3 bonds at the non-reducing ends of methoxylated galacturonic acid residues. These reactions also proceed faster with increasing temperature. Pectic acids and LM pectins are resistant to neutral and alkaline conditions since there are no or only limited numbers of methyl ester groups. Pectin is a weak acid, and is less soluble at low pH than at high pH. Thus, by changing the pH of the pectin during manufacture thereof, a pectin having lower or higher solubility is provided: The pH is typically increased through the use of bases such as alkali metal hydroxides or alkali metal carbonates, but other bases are equally use-able. For instance, by using sodium carbonate, sodium pectinate is formed and the higher the dosage of sodium carbonate and, thus, the higher the pH, the more of the carboxylic acids are transformed to their sodium salts. However, at higher pH the pectin starts to de-esterify during pH-adjustment, handling and storage. Thus the pH should be maintained at a level at or below pH 6. In some cases, pectin as manufactured is esterified in a block-wise fashion. WO 2004020472 describes this phenomenon as the block-wise de-esterification takes place in the raw material used for making pectin, and the disclosure relates to a method for eliminating this block-wise de-esterification. WO 8912648 discloses a method for transforming block-wise de-esterified pectin into pectin with a random distribution of ester groups. The method involves the use of polygalacturonase, which splits the pectin molecule in those areas of the pectin molecule that are non-esterified. Thus, this method provides a lower molecular weight pectin having a higher degree of esterification than the block-wise esterified starting pectin. According to Kertesz, Z. I: The Pectic Substances, Interscience Publishers, Ihc, New York, 1951, pectic materials occur in all plant tissues. However, apples, beets, flax, WO 2005/102262 PCT/DK2005/000285 4 grapefruit, lemons, limes, oranges, potatoes, and sunflower are of particular industrial importance. Lately, also the pectin in Aloe Vera has shown industrial utility. Pectin according to the present invention needs not be extracted from the pectin containing starting material. Such crude pectin preparations are disclosed in US 2,132,065, US 3,982,003, US 4,831,127, WO 9115517, US 5,354,851, US 5,403,612, US 5,567,ft62, US 5,656,734, and WO 9749734. Other esteriiied carboxy acid polymers include, but are not limited to Pectin ethyl ester, made using ethyl iodide and heating as disclosed by Kertesz, Z.I.: The Pectic Substances, Interscience Publishers, Inc., New York, 251, 1951. In addition, pectic acid and pectinic acid may be totally or partially es- terified with aliphatic, arylaliphatic, cycloaliphatic or heterocychc alcohols. i When the acid is only partially esterified, the remaining free carboxyl groups may be salified with inorganic or organic bases. The esters may be used in the pharmaceutical, biomedical, alimentary and cosmetic fields. The esters may be prepared from a quaternary ammonium salt of pectic acid or pectinic acid and an esterifying agent such as a halogenide as disclosed in US 5,384,400. Esterified polysaccharide manufactured with a ketene dimer using an enzyme as a catalyst under mild reaction conditions as disclosed in US 6,624,298, The polysaccharide used is at least one selected from the group consisting of cellulose ethers, hydroxyethylcelhuose, hydroxypropylcellulose, carboxymethyl-cellulose, guar, cationic guar, and hydroxypropylguar. Starch esters. Methods for the preparation of starch esters are described in the li article by Tessler, M. M. and Bilimers, R. L., Preparation of Starch Esters, in Journal of Environmental Polymer Degradation 4 (1996) 85-89 and further disclosed in US 6,605,715. WO 2005/102262 PCT/DK2005/000285 5 Polymerized sugar esters as described in US 5,859,217. Esters of alginic acid. Examples include ethylene glycol and propylene glycol esters, methyl ester, homologues of methyl ester, and esters of aromatic, ar-aliphatic, alicyclic and heterocyclic alcohols. Also included are esters deriving from substituted alcohols such as esters of bivalent aliphatic alcohols as disclosed in US 5,416,205. According to www.smartskincare.com, sweat is a salty, watery solution produced by sweat glands, numerous microscopic channels opening onto the skin surface. As se- ii bum and sweat mix up on the skin surface, they form a protective layer often referred to as the acid mantle. The skin is mildly acidic. In addition to helping protect skin from "the elements" (such as wind or pollutants), the acid mantle also inhibits the growth of harmful bacteria and fungi. If the acid mantle is disrupted or loses its acidity, the sldn becomes more prone to damage and infection. The loss of acid mantle is one of the side effects of washing the skin with soaps or detergents of moderate or high strength. i According to US 5,837,254, fungal infections of the vagina or urinary tract are difficult to eradicate and frequently recur but are rarely life threatening. The normal pH of the genital tract is 4.5 to 5, which is maintained by lactobacillus. The absence of lactobacillus and a normal pH promotes candidiasis as well as the herpes virus, birth control pills, a weak immune system, genetic factors, stress and a host of other factors, which foster the growth of yeast and fungal infections of the genital tract. Candida albicans grows readily in a moist environment at a pH of more than 5. In US 5,972,321 it is stated that aalthough body odor may be partially due to certain chemicals secreted by sebaceous glands and eccrine sweat glands, major axillary (underarm) foul odor is due to secretions of the apocrine glands, which contain special nutrient materials for microorganisms. The apocrine glands secrete a milky fluid that has a pH range of 5 to 6.5 and initially consists of lipids, proteins and carbohy- WO 2005/102262 PCT/DK2005/000285 6 drates. Although gram-positive bacteria, which thrive on substances found on the moist skin surface, appear to be responsible for the production of malodor, the precise mechanisms of odor production are still unclear. According to US 4,666,707, bath salt compositions are prepared by incorporating perfume, colorant, plant extract, organic acid and so on into an inorganic salt mixture comprising sodium sulfate, borax, sulfur, sodium chloride, carbonate salt, etc., and are used for ther purpose of providing the bath with perfume and/or color, or adequately stimulating the skin to thereby promote the blood circulation, the recovery from fatigue and/or the metabolism. Among such bath salt compositions, there are foaming bath salt compositions comprising a combination of a carbonate salt and an acid, which produces, in the bath, carbon dioxide gas bubbles to thereby cause a ii relaxing or refreshing sensation and render bathing enjoyable. According to US 6,589,923 and US 4,335,025, upon washing with soap, a pH of 8-10 is established in the wash liquor. This alkalinity neutralizes the natural acid mantle of the skin (pH 5-6). Although in normal skin this acid mantle is reformed relatively quickly, in sensitive or pre-damaged skin irritations may result. A further disadvantage of soaps is the formation of insoluble lime soaps in hard water. Being alkaline, soap emulsifies the oily layer covering the natural horny layer (stratum corneum) of a person's skin and neutralizes a likewise natural acid mantle of the epidermis, which has, 'normally, an acid pH of approximately 5.5-6.5. Failure to readily regenerate the acid and oily part of the epidermis—particularly among older people-often results in dermatological symptoms, such as itching, chapping and cracking of the epidermis, especially in cold weather. Of course, always to be considered is that significant segment of the population, which is allergic to or cannot tolerate conven- i tional soaps in view of a number of reactions (sensitivities) resulting from the use thereof. According to US ,6,551,987, US 6,013,618 and US 5,626,852, pro-fragrances are compounds, which under certain conditions break down to fragrances. For instance, WO 2005/102262 PCT/DK2005/000285 7 tris(9-decenyl) when exposed to suitable conditions (e.g., exposure to the acid mantle of human skin) breaks down to release a mixture of 9-decenol and 9-decenyl formate, both of whicn are fragrance raw materials. In US 6,352,700 it is stated that while products exist that are said to address the problems of skin irritation and inflamation, they inevitably fail to address the short-term impact of various additives on the pH balance of the skin, i.e., the skin's acid mantle. To put this into perspective, one need only to consider conventional facial tissue, toilet tissue, napkin and paper towel products that are used for wiping dry or wet skin. Upon contact with skin, the tissue products transfer some of the chemicals present in the tissue to the skin surface. According to US 6,150,405 and US 5,667,769, some hair care preparations particularly for treating hair loss, contain hydroxyl scavengers. According to US 4,761,279, the application of a conventional shaving preparation of high alkalinity is often irritating to the skin. US 2,253,389 discloses the use of alkali to make pectin, which does not require sugar and acid to form gels. A gel is formed by soluble pectin in a neutral or slightly alkaline aqueous medium in the presence of a metal compound, and it is stressed that the alkalinity must be insufficient to convert pectin to pectate. The resulting gelling agent is particularly useful for substituting gelatine in jellies of water and milk. GB 541,528 discloses the importance of applying low temperature for demethoxy-lating pectin. By controlling alkali hydrolysis of pectin at temperatures between 10C and the freezing point of the pectin solution, low ester pectin of high setting power and with a low setting temperature can be made. Hydrolysis is performed in an aqueous medium and the hydrolysis is terminated by neutralization. It is disclosed that the hydrolysis is very rapid at pH 12 and very slow at pH 8.5. WO 2005/102262 PCT/DK2005/000285 8 US 2,478,170 discloses pectin with 20-30% remaining acid groups, which gel by the addition of calcium ions, with or without sugar. Alkalis are alkali metal hydroxides, ammonium hydroxide, sodium carbonate, organic ammonium bases etc. and the process involves an aqueous solution or extract of pectin being adjusted to temperatures below 35°C and pH 10-12. When the desired methoxyl content is reached, pH is reduced to 4, and the pectinic acid is isolated. In "The Pectic Substances", Interscience Publishers, Inc., New York, 1951, Kertesz describes the effect of bases on pectin. When alkali is added to a pectin solution to an extent, which is higher than the amount needed for neutralizing the pectin, deli methoxylation commences. This process consumes the alkali and the pH of the solution soon drops. Kertesz also refers to other findings, which suggest that the consumption of alkali increases as a result of the alkali concentration, or the duration of i treatment with alkali, or as the temperature of the reaction is raised. Thus, he suggests that this alkali consumption may be utilized for determining the ester content of pectinic acids. JP 2001226220 discloses the use of alcohol extracted Citrus junos seed pectin to make a skin lotion composed of said pectin, deep sea layer water and sea water or water. The lotion is characterized by being non-sticky, non-irritant and by having a low pH. Conventionally, pectin is extracted in water, whereas alcohol is known to 'I- make pectin insoluble. In addition, the disclosure does not discuss the composition of the pectin. WO 02/14374 discloses the use of hydrocolloids as thickening or emulsifying agents for a variety of products, such as foodstuffs, pharmaceutical compositions, personal care products and beverages. WO 04/005352 discloses the use of amidated pectins, such as in cremes, lotions and household products. WO 2005/102262 PCT/DK2005/00028S 9 US 6,509,311 discloses a gel system comprising propylene glycol alginate as a gelling agent, as a water binder, as an emulsifier and as a stabiliser. A need for a composition remains, which is capable of providing buffering, thus avoiding a major increase in the pH of an aqueous system and/or useable for reduc-ing the pH of aqueous systems, in which alkalinity is formed as a result of chemical and/or biological reactions, or as a result of alkalinity being imposed on the aqueous system by the environment. In particular, there is a need for a composition, which will protect the acid mantle, and there is a need for incorporating such a composition in articles, which are in contact with the skin, either human skin or animal skin. Disclosure of Invention The present invention thus relates to a skin-protecting alkalinity-controlling compo- 'i sition comprising one or more carboxylic acid polysaccharides wherein at least one of said carboxylic acid polysaccharide(s) is a high DE carboxylic acid polysaccha-ride having a degree of estenfication (DE) in the range from about 70% to about 100%, more preferably from about 80% to about 100%. The present invention furthermore relates to a skin-protecting alkalinity-controlling composition comprising a mixture of at least one high DE carboxylic acid polysac-charide having a degree of esterification (DE) in the range from about 70% to about 100%, more preferably from about 80% to about 100%s and at least one low DE carboxylic acid polysacchande having a degree of esterification (DE) in the range from about 5 to about 70 %, more preferably from about 5% to about 40%, and most preferably from about 10% to about 35%. The present invention furthermore relates to the use of at least one carboxylic acid polysacchande for skin protection and / or alkalinity control. WO 2005/102262 PCT/DK2005/000285 10 The invention is disclosed in more detail in the following hy means of the accompanying drawings and exemplary embodiments of preferred embodiments of the invention. Brief Description of the Drawings Fig 1.1 shows the alkali consumption of pectins of different molecular weight, Fig 1.2 shows the pH-drop over time for the above pectins by dissolution at 70° C, Fig. 1.3 shows the pH-drop over time for the above pectins by dissolution at 20° C, Fig. 2.1 shows the alkali consumption of pectins of different degrees of esterification (DE), Fig. 2.2 shows the pH-drop of the above pectins by dissolution at 70° C, Fig. 2.3 shows the pH-!drop of the above pectins by dissolution at 20° C, Fig. 2.4 shows the initial about 130 minutes pH-drop of the above pectins dissolved either at 70° or at 20° C, Fig. 3.1 shows the alkali consumption of either a block-wise or randomly esterified pectin of similar DE, Fig. 3.2 shows the pH-drop of the above pectins dissolved at either 70° or 20° C, Fig. 3.3 shows the initial about 100 minutes pH-drop of the above pectins, Fig. 4.1 shows the pH-drop of a pectin held at various temperatures, WO 2005/102262 PCT/DK2005/000285 11 Fig. 5.1 shows the effect of multiple alkali dosages to a pectin, Fig. 6.1 shows the effect of pectin concentration on pH-drop, Fig. 7.1 shows the pH-drop of ion-exchanged water without addition of pectin or other additions, Fig. 8.1 shows the alkali consumption of propylene glycol alginates (PGA) of different degrees of esterification, Fig. 8.2 shows the pH-drop of the above PGAs by dissolution at 70° C7 Fig. 8.3 shows the pH-drop of the above PGAs by dissolution at 20° C, Fig. 8.4 shows the initial about 70 minutes pH-drop of the above PGAs by dissolution at either 70° or 20° C, Fig. 9.1 shows the effect of multiple alkali dosages to propylene glycol alginate, Fig. 10.1 shows the pH-drop of lotions containing pectin in either the water phase or the oil phase, Fig. 11.1 shows the pH-drop of cloth soaked in a solution of 0.01 % pectin of different molecular weights, Fig. 11.2 shows the pH-drop of cloth soaked in a solution of 0.05 % pectin of different molecular weights, Fig. 11.3 shows the pH-drop of cloth soaked in a solution of 0.10 % pectin of different molecular weights, WO 2005/102262 PCT/DK2005/000285 12 Fig. 11.4 shows the pH-drop of cloth soaked in a solution of 0.20 % pectin of different molecular weights, and Fig. 11.5 shows the pH-drop of cloth soaked in a solution of 0.50 % pectin of different molecular weights. Fig. 12.1 shows the alkali consumption of a mixture of 50% of a pectin having a DE of 93.4% and 50% of a pectin having a DE of 9.6% dissolved at 70 °C and compared with the alkali consumption of the individual components. Fig. 12.2 shows the pH-drop over time of the above mixture dissolved at 70 °C and compared with the pH-drop of the individual components. Fig. 13.1 shows the alkali consumption of a mixture of 50% of a pectin having a DE of 93.4% and 50% of a propylene glycol alginate (PGA) having a DE of 55% dissolved at 70 °C and compared with the alkali consumption of the individual components. Fig. 13.2 shows the pH-drop over time of the above mixture dissolved at 70 °C and compared with the pH-drop of the individual components. Fig. 14.1 shows the alkali consumption of a mixture of 50% of a propylene glycol alginate (PGA) having a DE of 85% and 50% of a pectin having a DE of 9.6% dissolved at 70 °C and compared with the alkali consumption of the individual components. Fig. 14.2 shows the pH-drop over time of the above mixture dissolved at 70 °C and compared with the pH-drop of the individual components. WO 2005/102262 PCT/DK2005/000285 13 Best Modes for Carrying out the Invention The skin-protecting alkalinity-controlling composition according to the invention comprises one or more high DE carboxylic acid polysaccharides selected from the group comprising pectin esters, esterified cellulose ethers, esterified hydroxyethyl-cellulose, esterified carboxymethylcellulose, esterified guar gum, esterified cationic guar gum, esterified hydroxypropyl guar gum, starch esters, and polymerized sugar , esters. A high DE carboxylic' acid polysaccharide provides for a rapid pH-drop due to the low amount of free carboxylic acid groups present. Thus, if a rapid pH-drop is needed, a high DE carboxylic acid polysaccharide should be used. This fact can be utilized in a range of products intended to be applied to the skin of humans or animals. Uses include but are not limited to lotions, creams, foundations, face masks, hair care products, genital lotions, deodorants, ostomy products, feminine hygiene products, laundry products, bath salt products, soap products, fragrance products, lo-tionized tissue products, and shaving products. Further, such pectin can be used in similar products to treat animals. In a preferred embodiment according to the invention, said high DE carboxylic acid polysacchande is a pectin ester, preferably a pectin ester of aliphatic, arylaliphatic, cycloaliphatic or heterdcyclic alcohols, more preferably an ester of methanol, etha-nol, propanol or isopropanol, and most preferably an ester of methanol. The advantage of using methanol esters of pectin is the natural occurrence of such ester. However, without being bound by theory, methyl esters of pectin are more ii prone to liberate the alcohol part thereof during de-estenfication. Esters of pectin with higher alcohols are not as prone to alkaline de-esterification. In a still more preferred embodiment of the invention, said pectin is of a molecular weight in the range from about 5,000 to about 140,000, preferably in the range from WO 2005/102262 PCT/DK2005/000285 14 about 10,000 to about 125,000, most preferably in the range from about 10,000 to about 40,000. As demonstrated in example 1 below, the molecular weight of pectin has no influence on the alkah consumption or on the pH drop encountered. However, by adjusting the molecular weight of the pectin it is possible to adjust the amount of pectin, which may be dissolved or suspended in a final product. Thus, as disclosed in more detail in example 11, a lower molecular weight pectin is easier to dissolve and the viscosity of the resulting pectin-containing solution is lower than hi a corresponding higher molecular weight-containing pectin. This fact can be utilized to obtain a relatively highly concentrated pectin-solution'having suitably low viscosity, e.g. for use in fabric-treating products. The pectin having a molecular weight below about 40,000 can be made at concentrations above about 10% without causing unacceptable high viscosity. Such pectin could be manufactured and marketed as a concentrated solution with a pectin concentration in excess of 10%. Alternatively, the possibility of making such pectin solution in concentrations above about 10% makes spray-drying of such solutions economically feasible. The degree of esterification indicates the average DE of any given polysaccharide. By controlling the distribution of ester groups along the polysaccharide chain to obtain either a random or a block-wise distribution of ester groups, it is possible to obtain a locally higher or lower DE polysaccharide. As demonstrated in example 3, the alkali consumption of a pectin having a block-wise ester group distribution is the same as the alkali consumption of a corresponding pectin having a random ester group distribution. However, the pH-drop of the two pectins is considerably larger for the block-wise esterified pectin, presumably because such pectm will act as a pectin with a higher average DE. Thus, by treating a block-wise esterified pectin with a polygalacturarase, which splits the pectin at non-esterified sites, a lower molecular weight pectin may be obtained having an increased DE. WO 2005/102262 PCT/DK2005/000285 15 In an alternative embodiment of the composition according to the invention, the ester groups of the polysaccharide thereof are thus distributed in a block-wise fashion. In another embodiment of the composition according to the invention, the ester groups of the polysaccharide are distributed in a random fashion. In another preferred embodiment according to the invention, the skin-protecting alkalinity controlling composition comprises a mixture of at least one high DE-carboxylic acid polysaccharide having a degree of esterification (DE) in the range from about 70% to about 100%, more preferably from about 80% to about 100%, and at least one low DE-carboxyhc acid polysaccharide having a degree of esterification (DE) in the range from about 5 to about 70 %, more preferably from about 5 to about 40 %, most preferably from 10 to about 35 %. A carboxylic acid polysaccharide having a relatively low DE provides for a large al-kali consumptionscapacity or buffer capacity. An advantage of a higher buffer capacity is the ability of the pectin to neutralize an initial high concentration of alkali. This is an advantage particularly when fabrics are insufficiently depleted for alkaline washing powder. Thus, by combining a low DE and a high DE carboxylic acid polysaccharide, an initial alkali consumption buffering can be obtained succeeded by a pH-reduction. In a preferred embodiment according to the invention, any of said high DE carboxylic acid polysaccharides and said low DE carboxylic acid polysaccharides is se-lected from the group comprising pectin esters, alginic acid esters, esterified cellulose ethers, esterified hydroxyethylcellulose, esterified carboxymethylcellulose, esterified guar gum, esterified catiomc guar gum, esterified hydrocypropyl guar gum, starch esters, and polymerized sugar esters. WO 2005/J 02262 PCT/DK2005/000285 16 In a particular embodiment according to the invention, any of said high. DE carbox-ylic acid polysaccharides and said low DE carboxylic acid polysaccharides is a pec- T tin ester, preferably a pectin ester of aliphatic, arylaliphatic, cycloaliphatic or hetero-cyclic alcohols, more preferably an ester of methanol, ethanol, propanol or isopro-panol, and most preferably an ester of methanol. In a more particular embodiment according to the invention, any of said high DE carboxylic acid polysaccharides and said low DE carboxylic acid polysaccharides is a pectin having a molecular weight in the range from about 5,000 to about 140,000, preferably in the range from about 10,000 to about 125,000, most preferably in the range from about 10,000 to about 40,000. In an alternative embodiment according to the invention, any of said high DE carboxylic acid polysaccharides and said low DE carboxylic acid polysaccharides is an esterifled alginic acid. In a preferred embodiment of the invention, any of said esterifled alginic acids is an alginic acid ester of aliphatic, aromatic, araliphatic, alicyclic and heterocyclic alcohols, including esters deriving from substituted alcohols such as esters of bivalent aliphatic alcohols, preferably ethylene glycol or propylene glycol alginate. US 5,416,205 discloses suitable alginic acid derivatives, and the reference is enclosed herewith in its entirety. In a further embodiment according to the invention, the ester groups of any of said high DE carboxylic acid polysaccharides and said low DE polysaccharides are distributed in a block-wise fashion. In another embodiment according to the invention, the ester groups of any of said high DE carboxylic acid polysaccharides and said low DE polysaccharides are distributed in a random fashion. WO 2005/102262 PCT7DK2005/000285 17 In another embodiment of the invention, a composition comprising at least one car-boxylic acid polysaccharide selected from the group comprising pectin esters, alginic acid esters, esterifled cellulose ethers, esterified hydroxyethylcellulose, es-terified carboxymethylcellulose, esterified guar gum, esterified catiordc guar gum, esterified hydropropyl guar gum, starch esters, and polymerized sugar esters is used for skin protection and / or alkalinity control. In a preferred embodiment according to the invention, said carboxylic acid polysaccharide is a pectin ester, preferably a pectin ester of aliphatic, arylaliphatic, cycloaliphatic or heterocyclic alcohols, more preferably an ester of methanol, etha-nol, propanol or isopropanol, and most preferably an ester of methanol. In another embodiment according to the invention, said carboxylic acid polysaccharide is a pectin having a molecular weight in the range from about 5,000 to about 140,000, preferably in the range from about 10,000 to about 125,000, most prefera-bly in the range from about 10,000 to about 40,000. I In another embodiment according to the invention, said carboxylic acid polysaccharide is an esterified alginic acid. In another embodiment according to the invention, said esterified alginic acid is selected from the group comprising alginic acid esters of aliphatic, aromatic, ar-aliphatic, alicyclic and heterocyclic alcohols, including esters deriving from substituted alcohols such as esters of bivalent aliphatic alcohols, preferably ethylene gly-col alginate or propylene glycol alginate. ii In another embodiment according to the invention, the ester groups of said polysaccharide are distributed in a block-wise fashion. In another embodiment according to the invention, the ester groups of said polysaccharide are distributed in a random fashion. WO 2005/102262 PCT/DK2005/000285 18 In another embodiment of the use according to the invention, at least one of said carboxylic acid polysaccharide(s) is a high DE carboxylic acid polysaccharide having a degree of esterification (DE) in the range from about 70% to about 100%, more preferably from [about 80% to about 100%. In another embodiment of the use according to the invention, at least one of said carboxylic acid polysaccharide(s) is a low DE carboxylic acid polysaccharide having a degree of esterification (DE) in the range from about 5 to about 70%, more preferably from about 5% to about 40%, and most preferably from about 10% to about 35%. In another embodiment according to 1he invention of the use of a composition, said composition comprises a mixture of at least one of carboxylic acid polysaccharide having a degree of esterification (DE) in the range from about 70% to about 100%, more preferably from about 80% to about 100%; and at least one carboxylic acid polysaccharide having a degree of esterification (DE) in the range from about 5 to about 70%, more preferably from about 5% to about 40%, and most preferably from about 10% to about 35%. The composition according to the invention is suitable for use in personal care products. In a preferred embodiment, said products are for use on human skin. In another embodiment, said products are for use on animal skin. In a particular embodiment according to the invention, the skin protecting alkalinity-controlling composition is used in a product selected from the group consisting of skin creams, skin lotions, deodorant products, fragrance products, hair care products, shaving products, soap products, and bath salt products. WO 2005/102262 PCT/DK2005/000285 19 In another embodiment according to the invention, the skin protecting alkahnity-controlling composition is used in a product selected from the group consisting of female hygiene products and diapers. A particular advantage of the present composition is the fact that they are capable of controlling the alkalinity of the surface, to which they are applied, for a prolonged time. As demonstrated in examples 5 and 8, the carboxylic acid polysacchandes are capable of controlling the alkalinity at multiple challenges of alkalinity. This fact can be utilized in e.g. deodorant products, diapers or female hygiene products, which are repeatedly exposed to sweat that is decomposed by micro-organisms to alkaline substances. Thus, a prolonged effective alkalinity control may be obtained by the products according to the present invention. In another embodiment according to the invention, the skin-protecting alkalinity-controlling composition is used in a product selected from the group consisting of ostomy products and wound care products. In ostomy products a low solubility polysaccharide, such as a low solubility pectin, should be used, since the ostomy product should remain insoluble for a longer period of time during flushing by body fluids. In this particular case a combination of a low DE and a low pH pectin would provide for a longer durability of the ostomy product during use. In a particular embodiment such low solubility low DE pectin should be combined with a higher solubility pectin having a higher DE to maintain a skin pH closer to the optimum skin pH of 5.5. In still another embodiment according to the invention, the skin-protecting alkalinity-controlling composition is used in a product selected from the group consisting of lotiomzed tissue products, fabric treating products, and laundry rinse products. WO 2005/102262 PCT/DK2005/000285 20 Materials and Methods a) Extraction of pectin Pectin is extracted using the following steps. The degree of esterification was controlled in the range of i about 76% to about 30% through shorter or longer extraction times. 1. 15 litres of water'was heated to 70°C in a stainless steel, jacketed vessel having i a volume of 18 litres and equipped with a stirrer, 2. 500 g dried citrus peel or dried beet cossets was added to the water, and the pH is adjusted to 1.7,- 1.8 by addition of 62% nitric acid. 3. Extraction was carried out at 70"C for 2-24 hours depending on the desired ¦ degree of esterification while stirring. 4. After extraction, the content of the vessel was filtered on a Bucher funnel using diatomaceous earth as filter aid. 5. The filtered extract was ion exchanged while stirring by adding 50ml resin (Amberlite SRIL'J produced by Rohm&Haas) per litre of filtered extract. While stirring, the ion exchange was carded out during 20 minutes while stirring. 6. The ion exchanged filtrate was filtered on a Bucher funnel equipped with a cloth. 7. The filtered ion exchanged filtrate was precipitated by adding it to three parts of 80% isopropanol while stirring gently. 8. The precipitate was collected on nylon cloth and pressed by hand to remove as 11, much isopropanol as possible. 9. The hand pressed precipitate was washed once in 60% isopropanol and then dried at 70°C in a drying cabinet at atmospheric pressure. 10. After drying, the pectin was milled. b) Preparation of pectin with degree of esterification below 30% WO 2005/102262 PCTYDK2005/000285 21 1. The pressed precipitate made according to the procedure under a) point 8 was suspended m 60% isopropyl alcohol at 5°C. 2. Concentrated NaOH solution was added and the slurry was stirred for about one hour. The amount of NaOH is calculated to produce the desired DE. 3. The pectin solid was separated on nylon cloth, and washed twice in 60% iso propyl alcohol at pH 4. 4. The pectin solid was separated on nylon cloth, dried at 70°C and milled. c) Preparation of pectin with different molecular weight 1. Pectin extracted according to a) was dissolved in about 80 °C ion exchanged water to form a 5% solution. 2. After cooling the solution to about 25 °C, pH was adjusted to 5.50 with NH3. 3. Samples of the cold solution were treated with pectin lyase in concentrations ranging from 0 to 1300 micro litres per 10 litres of pectin solution. 4. Each sample was treated with its enzyme preparation for 1 hour at 25 °C while stirring/ 5. After treatment, the pH was adjusied to 2.50 and the samples were heated at 80 °C for 10 minutes to inactivate the enzyme. 6. The samples were lastly precipitated in isopropyl alcohol, washed in isopropyl alcohol, dried and milled. d) Preparation of pectin with degree of esteriftcation above 80% 1. 50 g. pectin as prepared under a) was added 2.5 g. dimethylaminopyridine, 100 ml. methanol and 100 ml. heptane in suitable flask and the mixture was cooled to minus 4 °C. 2. 15 ml thionylchloride was over a period of 10 minutes added as drops to the mixture. 3. Over about 24 hours, the mixture was allowed to heat to about 21°C. WO 2005/102262 PCT/DK2005/000285 22 4. The solid was filtered, washed twice with first 60% isopropyl alcohol and sec ondly with 100% isopropyl alcohol. 5. The solid was dried at about 70°C. e) Preparation of pectin with different distribution of ester groups i 1. Pectin extracted .according to a) was dissolved in about 80 °C ion exchanged water to form a 2% solution. ¦I. 2. The solution was cooled to 45 °C and pH was adjusted to 4.5 with NH3. 3. Samples were added 2 - 4% of enzyme preparation while stirring: Plant es- terase (Collopulin) for a block wise de-esterification and bacterial esterase (Rheozyme) for random de-esteriiication. 4. The degree of esterification was monitored through titration with 2% NH3 at constant pH of 4.5. 5. After de-esterification3 decreasing the pH to 2.5 with HNO3 and subsequently heating the sample to 80 °C for 10 minutes inactivated the enzyme. 6. The sample was precipitated in isopropyl alcohol, washed in isopropyl alcohol, dried and milled. ' f) Determination of molecular weight fMw> and intrinsic viscosity (IV). For this, High Performance Size Exclusion Chromatography (HPSEC) with triple detection is used. Principle: A pectin sample is fractionated according to hydrodynamic volume, using size exclusion chromatography. After separation, the sample is analysed by a triple detector system, consisting of a refractive index (RJ) detector, a Right Angle Laser Light Scattering (RALLS) detector and a differential viscometer. Information from these detectors leads to determination of molecular weight (Mw) and intrinsic viscosity 23 (IV). The Mark-Houwink factor is calculated using the molecular weight and intrinsic viscosity as obtained using this method. Materials: 1. Pump model 515,' Waters, Hedehusene, Denmark. 2. Degasser, Gynkotek, Polygen Scandinavia, Arhus, Denmark. 3. Column oven, Waters, Hedehusene, Denmark. 4. AS-3500 Auto sampler, with sample preparation module, Dionex Denmark, Radovre, Denmark. 5. 3 linear mixed bed columns, TSK-GMPWXL, Supelco, Bellefonte PA, USA. 6. Liquid phase: 0.3 M lithium acetate buffer pH 4.8, Fluka Chemie AG, Buchs, Switzerland. i 7. Dual detector, RI, Viscometry, Model 250, Viscotek, Houston, Texas, USA. 8. RALLS Model 600, Viscotek, Houston, Texas, USA. Method: Approximately 2 mg of the sample is weighed into a 2000 pi vial. The sample is then dissolved in the auto sampler, by following schedule: 8 pi of ethanol is added, then 1300 pi of acetate buffer (0.3 M, pH 4.8), sample is heated to 15 °C and mixed for 9.9 minutes. 300 The specific refractive index increment (dn/dc) value for pectin is set at 0.144. Data from detectors are processed by tri-SEC software (Viscotek). g) Determination of degree of esterification (DE) and galacturonic acid CGA) in non-amide pectin 24 Principle: This method pertains to the determination of % DE and % GA in pectin, which does not contain amide and acetate ester. Apparatus: 1. Analytical balance 2. Glass beaker, 250 ml, 5 pieces 3. Measuring glass, 100 ml 4. Vacuum pump 5. Suction flask 6. Glass filter crucible no. 1 (Btichner funnel and filter paper) 7. Stop watch 8. Test tube 9. Drying cabinet at 105 °C 10. Dessicator 11. Magnetic stirrer and magnets 12. Burette (10 mlj' accuracy ± 0,05 ml) 13. Pipettes (20 ml: 2 pieces, 10 ml: 1 piece) 14. pH-meter/autoburette or phenolphtalein Chemicals: 1. Carbon dioxide-free water (deionized water) 2. Isopropanol (IPA), 60% and 100% 3. Hydrochloride (HC1), 0.5 N and fuming 37% 4. Sodium hydroxide (NaOH), 0.1 N (corrected to four decimals, e.g. 0.1002), 0.5 N 5. Silver nitrate (AgNO3), 0.1 N 6. Nitric acid (HNO3), 3 N II. 7. Indicator, phenolphtalein, 0.1% 25 Procedure - Determination of % DE and % GA (Acid alcohol: 100 nil 60% IPA + 5 ml HC1 fuming 37%): i 1. Weigh 2.0000 g pectin in a 250 ml glass beaker. 2. Add 100 ml acid alcohol and stir on a magnetic stirrer for 10 min. 3. Filtrate through a dried, weighed glass filter crucible. 4. Rinse the beaker completely with 6 x 15 ml acid alcohol. 5. Wash with 60% IPA until the filtrate is chloride-free (approximately 500 ml). 6. Wash with 20 ml 100% IPA. 7. Dry the sample for 2 14 hours at 105°C 8. Weigh the crucible after drying and cooling in desiccator. 9. Weigh accurately 0.4000 g of the sample in a 250 ml glass beaker. 10. Weigh two samples for double determination. Deviation between double de terminations must max. be 1.5% absolute. If deviation exceeds 1.5% the test must be repeated. 11. Wet the pectin with approx. 2 nil 100% IPA and add approx. 100 ml carbon di-oxide-free, deionized water while stirring on a magnetic stirrer. (Chloride test on ash-free and moisture-free basis: Transfer approximately 10 ml filtrate to a test tube, add approximately 3 ml 3 N HNO3, and add a few drops of AgNO3. The filtrate will^be chloride-free if the solution is clear, otherwise there will be a precipitation of silver chloride.) The sample is now ready for titration, either by means of an indicator or by using a pH-meter/autoburette. Procedure - Determination of % DE only (Acid alcohol: 100 ml 60% IPA + 5 ml HC1 fuming 37%): 1. Weigh 2.00 g pectin in a 250 nil glass beaker. 26 2. Add 100 ml acid alcohol and stir on a magnetic stirrer for 10 minutes. 3. Filtrate through a Biichner funnel with filter paper. 4. Rinse the beaker with 90 ml acid alcohol. 5. Wash with 1000 ml 60% EPA. 6. Wash with approximately 30 ml 100% EPA. 7. Dry the sample for approximately 15 minutes on Buchner funnel with vac uum suction. ¦I 8. Weigh approximately 0.40 g of the sample in a 250 ml glass beaker. 9. Weigh two samples for double determination. Deviation between double de terminations must max. be 1.5% absolute. If deviation exceeds 1.5% the test il must be repeated. 10. Wet the pectin with approximately 2 ml 100% IPA and add approx. 100 ml de-ionized water while stirring on a magnetic stirrer. The sample is now ready for titration, either by means of an indicator or by using a ii pH-meter/autoburette. i Note: It is very important that samples with % DE Titration using indicator: 1. Add 5 drops of phenolphtalein indicator and titrate with 0.1 N NaOH until i change of color (record it as Vi liter). 2. Add 20.00 ml 0.5 N NaOH while stirring. Let stand for exactly 15 min. When ¦i standing the sample must be covered with foil. 3. Add 20.00 ml 0.5 N HC1 while stirring and stir until the color disappears. 4. Add 3 drops of phenolphtalein and titrate with 0,1 N NaOH until change of i. color (record it as V2 titer). Blind test (Double determination is carried out): 27 1. Add 5 drops phenolphtalein to 100 ml carbon dioxide-free or dionized water (same type as used for the sample), and titrate in a 250 ml glass beaker with 0.1 N NaOH until change of color (1-2 drops). 2. Add 20.00 ml 0.5 N NaOH and let the sample stand untouched for exactly 15 minutes. When standing the sample must be covered with foil. 3. Add 20.00 ml 0.5 N HC1 and 3 drops phenolphtalein, and titrate until change of color with 0.1 N NaOH (record it as BJ. Maximum amount allowed for titra- tion is 1 ml 0.1 N NaOH. If titrating with more than 1 ml, 0.5 N HC1 must be diluted with a small amount of deionized water. If the sample has shown change of color on addition of 0.5 N HC1, 0.5 N NaOH must be diluted with a small amount of carbon dioxide-free water. Maximum allowed dilution with water is such that the solutions are between 0.52 and 0.48 N. Titration using pH-meter/Autoburette: Using Autoburette type ABU 80 the following settings may be applied: Sample with % DE Proportional band 0.5 5 Delay sec. 50 5 Speed-VI 10 5 Speed-V2 15 5 1. Titrate with 0.1 N NaOH to pH 8.5 (record the result as V! liter). 2. Add 20.00 ml 0.5 N NaOH while stirring, and let the sample stand without stir ring for exactly 15 minutes. When standing the sample must be covered with foil. 3. Add 20.00 ml 0.5 N HC1 while stirring and stir until pH is constant. 4. Subsequently, titrate with 0.1 N NaOH to pH 8.5 (record the result as V2 titer). Blind test (Double determination is carried out): 28 1. Titrate 100 ml carbon dioxide-free or deionized (same type as used for the sample) water to pH 8.5 with 0.1 N NaOH (1-2 drops). 2. Add 20.00 ml 0.5 N NaOH while stirring and let the blind test sample stand without stirring for exactly 15 min. "When standing the sample must be covered with foil. 3. Add 20.00 ml 0.5 N HC1 while stining, and stir until pH is constant. 4. Titrate to pH 8.5 with 0.1 N NaOH (record it as B]). Maximum amount allowed for titration is 1 ml 0.1 N NaOH. If titrating with more than 1 ml, 0.5 N HC1 must be diluted with a small amount of deionized water. If pH does not fall to below 8.5 on addition of 0.5 N HC1, 0.5 N NaOH must be diluted with a small amount of carbon dioxide-free water. Maximum allowed dilution with water is I) such that the dilutions are between 0.52 and 0.48 N. Calculation: Vt-V, + (V2-B!) % DE (Degree of Estenfication) - {(V2 - B0 x 100} / Vt % DFA (Degree of Free Acid) = 100 - % DE % GA* (Degree of Galacturomc acid) = (194.1 x Vt x N x 100) / 400 194.1: Molecular weight for GA N: Corrected normality for 0.1 N NaOH used for titration (e.g. 0.1002 N) 400: weight in mg of washed and dried sample for titration % Pure pectin = {(acid washed, dried amount of pectin) x 100} / (weighed amount of pectin) h) Determination of pH-drop 29 1. 1 g. pectin was dissolved in 100 g. deionized water at 70°C and at 20°C. 2. The solution was placed in a thermostatically controlled water bath and con- ¦i tinuously stirred. 3. 0.1 MNaOH was added to apH of between 9 and 10. 4. The pH was recorded as a function of time l) Determination of titration curves 1. 2 g. pectin was dissolved in 200 g. deionized water at 70°C and at 20°C. 2. The solution was placed in a thermostatically controlled water bath at 25°C and continuously stirred. ¦I 3. 0.1 M NaOH was added to the solution and pH recorded as a function of added 0.1 MNaOH. j) Propylene glycol alginate -¦ Quantitative determination of the ester groups is carried out by the saponification method described on pages 169-172 of "Ouan-titative organic analysis via functional groups". 4th Edition. John Wiley and Sons Publication. 1. Kelcoloid O manufactured by ISP Technologies, Inc. Esterification: High - about 85%. 2. Manucol Ester ER/K manufactured by ISP Technologies, Inc. Esterification: High - about 80%. 3. Kelcoloid HVF manufactured by ISP Technologies, Inc. Esterification: Me dium - about 55% ii k) Preparation of lotion and pH-drop in lotion Lotions were prepared according to the composition: Since the pH is low, the lotion can be preserved with conventional food-grade preservatives. Method 1: 1. Palmitate and emulsifier were mixed and heated to 75°C in order to melt the emulsifier. ' 2. Pectin and preservatives were dispersed in distilled water and heated to 75°C. 3. The hot oil phase was added to the hot water phase while stirring on magnetic stirrer. 4. The mix was cooled to about 30°C on cooling bath while stirring and fill into appropriate container. Method 2: 1. Palmitate and emulsifier were mixed and heated to 75°C in order to melt the emulsifier. i 2. Pectin was dispersed into the hot melt Pectin is insoluble in the oil phase and consequently easy to disperse therein without formation of lumps. 3. Preservatives were dissolved in distilled water and the solution was heated to 75°C. 31 4. The hot oil phase was added to the hot water phase while stirring on magnetic stirrer. 5. The mix was cooled to about 30°C on cooling bath while stirring and fill into 'I appropriate container. 1) Rinsing test - Note: This test is indicative, only. It is not possible to read the pH accurately. 1. A piece of cotton was cut to fit into a petri dish. i1' 2. The cotton piecejwas soaked in a pectin solution in distilled water and stirred on magnetic stirrer for about 5 minutes. 3. The wet cloth was hand-pressed and placed in a petri dish. 4. The cloth was dried over night in an oven at 50°C. 5. The dried cloth was wetted with 2 ml 0.001 M NaOH. 6. A piece of indicator paper (pH in the range 1-11) was placed on the cloth. If 7. The color change of the indicator paper over time was recorded. 32 Examples The following examples are non-limiting. Example 1: Effect of molecular weight Five samples of different molecular weight, but with similar DE made from dried lemon peel were titrated and the pH drop over time recorded for samples dissolved at 70°C and 20°C, respectively. The pH drop was measured at 30 - 32°C. Titration was done using 0.1008M NaOH, The comment "unstable" refers to the pH-meter, which at high pH values showed an unstable reading. 1. 97CP001-39-0: Mw=123.000; DE=71.4% Fig. 1.1 shows that thfe molecular weight of pectin has no influence on the alkali consumption. The data in fig. 1.2 do [not suggest a change in the pH-drop resulting from a change in molecular weight. In practice, this means that a pH controlling preparation made from pectin can be made thick (high molecular weight) or thin (low molecular !li weight) or basically with any viscosity between the two extremes. In addition, if the 111 alkali consumption is to be increased, a low molecular weight pectin preparation makes it possible to increase the concentration of pectin without making the alkali consuming preparationttoo viscous. Fig. 1.3 shows that dissolution temperature does not change the drop in pH. Thus, II irrespective of the molecular weight, pectin preparation for controlling pH can be III made either hot or cold: Example 2: Effect of Degree of Esterification Eight samples were prepared with different degree of esterification ranging from about 9 to 93%. The samples were made from dried lemon peel. All were titrated and the pH drop over time recorded for samples dissolved at 70°C and 20°C, respectively. The pH drop was measured at 30 - 32°C. Titration was done using 0.1008 M ill NaOH. The comment {'unstable" refers to the pH-meter, which at high pH values showed an unstable reading. Fig 2.1 shows that one pectin is characterized by a higher starting pH than the rest. Conventionally, pectin is neutralized with an alkali metal base to a pH in the range 3 — 4 or even higher. This is mainly in order to preserve the pectin, but it also has an impact on the solubility of the pectin. However, if one moves the curve for DE-9.6% upwards to connect with the other curves, the picture becomes clear: With increasing DE and consequently decreasing galacturonic acid, the pectin can consume less alkali. Thus, if pectin is used to neutralize alkali, the degree of esterifica-tion and the starting pH should be as low as possible. To further elaborate on this point, I define buffer capacity as ml. 0.1 M NaOH required to increase the pH by 1 pH unit, calculated from the part of the titration curve, which is steepest. Thus, the approximate buffer capacities as calculated from fig. 2.1 are: DE=9.6% and DE=34.4%: Buffer capacity about 26 DE=71%: Buffer capacity about 12 DE=93.4%: Buffer capacity less than 6 43 Fig. 2.2 show a dramatic increase hi the pH-drop as the degree of esterification is increased. Fig. 2.3 shows the same dramatic influence of DE even when the pectin is dissolved at 20°C. The figure shows that at the high DE, the pH is eventually decreased below 5.5. These results are compiled in fig. 2.4, in which the pH drop has been followed for the first up to about 130 minutes. It is evident that the pH-drop occurs to the same extent whether the pectin solution is made hot or cold. For DE=93.4%, time to reach pH=8 is 2 minutes, for DE=71% it takes 12 minutes, for DE=34.4% the time is 35 minutes and for DE=9.6% it takes 130 minutes. In order to reach pH=7, the difference is even bigger. Pectin with a DE=71 is about 9 times slower than pectin with DE==93.4, and pectin with DE lower than 71% are slower than a factor 10 compared to pectin with DE-93.4. Thus, if one needs to obtain a rapid pH decrease as a result of alkali generation, pectin with as high a DE as possible is preferred. If, on the other hand, the need calls for slower reduction of pH, then a lower DE would be preferred. Selecting pectin of a specific DE makes it possible to reduce the pH at a specific rate. Another aspect is to combine pectin preparations of different DE. For example, one migjit combine a low DE pectin and a high DE pectin to achieve initial alkali consumption or buffer capacity and to provide pH reduction, when the buffer capacity is used. Example 3: Effect of Methyl Ester Distribution Two samples were made from dried lemon peel. One was de-esterified with a bacterial pectin esterase, which results in a random distribution of the methyl ester WO 2005/102262 PCT/DK2005/000285 44 groups. The other was de-esterified with a plant pectin esterase, which results in a block wise distribution of the methyl ester groups. The samples were made to similar DE. Both samples were titrated and the pH drop over time recorded for samples dissolved at 70°C and 20°C, respectively. The pH drop was measured at 30 - 32°C. Titration was done using 0.1008 M NaOH. The comment "unstable" refers to the pH-meter, which at high pH values showed an unstable reading. Fig. 3.1 shows that the distribution of methyl esters in pectin has no impact on the alkali consumption. The galacturonic acid drives the alkali consumption. Fig. 3.2 indicates a difference in the rate of the pH-drop. It also shows, that identical pH-drop is achieved whether the pectin has been dissolved hot or cold. Fig. 3.3 shows the pH-drop in the first 120 - 130 minutes, and a random ester group distribution needs about 4 times longer to reach pH=8 compared to a blocky ester group distribution. Since the two pectin preparations have almost identical average DE, the faster pH-drop of a blocky ester distribution is explained by local concentration of ester groups. Thus, pectin with a blocky ester distribution will act as pectin with a higher average DE. In practice, this is important because one might treat a blocky pectin with polygalacturonase to increase the DE, which would constitute an easier way to make a high ester pectin than by using the process of re-methylation. 47 Example 4: Effect of temperature The pH drop for one sample having DE=71% and made from dried lemon peel was recorded at four different temperatures. The sample was prepared by dissolving the pectin at 70°C and subsequently cooling the solution to the recording temperature. The temperature was maintained with a thermostatically controlled water bath. Fig. 4.1 shows that the rate of the pH-drop increases with increasing temperature. The rate is particularly increased as the temperature increases above about 30°C. Example 5: Effect of multiple additions of alkali The pH drop for one sample having DB=71% and made from dried lemon peel was recorded at a temperature of 25 - 27°C. First, the pH was raised to about 10 with 19 ml. 0.1 M NaOH. When the sample had reached a pH of 6 - 7, the pH was again raised to about 10. This required 1.1 ml. 0.1 M NaOH. When the pH had reached 6 -7, the pH was raised a third time to about 10, which required 1.2 ml. 0.1 M NaOH. The sample was prepared by dissolving the pectin at 70°C and subsequently cooling the solution to the recording temperature. The temperature was maintained with a thermostatically controlled water bath. 1. SampleiwithDE=71% Fig. 5.1 shows that the rate of the pH-drop stays unchanged after at least three cycles, where the pH is first increased to about 10, then after the pH has dropped increased to about 10. After one cycle, the DE is decreased to about 66%, so the ability to continue reducing pH is caused by an incomplete de-esterification. Thus, if alkalinity is appears in pulses, for at least three times pectin is able to reduce the alkali. In fact, in one experiment, which went on for seven days, a 200 ml. 1% pectin solution of DE=71% consumed 73 ml. of a 0.1 MNaOH solution. After this period, the DE has .decreased to 9.1%. Thus, 2 g. pectin consumes 7.3 mmol NaOH, which corresponds to about 0.3 g. HI NaOH. It also means that about 0.23 g. methanol is produced, which in combination with the acid effect of pectin may explain the anti-microbial effect of pectin. WO 2005/102262 PCT/DK2005/000285 50 Example 6: Effect of pectin concentration The pH drop for one sample having DE=81.7% and made from dried lemon peel was recorded at a temperature of 30 - 32°C. The concentration of pectin was 0.05 -5 2%. The sample was prepared by dissolving the pectin at 70°C and subsequently cooling the solution to the recording temperature. The temperature was maintained with a thermostatically .pontrolled water bath. 1. Sample with|DE=81.7% 10 Fig. 6.1 shows that at pectin concentrations above 1%, the pH-drop appears to be in-Ill dependent of the pectin concentration. However, even at very low concentrations of 5 pectin, a clear drop in pH occurs. WO 2005/102262 PCT/DK2005/000285 51 Example 7: pH drop of water Carbon dioxide is soluble in water, and this experiment shows the pH drop of ion-5 exchanged water over time without the presence of pectin or other additions. The temperature of the water was kept at 25°C using a thermostatically controlled water bath. 1. Ion exchanged water Table 7 I pH drop of ion exchanged water Fig. 7.1 shows that over a period of about 5 hours, the "natural" drop of pH in water is about 0.5 pH-umts, so the error is tolerable. Example 8: Propylene Glvcol Alginate - Effect of esterification Three samples with degree of esierification ranging from about 55 to about 85% were tested. All were titrated and the pH drop over time recorded for samples dissolved at 70°C and 20°C, respectively. The pH drop was measured at 30 - 32°C. Ti- 54 4. Effect of multiple additions of alkali The pH drop for one sample, Manucol Ester ER/K, was recorded at a !i temperature of 30 - 32°C. First, the pH was raised to about 10 with 4 ml. .i 0.1 M NaOH. When the sample had reached a pH of 5 - 6, the pH was again raised^to about 10. This required 2.5 ml. 0.1 M NaOH. When the pH had reached 5-6, the pH was raised a third time to about 10, which required 2.0 ml. 0.1 M NaOH. When the pH had reached about 6, the pH ! was again increased to about 10, which required 1.5 ml. NaOH. The sample was prepared by dissolving the pectin at 70°C and subsequently cooling the solution to the recording temperature. The temperature was maintained with a thermostatically controlled water bath. 55 Table 8 4. Multiple pH drop of high DE PGA Fig. 8.1 shows that as the degree of esterifiaction increases in PGA, the less alkali can be consumed. Buffer capacities are calculated to PGA with DE about 85%: About 4.1 PGA with DE about 80%: About 5.7 PGA with DE about 55%: About 8.1 Thus, PGA provides less buffering effect compared to pectin. Fig. 8.2 shows that as for pectin, PGA provides a faster pH drop with increasing degree of esterification. Fig. 8.3 shows the same dramatic influence of esterification even when the propyl-ene glycol alginate is dissolved at 20°C. The figure shows that at the high DE, the pH is eventually decreased to below 5. Fig. 8.4 shows that the pH-drop occurs to the same extent whether the propylene glycol alginate solution is made hot or cold. WO 2005/102262 PCT7DK2005/000285 56 Example 9: Effect of multiple additions of alkali to propvlens jglvcol alginate The pH drop for one sample, Manucol Ester ER/K, was recorded at a temperature of 30 - 32°C. First, the pH was raised to about 10 with 4 ml. 0.1 M NaOH. When the sample had reached a pH of 5 - 6, the pH was again raised to about 10. This re-quired 2.5 ml. 0.1 M NaOH. When the pH had reached 5-6, the pH was raised a third time to about 10, which required 2.0 ml. 0.1 M NaOH. When the pH had reached about "6, the pH was again increased to about 10, which required 1.5 ml. NaOH. The sample was prepared by dissolving the pectin at 70°C and subsequently cooling the solution to;the recording temperature. The temperature was maintained with a thermostatically controlled water bath. Table 9.1: Mulbplo pH drop of high DE PGA WO 20Q5/102262 PCT/DK2005/000285 57 Fig, 9.1 shows a tendency for the pH-drop to become slower after two cycles. Example 10: pH-drop in lotion The pH drop in lotions made according to the two methods described in "Materials and Methods" section £.1 were measured using pectin of about DEH31.7%. 10 grams lotion was slurried in 50 ml distilled water and pH was adjusted with 0.1 M NaOH to about 10. Pectin concentration in slurry: 0.125%. Temperature: 30°C. It may seem that when pectin is dissolved in the water phase before mixing with the 011 phase provides for a more rapid pH-drop. However, when taking into considera- iji tion, that the curve for pecto dissolved in .file water phase starts at a slightly lower pH, the two curves are close to identical- Thus, there is nothing to suggest that one of the methods for making the lotion influences the effect of the pectin. WO 2005/102262 PCT/DK2005/000285 58 The lotions were tested by 12 persons - 6 females and 6 males, with the following remarks from the test persons: Easy to spread on the skin Non-sticky Non-greasy Softens skin witnin one minute after application Skin-softening remains for at least 24 hours Removes skin-itching within one minute after application Skin-itching does not reoccur within 24 hours Athlete's foot is effectively combated for at least 24 hours The lotion was also tested on one dog, which had developed a rash on the nose. Treatment of the nose with the lotion 'twice for one day reduced the rash visibly. To similar treatments over the next two days reduced to rash to an extent, where the rash was difficult to see. Example 11: pH-drop of cloth Cloths were prepared according to the method in "Materials and Methods" section 2.ra WO 2005/102262 PCT/DK2005/000285 61 Mw=123,000 becomes unacceptably stiff at concentrations in the soak above 0.10% Mw=95,000 becomes unacceptabl}' stiff at concentrations in the soak above 0.20% ill Mw=41,500 and Mw=25,000 become unacceptably stiff at concentrations in the soak above 0.50%. . A rinse is normally performed using 16 liters of water. Assuming that the rinse dos-age is 100 ml, then 0.01% pectin in the rinse corresponds to a pectin solution of 1.57%. 0.05% pectin in the rinse corresponds to a pectin solution of 7.4%. 0.10% pectin in the rinse corresponds to a pectin solution of 13.79%. 0.20% pectin in the rinse corresponds to a pectin solution of 26.41% and 0.05% pectin in the rinse corresponds to a pectin solution of 44.44%. The effect on Brookfleld viscosity of such pectin solutions are shown in table 11.2: I ! WO 2005/102262 PCT/DK2005/000285 62 It is clear that as the molecular weights drops, it becomes easier to dissolve the pectin, and in addition the viscosity becomes lower. This enables a rinse to contain more pectin in lower rinse dosage. For pectin with a molecular weight of 123,000, the maximum concentration of pectin in the rinse is about 2%, for a pectin with a molecular weight of 95,000, the 'I: maximum concentration of pectin in the rinse is about 3%, for a pectin with molecular weight of 41,500, the maximum concentration of pectin in the rinse is about 10% and for a pectin with molecular weight of 25,000, the maximum concentration of pectin in the rinse is about 12%. Example 12: Effect of blending pectin products Pectin products having a DE of 93.4% and 9.6%, respectively were blended 1:1 and 100 g. 1% solution was prepared, of the blend through heating to 70 °C. The consumption of alkali at 25 °C and the pH-drop over time at 30 - 32 °C was recorded. Titration was done using 0.1008 M NaOH. The comment "unstable" refers to the pH-meter, which at high pH values showed an unstable reading. i \\A [V,y3 [unstapie j WO 2005/102262 PCT/DK2005/000285 63 Table 12- Titration and pH drop of pectin blends Fig. 12.1 shows that blending high DE pectin and low DE pectin results in an alkali consumption in between the alkali consumption of the individual pectin products. Fig. 12.2 shows that the pH drop over time falls between the pH drop over time of the individual components. Compared to the individual components, the blend of high DE pectin and low DE pectin provides for an increase in alkali consumption compared to pure high DE i pectin and an increase in pH-drop compared to low DE pectin. Example 13: Effect of blending high ester pectin and low ester prorrylene glvcol alginate. A blend of 50% of a pectin having a DE of 93.4% and 50% of a propylene glycol alginate (PGA) having a DE of 55% was dissolved at 70 % in a similar manner as in example 12 and compared with the alkali consumption of the individual components. WO 2005/102262 PCT/DK2005/000285 64 Fig. 13.1 shows that the alkali consumption falls between the alkali consumption of the individual components, but the use of a mixture of a high DE pectin and a medium DE PGA results in a smaller increase in alkali consumption than observed with the mixture of a high DE pectin and a low DE pectin of example 12. Fig. 13.2 shows that the pH-drop of the blend falls between the pH-drop of the individual components. However, even a relatively low esterified PGA provides for a ill faster pH-drop than a much higher esterified pectin. Compared with the individual comporients the blend provides an increase in alkali consumption compared to the pectin product alone. WO 2005/102262 ' PCT/DK2005/000285 65 Example 14: Effect of blending high De propvlene glvcol alginate and low DE pectin, A blend of 50% of a pfopylene glycol alginate (PGA) having a DE of 85% and 50% of a pectin having a DE of 9.6% was dissolved at 70% in a similar manner as in example 12 and compared with the alkali consumption of the individual components. Table 14. Titration and pH drop of blend of high estei propylene glycol alginate and low ester pectin Fig. 14.1 shows that the alkali consumption of the blend falls in between the alkali ii. consumption of the individual components. Fig. 14.2 shows that the pH drop over time falls between the pH-drop of the individual components. Compared to the individual components, the blend provides for an increase in alkali consumption compared to propylene glycol alginate alone, and an increase in pH i drop compared to low DE pectin alone. DK0500285 Amended claims of February 20D6 Claims 1- A skin-protecting alkafinity-controiiing composition comprising one or more car- boxylic acid polysaccharides wherein at least one of said carboxylic acid polysaccha- i ride(s) is a high DE carboxyJic acid polysaccharide selected from the group comprising ii1 pectin esters having a degree of esterification (DE) in the range from about 80% to about 100%. 2. The composition according to claim 1, wherein said high DE carboxylic acid poly saccharide is a pectin ester of aliphatic, arylafiphatic, cycloaliphatic or heterocyclic al cohols, more preferably an ester of methanol, ethanol, propanof or isopropanol, and most preferably an ester of methanol, 3. The composition according to claim 1, wherein said hiqh DE carboxylic acid poly- I|I saccharide is a pectin having a molecular weight in the range from about 5,000 to iii about 140,000, preferably in the range from about 10,000 to about 125,000, most pref- I erably in the range from about 10,000 to about 40,000. 4. The composition according to claim 3, wherein the ester groups of said polysac charide are distributed in a block-wise fashion. 5. The composition according to claim 3, wherein the ester groups of said polysac charide are distributed in a random fashion. i 6. A skin-protecting alkalinity-controlling composition comprising a mixture of at least one high DE carboxylic acid polysaccharide selected from the group comprising pectin esters having a degree of esterification (DE) in the range from about 70% to about 100%, more preferably from about 80% to about 100%, and at least one low DE car boxylic acid polysaccharide having a degree of esterification (DE) in the range from about 5% to about 40%, and most preferably from about 10% to about 35%. 7. The composition according to clafm 6, wherein any of said low DE carboxylic acid polysaccharides is selected from the group comprising pectin esters, alginic acid es ters, esterified cellulose ethers, esterified hydroxyethyicellulose, esterified carboxy- methyiceliulose, esterified guar gum, esterified cationic guar gum, esterified hy~ droxypropylguargum, starch esters, and polymerized sugar esters. Amended claims of February 2006 8. The composition according to Iclaim 7, wherein any of said high DE carboxylic acid ill poiysaccharides and said low DE carboxylic acid polysaccharldes is a pectin ester, preferably a pectin ester of aliphatic, aryteliphatic, cycloaliphatic or heterocyclic alco- \\\ hols, more preferably an ester of mfethanoi, ethanoi, propanol or isopropanoi, and most preferably an estenof methanol. 9. The composition according to claim 8, wherein any of said higfyDE carboxyiic acid poiysaccharides and said low DIE carboxylic acid poiysaccharides is a pectin having a molecular weight in the range from about 5,000 to about 140,000, preferably in the ' ill ! range from about 10,000 to about 1125,000, most preferably in the range from about 10,000 to about 40,000. 10. The composition according to claim 6, wherein any of said high DE carboxylic acid poiysaccharides and said low DE! carboxylic acid poiysaccharides is an esterified alginicacid. 11. The composition according to claim 10, wherein any of said esterified alginic acids iii : is an alginic acid ester of aliphatic, aromatic, araliphattc, alicyclic and heterocyclic alco- III hols, including esters deriving fromisubstltuted alcohols such as esters of bivalent afi- III i phatic alcohols, preferably ethylene ^lycol or propylene glycol alginate. 12. The composition according toJ claim 6, wherein the ester groups of any of said high DE carboxylic acid poiysaccharides and said low DE poiysaccharides are distrib- uted in a block-wise fashion, 13. The composition according to jclaim 6, wherein the ester groups of any of said HI ! high DE carboxylic acid polysacchaiides and said low DE poiysaccharides are distrib- H1 uted in a random fashion 14. A use of a composition comprising at least one carboxyiic acid polysaccharide se- lf. . ! lected from the group comprising pectin esters having a degree of esterification of from , about 80% to about,100% forskin-prptectlon and/or alkalinity control. 15 The use according to claim 14, wherein said carboxylic acid polysaccharide is a pectin ester of aliphatic, arylaliphatic, cycloaliphatic or heterocyclic alcohols, more pref- Amended claims of February 2006 erably an ester of methanol, ethanol, propanol or isopropanol, and most preferably an ester of methanol. 16. The use according to claim 15, wherein said carboxylic acid polysaccharide is a pectin having a molecular weight in the range from about 5,000 to about 140,000, pref erably in the range from about 10,000 to about 125,000, most preferably in the range from about 10,000 to about 40,000. 17. The use according to claim 14, wherein the ester groups of said polysaccharide are distributed in a block-wise fashion- 18. The use according to claim 14, wherein the ester groups of said polysaccharide are distributed in a random fashion. 19. A use of a composition comprising at least one carboxylic acid polysaccharide for skin-protection and/or alkalinity control, wherein at least one of said carboxylic acid polysaccharide(s) iis a low DE carbpxylic acid polysaccharide having a degree of esterf- fication (DE) in the range from about 5% to about 40%, and most preferably from about 10% to about 35%'! 20. A use of a composition comprising at least one carboxylic acid polysaccharide for skin-protection and/or alkalinity control, said composition comprising a mixture of at least one carboxylic acid polysaccharide having a degree of esterification (DE) in the range from about 70% to about 100%, more preferably from about 80% to about 100%; and at least one carboxylic acid polysaccharide having a degree of esterification (DE) in the range from about 5% to about 40%, and most preferably from about 10% to about 35%. 21. The use according to claim 14 on human skin. 22. The use according to claim 14 on animal skin. 23. The use according to claim 14 in a product selected from the group consisting of skin creams, skin lotions, deodorant products, fragrance products, hair care products, shaving products, soap products, and bath salt products Amended claims of February 2006 69 24. The use according to claim 14 in a product selected from the group consisting of female hygiene products and diapers. 25. The use according to claim 14 selected from the group consisting of ostomy prod ucts and wound care products. 26. The use according to claim 14 selected from the group consisting of lotionized tis sue products, fabric treating proclucls, and laundry rinse products. A skin-protecting alkalinity-controlling composition comprises one or more carboxylic acid polysaccharids Said compositions are capable of providing buffering, and thus avoiding a major increase in the pH of an aqueous system and/or aer capable of reducing the pH of acueous systems, in which alkalinity is formed as a result of chemical and/or biological reactions. The compositions may be used in personal care products care products, such as skin creams and lotions, hygiene products, wound care products, fabric treating products etc.

Documents:

03102-kolnp-2006 abstract.pdf

03102-kolnp-2006 claims.pdf

03102-kolnp-2006 correspondence others.pdf

03102-kolnp-2006 description(complete).pdf

03102-kolnp-2006 drawings.pdf

03102-kolnp-2006 form-1.pdf

03102-kolnp-2006 form-3.pdf

03102-kolnp-2006 form-5.pdf

03102-kolnp-2006 international publication.pdf

03102-kolnp-2006 international search authority report.pdf

03102-kolnp-2006 pct other document.pdf

03102-kolnp-2006 priority document.pdf

3102-KOLNP-2006-(04-03-2014)-CORRESPONDENCE.pdf

3102-KOLNP-2006-(04-03-2014)-FORM-3.pdf

3102-KOLNP-2006-(08-02-2012)-CORRESPONDENCE.pdf

3102-KOLNP-2006-(08-02-2012)-OTHERS.pdf

3102-KOLNP-2006-(20-11-2014)-CORRESPONDENCE.pdf

3102-KOLNP-2006-(23-04-2013)-CORRESPONDENCE.pdf

3102-KOLNP-2006-(23-04-2013)-FORM 1.pdf

3102-KOLNP-2006-(23-04-2013)-FORM 13.pdf

3102-KOLNP-2006-(23-04-2013)-FORM 3.pdf

3102-KOLNP-2006-(23-04-2013)-FORM 5.pdf

3102-KOLNP-2006-(23-04-2013)-PA.pdf

3102-KOLNP-2006-(23-05-2014)-CORRESPONDENCE.pdf

3102-KOLNP-2006-(24-04-2014)-CORRESPONDENCE.pdf

3102-KOLNP-2006-(24-12-2014)-ABSTRACT.pdf

3102-KOLNP-2006-(24-12-2014)-CLAIMS.pdf

3102-KOLNP-2006-(24-12-2014)-CORRESPONDENCE.pdf

3102-KOLNP-2006-(24-12-2014)-FORM-1.pdf

3102-KOLNP-2006-(24-12-2014)-FORM-2.pdf

3102-KOLNP-2006-(24-12-2014)-OTHERS.pdf

3102-KOLNP-2006-(29-05-2012)-CORRESPONDENCE.pdf

3102-KOLNP-2006-(29-05-2012)-OTHERS.pdf

3102-KOLNP-2006-ABSTRACT 1.1.pdf

3102-KOLNP-2006-ABSTRACT 1.2.pdf

3102-KOLNP-2006-AMANDED CLAIMS 1.1.pdf

3102-KOLNP-2006-AMANDED CLAIMS.pdf

3102-KOLNP-2006-AMANDED PAGES OF SPECIFICATION.pdf

3102-KOLNP-2006-CORRESPONDENCE 1.2.pdf

3102-KOLNP-2006-CORRESPONDENCE-1.1.pdf

3102-KOLNP-2006-DESCRIPTION (COMPLETE) 1.1.pdf

3102-KOLNP-2006-DESCRIPTION (COMPLETE) 1.2.pdf

3102-KOLNP-2006-DRAWINGS 1.1.pdf

3102-KOLNP-2006-DRAWINGS 1.2.pdf

3102-KOLNP-2006-FORM 1 1.1.pdf

3102-KOLNP-2006-FORM 1-1.2.pdf

3102-kolnp-2006-form 18.pdf

3102-KOLNP-2006-FORM 2-1.1.pdf

3102-KOLNP-2006-FORM 2.pdf

3102-KOLNP-2006-FORM 3 1.1.pdf

3102-KOLNP-2006-FORM 3-1.1.pdf

3102-KOLNP-2006-FORM 3-1.2.pdf

3102-KOLNP-2006-OTHERS 1.1.pdf

3102-KOLNP-2006-OTHERS.pdf

3102-KOLNP-2006-PETITION UNDER RULE 137-1.1.pdf

3102-KOLNP-2006-PETITION UNDER RULE 137.pdf

3102-KOLNP-2006-REPLY TO EXAMINATION REPORT.pdf

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