Cosmetic compositions

FIELD: cosmetology.

SUBSTANCE: the present innovation deals with either antiperspirant or deodorizing composition either in solid or soften-solid form including either antiperspirant or deodorizing active substance and a continuous phase that contains a liquid water-unmixed carrier and, also, it contains a structurizing agent being either completely or partially esterifying cellobiose of formula (I), in which every Z independently represents either hydrogen or acyl group of formula (II)

,

in which R depicts hydrocarbon group containing 4-22 carbon atoms. Not more than a half of Z-groups represents hydrogen. The innovation, also, deals with the method to obtain the above-mentioned composition and method to prevent or deteriorate perspiration at human skin. This innovation enables to obtain antiperspirant or deodorizing compositions of improved properties that enable, in particular, to minimize the development of visible depositions on human skin.

EFFECT: higher efficiency.

32 cl, 14 ex, 28 tbl

The technical field to which the invention relates.

The present invention relates to cosmetic compositions for application to human skin. An important form of the invention associated with the antiperspirant compositions or compositions sweat for their application to human skin, especially in the armpit. However, the invention can also be applied to other forms of cosmetic compositions.

Background of the invention the level of equipment

In a wide variety of cosmetic compositions for application to human skin applied thickened or structured carrier liquid for delivery to dye or any other active material to the surface of the skin. An important example of such cosmetic compositions are compositions from sweat (antiperspirant compositions), which are widely used in order to enable their users to avoid or minimize the formation of wet spots on the skin, especially in the armpit.

Formulations of compositions from sweat are provided in the form of products of various forms. One of them is the so-called "core" or "wand", which is usually a pencil from the solid material held within the distributing container, which preserves the structural integrity and shape during use. When cha is part of the rod is carried out on the surface of the skin, film from the composition of the rod is transferred to the surface of the skin. Although the rod has the appearance of a solid product that can retain its shape for some time, the material usually has a structured liquid phase, so that the film composition can be easily transferred to another surface upon contact with the core.

Another possibility is that the rod is softened solid composition placed in the distributing container, which, when used squeezes the composition of one or more holes.

Rods from sweat can be divided into three categories. Suspension rods contain the active material from sweat in the form of particles, which is suspended in a structured liquid phase media. Emulsion rods typically have a hydrophilic phase containing substance from sweat, active in the solution, and this phase emulsifies with other, more hydrophobic liquid phase. The continuous phase of the emulsion is structured. Mortar bars usually contain the active substance from sweat, dissolved in a structured liquid phase, which may be a mixture of water and miscible with water and organic solvent. This classification is on suspension, emulsion and solution types can be used for both hard and softened Tertychnyi.

Other types of cosmetic compositions can also be provided in the form of a rod, and, again, the rod can be structured solution, emulsion or suspension. Examples of cosmetic compositions that come or may come on the market in the form of rods, are lipsticks, creams & lip pencils eyebrow.

There is an extensive literature on structuring or thickening of cosmetic compositions.

Traditionally, many rods structure using waxy materials of natural or synthetic origin. Examples of them include those fatty alcohols that are solid at room temperature, such as stearyl alcohol and hydrocarbon waxes or silicone waxes. Such materials are widely available and by a suitable choice of materials and their concentrations in the recipe you can get or softened, or hard solid materials. Examples of these rods is described in an article in the journal of Cosmetics and Toiletries, 1990, t, p.75-78 and in U.S. patent No. 5169626 and 4725432. However, when applied to human skin rods with structured fatty alcohols or waxes tend to leave visible white deposits, and deposits may also be transported on clothing when it is contact with the skin, and the consumer can find white spots, for example, nuprime items of clothing without sleeves.

Proposed some alternative structuring agents. Often use the term "gelling agent" or "gelling" instead of "structuring agent". In addition, you can use the term "thickener", when the final product is a liquid with high viscosity and is not solid or gel. For example, proposed the use of dibenzylideneacetone (DBS) or its derivatives as a gelling agent in a number of publications such as EP-A-512770, WO 92/19222, in U.S. patent No. 4954333, 4822602 and 4725430. Formulations containing such gelling agents may suffer from several disadvantages, including instability in the presence of acidic antiperspirant and relatively high temperature processing required upon receipt of the rods.

In WO 93/23008 and in U.S. patent No. 5429816 described, for example, a combination of amide N-acylaminoalkyl and 12-hydroxystearate acid to the gelatin nonaqueous formulations. However, to dissolve the gelling agent and prevent premature gel formation requires high temperature processing. When applied to the skin of the formulation may have difficulty when it is washed off, and the reform of the finished form of the composition to eliminate this problem may be impossible due to the need for high temperature processing.

The use of 12-hydroxystearic the acid without the amide N-acylaminoacyl as a secondary gelling agent disclosed in some documents, such as a patent application in Japan 05/228915 and in U.S. patent 5744130.

In the application WO 97/11678 (firm Helene Curtis, Inc.) describes the use of larosterna as a gelling agent to obtain soft gels, sometimes in combination with the derived starch hydrolysate, for songs from sweat. This document contains a brief reference to cellulose as a possible ingredient. Cellulose, of course, is a polymer.

In WO 98/34588 (firm Lancaster Group GmbH) described the use of larosterna as a gelling agent for cosmetic compositions based on oils containing cosmetically active material, and one of the listed materials is deodorant, although it is not confirmed by the example.

In EP-A-400910 disclosed cosmetic compositions, in which the absorbent liquid material is a powder form of cellulose. In one example of such a powder is used to absorb volatile silicone, and the resulting material is used as an ingredient in the form of particles in the rod, which also contains antiperspirant active substance in the form of particles and a binder polymer agent.

Emulsion rods from sweat without any material identified as structuring agent are disclosed in U.S. patent No. 4673570, 4948578 and 5587153.

Cosmetic compositions, other than funds from the sweat is, which take the form of structured liquids are disclosed, for example, in U.S. patent No. 3969087, which describes the use of N-acylaminoacyl and their derivatives as gelling agents, in U.S. patent No. 5486566 that uses 12-hydroxystearate acid.

The invention

The aim of the present invention is the provision of thickened or structured cosmetic compositions, particularly, but not exclusively, songs from the pot in which the liquid material of the medium is thickened or structured, using a structuring agent that is different from the above-mentioned agents. An additional aim of the invention is the provision of a structuring agent, which has improved properties, at least compared to some of the structuring agent, which was previously used.

Another aim of at least some forms of the invention is the provision of compositions that leave weakly visible fat.

Some particularly preferred form of the invention aim to provide compositions that have some transparency, i.e. they are translucent or even transparent.

In accordance with the first aspect of the present invention is the composition of the prophetic is TBA, suitable for cosmetic use, having a continuous phase that contains not miscible with water carrier liquid and structuring substance, which is a fully or partially esterified cellobiose, in which at least half of the available hydroxyl groups etherification and carries acyl groups containing at least four carbon atoms. This substance has the formula:

where each Z independently represents hydrogen or acyl group of the formula:

in which R means a hydrocarbon group containing from 4 to 22 carbon atoms, provided that not more than half of the groups Z are hydrogen.

Fully or partially esterified cellobiose serves as a structuring agent or thickener for liquid media, is not miscible with water, and when used in sufficient amounts, which probably is less than 15% of the entire composition, is able to structure the liquid in the gel with sufficient rigidity to maintain its form.

Not linking to any particular theory or explanation, suppose that the esterified cellobiose forms a network of fibers or filaments passing through the liquid phase. By heating the gel until the temperature of its melting yarn texturing agent are dissolved, and the liquid phase becomes more mobile.

In order to promote good sensory properties during use, preferably in a carrier liquid, is not miscible with water include silicone oil. The amount of silicone oil may be at least 10% by weight of the composition and/or at least 40% by weight of a liquid medium, is not miscible with water.

Ethanol gives a cooling effect when applied to the skin, as it is highly volatile. It is preferable that the content of ethanol or any monohydroxy alcohol with a vapour pressure of more than 1.3 kPa (10 mm Hg) did not exceed 15%, better not more than 8%, by weight of the composition.

As will be further explained below, the structured carrier liquid that is not miscible with water, may be the continuous phase of the composition with dispersed second phase, or emulsion, or a suspension of solids in the form of particles. Such solids may be active means of perspiration in the form of particles. The dispersed phase may be a solution of the active substance from the pot in water or another hydrophilic solvent.

Some preferred forms of the present invention relate to compositions, which are semi - or fully transparent. As already known, semi - or fully transparent composition can be obtained if it is possible to produce according the refractive indices of the various phases of the components present in the composition.

The authors found that covered by this invention, compositions which are new, semi - or fully transparent emulsions, can be obtained by preparing formulations of the composition according to two criteria. First, the dispersed phase and continuous phase (consisting of not miscible with water a liquid medium and structuring agent contained in the liquid) must be such that their refractive indices are consistent with each other. The value of the refractive index of the continuous phase should be close to the refractive index is not miscible with water a liquid medium in it. In order to achieve good light transmission throughout the composition, the refractive index of the continuous phase is not miscible with water, and the refractive index of the dispersed phase should be in the range of 0.003 units, preferably of 0.002 units.

Secondly, the values of the harmonized indices of refraction of these two phases must be in the interval, which corresponds approximately to the refractive index of the structuring agent. When structuring agent is an ester of cellobiose acids C₈or₉then there is the octane or nonanalog acids, found to be suitable are acid with an interval of from 1.40 to 1.50, prepact the tion from of 1.41 to 1.47, as will be explained in more detail below.

One significant advantage of the preferred structural material of this invention is that they have convenient refractive index, so that it is easy to find the composition of the rest of the song, so it was quite close to the value of the refractive index and, in addition, especially preferred structuring agents valid discrepancy between the values of their refractive indices and the harmonized indices of refraction of the continuous and dispersed phases.

Additional advantages of the preferred structural material of the present invention lies in the fact that they do not require high temperature processing, and they are chemically stable both during processing and in the resulting compositions. Avoid high temperature processing can be particularly valuable when the composition contains some amount of water or other volatile component.

The composition of this invention typically will be supplied to the market in containers, by means of which it can be applied during use. This container may be of the traditional type.

Another aspect of the invention, therefore, is the provision of a cosmetic product, including RA is predelay container, having at least one opening for delivering the contents of the container, means providing for movement of the contents of the container to the specified hole (or holes), and the composition in accordance with the first aspect of the invention in the container.

The compositions of this invention can be obtained by conventional methods of preparation of the suspension or emulsion, hard or softened solids.

Thus, according to the third aspect of the present invention provides a method of obtaining a cosmetic composition, comprising, not necessarily in any order, the following stages:

- inclusion in the carrier liquid, is not miscible with water, structuring agent, which is a fully or partially esterified to cellobiose,

- if necessary, mixing the liquid carrier with solid or dispersed in the liquid phase, suspendiruemye in him,

- heating liquid medium or containing the mixture to the elevated temperature at which the structure forming agent is soluble in is not miscible with water liquid medium, followed

- the introduction of the mixture into a form, which preferably is a distributing container, and then

the cooled mixture (forced or voluntary) to a temperature at which it thickens or saturdav is so

Suspended solids can be antiperspirant active substance, and the dispersed phase may be a solution of such an active substance in a hydrophilic or polar solvent.

In accordance with the fourth aspect of the present invention provides a method of preventing or reducing perspiration on human skin comprising topical application to the skin a composition comprising an active agent from sweat, not miscible with water carrier liquid and texturing agent for him, which is a fully or partially esterified to cellobiose.

A detailed description of the embodiments and variants

As mentioned above, the invention requires a fully esterified or partially esterified to cellobiose as a structural material for liquid phase that is not miscible with water. Depending on the nature of the composition can also be present in other materials. Will now alternately considered a variety of materials and will indicate the preferred characteristics and capabilities.

Tarifitsirovana of cellobiose

The core structure of the structuring agent is cellobiose. It contains two glucose residue attached via β -1,4-linkages. Cellobiose should be etherification acid in many, if not all, of the available hydroxyl the major groups. It is convenient to use cellobiose, which is completely etherification, but you can use the partially esterified to cellobiose provided that at least half of the hydroxyl groups etherification, preferably with a higher ratio, such as at least 5 or 6 out of every 8 hydroxyl groups.

Acyl group must contain at least 4 carbon atoms. It is unlikely that they can contain more than 22 carbon atoms. Preferably acyl groups were aliphatic 6-18 or 19 carbon atoms, and more specifically, it is preferable that each acyl group include alkyl or alkenylphenol chain with 5 to 12 or 18 carbon atoms so that the acyl group contains from 6 to 13 or 19 carbon atoms. Particularly preferred acyl groups include linear alkyl chain with 7-10 carbon atoms and, thus, they represent octanoyl, nonanoyl, decanoyl or undecanoyl.

Acyl groups can have a mixture of chains of different lengths, but preferably they have the same size and structure. Thus, it is preferable that all of the acyl groups were aliphatic and at least 90% of the acyl groups had a length of chain in this interval to a shorter and a longer chain in this interval differed by no more than two acomplete, that is, the length of the chain in the interval from (m-1) to (m+1) carbon atoms, where the average length of the acyl chain m has a value in the interval from 7 to 10 or 11. Industrially available raw materials for these acyl groups are likely to include a small percentage of acyl groups that differ from the majority and may have a branched rather than linear chain. Thus, it is likely that more than 90%but less than 100% of the acyl groups will correspond to the desired criterion chain length in the interval from (m-1) to (m+1) carbon atoms.

Linear aliphatic acyl group may be derived from natural sources, in this case, the number of carbon atoms in the acyl group, likely even, or they can be obtained by synthesis from petroleum sources, in this case, will be available chains with even and odd number of carbon atoms.

Synthetic methods of esterification of sugars are well known. The esterification of cellobiose was described by Takada and researcher. (Takada et al.) in journal of Liquid Crystals, 1995, t, s-448. This article outlines the procedure for obtaining alpha-anomers of Oct-alkanoates cellobiose by the esterification β -cellobiose using alanovoy acid with anhydride triperoxonane acid. In this same article also described receiving beta-anomers of Oct-alkanoates cellobiose using the synthetic method and the use of acid chloride of the appropriate acid in the presence of pyridine. However, the authors found that alpha-anomers are more effective structuring agent.

The quantity of structuring agent - esterified cellobiose in the composition of this invention, apparently, is from 0.1 or 0.5% to 15% by weight of the entire composition, and preferably from 0.5% up to 8 or 10%, probably from 1% to 8%. If the composition is an emulsion with a separate dispersed phase, the amount of structuring agent - esterified cellobiose is likely to be from 0.5 to 20% or even 25% by weight of the continuous phase, more likely from 1% to 15% of this phase.

Liquid media

Not miscible with water, the liquid medium contains one or a mixture of materials, which are relatively hydrophobic so that they are not miscible with water. The media may include some amount of hydrophilic liquids, provided that all the mixture of liquid media was not miscible with water. Usually it is desirable that the media was liquid (in the absence of a structuring agent) at temperatures of 15° C and above. He may have some volatility, but typically has a vapor pressure less than 4 kPa (30 mm Hg) at 25° so that this material could be attributed to the oil or mixture of oils. More specifically, it is desirable that at least 80% by weight of a hydrophobic liquid wear what I consisted of material with vapor pressure no higher than this value 4 kPa at 25° C.

Preferably, the hydrophobic material of the carrier include volatile liquid silicone that is liquid polyorganosiloxane. For reference to "the flying" this material should have a measurable vapour pressure at 20 or 25° C. Typically, the vapor pressure of the volatile silicone is in the range from 1 or 10 PA to 2 kPa at 25° C.

The inclusion of volatile silicone is desirable as it gives the feeling of "desiccant" applied film after application of the composition on the skin.

Volatile polyorganosiloxanes can be linear, or cyclic, or mixtures thereof. Preferred cyclic siloxanes include polydimethylsiloxane and especially those containing from 3 to 9 silicon atoms, and preferably not more than 7 silicon atoms, and most preferably from 4 to 6 silicon atoms, otherwise often called cyclomethicone. Preferred linear siloxanes include polydimethylsiloxane containing from 3 to 9 silicon atoms. Volatile siloxanes are usually themselves have a viscosity below 10^-5m²/s (10 CST) and, in particular above 10^-7m²/s (0.1 CST), linear siloxanes generally have a viscosity below 5× 10^-6m²(5 CST). Volatile silicones may also include a branched, linear or cyclic siloxanes, such as the above-mentioned linear or cycle the ical siloxanes, substituted by one or more side groups of-O-Si(CH₃)₃. Examples of industrially available silicone oils include oils having denote varieties: 344, 345, 244, 245 and 246 of the company Dow Corning Corporation; Silicone 7207 and Silicone 7158 company Union Carbide Corporation; and SF1202 company General Electric.

Hydrophobic media used in the compositions of the invention may alternatively or additionally include non-volatile silicone oils, which include polyallylamine, polyalkylacrylate and polyethylsiloxane copolymers. They can be appropriately selected from Dimethicone and sipolilo dimetikona. Industrial available non-volatile silicone oils include products from several Dow Corning 556 and Dow Corning 200.

Not miscible with water, the liquid carrier can contain from 0 to 100% wt. one or more liquid silicones. Preferred is a sufficient amount of liquid silicone to ensure at least 10%, better at least 15%, by weight of the entire composition. If you use silicone oil, the volatile silicone is preferably from 20 to 100% by weight of a liquid medium. In many cases, when there is non-volatile silicone oil, the ratio of its mass to the volatile silicone oil is chosen in the range from 1:3 to 1:40.

Instead of, or more preferably, in addition to liquid silicones that can be used is with a hydrophobic liquid, free from silicone. Hydrophobic organic liquid, free from silicone, which can be introduced into the composition include liquid aliphatic hydrocarbons such as mineral oil or hydrogenated polyisobutene, which is often chosen for the manifestation of the properties of low viscosity. Additional examples of liquid hydrocarbons are polydecene and paraffins and ISO, having at least 10 carbon atoms.

Other hydrophobic carriers are liquid aliphatic or aromatic esters, however, they can only be used as part of a liquid medium, preferably not more than 20%, and possibly less than 10% by weight of a liquid medium, is not miscible with water.

Suitable aliphatic esters contain at least one long-chain alkyl group, such as esters derived from alkanols With₁-C₂₀etherified alanovoy acid C₈-C₂₂or landiolol acid₆-C₁₀. Alkanol and acid fragment or a mixture thereof preferably are selected so that each of the components had a melting point below 20° C. Data esters include isopropyl ester myristic acid, laurierated, isopropyl, diisopropyl ether sabatinovka acid and diisopropyl ether adipine the th acid.

Suitable liquid aromatic esters, preferably having a melting point below 20° include fatty alkalemia esters of benzoic acid. Examples of such esters include₈-C₁₈-alkylbenzoates or mixtures thereof.

Further examples of suitable hydrophobic carriers include liquid aliphatic ethers obtained at least one fatty alcohol, such as derivatives miristinovoi simple ether, for example miristinovoi ether PPG-3, or lowest alkalemia ethers of polyglycols, such as butyl ether, PPG-4.

Aliphatic alcohols which are solid at 20° such as stearyl alcohol, preferably absent or present in low concentration, such as less than 5% by weight of the entire composition, as they lead to the appearance of white deposits using the composition.

However, it is possible to use aliphatic alcohols which are liquid at 20° C. They include alcohols with branched-chain with at least 10 carbon atoms, such as isostearoyl alcohol and octyldodecanol.

Liquid, free from silicone, can be from 0 to 100% is not miscible with water a liquid medium, however, it is preferable that the silicone oil was present and that the number of components, free from silicone, pre is respectfully made up to 50 or 60% and in many cases from 20 to 60% by weight of a liquid medium.

Liquid dispersed phase

If the composition is an emulsion, in which the esterified cellobiose plays the role of a structuring agent in the continuous phase, the emulsion contains more polar dispersed phase. The dispersed phase may be a solution of the active component.

Hydrophilic dispersed phase in the emulsion usually contains water as a solvent and may include one or more water soluble or miscible with water, liquids in addition to water or instead of it. The fraction of water in the emulsion according to the present invention is often chosen in the interval up to 60% and in particular from 10 to 40% or 50% of the entire formulation.

One class of water-soluble or miscible with water liquids includes short-chain monohydroxy alcohols, for example With₁-C₄and especially ethanol or isopropanol, which can give deodorizing ability recipe. An additional class of hydrophilic liquids include diols or polyols, preferably having a melting point below 40° or which is mixed with water. Examples of water soluble or miscible with water liquids with at least one free hydroxyl group include ethylene glycol, 1,2-propylene glycol, 1,3-butyleneglycol, hexyleneglycol, diethylene glycol, dipropyleneglycol, 2-ethoxyethanol, onomatology the ether of diethylene glycol, onomatology ether of diethylene glycol, onomatology ether of triethylene glycol and sorbitol. Particularly preferred are propylene glycol and glycerin.

In the emulsion of the dispersed phase, probably, is from 5 to 80% or 85% by weight of the composition, preferably from 5 to 50%, or 65%, more preferably from 25 or 35% to 50% or 65%, while the continuous phase contains structuring agent is from 15 or 35% to 95% by weight of the composition. Compositions with a high proportion of the dispersed phase, i.e. from 65 to 85% of the dispersed phase can also be favorable. They can provide good hardness, even though the concentration of the structuring agent, the esterified cellobiose, may constitute only a small percentage of the entire composition.

Usually the emulsion composition includes one or more emulsifying surfactants which may be anionic, cationic, zwitterionic and/or nonionic surfactants. The proportion of emulsifier in the composition is often selected in the range of up to 10 wt.% and in many cases from 0.1 or 0.25% to 5% by weight of the composition. Most preferred is an amount of from 0.1 or 0.25% to 3 wt.%. Nonionic emulsifiers are often classified by the amount of the hydrophilic-lipophilic balance (products HLB). It is desirable to use an emulsifier or mixture of emulsifiers is the total value of products HLB in the range from 2 to 10, preferably from 3 to 8.

It may be convenient to use a combination of two or more emulsifiers, which have different products HLB values above and below the desired value. Using the combined use of the two emulsifiers in the appropriate ratio easy achievement weighted average products HLB, which contributes to the formation of the emulsion.

Many suitable emulsifiers with high value products HLB are non-ionic, complex or simple ester emulsifiers containing polyoxyalkylene fragment or group, especially polyoxyethylene group, often containing from about 2 to 80, and particularly from 5 to 60 oxyethylene links, and/or contains polyhydroxy connection, such as glycerol or sorbitol or other alditol, as the hydrophilic group. The hydrophilic group may contain polyoxypropylene. Additional emulsifiers contain a hydrophobic alkyl, alkenylphenol or aracelio group, typically containing about 8-50 carbon atoms and especially from 10 to 30 carbon atoms. The hydrophobic group may be either linear or branched and is often busy, although it may be unsaturated, and optionally fluorinated. The hydrophobic group may include a mixture of chains of different lengths, such that originates from tall oil, lard is, palm oil, sunflower oil or soybean oil. Such nonionic surfactants can also occur from polyhydroxy compounds, such as glycerol or sorbitol or other alditol. Examples of emulsifiers include ceteareth-10 to -25, ceteth-10-25, steareth-10-25 (i.e. alcohols With₁₆-C₁₈, ethoxylated 10-25 ethylenoxide residues) and stearate or distearate of polyethylene glycol PEG-15-25. Other suitable examples include mono-, di - or triglycerides of fatty acids With₁₀-C₂₀. Additional examples include ethers of fatty alcohols With₁₈-C₂₂and oxides (from 8 to 12 parts of ethylene oxide).

Examples of emulsifiers which are usually of low value products HLB, often a value from 2 to 6, are complex mono - or perhaps diesters polyhydric alcohols, such as glycerin, sorbitol, aritra or trimethylolpropane with fatty acids. The group of fatty acyl often has₁₄to C₂₂and in many cases is intense and includes Cecil, stearyl, Arachidyl and behenyl. Examples include monoglycerides of palmitic or stearic acid mono - or diesters myristic, palmitic or stearic acid and sorbite and monoether of trimethylolpropane and stearic acid.

A particularly desirable class of emulsifiers includes copolymers of dimate is she, namely dimethylpolysiloxane modified with polyoxyalkylene. Polyoxyalkylene group is often polyoxyethylene (PoE) or polyoxypropylene (POP) or a copolymer of PoE and POP. The copolymers often have a terminal alkyl groups With₁-C₁₂.

Suitable emulsifiers and simulatory are widely available under different trademarks and names, including the Abil™ , Arlacel™ , Brij™ , Cremophor™ , Dehydrol™ , Dehymuls™ , Emerest™ , Lameform™ , Pluronic™ , Prisorine™ , Quest PGPR™ , Span™ Tween™ , SF1228, DC3225C and Q2-5200.

The active substance of funds from pot

If the composition is a means of perspiration, it contains the active substance from sweat. Antiperspirant active substance is preferably introduced in an amount of from 0.5 to 60%, in particular from 5 to 30% or 40% and especially from 5 or 10% up to 30 or 35% by weight of the composition.

Antiperspirant active substances for use according to the invention is often chosen from the active astringent salts, including, in particular, salts of aluminium, zirconium and mixed aluminium/zirconium salts, including both inorganic salts, salts with organic anions and complexes. Preferred binders salts include the halides of aluminum, zirconium, and aluminum/zirconium and halohydrin salts such as chlorhidrate.

Usually halohydrin aluminum which indicate the General formula Al ₂(OH)_xQ_y·wH₂O, in which Q represents chlorine atom, bromine or iodine, x is variable from 2 to 5 and x+y=6, whereas wH₂O represents a variable number of hydrated water. Especially effective halohydrin aluminium salts, known as activated chlorhydrate aluminum, described in EP-A-6739 (Unilever NV and others), the content of which is included in the description for details. Some activated salt does not retain its increased activity in the presence of water, but are useful in practically anhydrous formulations, i.e. formulations that do not contain an explicit aqueous phase.

Usually active zirconium compounds can be represented by the General empirical formula: ZrO (OH)_2n-nzB_z·wH₂O, in which z represents a variable in the range from 0.9 to 2.0 so that the value 2n-nz is zero or positive, n is the valency of b, and a is selected from the group consisting of chloride and other halides, sulpham, sulfate and mixtures thereof. Possible hydration in varying degrees, reflected by the expression wH₂O. it is Preferable that was chlorine, and the variable z was in the range of from 1.5 up to 1.87. In practice, these zirconium salts are typically not used by themselves, and as a component of the combined funds from sweat on the basis of the compounds of aluminum and zirconium.

Can be used multiple tools from sweat on the basis of the above-mentioned binders salts of aluminum and/or zirconium. The complex is frequently used in connection with the carboxylate group, which mainly is the amino acid. Examples of suitable amino acids include dl-tryptophan, dl-beta-phenylalanine, dl-valine, dl-methionine, beta-alanine, and preferably glycine which has the formula CH₂(NH₂)COOH.

Highly desirable use of complex combinations of glodgett aluminum and clorhidrato zirconium together with amino acids such as glycine, which is described in the U.S. patent And 3792068 (Luedders and others). Some of these complexes Al/Zr usually called in the literature ZAG. Usually active components ZAG contain aluminum, zirconium and chloride ratio Al/Zr in the range of from 2 to 10, especially from 2 to 6, the ratio of Al/CL from 2.1 to 0.9 and a variable number of glycine. The active components of this preferred type are usually available from firms Westwood, Summit and from Reheis.

Other active ingredients that may be used include binders titanium salt, such as salts, described in the patent UK A.

The share of solid antiperspirant salt in the composition typically includes the mass of any hydration water and any complexes agent, which may also be present in the solid active component. However, when the active salt is in solution, its mass does not include any water present.

If the composition is in the form of an emulsion, the antiperspirant active ingredient is dissolved in the dispersed phase. In this case, the antiperspirant active substance can often be from 3 to 60% by weight aqueous dispersed phase, in particular from 10 or 20% to 55 or 60% of this phase.

An alternative composition may take the form of a suspension in which antiperspirant active substance in the form of particles suspended in a liquid carrier, is not miscible with water. In such compositions, probably will be no separate aqueous phase, and it can conveniently be attributed to "virtually waterless", although it should be understood that some water may be present in the form associated with the antiperspirant active substance or in the form of a small amount dissolved in the liquid phase that is not miscible with water. In such compositions, the particle size of the antiperspirant salt is often in the range of from 0.1 to 200 μm, and the average particle size often varies from 3 to 20 μm. Can also be assumed to the larger, and smaller average particle sizes, such as from 20 to 50 μm, or from 0.1 to 1 micron.

Optional components

Optional components in the compositions of this invention may include deodorants, for example, in concentrations up to about 10% wt./wt. Suitable active deodorants may include deodorizing effective concentration of antiperspirant metal salts, deodorant perfume and/or microbicidal, especially including bactericides, such as chlorinated aromatics, including biguanide derivatives, which are known and deserve special mention, Irgasan DP300™ (Triclosan), Tricloban™ and Chlorhexidine. Another class of compounds includes biguanidine salts such as available under the trademark Cosmosil™ .

Other optional components include washing agents commonly present in amounts up to 10% wt./wt., which contribute to the removal of the composition from the skin or clothing. Such washing agents are typically non-ionic surfactants, such as simple and complex esters containing From₈-C₂₂is an alkyl group and a hydrophilic group, which can include polyoxyalkylene group (PoE or POP) and/or polyol.

Additional optional components of the formulation include one or more structuring agents that m is able to be applied in addition to the esterified cellobiose, which is the primary structuring agent. The number of such secondary structuring agents in the formulation often is zero and usually not more than 15% by weight of the formulation. Usually their number does not exceed the number of primary structuring agent.

Secondary structuring agents used in the invention can be polimernymi or polymer. May include solid linear fatty alcohols and/or waxes, but they are not preferred. Polimernye structuring agents, sometimes referred to as gelling agent may be selected from fatty acids or their salts such as stearic acid or sodium stearate, or 12-hydroxystearate acid. Other suitable gelling agents may include dibenzylideneacetone, such as dibenzylidene. Additional suitable gelling agents may include lanosterol selected derivatives of N-acylaminoacyl, including ester and amide derivatives, such as dibutylamine N-laurilsulfate acid, and these gelling agents can be combined with a 12-hydroxystearates acid, or its ester or amide derivative. Other additional gelling agents include amide derivatives of two - and trekhosnovnykh acids, such as alkyl-N,N'-dialkylacrylamide, for example dodecyl-NN'-dibutylamine.

Polymeric structuring agents that can be used may include organic polysiloxane elastomers such as the products of interaction of the polysiloxane with terminal vinyl groups and a crosslinking agent, or a poly(methylsiloxane), or poly(phenylsilane) siloxanes with terminal alkyl or alkyl-polyoxyalkylene groups. As structuring agents for hydrophobic liquids also described a number of polyamides. Polymers containing siloxane and hydrogen bonding groups, which could be used as a secondary structuring agents are disclosed in WO 97/36572 and WO 99/06473. If there is a water dispersed phase, the structuring or thickening of this aqueous phase can be used polyacrylamides, polyacrylates or polyalkylated.

Compositions according to the invention can include one or more cosmetic tools, which traditionally can be considered for solid or cushioned solid funds from sweat. Such cosmetic auxiliary means may include agents that enhance the feel of your skin, such as talc or finely powdered polyethylene, for example, in amounts of up to about 10%; the agents conducive to the skin, such as allantoin or lipids, for example, in an amount up to 5%; colouring agents; agents about lagausie skin, other than the already mentioned alcohols such as menthol and derivatives of menthol, often in amounts up to 2%, all of these percentages are given by weight of the composition. Usually used as an auxiliary means are spirits that are usually present in concentrations of from 0 to 4%, and in many recipes from 0.25 to 2% by weight of the composition.

Translucent/transparent composition

If the composition of the present invention is made in the form of an emulsion, it is possible to create such a formulation, the emulsion will be translucent or transparent. To enable this, the refractive index is not miscible with water continuous phase and a polar or aqueous dispersed phase should be consistent with each other and the agreed value of the refractive index also should be comparable to the refractive index of the structuring agent.

The refractive index of the fiber network structuring agent can be determined by use of a structuring agent for the gelatin oils or mixtures of oils with different refractive indices. When the obtained gel is transparent, the refractive index of the oil or mixture of oils (which can be identified using the traditional measure) is a good approximation to the refractive index of the structuring agent. Oil or mixture of oils to doljnabiti of those well heliroute under the action of structuring agent, in order to avoid side effects.

Using this method, the inventors determined the refractive index of the preferred slozhnoefirnoi cellobiose, namely Oct-nonanoate cellobiose, which is in the range between 1.45 and 1.50, approximately 1,48 with 22° C.

The inventors have found that when structuring agents are esters of cellobiose fatty acids₉or with a shorter chain, the value at which the matched refractive indices of the continuous phase and the dispersed phase may be slightly lower than the refractive index of structuring agent, until a value of 1.42 or even lower to 1.41 or of 1.40. The value is slightly higher 1,48 may also be acceptable, but its achievement is inconvenient.

When structuring agents are esters of cellobiose fatty acids₁₀or more long chain, it is necessary that the agreed refractive indices of the two phases were close to 1,48. For Oct-decanoate cellobiose it is necessary that the refractive index of the two phases was higher than the 1.44 and preferably above the 1.45 to obtain a high level of transparency.

For continuous phase free from silicone, is not miscible with water liquid oils are usually indicators of p is elmline in the range from USD 1.43 to 1.49 at 22° With, and they can be used alone or in mixtures, to give the free from silicone carrier liquid with a refractive index in the interval. Usually volatile silicone oils have a refractive index slightly below 1.40 at 22° With, however, a mixture of liquid media with refractive indices in the range from of 1.41 to 1.46 can be obtained by mixing volatile silicone with other oils. Typically, non-volatile silicone oils have refractive indices in the interval of 1.45 to 1.48 at 22° and therefore, if desired, you can enter them into the composition.

The refractive index of the continuous phase is very close to the refractive index of a liquid medium (usually a mixture of liquid media), which is its main component.

For the dispersed phase solution of antiperspirant active salt in water typically has a refractive index lower than 1,425. The refractive index can be increased by introduction into an aqueous solution of diol or polyol. It is considered that approval of the refractive index of the polar dispersed phase with a refractive index of network structuring agent within the continuous phase is new. Moreover, this can be achieved without using such a large amount of diol or polyol, which makes the song overly sticky.

If the composition of this invention is the VC who trated continuous phase without any dispersed phase, it can be made transparent or translucent approximation of the refractive index of a liquid medium and structuring agent esterified cellobiose according to the method described above.

For the composition, which is a suspension, the path to a transparent or translucent composition is to harmonize the refractive index of a liquid medium and suspended solids with a refractive index of the esterified cellobiose. Particles of antiperspirant active substances, which are anhydrous solids typically have a refractive index substantially higher than 1,50, which decreases with hydration, however, the inventors have found that it is not easy to get antiperspirant active substance with a refractive index of 1.48 or less, even if the active substance is partially hydrated to reduce its refractive index.

For this reason, the hallmark of the present invention is preferred emulsion form tools from sweat, when seeking to obtain a transparent or translucent product.

For regular production of compositions with optimal transparency may be desirable to control the refractive indices of the source materials, to detect any variation from batch to batch. If necessary, the composition of the liquid phase can be adjusted by varying the number of composite materials.

Mechanical properties and product packaging

The compositions of this invention are structured liquid and appearance can be hard or soft. Even less solid substance has the ability to retain its shape, for example, if it is removed from the mold without the influence of the shift, it will retain its shape for at least 30 seconds and usually longer.

The composition of this invention usually arrives on the market in the form of a product, including a container with a certain amount of songs in it, and the container has at least one opening for delivery of the composition and means for promotion of the composition in the container to the outlet. Traditional containers have a cylindrical shape with an oval cross section and a hole (holes) on one end of the cylinder.

The composition of this invention may be rigid enough so that it clearly is not deformed when compressed by hand and is suitable for use as the core of the product in which the number of compositions in the form of a rod is placed inside the cylinder container having an open end in which the end part of the rod composition is disclosed for use. The opposite end of the cylinder is closed.

Typically, the container includes a lid to open the second end portion sometimes called the lifting part or piston provided within the cylinder and capable of relative axial movement along it. The core composition is located in the cylinder between the piston and the open end of the cylinder. The piston is used to force movement of the rod composition along the cylinder. The piston and rod compositions can be moved axially along the cylinder manually by pressing with a finger or a rod inserted into the cylinder on the opposite side of the piston. Another possibility is that the rod is attached to the lugs of the piston through a slot (or slots) in the cylinder and is used to move the piston and rod. Preferably, the container also includes a transport mechanism to move the piston, comprising a screw shaft, which passes axially inside of the rod through the hole in the piston with a corresponding thread, and means for rotating the shaft, mounted on the cylinder. The rod is conveniently rotates with the flywheel mounted on the closed end of the cylinder, i.e. the end opposite the outlet.

If the composition is softer, but still able to keep its shape, it will be more suitable for release from the cylinder through the gate, and not an end, and this bolt has one or more holes, black is C which can be extruded composition from the cylinder. The number and design of such holes are provided at the discretion of the designer of the package.

Component parts of such containers are often made from thermoplastic materials such as polypropylene or polyethylene. Description suitable containers, some of which include additional distinctive features that can be found in U.S. patent No. 4865231, 5000356 and 5573341.

Defining properties

1) the Penetrometer

The hardness and stiffness of the composition, which is a hard solid substance can be determined using penetrometry. If the composition is softened solid, it will be observed almost complete absence of any resistance to probe penetration test (CPT).

A suitable procedure is to use laboratory-factory-PNT-penetrometer equipped with a needle Seta wax (weight 2.5 g), which must have a tapered angle at the point of the needle is equal to 9° 10’±15’. Use the sample composition with a flat upper surface. The needle drops to the surface of the composition and then carry out the measurement of the penetration hardness, allowing the needle together with the holder to fall under the action of their total weight (i.e. the combined weight of the needle and holder), 50 grams, 5 seconds, and then registers the depth of penetration. Preferably, this test was conducted at a series of points to the each sample and averaging the results. When using tests of this nature has been found that a suitable hardness for use in distributing the container with the open end corresponds to a penetration of less than 30 mm in the specified test, for example in the range from 2 to 30 mm, Preferably the amount of penetration is in the range from 5 to 20 mm.

In accordance with a specific Protocol of measurement for this test with the rod held in the cylinder with the rod. The push rod so that it protrudes from the open end of the cylinder, and then cut off, leaving a flat, uniform surface. The needle gently lowered to the surface of the rod and then carry out the measurement of the penetration hardness. This process is carried out in six different points on the surface of the rod. Given the hardness represent the average of six measurements.

2) the texture Analyser

The hardness of soft solids can be measured using a texture analyser. Using the device for the test, you can promote a blunt probe into the sample to or from a variable speed, with simultaneous measurement efforts. The parameter, which is defined as the hardness is a function of the peak force and serving area dents.

Concrete test report system used is s Stable Micro TA.XT2i texture analyzer. Metal sphere with a diameter of 9.5 mm is attached to the back side of the cell to load the texture analyzer (5 kg) so that it can be used to press the sample placed at the bottom of the base plate of the device. After placement of the sample is regulated by the position of the sphere until then, until it is directly above the sample surface. For forming the profile of the subsequent movements used in the method of testing software is applied Texture Expert Exceed. On this profile the sphere is initially pressed into the sample with the indentation speed of 0.05 mm/s until, until it reaches the preset force is chosen so that the penetration depth in the sample was less than the radius of the sphere. At this load, the direction of movement of the sphere immediately reversed to pull the field from the sample with the same speed of 0.05 mm/s during the test, record the following data: time (sec)distance (mm) force (Newton), and the rate at which data is equal to 25 Hz.

Suitable for measuring samples either contained in the cylinders for rods that have a screw mechanism, or in glass jars for 15 ml For samples in the cylinders, the rod extends until then, until you are above the edges of the cylinder, and then use a knife to remove the top layer with Qili the DRA, to have remained flat uniform surface. Then the rod is pushed back into the cylinder, as deeply as possible in order to minimize any mechanical interference arising from elastic deformation of the screw mechanism in the packaging. Usually produce two dents on each side of the screw. For samples in banks in 15 ml of surface preparation is not required, they only need to have sufficient surface area to conduct one test for indentation.

The data obtained in each test, processed using standard software for spreadsheet and calculate the hardness N (Newton/mm²) using the following equation:

where F_max(N) represents the peak load and a_p- the apparent size of the dents, remaining after removal of the load. This area can be calculated geometrically by the depth of the plastic dents. It is slightly less than the total depth of penetration, measured under load, due to the elastic deformation of the sample. The depth of plastic dents is calculated according to the schedule according to "the relief well efforts from the total depth of penetration". The initial slope of this curve unloading depends on restore the original elasticity of the sample. The depth of the plastic indentation assessment is more on the size of the segment between the axis zero load and a straight line held at a tangent to the initial plot of the slope of the unloading curve.

Similar hardness measurement was also performed using the stand Instron Universal Testing Machine (model 5566), equipped with a load cell of 10 Newton, and data analysis carried out in the same way.

3) Deposits and white deposits

Another test of the properties of the composition is the determination of the number of songs that come to the surface when this composition is carried out on the surface (which represents the application of the product of the rod to human skin). To conduct this test sediment sample compositions standardized shape and size adapted to the device, which hold the sample on the test surface under standard conditions. The amount of composition transferred to the surface, is defined as the increase in the mass of the substrate on which it is applied. Optionally, you can define the color, opacity or transparency deposits.

By a special procedure for such tests is used a device for applying deposits of the rod on the substrate under standard conditions, and then measure the average level of white deposits using image analysis.

Use the following substrates:

a) strip (12× 28 cm) grey abrasive paper (carborundum paper 3 is™ P800 WetorDry™ ),

b) strip (12× 28 cm) black Worsted woolen cloth.

The substrates were weighed before use. Cores not previously used and had intact domed upper surface.

The device includes a flat base on which is fixed a flat substrate with clamps on each end. Stand with holder for cylinder with rod standard size, is mounted on the lever that can move horizontally along the substrate by means of a pneumatic piston.

Each terminal is stored over night at ambient temperature (in the lab) before measurements. The push rod to the cylinder made a measured amount of the composition. Then the cylinder is placed in the device so that the spring has shifted the rod relative to the substrate with a preset force. The device is actuated so that the rod is passed over the surface of the substrate to eight times. The substrate is carefully removed from the tooling and re-weighed.

Whiteness deposits

Deposits from previous descriptions appreciate to white after about 24 hours Is carried out using a monochrome video camera Sony XC77 with Cosmicar lenses (focal length 16 mm), located vertically above the black table, is broadcast at a large angle tubular fluorescent lamps, to fix the shading. The device is first calibrated using a reference gray card, which include a fluorescent lamp in a period of time sufficient to obtain a stable lighting. Fabric or carborundum paper to sediments deposited in the previous test, is placed on the table and using the camera photographing the image. Choose the size of the image deposits and analyzed using the image analyzer Kontron IBAS. With this, the image is divided into many picture elements, each picture element is measured gray level on a scale from zero (black) to 255 (white). Calculate the average intensity of gray. It is a measure of white fat, and higher numbers indicate more white deposition. It is accepted that small numbers indicate deposition on a transparent, which allows you to see the color of the substrate.

Found that it is desirable to carry out the application of the standard composition of the core as described above and to determine the whiteness of the sediments as a control.

4) light Transmission

The degree of transparency of the composition can be measured by placing a sample of standard thickness in the path of the light beam of the spectrophotometer and measuring the transmittance in the percentage of light transmitted in the absence of a gel.

The authors of the image is to be placed has conducted this test, using a double-beam spectrophotometer. The sample composition was poured hot into a cuvette (4.5 mm), made of polymethylmethacrylate (emission spectra obtained for pure), and allow it to cool to the ambient temperature of 20-25° C. Such ditch network layer composition thickness 1 cm Measurement is carried out at a wavelength of 580 nm with an identical but empty cuvette in the way of comparative beam spectrophotometer after keeping the sample in the cuvette within 24 hours. The authors note that the composition, which makes this test so small deletion as 1%, is perceived by the eye as "translucent". If the rod is made of a composition with the transmission of 3%, you can see the cavity from drilling below the surface of the sample. On the contrary, the structure of the conventional rod with stearyl alcohol is so opaque that it is impossible to see anything under it. The transmittance measured at any temperature in the range from 20 to 25° With, is usually fairly accurate, but if you want greater accuracy, measurement at 22° C. In some preferred examples was achieved transmittance of 20% or higher.

Getting

The compositions of this invention can be obtained by conventional methods of preparation of the suspension or emulsion, hard or softened solids. Such methods include the formation of a heated mixture of the composition when the temperature is e, which is high enough to dissolve all of structuring agent - esterified cellobiose, pouring the mixture into a mold, which may take the form of distributing container, and then cooling the mixture, after which the structuring agent is solidified in the form of a network of fibers extending through not miscible with water in the liquid phase.

Convenient technological sequence for the composition, which is a suspension, includes, first, the formation of a solution structuring agent - esterified cellobiose is not miscible in water liquid. Usually this is done by stirring the mixture at a temperature high enough to dissolve all structuring agent (the temperature of dissolution), such as a temperature in the range from 50 to 120° C. After that, the dispersed component (component in the form of particles), for example, dispersion of antiperspirant active agent is mixed with the hot mixture. This must be done slowly, or solid dispersed particles should be preheated to avoid premature gel formation. Then the resulting mixture is injected into the distributing container, such as a cylinder rod. This is usually carried out at a temperature of 5-30° With higher deposition temperature of the composition. Then the container and the soda is way to cool to ambient temperature. Cooling can be accomplished nothing other than just leaving the container and its contents to cool. Cooling can be facilitated by blowing the container and the ambient air or even chilled air.

In accordance with a suitable procedure for producing the emulsion compositions of the esterified solution structuring agent in the liquid phase that is not miscible with water, is prepared at elevated temperature, as well as suspension rods. If you are using any emulsifier, it is convenient to mix this liquid phase. Separately prepared aqueous or hydrophilic dispersed phase by introducing the active antiperspirant agent in the liquid part of this phase (if necessary, the active antiperspirant agent may sometimes be supplied in an aqueous solution, which is used as such). This solution of antiperspirant active agent, which will become the dispersed phase, preferably heated to a temperature similar to the temperature of the continuous phase with a structuring agent in it, but not exceeding the boiling point of the solution, and then mixed with the continuous phase. An alternative solution is injected with the speed at which the temperature of the mixture. If necessary, can be used your device and press the m for to achieve higher temperatures, however, it is usually not necessary with structuring agents of the present invention. After mixing the two phases resulting mixture fill distributing containers, usually at a temperature of 5-30° With higher temperature curing compositions, and allow it to cool as described above for suspension rods.

Examples

The following examples were carried out using a range of materials are given below in the list, along with their brand names. All temperatures are given in degrees Celsius. The refractive indices were measured at 22° C.

1 and 2). Volatile cyclic silicones (cyclomethicone) DC DC 245 and 345 (Dow Corning).

3 and 4). Non-volatile silicone fluids DC 556 and DC 710 (Dow Corning).

5). Polydecene (Silkflo 364 NF from Albermarle).

6). Isostearoyl alcohol (abbreviated ISA Prisorine 3515 from the company Unichema).

7). With₁₂-C₁₅-Alkylbenzoic (Finsolv TN from Fintex).

8). Mineral oil (Sirius M70 from Dalton).

9). Simple butyl ether polypropylenglycol 14 (Fluid AP from Amercol).

10). Isopropyl ester of myristic acid (abbreviated IPM from Unichema).

11). Copolyol of acidisation (emulsifier Abil EM90 from Th. Goldschmidt).

12). Al/Zr Tetrachlorohydrex-glycine complex (AZAG-7167 from Summit).

13). 50%aqueous solution of Al/Zr pentachloride (Zirkonal 50 from Giulini).

14). Over ElkY talc (particle size about 5 μm, from Cyprus Minerals).

15). Glycerin (from Aldrich).

16). Propylene glycol (Fisons).

17). Al/Zr Tetrachlorohydrex-glycine complex, 30% propylene glycol (WA2Z 8106 from Westwood).

18). Al/Zr Tetrachlorohydrex-glycine complex (AZG-375 from Summit).

19). Isohexadecane (Permethyl 101A from Presperse Inc.).

20). Isoeicosane (Permethyl 102A from Presperse Inc.).

21). Bis-phenylpropylamine, non-volatile silicone fluid (SF 1555 from GE Silicones).

22). Polyglyceryl-polyricinoleate (Quest PGPR).

23). 1-Octyldodecanol (Eutanol G from Henkel/Cognis).

24). Hydrogenated polyisobutene (Panalene-L-14E from Amoco).

25). Hydrogenated polyisobutene (Fancol 800 from Fanning Corp.).

26). Polyglyceryl-3-diisostearate (Lameform TGI from Henkel/Cognis).

27). Polyglyceryl-2-dipolyhydroxystearate (Dehymuls PGPH from Henkel/Cognis).

28). Poly-alpha-olefins (Puresyn 4 from Mobil Chemical).

29). Ceteareth 20 (Eumulgin B2 from Henkel).

30). Alcohols With₂₀-C₄₀(Unilin 425 from Petrolite).

EXAMPLE 1

Cellobiose atrificial nonanalog acid, getting completely esterified product in the form of alpha-anomer; subsequent procedure in General is described in the article Takada and others, Liquid Crystals, t, s (1995).

We used the following materials:

beta-D-cellobiose, 20 g 0,058 mol,

novanova acid, 591,6 g, 3,74 mol,

triperoxonane anhydride, 297,6 g of 1.42 mol.

These materials were obtained from Acros Organics (Fisher Scientific.

A 2-liter vessel with a flange equipped with the upper mesh is coy, water fridge and a device to add, put nonnovel acid together with triperoxonane anhydride. The resulting clear mixture was stirred and heated to 100° using bath with silicone oil and the temperature sensor. During heating it is noted that the color of the reaction mixture darkens and appears dark brown. Mixture is allowed to mix for 1 hour at 100° and then slowly in the dark activated solution add cellobiose through the funnel for solid powder is formed, dirty-brown suspension, which is again dissolved with the formation of transparent black solution for 10-20 minutes.

Then the reaction vessel is maintained at 100° With only 6 hours and then cooled to room temperature. Then the contents of the vessel are transferred into 2 liters of methanol containing 10% deionized water in a 5-liter beaker, cooled by ice. Immediately from the solution is not quite white solid precipitates, which is filtered off and collected. The crude solid is subjected to recrystallization (only 4 times) from a solution of tetrahydrofuran/methanol, obtaining a white solid product.

The product is obtained in the amount of 31.5 g, representing a yield of 37%. It has a melting point of 110° C. In the infrared spectrum absorption peak is observed in 1739 with the ^-1from the carbonyl group of ester. The amount of free acid can be identified by the peak absorption at 1705 cm^-1.

Spectrum of nuclear magnetic resonance (NMR) shows the number of fully esterified cellobiose and the ratio of products that represent the alpha and beta anomers.

Follow the same procedure with the use of acids with different chain length. Used acid and characteristics of products presented in the following table.

EXAMPLE 2.

Samples of the esterified cellobiose obtained in accordance with example 1, is used for gelling different is not miscible with water, liquids and mixtures of liquids. The procedure is as follows.

Esterified to cellobiose (0.5 g) and 9.5 g of fluid (or other ratio, giving a total 10 g) is weighed directly into a glass jar for 15 or 30, the vessel is placed a small magnetic stirrer, which then placed the and hot plate. The mixture is stirred and heated to until all esterified cellobiose will not dissolve in the liquid. Note the temperature of dissolution". The vessel is then removed from the hot plate and remove the stirrer from the hot liquid. In the lower liquid thermometer and then the contents of the vessel leave quietly cool. Note the temperature of gelation, i.e. the temperature at which the content is transformed into a gel. The vessel is left to stand for 24 hours and then the contents of the vessel are examined visually, push the probe and qualitatively classified by its appearance as soft, medium or hard gel. Register the degree of transparency of the gel. In most cases, the gel is melted again, record the temperature of the re-melting and a certain amount of melt is poured into a plastic cuvette (polymethyl methacrylate) and again allowed to cool to ambient temperature in the laboratory to ditch the newly formed gel. Light transmission through the layer of gel with a thickness of 1 cm cuvette register at a wavelength of 580 nm using a spectrophotometer in the UV/visible region.

The following tables show the used fluid is not miscible with water, the percentage of structuring agent esterified cellobiose used for gelling liquid, and nekotoryye all information about the following: the temperature of dissolution, the gelation temperature (gelation), the appearance of the gel, re-melting temperature and the percentage of light transmittance (denoted as % P) through the layer of gel in 1 cm at 580 nm. In some cases, the gel formation was conducted in the form of a test on a smaller scale and could be registered less data.

EXAMPLE 3.

Cellobiose atrificial less than stoichiometric amount of nonanalog acid, getting partially esterified product, with the subsequent procedure in General similar to that described in example 1.

Used the following materials:

beta-D-cellobiose, 2.5 g, 0,0073 mol,

novanova acid, 5,78 g, 0,0365 mol,

triperoxonane anhydride, only 2.91 g, 0,0138 mol.

In a three-neck round bottom flask, equipped with a top stirrer, water-fridge and a device to add, put nonnovel acid together with triperoxonane anhydride. The resulting clear mixture was stirred and heated to 100° C. the Color of the reaction mixture darkens. Slowly add cellobiose and formed a grey suspension. The reaction mixture was kept at 100° C for 6 hours and then allow it to cool to room temperature. The contents of the reaction flask are mixed with 100 ml ice methanol containing 10% water. A white fine product. The product is filtered and washed with additional portions of aqueous methanol before drying in VA is yumnam Cabinet. The output is 2.5,

In the infrared spectrum of the product are observed absorption peaks at 1744 and 3340 cm^-1that correspond to the carbonyl group of ester and free hydroxyl groups, respectively. Mass spectrometer showed the presence palleroni cellobiose and Penta-, hexa-, hepta - and OCTA-nonanoate esters cellobiose. Mono-, di - and tri-esters could not be seen.

The capacity of the partially esterified cellobiose to georoute is not miscible with water liquid determined using the following procedure, according to which is used for comparison and a fully acylated cellobiose. In this procedure, you can get a large number of gels.

Gels prepared in 96-well (8 to 12 rows) glass tablet for micrometrology. Each hole has a volume of about 1 ml of About 0.01 g each esterified cellobiose material placed in 8 consecutive holes in one row. To each well add about 0.2 g of the required liquid. On top of the tablet is closed by a glass cover. The tablet is carefully placed for 2.5 hours in a thermostatically controlled oven with a fan at 150° C. the tablet Then removed from the rack and leave to cool spontaneously to room temperature. The contents of each well appreciate spusta hours. Testing is carried out both visually and by stykovanija the contents of each well by microspheres.

The following results are obtained:

The results show that it can be used partially esterified cellobiose, but fully esterified cellobiose better.

EXAMPLE 4.

Suspension rods from sweat were prepared using a liquid not miscible with water, or mixture of liquids that do not mix with water, the active substance is the means of sweat and the esterified cellobiose. In all cases the procedure was as follows: the liquid or mixture of liquids is heated to a temperature of 5-10° C above the temperature at which the preliminary test is observed dissolving the esterified cellobiose. During heating, the liquid is gently mixed using a stirrer of Silverstone. Add esterified to cellobiose and allow it to dissolve. Then to this solution add particles of the active substance from sweat. Then the resulting mixture is allowed to cool (or, if necessary, be heated) with gentle stirring until a temperature of about 5-10° With higher temperature gel formation. At this stage the mixture is then poured into the cylinders for solid products from the pot and leave to cool without further exposure until the recipe will not harden.

The resulting rods assessed after at least 24 hours at room temperature. In all cases registered with the appearance of the rod is determined by the hardness penetration or texture analyser and carry out tests on the sediments and white formed deposits by using the previously described procedures.

The table below presents the prepared formulations and properties of the output terminals. Hardness testing and white deposits are also held with industrial solid white CTE is hit (CBE), structured 15% stearyl alcohol and 3% castor wax, all percentages refer to the weight of the entire composition.

"Esterified cellobiose C₁₂" means cellobiose, esterified dodecanol acid as in example 1.

"Esterified cellobiose₉/S₁₀" means cellobiose, esterified equimolar mixture of nonanalog and decanoas acid, as in example 1.

EXAMPLE 5.

Were prepared two cushioned solid product having the following composition:

Fluid and structuring agent, esterified to cellobiose mixed together and heated with gentle stirring using a stirrer of Silverstone, to achieve a temperature of about 20-30° above the minimum temperature at which soluble esterified cellobiose. Add particles of the active substance from the pot, together with talc with more vigorous stirring. The mixture is allowed to further cool with continuous stirring until then, until the temperature drops to slightly below the temperature of gel formation, defined during the preliminary tests. Then the mixture (which is movable) poured into the cylinders for rods and allowed to cool to room temperature in the laboratory.

Both composition are softened solid products, with a gift for drawing and extrusion, which is the Eney can retain its shape during storage over a period of 24 hours at 50° C.

EXAMPLE 6.

Prepare opaque emulsion rods, formulations are given below in tables.

To obtain these rods cyclomethicone mixed with other organic liquids (if used), including copolyol of acidisation, which acts as an emulsifier (silicone surfactant), and the mixture is heated with gentle stirring to a temperature of 5-10° C above the temperature at which it is found that the structuring agent is dissolved. Then add esterified to cellobiose and allow it to dissolve.

The dispersed phase (also referred to as the internal phase) is aluminum-zirconium active substance dissolved in water or in a mixture of polyol and water. This dispersed phase is heated to the same temperature as the organic oil containing esterified to cellobiose, and slowly add to them within 1 minute under stirring with a stirrer of Silverstone. When you are finished adding the composition more intensively stirred for 5 minutes. Then the stirring speed of the mixture reduce for an additional 1 minute, after which the mixture was poured into cylinders for rods and allowed to cool without further exposure to room temperature in the laboratory. The resulting rods are experiencing is a penetrometer, the texture analyzer and determine the degree of whiteness of the deposits, in each case using the previously described procedures tests. All rods are opaque, though without the chalky white of industrial white rod, structured stearyl alcohol and castor wax.

EXAMPLE 7.

A number of oils with different values of refractive index heliroute complex Oct-ether cellobiose or other structuring agent specified in the table below. Appreciate the transparency of the gels by measuring the light transmittance at 580 nm when the gel layer thickness of 1 cm is placed in the cell on the path of the light beam of the spectrophotometer at 20-25° C.

The results are shown in the following table, where

"The inconsistency of refraction = the refractive index of the liquid minus the refractive index of the structuring agent.

You can see that the inconsistency indices of refraction reduces light transmission. OCTA-nonanoate cellobiose move more inconsistencies than the esters of cellobiose with more long-chain acid and gelling agents representing amide N-acylaminoacyl. 12-Hydroxystearate acid also carries an inconsistency, but requires that the fluid was consistent with its higher refractive index.

EXAMPLE 8.

Repeat the procedure of example 6 to obtain a range of emulsion rods with recipes that are listed in the following tables. Continuous and dispersed phase link so that they have values of refractive indices that are closely aligned with the values given in the tables. These rods were tested, as indicated above, and their properties are also shown in these tables.

In the table above example 8.17 is a rod with a high %content of the internal phase. It is noted that it has good transparency, but is not very solid (though able to keep its shape).

EXAMPLE 9.

Octanoate alpha cellobiose decelerat on the anomeric carbon atom interaction with a mixture of acetic acid and Ethylenediamine in adapting the procedures described in J.Carb.Chem., Vol.18, s-469 (1999).

Use the following procedure. Glacial acetic acid (0.6 g) is added slowly dropwise to a stirred solution of 1.2 g of Ethylenediamine in 250 ml of tetrahydrofuran (THF). A white precipitate is formed which does not change during the reaction. Then add Oct-nonanoate cellobiose (14.6 g) and the entire reaction mixture is stirred at room temperature generally within 48 hours. After this time, the contents of the flask is transferred into a 1-liter separating funnel, then add 100 ml of water and the mixture extracted with 250 ml of methylene chloride. Collect the organic layer and optionally washed with diluted (0.1 M) of hydrochloric acid in portions of 100 ml aqueous solution (1 M) of sodium bicarbonate and water. Then received organicheskoi the phase is dried over anhydrous magnesium sulfate, filtered and the remaining solvent is removed on a rotary evaporator. Get a slightly sticky no white crude solid, which was dissolved in 200 ml of THF in a conical 0.5-liter flask, which is heated on the steam bath, then slowly add about 150 ml of methanol; the resulting solution is kept on the steam bath for 3-4 minutes, then remove and allow to cool to room temperature overnight. The next morning the white solid precipitate is filtered, dried and collected.

Get the product in the amount of 6.8 g (yield 51%). It has a melting point of 100° and the purity of 98.5%, determined by HPLC method.

Product structure verified by mass spectrometry (molecular ion with a mass 1341) proton NMR and IR spectroscopy (peaks at 3446, 2923, 2853 and 1742 cm^-1). It was found that this material is beta-anomer hepta-nonanoate. Thus, the reaction can be represented as follows:

The material used for gelling liquids that do not mix with water as in example 2. The results are shown in the following table.

EXAMPLE 10.

The terminals receive and experience in accordance with the procedure described in example 6. The hardness of the rods is determined by the texture analyzer and/or by using a penetrometer. Found that the rods give sediments minor white, but numerical data were not recorded.

For some terminals in this example, the refractive index of the continuous phase is not miscible with water, and the solution of the active substance from sweat quite consistent with obtaining a translucent rods. Given some values of the light transmittance.

EXAMPLE 11.

Repeat the procedure of example 6 to obtain a range of emulsion rods with recipes that are listed in the following tables is H. As in example 8, the continuous and the dispersed phase link so that they have refractive indices that are closely aligned with the values given in the tables. The hardness of the rods is determined using the texture analyzer and/or penetration. Found that the rods give fat low degree of whiteness, which is consistent with their good transparency, but numerical data were not recorded.

Before making rods control the refractive indices of the samples of the liquid mixture, is not miscible with water, and solutions of the active substance from sweat. If necessary, the recipe very slightly modify to optimize the consistency of the refractive index.

EXAMPLE 12.

Using the procedure of example 6 to obtain a range of emulsion rods, the formulation of which is given in the following table. These rods do not contain active substance from sweat. They can be useful as a moisturizing with Erina or ointment for lips, and their compositions can be used as the basis for other, possibly opaque solid cosmetic products. Continuous and dispersed phase link so that they have refractive indices that are closely aligned with the values shown in the table, however, losses from evaporation during processing hinder the process. The rods are tested for hardness using the texture analyzer and/or penetration test (CPT).

EXAMPLE 13.

Using the procedure of example 6 to obtain a translucent emulsion rods, formulations are given below, in which the structuring agent is OCTA-undecanoate alpha cellobiose ("SW"). As in example 8, the continuous and the dispersed phase link so that they had a refractive index that is close agreement with the value given in the table. The rods are tested for hardness using the texture analyzer and/or penetration. Found that the rods give deposits a small degree of whiteness.

EXAMPLE 14.

Using the procedure of example 6 to obtain an opaque emulsion rod following formulation, which contains agents that promote flushing.

1. Antiperspirant or deodorant composition comprising antiperspirant or deodorant active material and a continuous phase, which contains not miscible with water carrier liquid is a structure forming agent therein, characterized in that the structuring agent is an at least partially esterified to cellobiose formula:

where each Z independently represents hydrogen or acyl group of the formula:

where R is a hydrocarbon group containing 4 to 22 carbon atoms, provided that not more than half of the groups Z are hydrogen.

2. The composition according to claim 1, in which at least five out of every eight groups Z are indicated acyl group.

3. The composition according to claim 1, in which at least three quarters of these groups Z are indicated acyl group.

4. The composition according to claim 1, in which R is alkyl or alkenylphenol a group of 5-18 carbon atoms.

5. The composition according to claim 4, in which R means an alkyl group with 5 to 12 carbon atoms.

6. The composition according to claim 5, in which the hydrocarbon group R contains from 7 to 11 carbon atoms, provided that at least 80% of the esterified cellobiose is fully esterified and at least 80% of the esterified cellobiose is present in the form of alpha-anomers.

7. The composition according to claim 1, in which R denotes a linear alkyl group with 7 to 9 carbon atoms.

8. The composition according to claim 1, in which from 90% to less than 100% of the acyl group-CO-R the chain length in the range from m+1 to m-1, where m is the length of the chain acyl group.

9. The composition according to claim 1 in which not more than 10% of the hydrocarbon groups R are hydrocarbon with a branched chain.

10. The composition according to claim 1, in which virtually all of the group Z are acyl groups in which R is a linear alkyl with 7 to 9 carbon atoms.

11. The composition according to claim 10, in which the acyl group-CO-R includes a mixture of nonanoate and decanoate.

12. The composition according to any one of the preceding paragraphs, containing 0.1-15 wt.% structuring agent.

13. The composition according to claim 1, which contains not more than 5 wt.% any fatty alcohol that is solid at 20°C.

14. The composition according to any one of the preceding paragraphs, which is an emulsion with a hydrophilic, preferably miscible with water is the dispersed phase, in addition to this is not miscible with water continuous liquid phase.

15. The composition according to 14, characterized in, that is not miscible with water carrier liquid contains a volatile silicone and optionally a non-volatile silicone and/or asilicone hydrophobic organic liquid selected from hydrocarbons, hydrophobic aliphatic esters, aromatic esters, hydrophobic hydrophobic alcohols and ethers.

16. The composition according to item 15, which is not miscible with water liquid carry the ü contains silicone oil in the quantity which is at least 10% by weight of the composition.

17. The composition according to 14, in which the dispersed phase contains a diol or polyol.

18. The composition according to 14, which contains 0.1 to 10 wt.% non-ionic emulsifier.

19. The composition according to 14, which contains not more than 8 wt.% ethyl alcohol or any monohydroxy alcohol vapour pressure above a 1.3 kPa at 22°C.

20. The composition according to any one of claims 1 to 13, which is a song from the pot containing the active substance from sweat in the form of particles in suspension in the specified is not miscible with water continuous phase.

21. The composition according to claim 20, characterized in, that is not miscible with water carrier liquid contains a volatile silicone and optionally a non-volatile silicone and/or silicone hydrophobic organic liquid selected from hydrocarbons, hydrophobic aliphatic esters, aromatic esters, hydrophobic hydrophobic alcohols and ethers.

22. The composition according to item 21, which is not miscible with water carrier liquid contains a silicone oil in an amount which is at least 10% by weight of the composition.

23. The composition according to claim 1 in which the antiperspirant active substance includes halohydrin aluminum and/or zirconium, activated halohydrin aluminum and/or zirconium, or a complex of aluminum and/or zirconium, or an act of virovanny complex of aluminum and/or zirconium.

24. The composition according to item 23, which represents halohydrin or complex, which contains aluminum, and zirconium.

25. Composition according to claims 1, 23, or 24, in which the amount of antiperspirant active substance is 5-40% by weight of the composition.

26. The composition according A.25, in which the antiperspirant active substance dissolved in the hydrophilic phase of the emulsion.

27. The composition according to claim 1, which is a hard gel that needle penetrometer cone angle 9°10' immersed in it not more than 30 mm when the needle drops freely under the action of the total weight 50 g for 5 sec.

28. The composition according to claim 1, which is translucent or transparent.

29. The composition according to p, which has a light transmittance at 580 nm through a layer of the composition with a thickness of 1 cm at 22°With at least 1% and preferably at least 3%.

30. A method of obtaining a composition according to claim 1, comprising not necessarily in any order stage of introduction is not miscible with water carrier liquid structuring agent that represents the specified completely or partly esterified to cellobiose, mixing the liquid carrier with solid or dispersed in the liquid phase, suspendiruemye in it, including antiperspirant or deodorant active agent, heating to elevated temperature at which the structure is Gent is not miscible soluble in water liquid media, with the subsequent forced or arbitrary cooling the mixture to a temperature at which it thickens or hardens.

31. The method of item 30, which includes a step of pouring the mixture at an elevated temperature in the distributing container and arbitrary cooling the mixture in the container.

32. A method of preventing or reducing perspiration on human skin comprising topical application to the skin the composition according to any one of claims 1 to 29.