cosmetic product containing sensitive ingredients

0001The present invention relates to a cosmetic which is composed of a dispenser and a preparation with sensitive ingredients.

0002The desire to look beautiful and attractive is inherently rooted in people. Even if the ideal of beauty has changed over time, the pursuit of a flawless appearance has always been the goal of people. The condition and appearance of the skin and the appendages of the skin play an important part in creating a beautiful and attractive exterior.

0003In order for the skin and the appendages, especially the hair and nails, to fully perform their biological functions, they need regular cleaning and care as well as protection against UV radiation. The cleaning serves to remove dirt, sweat and residues of dead body cells, which form an ideal breeding ground for pathogens and parasites of all kinds. Cosmetic cleaning products are usually offered in the form of gels, lotions and solids (bars of soap, washing syndets). Skin care products, usually creams, ointments or lotions, mostly serve to moisturize and regrease the skin and to supply the skin with cosmetic or dermatological active ingredients (e.g. vitamins, antioxidants, UV light protection filters). This is particularly important when the skin's natural ability to regenerate is not sufficient to compensate for the stresses caused by environmental influences, mechanical or chemical stimuli, sunlight and wind (which, among other things, accelerate skin aging) and damage the skin.

0004Conventional cosmetic preparations are stored and presented in different packaging materials depending on their viscosity and intended use. In addition to the long-known tubes, bottles, aerosol sprays, etc., mechanical pump dispensers have also been used more and more recently. These can be used not only to apply low-viscosity aqueous or aqueous-alcoholic preparations; they are increasingly used for applying / dosing milk and lotions on an emulsion basis.

0005Compared to bottles and tubes, for example, pump dispensers as storage and application devices for cosmetic and / or dermatological preparations have the advantage that, due to the delivery volume of the pump of the dispenser, the preparations can be dosed particularly easily, so that the amount of preparation removed is already from the manufacturer to the amount required for the application can be set. Overdosing and underdosing by the user can thus be avoided.

0006Another advantage of pump dispensers over conventional packaging is that the preparations can be removed from the storage container relatively cleanly and hygienically. Direct contact of the residual preparation remaining in the storage vessel with body surfaces (for example the hands) and consequent contamination with germs (for example Bacteria, fungi, etc.) is effectively avoided because the preparation is thrown out of the storage vessel under pressure.

0007Compared to the aerosol cans that have been known for years, pump dispensers have the great advantage that the hazard potential that results from possible damage to a compressed gas container (aerosol can) is completely avoided. Since pump dispensers do not use the flammable propellant gases, which are hazardous to the ozone layer or combustible, as a conveying medium, their use is particularly safe and environmentally friendly. Last but not least, pump dispensers are cheaper and more environmentally friendly to manufacture and dispose of.

0008A large number of mechanical pump dispensers (also called dispensers in the context of this description) for cosmetic preparations have therefore been developed in the past, with which even higher-viscosity formulations can be applied.

0009So dispensers with sliding sliding piston and hand-operated conveyor with a volume-variable delivery chamber are known as an outpatient reservoir in a variety of application examples, for. B. for personal care, in medicine for the application of medication or in the provision of pasty food in the trade. The design of the dispensers used for the provision of the very different pasty masses is correspondingly varied, above all with regard to their direct conveying and handling mechanism.

0010Such a dispenser is known for example from EP-A-0 230 252. In this known dispenser, the manually operable delivery device has a delivery piston, by means of which the volume of the delivery chamber can be changed. The delivery plunger is locked in place with a piece of pipe which is formed in one piece on the head part. When using the dispenser, the head piece is moved from an initial position by hand in the axial direction towards the container.

0011This displacement movement leads directly to a sliding movement of the delivery piston along the inner wall of the delivery chamber while reducing the volume thereof. The internal pressure built up in the delivery chamber initially leads to the opening of an elliptical check valve which covers an outlet opening of the delivery piston and through which the paste-like product then, with a further reduction in the volume of the delivery chamber in the direction of the delivery channel, for removal at a product delivery opening is formed on the head part is promoted.

0012With the previously known dispenser, an internal pressure that overcomes the closing forces of the check valve must first be built up in the delivery chamber.

0013The conveying of the pasty mass through the check valve also leads to a pressure loss, which is disadvantageous in that increased pressure forces have to be used to compensate for this pressure loss in order to axially shift the head part in the direction of the container.

0014The document WO 03/004374 discloses a dispenser which is improved in that an actuation with lower actuation forces is possible. The conveying device comprises a conveying element which is longitudinally displaceable relative to the container and the head piece and which has a conveying piston which is displaceable in the conveying chamber and which is connected to a conveying shaft, which surrounds a circumferential conveying channel, which has a conveying channel inlet opening communicating with the conveying chamber and a conveying channel outlet opening, which can be brought into a position by a displacement movement of the conveying element relative to the head piece, in which the conveying duct outlet opening opens towards the dispensing duct.

0015Prior art mechanical pump dispensers also have the following disadvantages:<ul id="ul0001" list-style="none" compact="compact"><li>The cosmetic preparation in the storage container is not adequately shielded from the environment. The volume of preparation removed from the storage container when using the cosmetic must be replaced by outside air, as a result of which moisture (water) and oxygen are introduced into the storage container and come into contact with the preparation. This entry of air into the storage container cannot be avoided with any pump dispenser. Contact with air is problematic for the preparation stored in the storage vessel, in particular when the formulation contains one or more ingredients (in particular active ingredients) which<ul id="ul0002" list-style="bullet" compact="compact"><li>oxidation sensitive to oxygen or air and / or</li><li>are sensitive to hydrolysis against water or humidity,</li><li>cause a change in the temperature of the preparation under the influence of water, air humidity and / or oxygen,</li><li>lose their physiological effectiveness under the influence of water, air humidity and / or oxygen and / or</li><li>which irritate human and / or animal olfactory receptors, for example contain fragrance and / or perfume substances and / or repellents.</li></ul></li></ul>

0016If a cosmetic or dermatological preparation contains at least one such ingredient, it increasingly loses and / or changes its effectiveness or its composition specified by the manufacturer over a longer storage period in the pump dispenser.

0017Experience has shown that the volume of air, that is to say oxygen and water, in particular, which is introduced into the storage vessel by volume exchange, plays a subordinate role in comparison to the air or oxygen and moisture contamination which results from the fact that the storage container itself is not adequately shielded from the environment. The outlet opening is particularly critical since the product is exposed to the environment without protection. In extreme cases, it will be impossible for the user to remove undecomposed product, since the product volume that is to be removed next is always exposed to the greatest exposure to ambient oxygen or air humidity. Even plugs that are supposed to close the outlet opening after use do not adequately solve the problem, since product is always squeezed out to the side. Through permanent (continuous) contact with "fresh" oxygen or Water from the ambient air leads to a loss of effectiveness or a change in the composition of the preparation in the storage container over a longer period of time, which is why pump dispensers according to the prior art cannot be used for preparations with the above-mentioned ingredients.

0018It was therefore the object of the present invention to eliminate the deficiencies of the prior art and to develop cosmetics which do not have the deficiencies described or only have them to a minor extent. In particular, a cosmetic should be developed with which, with the help of a mechanical pump dispenser, preparations with oxidation and / or moisture-sensitive ingredients can be stored and presented in a consistent quality.

0019Furthermore, the present invention was based on the object of improving a dispenser of the type mentioned at the outset such that actuation with lower actuation forces is possible and, moreover, impairment of the pasty product to be dispensed by oxidation is reduced.

0020The tasks are surprisingly achieved by a cosmetic comprising a) a dispenser for pasty products with an essentially cylindrical container (1) containing a cosmetic and / or dermatological preparation, which on the bottom side has a follower piston (22 which is slidable under the pressure of the outside atmosphere on the inside of the container) ) and at its upper end carries a head piece (3) which is slidable relative to the container (1), which has an output channel (32) for the product which can be communicatively connected to the container (1) and acts on a manually operable conveying device with a variable-volume conveying chamber (100) for the product, characterized in that the conveying device connects to the container (1) and the head piece (3) comprises a longitudinally displaceable conveying element (5) which has a conveying piston (51) which is displaceable in the conveying chamber (100), which is connected to a delivery shaft (50) which surrounds a delivery channel (50a) circumferentially, which has a delivery channel inlet opening (53) communicating with the delivery chamber (100) and a delivery channel outlet opening (58) which is relative by a displacement movement of the delivery element (5) can be brought to the head piece (3) in a position in which the conveying duct outlet opening (58) opens to the dispensing duct (32), and b) a cosmetic preparation containing one or more ingredients which have one or more of the following properties: I) sensitive to oxidation to oxygen or air, II) sensitive to hydrolysis to water or air humidity, III) irritating the smell receptors of humans and / or animals, IV) causing a temperature change under the influence of water, air humidity and / or oxygen of the preparation, V) their physiological Loss of effectiveness under the influence of water, air humidity and / or oxygen.

0021The objects are also surprisingly achieved by the use of a dispenser for pasty products with an essentially cylindrical container (1) containing a cosmetic and / or dermatological preparation, which has a follower piston (22) that is slidable on the bottom side of the container under the pressure of the external atmosphere and carries at its upper end a head piece (3) which is slidable relative to the container (1), which has an output channel (32) for the product which can be communicatively connected to the container (1) and acts on a manually operable conveying device with a variable-volume conveying chamber (100) for the product, characterized in that the conveying device connects to the container (1) and the head piece (3) comprises a longitudinally displaceable conveying element (5) which has a conveying piston (51) which is displaceable in the conveying chamber (100), which is connected to a delivery shaft (50) which surrounds a delivery channel (50a) circumferentially, which has a delivery channel inlet opening (53) communicating with the delivery chamber (100) and a delivery channel outlet opening (58) which is relative by a displacement movement of the delivery element (5) can be brought to the head piece (3) in a position in which the conveying duct outlet opening (58) opens to the dispensing duct (32), for the storage and presentation of cosmetic and / or dermatological preparations containing one or more ingredients which have one or more of the following properties: I) sensitive to oxidation to oxygen or air, II) sensitive to hydrolysis to water or air humidity, III) irritating the smell receptors of humans and / or animals, IV) causing a temperature change under the influence of water, air humidity and / or oxygen of the preparation, V) their physiological Loss of effectiveness under the influence of water, air humidity and / or oxygen.

0022After the product has been removed from the dispensers described, the delivery duct outlet opening is advantageously closed according to the invention, the filling material not being pressed outwards but inwards and thus being protected from the environment.

0023In the context of this disclosure, the term “according to the invention” refers both to the cosmetic, the dispenser and the preparation itself and to the uses thereof.

0024In the context of this disclosure, paste-like preparation according to the invention means that the preparation has a viscose of 500 to 20,000 mPas (measured with the aid of a viscometer of the type Viscotester VT 02 from Haake with the following measurement parameters: temperature: 25 ° C., rotating body diameter 24 mm, rotor speed 62.5 rpm).

0025It was also surprising for a person skilled in the art that the preparations according to the invention can be effectively protected against attack by microorganisms using a reduced amount of preservatives.

0026Advantageously according to the invention, the cosmetic or the dispenser used according to the invention in the preparation contains one or more ingredients which have one or more of the following properties: I) sensitive to oxidation to oxygen or air, II) sensitive to hydrolysis to water or air humidity, III) irritating the smell receptors of humans and / or animals, IV) causing a temperature change under the influence of water, air humidity and / or oxygen of the preparation, V) their physiological Loss of effectiveness under the influence of water, air humidity and / or oxygen, in each case in a total concentration of 0.01 to 5% by weight, preferably in a concentration of 0.05 to 3 and very particularly preferably in a concentration of 0.1 to 1% by weight, in each case based on the total weight of the preparation.

0027According to the invention, the cosmetic or the dispenser used according to the invention is characterized in that one or more ingredients which have one or more of the following properties: I) sensitive to oxidation to oxygen or air, II) sensitive to hydrolysis to water or air humidity, III) irritating the smell receptors of humans and / or animals, IV) causing a temperature change under the influence of water, air humidity and / or oxygen of the preparation, V) their physiological Loss of effectiveness under the influence of water, air humidity and / or oxygen, are selected from the group of antioxidants, vitamins, enzymes, coenzymes, Perfume substances, fragrances, repellents, self-tanners, unsaturated lipid oils, fats, waxes, polyphenols, enzymes, flavonoids and isoflavonoids, lignans, polyols, polyethylene glycols and plant extracts that contain one or more of the aforementioned active ingredients.

0028It is preferred according to the invention if the cosmetic or the dispenser according to the invention in the preparation has one or more ingredients selected from the group consisting of vitamin A and its derivatives; Vitamin B and its derivatives; Vitamin C and its derivatives; Vitamin E and its derivatives; Vitamin F; Polyphenols, ubiquinone Q 10 (also in its reduced form); 2,6-di-tert-butyl-4-methylphenol; Dihydroxyacetone; Niacinamide; Pantothenic acid and its salts; Panthenol; γ-oryzanol; Biotin; Creatine, creatinine; Subtilisin; α-glycosyl rutin; Allantoin; Tannin; Azulene; Bisabolol; Glycyrrhizin; Hamamelin; Urea; Genist; Genistein; Daidzin; Daidzein; Carnitine and its derivatives and octadecenedicarboxylic acid as active ingredients that have one or more of the following properties: I) sensitive to oxidation to oxygen or air, II) sensitive to hydrolysis to water or air humidity, III) irritating the smell receptors of humans and / or animals, IV) causing a temperature change under the influence of water, air humidity and / or oxygen of the preparation, V) their physiological Loss of effectiveness under the influence of water, air humidity and / or oxygen.

I. The preparation according to the invention

0029Advantageously according to the invention, the cosmetic according to the invention or the dispenser used according to the invention also contains one or more of the following ingredients in the preparation, which, depending on their chemical nature, may also fall under the active ingredients according to the invention:

0030The following compounds can be used, for example, as UV light protection filters which are advantageous according to the invention:

Inorganic pigments

0031Preferred inorganic pigments are metal oxides and / or other metal compounds which are sparingly soluble or insoluble in water, in particular oxides of titanium (TiO₂), Zinc (ZnO), iron (e.g. Fe₂O₃), Zirconium (ZrO₂), Silicon (SiO₂), Manganese (e.g. MnO), aluminum (Al₂O₃), Cers (e.g. Ce₂O₃), Mixed oxides of the corresponding metals and mixtures of such oxides, as well as the sulfate of barium (BaSO₄).

0032The titanium dioxide pigments can be present both in the rutile and anatase crystal modification and, for the purposes of the present invention, can advantageously be surface-treated ("coated"), with, for example, a hydrophilic, amphiphilic or hydrophobic character being formed or retained. This surface treatment can consist in that the pigments are provided with a thin hydrophilic and / or hydrophobic inorganic and / or organic layer by methods known per se. For the purposes of the present invention, the various surface coatings can also contain water.

0033Coated and uncoated titanium dioxides described can also be used in the sense of the present invention in the form of commercially available oily or aqueous predispersions. Dispersing aids and / or solubilizing agents can advantageously be added to these predispersions.

0034The titanium dioxides according to the invention are distinguished by a primary particle size between 10 nm to 150 nm. <tables id="tabl0001" num="0001"><table frame="all"><tgroup cols="4" colsep="1" rowsep="1"><colspec colnum="1" colname="col1" colwidth="39.37mm" /><colspec colnum="2" colname="col2" colwidth="39.37mm" /><colspec colnum="3" colname="col3" colwidth="39.37mm" /><colspec colnum="4" colname="col4" colwidth="39.37mm" /><thead valign="top"><row><entry namest="col1" nameend="col1" align="left"><b>Trade name</b></entry><entry namest="col2" nameend="col2" align="left"><b>Coating</b></entry><entry namest="col3" nameend="col3" align="left"><b>additional components of the predispersion</b></entry><entry namest="col4" nameend="col4" align="left"><b>Manufacturer</b></entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">MT-100TV</entry><entry namest="col2" nameend="col2" align="left">Aluminum hydroxide stearic acid</entry><entry namest="col3" nameend="col3" align="left">-</entry><entry namest="col4" nameend="col4" align="left">Tayca Corporation</entry></row><row><entry namest="col1" nameend="col1" align="left">MT-100Z</entry><entry namest="col2" nameend="col2" align="left">Aluminum hydroxide stearic acid</entry><entry namest="col3" nameend="col3" align="left">-</entry><entry namest="col4" nameend="col4" align="left">Tayca Corporation</entry></row><row><entry namest="col1" nameend="col1" align="left">MT-100F</entry><entry namest="col2" nameend="col2" align="left">Stearic acid iron oxide</entry><entry namest="col3" nameend="col3" align="left">-</entry><entry namest="col4" nameend="col4" align="left">Tayca Corporation</entry></row><row><entry namest="col1" nameend="col1" align="left">MT-500SAS</entry><entry namest="col2" nameend="col2" align="left">Alumina, silica silicone</entry><entry namest="col3" nameend="col3" align="left">-</entry><entry namest="col4" nameend="col4" align="left">Tayca Corporation</entry></row><row><entry namest="col1" nameend="col1" align="left">MT-100AQ</entry><entry namest="col2" nameend="col2" align="left">Silica aluminum hydroxide alginic acid</entry><entry namest="col3" nameend="col3" align="left">-</entry><entry namest="col4" nameend="col4" align="left">Tayca Corporation</entry></row><row><entry namest="col1" nameend="col1" align="left">Eusolex T-2000</entry><entry namest="col2" nameend="col2" align="left">Alumina Simethicone</entry><entry namest="col3" nameend="col3" align="left">-</entry><entry namest="col4" nameend="col4" align="left">Merck KgaA</entry></row><row><entry namest="col1" nameend="col1" align="left">Eosolex TS</entry><entry namest="col2" nameend="col2" align="left">Alumina, stearic acid</entry><entry namest="col3" nameend="col3" align="left">-</entry><entry namest="col4" nameend="col4" align="left">Merck KgaA</entry></row><row><entry namest="col1" nameend="col1" align="left">Titanium dioxide P25</entry><entry namest="col2" nameend="col2" align="left">None</entry><entry namest="col3" nameend="col3" align="left">-</entry><entry namest="col4" nameend="col4" align="left">Degussa</entry></row><row><entry namest="col1" nameend="col1" align="left">Titanium dioxide T805 (Uvinul TiO₂)</entry><entry namest="col2" nameend="col2" align="left">Octyltrimethylsilane</entry><entry namest="col3" nameend="col3" align="left">-</entry><entry namest="col4" nameend="col4" align="left">Degussa</entry></row><row><entry namest="col1" nameend="col1" align="left">UV Titan X170</entry><entry namest="col2" nameend="col2" align="left">Alumina Dimethicone</entry><entry namest="col3" nameend="col3" align="left">-</entry><entry namest="col4" nameend="col4" align="left">Kemira</entry></row><row><entry namest="col1" nameend="col1" align="left">UV-Titan X161</entry><entry namest="col2" nameend="col2" align="left">Alumina, silica stearic acid</entry><entry namest="col3" nameend="col3" align="left">-</entry><entry namest="col4" nameend="col4" align="left">Kemira</entry></row><row><entry namest="col1" nameend="col1" align="left">Tioveil AQ 10PG</entry><entry namest="col2" nameend="col2" align="left">Alumina silica</entry><entry namest="col3" nameend="col3" align="left">Water propylene glycol</entry><entry namest="col4" nameend="col4" align="left">Solaveil Uniquema</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">Mirasun TiW 60</entry><entry namest="col2" nameend="col2" align="left">Alumina silica</entry><entry namest="col3" nameend="col3" align="left">water</entry><entry namest="col4" nameend="col4" align="left">Rhone-Poulenc</entry></row></tbody></tgroup></table></tables>

0035For the purposes of the present invention, particularly preferred titanium dioxides are the MT-100 Z and MT-100 TV from Tayca Corporation, Eusolex T-2000 and Eusolex TS from Merck and the titanium dioxide T 805 from Degussa.

0036For the purposes of the present invention, zinc oxides can also be used in the form of commercially available oily or aqueous predispersions. Zinc oxide particles and predispersions of zinc oxide particles suitable according to the invention are distinguished by a primary particle size of &lt;300 nm and are available under the following trade names from the companies listed:<tables id="tabl0002" num="0002"><table frame="all"><tgroup cols="3" colsep="1" rowsep="1"><colspec colnum="1" colname="col1" colwidth="52.50mm" /><colspec colnum="2" colname="col2" colwidth="52.50mm" /><colspec colnum="3" colname="col3" colwidth="52.50mm" /><thead valign="top"><row><entry namest="col1" nameend="col1" align="left"><b>Trade name</b></entry><entry namest="col2" nameend="col2" align="left"><b>Coating</b></entry><entry namest="col3" nameend="col3" align="left"><b>Manufacturer</b></entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">Z-Cote HP1</entry><entry namest="col2" nameend="col2" align="left">2nd % By weight of dimethicone</entry><entry namest="col3" nameend="col3" align="left">BASF</entry></row><row><entry namest="col1" nameend="col1" align="left">Z-Cote</entry><entry namest="col2" nameend="col2" align="left">/</entry><entry namest="col3" nameend="col3" align="left">BASF</entry></row><row><entry namest="col1" nameend="col1" align="left">ZnO NDM</entry><entry namest="col2" nameend="col2" align="left">5 % By weight of dimethicone</entry><entry namest="col3" nameend="col3" align="left">MR</entry></row><row><entry namest="col1" nameend="col1" align="left">MZ 707M</entry><entry namest="col2" nameend="col2" align="left">7 % By weight of dimethicone</entry><entry namest="col3" nameend="col3" align="left">M. Tayca Corp.</entry></row><row><entry namest="col1" nameend="col1" align="left">Nanox 500</entry><entry namest="col2" nameend="col2" align="left">/</entry><entry namest="col3" nameend="col3" align="left">Elementis</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">ZnO neutral</entry><entry namest="col2" nameend="col2" align="left">/</entry><entry namest="col3" nameend="col3" align="left">MR</entry></row></tbody></tgroup></table></tables>

0037Z-Cote HP1 from BASF and zinc oxide NDM from Haarmann &amp; Reimer are particularly preferred zinc oxides for the purposes of the invention.

0038The total amount of one or more inorganic pigments in the finished cosmetic preparation is advantageously selected from the range 0.1% by weight to 25% by weight, preferably 0.5% by weight to 18% by weight.

Organic pigments

0039An advantageous organic pigment for the purposes of the present invention is 2,2'-methylene-bis- (6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol) [INCI : Bisoctyltriazole], which is available under the trade name Tinosorb® M from CIBA-Chemicals GmbH.

More UV light protection filters

0040Advantageous UV-A filter substances for the purposes of the present invention are dibenzoylmethane derivatives, in particular 4- (tert-butyl) -4'-methoxydibenzoylmethane (CAS No. 70356-09-1), which is available from Givaudan under the Parsol® 1789 brand and is sold by Merck under the trade name Eusolex® 9020.

0041Further advantageous UV-A filter substances are the phenylene-1,4-bis (2-benzimidazyl) -3,3'-5,5'-tetrasulfonic acid and its salts, especially the corresponding sodium, potassium or triethanolammonium salts , in particular the phenylene-1,4-bis (2-benzimidazyl) -3,3'-5,5'-tetrasulfonic acid bis-sodium salt with the INCI name bisimidazylate, which, for example, under the trade name Neo Heliopan AP from Haarmann &amp; Reimer is available.

0042Also advantageous are the 1,4-di (2-oxo-10-sulfo-3-bornylidenemethyl) benzene and its salts (especially the corresponding 10-sulfato compounds, especially the corresponding sodium, potassium or triethanolammonium salt) , which is also known as benzene-1,4-di (2-oxo-3-bornylidenemethyl-10-sulfonic acid).

0043Further advantageous UV-A filter substances are hydroxybenzophenones, which are characterized by the following structural formula:<chemistry id="chem0001" num="0001"><img file="EP1531129A1_D0001.tif" /></chemistry> wherein<ul id="ul0003" list-style="bullet" compact="compact"><li>R¹ and R² independently of one another hydrogen, C₁-C₂₀-Alkyl, C₃-C₁₀Cycloalkyl or C₃-C₁₀-Cycloalkenyl mean, where the substituents R¹ and R² together with the nitrogen atom to which they are attached can form a 5- or 6-ring and</li><li>R³ a C₁-C₂₀-Alkyl means rest.</li></ul>

0044A particularly advantageous hydroxybenzophenone for the purposes of the present invention is 2- (4'-diethylamino-2'-hydoxybenzoyl) benzoic acid hexyl ester (also: aminobenzophenone), which is available under the trade name Uvinul A Plus from BASF.

0045Advantageous UV filter substances in the sense of the present invention are also so-called broadband filters, ie filter substances that absorb both UV-A and UV-B radiation.

0046Advantageous broadband filters or UV-B filter substances are, for example, bis-resorcinyltriazine derivatives with the following structure:<chemistry id="chem0002" num="0002"><img file="EP1531129A1_D0002.tif" /></chemistry> where R¹, R² and R³ are independently selected from the group of branched and unbranched alkyl groups having 1 to 10 carbon atoms or a single hydrogen atom. The 2,4-bis - {[4- (2-ethylhexyloxy) -2-hydroxy] phenyl} -6- (4-methoxyphenyl) -1,3,5-triazine (INCl: aniso triazine) are particularly preferred ), which is available under the trade name Tinosorb® S from CIBA-Chemicals GmbH.

0047Particularly advantageous preparations within the meaning of the present invention, which are characterized by a high or very high UV-A protection, preferably contain several UV-A and / or broadband filters, especially dibenzoylmethane derivatives [for example the 4- (tert-butyl) -4'-methoxydibenzoylmethane], benzotriazole derivatives [for example the 2,2'- Methylene-bis- (6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol)], phenylene-1,4-bis (2-benzimidazyl) -3 , 3'-5,5'-tetrasulfonic acid and / or its salts, the 1,4-di (2-oxo-10-sulfo-3-bornylidenemethyl) benzene and / or its salts and / or the 2,4-bis - {[4- (2-ethylhexyloxy) -2- hydroxy] -phenyl} -6- (4-methoxyphenyl) -1,3,5-triazine, in each case individually or in any combination with one another.

0048Other UV filter substances; which is the structural motif<chemistry id="chem0003" num="0003"><img file="EP1531129A1_D0003.tif" /></chemistry> are advantageous UV filter substances for the purposes of the present invention, for example the s-triazine derivatives described in European patent application EP 570 838 A1, the chemical structure of which is given by the generic formula<chemistry id="chem0004" num="0004"><img file="EP1531129A1_D0004.tif" /></chemistry> is reproduced, whereby<dl id="dl0001" compact="compact"><dt>R</dt><dd>a branched or unbranched C₁-C₁₈-Alkyl radical, a C₅-C₁₂Cycloalkylrest, optionally substituted with one or more C₁-C₄Represents alkyl groups,</dd><dt>X</dt><dd>represents an oxygen atom or an NH group,</dd><dt>R₁</dt><dd>a branched or unbranched C₁-C₁₈-Alkyl radical, a C₅-C₁₂Cycloalkylrest, optionally substituted with one or more C₁-C₄- Alkyl groups, or a hydrogen atom, an alkali metal atom, an ammonium group or a group of the formula<chemistry id="chem0005" num="0005"><img file="EP1531129A1_D0005.tif" /></chemistry> means in which A is a branched or unbranched C₁-C₁₈-Alkyl radical, a C₅-C₁₂-Cycloalkyl- or aryl radical, optionally substituted with one or more C.₁-C₄-Alkyl groups, R₃  represents a hydrogen atom or a methyl group, n represents a number from 1 to 10,</dd><dt>R₂</dt><dd>a branched or unbranched C₁-C₁₈-Alkyl radical, a C₅-C₁₂Cycloalkylrest, optionally substituted with one or more C₁-C₄Represents alkyl groups when X represents the NH group, and a branched or unbranched C₁-C₁₈-Alkyl radical, a C₅-C₁₂Cycloalkylrest, optionally substituted with one or more C₁-C₄- alkyl groups, or a</dd></dl> Hydrogen atom, an alkali metal atom, an ammonium group or a group of the formula<chemistry id="chem0006" num="0006"><img file="EP1531129A1_D0006.tif" /></chemistry> means in which<dl id="dl0002" compact="compact"><dt>A</dt><dd>a branched or unbranched C₁-C₁₈-Alkyl radical, a C₅-C₁₂-Cycloalkyl- or aryl radical, optionally substituted with one or more C.₁-C₄-Alkyl groups,</dd><dt>R₃</dt><dd>represents a hydrogen atom or a methyl group,</dd><dt>n</dt><dd>represents a number from 1 to 10,</dd><dt>if X</dt><dd>represents an oxygen atom.</dd></dl>

0049A particularly preferred UV filter substance in the sense of the present invention is also an asymmetrically substituted s-triazine, the chemical structure of which is represented by the formula<chemistry id="chem0007" num="0007"><img file="EP1531129A1_D0007.tif" /></chemistry> is reproduced, which is also referred to below as dioctylbutylamidotriazon (INCl: dioctylbutamidotriazone) and is available under the trade name UVASORB HEB from Sigma 3V.

0050A symmetrically substituted s-triazine which is 4,4 ', 4 "- (1,3,5-triazine-2,4,6-triyltriimino) tris-benzoic acid tris (2- ethylhexyl ester), synonymous: 2,4,6-tris [anilino- (p-carbo-2'-ethyl-1'-hexyloxy)] - 1,3,5-triazine (INCI: octyl triazone), which is derived from the BASF Aktiengesellschaft is sold under the trade name UVINUL® T 150.

0051European laid-open specification 775 698 also describes bis-resorcinyltriazine derivatives which are to be used preferably, the chemical structure of which is represented by the generic formula<chemistry id="chem0008" num="0008"><img file="EP1531129A1_D0008.tif" /></chemistry> is reproduced, where R₁, R₂ and A₁ represent various organic residues.

0052Also advantageous for the purposes of the present invention are 2,4-bis - {[4- (3-sulfonato) -2-hydroxypropyloxy) -2-hydroxy] phenyl} -6- (4-methoxyphenyl) -1, 3,5-triazine sodium salt, the 2,4-bis - {[4- (3- (2-propyloxy) -2-hydroxypropyloxy) -2-hydroxy] phenyl} -6- (4-methoxyphenyl) - 1,3,5-triazine, the 2,4-bis - {[4- (2-ethylhexyloxy) -2-hydroxy] phenyl} -6- [4- (2-methoxyethylcarboxyl) phenylamino] -1 , 3,5-triazine, the 2,4-bis - {[4- (3- (2-propyloxy) -2-hydroxypropyloxy) -2-hydroxy] phenyl} -6- [4- (2-ethylcarboxyl) phenylamino] -1,3,5-triazine, the 2,4-bis - {[4- (2-ethylhexyloxy) -2-hydroxy] phenyl} -6- (1-methyl-pyrrol-2-yl) - 1,3,5-triazine, the 2,4-bis - {[4-tris (trimethylsiloxysilylpropyloxy) -2-hydroxy] phenyl} -6- (4-methoxyphenyl) -1,3,5-triazine, the 2,4-bis - {[4- (2 "-methylpropenyloxy) -2-hydroxy] phenyl} -6- (4-methoxyphenyl) -1,3,5-triazine and the 2,4-bis- { [4- (1 ', 1', 1 ', 3', 5 ', 5', 5'-heptamethylsiloxy-2 "-methyl-propyloxy) -2-hydroxy] phenyl} -6- (4-methoxyphenyl) -1,3,5-triazine. An advantageous broadband filter for the purposes of the present invention is 2,2'-methylenebis (6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol), which is used under the Trade name Tinosorb® M is available from CIBA-Chemicals GmbH.

0053Another advantageous broadband filter for the purposes of the present invention is 2- (2H-benzotriazol-2-yl) -4-methyl-6- [2-methyl-3- [1,3,3,3-tetramethyl-1 - [( trimethylsilyl) oxy) disiloxanyl] propyl] phenol (CAS No .: 155633-54-8) with the INCl name Drometrizole Trisiloxane.

0054The UV-B and / or broadband filters can be oil-soluble or water-soluble. Advantageous oil-soluble UV-B and / or broadband filter substances are e.g. B .:<ul id="ul0004" list-style="none" compact="compact"><li>■ 3-benzylidene camphor derivatives, preferably 3- (4-methylbenzylidene) camphor, 3-benzylidene camphor;</li><li>■ 4-aminobenzoic acid derivatives, preferably 4- (dimethylamino) benzoic acid (2-ethylhexyl) ester, 4- (dimethylamino) benzoic acid amyl ester;</li><li>2,4,6-trianilino- (p-carbo-2'-ethyl-1'-hexyloxy) -1,3,5-triazine;</li><li>■ esters of benzalmalonic acid, preferably 4-methoxybenzalmalonic acid di (2-ethylhexyl) ester;</li><li>■ esters of cinnamic acid, preferably 4-methoxycinnamic acid (2-ethylhexyl) ester, 4-methoxycinnamic acid isopentyl ester;</li><li>■ Derivatives of benzophenone, preferably 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone</li><li>■ as well as UV filters bound to polymers.</li></ul>

0055Advantageous water-soluble UV-B and / or broadband filter substances are e.g. B .:<ul id="ul0005" list-style="none" compact="compact"><li>■ salts of 2-phenylbenzimidazole-5-sulfonic acid, such as its sodium, potassium or triethanolammonium salt, and the sulfonic acid itself;</li><li>■ sulfonic acid derivatives of 3-benzylidene camphor, such as. B. 4- (2-oxo-3-bornylidene methyl) benzenesulfonic acid, 2-methyl-5- (2-oxo-3-bornylidene methyl) sulfonic acid and salts thereof.</li></ul>

0056Particularly advantageous UV filter substances which are liquid at room temperature for the purposes of the present invention are homomenthyl salicylate (INCI: homosalate), 2-ethylhexyl-2-hydroxybenzoate (2-ethylhexyl salicylate, octyl salicylate, INCI: octyl salicylate), 4-isopropyl benzyl salicylate and esters of preferably z 4-methoxycinnamic acid (2-ethylhexyl) ester (2-ethylhexyl-4-methoxycinnamate, INCI: octyl methoxycinnamate) and 4-methoxycinnamic acid isopentyl ester (isopentyl 4-methoxycinnamate, INCI: Isoamyl p-methoxycinnamate), 3- (4- (2,2-bis-ethoxycarbonylvinyl) -phenoxy) propenyl) methoxysiloxane / dimethylsiloxane copolymer (INCI: Dimethicodiethylbenzalmalonat) which is available for example under the trade name Parsol® SLX from Hoffmann La Roche.

0057Another light protection filter substance that can be used advantageously according to the invention is ethylhexyl-2-cyano-3,3-diphenylacrylate (octocrylene), which is available from BASF under the name Uvinul® N 539.

0058It can also be of considerable advantage to use polymer-bound or polymeric UV filter substances in preparations according to the present invention, in particular those as described in WO-A-92/20690.

0059The list of UV filters mentioned, which can be used in the sense of the present invention, should of course not be limiting.

0060The preparations according to the invention advantageously contain the substances which absorb UV radiation in the UV-A and / or UV-B range in a total amount of, for. B. 0.1 wt .-% to 30 wt .-%, preferably 0.5 to 20 wt .-%, in particular 1.0 to 15.0 wt .-%, each based on the total weight of the preparations to cosmetic To provide preparations that protect the hair or skin from the entire range of ultraviolet radiation. They can also serve as sunscreens for the hair or skin.

Vitamins and vitamin derivatives

0061These include vitamins A, B_1-6, B₁₂, C, D, E, F, H, K and PP and their derivatives. According to the invention, these can advantageously be present in a concentration of 0.001 to 10% by weight, preferably 0.05 to 7% by weight, particularly preferably 0.5 to 5% by weight, in each case based on the total weight of the preparation.

0062Retinyl palmitate, ascorbyl glucoside, tocopheryl acetate, tocopheryl palmitate, niacinamide, panthenol are used as preferred vitamin derivatives according to the invention.

0063It is advantageous according to the invention to use vitamins and their derivatives in a concentration of 0.05 to 1% by weight, preferably in a concentration of 0.01 to 0.5% by weight and very particularly preferably in a concentration of 0.05 up to 0.2% by weight, based in each case on the total weight of the preparation.

Enzymes

0064The cosmetic according to the invention or the dispenser advantageously used according to the invention advantageously contains enzymes. As enzymes, lipases, esterases, proteases and other hydrolases can advantageously be used for the purposes of the present invention, lipases being preferred according to the invention.

0065Enzyme extracts can advantageously be used as enzymes according to the invention <i>Alcaligenes sp.</i> (e.g. from Amano Enzyme Europe Ltd.), <i>Aspergillus niger</i> (e.g. from Amano Enzyme Europe Ltd. or Fluka), <i>Candida cylindracea</i> (e.g. from Sigma, Aldrich, Fluka, Amano Enzyme Europe Ltd., Boeringer-Mannheim), <i>Candida</i> lipolytica (e.g. from Amano Enzyme Europe Ltd., Fluka), <i>Chromobacterium viscosium</i> (e.g. from Sigma), <i>Humicola laguninosa</i> (e.g. from Amano Enzyme Europe Ltd.), <i>Mucor miehei</i> (e.g. from Amano Enzyme Europe Ltd., Novo), <i>Penecillium</i> roqueforti (e.g. from Fluka), <i>Porcine pancreas</i> (e.g. from Sigma, Aldrich, Fluka, Amano Enzyme Europe Ltd., Boeringer-Mannheim), <i>Pseudomonas aegruginosa</i> (e.g. from Amano Enzyme Europe Ltd.), <i>Pseudomonas</i> fluorescens (e.g. from Amano Enzyme Europe Ltd., Fluka), <i>Pseudomonas</i> sp. (e.g. from Sigma, Boeringer-Mannheim), <i>Rhizopus delemar</i> (e.g. from Sigma, Fluka, Boeringer-Mannheim), <i>Rhizopus japonicus</i> (e.g. from Amano Enzyme Europe Ltd.), <i>Rhizopus oryzae</i> (e.g. from Amano Enzyme Europe Ltd.), <i>Rhizopus sp.</i> (e.g. from Amano Enzyme Europe Ltd., Serva) and / or wheat germ (e.g. from Sigma).

0066Lipases from pig pancreas (<i>Porcine pancreas</i>), <i>Aspergillus niger, Chromobacterium viscosium, Geotrichum candidum, Penecillium camberti, Penecillium roqueforti</i> preferred according to the invention.

0067Lipases of the type are very particularly preferred according to the invention <i>Mucor miehei</i> (eg Lipozyme® from Novo Nordisk), <i>Humicola laguninosa, Pseudomonas aegruginosa, Pseudomonas fluorescens, Pseudomonas sp., Candida cylindracea</i> and or <i>Candida lipolytica.</i>

0068According to the invention, one or more enzymes are advantageously present in the form of an aqueous solution. According to the invention, their content of one or more enzymes is advantageously from 0.1 to 5% by weight, preferably from 1 to 5% by weight and very particularly preferably from 1 to 2% by weight, in each case based on the total weight of the preparation.

Antioxidants

0069The antioxidants are advantageously selected from the group consisting of amino acids (for example glycine, lysine, arginine, cysteine, histidine, tyrosine, tryptophan) and their derivatives (as salt, ester, ether, sugar, nucleotide, nucleoside, Peptide and lipid linkage), imidazoles (eg urocanic acid) and their derivatives (as salt, ester, ether, sugar, nucleotide, nucleoside, peptide and / or lipid linkage), peptides such as D, L-carnosine, D-carnosine, L-carnosine, anserine and their derivatives (e.g. as salt, ester, ether, sugar, thiol, nucleotide, nucleoside, peptide and lipid compound), carotenoids, carotenes (e.g. α-carotene, β-carotene, ψ-lycopene, phytoene,) and their derivatives (e.g. as salt, ester, ether, sugar, nucleotide, nucleoside, peptide and / or lipid compound), chlorogenic acid and their derivatives (as salt, ester, ether -, sugar, thiol, nucleotide, nucleoside, peptide and / or lipid compound), aurothioglucose, propylthiouracil and other thiols (e.g. Thioredoxin, lipoic acid, glutathione, cysteine, cystine, cystamine and their glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl and lauryl, palmitoyl, oleyl, γ-linoleyl, Cholesteryl and glyceryl esters) and their salts, dilauryl thiodipropionate, distearyl thiodipropionate, thiodipropionic acid and their derivatives (as set, ester, ether, sugar, thiol, nucleotide, nucleoside, peptide and / or lipid compound) and Sulfoximine compounds (e.g. Homocysteine ​​sulfoximine, buthionine sulfones, penta-, hexa-, heptathionine sulfoximine) in very low tolerable dosages (eg pmol to µmol / kg). Furthermore (metal) chelators (eg apoferritin, desferral, lactoferrin, α-hydroxy fatty acids, palmitic acid, phytic acid) and their derivatives (as salt, ester, ether, sugar, thiol, nucleotide, nucleoside, peptide) and / or lipid linkage), α-hydroxy acids (e.g. Citric acid, lactic acid, malic acid), humic acid, bile acid, bile extracts, bilirubin, biliverdin, EDTA, EGTA and their derivatives, unsaturated fatty acids and their derivatives (e.g. γ-linolenic acid, linoleic acid, oleic acid), folic acid and its derivatives, furfurylidene sorbitol and its derivatives, Ubiquinone, ubiquinol, plastoquinone and their derivatives (as salt, ester, ether, sugar, thiol, nucleotide, nucleoside, peptide and lipid compound), vitamin C and derivatives (e.g. Ascorbyl palmitate, Mg ascorbyl phosphate, ascorbyl acetate), tocopherols and derivatives (eg vitamin E acetate), and phenolic compounds and plant extracts containing them, such as, for. B. flavonoids (e.g. glycosylrutin, ferulic acid, caffeic acid), furfurylidene glucitol, butylated hydroxytoluene, butylated hydroxyanisole, nordihydroguajak resin acid, nordihydroguajaretic acid, trihydroxybutyrophenone and their derivatives (as salt, ester, nucleotide, sugar, Lipid connection). Uric acid and its derivatives, mannose and its derivatives (as salt, ester, ether, sugar, thiol, nucleotide, nucleoside, peptide and lipid compound). Zinc and its derivatives (e.g. ZnO, ZnSO₄), Selenium and its derivatives (e.g. selenium methionine, Ebselen), stilbenes and their derivatives (e.g. stilbene oxide, trans-stilbene oxide) and the derivatives suitable according to the invention (as salt, ester, ether, sugar, thiol, nucleotide, Nucleoside, peptide and / or lipid linkage) of these active ingredients.

0070The amount of the aforementioned antioxidants (one or more compounds) in the preparations is preferably 0.001 to 30% by weight, particularly preferably 0.05-20% by weight, in particular 1-10% by weight, based on the total weight of the Preparation.

0071If vitamin E and / or its derivatives represent the antioxidant (s), it is advantageous to choose their respective concentrations from the range of 0.001-10% by weight, based on the total weight of the formulation.

0072If vitamin A or vitamin A derivatives or carotenes or their derivatives represent the antioxidant or antioxidants, it is advantageous to use their respective concentrations in the range from 0.001-10% by weight, based on the total weight of the formulation, to choose.

Anti-wrinkle agents, plant extracts and other agents

0073Further advantageous active ingredients in the sense of the present invention are natural active ingredients and / or their derivatives, such as. B. alpha-lipoic acid, phytoene, D-biotin, coenzyme Q10, alpha-glucosylrutin, carnitine, carnosine, natural and / or synthetic isoflavonoids, creatine, creatinine, lignans, taurine and / or β-alanine.

0074According to the invention, however, other pharmaceutically or dermatologically active substances, such as substances that soothe and care for the skin, can also be incorporated. These include, for example, panthenol, allantoin, tannin and plant active ingredients such as azulene and bisabolol, glycyrrhizin, hamamelin and plant extracts such as chamomile, aloe vera, hamazelis and licorice root.

0075The amount of the aforementioned active substances (one or more compounds) in the preparations is preferably 0.001 to 30% by weight, particularly preferably 0.05-20% by weight, in particular 1-10% by weight, based on the total weight of the Preparation.

Self-tanner

0076According to the invention, the following are advantageously used as self-tanners: glycerol aldehyde, hydroxymethylglyoxal, γ-dialdehyde, erythrulose, 6-aldo-D-fructose, ninhydrin, 5-hydroxy-1,4-naphthoquinone (juglone), 2-hydroxy-1,4- naphtoquinone (Lawson).

0077For the purposes of the invention, 1,3-dihydroxyacetone (DHA) is particularly preferred. A concentration of 0.5 to 10% by weight of 1,3-dihydroxyacetone and particularly a concentration of 1 to 7% by weight, based on the total weight of the preparation, is advantageous.

Depigmenting agent

0078Dicarboxylic acids such as 8-hexadecen-1,16-dicarboxylic acid (dioic acid, CAS number 20701-68-2), kojic acid, ascorbic acid and azelaic acid and their derivatives can be used, for example, as depigmenting agents which are advantageous according to the invention.

0079According to the invention, the total concentration of depigmenting agents in the corresponding preparation is advantageously 0.001-10% by weight, preferably 0.005-8% by weight, in particular 0.05-5% by weight.

Repellents

0080According to the invention, the following can advantageously be used:<ul id="ul0006" list-style="none" compact="compact"><li>N, N-Diethyl-3-methylbenzamide (DEET), dimethyl phthalate (Palatinol M, DMP), 2,3; 4,5-bis (2-butylene) tetrahydro-2-furaldehyde (MGK-Repellent 11), butopyronoxyl (Indalone), N, N-caprylic acid diethylamide (Repellent 790), o-chloro-N, N-diethylbenzamide in a mixture with N, N-diethylbenzamide (Kik repellent), dimethyl carbate (Dimalone), di-n-propylisocinchomeronate (MGK- Repellent 326), 2-ethylhexane-1,3-diol (Rutgers 612), N-octyl-bicycloheptenedicarboximide (MGK 264 Insecticidesynergist), piperonyl-butoxide (PBO) and, particularly preferred according to the invention, ethyl 3- (Nn-butyl-N-acetylamino) propionate (also referred to as repellent 3535) and 1-piperidinecarboxylic acid 2- (2-hydroxyethyl) -1-methylpropyl ester (Bayrepel®).</li></ul>

0081According to the invention, a repellents content of 0.005 to 70.0% by weight is used, in particular 0.01 to 50.0% by weight and very particularly preferably 3 to 15% by weight, based on the total weight of the preparation.

Anhydrous polyols

0082It is preferred according to the invention if the polyalcohols are selected from the group of substances with a molecular weight between 200 and 600 g / mol, for example polyethylene glycol (200) (= PEG-4), polyethylene glycol (300) (= PEG-6), polyethylene glycol (400) (= PEG-8), polyethylene glycol (1000) (= PEG-5) and polyethylene glycol (1200) (= PEG-6). The polyalcohols which are particularly preferred according to the invention are the compounds polyethylene glycol (400) (= PEG-8), polyethylene glycol (1000) (= PEG-5) and polyethylene glycol (1200) (= PEG-6).

0083According to the invention, a polyalcohol concentration of 5 40 to 90% by weight and particularly preferably 40 to 85% by weight, based on the total weight of the preparation, is preferred.

0084According to the invention, “water-free” is understood to mean polyols whose water concentration is less than 5% by weight and preferably less than 3% by weight, in each case based on the weight of the polyol.

0085According to the invention, polyol-containing preparations are advantageously offered, in particular, as almost water-free preparations, so that they can be administered as so-called "self-heating" (because they release heat from contact with water) cosmetics or dermatics when used and in contact with water.

Dyes and effects

0086All of the compounds listed in the corresponding positive list of the Cosmetics Ordinance or the EC list of cosmetic colorants can be used as pigmentary dyes which are advantageous according to the invention. In most cases, they are identical to the colorants approved for food. In addition to color pigments, the preparations according to the invention can also contain further dyes. Advantageous color pigments are, for example, titanium dioxide, mica, iron oxides (e.g. Fe₂O₃, Fe₃O₄, FeO (OH)) and / or tin oxide. Advantageous dyes are, for example, carmine, Berlin blue, chrome oxide green, ultramarine blue and / or manganese violet. It is particularly advantageous to choose the dyes and / or color pigments from the list below. The Color Index Numbers (CIN) are that<i>Rowe Color Index, 3rd edition, Society of Dyers and Colorists, Bradford, England, 1971</i> taken. <tables id="tabl0003" num="0003"><table frame="all"><tgroup cols="3" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="52.50mm" /><colspec colnum="2" colname="col2" colwidth="52.50mm" /><colspec colnum="3" colname="col3" colwidth="52.50mm" /><thead valign="top"><row rowsep="1"><entry namest="col1" nameend="col1" align="left"><b>Chemical or other name</b></entry><entry namest="col2" nameend="col2" align="left"><b>CIN</b></entry><entry namest="col3" nameend="col3" align="left"><b>colour</b></entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">Pigment green</entry><entry namest="col2" nameend="col2" align="left">10006</entry><entry namest="col3" nameend="col3" align="left">green</entry></row><row><entry namest="col1" nameend="col1" align="left">Acid Green 1</entry><entry namest="col2" nameend="col2" align="left">10020</entry><entry namest="col3" nameend="col3" align="left">green</entry></row><row><entry namest="col1" nameend="col1" align="left">2,4-dinitrohydroxynaphthalene-7-sulfonic acid</entry><entry namest="col2" nameend="col2" align="left">10316</entry><entry namest="col3" nameend="col3" align="left">yellow</entry></row><row><entry namest="col1" nameend="col1" align="left">Pigment Yellow 1</entry><entry namest="col2" nameend="col2" align="left">11680</entry><entry namest="col3" nameend="col3" align="left">yellow</entry></row><row><entry namest="col1" nameend="col1" align="left">Pigment Yellow 3</entry><entry namest="col2" nameend="col2" align="left">11710</entry><entry namest="col3" nameend="col3" align="left">yellow</entry></row><row><entry namest="col1" nameend="col1" align="left">Pigment Orange 1</entry><entry namest="col2" nameend="col2" align="left">11725</entry><entry namest="col3" nameend="col3" align="left">orange</entry></row><row><entry namest="col1" nameend="col1" align="left">2,4-dihydroxyazobenzene</entry><entry namest="col2" nameend="col2" align="left">11920</entry><entry namest="col3" nameend="col3" align="left">orange</entry></row><row><entry namest="col1" nameend="col1" align="left">Solvent Red 3</entry><entry namest="col2" nameend="col2" align="left">12010</entry><entry namest="col3" nameend="col3" align="left">red</entry></row><row><entry namest="col1" nameend="col1" align="left">1- (2'-chloro-4'-nitro-1'-phenylazo) -2-hydroxynaphthalene</entry><entry namest="col2" nameend="col2" align="left">12085</entry><entry namest="col3" nameend="col3" align="left">red</entry></row><row><entry namest="col1" nameend="col1" align="left">Pigment Red 3</entry><entry namest="col2" nameend="col2" align="left">12120</entry><entry namest="col3" nameend="col3" align="left">red</entry></row><row><entry namest="col1" nameend="col1" align="left">Ceres red; Sudan red; Fat red G</entry><entry namest="col2" nameend="col2" align="left">12150</entry><entry namest="col3" nameend="col3" align="left">red</entry></row><row><entry namest="col1" nameend="col1" align="left">Pigment Red 112</entry><entry namest="col2" nameend="col2" align="left">12370</entry><entry namest="col3" nameend="col3" align="left">red</entry></row><row><entry namest="col1" nameend="col1" align="left">Pigment Red 7</entry><entry namest="col2" nameend="col2" align="left">12420</entry><entry namest="col3" nameend="col3" align="left">red</entry></row><row><entry namest="col1" nameend="col1" align="left">Pigment Brown 1</entry><entry namest="col2" nameend="col2" align="left">12480</entry><entry namest="col3" nameend="col3" align="left">brown</entry></row><row><entry namest="col1" nameend="col1" align="left">4- (2'-methoxy-5'-sulfonic acid diethylamide-1'-phenylazo) -3-hy-</entry><entry namest="col2" nameend="col2" align="left">12490</entry><entry namest="col3" nameend="col3" align="left">red</entry></row><row><entry namest="col1" nameend="col1" align="left">droxy-5 "-chloro-2", 4 "-dimethoxy-2-naphthoic acid anilide Disperse Yellow 16</entry><entry namest="col2" nameend="col2" align="left">12700</entry><entry namest="col3" nameend="col3" align="left">yellow</entry></row><row><entry namest="col1" nameend="col1" align="left">1- (4-sulfo-1-phenylazo) -4-amino-benzene-5-sulfonic acid</entry><entry namest="col2" nameend="col2" align="left">13015</entry><entry namest="col3" nameend="col3" align="left">yellow</entry></row><row><entry namest="col1" nameend="col1" align="left">2,4-dihydroxy-azobenzene-4'-sulfonic acid</entry><entry namest="col2" nameend="col2" align="left">14270</entry><entry namest="col3" nameend="col3" align="left">orange</entry></row><row><entry namest="col1" nameend="col1" align="left">2- (2,4-dimethylphenylazo-5-sulfonic acid) -1-hydroxynaphthalene</entry><entry namest="col2" nameend="col2" align="left">14700</entry><entry namest="col3" nameend="col3" align="left">red</entry></row><row><entry namest="col1" nameend="col1" align="left">4-sulfonic acid 2- (4-sulfo-1-naphthylazo) -1-naphthol-4-sulfonic acid</entry><entry namest="col2" nameend="col2" align="left">14720</entry><entry namest="col3" nameend="col3" align="left">red</entry></row><row><entry namest="col1" nameend="col1" align="left">2- (6-sulfo-2,4-xylylazo) -1-naphthol-5-sulfonic acid</entry><entry namest="col2" nameend="col2" align="left">14815</entry><entry namest="col3" nameend="col3" align="left">red</entry></row><row><entry namest="col1" nameend="col1" align="left">1- (4'-Sulfophenylazo) -2-hydroxynaphthalene</entry><entry namest="col2" nameend="col2" align="left">15510</entry><entry namest="col3" nameend="col3" align="left">orange</entry></row><row><entry namest="col1" nameend="col1" align="left">1- (2-sulfonic acid-4-chloro-5-carboxylic acid-1-phenylazo) -2-</entry><entry namest="col2" nameend="col2" align="left">15525</entry><entry namest="col3" nameend="col3" align="left">red</entry></row><row><entry namest="col1" nameend="col1" align="left">hydroxynaphthalene 1- (3-methylphenylazo-4-sulfonic acid) -2-hydroxynaphthalene</entry><entry namest="col2" nameend="col2" align="left">15580</entry><entry namest="col3" nameend="col3" align="left">red</entry></row><row><entry namest="col1" nameend="col1" align="left">1- (4 ', (8') - sulfonic acid naphthylazo) -2-hydroxynaphthalene</entry><entry namest="col2" nameend="col2" align="left">15620</entry><entry namest="col3" nameend="col3" align="left">red</entry></row><row><entry namest="col1" nameend="col1" align="left">2-hydroxy-1,2'-azonaphthalene-1'-sulfonic acid</entry><entry namest="col2" nameend="col2" align="left">15630</entry><entry namest="col3" nameend="col3" align="left">red</entry></row><row><entry namest="col1" nameend="col1" align="left">3-Hydroxy-4-phenylazo-2-naphthylcarboxylic acid</entry><entry namest="col2" nameend="col2" align="left">15800</entry><entry namest="col3" nameend="col3" align="left">red</entry></row><row><entry namest="col1" nameend="col1" align="left">1- (2-sulfo-4-methyl-1-phenylazo) -2-naphthylcarboxylic acid</entry><entry namest="col2" nameend="col2" align="left">15850</entry><entry namest="col3" nameend="col3" align="left">red</entry></row><row><entry namest="col1" nameend="col1" align="left">1- (2-sulfo-4-methyl-5-chloro-1-phenylazo) -2-hydroxy-</entry><entry namest="col2" nameend="col2" align="left">15865</entry><entry namest="col3" nameend="col3" align="left">red</entry></row><row><entry namest="col1" nameend="col1" align="left">naphthalene-3-carboxylic acid 1- (2-sulfo-1-naphthylazo) -2-hydroxynaphthalene-3-carboxylic acid</entry><entry namest="col2" nameend="col2" align="left">15880</entry><entry namest="col3" nameend="col3" align="left">red</entry></row><row><entry namest="col1" nameend="col1" align="left">1- (3-sulfo-1-phenylazo) -2-naphthol-6-sulfonic acid</entry><entry namest="col2" nameend="col2" align="left">15980</entry><entry namest="col3" nameend="col3" align="left">orange</entry></row><row><entry namest="col1" nameend="col1" align="left">1- (4-sulfo-1-phenylazo) -2-naphthol-6-sulfonic acid</entry><entry namest="col2" nameend="col2" align="left">15985</entry><entry namest="col3" nameend="col3" align="left">yellow</entry></row><row><entry namest="col1" nameend="col1" align="left">Allura Red</entry><entry namest="col2" nameend="col2" align="left">16035</entry><entry namest="col3" nameend="col3" align="left">red</entry></row><row><entry namest="col1" nameend="col1" align="left">1- (4-sulfo-1-naphthylazo) -2-naphthol-3,6-disulfonic acid</entry><entry namest="col2" nameend="col2" align="left">16185</entry><entry namest="col3" nameend="col3" align="left">red</entry></row><row><entry namest="col1" nameend="col1" align="left">Acid Orange 10</entry><entry namest="col2" nameend="col2" align="left">16230</entry><entry namest="col3" nameend="col3" align="left">orange</entry></row><row><entry namest="col1" nameend="col1" align="left">1- (4-sulfo-1-naphthylazo) -2-naphthol-6,8-disulfonic acid</entry><entry namest="col2" nameend="col2" align="left">16255</entry><entry namest="col3" nameend="col3" align="left">red</entry></row><row><entry namest="col1" nameend="col1" align="left">1- (4-sulfo-1-naphthylazo) -2-naphthol-3,6,8-trisulfonic acid</entry><entry namest="col2" nameend="col2" align="left">16290</entry><entry namest="col3" nameend="col3" align="left">red</entry></row><row><entry namest="col1" nameend="col1" align="left">8-amino-2-phenylazo-1-naphthol-3,6-disulfonic acid</entry><entry namest="col2" nameend="col2" align="left">17200</entry><entry namest="col3" nameend="col3" align="left">red</entry></row><row><entry namest="col1" nameend="col1" align="left">Acid Red 1</entry><entry namest="col2" nameend="col2" align="left">18050</entry><entry namest="col3" nameend="col3" align="left">red</entry></row><row><entry namest="col1" nameend="col1" align="left">Acid Red 155</entry><entry namest="col2" nameend="col2" align="left">18130</entry><entry namest="col3" nameend="col3" align="left">red</entry></row><row><entry namest="col1" nameend="col1" align="left">Acid Yellow 121</entry><entry namest="col2" nameend="col2" align="left">18690</entry><entry namest="col3" nameend="col3" align="left">yellow</entry></row><row><entry namest="col1" nameend="col1" align="left">Acid Red 180</entry><entry namest="col2" nameend="col2" align="left">18736</entry><entry namest="col3" nameend="col3" align="left">red</entry></row><row><entry namest="col1" nameend="col1" align="left">Acid Yellow 11</entry><entry namest="col2" nameend="col2" align="left">18820</entry><entry namest="col3" nameend="col3" align="left">yellow</entry></row><row><entry namest="col1" nameend="col1" align="left">Acid Yellow 17</entry><entry namest="col2" nameend="col2" align="left">18965</entry><entry namest="col3" nameend="col3" align="left">yellow</entry></row><row><entry namest="col1" nameend="col1" align="left">4- (4-Sulfo-1-phenylazo) -1- (4-sulfophenyl) -5-hydroxypyrazolone-3-carboxylic acid</entry><entry namest="col2" nameend="col2" align="left">19140</entry><entry namest="col3" nameend="col3" align="left">yellow</entry></row><row><entry namest="col1" nameend="col1" align="left">Pigment Yellow 16</entry><entry namest="col2" nameend="col2" align="left">20040</entry><entry namest="col3" nameend="col3" align="left">yellow</entry></row><row><entry namest="col1" nameend="col1" align="left">2,6- (4'-sulfo-2 ", 4" -dimethyl) bis-phenylazo) 1,3-dihydroxybenzene</entry><entry namest="col2" nameend="col2" align="left">20170</entry><entry namest="col3" nameend="col3" align="left">orange</entry></row><row><entry namest="col1" nameend="col1" align="left">Acid Black 1</entry><entry namest="col2" nameend="col2" align="left">20470</entry><entry namest="col3" nameend="col3" align="left">Black</entry></row><row><entry namest="col1" nameend="col1" align="left">Pigment Yellow 13</entry><entry namest="col2" nameend="col2" align="left">21100</entry><entry namest="col3" nameend="col3" align="left">yellow</entry></row><row><entry namest="col1" nameend="col1" align="left">Pigment Yellow 83</entry><entry namest="col2" nameend="col2" align="left">21108</entry><entry namest="col3" nameend="col3" align="left">yellow</entry></row><row><entry namest="col1" nameend="col1" align="left">Solvent yellow</entry><entry namest="col2" nameend="col2" align="left">21230</entry><entry namest="col3" nameend="col3" align="left">yellow</entry></row><row><entry namest="col1" nameend="col1" align="left">Acid Red 163</entry><entry namest="col2" nameend="col2" align="left">24790</entry><entry namest="col3" nameend="col3" align="left">red</entry></row><row><entry namest="col1" nameend="col1" align="left">Acid Red 73</entry><entry namest="col2" nameend="col2" align="left">27290</entry><entry namest="col3" nameend="col3" align="left">red</entry></row><row><entry namest="col1" nameend="col1" align="left">2- [4 '- (4 "-sulfo-1" -phenylazo) -7'-sulfo-1'-naphthylazo] -1-hydroxy-7-aminonaphthalene-3,6-disulfonic acid</entry><entry namest="col2" nameend="col2" align="left">27755</entry><entry namest="col3" nameend="col3" align="left">black</entry></row><row><entry namest="col1" nameend="col1" align="left">4 '- [(4 "-Sulfo-1" phenylazo) -7'-sulfo-1'-naphthylazo] -1-hydroxy-8-acetylaminonaphthalene-3,5-disulfonic acid</entry><entry namest="col2" nameend="col2" align="left">28440</entry><entry namest="col3" nameend="col3" align="left">black</entry></row><row><entry namest="col1" nameend="col1" align="left">Direct Orange 34, 39, 44, 46, 60</entry><entry namest="col2" nameend="col2" align="left">40215</entry><entry namest="col3" nameend="col3" align="left">orange</entry></row><row><entry namest="col1" nameend="col1" align="left">Food yellow</entry><entry namest="col2" nameend="col2" align="left">40800</entry><entry namest="col3" nameend="col3" align="left">orange</entry></row><row><entry namest="col1" nameend="col1" align="left">trans-ß-apo-8'-carotenaldehyde (C₃₀)</entry><entry namest="col2" nameend="col2" align="left">40820</entry><entry namest="col3" nameend="col3" align="left">orange</entry></row><row><entry namest="col1" nameend="col1" align="left">trans-apo-8'-carotenic acid (C₃₀) ethyl ester</entry><entry namest="col2" nameend="col2" align="left">40825</entry><entry namest="col3" nameend="col3" align="left">orange</entry></row><row><entry namest="col1" nameend="col1" align="left">Canthaxanthin</entry><entry namest="col2" nameend="col2" align="left">40850</entry><entry namest="col3" nameend="col3" align="left">orange</entry></row><row><entry namest="col1" nameend="col1" align="left">Acid Blue 1</entry><entry namest="col2" nameend="col2" align="left">42045</entry><entry namest="col3" nameend="col3" align="left">blue</entry></row><row><entry namest="col1" nameend="col1" align="left">2,4-disulfo-5-hydroxy-4'-4 "bis (diethylamino) triphenylcarbinol</entry><entry namest="col2" nameend="col2" align="left">42051</entry><entry namest="col3" nameend="col3" align="left">blue</entry></row><row><entry namest="col1" nameend="col1" align="left">4 - [(- 4-N-ethyl-p-sulfobenzylamino) phenyl- (4-hydroxy-2-sulfophenyl) - (methylene) -1- (N-ethylN-p-sulfobenzyl) -2,5-cyclohexadienimine]</entry><entry namest="col2" nameend="col2" align="left">42053</entry><entry namest="col3" nameend="col3" align="left">green</entry></row><row><entry namest="col1" nameend="col1" align="left">Acid Blue 7</entry><entry namest="col2" nameend="col2" align="left">42080</entry><entry namest="col3" nameend="col3" align="left">blue</entry></row><row><entry namest="col1" nameend="col1" align="left">(N-ethyl-p-sulfobenzyl-amino) -phenyl- (2-sulfophenyl) -methylene- (N-ethyl-Np-sulfo-benzyl) Δ^2,5-cyclohexadienimine</entry><entry namest="col2" nameend="col2" align="left">42090</entry><entry namest="col3" nameend="col3" align="left">blue</entry></row><row><entry namest="col1" nameend="col1" align="left">Acid Green 9</entry><entry namest="col2" nameend="col2" align="left">42100</entry><entry namest="col3" nameend="col3" align="left">green</entry></row><row><entry namest="col1" nameend="col1" align="left">Diethyl-di-sulfobenzyl-di-4-amino-2-chloro-di-2-methylfuchsonimmonium</entry><entry namest="col2" nameend="col2" align="left">42170</entry><entry namest="col3" nameend="col3" align="left">green</entry></row><row><entry namest="col1" nameend="col1" align="left">Basic Violet 14</entry><entry namest="col2" nameend="col2" align="left">42510</entry><entry namest="col3" nameend="col3" align="left">violet</entry></row><row><entry namest="col1" nameend="col1" align="left">Basic Violet 2</entry><entry namest="col2" nameend="col2" align="left">42520</entry><entry namest="col3" nameend="col3" align="left">violet</entry></row><row><entry namest="col1" nameend="col1" align="left">2'-Methyl-4 '- (N-ethyl-Nm-sulfobenzyl) -amino-4 "- (N-diethyl) -amino-2-methyl-N-ethyl-Nm-sulfobenzyl-fuchsonimmonium</entry><entry namest="col2" nameend="col2" align="left">42735</entry><entry namest="col3" nameend="col3" align="left">blue</entry></row><row><entry namest="col1" nameend="col1" align="left">4 '- (N-Dimethyl) amino-4 "- (N-phenyl) -aminonaphtho-N-dimethyl-fuchsonimmonium</entry><entry namest="col2" nameend="col2" align="left">44045</entry><entry namest="col3" nameend="col3" align="left">blue</entry></row><row><entry namest="col1" nameend="col1" align="left">2-hydroxy-3,6-disulfo-4,4'-bis-dimethylaminonaphthofuchsonimmonium</entry><entry namest="col2" nameend="col2" align="left">44090</entry><entry namest="col3" nameend="col3" align="left">green</entry></row><row><entry namest="col1" nameend="col1" align="left">Acid Red 52</entry><entry namest="col2" nameend="col2" align="left">45100</entry><entry namest="col3" nameend="col3" align="left">red</entry></row><row><entry namest="col1" nameend="col1" align="left">3- (2'-Methylphenylamino) -6- (2'-methyl-4'-sulfophenylamino) -9- (2 "-carboxyphenyl) xanthenium salt</entry><entry namest="col2" nameend="col2" align="left">45190</entry><entry namest="col3" nameend="col3" align="left">violet</entry></row><row><entry namest="col1" nameend="col1" align="left">Acid Red 50</entry><entry namest="col2" nameend="col2" align="left">45220</entry><entry namest="col3" nameend="col3" align="left">red</entry></row><row><entry namest="col1" nameend="col1" align="left">Phenyl-2-oxyfluorone-2-carboxylic acid</entry><entry namest="col2" nameend="col2" align="left">45350</entry><entry namest="col3" nameend="col3" align="left">yellow</entry></row><row><entry namest="col1" nameend="col1" align="left">4,5-dibromofluorescein</entry><entry namest="col2" nameend="col2" align="left">45370</entry><entry namest="col3" nameend="col3" align="left">orange</entry></row><row><entry namest="col1" nameend="col1" align="left">2,4,5,7-tetrabromofluorescein</entry><entry namest="col2" nameend="col2" align="left">45380</entry><entry namest="col3" nameend="col3" align="left">red</entry></row><row><entry namest="col1" nameend="col1" align="left">Solvent dye</entry><entry namest="col2" nameend="col2" align="left">45396</entry><entry namest="col3" nameend="col3" align="left">orange</entry></row><row><entry namest="col1" nameend="col1" align="left">Acid Red 98</entry><entry namest="col2" nameend="col2" align="left">45405</entry><entry namest="col3" nameend="col3" align="left">red</entry></row><row><entry namest="col1" nameend="col1" align="left">3 ', 4', 5 ', 6'-tetrachloro-2,4,5,7-tetrabromofluorescein</entry><entry namest="col2" nameend="col2" align="left">45410</entry><entry namest="col3" nameend="col3" align="left">red</entry></row><row><entry namest="col1" nameend="col1" align="left">4,5-diiodofluorescein</entry><entry namest="col2" nameend="col2" align="left">45425</entry><entry namest="col3" nameend="col3" align="left">red</entry></row><row><entry namest="col1" nameend="col1" align="left">2,4,5,7-tetraiodofluorescein</entry><entry namest="col2" nameend="col2" align="left">45430</entry><entry namest="col3" nameend="col3" align="left">red</entry></row><row><entry namest="col1" nameend="col1" align="left">Quinophthalone</entry><entry namest="col2" nameend="col2" align="left">47000</entry><entry namest="col3" nameend="col3" align="left">yellow</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">Quinophthalone disulfonic acid</entry><entry namest="col2" nameend="col2" align="left">47005</entry><entry namest="col3" nameend="col3" align="left">yellow</entry></row></tbody></tgroup></table></tables>

0087It may also be advantageous to choose one or more substances from the following group as the dye: 2,4-dihydroxyazobenzene, 1- (2'-chloro-4'-nitro-1'-phenylazo) -2-hydroxynaphthalene, ceres red, 2- (4-sulfo-1-naphthylazo) -1-naphthol-4-sulfonic acid , Calcium salt of 2-hydroxy-1,2'-azonaphthalene-1'-sulfonic acid, calcium and barium salts of 1- (2-sulfo-4-methyl-1-phenylazo) -2-naphthylcarboxylic acid, calcium salt of 1- (2nd -Sulfo-1-naphthylazo) -2-hydroxynaphthalene-3-carboxylic acid, aluminum salt of 1- (4-sulfo-1-phenylazo) -2-naphthol-6-sulfonic acid, Aluminum salt of 1- (4-sulfo-1-naphthylazo) -2-naphthol-3,6-disulfonic acid, 1- (4-sulfo-1-naphthylazo) -2-naphthol-6,8-disulfonic acid, aluminum salt of 8- Amino-2-phenylazo-1-naphthol-3,6-disulfonic acid, aluminum salt of 4- (4-sulfo-1-phenylazo) -1 - (4-sulfophenyl) -5-hydroxy-pyrazolone-3-carboxylic acid, 4 ' - [(4 "-Sulfo-1" -phenylazo) -7'-sulfo-1'-naphthylazo] -1-hydroxy-8-acetylaminonaphthalene-3,5-disulfonic acid, aluminum and zirconium salts of 4.5- Dibromofluorescein, Aluminum and zirconium salts of 2,4,5,7-tetrabromofluorescein, 3 ', 4', 5 ', 6'-tetrachloro-2,4,5,7-tetrabromofluorescein and its aluminum salt, aluminum salt of 2,4,5, 7-tetraiodofluorescein, aluminum salt of quinophthalone disulfonic acid, aluminum salt of indigodisulfonic acid, 4,4'-dimethyl-6,6'-dichlorothioindigo, complex salt (Na, Al, Ca) of carminic acid, red and black iron oxide (CIN: 77 491 (red ) and 77 499 (black)), iron oxide hydrate (CIN: 77 492), manganese ammonium diphosphate (CIN 77745), ultramarine (CIN 77007) and titanium dioxide.

0088Titanium dioxides according to the invention, which can be present both in the rutile and anatase crystal modification, are advantageously surface-treated ("coated") for the purposes of the present invention, where, for example, a hydrophilic, amphiphilic or hydrophobic character is to be formed or retained. This surface treatment can consist in that the pigments are provided with a thin hydrophilic and / or hydrophobic inorganic and / or organic layer by methods known per se. For the purposes of the present invention, the various surface coatings can also contain water.

0089Inorganic surface coatings in the sense of the present invention can consist of aluminum oxide (Al₂O₃), Aluminum hydroxide Al (OH)₃, or aluminum oxide hydrate (also: alumina, CAS no .: 1333-84-2), sodium hexametaphosphate (NaPO₃)₆, Sodium metaphosphate (NaPO₃)_n, Silicon dioxide (SiO₂) (also: silica, CAS No .: 7631-86-9), zirconium oxide (ZrO₂) or iron oxide (Fe₂O₃). These inorganic surface coatings can occur alone, in combination and / or in combination with organic coating materials. For this purpose, oxides, oxide hydrates or phosphates, for example of the elements Al, Si, Zr, are struck in dense layers on the pigment surface. The inorganic aftertreatment generally takes place in an aqueous suspension of the pigment by adding soluble aftertreatment chemicals, such as, for example Aluminum sulfate, and subsequent precipitation of the hydroxide, which is sparingly soluble in the neutral range, by specifically adjusting the pH with sodium hydroxide solution. After the inorganic aftertreatment, the coated pigments are separated from the suspension by filtration and washed carefully to remove the dissolved salts, and then the isolated pigments are dried.

0090For the purposes of this invention, particular preference is given to titanium dioxides to which aluminum hydroxide has been applied to the surface, such as, for example, the titanium dioxide types C47-051 and C47- 5175 available from Sun Chemical. Further preferred pigments are titanium dioxides containing aluminum and / or silicon oxides are coated, such as from Krosnos Titan: Kronos 1071 and 1075 or from Kingfisher: A310.03 Tudor Aspen.

0091Organic surface coatings in the sense of the present invention can consist of vegetable or animal aluminum stearate, vegetable or animal stearic acid, lauric acid, dimethylpolysiloxane (also: dimethicone), methylpolysiloxane (methicone), simethicone (a mixture of dimethylpolysiloxane with an average chain length of 200 to 350 dimethylsiloxane Units and silica gel) or alginic acid. These organic surface coatings can occur alone, in combination and / or in combination with inorganic coating materials.

0092Furthermore, it can be advantageous to use pearlescent pigments according to the invention. These include natural pearlescent pigments, such as B.<ul id="ul0007" list-style="none" compact="compact"><li>■ "fish silver" (guanine / hypoxanthine mixed crystals from fish scales) and</li><li>■ "mother-of-pearl" (ground mussel shells),</li></ul> monocrystalline pearlescent pigments such as B. bismuth oxychloride (BiOCl), Layer-substrate pigments: e.g. B. mica / metal oxide

0093Pearlescent pigments are based, for example, on powdered pigments or castor oil dispersions of bismuth oxychloride and / or titanium dioxide and bismuth oxychloride and / or titanium dioxide on mica. Particularly advantageous is e.g. B. the gloss pigment listed under CIN 77163.

0094The following pearlescent pigment types based on mica / metal oxide are also advantageous: <tables id="tabl0004" num="0004"><table frame="all"><tgroup cols="3" colsep="1" rowsep="1"><colspec colnum="1" colname="col1" colwidth="52.50mm" /><colspec colnum="2" colname="col2" colwidth="52.50mm" /><colspec colnum="3" colname="col3" colwidth="52.50mm" /><thead valign="top"><row><entry namest="col1" nameend="col1" align="left"><b><i>group</i></b></entry><entry namest="col2" nameend="col2" align="left">Coverage / layer thickness</entry><entry namest="col3" nameend="col3" align="left">colour</entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left"><b>Silver-white pearlescent pigments</b></entry><entry namest="col2" nameend="col2" align="left">TiO₂: 40 - 60 nm</entry><entry namest="col3" nameend="col3" align="left">silver</entry></row><row><entry namest="col1" nameend="col1" align="left"><b>Interference pigments</b></entry><entry namest="col2" nameend="col2" align="left">TiO₂: 60 - 80 nm</entry><entry namest="col3" nameend="col3" align="left">yellow</entry></row><row><entry namest="col1" nameend="col1" /><entry namest="col2" nameend="col2" align="left">TiO₂: 80-100 nm</entry><entry namest="col3" nameend="col3" align="left">red</entry></row><row><entry namest="col1" nameend="col1" /><entry namest="col2" nameend="col2" align="left">TiO₂: 100 - 140 nm</entry><entry namest="col3" nameend="col3" align="left">blue</entry></row><row><entry namest="col1" nameend="col1" /><entry namest="col2" nameend="col2" align="left">TiO₂: 120-160 nm</entry><entry namest="col3" nameend="col3" align="left">green</entry></row><row><entry namest="col1" nameend="col1" align="left"><b>Colored gloss pigments</b></entry><entry namest="col2" nameend="col2" align="left">Fe₂O₃</entry><entry namest="col3" nameend="col3" align="left">bronze</entry></row><row><entry namest="col1" nameend="col1" /><entry namest="col2" nameend="col2" align="left">Fe₂O₃</entry><entry namest="col3" nameend="col3" align="left">copper</entry></row><row><entry namest="col1" nameend="col1" /><entry namest="col2" nameend="col2" align="left">Fe₂O₃</entry><entry namest="col3" nameend="col3" align="left">red</entry></row><row><entry namest="col1" nameend="col1" /><entry namest="col2" nameend="col2" align="left">Fe₂O₃</entry><entry namest="col3" nameend="col3" align="left">red violet</entry></row><row><entry namest="col1" nameend="col1" /><entry namest="col2" nameend="col2" align="left">Fe₂O₃</entry><entry namest="col3" nameend="col3" align="left">Red Green</entry></row><row><entry namest="col1" nameend="col1" /><entry namest="col2" nameend="col2" align="left">Fe₂O₃</entry><entry namest="col3" nameend="col3" align="left">black</entry></row><row><entry namest="col1" nameend="col1" align="left"><b>Combination pigments</b></entry><entry namest="col2" nameend="col2" align="left">TiO₂ / Fe₂O₃</entry><entry namest="col3" nameend="col3" align="left">Gold tone e</entry></row><row><entry namest="col1" nameend="col1" /><entry namest="col2" nameend="col2" align="left">TiO₂ / Cr₂O₃</entry><entry namest="col3" nameend="col3" align="left">green</entry></row><row><entry namest="col1" nameend="col1" /><entry namest="col2" nameend="col2" align="left">TiO₂ / Berlin blue</entry><entry namest="col3" nameend="col3" align="left">deep blue</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" /><entry namest="col2" nameend="col2" align="left">TiO₂ / Carmin</entry><entry namest="col3" nameend="col3" align="left">red</entry></row></tbody></tgroup></table></tables>

0095The pearlescent pigments available from Merck under the trade names Timiron, Colorona or Dichrona are particularly preferred.

0096The list of the pearlescent pigments mentioned is of course not intended to be limiting. Pearlescent pigments which are advantageous in the sense of the present invention are obtainable in numerous ways known per se. For example, other substrates besides mica can be coated with other metal oxides, such as. B. silica and the like. Z are advantageous. B. with TiO₂ and Fe₂O₃ coated SiO₂Particles ("Ronaspheren"), which are distributed by the Merck company.

0097It can also be advantageous to completely do without a substrate such as mica. Pearlescent pigments which use SiO are particularly preferred₂ getting produced. Such pigments, which can also have gonichromatic effects, are e.g. B. available under the trade name Sicopearl Fantastico from BASF.

0098Pigments from Engelhard / Mearl based on calcium sodium borosilicate, which are coated with titanium dioxide, can also be used advantageously. These are available under the name Reflecks. Due to their particle size of 40 - 180 µm they have a glitter effect in addition to the color.

0099The dyes and pigments can be present both individually and in a mixture and can be coated with one another, different color effects generally being produced by different coating thicknesses.

0100The pigment pigments which are particularly preferred according to the invention are the blue pigments listed, such as INCI: Cl 77007, Outremer Supercosmetique W 6803 from Les Colorants Wackherr, INCI: Cl 77891 + Mica + Silica, Timiron Splendid Blue from Merck.

0101Also preferred according to the invention are mica coated with titanium dioxide and silicon dioxide, for example INCI: Mica + Cl 77891 + silica, Timiron Arctic Silver from Merck, INCl: Mica + Cl 77891, Timiron Gleamer Flake MP-45 from Merck; aluminum oxide or silicon dioxide coated with titanium dioxide and tin oxide, for example INCI: Silica + Cl 77891 + Tin Oxide, Xirona Magic Mauve from Merck; e.g. INCI: Alumina + Cl 77891 + Tin Oxide, Xirona Silver, with titanium dioxide and Berlin blue coated mica, e.g. INCI: Mica + Cl 77891 + Cl 77510, Colorona Light Blue and Colorona Dark Blue from Merck.

Pearlescent:

0102Also preferred is the use of pearlescent agents based on dialkyl ethers which are solid at 30 ° C. and have, for example: the following formula: RO-R '. R and R 'can be the same or different; straight-chain or branched, saturated or unsaturated alkyl radicals. These can consist of 12 to 30 carbon atoms, preferably 14 to 24 carbon atoms. R and R 'particularly preferably consist of a stearyl radical (for example INCI: distearyl ether, Cutina STE from Cognis). The dialkyl ethers used are insoluble in water at a concentration of more than 0.1% at 25 ° C.

0103Acylated radicals consisting of a fatty acid chain with 8 to 30 carbon atoms can preferably also be used. Each acylated derivative contains at least one RC (= O) group, where R is a fatty acid chain with 8 to 30 carbon atoms. In particular ethylene glycol monostearate and ethylene glycol distearate, e.g. INCI: Glycol Distearate, Cutina AGS from Cognis, INCI: Aqua + Glycol Distearate + Glycerin + Laureth-4 + Cocamidopropyl Betaine, Euperlan PK 3000 OK from Cognis, INCI: PEG-3 Distearate, Cutina TS from Cognis. According to the invention, these are advantageously used in a concentration between 0.5% and 2%.

Opacifiers:

0104The use of opacifiers is also advantageously possible according to the invention. The sodium salts of a polymer made of styrene with a monomer consisting of acrylic acid, methacrylic acid or another olefin and one of their esters, for example INCI: sodium styrene / acrylates copolymer, Acusol OP 301 from Rohm &amp; Haas, are preferred. According to the invention, these are advantageously used in a concentration between 0.5% and 2%.

0105Glitter and glitter particles can also advantageously be present in at least one of the preparations according to the invention.

0106According to the invention, the preparations according to the invention can advantageously contain one or more surfactants, it being possible to use both anionic, cationic, nonionic and zwitterionic surfactants.

0107Advantageous wash-active anionic surfactants for the purposes of the present invention are acylamino acids and their salts, such as<ul id="ul0008" list-style="none" compact="compact"><li>■ acylglutamates, especially sodium acylglutamate</li><li>Sarcosinates, for example myristoyl sarcosin, TEA lauroyl sarcosinate, sodium lauroyl sarcosinate and sodium cocoyl sarcosinate,</li></ul>

0108Sulfonic acids and their salts, such as<ul id="ul0009" list-style="none" compact="compact"><li>Acyl isethionates, for example sodium / ammonium cocoyl isethionate,</li><li>Sulfosuccinates, for example dioctyl sodium sulfosuccinate, disodium laureth sulfosuccinate, disodium lauryl sulfosuccinate and disodium undecylenamido MEA sulfosuccinate, disodium PEG-5 lauryl citrate sulfosuccinate and derivatives,</li></ul> as well as sulfuric acid esters, such as<ul id="ul0010" list-style="none" compact="compact"><li>■ Alkyl ether sulfate, for example sodium, ammonium, magnesium, MIPA, TIPA laureth sulfate, sodium myreth sulfate and sodium C._12-13 Parethsulfate,</li><li>■ Alkyl sulfates, for example sodium, ammonium and TEA lauryl sulfate.</li></ul>

0109Advantageous wash-active cationic surfactants for the purposes of the present invention are quaternary surfactants. Quaternary surfactants contain at least one N atom that is covalently linked to 4 alkyl or aryl groups. For example, alkyl betaine, alkyl amidopropyl betaine and alkyl amidopropyl hydroxysultain are advantageous.

0110Advantageous wash-active amphoteric surfactants for the purposes of the present invention are<ul id="ul0011" list-style="none" compact="compact"><li>Acyl- / dialkylethylenediamines, for example sodium acylamphoacetate, disodium acylamphodipropionate, disodium alkylamphodiacetate, sodium acylamphohydroxypropylsulfonate, disodium acylamphodiacetate and sodium acylamphopropionate,</li></ul>

0111Advantageous wash-active non-ionic surfactants for the purposes of the present invention are<ul id="ul0012" list-style="none" compact="compact"><li>Alkanolamides, such as Cocamide MEA / DEA / MIPA,</li><li>Esters which are formed by esterification of carboxylic acids with ethylene oxide, glycerol, sorbitan or other alcohols,</li><li>■ ethers, for example ethoxylated alcohols, ethoxylated lanolin, ethoxylated polysiloxanes, propoxylated POE ethers and alkyl polyglycosides such as lauryl glucoside, decyl glycoside and cocoglycoside.</li></ul>

0112Other advantageous anionic surfactants are<ul id="ul0013" list-style="none" compact="compact"><li>■ taurates, for example sodium lauroyl taurate and sodium methyl cocoyl taurate,</li><li>■ ether carboxylic acids, for example sodium laureth-13 carboxylate and sodium PEG-6 cocamide carboxylate, sodium PEG-7 olive oil carboxylate</li><li>Phosphoric acid esters and salts, such as DEA-Oleth-10 phosphate and dilaureth-4 phosphate,</li><li>■ Alkyl sulfonates, for example sodium cocosmonoglyceride sulfate, sodium C._12-14 Olefin sulfonate, sodium lauryl sulfoacetate and magnesium PEG-3 cocamide sulfate.</li></ul>

0113Other advantageous amphoteric surfactants are<ul id="ul0014" list-style="none" compact="compact"><li>■ N-alkylamino acids, for example aminopropylalkylglutamide, alkylaminopropionic acid, sodium alkylimidodipropionate and lauroamphocarboxyglycinate and N-coconut fatty acid amidoethyl-N-hydroxyethylglycinate sodium salts and their derivatives.</li></ul>

0114Further advantageous non-ionic surfactants are alcohols.

0115Other suitable anionic surfactants for the purposes of the present invention are also<ul id="ul0015" list-style="none" compact="compact"><li>Acylglutamates such as di-TEA-palmitoylaspartate and sodium caprylic / capric glutamate,</li><li>■ Acyl peptides, for example palmitoyl hydrolyzed milk protein, sodium cocoyl hydrolyzed soy protein and sodium / potassium cocoyl hydrolyzed collagen</li></ul> as well as carboxylic acids and derivatives, such as<ul id="ul0016" list-style="none" compact="compact"><li>For example lauric acid, aluminum stearate, magnesium alkanolate and zinc undecylenate,</li><li>Ester carboxylic acids, for example calcium stearoyl lactylate, laureth-6 citrate and sodium PEG-4 lauramide carboxylate,</li><li>■ alkylarylsulfonates.</li></ul>

0116Other suitable cationic surfactants for the purposes of the present invention are also<ul id="ul0017" list-style="none" compact="compact"><li>■ alkylamines,</li><li>Alkylimidazoles,</li><li>■ ethoxylated amines</li></ul> especially their salts.

0117Other suitable nonionic surfactants for the purposes of the present invention are also amine oxides, such as cocoamidopropylamine oxide.

0118It is advantageous to choose the wash-active surfactant or surfactants according to the invention from the group of surfactants which have an HLB value of more than 25, particularly advantageous are those which have an HLB value of more than 35.

0119Alkyl sulfates or alkyl ether sulfates or a surfactant combination of alkyl ether sulfates with amphoteric or nonionic surfactants are preferred according to the invention, a surfactant combination of alkyl ether sulfates with alkylamidopropyl betaines or alkyl amphoacetates or alkyl polyglucosides being particularly preferred. Combinations of alkyl ether sulfates with alkylamidopropyl betaines or alkyl amphoacetates and acyl glutamates are also particularly preferred.

0120For the purposes of the present invention, it is advantageous if the content of one or more detergent surfactants in the corresponding preparation is in the range from 1 to 30% by weight, preferably from 5 to 25% by weight, very particularly advantageously from 10 to 20% by weight is selected, in each case based on the total weight of the preparation.

0121Preparations containing surfactant can advantageously be used according to the invention as cleaning preparations. The surfactant content in the preparations according to the invention can, however, advantageously also be used according to the invention for foaming the preparations (embodiment: foam dispenser).

0122The preparations according to the invention can advantageously contain polysorbates. Polysorbates are a class of compounds derived from sorbitan, a furan derivative obtained from sorbitol by splitting off two equivalents of water. The hydroxyl groups of sorbitan are etherified with polyethylene glycols, the ends of which can be esterified with fatty acids. They can be generalized by the formula<chemistry id="chem0009" num="0009"><img file="EP1531129A1_D0009.tif" /></chemistry> R₁, R₂, R₃ = H, fatty acid residue represent.

0123Polysorbates which are advantageous in the sense of the invention are, for example<ul id="ul0018" list-style="dash" compact="compact"><li>Polyoxyethylene (20) sorbitan monolaurate (Tween 20, CAS No. 9005-64-5)</li><li>Polyoxyethylene (4) sorbitan monolaurate (Tween 21, CAS No. 9005-64-5)</li><li>Polyoxyethylene (4) sorbitan monostearate (Tween 61, CAS No. 9005-67-8)</li><li>Polyoxyethylene (20) sorbitan tristearate (Tween 65, CAS No. 9005-71-4)</li><li>Polyoxyethylene (20) sorbitan monooleate (Tween 80, CAS No. 9005-65-6)</li><li>Polyoxyethylene (5) sorbitan monooleate (Tween 81, CAS No. 9005-65-5)</li><li>Polyoxyethylene (20) sorbitan trioleate (Tween 85, CAS No. 9005-70-3).</li></ul>

0124According to the invention, these are advantageously used in a concentration of 0.1 to 5% by weight and in particular in a concentration of 1.5 to 2.5% by weight, based on the total weight of the preparation, individually or as a mixture of several polysorbates.

Hydrocolloids

0125The preparations according to the invention advantageously contain one or more hydrocolloids. "Hydrocolloid" is the technological short name for the more correct term "hydrophilic colloid". Hydrocolloids, also called thickeners or gel formers, are macromolecules that have a largely linear shape and have intermolecular interaction forces that enable secondary and main valence bonds between the individual molecules and thus enable the formation of a network-like structure. They are partially water-soluble natural or synthetic polymers that form gels or viscous solutions in aqueous systems. They increase the viscosity of the water by either binding water molecules (hydration) or by absorbing and enveloping the water in their intertwined macromolecules, while at the same time restricting the mobility of the water. Such water-soluble polymers represent a large group of chemically very different natural and synthetic polymers, the common feature of which is their solubility in water or aqueous media. The prerequisite for this is that these polymers have a sufficient number of hydrophilic groups for water solubility and are not too strongly crosslinked. The hydrophilic groups can be nonionic, anionic or cationic in nature, for example as follows:<chemistry id="chem0010" num="0010"><img file="EP1531129A1_D0010.tif" /></chemistry>

0126The group of cosmetically and dermatologically relevant hydrocolloids can be divided as follows:<ul id="ul0019" list-style="none" compact="compact"><li>organic, natural compounds such as agar agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, guar flour, locust bean gum, starch, dextrins, gelatin, casein, organic, modified natural substances, such as. B. carboxymethyl cellulose and other cellulose ethers, hydroxyethyl and propyl cellulose and the like, organic, fully synthetic compounds, such as. B. Polyacrylic and polymethacrylic compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides, inorganic compounds, such as. B. polysilicic acids, clay minerals such as montmorillonites, zeolites, silicas.</li></ul>

0127Hydrocolloids which are advantageous according to the invention are agar agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, guar flour, locust bean gum, starch, dextrins, gelatin, casein, cellulose ethers, hydroxyethyl and propyl cellulose derivatives, polyacrylic and polymethacrylic -Compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides, polysilicic acids, clay minerals, zeolites, silicas are used.

0128Hydrocolloids preferred according to the invention are, for example, methyl celluloses, as the methyl ethers of cellulose are referred to. They are characterized by the following structural formula<chemistry id="chem0011" num="0011"><img file="EP1531129A1_D0011.tif" /></chemistry> in which R can represent a hydrogen or a methyl group.

0129Particularly advantageous for the purposes of the present invention are the cellulose mixed ethers, which are generally also referred to as methyl celluloses and which, in addition to a dominant content of methyl, additionally contain 2-hydroxyethyl, 2-hydroxypropyl or 2-hydroxybutyl groups. (Hydroxypropyl) methyl celluloses are particularly preferred, for example those sold under the trade name Methocel E4M by Dow Chemical Comp. available.

0130Also advantageous according to the invention is sodium carboxymethyl cellulose, the sodium salt of the glycolic acid ether of cellulose, for which R in structural formula I can be a hydrogen and / or CH2-COONa. Particularly preferred is the sodium carboxymethyl cellulose available under the trade name Natrosol Plus 330 CS from Aqualon, also referred to as cellulose gum.

0131For the purposes of the present invention, preference is also given to xanthan (CAS No. 11138-66-2), also called xanthan gum, which is an anionic heteropolysaccharide which is generally formed from corn sugar by fermentation and is isolated as the potassium salt. It is produced by Xanthomonas campestris and some other species under aerobic conditions with a molecular weight of 2 × 106 to 24 × 106. Xanthan is formed from a chain with β-1,4-bound glucose (cellulose) with side chains. The structure of the subgroups consists of glucose, mannose, glucuronic acid, acetate and pyruvate. Xanthan is the name for the first microbial anionic heteropolysaccharide. It is produced by Xanthomonas campestris and some other species under aerobic conditions with a molecular weight of 2-15 106. Xanthan is formed from a chain with β-1,4-bound glucose (cellulose) with side chains. The structure of the subgroups consists of glucose, mannose, glucuronic acid, acetate and pyruvate. The number of pyruvate units determines the viscosity of the xanthane. Xanthan is produced in two-day batch cultures with a yield of 70-90%, based on the carbohydrate used. Yields of 25-30 g / l are achieved. The work-up takes place after killing the culture by precipitation with z. B. 2-propanol. Xanthan is then dried and ground.

0132Another advantageous gelling agent in the sense of the present invention is carrageenan, a gel-forming extract from northern Atlantic, which is similar to agar, and belongs to the florida red algae (Chondrus crispus and Gigartina stellata).

0133The term carrageen is often used for the dried algae product and carrageenan for the extract from it. The carrageenan precipitated from the hot water extract of the algae is a colorless to sand-colored powder with a molecular weight range of 100,000-800,000 and a sulfate content of approx. 25%. Carrageenan, which is very easily soluble in warm water; a thixotropic gel forms on cooling, even if the water content is 95-98%. The firmness of the gel is brought about by the double helix structure of the carrageenan. There are three main components in carrageenan: The gel-forming κ fraction consists of D-galactose-4-sulfate and 3,6-anhydro-α-D-galactose, which are alternately glycosidically linked in the 1,3- and 1,4-positions (In contrast, agar contains 3,6-anhydro-α-L-galactose). The non-gelling λ fraction is composed of 1,3-glycosidically linked D-galactose-2-sulfate and 1,4-linked D-galactose-2,6-disulfate residues u. Easily soluble in cold water. The τ-carrageenan composed of D-galactose-4-sulfate in 1,3-bond and 3,6-anhydro-α-D-galactose-2-sulfate in 1,4-bond is both water-soluble and gel-forming. Other types of carrageenan are also designated with Greek letters: α, β, γ, µ, ν, ξ, π, ω, χ. The type of cations (K⁺, NH₄⁺, N / A⁺, Mg²⁺, Approx²⁺) affects the solubility of carrageenans.

0134Polyacrylates are also advantageous gelators to be used in the sense of the present invention. Polyacrylates which are advantageous according to the invention are acrylate-alkyl acrylate copolymers, in particular those which are selected from the group of the so-called carbomers or carbopols (Carbopol® is actually a registered trademark of NOVEON Inc.). In particular, the acrylate-alkyl acrylate copolymers which are advantageous according to the invention are distinguished by the following structure:<chemistry id="chem0012" num="0012"><img file="EP1531129A1_D0012.tif" /></chemistry>

0135R 'represents a long-chain alkyl radical and x and y numbers which symbolize the respective stoichiometric proportion of the respective comonomers.

0136According to the invention, preference is given to acrylate copolymers and / or acrylate-alkyl acrylate copolymers, which, for example, under the trade names Carbopol® 1382, Carbopol® 981, Carbopol® 980 and Carbopol® 5984, Aqua SF-1 from NOVEON Inc. or as Aculyn® 33 by International Specialty Products Corp. are available.

0137Copolymers of C10-30-alkyl acrylates and one or more monomers of acrylic acid, methacrylic acid or their esters, which are crosslinked with an allyl ether of sucrose or an allyl ether of pentaerythritol, are also advantageous.

0138Compounds which have the INCl name "Acrylates / C 10-30 Alkyl Acrylate Crosspolymer" are advantageous. Particularly advantageous are those available under the trade names Pemulen TR1 and Pemulen TR2 from NOVEON Inc.

0139Also advantageous are compounds which have the INCI name "acrylates / C12-24 pareth-25 acrylate copolymer" (available under the trade names Synthalen® W2000 from 3V Inc.) and the INCI name "acrylates / steareth-20 methacrylate copolymer" "(under the trade name Aculyn® 22 from International Specialty Products Corp. available), the INCI name "acrylates / steareth-20 itaconate copolymer" (available under the trade names Structure 2001® from National Starch), the INCI name "acrylates / aminoacrylates / C10-30 alkyl PEG-20 itaconate copolymer "(available under the Trade Mark Structure Plus® from National Starch) and similar polymers.

0140The hydrocolloids which are particularly preferred according to the invention are: Acrylates Copolymer (AQUA SF-1), Acrylates / C 10-30 Alkyl Acrylate Crosspolyme (Carbopol ETD 2020), Xanthan Gum (Kelter).

0141The preparations according to the invention advantageously contain one or more hydrocolloids / gelling agents in a concentration of 0.1 to 8% by weight, preferably 0.2 to 6% by weight and very particularly preferably 0.3 to 4% by weight. , each based on the total weight of the preparation.

Film maker

0142According to the invention, the preparation can advantageously contain one or more film formers. Advantageous film formers according to the invention can be selected from the compounds listed in the table.<tables id="tabl0005" num="0005"><table frame="all"><tgroup cols="4" colsep="1" rowsep="1"><colspec colnum="1" colname="col1" colwidth="39.37mm" /><colspec colnum="2" colname="col2" colwidth="39.37mm" /><colspec colnum="3" colname="col3" colwidth="39.37mm" /><colspec colnum="4" colname="col4" colwidth="39.37mm" /><thead valign="top"><row><entry namest="col1" nameend="col1" align="left"><b>Designation according to INCI</b></entry><entry namest="col2" nameend="col2" align="left"><b>CAS number</b></entry><entry namest="col3" nameend="col3" align="left"><b>Polymer type</b></entry><entry namest="col4" nameend="col4" align="left"><b>Example (trade name)</b></entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">Polyquaternium-2</entry><entry namest="col2" nameend="col2" align="left">CAS 63451-27-4</entry><entry namest="col3" nameend="col3" align="left">Urea, N, N'- bis [3- (dimethylamino) propyl] -, polymer with 1, 1'-oxybis (2-chloroethane)</entry><entry namest="col4" nameend="col4" align="left">Mirapol® A-15</entry></row><row><entry namest="col1" nameend="col1" align="left">Polyquaternium-5</entry><entry namest="col2" nameend="col2" align="left">CAS 26006-22-4</entry><entry namest="col3" nameend="col3" align="left">Acrylamide, β-methacryloxyethyltriethyl ammonium methosulfate</entry><entry namest="col4" nameend="col4" /></row><row><entry namest="col1" nameend="col1" align="left">Polyquaternium-6</entry><entry namest="col2" nameend="col2" align="left">CAS 26062-79-3</entry><entry namest="col3" nameend="col3" align="left">N, N-dimethyl-N-2-propenyl-2-propene-aminium chloride</entry><entry namest="col4" nameend="col4" align="left">Merquat® 100</entry></row><row><entry namest="col1" nameend="col1" align="left">Polyquaternium-7</entry><entry namest="col2" nameend="col2" align="left">CAS 26590-05-6</entry><entry namest="col3" nameend="col3" align="left">N, N-dimethyl-N-2-propenyl-2-propene-aminium chloride, 2-propenamide</entry><entry namest="col4" nameend="col4" align="left">Merquat® S</entry></row><row><entry namest="col1" nameend="col1" align="left">Polyquaternium-10</entry><entry namest="col2" nameend="col2" align="left">CAS 53568-66-4, 55353-19-0, 54351-50-7, 68610-92-4, 81859-24-7</entry><entry namest="col3" nameend="col3" align="left">Quaternary ammonium salt of hydroxyethyl cellulose</entry><entry namest="col4" nameend="col4" align="left">Celquat® SC-230M</entry></row><row><entry namest="col1" nameend="col1" align="left">Polyquaternium-11</entry><entry namest="col2" nameend="col2" align="left">CAS 53633-54-8</entry><entry namest="col3" nameend="col3" align="left">Vinyl pyrrolidone / dimethyla minoethyl methacrylate copolymer / diethyl sulfate reaction product</entry><entry namest="col4" nameend="col4" align="left">Gafquat®755N</entry></row><row><entry namest="col1" nameend="col1" align="left">Polyquaternium-16</entry><entry namest="col2" nameend="col2" align="left">CAS 29297-55-0</entry><entry namest="col3" nameend="col3" align="left">Vinyl pyrrolidone / vinyl imide azolinum methochloride copolymer</entry><entry namest="col4" nameend="col4" align="left">Luviquat® HM552</entry></row><row><entry namest="col1" nameend="col1" align="left">Polyquaternium-17</entry><entry namest="col2" nameend="col2" align="left">CAS 90624-75-2</entry><entry namest="col3" nameend="col3" /><entry namest="col4" nameend="col4" align="left">Mirapol®AD-1</entry></row><row><entry namest="col1" nameend="col1" align="left">Polyquaternium-19th</entry><entry namest="col2" nameend="col2" align="left">CAS 110736-85-1</entry><entry namest="col3" nameend="col3" align="left">Quaternized water soluble polyvinyl alcohol</entry><entry namest="col4" nameend="col4" /></row><row><entry namest="col1" nameend="col1" align="left">Polyquaternium-20</entry><entry namest="col2" nameend="col2" align="left">CAS 110736-86-2</entry><entry namest="col3" nameend="col3" align="left">Quaternized polyvinyl octadecyl ether dispersible in water</entry><entry namest="col4" nameend="col4" /></row><row><entry namest="col1" nameend="col1" align="left">Polyquaternium-21</entry><entry namest="col2" nameend="col2" /><entry namest="col3" nameend="col3" align="left">Polysiloxane-polydimethyldimethylammonium acetate copolymer</entry><entry namest="col4" nameend="col4" align="left">Abil® B 9905</entry></row><row><entry namest="col1" nameend="col1" align="left">Polyquaternium-22</entry><entry namest="col2" nameend="col2" align="left">CAS 53694-17-0</entry><entry namest="col3" nameend="col3" align="left">Dimethyldiallyl ammonium chloride / acrylic acid copolymer</entry><entry namest="col4" nameend="col4" align="left">Merquat®280</entry></row><row><entry namest="col1" nameend="col1" align="left">Polyquaternium-24</entry><entry namest="col2" nameend="col2" align="left">CAS 107987-23-5</entry><entry namest="col3" nameend="col3" align="left">Polymeric quaternary ammonium salt of hydroxyethyl cellulose</entry><entry namest="col4" nameend="col4" align="left">Quartisoft® LM-200</entry></row><row><entry namest="col1" nameend="col1" align="left">Polyquaternium-28</entry><entry namest="col2" nameend="col2" align="left">CAS 131954-48-8</entry><entry namest="col3" nameend="col3" align="left">Vinyl pyrrolidone / methacrylic amidopropyl trimethyl ammonium chloride copolymer</entry><entry namest="col4" nameend="col4" align="left">Gafquat®HS-100</entry></row><row><entry namest="col1" nameend="col1" align="left">Polyquaternium-29</entry><entry namest="col2" nameend="col2" align="left">CAS 92091-36-6, 148880-30-2</entry><entry namest="col3" nameend="col3" align="left">Chitosan, which reacted with propylene oxide u. was quaternized with epichlorohydrin</entry><entry namest="col4" nameend="col4" align="left">Lexquat® CH</entry></row><row><entry namest="col1" nameend="col1" align="left">Polyquaternium-31</entry><entry namest="col2" nameend="col2" align="left">CAS 136505-02-7, 139767-67-7</entry><entry namest="col3" nameend="col3" align="left">Polymeric, quaternary ammonium salt, which by the reaction of DMAPA acrylates / acrylic acid / acrylic onitrogens copolymers u. Diethyl sulfate is produced</entry><entry namest="col4" nameend="col4" align="left">Hypan® QT 100</entry></row><row><entry namest="col1" nameend="col1" align="left">Polyquaternium-32</entry><entry namest="col2" nameend="col2" align="left">CAS 35429-19-7</entry><entry namest="col3" nameend="col3" align="left">N, N, N-Trimethyl-2 - {[82-methyl-1-oxo-2-propenyl) oxy] ethanolamine chloride, polymer with 2-propenamide</entry><entry namest="col4" nameend="col4" /></row><row><entry namest="col1" nameend="col1" align="left">Polyquaternium-37</entry><entry namest="col2" nameend="col2" align="left">CAS 26161-33-1</entry><entry namest="col3" nameend="col3" /><entry namest="col4" nameend="col4" /></row><row><entry namest="col1" nameend="col1" align="left">Polyquaternium-44</entry><entry namest="col2" nameend="col2" /><entry namest="col3" nameend="col3" align="left">Copolymer quaternary ammonium salt from vinyl pyrrolidone and quaternized imidazoline</entry><entry namest="col4" nameend="col4" /></row><row rowsep="1"><entry namest="col1" nameend="col4" align="justify">Advantageous film formers according to the invention</entry></row></tbody></tgroup></table></tables>

0143Further film formers advantageous according to the invention are cellulose derivatives and quaternized guar gum derivatives, in particular guar hydroxypropylammonium chloride (for example Jaguar Excel®, Jaguar C 162® from Rhodia, CAS 65497-29-2, CAS 39421-75-5).

0144Also non-ionic poly-N-vinylpyrrolidone / polyvinyl acetate copolymers (e.g. Luviskol VA 64W®, BASF), anionic acrylate copolymers (e.g. Luviflex soft®, BASF), and / or amphoteric amide / acrylate / methacrylate copolymers (e.g. Amphomer®, National Starch) can advantageously be used according to the invention as film formers.

Complexing agent

0145It is also advantageous to add complexing agents to the preparation according to the invention. The complexing agents are advantageously selected from the group consisting of ethylenediaminetetraacetic acid (EDTA) and its anions, nitrilotriacetic acid (NTA) and its anions, hydroxyethylenediaminotriesacetic acid (HOEDTA) and its anions, diethyleneaminopentaacetic acid (DPTA) and its anions, trans-1,2-diaminocetic acid (tetraacetic acid) CDTA) and their anions, tetrasodium iminodisuccinate, trisodium ethylenediamine disuccinate.

Lipids

0146An optionally desired oil component of the cosmetic or dermatological preparation within the meaning of the present invention is advantageously selected from the group of esters from saturated and / or unsaturated, branched and / or unbranched alkane carboxylic acids with a chain length of 3 to 30 carbon atoms and saturated and / or unsaturated , branched and / or unbranched alcohols with a chain length of 3 to 30 carbon atoms, from the group of esters of aromatic carboxylic acids and saturated and / or unsaturated, branched and / or unbranched alcohols with a chain length of 3 to 30 carbon atoms. Such ester oils can then advantageously be selected from the group of isopropyl myristate, isopropyl palmitate, isopropyl stearate, isopropyl oleate, n-butyl stearate, n-hexyl laurate, n-decyl oleate, isooctyl stearate, isononyl stearate, isononylisononanoate, 2-ethylhexyl ethylhexyl palate, Octyldodecyl palmitate, oleyl oleate, olerlerucate, erucyl oleate, erucylerucate as well as synthetic, semi-synthetic and natural mixtures of such esters, e.g. B. Jojoba oil.

0147Furthermore, the oil component can advantageously be selected from the group of branched and unbranched hydrocarbons and waxes, the silicone oils, the dialkyl ethers, the dialkyl carbonates, the group of saturated or unsaturated, branched or unbranched alcohols, and also the fatty acid triglycerides, especially the triglycerol esters, saturated and / or unsaturated, branched and / or unbranched alkane carboxylic acids with a chain length of 8 to 24, in particular 12 to 18, carbon atoms. The fatty acid triglycerides can for example be advantageously selected from the group of synthetic, semi-synthetic and natural oils, e.g. As olive oil, sunflower oil, soybean oil, peanut oil, rapeseed oil, almond oil, palm oil, coconut oil, palm kernel oil and the like.

0148Any mixtures of such oil and wax components can also be used advantageously for the purposes of the present invention.

0149The oil component is advantageously selected from the group 2-ethylhexyl isostearate, octyldodecanol, isotridecyl isononanoate, isoeicosane, 2-ethylhexyl cocoate, C12-15 alkyl benzoate, caprylic capric acid triglyceride, dicaprylyl ether.

0150Mixtures of C12-15 alkyl benzoate and 2-ethylhexyl isostearate, mixtures of C12-15 alkyl benzoate and isotridecyl isononanoate and mixtures of C12-15 alkyl benzoate, 2-ethylhexyl isostearate and isotridecyl isononanoate are particularly advantageous.

0151Of the hydrocarbons, paraffin oil, squalane and squalene can be used advantageously for the purposes of the present invention.

0152Advantageously, the oil component can also have a content of cyclic or linear silicone oils or consist entirely of such oils, although it is preferred to use an additional content of other oil phase components in addition to the silicone oil or the silicone oils.

0153Cyclomethicone (octamethylcyclotetrasiloxane) is advantageously used as the silicone oil to be used according to the invention. However, other silicone oils can also be used advantageously for the purposes of the present invention, for example hexamethylcyclotrisiloxane, polydimethylsiloxane, poly (methylphenylsiloxane).

0154Mixtures of cyclomethicone and isotridecyl isononanoate, cyclomethicone and 2-ethylhexyl isostearate are also particularly advantageous.

0155The oil component is also advantageously selected from the group of the phospholipids. The phospholipids are phosphoric acid esters of acylated glycerols. Of great importance among the phosphatidylcholines are, for example, the lecithins, which are characterized by the general structure<chemistry id="chem0013" num="0013"><img file="EP1531129A1_D0013.tif" /></chemistry> distinguish, where R 'and R "typically represent unbranched aliphatic radicals having 15 or 17 carbon atoms and up to 4 cis double bonds.

Aqueous phase

0156In addition to water, an aqueous phase according to the invention can also contain water-soluble ingredients, for example alcohols, diols or polyols of low C number, and their ethers, preferably ethanol, isopropanol, propylene glycol, glycerol, ethylene glycol, ethylene glycol monoethyl or monobutyl ether, propylene glycol monomethyl, monoethyl or monobutyl ether , Diethylenglykolmonomethyl- or -monoethylether and analogous products, furthermore low C-number alcohols, eg Ethanol, isopropanol, 1,2-propanediol, methylpropanediol and glycerin.

0157Advantageously according to the invention, the cosmetic according to the invention or the preparation which is contained in the dispenser used according to the invention is in the form of an emulsion, an aqueous solution or as an anhydrous formulation.

0158Advantageously according to the invention, a preparation according to the invention can contain one or more oil phases in addition to one or more water phases and can be present, for example, in the form of W / O, O / W, W / O / W or O / W / O emulsions. Such formulations can preferably also be a microemulsion (e.g. a PIT emulsion), a solid emulsions (ie an emulsion which is stabilized by solids, e.g. a Pickering emulsion), with transparent or translucent microemulsions being particularly preferred according to the invention.

0159According to the invention, the preparation can advantageously be in the form of an emulsion or dispersion, with both macro and microemulsions, O / W emulsions, W / O emulsions, S / W emulsions, W / S emulsions and also multiple emulsions being advantageous sense of the present invention can be used.

0160According to the invention, the compositions contain, in addition to the abovementioned substances, optionally further additives customary in cosmetics, for example perfume, dyes, antimicrobial substances, lipid-replenishing agents, complexing and sequestering agents, pearlescent agents, plant extracts, self-tanners (e.g. DHA), depigmenting agents, antidandruff agents, vitamins, other agents, complexes of gamma-oryzanol and calcium salts, niacinamide and its derivatives, panthenol and its derivatives, subtilisin, minerals, preservatives, bactericides, pigments that have a coloring effect, thickeners, softening agents, moisturizing and / or moisturizing substances, or other usual components of a cosmetic or dermatological formulation such as alcohols, polyols, polymers, Foam stabilizers, electrolytes, organic solvents or silicone derivatives. The pH of the preparations according to the invention is adjusted in the manner customary for the person skilled in the art with the appropriate acids (lactic acid, citric acid, phosphoric acid etc.) and bases (for example NaOH).

0161According to the invention, the preparation of the cosmetic or dispenser used according to the invention advantageously has a viscosity of at least 500 mPas.

0162The viscosity values ​​of the preparations and individual substances listed in the context of the present document were determined with the aid of a viscometer VT 02 from Haake (temperature: 25 ° C., rotating body diameter 24 mm, rotor speed 62.5 rpm).

II. The donor according to the invention

0163To achieve the objects on which the invention was based, the present invention improves the dispenser mentioned at the outset (this is the dispenser disclosed in EP-A-0 230 252) in such a way that the conveyor device is displaceable longitudinally with respect to the container and the head piece Conveying element which has a delivery piston which is slidable in the delivery chamber and which is connected to a delivery shaft which surrounds a delivery channel circumferentially, which has a conveying channel inlet opening communicating with the conveying chamber and a conveying channel outlet opening which can be brought into a position by a displacement movement of the conveying element relative to the head piece, in which the conveying channel outlet opening opens to the discharge channel.

0164In the case of the dispenser according to the invention, the delivery chamber opens to the dispensing channel via a delivery channel outlet opening, which is released via a longitudinal displacement of the delivery element relative to the head piece. This relative movement is preferably achieved in that the head piece is manually operated, ie is slid in the axial direction in the direction of the container. The passage of the pasty product from the delivery chamber to the product delivery opening at the end of the delivery channel is accordingly already released by a translatory movement of the head piece relative to the delivery element. A previous pressure build-up in the delivery chamber, as was required in the generic state of the art to release the passage, is not necessary. The actuation forces for dispensing pasty products from the dispenser are correspondingly reduced.

0165In the dispenser according to the invention, a delivery channel is provided downstream of the delivery chamber and is surrounded by a delivery shaft. At the end of this conveying channel, the pasty product conveyed out of the conveying chamber is discharged through the conveying channel outlet opening into the discharge channel. Only after the product has been dispensed from the conveying duct outlet opening does it appear in the dispensing duct.

0166In any case, the remaining output channel is shorter than that of the commonly used dispensers. Accordingly, significantly less volume of pasty mass is impaired by possible oxidation processes. The remaining length of the output channel can be shortened, in particular in the case of products which are highly susceptible to oxidation, in that the output channel opens outwards as an extension of the end face of the head piece.

0167In an advantageous embodiment of the dispenser according to the invention, the conveying channel outlet opening is recessed on the circumferential surface of the conveying shaft and a bushing covering the conveying channel outlet opening in the starting position of the conveying device is provided on the head piece, so that when the head part is lifted to discharge pasty mass, the release is easy Conveyor duct outlet opening results in that the delivery shaft is moved relative to the bush. This preferred embodiment is not only simple, but also allows the conveying channel outlet opening to be arranged in the immediate vicinity of the inlet opening of the dispensing channel for the product to be conveyed.

0168In view of good axial guidance of the conveyor device relative to the head piece, the aforementioned bushing is preferably designed as a guide bushing for the conveyor device and has at least one guide surface which interacts with the peripheral surface of the delivery shaft.

0169With regard to an inevitable closure of the conveying channel outlet opening when the head piece is returned to the starting position, it is proposed according to a preferred development of the present invention that driver means are provided on the head part and on the conveying device, by means of which the conveying device after manual actuation when the head part is returned to the starting position is taken away.

0170The aforementioned driver means are preferably formed in a simple manner by a driver shoulder formed on the bushing, which cooperates with a driver rim molded onto the conveyor shaft. This entrainment ring is preferably integrally formed on the end of the conveying shaft, so that the conveying channel outlet opening which is recessed below the entrainment ring can be sealed in the starting position by contacting the entrainment ring on the walls of the head part.

0171In the aforementioned preferred embodiment, the volume present in the output channel can be further reduced by the fact that the driver shoulder is formed at the end of the socket and at the transition to the output channel and the driver rim in the front end region of the end of the closed delivery shaft, as is the case in a preferred development of the present invention is proposed. In this preferred embodiment, the end cap arranged on the end of the conveying shaft covers the dispensing channel essentially flush in the starting position of the conveying device and preferably has the driver rim.

0172According to a preferred development of the present invention, the delivery piston is preferably actuated via the end faces of the guide bush. In this preferred development, the delivery piston projects radially beyond the delivery shaft to form an annular contact surface for a pressure surface, which is formed on the end face of the guide bush and which is arranged in the starting position with an axial distance from the contact surface and by axially displacing the head piece in the direction of the container the contact surface can be created.

0173Also with a view to simplifying the construction, it is proposed according to a further preferred embodiment of the present invention to form the inner wall of the delivery chamber by means of an inner sleeve which is provided on the end face side of the container. The inner sleeve projects beyond the end face of the container on the side facing the head piece. The inner sleeve is preferably integrally formed on the container in order to reduce the number of components.

0174For easy centering of the head piece during assembly of the dispenser and easy attachment of the head piece to the container, a head counterpart is proposed according to a preferred development of the present invention, which has a pot-shaped holding cylinder placed on the aforementioned inner sleeve and a concentric to the holding cylinder, the sliding displacement of the Headpiece leading guide cylinder. The guide cylinder and / or the holding cylinder allow a slight concentric alignment of the head part with the cylinder. Furthermore, the guide cylinder improves the guidance of the lifting movement of the head piece when the dispenser is actuated.

0175In a further preferred embodiment of the dispenser according to the invention, in which the end of the guide cylinder on the delivery chamber side forms a delivery piston stop for the delivery piston, on the one hand a relatively elongated guide for the delivery piston and on the other hand a stroke limitation of the delivery piston is provided in a simple manner. Such a stroke limitation holds the head part in the initial position on the container when the driver means are in operative connection.

0176The holding cylinder preferably has a ring shoulder on the bottom, which forms a contact surface for a helical spring, which holds the head piece under tension in the starting position. This has the advantage that the outer circumferential surface of the holding cylinder surrounds the helical spring on the inside and thus prevents the spring from buckling. In this preferred embodiment, the annular shoulder is placed on the end face of the container and is therefore particularly suitable for fixing the head counterpart in the axial direction with respect to the container.

0177According to a further, particularly preferred embodiment, the head counterpart and the head piece are designed as prefabricated dispenser components. In this case, the head piece and the head counter piece with their outer circumferential surface are in each case pushed over one another in a cup-shaped manner, the head counter piece having at least one stop for limiting the axial displacement movement of the head piece relative to the head counter piece. In such an embodiment, the interior space surrounded by the lateral surfaces preferably contains a restoring element, for example the helical spring mentioned above, which holds the head piece and the head counter piece spaced apart in the axial direction under pretension. The abovementioned stop limits the axial displacement movement of the head piece, ie After assembly of the head piece and head counter piece, including the spring, ensures that the two components, which are movable against each other, are held together. The dispenser component formed in this way can be placed on differently designed containers, which allows economical production of the dispenser for very different applications and container volumes.

0178A particularly simple and durable connection between the prefabricated dispenser component and the container is formed in that the dispenser component is latched to the container by means of latching means formed on the head counterpart and the end face of the container.

0179In the dispenser according to the invention, the head piece is preferably displaceable in length, that the headpiece can be brought into a central position by manual actuation from the initial position initially by a first axial distance to bear against the delivery piston with simultaneous exposure of the delivery channel outlet opening in the output channel, and the head part can then be moved from the central position to an output with progressive axial displacement taking the delivery piston with it -End position can be brought, in which the delivery chamber has reached its smallest volume by moving the delivery piston. In this preferred embodiment, the delivery channel outlet opening is exposed and the substance is compressed in the delivery channel as part of a rectified movement of the head piece in the direction of the container. This preferred embodiment permits a structurally simple solution of the dispenser according to the invention, in which the head piece acts directly on the delivery piston and drives it to convey pasty mass after the delivery channel outlet opening has been exposed. This movement of the head piece usually takes place against the force of a prestressing element, for example a spring, which ensures that when the head piece is relieved, it presses away from the dispensing end position away from the container. During this movement, the axial distance a is first covered, ie the feed channel outlet opening is closed again. During this closing movement, there is a relative movement between the delivery shaft and the discharge channel, in which the volume of the discharge channel at its inlet is increased. As a result, the pasty mass located in the discharge channel is withdrawn in the direction of the pump chamber, that is to say it is removed from the product discharge opening of the discharge channel in the head part.

0180According to the preferred embodiment of claims 15 to 18, a closing part is located at this product delivery opening. The closing part is preferably designed such that it opens due to a pressure difference between the discharge channel and the atmosphere for dispensing the pasty product. As mentioned above, if the pasty mass in the delivery channel is withdrawn away from the product delivery opening, this leads to a relative negative pressure in the delivery channel, which ensures that the closing part seals the product delivery opening particularly effectively.

0181In order to achieve the best possible seal, it is preferable to form the product discharge opening around a sealing pin arranged in the discharge channel.

0182This locking pin is preferably formed in one piece on the head part. The closure part, which is also ring-shaped, has a sealing lip which can be sealingly attached to the closure mandrel and which effectively closes the dispensing channel when there is an effective negative pressure, but when the pasty product is conveyed out, it releases a relatively large product dispensing opening through which the product can be conveyed out with a relatively low pressure loss.

0183A highly effective closing part can be formed particularly economically on the head part by means of two-component injection molding, as is proposed according to a preferred development of the present invention. In this embodiment, the closing part is firmly connected to the head part. The closing part is preferably formed from a flexible plastic, particularly preferably from a thermoplastic elastomer. It has been shown that, in particular, a thermoplastic elastomer can effectively seal the product discharge opening.

0184It has been shown that the material for the sealing part can be used particularly preferably to form a functional surface on the front outer surface of the head part. Such a functional surface can be, for example, a pusher surface which improves the haptic properties and against which the user of the dispenser presses when using it. Such a functional surface is preferably formed by a coating at least on the end face on the outside of the head part. The closing part and the cover are formed in one piece, preferably by means of two-component injection molding after the injection molding of the head part.

0185Further details, advantages and features of the present invention result from the following description of an exemplary embodiment in conjunction with the drawing. In this show:<ul id="ul0020" list-style="none" compact="compact"><li>Figure 1 is a longitudinal sectional view of a first embodiment of a dispenser according to the invention;</li><li>Figure 2 is a longitudinal sectional view of a second embodiment of the dispenser according to the invention.</li></ul>

0186The exemplary embodiment of a dispenser according to the invention shown in FIG. 1 has a container 1 which is cup-shaped and is connected on its underside to a base plate 2 which is latched to the container 1. On its other end face, the container 1 has a cover 10 on the head side, in which a container opening 11 is recessed. This cover 10 is formed on the side facing away from the container 1 for receiving a dispenser head consisting of a head piece 3, a head counter piece 4 and a pressure piston 5. The dispenser also has a closure cap 6 which is pushed onto an outer sleeve 12 of the container 1 which extends above the cover 10. The container 1, the base plate 2, the head counterpart 4 and the pressure piston 5 are designed as rotationally symmetrical components and are arranged concentrically to a central longitudinal axis X. Between the head piece 3 and the head counter piece 4 there is a schematically indicated helical spring 7, by means of which the head piece 3 is held biased in relation to the head counter piece 4 in the starting position shown in FIG.

0187The head piece 3 has a cylindrical outer jacket 30, which is arranged radially inside immediately adjacent to the outer sleeve 12 of the container 1 and concentrically to the latter. The outer sleeve 12 of the container 1 projects beyond the container-side end of the outer jacket 30 in the axial direction. Accordingly, the embodiment of the dispenser shown in FIG. 1 appears as a closed unit consisting of the container 1 and the head piece 3 even when the closure cap is removed. As will be explained in more detail below, the head piece 3 and the pressure piston 5 are held in a longitudinally displaceable manner relative to the container 1, the pressure piston 5 also being longitudinally displaceable in relation to the head piece 3.

0188The cylindrical wall of the container 1 encloses an interior 10a for receiving the cosmetic or dermatological preparation. In the container opening 11 extend star-shaped retaining webs 11 a. On the side of the cover 10 facing away from the interior 10a, a cylindrical inner sleeve 13 is arranged concentrically to the container opening 11, which is surmounted in the axial direction by the outer sleeve 12 and which surrounds a delivery chamber 100. The inner wall of the inner sleeve 13 is smooth. The bottom of the delivery chamber 100 is formed by the cover 10 of the container 1. The cover 10 has an annular ring 15 protruding into the delivery chamber 100, which surrounds the container opening 11 and forms an annular gap 16 between it and the inner sleeve 13.

0189The pressure piston 5 has a substantially cylindrical, internally hollow delivery shaft 50, at one end of which a delivery piston 51 is integrally formed. The delivery plunger 51 projects radially beyond the delivery shaft 50 and has upper and lower sealing lips 52 on its outer circumferential surface, which protrude axially from the delivery ring 51, which is essentially ring-shaped. On an end face facing the delivery shaft 50, the delivery piston 51 forms an annular contact surface.

0190The delivery shaft 50 has at one end a delivery channel inlet opening 53 which is recessed in the middle of the annular delivery piston 51. At its other end, the delivery shaft 50 is closed at the end by a butt plate 54. The butt plate 54 covers a cylinder section 55 of the delivery shaft 50, which is enlarged in diameter compared to the rest of the shaft area 56. Between this shaft area 56 and the cylinder section 55 there is an obliquely outwardly inclined driving ring 57. Between the driving ring 57 and the butt plate 54, a plurality of delivery channel outlet openings 58 are cut out on the outer peripheral surface of the cylinder section 55. Retaining webs, which carry the butt plate 54, extend in the circumferential direction between the conveying channel outlet openings 58. The conveying channel inlet opening 53 communicates with the conveying channel outlet openings 58 via a conveying channel 50a which is surrounded by the conveying shaft 50 and forms a conveying passage for the pasty substance which is free of non-return valves.

0191The head piece 3 has a cylindrical outer jacket 30, to which an internally hollow guide bush 31 is arranged, which communicates with an output channel 32. The front end of the guide bush 32 forms an end pressure surface 33, which is surmounted in the axial direction by the outer jacket 30. The guide bushing 31 has a first bushing section adjacent to the end pressure surface 33, which has a smaller inner diameter than the second bushing section lying behind in the conveying direction of the pasty substance. A driver shoulder 34 is formed between the first and the second bushing section, which connects the two sections of different bushing diameters to one another via a slope. The second bushing section opens into an outlet channel 32 that extends laterally from the central longitudinal axis X.

0192The head piece 3 has spring contact surfaces 37 formed on ribs 36 in an approximately rectangular extension to the central longitudinal axis X. The ribs 36 extend approximately in a star shape from the bush 31 to the inner surface of the outer shell 30. Accordingly, an annular space 38 open to the underside of the head piece 3 is formed between the inner surface of the outer shell 30, the outer surface of the guide bush 31 and the spring contact surfaces 37.

0193The head part 3 is open to the container-side side of the outer casing 30 and is formed above this end face essentially in the manner of a cap. A product delivery opening 39 of the delivery channel 32 is located on the upper side of the head part 3 facing away from the end face of the outer jacket 30.

0194The head counterpart 4 essentially has two concentric cylinder sections, namely an outer holding cylinder 41 and a guide cylinder 42 with a smaller diameter. The holding cylinder 41 projects beyond the guide cylinder 42 on the side facing the container 1, whereas the guide cylinder 42 on the other side towered over. On the front side of the holding cylinder 41 facing away from the container 1 there is an annular web which extends radially inwards from there and abuts the outer surface of the guide cylinder 42 approximately in the center.

0195The holding cylinder 41 has on its front side on the container side an outwardly projecting circumferential annular shoulder. The end face of the guide cylinder 42 on the container side forms a delivery piston stroke.

0196In the assembled state, the delivery piston 51 of the pressure piston 5 is slidably displaceable in the inner sleeve 13 of the container 1 and thus covers the delivery chamber 100 on the end face. The head counterpart 4 is arranged concentrically to the inner sleeve 13 and pushed with its holding cylinder 41 in a pot shape over the inner sleeve 13. The ring shoulder of the head counterpart 4 rests on the front side of the cover 10 facing away from the container 1.

0197The ring shoulder of the head counterpart 4 is located approximately in the region of the front end of the inner sleeve 13. The guide cylinder 42 adjoining it radially inward surrounds the end of the guide bushing 31 of the head part 3. Radially inside this guide bushing 31, the delivery shaft 50 with its shaft region 56 is smaller Diameter. The delivery piston 51 of the pressure piston 5 is slidably disposed on the inner wall of the inner sleeve 13. The annular contact surface of the delivery piston 51 abuts the delivery piston stop of the guide cylinder 42 on the end face. As a result, the prestressing force exerted by the spring 7 on the head piece 3 is held, which prestresses the pressure piston 5 in a direction away from the container 1 via the contact of the driving shoulder 34 and driving ring 57.

0198Between the delivery chamber 100 and the interior 12 of the container 1 there is a container valve 20 which is designed in a known manner and which bears with its sealing washer 21 against the ring rim 15 of the cover 10 and seals the interior 10a with respect to the delivery chamber 100.

0199When not in use, the dispenser is in the initial position (0).

0200When using the dispenser, a user presses the head piece 3 in the direction of the container 1. Due to the incompressibility of the substance contained in the delivery chamber 100 and the delivery channel 50a, the pressure piston 5 remains in its position. The head piece 3 moves relative to the pressure piston 5 in the direction of the container 1. The form-fitting contact between the driving ring 57 and the driving shoulder 34 is released until the butt plate 54 abuts against the inner surface of the socket head 35 or - depending on the configuration - the end-side pressure surface 33 at the end of the guide bush 31 on the annular contact surface 51a of the delivery piston 51 System (middle position M) comes. After this axial displacement by the displacement path a, the conveyor channel outlet openings 53 are exposed in the output channel 32.

0201The head piece 3 is slidably guided in this as well as in any other axial relative movement between the head piece 3 and the head counterpart 4 or between the head piece 3 and the container 1 by the contact of the outer peripheral surface of the guide bush 31 on the inner peripheral surface of the guide cylinder 42. The relative movement between the head piece 3 and the pressure piston 5 is carried out via the abutment of the peripheral surface of the second shaft section on the shaft region 56.

0202As the pressure movement of the head piece 3 progresses towards the container 1, the pressure piston 5 is taken along. Here, the volume of the delivery chamber 100 is reduced, so that the pasty product located in the delivery direction behind the container valve 30 is discharged into the delivery channel 32 via the delivery channel outlet opening 53. The pasty product leaves the delivery channel via its product delivery opening 39.

0203At the end of this relative movement of the head piece 3 in the direction of the container 1, the sealing lips 52 of the pressure piston 5 on the container side abut against the end face of the annular gap 16. In this output end position V, the delivery chamber 100 has reached its smallest volume.

0204If the head piece 3 is now released by the user, the helical spring 7 presses the head piece 3 back in the opposite direction. In this case, the pressure piston 5 initially remains in its output end position V. Only the head piece 3 moves away from the container 1, namely until the driving shoulder 34 comes to rest against the driving ring 57.

0205During this axial displacement by the distance a, the pasty product located in the discharge channel 32 is withdrawn into the space formed here between the butt plate 54 and the inside of the socket head 35. At the end of this displacement movement, the pasty product then no longer lies directly against the product discharge opening 39 of the discharge channel 32, which prevents paste-like product from dripping out of the discharge channel 32 at the end of the conveying process or is impaired by contamination in the area of ​​the product discharge opening 39.

0206After the displacement by the distance a and the contact of the driving ring 57 and driving shoulder 34, the pressure piston 5 is also moved back as the head piece 3 moves towards the starting position, which is achieved when the feed piston stop abuts the annular contact surface of the feed piston 51 . When the pressure piston 5 moves relative to the container 1, pasty product is conveyed from the interior 10a of the container 1 through the container opening 11 into the delivery chamber 100. The relative negative pressure which arises in the interior 10a leads in a manner known per se to a wake movement of the wake piston 22 located in the interior 12.

02072 shows a second exemplary embodiment of the dispenser according to the invention.

0208In this exemplary embodiment, the same parts are identified with the same reference symbols as those previously discussed. The container 1 of the exemplary embodiment shown in FIG. 7 is essentially identical to the container described above with an outer container wall which surrounds an interior 10a in which a trailing piston 22 is arranged to be longitudinally displaceable and which is closed by a base plate 2. In contrast to the exemplary embodiment described above, the container 1 has a circumferential locking ring 17 on its front cover. The head counterpart 4 is extended radially outwards via the annular shoulder 44 and has a cylindrical outer wall 46 which extends essentially parallel to the holding cylinder 51 and whose diameter is larger than the diameter of the outer jacket 30 of the head part 3. Between the outer wall 46 and the holding cylinder 41, a locking recess 47 is formed on the lower side of the head counterpart 4, which cooperates with the locking ring 17 to form a locking connection between the head piece 4 and the container 1.

0209In the exemplary embodiment shown in FIG. 2, the head counterpart 4 is designed together with the head part 3 as a prefabricated dispenser component. The free end of the outer wall 46 of the head counterpart 4 facing away from the container 1 is bent radially inward to form a locking lug 46a and projects in the axial direction over an annular bead 30a which is provided on the outside of the outer casing 30 on the head part 3. This forms a stop by which the head counterpart 4 is captively connected to the head piece 3. This stop holds the spring forces applied by the spring 7. The dispenser component comprising the head piece 3 and the head counter piece 4 can thus be preassembled on the container 1 before assembly. For this purpose, the spring 7 is inserted into the cavity between the head piece 3 and the head counter piece 4. The two components 3, 4 are pushed into one another in the axial direction until the annular bead 30 a has slipped past the end of the outer wall 46 that is bent inward.

0210In the exemplary embodiment shown in FIG. 2, the pressure piston 5 has a driver rim 57 which is formed on the butt plate 54. Accordingly, the driver rim 57 seals the output channel 32 in the starting position shown in FIG. 2. The conveyor shaft 50 has a shaft region 56 with a reduced diameter, the longitudinal extent of which corresponds to the axial distance a. Accordingly, the axial displaceability of the pressure piston 5 relative to the head part 3 is determined by the butt plate 54 on the one hand and the longitudinal extent of the shank region 56 with a reduced diameter on the other hand.

0211In the exemplary embodiment shown in FIG. 2, there is a further difference compared to the aforementioned first exemplary embodiment in that a closure pin 32a is provided in the discharge channel 32, which is integrally formed on the head piece 3. The product delivery opening 39 becomes ring-shaped due to the locking pin 32a. In the exemplary embodiment shown, the product discharge opening 39 is covered by an annular closure part 60, which is connected to the head piece 3 as a separate component made of a thermoplastic elastomer. In the initial position in FIG. 7, the closing part 60 lies against the outer peripheral surface and on parts of the end face, but in particular on the peripheral surface of the closing mandrel 32a, and thus seals the dispensing channel 32. In one piece with the closing part 60 is a cover 61 which is of identical material to the closing part 60 and which extends over a predominant part of the front cover of the head piece 3. This cover 61 forms a non-slip functional surface on the head piece 3.

0212When the dispenser shown in FIG. 2 is actuated, the processes explained above, in particular with reference to FIG. 1, take place. However, there is the difference here compared to the aforementioned embodiment that when the pressure piston 5 and the head piece 3 are reset, the delivery channel is sealed off from the surroundings. When the pressure piston 5 moves relative to the head piece 3 in the direction of the container 1, the product located in the discharge channel 32 - as already mentioned above - is drawn back into the interior of the head piece 3 against the conveying direction. In the case of Fig. 2nd In the illustrated embodiment, the pressure gradient that arises between the atmosphere and the discharge channel 32 causes the closing part 60 to lie completely tight against the surfaces of the closing mandrel 32a. Accordingly, pasty product present in the discharge channel 32 remains almost unaffected by any oxidation processes. In addition, the butt plate 54 seals the delivery channel 50a with respect to the delivery channel 32, so that in particular an impairment of pasty product in the delivery channel 50a by air possibly penetrating into the delivery channel 32 is avoided in any case.

0213The two exemplary embodiments described above together have the advantage that the delivery channel openings 58 are only exposed in the output channel 32 after a relative movement between the head part 3 and the pressure piston 5. In order to convey the pasty product from the conveying chamber in the direction of the product discharge opening 32a, it is not necessary that the internal pressure initially built up in the conveying chamber 100 is used to open a check valve located behind it in the conveying direction. Accordingly, the pasty product can be removed with less effort. Furthermore, both of the above-mentioned exemplary embodiments offer the advantage that the pasty product is withdrawn against the conveying direction after the headpiece has been actuated in the discharge channel 32, the process shown in FIG. 2nd The exemplary embodiment shown has the permissible advantage that the pasty product contained in the dispenser is reliably protected against impairment, for example by oxygen in the air, by the sealing part of the closure part 60 on the closure mandrel 32a.

Reference list

0214<dl id="dl0003" compact="compact"><dt>1</dt><dd>container</dd><dt>2</dt><dd>Base plate</dd><dt>3</dt><dd>Headpiece</dd><dt>4</dt><dd>Head counterpart</dd><dt>5</dt><dd>Pressure piston</dd><dt>6</dt><dd>Sealing cap</dd><dt>7</dt><dd>Coil spring</dd><dt>10</dt><dd>cover</dd><dt>10a</dt><dd>inner space</dd><dt>11</dt><dd>Container opening</dd><dt>11a</dt><dd>Landing stage</dd><dt>12</dt><dd>Outer sleeve</dd><dt>13</dt><dd>Inner sleeve</dd><dt>15</dt><dd>Ring wreath</dd><dt>16</dt><dd>Annular gap</dd><dt>17</dt><dd>Locking ring</dd><dt>20</dt><dd>Tank valve</dd><dt>21</dt><dd>Valve disc</dd><dt>22</dt><dd>Trailing piston</dd><dt>30</dt><dd>Outer jacket</dd><dt>30a</dt><dd>Ring bead</dd><dt>31</dt><dd>Guide bushing</dd><dt>32</dt><dd>Output channel</dd><dt>32a</dt><dd>Locking pin</dd><dt>33</dt><dd>Printing area</dd><dt>34</dt><dd>Driving shoulder</dd><dt>36</dt><dd>rib</dd><dt>37</dt><dd>Spring contact surface</dd><dt>38</dt><dd>Annulus</dd><dt>39</dt><dd>Product delivery opening</dd><dt>41</dt><dd>Holding cylinder</dd><dt>42</dt><dd>Guide cylinder</dd><dt>44</dt><dd>Ring shoulder</dd><dt>46</dt><dd>Outer wall</dd><dt>46a</dt><dd>Latch</dd><dt>47</dt><dd>Notch</dd><dt>50</dt><dd>Funding</dd><dt>50a</dt><dd>Conveyor channel</dd><dt>51</dt><dd>Delivery piston</dd><dt>52</dt><dd>Sealing lips</dd><dt>53</dt><dd>Delivery channel inlet opening</dd><dt>54</dt><dd>Butt plate</dd><dt>55</dt><dd>Cylinder section</dd><dt>56</dt><dd>Shaft area</dd><dt>57</dt><dd>Carrier ring</dd><dt>58</dt><dd>Delivery channel outlet opening</dd><dt>60</dt><dd>Wear part</dd><dt>61</dt><dd>coating</dd><dt>100</dt><dd>Conveyor chamber</dd></dl>

0215The use of the cosmetic according to the invention or the dispenser according to the invention for cleaning and care of the skin and / or skin appendages is according to the invention. The skin appendages are understood to be in particular the hair and nails.

0216According to the invention, the use of a dispenser for pasty products with an essentially cylindrical container (1) containing a cosmetic and / or dermatological preparation, which has a follower piston (22) which is slidable on the inside wall of the container under the pressure of the outside atmosphere and at its upper end carries a head piece (3) which is slidable relative to the container (1), which has an output channel (32) for the product which can be communicatively connected to the container (1) and acts on a manually operable conveying device with a variable-volume conveying chamber (100) for the product, characterized in that the conveying device connects to the container (1) and the head piece (3) comprises a longitudinally displaceable conveying element (5) which has a conveying piston (51) slidably displaceable in the conveying chamber (100), which is connected to a delivery shaft (50) which surrounds a delivery channel (50a) circumferentially, which has a delivery channel inlet opening (53) communicating with the delivery chamber (100) and a delivery channel outlet opening (58) which is relative by a displacement movement of the delivery element (5) can be brought to the head piece (3) in a position in which the conveying duct outlet opening (58) opens to the dispensing duct (32), for the storage and presentation of cosmetic and / or dermatological preparations as described in the context of this disclosure.

0217In particular, the use of the preparation of the cosmetic according to the invention or of the dispenser according to the invention as a shower gel, bath tub or shampoo (hair shampoo) is according to the invention.

0218According to the invention, the use of the preparation of the cosmetic according to the invention or of the dispenser according to the invention as a skin cream, lotion or gel for skin care is advantageous according to the invention. It is preferred according to the invention if the cosmetic and / or dermatological preparation is a preparation for protecting the skin from sunlight (sunscreen) or for the prophylaxis, treatment and or care of dry skin, impure to oily skin, acne, aging skin, Skin aging, baby skin and / or neurodermatitis.

0219Furthermore, the products according to the invention are outstandingly suitable for cleaning and maintaining everyday objects (for example dishes, table and cupboard surfaces, cars, clothing, laundry).

0220The following examples are intended to illustrate the present invention without restricting it. Unless otherwise stated, all quantities, proportions and percentages are based on the weight and the total amount or on the total weight of the preparations.

<u>Sample formulations for cosmetic and / or dermatological preparation</u>

O / W emulsions

0221<tables id="tabl0006" num="0006"><img file="EP1531129A1_D0014.tif" /></tables><tables id="tabl0007" num="0007"><img file="EP1531129A1_D0015.tif" /></tables><tables id="tabl0008" num="0008"><img file="EP1531129A1_D0016.tif" /></tables><tables id="tabl0009" num="0009"><img file="EP1531129A1_D0017.tif" /></tables><tables id="tabl0010" num="0010"><img file="EP1531129A1_D0018.tif" /></tables><tables id="tabl0011" num="0011"><img file="EP1531129A1_D0019.tif" /></tables><tables id="tabl0012" num="0012"><img file="EP1531129A1_D0020.tif" /></tables><tables id="tabl0013" num="0013"><img file="EP1531129A1_D0021.tif" /></tables><tables id="tabl0014" num="0014"><img file="EP1531129A1_D0022.tif" /></tables><tables id="tabl0015" num="0015"><img file="EP1531129A1_D0023.tif" /></tables>

W / O emulsions

0222<tables id="tabl0016" num="0016"><img file="EP1531129A1_D0024.tif" /></tables><tables id="tabl0017" num="0017"><img file="EP1531129A1_D0025.tif" /></tables><tables id="tabl0018" num="0018"><img file="EP1531129A1_D0026.tif" /></tables>