A single composition for simultaneous coloring and highlighting hair to provide hair fibers having variations in tonality and hue, comprising, 1-10% inorganic persulfate, 1-20% hydrogen peroxide, 0.001-20% of at least one primary intermediate and, optionally, at least one coupler for the formation of oxidation dyes; and 0.01-20% of one or more surfactants; as well as a one step method for simultaneously color and highlighting hair to provide hair fibers having variations in tonality and hue comprising, combining, immediately prior to use, a powder composition comprised of at least one alkali metal or alkaline earth metal persulfate, an aqueous developer composition comprised of hydrogen peroxide; and an aqueous based colorant composition comprised of at least one primary intermediate and, optionally, at least one coupler for the formation of oxidation dyes; and applying the mixture to the hair for a period of time sufficient to cause coloration and highlighting of the hair.

The invention is in the field of coloring hair, including compositions and methods for use therein.
Hair color is used by a large percentage of the population. The reasons consumers may color hair vary from a desire to change hair color, cover grey hair, or provide unique effects such as streaking, highlighting and the like. One common complaint among haircolor users is that dyed hair often looks artificial because it does not provide the variations in tonality and hue found in natural hair. Thus, there is a need to develop methods and compositions for coloring hair that will provide more natural looking hair.
One known method for providing dyed hair with greater variability in tonality and hue is a two step procedure whereby the hair is first bleached to remove color. In the second step, hair color is applied to the bleached hair. Because the bleaching process provides uneven stripping of color from the hair, the subsequently applied color then dyes the stripped hair fibers in different shades, depending on how much color was removed by the bleaching process. This two step process is disadvantageous because it takes twice the time, and may cause increased damage to sensitive hair because both the bleach and the colorant are most often highly alkaline and are on the hair consecutively. This current method is particularly disadvantageous for those who use other hair products such as permanent waves and relaxers, which also may damage to overly sensitive hair.
U.S. Pat. No. 5,688,291 teaches a method and compositions for simultaneously lightening and coloring hair where an aqueous colorant composition containing Disperse dyes is combined with a powder bleach composition containing persulfate. The mixture is made immediately prior to use and applied to the hair. The patentee claims that hair dyed with this composition is capable of providing hightlights, or lift, to the hair. However, the Disperse dyes used in this formula are semi-permanent dyes, thus do not provide permanent color to the hair.
Japanese Patent Publication No. 08175940, published Jul. 9, 1997, teaches the combination of a xanthene-based hair dyeing agent, a peroxide based developer, and a persulfate based bleaching compound. The pH of the solution is about 7-10. However, the xanthene based dyes taught in this composition are also semi-permanent dyes and do not provide permanent color to the hair. Moreover, the xanthene based dye may be unstable in the alkaline mixture.
The object of the invention is to provide a one step method for simultaneously coloring and hightlighting hair with permanent color, to provide hair having variations in tonality and hue.
The object of the invention is to provide a one step method for coloring and hightlighting hair, particularly hair which has already been treated with coloring agents.
The object of the invention is to provide a method for coloring and highlighting hair with oxidation dyes that provide permanent color to hair.
The object of the invention is to provide a single composition for coloring and hightlighting hair without causing undue hair damage.
The invention comprises a composition for simultaneously coloring and highlighting hair to provide hair fibers having variations in tonality and hue, comprising, by weight of the total composition:
(a) 1-10% inorganic persulfate,
(b) 1-20% hydrogen peroxide,
(c) 0.001-20% (combined weight) of at least one primary intermediate and, optionally, at least one coupler for the formation of oxidation dyes; and
(d) 0.01-20% of one or more surfactants.
The invention also comprises a one step method for simultaneously coloring and highlighting hair to provide hair fibers having variations in tonality and hue comprising the steps of:
(a) combining, immediately prior to use, (i) a powder composition comprised of at least one inorganic persulfate, (ii) an aqueous developer composition comprised of hydrogen peroxide; and (iii) an aqueous based colorant composition comprised of at least one primary intermediate and, optionally, at least one coupler for the formation of oxidation dyes; and
(b) applying the mixture of (a) to the hair for a period of time sufficient to cause coloration and highlighting of the hair.
The invention comprises both a composition used to provide highlighting and coloration to hair as well as a one step method for coloring and highlighting hair. All percentages mentioned herein are percentages by weight unless otherwise indicated.
I. The Composition
The composition for simultaneously coloring and highlighting hair to provide hair fibers having variations in tonality and hue, comprises about:
(a) 1-10% inorganic persulfate,
(b) 1-20% hydrogen peroxide,
(c) 0.001-20% (combined weight) of at least one primary intermediate and at least one coupler for the formation of oxidation dyes; and
(d) 0.01-20% of one or more cationic surfactants.
The composition is prepared by mixing (i) a powder bleach composition, (ii) an aqueous developer composition; and (iii) an aqueous based colorant composition comprised of at least one primary intermediate and, optionally, at least one coupler for the formation of oxidation dyes prior to application to the hair.
A. The Powder Bleach Composition
The powder bleach composition is generally a mixture of persulfate compounds which are capable of bleaching the hair, particulate fillers, and, if desired, inorganic particulate colorants.
1. Persulfates
The powder bleach composition comprises 15-65%, preferably 20-60%, more preferably 25-55% by weight of the total composition of at least one inorganic persulfate which may be ammonium persulfate, or an alkali metal or alkaline earth metal persulfate. Preferred are alkali metal or alkaline earth metal persulfates. Examples of alkali metal persulfates include lithium, sodium, potassium, cesium, and the like. Examples of suitable alkaline earth metals include magnesium, calcium, and the like. Particularly preferred are sodium and potassium persulfates. The persulfates are generally in particulate form, and have particle sizes ranging from about 0.1 to 200 microns.
2. Particulate Fillers
The remainder of the powder bleach composition comprises particulate fillers. Preferably, the powder bleach composition comprises 5-60%, preferably 8-55%, more preferably 10-50% by weight of the total composition of the particulate fillers. The term xe2x80x9cparticulate fillerxe2x80x9d means a generally inert particulate having a particle size of about 0.1-250 microns. The particulate fillers provide volume and, when mixed with the persulfates, dilute the persulfate particles. A variety of particulate fillers are suitable including inorganics, inorganic salts, hydrophilic colloids, carbohydrates, soaps, alkyl sulfates, and the like.
(a) Inorganics
Examples of inorganics include silica, hydrated silica, alumina, attapulgite, bentonite, calcium oxide, chalk, diamond powder, diatomaceous earth, fuller""s earth, hectorite, kaolin, mica, magnesium oxide, montmorillonite, pumice, talc, tin oxide, zeolite, zinc oxide, and the like.
(b) Inorganic Salts
Examples of suitable inorganic salts include aluminum, sodium, potassium, and magnesium salts of inorganic or organic acids. Examples of suitable salts include sodium metasilicate, sodium chloride, sodium silicate, aluminum citrate, calcium saccharin, calcium salicylate, calcium citrate, calcium benzoate, magnesium acetate, magnesium ascorbate, magnesium PCA, magnesium gluconate, potassium acetate, potassium benzoate, potassium citrate, potassium sorbate, sodium acetate, sodium ascorbate, sodium citrate, sodium gluconate, sodium pyruvate, and mixtures thereof.
(c) Hydrophilic Colloids
Examples of suitable hydrophilic colloids include hydroxyethylcellulose, locust bean, maltodextrin, methylcellulose, agar, dextran, dextran sulfate, gelatin, pectin, potassium alginate, sodium carboxymethylchitin, xanthan gum, and the like.
(d) Carbohydrates
Examples of suitable carbohydrates include sugars such as glucose, sucrose, maltose, xylose, trehelose, and derivatives thereof, in particular sugar esters of long chain, C14-30 fatty acids, as well as dextrins, cellulosics, and derivatives thereof.
(e) Soaps and Alkyl Sulfates
Examples of soaps and alkyl sulfate particles that may act as particulate fillers include the aluminum, sodium, and potassium salts of fatty acids such as aluminum distearate, aluminum isostearate, aluminum myristate, calcium behenate, calcium stearate, calcium behenate, magnesium stearate, magnesium tallowate, potassium palmitate, potassium stearate, potassium oleate, sodium stearate, sodium oleate, sodium myristate, sodium palmitate, and the like. Suitable alkyl sulfates include sodium lauryl sulfate, sodium cetyl sulfate, sodium myristyl sulfate, sodium octyl sulfate, and the like.
3. Inorganic Colorants
If desired, the powder bleach composition may comprise 0.01-2%, preferably 0.05-1%, more preferably about 0.1-1% of an inorganic colorant. The inorganic colorant is preferably in the particulate form and will provide a subtle coloration to the powder composition to make it more aesthetically pleasing for commercial purposes. Particularly preferred for use in the bleach composition is ultramarine blue.
B. The Aqueous Developer Composition
The aqueous developer composition comprises, by weight of the total composition, 50-99% water, 1-30% hydrogen peroxide, and 0.01-30%, preferably 0.05-20%, more preferably 0.1-15% of an oily phase. The aqueous developer composition may be in the form of a water-in-oil or oil-in-water emulsion.
1. Oily Phase Ingredients
Suitable oils are liquid at room temperature (25xc2x0 C.) and include hydrocarbon oils and/or silicone oils which are volatile or nonvolatile, and glyceryl esters of fatty acids. The term xe2x80x9cvolatilexe2x80x9d means that the oil has a measureable vapor pressure, i.e. a vapor pressure of at least 2 mm. of mercury at 20xc2x0 C. The term xe2x80x9cnonvolatilexe2x80x9d means that the oil has a vapor pressure of less than 2 mm. of mercury at 20xc2x0 C. Suitable volatile oils generally have a viscosity of 0.5 to 10 centistokes at 25xc2x0 C., and include linear silicones, cyclic silicones, paraffinic hydrocarbons, or mixtures thereof.
(a) Volatile Silicones
Cyclic silicones (or cyclomethicones) are of the general formula:
wherein R1 and R2 are each independently H, C1-8 alkyl, aryl, aralkyl, alkenyl, or a cyclic or alicyclic ring, preferably a C1-4 alkyl, most preferably methyl, and wherein n=3xe2x88x927.
Linear volatile silicones in accordance with the invention have the general formula.
(CH3)3Sixe2x80x94Oxe2x80x94[Si(CH3)2xe2x80x94O]nxe2x80x94Si(CH3)3
where n=0xe2x88x926, preferably 0xe2x88x925.
Linear and cyclic volatile silicones are available from various commercial sources including Dow Corning Corporation and General Electric. The Dow Corning volatile silicones are sold under the tradenames Dow Corning 244, 245, 344, and 200 fluids. These fluids comprise octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, hexamethyldisiloxane, and mixtures thereof.
(b) Volatile Paraffinic Hydrocarbons
Also suitable as the volatile oils are various straight or branched chain paraffinic hydrocarbons having 5 to 40 carbon atoms, more preferably 8-20 carbon atoms. Suitable hydrocarbons include pentane, hexane, heptane, decane, dodecane, tetradecane, tridecane, and C8-20 isoparaffins as disclosed in U.S. Pat. Nos. 3,439,088 and 3,818,105, both of which are hereby incorporated by reference. Preferred volatile paraffinic hydrocarbons have a molecular weight of 70-225, preferably 160 to 190 and a boiling point range of 30 to 320, preferably 60-260 degrees C., and a viscosity of less than 10 cs. at 25 degrees C. Such paraffinic hydrocarbons are available from EXXON under the ISOPARS trademark, and from the Permethyl Corporation. Suitable C12 isoparaffins are manufactured by Permethyl Corporation under the tradename Permethyl 99A. Another C12 isoparaffin (isododecane) is distributed by Presperse under the tradename Permethyl 99A. Various C16 isoparaffins commercially available, such as isohexadecane (having the tradename Permethyl R), are also suitable. Transfer resistant cosmetic sticks of the invention will generally comprise a mixture of volatile silicones and volatile paraffinic hydrocarbons.
(c) Nonvolatile Silicones
Nonvolatile silicones, both water soluble and water insoluble, are also suitable as the oil component. Such silicones preferably have a viscosity of 10 to 600,000 centistokes, preferably 20 to 100,000 centistokes at 25xc2x0 C. Suitable water insoluble silicones include amodimethicone, bisphenylhexamethicone, dimethicone, hexadecyl methicone, methicone, phenyl trimethicone, simethicone, dimethylhydrogensiloxane, stearoxytrimethylsilane, vinyldimethicone, and mixtures thereof. Also suitable are water soluble silicones such as dimethicone copolyol, dimethiconol, and the like. Such silicones are available from Dow Corning as the 3225C formulation aid, Dow 190 and 193 fluids, or similar products marketed by Goldschmidt under the ABIL tradename.
(d) Esters
Other nonvolatile oils include esters of the formula RCOxe2x80x94ORxe2x80x2 wherein R and Rxe2x80x2 are each independently a C1-25, preferably a C4-20 straight or branched chain alkyl, alkenyl or alkoxycarbonylalkyl or alkylcarbonyloxyalkyl.
(e) Glyceryl Esters of Fatty Acids
Also suitable are naturally occuring glyceryl esters of fatty acids, or triglycerides as well as synthetic or semi-synthetic glyceryl esters.
(f) Nonvolatile Hydrocarbons
Also suitable for use are nonvolatile hydrocarbons such as isoparaffins, hydrogenated polyisobutene, mineral oil, squalene, and so on.
(g) Vegetable Oils
Also suitable for use are one or more vegetable oils obtained from plants such as flowers or vegetables. Examples of such oils include meadowfoam seed oil, borage oil, cottonseed oil, linseed oil, peanut oil, and so on.
2. Nonionic Surfactants
If desired, the aqueous developer composition may contain one or more nonionic surfactants. Recommended ranges are 0.01-10%, preferably 0.05-8%, more preferably 0.1-7% by weight of the total composition.
(a) Alkoxylated Alcohols
Suitable nonionic surfactants include alkoxylated alcohols, or ethers, formed by the reaction of an alcohol with an alkylene oxide, usually ethylene or propylene oxide. Preferably the alcohol is a fatty alcohol having 6 to 30 carbon atoms, and a straight or branched, saturated or unsaturated carbon chain. Examples of such ingredients include Beheneth 5-30, which is formed by the reaction of behenyl alcohol and ethylene oxide where the number of repeated ethylene oxide units is 5 to 30; Ceteareth 2-100, formed by the reaction of a mixture of cetyl and stearyl alcohol with ethylene oxide, where the number of repeating ethylene oxide units in the molecule is 2 to 100; Ceteth 1-45 which is formed by the reaction of cetyl alcohol and ethylene oxide, and the number of repeating ethylene oxide units is 1 to 45, and so on. Particularly preferred is Ceteareth 20, which is the reaction product of a mixture of cetyl and stearyl alcohol and ethylene oxide, wherein the number of repeating ethylene oxide units in the molecule is 20. Also preferred are C12-16 pareth-9, which is the reaction product of C12-16 fatty alcohols and ethylene oxide wherein the number of repeating ethylene oxide units in the molecule is nine; and trideceth-12, which is the reaction product of tridecyl alcohol and ethylene oxide wherein the average number of repeating ethylene oxide units in the molecule is 12.
(b) Alkoxylated Carboxylic Acids
Also suitable as the nonionic surfactant are alkyoxylated carboxylic acids, which are formed by the reaction of a carboxylic acid with an alkylene oxide or with a polymeric ether. The resulting products have the general formula:
where RCO is the carboxylic ester radical, X is hydrogen or lower alkyl, and n is the number of polymerized alkoxy groups. In the case of the diesters, the two RCO-groups do not need to be identical. Preferably, R is a C6-30 straight or branched chain, saturated or unsaturated alkyl, and n is from 1-100.
(c) Sorbitan Derivatives
Other suitable nonionic surfactants include alkoxylated sorbitan and alkoxylated sorbitan derivatives. For example, alkoxylation, in particular, ethoxylation, of sorbitan provides polyalkoxylated sorbitan derivatives. Esterification of polyalkoxylated sorbitan provides sorbitan esters such as the polysorbates. Examples of such ingredients include Polysorbates 20-85, sorbitan oleate, sorbitan palmitate, sorbitan sesquiisostearate, sorbitan stearate, and so on.
d) Alkyl Polysaccharides
Also suitable are alkyl polysaccharides having a hydrophobic group of 6 to 30, preferably 10, carbon atoms and a polysaccharide group such as glucose, galactose, etc. Suitable alkyl polysaccharides are octyl, nonydecyl, undecyldodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl, di-, tri-, tetra-, penta-, and hexaglucosides, galactosides, lactosides, glucoses, fructosides, fructoses, and so on.
3. Thickening Agents
The aqueous developer composition may also comprise a thickening agent, if desired. Preferably, the amount of thickening agent is 0.001-5%, preferably 0.005-4%, more preferably 0.005-3% by weight of the total composition.
(a) Acrylic Copolymer Thickeners
One type of thickening agent for use in the developer composition is an acrylic polymer comprised of monomers A and B wherein A is selected from the group consisting of acrylic acid, methacrylic acid, and mixtures thereof; and B is selected from the group consisting of a C1-22 alkyl acrylate, a C1-22 alkyl methacrylate, and mixtures thereof. Preferably, the A monomer comprises one or more of acrylic acid or methacrylic acid, and the B monomer comprises is selected from the group consisting of a C1-10, most preferably C1-4 alkyl acrylate, a C1-10, most preferably C1-4 alkyl methacrylate, and mixtures thereof. Most preferably the B monomer is one or more of methyl or ethyl acrylate or methacrylate. Most preferably, the acrylic copolymer is supplied in an aqueous solution having a solid content ranging from about 10-60%, preferably 20-50%, more preferably 25-45% by weight of the polymer, with the remainder water. Preferably, the thickening agent is a polymer comprised of A, B, and C monomers wherein A and B are as defined above, and C has the general formula:
Preferably, in the copolymer used for the secondary thickening agent in the preferred embodiment of the invention, A and B are as above defined; and in the C monomer Z is (CH2)m, m is 1-2, n is 2, and o is 2-100, and R is a C12-22 straight or branched chain alkyl. More preferably in the C monomer m is 1, n is 2, o is 10, and R is C18 or stearyl, and the compound is steareth-10 allyl ether/acrylate copolymer, which may be purchased from Allied Colloids under the tradename Salcare SC90.
C. The Aqueous Based Hair Colorant
The aqueous based hair colorant composition contains at least one primary intermediate and, optionally, at least one coupler for the formation of oxidation dyes in aqueous medium. Preferably, the aqueous based colorant composition has a pH of about 7 to 11, and may be in the form of a water-in-oil or oil-in-water emulsion. The colorant composition may additionally comprise one or more of a quaternary ammonium surfactant, protein derivative, silicone oil, and a nonionic, zwitterionic, or betaine surfactant.
1. Primary Intermediates and Couplers
The aqueous based hair colorant composition comprises about 0.001-20%, 0.005-8%, more preferably 0.01-7% (combined weight) of one or more primary intermediates and, optionally, couplers for oxidation dyes. Preferably, the range of primary intermediate will be about 0.0001-5% by weight and the range of coupler will be about 0.0001-5% by weight. Primary intermediates and couplers are well known hair coloring ingredients, and include ortho, meta, or para substituted aminophenols or phenylenediamines, such as para-phenylenediamines of the formula:
wherein R1 and R2 are each independently hydrogen, C1-6 alkyl, or C1-6 alkyl substituted with one or more hydroxy, methoxy, methylsulphonylamino, aminocarbonyl, furfuryl, unsubstituted phenyl, or amino substituted phenyl groups; R3 and R6 are each independently hydrogen, C1-6 alkyl, C1-6 alkoxy, halogen, or C1-6 alkyl substituted with one or more hydroxyl groups; and R4 and R5 are each independently hydrogen, C1-6 lower alkoxy, C1-6 lower alkyl, or halogen. Examples of suitable primary intermediates are para-aminophenol, resorcinol, ortho-aminophenols, ortho-phenylenediamines, and heterocyclic compounds. Examples of suitable primary intermediates include para-phenylenediamine, 2-methyl-1,4-diaminobenzene, 2,6-dimethyl-1,4-diaminobenzene, 2,5-dimethyl-1,4-diaminobenzene, 2,3-dimethyl-1,4-diaminobenzene, 2-chloro-1,4-diaminobenzene, 2-methoxy-1,4-diaminobenzene, 1-phenylamino-4-aminobenzene, 1-dimethylamino-4-aminobenzene, 1-diethylamino-4-aminobenzene, 1-bis(beta-hydroxyethyl)amino-4-aminobenzene, 1-methoxyethylamino-4-aminobenzene, 2-hydroxymethyl-1,4-diaminobenzene, 2-hydroxyethyl-1,4-diaminobenzene, 2-isopropyl-1,4-diaminobenzene, 1-hydroxypropyl-4-aminobenzene, 2,6-dimethyl-3-methoxy-1,4-diaminobenzene, 1-amino-4-hydroxybenzene, and derivatives thereof.
Preferred primary intermediates are p-phenylenediamine, p-aminophenol, o-aminophenol, N,N-bis(2-hydroxyethyl)-p-phenylenediamine, 2,5-diaminotoluene, their salts and mixtures thereof.
Suitable couplers include, for example, those having the general formula:
wherein R1 is unsubstituted hydroxy or amino, or hydroxy or amino substituted with one or more C1-6 hydroxyalkyl groups, R3 and R5 are each independently hydrogen, hydroxy, amino, or amino substituted with C1-6 alkyl, C1-6 alkoxy, or C1-6 hydroxyalkyl group; and R2, R4, and R6 are each independently hydrogen, C1-6 alkoxy, C1-6 alkoxy, C1-6 hydroxyalky, or C1-6 alkyl, or R3 and R4 together may form a methylenedioxy or ethylenedioxy group. Examples of such compounds include meta-derivatives such as phenols, meta-aminophenols, meta-phenylenediamines, and the like, which may be unsubstituted, or substituted on the amino group or benzene ring with alkyl, hydroxyalkyl, alkylamino groups, and the like. Suitable couplers include 3,4-methylenedioxyphenol, 3,4-methylenedioxy-1-[(beta-hydroxyethyl)amino]benzene, 1-methoxy-2-amino-4-[(beta-hydroxyethyl)amino]benzene, 1-hydroxy-3-(dimethylamino)benzene, 6-methyl-1-hydroxy-3[(beta-hydroxyethyl)amino]benzene, 2,4-dichloro-1-hydroxy-3-aminobenzene, 1-hydroxy-3-(diethylamino)benzene, 1-hydroxy-2-methyl-3-aminobenzene, 2-chloro-6-methyl-1-hydroxy-3-aminobenzene, 1,3-diaminobenzene, 6-methoxy-1,3-diaminobenzene, 6-hydroxyethyloxy-1,3-diaminobenzene, 6-methoxy-5-ethyl-1,3-diaminobenzene, 6-ethyloxy-1,3-diaminobenzene, 1-bis(beta-hydroxyethyl)amino-3-aminobenzene, 2-methyl-1,3-diaminobenzene, 6-methoxy-1-amino-[(beta-hydroxyethyl)amino]-benzene, 6-(beta-aminoethyloxy)-1,3-diaminobenzene, 6-(beta-hydroxyethyloxy)-1-amino-3-(methylamino)benzene, 6-carboxymethyloxy-1,3-diaminobenzene, 6-ethyloxy-1-bis(beta-hydroxyethyl)amino-3-aminobenzene, 6-hydroxyethyl-1,3-diaminobenzene, 1-hydroxy-2-isopropyl-5-methylbenzene, 1,3-dihydroxybenzene, 2-chloro-1,3-dihydroxybenzene, 2-methyl-1,3-dihydroxybenzene, 4-chloro-1,3-dihydroxybenzene, 5,6-dichloro-2-methyl-1,3-dihydroxybenzene, 1-hydroxy-3-amino-benzene, 1-hydroxy-3-(carbamoylmethylamino)benzene, 6-hydroxybenzomorpholine, 4-methyl-6-dihydroxypyridine, 2,6-dihydroxypyridine, 2,6-diaminopyridine, 6-aminobenzomorpholine, 1-phenyl-3-methyl-5-pyrazolone, 1-hydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, and mixtures thereof.
Preferred couplers include resorcinol, 1-naphthol, 5-amino-o-cresol, 2-methylresorcinol, m-aminophenol, m-phenylenediamine, 1-phenyl-3-methyl-pyrazol-5-one, their salts, or mixtures thereof.
2. Cationic Surfactants
Preferably the aqueous based colorant composition comprises 0.001-10%, more preferably 0.005-8%, most preferably 0.01-5% of a cationic surfactant. Suitable cationic surfactants include cationic polymers, quaternary ammonium salts or the salts of fatty amines.
(a) Quaternary Ammonium Compounds
Quaternary ammonium compounds, or salts, have the formula:
wherein R1, R2, R3, and R4 are each independently an aliphatic group of 1 to 22 carbon atoms, or aromatic, alkyl, hydroxyalkyl, aryl, or alkaryl group having 12 to 22 carbon atoms; with the proviso that there is at least one alkyl group having 12 to 22 carbon atoms. Preferably at least one of R1, R2, R3, and R4 are methyl while the remaining substituents are C12-22 aliphatic radicals. X is an anion selected from halogen, acetate, phosphate, nitrate and methyl sulfate, tosylate, and hydroxide radicals. The aliphatic groups may contain, in addition to carbon atoms, ether linkages as well as amido groups. Suitable quaternary ammonium compounds may be mono-long chain alkyl, di-long chain alkyl, tri-long chain alkyl, and the like. Examples of such quaternary ammonium salts include behenalkonium chloride, behentrimonium chloride, behentrimonium methosulfate, benzalkonium chloride, benzethonium chloride, benzyl triethyl ammonium chloride, cetalkonium chloride, cetrimonium chloride, cetrimonium bromide, cetrimonium methosulfate, cetrimonium tosylate, cetylpyridinium chloride, dibehenyl/diarachidyl dimonium chloride, dibehenyldimonium chloride, dibehenyldimonium methosulfate, dicapryl/dicaprylyl dimonium chloride, and the like.
Other quaternary ammonium salts useful as the cationic surfactant include compounds of the general formula:
wherein at least one of R1-6 is an aliphatic group having 16 to 22 carbon atoms, and the remaining R1-6 are the same or different and are selected from alkyls having 1 to 4 carbon atoms and X is an anion as above defined.
(b) Amides
Amides which exhibit the general formulas set forth below are also suitable cationic surfactants:
wherein R is a straight or branched chain saturated or unsaturated alkyl having 6 to 30 carbon atoms, n is an integer from 1 to 4, and X and Y are each independently H, or C1-6 alkyl.
Preferred is an amide of the formula:
wherein R is a C12-22 straight or branched chain alkyl, n is an integer from 1 to 4, and X is lower alkyl, preferably methyl.
(c) Amidoamine Salts
Also suitable are amidoamine salts, which are the condensation products of fatty acids with a polyfunctional amines, for example, those having the formula RCONH(CH2)nNR1R2 where RCO is a fatty acyl group such as stearoyl, R1 and R2 are methyl or ethyl, and n is 2 or 3. Examples of such compounds include stearamidopropyl dimethylamine. Particularly preferred are amidoamine compounds complexed with a mild dimer acid, such as di(behenamidopropyl dimethyl amine) dimer dilinoleate or di(linoleamidopropyl dimethyl amine) dimer linoleate. Both ingredients are sold by Alzo, Inc. under the NECON tradename.
(d) Quaternary Imidazolinium Salts
Also, quaternary imidazolinium salts having the following general formula are suitable as the cationic surfactant:
wherein R5 is hydrogen or a C1-4 alkyl; R6 is a C1-4 alkyl; R7 is a C8-22 alkyl; and R8 is hydrogen, or a C1-22 alkyl; and X is an anion as defined above.
(e) Amine Salts
Also suitable as the cationic surfactant are salts of fatty primary, secondary, or tertiary amines, wherein the substituted groups have 12 to 22 carbon atoms. Examples of such amines include dimethyl stearamine, dimethyl soyamine, stearylamine, myristylamine, tridecylamine, ethyl stearamine, and so on.
(f) Cationic Polymers
Also suitable as the cationic surfactant are cationic polymers such as:
Examples of quaternary derivatives of cellulose ethers are polymers sold under the tradename JR-125, JR-400, JR-30M, which have the CTFA name Polyquaternium-10. These polymers are quaternary ammonium salts of hydroxyethylcellulose which is reacted with trimethyl ammonium substituted epoxide.
Copolymers of vinylpyrrolidone having monomer units of the formula:
wherein R1 is hydrogen or methyl, preferably methyl;
y is 0 or 1, preferably 1
R2 is O or NH, preferably NH;
R3 is CxH2x where x is 2 to 18, or xe2x80x94CH2xe2x80x94CHOHxe2x80x94CH2, preferably CxH2x where x is 2;
R4 is methyl, ethyl, phenyl, or C1-4 substituted phenyl, preferably methyl; and
R5 is methyl or ethyl, preferably methyl.
Preferably the copolymer is a polymeric quaternary ammonium salt consisting of vinyl pyrrolidone and dimethyl aminopropyl methacrylamide monomers which has the CTFA name Polyquaternium-28.
Homopolymers of dimethyldiallylammonium chloride, or copolymers of dimethyldiallylammonium chloride and acrylamide are also suitable. Such compounds are sold under the tradename MERQUAT by Merck.
Homopolymers or copolymers derived from acrylic or methacrylic acid, selected from monomer units acrylamide, methylacrylamide, diacetone-acrylamide, acrylamide or methacrylamide substituted on the nitrogen by lower alkyl, alkyl esters of acrylic acid and methacrylic acid, vinylpyrrolidone, or vinyl esters are suitable for use.
As used herein, the term xe2x80x9ccationic siliconexe2x80x9d means any silicone polymer or oligomer having a silicon backbone, including polysiloxanes, having a positive charge on the silicone structure itself. Cationic silicones that may be used in the compositions of the invention include those corresponding to the following formula, where the ratio of D to T units, if present, are greater than about 80 D units to 1 T unit:
(R)aG3xe2x88x92axe2x80x94Sixe2x80x94(xe2x80x94OSiG2)nxe2x80x94(xe2x80x94OSiGb(R1)2xe2x88x926b) mxe2x80x94Oxe2x80x94SiG3xe2x88x92a(R1)a
in which G is selected from the group consisting of H, phenyl, OH, C1-10 alkyl, and is preferably CH3; and a is 0 or an integer from 1 to 3, and is preferably 0; b is 0 or 1, preferably 1; the sum n+m is a number from 1 to 2,000 and is preferably 50 to 150; n is a number from 0 to 2000, and is preferably 50 to 150; and m is an integer from 1 to 2000, and is preferably 1 to 10; R is a C1-10 alkyl, and R1 is a monovalent radical of the formula CqH2qL in which q is an integer from 2 to 8 and L is selected from the groups:
in which R2 is selected from the group consisting of H, phenyl, benzyl, a saturated hydrocarbon radical, and is preferably an alkyl radical containing 1-20 carbon atoms; and Axe2x80x94 is a halide, methylsulfate, or tosylate ion.
Also suitable are polymeric quaternary ammonium salts such as Polyquaternium 31, 33, 34, 35, 36, 37, and 39.
Also suitable are diquaternary polydimethylsiloxanes such as Quaternium-80, sold by Goldschmidt Corporation under the tradename ABIL-Quat 3272.
Examples of other cationic polymers that can be used in the compositions of the invention are disclosed in U.S. Pat. Nos. 5,240,450 and 5,573,709, which are hereby incorporated by reference.
The preferred aqueous based colorant compositions of the invention contain 0.001-10% by weight of a cationic surfactant which comprises one or more cationic polymers, in particular, derivatives of cellulose ether either alone or in combination with a copolymer of vinyl pyrrolidone. Most preferred is a composition comprising a mixture of Polyquaternium-10 and Polyquaternium-28.
3. Oily Ingredients
The aqueous based colorant composition may additionally comprise one or more oils, as described above with respect to the aqueous developer composition. Preferably the aqueous based colorant composition comprises 0.001-20%, more preferably 0.005-15%, most preferably 0.01-10% by weight of the total composition of one or more oils. The colorant may be in the form of a water-in-oil or oil-in-water emulsion form. Preferably the oils are either volatile or nonvolatile silicones as discussed herein with respect to the aqueous developer. Particularly preferred are silicones such as dimethicone copolyol, dimethicone, and cyclomethicone.
4. Humectants
It may be desireable to incorporate one or more humectants into the aqueous colorant composition. Preferably the colorant composition comprises 0.01-10%, more preferably 0.05-8%, most preferably 0.1-5% by weight of the total composition of humectant. Suitable humectants include monomeric, homopolymeric, and/or block copolymeric ethers as well as mono-, di-, or polyhydric alcohols.
Suitable ethers are formed by the polymerization of monomeric alkylene oxides, generally ethylene or propylene oxide. Such polymeric ethers have the following general formula:
wherein R is H or lower alkyl and n is the number of repeating monomer units, and ranges from 1 to 500.
Also suitable are polyols such as glycerine or C1-4 alkylene glycols and the like. Particularly preferred are C1-4 alkylene glycols, in particular propylene and/or butylene glycol and ethoxydiglycol.
5. Anionic Zwitterionic Betaine, or Noninic Surfactants
If desired, the aqueous colorant composition may comprise one or more of an anionic, zwitterionic, betaine, or nonionic surfactant, in the range of about 0.01-15%, preferably 0.05-10%, more preferably 0.1-8% by weight of the total composition.
(a) Anionic Surfactants
Suitable anionic surfactants include alkyl and alkyl ether sulfates generally having the formula ROSO3M and RO(C2H4O)xSO3M wherein R is alkyl or alkenyl of from about 10 to 20 carbon atoms, x is 1 to about 10 and M is a water soluble cation such as ammonium, sodium, potassium, or triethanolamine cation.
Another type of anionic surfactant which may be used in the compositions of the invention are water soluble salts of organic, sulfuric acid reaction products of the general formula:
R1xe2x80x94SO3xe2x80x94M
wherein R1 is chosen from the group consisting of a straight or branched chain, saturated aliphatic hydrocarbon radical having from about 8 to about 24 carbon atoms, preferably 12 to about 18 carbon atoms; and M is a cation. Examples of such anionic surfactants are salts of organic sulfuric acid reaction products of hydrocarbons such as n-paraffins having 8 to 24 carbon atoms, and a sulfonating agent, such as sulfur trioxide.
Also suitable as anionic surfactants are reaction products of fatty acids esterified with isethionic acid and neutralized with sodium hydroxide. The fatty acids may be derived from coconut oil, for example.
In addition, succinates and succinimates are suitable anionic surfactants. This class includes compounds such as disodium N-octadecylsulfosuccinate; tetrasodium N-(1,2-dicarboxyethyl)-N-octadecylsufosuccinate; and esters of sodium sulfosuccinic acid e.g. the dihexyl ester of sodium sulfosuccinic acid, the dioctyl ester of sodium sulfosuccinic acid, and the like.
Other suitable anionic surfactants include olefin sulfonates having about 12 to 24 carbon atoms. The term xe2x80x9colefin sulfonatexe2x80x9d means a compound that can be produced by sulfonation of an alpha olefin by means of uncomplexed sulfur trioxide, followed by neutralization of the acid reaction mixture in conditions such that any sulfones which have been formed in the reaction are hydrolyzed to give the corresponding hydroxy-alkanesulfonates. The alpha-olefin from which the olefin sulfonate is derived is a mono-olefin having about 12 to 24 carbon atoms, preferably about 14 to 16 carbon atoms.
Other classes of suitable anionic organic surfactants are the beta-alkoxy alkane sulfonates or water soluble soaps thereof such as the salts of C10-20 fatty acids, for example coconut and tallow based soaps. Preferred salts are ammonium, potassium, and sodium salts.
Still another class of anionic surfactants include N-acyl amino acid surfactants and salts thereof (alkali, alkaline earth, and ammonium salts) having the formula:
wherein R1 is a C8-24 alkyl or alkenyl radical, preferably C10-18; R2 is H, C1-4 alkyl, phenyl, orxe2x80x94CH2COOM; R3 is CX2xe2x80x94 or C1-2 alkoxy, wherein each X independently is H or a C1-6 alkyl or alkylester, n is from 1 to 4, and M is H or a salt forming cation as described above. Examples of such surfactants are the N-acyl sarcosinates, including lauroyl sarcosinate, myristoyl sarcosinate, cocoyl sarcosinate, and oleoyl sarcosinate, preferably in sodium or potassium forms. Amphoteric surfactants that can be used in the compositions of the invention are generally described as derivatives of aliphatic secondary or tertiary amines wherein one aliphatic radical is a straight or branched chain alkyl of 8 to 18 carbon atoms and the other aliphatic radical contains an anionic group such as carboxy, sulfonate, sulfate, phosphate, or phosphonate.
(b) Amphoteric Surfactants
Suitable amphoteric surfactants may be imidazolinium compounds having the general formula:
wherein R1 is C8-22 alkyl or alkenyl, preferably C12-16; R2 is hydrogen or CH2CO2M, R3 is CH2CH2OH or CH2CH2OCH2CHCOOM; R4 is hydrogen, CH2CH2OH, or CH2CH2OCH2CH2COOM, Z is CO2M or CH2CO2M, n is 2 or 3, preferably 2 M is hydrogen or a cation such as an alkali metal, alkaline earth metal, ammonium, or alkanol ammonium cation. Examples of such materials are marketed under the tradename MIRANOL, by Miranol, Inc.
Also suitable amphoteric surfactants are monocarboxylates or dicarboxylates such as cocamphocarboxypropionate, cocoamphocarboxypropionic acid, cocamphocarboxyglycinate, and cocoamphoacetate.
Other types of amphoteric surfactants include aminoalkanoates of the formula
Rxe2x80x94NH(CH2)nCOOM
or iminodialkanoates of the formula:
Rxe2x80x94N[(CH2)mCOOM]2
and mixtures thereof; wherein n and m are 1 to 4, R is C8-22 alkyl or alkenyl, and M is hydrogen, alkali metal, alkaline earth metal, ammonium or alkanolammonium. Examples of such amphoteric surfactants include n-alkylaminopropionates and n-alkyliminodipropionates, which are sold under the trade name MIRATAINE by Miranol, Inc. or DERIPHAT by Henkel, for example N-lauryl-beta-amino propionic acid, N-lauryl-beta-imino-dipropionic acid, or mixtures thereof.
(c) Zwitterionic Surfactants
Zwitterionic surfactants are also suitable for use in the compositions of the invention. The general formula for such surfactants is:
wherein R2 contains an alkyl, alkenyl or hydroxy alkyl radical of from about 8 to about 18 carbon atoms, from 0 to about 10 ethylene oxide moieties and 0 or 1 glyceryl moiety; Y is selected from the group consisting of nitrogen, phosphorus, and sulfur atoms; R3 is an alkyl or monohydroxyalkyl group containing about 1 to 3 carbon atoms; X is 1 when Y is a sulfur atom, and 2 when Y is a nitrogen or phosphorus atom; R4 is an alkylene or hydroxyalkylene of from about 1 to about 4 carbon atoms, and Z is a radical selected from the group consisting of carboxylate, sulfonate, sulfate, phosphonate, and phosphate groups.
Zwitterionics include betaines, for example higher alkyl betaines such as coco dimethyl carboxymethyl betaine, lauryl dimethyl carboxymethyl betaine, lauryl dimethyl alphacarboxyethyl betaine, cetyl dimethyl carboxymethyl betaine, lauryl bis-(2-hydroxyethyl)carboxymethyl betaine, stearyl bis-(2-hydroxypropyl)carboxymethyl betaine, oleyl dimethyl gamma-carboxylethyl betaine, and mixtures thereof Also suitable are sulfo- and amido-betaines such as coco dimethyl sulfopropyl betaine, cocamidopropyl betaine, stearyl dimethyl sulfopropyl betaine, and the like. Particularly preferred for use in the aqueous colorant composition is a betaine surfactant, in particular, cocamidopropyl betaine.
(d) Nonionic Surfactants
Suitable nonionic surfactants are those mentioned above with respect to the developer composition, and in the same percentage ranges.
6. Protein Derivatives
It may be desired to incorporate one or more protein derivatives into the colorant composition to provide hair conditioning and moisturizing benefits in a range of about 0.01-15%, preferably 0.05-10%, more preferably 0.1-8% by weight of the total composition. The protein derivatives are generally formed by subjecting animal or vegetable proteins to enzymatic or chemical hydrolysis. If desired, the hydrolysate may be further reacted with other compounds to provide further derivatives. Examples of protein derivatives which are suitable for use in the compositions include hydrolysates of collagen, casein, albumen, egg protein, elastin, keratin, silk, soy protein, vegetable protein, wheat protein, wheat starch, wheat gluten, pea protein, oat protein, placental protein, and so on. Also suitable are derivatives of such hydrolysates, such as the reaction product of the hydrolysate with various fatty acids. Examples of such reaction products include potassium cocoyl hydrolyzed casein, collagen, corn protein, keratin, potato protein, rice bran protein, silk, marine collagen, and so on. Particularly preferred are hydrolysates of wheat protein.
II. The Method
Immediately prior to use, the powder bleach composition, the aqueous developer, and the aqueous colorant composition are mixed to form the following composition:
(a) 1-10% alkali metal or alkaline earth metal persulfate,
(b) 1-20% hydrogen peroxide,
(c) 0.01-10% of one or more primary intermediates and couplers for oxidation dyes; and
(d) 0.01-20% of one or more cationic surfactants.
Preferably, the above composition is obtained by combining about 1-20% of the bleach powder, about 50-90% of the aqueous developer, and about 10-60% of the aqueous colorant composition, all percentages being by weight of the total mixture. More preferably, the mixture is made by combining about 4.2% bleach powder, 72% aqueous developer, and 23.8% aqueous colorant composition.
The mixture is prepared immediately prior to use and applied to the hair. The mixture may be applied to the entire head of hair. It may also be desired to apply the mixture only to select strands of hair. In this case, a streaking cap or something similar is applied to the hair and as strands of hair are pulled through the holes in the cap. The mixture is applied to the hair and allowed to remain for about 5-35, preferably 10-25 minutes, or until the color has had an adequate amount of time to lighten the original color and to deposit new color on the hair. The hair is then rinsed well with water to remove the colorant. The hair is then either directly conditioned with a hair conditioner, or if desired, the hair is first shampooed and then treated with a conditioner. The colored hair has variations in tonality and hue which make it look very natural. In addition, the hair is soft and healthy, and does not exhibit the dry, damaged feel and appearance that often characterizes hair colored with oxidation dyes.
The invention will be further described in connection with the following examples, which are set forth for the purposes of illustration of only.

One step method and compositions for simultaneously coloring and highlighting hair


A device for actuating a flap, in particular a wastegate flap in an exhaust gas turbocharger for an internal combustion engine, includes a control rod, which can be moved by an actuator substantially in an axial direction and is guided in a fist gate via a first pin at the side thereof facing away from the actuator. A carriage is articulated on the first pin and is guided in the first gate via a second pin on the side facing away from the first pin, wherein a pivot lever is articulated on the second pin and, on the side facing away from the second pin, the pivot lever is rotatably mounted in a machine housing, preferably a turbine housing, and the flap is arranged on the pivot lever on the side facing away from the second pin. By way of the articulated design, a non-linear adjustment of the flap is possible.

The invention relates to a device that is configured for actuating a flap and, in particular, to a device that is configured for actuating a wastegate flap in an exhaust gas turbocharger for an internal combustion engine, the device having a control rod, which can be displaced largely in an axial direction by an actuator and which is guided in a first slotted link by way of a first pin on a side of the control rod that faces away from the actuator.
The invention is based on exhaust gas turbochargers that are arranged in series and that implement a boost pressure control facility by use of a wastegate flap (bypass flap) that is actuated by negative pressure. In this case the force that is generated in a negative pressure box is transferred to the wastegate flap by way of a rod.
With respect to the technical environment reference is made, for example, to the German published patent application DE 100 27 668 A1, on which this invention is based. This German published patent application describes a device for controlling the delivery rate of the compressor of an exhaust gas turbocharger that is connected to an internal combustion engine.
The invention proposes to open and close a wastegate valve by way of a twin pressure box that includes a pressure chamber (overpressure actuator), which is connected to a pressure source, and that includes another pressure chamber (negative pressure actuator), which is connected to a suction pump. The invention has the advantage that the entire setting range of the wastegate valve or, more specifically the wastegate flap, can always be used independently of the operating state of the internal combustion engine. This feature has, in particular, the advantage that when the internal combustion engine is operating under partial load without the need for a boost pressure, the wastegate valve can be totally opened; and, in so doing, the throttling losses and the backpressure losses can be reduced.
This design, as defined in the preamble, makes it possible to achieve an almost linear pressure/stroke curve over the entire setting range.
Especially in the case of a wastegate actuator that is actuated via the application of negative pressure, both the force, which is generated in the negative pressure box, and also the rod stroke of the actuator, are extremely limited. The result of this feature is that the wastegate flap can execute, in practice, only a small opening angle; and, in so doing, the wastegate channel in turn can be released only to a limited extent from a flow engineering viewpoint. However, under some circumstances and requirements, which the exhaust gas system and the charging system must meet, it may be necessary to open the wastegate (also called the bypass), very wide and, as a result, beyond the maximum opening angle that is customary at the present time.
For example, it is possible to achieve a very fast start of the catalytic converter (that is, the catalytic converter has reached 50% of its conversion temperature, a prerequisite for meeting the future exhaust gas emission standards, such as EU6), if in the first seconds after starting the internal combustion engine the hot exhaust gas is routed through the wastegate and reaches directly the honeycomb core of the catalytic converter, where the exhaust gas accelerates specifically the so-called "light-off" of the catalytic converter without a significant loss of enthalpy, which is the case on the flow path through the turbine of the exhaust gas turbocharger.
As a rule, a permanent change in the lever ratios between the internal lever and the external lever of the wastegate flap in order to enlarge the possible opening range is useful only to a limited extent for this purpose, because in this case the amount of force that the actuator has to generate increases. It is exactly in this range that the negative pressure systems, as they are commonly used at the present time, are extremely limited. Since the maximum force of a negative pressure box is the product of the maximally possible negative pressure and the achievable diaphragm area in the actuator, the limits of the system become immediately apparent. The maximum negative pressure is physically limited at theoretically 1 bar relative (in practice approximately 800 to 900 mbar relative); and the maximum diaphragm area, or more specifically the maximum diameter of the diaphragm, is usually defined by the installation space that is present and is limited by this installation space. Since the diaphragm at its given diameter can be deformed only up to a certain degree, the result is that the stroke of the actuator is also limited.
Systems that are actuated via the application of an overpressure can generate higher forces due to the higher levels of relative pressure that can be achieved, but these systems are just as limited in terms of the stroke.
Although systems with an electric actuator can achieve higher forces while at the same time increasing the stroke length, the size of the actuator with an integrated transmission is usually considerably larger than the vacuum cells, or more specifically the pressure boxes, that are often used.
The object of the present invention is to provide a measure by which larger flap angles (or more specifically higher forces) can be achieved with the same stroke of the actuator.
This and other objects are achieved by a device that is configured for actuating a wastegate flap in an exhaust gas turbocharger for an internal combustion engine, the device having a control rod, which can be displaced largely in an axial direction by an actuator and which is guided in a first slotted link by way of a first pin on a side of the control rod that faces away from the actuator. A carriage is arranged in an articulated manner on the first pin and is guided in the first slotted link by way of a second pin on the side facing away from the first pin, wherein a pivot lever is arranged in an articulated manner on the second pin. The pivot lever is mounted in a rotatable manner in a machine housing, preferably a turbine housing, on the side facing away from the second pin. The flap is arranged on the pivot lever on the side facing away from the second pin.
The present invention provides a "slotted link-guided" control system that is configured for the wastegate flap. The invention is characterized, in particular, in that it enables a variable lever ratio at the wastegate lever, the pivot lever. When the wastegate lever is closing, the force engagement point of the control rod engages with the wastegate lever with a lever that becomes increasingly larger and, in so doing, enables a high closing force (or more specifically a high locking force) of the wastegate flap. In the other direction, in which the wastegate flap opens, the lever decreases with the result that a larger opening angle of the wastegate flap can be attained with the stroke of the control rod. When the lever ratios and the angle ratios of such a kinematic arrangement are appropriately configured, the force ratios and the stroke ratios can be designed to meet the requirements of the respective application in a way that is conducive to achieving the objective.
A plurality of kinematic arrangements are contemplated, depending on the boundary conditions and the specific requirements that the system must meet. The system, shown in FIG. 1, shows only one possible arrangement as an example. The slotted links (gates), in which the carriage runs, can be configured, as shown, as separate slotted links or as one continuously connected slotted link. In this context, the slotted links can be shaped in the form of a straight line or in the form of an arc in the various exemplary embodiments or can even be represented in arbitrary curves. In this respect the shaping of the slotted links is a control variable in order to influence the stroke/angle function, with which the actuator moves the wastegate flap.
Similarly, the stroke/angle function can be influenced by the distance between the first pin and the second pin at the carriage, which runs in the one slotted link or in the slotted links by use of these two pins. The force engagement points of the control rod at the carriage and the force engagement points of the carriage at the pivot lever can be selected totally independently of the position of the two pins. In FIG. 1, the two pins are congruent with the force engagement points and, hence, can be produced very easily, so that the number of components and the assembly costs are kept low.
Furthermore, it is also possible to dispense with the carriage in that the above-described force engagement points of the carriage and the force engagement points of the control rod at the pivot lever are combined and are guided in one common slotted link. Since, however, in this case the attachment point of the control rod in the slotted link guide itself has to perform an increased transverse motion relative to the axis of the rod, the result is a higher load on the diaphragm or, more specifically, the actuator. This higher load may reduce the service life of the diaphragm or, more specifically, the actuator. In order to prevent this higher load, the control rod is guided axially in an additional alternative, so that the control rod cannot deviate transversely to its main direction of motion. In this case the force engagement point of the control rod can be connected to a lever with the slotted link-guided force engagement point of the pivot lever in such a way that the control rod does not have to have its own slotted link guide.
Another embodiment can provide two or more carriages, so that a setting motion of the flap can be designed in a way that it is even more targeted.
Even the choice of the geometry of the slotted links, the position of the attachment points of the control rod, the position of the attachment points of the pivot lever, the distance between the guide points of the carriage(s), the other lever ratios and the geometric ratios and the respective angle adjustments at various operating points are based on the requirements of the system to be designed and can be selected as required.
According to an embodiment wherein the second pin is mounted in a third slotted link in the pivot lever, the variable lever ratio between the internal lever and the external lever of the wastegate flap can be achieved in an advantageous way.
An embodiment wherein at least one of the first and third slotted links has a curved shape is an especially preferred design variant, which allows a number of different kinematics.
An embodiment wherein at least one of the first and second pins is mounted on anti-friction bearings in the first and/or third slotted link reduces the friction in the device and reduces the wear.
An embodiment wherein the first slotted link is arranged stationarily in a link plate is an especially preferred design variant.
An embodiment wherein the first slotted link is divided into the first slotted link and a second slotted link is a design that has proven to be especially effective with respect to the kinematics and that at the same time exhibits a high mechanical strength.
In a preferred embodiment, the actuator can be actuated pneumatically, electromechanically or hydraulically. Further, the actuator may be an overpressure actuator or a negative pressure actuator.
Other objects, advantages and novel features of the present invention will become apparent from the following detailed description of one or more preferred embodiments when considered in conjunction with the accompanying drawings.

Bayerische Motoren Werke Aktiengesellschaft


A powder coating composition comprising a powdered solid ethylenically unsaturated material having a melting point from 60xc2x0 to 120xc2x0 C. obtained by reacting a polyisocyanate with an at least stochiometric amount of an alcoholic component comprising: at least a monovalent alcohol, a part of which bears an ethylenic unsaturation derived from acrylic acid or methacrylic acid, and optionally at least a monomeric polyol. This composition is useful for coating substrates.

This invention is concerned with improvements relating to powder coating compositions and methods of coating substrates using such compositions.
Powder coating is a well-established process, basically comprising the application of a powdered fusible material to a substrate, heating of the powder in contact with the substrate to cause the powder to melt and reflow, and cooling the resultant melt to form a solid coating on the substrate. The coating material may simply comprise a film-forming thermoplastic material or may comprise a reactive material, e.g. an epoxy resin together with a curing agent therefore, so that during the course of melting and reflowing reaction occurs to cure the material in situ on the substrate. In any event, powder coating materials are generally such that they have to be melted and reflowed at relatively high temperatures, e.g. 150xc2x0 C. or more. As a result, powder coating processes are generally not suitable for the coating of heat-sensitive materials such as wood or plastics material. In order to coat such materials, it would be necessary to have a product which had a relatively low melting temperature, e.g. below about 120xc2x0 C., whilst at the same time being solid at ambient temperature, which material could subsequently be cured in situ on the substrate during the melting/reflowing stage or, afterwards.
U.S. Pat. No. 4,093,674 discloses a thermosetting powder coating composition comprising a solid resin having a Tg from 5xc2x0 to 150xc2x0 C. and free hydroxyl groups and a solid polyisocyanate compound, with a molar ratio of isocyanate groups in the latter to active hydrogen in the former of 0.2 to 2. Among examples of the solid resin are the polymers of hydroxyalkylacrylates preferably with Mn from 1,000 to 30,000. This powder coating composition is said to provide advantages over isocyanate crosslinking-type urethane resins wherein all the isocyanate groups are previously blocked with a phenol or an alcohol.
G.B.-A-1,590,413 discloses a urethane resin having at least 2 terminal ethylenically unsaturated groups and comprising the reaction product of at least one isocyanate-functional prepolymer and at least one unsatured monomer having a single isocyanate-reactive-hydrogen-containing group, said isocyanate-functional prepolymer being the reaction product of (i) at least one diisocyanate and (ii) a mixture of at least 2 polyols (at least 30 mole % being polymeric and at most 70 mole % being monomeric in the said mixture) in an NCO:OH ratio of at least 2.3. This urethane resin is mixed with similar unsaturated materials derived from polymeric polyols, with the unreacted excess of diisocyanate and with a reactive diluent which at the end produces flowable and fluid compositions with viscosities of about 4.5 Pa.s. No mention of powder coating may be found in this document.
U.S. Pat. No. 4,500,696 discloses powder surface coatings comprising polyols and a polyisocyanate component comprising blocked adducts of aliphatic diisocyanates. They involve no unsaturated alcohol.
U.S. Pat. No. 5,089,586 discloses acrylate-free water-dispersible allyl urethanes prepared from a polyglycol or its reaction product with an unsaturated dicarboxylic acid, a hydroxyallyl compound (preferably an allyl ether) and a diisocyanate.
International Application WO-93/19132 discloses mixtures, in a binder composition for powder coatings, of an unsaturated polyester and an oligomer having a plurality of allyl ether groups and having further urethane groups.
EP-A-0 410 242 relates to a powder coating composition which comprises the reaction product of one or more organic polyisocyanates with one or more monovalent alcohols containing (meth)acryloyl groups, and one or more compounds which are free from (meth)acryloyl groups and contain at least two isocyanate-reactive groups.
FR-A-2 091 106 relates to a process for preparing a polymer having C=C double bonds, capable of being polymerized, comprising a polyisocyanate which allows to bind an ester which contains polymerizable C=C double bonds and which has active H, to a matter containing several H.
GB-1 443 715 refers to a copolymerizable fluid composition comprising a photocopolymerizable ethylenically unsaturated liquid monomer, a photosensitizer and a photopolymerizable divinylurethane monomer prepared from xylylene diisocyanate, (meth)acrylic esters having a hydroxyl group and di-, tri-, tetra-, penta- or hexavalent alcohol.
U.S. Pat. No. 4,078,015 concerns a copolymerizable composition including a polymerizable acrylic diurethane and a polymerizable polyacrylic polyurethane which is the reaction product of an organic diisocyanate, a xcex2-hydroxy alkyl ester of an acrylic acid, and a diol.
It has now been found, in accordance with the present invention, that useful solid ethylenically unsaturated materials, having relatively low melting point and suitable for use in powder coating compositions may be prepared by reacting a diisocyanate with one or more monohydric alcohols, optionally in combination with a monomeric polyol such as a dihydric alcohol.
According to one embodiment of the invention, therefore, there is provided a powder coating composition comprising a powdered solid ethylenically unsaturated material having a melting point from about 60xc2x0 to 120xc2x0 C. obtained by reacting a polyisocyanate with an at least stoechiometric amount of an alcoholic component comprising
at least two monovalent alcohols, some of them bearing an ethylenic unsaturation derived from acrylic acid or methacrylic acid, and optionally
at least a monomeric polyol.
Said monomeric polyol can be a dihydric aliphatic alcohol or a dihydric polyalkylene glycol.
In accordance with a preferred embodiment of the invention the polyisocyanate is reacted with an at least stoichiometric amount of :
(i) a monohydric alcohol component, or
(ii) a monohydric alcohol component followed by another different monohydric alcohol component, or
(iii)a monohydric alcohol component, followed by a dihydric alcohol component, followed by a monohydric alcohol component, or
(iv) a dihydric alcohol component, followed by a monohydric alcohol component alone or in admixture with a dihydric alcohol component,
the monohydric alcohol component(s) comprising a monohydric aliphatic alcohol or an etherified or esterified dihydric aliphatic alcohol or dihydric polyalkylene glycol, at least a part of which bearing an ethylenic unsaturation derived from acrylic acid or methacrylic acid and the dihydric alcohol component comprising a dihydric aliphatic alcohol or a dihydric polyalkylene glycol and being preferably used in an amount not more than 50%, preferably not more than 25%, of the stoichiometric amount of hydroxyl groups required to react with the isocyanate groups on the polyisocyanate.
As noted above, it is a requirement of the present invention that the material obtained (hereinafter simply referred to as an xe2x80x9coligourethanexe2x80x9d, xe2x80x9curethane acrylatexe2x80x9d or xe2x80x9coligomerxe2x80x9d) have a melting point of from 60 to 120xc2x0 C. (the term xe2x80x9cmelting pointxe2x80x9d as used herein means the melting point as determined by the ring and ball method).
It is also most often preferred that the powdered solid material of the invention have a viscosity in the range from 0.1 Pa.s to 2.5 Pa.s.
Suitable polyisocyanates for use in the preparation of the oligourehanes include toluene diisocyanate, diphenylmethane-4,4xe2x80x2-diisocyanate, hexamethylene-1,6-diisocyanate, napthylene-1,5-diisocyanate, 3,3,xe2x80x2-dimethoxy-4,4,xe2x80x2-biphenyldiisocyanate, 3,3xe2x80x2-dimethyl-4,4,xe2x80x2-biphenyldiisocyanatei phenylene diisocyanate, 4,4xe2x80x2-biphenyldiisocyanate, isophorone diisocyanate, trimethylhexamethylene diisocyanate and tetramethylene xylene diisocyanate.
A wide variety of monohydric aliphatic alcohols may be used to produce the oligourethanes, e.g. C1 to C22 alcohols. Typical etherified dihydric alcoholic materials which may be used as monohydric alcoholic component include propylene glycol methyl ether, dipropylene glycol methyl ether, ethylene glycol butyl ether, diethylene glycol butyl ether, tripropylene glycol butyl ether and propylene glycol phenyl ether. Dihydric alcohols which may be used include, for example, saturated aliphatic diols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, butylene glycols, neopentyl glycol, 1,3- and 1,4-butane diols, 1,5-pentane diol, 1,6-hexanediol, 2-methyl-1,3 propanediol, glycerol, and 1,1,1-trimethylolpropane.
The reaction between the polyisocyanate and the monohydric/dihydric alcohol component is suitably carried out in the presence of a catalyst. As such a catalyst the following may be mentioned :
(a) tertiary amines such as bis(dimethyl amino ethyl)ether, trimethyl amine, triethyl amine, N-methyl morpholine, N-ethyl morpholine, N,N-dimethyl benzylamine, N,N-dimethyl ethanol amine, N,N,Nxe2x80x2,Nxe2x80x2-tetramethyl-1,3-butane diamine, triethylanol amine, 1,4-diazabicyclo(2.2.2.)octane and pyridine oxide,
(b) tertiary phosphines such as trialkyl phosphines and dialkyl benzyl phosphines,
(c) strong bases such as the hydroxides, alcoholates and phenolates of alkali metals and alkaline earth metals,
(d) metal salts of strong acids such as ferric chloride, stannic chloride and bismuth chloride, antimony trichloride and bismuth nitrate,
(e) chelates, such as those which can be obtained from acetyl acetone, benzoyl acetone, trifluoroacetyl acetone, ethyl acetoacetate, salicylaldehyde, cyclopentanone-2-carboxylate, acetyl acetoimine, bis-acetyl acetone alkylene diimines, salicylaldehyde imine, and from metals such as beryllium, magnesium, zinc, cadmium, lead, titanium, zirconium, tin, arsenic, bismuth, chromium, molybdenum, manganese, iron, cobalt and nickel,
(f) alcoholates and phenolates of metals, such as Ti(OR)4, Sn(OR)4, Sn(OR)2 and Al(OR)3, in which R is an alkyl or aryl group,
(g) the salts of organic acids and of metals, such as alkali metals and alkaline earth metals, aluminium, tin, lead, manganese, cobalt, nickel and copper, for example sodium acetate, potassium laurate, calcium hexanoate, stannous acetate, stannous octoate and stannous oleate, lead octoate, manganese and cobalt napthenates, and
(h) iron and cobalt metal carbonyls and organometallic derivatives of tetravalent tin, of trivalent and pentavalent arsenic, of antimony and of bismuth ; particularly preferred are the salts of dialkyl tin carboxylic acids, such as dibutyl tin diacetate, dibutyl tin dilaurate, dibutyl tin maleate, dilauryl tin diacetate, dioctyl tin diacetate, dibutyl tin bis(4-methylamino benzoate), dibutyl tin bis(6-methylamino caproate), trialkyl tin hydroxides, dialkyl tin oxides, dialkyl tin dialcoxides and dialkyl tin dichlorides.
Said catalyst is generally used at a rate of from 0.01 to 2% by weight of the polyisocyanate.
The molecular weight of the final solid, ethylenically unsaturated material is suitably from 500 to 3,000, preferably from 500 to 1,500.
For some applications it is desirable that the oligourethanes be clear. It is not possible to predict whether any particular oligourethane produced in accordance with the invention will, or will not, have the desired optical properties in this respect. However, here again it is a matter of simple routine trial and experiment.
The ethylenically unsaturated solid material forming a part of the powder coating composition in accordance with the invention is in powdered form, e.g. has an average particle size from 10 to 250 xcexcm, especially from 10 to 90 xcexcm. In addition to the particulate, ethylenically unsaturated material, a powder coating composition in accordance with the invention preferably further comprises a curing system for the ethylenically unsaturated material.
In accordance with one embodiment of the invention, the curing system may comprise a thermally initiated free radical-generating catalyst, of the peroxide type or like, optionally together with one or more promoters therefore. Suitable examples of such free radical-generating catalysts include 1,1-bis(t-butylperoxy)-3,5,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)-cyclohexane, t-butylperoxy-isopropyl carbonate, t-butyl perisononanoate, t-butyl peracetate, t-butyl perbenzoate, dicumyl peroxide, di-t-butyl peroxide, t-butyl hydroperoxide, t-butyl perneodecanoate, diisooctanoyl peroxide, dibenzoyl peroxide, and azo bis (isobutyronitrile).
Preferably, the catalyst system is selected so that the powder can melt and reflow prior to curing. This makes it possible to obtain a level film, in contrast to conventional epoxy/acid powders in which curing is effected during melting and reflowing, leading to an orange peel effect.
In accordance with another embodiment of the invention, the curing system may further comprise one or more photoinitiators, sensitive to ultraviolet light, optionally together with sensitizers therefore. By operating with such a system, the coating composition may be allowed to cool and solidify after melting/reflowing and then be subjected to appropriate irradiation to cure the coating.
Examples of suitable photoinitiators include benzyldimethyl ketal, trimethylbenzophenone, isopropylthioxanthone, ethyl 4-dimethylamino benzoate, benzophenone, 2-chloro and 2-ethyl-thioxanthone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyaceto-phenone, 2-hydroxy-2-methyl-1-phenyl-propanone, 4-benzoyl-4xe2x80x2-methyl-diphenyl sulphide, 1-hydroxycyclohexyl-acetophenone, and 2-ethyl-hydroquinone.
Examples of suitable sensitizers include 4,4-dimethylamino-benzophenone, triethanolamine, N-methyl-diethanolamine, 2-(butoxy)ethyl, 4-dimethylamino benzoate and acrylated amines.
In accordance with another embodiment of the invention, the curing system may be absent and curing of the solidified coating on the substrate may be effected by electron beam.
In addition to the basic components noted above, powder coating compositions in accordance with the invention may, and often do, contain at least one other ingredient particularly selected from colorants such as pigments or dyestuffs, flow aids, anti-cissing agents, flexibilizers, degassing agents and inorganic fillers.
The invention also provides a powder coating process for coating a substrate which comprises applying a powder coating composition in accordance with the invention to the substrate, heating the composition to melt and reflow it on the substrate, and allowing the composition to cool on the substrate. In the case of the first embodiment of the invention discussed above, curing of the coating will preferably be effected by free radical polymerisation after the melting/reflowing step, whereas in the second embodiment of the invention an additional curing step is required that is the substrate bearing the cured coating must be subjected to ultraviolet or electron beam radiation.
In order that the invention may be well understood the following examples are given by way of illustration only. Unless stated otherwise, all amounts are expressed by weight.

Powder coating compositions and a method for coating a substrate


The invention relates to a measuring apparatus (1) for fluids with the following features:

The invention relates to a measuring apparatus for fluids, it being understood that under xe2x80x9cfluidsxe2x80x9d, both a gas and also a liquid are encompassed.
In the state of the art, measuring apparatuses have been developed in which a rotor is maintained in an equilibrium position within a carrier tube by magnetic field forces. Thus in DE-A-29 19 236, a turbine wheel counter is described for the flow-through measurement of liquids in which the rotor has, for radial stability, two spaced apart rotor magnets formed as permanent magnets which are juxtaposed pairwise with stator magnets also formed as permanent magnets, which surround the carrier tube. Thus the rotor magnets and stator magnets are magnetized in the axial direction so as to repel one another.
Between the stator magnets, an electromagnet coil is arranged which surrounds the carrier tube in an annular manner. The magnet coil cooperates with a ferromagnetic flux conductive piece on the rotor which is arranged between the rotor magnets.
Additionally, a sensor is provided that detects the axial position of the rotor and cooperates with a control unit which regulates the electric current flow in the magnet coil. As soon as the field forces of the rotor magnets and the stator magnets are engendered by an axial shift of the rotor to accelerate the rotor out of the equilibrium position in the axial direction there is generated a signal of the axial shift of the rotor as measured by the sensor which produces in the magnet coil a counteracting stabilizing field force. The rotor is thus, upon an axial shift in position in one or the other direction, always returned to its setpoint position. The stabilizing axial force countering the axial shift is so phase-shifted in time in a known manner that the rotor is held stably in its setpoint position by restoring as well as damping forces.
A drawback of the aforedescribed measuring device is that the rotor has only a relatively limited positional stiffness in the radial direction. The origin of that problem is the large distance between the stator and rotor magnets because of the annular channel between the support pipe and the rotor for the throughflow of the fluid.
In DE-A-24 44 099, a magnetic bearing for rapidly movable bodies is described. This magnetic bearing has a sleeve-shaped rotor whose ends have pole pieces provided with permanent magnets and whereby, based upon tractive forces on the rotor, the latter is held in a stable position. By means of a contactless position sensor, deviations from the equilibrium position are determined. Such deviations are compared by a powerless electromagnetic stray field control for which annular coils are provided which are arranged proximal to the gaps on the pole pieces of the rotor. Such a magnetic bearing is not suitable for disposition in a carrier tube through which a fluid is conducted on spatial grounds.
Magnetic bearings have also been used for blood pumps. Thus in U.S. Pat. No. 5,695,471, a blood pump is known which is formed as a radial pump with a radial rotor. The radial rotor is disposed within a carrier tube and has in an inlet side extension, a multiplicity of rotor magnets which are juxtaposed with stator magnets on the carrier tube. Additionally the radial rotor has distributed over the periphery a multiplicity of rod-shaped rotor magnets extending in the axial direction and which are juxtaposed with ring-shaped stator magnets on both sides of the radial rotor toward the carrier tube. These rotor and stator magnets should support the radial journaling in the region of the extension of the rotor. In the axial direction, the rotor is held purely mechanically with one end on a ball and another end on a point journal. The rotor is driven by a brushless rotary field motor. On sides of the carrier tube a coil is arranged which cooperates with a spoked-wheel magnet set into the radial rotor. A drawback of this blood pump is that the bearing stability in the radial direction is not optimal and that the pump because of the multiplicity of rotor and stator magnets has a high spatial requirement and high weight. In addition, the purely mechanical bearings give rise to wear in the axial direction.
The are also axial blood pumps. Here the journaling is effected exclusively mechanically in impeller wheels which are arranged at fixed locations in the carrier pipe ahead of and behind the rotor (Wernicke et al., A Fluid Dynamic Analysis Using Flow Visualization of the Baylor/NASA Implantable Axial Flow Blood Pump for Design Improvement, Artificial Organs 19(2), 1995, Pages 161-177). Such mechanical bearings are subject to wear and have an unsatisfactory effect on sensitive liquids, especially body liquids like blood.
An object of the invention is to provide a measuring device of the type described at the outset which has a substantially higher bearing stiffness, especially in the radial direction, and which therefore has numerous applications.
This object is achieved by the following features in accordance with the invention:
a) the measuring device has a carrier tube;
b) a rotor is journaled rotatably in the carrier tube;
c) the rotor is configured for interaction with the fluid found in the carrier tube;
d) the rotor has at both ends axially magnetized permanent magnet rotor magnets;
e) the ends of the rotor are juxtaposed with axially opposite permanently magnetic stator magnets connected to the carrier tube;
f) each stator magnet has such axial magnetism that it attracts the neighboring stator and rotor magnets; and
g) the measuring device has a magnetic axial stabilizing device for the rotor.
Alternatively, the object is achieved by a measuring device with the following features:
a) the measuring device has a carrier tube;
b) a rotor is rotatably journaled in the carrier tube;
c) the rotor is configured for the interaction with the fluid found in the carrier tube;
d) at the ends of the rotor there are respective axially magnetized permanently magnetic magnets opposite a flux conductive member whereby the magnets are either mounted on the rotor as rotor magnets or are connected to the carrier tube as stator magnets; and
e) the measuring device has a magnetic axial stabilizer unit.
The basic concept of the invention is thus, by means of rotor magnets and stator magnets arranged at the ends of the rotor, to generate a magnetic field in the axial direction respectively bridging the gaps between the rotor and stator magnets which respectively draws the opposing pairs of rotor and stator magnets in opposite directions toward one another. As a result, a bearing stiffness with the same geometry with respect to the magnet bearing of DE-A-29 19 236 can be obtained, but increased by at least one power of ten without thereby significantly affecting the annular passage between the carrier tube and the rotor hub. The aforedescribed effect also can be obtained when each magnet assembly has a magnet on one side and a flux-conducting device on the other side, as opposed to a system where each magnet assembly consists of two magnets, such as the rotor and stator magnets, which are juxtaposed. Thus, as an alternative, the magnet can be a rotor magnet mounted on the rotor and the flux-conducting member can be connected to the carrier tube or the flux-conducting member can be arranged on the rotor and the magnet fixed as a stator magnet on the carrier tube. For generating a high bearing stiffness, additional electric magnet coils can be provided for amplifying the magnetization of the flux-conducting member in the sense of increasing the attractive force between the magnets and the flux-conducting members.
To the extent that rotor and stator magnets pairwise are disposed opposite one another, they should preferably be composed of at least two interfitted partial magnets whereby respectively radially neighboring partial magnets are oppositely magnetized. Through this configuration of the rotor and stator magnets, a further increase in the bearing stiffness by a factor of 40 can be produced.
The rotor is preferably formed as an axial rotor so that there is an axial flow in the support tube. Such an axial rotor is substantially less expensive to shape than a radial rotor.
According to the invention, further, the rotor is provided with a rotor hub and the rotor magnets or flux guiding pieces are arranged in the rotor hub, whereby stator magnets or the flux-conducting pieces are disposed opposite the end faces of the rotor hub. The stator magnets or flux-conducting pieces can be connected with the carrier tube via ribs configured to promote flow. With this arrangement, a compact construction results which avoids to the greatest possible extent detrimental cracks. The stator magnets or flux-conductive pieces should be disposed in radial stabilizers whose contours do not project beyond the rotor hub whereby the radial stabilizers preferably have the same contours as the rotor hub.
In a further feature of the invention, at least one of the respective oppositely lying end faces of the radial stabilizers and the rotor can be of spherical configuration. With this configuration, it is possible to avoid, upon axial shifting of the rotor, a mechanical contact of axially spaced portions of the rotor and radial stabilizer. To limit the radial and/or axial mobility of the rotor it is advantageous to provide the respective oppositely lying end faces of the radial stabilizer and the rotor with mutually interdigitating complementary bearing pins and pin recesses, whereby a corresponding radial play is ensured such that bearing pins and bearing recesses will come into contact only upon relatively large deflections of the rotor in the radial direction.
According to a further feature of the invention, the rotor magnets and the stator magnets or flux-conducting pieces are arranged directly opposite one another respectively to ensure the strongest possible magnetic field.
According to the invention it is further proposed that the axial stabilization device have at least one electromagnetic coil as well as a control unit with a sensor detecting the axial movement of the rotor, whereby the control unit so influences the electric current flux in the magnet coil or the magnet coils that the magnetic field of the magnet coils counteracts an axial movement of the rotor out of its setpoint position. Such an axial stabilization device in principle is already known from DE-A-29 19 236 and DE-A-24 44 099 and has been found to be effective. Advantageously, the axial stabilizer can have two magnet coils which are arranged in the region of the stator magnets and/or the end faces of the rotor, whereby the axial stabilization is especially effective.
Thus there are two possibilities for arrangement of the magnet coils, namely, one in such manner that they surround the carrier tube and the second in which they are provided in the radial stabilizer itself whereby, however, then facilities must be provided for leading the conductors to and from the magnet coils. Preferably the magnetizable flux-conducting pieces of the radial stabilizer should be in such a configuration and arrangement that the axial magnetic field generated by the reactor and stator magnets is superimposed in the gap between the end of the radial stabilizer and reactor with the magnetic field generated by the magnet coils in axial direction and thus in a manner counteracting an axial movement of the rotor out of its intended position. The magnet coils can be used as sensors themselves. The flux-conducting pieces are preferably arranged at the level of the magnetic coils.
Advantageously the rotor has a pulse generator and the carrier tube a pulse pickup, whereby the pulse generator produces pulses detected by the pulse pickup and representing the speed of the rotor. This can be achieved in a simple manner by forming the pulse generator as pulse magnets and the pulse pickup as a coil so that in the coil an electric current is induced upon rotation of the rotor.
In a further feature of the invention it is provided that the carrier tube has at the level of the rotor, a three-phase stator which can be fed with three-phase current and the rotor has a radially magnetized plurality of spoked wheel magnet poles. The result is a synchronous motor which by supply of the three-phase stator with three-phase current generates a rotary field which entrains the rotor so that a rotary movement is imposed on the rotor. The measuring device in this case has motor properties. Preferably the magnets on the pole spokes are four magnetic segments magnetized in four different radial directions to counteract wobbling of the rotating rotor resulting from magnetic field asymmetry in the region of the bearing gap between rotor and radial stabilizer. The rotary field stator should be connected with an electronic three-phase generator operating with load angle regulation. The desired regulation of the load angle can be effective to set and stabilize the rotary field and torque applied to the motor depending upon the amount and direction of adjustment of the load angle.
The rotor can be matched to the respective purpose. For example, the rotor can have vane-type projections when the measuring device according to the invention is to be used as a centrifugal or turbine measuring unit for flowthrough measurements. The surface of the rotor can, however, be configured to be smooth and especially cylindrical, to the extent that the measuring device is configured in the aforedescribed manner as a synchronous motor for measurement of the viscosity of gaseous or liquid media by determining the electrical power utilized by the synchronous motor for maintaining a certain rotor speed. The viscosity is substantially proportional to the friction work at the outer surface of the motor so that the friction work in turn represents a measurement of the viscosity of the medium surrounding the rotor.
According to a further feature of the invention, it is proposed that the outer surface of the rotor have at least one radial outwardly extending projection and that a sensor is provided which detects the axial position of the rotor and generates a signal proportional to the axial position. The projection, preferably in the form of an annular rib, enables the possibility of measurement of the axial flow velocity of gaseous or liquid medium in which the axial force transmitted via the projection to the rotor is detected through the corresponding axial position shift of the rotor, whereby the axial stabilizing device generates a corresponding signal. Both features can be combined to the extent that the measuring device is provided with a synchronous motor in the above-described manner. Then the axial shift of the rotor and the drive power supplied to the rotor can be detected through the use of the synchronous motor so that both the flow velocity and the viscosity of the flow can be measured at the same time.

Abstract: a) the measuring apparatus (1) has a support tube (2);

Abstract: b) a rotor (3, 36, 42) is rotatably journaled in the support tube (2);

Abstract: c) the rotor (3, 36, 42) is configured for interaction with the fluid found in the support tube (2);

Abstract: d) the rotor (3, 36, 42) has at both ends axially-magnetized permanently magnetic rotor magnets (7, 8; 46; 47);

Abstract: e) permanent magnetic stator magnets (18, 19; 52, 53) connected with the support tube (2) are axially juxtaposed with the ends of the rotor (3, 36, 42);

Abstract: f) each stator magnet (18, 19; 52, 53) has such axial magnetization that the neighboring stator and rotor magnets (18, 19; 7, 8; 46, 47; 52, 53) are oppositely attractive.

Abstract: g) the rotor device (1 [sic]) has a magnetic axially-stabilizing device (22, 23, 27; 58, 59, 66) for the rotor (3, 36, 42).


Blade tracker apparatus for tracking rotating helicopter blades includes an antenna which transmits a signal beam in the direction of the rotating blade. The impedance of the antenna changes as one of the blades enters the transmission beam and the amount by which the impedance changes varies as a function of the physical distance between the antenna and the blade. The varying impedance caused by a blade passing the antenna will amplitude modulate the transmitted signal and provide an indication of the distance of each of the several blades of a rotor as each of the blades passes through the field of the antenna.

1. Field of the Invention
The invention relates to method and apparatus for sensing the presence of a moving object and for generating outputs indicative of the path of travel of moving objects and more particularly to method and apparatus for sensing the presence and/or relative position of a rotating fan blade or helicopter blade.
2. Background Art
It is well known that vibration resulting from rotating objects are often detrimental. Both military and commercial rotorcraft operators wage a continual battle against vibration, both to extend the life of the rotorcraft and to enhance the comfort of the crew and passengers. The rotor itself is a principal contributor to vibration. However, rotor vibration can be reduced through proper balancing of the rotor blades. Various devices have been developed and sold over the last several decades to provide the information required to accurately and efficiently balance a rotor. The more accurate and efficient rotor track and balance systems incorporate a blade tracking device to measure blade height and lead/lag between the respective blades of the rotor. Measurements of these blade parameters may be used in a balancing algorithm to generate indicia representing recommended changes in blade adjustments in order to minimize vibration. In addition, blade tracking information is required in an over-all rotorcraft tuning algorithm and for the successful completion of various required maintenance actions.
In order to reduce damage to the engine, transmission, and airframe caused by the vibration of helicopter blades, it is important that all blades of a rotor travel in the same plane and that all blades rotate with a fixed angular separation. To detect that the several blades of a helicopter rotor or the like travel in the same plane, it is a common practice to measure the distant of each of the blades from a fixed point on the craft when the blades are in predefined position relative to the fixed point. Prior art blade tracking systems primarily use strobe lights and optical sensors which measure light reflected from the rotating blades to determine the relative position of the moving blades. Some blade tracking systems have used electrostatic sensing probes or radiation, whereby a lens focuses a beam of radiation in a plane and the sensing probes detect the presence of an object as it passes through the radiation beam. Other prior art systems employ an oscillator connected to a large capacitive element positioned adjacent the plane of rotation of the blades of a rotor. In such a system, blade tracking measurements are derived from frequency modulations, resulting from a change in capacitance, and displayed on an oscilloscope.
A general problem with tracking devices known from the prior art is the lack of accuracy of the generated output signals. Prior art tracking devices using electrostatic probes are prone to error due to undefined static sources and electrostatic changes in the atmosphere which may influence accuracy of any static electricity detectors. Most earlier blade tracking systems, including those systems relying on change in capacitance, typically measure the position of the several blades of a propeller while the craft is on the ground. However, it is highly desirable that improper tracking be detected in flight, since blade dynamics vary based on engine speed and load. Commonly used tracking devices which rely on reflected optical signals are generally inaccurate because of interference due to ambient light and cannot be used at night unless the blades are artificially illuminated. In addition, reflective tape is commonly required on the blades. Furthermore, optical tracking systems tend to be sensitive to color. On helicopter rotors, color may vary from blade to blade and is often white or shades of gray. Optical sensors have been known to be incorrectly triggered by rotor shadows and to be sensitive to varying ultraviolet light levels across the zenith.
Known optical devices detect the passage of rotor blades through their field of view and generate pulse edges as each rotor blade enters and leave the optical sensing region. The path of the rotating blade is detected by using two such optical devices, such that their corresponding optical sensors are separated by a known angle. Precise time measurements of the pulse edges detected at the two optical sensing regions, coupled with rotor speed and installation parameters, allow blade height to be calculated. Synchronized timer circuits are used to identify the time that each blade enters or leaves the optical sensing region of each sensor. A once-per-revolution timing pulse is simultaneously measured to provide both rotational phase and rate information. Specifically, what is measured is the time at which the rotor blade enters the field of view and leaves the field of view of each of the two sensors. Based on this information and using well-known geometric equations, the track height of the rotor blade can be readily determined in a well-known fashion. Furthermore, the actual blade angular velocity can be calculated as well. The accuracy of blade velocity calculations is determined, in large measure, by the ability to accurately identify both leading and trailing blade edges of the blades as they pass through a measurement space. One of the problems with prior art optical systems is the inability of the track sensors to properly respond to light level changes as the blades enter and leave their fields of view. This problem is often aggravated by differences in paint and/or paint erosion on the several blades, which further tends to affect the accuracy of the blade height calculations.
Radio frequency or microwave devices such as the well-known Doppler or pulsed radar systems have commonly be(n used as locating and tracking devices. However, known radar devices such as Doppler radar depends on change in frequency and uses complex circuitry to measure changes in transmit frequency. Pulsed radar typically can be used effectively only when the distance between the source and the target is greater than 100 meters and is therefor not suited for use as a helicopter blade tracking device, where the tracking device may have to be mounted approximately one meter from the track of the rotor blades.
These and other problems of the prior art are overcome in accordance with the present invention by means of tracking apparatus comprising a radiating antenna having a predefined antenna impedance and detection circuitry for detecting deviation in antenna impedance resulting from movement of an object within the field of radiation of the antenna. Advantageously, the antenna may be positioned in close proximity to the projected path of a moving object, e.g. at a distance of on the order of one meter or less.
In accordance with one aspect of the invention, the tracking apparatus is used in a system for tracking the several blades of a helicopter rotor and the antenna is directed toward the path of travel of the rotor blades. A signal source connected to the antenna transmits radio frequency signals to the antenna, causing the antenna to radiate an electromagnetic field in the path of the helicopter rotor blades. Signal detection circuitry, connected to the antenna, provides an output signal when an a change in antenna impedance occurs due to the entry of a rotor blade in the field of the antenna. A computation of distance of each blade from the antenna is derived in a standard fashion to provide a measure of tracking of the rotor blades.
In a specific embodiment of the invention, a radio frequency (RF) generator connected to the antenna provides a continuous wave unmodulated signal. As a moving blade enters the beam, it causes a change in the antenna field impedance, resulting in a modulation of the transmitted signal. The modulated signal is received by the antenna and is detected and amplified by circuitry connected to the antenna.
Advantageously, the tracking arrangement of the present invention comprises a compact antenna structure consisting of printed circuit boards which are readily and unobtrusively mounted.
In a particular embodiment of the invention, a tracking arrangement comprises a pair of spaced apart antennas, each connected to a circuit arrangement including a signal source and circuitry of the present invention for detection of change in impedance, whereby distance of a moving object from a predetermined location may be computed from signals indicative of time of detection at the spaced apart antennas.
In accordance with one aspect of the present invention, a signal source transmits an RF signal to an antenna, directed toward the path of an object to be detected, causing the antenna to radiate an electromagnetic field in the direction of the path of the object. The antenna preferably has a well predefined antenna impedance resulting in a well defined return loss. As the object passes through the electromagnetic field of the antenna, the impedance of the antenna changes, resulting in a change in the return loss. Effectively, movement of the object through the antenna field causes an amplitude-modulation of the carrier signal. In addition to causing a change in the amplitude of the return signal, the moving object also causes a change in the phase of the return signal with respect to the transmitted signal, resulting in a phase modulation.
Advantageously, the blade tracking device in accordance with the invention acts as a motion detector which is sensitive to change in distance between the antenna and the moving objects.
Advantageously, the detector device of the present invention is not sensitive to light and can be used in bright sunlight as well as in darkness. Neither do clouds, nor fog, nor the color of the items being tracked have any effect on the measurements obtained by the tracking device of this invention. Furthermore, the antenna detector device of the present invention is small and may be housed in a standard radome capable of withstanding normal environmental changes such as moisture, sand, dust, and dirt as well as vibration and shock or exposure to manmade corrosives such as fuels and lubricants.