A process for making a hair dye preparation involving: (a) providing an aqueous surface-active fatty alcohol dispersion containing: (i) a fatty alcohol; and (ii) a surfactant; (b) providing an oil component; (c) providing a hair dye component; and (d) combining (a)-(c), at a temperature of from 18 to 25xc2x0 C., to form the hair dye preparation.

1. Field of the Invention
The invention relates to a method for the cold-production of hair coloring preparations, preferably coloring creams, in which surface-active fatty alcohol dispersions are used.
For the production of hair coloring preparations, such as, for example, creams of the oil-in-water type, fatty alcohols are normally used to adjust the viscosity. The emulsions are prepared here by the hot-method, i.e. the constituents are mixed above the melting point of the highest-boiling component and then slowly cooled with intensive homogenization. For reasons of efficiency, however, it is desirable to prepare such preparations by a cold method, for example using known PIT or microemulsion technology. However, in this connection, a problem arises inasmuch as adjustment of high viscosities is possible only with very great difficulty, particularly when lamellar gels are prepared using fatty alcohols.
Consequently, the object of the invention was to provide a method for the cold-production of hair coloring preparations, in particular creams of the O/W type, which can also be used to produce lamellar gels having particularly good storage stability.
2. Description of the Invention
The invention provides a method for producing hair coloring preparations with improved viscosity, in which aqueous surface-active fatty alcohol dispersions are stirred up with oil components and hair dyes in the cold.
Surprisingly, we have found that it is also possible to prepare O/W cream preparations for the coloring of hair by a cold method if surface-active fatty alcohol dispersions, preferably fatty alcohol microdispersions, are used to adjust the consistency. The resulting compositions are in the form of lamellar gels which are notable for particularly high stability, even during storage above room temperature.
Fatty Alcohols
The dispersions to be used for the purposes of the method according to the invention may comprise fatty alcohols of the formula (I)
R1OHxe2x80x83xe2x80x83(I)
in which R1 is a linear or branched, saturated or unsaturated alkyl radical having 6 to 30 carbon atoms. Typical examples are caproic alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, linolyl alcohol, linolenyl alcohol, elaeostearyl alcohol, arachidyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol, and technical-grade mixtures thereof, which are produced, for example, during the high-pressure hydrogenation of technical-grade methyl esters based on fats or oils or aldehydes from the Roelen oxo synthesis, and as monomer fraction during the dimerization of unsaturated fatty alcohols. Preference is given to technical-grade fatty alcohols having 12 to 18 carbon atoms, such as, for example, coconut, palm, palm kernel, cetearyl or tallow fatty alcohol. The proportion of fatty alcohols in the dispersions can here be 5 to 50% by weight and preferably 25 to 40% by weight.
Surfactants
The fatty alcohol dispersions to be used for the purposes of the method according to the invention may comprise anionic, nonionic, cationic and/or amphoteric or zwitterionic surfactants. Typical examples of anionic surfactants are soaps, alkylbenzenesulfonates, alkanesulfonates, olefinsulfonates, alkyl ether sulfonates, glycerol ether sulfonates, xcex1-methyl ester sulfonates, sulfofatty acids, alkyl sulfates, fatty alcohol ether sulfates, glycerol ether sulfates, fatty acid ester sulfates, in particular lauric acid+1EO sulfate, hydroxy mixed ether sulfates, monoglyceride (ether) sulfates, fatty acid amide (ether) sulfates, mono- and dialkyl sulfosuccinates, mono- and dialkyl sulfosuccinamates, sulfotriglycerides, amide soaps, ether carboxylic acids and salts thereof, fatty acid isethionates, fatty acid sarcosinates, fatty acid taurides, N-acylamino acids, such as, for example, acyl lactylates, acyl tartrates, acyl glutamates and acyl aspartates, alkyl oligoglucoside sulfates, protein fatty acid condensates (in particular vegetable products based on wheat) and alkyl (ether) phosphates. If the anionic surfactants comprise polyglycol ether chains, these can have a conventional homolog distribution, but preferably have a narrowed homolog distribution. Typical examples of nonionic surfactants are fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, fatty acid polyglycol esters, fatty acid amide polyglycol ethers, fatty amine polyglycol ethers, alkoxylated triglycerides, mixed ethers and mixed formals, optionally partially oxidized alk(en)yl oligoglycosides and glucuronic acid derivatives, fatty acid N-alkylglucamides, protein hydrolyzates (in particular vegetable products based on wheat), polyol fatty acid esters, sugar esters, sorbitan esters, polysorbates and amine oxides. If the nonionic surfactants comprise polyglycol ether chains, then these can have a conventional homolog distribution, but preferably have a narrowed homolog distribution. Typical examples of cationic surfactants are quaternary ammonium compounds and ester quats, in particular quaternized fatty acid trialkanolamine ester salts. Typical examples of amphoteric or zwitterionic surfactants are alkylbetaines, alkylamidobetaines, aminopropionates, aminoglycinates, imidazoliniumbetaines and sulfobetaines. Said surfactants are exclusively known compounds. With regard to structure and preparation of these substances, reference may be made to relevant review articles, for example, J. Falbe (ed.), xe2x80x9cSurfactants in Consumer Productsxe2x80x9d, Springer Verlag, Berlin, 1987, pp. 54-124 or J. Falbe (ed.), xe2x80x9cKatalysatoren, Tenside und Minerxc3x6ladditivexe2x80x9d [Catalysts, Surfactants and Mineral Oil Additives], Thieme Verlag, Stuttgart, 1978, pp. 123-217. The proportion of surfactants in the fatty alcohol dispersions can be 0.1 to 10% by weight and preferably 0.5 to 5% by weight.
Fatty Alcohol Dispersions
The fatty alcohol dispersions can be prepared, for example, by the microdispersion method. Microdispersions are optically isotropic, thermodynamically stable systems which comprise a water-insoluble oil component (here: fatty alcohol), dispersantsxe2x80x94preferably alkyl glucosidesxe2x80x94and water. The clear or transparent appearance of the microdispersions is a consequence of the small particle size of the dispersed emulsion droplets. In this connection, it has been found that fatty alcohol microdispersions have a particularly advantageous effect on the production and storage stability of the resulting coloring preparations. Preference is given to using dispersions which have a particle size of less than 50 xcexcm, in particular of less than 20 xcexcm and particularly preferably less than 10 xcexcm. Reviews on the preparation and use of microdispersions are given by H. Eicke in Sxc3x96FW-Journal, 118, 311 (1992) and Th. Fxc3x6rster et al. in Sxc3x96FW-Journal, 122, 746 (1996); reference may further be made to the publications DE-A1 4411557 (Henkel) and EP-A1 0687206 (L""Orxc3xa9al).
Oil Components
Suitable oil components are, for example, Guerbet alcohols based on fatty alcohols having 6 to 18, preferably 8 to 10, carbon atoms, esters of linear C6-C22-fatty acids with linear C6-C22-fatty alcohols, esters of branched C6-C13-carboxylic acids with linear C6-C22-fatty alcohols, esters of linear C6-C22-fatty acids with branched alcohols, in particular 2-ethylhexanol, esters of linear and/or branched fatty acids with polyhydric alcohols (such as, for example, propylene glycol, dimerdiol or trimertriol) and/or Guerbet alcohols, triglycerides based on C6-C10-fatty acids, liquid mono-/di-/triglyceride mixtures based on C6-C18-fatty acids, esters of C6-C22-fatty alcohols and/or Guerbet alcohols with aromatic carboxylic acids, in particular benzoic acid, esters of C2-C12-dicarboxylic acids with linear or branched alcohols having 1 to 22 carbon atoms or polyols having 2 to 10 carbon atoms and 2 to 6 hydroxyl groups, vegetable oils, branched primary alcohols, substituted cyclohexanes, linear C6-C22-fatty alcohol carbonates, Guerbet carbonates, esters of benzoic acid with linear and/or branched C6-C22-alcohols (e.g. Finsolv(copyright) Tennessee), dialkyl ethers, ring-opening products of epoxidized fatty acid esters with polyols, silicone oils and/or aliphatic or naphthenic hydrocarbons.
Hair Dyes
Suitabe hair dyes are in this connection, for example, direct dyes, e.g. from the group of nitrophenylenediamines, nitroaminophenols, anthraquinones or indophenols, such as, for example, the compounds known under the international names or trade names HC Yellow 2, HC Yellow 4, Basic Yellow 57, Disperse Orange 3, HC Red 3, HC Red BN, Basic Red 76, HC Blue 2, Disperse Blue 3, Basic Blue 99, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Disperse Black 9, Basic Brown 16, Basic Brown 17, picramic acid and Rodol 9 R, and also 4-amino-2-nitrodiphenylamine-2xe2x80x2-carboxylic acid, 6-nitro-1,2,3,4-tetrahydroquinoxaline, (N-2,3-di-hydroxypropyl-2-nitro-4-trifluoromethyl)aminobenzene and 4-N-ethyl-1,4-bis(2xe2x80x2-hydroxyethyl-amino)-2-nitrobenzene hydrochloride. Furthermore, it is also possible to add to the emulsions naturally occuring dyes, such as, for example, henna red, henna neutral, henna black, camomile blossoms, sandalwood, black tea, buckthorn bark, sage, logwood, madder root, catechu, sedre and alkanna root.
As well as the direct dyes, oxidation dyes, consisting of developer and coupler component, can also be added to the emulsions. The developer components used are, for example, primary aromatic amines having a further free or substituted hydroxyl or amino group situated in the para- or ortho-position, diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazolone derivatives, and 2,4,5,6-tetraaminopyrimidine and derivatives thereof. Specific representatives include p-toluylenediamine, p-aminophenol, N,N-bis(2-hydroxyethyl)-p-phenylenediamine, 2-(2,5-diaminophenoxy)ethanol, 1-phenyl-3-carboxyamido-4-amino-5-pyrazolone and 4-amino-3-methylphenol, 2-(2-hydroxyethyl)-1,4-amino-benzene and 2,4,5,6-tetraaminopyrimidine. The coupler components used are generally m-phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones, m-aminophenols, and pyridine derivatives. Suitable coupler substances are, in particular, 1-naphthol, pyrogallol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinolmonomethyl ether, m-phenylenediamine, 1-phenyl-3-methyl-5-pyrazolone, 2,4-dichloro-3-aminophenol, 1,3-bis(2,4-diaminophenoxy)propane, 2-chlororesorcinol, 2-chloro-6-methyl-3-aminophenol, 2-methylresorcinol, 2,5-dimethyl-resorcinol, 2,6-dihydroxypyridine and 2,6-diaminopyridine.
As regards further dye components, reference is made expressly to the Colipa list, published by the Industrieverband Kxc3x6rperpflege und Waschmittel [Industrial Association for Body Care and Detergents], Frankfurt. A review of suitable dyes is further given in the publication xe2x80x9cKosmetische Fxc3xa4rbemittelxe2x80x9d [Cosmetic Colorants] from the Farbstoffkommission der Deutschen Forschungsgemeinschaft [Dyes Commission of the German Research Society], Verlag Chemie, Weinheim, 1984, pp. 81-106. The hair colors can be present in amounts of from 0.1 to 15% by weight, preferably 0.5 to 10% by weight and in particular 1 to 5% by weight, based on the hair coloring preparations.
Polymeric Thickeners
In a further preferred embodiment of the invention, as well as comprising the surface-active fatty alcohol dispersions, the hair coloring preparations comprise polymeric thickeners, such as, for example, polysaccha-rides, in particular xanthan gum, guar guar, agar agar, alginates and tyloses, carboxymethyl-cellulose and hydroxyethylcellulose, and also relatively high molecular weight polyethylene glycol mono- and diesters of fatty acids, polyacrylates, (e.g. Carbopole(copyright) from Goodrich or Synthalene(copyright) from Sigma), polyacrylamides, polyvinyl alcohol and polyvinylpyrrolidone. The polymers can be used in amounts of from 0.1 to 5% by weight, preferably 0.5 to 2% by weight, based on the hair coloring preparation.
Industrial Applicability
Using the surface-active fatty alcohol dispersions it is possible to produce, also by a cold method, i.e. at temperatures in the range from 18 to 25xc2x0 C., hair coloring preparations which are in the form of lamellar gels. The invention therefore further relates to the uses of surface-active fatty alcohol dispersions, preferably fatty alcohol microdispersions, as bodying agents for the production of hair coloring preparations, preferably of O/W coloring creams, in which they may be present in amounts of from 10 to 70% by weight and preferably 25 to 35% by weight.
Further Auxiliaries and Additives
The hair coloring preparations according to the invention are preferably O/W creams, which may comprise, as further auxiliaries and additives, co-emulsifiers, superfatty agents, pearlescent waxes, stabilizers, further bodying agents, electrolyte salts, cationic polymers, silicone compounds, biogenic active ingredients, antidandruff agents, film formers, preservatives, hydrotropic agents, solubilizers, UV light protection filters, perfume oils and the like.
The surfactants present in the fatty alcohol dispersions which act therein as dispersants can likewise serve as emulsifiers in the end preparations. In addition, it is also possible to add other surfactants or co-emulsifiers to the hair coloring preparations, such as, for example:
(1) addition products of from 2 to 30 mol of ethylene oxide and/or 0 to 5 mol of propylene oxide to linear fatty alcohols having 8 to 22 carbon atoms, to fatty acids having 12 to 22 carbon atoms and to alkylphenols having 8 to 15 carbon atoms in the alkyl group;
(2) C12/18-fatty acid mono- and diesters of addition products of from 1 to 30 mol of ethylene oxide to glycerol;
(3) glycerol mono- and diesters and sorbitan mono- and diesters of saturated and unsaturated fatty acids having 6 to 22 carbon atoms and the ethylene oxide addition products thereof;
(4) alkyl mono- and oligoglycosides having 8 to 22 carbon atoms in the alkyl radical and the ethoxylated analogs thereof;
(5) addition products of from 15 to 60 mol of ethylene oxide to castor oil and/or hydrogenated castor oil;
(6) polyol and, in particular, polyglycerol esters, such as, for example, polyglycerol polyricinoleate, polyglycerol poly-12-hydroxystearate or polyglycerol dimerate. Likewise suitable are mixtures of compounds from two or more of these classes of substance;
(7) addition products of from 2 to 15 mol of ethylene oxide to castor oil and/or hydrogenated castor oil;
(8) partial esters based on linear, branched, unsaturated or saturated C6/22-fatty acids, ricinoleic acid, and 12-hydroxystearic acid and glycerol, polyglyerol, pentaerythritol, dipentaerythritol, sugar alcohols (e.g. sorbitol), alkyl glucosides (e.g. methyl glucoside, butyl glucoside, lauryl glucoside), and polyglucosides (e.g. cellulose);
(9) mono-, di- and trialkyl phosphates, and mono-, di- and/or tri-PEG alkyl phosphates;
(10) woolwax alcohols;
(11) polysiloxane-polyalkyl-polyether copolymers and corresponding derivatives;
(12) mixed esters of pentaerythritol, fatty acids, citric acid and fatty alcohol as in German Patent 1165574 and/or mixed esters of fatty acids having 6 to 22 carbon atoms, methylglucose and polyols, preferably glycerol, and
(13) polyalkylene glycols.
The addition products of ethylene oxide and/or of propylene oxide to fatty alcohols, fatty acids, alkylphenols, glycerol mono- and diesters, and sorbitan mono- and diesters of fatty acids or of castor oil are known, commercially available products. These are homolog mixtures whose average degree of alkoxylation corresponds to the ratio of the amounts of ethylene oxide and/or propylene oxide and substrate with which the addition reaction is carried out. C12/18-fatty acid mono- and diesters of addition products of ethylene oxide to glycerol are known from German Patent 20 24 051 as refatting agents for cosmetic preparations.
C8/18-Alkyl mono- and oligoglycosides, their preparation and their use are known from the prior art. They are prepared, in particular, by reacting glucose or oligosaccharides with primary alcohols having 8 to 18 carbon atoms. As regards the glycoside radical, both monoglycosides, in which a cyclic sugar radical is bonded glycosidically to the fatty alcohol, and also oligomeric glycosides having a degree of oligomerization up to, preferably, about 8 are suitable. The degree of oligomerization is a statistical average value which is based on a homolog distribution customary for such technical-grade products.
Furthermore, the emulsifiers used can be zwitterionic surfactants. The name zwitterionic surfactants is used for those surface-active compounds which carry at least one quaternary ammonium group and at least one carboxylate and a sulfonate group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines, such as N-alkyl-N,N-dimethylammonium glycinate, for example cocoalkyldimethylammonium glycinate, N-acylaminopropyl-N,N-dimethylammonium glycinate, for example cocoacylaminopropyldimethylammonium glycinate, and 2-alkyl-3-carboxymethyl-3-hydroxyethylimidazolines having in each case 8 to 18 carbon atoms in the alkyl or acyl group, and cocoacylaminoethylhydroxyethylcarboxymethyl glycinate. Particular preference is given to the fatty acid amide derivative known under the CTFA name Cocamidopropyl Betaine. Likewise suitable emulsifiers are ampholytic surfactants. The term xe2x80x9campholytic surfactantsxe2x80x9d means those surface-active compounds which, apart from a C8/18-alkyl or -acyl group in the molecule, contain at least one free amino group and at least one xe2x80x94COOHxe2x80x94 or xe2x80x94SO3Hxe2x80x94 group and are able to form internal salts. Examples of suitable ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids having in each case about 8 to 18 carbon atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate and C12/18-acylsarcosine. As well as the ampholytic emulsifiers, quaternary emulsifiers are also suitable, those of the ester quat type, preferably methyl-quaternized difatty acid triethanolamine ester salts, being particularly preferred.
The superfatting agents used may be substances such as, for example, lanolin and lecithin, and polyethoxylated or acylated lanolin and lecithin derivatives, polyol fatty acid esters, monoglycerides and fatty acid alkanolamides, the latter also serving as foam stabilizers.
Examples of suitable pearlescent waxes are: alkylene glycol esters, specifically ethylene glycol distearate; fatty acid alkanolamides, specifically coconut fatty acid diethanolamide; partial glycerides, specifically stearic acid monoglyceride; esters of polyhydric, optionally hydroxy-substituted carboxylic acids with fatty alcohols having 6 to 22 carbon atoms, specifically long-chain esters of tartaric acid; fatty substances, such as, for example, fatty alcohols, fatty ketones, fatty aldehydes, fatty ethers and fatty carbonates which have a total of at least 24 carbon atoms, specifically laurone and distearyl ether; fatty acids, such as stearic acid, hydroxystearic acid or behenic acid, ring-opening products of olefin epoxides having 12 to 22 carbon atoms with fatty alcohols having 12 to 22 carbon atoms and/or polyols having 2 to 15 carbon atoms and 2 to 10 hydroxyl groups, and mixtures thereof.
As well as the fatty alcohols, other suitable bodying agents are partial glycerides in particular. Preference is given to a combination of these substances with alkyl oligoglucosides and/or fatty acid N-methylglucamides of identical chain length and/or polyglycerol poly-12-hydroxystearate.
Examples of suitable cationic polymers are cationic cellulose derivatives, such as, for example, a quaternized hydroxyethylcellulose obtainable under the name Polymer JR 400(copyright) from Amerchol, cationic starch, copolymers of diallylammonium salts and acrylamides, quaternized vinylpyrrolidone/vinylimidazole polymers, such as, for example, Luviquat(copyright) (BASF), condensation products of polyglycols and amines, quaternized collagen polypeptides, such as, for example, lauryldimonium hydroxypropyl hydrolyzed collagen (Lamequat(copyright)L/Grxc3xcnau), quaternized wheat polypeptides, polyethyleneimine, cationic silicone polymers, such as, for example, amidomethicones, copolymers of adipic acid and dimethylaminohydroxypropyldiethylenetriamine (Cartaretine(copyright)/Sandoz), copolymers of acrylic acid with dimethyldiallylammonium chloride (Merquat(copyright) 550/Chemviron), polyaminopolyamides, as described, for example, in FR-A 2252840, and crosslinked water-soluble polymers thereof, cationic chitin derivatives, such as, for example, quaternized chitosan, optionally microcrystalline-dispersed, condensation products of dihaloalkylene, such as, for example, dibromobutane with bisdialkylamines, such as, for example, bis-dimethylamino-1,3-propane, cationic guar gum, such as, for example, Jaguar(copyright) CBS, Jaguar(copyright) C-17, Jaguar(copyright) C-16 from Celanese, quaternized ammonium salt polymers, such as, for example, Mirapol(copyright) A-15, Mirapol(copyright) AD-1, Mirapol(copyright) AZ-1 from Miranol.
Examples of suitable silicone compounds are dimethylpolysiloxanes, methylphenylpolysiloxanes, cyclic silicones, and amino-, fatty-acid-, alcohol-, polyether-, epoxy-, fluorine-, glycoside- and/or alkyl-modified silicone compounds, which can either be liquid or in resin form at room temperature. Typical examples of fats are glycerides, and suitable waxes are inter alia beeswax, carnauba wax, candelilla wax, montan wax, paraffin wax or microcrystalline waxes, optionally in combination with hydrophilic waxes, e.g. cetylstearyl alcohol or partial glycerides. Stabilizers which can be used are metal salts of fatty acids, such as, for example, magnesium, aluminum and/or zinc stearate. The term biogenic active ingredients means, for example, tocopherol, tocopherol acetate, tocopherol palmitate, ascorbic acid, deoxyribonucleic acid, retinol, bisabolol, allantoin, phytantriol, panthenol, AHA acids, amino acids, ceramides, pseudoceramides, essential oils, plant extracts and vitamin complexes. The antidandruff agents used may be climbazole, octopirox and zinc pyrethione. Customary film formers are, for example, chitosan, microcrystalline chitosan, quaternized chitosan, polyvinylpyrrolidone, vinylpyrrolidone-vinyl acetate copolymers, polymers of the acrylic acid series, quaternary cellulose derivatives, collagen, hyaluronic acid and salts thereof, and similar compounds. Possible swelling agents for aqueous phases are montmorillonites, clay mineral substances, Pemulen, and alkyl-modified Carbopol grades (Goodrich).
The term xe2x80x9cUV light protection filtersxe2x80x9d are organic substances which are able to absorb ultraviolet rays and give off the absorbed energy again in the form of longer-wavelength radiation, e.g. heat. UVB filters can be oil-soluble or water-soluble. Examples of oil-soluble substances are:
3-benzylidenecamphor and derivatives thereof, e.g. 3-(4-methylbenzylidene)camphor;
4-aminobenzoic acid derivatives, preferably 2-ethylhexyl 4-(dimethylamino)benzoate, 2-octyl 4-(dimethylamino)benzoate and amyl 4-(dimethylamino)benzoate;
esters of cinnamic acid, preferably 2-ethylhexyl 4-methoxycinnamate, isopentyl 4-methoxycinnamate, 2-ethylhexyl 2-cyano-3-phenylcinnamate (octocrylene);
esters of salicylic acid, preferably 2-ethylhexyl salicylate, 4-isopropylbenzyl salicylate, homomenthyl salicylate;
derivatives of benzophenone, preferably 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4xe2x80x2-methylbenzophenone, 2,2xe2x80x2-dihydroxy-4-methoxybenzophenone;
esters of benzalmalonic acid, preferably di-2-ethylhexyl 4-methoxybenzylmalonate;
triazine derivatives, such as, for example, 2,4,6-trianilino(p-carbo-2xe2x80x2-ethyl-1xe2x80x2-hexyloxy)-1,3,5-tri-azine and octyltriazone,
propane-1,3-diones, such as, for example, 1-(4-tert-butylphenyl)-3-(4xe2x80x2-methoxyphenyl)propane-1,3-dione.
Suitable water-soluble substances are:
2-phenylbenzimidazole-5-sulfonic acid and the alkali metal, alkaline earth metal, ammonium, alkylammonium, alkanolammonium and glucammonium salts thereof;
sulfonic acid derivatives of benzophenones, preferably 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its salts;
sulfonic acid derivatives of 3-benzylidenecamphor, such as, for example, 4-(2-oxo-3-bornylidenemethyl)-benzenesulfonic acid and 2-methyl-5-(2-oxo-3-bornylidene)sulfonic acid and salts thereof.
Suitable typical UV-A filters are, in particular, derivatives of benzoylmethane, such as, for example, 1-(4xe2x80x2-tert-butylphenyl)-3-(4xe2x80x2-methoxyphenyl)propane-1,3-dione or 1-phenyl-3-(4xe2x80x2-isopropylphenyl)propane-1,3-dione. The UV-A and UV-B filters can of course also be used in mixtures. As well as said soluble substances, insoluble pigments, namely finely disperse metal oxides or salts, are also suitable for this purpose, such as, for example, titanium dioxide, zinc oxide, iron oxide, aluminum oxide, cerium oxide, zirconium oxide, silicates (talc), barium sulfate and zinc stearate. The particles should here have an average diameter of less than 100 nm, preferably between 5 and 50 nm, and in particular between 15 and 30 nm. They can have a spherical shape, although it is also possible to use particles which have an ellipsoid shape or a shape deviating in some other way from the spherical form. As well as the two abovementioned groups of primary light protection substances, it is also possible to use secondary light protection agents of the antioxidant type, which interrupt the photochemical reaction chain which is triggered when UV radiation penetrates the skin. Typical examples thereof are superoxide dismutase, tocopherols (vitamin E) and ascorbic acid (vitamin C). Other suitable UV light protection filters are given in the review by P. Finkel in Sxc3x96FW-Journal 122, 543 (1996).
To improve the flow behavior, it is also possible to use hydrotropic agents, such as, for example, ethanol, isopropyl alcohol, or polyols. Polyols which are suitable here preferably have 2 to 15 carbon atoms and at least two hydroxyl groups. Typical examples are
glycerol;
alkylene glycols, such as, for example, ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, hexylene glycol, and polyethylene glycols having an average molecular weight of from 100 to 1000 daltons;
technical-grade oligoglycerol mixtures having a degree of autocondensation of from 1.5 to 10, such as, for example, technical-grade diglycerol mixtures with a diglycerol content of from 40 to 50% by weight;
methylol compounds, such as, in particular, trimethylolethane, trimethylolpropane, trimethylolbutane, pentaerythritol and dipentaerythritol;
lower alkyl glucosides, in particular those with 1 to 8 carbon atoms in the alkyl radical, such as, for example, methyl and butyl glucoside;
sugar alcohols having 5 to 12 carbon atoms, such as, for example, sorbitol or mannitol,
sugars having 5 to 12 carbon atoms, such as, for example, glucose or sucrose;
amino sugars, such as, for example, glucamine.
Examples of suitable preservatives are phenoxyethanol, formaldehyde solution, parabens, pentanediol or sorbic acid.
Perfume oils which may be mentioned are extracts from flowers (lavender, rose, jasmine, neroli), stems and leaves (geranium, patchouli, petitgrain), fruits (aniseed, coriander, cumin, juniper), fruit peels (bergamot, lemon, orange), roots (mace, angelica, celery, cardamon, costus, iris, calmus), woods (sandalwood, guaiac wood, cedarwood, rosewood), herbs and grasses (taragon, lemon grass, sage, thyme), needles and branches (spruce, fir, pine, dwarf-pine), resins and balsams (galbanum, elemi, benzoin, myrrh, olibanum, opoponax). Animal raw materials are also suitable, such as, for example, musk, civet and castoreum. Suitable synthetic or semisynthetic perfume oils are ambroxan, eugenol, isoeugenol, citronellal, hydroxycitronellal, geraniol, citronellol, geranyl acetate, citral, ionone and methylionone.

Method for producing hair coloring preparations with improved viscosity


A content searching and presentation method in a terminal of an original user having a playlist includes the steps of accessing a playlist of a different user from the terminal and obtaining the playlist of the different user; computing a similarity between the obtained playlist of the different user and the playlist of the original user, which is a playlist owned by the terminal, in accordance with a predetermined computation equation; and presenting, as a searched result, content that is contained in the playlist of the different user and that is not contained in the playlist owned by the terminal when the computed similarity exceeds a predetermined threshold value.

1. Field of the Invention
The present invention relates to a user terminal, such as a PC (personal computer) or a cellular phone terminal, in which content such as musical pieces is recorded, and to a content searching and presentation method in the user terminal.
2. Description of the Related Art
As music distribution through a network has become popular and storage has become larger, the number of users who have a large number of musical pieces in a terminal such as a PC or a music player and who create a playlist and manage musical pieces has increased. Among them, there are many users who make their playlists public on the web.
Examples of a method for automatically creating a playlist include, as a well-known technology, a method for selecting a musical piece by the number of times of playback, by the date at which a musical piece was played back last, by the year in which the musical piece was sold, and by the date at which a musical piece was added to one's collection; a method for selecting a musical piece containing a key word specified by a user in the music title, the album title, and the artist name; a method for selecting a musical piece by genre; and a method for selecting a musical piece according to a rank made by the user himself/herself.
Even in a form other than a playlist, there are lots of musical piece information that can be used from a PC, a cellular phone terminal, etc., on a network.
Accordingly, by using these playlists that are made public, musical piece information on the network, etc., the user can register, in a playlist, musical pieces owned by themselves in a new combination, and can enjoy a new way of enjoying music, such as finding a musical piece that is not known to the user and purchasing it.
In Japanese Unexamined Patent Application Publication No. 2004-54023, it is disclosed that each user holds a list of musical pieces recommended by each user in a portable terminal of each user, the list of recommended musical pieces is exchanged among terminals, and in a portable terminal of a certain user, a list of collected musical pieces in which the list of musical pieces recommended by another user is created, and a musical piece is selected on the basis of the number of users who recommend the musical piece.

This patent is subject to a terminal disclaimer.

User terminal and content searching and presentation method


An anode for a lithium-ion battery is presented as well as a process for producing an anode for a lithium-ion battery. The anode is formed from a generally continuous sheet of particles of exfoliated graphite having a thickness of no more than about 350 microns, itself or in a laminate with a metallic substrate. The process involves laminating particles of exfoliated graphite to a metallic substrate, such that the particles of exfoliated graphite form a generally continuous sheet of graphite having a thickness of no more than about 350 microns. The inventive anode reduces or eliminates capacity fading due to contact loss and has superior permeability to lithium.

The present invention relates to a process for producing an anode for a lithium-ion battery and the anode itself. More particularly, the invention relates to the use of a generally continuous flexible graphite sheet as the anode of a lithium-ion battery. Moreover, a process is presented involving laminating particles of exfoliated graphite to a metallic substrate, so the particles of exfoliated graphite form a generally continuous sheet of graphite having a thickness of no more than about 350 microns, and the use of the resulting laminate as an anode for a lithium-ion battery.
Lithium-ion electrochemical cells useful for electrical storage usually consist of a lithium anode and a cathode formed from an electrochemically active material that can take up ions of the metal. An electrolyte containing ions of the metal is placed in contact with the anode and the cathode. During discharge of the cell, metal ions leave the anode, enter the electrolyte and are taken up in the active material of the cathode, resulting in the release of electrical energy.
Provided that the reaction between the metal ions and the cathode-active material is reversible, applying electrical energy to the cell can reverse the process. If such a reversible cathode-active material is provided in a cell having the appropriate physical configuration and an appropriate electrolyte, the cell can be recharged and reused. Rechargeable cells are commonly referred to in the electrochemical cell art as xe2x80x9csecondaryxe2x80x9d cells.
Various proposals have been made for increasing the energy densities of electrochemical cells through the application of highly reactive metals (e.g., the alkali metals) as anodic materials. Lithium metal has received the most attention in this regard due to its low atomic weight and because it is the most electronegative of all the metals. Electrochemical cells containing lithium or other alkali metal anodes are generally provided with non-aqueous electrolytic solutions in which electrically conductive salts are dissolved in organic aprotic solvents. Among the numerous electrically conductive salts which have heretofore been employed in non-aqueous electrolytic solutions are the alkali metal salts of such anions as the halides, halates, perhalates, haloaluminates, haloarsenates, halophosphates, haloacetates, phosphates, thiocyanates, sulfides, sulfates, cyanides, picrates, acetylacetonates, fluoroborates, hydrides, borohydrides, and so forth. These electrically conductive salts have been dissolved in a wide variety of organic aprotic solvents including Lewis bases such as the tertiary amines; amides and substituted amides such as formamide; nitriles such as acetonitrile, propionitrile and benzonitrile; open chain and cyclic esters such as propylene carbonate, alkyl acylates and butyrolactone; oxysulfur compounds such as dimethylsulfoxide, dimethylsulfite and tetramethylene sulfone; and, open chain and cyclic ethers such as the poly(alkyleneoxy) glycols, dioxane and the substituted dioxanes, dioxolane, tetrahydrofuran and tetrahydropyran.
The use of non-aqueous electrolytic solutions does not eliminate all problems associated with the use of lithium metal in the anodes of electrochemical cells. For example, the problem of avoiding contact of the lithium metal with moisture during assembly of the cell remains. Hence, efforts have been made to develop a rechargeable lithium cell containing no metallic lithium. As a result of such efforts, cells have been developed using, instead of a lithium metal anode, an anode comprising lithium intercalated or inserted in a material (an xe2x80x9cintercalation hostxe2x80x9d) that operates near the potential of lithium (see U.S. Pat. N0. 5,069,683).
Intercalation involves the formation of ionic bonds between the lithium atoms and the ions of the intercalation host. Graphite and coke are known intercalation hosts for lithium. In graphite, each lithium atom is associated with six carbon atoms of the crystalline graphite structure. Such xe2x80x9cLiC6xe2x80x9d combinations are regarded as the ideal for lithium intercalation in carbon. During cell operation, the lithium ion is released from the intercalation host and migrates into the cathode material (e.g., crystalline manganese dioxide) that can also reversibly incorporate lithium. Cells wherein both electrodes can reversibly incorporate lithium are known as xe2x80x9crocking chairxe2x80x9d (or xe2x80x9clithium ionxe2x80x9d) batteries. They have been called the rocking chair batteries because lithium ions xe2x80x9crockxe2x80x9d back and forth between the electrodes during the charge/discharge cycles.
The output voltage of cells of the rocking chair type is determined by the difference between the electrochemical potential of lithium within the two electrodes. It is important to have, as the positive and negative electrodes, materials that can reversibly intercalate (or otherwise retain) lithium at high and low voltages, respectively. Among the host materials proposed for lithium-ion battery anodes are WO2, MoO2, Mo6Se6 or carbon (e.g., coke or graphite), with the latter providing the best compromise between large specific capacity and reversible cycling behavior. However, in rocking chair cells a price is paid in terms of average output voltage and energy density when compared to a lithium metal cell; thus strongly oxidizing compounds (i.e., compounds which reversibly incorporate lithium above 4 volts) must be used as the positive electrode. LiNiO2, LiCoO2, and LiMn2O4 satisfy this requirement. These lithium-bearing positive electrode (cathode) materials are not moisture sensitive and can be handled in ambient atmospheres as can lithium-free carbon anode materials. The rocking chair (or lithium-ion cell) is assembled in its discharged state, where the output voltage is close to zero, and needs to be charged prior to use.
Replacing lithium metal anodes with lithium ion intercalation host anodes removes the restrictions lithium metal places upon cell design and choice of electrolytes and also the adverse effect lithium metal places upon cycling performance and safety in the finished cell. In particular, highly graphitic carbonaceous materials are very suitable lithium intercalation hosts because highly graphitic carbonaceous materials (particularly graphite) are inexpensive, non-toxic and are capable of incorporation into electrochemical cells having relatively high specific capacities.
Rechargeable (also referred to as secondary) lithium-ion batteries are increasingly used for portable electronics, such as laptop computers and cellular phones. Typically, the anode of a lithium-ion battery is made by coating graphite powder on both sides of a thin copper foil, or expanded copper mesh material. The graphite coating can be applied to the copper foil by using a slurry consisting of an organic solvent, graphite powder and an inert, non-conductive binder. A typical formulation for the slurry utilizes an about 50/50 mixture of organic solvent and graphite powder along with up to about 10 parts or more by weight of binder. After evaporation of the solvent, the resulting coating of graphite can be as thin as about 100 microns. The resulting graphite-coated copper mesh is then itself laminated to separator membranes and the battery cathode to complete the battery. The overall laminate is then slit to width and cut to size prior to insertion in the battery case.
The anodes of this type for lithium-ion batteries have severe drawbacks, however. It is often found that loss of interparticle contact in the graphite layer during cycling of the battery leads to capacity fading. It is believed that the swelling and contraction of the graphite because of intercalation and deintercalation causes this contact loss, possibly because of the presence of binder material, which creates spacing between the graphite particles.
What is desired, therefore, is an anode for a lithium-ion battery which uses graphite as a lithium intercalation host, but which reduces or eliminates capacity fading due to contact loss. The preferred anode has superior permeability to lithium and can be formed as an extremely thin sheet.
It is an object of the present invention to provide a process for producing an anode for a lithium-ion battery that utilizes graphite as an intercalation host for the lithium.
It is another object of the present invention to provide a process for producing an anode for a lithium-ion battery where the graphite is provided on the anode without the presence of a binder.
It is still another object of the present invention to provide a process for producing an anode for a lithium-ion battery where the graphite is present in the anode as a thin sheet.
It is a further object of the present invention to provide an anode for a lithium-ion battery without the need for inclusion of a copper substrate in the anode.
It is yet another object of the present invention to provide an anode for a lithium-ion battery that avoids the capacity fading observed with prior anodes produced using graphite as the lithium intercalation host.
It is still another object of the present invention to provide an anode for a lithium-ion battery produced according to the inventive process.
These objects and others that will become apparent to the artisan upon review of the following description can be accomplished by a process for producing an anode for a lithium-ion battery, the process involving laminating particles of exfoliated graphite to a metallic substrate, such that the particles of exfoliated graphite are in the form of a generally continuous sheet of graphite having a thickness of no more than about 350 microns. The particles of exfoliated graphite are preferably laminated to the metallic substrate via compression. It will be recognized, that the particles of exfoliated graphite can be compressed into sheet-form prior to being laminated to the substrate, or the very act of lamination of the particles by compression can form the graphite sheet.
Furthermore, fibers of carbon or graphite are advantageously admixed with the particles of exfoliated graphite prior to laminating the particles of exfoliated graphite to the metallic substrate. The fibers of carbon or graphite more advantageously have a length less than the thickness of the sheet of graphite, and are no more than about 50 microns in length. In another embodiment, the fibers of carbon or graphite have a length of at least about 150 microns, and have a radial structure. Preferably, sulfur and phosphorus are bonded on the edge planes of the sheet of graphite, with phosphorus present in an amount of about 200 ppm to about 2000 ppm and sulfur present in an amount of about 150 ppm to about 700 ppm.
In another advantageous aspect of the present invention, the inventive anode comprises the generally continuous sheet of graphite having a thickness of no more than about 150 microns, without the use of a substrate.
Graphite starting materials suitable for use in the present invention include highly graphitic carbonaceous materials capable of reversibly intercalating alkali metals. These highly graphitic carbonaceous materials have a degree of graphitization above about 0.80 and most preferably about 1.0. As used in this disclosure, the term xe2x80x9cdegree of graphitizationxe2x80x9d refers to the value g according to the formula:   g  =            3.45      -              d                          (          002          )                      0.095
where d(002) is the spacing between the graphitic layers of the carbons in the crystal structure measured in Angstrom units. The spacing d between graphite layers is measured by standard X-ray diffraction techniques. The positions of diffraction peaks corresponding to the (002), (004) and (006) Miller Indices are measured, and standard least-squares techniques are employed to derive spacing which minimizes the total error for all of these peaks. Examples of highly graphitic carbonaceous anode materials include synthetic graphites and natural graphites from various sources, as well as other carbonaceous materials such as petroleum cokes heat treated at temperatures above 2500xc2x0 C., carbons prepared by chemical vapor deposition or pyrolysis of hydrocarbons and the like.
The graphite starting materials used in the present invention may contain non-carbon components so long as the crystal structure of the starting materials maintains the required degree of graphitization. Generally, any carbon-containing material, the crystal structure of which possesses the required degree of graphitization, is suitable for use with the present invention. Such graphite preferably has an ash content of less than six weight percent. More preferably, the graphite used as the anode for a lithium-ion battery is at least about 97%, and most preferably at least about 99% pure.
Graphites are made up of layer planes of hexagonal arrays or networks of carbon atoms. These layer planes of hexagonally arranged carbon atoms are substantially flat and are oriented or ordered so as to be substantially parallel and equidistant to one another. The substantially flat, parallel equidistant sheets or layers of carbon atoms, usually referred to as basal planes, are linked or bonded together and groups thereof are arranged in crystallites. Highly ordered graphites consist of crystallites of considerable size, the crystallites being highly aligned or oriented with respect to each other and having well ordered carbon layers. In other words, highly ordered graphites have a high degree of preferred crystallite orientation. Graphites possess anisotropic structures and thus exhibit or possess many properties such as electrical conductivity that are highly directional. Briefly, graphites may be characterized as laminated structures of carbon, that is, structures consisting of superposed layers or laminae of carbon atoms joined together by weak van der Waals forces. In considering the graphite structure, two sets of axes or directions are usually noted, to wit, the xe2x80x9ccxe2x80x9d axis or direction and the xe2x80x9caxe2x80x9d axes or directions. For simplicity, the xe2x80x9ccxe2x80x9d axis or direction may be considered as the direction perpendicular to the carbon layers. The xe2x80x9caxe2x80x9d axes or directions may be considered as the directions parallel to the carbon layers (parallel to the planar direction of the crystal structure of the graphite) or the directions perpendicular to the xe2x80x9ccxe2x80x9d direction.
As noted above, the bonding forces holding the parallel layers of carbon atoms together are only weak van der Waals forces. Graphites can be treated so that the spacing between the superposed carbon layers or laminae can be appreciably opened up so as to provide a marked expansion in the direction perpendicular to the layers, that is, in the xe2x80x9ccxe2x80x9d direction and thus form an expanded graphite structure (also referred to as exfoliated or intumesced graphite) in which the laminar character of the carbon layers is substantially retained.
Graphite flake which has been greatly expanded and more particularly expanded so as to have a final thickness or xe2x80x9ccxe2x80x9d direction dimension which is at least 80 or more times the original xe2x80x9ccxe2x80x9d direction dimension can be formed without the use of a binder into cohesive or integrated articles and flexible graphite sheets of expanded graphite, e.g. webs, papers, strips, tapes, or the like. The formation of graphite particles which have been expanded to have a final thickness or xe2x80x9ccxe2x80x9d dimension which is as much as about 80 or more times the original xe2x80x9ccxe2x80x9d direction dimension into integrated articles and flexible sheets by compression, without the use of any binding material, is believed to be possible due to the excellent mechanical interlocking, or cohesion, which is achieved between the voluminously expanded graphite particles.
Generally, the process of producing flexible, binderless anisotropic graphite sheet material, e.g. web, paper, strip, tape, foil, mat, or the like, comprises compressing or compacting under a predetermined load and in the absence of a binder, expanded graphite particles which have a xe2x80x9ccxe2x80x9d direction dimension which is as much as about 80 or more times that of the original particles so as to form a substantially flat, flexible, integrated graphite sheet. The expanded graphite particles that generally are worm-like or vermiform in appearance, once compressed, will maintain the compression set and alignment with the opposed major surfaces of the sheet. Controlling the degree of compression can vary the density and thickness of the sheet material. The density of the sheet material can be within the range of from about 0.1 grams per cubic centimeter to about 1.5 grams per cubic centimeter.
The present invention relates to a process for producing an anode for a lithium-ion battery. As noted, the process may involve laminating a generally continuous sheet of exfoliated (or expanded) graphite particles to a substrate, such as a copper foil or expanded copper mesh material, or simply forming a graphite sheet without the need for a metallic substrate. The sheet of exfoliated graphite particles can be formed by compressing particles of exfoliated graphite and using as is, or then laminating the resulting sheet to the copper substrate. Alternatively, the generally continuous sheet of exfoliated graphite can be formed by compressing particles of exfoliated graphite to the substrate material, the act of compressing the particles functioning to form the generally continuous sheet.
By generally continuous sheet of exfoliated graphite is meant a sheet of compressed, exfoliated graphite, especially natural graphite. As discussed above, graphite is a crystalline form of carbon comprising atoms covalently bonded in flat layered planes with weaker bonds between the planes. By treating particles of graphite, such as natural graphite flake, with an intercalant of, e.g., a solution of sulfuric and nitric acid, the crystal structure of the graphite reacts to form a compound of graphite and the intercalant. The treated particles of graphite are referred to as xe2x80x9cparticles of intercalated graphite.xe2x80x9d Upon exposure to high temperature, the particles of intercalated graphite expand in dimension as much as 80 or more times their original volume in an accordion-like fashion in the xe2x80x9ccxe2x80x9d direction, i.e. in the direction perpendicular to the crystalline planes of the graphite. The exfoliated graphite particles are vermiform in appearance, and are therefore commonly referred to as worms. The worms may be compressed together into flexible sheets that, unlike the original graphite flakes, can be formed and cut into various shapes.
A common method for manufacturing graphite sheet is described by Shane et al. in U.S. Pat. No. 3,404,061, the disclosure of which is incorporated herein by reference. In the typical practice of the Shane et al. method, natural graphite flakes are intercalated by dispersing the flakes in a solution containing e.g., a mixture of nitric and sulfuric acid. The intercalation solution contains oxidizing and other intercalating agents known in the art. Examples include those containing oxidizing agents and oxidizing mixtures, such as solutions containing nitric acid, potassium chlorate, chromic acid, potassium permanganate, potassium chromate, potassium dichromate, perchloric acid, and the like, or mixtures, such as for example, concentrated nitric acid and chlorate, chromic acid and phosphoric acid, sulfuric acid and nitric acid, or mixtures of a strong organic acid, e.g. trifluoroacetic acid, and a strong oxidizing agent soluble in the organic acid. Alternatively, an electric potential can be used to bring about oxidation of the graphite. Chemical species that can be introduced into the graphite crystal using electrolytic oxidation include sulfuric acid as well as other acids.
In a preferred embodiment, the intercalating agent is a solution of a mixture of sulfuric acid, or sulfuric acid and phosphoric acid, and an oxidizing agent such as nitric acid, perchloric acid, chromic acid, potassium permanganate, hydrogen peroxide, iodic or periodic acids, or the like. Although less preferred, the intercalation solution may contain metal halides such as ferric chloride, and ferric chloride mixed with sulfuric acid, or a halide, such as bromine as a solution of bromine and sulfuric acid or bromine in an organic solvent.
After the flakes are intercalated, any excess solution is drained from the flakes and the flakes are water-washed. The quantity of intercalation solution retained on the flakes after draining may range from about 50 to 150 parts of solution by weight per 100 parts by weight of graphite flakes (pph) and more typically about 50 to 120 pph. Alternatively, the quantity of the intercalation solution may be limited to between 10 to 50 parts of solution per hundred parts of graphite by weight (pph) which permits the washing step to be eliminated as taught and described in U.S. Pat. No. 4,895,713, the disclosure of which is also herein incorporated by reference. Upon exposure to high temperature, e.g. about 300xc2x0 C., and even about 700xc2x0 C. to 1000xc2x0 C. and higher, the particles of intercalated graphite expand as much as 80 to 1000 or more times their original volume in an accordion-like fashion in the c-direction (in the direction perpendicular to the crystalline planes of the constituent graphite particles) to form expanded graphite particles or worms. The resulting worms may be compressed together into flexible sheets.
Flexible graphite sheet is coherent, with good handling strength, and is suitably compressed, such as by roll-pressing, to a thickness of about 350 microns and below, and even 75 microns and below and a density of 0.1 to 1.5 grams per cubic centimeter. Briefly, the process of producing flexible, binderless graphite sheet material, e.g., web, paper, strip, tape, foil, mat, or the like, comprises compressing or compacting under a predetermined load and in the absence of a binder, expanded graphite particles which have a xe2x80x9ccxe2x80x9d direction dimension which is as much as about 80 times that of the original particles so as to form a substantially flat, flexible, integrated graphite sheet. The expanded graphite particles that generally are worm-like or vermiform in appearance, once compressed, will maintain the compression set and alignment with the opposed major surfaces of the sheet. The density and thickness of the sheet material can be varied by controlling the degree of compression. The density of the sheet material is preferably within the range of from about 0.5 to about 1.4 grams per cubic centimeter to provide the desired level of permeability to the graphite sheet.
It is significant that the sheet of compressed exfoliated graphite particles is formed, and maintains its set, without the use of binders, this reducing the capacity fading caused by interparticle contact loss exacerbated by the presence of binders. Moreover, because of the conformability of the graphite from which the generally continuous sheet is formed, the laminate of graphite to copper substrate does not require an adhesive or other laminating agent, which would otherwise interfere with functioning of the resulting anode. Rather, simply compressing the graphite sheet to the substrate is sufficient to form the desired laminate.
Alternatively, rather than form the particles of exfoliated graphite into a sheet, which is then laminated to the substrate, the particles themselves can be laminated to the copper substrate directly, with the very act of laminating serving to form the particles of exfoliated graphite particles into a generally continuous sheet of the desired thickness. Lamination of the particles to the copper substrate can be accomplished by simply arraying the exfoliated particles on the substrate in a generally continuous fashion, and then applying a compressive force sufficient to compress the particles into a generally continuous sheet of the desired thickness.
Regardless of whether the particles of exfoliated graphite are formed into a generally continuous sheet prior to lamination to the substrate, or as part of the lamination process, a generally continuous sheet of exfoliated graphite is formed on the substrate, without the use of binders or adhesives. Because both the thickness and density of the graphite sheet can be adjusted by the manner and degree of compression, as would be readily ascertainable by the artisan, the capacity of the resulting anode can be maximized while optimizing the rate of intercalation of lithium into the anode.
Advantageously, as discussed above, a generally continuous sheet of exfoliated graphite can be formed using the methods described, and that sheet itself utilized as the anode of a lithium-ion battery, without lamination to a substrate material. In this way, copper, or another metallic material, commonly used as or in a lithium-ion battery anode is eliminated, resulting in significant savings of weight and cost.
In another embodiment of the invention, if it is desired to further increase the rate of penetration and intercalation of lithium into the graphite sheet, the alignment of the graphite crystals can be partially disrupted by admixing carbon or graphite fibers among the particles of exfoliated graphite prior to forming of the generally continuous sheet, whether the sheet is formed prior to lamination or as part of the lamination process (or not laminated at all). Preferably, the fibers are present at a level of about 1.5% to about 30% by weight and are of a length no greater than the thickness of the graphite sheet; most preferably, the fibers are no more than about 50 microns in length. In addition to disrupting the crystallite alignment of the graphite sheet, the carbon or graphite fibers have the further advantage of themselves being able to intercalate lithium; thus the fibers add to the capacity of the anode and do not contribute dead space to the battery.
Additionally, longer fibers, having a length of 150 microns or greater, can also be incorporated into the generally continuous graphite sheet at a level of about 1.5% to about 30% by weight, by admixing the fibers with the particles of exfoliated graphite prior to formation of the sheet. These longer carbon or graphite fibers should also have a radial structure. The longer fibers orient parallel to the length of the copper substrate, and the radial structure causes the edge plane of the fibers to be exposed to the lithium ions on the surface of the graphite sheet, thereby providing a chemical pathway for the intercalation of lithium into the interior of the laminate.
It has been observed that certain electrolyte solvents, such as propylene carbonate, can decompose on the surface of graphite, resulting in the formation of gas and Li2CO3, and reducing the efficiency of the use of lithium in the battery. In order to help avoid such decomposition of electrolytic solvents, the graphite particles can be modified by reacting them with a chemical compound or with a mixture of chemical compounds (herein referred to as a xe2x80x9cchemical modifierxe2x80x9d) capable of chemically bonding fluorine, chlorine, iodine or phosphorus to the graphite particles, with phosphorus being preferred. Suitable chemical modifiers for bonding fluorine to the graphite particles include fluorine gas. Suitable chemical modifiers for bonding chlorine include aqua regia (i.e., a mixture of water, HCl and HNO3 ), NaOCl, chlorine gas and any other agent that generates chlorine. Suitable chemical modifiers for bonding phosphorus to the graphite particles include ammonium dihydrogen phosphate (NH4H2PO4), P2O5, POCl3, H3PO4 and (NH4)2 HPO4.
The manner in which the chemical modification of the graphite particles is conducted depends largely on the specific chemical modifier used in the particular case. Known methods for establishing chemical bonds between carbon and fluorine, chlorine, iodine and phosphorus are applicable to the practice of the present invention. By way of illustration, chlorine gas can be used at 25xc2x0 C. to 100xc2x0 C. without a solvent while liquid chlorinating agents (e.g., NaOCl) can be used at 10xc2x0 C. to 80xc2x0 C. in aqueous solution. Iodine gas or ICl can be used to bond iodine to the graphite particles. Preferably from 20 parts per million to 500 parts per million of fluorine, chlorine or iodine or from 200 parts per million to 600 parts per million of phosphorus are chemically incorporated in the graphite particles. Such chemical modification occurs at the edge plane of the graphite particles. Bromine is not used as a chemical modifier in the present invention because it intercalates the graphite and so interferes with the intercalation of the alkali metal.
When acting in combination with sulfur, which can remain present on the edge planes of the graphite sheet after the exfoliation process at levels of between about 250 ppm to about 700 ppm, the decomposition of electrolytic solvents is greatly reduced.
The following example is presented to further illustrate and explain the present invention and should not be viewed as limiting in any regard.


An inverter apparatus converts a DC power of a capacitor charged via a rectifier circuit connected to a first AC power system into an AC power, and supplies the AC power to a second AC power system. The inverter apparatus includes a discharge circuit, a control circuit, a trigger circuit, a first voltage-sag detection circuit, a control power circuit, and a second voltage-sag detection circuit. When the second voltage-sag detection circuit detects a voltage sag of the control power circuit below a threshold, the trigger circuit generates a discharge command signal for causing the discharge circuit to discharge a charge from the capacitor.

1. Field of the Invention
The present invention relates to an inverter apparatus.
2. Description of the Related Art
When a break or a voltage sag occurs in an alternate-current power system (hereinafter, "system-voltage sag or the like"), a conventional inverter apparatus causes each of switching elements of an inverter to turn off, thereby avoiding any abnormal current passing through the switching elements. However, even when giving a stop command signal to each of the switching elements, if a power voltage of a control circuit that controls the switching elements decreases, sometimes the control circuit cannot maintain the stop command signal, and an abnormal switching command may be output to the switching elements in some cases. For example, if an abnormal switching command that establishes a short circuit in an inverter main circuit is output to each of the switching elements of the main circuit, there is a possibility that an overcurrent based on a charge stored in a capacitor for a direct-current power circuit may pass through the switching elements.
On the other hand, an inverter apparatus disclosed in Japanese Patent Application Laid-open No. H2-269479 is configured to give a stop command signal to switching elements upon an occurrence of a system-voltage sag or the like based on a detection signal about the event that is detected, and to cause a discharge circuit to discharge a charge in the capacitor after the switching elements are turned to a steady OFF-state, and operation of an inverter is stopped. Accordingly, even if the power voltage of the control circuit decreases and the control circuit can no longer maintain the stop command, the charge stored in the capacitor does not pass through the switching elements as an overcurrent.
However, in the inverter circuit described above, because the charge stored in the capacitor is discharged when a system-voltage sag or the like occurs, the capacitor needs to be recharged when restarting the inverter apparatus. Consequently, when restarting the inverter apparatus, there is a problem that a charging time is required for storing a predetermined charge in the capacitor.

Inverter apparatus with control and voltage-sag circuitry to quickly restart when recovering from a mini power failure


Osteoarthritis is treated by a composition containing both apocynin and an inhibitor of inducible nitric oxide synthase such as curcumin. Further components such as boswellic acids, glucosamine, acetylcysteine and boron further enhance the beneficial effect of apocynin and curcumin.

The invention is concerned with compositions for the treatment of osteoarthritis and related diseases and with methods for treating osteoarthritis.
Osteoarthritis (OA) is a degenerative joint disease, which develops by wear and tear of the joints during aging. OA mostly affects the weight-bearing joints such as spine, knees and hips, but thumb and finger joints may also be affected. Repetitive mechanical injury of the cartilage eventually results in loss of cartilage and damage to joint surfaces and adjacent bone. As a result of the tissue destruction, inflammatory cells invade the joint and the synovial membrane which is manifested by pain, swelling and stiffness of the affected joints. The repetitive mechanical injury leads to pathological changes that result in loss of proteoglycans and collagen from the cartilage matrix, which in turn leads to surface erosion and decreased loading capacity, In OA, chondro-cytes show a reduced potential to synthesize matrix constituents (proteoglycans and collagen fibers) and the expression of proteolytic enzymes (called matrix metallo-proteases, MNMP""s) contributes to cartilage destruction and release of proteoglycan fragments in the synovial fluid. The inflammatory responses to the mechanical insults further contribute to cartilage destruction. The inflammatory mediator interleukin I (IL-1) is considered as the principal mediator of cartilage destruction. It induces a number of changes in chondrocytes, including the concurrent generation of significant amounts of NO (nitrogen oxide) and superoxide radicals by inducible NO synthase (iNOS) and NADPH oxidase, respectively. NO reacts with superoxide to form peroxynitrite, which is largely responsible for the decrease in proteoglycan synthesis induced by IL-1. The role of superoxide was further demonstrated by the ability of superoxide dismutase to reverse the decrease in proteoglycan synthesis. The prevention of peroxynitrite formation via selective inhibition of iNOS and thus NO formation in vivo resulted in a marked decrease of MMP""s. In addition, intra-articular treatment of OA patients with superoxide dismutase reduces symptoms of OA for prolonged periods. These studies demonstrate that induction of catabolic enzymes (MMP""s) and cartilage destruction is mediated via the formation of NO and O2xe2x88x92radicals by chondrocytes or inflammatory cells. While the primary cause of OA is mechanical damage, rheumatoid arthritis (RA) is mainly the result of an autoimmune response that leads to chronic inflammation in the joint. Contrary to OA, typical manifestations of RA are an increase of parameters that are associated with inflammation, such as haematocrite and white blood cell count and pannus formation or hyperplasia of the joint capsule that leads to deformed joints. This in turn leads to morning stiffness. Although the (primary) aetiology of RA and OA are different, the pathological processes at a later stage result in some manifestations that are similar such as joint pain, cartilage degradation and general joint disability.
Lafeber et al. (Rheumatology, 1999 (38) 1088-1093) describe in vitro studies on the utility of apocynin (4-hydroxy-3-methoxy-acetophenone, acetovanillone) for the treatment of rheumatoid arthritis.
WO 95/22323 describes the use of analogues of apocynin, in particular the 4-hydroxyethoxy analogue, for controlling free radical generation by inflammatory cells in e.g. inflammatory bowel disease, rheumatoid arthritis and several other inflammatory conditions.
U.S. Pat. No. 5,629,351 discloses a fraction of boswellic acids isolated form Boswellia serrata, including a hitherto unknown 2-hydroxyboswellic acid, having anti-inflammatory, anti-arthritic and anti-ulcerogenic activities. WO 97/07796 claims the use of boswellic acid for the treatment of diseases, such as lung emphysema, cystic fibrosis, rheumatoid arthritis etc, which are induced by leucocytic elastase or plasmin activity.
U.S. Pat. No. 5,401,777 relates to the use of curcumin for treating conditions associated with formation of leucotrienes from arachidonic acid, such as inflammatory bowel diseases, chronic hepatitis, bronchial asthma and psoriasis.
U.S. Pat. No. 5,494,668 describes a product to be used for the treatment of OA and other musculoskeletal diseases, containing combined extracts from Withania somnifera (Ashwaganda) roots, Boswellia serrata (Sallai guggul) gum exudate (boswellic acids), Curcuma longa (turmeric) rhizomes (curcumin) and Zingiber officinale (ginger).
It was found that osteoarthritis can be effectively treated by administration of a suitable amount of apocynin or its functional and structural analogues, preferably in the form of an extract from a Picrorhiza plant, and preferably together with further components enhancing the beneficial effect of the apocynin. Thus, the invention in a first aspect provides compositions for the treatment of osteoarthritis, containing an effective amount of apocynin or its analogues.
In a second aspect, the invention provides methods for treating osteoarthritis comprising administering to a person in need of said treatment an effective amount of apocynin or its analogues. In a third aspect, the invention provides compositions comprising apocynin or analogues and methods for the treatment of arthritis in general as caused by wear-and-tear processes, due to labour, ageing or obesity, for the treatment of developed arthritis and for the-treatment of the first symptoms of joint disorders in patients not having a familial history of rheumatism.
In a fourth aspect the invention provides compositions that are characterized by the simultaneous presence of apocynin or analogues and other components, in particular an inhibitor of inducible nitric oxide synthase and methods for treatment of arthritis in general caused by wear-and-tear, autoimmune responses in the joints, goute, or other causes of cartilage degradation.
According to the invention apocynin is a highly useful component for treating osteoarthritis and related conditions. In particular, apocynin was found to be effective in retarding progression of osteoarthritis. It was found furthermore, that the inflammatory processes in arthritis can be controlled and the accompanying symptoms of stiffness and pain can be alleviated by combined administration of an inhibitor of NADPH oxidase, such as apocynin, and an inhibitor of inducible nitric oxide synthase (iNOS), such as curcumin.
Consequently, the composition of the invention contains at least 50 xcexcg, preferably at least 100 xcexcg, up to 1000 mg of apocynin on the basis of daily intake. The preferred daily intake is between 1 and 100 mg. Apocynin (acetovanillone) is a known compound (4-hydroxy-3-methoxy-acetophenone); most preferred is a dosage of at least 15 mg/day. According to the invention, analogues of apocynin may be used instead of or in addition to apocynin. Such analogues are in particular those in which the 4-hydroxyl group is etherified, especially with a hydroxylated alkyl group, such as 2-hydroxyethyl, 2,3-dihydroxypropyl or a sugar moiety. The latter analogue in which the sugar moiety is xcex2-D-glucose, is commonly known as androsin. This is the usual form in which apocynin is present in fresh plants.
Preferably apocynin and/or its analogues are present in an extract obtained from apocynin- or androsin-containing plant or plant parts, such as Picrorhiza species, for example P. kurrooa and P. scrophulariiflora; the latter is also known as Neopicrorhiza scrophulariiflora. Cucurbitacins are known to be present in both Picrorhiza species (Stuppner et al., 1991, Wang et al., 1993). As some cucurbitacins are reported to induce immune responses and might potentially lead to adverse health effects, a prepartion is preferably chosen in which cucurbitacins are largely absent, i.e. in which the cucurbitacin level is lower than 40%, preferably lower than 20%, especially lower than 10% of the level of apocynin or its analogue. The total daily intake of cucurbitacins should preferably be below 10 mg, more preferably below 4 mg.
The Picrorhiza extract can be obtained by extracting the rhizomes (roots) of Picrorhiza species or by subjecting an extract to column chromatography. Alternatively, extracts with high amounts of phenolic compounds can be obtained by pretreating the plant material with mineral acid to convert glycosides to their respective aglycones (e.g. androsin to apocynin). If desired, the material may then be defatted shortly to remove wax and other highly lipophilic matter. The material is extracted, for example with ethyl acetate and/or ethanol. The organic solvent is removed and an aqueous solution is obtained. The pH of the extract is increased to 10, e.g. with sodium hydroxide, to deprotonate phenolic compounds and to retain them in the aqueous phase. The aqueous solution is then washed e.g. with diethyl ether to remove cucurbitacins. The aqueous phase is then reacidified to neutralise phenolic compounds and again extracted with e.g. diethyl ether. The organic phase is collected and the solvent removed.
Apocynin may also be obtained from other sources, e.g. from the rhizome of Canadian hemp (Apocymum cannabinum) or other Apocynum species (e.g. A. androsaemifolium) or from the rhizomes of Iris species, provided that the extracts do not contain substantial amounts of cardiac glycosides.
Although the inventors do not wish to be bound by a specific theory, it is believed that the inhibitory effect of apocynin on NADPH oxidase restores the human system""s potential to prevent cartilage destruction that is associated with osteoarthritis.
This effect of apocynin was found to be enhanced by compounds that are capable of inhibiting inducible NO synthase (iNOS) and thus to reduce the formation of peroxynitrite. These combined effects are believed to be important in an effective control of the inflammation and its consequences in OA and OA-related diseases. Thus, the composition according to invention preferably also contains a component that inhibits iNOS. Phenolic compounds, in particular those which contain at least a p-hydroxycinnamoyl group (HOxe2x80x94C6H4xe2x80x94CHxe2x95x90CHxe2x80x94COxe2x80x94, p-coumaroyl), preferably a 3,4-di-hydroxycinnamoyl (caffeoyl) or 4-hydroxy-3-methoxycinnamoyl (feruloyl) group, and/or a dihydroxyphenyl group, preferably a dihydroxybenzopyran group, were found to be useful in this respect. Examples of suitable phenolic compounds include curcuminoids, resveratrol, quercetin and other hydroxyflavones, catechins such as epicatechin, catechin, gallocatechin, afzelechin, epigallocatechin gallate, epicatechin gallate, compounds having activated phenolic groups as do occur in ginkgo biloba extracts, luteolin but also procyanidins, caffeic acid, chlorogenic acid, ferulic acid, carnosic acid and rosmarinic acid and their natural derivatives as occur in herb extracts appeared to be useful in this respect. The amount of iNOS inhibitor is preferably between 200 xcexcg and 2000 mg per day; most preferably between and 20 and 500 mg/day.
Especially suitable are curcuminoids. These compounds are obtainable from plant parts, especially rhizomes of Zingiberaceae. A common prominent member of this family is Curduma longa. Curcumin (1,7-bis(4-hydroxy-3-methoxyphenyl)hepta-1,6-dien-3,5-dione) is the most prominent example of these active compounds. The recovery of curcumin from Curcuma rhizomes is well-known in the art. It is especially preferred to use preparations that comprise more than 85% curcumin, in particular more than 92% curcumin in order to avoid undesired side effects.
Said combination of apocynin and iNOS inhibitors is advantageously combined with other components that can further enhance the effects such as:
boswellic acids: these can be obtained by extracting Boswellia (Sabinsa) in particular Boswellia serrata by applying methods known in the art. It is preferred to use an acid fraction that comprises at least 15% and more preferably more than 23% boswellic acids; between 10 and 1000 mg preferably 80-400 mg should be administered per day; the boswellic acids are usually assayed as 65% of the boswellia extract, based on acid titration; this level, however, corresponds to a true boswellic acid level of about 25%;
glucosamine can be administered as sulfate or chloride salt or other food-grade form in an amount between 750-2500 mg preferably between 1 and 2 g;
chondroitin can be administered in an amount of 0.6-2.4 g, e.g. as sulfate but preferably in a form that is better available,
between 10 and 500 mg gingerols, preferably isolated from ginger oil,
extract from (Urtica dioica especially from the leaves,
N-acetyl cysteine in an amount per daily dose of 50 mg and 1 g, preferably 0.1-0.8 g, optionally as equivalent cysteine or thioproline;
boron 1-20 mg preferably 2-10 mg, e.g. as inorganic salt,
manganese 0.5-20 mg, preferably 1-10 mg and as inorganic salt such as MnO;
vitamins, minerals and trace elements such as vitamin B5, B6, C, D, E, folic acid, zinc and selenium.
The products according to the invention can be supplements such as tablets, pills, concentrates, powders, bars or cereals sauces, emulsions, liquids, or other dietetic preparations that can comprise the active components. The preparations are meant to be used for oral administration.

Composition for the treatment of osteoarthritis


An improved pitching machine is provided. The invented pitching machine may be capable of consecutively throwing balls that each have a different predetermined trajectory, rotational velocity, and velocity, without resetting the machine. The machine may be capable of simulating a pitch sequence, as thrown by a pitcher in a game situation, which may effectively train batters. The machine includes a pair of rotating belts that are vertically spaced and extend parallel to each other and generally horizontally. Once a ball is seized between the belts, the ball is rapidly conveyed by the belts and thrown in a predetermined direction and at a selected velocity. The velocity of the belts may be independently adjusted for imparting a predetermined rotational velocity on balls conveyed by the belts, for throwing balls of different predetermined trajectories. A control system is provided for selecting a pitch type for each ball thrown by the machine. The control system is used to select the velocity of each belt and horizontal and vertical inclination of the belts to enable the machine to throw balls of selected pitch types. The control system can be activated between each ball thrown, so that each consecutive ball thrown may have a different pitch type.

1. Field of the Invention
The present invention relates generally to devices used to propel balls, and more particularly, to a pitching machine that can make dynamic pitch changes in real-time and that significantly reduces deterioration typically suffered by the balls used in such machines.
2. Description of Related Art
Pitching machines are well known in the prior art. Pitching machines have long been used for propelling, or throwing spherical balls, such as baseballs, softballs, and tennis balls for example, or oval balls such as a football. Primarily pitching machines are used for throwing baseballs and softballs during activities such as batting practice, where the pitching machine is used to simulate a human pitcher. Modern pitching machines can effectively throw most pitch types thrown by today""s pitchers including fastballs, curveballs, sliders, knuckle-balls, and change-ups.
However, known pitching machines require setup for each type of pitch thrown, and must be reset for each different pitch type desired to be thrown to the batter. For instance, if it is desired to throw fastballs to a batter, the pitching machine is setup to throw fastballs. When it is desired to throw another type of pitch to the batter, such as curveballs, the machine is stopped and then re-sets for throwing balls of the new pitch type.
Another disadvantage of known pitching machines is that there is a substantial time delay between throwing different type pitches, due to the time required for resetting the machine. A more important disadvantage, is that the batter knows exactly what type of pitch is being thrown and can adjust their swing and stance for the anticipated speed and location of the pitch. In a game situation, the batter must be prepared for any type of pitch that may be thrown by the pitcher. Thus, pitching machine capable of consecutively throwing different type pitches, without requiring re-setup for the different type pitches to effectively simulate a game situation, would be advantageous over the prior art.
Known pitching machines include a pitching assembly that is supported by a base that may be a tripod or other suitable configuration. The pitching assembly may be coupled to the base such that the pitching assembly may pivot, or swivel, about on the base.
The pitching assembly typically includes a motor that may drive at least one ball throwing wheel. In a first common embodiment, one ball throwing wheel is provided for propelling, or throwing, balls. A fixed pad may be positioned adjacent to a confronting surface of the wheel to form a constricting space therebetween. A ball infeed chute may be coupled to the pad and is positioned to deliver the ball into the constricting space. The motor rotates the wheel at a desired speed to propel, or throw, the ball therefrom at a selected velocity. When a ball is placed in the infeed chute, the ball is momentarily seized between the pad and rotating wheel. The confronting surface of the rotating wheel instantly draws the ball across the pad and propels the ball in a desired direction and at the selected velocity. The line on which the ball is propelled between the pad and wheel is adjustable about a horizontal axis and the speed of the wheel is variable to adjust the trajectory of the thrown ball. Thus, the pitching assembly can be adjusted for throwing balls higher or lower and closer to, or farther from, a desired object such as a batter.
In another common embodiment, the pitching assembly includes a pair of throwing wheels spaced a distance apart and mounted on a base for axial rotation in a common plane. The space between the confronting surface of the wheels is less than the diameter of a ball to be thrown. A first wheel is rotated in a first direction, such as clockwise and a second wheel is rotated in an opposing direction, such as counterclockwise. The ball infeed chute is mounted for rotational adjustment about the ball projecting line between the spaced wheels for rotational adjustment about the ball projecting line between the spaced wheels. This maintains the infeed chute in a gravity feeding position irrespective of the angular disposition of the common plane of the ball projecting wheels. When a ball is placed in the infeed chute, the ball is momentarily seized between the two rotating wheels and thrown in the desired direction.
Electrical controls are provided for controlling the rotational speeds of the two coacting wheels. The controls may be adjusted to enable the pitching assembly to throw different types of pitches. The controls may comprise potentiometers, or other known means, to independently vary the rotational speed of each wheel. Rotating each wheel at a different speed causes balls thrown thereby to have curvilinear trajectories. A variety of different ball throwing wheels have been tried.
A disadvantage of known pitching assemblies, and in particular, their ball throwing wheels is that they are somewhat destructive to baseballs used in the machines. Since the balls are abruptly seized by the confronting surfaces of the ball throwing wheels or the fixed pad, the balls tend to be abraded during use. Thus, the life span of baseballs used by prior art pitching machines may be substantially reduced. Furthermore, the delivery of a ball to the strike zone from a standard pitching distance can vary by more than 4 to 10 inches from one pitch to the next. There are a number of possible sources of inaccuracy. For example, a slight out of balance on one wheel, a variation in hardness between the wheels, and the alignment of the stitches on the ball when the ball contacts the wheel, are some of the possible sources of error inherent in the design of pitching wheel machines.
Thus, there exists a need for a pitching machine that is capable of accurately consecutively throwing different type pitches, without requiring manual resetting of the machine between different pitch types, that can switch pitch types relatively quickly, and that does not significantly reduce the life span of baseballs used in the machine.
The present invention comprises an improved device for propelling, or throwing balls in a desired trajectory and at a selected velocity, commonly known as a pitching machine. The pitching machine of the present invention is capable of consecutively propelling, or throwing balls, each ball having a different predetermined trajectory, rotation, and velocity that characterize a desired kind of pitch, without resetting the machine. The pitching machine is capable of consecutively, and in any desired order, throwing several balls having different known pitch types including fastballs, curveballs, sliders, knuckle-balls, and change-ups, without resetting the machine and without unnecessary time delay therebetween.
The pitching machine may be capable of simulating a pitch sequence, a number of balls thrown with each ball potentially having a different pitch type (different trajectory, rotation, and velocity), as if thrown by a human pitcher during an at-bat in a game situation. During an at-bat in a game, a batter does not know what type of pitch is being thrown and cannot pre-adjust their swing and stance for an anticipated speed, trajectory, and location of the pitch. Since the invented pitching machine is capable of consecutively throwing balls of different pitch types, without requiring resetting therebetween, the invented machine may be capable of more effectively training batters, as compared to prior art pitching machines.
The pitching machine of the present invention comprises a pitching assembly that may be pivotably coupled to a base. The base may be a tripod, or other appropriate configuration that supports the pitching assembly a desired distance above the ground.
The pitching assembly includes a ball throwing assembly coupled to a support plate. The ball throwing assembly may comprise a pair of belt assemblies that are vertically spaced and extend generally horizontally along the support plate and are coupled thereto. Each belt assembly may comprise a front pulley and a rear pulley and a belt that extends around both pulleys and generally horizontally along the plate. Each belt assembly may additionally include a motor that may drive, or rotate, at least one pulley at a desired speed for rotating the belt coupled to the pulley. Thus, a pair of vertically spaced belts that rotate generally horizontally along the support plate for propelling or throwing balls are provided by the invented ball throwing assembly. The use of two roughly parallel belts allows may reduce the number of potential sources of inaccuracy, compared to other kinds of pitching machine designs.
A ball infeed chute is positioned adjacent to the rear pulleys of the belt assemblies. The infeed chute has an outlet positioned to dispose balls info the space between the two rotating belts. When a ball is placed in the infeed chute, the ball falls through the outlet of the chute and is seized between the two rotating belts. The ball is rapidly conveyed by the rotating belts toward the front pulleys. Once the ball reaches the front pulleys, the ball is propelled, or thrown in a predetermined direction and at a selected velocity.
Conveyance of the ball by the belts, as opposed to momentarily seizing the ball between two rotating wheels or between a rotating wheel and a fixed pad, may reduce wear on balls used by the invented machine and increase the life span of the balls. Additionally, since balls are conveyed by the belts for a brief time period, as opposed to being momentarily seized between two wheels, the balls may be more accurately thrown toward a desired target. The rotational speed of the two spaced belts may be independently adjusted for imparting a desired rotation on balls. As the baseballs are conveyed for a brief time by the two rotating belts, it may also be possible to accelerate the baseball over the period of time, during which the baseball is between the rotating belts.
The support plate may be rotated around three axis, x-axis, y-axis, and z-axis. The x-axis runs horizontally along a path roughly parallel to the long axis of the belts and between the belts. Rotation around the x-axis (roll) allows the angle of the spin imparted to the ball to be varied. The y-axis is vertical and rotation around the y axis (yaw) allows left and right horizontal adjustment in the direction the ball is propelled. The z-axis is horizontal, but perpendicular to the x-axis. Rotation around the z-axis allows adjustment to the vertical inclination of the trajectory of the ball. Thus, the pitching machine of the present invention may be capable of throwing balls having different predetermined selected trajectories, velocities, and rotational velocities.
A control system may be provided for selecting a predetermined pitch type for each ball to be thrown by the invented pitching machine. The control system may be capable of either increasing or decreasing the rotational speed of either belt or both belts simultaneously. The control system may further be capable of rotating the support plate around the x-axis and rotating the plate around the y-axis. Thus, the control system may be used to select a desired rotational speed of each belt and horizontal position, vertical inclination, and roll position, of the throwing assembly, to enable the invented pitching machine to throw a ball of a predetermined pitch type. The control system may by activated between each ball thrown, so that each consecutive ball thrown may have a different predetermined trajectory, rotation, and velocity, and thus pitch type, without resetting the machine. Therefore, the pitching machine of the present invention is capable of consecutively throwing balls of different pitch types, which may more effectively train batters. The control system may by operated by remote control or it may by programmed to throw a predetermined series of pitches.