A method for applying a coating to deep-fry products, such as fried potato chips, wherein the deep-fry products are died and wherein a layer of aqueous flour batter is applied to the deep-fry products. The coating is applied to the deep-fry products before the deep-fry products are dried. The coating is then applied to the deep-fry products while the deep-fry products are contacted with a dipping solution. In the dipping solution, the flour batter is added in a suspension.

The disclosure relates to a method for providing a coating on deep-fry products, such as fried potato chips, where the deep-fry products are dipped and where a layer of aqueous flour batter is applied to the deep-fry products.
Such a method is known from U.S. Pat. No. 5,622,741 and is generally applied in the industry these days. Non-coated deep-fry products relatively rapidly lose the crispness which makes them so popular, and instead become soft, tough and sticky. This is due to migration of moisture from the inside of the deep-fry product into the dry, crispy crust. Coated deep-fry products have a clearly better crispness after frying, which can be maintained longer.
What is meant by deep-fry products, are potato products, such as fried potato chips, or the like, such as potato slices. Other deep-fry products can be provided with a coating, such as deep-fry snacks and the like. In particular, the disclosure relates to pre-fried deep-fry products. In an industrial process, such products are pre-fried in a frying oven in hot fat or oil, and can be finish-fried, for example, at home or in a catering establishment to a consumable product. This finish-frying can be done by deep-frying, but, in some cases, it is also possible to finish-fry the products in a hot air oven or even in a microwave oven, depending on the nature and composition of the product and the coating. Preparation of potato products will be described further. However, the invention also relates to the preparation of deep-fry products not related to potatoes.
The preparation of fried potato chips is substantially as follows: potatoes are peeled and divided into segments such as slices, sticks, or the like. After sorting, during which segments with a deviant color or shape are removed, the segments are blanched. Subsequently, coloring agents such as reducing sugars, agents for preventing greying (such as sodium pyrophosphate) and flavoring substances (salt) are added. After this xe2x80x9cdip-stepxe2x80x9d, the segments are dried, before the aqueous flour batter is applied to the deep-fry products. This application can be done in several manners. The batter can be sprayed in an aqueous form onto the segments, or the batter is contained in a bath, through which the segments can be passed. The batter is an aqueous flour batter, of for instance rice flour or wheat flour, and usually further contains starch, dextrin, laved agents and salt. The batter forms a very crispy crust around the potato. Because of this coating, the chips cool less rapidly. The holding time after finish-frying (during which the chips are often kept warm under a heat lamp) can thereby be considerably improved, so that chips, instead of about 3-5 minutes, can stay crispy for as long as 10-20 minutes.
For compositions of batter, reference is made to patent specifications EP-A-0,499,684, WO-A-097,42827 and EP-A-0,899,902. The processes described there all include a step where the segments are dried before the batter is applied. This step is considered necessary for a good adhesion of the batter to the segment. The drying of the blanched segments generally takes place by transporting them via a belt dryer to a batter bath, i.e. a place where the batter is applied.
A drawback of the current processing of batter is that, because of its adhesive action, it not only sticks to the surface of the potato segment, but also makes the segments cake together. In process, problems are experienced with caked-together segments, such as during the pre-frying, are fried together into one mass, such a mass leads to loss in production and quality.
Solutions to this problem have been sought in different directions. For instance, agents are added to the batter for reducing the effect of agglomeration. Many of the publications mentioned appear to claim that the newly developed batter does not have this effect of caking together, or, at least, to a reduced extent. In practice, however, it appears that it is still necessary to take additional measures to prevent caking together of the segments. Such measures include, in particular, installing a conveyor belt on which the segments are brought in a single layer (such as a singling belt), where, by means of air, excess batter is blown off the segments (also called an air knife). The batter that is blown off can be re-used by applying a recovering system. Additionally, the chips can be initially fried for 10-15 seconds in a first deep-fry oven to harden the batter, and then placed on a vibrator to separate the chips. The chips are then fried again in a second deep-fry oven.
Such measures are disadvantageous to the efficiency of the process. Moreover, installing such a vibrator and second frying oven in an existing production line involves very high costs. Additionally, this extra step entails a loss of capacity. Investments, loss of capacity, additional work and the cost of the batter itself thus lead to a considerable increase of the cost of the product to consumers.
The process of the present disclosure avoids the above-mentioned drawbacks and provides a method where a layer of batter can be applied to the segments. This method is considerably less expensive, more efficient, and without the problems of agglomeration as the methods described above.
This object is achieved with a method of the type mentioned above, wherein the deep-fry products, before dry, are contacted with a dipping solution, to which a flour batter has been added in a suspension. When applying the method, it appears that, despite the fact that the batter can adhere to a much lesser extent to the potato segment, this adhesion is sufficient to form a coating which is advantageous to the taste and the crispness of the deep-fry product, and whose holding is still considerably better than when no coating has been applied. In an experiment, 100% of the deep-fried chips passed a xe2x80x9cbreak testxe2x80x9d. In fast food restaurants, the break test is a standard for the crispness. After a certain amount of time, sticks of chips should still break for a large part, for instance after having been kept under a heat lamp for 10 minutes. Surprisingly, the adhesive action between the individual segments is largely lost. By applying the present method expensive additional measures such as the extra batter bath, the air knife, the singling belt, the vibrator and the second deep-fry oven, are not necessary. It is sufficient to add the batter in an exiting production press, in the step before the drying.
Incidentally, it is noted, that from the U.S. Pat. Nos. 5,302,410 and 5,393,552 it is known per se, in the dipping step, to add additives which comprise a hydrolysis starch such as a (malto)dextrin. However, this method cannot be compared to what is meant here, which is, adding a batter. Although this batter also contains dextrin, it comprises in particular flour products, so that the batter forms a separate, crispy layer on the surface of the potato. In the above-mentioned US-publications dexter is rather used to achieve, in combination with a specific acidity a sloughing effect, so that the structure of the potato surface itself is changed without a separate crispy layer being formed therearound. Such a specific acidity is of no importance with a batter.
Applying a coating to the deep-fry products is, according to the method, carried out during the dipping step mentioned earlier. In the industry, this dipping step can for instance take place in a screw balancer, a dipping bath or a so-called flume. The latter is a tube, through which the blanched segments are transported with water. The segments are contacted with a dipping solution, which solution can comprise colorants, agents for preventing greying, and flavorings. In the dipping solution, the batter is added as suspension.
A batter can be successfully applied in a conventional production on, in which, normally, deep-fry products are not provided with a layer of batter. By simply adding the batter to the customary dipping solution, a suspension is formed, from which the deep-fry products still absorb a layer of batter (albeit a relatively small one). Then, the deep-fry products are dried in the customary steps and supplied to a deep-fry oven, after which they are prepared for shipment by cooling and freezing them.

Method for providing a coating on pre-fried deep-fry products


The coating quality of an adhesive layer applied in direct contact on a polyester film is improved by using an alkyl (poly)glycoside as surfactant. A polyester film carrying such layer is suitable as support for a photosensitive material.

The present invention relates to a polyester film carrying in direct contact an adhesive layer and the use of such a film as support for photosensitive materials, e.g. photographic materials.
In order to ensure a perfect adhesion of hydrophilic layers such as photographic light-sensitive emulsion layers to dimensionally stable polyester film supports, i.e. polyester films that have been biaxially stretched and heat-setted, it is known for long time to apply several intermediate layers between the support and the light-sensitive emulsion layer(s). In most cases two intermediate layers are needed. A first one, known as the adhesive layer or primer layer or resin subbing layer or latex subbing layer, shows a good adhesion to the polyester film and at the same time possesses good attaching properties in respect to the second layer, known as the subbing layer or gelatin subbing layer or gelatin sublayer, which usually is formed to a great extent of a hydrophilic colloid such as gelatin. For sake of uniformity we will further refer to the first intermediate layer defined above as the adhesive layer.
A preferred polyester film for use as support for imaging elements such as photographic materials is polyethylene terephthalate (PET). This and other polyester film supports are preferably biaxially stretched at an elevated temperature of e.g. 70-120xc2x0 C., reducing their thickness by about {fraction (1/9)} to {fraction (1/16)} or more and increasing its area 9 to 16 times. The stretching may be accomplished in two stages, longitudinal and then transversal, or simultaneously. The adhesive layer, when present, may be applied by aqueous coating before or after the biaxial stretch or between the longitudinal and transversal stretch, in a thickness of 0.05 to 5 xcexcm. An essential ingredient of this layer is an adhesion-promoting (co)polymer. In some preferred embodiments, disclosed e.g. in GB 1 234 755, GB 2 068 004 and EP 0 464 906, this (co)polymer contains as one of its structural units a monomer comprising covalently bound chlorine. Examples of said homopolymers or copolymers suitable for use in the adhesive layer are e.g. polyvinyl chloride; polyvinylidene chloride; a copolymer of vinylidene chloride, an acrylic ester and itaconic acid; a copolymer of vinyl chloride and vinylidene chloride; a copolymer of vinyl chloride and vinyl acetate; a copolymer of butylacrylate, vinyl acetate and vinyl chloride or vinylidene chloride; a copolymer of vinyl chloride, vinylidene chloride and itaconic acid; a copolymer of vinyl chloride, vinyl acetate and vinyl alcohol etc. Further patents disclosing such (co)polymers include U.S. Pat. Nos. 2,627,088, 2,698,235, 2,698,240, 2,943,937, 3,143,421, 3,201,249, 3,271,178, 3,443,950 and 3,501,301.
The adhesive layer is preferably coated from an aqueous medium which is ecologically and economically advantageous. Relatively little is published about the surfactants, also called coating aids or wetting agents, used in the coating solution of the adhesive layer. In the examples of GB 1 533 555 and GB 1 571 583 ULTRAVON W is disclosed as surfactant for the coating solution of the adhesive layer. ULTRAVON W, registered trade mark of Ciba-Geigy, is the disodium salt of heptadecylbenzimidazole disulphonic acid.
Depending on the actual composition there is a some cases a tendency to the formation of repellency spots in the coated and dried adhesive layer when ULTRAVON W is used as surfactant. A repellency is a round, or comet-shaped indentation or crater, or a vestige of such a disturbance which has partially healed after formation. Imperfections of this kind are formed during the coating process or shortly thereafter when the coating composition is still fluid and mobile. When subsequent layers such as the gelatin subbing layer and the photosensitive layer are coated on top of the adhesive layer this imperfection can propagate in these other layers and become visible in the final developed image.
So there is a permanent need for new classes of surfactants which overcome or strongly reduce the tendency to the formation of repellencies in the adhesive layer.
It is an object of the present invention to provide a polyester film carrying in immediate contact an adhesive layer showing none or a very limited number of repellency spots.
It is a further object of the invention to provide imaging elements, in particular photosensitive elements, which use such an improved polyester film as support.
The objects of the present invention are realized by providing a polyester film carrying in direct contact an adhesive layer comprising an alkyl (poly)glycoside surfactant according to following formula (I):
CnH2n+1xe2x80x94Oxe2x80x94(C6H10O5)xxe2x80x94H,xe2x80x83xe2x80x83(I),
wherein C6H10O5 represents a monosaccharide unit,
n=5 to 20,
x represents an integer or fractal mean value between 1 and 4.
An imaging element, in particular a radiation-sensitive element such as a photographic element, using a polyester film as defined above also belongs to the scope of the present invention.
The polyester film supports which can be advantageously employed in this invention are well known and widely used materials. Such film supports are typically prepared from higher molecular weight polyesters derived by condensing dihydric alcohol with a dibasic saturated fatty carboxylic acid or derivative thereof. Suitable dihydric alcohols for use in preparing polyesters are well known in the art to include any glycol wherein the hydroxy groups are on the terminal carbon atom and that contains from 2 to 12 carbon atoms such as, for example, ethylene glycol, propylene glycol, trimethylene glycol, hexamethylene glycol, decamethylene glycol, dodecamethylene glycol, and 1,4-cyclohexane dimethanol. Dibasic acids that can be employed in preparing polyesters include those dibasic acids containing from 1 to 16 carbon atoms. Specific examples of suitable dibasic acids include adipic acid, sebacic acid, isophtalic acid and terephthalic acid. The alkyl esters of the above-enumerated acids can also be used satisfactorily.
Specific preferred examples of polyester resins, which may be used in the form of webs or sheets are polyethylene terephthalate (PET), poly(cyclohexane 1,4-dimethylene terephthalate), and poly(ethylene naphtalate). The most preferred example is PET.
The thickness of the polyester film is not critical and depends on the application. For instance, polyester film of a thickness ranging between 0.05 to about 0.25 mm can be used with satisfactory results.
In a typical process for the manufacture of a polyester photographic film support, the polyester is melt extruded through a slit die, quenched to the amorphous state, oriented by longitudinal and transverse stretching, and heat set under dimensional restraint. In addition to being directionally oriented and heat set, the polyester film can also be subjected to a subsequent heat relax treatment to provide still further improvement in dimensional stability and surface smoothness.
The adhesive layer or latex subbing layer can be coated on top of the finished polyester film before or after the biaxial stretching or between the longitudinal and transverse stretching. It is the essence of the present invention that the coating solution from the adhesive layer contains, apart from the latex (co)polymer an alkyl-(poly)glycoside as surfactant.
The history, the synthesis of alkyl (poly)glycosides (APG""s), and their industrial application as surfactants are extensively reviewed by W. von Rybinski and K. Hill in Angewandte Chemie (1998) Vol 110, p. 1394-1412.
The first alkyl glucoside was synthesized and identified by E. Fisher more than 100 years ago. In later developments, Fisher""s early work which was concerned with the lower hydrophilic alcohols was extended to hydrophobic alcohols with longer alkyl chains, the typical fatty alcohols. In these industrial processes not pure alkyl monoglucosides but a complex mixture of alkyl mono-, di-, tri-, and oligoglycosides is produced. Because of this, the industrial products are called alkyl polyglycosides (APG). The products are characterized by the length of the alkyl chain, and the average number of the monosaccharide units, mostly glucose units, linked to it, the degree of polymerization. It will be clear that this average number (x in general formula I) will be a fractal number in most cases.
APG""s are now offered on an industrial scale by different manufacturers such as Rohm and Haas, BASF, SEPPIC, Akzo Nobel, Procter and Gamble and Henkel.
It is to our knowledge the first time that APG""s are described as surfactants for the adhesive layer coated directly onto a polyester film, such as polyethylene terephthalate, which is a widely used support in the manufacturing of photographic materials. Such adhesive layers are usually free of gelatin and comprise an adhesive promoting (co)polymer as explained above. APG""s have been disclosed in hydrophilic, gelatin containing photographic layers. They have been described in U.S. Pat. No. 5,358,831 and U.S. Pat. No. 5,591,568 as viscosity decreasing and rheology controlling agents in photographic layers containing gelatin and small-particles dispersions. In U.S. Pat. No. 5,300,418 APG""s are one of numerous amphiphilic species capable of reducing the viscosity of melts comprising gelatin and an anionically charged, hydrophobic group containing compound. According to EP 0 549 496 long chain APG""s are used together with an auxiliary anionic or nonionic surfactant to improve the thickness uniformity of gelatinous layers.
The APG surfactants used in accordance with the present invention are added to the coating solution of the adhesive layer in a preferred concentration range between 1 and 10 mmol/l, and most preferably in a concentration of about 5 mmol/l.
As explained earlier another essential ingredient of the coating composition of the adhesive layer is the adhesion-promoting latex (co)polymer. A preferred class of latex polymers for the purposes of this invention are vinylidene chloride-containing copolymers having carboxyl functional groups. Illustrative of such polymers are (1) copolymers of vinylidene chloride and an unsaturated carboxylic acid such as acrylic or methacrylic acid, (2) copolymers of vinylidene chloride and a half ester of an unsaturated carboxylic acid such as the monomethylester of itaconic acid, (3) terpolymers of vinylidene chloride, itaconic acid and an alkyl acrylate or methacrylate such as ethyl acrylate or methyl methacrylate, and (4) terpolymers of vinylidene chloride, acrylonitrile or methacrylonitrile and an unsaturated carboxylic acid such as acrylic acid or methacrylic acid.
In a most preferred embodiment the latex polymer is co(vinylidene chloride-methyl acrylate-itaconic acid; 88%/10%/2%). This copolymer is prepared by emulsion polymerization using 0.5% MERSOLAT H (trade-mark of Bayer AG) as emulsifying agent. It is necessary to add extra surfactant, a so-called post-stabilizer, to the latex in order to assure a good stability on storage. An excellent storage stability is obtained when 1% of DOWFAX 2A1 (trade-name of Dow Co.) is added to the actual latex described above. When a coating composition based on such a post-stabilized latex is coated on PET a lot of repellencies are obtained when no surfactant or a conventional surfactant is added. This problem is solved in the present invention by the use of an APG as surfactant.
As a further preferred ingredient of the coating solution of the latex subbing layer colloidal silica may be added as a binder. A preferred compound is KIESELSOL 100F (trade-mark of Bayer AG), average particle size 25-30 nm. The ratio of the amount of latex to silica is preferably about 80/20.
The adhesive layer may be coated on top of the polyester film using one of the well known coating techniques. Air-knife coating technique is preferred.
When the polyester film of the present invention is meant to serve as support for a photosensitive material usually a second intermediate layer is applied on top of the first adhesive layer, namely the gelatin subbing layer or xe2x80x9cgel subxe2x80x9d.
The gelatin subbing layer preferably contains a mixture of gelatin and colloidal silica. A preferred compound is KIESELSOL 300F (trade-mark of Bayer AG) having an average particle size between 0.1 xcexcm and 0.5 xcexcm. A plasticizing compound can be used in order to avoid the formation of cracks in the dried layer due to the occurence of excessive shrinking of the layer during drying. Plasticizing agents are well-known in the art. Low-molecular weight compounds (e.g. acetamide, glycerin) as well as polymeric latices (e.g. polyethylacrylate, poly-n.-butylacrylate) can be used for this purpose.
When the photosensitive material is a silver halide based photographic layer then one or more emulsion layers and a protective layer are coated on top of the subbing layer(s).
The silver halide emulsion or mixture of emulsions of the photographic material in connection with the present invention can be incorporated in one single layer but, alternatively, a double emulsion layer or even a multiple layer pack can be applied.
The halide composition of the silver halide emulsions used in accordance with the present invention is not specifically limited and may be any composition selected from e.g. silver chloride, silver bromide, silver iodide, silver chlorobromide, silver bromoiodide, and silver chlorobromoiodide.
The photographic emulsion(s) can be prepared from soluble silver salts and soluble halides according to different methods as described e.g. by P. Glafkides in xe2x80x9cChimie et Physique Photographiquexe2x80x9d, Paul Montel, Paris (1967), by G. F. Duffin in xe2x80x9cPhotographic Emulsion Chemistryxe2x80x9d, The Focal Press, London (1966), and by V. L. Zelikman et al in xe2x80x9cMaking and Coating Photographic Emulsionxe2x80x9d, The Focal Press, London (1966). They can be prepared by mixing the halide and silver solutions in partially or fully controlled conditions of temperature, concentrations, sequence of addition, and rates of addition. The silver halide can be precipitated according to the single-jet method, the double-jet method, the conversion method or an alternation of these different methods.
The silver halide particles of the photographic emulsion(s) may have a regular crystalline form such as a cubic or octahedral form or they may have a transition form. They may also have an regular crystalline form such as a spherical form or a tabular form, or may otherwise have a composite crystal form comprising a mixture or said regular and irregular crystalline forms.
The silver halide grains may have a multilayered grain structure. According to a simple embodiment the grains may comprise a core and a shell, which may have different halide compositions and/or may have undergone different modifications such as the addition of dopes. Besides having a differently composed core and shell the silver halide grains may also comprise different phases inbetween.
Two or more types of silver halide emulsions that have been prepared differently can be mixed for forming a photographic emulsion for use in accordance with the present invention.
The average size of the silver halide grains may range from 0.05 to 1.0 micron, preferably from 0.2 to 0.5 micron. The size distribution of the silver halide particles can be homodisperse or heterodisperse.
The silver halide emulsions can be doped with various metal salts or complexes such as Rhodium and Iridium dopants.
The emulsion can be desalted in the usual ways e.g. by dialysis, by flocculation and re-dispersing, or by ultrafiltration.
The light-sensitive silver halide emulsions are preferably chemically sensitized as described e.g. in the above-mentioned xe2x80x9cChimie et Physique Photographiquexe2x80x9d by P. Glafkides, in the above-mentioned xe2x80x9cPhotographic Emulsion Chemistryxe2x80x9d by G. F. Duffin, in the above-mentioned xe2x80x9cMaking and Coating Photographic Emulsionxe2x80x9d by V. L. Zelikman et al, and in xe2x80x9cDie Grundlagen der Photographischen Prozesse mit Silberhalogenidenxe2x80x9d edited by H. Frieser and published by Akademische Verlagsgesellschaft (1968). As described in said literature chemical sensitization can be carried out by effecting the ripening in the presence of small amounts of compounds containing sulphur e.g. thiosulphate, thiocyanate, thioureas, sulphites, mercapto compounds, and rhodamines. The emulsions can be sensitized also by means of gold-sulphur ripeners, gold-selenium ripeners or by means of reductors e.g. tin compounds as described in GB 789,823, amines, hydrazine derivatives, formamidine-sulphinic acids, and silane compounds. Chemical sensitization can also be performed with small amounts of Ir, Rh, Ru, Pb, Cd, Hg, Tl, Pd, Pt, or Au. One of these chemical sensitization methods or a combination thereof can be used.
The light-sensitive silver halide emulsions can be spectrally sensitized with proper dyes such as those described by F. M. Hamer in xe2x80x9cThe Cyanine Dyes and Related Compoundsxe2x80x9d, 1964, John Wiley and Sons. Dyes that can be used for the purpose of spectral sensitization include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly valuable dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes.
The silver halide emulsion(s) for use in accordance with the present invention may comprise compounds preventing the formation of fog or stabilizing the photographic characteristics during the production or storage of photographic elements or during photographic treatment thereof. Many known compounds can be added as fog-inhibiting agent or stabilizer to the silver halide emulsion. Suitable examples are e.g. the heterocyclic nitrogen-containing compounds such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles, mercaptopyrimidines, mercaptotriazines, benzothiazoline-2-thione, oxazoline-thione, triazaindenes, tetraindenes and pentazaindenes, especially those described by Birr in Z. Wiss. Photo. 47 (1952), pages 2-58, triazolopyrimidines such as those described in GB 1,203,757, GB 1,209,146, JA-Appl. 75-39537, and GB 1,500,278, and 7-hydroxy-s-triazolo-[1,5-a]-pyrimidines as described in U.S. Pat. No. 4,727,017, and other compounds such as benzenethiosulphonic acid, benzenethosulphinic acid and benzenethiosulphonic acid amide. Other compounds that can be used as fog-inhibiting compounds are metal salts such as e.g. mercury or cadmium salts and the compounds described in Research Disclosure Nxc2x0 17643 (1978), Chapter VI.
The fog-inhibiting agents or stabilizers can be added to the silver halide emulsions prior to, during, or after the ripening thereof and mixtures of two or more of these compounds can be used.
Besides the silver halide another essential component of a light-sensitive emulsion layer is the binder. The binder is a hydrophilic colloid, preferably gelatin. Gelatin can, however, be replaced in part or integrally by synthetic, semi-synthetic, or natural polymers. Synthetic substitutes for gelatin are e.g. polyvinyl alcohol, poly-N-vinyl pyrrolidone, polyvinyl imidazole, polyvinyl pyrazole, polyacrylamide, polyacrylic acid, and derivatives thereof, in particular copolymers thereof. Natural substitutes for gelatin are e.g. acids, aminoalkyl sulphates or phosphates, alkyl betaines, and amine-N-oxides; and cationic agents such as alkylamine salts, aliphatic, aromatic, or heterocyclic quaternary ammonium salts, aliphatic or heterocyclic ring-containing phosphonium or sulphonium salts. Other suitable surfactants include perfluorinated compounds. Such surface-active agents can be used for various purposes e.g. as coating aids, as compounds preventing electric charges, as compounds improving slidability, as compounds facilitating dispersive emulsification, as compounds preventing or reducing adhesion, and as compounds improving the photographic characteristics e.g higher contrast, sensitization, and development acceleration.
Beside the light sensitive emulsion layer(s) the photographic material can contain several non light sensitive layers, e.g. an anti-stress top layer, one or more backing layers, and one or more intermediate layers eventually containing filter- or antihalation dyes that absorb scattering light and thus promote the image sharpness. Suitable light-absorbing dyes are described in i.a. U.S. Pat. No. 4,092,168, U.S. Pat. No. 4,311,787 and DE 2,453,217. One or more backing layers can be provided at the non-light sensitive side of the support. This layers which can serve as anti-curl layer can contain i.a. matting agents e.g. silica particles, lubricants, antistatic agents, light absorbing dyes, opacifying agents, e.g. titanium oxide and the usual ingredients like hardeners and wetting agents.
The backing layer(s) may further contain an antistatic agent. Suitable antistatic polymers for incorporation in a backing layer are disclosed in e.g. Research Disclosure, April 1990, Item 31237. Further references on ionic conductive polymers include U.S. Pat. No. 4,585,730, U.S. Pat. No. 4,701,403, U.S. Pat. No. 4,589, 570, U.S. Pat. No. 5,045,441, EP-A-391 402 and EP-A-420 226. An antistatic agent can also be incorporated in a separate layer or in a subbing layer. Relatively recently electrically conducting conjugated polymers have been developed that have electronic conductivity. For ecological reasons the coating of antistatic layers should proceed where possible from aqueous solutions by using as few as possible organic solvents. The production of antistatic coatings from aqueous coating compositions being dispersions of polythiophenes in the presence of polyanions is described in EP 0 440 957.
The photographic elements in connection with the present invention may further comprise various other additives such as e.g. compounds improving the dimensional stability of the photographic element, UV-absorbers, spacing agents and plasticizers.
Suitable additives for improving the dimensional stability of the photographic elements are e.g. dispersions of a water-soluble or hardly soluble synthetic polymer e.g. polymers of alkyl(meth)acrylates, alkoxy(meth)acrylates, glycidyl(meth)acrylates, (meth)acrylamides, vinyl esters, acrylonitriles, olefins, and styrenes, or copolymers of the above with acrylic acids, methacrylic acids, xcex1-xcex2-unsaturated dicarboxylic acids, hydroxyalkyl(meth)acrylates, sulphoalkyl(meth)acrylates, and styrene sulphonic acids.
Spacing agents can be present, preferably in the top protective layer. In general the average particle size of such spacing agents is comprised between 0.2 and 10 micron. They can be soluble or insoluble in alkali. Alkali-insoluble spacing agents usually remain permanently in the photographic element, whereas alkali-soluble spacing agents usually are removed therefrom in an alkaline processing bath. Suitable spacing agents can be made e.g. of poly(methylmethacrylate), of copolymers of acrylic acid and methylmethacrylate, and of hydroxypropylmethyl cellulose hexahydrophthalate. Other suitable spacing agents have been described in U.S. Pat. No. 4,614,708.
The photographic material is exposed and processed according to its particular composition and application.


Described is a method of optimizing tire pressures in order to obtain maximum tire tread life and performance. The method involves calculation of the live and dead loads on each individual tire of the vehicle. Grown diameter of the tires in use is obtained from published data sheets. The grown diameter is then multiplied by an empirically derived tread length determining factor to obtain an optimum tread length in contact with the road surface. In turn the tread length is multiplied by effective tread width to obtain a footprint area for the tires. Finally, the load carried by the individual tires is divided by the footprint area to obtain an optimum inflation pressure.

The present invention is directed to a method for significantly improving tread wear of the tires used on all types of vehicles.
Many improvements have been made over the years in durability of pneumatic tires used on cars, sport utility vehicles, trucks, trailers and other types of vehicles. While 20,000 miles was once considered excellent tire life for a passenger car, improved tire manufacturing and components have now extended this by a factor of two to three under normal conditions. xe2x80x9cNormal conditionsxe2x80x9d include maintenance of recommended inflation pressures, regular rotation of tires, and driving principally on a relatively smooth road surface at moderate speeds. In the real world these conditions are rarely met and tires must be replaced far earlier than might otherwise be required. Of the conditions listed above, only the road surface is not under possible control of the driver. However, human nature being what it is, most drivers are lax about routine tire maintenance. Rotation is an occasional event, if done at all, and tire pressure checks are often left undone until it is obvious from tire appearance and tread indications that something is wrong. To further act against obtaining longer tread life, the inflation recommendations given by auto manufacturers often seem to be pulled out of thin air rather than based on their own product data publications. These pressures are usually found on a plate on a vehicle door frame or published in the Owner""s Manual. Equal pressures are often recommended for all tires on a given vehicle regardless of the fact that in most instances front and rear tires carry significantly different loads. This condition is further exaggerated in front wheel drive vehicles. Strangely, even when they are inflated to the same pressures, front and rear tires are expected to perform equally despite these load differences.
Empirical studies have found that front and rear tires inflated to similar pressures show very different wear patterns on their treads after only a relatively few thousands of miles. Front tires usually show much more wear along the tread edges. This is a result of excessive tire deflection or deformation that takes place as the tire contacts the road surface. xe2x80x9cDeflectionxe2x80x9d is the term used to measure the differences in radii from the center point to the top of the tire and the center of the tire to the road contact surface. Deflection is caused by the necessity for the tire to flatten as it contacts the road surface in order to distribute its load carrying capacity. This condition of excessive edge wear is often called xe2x80x9cswipingxe2x80x9d when tires wear unevenly across the tread due to under inflation.
In contrast to the usual pattern of front tire wear, rear tires frequently show greater wear in the center portion of the tread. In most instances this is due to over inflation. This can cause internal stresses within the tire, stresses which the tire is least designed to resist.
Under inflation in particular is destructive to tire life since the tire experiences much greater flexing and heat buildup during use. It must be remembered that at 60 mph the average tire rotates 14 times per second.
The set of conditions described above creates an undesirable environment for optimum tire life and performance. It is not the purpose of the present invention to recommend vehicle and tire size match-ups. The invention is based on the discovery that each tire size has its own optimum deflection which should remain constant, regardless of load carried. Stated otherwise, since deflection correlates directly with xe2x80x9cfootprintxe2x80x9d, each tire should maintain a constant optimum footprint regardless of load carried.
The present invention offers a means of calculating optimum tire pressures to obtain maximum tire life and performance. It is based in part on correlating tire loading, tire pressure, and tire deflection in order to obtain optimum xe2x80x9cfootprintsxe2x80x9d for every combination of tire load and tire position on any vehicle. xe2x80x9cFootprintxe2x80x9d, also called xe2x80x9ccontact patchxe2x80x9d, is the area of tread in contact with the road surface at any given instant. The method is useful not only for passenger cars but also for light and heavy trucks, trailers, or any vehicle which may be equipped with either single or dual wheels. It can accommodate any combination of axles, tire load, tire position and tire size. Rear wheels may be single or dual and the vehicle may have a plurality of rear axles. The method is readily applicable when replacement tires are of a different size than the original tires used.
The method involves several steps. The first step is to determine vehicle curb mass/weight distributed to the front and rear axles or any axle combinations. Curb mass/weight is the weight of a vehicle without occupants. This information is found within the extensive specification sheets published by vehicle manufacturers for every make and model they produce. Similar information for all nameplates can also be found in Motor Vehicle Manufacturers Specifications, published by the American Automobile Manufacturers Association. These publications are readily available in many libraries. The vehicle owner can provide the passenger and cargo weights and their location in the vehicle. Total operating dead loads and live loads and their distribution can then be determined. This will include curb mass/weight, occupants, and cargo. The percentage of this added weight to each axle is then assigned, again using manufacturers data; e.g., percentage distribution of weight in front and/or rear seats to each axle. Total weight is then easily converted to weight carried by each axle and on each individual tire. This information is part of that which is essential to derive optimum conditions of tire inflation for maximum tread life and performance. Optionally, the vehicle may be weighed on a scale to determine axle loads.
Extensive data sheets are also available for every size and type of tire produced. This data is available in trade publications of the Tire and Rim Manufacturers Association, Inc. (TRA), Copley, Ohio. Among the numerous parameters available in TRA publications is xe2x80x9cgrown tire diameterxe2x80x9d. Grown diameter is tire diameter under designated inflation conditions and after a prescribed minimum amount of use. Any given tire size has a fixed section width, although this does not indicate effective tread width. Actual effective tread width should be measured on the particular tires in use at the time. The tread length in contact with the road surface can vary dramatically with the ratio of tire pressure to applied load. This then becomes the effective tread length in contact with the road surface under one condition of use. Effective tread length multiplied by effective tread width determines the footprint (or contact patch) area.
Critical to the present invention are empirically determined xe2x80x9ctread length determining factorsxe2x80x9d which are key to determining optimum tire tread wear. These factors have been determined by extensive experimentation. The grown diameter is multiplied by the tread length factor to determine optimum tread length in contact with the road surface. The factors for both front and rear tires are dimensionless numbers within the range of about 0.190 to 0.210, most preferably in the range of about 0.200 to 0.205. The factor for front tires is normally somewhat smaller, being about 96% to 98% of that of the rear tires. Ideally the front tire factor will be about 0.200 and the rear tire factor about 0.205. The factor is smaller for the front tires due to the more demanding requirements, such as steering and a proportionately heavier load.
Tread width contacting the road surface must usually be determined by actual measurement of the tires being used. Multiplying tread width by calculated optimum tread length gives the area of tire contact with the surface or the tire""s xe2x80x9cfootprintxe2x80x9d. Finally, dividing the individual load on a tire by footprint area will give optimum inflation pressure. This method of optimizing deflection and corresponding footprint area has been found to significantly extend tire life; e.g., often to double or triple tread life, as opposed to using usual manufacturer recommended pressures.
It thus becomes possible for individuals to customize their tire pressures according to vehicle weight and load distributions for any given set of conditions of use. By so doing they will significantly extend tire tread life and achieve better tire performance.
It is an object of the present invention to provide a method of extending tire tread life and tire performance by determining optimum inflation pressures.
It is a further object to provide a method that determines air pressure in individual tires in any position of use on a vehicle to create an optimum road-contact footprint for the particular tires in use.
It is also an object to provide a method whereby the air pressure in each individual tire can be determined to enable a driver to inflate tires so that tread length in contact with the road conforms to optimum values defined by the formula of the invention.
It is yet an object to provide a method whereby tire pressure is adjusted based on the actual load borne by individual tires.
These and many other objects will become readily apparent to those skilled in the art upon reading the following detailed description.
The invention is best understood by considering an example in which a specific make and model of car and size of tires is assumed. The products noted in the following description are used only as a matter of convenience in explanation. This is not intended to be an endorsement of these or any similar products.
As an example, a 1998 model year Lincoln Continental may be chosen. This is equipped with P255/60 R16 Michelin tires on all four wheels. In TRA tire designations P indicates a passenger car tire, 225 is the tire section width in mm, 60 indicates that the section height is 60% of the section width, R indicates radial construction, and 16 designates the rim diameter in inches. The recommended manufacturer tire inflation pressure is 32 psi for the front tires and 28 psi for the rear tires. It should be noted that section width is not a measure of tread width. Though section width is an industry standard measure of width for a specific tire designation, tread widths will vary significantly within the same tire size designation from manufacturer to manufacturer.
Referring to the Motor Vehicle Manufacturers Specifications, published by the American Automobile Manufacturers Association (AAMA) and by the Ford Motor Company it is found that the curb mass/weight is 3880 lb with an operational weight of 4000 pounds. This weight is distributed 62% (2480 pounds) to the front axle and 38% (1520 pounds) to the rear axle. Front seat passenger mass is distributed 51% to the front axle and 49% to the rear axle. Only 18% of the rear seat passenger mass is carried on the front axle and the remaining 82% is distributed to the rear axle.
The Tire and Rim Manufacturers Association (TRA) cites 27.01 inches as the grown diameter of the tire in the examples. These standards are available for any tire size and are used in part by vehicle manufacturers in designing for tire clearances.
Assume as one example that the car is used for a daily commute and carries two passengers weighing a total of 340 pounds. A second example might be when the car is used for an extended trip with luggage in the trunk and two additional passengers in the rear seat. The rear seat passengers and luggage will add an additional 340 pounds to the load.

Method for improving vehicle tire tread wear


A template is treated to provide a surfactant rich region and a surfactant depleted region. A contact angle at the surfactant rich region may be greater than, less than, or substantially similar to a contact angle of the surfactant depleted region.

Nano-fabrication includes the fabrication of very small structures that have features on the order of 100 nanometers or smaller. One application in which nano-fabrication has had a sizeable impact is in the processing of integrated circuits. The semiconductor processing industry continues to strive for larger production yields while increasing the circuits per unit area formed on a substrate, therefore nano-fabrication becomes increasingly important. Nano-fabrication provides greater process control while allowing continued reduction of the minimum feature dimensions of the structures formed. Other areas of development in which nano-fabrication has been employed include biotechnology, optical technology, mechanical systems, and the like.
An exemplary nano-fabrication technique in use today is commonly referred to as imprint lithography. Exemplary imprint lithography processes are described in detail in numerous publications, such as U.S. Patent Publication No. 2004/0065976, U.S. Patent Publication No. 2004/0065252, and U.S. Pat. No. 6,936,194, all of which are hereby incorporated by reference herein.
An imprint lithography technique disclosed in each of the aforementioned U.S. patent publications and patent includes formation of a relief pattern in a formable (polymerizable) layer and transferring a pattern corresponding to the relief pattern into an underlying substrate. The substrate may be coupled to a motion stage to obtain a desired positioning to facilitate the patterning process. The patterning process uses a template spaced apart from the substrate and a formable liquid applied between the template and the substrate. The formable liquid is solidified to form a rigid layer that has a pattern conforming to a shape of the surface of the template that contacts the formable liquid. After solidification, the template is separated from the rigid layer such that the template and the substrate are spaced apart. The substrate and the solidified layer are then subjected to additional processes to transfer a relief image into the substrate that corresponds to the pattern in the solidified layer.


A simplified continuously variable transmission system control provides a variable clamping force and a differential cylinder pressure manipulation to change sheave ratios. The system control uses two pumps. The first pump provides the variable clamping force. The second pump provides pressure changes to effect ratio changes. The clamping force can be varied based upon operator demand on an associated engine.

1. Field of the Invention
The present invention generally relates to simplified electronic-free continuously variable transmission (CVT) control arrangements that control pressurizing and providing variable pressure control of a hydraulic system in a belt or chain drive CVT.
2. Description of the Related Art
A typical vehicle CVT comprises two V shaped pulleys and a steel chain or belt disposed between them. The chain or belt transfers power from one pulley to the other pulley during pulley rotation. Both pulleys are capable of axial displacement of a belt track in order to change the ratio of the vehicle drive line. The pulleys usually are hydraulically actuated for ratio changing by integral hydraulic cylinders, which also supply a variable clamping force on the chain. The clamping force is modulated, depending on the torque load, to reduce the likelihood of chain slippage under high torque conditions but without applying unnecessary force that would increase the chain wear at low torque conditions.
Many CVT control systems are in existence and in use around the world that satisfy the above-described functions. These generally are computer-controlled systems that gather information from engine and driveline sensors, including the driver actuated throttle position. This information is used to control the ratio changing and chain clamping forces by selective manipulation of the hydraulic system pressures. These systems are complex and feature many components that increase the cost of manufacture.

This patent is subject to a terminal disclaimer.

Mechanical function control of continuously variable transmission hydraulic system


The present invention comprises novel combinations of ginseng berry juice and extracts combined with other skin nutrients and moisturizers which may be used to soften and moisturize the skin while providing essential vitamins and nutrients to the skin in a natural way.

The present invention relates generally to the field of skin care products and more particularly to products and methods which deliver fresh vitamins and other nutrients to the skin by topical application of a novel, vitamin-rich fruit composition. The present invention comprises ginseng berry extract and other skin nutrients and, preferably, other skin nutrients and moisturizers which are beneficial to the skin.
Human skin is extremely susceptible to the temperature and humidity extremes of our environment. However, when skin care products are properly used to counteract adverse environmental conditions, skin can remain healthy and beautiful under a variety of extreme environmental conditions. The environmental factors that most often affect the skin adversely are ultraviolet radiation and humidity.
Ultraviolet radiation varies with time of day, from day to night, with seasons of the year and weather conditions. The geographic region where one lives and the climate will also affect the amount of radiation to which one""s skin is exposed. The sun""s rays can dry skin through direct moisture loss or through the effects of radiation on the skin which may cause tanning and burning as well as moisture loss.
Skin may also face adverse conditions in the workplace where excessive temperatures or low humidity may harm skin. Exposure to chemicals may also remove moisture from the skin causing damage and actual skin chafing and loss if not treated properly.
Consequently, a mild skin moisturizer that nourishes the skin with natural ingredients and that can be repeatedly applied to the skin is beneficial in areas where skin is particularly susceptible to environmental damage.
In addition to environmental factors, skin must also be properly nourished. Maintaining healthy skin requires maintenance of proper moisture in the skin as well as delivery of essential vitamins to the skin. Vitamins may be consumed in the diet or may be applied directly to the skin.
For some people, oral consumption of vitamin C, especially in large doses, can have detrimental side effects ranging from mouth irritation to overdose. Yet large doses are sometimes considered beneficial to provide the skin with an effective amount of vitamin C. Vitamin C promotes collagen synthesis through its free radical scavenging attributes and its enzyme reactions which, in turn, promotes wound healing and skin health. Vitamin C is also toxic to many cancer cells including melanoma and has been found to catalyze the immune reaction to viral and bacterial infections.
Natural skin care products and remedies are popular among health-conscious consumers today. Many people prefer to enhance their appearance and health with vitamins and other nutrients in a xe2x80x9cnaturalxe2x80x9d way from naturally occurring sources. xe2x80x9cNaturalxe2x80x9d products including natural vitamins are now in high demand. These are vitamins which are found in a product in its natural state without vitamin supplements or vitamin xe2x80x9cfortification.xe2x80x9d While fruit and vegetable juices are known to have high concentrations of vitamins in their natural state and are often a preferred source of vitamins for internal consumption, many natural fruit and vegetable products are largely overlooked as a topical skin application.
What is needed is a skin care product and method that delivers natural vitamins, nutrients and other beneficial products to the skin without oral consumption and its adverse side-effects. Also needed is a natural product which can moisturize as well as nourish the skin.
Accordingly, it is an object of the present invention to provide a product and method which can deliver natural vitamins, skin nutrients and skin protectants to the skin in a topical application that nourishes and moisturizes the skin naturally.
The present invention comprises novel compositions of extracts from ginseng berry, herbs and preferably also other skin care ingredients which are mixed to form a topical application.
It is an object of preferred embodiments of the present invention to deliver natural vitamins to the skin.
It is another object of preferred embodiments of the present invention to deliver natural fruit and vegetable extracts to the skin so that the skin may benefit from natural vitamins, emollients and other healthful ingredients.
It is yet another object of preferred embodiments of the present invention to deliver natural and healthful herbs to the skin.
It is a further object of preferred embodiments of the present invention to moisturize the skin.
The present invention may be embodied in other specific forms without departing from its spirit or essential characteristics. The described embodiments are to be considered in all respects only as illustrative, and not restrictive. The scope of the invention is, therefore, indicated by the appended claims, rather than by the foregoing description. All changes which come within the meaning and range of equivalency of the claims are to be embraced within their scope.
The present invention is directed towards skin care products and topical skin products containing juice from the ginseng berry. Although the ginseng root is sometimes used as an herbal supplement, the ginseng berry has been overlooked due, at least in part, to its high seed content. Ginseng berries contain a large number of seeds which make up a large percentage of the berry""s volume. These seeds must be removed in order to make a liquid suitable for use in topical skin applications.
Laboratory analysis of the juice from ginseng berries used for preferred embodiments of the skin care products of the present invention shows a high concentration of essential vitamins. The following Table 1 gives the result of a laboratory analysis of the essential vitamins and ingredients found in ginseng berry juice.
Advantageously, ginseng berry juice also acts as an anti-oxidant. Laboratory analysis reveals that one gram of ginseng berry contains 1.4 times more antioxidant that 10 mg of Vitamin C.
Modern machinery may be used to produce juice from ginseng berries, however one presently preferred method of the present invention comprises a manual process. In this process, whole ginseng berries are crushed in a press thereby removing the majority of the juice. The seeds are then removed from the juice by filtration through a coarse screen filter. When a solids-free liquid is desired, the juice is further filtered in a 0.2 micron micro-filtration system to remove even finer solids. Some solids content may be acceptable or desired to improve texture or add fiber to the final product. When this is the case, the micro-filtration step may be omitted.
After the juice has been extracted, it is preferably blended with other natural ingredients which may add moisturizing effects, provide UV protection, or provide other physiological benefits.
Application of natural herb products along with the beneficial vitamins contained in ginseng berry juice may also increase health and vitality. The effects of various herbs and plant products are beneficial to the nervous, digestive and circulatory systems as well as other physiological functions. Herbs which, when applied to the skin, are beneficial to one""s health and vitality may be considered to be xe2x80x9cnatural skin supplements.xe2x80x9d The combination of herbal ingredients with healthful and rejuvenating ginseng berry juice products offers the health advantages of natural vitamins and herbs in an aromatic, pleasing and healthful skin application.
Ginseng root also has beneficial physiological effects. It is believed to help regulate blood pressure and increase the body""s resistance to adverse physical, chemical and biological influences. Ginseng root can stimulate physical and mental activity and protect against the adverse effects of mental and physical stress. It may also improve concentration and stimulate brain cells. Ginseng root may be considered to be an herbal stimulant.
Ginseng root also has beneficial physiological effects. It is believed to help regulate blood pressure and increase the body""s resistance to adverse physical, chemical and biological influences. Ginseng root can stimulate physical and mental activity and protect against the adverse effects of mental and physical stress. It may also improve concentration and stimulate brain cells. Ginseng root may be considered to be a natural skin supplement. In the prior art, like some vitamins, ginseng root is often offered in capsules or tablets in a raw form. This can be difficult for some to ingest due to gag reflexes, physical impairment or psychological aversion to tablet or capsule consumption. A topical skin application allows a user to benefit from many of the beneficial effects of ginseng root without the requirement of ingesting the substance.
Preferred embodiments of the present invention combine the juice of ginseng berries with herbal supplements and stimulants and/or other natural skin supplements to create an application that has pleasurable sensory effect on the user and which provides a great variety of ingredients essential to health and vitality.
Other products within the scope of the present invention may be created from ginseng berry juice. Ginseng berry juice may be concentrated by known techniques to form a concentrated extract or syrup. This concentration may be performed on the pure juice of the ginseng berry or it may be performed after mixing the juice with natural skin supplements or other ingredients. The concentrated extract or syrup may then be diluted with water to return it to a juice state as needed. When more fiber or texture is desired, the final filtration step of the juice making process using a 0.2 micron filter may be omitted or replaced with a step which utilizes a coarser filter. Alternatively, fiber and texture producing ingredients may be added as needed.
The novel method and composition of the present invention allows users to apply natural vitamins, anti-oxidants and emollients directly to the skin.
The following tables further illustrate the ingredients currently used in the certain presently preferred embodiments. Ingrdients listed in these tables are given by weight percentage of the total mixture.


There is provided a composition for the nasal delivery of a cannabinoid which comprises a cannabinoid in a biphasic delivery system or a cannabinoid in a microsphere delivery system.

This invention relates to pharmaceutical compositions for nasal delivery of cannabinoids and pharmaceutically acceptable salts and prodrugs thereof. The present invention also relates to the delivery of cannabinoids across the nasal mucosa of animals, especially humans, for the treatment of conditions such as pain, nausea and to stimulate appetite.
It is known that the active ingredients of cannabis, in the form of cannabinoids, can be useful in medical practice. The material delta-9-tetrahydrocannabinol (THC) is useful in the treatment of AIDS (J. Pain. Symptom Manage. 1995, 10, 89-97) when given orally. The drug is called Dronabinol and is formulated in sesame oil for oral delivery. The material is available commercially as the product Marinola(copyright) sold by Roxane in the USA.
Dronabinol (9-delta THC or THC) exhibits complex effects on the central nervous system (CNS), including central sympathomimetic activity. Dronabinol has been shown to have a marked appetite stimulant effect and has been used in the treatment of AIDS-related anorexia. Dronabinol also demonstrates effects on mood, cognition, memory and perception. Furthermore, the drug has anti-emetic properties and is used for the control of nausea and vomiting associated with cancer chemotherapy. These effects appear to be dose related. After oral administration, Dronabinol has an onset of action of approximately 0.5 to 1 hour and a peak effect at 2-4 hours. The duration of action for psychoactive effects is 4-6 hours, but the appetite stimulant effect may continue for 24 hours or longer after administration. Dronabinol is almost completely absorbed (90-95%) after single oral doses. However, due to a combined effect of first pass hepatic metabolism and high lipid solubility only 10-20% of the administered dose reaches the systemic circulation.
Studies on the use of THC in pain have been described in Pharm. J. 259, 104, 1997 and in Pharm. Sci. 3, 546, 1997. Nabilone, a synthetic cannabinoid has been reported to be an anti-emetic and anxiolytic, and also useful for treating pain of various etiologies such as multiple sclerosis (MS), peripheral neuropathy and spinal injuries (Lancet, 1995, 345, 579, Pharm. J. 259, 104, 1997). It is also known that inhaling cannabis by smoking can lead to a more rapid onset of action than oral ingestion.
A nasal formulation for the improved delivery of cannabinoids would be advantageous. Absorption of drugs from the nasal route tends to be rapid due to the large surface area available and the extensive blood supply. In addition, the drug is delivered directly to the systemic circulation and there is no loss due to xe2x80x9cfirst passxe2x80x9d metabolism in the liver.
The nasal route is known to provide advantages for the delivery of drugs, and for some drugs the pharmacokinetic profile following nasal administration is similar to that found after intravenous administration. However, THC is in the form of an oily liquid which is highly lipid soluble and only sparingly soluble in water. Hence, the person skilled in the art would consider it impossible to produce a simple nasal solution or other simple gel or suspension formulation that could produce sufficient nasal absorption and therapeutic plasma levels.
The nasal administration of cannabinoids and their analogues has been described in U.S. Pat. No. 4,464,378. It was suggested that the drugs would be administered as simple nasal sprays, ointments, gels or suspensions, though no examples of formulations produced with THC were described. As explained above, the person skilled in the art would not expect such simple formulations of THC to be successful due to the low water solubility.
We have found surprisingly that cannabinoids and especially THC can be formulated successfully into a nasal product by using a biphasic delivery system and that such a biphasic delivery system provides improved nasal absorption and therapeutically relevant plasma levels. We have also found surprisingly that cannabinoids and especially THC can be delivered successfully via the nasal route by formulating into a microsphere system and particularly an albumin microsphere system.
According to a first aspect of the present invention there is provided a composition for the nasal delivery of a cannabinoid comprising a cannabinoid in a biphasic delivery system.
According to a second aspect of the present invention there is provided a composition for the nasal delivery of a cannabinoid comprising a cannabinoid in a microsphere delivery system.
By the term xe2x80x9ccannabinoidxe2x80x9d we include, inter alia, delta-8-tetrahydrocannabinol, delta-9-tetrahydrocannabinol, cannabidol, olivetol, cannabinol, cannabigerol, nabilone, delta-9-tetrahydro cannabinotic acid. The non-psychotropic cannabinoid 3-dimethylnepty 11 carboxylic acid homologine 8, delta-8-tetrahydrocannabinol, (J. Med. Chem. 35, 3135, 1992) as well as the prodrugs and pharmaceutically acceptable salts of cannabinoids are also suitable for the present invention and are included in the term xe2x80x9ccannabinoidxe2x80x9d. A suitable prodrug is THC-hemisuccinate.
By a xe2x80x9cbiphasic delivery systemxe2x80x9d we are referring to a pharmaceutical composition comprising two phases of which one phase contains the dissolved, dispersed, solubilised or dissoluted drug and the other phase provides the carrier for the composition, for example the outer (surrounding) water phase in an emulsion system or the matrix of a microcapsule or microsphere system.
By xe2x80x9cimproved nasal absorptionxe2x80x9d we mean more than 10%, preferably more than 20% and most preferably more than 30% bioavailability of the drug after nasal administration. By the term bioavailability, we mean the absorption of the drug as measured by the area under the plasma level versus time profile following nasal administration as compared to the same parameter when the drug is given by intravenous injection; the values for the area being corrected for the dose of the drug if necessary.
Biphasic delivery systems may be in the form of emulsion systems, such as an oil-in-water (O/W) emulsion, aqueous systems containing a solubilising or dispersing agent or microsphere systems where the phase containing the drug can be encapsulated by or dispersed on the surface of the microspheres.
An oil-in-water emulsion can be prepared using a combination of a pharmaceutically acceptable oil and emulsifier. The drug is dissolved in the oil phase which is then mixed with an aqueous phase typically containing a stabiliser under vigorous mixing, milling or homogenisation. Such emulsification methods are well described by Idson, Pharmaceutical Emulsions, Ch. 6, Pharmaceutical Dosage Forms, Disperse Systems. Vol. 1. Ed. Lieberman et al. Dekker, New York, 1988.
Preferred oils are vegetable oils such as soybean oil, olive oil, cotton seed oil, peanut oil, sesame oil and castor oil, with sesame oil and castor oil being preferred.
Vitamin E (tocopherol) can also be used as the oil phase. This material is also an antioxidant and can help to stabilise the chosen cannabinoid which tend to be prone to oxidation.
By the term Vitamin E (tocopherol) we include the xcex1-, xcex2-, xcex3- and xcex4-forms of tocopherol that differ by the number and position of methyl groups on the chromanol ring as well as the various isomers of these compounds. Pharmaceutically acceptable derivatives of tocopherol are also included, such as the esters of tocopherol, e.g. the linoleate, nicotinate, acetate or acid succinate ester.
The United States Pharmacopoeia describes Vitamin E as a form of xcex1-tocopherol. This includes d- or d, 1-xcex1-tocopherol, d- or d, 1-xcex1-tocopherol acetate and d- or d, 1-xcex1-tocopherol succinate. The term Vitamin E is also used as a generic description for all tocopherol and tocotrienol derivatives that exhibit Vitamin E activity. Thus, the term tocopherols is synonymous with Vitamin E, but also for methyl tocols.
A preferred Vitamin E composition for use in the emulsions of the present invention is xcex1-tocopherol as described in the United States Pharmacopoeia, Volume 23, 1995 which is also known as all-rac-xcex1-tocopherol. This material can be obtained from Roche Products Ltd., Heanor, UK.
The chosen emulsifier will be one that confers good stability to the emulsion and is pharmaceutically acceptable.
One preferred emulsifier is a block copolymer containing a polyoxyethylene block, i.e. a block made up of repeating ethylene oxide moieties. A suitable emulsifier of this type is Poloxamer, i.e. a polyoxyethylene-polyoxypropylene block copolymer, such as Poloxamer 188. See the Handbook of Pharmaceutical Excipients, p.352, 2nd Edn. Pharmaceutical Press, London, 1994, Eds, Wade and Weller.
Another preferred emulsifier is a phospholipid emulsifier. This can be any pharmaceutically acceptable material derived from soybeans or eggs, e.g. soy or egg lecithins. Egg lecithins, such as the material provided by Lipoid (Germany) known as Lipoid E80, which contains both phosphatidylcholine and phosphatidyl ethanoline, are preferred, although other phospholipid materials could be used including phospholipid-polyethylene glycol (PEG) conjugates (PEGylated phospholipids) that have been described for use in liposome systems, e.g. by Litzinger et al, Biochem Biophys Acta, 1190 (1994) 99-107.
The stability of the emulsion can be enhanced by the addition of a pharmaceutically acceptable co-emulsifier. Suitable co-emulsifiers include the fatty acids and salts thereof and bile acid and salts thereof. Suitable fatty acids are those having greater than 8 carbon atoms in their structure with oleic acid being a preferred material. A preferred bile acid is deoxycholic acid. Suitable salts are the pharmaceutically acceptable salts such as the alkali metal, e.g. Na and K, salts. These co-emulsifiers can be added at a concentration of 1% w/v, i.e. 1 g of co-emulsifier per 100 mls, or less of the total emulsion. Bile salts and oleic acid are preferred co-emulsifiers.
The quantity of oil in the emulsion can be from 5 to 50% on a v/v basis, preferably from 10 to 50% v/v and more preferably from 15 to 25% v/v. The drug is typically dissolved in the oil phase at a concentration of 0.1 to 20% w/v, preferably from 1 to 10% w/v, i.e. from 0.1 to 20, preferably from 1 to 10 g of drug in 100 ml of oil.
The emulsion formulation can be delivered to the nasal cavity using nasal spray devices known in the art such as those available from Pfeiffer and Valois. Such devices are familiar to the skilled artisan and can be single or multiple dosing systems.
The preferred volume for nasal administration is 150 xcexcl (per nostril) containing a dose of about 1 mg of THC.
The biphasic delivery systems may also comprise a solubilising agent (solubilising phase) in an aqueous phase or in a solid phase. The solubilisation of the cannabinoid may be achieved by the use of a cyclodextrin or derivative thereof. Cyclodextrins are cyclic oligosaccharides which comprise glucopyranose units and cyclodextrins for use as pharmaceutical excipients have been described in detail by Thompson, Crit, Rev. Ther. Drug Carrier Sept. 14 1 (1997). Cyclodextrin and cyclodextrin derivatives which may be useful in the present invention include xcex1-cyclodextrin, xcex2-cyclodextrin, xcex3-cyclodextrin, hydroxypropyl-xcex2-cyclodextrin, dimethyl-xcex2-cyclodextrin, sulphobutylether cyclodextrin, 2,6-dimethyl 14-xcex2 cyclodextrin, 2,3,6-trimethyl 21-xcex2 cyclodextrin.
The solubilising agent/cannabinoid formulation can be a simple aqueous product in which the drug is associated with the solubilising agent molecule, e.g. as a guest-host complex in which the drug (guest) is contained within a cavity in the solubilising agent molecule (host). Alternatively, the solubilising agent/cannabinoid formulation can be combined with the emulsion product described earlier when some of the drug can be present in the aqueous phase of the emulsion, solubilized in the solubilising agent, and a proportion of the drug can be present dissolved in the oil phase of the emulsion.
Alternatively, a guest-host product between a solubilising agent and a cannabinoid can be freeze dried to produce a powder material and then mixed with a bioadhesive microsphere such as a bioadhesive swelling starch microsphere as described in PCT/GB88/00836.
Other bioadhesive microspheres that may be used in the present compositions include those made from chitosan, polyvinyl pyrrolidone, alginate, polycarbophil, pectin, hyaluronic acid (and esters thereof), agar agarose, dextran, ovalbumin, collagen, casein.
By bioadhesion we mean a material that can interact with mucus or a mucosal surface and thereby provide retention of a drug at a mucosal surface for a period of time longer than that found for a simple liquid or powder system. The concept of bioadhesion has been well discussed in books and reviews such as Bioadhesive Drug Delivery Systems, Ed. Lenaerts and Gurney, CRC Press, Bala Raton, 1990 and Bioadhesion possibilities and future trends. Ed. Gurney and Junginger, Wissenschaftliche, Verlagsgellschaft mbh, Stuttgard, 1990.
Such a system will demonstrate good stability with high bioavailability when administered via the nasal route.
The weight ratio of solubilising agent to cannabinoid is typically in the range of from 100:1 to 5:1, preferably in the range of from 50:1 to 10:1 and more preferably in the range of from 30:1 to 10:1. The weight ratio of solubilising agent/cannabinoid guest-host product to carrier, e.g. water or microspheres, can be varied but is typically in the range of from 1:100 to 1:5, preferably in the range of from 1:50 to 1:10 and particularly in the range of from 1:25 to 1:15.
The systems containing a solubilising agent can also be mixed with a gelling system based on a polysaccharide such as gellan or pectin. These materials can be used to formulate a nasal liquid that can be sprayed into the nasal cavity but will then gel in the presence of endogenous cations. This gelling may prolong the contact time of the formulation in the nasal cavity either through bioadhesive interactions and/or the increase in viscosity. Pectin is a preferred material which can form gels in the presence of divalent cations such as calcium. Pectins with a low degree of esterification, i.e. less than 50%, for example, less than 35%, are suitable and these can be obtained from Copenhagen Pectin A/S as the commercial material known as Slendid Type 100 and Slendid Type 110. These pectins have been extracted from citrus peel and standardised by the addition of sucrose. The degree of esterification is less than 50% for both pectins and of the order of 10% for type 100 and 35% for type 110. Further suitable materials include GENU pectin types LM1912CS and Pomosin pectin types LM12CG and LM18CG. The concentration of pectin in the composition can be from 0.1% to 10% w/w, but is preferably from 0.5 to 5% w/w on the total weight of the composition.
The powdered product can be delivered nasally using an insufflator device of the type which is familiar to those skilled in the art. Such devices are manufactured by Teijin (Rhinocort(trademark) insufflator), Bespak UK (nasal delivery device), Valois Monopoudre(trademark), France.
A further embodiment of this invention is to incorporate a cannabinoid into a microsphere. It has been found that cannabinoids can be loaded into albumin microspheres and that it is possible to recover such microspheres in a dry powder for nasal administration. Other materials suitable for the preparation of microspheres include agar, alginate, chitosan, starch, hydroxyethyl starch, ovalbumin, agarose, dextran, hyaluronic acid, gelatin, collagen and casein. The microspheres can be produced by various processes known to the person skilled in the art such as a spray drying process or an emulsification process.
For example, albumin microspheres can be prepared by adding rabbit serum albumin in phosphate buffer to olive oil with stirring to produce a water in oil emulsion. Glutaraldehyde solution is then added to the emulsion and the emulsion stirred to cross-link the albumin. The microspheres can then be isolated by centrifugation, the oil removed and the spheres washed, e.g. with petroleum ether followed by ethanol. Finally, the microspheres can be sieved and collected and dried by filtration.
Starch microspheres can be prepared by adding a warm aqueous starch solution, e.g. of potato starch, to a heated solution of polyethylene glycol in water with stirring to form an emulsion. When the two-phase system has formed (with the starch solution as the inner phase) the mixture is then cooled to room temperature under continued stirring whereupon the inner phase is converted into gel particles. These particles are then filtered off at room temperature and slurried in a solvent such as ethanol, after which the particles are again filtered off and laid to dry in air.
The microspheres can be hardened by well known cross-linking procedures such as heat treatment or by using chemical cross-linking agents. Suitable agents include dialdehydes, including glyoxal, malondialdehyde, succinicaldehyde, adipaldehyde, glutaraldehyde and phthalaldehyde, diketones such as butadione, epichlorohydrin, polyphosphate and borate. Dialdehydes are used to cross-link proteins such as albumin by interaction with amino groups, and diketones form schiff bases with amino groups. Epichlorohydrin activates compounds with nucleophiles such as amino or hydroxyl to an epoxide derivative.
Doses of the drug, e.g. THC, in the range 0.25 to 40 mg per day can be administered, a preferred range is 0.5 to 30 mg per day and a more preferred range 1 to 20 mg per day.
The present invention is now illustrated but not limited with reference to the following examples.

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