A method for guiding a missile to a target. The method includes the step of providing a surface-based radar system having an electronically beam steerable antenna system adapted for continuous mechanical rotation about an axis. During a pre-terminal, semi-active missile homing guidance phase, the beam produced by the antenna system is electronically rotated by the antenna system in a direction counter to the direction of the mechanical rotation of the antenna system to thereby increase radar system illumination time on the target. Further, during the increased illumination time, the beamwidth of the surface-based radar system beam is increased. During, a subsequent terminal, active homing missile guidance phase, guiding the missile to the target with the pre-terminal, semi-active missile homing guidance phase using the surface-based radar system and establishing an angular orientation for a missile-borne antenna system at the commencement of the terminal, active missile homing guidance system phase.

This invention relates generally to missile guidance systems and more particularly to radar guided missile systems.
As is known in the art, a missile may be guided to a target by guidance signals developed from tracking data obtained either at a surface-based radar station or by radar means located totally, or partially, within the missile. The former system is commonly referred to as a command guidance system and the latter as a missile homing guidance system. For example, in a command guidance system where a missile is used to intercept an airborne target, a large, remotely located, high resolution surface-based radar system and high speed digital computer are provided for selecting one of a plurality of targets, tracking both the missile and the selected target, calculating proper guidance signals for the missile from the generated tracking data, and transmitting such signals to the missile to enable the missile to intercept the target. As is known, a reference element, such as an attitude stabilized platform is generally required to be contained within the missile for transformation of the transmitted signals into missile control signals.
In a missile homing guidance system, a smaller, light weight, lower power target tracking radar system may be provided for generation of both target tracking data and guidance signals. In one type of missile homing guidance system, both the radar transmitter and receiver are located in the missile and in another type of homing system the radar transmitter is located remotely from the missile while the receiver is located in the missile. The former missile homing system is referred to as an active guidance system and the latter as a semi-active guidance system. Generally, such semi-active guidance system includes a target tracking radar antenna gimballed within the missile and coupled to a control system (i.e., the antenna and control system therefore being referred to collectively as a missile seeker) for tracking the target and to thereby generate guidance signals for the missile.
In one type of missile system, the features of command guidance and semi-active guidance techniques are combined. During the early portion of the missile's flight, the missile is guided by a command guidance phase where the guidance command signals are developed by the digital computer operated in response to signals obtained by tracking both the missile and a selected target with a remote, high resolution, surface-based radar system. During the later portion of the flight, the missile is guided by a semi-active guidance phase where guidance signals are obtained by tracking the target with the missile-borne radar receiver fed by the gimballed antenna system which receives reflected power from target illuminations by the surface-based radar system. In one system, the antenna provides a stable reference for the command guidance phase, such system being described in U.S. Pat. No. 4,142,695 entitled "Vehicle Guidance System" issued Mar. 6, 1979 and assigned to the same assignee as the present invention.
As is also known in the art, the use of an initial command guidance system phase followed by an active, missile homing guidance system terminal phase has been suggested. In such suggested arrangement, after the initial command guidance system phase (i.e., at the commencement of the active terminal phase), the missile seeker would first go through a search phase to search for the target and then, once the target is acquired, the missile seeker would go into a target tracking mode to thereby guide the missile to the target. With small targets, the search phase may be relatively long thereby reducing the time to guide the missile to the target. Generally, however, the shorter the time the missile has to guide to the target, the less likelihood the missile will successfully intercept the target.


A semiconductor device comprises a substrate, a cathode, an outer ring, an anode, an electrically insulating layer, and an electrically conducting layer. The substrate includes a semiconducting material having a first conduction type. The substrate has a first face and a second face substantially parallel to the first face. A cathode is disposed at the second face and has the first conduction type. An outer ring, having the first conduction type, is disposed at an outer perimeter of the first face of the substrate. An anode, having the second conduction type, is disposed at the first face of the substrate within an inner perimeter of the outer ring. An electrically insulating layer is disposed over the outer ring. An electrically conducting layer is disposed over the electrically insulating layer and over the outer ring. The electrically conducting layer electrically is insulated from the outer ring by the electrically insulating layer.

Shown in FIGS. 10-11 is a semiconductor device 100. The semiconductor device 100 can be a PIN diode. The semiconductor device 100 comprises a substrate 12, a cathode 23, an outer ring 22, an anode 14, and a guard ring 13.
The substrate has a first face 12f and a second face 12s, with the second face 12s being substantially parallel to the first face 12f.
The cathode 23 can be disposed at the second face 12s of the substrate 12. The outer ring 22 can be disposed at an outer perimeter of the first face 12f of the substrate 12. The anode 14 can be disposed at the first face 12f of the substrate 12 within an inner perimeter 22i of the outer ring 22. The guard ring 13 can be disposed at the first face 12f of the substrate 12 between the outer ring 22 and the anode 14. The guard ring 13 can be separated from the anode 14 by substrate 12b and from the outer ring 22 by substrate 12a. A purpose of the outer ring 22 is to prevent a depletion region which may be formed in the substrate from extending to an edge of the semiconductor device 100. The guard ring 13 can capture leakage current originating from an outer periphery of the semiconductor device 100.
The cathode 23, the outer ring 22, the anode 14, and the guard ring 13 can be embedded in the substrate 12 such as by implantation. The substrate 12, the cathode 23, and the outer ring 22 can comprise a semiconducting material having a first conduction type, such as n for example. The cathode 23 and the outer ring 22 can be more highly doped than the substrate 12 (n+ for example). The anode 14 and the guard ring 13 can be more highly doped than the substrate 12, and can be a second conduction type (p+ for example). The first conduction type can be opposite of the second conduction type. One conduction type may be a material that tends to have an excess of electrons, and the other conduction type may be a material that tends to have an excess of holes.
Following is an example of one use of the semiconductor device 100 for x-ray fluorescence analysis of elements in a sample, such as to determine element concentration. The anode 14 can have a voltage that is zero or close to zero. The cathode 23 can be connected to a positive voltage of around 120 volts. Due to temporary flow of electrical current through the substrate 12, the outer ring 22 can have a voltage similar to that of the cathode 23 (about 120 volts in this example).
The sample can absorb x-rays from an x-ray source. The sample can then emit elemental-specific x-rays which can impinge on the semiconductor device 100. The elemental-specific x-rays can be absorbed by the substrate 12, resulting in formation of free electrons and holes. Due to the large positive voltage on the cathode 23, and the less positive voltage (or even negative voltage) on the anode 14, the free electrons can flow to the anode 14.
The anode 14 can be connected by a wire bond 15 to an outer circuit 16. The wire bond 15 can extend over the outer ring 22 without touching the outer ring 22. Free electrons can flow from through the wire bond 15 between the anode 14 and the outer circuit 16. The free electrons are a signal that can be analyzed by the outer circuit 16 to determine elemental-specific x-ray energy, and from this elemental-specific x-ray energy, the element that emitted the x-ray.
There is a capacitance C between the wire bond 15, with a voltage typically around zero volts, and the outer ring 22, with a voltage of 120 volts in this example. A problem with operation of the semiconductor device 100 is that the wire bond 15 is typically made of very fine gage wire, which can easily vibrate 111. This wire vibration 111 can cause the capacitance C, between the wire bond 15 and the outer ring 22, to change or oscillate. A distance d between two conductors is one factor that determines capacitance. Thus a change in distance d between the outer ring 22 and the wire bond 15, due to movement or vibration of the wire bond 15, can cause a change in capacitance between the outer ring 22 and the wire bond 15.
Changing capacitance C can induce noise into the wire bond 15 as indicated by the equation Q=CV, in which Q is charge and V is voltage differential between the two conductors (120 volts in this example). Because the voltage differential V is high, changes in capacitance can result in substantial changes in charge Q. The changes in charge Q will be analyzed by the outer circuit 16. The outer circuit 16 cannot distinguish between electrons resulting from x-rays absorbed by the substrate 12 and electrons resulting from the changing capacitance. Thus, the changing capacitance C can introduce undesirable electronic noise into the signal, adversely affecting analysis of the signal, such as by causing poor resolution. This poor resolution can make it difficult to distinguish different elements in the sample. It would be beneficial to eliminate or reduce this electronic noise induced into the signal due to the changing capacitance C between the wire bond 15 and the outer ring 22.

Vibration noise shield in a semiconductor sensor


A solid pesticide composition is described wherein the composition contains a seem seed extract and at least one saccharide. The solid pesticide composition is preferably storage stable, has higher pesticidal activity, and can be easily dissolved and/or dispersed in a liquid medium, such as a water-based medium.

The present invention relates to compositions containing neem seed extracts such as azadirachtins. The present invention further relates to methods to prepare a stabilized pesticide composition containing neem seed extracts.
Extracts of various parts of the neem tree (Azadirachta indicia) such as leaves, bark, seeds, etc. have been long known to have insecticide activity. The seed kernel, in particular, processes the most active limonoids, such as Azadirachtin A and B and structurally related compounds such as C, D, E, F, G, H, I, J, K, and the like, along with nimbin, salannin, azadiradione, and the like. All the natural azadirachtins have reported a very high growth disturbing activity against Epilachna varivestis, with LC50s in the range of 0.3 to 2.8 ppm (H. Rembold and I. Puhlmann, 1995). More than 100 terpenoid metabolites are reported from the neem seed/fruit of the neem tree. Various methods have been described to extract these active components in the crude or semi crude forms to be used in commercially acceptable vehicles in the form of liquid and solid formulations. The crude neem seed extracts obtained, after removal of lipid components, normally contain about 20-45% by weight of Azadirachtin A and B and have been shown to be potent insect growth regulators and feeding deterrents and are potential active ingredients in commercial pest control formulations. The active molecules, however, of the neem seed extracts are rather large and complex, and having acid and base sensitive functional groups, they tend to be unstable in these vehicles thus posing a major limitation for commercial use of these extracts.
So far azadirachtin has been widely formulated in liquid forms to be applied as an emulsion or solution to agriculture crops. Various organic solvents and other inorganic additives have been used as carriers in order to make a cost effective and efficacious delivery system. The use of such carriers is rather limited, however, since many solvents are deleterious to the stability of azadirachtin. Dureja (1999) has studied the degradation of azadirachtin A in various solvents for 25 days at 29+/xe2x88x921xc2x0 C. The results indicated 50% degradation of azadirachtin A in methanol and acetone, 75-80% degradation in methylene chloride, carbon tetrachloride and chloroform, and about 85% degradation in ethanol and water.
Storage-stable azadirachtin formulations and methods of preparing stable azadirachtin compositions have been proposed. U.S. Pat. No. 4,556,562 reports that the stability of azadirachtin in ethanol emulsions increased by diluting the concentration of azadirachtin to between 2000 and 4000 ppm and adjusting the pH to between 3.5 and 6.0. U.S. Pat. No. 4,946,681 (Walter) reports greater stability for azadirachtin in solutions of aprotic solvents containing less than 2-5% of water. U.S. Pat. No. 5,001,146 indicates that azadirachtin stability is improved by adjusting the concentration of the polar aprotic solvent to at least 50% by volume and by decreasing the water content to less than 15% by volume. Moreover, U.S. Pat. No. 5,001,146 further indicates that azadirachtin stability depends upon the type of solvent employed, and that stability requires storage in large quantities of certain enumerated aprotic and alcohol solvents. Murali (U.S. Pat. No. 5,736,145) reports a storage stable aqueous composition containing azadirachtin A and U.S. Pat. No. 5,827,521 indicates a stable azadirachtin formulation containing aliphatic dihydroxylated alcohols of more than 80% by volume and optionally with sunscreens and antioxidants.
U.S. Pat. No. 5,352,697 describes the stability enhancement of azadirachtin in solution by the presence of epoxide, preferably an epoxidized vegetable oil. These methods describe the enhancement of azadirachtin containing extracts in the liquid form prepared from neem seed kernel with organic solvents.
European Patent No. 579,624 describes making an extract of neem seed in solid form with greater stability. The stability of azadirachtin in neem extracts is reported to be improved by removing the lipid impurities from extracts (India Patent Application No. 1855). Walter (U.S. Pat. No. 5,635,193) reports that an azadirachtin containing solid is stable by limiting moisture and volatile polar solvents to less than 1% and 5%, respectively. A formulation containing 0.05% to 2% surfactant and 99% of solid diluent has been claimed as a stable bio-control agent by retention of at least 75% of azadirachtin after 2 weeks of storage at 54xc2x0 C. Such a formulation may be used as a dust and wettable powder, but the efficacy of azadirachtins in such vehicular formulations is not practically reported.
Another formulation is a solid form of neem seed extract prepared from the kernel of neem seed as per the methods described in U.S. Pat. No. 5,695,763, European Patent No. 579,624, and IN 181,845. The product is quite stable with respect to its active ingredients viz Azadirachtin A, B, nimbin, salannin, and the like.
Though various extracts with stable azadirachtin have been reported, stability of azadirachtin in a formulated state is still a concern. Azadirachtin is highly unstable in various surfactants, organic solvents, and in different combinations of solvents and surfactants in liquid formulations which is a serious limitation for the development of a shelf stable commercial product.
Normal pesticide formulations contain various solvents made mostly from petroleum, and there is a concern that usage of such solvents in specialty pesticide formulations, especially meant for organic farming, veterinary application, and the like, is discouraged. The use of such solvents, even at a lower rate, demands large amounts of surfactants and other additives which makes the cost of the formulations high.
The use of a broader range of ingredients in liquid formulations and the associated problem of instability in such formulations is also a serious concern for the commercial success of azadirachtin containing crop protection agents. Accordingly, there is still a need for a formulation containing simple, safe, and cost effective vehicles which yet provides stable and efficacious products.
As noted above, the pesticidal effect of neem active compounds, such as azadirachtins, is mostly through insect growth regulation, molting inhibition, antifeedant, ovicidal, and other physiological effects and is normally slow compared other synthetic pesticides which result in immediate knockdown. Hence, there is a need to identify ways and methods to enhance the efficacy of neem extracts for their wide spread acceptance as a pesticide.
Accordingly, there is a need to develop environmentally safe pesticide formulations which contain azadirachtin and which are further storage stable, efficacious, and economical.
The aim of the present invention is to develop a delivery system for azadirachtin containing neem seed extracts, free from any organic solvent, and which is completely soluble in water and efficacious at a dosage lower than the normal desired dose of azadirachtin containing neem seed extracts for pest control.
All of the patents and publications mentioned throughout this application are incorporated herein in their entirety.
A feature of the present invention is to provide a delivery system for neem seed extracts such as azadirachtin and the like, which is preferably free from any organic solvent and completely soluble in water.
Another feature of the present invention is to provide a neem seed extract in solid form which is stable and flowable.
An additional feature of the present invention is to provide a neem seed extract in efficacious solid form which is water soluble and thus is quite easily used to control insect pests.
Additional features and advantages of the present invention will be set forth in part in the description which follows, and in part will be apparent from the description, or may be learned by practice of the present invention. The objectives and other advantages of the present invention will be realized and obtained by means of the elements and combinations particularly pointed out in the written description and appended claims.
To achieve these and other advantages and in accordance with the purpose of the present invention, as embodied and broadly described herein, the present invention relates to a solid pesticide composition comprising neem seed extract comprising azadirachtin and at least one saccharide.
The present invention further relates to a liquid formulation having the above-described solid pesticide composition dissolved and/or dispersed therein.
Further, the present invention relates to a method to increase the pesticidal effectiveness of a composition containing azadirachtin by introducing at least one saccharide into the composition.
It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are intended to provide further explanation of the present invention, as claimed.
The present invention relates to pesticide compositions containing neem seed extracts, such as azadirachtins. In particular, the present invention relates to a solid pesticide composition which contains neem seed extract and at least one saccharide. Preferably, the neem seed extract contains at least azadirachtin. Further, the neem seed extract can contain nimbin, salannin, and/or azadiradione, and the like. The azadirachtin that is preferably present in the neem seed extract can be one or more types of azadirachtin compounds and are more preferable azadirachtin A and/or B but can also be or include structurally related compounds such as azadirachtin D, E, F, H, I and/or K, and the like.
The neem seed extract is present in the pesticide composition in an amount effective to reduce or eliminate insecticidal activity, such as on vegetation. Preferably, the neem seed extract contains from about 0.03 to about 5.0 weight %, and more preferably from about 0.1 to about 1.0 weight % based on the weight of the pesticide composition. Generally, the azadirachtin will be present in the neem seed extract in an amount of from about 20% to about 50% by weight of the neem seed extract, though other amounts below 20% and above 50% are possible. Most preferably, from about 20% to about 50% of the neem seed extract, by weight of the neem seed extract, is an azadirachtin A and/or B.
The neem seed extract can be obtained following the process recited in U.S. Pat. No. 5,695,763 which is incorporated in its entirety by reference herein or using other extraction processes. In general, the azadirachtin is recovered preferably from the seeds of a neem tree by crushing the seeds and then extracting the azadirachtin and other active ingredients from the crushed seeds with water. The extraction of azadirachtin and other active ingredients from the water is preferably accomplished using a non-aqueous solvent which is not miscible with water and has a higher solubility with azadirachtin than water, or by using a surfactant having a turbidity temperature between 20xc2x0 and 80xc2x0 C. The concentrated azadirachtin is then recovered from the second extracting solution. The azadirachtin containing solution is then concentrated to produce an azadirachtin concentrate which is added to a liquid hydrocarbon, thus forming an azadirachtin precipitate that is then recovered for use in pesticide formulations. The method described in Indian Pat. No. 181,845 can also be used for the preparation of azadirachtin containing extracts. The azadirachtin can also be recovered by the techniques set forth in U.S. Pat. Nos. 4,556,562 and 5,124, 349 and other conventional methods.
The solubility of such neem extracts (Aza 20-50%) in water is less than 0.1% which can yield 200-500 ppm of azadirachtin in solution. However, the recommended dose of azadirachtin for control of various pest control in the field is about 30 ppm which can be prepared by dissolving 0.06-0.15 g of extracts in 1000 ml of water. But handling such small quantities by the user is cumbersome and can be avoided by formulating/diluting the concentrated extracts in inert carriers. Several diluents such as talc, stealite, soap stone, pyrophyllite and yellow talc, kaolin and related carriers can be used in compositions and formulations, but are unsuitable for azadirachtin based formulations as they may degrade azadirachtin because of their acidity or alkalinity. More particularly, these diluents are not suitable for a water soluble type formulation. In search of alternate diluents, various sugars were studied for their suitability in formulations in terms of stability and other properties of a ready to use formulation. One of the major problems in using sugars, as observed in other pesticide formulations, is the undesired formation of cake type mass of the formulated product during storage due to the hygroscopic nature of these substances. However, unexpectedly, no such problem is encountered with neem seed extracts which may be due to anticaking properties of the fine powdery extracts. A wetting agent, with or with out a sticker, are preferred in preparing the formulation to be used in the field. Two of the compositions (1.25% and 6.12% Aza) of neem seed extracts with sucrose (87.26%) and methyl cellulose (10%) were prepared and their stability evaluated under accelerated conditions at 54xc2x0 C. The results indicated that the azdirachtin is more stable in the formulation than in the neem seed extract which shows that these saccharides impart an additional stabilizing effect on azadirachtin in the formulated form. In addition to the enhancement of stability, the formulation surprisingly showed higher pesticidal activity, particularly imparting early mortality of the insect larvae. Thus, the present invention provides methods to increase the pesticidal effectiveness of azadirachtin and compositions containing azadirachtin. Further, the present invention provides a method to expedite the mortality rate of compositions containing azadirachtin by introducing an effective amount of at least one saccharide. The present invention also has the ability to increase storage stability of the azadirachtin, improve the growth inhibition of the azadirachtin towards insects, and/or make the mortality rate of an insect and other pesticidal activities occur faster by introducing an effective amount of saccharide. The insect can be in any stage of maturity or development.
With respect to the saccharide, one or more saccharides can be present in the pesticide composition. Preferably at least two different saccharides are present in the pesticide composition. More preferably, at least one saccharide is a di-saccharide and at least one other saccharide is a polysaccharide. Even more preferably, the saccharides present in the preferred pesticide composition is at least one di-saccharide and a cellulose derivative, such as methyl cellulose. The mono-saccharide is preferably a simple sugar, such as glucose, fructose, and/or galactose. The saccharide can also be a di-saccharide such as sucrose. Most preferably, the saccharide is a methyl cellulose and a sucrose. The saccharides are preferably present in an amount of from about 20% to about 99.9% by weight of the pesticide composition. More preferably, this saccharide is present in an amount of from about 70 weight % to about 80 weight %.
Most preferably, the saccharide is a cellulose derivative such as a methyl cellulose which is present from about 0.1 to about 20 weight % by weight of the pesticide composition and the disaccharide, such as sucrose, is present in an amount of from about 0.5% to about 90% by weight of the pesticide composition.
If desired, carriers such as conventional sticking agents, like natural polymers, for example gum arabic, guar gum, polyvinyl cellulose and the like, in the form of powders, granules, or lattices can be used in the compositions to improve the adherence of the pesticide.
The ingredients forming the pesticide composition may be combined after the ingredients are intimately ground to a particle size of 10-100xcexc and mixed together by blending, preferably mechanically, to result in a free flowing powder. Alternatively, the neem seed extracts may be dissolved in a suitable organic solvent and the solution combined with saccharides and then the solvents removed, such as being stripped off under vacuum. The mixture is then intimately ground to a particle size, such as to a range of from 10-100xcexc, and mixed together such as by blending. It is believed that the azadirachtin present further serves to prevent any caking of the saccharides in the pesticide composition.
The solid pesticide composition is preferably in powder form but can be present in other solid forms such as pellets and the like, and is preferably stable for long periods of time. For instance, the solid pesticide compositions of the present invention can maintain at least 90% by weight of the azadirachtins originally present even after four weeks of storage at 54xc2x0 C. in a sealed container. Accordingly, the pesticide compositions of the present invention are storage stable.
More advantageously, the solid pesticide compositions of the present invention can be easily formed into a liquid formulation by introducing the solid pesticide composition into a liquid medium. The liquid medium is preferably a water-based solution such as water. The liquid medium can also contain other ingredients such as from about 1% to about 5% by weight of the pesticide composition are possible with the present invention. However, a concentration of about 0.0065% by weight of the pesticide may be sufficient for most of the applications.
The pesticide compositions of the present invention can also include conventional additives, such as carriers, biocides, anti-foamers, and the like.
The pesticide compositions of the present invention can be used in any suitable form, such as, but not limited to, dispersions, suspensions, dusting powders, granules, baits, aerosols, fumigating release devices, powders, pellets, and the like.

Compositions containing neem seed extracts and saccharide


An automatic high-speed wrapping system for wrapping packages in heat sealable thermoplastic film includes a film delivery unit wherein the film is dispensed and wrapped around the packages at a high rate of speed as the packages travel through the system. The packages travel continuously in a straight line through the system and are delivered at the input end of the system by a feed conveyor into a wrapping station where the packages are surrounded by the film, thence to the side sealing mechanism which forms a seal while severing the salvage from the packages, then into an end sealing mechanism where both ends of the packages are sealed and the film web connecting succeeding packages is severed. The film is delivered to the wrapping station in two plies and subsequently inverted for wrapping around the products. The positions of the wrapping station and film delivery units are adjustable to efficiently accommodate a variety of product heights while providing proper film delivery geometry.

This invention relates generally to the art of film wrapping systems for use in wrapping objects with shrink wrap film, such as polyurethane wrapping film, and more particularly to improvements directed to dispensing such film from a film roll.
A wide variety of systems are known for wrapping packages in thermoplastic film. Some of these machines are known as L-sealers because they form xe2x80x9ctrim sealsxe2x80x9d utilizing a web of center folded film. More recent machines have utilized a continuous longitudinal sealer and a cross sealer which moves at approximately the velocity of the packages as they travel through the machine so that it is not necessary to stop the packages while performing the end sealing operation. Such prior art machines have generally been of three types. One type had a continuous side sealer and a complex series of multiple flighted end sealing jaws which were spaced for a particular product. This type required substantial set-up time for change in length of product to be wrapped. A second machine of this type, while making packages similar to those produced on an L-sealer worked by drawing film off a roll under tension, folding it around the product, drawing it past a hot knife side sealing mechanism and then formed the end seal with a moving end sealer.
A third type of machine had an overlapped longitudinal seal on the top or bottom of the wrapped packages. Since the overlap not only ran along the bottom of the packages but also ran halfway up both ends, the packages lacked the neat appearance and hence the sales appeal of the trim sealed packages as made on the L-sealers. Since many of the products so wrapped are sold in self-service retail stores, the appearance of the package has an important effect on the sales of the product. An additional disadvantage of the overlapped seal is that the width of the web of film must be precisely correct, requiring an exact width film for each size of product.
Shrink wrap packaging systems of these types process and wrap a variety of different products. Commonly, such products are of differing shapes, sizes and dimensions. For example, shrink wrap packaging systems may process and wrap a single compact disc (CD) package which is very thin or other consumer retail items which have a significantly greater height and larger vertical dimension.
One problem associated with most known shrink wrap packaging system is the difficulty to efficiently process and wrap a wide variety of packages and products, especially those having distinctly different dimensions and heights. For example, most known shrink wrap packaging systems utilize film which is provided on a roll in two plies with each ply being joined together by a longitudinal fold line. The two-ply film is dispensed from the supply roll typically in a direction generally perpendicular to the feed direction of the products to be wrapped. As the film is dispensed and delivered to a wrapping station of the shrink wrap packaging system, it is commonly inverted and reoriented to provide an opening for convenient access and entry of the products between the dual plies of the film. The film is reoriented by an upper and a lower film inverting rod or plow system. The upper and lower film inverting rods are positioned above and below, respectively, the feed conveyor which is advancing the products to be wrapped. Examples of such an arrangement are shown in U.S. Pat. Nos. 3,583,888; 3,583,889; 4,035,983; and 4,219,988, each of which are incorporated by reference herein.
The film inverter rods disclosed in the above-identified patents are each fixed relative to one another so that the spacing between the inverter rods is fixed. Recent advancements in the art of shrink wrap packaging systems have included adjustable film inverter rods to accommodate a variety of differing height products being wrapped. As such, the spacing between the film inverter rods may be adjustable.
However, one problem associated with adjustable film inverter rods is that the delivery of the two-ply film to the film inverter rods is often misaligned providing for poor geometry for the film being delivered to the film inverter rods once the spacing between the inverter rods is changed. Optimally the free edges of the upper and lower plies should be generally aligned with one another downstream from the film inverter rods for proper wrapping of the products and positioning of the side seam on the product. However, when the upper film inverter rod is moved relative to the lower film inverter rod for a different height product, the geometry of the film being delivered and processed at the wrapping station becomes misaligned. As a result, the film will not track properly and will not be in the required tubular configuration at the wrapping station. This requires readjustment and/or refeeding of the film through the various rollers, significant operator involvement and down time of the packaging system. The misalignment of the upper and lower plies of the film results in improperly wrapped products, side seals on the products which are located in a conspicuous or improper location, inefficient use or waste of the film wrapping material and other associated problems.
Therefore, a need exists in the shrink wrap packaging industry for a packaging system which can readily accommodate a wide variety of product configurations and heights without the above-described problems associated with known film delivery systems and wrapping operations.
These and other objectives have been achieved with this invention, which in one embodiment includes a film delivery unit for a shrink wrap packaging system. The film wrapping system includes a feed conveyor to delivery a series of products to a wrapping station. The wrapping station includes a pair of film inverter rods which are adjustable for spacing from one another to correspond to the height of the product being wrapped. A film delivery unit dispenses a supply of two-ply film in a direction generally perpendicular to the feed direction of the products. The two-ply film is inverted by the inverter rods at the wrapping station where the products are inserted between the plies of the film. The system includes a film inverter rod adjustment mechanism to adjust the spacing between the rods.
The system also includes a film delivery unit adjustment mechanism to adjust a position of the film delivery unit and the film being delivered to the wrapping station as a function of the spacing between the film inverter rods and, consequently, the height of the product being wrapped. In one embodiment of this invention, the film delivery unit adjustment mechanism moves the film delivery unit and the supply of film upstream in the feed direction relative to the film inverter rods for larger height products and downstream for smaller height products. Additionally, the system in another embodiment includes an adjustable roller positioned between the film delivery unit and the wrapping station to deliver the film to the wrapping station at a desired height relative to the position of the film inverter rods.
The shrink wrap packaging system also includes a side seal mechanism and an end seal mechanism each located downstream in the feed direction from the wrapping station to join the first and second plies together and enclose each of the products in individually wrapped packages. A heat shrink tunnel in one embodiment is located downstream from the sealing mechanisms to heat the film and thereby shrink it around the product as is well known in the industry.
As a result of the film delivery unit and associated adjustment mechanism according to this invention, a variety of product configurations and heights can be conveniently and efficiently wrapped while adjusting the spacing between the film inverter rods without fouling the geometry of the film delivery system and thereby avoiding the associated problems and disadvantages of shrink wrap packaging systems in the prior art.

Film delivery unit for shrink wrap packaging system and associated method


A method is provided for the pretreatment of superposed layers of thermosplastic film which are to be heat sealed together, longitudinally, along a predetermined area. The film layers to be heat sealed are preheated utilizing heated air along a defined, continuous longitudinally extending area of the film layers. The preheated area is subsequently passed through a slit-seal device which simultaneously severs the preheated film layers and seals the severed edges together. The method is particularly useful for the slit-sealing of a continuously advancing flattened tube of thermoplastic which is characterized by having a non-uniform gauge in cross-section.

1. Field of the Invention
This invention relates to a novel system for the production of tubes of thin gauge thermoplastics and, more specifically, relates to a system for continuously preheating a continuously advancing flattened tube of thermoplastic material in an area which is subsequently subjected to slitting and sealing whereby a plurality of tubes are produced from a single tube.
2. Description of the Prior Art
U.S. Pat. No. 3,156,010, the disclosure of which is incorporated herein by reference, discloses a method and apparatus which may be employed for slit-sealing a continuously advancing flattened tube of a thermoplastic material whereby a plurality of individual tubes are formed. As the patent discloses, a single, continuously advancing, flattened tube is passed directly into the path of a heated wire, the heated wire serving to simultaneously slit and seal the edges of the tubes being formed. Instead of utilizing a heated wire other slit-seal elements may be employed such as a hot knife or razor to effect the slit-sealing of the tube. When the thermoplastic film which forms the tube which is being treated, i.e., slit-sealed, is of substantially uniform gauge, such prior art slit-sealing devices perform generally satisfactorily. However, when the gauge of the film is not uniform and, for example, if the film is a profile extrusion characterized by having ribs (as for example the ribbed film product disclosed in U.S. Pat. No. 3,984,047, the disclosure of which is incorporated herein by reference) or thickened areas running longitudinally thereof the ribs serve to prevent (mechanically) the superposed layers of film from being completely sealed at their edges when such prior art slit-seal devices are employed. The individual ribs running against and across the slit-seal element cause the film layers to flutter forcing them further apart and results in poor seal formation evidenced by pin holes in the seal or even resulting in the formation of extremely weak or open seals, i.e., lengths of film in the seal area which are completely unsealed.

Pretreatment of thermoplastic film for improved sealing


A new method for the inhibition of human sweating and body malodour is described. An agent capable of blocking calcium channels in the secretory coil cells of human sweat glands is topically applied; on reaching the secretory coil cells, the action of this agent results in reduced sweat production. Preferred agents are natural plant extracts. The transport of the agent to the secretory coil is preferably enhanced in some way, for example by iontophoresis or the use of a skin penetration enhancer. Antiperspirant products comprising a calcium channel blocking agent and a pore-blocking antiperspirant active are also claimed.

This invention relates to antiperspirant and deodorant products and to cosmetic methods of reducing perspiration and unpleasant body odours.
Cosmetic antiperspirant and deodorant compositions are known. Typical antiperspirant compositions comprise topically acceptable compositions containing a metal salt, such as an astringent aluminium or aluminium/zirconium salt, in combination with a cosmetically suitable vehicle. Typical deodorant compositions comprise topically acceptable compositions containing one or more agents that mask or inhibit the formation of unpleasant body odours; antimicrobial agents are widely used for this purpose. Such cosmetic antiperspirant and deodorant products may be available in a variety of product forms, for example as sticks, roll-on lotions, aerosols and pump spray formulations.
Whilst such compositions provide a degree of malodour reduction, there are problems associated with their use. For example, some people find that such compositions are insufficiently effective. Others find that the application of astringent antiperspirant salts or certain anti-microbial agents leads to skin irritation. Other problems include formulation difficulties with the high levels of active ingredients sometimes required. It has long been desirable to achieve excellent protection from body malodour without the use of high concentrations of conventional antiperspirant or deodorant agents. This could lead to antiperspirant and deodorant products being cheaper, easier to formulate (by virtue of the reduced amount of antiperspirant active used), or generally having improved sensory properties. Other benefits of requiring lesser amounts of conventional antiperspirant or deodorant agents include the reduced concentration on the body of such xe2x80x98foreignxe2x80x99 agents and the reduced impact on the environment, in terms of chemical usage and processing.
The use of numerous xe2x80x9cnon-conventionalxe2x80x9d antiperspirant or deodorant agents are described in the prior art. For example, the use of anticholinergic materials is described in U.S. Pat. No. 3,312,709 (MacMillan, 1967); U.S. Pat. No. 4,022,787 (Soldati et al, 1977); and a series of patents by Felger et al (U.S. Pat. No. 4,517,176, 1985; U.S. Pat. No. 4,546,096, 1988; U.S. Pat. No. 4,720,494, 1988). Such materials are claimed to reduce perspiration at source, that is to say at the secretory coil of the sweat glands.
The present invention is concerned with materials that can be termed xe2x80x9ccalcium channel blocking agentsxe2x80x9d (xe2x80x9cCCBAxe2x80x9ds, vide infra). One such material, methoxy-verapamil, has been shown, in vitro, to reduce sweat production from isolated cannulated monkey palm eccrine sweat glands (Sato and Sato, Am. J. Physiol., 1981, 241, C113-C120). Other CCBAs have been demonstrated to be physiologically active in various types of tissue; for example, tetrandrine, an alkaloid isolated from the root of Stephania tetrandra, has been shown to be capable of inhibiting calcium influx into the aortic smooth muscle cells of rats (Wu et al, Eur. J. Pharmacol., 1997, 327, 233-238) and Panax ginseng root extract has been shown to inhibit calcium channels in rat sensory neurons (Nah and McCleskey, J. Ethnopharmacol., 1994, 42, 45-51). In another application, all CCBAs, together with substances that reduce the binding of calcium to intracellular proteins, are claimed to relax and/or loosen cutaneous and/or subcutaneous tissue (EP 1,053,745, 2000).
Plant extracts that may comprise CCBAs are described as components in various cosmetic or pharmaceutical preparations. For example, Chinese patent application CN 1117868A claims a Chinese medicine with ginseng that cures night sweating; CN 1135346A claims medicinal compositions with ginseng that induce sweating and JP 62221619A claims that Panax ginseng promotes perspiration; CN 1107061A claims that Stephania tetrandra deodorises and stops sweating and Russian patent RU 2045263 claims body antiperspirants comprising ginseng extract.
According to a first aspect of the present invention, there is provided use of a calcium channel blocking agent (CCBA) in a cosmetic product, or in the preparation of a cosmetic product, intended for the reduction of perspiration and/or body malodour, characterised in that said CCBA is of molecular weight less than 750.
According to a second aspect of the present invention, there is provided a cosmetic method of reducing underarm perspiration, said method comprising topical application to the underarm area of a cosmetic product comprising a CCBA of molecular weight less than 750.
According to a third aspect of the present invention, there is provided a cosmetic product comprising a CCBA of molecular weight less than 750 and an anti-microbial agent, characterised in that said anti-microbial agent has an MIC of 1 mg.mlxe2x88x921 or less.
According to a fourth aspect of the present invention, there is provided a cosmetic product comprising a CCBA, characterised in that said product comprises an additional agent that enhances the perceived antiperspirancy benefit.
According to a fifth aspect of the present invention, there is provided a cosmetic method of obtaining an antiperspirancy benefit, comprising the topical application of a cosmetic product according to the aforementioned fourth aspect of the invention.
The method of reducing sweat production described herein represents a major step forward in the cosmetic treatment of sweating and body malodour. We have discovered that it is possible to reduce, or even prevent, sweat production from human sweat glands by topical administration of cosmetic products according to the invention. The invention is of greatest benefit when used in the treatment of the more sweaty areas of the body, in particular the underarm areas and, in some embodiments, the feet.
It is believed that the CCBA serves to reduce sweat production at source, that it to say, the CCBA reduces secretion of primary sweat from the secretory coil cells of the sweat glands. Sweat production is triggered by either cholinergic or adrenergic stimulation of the cells of the secretory coil. In response to this stimulation, there is an increase in the intracellular calcium concentration, which in turn initiates a cascade of events resulting in the production of primary sweat. The required elevated level of calcium within the cells of the secretory coil is sustained by an influx of calcium into the cells via calcium channels in the basolateral and/or apical cell membrane. By blocking these calcium channels production of sweat can be reduced or even prevented.
The eccrine sweat glands are the preferred target for the prevention of sweating, these being involved in the body""s thermoregulatory responses as well as emotional responses. Prevention of sweat production from the apocrine secretory coil cells offers benefits when sweat stimulation is brought about by pain or an emotive trigger, for example nervousness. For optimum protection from sweat production, whatever the cause, it is preferred that the CCBA acts upon both the eccrine and apocrine secretory coil cells.
This new method of sweat reduction can be used to augment or replace methods involving the use of pore-blocking antiperpirant actives. When used to augment the use of such actives, the cosmetic product used comprises a CCBA and a pore-blocking antiperpirant active. Such pore-blocking antiperspirant actives include astringent metal salts of the type described hereinafter. Typically, the CCBA employed in such products has a molecular weight less than 750.
The present invention involves topical application of the CCBA, which must penetrate through the skin and reach the secretory coil cells of the sweat glands in sufficient concentration to be effective. Transport of the CCBA from the skin surface to the secretory coil cells may be enhanced in a number of ways.
In one embodiment of the present invention, the transport of the CCBA is enhanced by iontophoresis. Iontophoresis is a method of aiding the passage of polar molecules into the skin by applying a small electrical current. A low voltage (usually from a battery) is applied to a solution of the CCBA in contact with the subject""s skin. The voltage serves to drive charged ions through the skin, thereby delivering the CCBA, in charged form.
In a preferred embodiment of the invention, the transport of the CCBA is enhanced by the presence of a skin penetration enhancer (SPE) that helps the CCBA to penetrate the skin.
In cosmetic products comprising a CCBA and a pore-blocking antiperspirant active and/or an SPE, it is not essential that these components are part of the same composition. The antiperspirancy benefit derived from use of the invention may be gained by independent application of the components. Such application may be concurrent or consecutive, provided that the body experiences the presence of the components at the same time. When the components are applied from independent compositions, it is preferred that the product also comprises a means for, and/or instruction for, each of the compositions to be applied to the body.
For convenience, it is preferred that the components are present in the same composition.
Other components are also desirably present, particular examples including anti-microbial agents, and/or a carrier material, and/or a transition metal chelator (vide infra).
Calcium Channel Blocking Agent (CCBA)
The CCBAs of the present invention may block any of the calcium channels that exist in the basolateral and/or apical cell membrane. Such calcium channels may be classified as being either voltage-dependent or voltage-independent. The former group is operated by changes in membrane potential and includes six types of channel (L, N, T, P Q, and R). Detailed information on voltage dependent channels and the agents that block them is given by Glossmann and Streissnig in Rev. Phys. Biochem. Pharmacol., 1990, 114, 1-105. Voltage-independent channels are either operated by membrane receptors or by the depletion of calcium stores in the cytoplasm (store operated channels [SOCs]). Detailed information on voltage independent channels and the agents that block them is given by Clementi and Meldolesi in Cell Calcium, 1996, 19(4), 269-279. Of the SOCs, the transient receptor potential (TRP) family is particularly well characterised (see Harteneck, Plant, and Schultz, Trends in Neurosciences, 2000, 23(4), 159-166).
Examples of CCBAs include those mentioned in the three publications referred to in the above paragraph and those mentioned in EP 1,053,745, 2000. Particular examples include phenylalkylamines, such as D600 (methoxy-verapamil), verapamil, desmethoxy-verapamil, anipamil, gallopamil, devapamil, falipamil, and tiapamil; dihydropyridines, such as nifedipine, amlodipine, dazodipine, felodipine, isradipine, lanicarpidine, nimodipine, nisoldipine, nitrendipine, and ryosidine; benzothiazepines, such as diltiazem; and diphenylpiperazines, such as cinnarizine and flunarizine; toxins, such as apamin; 2-aminoethoxydiphenyl berate; SDZ-202 791 R(xe2x88x92), from Sandoz; and SKandF 96365, Smith, Kline, and French.
Our studies have shown, for the first time, that CCBAs have the ability to reduce calcium influx into the secretory coil cells of human eccrine or apocrine glands. The following procedure, or one essentially the same, may be used to test a material for this ability.
The procedure is performed on an isolated human sweat gland. Collapsed segments of secretory coil are held between two glass pipettes in the perfusion bath of an inverted microscope and bathed at 37xc2x0 C. in a solution buffered to pH 7.4. Intracellular calcium may be measured by any convenient means; in our tests the fluorescent dye FURA-2 AM was used (full details are given in Examples 1 and 2). The calcium influx induced by the administration of methylcholine at 1 xcexcmol.dmxe2x88x923 is compared before and after the introduction of the test material into the buffer solution. Test materials are classed as CCBAs if they are able to reduce the methylcholine-induced calcium influx into the cells, preferably by at least 20%, more preferably by at least 50%. The concentration of test material used should be between 1 and 100 xcexcmol.dmxe2x88x923 for pure compounds, 25 xcexcmol.dmxe2x88x923 being a typical concentration of use. When the test material used is not a pure compound, for example when it is a plant extract, allowance must be made for the non-active components in the extract when choosing the test dosage.
Blocking of voltage dependent calcium channels, in particular L-type calcium channels, is believed to be particularly valuable in reducing sweat production from the secretory coil of human sweat glands. Hence, voltage dependent CCBAs, in particular L-type CCBAS, are preferred in all aspects of the present invention. Especially preferred L-type CCBAs are verapamil (including salts thereof) and methoxy-verapamil (including salts thereof). Other preferred CCBAs are cosmetic ingredients, especially those included in the database of the Cosmetic Toiletries and Fragrance Association. Particularly preferred agents are present in plant extracts, for example those derived from Stephania sp., in particular Stephania tetrandra; Salvia sp., in particular Red Sage (Salvia miltiorrhiza); Magnolia sp., in particular Magnolia offinalis and Magnolia fargesii; and Astragalus sp., in particular Milk vetch (Astragalus membranaceus). The active components in these extracts are all natural ingredients and such ingredients are particularly preferred. An especially preferred agent is Safrole, which is present in many natural extracts, including those obtained from Sassafras albidum, Myristica frangrans, and Ocimum basilicium. Other especially preferred agents present in natural extracts are tanshinone (ex Red Sage), magnolol (ex Magnolia officinalis), and denudin B, (ex Magnolia fargesii).
The transport of the CCBA from the skin surface to the secretory coil cells of the sweat glands is aided by the CCBA being of relatively low molecular weight. In certain aspects of the invention, it is essential that the CCBA has a molecular weight of less than 750. In all aspects of the invention, it is preferred that the CCBA has a molecular weight of less than 650, in particular less than 600. In general, the molecular weight will be above 100 and usually above 150. Skin penetration is also aided by the CCBA having a moderate to high hydrophobicity, that is to say having a c.logP of between xe2x88x921 and 5, where c.logP is the logarithm to the base 10 of the calculated octanol/water partition coefficient. By way of example, verapamil has a c.logP of 4.47 and nifedipine has a c.logP of 3.42.
It is highly preferred that the CCBA employed is of low irritancy. Such materials, when applied as a 0.1% solution by weight in a suitable solvent, have an erythema grading of less than 5, in particular less than 4, and especially less than 3, as assessed by the method described by Basketter et al in Contact Dermatitis, 1997, 37, 218-220. For this reason and/or others it is preferred that the CCBA does not possess any strongly acidic functional groups (eg. sulphonic acid groups) or any phenolic functional groups.
Mixtures of CCBAs may be employed and references to preferred amounts of CCBA refer to the total amount of all CCBAs present. This statement also applies, mutatis mutandis, to the other components that may be present.
It is preferred that the CCBA be used at a concentration sufficient to deliver at least 1 xcexcmol.dmxe2x88x923 to the environs of the secretory coil cells. More preferably the level delivered is from 1 to 1000 xcexcmol.dmxe2x88x923, especially from 10 to 1000 xcexcmol.dmxe2x88x923, and most especially from 10 to 100 xcexcmol.dmxe2x88x923. The level required in a cosmetic composition for topical administration is approximately 10 to 5000 times these concentrations, due to dilution on permeation through the skin. Hence, embodiments of the invention preferably involve cosmetic compositions comprising approximately from 0.1 to 250 mmol.kgxe2x88x921 of CCBA. With suitable delivery enhancement present, for example in compositions also comprising an SPE, the amount of CCBA required may be somewhat less, preferred levels being 0.1 to 100 mmol.kgxe2x88x921, more preferably 0.1 to 50 mmol.kgxe2x88x921.
Additional Components
A pore-blocking antiperspirant active is a desirable component in certain embodiments of the invention. Such materials include astringent metal salts conventionally used as antiperspirant salts. Examples include aluminium, zirconium and mixed aluminium/ zirconium salts, including both inorganic salts, salts with organic anions and complexes. Preferred astringent salts include aluminium, zirconium and aluminium/zirconium halides and halohydrate salts, such as chlorohydrates. When included, preferred levels of incorporation are from 0.5% to 60%, particularly from 5% to 30% or 40% and especially from 5% or 10% to 30% or 35% by weight of the composition. Especially preferred aluminium halohydrate salts, known as activated aluminium chlorohydrates, are described in EP 6,739 (Unilever PLC and NV). Zirconium aluminium chlorohydrate actives are also preferred materials, as are the so-called ZAG (zirconium-aluminium-glycine) complexes, for example those disclosed in U.S. Pat. No. 3,792,068 (Procter and Gamble Co.).
An additional component that can sometimes augment the ability of the compositions of the invention to reduce body odour is an anti-microbial agent. Most of the classes of agents commonly used in the art can be incorporated into compositions of the invention. Levels of incorporation are preferably from 0.01% to 3%, more preferably from 0.03% to 0.5% by weight of the non-volatile components of the composition.
In the context of this invention, a non-volatile component is one having a boiling point of at least 50xc2x0 C., at atmospheric pressure.
Preferred compositions of the invention comprise an anti-microbial agent having a minimum inhibitory concentration (MIC) of 1 mg.mlxe2x88x921 or less, particularly 200 xcexcg.mlxe2x88x921 or less, and especially 100 xcexcg.mlxe2x88x921 or less. The MIC of an anti-microbial agent is the minimum concentration of the agent required to significantly inhibit microbial growth. Inhibition is considered significant if an 80% or greater reduction in the growth of an inoculum of a relevant micro-organism is observed, relative to a control medium without an anti-microbial agent, over a period of 16 to 24 hours at 37xc2x0 C. A relevant micro-organism that may be used is Staphylococcus epidermidis. Details of suitable methods for determining MICs can be found in xe2x80x9cAntimicrobial Agents and Susceptibility Testingxe2x80x9d C. Thornsberry, (in xe2x80x9cManual of Clinical Microbiologyxe2x80x9d, 5th Edition, Ed. A. Balows et al, American Society for Microbiology, Washington D.C., 1991). A particularly suitable method is the Macrobroth Dilution Method, as described in Chapter 110 of above publication (pp. 1101-1111) by D. F. Sahm and J. A. Washington II. MICs of anti-microbials suitable for inclusion in the compositions of the invention are triclosan: 0.01-10 xcexcg.mlxe2x88x921 (J. Regos et al., Dermatologica (1979), 158: 72-79) and farnesol: ca. 25 xcexcg.mlxe2x88x921 (K. Sawano, T. Sato, and R. Hattori, Proceedings of the 17th IFSCC International Conference, Yokahama (1992) p.210-232). By contrast ethanol and similar alkanols have MICs of greater than 1 mg.mlxe2x88x921. Preferred anti-microbials are bactericides, in particular organic bactericides, for example quaternary ammonium compounds, like cetyltrimethylammonium salts; chlorhexidine and salts thereof; and diglycerol monocaprate, diglycerol monolaurate, glycerol monolaurate, and similar materials, as described in xe2x80x9cDeodorant Ingredientsxe2x80x9d, S. A. Makin and M. R. Lowry, in xe2x80x9cAntiperspirants and Deodorantsxe2x80x9d, Ed. K. Laden (1999, Marcel Dekker, New York). More preferred anti-microbials are bactericides having an MBC (minimum bactericidal concentration) of 1 mg.mlxe2x88x921 or less, particularly 200 xcexcg.mlxe2x88x921 or less, and especially 100 xcexcg.mlxe2x88x921 or less. Examples of preferred anti-microbials are polyhexamethylene biguanide salts (also known as polyaminopropyl biguanide salts), an example being Cosmocil CQ available from Zeneca PLC, preferably used at up to 1% and more preferably at 0.03% to 0.3% by weight; 2xe2x80x2,4,4xe2x80x2-trichloro, 2-hydroxy-diphenyl ether (triclosan), preferably used at up to 1% by weight and more preferably at 0.05-0.3% by weight of the non-volatile components of the composition; and 3,7,11-trimethyldodeca-2,6,10-trienol(farnesol), preferably used at up to 1% and more preferably at up to 0.5% by weight of the non-volatile components of the composition.
Inorganic anti-microbial agents may also be employed, for example zinc phenol sulphonate, preferably at up to 3% by weight of the non-volatile components of the composition.
Skin penetration enhancers (SPEs) are desirable components in certain embodiments of the invention. Such materials are capable of aiding the transport of the CCBA from the skin surface to the eccrine and/or apocrine secretory coil cells. It is highly preferably that such materials are co-soluble with the CCBA employed. Generally, the SPE can be a solvent for the CCBA, the CCBA preferably having a solubility in the SPE of greater than 50 mmol.dmxe2x88x923, more preferably greater than 100 mmol.dm. Suitable SPEs include oleic acid, azone, urea, transcutol, and ethanol. Preferred SPEs are short chain polyhydric alcohols, in particular C2 to C5 alcohols with 2-5 hydroxy groups, especially glycerol and propylene glycol. The SPE may be present at a level of 0.5-90% by weight of the composition in which it is employed, excluding any propellant that may be present. Preferably this level is 1-50% by weight, more preferably from 2-30%, and most preferably from 3-12%.
The ratio of SPE to CCBA in the compositions of the invention is also important. It is preferred that the weight ratio of SPE:CCBA is from 1:1 to 100:1, especially from 2:1 to 50:1, and most especially from 5:1 to 10:1.
A carrier material for the CCBA, is a preferred additional component in the compositions used in the present invention. The carrier material may be hydrophobic or hydrophilic, solid or liquid. Preferred carrier materials are liquids at ambient temperature and atmospheric pressure. Hydrophobic liquids suitable for use include liquid silicones, that is to say, liquid polyorganosiloxanes. Such materials may be cyclic or linear, examples include Dow Corning silicone fluids 344, 345, 244, 245, 246, 556, and the 200 series; Union Carbide Corporation Silicones 7207 and 7158; and General Electric silicone SF1202. Alternatively, non-silicone hydrophobic liquids may be used. Such materials include mineral oils, hydrogenated polyisobutene, polydecene, paraffins, isoparaffins of at least 10 carbon atoms, and aliphatic or aromatic ester oils (eg. isopropyl myristate, lauryl myristate, isopropyl palmitate, diisopropyl sebecate, diisopropyl adipate, or C8 to C18 alkyl benzoates).
Hydrophilic liquid carrier materials, for example water, may also be employed.
Particularly preferred liquid carrier materials comprise organic solvents. Preferred organic solvents have a melting point of less than 10xc2x0 C., preferably less than 5xc2x0 C.; this can benefit both low temperature storage stability and ease of manufacture. A class of preferred organic solvents are aliphatic alcohols (monohydric or polyhydric, preferably having 2 to 8 carbon atoms) and polyglycol ethers, preferably oligoglycol ethers having only 2 to 5 repeat units. Examples include dipropylene glycol, glycerol propylene glycol, butylene glycol, ethanol, propanol, isopropanol, and industrial methylated spirits. The most preferred organic solvents are aliphatic alcohols, in particular those having 2 to 3 carbon atoms, especially ethanol and isopropanol. Especially preferred liquid carrier materials are also able to function as SPEs (vide supra), for example ethanol.
Mixtures of carrier materials may also be used. The total amount of carrier material employed is preferably from 30% to 99%, more preferably 60% to 98%, expressed as a weight percentage of the total weight of the composition of which it is a part, excluding any volatile propellant that may be present.
In certain embodiments of the invention, a transition metal chelator is desirably present. Such materials may enhance deodorancy benefits and/or the perceived antiperspirancy benefit; the latter benefit also being common to pore-blocking antiperspirant actives. Examples of transition metal chelators are described in U.S. Pat. No. 4,356,190 (Personal Products Co.) and our co-pending application PCT/EP01/00118 (Unilever). Often such materials are acids, although they may be used in their acid form or as salts, for the purposes of this invention. Preferred transition metal chelators have an iron (III) binding constant of greater than 1026; examples including diethylenetriaminepentaacetic acid (DTPA), trans-1,2-diaminocyclohexane-N,N,Nxe2x80x2,Nxe2x80x2-tetraacetic acid (CDTA), and triethylenetetraaminehexaacetic acid (TTHA). Particularly preferred is DTPA. Such agents may be used in concentrations ranging from 0.001 to 10% by weight of the composition, preferably from 0.01 to 3%, excluding any volatile propellant that may also be present in the composition.
Structurants and emulsifiers are further additional components that are highly desirable in certain product forms. Structurants, when employed, are preferably present at from 1% to 30% by weight of the composition of which they are a part, whilst emulsifiers are preferably present at from 0.1% to 10% by weight. In roll-ons, such materials help control the rate at which product is dispensed by the roll ball. In stick compositions, such materials can form gels or solids from solutions or suspensions of the chelator salt in a carrier fluid. Suitable structurants for use in such compositions of the invention include cellulosic thickeners such as hydroxy propyl cellulose and hydroxy ethyl cellulose, and dibenzylidene sorbitol. Emulsion pump sprays, roll-ons, creams, and gel compositions according to the invention can be formed using a range of oils, waxes, and emulsifiers. Suitable emulsifiers include steareth-2, steareth-20, steareth-21, ceteareth-20, glyceryl stearate, cetyl alcohol, cetearyl alcohol, PEG-20 stearate, and dimethicone copolyol. Suspension aerosols, roll-ons, sticks, and creams require structurants to slow sedimentation (in fluid compositions) and to give the desired product consistency to non-fluid compositions. Suitable structurants include sodium stearate, stearyl alcohol, cetyl alcohol, hydrogenated castor oil, synthetic waxes, paraffin waxes, hydroxystearic acid, dibutyl lauroyl glutamide, alkyl silicone waxes, quaternium-18 bentonite, quaternium-18 hectorite, silica, and propylene carbonate. Some of the above materials also function as suspending agents in certain compositions.
Further emulsifiers desirable in certain compositions of the invention are perfume solubilisers and wash-off agents. Examples of the former include PEG-hydrogenated castor oil, available from BASF in the Cremaphor RH and CO ranges, preferably present at up to 1.5% by weight, more preferably 0.3 to 0.7% by weight. Examples of the latter include poly(oxyethylene) ethers.
Certain sensory modifiers are further desirable components. Such materials are preferably used at a level of up to 20% by weight of the composition of which they are a part. Emollients, humectants, volatile oils, non-volatile oils, and particulate solids which impart lubricity are all suitable classes of sensory modifiers. Examples of such materials include cyclomethicone, dimethicone, dimethiconol, isopropyl myristate, isopropyl palmitate, talc, finely-divided silica (eg. Aerosil 200), polyethylene (eg. Acumist B18), polysaccharides, corn starch, C12-C15 alcohol benzoate, PPG-3 myristyl ether, octyl dodecanol, C7-C14 isoparaffins, di-isopropyl adipate, isosorbide laurate, PPG-14 butyl ether, glycerol, hydrogenated polyisobutene, polydecene, titanium dioxide, phenyl trimethicone, dioctyl adipate, and hexamethyl disiloxane.
Fragrance is also a desirable additional component in the compositions of the invention. Suitable materials include conventional perfumes, such as perfume oils and also include so-called deo-perfumes, as described in EP 545,556 and other publications. Levels of incorporation are preferably up to 4% by weight, particularly from 0.1% to 2% by weight, and especially from 0.7% to 1.7% by weight of the composition of which they are a part.
It should be noted that certain components of compositions perform more than one function. Such components are particularly preferred additional ingredients, their use often saving both money and formulation space. Examples of such components include ethanol, isopropyl myristate, and the many components that can act as both structurants and sensory modifiers, for example silica.
Further additional components that may also be included are colourants and preservatives, for example C1-C3 alkyl parabens.
Product Forms
The compositions employed may take any form. Examples include wax-based sticks, soap-based sticks, compressed powder sticks, roll-on suspensions or solutions, emulsions, gels, creams, squeeze sprays, pump sprays, and aerosols. Each product form contains its own selection of additional components, some essential and some optional. The types of components typical for each of the above product forms may be incorporated in the corresponding compositions of the invention. Roll-on compositions particularly suited to the invention are simple solutions in organic solvents, although water can be tolerated in such compositions. In addition, emulsion compositions, for example oil-in-water and water-in-oil emulsions, are not excluded. Stick compositions of the invention are preferably based on either a monohydric or polyhydric alcohol organic solvent base. They are often gelled with sodium stearate, although dibenzylidene sorbitol (DBS) may alternatively be used, preferably in combination with hydroxypropyl cellulose.
Aerosol compositions of the invention may comprise from 30 to 99 parts by weight, and particularly 30 to 60 parts by weight of propellant and the remainder (respectively 70 to 1 and particularly 70 to 40 parts by weight) of the antiperspirant/deodorant base composition.
The propellant in the aerosol compositions may be selected from liquified hydrocarbons or halogenated hydrocarbon gases (particularly fluorinated hydrocarbons such as 1,1-difluoroethane and/or 1-trifluoro-2-fluoroethane) that have a boiling point of below 10xc2x0 C. and especially those with a boiling point below 0xc2x0 C. It is especially preferred to employ liquified hydrocarbon gases, and especially C3 to C6 hydrocarbons, including propane, isopropane, butane, isobutane, pentane and isopentane and mixtures of two or more thereof. Preferred propellants are isobutane, isobutane/isopropane, isobutane/propane and mixtures of isopropane, isobutane and butane. Other propellants that can be contemplated include alkyl ethers, such as dimethyl ether or compressed non-reactive gasses such air, nitrogen or carbon dioxide.
Methods of Manufacture
The compositions of the invention may be manufactured by any convenient method. In a particular embodiment of present invention, a suitable composition is manufactured by the addition of a CCBA and an SPE for said CCBA to an appropriate carrier material, the components being agitated to give a homogeneous mixture. Said mixture may be used in any of the product forms described above, with the incorporation of the appropriate additional components.

Antiperspirant and deodorant products and methods for their use

Unilever Home and Personal Care USA, division of Conopco, Inc.