A method for preparing novel dibenzoylresorcinol-based compounds is disclosed, wherein the dibenzoylresorcinol is bonded to a substituted or unsubstituted aryl group which does not include a pendent hydroxyl group. The groups attached to the dibenzoylresorcinol may contain a wide variety of functional sites which permit further reaction, e.g., copolymerization. The described compounds are very useful as UV light absorbers and may be used to form improved coating compositions which usually include a transparent, polymeric matrix material. The coating compositions may be applied to various substrates, e.g., thermoplastics, to afford a selection of enhanced properties, such as UV light resistance and abrasion resistance.

This invention relates generally to chemical technology, and more particularly, to chemical compounds and compositions based on dibenzoylresorcinol.
Thermoplastic resins often possess an attractive set of mechanical and physical properties, such as high heat resistance, impact resistance, dimensional stability, high ductility, and optical clarity. Polycarbonates are a good illustration of materials exhibiting many of these attributes. While these properties serve to encourage the use of thermoplastics in many commercial applications, other, less favorable properties often need to be rectified or somehow addressed. As an example, thermoplastics often exhibit low resistance to abrasion and chemical solvents. Moreover, thermoplastic materials are usually susceptible to photodegradation by ultraviolet (UV) light. This type of degradation typically leads to erosion and yellowing of the polymer surface. The discoloration represents a large problem in using products like those based on polycarbonate, which are especially noted for their transparency.
Efforts to alleviate these problems have been undertaken in the past. As an example, coating compositions that include ultraviolet light absorbers have been applied onto thermoplastic substrates and then cured. For the case of polycarbonates, the coating material is often based on a silicone hardcoat matrix, which when cured, provides a good abrasion barrier. The UV absorbing agents incorporated into the hardcoat matrix are often based on benzophenone or benzotriazoles. As described in U.S. Pat. No. 5,391,795 (J. Pickett), various patents disclose this general type of strategy for protecting thermoplastics. For example, U.S. Pat. No. 4,373,061 describes the use of a silicone hardcoat composition comprising benzophenones as the UV absorbing agents, while U.S. Pat. No. 4,278,804 discloses a matrix composition based in part on silanol-reactive alkoxysilyl- or alkanoyloxysilylalkyl ether adducts of aromatic UV absorbing agents. U.S. Pat. No. 5,391,795 itself describes the use of silylated derivatives of 4,6-dibenzoylresorcinols as UV absorbers for hardcoat compositions.
The UV absorbing agents themselves sometimes decompose to some degree, upon exposure to UV light. The decomposition can in turn lead to microcracks in the hardcoat, exposing the underlying polymer surface to the degrading effects of UV light, abrasion, and the like. Thus, the purpose of the hardcoat in protecting the thermoplastic substrate is defeated to some extent.
It""s quite apparent that there is a continuing need for new compounds which are effective in providing UV protection for thermoplastics. The compounds should themselves exhibit a high degree of UV stability, i.e., photostability, while still being effective in protecting the substrate. Moreover, the new compounds should be amenable to various forms of use, e.g., they should be capable of being incorporated into a hardcoat composition which is coated onto the surface being protected. The new UV absorbing compounds should also be physically and chemically compatible with the substrate material, and with any type of hardcoat composition being employed. They should not interfere with any of the other properties possessed by the thermoplastic substrate, such as transparency. Furthermore, the new compounds should be relatively easy to manufacture, and their use should not involve an excessive increase in the cost of the thermoplastic product.
The present invention satisfies substantially all of the needs discussed above. One embodiment is directed to a dibenzoylresorcinol-based compound having the general formula (I):
wherein Ar1 and Ar2 are independently substituted or unsubstituted monocyclic or polycyclic aryl groups; and R is hydrogen, an aryl group, or a linear or branched all chain having less than about 10 carbon atoms. The group designated as xe2x80x9cAxe2x80x9d can be a radical derived from a very wide variety of alcohols or carboxylic acids. In that instance, the compound can be made in a process which usually involves two steps, in which a methylene carboxylate intermediate of 4,6-dibenzoylresorcinol is first prepared, and then reacted with an alcohol or a carboxylic acid to form the desired product. The product can include functional sites which permit further reaction with other materials.
xe2x80x9cAxe2x80x9d can alternatively be a substituted or unsubstituted aryl group which does not include a pendent hydroxyl group. Various types of aryl groups may be present, such as phenyl, alkyl-substituted phenyl groups, halogen-substituted phenyl groups, and alkoxy-substituted phenyl groups. The desired compounds of this type are prepared in a reaction which usually includes one primary step, involving the reaction of 4,6-dibenzoylresorcinol with a benzyl halide compound, an aqueous base, and a compatible phase transfer catalyst. Again, the product can include functional sites suitable for further reaction.
Another embodiment of this invention is directed to improved coating compositions for protecting thermoplastic substrates. Much of the improvement is a result of the enhanced photostability of the dibenzoylresorcinol compounds briefly described above. The coating compositions include those compounds, incorporated into a matrix composition which may be formed from a variety of materials, such as acrylics.
The protection afforded to the substrates usually relates to ultraviolet light resistance, and can also include other enhancements, such as abrasion resistance. Thus, another embodiment of this invention is directed to improved articles which comprise a substrate (usually thermoplastic), coated with a protective composition which comprises the dibenzoylresorcinol-based compounds described above, incorporated into a matrix composition.
Numerous other details regarding these inventive embodiments are provided below.
As briefly mentioned previously, the compounds of the present invention have the formula
wherein Ar1 and Ar2 are independently substituted or unsubstituted monocyclic or polycyclic aryl groups; and R is hydrogen, an aryl group, or a linear or branched alkyl chain having less than about 10 carbon atoms. In preferred embodiments, Ar1 and Ar2 are phenyl or substituted phenyl groups. R is preferably hydrogen or phenyl.
In one primary embodiment of this invention, A is a radical deriving from an alcohol or a carboxylic acid, i.e., the group which results when an alcohol or a carboxylic acid is reacted with the dibenzoylresorcinol compound. The examples which follow provide an illustration of some of the possible alcohols and carboxylic acids which could be used according to this invention. However, it appears that almost any alcohol or carboxylic acid would be suitable.
For example, the alcohol could be a linear or branched aliphatic group, usually containing from 1 to about 20 carbon atoms. As a non-limiting illustration, the aliphatic portion of the alcohol could be methyl ethyl, propyl, isopropyl butyl, isobutyl, sec-butyl, tert-butyl, amyl, isoamyl, hexyl, octyl, decyl, dodecyl, and the like. Included within the definition of xe2x80x9calcoholxe2x80x9d herein are the many derivatives, e.g., alcohols containing substituents such as halogens, or those containing carbocyclic or heterocyclic rings attached to the main aliphatic chain, or to a branch which itself is attached to the main chain.
The alcohol itself could alternatively be carbocyclic or heterocyclic, and can contain at least one aliphatic branch or aromatic ring which comprises from 1 to about 20 carbon atoms. Examples of carbocyclic alcohols are cyclohexanol, cyclopentanol, cyclooctanol, cyclodecanol, cyclododecanol, exo-norborneol, and derivatives of any of the foregoing which contain at least one aliphatic branch or aromatic carbon ring. These types of compounds are available commercially, or can usually be made by those skilled in the art, without undue effort.
Heterocyclic alcohols (containing one or more ring-structures) are also readily available. Most often, these alcohols include at least one nitrogen atom, sulfur atom, or oxygen atom in at least one of the cyclic chains. An example of a heterocyclic alcohol is piperidinol. Substituted piperidinols are also suitable, e.g., alkylated derivatives. One piperidinol-based compound of particular interest is 2,2,6,6-tetramethyl piperidinol, which functions as a hindered amine light stabilizer (xe2x80x9cHALSxe2x80x9d) for plastics. Thus, the chemical attachment of a HALS group to a dibenzoylresorcinol compound is within the scope of the present invention.
The alcohol from which group A is derived could also be a diol, a derivative of a diol, a polymerized diol, or a derivative of a polymerized diol. All of these types of materials are also well-known in the art. As but one example, the diol could be alkane-based, e.g., one containing from about 2 to about 20 carbon atoms, such as propanediol, butanediol, pentanediol, and hexanediol. (This invention embraces all known versions of such compounds. For example, xe2x80x9cpropanediolxe2x80x9d is meant to include 1,2-propane diol or 1,3-propane diol, alternatively known as 1,2-propylene glycol and trimethylene glycol, respectively.). Various other glycols could be used, such as ethylene glycol or neopentyl glycol. Moreover, exemplary polymerized diols include polyethylene glycol and polypropylene glycol.
Those of ordinary skill in the polymer arts are familiar with derivatives of diols or polymerized diols which could be suitable for the present invention, based on the teachings herein. For example, one of the hydroxyl sites on the diols could be esterified by dehydration or catalytic agents to form the corresponding ester. Selection of a particular derivative will be determined in large part by the desired requirements for the compound being prepared, as well as the requirements for the end use-situation in which the compound is being utilized, e.g., as a coating composition for a particular thermoplastic.
The alcohol could alternatively be a polyol, i.e., a compound containing three or more hydroxyl groups. Examples of suitable polyols are glycerol, pentaerythritol, or dipentaertitol. Moreover, in some embodiments, the polyol could be partially esterified, e.g., an ester could be formed at at least one of the hydroxyl sites, while a remaining, free hydroxyl group forms an ether linkage with the dibenzoylresorcinol moiety. The ester or another free hydroxyl group could in turn undergo further reaction for additional functionalization, e.g., reaction with vinyl chloride or with an acrylic or methacrylic group for the purpose of adding vinyl-type functionality.
In general, polyfunctional alcohols represent yet another class from which group A could be derived. The polyols could fall into this class. As an illustration, a material like the above-mentioned dipentaerythritol contains six primary hydroxyl groups which are functional sites, e.g., which are each esterifiable. Other polyfunctional alcohols could include at least one carboxylic acid group in addition to a hydroxyl group. Those skilled in organic synthesis are familiar with techniques for selectively reacting individual functional sites to obtain a particular organic product.
As mentioned previously, there is no restriction on the type of carboxylic acid which could be used to form group A of formula I. Usually, the acid belongs to one of the following classes: polycarboxylic acids, branched derivatives of mono- or polycarboxylic acids; cyclic derivatives of mono- or polycarboxylic acids, and functional derivatives of mono- or polycarboxylic acids. Some related compounds are described in the referenced, U.S. Pat. No. 5,763,674 of James E. Pickett et al.
Non-limiting examples of suitable polycarboxylic acids from which group A could be derived are succinic acid, glutaric acid, adipic acid, suberic acid, palmitic acid, azelaic acid, malonic acid, oxalic acid, maleic acid, fumaric acid, and phthalic acid. Many ester derivatives of these acids could also be employed. In other words, one or more of the carboxylic groups could be esterified, while a remaining, free carboxylic group forms an ester linkage with the dibenzoylresorcinol moiety.
Moreover, the carboxylic acid could contain various other types of chemical groups. For example, the acid could include at least one polyether linkage within a carbon atom chain. Furthermore, the polyether linkage could itself be readily substituted with various pendent chains, cyclic groups, or heterocyclic groups. Depending on various factors, such as the desired solubility for the final product-compound, one or more of the pendent chains could be acid-functionalized. Hydroxyl groups could also be incorporated into the polymer chains.
Other functional derivatives of the mono- and polycarboxylic acids could be prepared by the inclusion of at least one vinyl group or allyl group. As mentioned earlier, techniques for this type of functionalization are well-known in the art. In some preferred embodiments, the derivative is formed by the incorporation of at least one acrylic group or methacrylic group, as shown in the examples which follow. In general, the use of the vinyl group or allyl group permits a very effective reaction of the resulting compound with a copolymerizable monomer. Examples of the suitable copolymerizable monomers are acrylates, methacrylates, styrenes, and substituted derivatives of any of the foregoing materials. These types of reactions would result in the formation of very useful copolymers. For example, the copolymerizable monomers could constitute a portion of a matrix composition (as discussed below) for a UV-absorbing coating. Thus, copolymer linkages would be established between the matrix and the dibenzoylresorcinol compound.
Another aspect of the present invention is directed to methods for preparing compounds of formula 1. When A is a radical deriving from an alcohol or a carboxylic acid, the compound is usually prepared by a process which comprises:
(a) reacting a mixture of a 4,6-dibenzoylresorcinol and a para-aldehyde with a secondary amine catalyst and a carboxylic acid solvent under reactive conditions to form a methylene carboxylate intermediate in which the methylene bridge forms a linkage between the dibenzoylresorcinol residue and a carboxylate moiety; and then
(b) reacting the methylene carboxylate compound formed in step (a) with an alcohol or a carboxylic acid in a reactive medium to form the derivative.
Suitable processes for carrying out step (a), i.e., formation of the intermediate, are described in U.S. Pat. No. 5,763,674 mentioned above. A similar process (which may be thought of as a variation of the Mannich reaction) is also described in JP 79/19,950 (CA 91: 20116z). Thus, the present teachings do not need to be exhaustive in regard to this step. Briefly, examples of para-aldehydes suitable for the first step of the reaction are paraformaldehyde and paracetaldehyde (paraldehyde), with paraformaldehyde usually being the material of choice. Any secondary amine appears to be suitable for catalysis, such as diethylamine, dipropylamine, dibutylamine, dihexylamine, and dioctylamine. Various carboxylic acid solvents could be used, with acetic acid usually being selected, based in part on cost considerations.
The JP 79/19950 reference mentioned above calls for the use of relatively high levels of amine catalystxe2x80x94about 40 mole %. However, it has recently been discovered that lower levels of catalyst reduce the amount of undesirable diethylamine-substituted derivatives. Thus, in the present invention, the amount of secondary amine catalyst employed in step (a) should usually be less than about 20 mole %, based on the molar weight of the 4,6-dibenzoylresorcinol. In preferred embodiments, the amount of secondary amine catalyst is less than about 10 mole %.
Some of the specific process details for carrying out step (a) and ensuring suitable xe2x80x9creaction conditionsxe2x80x9d would be familiar to those of ordinary skill in the art. In a typical embodiment, the reaction is carried out at a temperature of at least about 80xc2x0 C. Following reaction, the mixture can be filtered, and the filtrate may then be diluted with additional carboxylic acid solvent. The filtrate could then be cooled, and the methylene acetate intermediate could be recovered in solid form by conventional separation techniques.
Step (b) of the process involves the reaction of the methylene acetate intermediate with an alcohol or a carboxylic acid, such as those described in detail previously. Many of the specific details regarding this step are provided in the examples which follow. Generally, the reactive medium is acidic, or at least neutral. This stage of the reaction is usually carried out at temperature in the range of about 20xc2x0 C. to about 120xc2x0 C. Recovery of the product can be accomplished by conventional procedures.
It should be apparent from this discussion that step (b) results in the formation of an ether or ester link (depending on the use of either an alcohol or carboxylic acid, respectively) between the methylene carboxylate intermediate of the dibenzoylresorcinol molecule and the xe2x80x9cAxe2x80x9d group. In the case of using an alcohol, this result is somewhat surprising to those skilled in organic synthesis, since one might have expected the primary reaction to have involved displacement at the carbonyl site of the carboxylate intermediate, to form a less desirable product by transesterification.
Thus, in one respect, the reaction to form the compound of structure I, when A is a radical deriving from an alcohol, can be viewed as an etherification reaction which involves the combination of a compound of structure
with an alcohol in a suitable reaction medium, wherein R, Ar1 and Ar2 are as described above, and R2 is a linear or branched alkyl chain containing less than about 10 carbon atoms. The R2 moiety is usually introduced as part of the reaction medium. For example, if acetic acid is employed, then R2 would be a methyl group; and if propionic acid is used, then R2 would be an ethyl group. Other conventional details regarding the reaction medium are described in this specification, and would also be apparent to those of ordinary skill in the art.
As set forth above, another class of compounds from which the xe2x80x9cAxe2x80x9d group of formula I could be derived are substituted or unsubstituted aryl groups which do not include a pendent hydroxyl group. Suitable examples of this class are phenyl, alkyl-substituted phenyl groups, halogen-substituted phenyl groups, and alkoxy-substituted phenyl groups. These general types of groups are themselves known in the art, as are substituted versions, e.g., groups having pendent alkyl chains, pendent aromatic rings, pendent carbocyclic rings, and/or pendent heterocyclic rings.
Of particular interest for some embodiments of the present invention are aryl compounds in which a vinyl group is attached thereto (e.g., styryl derivatives). The vinyl group is usually attached to the 3-position or the 4-position on the aryl ring, relative to the attachment site of group A of formula I. Mixtures of isomers of such groups in both the 3-and 4-positions are also within the scope of the present invention. The vinyl-functionality permits the preparation of various, useful copolymer products, such as co-polymerizable UV absorbers.
In brief, the compounds in which the xe2x80x9cAxe2x80x9d group is derived from a substituted or unsubstituted aryl group can be prepared by a process (usually one-step) which comprises reacting a 4,6-dibenzoylresorcinol with a benzyl halide compound, an aqueous base, and a compatible phase transfer catalyst under conditions suitable for obtaining a substantial yield of the compound. The reaction is usually carried out at a temperature in the range of about 40xc2x0 C. to about 120xc2x0 C. Many different benzyl halide compounds could be used, depending on the desired product-structure. Non-limiting examples are benzyl bromide, benzyl chloride, 3-vinyl benzyl chloride, 3-vinyl benzyl bromide, 4-vinyl benzyl chloride, and 4-vinyl benzyl bromide.
There also appears to be no restriction on the type of base used. Examples are sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, lithium hydroxide, and lithium carbonate. Moreover, a wide variety of phase transfer catalysts could be employed, such as tetrabutylammonium bromide, tetrabutylammonium chloride, benzyl trimethylammonium chloride, benzyl trimethylammonium bromide, tetraethylammonium bromide, and tetraethylammonium chloride. Those of ordinary skill in the art will be able to select the most appropriate starting materials and quantities of materials to obtain a substantial yield of a desired compound-product, based on the teachings herein, as well as a general knowledge of organic synthesis. The product can be recovered by conventional techniques.
Yet another aspect of the present invention is directed to a novel coating composition based in part on the dibenzoylresorcinol compounds described above. In general, these coating compositions exhibit a relatively high degree of photostability, and are capable of absorbing ultraviolet light. The compositions include a polymer matrix (usually transparent) which is compatible with the dibenzoylresorcinol compounds, e.g., in which there is very little phase separation when the components are mixed together. A wide variety of matrices may be used, such as polymer materials based on urethanes, melamines, acrylics, and methacrylics, as well as polycarbonates, polystyrenes, and the like. Various mixtures of any of these materials may also be employed, as well as copolymers. Poly(methyl methacrylate) is the preferred matrix material in some embodiments. The coating compositions usually comprise at least about 1% by weight of the dibenzoylresorcinol-based compounds described above, based on the total weight of the coating. In many preferred embodiments, the coating compositions comprise at least about 10% by weight of the dibenzoylresorcinol-based compounds, while in some especially preferred embodiments, the level is at least about 35% by weight. The most appropriate level will of course depend on various factors, such as the particular compound being used, the particular substrate being treated, and the degree of UV protection required for a particular end use.
Many of the materials (such as the acrylic polymers) may be used in conjunction with organic solvents. Moreover, aqueous emulsions of some of the materials may be utilized, e.g., acrylic emulsions in which the dibenzoylresorcinol-based compounds are dispersed. Techniques for preparing these types of coating compositions are well-known in the art, and are described in many references, such as U.S. Pat. Nos. 5,391,795; 4,373,061; 4,322,455; and 4,278,804, each of which is incorporated herein by reference. The compositions may contain various other components and additives in effective amounts, such as catalysts, photoinitiators, surfactants, dispersants, stabilizers, anti-setting agents, abrasion resistance agents (e.g., silica); and additional UV absorbers.
A further aspect of the present invention relates to solid substrates on which coating compositions like those described above are applied. There is generally no limitation with respect to the type of substrate which may be coated. Examples include polymer substrates such as those based on acrylics (e.g., poly(methyl methacrylate); polyesters such as poly(ethylene terephthalate) and poly(butylene terephthalate); polyamides, polyimides, acrylonitrile-styrene copolymers; styrene-acrylonitrile-butadiene copolymers; polyvinyl chloride, polystyrene, blends of polystyrene and polyphenylene ether; butyrates, polyethylene, and the like, as well as various copolymers which include any of the above-listed materials. Moreover, the coating compositions may be applied to other types of substrates, e.g., metal substrates, painted surfaces, glass, ceramics, and textiles.
Thermoplastic substrates are frequently provided with protective coatings. Within that class, polycarbonates and copolymers such as polyesterpolycarbonates are often the substrates which receive the most benefit from the coating compositions of the present invention. These types of polymers are well-known in the art and described in numerous patents and other references, such as Organic Polymer Chemistry, by K. J. Saunders, 1973, Chapman and Hall Ltd. The polycarbonates are usually prepared from aromatic dihydroxy compounds such as bisphenol A, using well-known techniques, such as interfacial polymerization or melt polymerization.
Methods for applying the protective coatings to the substrate are also known in the art, and described in many of the references set forth above. Usually, a relatively thin layer of the matrix material is applied to the substrate by various techniques, such as spraying, dipping, flow-coating, roll-coating, and the like. After the coating has been applied to the substrate, substantially all of the volatile components (e.g., water or organic solvents) are evaporated - usually, by air-drying or heating. A relatively uniform polymer layer containing the dibenzoylresorcinol-based compound remains. Additional heating steps may be used to remove any residual solvents. The thickness of this coating layer after removal of the volatile components is usually in the range of about 0.01 micron to about 50 microns, and preferably, from about 0.1 micron to about 10 microns.
Coatings based on thermosetting polymers or emulsions usually require baking at elevated temperature to effect curing. Those of ordinary skill in the art are familiar with procedures for curing other types of coating systems also, e.g., radiation-curable coatings such as those described in U.S. patent application Ser. No. 08/699,254 (RD-25, 142), filed on Aug. 15, 1996.

Compounds based on dibenzoylresorcinol and related compositions and articles


The invention relates to a stacking device as well as to a method for depositing sheets on a stack. The task of the invention is to provide a stacking device that deposits sheets on a stacking unit quickly, cost effectively and reliably. The invention solves this task with a method for depositing sheets and a stacking device that contains two gripping devices for alternately gripping and depositing sheets.

The invention relates in general to a method and apparatus for stacking sheets in a printing press. More specifically, after the run through the printing module of a printing press, the printed sheets are stacked in a stacking unit of the printing press where various solutions are used to pick up the sheet from the sheet path and to deposit it on the stacking unit.
One prior art mechanism for stacking sheets involves the gripping of the sheet in a transport path with a mechanical gripper, which has two gripper plates that partially grasp the sheet and carry it from the path to a stacking unit. The gripper then deposits the sheet on the stacking unit. However, the speed of this stacking solution is limited, since only one sheet per run is grasped by the gripper and carried to the stacking unit. The speed characteristic is an important criterion for modern high speed, high productivity printing machines.
This invention deposits sheets on a stacking unit quickly, cost effectively and reliably. The invention is directed to a method for depositing sheets, and a stacking device that contains two gripping devices, for alternately picking up and depositing sheets relative to a stack. A first gripping device picks up a sheet advantageously within reach of the sheet transport, while a second gripping device simultaneously holds the sheet stack, whereby the sheets to be deposited are at a lower level to prevent the sheet stack from moving during this process. The arrangement of the sheet on this sheet stack is in registered alignment, or stacking may also be offset lengthwise to the sheet transport path. Conveyor rollers are used for this purpose, which slow down the run of the transported sheet at a specific point in time and thus determine the stacking of various sheets in an offset manner in the lengthwise direction. The sheets may then be removed by the operator in stacks from the printing press at the rate of approximately one offset stack per printing job.
The invention and its advantages will be better understood from the ensuing detailed description of preferred embodiments, reference being made to the accompanying drawings in which like reference characters denote like parts.


A massaging system includes a base sheet carrying a plurality of expandable bags arranged in a plane of the base sheet, and a charging and discharging unit connected to the bags for selectively supplying and discharging a pressurized fluid into and from the bags so as to inflate and deflate the bags, selectively. At least one applicator projects from each of the bags in contact with a portion of a human body for applying a massaging action. Each bag has a flexible top end capable of deforming into a curved contour when being inflated. The applicator is made of a hard material and projects directly from the top end wall of the bag as an integral part of the bag such that the applicator is caused to displace in a direction different from a direction along which the bag inflates and deflates principally, as a consequence of that the flexible top end wall deforms into the curved contour. Thus, the applicator can concentrate a massaging force resulting from the inflation of the bag to a particular portion of the user""s body, giving a relatively strong local massage action sufficient for optimum treatment. Further, since the applicator takes a lateral movement in the direction generally perpendicular to the inflating direction during the inflation of the bag, the applicator can give a rubbing action, in addition to the pressing action, to the user""s body for realizing effective and comfortable massage treatment analogous to that made by a human therapeutic massager.

1. Field of the Invention
The present invention is directed to a massaging system, and more particularly to a massaging system utilizing a pressurized fluid to inflate and deflate selective ones of expandable bags arranged in an array for producing a massaging action to a human body.
2. Description of the Prior Art
U.S. Pat. No. 4,622,706 discloses a prior massaging system in the form of an air mat which comprises an array of expandable bags. A source of pressurized air is connected to the individual bags for selectively inflating and deflating the bags to give a massaging force applied to a human body lying on the mat. However, since the force generated by the inflation of the bag is distributed over substantially the entire surface of the bag, it is difficult to concentrate a relatively large force to a particular portion of a human body, failing to realize a strong massage action. This problem is somewhat solved in another massaging system as disclosed in U.S. Pat. No. 5,741,218. The patent utilizes a plurality of air bags each actuating an applicator in the form of a kneading ring so as to force the applicator against a user""s body by inflating the corresponding bag. Thus, the inflation of the bag is translated into the massaging movement of the applicator. However, there is required a complicated structure for supporting the applicator on the bag in such a manner as to transmit the inflation of the bag made of the flexible bag to the massaging movement of the applicator made of a hard material. In fact, the applicator is mounted on a separate plate which is in turn supported to a base frame through a link mechanism allowing the applicator to move towards away from the base frame, while the bag is placed between the base frame and the plate. The use of such supporting mechanism makes it difficult to realize a compact massaging system at a minimum number of components, and particularly to design the massaging system which covers a wide area of the human body, yet which is light-weight and compact sufficient for easy adaptation in a bed, a bed, backrest of the chair, or even in a band placed around a leg or arm of the user.
The above problem and insufficiency have been reduced in a unique massaging system of the present invention. The massaging system comprises a base sheet carrying a plurality of expandable bags arranged in a plane of the base sheet, and a charging and discharging unit connected to the bags for selectively supplying and discharging a pressurized fluid into and from the bags so as to inflate and deflate the bags, selectively. At least one applicator projects from each of the bags and is adapted in use to come into contact with a portion of a human body for applying a massaging action. Each of the bags has a flexible top end wall which is capable of deforming into a curved contour when being inflated. The applicator is made of a hard material and projects directly from the top end wall of the bag as an integral part of the bag such that the applicator is caused to displace in a direction different from a direction along which said bag inflates and deflates principally, as a consequence of that the flexible top end wall deforms into the curved contour. Thus, the applicator can concentrate a massaging force resulting from the inflation of the bag to a particular portion of the user""s body, giving a relatively strong local massage action for optimum treatment. In addition, since the applicator takes a lateral movement in the direction generally perpendicular to the inflating direction during the inflation of the bag, the applicator can give a rubbing action, in addition to the pressing action, to the user""s body for realizing effective and comfortable massage treatment analogous to that made by a human therapeutic massager.
Accordingly, it is a primary object of the present invention to provide a massaging system which is capable of giving a relatively strong massage treatment locally to a particular portion of the user""s body in an effective and comfortable manner, even with the use of the pressurized fluid for inflating and deflating the bags.
Preferably, each of the bags is formed of a flexible material in its entirety including the top end wall. Each of the applicators is made of a hard material which is inserted into a flexible sheath bonded to the top end wall of each bag. Thus, the applicator can be easily integrated with the bag without requiring any additional intervening supporting mechanism, assuring easy fabrication of the system.
The base sheet may be shaped into a rectangular configuration having a length and a width, and carry the bags which are of elongated configuration extending along the length of the base and are arranged in parallel with each other. The applicator on each of the bags is in the form of an elongated fin extending along a length of the bag, thereby enabling to concentrate the massage action over an extended portion of the user""s body at a time.
In this connection, each bag may be provided with a parallel pair of the applicators which are so positioned on the flexible top end wall as to displace distal ends of the applicators away from each other as the bag is caused to inflate. Therefore, the applicators in the pair can act to stretch the portion of the user""s body confined between the applicators, thereby realizing a comfortable treatment.
The bag is preferred to have a side wall in the form of a bellows so as to inflate the bag sufficiently without necessitating any substantial elastic deformation of the bag.
The charging and discharging unit responsible for inflating and deflating the bags may be configured to include a charging pump of supplying the pressurized fluid into the individual bags respectively through fluid channels, and a plurality of two-way valves provided respectively in the fluid channels for charging and discharging the pressurized fluid into and from the bags to inflate and deflate the bags. A suction pump is included to be connected to the valves through a common exhaust path for positively discharging the pressurized fluid out of the bags. Thus, the bags can be inflated and deflated at an increased rate to strengthen the massage action applied to the user""s body.
The charging pump is connected to a common feed path from which the individual fluid channels are branched. The system may be additionally provided with a single temperature control unit which is disposed around the common feed path so as to heat or cool the pressurized fluid being supplied to the bags. Whereby, the user can enjoy the massage treatment in combination with a hot or cool treatment.
Alternatively, a plurality of temperature control units may be provided respectively around the individual fluid channels in order to control the temperature of the bags individually for realizing an optimum temperature distribution over the assembly of the bags.
It is preferred that the bags are grouped into a plurality of modules each having more than one bags. The modules are arranged within the plane of the base sheet to constitute a two-dimensional array having rows and columns of the bags. The system includes a controller which is programmed to inflate and deflate the bags successively along either one of the rows and columns. Thus, the massaging action can proceed selectively in different directions for optimum treatment to different portions of the user""s body. In this connection, the bags of the elongated configuration extend along one of the rows and columns in parallel with each other within each module. The bags in each module are controlled to inflate and deflate successively to give a massaging wave proceeding in the order of the bags for applying successive treatment over a wide area of the user""s body.
The base sheet may be made flexible to be deformable together with the bags into a desired contour so that it can be wound around arm or leg of the user to give the massage treatment thereto.
Further, at least one of the bags may be disposed to have the corresponding applicator positioned at a higher level than those of the remaining bags with respect to a general plane of the base sheet. Thus, the bags can be arranged in conformity with a curved contour of the human body so as to give a sufficient massage treatment to a recessed portion, for example, the lower back of the user""s body.
These and still other objects and advantageous features of the present invention will become more apparent from the following description of the preferred embodiments when taken in conjunction with the attached drawings.


This invention provides organic-inorganic hybrid particles containing as the essential components a block copolymer comprising an uncharged hydrophilic polymer chain segment and a polymer chain segment containing a repeated structural unit having a carboxylate ion group at its side chain; calcium ion (Ca2+), phosphate ion (PO43−) or carbonate ion (CO32−), or a mixture of these anions; and a contrast agent. The particles provide, in particular, carriers for stably delivering an MRI contrast agent to a target site.

The importance of early detection of cancer for improving the patients' quality of life (QOL) has been pointed out in recent years. For example, according to a graph on 5-year survival rate of stomach cancer cases, the survival rate of patients whose stomach cancer is detected in the initial stage (first stage) is 90%. By contrast, the survival rate of the end stage (fourth stage) stomach cancer patients is less than 10%. This demonstrates the high importance of early diagnosis of cancer in patients for the current therapy. Also because of frequent lack of subjective symptom of primary cancer, it is necessary to give cancer diagnosis to quite healthy people, in order to ensure the early detection. For this purpose, development of non-invasive and safe method of the diagnosis is desired.
From the viewpoint of non-invasiveness and safety, utilization of MRI (magnetic resonance imaging) appears recommendable, as it uses magnetic field or radio waves and is free of fear of exposure to radiation. However, the present state of art is still unable to detect primary cancer with MRI. Many and various contrast agents in forms easy of handling are being proposed, with the view to obtain still higher contrast to raise sensitivity of MRI (for example, see the Non-patent References 1, 2 and 3 in the collective listing given later, and so forth). While these contrast agents include actually widely used excellent contrast agents such as Gd-DTPA (gadodiamide), it may worth continual investigations if further improvements are possible.
On the other hand, we have developed a drug delivery system using specific block copolymers and succeeded in offering certain anti-cancer drug with increased tumor tissue-selective accumulation, whose favorable therapeutic effect has been clinically confirmed.
Furthermore, there was a method proposed in the past as a means to introduce DNA into cells, which used a complex formed by making use of the property of calcium phosphate (hydroxyapatite) crystals to bind to DNA, the crystals being formed when an aqueous calcium solution and aqueous phosphoric acid solution were mixed to bring about oversaturated condition. A part of us discovered that, in the attempt to improve the disadvantage incidental to the method, the calcium phosphate particles could be formed with controlled size, when incubated with the specific block copolymer containing a hydrophilic, nonionic polyethylene glycol (PEG) segment and a polyanionic segment derived from carboxyl group. We furthermore confirmed that the so obtained particles had not only relatively narrow particle size distribution and that their average particle size could be controlled to be less than submicron order (several hundreds nm) where necessary, but also aqueous dispersion systems containing these particles could be stably stored under ambient conditions, without inducing sedimentation. In consequence, we proposed a novel organic-inorganic hybrid particle system which could carry, as the drug, DNA or other bioactive substances and deliver the drug to cancer tissues or cancer cells (see Patent Reference 1).

Organic-inorganic hybrid particles containing contrast agent


This invention relates generally to a new class of chemoselective polymer materials. In particular, the invention relates to linear and branched polysiloxane compounds for use in various analytical applications involving sorbent polymer materials, including chromatography, chemical trapping, analyte collection, and chemical sensor applications. These polymers have pendant and terminal aryl, alkyl, alkenyl, and alkynyl groups that are functionalized with halogen substituted alcohol or halogen substituted phenol groups, having the general structure:

1. Field of the Invention
This invention relates generally to a new class of chemoselective polymer materials. In particular, the invention relates to linear and branched polysiloxane compounds for use in various analytical applications involving sorbent polymer materials, including: chromatoghraphy, chemical trapping, and chemical sensor applications. These polymeric materials are primarily designed to sorb hydrogen bond basic analytes such as organophosphonate esters (nerve agents and precursors), and nitroaromatics (explosives).
2. Description of the Related Art
The use of sorbent chemoselective polymers for chromatography, chemical trapping, and chemical sensor applications is well established for technologies such as gas liquid chromatography, solid phase microextraction (SPME), and surface acoustic wave (SAW) sensors respectively. In each application, the sorbent polymer is applied to a substrate as a thin film and analytes are sorbed to the polymer material. A typical configuration for a chemical sensor incorporates a thin layer of sorbent polymer deposited on a transducer that monitors changes in the physicochemical properties of the polymer film and translates these changes into an electrical signal that can be recorded. By careful design of the polymer, both sensitivity and selectivity of a chemical sensor can be enhanced with respect to specific classes or types of analytes. Typically, a chemoselective polymer is designed to contain functional groups or active sites that can interact preferentially with the target analyte through dipolexe2x80x94dipole, van der Waals, or hydrogen bonding forces. The interaction between a chemoselective polymer and the analyte can even be regarded as a xe2x80x9clock and keyxe2x80x9d type interaction if multiple active sites in the polymer are spatially controlled so that an analyte with multiple functional sites can simultaneously interact with the polymer active sites.
The ideal polymer film for extended chemical sensor applications should exhibit reversible binding of analyte, high selectivity and high sorptivity, long term stability; and, as a thin film, offer fast sorption and desorption properties. To achieve these characteristics a polymer must have physical properties that are amenable to rapid analyte sorption and desorption, suitable choice of functional groups, and a high density of functional groups to increase the sorptive properties for target analytes. Polymers with suitable analyte sorption characteristics can be obtained commercially for most analytes of interest with the exception of hydrogen bond acid polymers for sorption of hydrogen bond basic vapors. Of the few polymers that are commercially available (such as polyvinylalcohol, polyphenol, and fomblin zdol), either the physical properties are not ideal with glass transition temperatures above room temperature, the hydrogen bond acidity is relatively weak, or the density of functional groups is low.
Fluorinated polymers with hydroxyl groups as part of the polymer repeating unit and, in particular, polymers containing the hexafluoroisopropanol (HFIP) functional group are a well established class of hydrogen bond acid polymers. (See McGill, R. A.; Abraham, M. H.; Grate, J. W. CHEMTECH 1994,24 (9), 27; Ballantine, D. S.; Rose, S. L.; Grate, J. W.; Wohltjen, H. Anal. Chem. 1986, 58,3058; Snow, A. W.; Sprague, L. G.; Soulen, R. L.; Grate, J. W.; Wohltjen, H. J. Appl. Pol. Sci., 1991, 43, 1659; Houser, E. J.; McGill, R. A.; Mlsna, T. E.; Nguyen, V. K.; Chung, R.; Mowery, R. L. Proc. SPIE, Detection and Remediation Technologies for Mines and Minelike Targets IV, Orlando, Fla., 1999, 3710, 394-401; Houser, E. J.; McGill, R. A.; Nguyen, V. K.; Chung, R.; Weir, D. W. Proc. SPIE, Detection and Remediation Technologies for Mines and Minelike Targets V, Orlando, Fla., 2000, 4038; Houser, E. J.; Mlsna, T. E.; Nguyen, V. K.; Chung, R.; Mowery, R. L.; McGill, R. A. Talanta, 2001, 54,469 ; Grate, J. W.; Patrash, S. J.; Kaganove, S. N.; Wise, B. M. Anal. Chem. 1999, 71,1033; all of which are incorporated herein by reference). The polymer fluoropolyol (FPOL) has become a standard material for many polymer based chemical sensor applications requiring hydrogen bond-acid polymers. (See: Ballantine, D. S.; Rose, S. L.; Grate, J. W.; Wohltjen, H. Anal. Chem. 1986, 58, 3058; Snow, A. W.; Sprague, L. G.; Soulen, R. L.; Grate, J. W.; Wohltjen, H. J. Appl. Pol. Sci., 1991, 43, 1659; all of which are incorporated herein by reference). Recently reported polymers such as BSP3, SXFA, and CS3P2 have yielded improvements in sensitivity and response time relative to FPOL. (See: Houser, E. J.; McGill, R. A.; Mlsna, T. E.; Nguyen, V. K.; Chung, R.; Mowery, R. L. Proc. SPIE, Detection and Remediation Technologies for Mines and Minelike Targets IV, Orlando, Fla., 1999,3710,394-401; Houser, E. J.; McGill, R. A.; Nguyen, V. K.; Chung, R.; Weir, D. W. Proc. SPIE, Detection and Remediation Technologies for Mines and Minelike Targets V, Orlando, Fla., 2000, 4038; all of which are incorporated herein by reference).
Determining and/or monitoring the presence of certain chemical species within a particular environment, e.g., pollutants, toxic substances and other predetermined compounds, is becoming of increasing importance with respect to such areas as defense, health, environmental protection, resource conservation, police and fire-fighting operations, and chemical manufacture. Devices for the molecular recognition of noxious species or other analytes typically include (1) a substrate and (2) a molecular recognition coating upon the substrate. These devices may be used, for example, as stand-alone chemical vapor sensing devices or as a detector for monitoring different gasses separated by gas chromatography. Molecular recognition devices are described in Grate et al., Sensors and Actuators B, 3, 85-111 (1991); Grate et al., Analytical Chemistry, Vol. 65, No. 14, Jul. 15, 1993; Grate et al., Analytical Chemistry, Vol. 65, No. 21, Nov. 15, 1993; and Handbook of Biosensor and Electronic Noses, ed. Kress-Rogers, CRC Press, 1996; all of which are incorporated herein by reference.
Frequently, the substrate is a piezoelectric material or an optical waveguide, which can detect small changes in the mass or refractive index, respectively. One illustrative example of a device that relies upon selective sorption for molecular recognition is known as a surface acoustic wave (SAW) sensor. SAW devices function by generating mechanical surface waves on a thin slab of a piezoelectric material, such as quartz, that oscillates at a characteristic resonant frequency when placed in a feedback circuit with a radio frequency amplifier. The oscillator frequency is measurably altered by small changes in mass and/or elastic modulus at the surface of the SAW device.
SAW devices can be adapted to a variety of gas and liquid phase analytical problems by designing or selecting specific coatings for particular applications. The use of chemoselective polymers for chemical sensor application is well established as a way to increase the sensitivity and selectivity of a chemical sensor with respect to specific classes or types of analytes. Typically, a chemoselective polymer is designed to contain functional groups that can interact preferentially with the target analyte through dipolexe2x80x94dipole, van der Waals, or hydrogen bonding forces. For example, strong hydrogen bond donating characteristics are important for the detection of species that are hydrogen bond acceptors, such as toxic organophosphorus compounds. Increasing the hydrogen bond acidity and the density of hydrogen bond acidic binding sites in the coating of a sensor results in an increase in selectivity and sensitivity of the sensor for hydrogen bond basic analytes.
Chemoselective films or coatings used with chemical sensors have been described by McGill et al. in Chemtech, Vol. 24, No. 9, 27-37 (1994), incorporated herein by reference. The materials used as the chemically active, selectively absorbent layer of a molecular recognition device have often been polymers, as described in Hansani in Polymer Films in Sensor Applications (Technomic, Lancaster, Pa. 1995). For example, Ting et al. investigated polystyrene substituted with hexafluoroisopropanol (HFIP) groups for its compatibility with other polymers in Journal of Polymer Science: Polymer Letters Edition, Vol.18,201-209 (1980). Later, Chang et al. and Barlow et al. investigated a similar material for its use as a sorbent for organophosphorus vapors, and examined its behavior on a bulk quartz crystal monitor device in Polymer Engineering and Science, Vol. 27, No. 10, 693-702 and 703-15 (1987). Snow et al. (NRL Letter Report, 6120-884A) and Sprague et al. (Proceedings of the 1987 U.S. Army Chemical Research Development and Engineering Center Scientific Conference on Chemical Defense Research, page 1241) reported making materials containing HFIP that were based on polystyrene and poly(isoprene) polymer backbones, where the HFIP provided strong hydrogen bond acidic properties. These materials were used as coatings on molecular recognition devices, such as SAW sensors, and showed high sensitivity for organophosphorus vapors. However, both the parent polymers and the HFIP-containing materials were glassy or crystalline at room temperature. Because vapor diffusion may be retarded in glassy or crystalline materials, the sensors produced were slow to respond and recover. Additional information is reported in Polym. Eng. Sci., 27, 693 and 703-715 (1987).
Grate et al. in Analytical Chemistry, Vol. 60, No. 9, 869-75 (1988), which is incorporated herein by reference, discloses a compound called xe2x80x9cfluoropolyolxe2x80x9d (FPOL), which is useful for detecting organophosphorus compounds. FPOL has the formula:
An HFIP-containing polymer based on a polysiloxane backbone was described and demonstrated to be a good hydrogen-bond acid by Abraham et al., xe2x80x9cHydrogen Bonding XXIX. The Characterisation of Fourteen Sorbent Coatings for Chemical Microsensors Using a New Salvation Equationxe2x80x9d, J. Chem. Soc., Perkin Trans. 2, 369-78 (1995), herein incorporated by reference. The polysiloxane backbone provided a material with a Tg well below room temperature. However, physical properties were not quantified.
Grate, U.S. Pat. No. 5,756,631, incorporated herein by reference, discloses the use of HFIP-substituted siloxane polymers having the structure:
wherein R2 has the formula xe2x80x94(CH2)mxe2x88x921xe2x80x94CHxe2x95x90CHxe2x80x94CH2xe2x80x94C(CF3)2xe2x80x94OH, n is an integer greater than 1, R1 is a monovalent hydrocarbon radical, and m is 1 to 4.
Grate et al., U. S. Pat. No. 6,015,869, incorporated herein by reference, discloses a strongly hydrogen bonding acidic, sorbent oligomer or polymer having a glass-to-rubber transition temperature below 25xc2x0 C. The polymer has (1) fluoroalkyl-substituted bisphenol segments containing interactive groups and (2) oligodimethylsiloxane segments. These siloxane polymers are said to provide improved coatings and vapor sorption compositions for chemical sensors that are sensitive, reversible and capable of selective absorptions for particular vapors, particularly the hydrogen bond accepting vapors, such as organophosphorus compounds.
The present invention discloses a newly discovered class of siloxane polymers that can be used to produce hydrogen bond acidic coatings for chemical sensor applications. Use of these siloxane polymers with highly functionalized units can result in significant selectivity and sensitivity improvements.
Further, the chemoselective siloxane polymer materials of the present invention exhibit, not only improved sensitivity to organophosphorus species, but also high selectivity and sensitivity toward nitroaromatic vapors, and are thus also useful for detecting the presence of explosives. Conventional explosives, such as trinitrotoluene (TNT), hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), and octahydro-1,3,5-trinitro-1,3,5,7-tetrazocine (HMX), may be contained in unexploded munitions, e.g., buried below the surface of the ground. Such munitions exude or leak vapors of the explosive. These vapors are typically concentrated in the surrounding soil and then migrate to the surface where they can be detected by the compounds, devices and methods disclosed by the present invention.
It is well known that dogs can be used to locate land mines demonstrating that the canine olfactory system is capable of detecting and identifying explosive related analyte signatures. In order to improve land mine detection capability, the use of sensors for the detection of chemical vapors associated with explosives is of great interest. Of particular interest in developing chemical sensors is the ability to detect unexploded ordnance, e.g., the polynitroaromatic compounds that are frequently present in the chemical signature of land mines.
This invention relates to the preparation of new linear and branched chemoselective polymeric materials for chemical sensor, chromatography, dosimeter, analyte collector, and air filtration applications.
According to a first aspect of the present invention, there is provided a siloxane polymer with pendant and terminal groups that are functionalized with halogen substituted alcohol or phenol groups having the general structure:
wherein n is an integer greater than 1;
wherein at least one of R1 and R2 includes an aryl or alkynyl group having at least one halogen substituted alcohol or halogen substituted phenol group attached thereto, or wherein both R1 and R2 are alkenyl groups having at least one halogen substituted alcohol group attached thereto;
wherein any said R1 and R2 aryl groups are attached to said [Sixe2x80x94Oxe2x80x94]n, the polymer backbone, directly or through a short hydrocarbon chain;
wherein any remaining R1 or R2 group is an alkyl, alkenyl, alkynyl, or aryl group having between one and sixteen carbons; and
wherein Z is an end group independently selected from the group consisting of saturated hydrocarbons, unsaturated hydrocarbons, alkyl silanes, aryl silanes, hydroxyl, silicon hydride, alkoxides, halogen substituted alcohol, halogen substituted phenol, and combinations thereof.
According to a second aspect of the invention, there is provided a siloxane polymer with pendant and terminal aryl or allyl groups that are functionalized with halogen substituted alcohol or halogen substituted phenol groups that are primarily designed for the sorption of organophosphonate esters, nitroaromatics, and other hydrogen-bonding basic analytes.
According to a third aspect of the invention, there is provided a device for selective molecular recognition, the device comprising a sensing portion, wherein the sensing portion includes a substrate or multiple substrates having coated thereon a layer, the layer comprising any one of the polymeric compounds of the invention.
According to another aspect of the invention, there is provided a method of detecting a hydrogen bond basic analytes such as the organophosphonate esters or nitroaromatic compounds, comprising the steps of:
(a) contacting the molecules of such a analyte with the sensing portion of the device of the invention;
(b) collecting the molecules on the layer of the device, the molecules altering a specific physical property of the layer; and
(c) detecting the amount of change with respect to the physical property from before the contacting step (a) and after the collecting step (b).
According to a yet another aspect of the invention, there is provided a chemical vapor collector comprising an amount of any one of the polymeric compounds of the invention effective to collect hydrogen bond basic vapors or nitroaromatic compounds.
The present invention relates to the preparation of new linear and branched chemoselective polymeric materials for chemical sensor, chromatography, analyte dosimeter, analyte collector, and air filtration applications. These polymers have pendant and terminal groups that are functionalized with halogen substituted alcohol or halogen substituted phenol groups. Pendant aryl groups can be attached to the siloxane polymer backbone either directly or through a hydrocarbon chain. These polymeric materials are primarily designed for the chemical detection of organophosphonate esters (nerve agents and precursors), and nitroaromatics (explosives) but may also have applications in detecting other hydrogen-bonding basic analytes.
In designing sorptive polymers for nitroaromatic analytes, hexafluoroisopropanol (HFIP) functionalized terminal alkene groups or aryl rings were chosen as the interactive portion of the polymer because of the high hydrogen-bonding acidity of these groups. Polynitroaromatic compounds possess multiple basic sites through the oxygen atoms of the nitro group and the hydrogen-bond acidity of the hexafluoroisopropanol group is complimentary to these basic sites. The hydrogen bond acidity of alcohols increases with the number of perfluoroalkyl groups bound to the carbinol group making the HFIP group an excellent hydrogen bond acid. In addition, the hydrogen bond basicity imparted by the oxygen atom of the hydroxyl group is substantially reduced thereby increasing the selectivity of the hydroxyl group for hydrogen bond basic analytes.
In addition to contributing to the hydrogen bond acidity of the hydroxyl group in the polymer, the fluorocarbon group also imparts substantial chemical stability to the polymer due to the inertness of the Cxe2x80x94F bond. A further advantage is the steric bulk of the CF3 groups and phenyl rings which hinders access to the polymer backbone thereby decreasing the effective hydrogen bond basicity of the polymer by limiting access to any electron rich atoms, such as oxygen, present in the polymer backbone. Use of the aromatic pendant groups provides two additional advantages in that they generally lead to more hydrogen bond acidic systems than comparable saturated hydrocarbons and they are better spatially oriented to interact with the electron rich oxygen atoms of the nitro groups on the nitroaromatic analytes.
The nitroaromatic analytes are dipolar and highly polarizable molecules that exhibit hydrogen-bond basic properties increasing with the number of nitro groups on the molecule. The hydrogen bond acidic polymers are designed to interact with the available electron density located on the oxygen atoms of the nitro groups of the polynitroaromatics. The hydrogen-bond basicities of some common nitroaromatics are 0.25 for 3-nitrotoluene, 0.47 for 2,4-dinitrotoluene and 0.61 for 2,4,6-trinitrotoluene demonstrating that the basicity of additional nitro groups is additive. These hydrogen bond basicities can be compared to those of hexane (0.0) and toluene (0.14). It should also be noted that the nitroaromatics are relatively large molecules and therefore also have significant van der Waals interactions with other materials.
In order to develop hydrogen bond acid polymers with improved physicochemical properties, preparation of new polymers with higher density of perfluoroalcohol functional groups and physical properties amenable to rapid vapor sorption/desorption kinetics have been targeted. Aryl rings were found to be preferable to the allyl group as a framework for fluoroalcohol functionalization because the hexafluoroisopropanol substituted allyl tends to exhibit a higher sorptivity for water molecules.
The compounds of the present invention can be synthesized by reacting hexafluoroacetone with the parent molecule, comprising a core polymer and a number of pendant unsaturated groups, taking advantage of the reactivity of perfluoroketones with terminally unsaturated groups, as described by Urry et al., J. Org. Chem., Vol. 33,2302-2310 (1968), incorporated herein by reference.
Once synthesized, these polymers can be coated to a controlled film thickness on a substrate, either alone or mixed with a solvent or similarly functionalized polymer. Useful substrates include planar chemical sensors, such as surface acoustic wave (SAW) substrates; optical fibers; and the interior surfaces of capillaries. The substrate chosen is based on the sensing mechanism being used.
The principle of operation of an acoustic wave device transducer involves the production of an acoustic wave that is generated on the surface or through the bulk of a substrate material and allowed to propagate. To generate the acoustic wave typically requires a piezoelectric material. Applying a time varying electric field to the piezoelectric material will cause a synchronous mechanical deformation of the substrate with a coincident generation of an acoustic wave in the material. The time varying electric field is generated in the surface by the action of the time varying electrical field applied through one or more electrodes that are connected to the piezoelectric material via one or more metal wire bonds and to an electrical circuit. Another electrode or electrodes receives the wave at a distance from the first electrode or electrodes. The second electrode or electrodes is also connected via metal wire bonds to the electrical circuit and the piezoelectric material. Such devices are operable in a frequency range of about 1 kilohertz to 10 gigahertz, preferably from about 0.2 megahertz to about 2 gigahertz and, more preferably, in the range of between about 200 to 1000 megahertz.
For piezoelectric sensors, piezoelectric substrates known in the art are useful in accordance with the invention, e.g., ST-cut quartz. In addition to quartz crystals, piezoelectric ceramics, such as those of the barium titanate and lead titanate zirconate families, are suitable substrates. These include LiNbO3; BaTiO3; 95 wt. % BaTiO3/5% GaTiO3; 80 wt. % BaTiO3/12% PbTiO3/8% CaTiO3; PbNb2O6; Na0.5K0.5NbO3; PbO0.94Sr0.06(Ti0.48SrO0.52)O3; and Pb0.94(Ti0.48Sr0.52)O3. In some cases, the substrate may comprise a piezoelectric coating material, such as ZnO or AlN, applied to a non-piezoelectric material, such as a silicon or silicon carbide surface used in a micromachined device. The piezoelectric properties of these and other suitable materials are provided in CRC Handbook of Materials Science, Vol. III, Charles T. Lynch, CRC Press: Boca Raton, 198 (1975).
The sensing portion of an acoustic wave device of the invention is the area under the chemoselective layer, where the chemoselective layer covers the transducer. The area of the sensing portion of such a device can be on the order of about 0.0001-10 cm2.
An optical waveguide chemical sensor consists of a light source, an optical waveguide, a chemoselective film or layer, and a detector to analyze the light after interacting with the layer. The waveguide is used to propagate light to a sensing portion of the device that contains the chemoselective layer. The light travels towards this coating and interacts with it. If the analyte being detected is present in the layer, the optical characteristics of the light may be altered, and the change is detected by some optically sensitive detector. In certain cases, the chemoselective layer may consist of a composite of polymer and one or more dyes.
An optical chemical sensor, commonly referred to as an optrode, includes a light source such as a semiconductor laser, light-emitting diode, or a halogen lamp; an optical waveguide such as a fiber optic or a planar waveguide substrate; a chemoselective layer deposited on the sensing portion of the optrode exposed to an analyte; and a detector to monitor the optical characteristics of the optrode. Sorption of the analyte to the chemoselective layer modifies the optical characteristics of the optrode, and this is detected as a change in refractive index or light intensity at one or more wavelengths of light. Thus, for optical sensors, optical fibers and optical wave guides are useful and are known in the art.
Fiber optic waveguides for sensor applications are commonly manufactured from silica glass or quartz as the core of the fiber. Surrounding this core is a cladding material that exhibits a lower refractive index than the cladding to achieve internal reflectance. The chemoselective layer is typically applied at the distal tip of the fiber optic or along the side of the fiber optic where a portion of the cladding material has been removed.
Planar waveguide optical sensors use a planar substrate device as a light guide. The use of a planar waveguide normally involves the use of evanescent wave techniques to take advantage of the large active surface area. Many of these sensors use the fluorescent properties of a chemoselective layer and are thus called Total Internal Reflection Fluorescence (TIRF) sensors.
Preferably, SAW devices are used as the substrate for the device of the invention. Particularly preferred SAW devices are 915 MHz two-port resonators made of ST-cut quartz with aluminum metallization and a thin silicon dioxide overcoat. SAW resonators and oscillator electronics to drive them are available from RF Monolithics and SAWTEK Inc.
Before application of a coating to form the sensor portion of the device of the invention, the substrate is cleaned. The cleaning procedure typically involves rinsing the device in an organic solvent and then subjecting it to plasma cleaning, as is well-known. Optionally, the substrate can be silanized with a material such as diphenyltetramethyldisilazane (DPTMS) by immersing the cleaned substrate surface in liquid DPTMS, placing the immersed surface into a partially evacuated chamber while heating the device to about 170xc2x0 C. for about 12 hours. The silanized substrate is then removed and solvent cleaned with, for example, toluene, methanol, chloroform, or a physical or serial combination thereof, before applying the layer of the sensor portion of the device.
The method used for coating the compounds of the invention onto a substrate is not critical, and various coating methods known in the art may be used. Typically, the coating is applied to the substrate in solution, either by dipping, spraying or painting, preferably by an airbrush or spin coating process. The concentration of the compound of the invention in the coating solution should be sufficient to provide the viscosity most appropriate for the selected method of coating, and may easily be determined empirically. The solvent used, although not critical, should be sufficiently volatile as to facilitate quick and easy removal, but not so volatile as the complicate the handling of the coating solution prior to being deposited on the substrate. Examples of useful solvents include, for example, hexane, chloroform, methanol, toluene, tetrahydrofuran, and water. J. W. Grate and R. A. McGill in Analytical Chemistry, Vol. 67, No. 21, 4015-19 (1995), the subject of which is incorporated herein by reference, describe making chemical acoustic wave detectors by applying a thin film to a surface acoustic wave device. The thickness of the chemoselective layer preferably does not exceed that which would reduce the frequency of a chemical sensor operating at 250 megahertz by about 250 kilohertz and, typically, is in the range of about 0.5 nm to 10 microns, preferably in the range of 1 to 300 nm.
The coating may comprise a single layer or multiple layers. With multiple layers, a layer containing the compound of the invention may be combined with at least one other layer that provides pores suitable for physically eliminating some chemical species of large size that are not to be monitored.
The process of sorption plays a key role in the performance of chemical sensors for gas phase analysis. For example, microsensors, which consist of a physical transducer and a selective sorbent layer, sense changes in the physical properties, such as mass, in the sorbent layer on the surface of the transducer, due to the sorption of analyte molecules from the gas phase into the sorbent layer. Coating material properties that are known to elicit a detectable SAW sensor response are mass (i.e., as determined by the thickness and density of the coating), elasticity, viscoelasticity, conductivity, and dielectric constant. Changes in these properties can also result in changes in the attenuation (i.e., loss of acoustic power) of the wave. In some situations, monitoring attenuation may be preferable to monitoring velocity. Alternatively, there are some situations where simultaneously monitoring both velocity and attenuation can be useful. In any event, it is the modification of the sensed properties of the sorbent layer, as a result of analyte sorption, that results in the measurable response when analyte molecules are present in the gas or liquid phases being monitored. SAW devices coated with compounds of the invention are capable of detecting mass changes as low as about 100 pg/cm2. Further, vapor diffusion is rapid providing fast detection capability in a sub second time frame.
Sensor selectivity, the ability to detect a chemical species in an environment containing other chemical species, is generally determined by the ability of the coated layer to specifically sorb the species to be detected to the exclusion of others. For most coatings, selectivity is obtained based on providing stronger chemical interactions between the coated layer and the target species than occurs between the layer and species that are not to be detected. The method of selectively detecting the presence of a chemical entity within an environment comprises (a) placing the sensing portion of the device of the invention in the environment and (b) detecting changes in the coated layer of the sensing portion of the device. The environment may be gaseous or liquid.
More than one device may be provided. For example, a plurality of sensor portions could be used in a sensor array with, e.g., associated control devices and software, in a manner similar to conventional procedures employed with sensor arrays.
After an initial sensing has taken place, the coated sensor layer can be purged or cleaned by a second stream, allowing sensing of a new third stream to take place. For example, air, water- or acid-base solutions could be used as purging or cleaning solutions, depending on the species being detected and the nature of the layer.
In the devices and methods of the invention, the compounds are excellent sorbents for both hydrogen bond basic vapors, such as organophosphorus compounds, and also for nitroaromatic materials, such as explosives. It is expected that the chemical sensor systems of the present invention could weigh between 1-32 ounces and could, therefore, be easily mounted on a remote or robotic vehicle for automatically detecting buried explosives or munitions. Alternatively, such a device would also be useful for remotely detecting chemical agents or explosives secreted upon a person intending the destruction of private property and/or personnel, such as, for example, at crowded public places like airports or arenas where terrorist activities may be suspected.
If desired, it is possible to increase the concentration of explosive vapors contained in the area being monitored, i.e., speed up their release from buried or otherwise hidden munitions or explosives, by irradiating the area with electromagnetic radiation. Increasing the concentration of vapor in the soil or other environment surrounding a munition will produce a stronger signal following the reaction with sensor portion of the device of the present invention.
The chemoselective, siloxane polymers of the invention exhibit high selectivity and sensitivity toward nitroaromatic vapor, due at least in part to the sensitivity and selectivity of the multiple 1,1,1,3,3,3-hexafluoroisopropanol groups that are present. The presence of these functional groups is also directly responsibility for the sensitivity of these materials to hydrogen bond basic vapors. The functionalized polysiloxane compounds of the invention also have the advantage of high-yield preparation methods, ready purification, in addition to having an increased density of functional groups, as compared with polymeric coatings.
Moreover, the flexibility in the synthesis of these materials allows one to tailor a wide variety of related chemoselective compounds.

Linear and branched chemoselective siloxane polymers and methods for use in analytical and purification applications

Abstract: wherein:

Abstract: n is an integer greater than 1;

Abstract: wherein at least one of R1 and R2 includes an alkyl, alkenyl, alkynyl, or aryl group having at least one halogen substituted alcohol or halogen substituted phenol group attached thereto;

Abstract: Z is a polymer end group independently selected from the group consisting of saturated hydrocarbons, unsaturated hydrocarbons, alkyl silanes, aryl silanes, hydroxyl, hydride, alkoxides, halogen substituted alcohol, halogen substituted phenol, and combinations thereof.

Abstract: These polymeric materials are primarily designed to sorb hydrogen bond basic analytes such as organophosphonate esters (nerve agents and precursors) and nitro-substituted compounds (explosives).

The United States of America as represented by the Secretary of the Navy


Materials and methods for preparing reactive lignin and for preparing a bio-based adhesive are described herein.

Lignin is the second most abundant natural polymer behind cellulose, yet lignin has very little commercial value despite years of research. Lignin is one of the major components of the cell wall in wood and other plant based materials such as hemp or crop wastes. It is produced in enormous quantities each year, primarily as a by-product in the pulp and paper industries. Lignin has little economic value and the majority of lignin is burned as a low grade fuel or is discharged into the aquatic ecosystem as waste, causing a significant impact on the environment. For example, the majority of the Biological Oxygen Demand (BOD) from pulp mill effluents is due to waste lignin. In addition, an increase in the production of cellulosic ethanol from corn stalk and other biomass resources will add significantly to this glut of lignin.
This tremendous oversupply of lignin presents an enormous opportunity for the development of renewable biomaterials to replace non-biodegradable petroleum-based products, and the present disclosure provides for commercially-viable and inexpensive methods of making reactive lignin that can be used to make a wide variety of lignin-based products.
In a similar vein, there is a growing demand for developing non-petroleum-based materials to replace traditional plastics. There is a critical need to replace the commonly used formaldehyde-based resins found in many building materials such as plywood and particle boards. Formaldehyde-based resins have raised alarming health concerns because formaldehyde is highly toxic, allergenic and a classified carcinogenic. The off-gassing of formaldehyde-based resins is a significant source of indoor air pollution, particularly from formaldehyde pressed-wood products.
Thus, this disclosure also describes the development of a class of formaldehyde-free, bio-based reactive adhesives for binding renewable biodegradable material such as lignin, cellulose, wood chips and crop waste to fabricate useful solid materials and composites.

Methods of making and using lignin derivatives


A communications handset support for handless operation of a handheld communications device including a cradle assembly for releasably receiving and supporting the communications handset. The cradle assembly including a pair of elongate spaced-apart rods wherein a first resilient one of the elongate rods is fixed along a portion of its length so as to be cantilevered. A clamp is supported upon the pair of spaced-apart rods that includes a semi-hollow beam having a central passageway and that is supported a second one of the elongate rods. An adjustable beam is slidingly received within the central passageway of the semi-hollow beam, and is fastened to an end of the first resilient one of the rods so that when the adjustable beam is slid outwardly and away from the semi-hollow beam, the first resilient one of the rods is biased thereby gripping a portion of the communications handset.

Telephone handsets are devices commonly used to receive telephone voice transmissions and to send user voice data. The term "handset," as used herein, refers to any communication instrument equipped with a receiver and a transmitter that enables a user to receive and transmit data, regardless of the type of data transmitted or received, be it analog or digital, or the means by which the data is routed, be it over a traditional telephone line, radio waves, coaxial cable, voice over IP, Ethernet, fiber optics, or any other means used now or contemplated in the future for transmitting and receiving data. Handsets have been used in a plethora of different devices, including conventional corded telephones, cordless telephones, modular cellular mobile telephones, or any other portable communication device found in the marketplace. During a telephone call, a person typically holds the telephone handset in one hand so as to position it in close proximity to the person's ear and mouth for the duration of the telephone call. While this is not an especially laborious task for the user, it nonetheless severely limits the user from carrying out other activities during the telephone call that would otherwise require the use of both of the user's hands.
People frequently use telephone handsets, particularly cordless and mobile telephones, to carry on conversations while engaged in other activities. These activities include, for example, using a computer, cooking, cleaning, walking, driving a motor vehicle, etc. With the increased prevalence and use of mobile telephones and other portable communication devices, there is a growing need for users to operate such devices without the use of their hands, thereby allowing users to carry out other tasks simultaneously. For example, mobile telephone users may have the need to talk on a mobile telephone and drive a vehicle at the same time. For safety purposes, it is advantageous for a driver to use both hands while driving and not have to hold a mobile telephone with one hand and drive with the other hand. Likewise, while talking on a mobile telephone, a mobile telephone user may need to carry out tasks that require both hands, such as typing on a computer or carrying out other administrative tasks. Many of these activities can be performed easier, more efficiently and safer via the use of two hands rather than the use of one hand. By being able to utilize both hands while talking on a mobile telephone or other such communication device, a user is able to increase efficiency and productivity. An apparatus and method that would allow hands free use of a telephone handset would ameliorate the problems prevalent in the prior art.
A number of telephone handset holders have been suggested and developed in the prior art in an effort to address the need to utilize such devices without the use of an individual's hand. One such attempt to resolve the above-described problem is provided in U.S. Pat. No. 4,048,453, issued to Seidel, which discloses a telephone handset support device. The device employs a standard headband, which fits over the user's entire head. One portion of the assembly is secured to the telephone earpiece via a one-piece molded plastic component. The telephone is attached to the headband assembly by unscrewing the telephone earpiece and inserting the earpiece section between the handle portion of the telephone hand set and the removable earpiece, before re-screwing the telephone earpiece. A user apparently must wear a large and inflexible headband, which is cumbersome and difficult to transport. Furthermore, the device can only be used with traditional non-mobile telephones, and cannot be used with more modern mobile telephones due to the lack of a removable earpiece found in devices.
A similar attempt to the Seidel patent is found in U.S. Pat. No. 4,121,061, issued to Donaldson. The telephone handset holder disclosed in Donaldson comprises a band that fits over the user's head and that connects to the telephone handset via a permanently affixed flexible joint. As with previous attempts to create user friendly telephone holding devices, the device disclosed by Donaldson does not completely solve the problems found in the prior art. The headband that supports the telephone is large in size and difficult to transport. In addition, the device disclosed by Donaldson requires the permanent installation of a flexible connector joint to the phone. Installing such a connector joint is time consuming and adversely affects the appearance of the phone by adding unnecessary weight to the mobile phone and disrupting a mobile phone's otherwise ergonomic design. Other U.S. patents have also disclosed a headband and a coupling mechanism fitted to the exterior of a telephone handset. For example, U.S. Pat. No. 4,881,256, issued to Malekos, discloses the use of a movable ball and socket coupling device which is attached to the exterior of the telephone handset. As with other prior art attempts, the device disclosed by Malekos adversely affects the design and appearance of the telephone handset, and consequently fails to adequately solve the problems found in the prior art.
Other prior art efforts have recognized the problems in using rigid head bands to support the telephone handset. In U.S. Pat. No. 4,367,378, issued to Jordan, a telephone holder is disclosed that comprise a rigid one-piece handset that affixes to a user's head via a flexible elastic band. The elastic band is connected to the telephone receiver by means of Velcro®. While the use of an elastic band solves the problem of transporting a rigid headpiece, the use of Velcro® to attach the elastic band to the telephone is not advantageous. Proper use of the handset disclosed by Jordan requires the installation of a Velcro® fastening component to the face of the telephone, which adversely affects the telephone's appearance and is not desirable to the end user. The use of Velcro® to bind a telephone handset to a holding device is also cited in other U.S. patent applications. For example, U.S. Pat. No. 5,689,558, issued to Osgood et al., discloses a telephone hand set holder that mounts to the user's head or headgear via the hock and loop fasteners that typically embody Velcro®. Just as with other prior art attempts that employ Velcro® to bind a telephone handset to a holding device, the support provided by Velcro® fails to adequately support the weight of most telephone handsets, thereby creating a large likelihood that the telephone handset could fall and become damaged.
Some prior art telephone handset holders have employed alternative means of supporting a telephone handset other than the use of a head band fitted around the user's head. For instance, in U.S. Pat. No. 4,802,211, issued to Huntley, the telephone handset is supported via a structure that fits over the user's head, rests on the user's shoulders, and is secured to the user via an adjustable strap that fits under the user's arms. The support structure is made of metal and has a rectangular is shape comprising two L-shaped components fitted with a vertical phone support cradle attached to one end of one of the L-shaped members. While the structure disclosed by Huntley enables a person to use a telephone without support from the user's hand, the structure is bulky, immobile, and time consuming to properly attach to the user.
Likewise, U.S. Pat. No. 4,821,317, issued to Wong, discloses a telephone handset support device that uses a combination of an elastic headband and a retractable metal rod to support the telephone handset. The elastic telephone support device disclosed in Wong comprises an extendable elastic loop that is placed around the user's head to support the upper end of the telephone headset, while an extendable support rod rests on the shoulder of the person to support the lower end of the telephone hand set. Both the elastic loop and the extendable support rod retract into the interior of the handset. Although the telephone support device disclosed by Wong is easier to carry and use than other prior art attempts to create a telephone support device, the device still has its deficiencies. The device only works with traditional telephone handsets, and does not work with more modern mobile phone embodiments because the extendable support rod does not fit in the interior of a mobile phone or other such communication device.
Other prior art attempts have employed various permutations of previous prior art efforts. U.S. Pat. No. 5,407,113, issued to Golliher, discloses a hands free telephone support device comprising an elongate strap that fits over the top of the user's head and wraps around the user's chin. Each end of the elongate strap is affixed to an end of the telephone receiver, with one end affixed via Velcro® and the other end of the elongate strap wrapped around the opposite end of the telephone receiver. The elongate strap is fully adjustable to a variety of head sizes, and can be used on the left or right ear of an individual, and used on a variety of different telephone types and/or telephone receivers. While the invention disclosed by Golliher attempts to solve some of the deficiencies found in other prior attempts, the device disclosed in Golliher is still flawed. The Golliher telephone support device comprises several pieces, requiring a user to put the device together before being able to speak into the phone without the use of the user's hands. This solution is inconvenient for the user and requires the expenditure of an inordinate amount of time. Moreover, because the elongate straps wrap around a user's chin and mouth area, a user's speaking patterns may become impeded and garbled due to the device's restrictive strap.
There have been some prior art efforts to create a telephone handset holding device that can specifically be used in conjunction with mobile telephones. For example, U.S. Pat. No. 5,668,869, issued to Zinno, discloses a mobile telephone handset holder that can be used in a motor vehicle. The mobile phone is supported via a device that slides onto a standard car seat belt. While the invention disclosed in Zinno provides adequate support for a mobile telephone, its limitations are clear. The mobile telephone holder disclosed by Zinno can only be used in a car and can not be utilized by a mobile phone user outside the car. Moreover, the positioning of the mobile phone holder is limited by the position of the seatbelt, thereby severely affecting the possible range of desired positions for the mobile telephone.
U.S. Pat. No. 5,729,615, issued to Yang, discloses an earphone for a mobile telephone handset that fits in the user's ear via a hanger. Yang incorporates a separate speaker element that fits into the user's ear and that must also be connected to the mobile phone via a cord and plug. Although the earphone is easy to transport, it nonetheless requires an additional means of attaching the mobile phone to some other part of the user's body to properly allow the user to utilize the mobile phone without the use of the user's hand. The various components are cumbersome and require multiple installation steps before the user can answer an incoming call or make an outgoing call.
U.S. Pat. No. 6,374,090, issued to Morales, discloses a cellular telephone handset holder that uses a clamp gripping device to support the sides and bottom of a mobile phone, before clipping it to a user's ear. The handset holder comprising multiple pieces and has an inner and outer clip portion that "pinches" the front and back lobes of a user's ear. The Morales' device apparently only works with mobile telephones that are "single piece," i.e., a phone without any movable components or a phone that doesn't have a "flip open" feature, which is found in many modern mobile telephone handset embodiments. Consequently, the invention disclosed in Morales is limited in use and does not adequately account for the various different types of mobile telephone handset shapes and sizes that permeate today's marketplace.
U.S. Pat. No. 6,639,985, issued to Liu, discloses a phone that utilizes an ear hanger assembly that hangs from a user's ear. While the invention disclosed in Liu addresses some of the problems found in the prior art, it nonetheless requires the permanent installation of the phone hanger to the mobile phone. Consequently, a user is required to physically attach the phone hanger to the mobile phone, adding extra time and cost. Moreover, permanently attaching the phone hanger to the telephone adds unnecessary thickness, girth and weight to the mobile phone, which is disadvantageous given the growing trend of mobile phone manufacturers creating lightweight and slim mobile phones to satiate consumer demand for compactness.
There is a need for a mobile telephone handset holding device that is small in size, easy to transport, requires little to no assembly and does not adversely affect the appearance or design of the mobile telephone. Moreover, there is a need for a mobile telephone handset holding device that can be used on a plethora of different types of mobile telephone models or other portable communication devices and that can account for variations in shapes, sizes and methods of operation.

Ear mount assembly for a communication device