A head and neck support for salon shampoo bowls is disclosed. The device is constructed and arranged to support a client""s head and neck over a shampoo bowl in order to reduce the likelihood of strains and discomfort to the client and the hair stylist. The head and neck support is constructed to be received within a shampoo bowl and suspended by a strap provided with grasping elements for being passed over the sides of the bowl, and a hook like extended tongue passed through and supported by a neck depression defined within a front wall of the bowl.

The invention relates in general to the health and beauty industry, and devices used therewith. More particularly, the invention relates to a head and neck support for use in supporting the head of a person over a salon shampoo bowl while receiving a shampoo or other hair or facial treatments.
As known, the clients of a beauty salon, for example, who receive any type of a treatment or procedure which requires the washing or wetting of their hair, or a facial treatment, typically recline in a chair and place their neck through and onto a U-shaped opening formed in the side of a shampoo bowl, and lean their head back into the bowl. Without support, this posture causes the neck of the client to lie at an unnatural angle and may strain the client""s neck, spine, and back muscles. The weight of the client""s head with wetted hair combined with the forces exerted by a cosmetologist applying treatment or washing the hair can hyperextend the client""s neck causing strain to neck muscles, damage to cervical vertebrae, and retard the flow of oxygen to the brain causing strokes or transient ischemic attacks.
Salon sink radiculopathy, or injury to nerve roots leading from the spinal cord to the extremities, is a medical condition believed to pose an increased risk of injury to people with problems such as arthritis or prior neck injuries resulting from traffic, work, or sports accidents. Treatments for radiculopathy include medication, therapy, and even surgery. To prevent neck and spinal discomfort or injury to a client, therefore, a cosmetologist oftentimes has to physically grasp and support the client""s head during any such treatments or procedures which in turn induces a strain in the cosmetologist""s back, neck, and arms, and may also lead to him/her coming into contact with the chemicals and/or solutions being used for the client""s treatment.
Prior attempts have been made to deal with this problem. For example, the patent to Page, U.S. Pat. No. 5,862,542, discloses a shampoo headrest with a support post atop of which is a cup onto which the client lays their head. The cup provides some support for the client""s head, and allows the cosmetologist to use both of their hands during a hair care treatment, for example. Problems with the device of the ""542 patent, however, are that it appears to be complicated to install, does not provide any neck support for the user, provides little support to the entire head as the client""s head rests only on the small area of the cup, and there is little room allowed for the client to turn their head without otherwise falling off of the support. Moreover, as the cosmetologist must lift the client""s head for rinsing, the design of the device makes it difficult to rinse the client""s hair, and it appears this device would be uncomfortable for use with perm rollers and the like.
U.S. Pat. No. 5,177,820 to Varallo, discloses a hairdressing head support which mounts on a shampoo bowl. The head support holds the client""s head upright while partially enveloping the client""s head. The device of Varallo has disadvantages in that the customer""s head appears to remain upright, thus allowing the client""s face and/or shoulders to get wet when their hair is being washed and/or rinsed. The ""820 device is also complex with many parts to adjust, and makes the rinsing and moving of the client""s head difficult.
Another headrest for shampoo bowls and sinks is disclosed in U.S. Pat. No. 5,239,711, which illustrates a rectangular mesh strip which spans a shampoo bowl and attaches to either side thereof. The mesh strip may be adjusted to fit varying sizes of bowls and may be moved to various positions relative to the front of the bowl. The disadvantages of this device, however, are that it provides no support to the client""s neck, cannot be adjusted in height, perm rods and rollers, and possibly the stylist""s fingernails, may get caught in the device, the client""s hair may also could get caught in the device, and the device makes it difficult to rinse the client""s hair.
The sealed neck support for shampoo bowls of U.S. Pat. No. 4,649,580 is adapted to be installed in the U-shaped indention in the side of a shampoo bowl, and is designed to cushion the client""s neck. The product clips onto the U-shaped portion of the bowl opening, and has a membrane which forms a leak barrier to keep the client from getting wet. A disadvantage of the ""580 device, however, is that it does not provide support for the client""s head as it only cushions or seals against the neck in the U-shaped opening.
U.S. Pat. No. 4,998,303 illustrates a head support for a salon basin having a perforated headrest plate that sits inside the shampoo bowl, and is formed to be concave to fit the client""s head. The plate is attached to the front rim of the bowl with bendable hooks and is further supported by a threaded support member which is adjustable in length and engages the inner surface of the bowl. The device of the ""303 patent appears to be shaped in such a manner so as to not allow the client""s head to turn completely from side to side during shampooing or rinsing. Further, the holes in the plate appear to be large enough to allow hair to pass therethrough during hair treatment procedures, the device provides no support to the neck, and the height of the device relative to the top of the shampoo bowl cannot be raised or lowered for various hair and facial treatments.
The permanent wave headrest attachment of U.S. Pat. No. 4,352,216 was designed for supporting the head while rinsing permanent waves. This device provides a plastic frame covered with a mesh panel to support the head. The device hooks to the shampoo bowl via a rigid strap hanger which adjusts to fit various bowls. The design of the ""216 patent appears to be such that hair and rollers would easily be caught in the mesh panel, however. In addition, the device is suitable for use only for a shampoo bowl with a downturned lip at an outer edge, therefore use of the device with a bowl of alternate edge construction does not appear possible.
What is needed, but seemingly unavailable from the known devices, is a head and neck support adapted for use as a salon sink or shampoo bowl, that can be easily fit to any such sink or bowl, and which fully supports the head of a client to prevent hyperextehsion of the client""s neck and damage to cervical vertebrae. Also needed is a head and neck support so constructed and installed that a cosmetologist or other beauty care professional need not physically support the patron""s head during the desired treatments or procedures.
An improved head and neck support for use with a salon shampoo bowl which overcomes some of the design deficiencies of the art is disclosed. The head and neck support of this invention is constructed and arranged to be suspended within the shampoo bowl and to support a salon client""s head over the shampoo bowl in hands-free fashion with the client""s neck in a neutral position, and which also will reduce the likelihood of strains and discomfort to both the client and the hair stylist.
This is accomplished by providing a head and neck support for use with a shampoo bowl comprising a head support piece, at least one elongate strap, and at least one, and preferably a pair, of grasping elements affixed to the at least one strap. The grasping elements are each sized and shaped to be passed over the edge or lip of the shampoo bowl side walls, and the support piece is suspended within the bowl by the at least one strap and the grasping elements as they each grasp the top edge of the shampoo bowl side wall(s), and by an elongate tongue extended from the support piece which is sized and shaped to be passed through and supported on a U-shaped neck depression or opening defined within a front wall of the shampoo bowl. The support piece may also comprise an elongate shelf with a series of slots defined therein for passing the at least one strap therethrough.
The head and neck support device of this invention, constructed and suspended within the shampoo bowl as described above, may thus be raised or lowered relative to the plane of the shampoo bowl by adjusting the length of the at least one strap, which thus enables the position of the client""s head to be changed during various hair and/or facial treatments. The shape of the head pan allows clients to easily turn their head during a hair treatment without the head otherwise falling off of the head and neck support, or otherwise catching any rollers, perm rods, and other accessories used for either the hair or facial treatment the client is receiving. The device is also designed to allow the hair and the head to be easily rinsed, and may be used for multiple procedures, such as shampooing, rinsing, perms, waxing, facials, and the like.
The design of the head support piece also allows the cosmetologist to move their hands freely about the client""s head and within the bowl, and allows the cosmetologist to use both of their hands during any such procedures without having to otherwise physically support the client""s head themselves, thus reducing the likelihood of back and neck strain to the cosmetologist. An additional feature of the head and neck support device of this invention is that it also allows cosmetologists to minimize the contact of their hand(s) with any harsh chemicals, for example a bleach, that might be used in the treatment the client is receiving as the hand(s) are not used to support the client""s head.
The head and neck support is preferably made of durable materials which will be impervious to chemicals of the type used in the salon, yet comfortable to the user when their head is received thereon and supported during the desired beauty care treatments. The device is designed to fit a wide variety and size of shampoo bowls, and the tongue of the support piece is narrow enough to fit in nearly all U-shaped neck openings of such shampoo bowls, yet is still wide enough to provide adequate and comfortable support for the client""s neck during the use of the device. The arc of the neck piece has also been shaped to provide the client maximum comfort, and the device is easily cleaned.
The head and neck support also includes a shelf extended therefrom and through which the strap or straps used with the device is/are threaded, and ribbing on the underside of the head support piece to provide maximum strength thereto. The device is simple and easy to install within and remove therefrom virtually all known types of shampoo bowls.

Head and neck support for salon shampoo bowl


An improved device for reflecting, radiating, or receiving electromagnetic radiation, acoustic waves, or other energy forms through the use of a membrane stretched across a lightweight, round, frame structure. A near perfectly round and flat semi-rigid backplane surface (1) and a near perfectly round ring or stack of rings (2) are mutually reinforced, forming a raised circumferential planar surface, and a cavity within. A membrane (3) is attached to the top of the rings, forming one wall of a sealed chamber. A source of sub-ambient pressure (4) is applied to the chamber, causing a primary uniform deformation in the membrane for the purpose of manipulating electromagnetic radiation, acoustic waves, or other energy. The backplane surface also deforms uniformly, increasing the strength of the structure. A flat, rigid floating batten (5) prevents waves or wrinkles from forming in the membrane material. A circumferential heating element (6) and insulation (7) provides tensioning of the membrane by slightly controlling the circumference of the device.

Membranes, esp. polymeric membranes, provide an economical method of presenting large surfaces to electromagnetic, acoustic, or other energy, for the purpose of absorbing, reflecting, focusing, or other manipulation of this energy.
Flint (U.S. Pat. No. 2,300,251, 1941) describes fabricating a lens by using two transparent membranes with a clear fluid between. Focal adjustment is made by mechanically adjusting the frame, or by varying the fluid pressure between the membranes, or diaphragms.
Membranes have also enabled the design of inexpensive mirrors when a membrane is coated with a reflective coating, and then are stretched over a suitable frame.
Martinez (U.S. Pat. Nos. 3,687,524, 3,757,479, and 3,877,139 1972-1975) described a flat "glassless" mirror stretched over a sheet metal "pan".
Additionally, the shaping of such stretched reflective membrane mirrors into a concave or convex lens shape enables the mirror surface to now become a reflective lens with an approximate spherical/parabolic shape useful for radiating, receiving, reflecting or focusing electromagnetic radiation or acoustic waves. A concave shape may be established by applying a vacuum within the sealed chamber formed by the membrane and it's supporting frame. A convex shape can be established by applying a positive pressure within the sealed chamber. For space-based applications where near vacuum ambient conditions exist, a second clear membrane may be placed over the reflective membrane, and positive pressure introduced between the two membranes to induce a concave shape into the reflective inner membrane.
Such designs have been suggested for use in solar concentrating dishes, radio antennas and also for imaging applications such as telescopes and holographic projection.
Prior art with reference to utilizing a stretched membrane material as a lens, or reflective lens include:
Pajes (U.S. Pat. No. 2,952,189, 1960) designed a drum which is evacuated to induce a concave shape.
Kopitko (U.S. Pat. No. 3,031,928, 1962) described a dual diaphragm system and a controlling method to maintain curvature.
Bochmann (U.S. Pat. No. 3,610,738, 1971) depicted an arrangement whereby a diaphragm was pulled by a cam to induce a vacuum, and hence concave shape.
Brantley, Jr. et al, (U.S. Pat. No. 4,033,676 1977) depicted two hoops separated by vertical strut members. The two membranes form a cavity inside the circumference, and membranes also form a pressure barrier around the strut members. The frame function is separate from the sealing pressure barrier.
Kojabashian (U.S. Pat. No. 3,880,500, 1975) described a frame design and a method utilizing two films that equalize the pneumatic forces on the supporting structure.
Soliday, et al. (U.S. Pat. No. 5,680,262 1997) utilizes a tubular frame of square cross section, and describes a tensioning method for the stretched membrane utilizing a plurality of pneumatic cylinders.
Carreras, et al (U.S. Pat. No. 6,332,687, 2001) describe utilizing a vacuum for primary deformation, and also using an outer mechanical ring and central plunger to achieve a more parabolic shape.
Each of these designs utilized some type of frame over which the reflective membrane is stretched:
Pajes (U.S. Pat. No. 2,952,189, 1960) and Bochmann (U.S. Pat. No. 3,610,738, 1971) utilized a drum design.
Kopitko (U.S. Pat. No. 3,031,928, 1962) utilized two parallel plates, with the film stretched at the midpoint.
One problem with previous designs is that although the reflective membrane affords an inexpensive method of presenting and manipulating large surfaces for the purpose of directing electromagnetic radiation or other energy, the framework for the membrane must be very strong to withstand the considerable pneumatic forces required to establish the membrane shape with minimal distortion. The primary aim of the frame is to establish a nearly perfect round shape with a circumferential raised portion that establishes a near perfect plane for the attachment and sealing of a non-porous membrane to the frame structure. An internal cavity is required to allow for the deformation of the membrane material. These past designs often utilized heavy and expensive frames.
Kopitko (U.S. Pat. No. 3,031,928, 1962), and Brantley, Jr. et al, (U.S. Pat. No. 4,033,676 1977), Kojabashian (U.S. Pat. No. 3,880,500,1975), Leonhardt, et al (U.S. Pat. No. 4,352,112 1982), and Soliday, et al. (U.S. Pat. No. 5,680,262 1997) all address this problem by utilizing two membranes with the vacuum or pressure within, thus equalizing much of the resulting forces. This has the disadvantage in that since both membranes stretch, the frame needs to be of considerable width to prevent the two membranes from touching in the middle when a vacuum is applied. Also, the sole structural element becomes the outer ring or drum, which can still oval and warp, distorting the desired focus or other manipulation of the directed electromagnetic or other radiation. The ovaling stress is non-uniform, and also tends to exacerbate the formation of wrinkles or waves in the membrane surface.
Inflatable systems eliminate much of the weight problem, and add a portability function, but tend to experience more distortion.
Mcreary (U.S. Pat. No. 3,056,131, 1962) circumvents the frame with an inflatable dish with reflective material on the back side, and transparent material at the front.
Wladimir von Maydell et al. (U.S. Pat. No. 3,326,624) describes an inflatable mirror for use in space-based applications.
One object of this invention that is believed to solve many of these problems is an improved frame design, utilizing a combination of two basic geometric shapes (a ring and a flat plane) which are mutually reinforced to arrive at a lightweight, rigid and true structure for supporting the stretched membrane.
Leonhardt, et al (U.S. Pat. No. 4,352,112 1982) describe utilizing a circumferential ring or rings with a vertical member to increase height in a drum-like arrangement. The ring or rings, however are described with two membrane surfaces forming the top and bottom walls of the structure.
Ring reinforcement has been applied in the past for a wide variety of unrelated applications, such as rolling a lip into the rim of a paper cup, a formed lip of a jar lid, and as with the molded lip on a container or with flying discs:
Schmidt (U.S. Pat. No. 4,130,234, 1978) and others discuss improved methods of rolling a lip surface into a cup design for greater strength. The goal here is to economically increase the strength of the rim.
Sassak (U.S. Pat. No. 5,116,275, 1992) discusses a flying toy with a reinforcing lip, but molded in.
Weiss (U.S. Pat. No. 5,366,403, 1994) discusses utilizing a reinforcing ring to convert a disposable plate into a flying toy.
Gilliam, et al. 6,761,283 2004 and others describe molding a lip, or "brow ridge" into a container and closure for same as a way of increasing the strength.
The primary function of the ring in this invention is unique—to provide mutual reinforcement along with a backplane element for the purpose of establishing a nearly perfect round shape with a circumferential raised portion that establishes a near perfect planar surface for the attachment and sealing of the membrane. Further, the application of negative or positive pressure inside the proposed structure causes a uniform warpage of the backplane element, increasing the strength of the structure without distortion of the manipulated electromagnetic, acoustic, or other energy.
Another object of this invention are methods of preventing wrinkles when a stretched membrane (esp. of polymeric material) is tensioned in multiple directions, as when it is stretched over a frame in a uniform manner, and then pneumatically deformed.
Sail battens have been utilized for minimizing wrinkling of sails, and also for shaping sails into an ideal aerodynamic form. Also similar to this invention, sail battens float on (are solely support by) the stiffened sail surface.
Mauney (U.S. Pat. No. 2,743,510 1956) describes an inflatable batten, and also one that forms an arc, but not a complete circle
Leonhardt, et al (U.S. Pat. No. 4,352,112 1982) describes prestressing a diaphragm in order to eliminate folds, and also discusses various reinforcing strips for the purpose of altering the stressed membrane configuration. The reinforcing ring depicted forms only an arc, and is not completely annular.
Henderson (U.S. Pat. No. 5,333,569 1994) describes an inflatable sail batten
Baird (U.S. Pat. No. 5,095,837 1992) describes a ram air inflatable form for a spinnaker sail, again with a curved surface, but not a completely round surface.
None of this prior art relates to preventing wrinkles in 360 degree round structure through the use of a circumferential batten.
Another object of this invention is to provide a means of uniformly tensioning the reflective membrane without inducing distortion via the application of heat to the circumference of the ring. Ambient temperature changes may affect the membrane material in a different way than the supporting structure, due to differences in thermal coefficient of expansion. The membrane may remain tightly stretched at one ambient temperature, but become loose when the ambient temperature is lowered, or vica versa. This problem increases as the size of the structure increases.
Martinez (U.S. Pat. Nos. 3,687,524, 3,757,479, and 3,877,139 1972-1975) described a method of tensioning a membrane mirror surface through the application of heat to shrink the film. This is a one-time manufacturing process, however, as opposed to a method of controlling the tension to accommodate changing ambient temperatures.
Sallis, (U.S. Pat. No. 4,741,609 1988) described a tensioning method for a membrane reflector utilizing an inflatable bladder, but no thermal component is mentioned.
Deppert, et al. (U.S. Pat. No. 4,987,826 1991) describes a dynamic thermal tensioning method for a piston rod-to-cylinder sealing ring, but utilizing a fluid filling medium.
Moore (U.S. Pat. No. 5,590,497 1997) discussed mechanical circumferential tensioning of prestress cables in a concrete tank.
Smith, et al. (U.S. Pat. No. 5,813,830 1998) utilizes springs for circumferential tensioning of a carbon seal containment barrier system inside a turbine engine.
Henderson, et al. (U.S. Pat. No. 5,990,851 1999) discusses circumferential tensioning of a space-based antennae, but not by thermal means.
Papadopoulas (U.S. Pat. No. 6,716,017 2004) discusses circumferential tensioning of an embossing roll, but not by thermal means.


Acylated terminal aminoalkyl organopolysiloxane fluids exhibit improved color properties and wetting time properties while maintaining good hand, when used as textile softeners.

1. Field of the Invention
The present invention is directed to organopolysiloxane compositions useful as softeners for textile products, to a process for softening textile products with such compositions, and to the products thus treated.
2. Background Art
Textile xe2x80x9cfinishesxe2x80x9d represent a large commercial market. Many types of such finishes are available, and are formulated with specific reference to their end use. For example, many fiber lubricant compositions are available which lower the coefficient of friction of fibers during processing. Other textile finishes are applied to yarns and woven textiles to make these products water repellent, while still further compositions are added to wovens and non-wovens to impart increased strength characteristics. The present application is not directed to finishes generally, but to a particular class of finishes known as xe2x80x9csoftenersxe2x80x9d.
Softeners are applied to textile products such as fibers, yarn, wovens or non-wovens, to impart a soft feel, or xe2x80x9chandxe2x80x9d. This increased softness is readily perceptible to the ultimate consumer, and thus softeners represent important items of commerce. To be commercially acceptable, softeners must exhibit several important characteristics following application to a textile substrate. The textile will desirably possess a soft hand; the textile must be readily wettable; and the softener must not cause yellowing of the product.
The above characteristics are often conflicting, and it is difficult to obtain all these properties in a given softener composition. For example, organopolysiloxane fluids such as polydimethylsiloxanes (xe2x80x9cPDMS fluidsxe2x80x9d) are known to provide some improvement in softness. However, these products must be emulsified with considerable quantities of surfactants, which leave a residue which can cause undesirable changes in color. Use of organic solvents such as white oils in lieu of water allows elimination of surfactants. Use of organic solvents is not desirable, however. Moreover, the treated fabrics tend to be hydrophobic, with long wetting times, and only modest improvement of hand is achieved.
In U.S. Pat. No. 4,247,592 it is proposed to employ aminoalkyl-functional polyorganosiloxanes as fabric softeners. Such products require somewhat less emulsifier, and can produce an outstanding pleasing, soft hand. However, fabrics treated with compositions containing aminofunctional PDMS fluids are prone to yellowing over time, believed to be caused by oxidation of the aminoalkyl groups by atmospheric oxygen or ozone. A variety of proposals have been made to eliminate the yellowing problem. However, the majority of these either result in only modest improvement, or do so at greatly increased cost. Modest improvement in yellowing at some sacrifice of hand is disclosed by U.S. Pat. No. 4,978,363, wherein fatty acid salts of amimoalkyl-substituted organopolysiloxane are employed.
Softeners have been proposed where piperidinyl or morpholinyl moieties have been substituted for the readily available aminoalkyl functionality. An example is U.S. Pat. No. 5,540,952. However, the synthesis of such compounds tends to be difficult and expensive.
U.S. Pat. No. 4,507,455 discloses softeners prepared by N-acylation of organopolysiloxanes with pendant aminoalkyleneaminoalkyl groups. While these acylated softeners show improvements in yellowing behavior, their softening characteristics are not ideal. Indeed, in U.S. Pat. No. 4,978,561 and commonly assigned U.S. Pat. No. 5,100,991, it is stated that such acylated amino-functional silicone fluids do not provide a particularly soft hand, but rather impart a harsh feel. The ""561 and ""991 patents disclose acylation of pendant aminoalkyl and polyaminopolyalkylene organopolysiloxanes with lactones to produce N-(hydroxyalkyl)acylated products.
Neat N-acylated amino-functional silicones and silanes have been disclosed as being useful for coupling agents in fiber reinforced composites. In such applications, as typified by U.S. Pat. Nos. 2,929,829 and 3,440,261, neat silicone or silicone dissolved in volatile organic solvent is applied to glass fiber or carbon fiber reinforcement, glass microballoons, etc., prior to impregnating with thermosetting resin. The cured composites are said to exhibit greater strength characteristics due to increased adhesion between reinforcement and polymer matrix.
In U.S. Pat. No. 5,302,659 is disclosed a novel method of preparing N-acylated, aminoalkyl-functional organopolysiloxanes useful as softeners. In this process, organopolysiloxanes having hydroxyl-(silanol) or alkoxy-functional end groups and pendant aminoalkyl groups are reacted with an acyclic carboxylic acid anhydride or a cyclic dicarboxylic acid anhydride to form, in the former case, an N-acylated product having an
acyl group where R is alkyl, or in the latter case, a
group where R is alkylene or alkenylene. The N-acylation takes place in the dispersed phase, but requires a large amount of anhydride. Moreover, the products exhibit only modest improvement in hand over untreated textile, and a longer than desired wetting time.
It would be desirable to provide a softener composition which provides excellent softening, which is readily wettable, and which resists yellowing. Such a softener should also be manufacturable at a cost which is commercially viable.
The present invention pertains to softeners based on acylated aminoalkyl-functional organopolysiloxanes which are readily emulsifiable, and which produce fabrics with soft hand, rapid wettability, and high yellowing resistance. The softeners are amides formed by acylating xcex1,xcfx89-aminoalkyl-functional organopolysiloxane fluids.
The subject invention softeners are prepared by N-acylating (hereinafter, xe2x80x9cacylatingxe2x80x9d) xcex1,xcfx89-aminoalkyl-functional organopolysiloxane fluids. The degree of acylation may vary, but is preferably at least 50 mol percent based on moles of primary and/or secondary amino groups present, more preferably at least 75 mol percent, and yet more preferably 90 mol percent or more. Most preferably, all amino groups are acylated. The acylation produces amide groups, and may, in addition, produce a limited, minor amount of imide groups in certain instances. Imide groups are preferably absent.
The xcex1,xcfx89-aminoalkyl-functional organopolysiloxanes are preferably of the formula
XR2SiOxe2x80x94(XRSiO)mxe2x80x94(R2SiO)nxe2x80x94SiR2X
where X is an aminoalkyl group as defined hereafter, R is a hydrocarbon(oxy) group, and n and m are such that the fluid has a neat viscosity at room temperature from 1 cP to 100,000 cP. In the above formula, and in the claims, it does not depart from the spirit of the invention to include a minor quantity of RSiO3/2, XSiO3/2, or SiO4/2 moieties, so long as the product is substantially linear, i.e., remains a liquid at room temperature. The organopolysiloxane may also contain interspersed linking groups, preferably alkylene groups such as ethylene, hexylene, etc., or polyoxyalkylene residues bonded to Si either at an oxygen, or preferably at carbon of the polyoxyalkylene moiety.
In the above formula, R is preferably a C1-20 alkyl group, more preferably a C1-8 alkyl group or phenyl group, yet more preferably a methyl, ethyl, or phenyl group, and most preferably, methyl. In some formulations, some R may be alkoxy, preferably C1-8 alkoxy, more preferably C1-4 alkoxy, and most preferably methoxy or ethoxy, hydroxyl (xe2x80x94OH), substituted alkyl, e.g., haloalkyl, preferably chloroalkyl or fluoroalkyl. The nature of the various R groups is not overly critical, provided the advantageous properties of the softener are not affected thereby. A limited number of R may be polyoxyalkylene, i.e., pendant as opposed to xe2x80x9cin chainxe2x80x9d polyoxyalkylene groups.
Examples of preferred amino-functional radicals xe2x80x9cXxe2x80x9d are radicals of the general formula (II)
xe2x80x94R1xe2x80x94[NR2(CH2)a]bNHR2xe2x80x83xe2x80x83(II)
and ammonium salts thereof which can be prepared by reaction with mineral or carboxylic acids, in which
R1 is preferably a divalent C1- to C18-hydrocarbon radical,
R2 is preferably a hydrogen atom or an optionally fluorine-, chlorine- or bromine-substituted C1- to C18-hydrocarbon radical,
a has the values 2, 3, 4, 5 or 6 and
b has the values 0, 1, 2, 3 or 4.
Examples of the divalent C1- to C18-hydrocarbon radicals R1 are preferably unsaturated straight- or branched-chain or cyclic alkylene radicals, such as the methylene and ethylene radical, as well as propylene, butylene, pentylene, hexylene, 2-methylpropylene, cyclohexylene and octadecylene radicals, or unsaturated alkylene radicals or arylene radicals, such as the hexenylene radical and phenylene radicals, the n-propylene radical and the 2-methylpropylene radical being particularly preferred.
Examples of the hydrocarbon radicals R2 are preferably the examples mentioned for R. Examples of halogen-substituted hydrocarbon radicals R2 are haloalkyl radicals, such as the 3,3,3-trifluoro-n-propyl radical, the 2,2,2,2xe2x80x2,2xe2x80x2,2xe2x80x2-hexafluoroisopropyl radical and the heptafluoroisopropyl radical, and haloaryl radicals, such as the o-, m- and p-chlorophenyl radical. In the above general formula (II), preferably, R1 is a divalent C2- to C6-hydrocarbon radical, R2 is a hydrogen atom or a methyl or cyclohexyl radical, a has the value 2 or 3 and b has the value 0 or 1.
The aminoalkyl-functional organopolysiloxanes are commercially available or may be made by standard synthetic methods. For example, aminoalkyl-functionality can be introduced into silanol-terminated PDMS, e.g., HOxe2x80x94(Si(CH3)2xe2x80x94O)nxe2x80x94H by reaction with an aminoalkylalkoxysilane. Reaction of xcex1,xcfx89-silanol-terminated PDMS with aminoethylaminopropyldimethylmethoxysilane creates an xcex1,xcfx89-aminoethylaminopropyl-terminated PDMS. Reaction with both a mono-functional silane, for example, such a monofunctional silane and aminoethylaminopropylmethyldimethhoxysilane, a difunctional silane, creates a product with both terminal and pendant aminoethylaminopropyl groups. In addition to these synthetic methods, aminoalkyl-functional silicones may be made by equillibrating aminoalkyl-functional silicones of different molecular weights, by reaction of unsaturated amino-functional hydrocarbons with Sixe2x80x94H functional silicones, and other methods known to those skilled in the art.
Acylation of the aminoalkyl-functional silicones requires an acylating agent. While carboxylic acids such as acetic and propionic acids could theoretically serve as acylating agents with removal of water, such reactions are time consuming and energy intensive. Water must be removed to induce acylation. In the absence of removal of water, salt formation rather than acylation occurs. Use of acylating agents such as acylhalides is more rapid. The byproduct hydrogen halides may form salts with any remaining amino groups. It is preferable, however, to acylate employing carboxylic acid anhydrides such as acetic anhydride. In such cases, the byproducts of the reaction are carboxylic acids, which often assist in emulsifying the acylated product.
The acylation may take place neat or in suitable solvent. When carboxylic acids are used for acylation, toluene, xylene, or another organic solvent which forms an azeotrope with water liberated in the reaction may be used. In the case of acyl chlorides, similar solvents may be used, or solvents such as glyme, diglyme, and similar hydroxyethers or diethers may be used. Diethylene glycol bis(n-butyl ether) is a preferred solvent, particularly with acylation by carboxylic acid anhydrides.
The amount of acylating agent should be sufficient to acylate at least 25 mol percent of the acylatable amino nitrogens, preferably at least 33 mol percent, more preferably at least 50 mol percent. Most preferably the degree of acylation is in the range of 50 mol percent to 100 mol percent, most preferably in the range of 60 mol percent to 100 mol percent, and most preferably in the range of 75 mol percent to 90 mol percent or higher. While N-acylation is the expected reaction, particularly at low equivalent ratios of acylating agent to amino group, it is also possible to form a minor amount of imide groups, although this is not the preferred reaction. Imide formation is more likely when employing cyclic anhydrides under xe2x80x9cforcingxe2x80x9d conditions, i.e., with concurrent removal of water. Minor amounts i.e., less than 50 mol percent of total acylating agent, more preferably less than 30 mol percent, and most preferably less than 15 mol percent, may comprise cyclic anhydrides, preferably saturated anhydrides such as succinic anhydride. Ratios of anhydride to amino nitrogen in excess of 1:4 are preferred, more preferably in excess of 0.5:1, and most preferably in the range of 0.8-1.2:1.
Following acylation, the acylated product may, if desired, be washed with water to remove excess acylating agent and byproducts. For example, when employing acyl chlorides, byproduct HCl may be removed, or in the case of dicarboxylic acid anhydrides, byproduct carboxylic acid may be removed. Removal efficiency may be enhanced by use of basic aqueous washes, for example aqueous sodium hydroxide, sodium carbonate, or sodium bicarbonate. Washing of the product is not preferred.
The desired product will contain amide groups where the starting material contained amino groups. The amide groups preferably have the formula
in the case of primary amino groups, and
in the case of secondary amino groups. In these formulae, R4 is an optionally substituted C1-20 hydrocarbon group, more preferably a C1-4 hydrocarbon group. Suitable substituents are any which do not interfere with the preparation of the acylated product or which render the acylated product unstable. Examples are hydroxyl, cyano, halo, preferably chloro or fluoro, carboxylic acid, and the like. Most preferably, R4 is methyl or ethyl. R4 moieties containing carboxylic acid group substituents may be prepared by employing a cyclic anhydride. For example, use of succinic anhydride will generate xe2x80x94(CH2)2xe2x80x94COOH groups in the absence of imidization, while reaction with a cyclic lactone will generate a hydroxyalkyl R4 group. These groups are not preferred, however.
Thus, the preferred acylated aminoalkyl-functional silicones are those of the formula
where R, R1, and R2 have the meanings given heretofore, and R3 is H or
and at least 25 mol percent of R3 are
Preferably, the acylated products or the present invention are those of the formula
where R and R2 are defined as before, and are preferably methyl, and Z is an acylated aminoalkyl group
where R3 is R2 or
where R4 is preferably C1-4 alkyl, more preferably ethyl or methyl, and most preferably methyl, a is 2-6, preferably 0 or 1 and more preferably 1, and R1 is an ethylene or propylenediradical, i.e., xe2x80x94CH2CH2xe2x80x94 or xe2x80x94CH2CH2CH2xe2x80x94, m is 0 to 20, and n is 10 to 1000.
Most preferably, the acylated organopolysiloxanes of the subject invention are those of the formula
where Z1 is selected from the group consisting of
and salts thereof. The salts are formed by reaction of an acid, for example an acid liberated during acylation, with one or more nitrogen atoms. More preferably, the acylated products of the subject invention are polydhnethylsiloxanes having terminal aminopropyl-, aminoethylaminopropyl-, N-acyl-aminopropyl-, or N-acylaminoethylaminopropyl-dimethylsilyl groups, and optionally aminopropyl-, aminoethylaminopropyl-, N-acylaminopropyl-, or N-acylaminoethylaminopropyl-methylsiloxy units (pendant aminoalkyl or N-acylaminoalkyl groups). By the term xe2x80x9cN-acylxe2x80x9d as it modifies polyalkylenepolyamines such as aminoethylaminopropyl groups is meant that one or more of the nitrogens are acylated. It should be noted that the various siloxy groups, i.e. those with hydrocarbon, hydrocarbonoxy, or aminoalkyl-substituents, may be positioned in any order in the organopolysiloxane.
Following preparation of the acylated product, and optional purification, the resultant oil is emulsified into water. The solids content (by xe2x80x9csolids here is meant the active ingredient acylated product only) may range from as little as 5 weight percent based on total emulsion weight, to xe2x80x9cconcentratesxe2x80x9d having as much 50%, 60%, or 70% solids. However, it is preferably to produce working emulsions which may be used as delivered, or with only moderate dilution. Some manufactures may choose to add proprietary additives to the final emulsion or concentrate, for example mildewcides, bacteriostats, antistatic agents, or the like. Alternatively, these may be added following or during formulation of the emulsion. Most preferably, the emulsions contain from 10% to 40% solids, more preferably 15% to 30%. End use emulsions containing 15% to 25% solids are preferred.
The acylated amino-alkyl-functional organopolysiloxanes may be emulsified with known surfactants, including anionic, non-ionic, cationic, amphopteric, and the like.
Suitable anionic emulsifiers are, in particular:
1. Alkyl sulfates, especially those which have a chain length of from 8 to 18 C atoms, and alkyl ether sulfates which have 8 to 18 C atoms in the hydrophobic radical and 1 to 40 ethylene oxide (EO) or propylene oxide (PO) units.
2. Sulfonates, in particular alkylsulfonates having from 8 to 18 C atoms, alkylarylsulfonates having from 8 to 18 C atoms, taurides and esters and half-esters of sulfosuccinic acid with monohydric alcohols or alkylphenols having from 4 to 15 C atoms; in which the alcohols or alkylphenols can optionally be ethoxylated with from 1 to 40 EO units.
3. Alkali metal salts and ammonium salts of carboxylic acids having from 8 to 20 C atoms in the alkyl, aryl, alkaryl or aralkyl radical.
4. Phosphoric acid partial esters and their alkali metal salts and ammonium salts, and in particular alkyl phosphates and alkaryl phosphates having from 8 to 20 C atoms in the organic radical and alkyl ether-phosphates and alkaryl ether-phosphates having from 8 to 20 C atoms in the alkyl or alkaryl radical and from 1 to 40 EO units.
Suitable nonionic emulsifiers are, in particular:
1. Alkyl polyglycol ethers, preferably those having from 8 to 40 EO units and alkyl radicals of from 8 to 20 C atoms.
2. Alkylaryl polyglycol ethers, preferably those having from 8 to 40 EO units and from 8 to 20 C atoms in the alkyl and aryl radicals.
3. Ethylene oxide/propylene oxide (EO/PO) block copolymers, preferably those having from 8 to 40 EO and PO units.
4. Fatty acids having from 6 to 24 C atoms.
5. Natural substances and their derivatives, such as lecithin, lanolin, saponin and cellulose; cellulose alkyl ethers and carboxyalkylcelluloses, in which the alkyl groups each have up to 4 carbon atoms.
6. Straight-chain organo(poly)siloxanes containing polar groups, and in particular those containing alkoxy groups having up to 24 C atoms and/or up to 40 EP and/or PO groups.
Suitable cationic emulsifiers are, in particular:
1. Salts of primary, secondary and tertiary fatty amines having from 8 to 24 C atoms with acetic acid, sulfuric acid, hydrocholoric acid and phosphoric acids.
2. Quaternary alkylbenzeneammonium salts, in particular those in which the alkyl group has from 8 to 24 C atoms, and in particular the halides, sulfates, phosphates and acetates.
3. Alkylpyridinium, alkylimidazolinium and alkyloxazolinium salts and in particular those in which the alkyl chain has up to 18 C atoms, especially the halides, sulfates, phosphates and acetates.
Additional suitable emulsifiers which may be employed in the preparation of the emulsions are fatty acid polyglycol esters, polyethoxylated fatty acid glycerides and sorbitan esters, alkyl polyglycosides, fatty acid alkylolamides, alkyl ether-carboxylic acids, alkaryl ether-carboxylic acids, ethoxylated quaternary ammonium salts, amine oxides, betaines, sulfobetaines and sulfosuccinates.
Further emulsifiers include alkyl polyglycosides which are described in EP-A 418 479, of the general formula;
Rxe2x80x3xe2x80x94Oxe2x80x94Zo,
in which
Rxe2x80x3 is preferably a linear or branched, saturated or unsaturated alkyl radical having on average 8 to 24 carbon atoms, preferably 8 to 16 carbon atoms, and
Zo is preferably an oligoglycoside radical having on average o=1 to 10, preferably 1 to 5 hexose or pentose units, or mixtures thereof.
Alkyl polyglycosides with a saturated alkyl radical having on average 8 to 14 carbon atoms and an average degree of glycosidation n of between 1.1 and 3 are particularly preferred.
Cosurfactants may be used. Cosurfactants include water miscible lower alcohols, glycols, ketones and ethers, more generally polar organic compounds of moderate molecular weight. Examples of particularly suitable cosurfactants are, preferably, 1-butanol, 2-butanol, 2-methyl-2-propanol, 1-pentanol, 2-pentanol, 3-pentanol, 1-hexanol, 2-hexanol, 3-hexanol, 1-heptanol, 2-heptanol, 3-heptanol, 4-heptanol, 1-octanol, 2-octanol, 3-octanol and 4-octanol; diethylene glycol monomethyl, monoethyl and monobutyl ethers; diethylene glycol dimethyl and diethyl ethers; 1-aminobutane, 2-aminobutane, 2-amino-2-methylpropane, 1-aminopentane, 2-aminopentane, 1-aminohexane, 1-aminoheptane and 1-aminooctane; ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl and hexyl acetates; methyl, ethyl and tert-butyl propionates; methyl, ethyl, propyl and butyl butyrates; 2-butanone, 2-pentanone, 3-pentanone, 4-methyl-2-pentanone, 2-hexanone, 3-hexanone, 2-heptanone, 3-heptanone, 4-heptanone, 5-methyl-3-heptanone, 2-octanone and 3-octanone.
Examples of preferred cosurfactants are 1-alkanols of the examples listed above with C5 to C8 chains, diethylene glycol monobutyl ethers, diethylene glycol dimethyl and diethylene glycol diethyl ether, propyl, butyl and pentyl acetates, and 2-pentanone.
Particularly preferred cosurfactants are 1-pentanol, 1-hexanol and 1-octanol, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether and butyl acetate.
In addition to organopolysiloxane (a), alkyl polyglycosides (b), water and, where appropriate, cosurfactant, the emulsions employed according to the invention can also comprise additives. These are, in particular, bactericides, fungicides, algicides, microbicides, fragrances, corrosion inhibitors, dyes, pigments, thickeners and fillers. The emulsions according to the invention preferably comprise additives each in amounts of 0 to 1 percent by weight, in particular 0 to 0.2 percent by weight, in each case based on the total weight of the finished emulsion.
All the components of the emulsion employed according to the invention can be mixed in any desired sequence using emulsifying apparatuses or by stirring together without exerting high shear forces. For example a homogeneous mixture of organopolysiloxane (a), alkyl polyglycosides (b) and water may first be prepared and the cosurfactants and additives, if employed, stirred into this mixture without exerting high shear forces.
The pressure exerted on the particular components or mixtures is preferably atmospheric pressure, increased, where appropriate, by the action of the mixing apparatus while the correspondingly prevailing temperature is preferably the room temperature, increased, where appropriate, by the action of the mixing apparatus.
The preparation of the acylated xcex1,xcfx89-aminoalkyl-terminated organopolysiloxanes is preferably accomplished employing an aliphatic, saturated carboxylic acid anhydride, most preferably because of economics, acetic anhydride. The anhydride may be added to the amino-functional fluid neat, or with either component dissolved in solvent. The addition should preferably take place at a rate such that high temperature excursions are avoided, as the reaction is quite exothermic. The actual addition rate will depend in large measure on the cooling and agitation capabilities of the reaction vessel. Continuous preparation may also be accomplished in tubular reactors, adding the ingredients at the inlet only, or along the length of the reactor.
The xcex1,xcfx89-aminoalkyl-functional organopolysiloxanes may be made by any method known to the art, including equilibration of lower molecular weight products such as 1,2-bis(aminoethyllaminopropyl)tetramethyldisiloxane. However, a convenient method of synthesis is condensation of an xcex1,xcfx89-disilanol-functional fluid with an aminoalkyldiorganoalkoxysilane such as aminoethylaminopropyldimethylmethoxysilane. The starting silanol fluid is preferably an xcex1,xcfx89-dihy-terminated polydimethylsiloxane.
If pendant aminoalkyl groups are desired, the starting silanol-terminated fluids may have pendant aminoalkyl groups, as disclosed in U.S. Pat. No. 5,302,659, but of higher molecular weight than the fluids used in that disclosure. These fluids are then reacted with the aminoalkylmethoxysilane. Alternatively, a lower molecular weight silanol-terminated fluid may be employed and reacted sequentially or concurrently with an aminoalkyl-substituted monoalkoxysilane and an aminoalkyl-substituted dialkoxysilane. In all cases, the reaction is continued until the viscosity of the product stabilizes, indicating that the reaction is complete. Alternative methods of determining degree of completion may also be used. It must be mentioned also, that incompletely reacted products, i.e., those containing minor amounts if alkoxy or silanol functionality are also useful, and within the scope of the invention unless otherwise indicated. Equilibration of the various species is accomplished by addition of common equilibration catalysts such as sodium or potassium hydroxide or phosphonitrilic cholorides.
The reaction of the alkoxysilane with silanol-terminated fluid preferably takes place at elevated temperature, for example above 60xc2x0 C., and most preferably in the range of 80-120xc2x0 C. If the temperature is excessive, return of silane to the reaction vessel by reflux may be desirable. The reaction may take place in air, or under a nitrogen blanket. Modest agitation is preferred.
Following preparation, the product is emulsified by standard techniques. Any conventional emulsification technique may be used, including preparation of invert emulsion xe2x80x9cgreasesxe2x80x9d followed by stepwise dilution and inversion into oil-in-water emulsions. The products may also be dissolved in organic solvent, dispersed, and the solvent removed by stripping or by distillation.
The subject invention may be illustrated by the following examples, which are not to be construed as limiting the scope of the invention in any way. All parts are parts by weight unless indicated otherwise.

Hydrophilic non-yellowing organopolysiloxane textile softener compositions


Guidewire for catheters which can be inserted into cavities, preferably coronary vessels of humans or animals, said guidewire being provided with electromagnetic receive or transmit locate to position its position in conjunction with corresponding external electromagnetic transmit or receive antennas, as well as with signal lines guiding the processing unit controlling the transmit antennas or transmit coils.

One of the most common fatal diseases is vascular disease, in particular cardiac infarction. This is caused by diseases of the coronary arteries (arteriosclerosis). With such diseases, deposits (atherosclerotic plaque) cause a 'blockage' in the coronary vessels.
A PTCA (Percutaneous transluminal coronary angioplasty) is used nowadays in the majority of cases if the coronary angiography shows severe narrowing (stenoses) of the coronary arteries, which cause angina pectoris, restrict a persons capability and/or endanger his/her life. For this purpose, the narrowings of the coronary vessels are dilated with the so-called "balloon catheter".
In this case, a maneuverable guidewire is typically guided through the vascular system starting from the femoral artery to the coronary narrowings to be treated. A guide catheter can then be pushed over the guidewire to the ostium of the coronary arteries. Within the guide catheter, a balloon catheter is fed over the guidewire ("Over-the-wire"). The balloon present at the distal end of the catheter is inflated until the stenosis is expanded.
This treatment of the coronary vessels has essentially been carried out previously by means of a coronary angiography using contrast means subject to x-ray control. The disadvantage of this method is that only the vessel diameter and/or the narrowing which can be used by the blood flow is displayed here as a two-dimensional silhouette. The guidewire and the catheter are similarly displayed as a two-dimensional overlay image within the angiographic x-ray image. The disadvantage with this method is that the guidewire, catheter and organic tissue are displayed with different qualities in the x-ray image. As a rule, the x-ray system can only be optimized to one object type, typically the organic tissue. An effective display of all objects is desirable both for patients and medical staff, in particular with a spatial assignment in patients and a reduction of x-ray radiation.
U.S. Pat. No. 5,596,996 describes a heavy loadable guidewire made of a tubular nitinol having transition elements made of plastic with a diameter of 0.25 mm to 0.35 mm, this being provided with a marker band to improve visibility. This also only achieves a slight improvement in the two-dimensional overlay image. U.S. Pat. No. 5,365,943 describes an anatomically adjusted maneuverable PTKA guidewire which can be inserted easily but does not achieve an improvement in the visibility.
A new imaging method is already used in several clinics. In this case, an IVUS catheter is inserted into the coronary vessel and is subsequently pulled back out of the vessel ("pullback"). The method is described for example in U.S. Pat. No. 5,924,990. The disadvantage of this method lies in the additional catheter which has to be pushed into the vessel in order to obtain these photos. As above, these are again only two-dimensional images. This catheter has to be removed again before the guidewire for the balloon catheter can be inserted.
A device displaying the guidewire in spatial association to the human body using a low radiation dose is desirable. A guidewire which is inserted in the human vascular system is used with the majority of medical aids. Furthermore, the guidewire is advantageous in that, in contrast with other medical aids, it remains in the patient throughout the medical procedure until the procedure has ended. Other medical instruments, such as guide catheters, balloon catheters, catheters for positioning stents, are only inserted for the specific part of the application. Furthermore, a guidewire is relatively cost-effective to manufacture in comparison with other medical devices.
DE 42 15 901 A1 discloses a catheter with a locatable end region. As mentioned above however, this solution involves a catheter rather than a guidewire. Furthermore, this solution is disadvantageous in that the human body is assumed as the model of an endless, homogenous, conductible half-space and that additionally the measuring device has to be positioned in a shielding chamber.
A system is known from a further patent application which provides 3D images from IVUS and OCT. Nevertheless this system is also a catheter which is moreover equipped with relatively expensive sensors.
U.S. Pat. No. 6,233,476 (Medical Positioning System, Strommer et al.), US 2001/0031919 (Medical Imaging Navigation System, Strommer et al.), US 2002/0049375 (Method and Apparatus for Real Time Quantitative Three-Dimensional Image Reconstruction of a Moving Organ and Intra-Body Navigation, Strommer et al.) describes a spatial positioning of a medical catheter partially in combination with an IVUS sensor. The main disadvantage of this device is that in this case it is not a guidewire which can be used for a multiplicity of medical aids, but is instead a special catheter which is inserted into the body and only allows special medical applications and must be withdrawn from the body when the medical aid is changed.
SUMMARY OF INVENTION
An object underlying the invention is thus to design a guidewire such that it can be positioned in a simple and precise manner, so that with the aid of a guide wire remaining in the body throughout a long examination period, the actual working catheter, which in its turn can be embodied without the need for any complicated navigation devices, can be very easily positioned.
To achieve this object provision is made in accordance with the invention for the guidewire to be provided with electromagnetic receive and transmit coils in order to locate its position in conjunction with corresponding external electromagnetic transmit and/or receive antennas and also with signal lines guiding the processing unit controlling the transmit antennas or coils.
The inventive equipping of the guidewire, preferably with receive coils which record signals from external antennas, allows a very precise positioning which not only facilitates the advance of the guidewire, but above all allows the position to be displayed in medical images acquired in other ways, for instance 3D images, as can be generated with the aid of a mobile C-arm device.
To achieve an even better miniaturization, provision can be made according to a further feature of the invention to arrange the coils not exclusively orthogonally, but at any other angle, for instance 60°, thereby allowing the position sensors to be inserted far more effectively into the guidewire. The deviation from the orthogonal arrangement is corrected by the corresponding computing algorithms in the image processing device.
In order to improve the miniaturization, only one electrical conductor per sensor coil is fed back to the signal interface links in each instance. The conductive guidewire and the human body with its blood vessels are used as "neutral electrodes". In addition, a signal multiplexer can be integrated into the tip of the guidewire, said signal multiplexer cyclically interrogating the receive antenna which results in a further reduction in the signaling lines.
Moreover, nanotechnology can be used to further increase the miniaturization.
For calibration purposes, the tip of the guidewire is recorded at least once by means of at least two x-ray projections in the chamber (x, y, z) and the position in the chamber is determined at least once by the magnetic positioning system (x′, y′, z′). The transformation allows the two positions to be calibrated together one after the other. It is advantageous for the calibration to be carried out only following installation in the clinic. The use of the body phantom and a calibration with several points can increase the accuracy of the calibration.
The image information of the guidewire acquired using the position sensors is added and/or superimposed using 3D-images (registration, fusion). These 3D x-ray images were generated using methods of the discrete tomography from minimal projections. A method for discrete tomography is described for instance in DE 102 24 011 ("Computerized reconstruction method for a three-dimensional object", Hornegger, Schnörr et al). This is advantageous in that the patient and the clinical personnel are only exposed to a minimal exposure dose.
The spatial coordinates of both objects need to be transferred into a common coordinate system in order to register (superimpose) the image data of the patient with the position data. Movements of the patient on the examination table are determined in U.S. Pat. No. 6,233,476 using a magnetic auxiliary sensor. Alternatively it is proposed to detect the position of the patient by means of an optical camera and to determine the patients' movements/displacements using computerized methods of pattern recognition and to correct these in the image processing unit. Additionally the patient can be scanned using a laser beam thereby determining and correcting the position displacement.
Provision is made in one embodiment of the invention such that the guidewire is woven together from individual strands, of which at least one is provided with an insulation and serves as a signal line for the receive or transmit coils. With regard to the preferred use of receive coils in the guidewire, the following only refers simplistically to these receive coils and reference is not made each time such that an exchange would be possible in which transmit coils are accommodated in the guidewire to which external receive antennas are assigned.
This integration of signal lines into the guidewire is thus completely uncomplicated, since the structure is made of individual strands woven together and in any event is the preferred structure of a guidewire of this type in respect of a desired flexibility on the one hand and of a displacement rigidity on the other hand.
In the field of the invention, provision is thus further made for the guidewire to be provided with a slide coating which serves to ease the movement of the catheters, for example a silicon coating or a coating in the form of a hydrophilic coating.
In order to prevent magnetic fields from influencing the signals, in particular the magnetic fields of the transmit antennas, the signal lines are to be provided with shields against magnetic fields, for example by embodying the signal lines as grounded coaxial cables.
To enable the guidewire to be magnetically navigated, provision can be made for electromagnets or permanent magnets for strong external magnetic fields, which can be realized in a particularly favorable manner, such that the magnetic receive coils optionally provided with iron cores for position determination purposes can be optionally operated for the magnetic navigation as receive antennas or as electromagnets.
In order to prevent the magnetic fields induced by the navigation magnets from falsifying the measurement results of the magnetic positioning system (transmitter and receiver), provision can be made in accordance with a further feature of the present invention for the processing device to comprise a storage device for recording the field line curves of the navigation magnet system following the system installation, so as to enable said storage device to be used during the reconstruction of the magnetic position vectors for correction purposes.
To increase the accuracy of the positioning, it is possible to operate and evaluate the transmit coils cyclically at specific time segments with different frequencies. Furthermore, it would also be possible to install additional ultrasonic sensors in the tip. In addition to an arrangement, in which an ultrasonic sensor is supported so that it can rotate, a number of annular US sensors can be arranged in a distributed fashion and scanned cyclically by means of a multiplexer.
Finally, provision is made within the field of the invention to install an OCT and/or IVUS image sensor in the tip of the guidewire such that at least individual signal links are configured wirelessly, in particular with a Bluetooth transmit unit, so that fewer cable links to the patient are needed.
In addition to the possibility of providing the guidewire with markings which are easily visible in the x-ray image, a further favorable representation of the progress of the guidewire also exists in the embodiment of the invention, in that an envelope curve and from this the vessel centerline are able to be calculated from the boundary points when its tip comes into contact with the vessel wall, in other words from the specific boundary positions of the tip of the guidewire in each instance.


The invention relates to the diagnosis in a human or lower animal subject of a gastrointestinal disorder of the upper gastrointestinal tract caused by bacteria using a breath test. In one aspect the invention provides a process for the preparation of a reactive pharmaceutical product for the detection of gastrointestinal disorder caused by bacteria in the superior gastrointestinal tract, characterized by the preparation of a dense powdered vehicle or granules of sugar, or granules of Nu-pareil seeds, of a specific diameter between 0.12 to 3.0 mm and soluble in gastric fluids; dispersing in or coating on the vehicle a micro dose of 14C-urea; and coating or encapsulating the resulting blend with an inert gelatin substance that dissolves rapidly, thereby obtaining a capsule, wherein the density of the vehicle is such that it allows deposition of the isotope contained in the capsule onto the gastrointestinal tract mucosa.

Factors adversely affecting the function of the gastrointestinal system in humans are exceedingly varied in their nature. Such disorders may arise in the upper or lower gastrointestinal tracts or both. There is a broad range of causes of gastrointestinal disorders, including genetic, physiological, environmental and psychogenic factors. Accordingly, the diagnosis and management of these disorders can be exceptionally difficult.
Among the chronic disorders of the upper gastrointestinal tract are those which fall under the general categories of gastritis and peptic ulcer disease. The gastrointestinal tract is generally defined as including the esophagus, the stomach, the duodenum, the jejunum and ileum. Peptic ulcers are lesions of the gastrointestinal tract lining, characterized by the loss of tissue due to the action of digestive acids and pepsin. It has generally been held that peptic ulcers are caused by gastric hypersecretion, decreased resistance of the gastric lining to digestive acids and pepsin or both. Gastritis is, by definition, an inflammation of the stomach mucosa. In practice, though, the disorder is manifested by a broad range of poorly defined, and heretofore inadequately treated, symptoms such as indigestion, xe2x80x9cheart burnxe2x80x9d, dyspepsia and excessive eructation.
However, the diagnostic methods typically employed in the art are often slow, cumbersome, costly and may yield equivocal or inaccurate results. Such patients may simply be treated with conventional therapies, such as with antacids or drugs which inhibit stomach acid secretion. While such therapies might provide temporal symptomatic relief, a cure is often not effected. In particular, it has been discovered that many such gastrointestinal disorders are mediated by infection of the gastric mucosa by bacteria. Thus treatment of the bacterial infection may be required in order to effectively treat the manifested gastrointestinal disorder.
Accordingly, a simple diagnostic test for gastrointestinal disorders could afford substantial advantages in the proper end effective treatment of patients having gastrointestinal disorders. Such a test should be easily performed, allowing definitive interpretation, and yield a result with a high degree of correlation to the presence or absence of the gastrointestinal disorder.
It was disclosed in U.S. Pat. No. 4,830,010, the subject matter of which is incorporated herein by reference, that gastrointestinal disorders of the upper gastrointestinal tract may be detected and diagnosed by methods involving the administration of urea to a human or lower animal subject followed by analyzing the breath of the subject to detect the presence of products of urea hydrolysis. The methods disclosed in U.S. Pat. No. 4,830,010 provided a rapid, inexpensive, non-invasive diagnosis, however, accuracy was compromised by several factors.
The 14C-urea was administered in liquid form and caused contamination of the mouth and generation of labelled carbon dioxide from the oropharynx. When the solution of 14C-urea contacts the oropharynx, a small amount of 14CO2 is generated by the hydrolysis of the urea as a result of urease from mouth bacteria contaminating the mouth. This contamination results in the generation of 14CO2, which peaks approximately one minute after swallowing the solution and is generally detectable for 12 minutes. In some cases, excessive mouth hydrolysis results in continuation of this peak for up to 20 minutes, producing a possible false positive result. The liquid also was likely to empty quickly from the stomach through the pylorus. This prevented adequate contact between the 14C-urea and the gastric mucosa, where the bacterial urease of Helicobacter pylori is located. Therefore, urea hydrolysis tended to be slowed and larger doses of isotope or breath volume collection bottles greater than 1.5 liters were necessary. The liquid additionally increased the possibility of spillage and safe transport of the isotope was difficult.
The shelf life of isotope in the solution was short leaving a possibility that contamination of the isotope with microorganisms could result in hydrolysis of the urea. To prevent the contamination, refrigeration and/or the addition of a preservative was necessary.
The breath samples were collected by blowing through a tube into a collecting bottle. Patients exhaled at a different rates, thereby introducing an unwanted variability into the test result. Because of this variability, several samples were necessary and the collection bottles were relative large to prevent spillage of bubbles and solution. It was found that the slow transit of lung air through the mouth caused heavy contamination of breath by labelled 14CO2 arising in the oropharynx.
Vxc3xa1szquez and others U.S. Pat. No. 4,851,209 describe in-vivo procedure of in-vivo diagnostics for the clinical evaluation of gastrointestinal ulcer illness that uses radioactive isotopes. The procedure involves the previous administration of a pharmaceutical followed by cintigraphic imagery of the gastrointestinal area of interest, with equipment of cintigraphic imagery.
Even when the use of urease or other indicators have been used in combination with pH indicators, all except Vxc3xa1szquez are conducted in-vitro.
It has now been found that the problems of the prior art relating to the diagnosis in a human or lower animal subject of a gastrointestinal disorder of the upper gastrointestinal tract caused or mediated by bacteria which result in the gastric materials of the subject to contain relatively large quantities of urease, can be overcome through the use of a novel method of detection of urease that uses a reactive encapsulated product for the detection of urease by breath and a device (kit) specially designed for quick tests.
It is therefore an object of this invention to provide a procedure for preparing a reactive product for pharmaceutical use for detecting urease caused by gastrointestinal disorders.
Another object of the present invention is to provide an encapsulated reactive product for pharmaceutical use comprising a safe amount of isotope-labelled urea, that is orally administered, and allows by breath analysis of the subject to determine the presence of the product of the hydrolysis of urea.
The present invention relates to with a procedure for obtaining a pharmaceutical product useful to detect a gastrointestinal disorder of the upper gastrointestinal tract in a human or lower animal, as well as the pharmaceutical product thereof.
Accordingly in a first aspect the present invention provides a process for the preparation of a reactive pharmaceutical product for the detection of gastrointestinal disorder caused by bacteria in the superior gastrointestinal tract, characterized by the preparation of a dense powdered vehicle or granules of sugar, or granules of Nu-pareil seeds, of a diameter from 0.12 to 3.0 mm and soluble in gastric fluids; dispersing in or coating on the vehicle a micro dose of 14C-urea; and coating or encapsulating the resulting blend with a gelatin substance that dissolves rapidly, thereby obtaining a capsule, wherein the density of the vehicle is such that it allows deposition of the isotope contained in the capsule onto the gastrointestinal tract mucosa.
In a second aspect the invention provides a pharmaceutical product for breath tests for the detection of gastrointestinal disorder that comprises an isotope of 14C-urea dispersed in or coated on a dense powdered or granulated vehicle of sugar, or Nu-pareil seeds, the resulting blend being coated with or enclosed in gelatin substance that dissolves rapidly in the presence of gastric juice, wherein the vehicle has a density sufficient to allow the capsule contents to be deposited onto the gastrointestinal tract mucosa, and wherein the granules have a diameter of from 0.12 and 3.0 mm.
Urea has the formula H2NCONH2 and is a product that occurs naturally in the metabolism of proteins. The gastric materials of humans or animals that have gastrointestinal disorders, contain relatively large quantities of urease (urea amino hydrolase) if the bacteria helicobacter pylori resides in the gastric tissue of the stomach of the subject, this urease hydrolyses the urea to ammonia bicarbonate or ammonia and carbon dioxide. Normally the urease exists in the body in minimum quantities. H. pylori increases the amounts of urease above the normal levels leading to an unusually high rate of decomposition of urea in the affected areas. The urease reacts with urea to produce ammonia.
The isotope is encapsulated in a gelatin capsule and delivered to the gastric mucosa along with a dense powdered vehicle of a food product. Sugar, lactose, Nu-pareil seeds (candy beads or sugar spheres), and sucrose granules coated with urea are among the materials which can be used. The term xe2x80x9cNu-pareil seedsxe2x80x9d as used herein refers to sugar spheres or candy beads, in particular those comprising a sugar, such as sucrose, and a starch.
The Isotope-labelled Urea is 14C-urea
The 14C-urea is added to a dense vehicle dissolvable in gastric juices to approximately 1 to 20 grams per kilogram of vehicle, the preferred vehicles are granules such as Nu-pareils, although other vehicles approved for pharmaceutical use can be used when they have enough density to deposit the capsule in the mucosa of the stomach. The density of the vehicle is critical because it has to be able to migrate to the gastric mucosa. One method of coating the vehicle with the isotope is to spray a solution of the isotope in a volatile solvent, such as alcohol, onto the granules. Preferably the granules are agitated to ensure an even coating. A dye, such as fluorescein, may be added to the solution as an indicator of spills of the isotope solution. A convenient method for agitating the granules is by means of a mixing drum.
The breath sample is collected by exhaling into a non-air permeable bag through an inlet tube. The non-air permeable bag is transported to a testing site and the breath sample is transferred from the non-air permeable bag through use of a low vacuum pump to an analysis solution. The non-air permeable bag can be aluminumized foil or plastic. The non-air permeable bag has an inlet which can be sealed to prevent the breath sample from escaping. An alternate embodiment has a sealable air outlet for removal of the breath sample. A pressure locking strip allows for the bag to be opened and sealed for repeated samples.
In the present invention the natural dispersion of the granules over the mucosa covers an area sufficient to react with at least a few colonies of the bacteria. If granules are used which float, the indicators disperse and do not have a great chance to come into direct contact with the affected area and less rapid or less exact results will ensue.
As mentioned above, other types of dense vehicles approved for pharmacological use can be used in all its line if they are capable of absorbing the required reactives indicators and that they have enough density to ensure the capsule and/or its contents end up resting over the mucosa and dissolve there in a few minutes. When powdered vehicles are used the reactives are combined with the vehicle. This can be dried and if necessary ground to form more powder. The granules have the advantage that they are easy to produce, cover about the same area as a powder with the reactives and give good results.
When 14C-urea contacts with the oropharynx, a small amount of 14CO2 is generated by the hydrolysis of the urea due to the urease from the mouth bacteria contaminating the mouth. The contamination generates CO2 which peaks approximately one minute after swallowing the solution and is detectable for 12 to 20 minutes.
This contamination can produce a xe2x80x9cfalse positivexe2x80x9d result to the test. It has been found that when the 14C-urea solution is administered directly into the esophagus, the oropharyngeal isotope peak does not occur. This is yet another reason why the encapsulated product according to the invention provides a more accurate result as the beads or granules (with their attached indicators) do not come into contact with the oropharynx. Instead, the beads or granules are only exposed to the bacteria when the capsule dissolves in the stomach.
The process for preparing the pharmaceutical vehicle for the detection of gastrointestinal disorder, is characterized by the steps of incorporating a micro curie of isotope of the 14C-urea in an inert gelatin capsule with a dense soluble granulated or powdered vehicle, where the preferred capsule is manufactured from an inert, gelatin substance, which preferably breaks open after about 1 to 5 minutes. The dense carrier or vehicle, is advantageously a food product such as a sugar, or Nu-pareil seeds in which 14C-urea is preferably dispersed, to form a dense vehicle, that dissolves rapidly in gastric juice in approximately 1 to 20 grams per L. Additionally, compressed lactose powder or sucrose granule coated with urea can be included.
The pharmaceutical product obtained for the breath tests comprises a micro curie of isotope of the 14C-urea dispersed in a vehicle of dense powder such as a sugar, or Nu-pareil seeds, or compressed lactose powder or sucrose granules, coated with an inert, gelatin substance, that dissolves rapidly in the gastric juice, with an exact density that allows the capsule to be deposited on the mucosa of the gastrointestinal tract, and with a bead size filtered between a critical diameter of 0.012 to 3.0 mmn, that allows a better placement of dispersion of the 14C-urea onto the stomach mucosa.
Compressed lactose has suitable solubility and forms a dense solution which utilizes gravity to place the 14C-urea onto the gastric mucosa. The density of the vehicle draws the 14C-urea to the bottom of the gastric juice pool, thereby preventing dilution of the 14C-urea throughout the gastric contents and permitting intimate contact between the isotope and the gastric mucosa.
This is in contrast to the use of a liquid which is liable to empty quickly from the stomach through the pylorus, preventing adequate contact between the urea and the gastric mucosa. Additionally, a liquid vehicle has isotope dispersed throughout its volume rather than specifically adjacent to the gastric lining. Since urease is inactivated in acid, urea within the volume of the gastric juice is unlikely to react, thus leading to a muted or dampened liberation of labelled CO2.
To further ensure that the capsule dissolves, a small volume of water, approximately 20 ml, can be swallowed after the capsule to avoid the possibility that the capsule can lodge in the oesophagus and dissolve there.
The 14C-urea decomposes more rapidly in the presence of hydrogen ion and even in a solution of pH neutral water. Thus, storage of the urea in the dry medium of the vehicle maintains the 14C-urea in a stable form.
The capsule decreases the time required for the test to be performed as the radioisotope is quickly broken down in the mucosa, thus declaring the presence of the Helicobacter pylori. A large bolus of urea is quickly delivered adjacent to the mucosa and the bacteria as soon as the capsule dissolves and delivers its contents of dense granules (or vehicle). This allows the 14CO2 to appear in the breath very rapidly, shortening the breath test time to less than 20 minutes, normally between 10 to 15 minutes. A similar test with liquid solution takes at least 20 minutes for an initial diagnostic sample, and normally at least double the time needed according to the method of the present invention. The shortened time is also because of the elimination of the spurious urease activity and the accompanying variability discussed supra.
In the case where the Helicobacter Pylori is not found in the gastric tissue of the subject, the 14C-urea is not hydrolysed and the 14C-urea is excreted in the urine of the subject.
The invention will now be described with reference to an example which illustrates a preferred aspect of the present invention. However it is to be understood that the following description of the invention is not to supersede the generality of the invention previously described.

Process for preparing a reactive pharmaceutical product for the detection of gastrointestinal disorder caused by bacteria in the gastrointestinal superior tract

Abstract: In another aspect the invention provides a pharmaceutical product for breath tests for the detection of gastrointestinal disorder that comprises an isotope of 14C-urea dispersed in or coated on a dense powdered or granulated vehicle of sugar, Nu-pareil seeds, and the resulting blend being coated with or enclosed in inert gelatin substance that dissolves rapidly in the presence of gastric juice, wherein the vehicle has a density sufficient to allow the capsule contents to be deposited onto the gastrointestinal tract mucosa, and wherein the granules have a diameter of between 0.12 to 3.0 mm.