A process and system for purifying an impure gas to produce a purified gas in a gas purification system and protecting the system from damage by a) passing a portion of a first gas stream into a reactor vessel, which exits as a second purified gas stream; b) combining a portion of the second purified gas stream with another portion of the first gas stream to form a combined gas stream; and c) passing the combined gas stream into a sensing device to regulate the flow of the first and second gas streams into the reactor vessel.

Ultra-high purity (UHP) gas purification systems are generally used to supply customers with UHP nitrogen. The initial source of nitrogen (the distillation plant, or the liquid nitrogen supply) typically contains about 1 ppm oxygen by volume. The oxygen level is monitored by an oxygen analyzer before passing into the gas purification vessel, which contains material that reacts with impurities in the nitrogen to produce purified gas.
Ultra-high purity inert gas purification systems generally employ a getter metal that is comminuted by some means, and then dispersed in a matrix of a comparatively inert substrate material (usually alumina or similar). Once activated by a reduction process of some kind, this high surface area metal can then react extremely rapidly with various impurity gases (oxygen, hydrogen and others, depending on the getter material and temperature) to chemically bond with reactive gases, and so remove them from the gas stream: a process known as chemisorption.
The speed of the reaction, plus its highly exothermic (heat-evolving) nature means that processing inert gases containing high levels of a reactive impurity may cause significant damage and personal danger. For example, it is known that exposing activated nickel-based getters to oxygen concentrations greater than 1% by volume (10,000 ppm O2) will generally cause heat-damage to the getter bed, and possibly also to the reactor vessel and downstream customer equipment. The cost of the damage in such an instance ranges from tens of thousands to millions of dollars, when the impact on downstream processing is accounted for.
It is therefore a priority to ensure that such instances are avoided. As such, safety schemes have been devised to protect the bed from excessive levels of contaminant, and thus excessively high temperatures.
One safety scheme is to measure the temperature of the bed using judiciously placed temperature measuring devices, such as thermocouples. If the bed temperature rises due to the exothermic reactions, action is taken to safeguard the bed. This action will typically consist of diverting the feed gas and venting the purifier to rid it of remaining reactive gases and preventing additional reactive gases from entering. This will typically be performed automatically using a control unit that recognizes that a temperature setpoint has been reached and actuates valves to the shutdown condition. A major problem with this approach is that it requires that the bed be exposed to high levels of reactive impurities before action is taken, since this is necessary to raise the temperature of the bed.
Another safety scheme is to sample the gas stream prior to entering the bed. When a predetermined level of contaminants is reached, typically orders of magnitude above that normally present in the feed gas, action is taken to safeguard the bed. There are several types of measuring device. Typically, commercially available gas analyzers can be used. The approach of measuring the gas stream prior to entering the bed has the advantage that it can potentially react more rapidly than thermocouples placed inside the purifier that is being protected, i.e. it can take action to safeguard the bed before the bed is exposed to high levels of reactive species. Further, it is possible to detect levels of reactive species that are higher than normal operation but are below that required to raise the temperature of the bed significantly. Thus it is possible to design a system that is more sensitive to reactive species than one that simply embeds thermocouples inside the purifier bed and waits for these to register an increase in temperature.
One drawback to this approach is the cost of the unit, both in terms of the initial purchase cost and the maintenance required to keep the analyzer in good working order. For example, oxygen is commonly the species that the purifier must be protected from. Two standard varieties of oxygen-detection cell provide an electrical current output from either (i) a cell that operates at ambient temperature, containing salt solution that needs to be maintained at a fairly constant level by continuous replenishment with deionized water or new salt solution, or (ii) a zirconia (ZrO2) cell maintained at high temperature (typically greater than 600° C.), that has a typical lifetime of two years or less.
The cost of using analysis external to the bed is compounded by the need to protect the gas from a backflow condition. Backflow may occur due to errors in operation or piping hook-up, or as a result of upset conditions that cause the pressure within the purifier to be lower than the pressure downstream and thus cause gas to enter the bed in a direction counter to that during normal operation. Protection against backflow requires that both the streams entering and leaving the purifier must be sampled. This increases cost and reduces system reliability by requiring two measuring devices as opposed to one. The cost and reliability implication of monitoring the purifier both upstream and downstream is the problem that this current invention addresses.
U.S. Pat. Nos. 6,068,685 and 6,156,105 disclose the need to protect the purifier both upstream and downstream. A first temperature sensor is disposed in a top portion of the getter material that constitutes the purifier bed. The first temperature sensor is located in a melt zone to detect rapidly the onset of an exothermic reaction which indicates the presence of excess impurities in the incoming gas to be purified. A second temperature sensor is disposed in a bottom portion of the getter material. The second temperature sensor is located in a melt zone to detect rapidly the onset of an exothermic reaction which indicates that excess impurities are being backfed into the getter column. In these patents, a purifier vessel contains getter material. A gas stream enters the purifier vessel and a separate stream exits from the vessel. A thermocouple is placed at the inlet side of the bed. Another thermocouple is located near the exit of the bed. The temperature at both locations is sent to a control unit. The registered temperatures are compared with setpoint values. Action is taken to protect the bed if the setpoint is exceeded in either thermocouple.
U.S. Pat. No. 6,168,645B1 also discloses the need to protect the purifier both upstream and downstream. A first safety device is located upstream of a purifier and a second safety device is located downstream of the purifier. A sample stream is drawn from the feed stream, upstream of the purifier, and sent to an upstream safety device. Similarly, a sample stream is drawn downstream of the purifier and sent to the downstream safety device. The level of reactive species is sent from both safety devices to the control unit. If either safety device registers levels of reactive species is in excess of some defined setpoint, action is taken to safeguard the bed. On passing through the safety devices, the sample streams are typically sent to vent. Since this represents loss of product gas, there is a motivation to minimize the quantity of sample streams withdrawn.
Also disclosed in the '645 patent are low cost means of measuring the quantity of reactive species in the stream downstream of the purifier. In one embodiment, the safety device is simply a small sample of the getter material inside the purifier. The temperature rise in this guard bed is used as an indicator of the level of reactive species. Such an approach is not suitable for monitoring the upstream case because the level of reactive species is such that the bed material would react with the oxygen over time and thus become inert to the presence of additional reactive species. For example, activated nickel getter, commonly used to remove oxygen, hydrogen and carbon monoxide from bulk inert gases, has a limited capacity to react with oxygen, hydrogen and other impurities. The oxidation reaction is:Ni+½O2-->NiO+heatOnce all the nickel has reacted in this way, there will be no further heat output by the purification material, no matter how high the oxygen concentration in gas or other fluid passing over it.
It is believed that the number of patents describing safety schemes for getter-based purifiers is limited. A series of patents disclose determining the end-of-life of a purifier, meaning the point at which the purifier allows unacceptable concentrations of impurities to break through. U.S. Pat. No. 5,150,604 discloses the use of pressure drop across the bed to determine the end of its useful life. The '604 patent discloses pressure transmitters that are located up and downstream of the purifier. The signals from these transmitters are sent to a control device to see if the pressure drop is above some setpoint.
There is therefore a need in the art to provide for a low cost and reliable process or system for monitoring the purifier both upstream and downstream of the getter.


Various implementations include a device for assisting with and controlling stretching of a limb of a patient. The device includes a limb support for receiving the limb, a base, and a coupling that rotatably couples the limb support and the base. The coupling allows the limb support to rotate through various axes of rotation individually, depending on the range of motion expected for the limb. For example, for a device designed for the foot, the coupling allows a foot support to rotate about a first axis, a second axis, and a third axis, wherein the three axes are orthogonal to each other. In other implementations, the device may be designed for other portions of limbs, such as the hand, the forearm, the upper arm, the lower leg, and the upper leg.

Patients having paralysis or recovering from a physical injury to a limb may need physical therapy to restore normal range of motion or improve range of motion for a joint or limb. The therapy may include regularly stretching the limb (e.g., via the ankle or wrist joints). The limb is moved through its various stretches manually by a physical therapist or other caregiver until the normal range of motion of the limb is restored. For example, if there is an injury to the foot or leg, the foot may be stretched relative to the lower leg by twisting the forefoot side to side relative to the ankle joint within a horizontal plane, rolling the medial and lateral sides of the foot up and down, and flexing the forefoot in the plantar (downward) and dorsal (upward) directions relative to the heel.
Manual manipulation may have several drawbacks. First, the therapist or caregiver may over extend the limb past its normal range of motion, especially for patients having paralysis in the limb. This over extension can injure the patient or prevent recovery. Second, the movement may not be around the correct axis, which can slow recovery or cause other injury.
Thus, a device for assisting with and controlling stretching of a limb of a patient is needed.


To provide a substrate for optics for enabling the color shift caused by diffraction of light to be reduced, a substrate for optics (12) is provided with a fine-structure layer including dots (31) comprised of a plurality of convex portions or concave portions extending in the direction of from a main surface of a substrate to outside the surface, the fine-structure layer has a plurality of dot lines in which a plurality of dots is arranged with a pitch (Py) in the first direction inside the main surface of the substrate, while having a plurality of dot lines in which a plurality of dots is arranged with a pitch (Px) in the second direction orthogonal to the first direction inside the main surface of the substrate, and both of the pitch Py and the pitch Px are inconstant intervals and are of nano-order.

In recent years, to improve luminous efficiency in a light emitting device such as organic EL, fluorescence and LED, improvements have been studied in light emitting materials, low voltage, light extraction efficiency and the like.
As a method of improving light extraction efficiency, it is studied to introduce a light scattering layer and low refractive index layer in a light emitting device, and the like (Patent Documents 1 and 2). Further, such a method is known that the travel direction of light in the waveguide mode is polarized to the direction of the light emitting device surface using diffraction of light to improve light extraction efficiency (Patent Document 3). Furthermore, such a technique is invented that metal periodical grid structure or fine-particle dispersing element is provided near a light emitting portion in a light emitting device to excite surface plasmons, thereby extracting light to the outside with high efficiency (Patent Documents 4 and 5, Non-patent Documents 1 to 5).
In propagating surface plasmons on a metal surface, a polarized wave of free electrons generated by an electromagnetic wave (visible light, etc.) incident upon a conductive material surface such as a metal forms an electric field of the transverse wave on the surface. In the case of propagating surface plasmons existing on a flat metal surface, the dispersion straight line of propagated light does not cross a dispersion curve of plasmons, and therefore, the propagated light is not able to directly excite plasmons. However, when the periodical grid structure exists on the metal surface, diffracted light Bragg-reflected by the grid crosses a dispersion curve of plasmons, and the incident electromagnetic wave and the polarized wave of free electrons on the metal surface are capable of generating a resonance state (Non-patent Document 6).
At this point, the wave number vector of surface plasmons is a value equal to the wavelength of light, and exciton and light is coupled coherently to be exciton polariton. Polariton is a state in which the polarized wave of free electron and electromagnetic wave exchange energy by resonance. When the pitch and height of the periodical grid structure are substantially constant, i.e. when crystalline of the periodical grid structure is high, the surface plasmons have one wave number vector, are coupled to light with particular incident angle and wavenumber (wavelength), and an emission enhancement phenomenon is observed by the so-called surface plasmon resonance.
For example, in Non-patent Document 5, it is disclose that, to induce coupling of light and surface plasmons in a light emitting layer inside an organic light emitting device, a grid structure of a periodical waveform is used, thereby prevent transmission and waveguide in the transverse direction of emitted light while enhancing light output and efficiency of the structure body. According to this method, theoretically, it is possible to couple light emitted from the organic light emitting material inside the organic EL light emitting device up to maximum 93%.
Further, Non-patent Document 3 shows that luminous efficiency of blue light by UV excitation of semiconductor quantum well structure is enhanced by periodical structure of silver. Furthermore, Non-patent Document 4 shows that luminous efficiency of an LED is enhanced also by periodical structure of silver.
Moreover, the light emitting device of organic EL or the like adopts a configuration that a high refractive index region is sandwiched between low refractive index regions. Since a light emitting portion is included in the high refractive index region, light emitted in the light emitting portion becomes the waveguide mode, and is confined within the high refractive index region, while being absorbed in the waveguide process to attenuate. Accordingly, it is not possible to extract light outside the device, and light extraction efficiency significantly decreases.
In order to effectively improve light extraction efficiency, it is necessary to disturb the waveguide mode at an early stage before the emitted light attenuates. Therefore, to improve light extraction efficiency, proposed is a method for forming an intermediate refractive index layer between the low refractive index region and the high refractive index region (Patent Document 6).
However, in the method as disclosed in Patent Document 6, it is not possible to disturb total reflection, the totally reflected light maintains the waveguide mode and attenuates, and therefore, significant improvements in light extraction efficiency are not expected. On the other hand, as an example of disturbing the waveguide mode and improving light extraction efficiency, proposed is a method for extracting light confined by the waveguide mode with a periodical structure provided near a substrate as diffracted light (Patent Document 7).

This patent is subject to a terminal disclaimer.

Substrate for optics and light emitting device


A method of treating tissue within a body includes aiming an ultrasound transducer towards target tissue, and delivering ultrasound energy towards the target tissue to thereby reduce pain at the target tissue. A method of treating tissue within a body includes aiming an ultrasound transducer towards target tissue, and delivering ultrasound energy towards the target tissue to increase nitric oxide at the target tissue. An ultrasound system includes a first ultrasound transducer for emitting ultrasound energy from outside a patient, and drive circuitry coupled to the first ultrasound transducer, wherein the drive circuitry is configured to generate a drive signal at a frequency that is between 20 kHz and 100 kHz for the first ultrasound transducer.

Peripheral arterial disease is the most common form of atherosclerosis that affects many people worldwide. As a result of such disease, many people experience pain during walking. Such condition may be treated medically with exercise and drugs, such as Cilostazol, which modestly improves walking ability by inhibition of platelet aggregation. However, in many cases, patients do not follow the prescribed exercise therapy because of pain associated with the disease. Other types of drugs have also been used to treat ischemia, but many of these drugs have side effects.
Medical interventions such as balloon angioplasty, stenting, and surgery are options to treat patients who are suffering from peripheral arterial diseases and critical limb ischemia. However, many of such procedures may fail. Consequences of graft failure include continued ischemia, poor wound healing, gangrene, or amputation of a patient's limb.
Ultrasound devices have been used to diagnose patients. For example, ultrasonic energy may be employed to obtain images of a part of a patient during a diagnostic procedure. In addition, ultrasound systems have been used for treating tissue, e.g., by directing acoustic energy towards a target tissue region within a patient, such as a cancerous or benign tumor, to heat the tissue region. For example, an ultrasound transducers may be disposed adjacent a patient's body and operated (generally at a frequency that is in the megahertz range) to deliver high intensity acoustic waves, such as ultrasonic waves, at an internal tissue region of a patient to heat the tissue region, thereby injuring target tissue at the tissue region.

Ultrasound systems and methods for treating ischemic limbs or tissue affected by peripheral arterial disease


A low profile impact absorbing base in which the base comprises downwardly and outwardly tapering top and peripheral walls which collectively define a hollow interior except for resilient deformable ribs, and a central hub integrally formed with the top wall of the base. A separate post is mounted on a carrier sleeve, with the post being constructed to fit into an embedded retaining sleeve or capable of being inserted directly into the ground. The outside surface of the carrier sleeve and the inside surface of the central hub are complementarily configured so that the post and sleeve can be inserted upwardly into the central opening in the hub and frictionally retained therein. The thickness and spacing of the ribs are such that the ribs can be laterally inwardly deformed as a result of sliding impact forces so that such forces can be absorbed without injury to the player. The base is relatively low in height thereby providing an additional safety factor in that players normally tend to slide over the base as opposed to sliding directly into a side wall of the base causing the noted lateral inward deformation.

The present invention relates as indicated to an impact absorbing base, and relates more particularly to a base which can be used for playing baseball or softball and which greatly minimizes injuries to players contacting, particularly sliding into, the base.
Bases must possess certain characteristics, one of which is that the base must not be shiftable when touched, stepped upon or slid into. That is, the base must not be allowed to laterally shift. Bags are frequently retained in place by long spikes which are separate members and adapted to receive a strap attached to the bottom of the bag for securing the base to the spike which is driven into the ground. A second form of base and one which is used at the major and minor league levels comprises a base formed with a downwardly extending post on the undersurface of the base, with the post extending into a complementary shaped retaining sleeve embedded in the soil. The connection is typically non-rotating, with the post and retaining sleeve assembly thus precluding the base from either rotating or shifting laterally.
Break away bases are also known. This type of base breaks away from its mounting when impact forces above a certain level are encountered. One of these break away bases is shown in U.S. Pat. No. 4,398,715, issued to Hall. The patented arrangement comprises a base top which is detachably secured to a ground plate or equivalent holding device. The momentum of a sliding player shears or breaks away the detachable upper portion of the base from the fixed ground plate. This type of base has the disadvantage that the base must be retained in place on the fixed ground plate unless and until certain energy levels are reached, thereby requiring rather elaborate interconnecting means between the base and the fixed ground plate. There are numerous anchoring points, all of which must be secured in order to re-attach the base to the plate after the base has been broken away. Moreover, when impact forces cause the base to break away from its associated mounting, the base frequently is separated from the sliding player, thereby making rulings of safe and out relatively difficult. Further, if the base is detached from its mounting when not in use, for example, to prevent theft, the anchoring portion of the assembly is exposed to damage from weather or vandalism when the playing field is not in use.
A further solution is proposed in U.S. Pat. No. 5,000,447, issued to the present inventor. While the base disclosed in the '447 patent has performed very well and has been commercially successful, its size and mounting do present certain difficulties. The base was primarily designed for use on playing fields particularly adapted for relatively advanced players. The base is therefore comparable to bases then and still being used at the high school, college, minor and major league levels. In addition, the base was mounted by means of a specially configured post adapted to extend into an embedded retaining sleeve for anchoring the base in such sleeve. This requires relatively permanent base installations thereby increasing both the purchasing and installation costs for a set of bases of the type disclosed in the patent. This has proven to be a particular problem for operators of fields for very young players, where budget limitations normally do not justify the purchase of the more advanced base assemblies disclosed in the '447 patent, despite the concern of virtually everyone for the safety of young players.
From the above discussion it will be understood that there are number of design parameters that must be considered in the design of an impact absorbing base. The base must be rigid enough to be stepped on without deforming, and at the same time resilient enough to deform and absorb the impact of a player sliding into it. The impact absorption characteristic of the base must be such that it adequately absorbs impact forces of younger, lighter weight players, as well as older, heavier players, from the substantial impact forces resulting from sliding into the base. Moreover, the base and anchoring arrangement must be such that it meets the above criteria while at the same time being affordable to the widest possible range of field environments, from the very youngest players to the most experienced professional players.


A storage device configured for hardware verification is disclosed. The storage device comprises a first hardware component comprising a connector and a first verification logic. The first validation logic is configured to detect a criterion and generate a first signal via the connector in response to detecting the criterion. The storage device also comprises a second hardware component coupled to the first hardware component via the connector. The second hardware component comprises a second validation logic, where the second validation logic is configured to monitor and receive the first signal via the connector. In response to receiving the first signal, the second validation logic is configured to compare the received first signal to an expected signal and generate a result. The storage device is configured to take an action in response to the result.

It may be desirable to use a computational storage device (e.g., a solid state drive (SSD) with an embedded processor or Field Programmable Gate Array (FPGA)), for various data processing tasks, as such a storage device may help provide efficient and cost-effective data processing solutions. For example, a computational storage device may provide a platform for performing at least a portion of the data processing functions that may otherwise be performed by a host CPU processor, within the storage device itself.
Thus, it is desirable to have a system and method for quickly determining whether one or more components of a computational storage device are verified components.

Device and method for verifying a component of a storage device


A conductive ball mounting apparatus for mounting conductive balls by providing an array mask having through holes, into which conductive balls are to enter, above a mounting target placed on a stage, by arranging a ball reservoir having an opening for reserving a plurality of conductive balls, in the bottom, by moving the ball reservoir along the array mask, by dropping the conductive balls into the individual through holes of the array mask, adopts the following means. Firstly, the conductive ball mounting apparatus comprises moving means for moving the array mask and the stage relative to each other in horizontal directions. Secondly, the positions of the conductive balls in the through holes are arranged by finely moving at least one of the array mask and the stage relative to each other in the horizontal directions after the balls were dropped.

1. Field of the Invention
The present invention relates to an improvement in an apparatus for mounting a number of conductive balls by moving a ball reservoir for reserving the conductive balls along the upper face of an array mask and, more particularly, to a conductive ball mounting apparatus which is improved with a main view to improving the positional precision of the conductive balls in the through holes of the array mask.
2. Description of the Related Art
As the conductive ball mounting apparatus for mounting conductive balls after the adhesive material was applied to individual electrodes formed in a predetermined array pattern on the mounting target, there exists in the related art an apparatus for mounting the conductive balls, after sucked, arrayed and adsorbed by the ball mounting head having an array plate, on the individual electrodes on the mounting target, as disclosed in JP-A-2001-358451. However, as the mounting target product such as a wafer becomes larger, the number of solder balls to be mounted at one time exceeds one million. This makes it difficult at present to reduce the defects in the array of solder balls and the defects at the mounting time.
As disclosed in JP-A-2002-538970 and Japanese Patent No. 3177370, therefore, there has been provided an apparatus, in which an electronic substrate or a mounting target printed with flux is provided with an array mask and in which solder balls are directly dropped onto electrodes of the electronic substrate. As compared with the diameter of the conductive balls, however, the diameter of the through holes of the array mask is larger. This raises a problem that the positions of the conductive balls in the through holes are not arranged merely by dropping the conductive balls into the through holes of the array mask.


An electromagnetic interference diminishing structure of a connector assembly. The connector assembly includes a socket and a plug. The socket includes a main body enclosed by a metal housing connected to the grounding circuit of a circuit board. The plug includes a shield metal housing formed with grounding sections. A terminal main body is inserted in the shield metal housing. An insulating housing is fitted around the shield metal housing. When a front section of the plug is plugged into the socket, the metal housing of the socket and the grounding sections of the shield metal housing of the plug contact with each other through the holes of the insulating housing of the plug. Accordingly, the electromagnetic interference can be effectively diminished.

1. Field of the Invention
The present invention is related to an electromagnetic interference diminishing structure of a connector assembly.
2. Description of the Prior Art
The shield metal housing of the plug is formed with grounding sections respectively aligned with corresponding holes of the insulting housing enclosing the shield metal housing. When a front section of the plug is plugged into the socket, the metal housing of the socket and the grounding sections of the shield metal housing of the plug contact with each other through the holes of the insulating housing of the plug. Therefore, the induced electromagnetic wave of the shield metal housing of the plug can be grounded and diminished through the grounding circuit of the circuit board connected with the socket. Accordingly, the electromagnetic interference can be effectively diminished.
FIGS. 9 to 11 show an existent connector assembly such as P1394b-9pin connector assembly. The connector unit includes a socket 50 and a plug 60. The socket 50 has a main body 51 in which multiple terminals are inlaid. The main body 51 is enclosed by a metal housing 52. The main body 51 and the metal housing 52 define therebetween an insertion cavity 53. The plug 60 includes a shield metal housing 61 in which a terminal main body 62 is inserted. An insulating housing 63 is fitted around the shield metal housing 61. After the terminals in the terminal main body 62 are respectively connected with the leads, the rear section of the insulating housing 63 is wrapped with an insulating layer 64 by way of injection.
The terminal main body 62 is enclosed by the shield metal housing 61 for reducing the electromagnetic wave generated by the terminals when transmitting signals or shielding the terminals from external electromagnetic interference. Such measure works under low frequency, for example, below 800 MHz. However, the current signal transmission frequency is often up to 1.6 GHz or even over 3.2 GHz. Under such circumstance, the shield metal housing 61 enclosing the terminal main body 62 can simply partially reduce the electromagnetic interference. Moreover, in the case that the transmission frequency is further enhanced, the shield metal housing 61 can hardly diminish the electromagnetic interference.

Electromagnetic interference diminishing structure of a connector assembly


The invention provides dental cement compositions and methods of using them for binding hard tooth material, metal and ceramic. The cement compositions include shelf stable complexes of ethylenically unsaturated monomers reacted with cations. The cements have superior adhesion to tooth without separately acid etching dentin or enamel. Compositions of are useful as dental luting cements, liners, pit and fissure seal bases and restoratives.

The invention relates to dental compositions and methods of use thereof to bind hard tooth, metal and ceramic. The invention provides compositions including complexes formed by reacting multivalent cation with acid moieties of ethylenically unsaturated Monomers and prepolymers. The invention provides compositions with superior adhesion to dentin, enamel and cementum without the need for separate steps of acid etching dental enamel to adhere thereto. Compositions of the invention are useful as dental luting cements, liners, bases and restoratives. The compositions of the invention are hydrolytically stable. The heterogeneous multi-phase dental compositions of the invention show improved mechanical strength, for example, improved bond strength to tooth and are less sensitive to the effects of moisture.
Glass ionomers are described by A. Wilson in U.S. Pat. Nos. 5,079,277 and 4,758,612. Prior art glass ionomer compositions are combinations of a polyalkenoic acid polymer such as polyacrylic acid and an elutable glass which provides a source of cations to react with the polyacrylic acid. Prior art glass ionomers are brittle and weak in high stress applications and set poorly in the presence of moisture unless protected from water. Prior art pit and fissure materials include polymerizable hydrophobic resins with essentially no adhesion to tooth. They are adhered by infiltrating micromechanical undercuts produced by acid etching. They harden in-situ to protect the tooth from colonization by bacteria in order to reduce caries, but because they are difficult to use they are not universally employed to achieve this valuable result. They require the tooth be cleaned, acid etched, washed, dried and isolated by rubber dam to maintain dryness, to avoid contamination by saliva, and achieve suitable results. The procedure is thus uncomfortable for the patient and laborious for the dentist. The present invention provides pit and fissure sealant compositions which are applied to tooth without a separate acid etching step.
Olivier in U.S. Pat. No. 3,234,181 discloses melt-fabricable end-capped aromatic polyimides.
Lonerini in U.S. Pat. No. 3,407,176 discloses polyamide-acids and polymide from a mixture of dianhydrides.
Gall in U.S. Pat. No. 3,422,061 discloses coalesceable polyimide powders from a polycarboxylic aromatic dianhydride and phenylene diamine.
Angelo in U.S. Pat. No. 3,424,718 discloses copolymers of aromatic tetracarboxylic acids with at least two organic diamines.
Rogers in U.S. Pat. No. 3,959,350 discloses melt-fusible linear polyimide of 2,2-bis(3,4-dicarboxyphenyl)-hexafluoropropane dianhydride.
Madsen in U.S. Pat. No. 4,322,207 discloses dental cleaning slurry.
Beede et al in U.S. Pat. No. 4,324,591 discloses modifying agents for ion-leachable cement compositions.
Gibbs in U.S. Pat. No. 4,336,175 discloses polymide precursor solutions.
Schmitt et al in U.S. Pat. No. 4,372,836 disclose light curable acrylic dental composition with calcium fluoride pigment.
Smyth in U.S. Pat. No. 4,401,773 discloses highly reactive ion-leachable glass.
Denyer et al in U.S. Pat. No. 4,457,818 discloses dental compositions from urethane acrylate, diacrylate monomer, camphorquinone and dimethylaminoethyl methacrylate.
Ratcliffe et al in U.S. Pat. No. 4,459,193 discloses dental compositions containing camphorquinone and organic peroxide as catalyst.
Denton, Jr. et al in U.S. Pat. No. 4,492,777 discloses heat treated barium or strontium glass.
Bowen in U.S. Pat. No. 4,514,527 discloses method for obtaining strong adhesive bonding of composites to dentin enamel and other substrates.
Bowen in U.S. Pat. No. 4,521,550 discloses method for obtaining strong adhesive bonding of composites to dentin, enamel and other substrates.
Martin in U.S. Pat. No. 4,525,256 discloses photopolymerizable composition including catalyst comprising diketone plus 4-(N,N-Dimethylamino)benzoic acid or ester thereof.
Bowen in U.S. Pat. No. 4,588,756 discloses multi-step method for obtaining strong adhesive bonding of composites to dentin, enamel and other substrates.
Ratcliffe et al in U.S. Pat. No. 4,602,076 discloses photopolymerizable compositions.
Peters in U.S. Pat. No. 4,612,361 discloses poly(etherimides) and compositions containing the same.
Blackwell et al in U.S. Pat. No. 4,657,941 discloses biologically compatible adhesive containing a phosphorus adhesion promoter and a sulfinic accelerator.
Bowen in U.S. Pat. No. 4,659,751 discloses simplified method for obtained strong adhesive bonding of composites to dentin, enamel and other substrates.
Gallagher et al in U.S. Pat. No. 4,680,373 discloses process for the production of a random copolymer containing repeating polyimide units and repeating polyetherimide units.
Aasen et al in U.S. Pat. No. 4,719,149 discloses method for priming hard tissue.
Berdahl et al in U.S. Pat. No. 4,794,157 discloses polyetherimide copolymers, and method for making.
Engelbrecht et al in U.S. Pat. No. 4,806,381 discloses polymerizable compounds containing acid and acid derivatives, mixtures containing the same, and use thereof.
Blackwell et al in U.S. Pat. No. 4,816,495 discloses biologically compatible adhesive visible light curable compositions.
Calla et al in U.S. Pat. No. 4,864,015 discloses method for making thianthrene dianhydride and polyimides obtained therefrom.
Engelbrecht in U.S. Pat. No. 4,872,936 teaches dental cement mixtures containing polymerizable unsaturated monomers and/or oligomers and/or prepolymers containing acid groups and/or their reactive acid-derivative groups.
Aasen et al in U.S. Pat. No. 4,880,660 discloses method for priming hard tissue.
Kawaguchi et al in U.S. Pat. No. 4,918,136 discloses adhesive composition.
Ibsen et al in U.S. Pat. No. 4,964,911 discloses adhesive bonding of acrylic resins, especially in dentistry.
Huang et al in U.S. Pat. No. 4,966,934 discloses biological compatible adhesive containing a phosphorous adhesion promoter and accelerator.
Hirasawa et al in U.S. Pat. No. 4,985,198 discloses tooth-adhesive compounds.
Okada et al in U.S. Pat. No. 5,055,497 discloses curable resinous composition.
Akahane et al in U.S. Pat. No. 5,063,257 discloses dental glass ionomer cement compositions.
Wilson et al in U.S. Pat. No. 5,079,277 discloses polyvinylphosphonic acid and metal oxide or cermet or glass ionomer cement.
Mitra in U.S. Pat. No. 5,130,347 discloses photocurable ionomer cement systems.
Mitra et al in U.S. Pat. No. 5,154,762 discloses universal water-based medical and dental cement.
Ohno et al in U.S. Pat. No. 5,171,763 discloses curable composition.
Rambosek in Canadian Patent 873,935 discloses lithium aluminum silicate, polymer dental filling compositions.
Rossi in Canadian Patent 934,085 discloses dental restorative material of improved polishability.
Spoor in Canadian Patent 968,741 discloses production of coatings by curing with ionizing radiation.
Knight in Canadian Patent 969,299 discloses resins prepared from vinyl-ended polyurethane prepolymers.
Wailer in Canadian Patent 983,190 discloses photopolymerizable acrylic dental products.
Lee et al in Canadian Patent 1,018,294 discloses dental filling package.
O""Sullivan in Canadian Patent 1,020,687 discloses urethaneacrylate dental filling composition.
Rockett et al in Canadian Patent 1,028,441 discloses three package dental restoration system.
Lorenz in Canadian Patent 1,117,242 discloses coating composition comprising N-vinyl-2-Pyrrolidone and an oligomer.
Osborn in Canadian Patent 1,131,388 discloses radiation curable urethane compositions.
Davies et al in Canadian Patent 1,136,796 discloses potopolymerizable compositions.
Skudelny et al in Canadian Patent 1,154,895 discloses flowable mixture and use of synthetic calcium silicate.
Schaefer in Canadian Patent 1,159,984 discloses dental material having a plastics material base.
Munk in Canadian Patent 1,164,124 discloses pourable solid mixture.
Chevreux et al in Canadian Patent 1,176,787 discloses photosetting adhesive composition.
Gruber et al in Canadian Patent 1,179,094 discloses radiation curable coating composition comprising an oligomer and a copolymerizable ultra-violet absorber.
Morgan in Canadian Patent 1,194,637 discloses UV and thermally curable, thermoplastic-containing compositions.
Ratcliffe et al in Canadian Patent 1,198,847 discloses dental Compositions.
Szycher et al in Canadian Patent 1,200,647 discloses actinic radiation cured polyurethane acrylic copolymer.
Temin et al in Canadian Patent 1,213,699 discloses dental restorative composition.
Moran in Canadian Patent 1,216,982 discloses cure to elastomers composition
Ibsen et al in Canadian Patent 1,243,796 discloses dental composite and porcelain repair.
Ibsen in Canadian Patent 1,244,177 discloses methacrylate functional resin dental composite and porcelain repair compositions.
Ying in Canadian Patent 1,259,149 discloses dental restorative composition containing monofunctional monomer.
Randklev in Canadian Patent 1,261,992 discloses orthodontic bracket adhesive compositions.
Waknine in Canadian Patent 1,262,791 discloses a two component (Paste-Paste) self curing dental restorative.
Dougherty et al in Canadian Patent 1,262,981 discloses methods for posterior dental restoration employing light curable packable compositions.
Waknine in Canadian Patent 1,269,790 discloses dental restorative material.
Heid et al in Canadian Patent Application 2,009,471 discloses Hybrid plastic filling material.
Ibsen et al in Canadian Patent Application 2,011,438 discloses light-curable ionomer dental cement.
Rheinberger et al in Canadian Patent Application 2,038,695 discloses polymerizable dental materials.
Rheinberger et al in Canadian Patent Application 2,051,333 discloses polymerizable dental material.
Billington in European Patent Application 0 241 277 discloses glasses and poly(carboxylic acid) cement compositions containing them.
Billington in European Patent Application 0 244 959 discloses glass/poly(carboxylic acid) cement compositions.
Montgomery in European Patent Application 0 325 038 discloses surface priming composition for proteinaceous substrates, method of making and using same.
Kawaguchi et al in European Patent Application 0 335 645 discloses adhesive composition.
Griffin et al in European Patent Application 0 470 446 A1 discloses High glass transition temperature mixed polyimides and composites formed therefrom.
Masuhara in U.K. Patent Application 2 000 789 A discloses curable composition.
Hirasawa in U.K. Patent Application 2 156 347 a discloses (Meth) acrylic acid ester compounds boundable to tooth substrates.
Akahane et al U.K. Patent Application 2 202 221 discloses glass powders for dental glass ionomer cements.
U.S. Pat. No. 4,588,756 relates to aromatic based compositions employed in dentistry as a component in a dental adhesive system requiring multiple pretreatment steps including application of an acid.
Engelbrecht in U.S. Pat. No. 4,872,936 broadly teaches dental cement mixtures containing polymerizable unsaturated monomers and/or oligomers and/or prepolymers containing acid groups and/or their reactive acid-derivative groups.
Mitra in U.S. Pat. No. 5,130,347 discloses a photocurable ionomer cement having a photocurable amid monomer.
Mitra in U.S. Pat. No. 5,154,762 discloses water soluble reducing and oxidizing agents.
It is an object of the invention is to provide new dental compositions useful as filling materials, cavity liners and bases, cements, and pit and fissure sealants other restorative materials which are adhesive to tooth structure.
It is an object of the invention to provide a composition which reduces the steps and time required to adhere metal or ceramic to tooth structure.
It is an object of the invention to provide an adhesive composition for adhesion between tooth structure and/or bone and polymeric composites.
It is an object of the invention to provide dental compositions that are relatively inexpensive and easy to manufacture.
xe2x80x9cMonomerxe2x80x9d as used herein means monomer or oligomer.
xe2x80x9cSetxe2x80x9d as used herein means a polymerizable composition undergoes a change so that it becomes firm, stiff and nonpliable.
As used herein xe2x80x9cThe MAX Litexe2x80x9d means THE MAX(trademark), a curing unit for light-polymerizable dental materials sold by Dentsply International Inc. through its L. D. Caulk Division.
Throughout this disclosure unless otherwise specified amounts of each component of a composition are in percent by weight.
The invention provides dental compositions and methods of using them for adhering to hard tooth structures, metal and ceramic. The compositions include shelf stable complexes of ethylenically unsaturated monomers reacted with cations. These compositions have superior adhesion to tooth without separately acid etching dentin or enamel. Compositions of the invention are useful as dental luting cements, liners, bases and restoratives pit and fissue sealants. In accordance with a method of polymerization of the invention is provided the sequence of steps of forming a substantially pliable polymerizable composition, including polymerizable complex coated particles within the scope of the general formula:
wherein each Moiety independently is a moiety having at least one acid group and at least one polymerizable group each M is a multivalent cation of Particle which forms a complex by bonding to one or more Moiety, and t, r and q each independently is a number having an average value of 1 or more, storing the polymerizable composition for at least 12 hours, and applying the polymerizable composition to a tooth.
Compositions of the invention provide superior adhesion to dentin, enamel and bone. In a preferred embodiment compositions of this invention are used without a separate step of etching the surfaces to be joined. The adhesive dental materials provided by this invention include restorative materials especially cavity bases and liners, luting cements, pit and fissure sealants and filling materials.
In accordance with the invention is provided a method of polymerizing polymerizable composition which includes a polymerizable salt (complex) within the scope of the general formula (A1) and/or a novel material within the scope of general formula (A1xe2x80x2):
wherein each Moiety independently is a moiety having at least one acid group and at least one polymerizable group, each M is a multivalent cation which forms a complex by bonding to one or more Moieties; Particle is a particle, r, t, and q each individually is a number having an average value of 1 or more. In general formula A1xe2x80x2 M is a cation of Particle. Preferably, the Particle is glass or ionomeric polymer. The composition is stable and adapted to not set in order of increasing preference for at least 12 hours, 24 hours, or 36 hours, more preferably for at least 7 days and most preferably for at least 1 year in the absence of polymerization initiation. The letter is preferably greater than 100, more preferably greater than 1,000 and most preferably greater than 10,000. A composition in accordance with a preferred embodiment of the invention includes a substantial portion of polymerizable salt within the scope of general formula A1 in equilibrium with polymerizable acid(s) and a source of multivalent cation(s). The polymerizable salt in such compositions is preferably formed by mixing a polymerizable acid and a source of multivalent cations in the presence of water. The polymerizable salt is preferably in equilibrium with the polymerizable acid and a source of multivalent cations for extended periods of time, for example, more than one year. These compositions do not require hermetic sealing to prevent substantial setting as is required by prior art compositions. Thus, these compositions advantageously form, for example, one component compositions which do not substantially set, and are thus, shelf stable preferably for more than one year. It is preferred that the salt forms on the outer surface, perferably as a coating on glass particles used as multivalent cation sources, and that upon polymerization of the polymerizable group a stronger material is formed than in prior art compositions which are multicomponent systems and/or do not include water as a component of the composition applied to a tooth. Preferably these compositions are mixed with Monomers and/or prepolymers and applied to a tooth. These compositions preferably include at least one Monomer and/or polymers which does not include an acid moiety.
More specifically the invention provides a polymerizable composition which includes a polymerizable salt (complex) within the scope of the general formula (B1) and/or a novel material within the scope of the general formula (B1xe2x80x2):
wherein each Group independently is a polymerizable group, each A independently is an acid group, each Divalent independently is a divalent organic moiety, each M independently is a multivalent cation which forms a complex by bonding to one or more A; Particle is a particle and o, p, q, r, s and t each independently is a number having an average value of at least 1. Preferably M is a multivalent ion of a glass particle. This composition is adapted to not set for at least 24 hours in the absence of polymerization initiation.
Preferably polymerizable compositions in accordance with the invention include at least 1 percent by weight, more preferably at least 3 precent by weight of polymerizable complexes within the scope of general formula (A1).
Complexes within the scope of general formulas, A1 and B1, preferably have molecular weights less than 100,000; more preferably less than 20,000 and most preferably less than 5,000 and especially preferred are such complexes having molecular weights less than 1,000.
Particulate material within the scope of general formulas A1xe2x80x2 and B1xe2x80x2 preferably have a particle size having a longest dimension in order of increasing preference of: less than 1 mm, less than 0.1 mm, less than 0.01 mm or less than 0.001 mm.
Dental compositions of the invention include polymerizable unsaturated substituted aromatic complexes within the scope of the general formula (I):
wherein X is
wherein
R1 and R2 each independently is a polymerizable unsaturated moiety having from 2 to 13 carbon atoms,
R3, R4, R5, and R6 each independently is hydrogen, halogen, alkyl having from 1 to 10 carbon atoms or halogenated alkyl of from 1 to 10 carbon atoms,
R9, R10, R11, R12, R13 and R14 each independently is hydrogen, alkyl having from 1 to 10 carbon atoms or aryl having from 6 to 10 carbon atoms,
Z1 and Z2 each independently is a moiety including an acid group,
a, m and n each independently is 0 or 1,
b, and p independently is an integer from 1 to 10, l is from 1 to 3, and
M is a multivalent cation which reacts with acid moieties to form a complex.
In accordance with a preferred embodiment of the invention R1 and R2 each independently is:
wherein
R7 a divalent carbon containing radical and
R8 is hydrogen, halogen or alkyl having from 1 to 10 carbon atoms.
In a preferred embodiment of the invention compounds are provided within the scope of general formula I wherein n and m are zero, X is oxygen, sulfonyl or ditrifluoromethyl; and R1 and R2 are
Most preferably compounds within the scope of general formula I are those wherein X is oxygen or ditrifluoromethyl, and M is barium, calcium, strontium or aluminium. Preferred polymerizable unsaturated groups R1 and R2 independently are alkenyl, alkenoxy, cycloalkenyl, arylalkenyl, and alkenaryl moieties; with vinyl, and styryle moieties being more preferred, and acryl and methacryl moieties that constitute the polymerizable groups of many monomers in dental materials being especially preferred.
Exemplary R1 and R2(meth)acrylate moieties include:
where n preferably is an integer from 1 to 10. Preferably R1 and R2 are (meth)acryloyloxyethyl moieties.
Preferred compounds for use in complexes within the scope of formula I include diesters which are the adducts of 2,2-bis(3,4-dicarboxylphenyl)hexafluoropropane anhydride, 4,4xe2x80x2-oxydiphthalic anhydride, 4,4xe2x80x2-sulfonyldiphthalic anhydride, respectively with 2-hydroxyethyl methacrylate. In a preferred embodiment at least two aromatic rings of a compound for use in complexes with the scope of formula I are joined through at least one saturated carbon, oxygen or sulfonyl.
Aromatic dianhydrides preferred for making compounds for use in complexes within the scope of general formula I react to form partial esters and carboxylic acid functionality. Dianhydrides having at least two aromatic rings are more preferred. Most preferably at least two aromatic rings are joined as shown in formula I to provide disruption of conjugation between the aromatic rings. It has been found that such compositions are less sensitive to light induced changes in color, and are therefore preferred when esthetic considerations are of importance. Most preferred examples are 4,4xe2x80x2-oxydiphthalic anhydride and 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride.
Dental compositions in accordance with a preferred embodiment of the invention include an acid functional polymerizable organic ester for use in complexes within the scope of general formula I, water, cation elutable glass filler, and a polymerization catalyst system. Optionally, additional polymerizable monomers and/or prepolymers are included.
A composition in accordance with a preferred embodiment of the invention provides polymerizable monomer having at least one acid radical or reactive acid derivative, and a source of cations reactive with the acid moiety, and a catalyst system. Preferably the catalyst system promotes free radical polymerization and preferably includes visible light curing and/or a redox catalyst system. Preferably the composition includes liquid diluents, and/or filler adjuvants. Diluent preferably co-polymerizes with the polymerizable monomer within the scope of general formula A1. Alternatively the diluent is nonreactive with the polymerizable monomer. Water or low boiling alcohols such as methanol, ethanol, and isopropanol are nonreactive diluents. Suitable polymerizable co-monomers are disclosed in U.S. Pat. No. 4,657,941 particularly at column 3 line 5 through column 5 line 59 and U.S. Pat. No. 4,514,342 both of which are incorporated herein by reference. The filler adjuvants are preferably reactive, for example by providing a source of cations which are reactive with the acid moiety of the polymerizable monomer. Nonreactive filler is preferably included in compositions in accordance with a preferred embodiment of the invention. Optionally, fillers have surface treatments to improve compatibility and strength of the resulting composition. Exemplary fillers include silica, silicates, alumina, aluminates, calcium fluoride, strontium fluoride, glasses including fluorine glasses, ceramics and minerals including mica, zeolites, ceramics, calcium apatites and organic polymers and those disclosed in U.S. Pat. Nos. 4,758,612 and 5,079,277.
A preferred composition of the invention includes a monomer compound for use in complexes within the scope of general formula A1, at least one finely divided reactive filler which provides a source of cations reactive with the acids or acid derivative of the monomer compound and curing agent. A dental composition in accordance with the invention includes a compound for use in complexes of general formula A1, catalysts, initiators, accelerators, filler, adjuvants, source of cations, water, and diluent. Dental cements and dental filling compositions in accordance with a preferred embodiment of the invention include monomer compounds for use in complexes within the scope of general formula A1.
The compounds for use in complexes within the scope of general formula A1 have at least two different functional substituent groups, one of which is capable of addition polymerization and the other of which is carboxyl or other acid or reactive acid derivative. Most preferably these compounds include at least one polymerizable group and one or more acid or reactive acid derivative groups. Preferred compounds within the scope of general formula A1 are derived acid formed from the reaction of 4,4xe2x80x2-oxydiphthalic anhydride or 2,2-bis(3,4-dicarboxylphenyl)hexafluorpropane dianhydrides with a polymerizable hydroxyl or polyhydric compound to form esters and partial esters thereof.
The new salt compounds of the invention are capable of being polymerized to form linear or crosslinked polymers which contain multiple acid groups or reactive acid derivative groups that have been reacted with cations, especially those of valence 2 or greater to form poly-salts. Because the salt compounds are monomers of relatively low molecular weight with a high density of both ethylenic unsaturation and carboxylic reactive acid derivative sites, excellent curing with superior integrity occurs. The carboxyl group itself is most preferred over other acid moieties or the reactive acid derivative ions. Especially appropriate acid moieties are all those that react with oxidic, mineral, ceramic, vitreous, or metallic fillers. Examples of these other acid moieties include:
of phosphorus acids wherein R is alkyl, aryl, or vinyl; the moieties xe2x80x94SO2H, SO3H, or xe2x80x94Oxe2x80x94SO3H of sulfuric acids; the moieties:
of boron acids wherein R is alkyl, aryl, or vinyl and cationic acid moieties including xe2x80x94NR2H+ wherein R is H or alkyl. The reactive acid derivatives can be substituted with acid halides, with acid anhydrides, and with acid amides, nitrites, and esters that readily hydrolyze into acid, such as can enter into ion-exchange, neutralization, salt formation, or chelation reactions with the reactive filler. Preferred acid or reactive acid derivatives are carboxylate, phosphate, phosphonate, sulfonate, or borate acid moieties and/or of their reactive derivatives.
The compositions of the invention are formulated as one, two or more components, visible light curable, self cure, and/or dual cure product or combinations of these. The composition of a preferred embodiment of the invention includes polymerizable carboxylic acid monomer, an optional filler and/or diluent, a cationic elutable glass or other source of polyvalent cations, and a polymerization catalyst system. The polymerizable carboxylic acid monomers are chosen to provide a suitable balance of hydrophobic and hydrophilic moieties in order to provide a balanced set of properties including adhesion to metal, ceramics and tooth. They are essentially non-volatile and not critically affected by moisture during hardening within the oral cavity; and provide the ability to be used on hydrated surfaces such as found on and in teeth; and in a preferred embodiment do not require the separate steps of acid etching and adhesive priming to achieve adhesion to tooth structure.
For a better understanding of the characteristics and method of producing the preferred ethylenically unsaturated carboxylic compounds for use in complexes of the present invention the preparation of a preferred series of the compounds is carried out as follows:
In the presence of acid, base or other suitable catalyst one mole 4,4xe2x80x2-oxydiphthalic anhydride is reacted with two moles of a compound of the general formula Rxe2x80x94OH, wherein R is a polymerizable unsaturated moiety having from 2 to 13 carbon atoms. This yields a liquid product which is believed to be a mixture of isomer monomers of general formulas II-IV:
As discussed in detail in Example 3 by reacting one mole of oxydiphthalic anhydride with two moles of methacryloyloxyethyl alcohol also known as 2-hydroxyethyl methacrylate (HEMA) in the presence of catalyst a liquid product is formed which is believed to be a mixture of isomer monomers V-VII:
Monomer compounds for use in complexes within the scope of general formula I are reactive esters which have at least one unreacted carboxylic acid group and one polymerizable group in the monomer. The number of reacted or unreacted carboxylic acid groups in the monomer is controlled by varying the reaction conditions and molar ratio of reactants. The monomer compounds of the invention polymerize by addition polymerization through the ethylenically unsaturated group. Curing agents, catalysts, initiators and/or accelerators, are used to expedite and control the polymerization. A peroxide initiator, for example benzoyl peroxide, and/or heat are useful to initiate the reaction. Accelerators enhance the reaction so that it may proceed more expeditiously at room temperature. Accelerators preferably include reducing agents such as amines or sulfinates, and/or transition metal ions. Ultraviolet and/or visible light are used with initiators and accelerators to initiate and accelerate the polymerization. Visible light curing is preferred for curing the compositions of the invention in the mouth. For preformed objects, or those cured outside the body, other forms of radiation, for example ultraviolet ionizing radiation is preferred for curing the compositions of the invention.
In accordance with the method of the invention in-vivo polymerization does not harm the patient within whom polymerization of monomer compound (or complexes) within the scope of general formula I occurs. Preferably a single part composition is induced to polymerize by the application of heat or light. To initiate by irradiation with ultraviolet or visible light the initiator, for example a benzophenone or camphorquinone is preferably used to form a single, premixed, ready to use shelf-stable composition. A preferred embodiment of the composition of the invention includes a polymerization catalyst system having a light sensitive polymerization initiator such as camphorquinone, a reducing agent such as ethyl 4-dimethylaminobenzoate (EDAB) and an oxidizing agent such as benzoyl peroxide. Redox polymerization systems known to the art are preferably used to polymerize the composition of the invention. Preferred redox polymerization catalyst systems for use in accordance with the invention include, a peroxide and tributyl boron and/or a transition metal salt. Redox polymerization catalysts and catalyst systems are those disclosed in U.S. Pat. No. 4,657,941 at column 7 line 10 through column 8 line 27 incorporated herein by reference. A particular polymerization method and system may be preferred depending on the application requirements of the material. Whatever the mode of polymerization, or xe2x80x9cset or curexe2x80x9d of the composition including the salt monomers, an important characteristic of the polymers which form is that they have been prereacted with di- or polyvalent cations. The salt compounds and compositions of the invention exhibit adhesion between the resin and a cation containing surface, metal, metal oxide, tooth, and/or bone against which they are polymerized.
Fillers which are especially suited for use in compositions of the invention are inorganic glasses such as are used in glass ionomer cements. Exemplary of such fillers are those of U.S. Pat. No. 4,814,362 which is incorporated herein by reference in its entirety. Preferred fillers are glasses formed from or including, barium, calcium, strontium, lanthanum, tantalum, and/or tungsten silicates and aluminates and/or aluminosilicates, silica, including submicron silica, quartz, and/or ceramics for example, calcium hydroxy apatite. In a preferred embodiment of the invention reactive cations, especially those of calcium, strontium and aluminum, and anions especially fluoride ions; are eluted from the fillers. The fillers used in the invention preferably are reduced in particle size and in a preferred embodiment are silanated before they are incorporated into such compositions. Preferred levels of filler are from about 20% to about 85% based on the total weight of the cement composition, with from about 40% to about 85% being more preferable and about 50-80% being most preferred. If a more finely particulated filler is used, amounts of filler may be decreased due to the relative increase in surface area which attends the smaller sizes of particles. Preferred particle size distributions are from 0.02 to 50 microns, more preferably 0.1 to 10 microns, and most preferably 1 to 6 microns.
In a preferred embodiment of the invention the cations of the salts are di- and polyvalent cations, such as Sr, Ca, Al and Ba. In another preferred embodiment compositions of the invention include solvents, plasticizers, pigments, anti-microbials and therapeutics which may be time released from the composition, and oxidation inhibitors such as butylated hydroxytoluene. In addition to compounds within the scope of general formula I compositions in accordance with the invention preferably include polymerizable unsaturated diluent monomers, oligomers and/or prepolymers that do not contain any acid groups and/or salts thereof and/or reactive readily hydrolyzing acid-derivative groups thereof. One such preferred monomer is hydroxyalkyl methacrylates. Compositions of the invention may also preferably include compounds having acid groups and/or their salts and/or their readily reactive hydrolyzing derivative groups but do not contain any groups that are unsaturated and polymerizable, such as multi-basic acids or their reactive, readily hydrolyzing derivatives. Especially preferred multibasic acids are hydroxy acids such as tartaric or citric acid.
Compounds that have chelating groups but do not contain carboxylic acid groups or readily hydrolyzing acid-derivative groups are preferably included in composition in accordance with the invention, for example vanillates, syringates, and salicylates.
Mixing the compositions of the present invention may be achieved using standard compounding techniques. For example, liquids, photoinitiator(s), and accelerator(s) are blended first, and fillers are added incrementally thereafter. When blending light sensitive compositions, however, a photosafe room illumination, i.e., one that does not contain substantial amounts of wavelengths of electromagnetic radiation that would activate the photoinitiating system is used to avoid initiating polymerization of the composition prematurely.
Cements
The salt compounds of compositions of the present invention also have medical applications such as in self adhesive bone cements. However, they are most preferred to use in dental treatment by application to a tooth or a number of teeth in vivo, in the mouth of a live patient by a dentist or dental practitioner.
The application of the compositions of the invention is preferably as a dental cement applied to tooth. The dental cement compositions of the invention preferably include a salt compound within the scope of general formula I, and other ingredients, such as curing catalysts, initiators, accelerators, diluents and/or adjuvants. The composition is applied as a cement using conventional techniques and preferably cured with application of visible light in a conventional manner. Cements in accordance with the invention are self adhesive to dentin and enamel. These cements are used in bonding dentin to structures, for example, to bond a ceramic inlay to a prepared cavity of a tooth. Inlays preferably are polymers, or ceramics which are cast or built-up from porcelain frits and fired. Alternatively, inlays are machined from metal such as titanium or gold or preformed polymeric composite or homogeneous monolithic polymer compositions, for example by CAD-CAM procedures. In accordance with a preferred embodiment of the invention metal or ceramic superstructures for crowns, and bridges and/or orthodontic appliances are bonded to teeth using cement compositions of the invention. Such cement compositions join metal or ceramic to tooth by application of the cement composition by bringing them into contact until the cement hardens.
A preferred composition of the invention includes a two-part system. One part includes a curing agent. The two parts are spatuled to form a cement prior to placement on tooth. The placement is by standard technique(s). Preferably the cement includes a visible light and/or a self-curing redox polymerization initiator system. In a preferred embodiment of the invention luting cement compositions have low viscosity and film thicknesses less than about 25 xcexcm to bond close fitting appliances to prepared teeth. In one embodiment luting cement compositions of the present invention may be prepared of such high viscosity and consistency that they form adhesive xe2x80x9cgluexe2x80x9d lines of thicknesses up to several hundred microns to lute less close fitting restorations, for example inlays prepared using present state-of-the-art CAD-CAM devices. Compositions of the invention are mechanically strong, abrasion resistant, and are esthetically suitable and serve as the sole structural element to retain inlay, crowns and bridges or other appliances to tooth structure.
Filling Compositions
A preferred dental treatment in accordance with the invention is the application of dental filling compositions which include a curing agent and at least one salt compound within the scope of general formula I. Preferably the dental filling composition includes finely divided reactive filler that can react ionically with the acids or acid derivatives of the monomer. Preferably the composition is applied to a tooth as a filling material using conventional techniques as a one-component material and is cured with application of visible light in conventional manner.
Pit and Fissure Sealants
In a preferred embodiment of the invention a one or two component pit and fissure sealant which includes at least one salt compound within the scope of general formula I is applied to anatomic defects and/or the exterior of teeth. The sealant limits the ability of caries-forming bacteria to colonize the pits, fissures and other surfaces of the teeth. Pit and fissure sealant compositions in accordance with the invention are an especially valuable means of reducing caries by filling and eliminating enamel defects. The pit and fissure sealants of the invention are preferably applied without prior acid etching or the use of rubber dam to teeth. In one embodiment fluoride eluting compounds and glasses are preferably included in compositions of the invention. Fluoride is eluted to reduce the incidence of caries in tooth substance adjacent the compositions of the invention.
In accordance with the method of the invention cement and restorative compositions include at least one polymerizable acid reactive ethylenically unsaturated compound within the scope of general formula I. Such compositions are applied to tooth without prior etching of the tooth.
Method for Measurement of Compressive Strength Using International Standard Organization(ISO) 9917:1991(E) at pages 5-7 Dental Water-based Cements
For each material to be tested, cylinders 4 mm diameter and 6 mm long were prepared by filling the mixed material into teflon molds and light curing from each end for 40 seconds using The MAX Lite. The cylinders were removed from the molds and stored in water at 37xc2x0 C. for 24 hours prior to testing. The force needed to load the specimens to breaking point was measured using a universal testing machine operating at a crosshead speed of 5 mm/min.
Method of Transverse Flexural Strength Using International Standard Organization(ISO)4049:1988(E) at pages 6-8 Resin-based Filling Materials
The uncured material was filled into a split Teflon(copyright) mold with internal dimensions 25 mmxc3x972 mmxc3x972 mm. The exposed faces were then covered with polyester foil and clamped between transparent plastic blocks. The material was light cured for a total of 120 seconds by moving a dental curing light evenly backwards and forwards along the mold with the wand of the light in contact with the plastic blocks. After curing, the hardened specimens were stored in water at 37xc2x0 C. for 24 hours. Before being tested, any remaining flash along the edges of the specimens was carefully removed and the exact dimensions of each specimen measured. The specimens were then tested in three point bending mode using a universal testing machine set to a crosshead speed of 0.75 mm/min, with the sample resting on supports 20 mm apart and being loaded at the mid point. The transverse bending strength was calculated from the standard formula in Megapascals (MPa).
Method for Measurement of Diametral Tensile Strength
Modified procedures of ADA Specification No. 9 and No. 27 were utilized for all materials tested. Split teflon molds with internal dimensions of 3 mmxc2x10.1 mm high and 6 mmxc2x10.1 mm diameter were used. Mylar film was placed at the bottom of the mold. After the mixed material was conveyed into the mold in excess, a second piece of mylar film was placed on top of the mold and pressed with a metal plate to squeeze out excess material. The plate was then removed with the mylar still in place on top of the material and each side was cured for one minute using The MAX Lite. After being stored in 37xc2x0 C. water for 24 hours, specimens were tested on an Instron device for measurement of diametral tensile strength rising a 10 mm/minute crosshead speed.
Measurement of Adhesion to Dentin: Bond Strength to Dentin
Extracted human teeth used for the shear bond strength test was treated in 1% sodium hypochlorite for 18 to 24 hours and stored in distilled water in a refrigerator at about 4xc2x0 C. until needed. The teeth were washed with water, mechanically sanded with 120/320/600 grit carborundum paper until a flat dentin surface was exposed.
The teeth were then individually prepared as follows. Each tooth was blown dry with compressed dry air to ensure the dentin surface was free from noticeable moisture. A small plastic straw with 3.7 mm inner diameter and 2 to 3 mm in length was filled with mixed material and seated on the dentin so as to form a post without pressure. The upper open end of the straw was covered with a thin film and cured with The MAX Lite for 40 seconds. The specimens were then stored in distilled water at 37xc2x0 C. for more than 24 hours. The teeth were then vertically mounted in a one inch phenolic ring using self curing polymethyl methacrylate resin to provide a base for testing with the post at right angles thereto. The mounted specimens were loaded in shear in an Instron device for measurement of adhesion of the post to dentin at 5 mm/minute crosshead speed. The load was applied parallel to the prepared tooth surface and at right angles to the post until fracture occurred. The shear bond strength was calculated.
Method of Fluoride Releasexe2x80x94Static Extraction
A 1 mm thick by 20 mm diameter chip of the material was cured for 1 minute on each side with the Max Lite. A tiny hole was drilled in the chip. The specimen was tied with a nylon thread, suspended in 10 ml deionized water in a plastic jar caped with a lid, and stored in 37xc2x0 C. oven for one week, or otherwise indicated. Water in each jar was decanted to a separate 30 ml plastic beaker. The specimen in the jar was washed in 1 ml deionized water, and the water rinse was added to the respective beaker. To the jar, 10 ml of fresh deionized water was added and put back in the 37xc2x0 C. oven for the next measurement. The solution was diluted with 11 ml Total Ionic Strength Adjustor Buffer (TISAB) solution and measured with fluoride electrodes.
This method is used to simulate what happens in the mouth over a long period of time. The water is changed weekly. The values are reported in ppm, in micrograms of fluoride per gram of sample, and in micrograms of fluoride per centimeter square of sample surface.
Having generally described the invention, a more complete understanding can be obtained with reference to certain specific examples, which are included for purposes of illustration only. It should be understood that the invention is not limited to the specific details of the Examples.


Through holes formed on an atomization pipe can prevent fuel adhering on inner walls of the through holes from escaping. In addition, when fuel adhering on an inner circumferential surface of the atomization pipe flows toward a downstream side, the fuel enters the through holes. Thus, the fuel can be confined therein. Furthermore, an absorbing member can absorb the fuel that has adhered to a downstream inner wall of the atomization pipe and flows toward the downstream side. Moreover, a periphery of the intake passage hole of a gasket protrudes from the inner wall, so that flow of the fuel that the absorbing member fails to absorb toward the downstream side can be blocked. Accordingly, a rapid increase in the amount of fuel flowing into the engine body can be reliably prevented. Therefore, fluctuation in the number of revolutions of the engine can be sufficiently restrained.

1. Field of the Invention
The present invention is related to a two-cycle engine.
2. Description of Related Art
Conventionally, a two-cycle engine including an engine body, a carburetor, and an inlet pipe that connects the engine body and the carburetor is known. Being simple in mechanism and light in weight, such a two-cycle engine is often installed in a portable work machine such as a chain saw.
In the engine, a fuel ingredient in a mixture gas adheres on an inner wall of an inlet pipe. When negative pressure in the inlet pipe is elevated, this fuel (fuel ingredient) is suctioned into the engine body. Such a suction causes an excessive fuel delivery to flow into the engine body until fuel is delivered again in a standard amount, lowering the number of revolutions and thus making the engine unstable. Such an excessive suction of fuel by the engine may occur periodically, Besides, when a posture of a portable work machine in which the engine is installed changes, fuel (mixture gas) staying in the inlet pipe flows into the engine body, which is another cause of the fluctuation of the number of revolutions.
In view of the above, fluctuation of the revolutions have conventionally been restrained by increasing the revolving inertia of the engine with a flywheel or the like. However, in recent years, an engine without a flywheel or the like is occasionally employed for weight reduction. Because the revolving inertia of such an engine is small, the fluctuation of the revolutions cannot be restrained by the revolving inertia.
To solve the problem, an engine in which a large number of projections shaped in tetrangular pyramids are provided on the inner wall of the inlet pipe is known (e.g., Document 1: JP-A-62-206263). In the engine of Document 1, the projections can restrain the fuel adhering on the inner wall of the inlet pipe from flowing toward the engine body, so that the fluctuation of the number of revolutions can be restrained.
However, with the engine of Document 1, flow of the fuel (mixture gas) staying in the inlet pipe into the engine body due to change in posture of the portable work machine in which the engine is installed cannot be sufficiently prevented In addition, when the negative pressure in the inlet pipe is elevated, the fuel adhering on the inner wall of the inlet pipe inevitably flows into the engine though the flow amount may be small. Therefore, improvement can be made to the engine of Document 1 with in terms of restraining fluctuation of the number of revolutions.


A guide for positioning a tibial tunnel in anterior cruciate ligament (ACL) reconstruction. The guide includes a guide arm and a drill sleeve connected to the guide arm. A distal tip of the guide arm is configured to contact a femoral surface, and a distal tip of the drill sleeve is configured to contact a tibial surface when the distal tip of the guide arm contacts the femoral surface.

A damaged ACL is often replaced with a graft from a patellar tendon or a semitendinosus tendon. Generally, the patellar tendon graft has small bone pieces attached to its ends, whereas the semitendinosus tendon graft does not. Tunnels are formed in the tibia and femur for use in implanting the graft in the patient's knee. The graft is then secured in the tunnels by fixation means, such as, for example, interference screws or sutures tied to screw posts.


An engine control apparatus for a multi-cylinder compression ignition internal combustion engine includes a combustion status sensor and a controller. The combustion status sensor is installed in a selected one of cylinders of the engine. The controller works to sample an output from the combustion status sensor to determine a combustion status parameter and determine injection timings so as to bring the combustion status parameter into agreement with a target value. The controller also corrects the injection timing for at least one of the cylinders in which the combustion status sensor is not installed so that a combustion status parameter of the at least one of the cylinders lies on an advanced side of that of the one of the cylinders in which the combustion status sensor is installed, thereby avoiding the deterioration of quality of combustion of the fuel arising from a shift of the time of the ignition in the retarded direction from a desired time point.

1 Technical Field of the Invention
The present invention relates generally to an engine control apparatus for multi-cylinder compression ignition internal combustion engine which is designed to correct injection timings based on the time of ignition of fuel in the engine.
2 Background Art
Typical multi-cylinder compression ignition internal combustion engines such as diesel engines have installed therein fuel injectors to inject fuel directly into cylinders thereof to produce combustible air-fuel mixture. Engine control systems for such a type of engines are usually designed to correct times of injection of the fuel into the cylinders (i.e. injection timings) based on the status of combustion of the engine in order to ensure desired levels of output of and quality of emissions from the engine. Specifically, the engine control systems work to sample an output from a combustion pressure sensor installed in the engine to determine an actual time of ignition of the fuel in the engine and correct the injection timings so as to bring the actual time of ignition into agreement with a target value.
Use of combustion pressure sensors in all the cylinders of the engine to correct the injection timings independently on a cylinder basis result in disadvantage in terms of cost. In order to alleviate this problem, there may be proposed systems which have a combustion pressure sensor installed only in one of cylinders of the engine to sample an actual time of ignition of fuel therein, determine the injection timing for the one of the cylinders so as to compensate for an ignition lag that is a difference between the actual time of ignition, as sampled, and a target time, and correct injection timings for the other cylinders based on the ignition lag under assumption that the other cylinders usually undergo the same ignition lag.
When the time of ignition of the fuel is retarded from some time point, it usually results in an undesirable drop in output from the engine. This is because the ignition of the fuel upon a drop in pressure in the cylinder results in a lack in utilizing combustion energy or a misfire in the course of combustion of the air-fuel mixture without adequate expansion thereof, leading to a reduction in the combustion energy.
In order to avoid the above problem, Japanese Patent First Publication No. 2000-130224 teaches an engine control system for internal combustion engines equipped with an EGR (Exhaust Gas Recirculation) system working to return or recirculate a portion of exhaust gas of the engine (i.e., EGR gas) into an intake pipe. The engine control system has a combustion pressure sensor installed in only one of cylinders of the engine which is the greatest in ratio of the amount of the EGR gas to the amount of intake air in the engine and works to determine and correct all target times of injection of fuel (i.e., injection timings) into the cylinders based on an actual time of ignition of the fuel, as determined using an output of the combustion pressure sensor. The engine control system is designed based on the fact that the one of the cylinders that is the greatest in the EGR gas-to-intake air ratio is apt to experience a misfire due to a drop in concentration of oxygen in the intake air arising form addition of the EGR gas thereto to correct the injection timings based on the actual time of the ignition in the one of the cylinders in which the combustion pressure sensor is installed to avoid the misfire.
However, fuel injectors have usually individual variability in injecting fuel into cylinders of the engine. A crank angle sensor has also individual variability in measuring the angular position of a crankshaft of the engine arising from manufacturing tolerances thereof. This will result in a variation in time of ignition of the fuel among the cylinders of the engine, which may lead to an undesirable shift of the times of ignition of the fuel in the cylinders in the regarded direction from a time point at which the quality of combustion of the fuel is deteriorated, resulting in a drop in torque, as produced by the engine.

Compression ignition engine control apparatus ensuring desired output of torque


The disclosure relates to compositions and methods of using the compositions to color hair. The composition contains at least one polyamine, at least one acid, at least one water-insoluble ingredient, at least one hair colorant, solvent and optionally at least one auxiliary ingredient. The methods for coloring involve contacting hair with the composition of the disclosure.

The disclosure relates to compositions and methods for coloring hair. Typically, hair is colored by application of dyes and/or bleaching agents (coloring agents). For optimum efficiency during the dyeing and/or the bleaching process, the coloring agents should be concentrated as much as possible on the hair fiber. In addition, a barrier to aid in highlighting and lowlighting hair would be useful. Such a barrier would allow coloring agents to selectively color portions of hair while leaving other portions of hair protected and uncolored thus giving highlights or lowlights in selected portions of the hair. Accordingly, a hair coloring composition that aids in the distribution of coloring agents onto the hair fiber would be useful in making more efficient use of hair coloring agents.


The device has flexure correcting means for operating to rotate a first eccentric cam provided at a central part of a first side of a reflecting mirror, thereby moving up and down the central part of the first side to correct the flexure of the reflecting mirror, torsion correcting means for operating to rotate a second eccentric cam or/and a third eccentric cam provided at the ends of a second side opposed to the first side of the reflecting mirror, thereby moving up and down both ends of the second side of the reflecting mirror to correct the torsion of the reflecting mirror, and a rotation operation portion provided at each of extended ends of camshafts provided at the eccentric cams to correct the flexure and torsion of the reflecting mirror.

1. Field of the Invention
This invention relates to a projection type image display device that changes the optical path of an image from a projector using a reflecting mirror and projects a resultant image on a screen from behind, and more particularly to an image distortion correcting mechanism used to correct image distortions generated by the use of the reflecting mirror.
2. Description of the Related Art
As shown in FIG. 9, a multivision device includes a plurality of rear projection type image display devices (rear projectors) arranged in the vertical and horizontal directions, and the output images of the projectors are projected to display an image on a large screen.
In FIG. 9, a projector 1 provided in a prescribed lower position in a cabinet 7 emits an output image upwardly from its projection lens. The emitted output image has its optical path changed by a reflecting mirror 3 provided in a prescribed position in the cabinet and projected on a screen 4 provided at the front surface of the cabinet 7. A position adjuster 2 having the projector 1 thereon can adjust the position of the image to be projected on the screen 4 relative to the screen 4.
In the rear projection type image display device having the conventional reflecting mirror 3, it is difficult to accurately project an image from the projector 1 on the screen 4, and therefore the position adjuster (six-axis adjuster) is used to adjust the image in the optimum position. However, the position adjuster 2 is capable of adjusting only the position of the projector 1 in the vertical and horizontal directions, the magnifying/reducing direction, the rotation direction, and the vertical trapezoidal and horizontal trapezoidal directions, and is not capable of correcting image distortions generated by the reflecting mirror 3 and optically caused image distortions.
In order to improve the disadvantage, an adjusting mechanism that changes the flatness of the reflecting mirror 3 at its periphery depending on each necessary unit of the reflecting mirror 3 (see for example JP-A-2001-109071) is provided or the phenomenon that a projected image is distorted at the periphery (pincushion distortion) is corrected by pressing in a setscrew to press the vicinity of the center of each of the sides of the reflecting mirror 3 so that the reflecting mirror is deformed into an arch shape (see for example JP-A-2002-77777).


A smart card system is disclosed for secure transmission of post issuance data to a embedded chip using a chip relay module, a plurality of hardware security modules, a first communication system having two security layers and a second communication system having four security layers.

Most smart cards in use today are flat, rectangular pieces of plastic resembling credit cards having electronic circuitry embedded therein. A typical smart card includes a microprocessor coupled to a memory, and the microprocessor executes instructions and performs operations on data of at least one software application program stored in the memory. The smart card provides a compact and portable computation resource for executing transactions in areas such as banking, sales, or security. Smart cards commonly appear in the form of credit cards, key-shaped tokens, and subscriber identity modules (SIMs) used in certain types of cellular telephones.
Many smart cards have a set of electrically conductive contacts arranged on an upper surface. A smart card reader/writer for communicating with such smart cards has a similarly arranged set of electrically conductive contacts. When a smart card is inserted in the smart card reader/writer, corresponding members of the two sets of contacts come into physical contact with one another. The main standards in the area of smart card and reader/writer interoperability are the International Standards Organization (ISO) 7816 standards for integrated circuit cards with contacts. The ISO 7816 standards specify interoperability at the physical, electrical, and datalink protocol levels. Other types of smart cards are "contactless." In this situation, both the smart card and the smart card reader/writer include wireless communication interfaces for communicating wirelessly (i.e., without electrical contact).
Many smart cards provide secure storage for data, including cryptographic keys used to carry out secure transactions, and are capable of performing cryptographic operations. Cryptography is, in general, a technique commonly used to protect sensitive information by encrypting a message to protect the information in the message. One method of encryption is to use a key to mathematically transform the information into an unreadable format. A key may include without limitation a code or series of characters. Only those possessing the key can decrypt the message to reveal the information.
In one likely scenario, issuers of smart cards will use one or more issuer's master keys to encrypt data for transmission to a smart card after issuance to ensure only changes authorized by the issuers are made to issued smart cards. Since an issuer's master keys may also be used to make unauthorized changes to issued smart cards, security of the issuer's master keys is essential.
U.S. Pat. No. 6,131,090 describes a method and system for providing controlled access to information stored on a smart card. The information is stored in encrypted form. A data processing center provides an access code, including a key for decrypting the information by authorized service providers. The smart card receives and verifies access codes, uses the access code to decrypt requested information, outputs the requested information, and computes a new encryption key as a function of information unique to the access session.
U.S. Pat. No. 6,481,632 discloses a smart card architecture wherein a card issuer empowers application providers to initiate approved changes to smart cards. Loading an application onto a smart card involves a card acceptance device issuing a load command. The load command includes an appended command authentication pattern used to verify the load command. The card acceptance device provides the application to the smart card. The application includes an appended application authentication pattern used to verify the application. After verification, the application is loaded into a memory of the smart card.
A need arises for a system and/or method to enable an end-user to manage the information on a chip that the end-user is entitled to manage, on any platform, in a manner such that all transactions are secure, authenticated and authorized while ensuring that the issuer's master key remains secure.

Smart card data transaction system and methods for providing high levels of storage and transmission security

Abstract: The first communication system may be considered a server side system and comprises a chip management system, a security server having a first hardware security module, a distribution server having a second hardware security module and a computer system connected by a network. The first communication system has a first security layer and a second security layer. The first security layer comprises mutual authentication that makes each component of the first communication system a trusted node to the others through client mutual authentication. The second security layer comprises system keys for secure communication between the hardware security modules.

Abstract: The second communication system may be considered a client side system and comprises the computer system connected to the distribution server by a network, a PC/SC card reader driver, a Web browser application, and a chip relay module and is for secure communication between the distribution server and the chip of a smart card inserted in the card reader/writer. The second communication system has a third, fourth, fifth and sixth security layer.

International Business Machines Corporation