An apparatus includes a capture device and a processor. The capture device may be configured to generate a plurality of video frames corresponding to an interior view of a vehicle. The processor may be configured to perform operations to detect objects in the video frames, detect (a) occupants of the vehicle and (b) seats of the vehicle based on the objects detected in the video frames, determine a status of a seatbelt for each of the occupants and select a reaction based on (a) a state of the seatbelt and (b) characteristics of the occupants. The reaction may be selected to encourage proper usage of the seatbelt based on the characteristics of the occupants. The characteristics may be determined by performing the operations on each of the occupants.

Seatbelts save lives. However, many vehicle occupants do not want to wear a seatbelt, forget to wear a seatbelt and/or wear a seatbelt improperly. An improperly worn seatbelt (i.e., strapped under the arm instead of over the shoulder) can also cause significant harm to occupants. During an impact scenario, or when a driver brakes rapidly, properly worn seatbelts can mitigate harm to the occupants.
Some car seats are designed to make an assumption about whether the seat is occupied by sensing pressure. Combined with sensors that detect whether a seatbelt is connected, some vehicles provide audio warnings when the assumption is made that a seat is occupied and the belt is disconnected. However, audio warnings can be a nuisance to drivers when the assumptions made are wrong (i.e., the seat is occupied by a grocery bag that the pressure sensors assumes is a person). Without knowledge of the occupants within the vehicle, proper seatbelt use cannot be accurately detected. The assumptions made by traditional occupant detection sensors do not account for various traits and/or conditions of different occupants. Furthermore, without knowledge of the occupants of the vehicle, methods to encourage proper seatbelt use are limited to simple warnings.
It would be desirable to implement seatbelt detection using computer vision.

Seatbelt detection using computer vision


An apparatus for fixating and elevating an interconnected rebar lattice having individual longitudinal and transverse rebar intersections for use as support for poured concrete in highway and other construction. The apparatus including a holding portion having an open ended recess with two opposing walls being generally U-shaped. The recess has a longitudinal axis and is sized and shaped to receive a longitudinal rod. An arc-shaped portion extends laterally outward from each opposing wall and perpendicular to the longitudinal axis of the recess. The arc-shaped portion has a transverse axis and is sized and shaped to receive a longitudinal rod. The arc-shaped portion includes a recess and opposing walls with each wall including a snap-type lock. A locking member has a generally arc-shaped portion and includes a snap-type lock for attaching to the arc-shaped portions and engaging with the snap-type lock of the arc-shaped portions. A leg portion extends downwardly from the holding portion and is integrally attached to a base.

For many years concrete roadways and other concrete slabs have incorporated reinforcing steel laid out in a rectangular lattice pattern for the purpose of adding strength to the concrete in order to resist slab failure when cracks develop in the concrete due to normal environmental conditions and heavy use. When cracks in the concrete develop, the mat lattice structure of the reinforcing bars perform the function of holding the concrete together at the point of the cracks, preventing separation of the concrete and failure of the slab. In order for the reinforcing bars to effectively perform this function, however, engineers have determined that the rebar mat should be located at the center of the poured slab. The normal preferred location is in the center of the slab, referred to as Thickness/2 or t/2. The rebar mat must also retain its designed rectangular lattice shape in order for the longitudinal and transverse rebar sections to provide the maximum reinforcing strength at anticipated cracking areas, and in order for the rebar ends of each section to line up with the rebar ends of adjoining sections of rebar mat as additional lanes are constructed. For many years contractors and public road building engineers have been aware that current methods for building the rebar mat and elevating the mat off the surface of the roadbed or slab often fail to maintain the rebar mat in a rectangular shape and in the desired location within the slab after the placement of concrete which results in premature failure of the concrete road or slab.
Currently, rebar mats used in road construction are built using a three step method: (1) laborers lay out rebar sections on the roadbed in the location where the rebar mat section is to be assembled forming a template with the transverse bars spaced properly and usually 3, 4 or 5 longitudinal bars laid out on top of the transverse bars, and tied with wire at the rebar intersections to form the template; (2) once the template has been laid out and tied together with wire, the rebar template is lifted off the surface of the roadbed and devices, known as "rebar chairs, " are placed under each transverse bar in the rebar template, with an adequate number of rebar chairs being used to elevate the rebar mat to the desired height and then setting the rebar on top of the rebar chairs, usually in a slot built into the chair; and (3) placing the remaining longitudinal rebar sections on top of the elevated template, and wire tying them at alternating intersections to complete construction of the rebar mat.
This traditional method for building rebar mats is deficient in two major respects. First, the rebar chairs are held upright by the base of the chair sitting on the roadbed and are not firmly locked to the rebar mat sections. When lateral forces, common on the job site, are exerted against the rebar mat, the chairs can rotate off of or around the rebar mat section and the entire rebar mat can fall to the roadbed. This situation can also occur during the pouring of the concrete when the lateral forces exerted by the in-flowing concrete can wash the rebar chairs out from under the rebar mat causing the mat within the slab to sag to the ground where the chairs have failed after the concrete is poured. Second, the wire tied rebar intersections provide no strength against angular deflection of the rebar, known as racking, when extreme forces of the concrete placement and the paving vibrator are applied. This method of mat construction can result in a rebar mat that is deformed into a parallelogram shape, that has less effective reinforcing capacity, and that causes the misalignment of rebar ends for attaching to the next adjoining section of rebar mat. These problems have been exacerbated in recent years with the growing use of less viscous, quick drying concrete mixtures.
Since this is such a difficult problem, there have been a number of attempted solutions. One solution known to the inventor is a device described in U.S. Pat. No. 3,378,981 that includes a generally rectangular box-like support made of sheet metal that has first and second vertically extending walls with each wall including a recess to receive rebar. Tabs stamped into the metal shape can be bent over to hold the rebar in place. The difficulty with this device is that the rebar connector is metal, which by being in contact with the road bed, forms a path for corrosion to travel to the rebar mat and greatly accelerates the corrosion of the entire rebar mat.
Oxidation (formed by corrosion) of the rebar mat produces internal expansion forces that will cause the entire slab to crack and fail.
Consequently, these metal chairs are unacceptable for use in today's road construction. Moreover, the basic design of this generally rectangular box-like connector results in a space or pocket being formed by the intersection of three planes which will completely fill with concrete during concrete placement. This produces a void or hollow space in the concrete roadbed. This "voiding" problem has been exacerbated today because of the use of "stiffer" concretes, that are poured with a viscosity higher than in previous years. Consequently, the propensity for forming "voids" in the concrete prevent the use of these rectangular metal chairs in any publicly funded roadway and highway construction. In addition, because the chairs are constructed of metal they offer no resistance to racking forces. The metal chairs simply bend to accommodate to the deformed shape of a racked rebar mat.
The most popular rebar chair in use today is a plastic "tee-pee" shaped chair having a triangular shape, that is wider at the bottom and narrows to a point at the top where a U-shaped saddle acts as a receiver for rebar placed on top of the chair. Often the U-shaped saddle section is formed so as to snap around a portion of the rebar when it is lowered into the saddle section. The tee-pee chairs are made of various types of plastic, selected primarily upon manufacturing costs considerations. The design of this chair provides no means to prevent the chair from rotating off the rebar when lateral forces are applied to the mat, either before or during the concrete pour. Furthermore, these tee-pee shaped chairs offer no resistance to the racking forces applied to the rebar mat during the concrete pour.
Another similar type of rebar chair in commerce usage is referred to as the "square base chair." In function, it is identical to the "tee-pee" chair in that it is simply placed under the rebar mat, and snaps to a single section of bar. The larger base of this chair provides some additional strength, but offers no significant anti-rotation or anti-racking capabilities. Furthermore, both the "tee-pee" chair and the "square base chair" present significant voiding potential at the chair base at the intersection of the three vertical planes which form the support for the rebar mat.
Another type of chair used in some locations, referred as the "high-chair," has four round vertical plastic legs connect at the top with an "X" pattern to form a cradle for the rebar, and depending on the chair height, a second "X" between the legs in the lower part of the chair for strength. This rebar chair eliminates the voiding potential present in the "tee-pee and square base chairs; but again provides no anti-rotation or anti-racking forces. Furthermore, the "high-chair" must be tied to the mat itself adding an additional labor procedure to complete the mat.
The practice of tying the rebar intersections with wire somewhat mitigates against the transverse rebar sections from moving out of the designed location during the concrete pour, although this effect is not entirely eliminated. The wire tied joints, however, provide no support at the rebar intersections for resisting the forces that tend to deform the entire mat into a parallelogram. Thus, racking of the rebar mat remains a constant problem with today's less viscous concrete mixes used in roadway and other slab-type construction.
A primary concern for the contractor is that the current method of constructing rebar mats is extremely labor intensive. As discussed above, three separate steps are required to be performed by laborers on the location of the mat building. These steps include (1) laying out the rebar mat template, and tying it together with wire, (2) installing the chairs under the rebar mat template, in sufficient quantities to hold the mat off the roadbed, and (3) placing the remaining rebar sections on the template, after it is elevated off the roadbed, and making a second trip down the rebar mat to wire tie the rebar intersections together.
The present invention overcomes these problems by providing chairs that will not rotate off the rebar when lateral forces to the rebar mat are encountered. This anti-rotation feature results from the unique locking mechanism in the chair base and cap which uses the rebar mat itself to hold the chair in an upright position. Once the chair is locked on to the rebar mat at selected intersections, the rebar in the mat serves as a back-lock to prevent the cap from disengaging from the chair as rotational forces are applied. This feature of the present invention eliminates chair rotation. All other chairs use the chair base to retain the rebar support device in the vertical, upright, position. Consequently, all current chairs in use will rotate over when lateral forces are applied.
In addition, the inventive chairs eliminate wire tying the rebar mat template together, and permit the first and second steps of building and elevating the rebar template off the ground to be performed in a single step, which results in decreased labor costs. With the present invention, the rebar template sections are fastened together as the chairs are placed under the template to elevate the mat off the road bed. This feature eliminates over 50% of the required wire tie joints, and combines two steps of mat assembly into a single step.
The chairs of the present invention also provide substantial anti-racking support at the rebar intersections. After all the chairs are affixed to the rebar mat, they work together as a unit to prevent the mat from being deformed out of square.
The chairs and locking caps of the subject invention, when used as a system, virtually eliminate the possibility of mat failure during the concrete pour, either due to collapse of the mat to the road bed or from racking. The system of the subject invention also substantially lowers the amount of labor required to build the rebar mat by allowing the mat building process to be completed in a single trip down the mat.
The invention also incorporates an apparatus relating to the construction of multiple layer rebar mats that are in common usage in high traffic volume highways, particularly in urban areas. Current methods for building double and triple layer rebar mats involve simply building multiple mats on top of one another, using increasingly higher chairs for the upper level mats. This method retains all of the disadvantages of current rebar mat construction described above, and is further subjected to two additional and more serious problems. First, as the chairs become increasing higher in length, their propensity to rotate or tip over increases. Thus, the potential of upper layers of rebar mat falling onto the lower layers is always present, in spite of the use of expensive high rise chairs purportedly designed to mitigate against this problem.
Second, specifications for multiple layer mats require that the rebar sections be aligned along the same vertical planes. The only chair known to the inventors at this time which will allow the proper alignment of the upper layer mat, is a "spider-leg" chair, with four metal legs that allow it to be placed on top of the lower mat rebar intersection. Because this chair design requires that the chair be made of metal, a rust path to the upper rebar mats results, which is unacceptable for the same reasons described above regarding other metal chairs. When plastic chairs are used, they must be installed adjacent to the lower rebar sections, thus preventing the alignment of the upper mat bars with the lower mat bars. Thus, neither above described chair meets the accepted specifications for building multiple layer rebar mats.
The chair of the present invention, can include a special locking section which allows multiple rebar mats to be constructed on the same chair base. This assures the uniform separation of the multiple mats as designed by the project engineers and assures proper alignment of the bars in the lower and upper mats. Presently, there is no known rebar chair that allows for the use of a single chair to construct and lock multiple layer rebar mats together at the predetermined height.
The chairs of the present invention are also designed so as to virtually eliminate the phenomenon of concrete voiding, which is commonplace with all types of today's plastic chairs, with the exception of the "high-chairs". The chair legs of the present invention tapper to the road bed or their base, greatly reducing the size of the three plane intersections below the rebar mat. This results in minimal voiding potential. As discussed above, concrete voiding occurs at the intersection of the three planes that are designed into the base of all plastic chairs for vertical support. Because the chairs must be located beneath the rebar mat, the vibrators used in the concrete placement cannot exert direct forces on the concrete slurry below the mat. This results in air pockets forming in the chairs corners where the three planes (two vertical and one horizontal) intersect, creating voids in the base of the slab. Where voids are sufficiently numerous, the upward support force of the concrete is no longer uniform, which over time increases the likelihood of slab failure. Concrete cracking tends to run toward the voided areas.
The locking cap of the chairs of the present invention also provides another significant advantage in the economics of rebar mat construction for roadways and other slabs. The rebar mats of the present invention, once assembled, provide sufficient anti-racking force to the entire mat allowing the mats to be lifted and moved as a single unit. This allows for offsite construction of the mats and transportation to the job site as needed. This feature allows for substantial savings in the cost of rebar mat building and for faster completion of roadbed construction or other slab construction, resulting in as much as an 80% decrease in on-site time for laying the rebar mats. This offsite construction is particularly suited for tilt wall and retaining wall applications, where the rebar mats are small enough to allow transportation as a single unit.
Lastly, the inventive chairs are particularly well suited for use in tilt wall construction, where concrete slabs are poured on the ground over a rebar mat, and then tilted up into place. In tilt wall applications, the base of the chair will be visible on the underside of the wall after it has tilted upright. Because the current invention uses the rebar mat to hold it upright, rather than a large base, the support leg can be tapered to a point at the base, virtually eliminating any chair footprint after the tilt wall section has been tilted into the vertical position. Additionally, the chairs and locking caps of the present invention also include features that allow for the construction of rebar mats for vertical slabs and the construction of rebar mats on sloping surfaces.

System for affixing rebar lattice to receive concrete


The invention relates to a valve drive of an internal combustion engine, comprising at least one camshaft whereon at least one cam carrier is arranged in a rotationally fixed and axially displaceable manner. Means for applying axial tension are formed between the at least one camshaft and the at least one cam support, thereby enabling the at least one cam support to be fixed in an axial manner.

This invention relates to a valve drive of an internal combustion engine comprising a cylinder head.
Mechanical devices designed to improve the thermodynamic properties of internal combustion engines have been disclosed, devices which affect the operating cycle of the valve drive and, for example, affect the timing of the valve drive and, for example, enable speed-dependent variation of the opening times or the lift of charge-cycle valves.

Valve drive of an internal combustion engine comprising a cylinder head


A thermoplastic resin is molded by a press-molding method wherein a thermoplastic resin in a molten state is compressed to flow between a pair of female and male molds so as to be formed into a predetermined shape. A compression rate of the mold is controlled so that the following expression (1) is satisfied: EQU 0.5.ltoreq.B/A.ltoreq.2 (1). wherein A (mm/s.sup.2) is an acceleration which is realized at a time when the compression rate is 75% of a maximum rate in a compression-acceleration region, which region is defined as a period of time from a moment when the compression of the molten thermoplastic resin is started to a moment when the compression rate reaches the maximum rate; and B (mm/s.sup.2) is a deceleration which is realized at a time when the compression rate is 75% of the maximum rate in a compression-deceleration region, which region is defined as a period of time from a moment when the compression rate reaches the maximum rate to a moment when the closing of the molds is complete. By this method, a molded article having excellent surface appearance free from unevenness of gloss and surface irregularity can be obtained.

1. Field of the Invention
The present invention relates to a method of press-molding a thermoplastic resin. Hereafter, a thermoplastic resin is referred to as a "resin".
2. Description of the Prior Art
A well known method of press-molding a resin involves supplying a resin in a molten state between a female mold and a male mold which are in an unclosed state. The resin is then compressed between the molds so as to be formed into a predetermined shape. In such a molding method, a short shot of the resin (that is, insufficient filling of the resin into a mold cavity), results in sink or warpage on a surface of a product. There have been efforts to reduce such defects by increasing or reducing a compression rate in a compression step in accordance with the size of the product, so as to absolutely control the compression rate. One such effort is described, for example, in Japanese Patent Kokai No. 241417/1989, and its counterpart U.S. Pat. No. 5,057,255.
However, even the above-mentioned method in which the compression rate is controlled has proven unsatisfactory in preventing defects in the appearance of a resin molded article; surface defects, such as unevenness of gloss and irregularity of the surface of the molded article tend to remain.

Method of press-molding thermoplastic resin


A power system includes a current regulator coupled to a load and for generating an output current having a substantially constant ripple magnitude, and for adjusting the output current according to a sense signal indicative of the output current. In addition, the power system includes a filter element coupled in parallel with the load and for passing an AC (alternating-current) portion of the output current. Furthermore, the power system includes a current sensor coupled between ground and the parallel-coupled filtering element and load, and for providing the sense signal indicative of the output current.

Currently, light sources such as LEDs (light emitting diodes) can be used in many applications, such as traffic lights, backlight for LCD (liquid crystal display) TVs, computer monitors, etc. In conventional LED driven systems, linear regulators can be used to drive the LEDs. However, a considerate amount of power may be dissipated on the linear regulators, which may reduce the efficiency of the regulators. In addition, the conventional regulators may not regulate an output current to a desirable level accurately enough.


Methods and systems for managing alerts in a database are provided, whereby the alerts originate from at least one business application due to exceptional situations, and whereby the alerts are represented as objects, each object corresponding to one of a number of configurable alert types. Each of the alert type may be configured, so that alerts of that alert type comprise at least one of: an ID for uniquely identifying the alert, information representative of the type of alert, message text being descriptive of the alert, a set of parameters representative of business or control objects associated with the alert, an alert scope being representative of the relevance for partners or users, feedback information being representative of time and identity of acknowledging the alert by a partner or user, status information for controlling follow-up actions, validity time information, and priority information.

Computer systems, in particular distributed computer networks that execute application programs may detect exceptional situations. These exceptional situations may be unexpected, and may have impact on other parties participating in the network. Therefore, the applications of the computer systems or of the distributed computer network generate alerts to inform one or more users about the exceptional situation. Such kinds of alerts may be the termination of a contract, a delivery problem for an order, a potential out-of-stock situation, or technical problems in a system.
Alerts are objects that consist of general attributes regarding partners, users and time of creation or change, a message text with configurable place holders and data structure for application data that can be configured. The alert type of the alert describes this configuration. The scope of the alerts themselves can be restricted, either to specific partners, or more specifically according to the application data.


A resin injection molding method of molding a resin by injection-filling an inside of a mold cavity formed by mold-clamping a pair of a design surface mold and a non-design surface mold, with a melted thermoplastic polypropylene resin composition, the method including: setting a temperature of each cavity-forming surface of the design surface mold and the non-design surface mold prior to the injection filling to 60° C. to 120° C., with the temperature of the cavity-forming surface of the design surface mold being 5° C. to 50° C. higher than the temperature of the cavity-forming surface of the non-design surface mold; and causing the resin pressure to reach a negative pressure within 7 seconds after injection filling is complete, wherein the thermoplastic polypropylene resin composition contains a crystalline polypropylene resin and a rubber component and a content of the rubber component is 1 mass % to 40 mass %.

An injection molded product which is injection-molded using resins such as polyolefin resins, polystyrene resins, ABS resins, polycarbonate resins, and polyamide resins has been widely used as a resin product. For example, in automobile interior parts, an injection molded product which is provided with a rib or boss for providing rigidity, structural strength, or the like, or a clip and the like (hereinafter, referred to as "rib and the like") for attachment, on a non-design surface (rear surface) of a plate-like portion, has been used.
Such an injection molded product can be obtained by, for example, molding and forming a resin by injection-filling a mold cavity, which is formed by mold-clamping a design surface mold forming a design surface side of the injection molded product and a non-design surface mold forming a non-design surface side. In the molding of the injection molded product, in some cases, a sink mark is generated on a surface of the obtained injection molded product caused by volume shrinkage of the resin which is injection-filled in the mold cavity. Particularly, in the case of the above-described injection molded product provided with the rib and the like on a non-design surface side of a plate-like portion, the resin of the portion coming into contact with the rib and the like on the plate-like portion is easily drawn to the side of the rib and the like during molding, and thus, sink marks are easily generated on a design surface of the portion.
Examples of the method of controlling the generation of sink marks on the design surface of the injection molded product includes the following methods (i) to (iv).
(i) A method of performing injection molding in a state in which the temperature of a cavity-forming surface of a mold is maintained at greater than or equal to a glass transition temperature of a resin (Patent Document 1).
(ii) A method of injection-filling the inside of a mold cavity with a resin, subsequently injecting gas into the mold cavity from a non-design surface mold side, and molding the resin by pressing the resin into the cavity-forming surface of a design surface mold using the gas pressure (Patent Document 2).
(iii) A method of injection-filling a mold cavity of a mold, which is heated to a temperature higher than or equal to a glass transition temperature or higher than or equal to a thermal deformation temperature of a resin, with the resin, and subsequently lowering the temperature of the mold of a design surface mold and subsequently a non-design surface mold to a temperature lower than or equal to the glass transition temperature or lower than or equal to the thermal deformation temperature, and subsequently lowering the temperature of the mold a non-design surface mold to the temperature lower than or equal to the glass transition temperature or lower than or equal to the thermal deformation temperature (Patent Document 3).
(iv) A method of performing injection-molding using a mold in which a heat insulation layer is formed on a cavity-forming surface of a design surface mold and a surface metal layer is further formed on the heat insulation layer (Patent Document 4).
Meanwhile, in automobile interior parts, a crystalline polypropylene resin is used for the injection molding in many cases. The crystalline polypropylene resin shrinks volume greatly due to crystallization. For this reason, sink marks are easily generated in an injection molded product using the crystalline polypropylene resin compared to an injection molded product using other resins. For example, as to the method (i), molding of the polypropylene resin is generally performed at about 40° C. of a surface temperature of a mold. In addition, it has been known that the glass transition temperature of the polypropylene resin is −20° C. That is, the general molding condition of the polypropylene resin meets the condition disclosed in Patent Document 1, but it is a well-known fact that it is impossible to suppress sink marks formed during molding even under such a condition.
Similarly, even in the methods (ii) and (iv), it is impossible to sufficiently suppress the generation of sink marks on the design surface when molding the polypropylene resin.
In addition, in fields such as automobile interior parts, reduction of the thickness of an injection molded product has been carried out in view of weight reduction or energy conservation. When the thickness of the injection molded product provided with a rib and the like on the non-design surface side of the plate-like portion is reduced, the thickness ratio of the portion which is provided with the rib and the like to the portion which is not provided with the rib and the like in the injection molded product becomes large. Accordingly, the resin forming the plate-like portion is drawn to the rib and the like during the molding, thereby promoting generation of noticeable sink marks on the design surface of the portion. Therefore, it is more difficult to perform the suppression of sink marks.
From the above, in the injection molded product using the crystalline polypropylene resin, the flexibility of design of the product has been impaired when reducing the thickness of the product for the purpose of weight reduction.
In addition, in the method (iii), there is a problem in that energy loss is extremely great since heating and cooling of the mold is repeated while continuously manufacturing the injection molded product. In addition, it is necessary to use a special mold in the method (iv), which is disadvantageous even in view of maintenance of the mold.

Resin injection molding method and resin injection molded product


Methods for inducing immunosuppression in animals which need immunosuppressive treatment involving administration to animals of a therapeutically effective amount of the cyclic AMP agent HE-33 or its nucleoside.

1. Field of the Invention
This invention relates to immunosuppressive agents and their use in transplantation therapy. In particular, the invention is directed to the use of cyclic AMP compounds, their nucleoside derivatives, and agonists thereof for suppressing graft rejection.
2. Background Art
Many human diseases are characterized by excessive or inappropriate immune responses. In transplantation, the immune system attacks major histocompatibility complex (MHC)-disparate donor tissue leading to graft rejection. In autoimmune disease, the immune system attacks normal tissues. In allergy, the immune system is hyperresponsive to otherwise harmless environmental antigens. It is now recognized that immunosuppressive therapy is appropriate for treating each of these disorders (Blood Reviews, 1995, 9:117-133).
There has been a phenomenal increase in the success of organ transplants since the 1950s, and transplantation has become the treatment of choice for end-stage renal and cardiac failure. A number of advances have recently been made in understanding immune regulation, and in the development and use of immunosuppressive therapies (Thomson, A. W. et al., Immunol.. Rev., 1993, 136:71-98; Allison, A. C. et al. eds, 1993, Ann. NY Acad. Sci. 696:1-419; Kahan, B. D., 1994, Therapeutic Immunol.. 1:33-44; Thomson, A. W., et al., eds., 1994, Immunosuppressive Drugs, London: Edward Arnold). Although the development of drugs such as cyclosporin A (CsA) and FK506 has led to substantial improvements in preventing graft rejection, especially over the first year (Sigal, N. H., et al, 1992, Ann. Rev. Immunol.. 10:519-560; Thomson, A. W., et al., 1994, Clin. Exp. Immunol.. 98:351-357), there are serious side effects associated with use, such as nephrotoxicity and neurotoxicity (Kahan, B. D., et al., 1985, Surgery 97:125). In addition, the widely used immunosuppressive drugs are not soluble or orally available in pill form, and require administration by injection.
Graft-versus-host disease (GVHD) occurs when genetically disparate lymphocytes are transferred into an immunologically compromised recipient incapable of rejecting the donor graft (Billingham, R. E. Harvey, Lect,, 1967, 62: 21-78; Nash, R. A. and Storb, R., Current Opinion in Immunology, 1996, 8: 674-680). Acute GVHD is a major and frequent complication of bone marrow transplantation (BMT) (Ferrara, J. L. M. et. al., Transplantation, 1989, 47: 50-54). Although T cells are clearly required for the induction of the disease in both clinical and animal models of BMT, natural killer (NK) cells have been implicated in target tissue damage (Ferrara, J. L. M. et. al., Transplantation, 1989, 47: 50-54; Ghayur, T. et. al., Transplantation, 1987, 44: 261-267; Nash, R. A. and Storb, R., Current Opinion in Immunology, 1996, 8: 674-680). Prevention of GVHD has been attempted most often with pharmacological immunosuppression. The most commonly used agents are cyclosporine-A (CsA), methrotrexate, prednisone and FK506 (Storb, R. et. al., New England Journal of Medicine, 1986, 314: 729-735; Storb, R. et. al., Blood, 1990, 76: 1037-1045; Nash, R. A. et. al., Blood, 1995, 85: 3746-3753). However, these agents have potential side effects, such as nephrotoxicity, increased hair growth on the body, and neurotoxicity (Kahan, B. D. et. al., Surgery, 1985, 97: 125; Fay, J. W. et. al., Blood, 1996, 87: 3514-3519). There is, therefore, a clinical need to provide new compounds for effective immunosuppression without these side effects and with greater ease of administration.


The present invention relates to a process for producing vitamin B12, wherein said process comprises the steps of (a) culturing a strain of the genus Propionibacterium in a first fermenter under anaerobic conditions to obtain a culture of Propionibacterium, (b) transferring at least part of the culture obtained in (a) to a second fermenter and subjecting this culture to oxygen, (c) replacing in the first fermenter part of the volume transferred in (b) with fresh culture medium and (d) repeating steps (a), (b) and (c) at least once.

The present invention relates to a fermentation process for the production of vitamin B12.
Vitamin B12 is an important vitamin for humans and animals. It is used to treat pernicious anaemia and peripheral neuritis, and is used as a dietary supplement. Vitamin B12 is also an important animal feed supplement as growth enhancer.
The term vitamin B12 is used to describe compounds of the cobalt corrinoid family, in particular those of the cobalamin group. The most used compound of this group is cyanocobalamin and as such the term vitamin B12 is sometimes used to refer to cyanocobalamin. In this specification the term vitamin B12 should be attributed its broad meaning so as to include all the cobalt corrinoids of the cobalamin group, which include in particular cyanocobalamin, hydroxocobalamin, methylcobalamin and 5xe2x80x2desoxyadenosylcobalamin, characterised by a cyano, hydroxyl, methyl or 5xe2x80x2-desoxyadenosyl radical respectively. The methylcobalamin and 5xe2x80x2desoxyadenosylcobalamin compounds are known to be unstable to light in isolated form and are easily transformed to hydroxocobalamin in aqueous solution.
For this reason, almost all commercial vitamin B12 preparations consist of the stable cyanocobalamin, which as such is not the chemical form in which vitamin B12 can be found in nature. In this specification the term natural vitamin B12 is defined so as to comprise all chemical forms of vitamin B12 naturally occurring in nature, cyanocobalamin thus being excluded.
Vitamin B12 is produced industrially by microbial fermentation, using almost exclusively Pseudomonas denitrificans and Propionibacterium species (as reviewed by Spalla et al, 1989 xe2x80x9cMicrobial production of vitamin B12xe2x80x9d, In: Biotechnology of vitamins, pigments and growth factors, E. J. Vandamme ed., Elsevier, London, N.Y., pp. 257-284). Contrary to Pseudomonas, Propionibacteria are food-grade. Processes using Propionibacterium species thus have the advantage that they allow to formulate natural vitamin B12 together with the biomass in which it is produced, as recently described in EP-A-0 824 152. Such processes avoid the conversion of natural vitamin B12 into the cyanocobalamin form by chemical processes including cyanidisation followed by extraction and purification steps using organic solvents. The chemical conversion step and any subsequent purification steps cause this production process to be expensive, unsafe to the operators and environmentally unfriendly.
Propionibacteria are Gram-positive bacteria capable of producing valuable compounds in a variety of industrial processes. Propionibacteria are, for instance, important in the production of cheese, propionic acid, flavours and vitamin B12.
Propionibacteria are, as the name suggested, characteristic in the production of propionic acid. Glucose is commonly used as carbon source, but other substrates, i.e. fructose, mannose, galactose, glycerol and milk, can be used for growth. Besides propionic acid, acetic acid is produced under anaerobic conditions, with a ratio of 2:1 for propionic acid : acetic acid. The production of propionic acid is a clear advantage over other species as this compound is toxic in low levels for many other organisms, like lactic acid bacteria, acetic acid bacteria and yeasts. As a result there is little chance of contamination with other microorganisms during fermentation. The upper tolerance level for propionic acid for Propionibacterium is approximately 20-40 g/l (with a fermentation around pH 7): this is the level where the propionic acid starts to inhibit growth. The undissociated propionic acid is the actual toxic component for Propionibacteria, as is shown by Nanba et al. (1983, J. Ferment. Technol., 61: 551-556) for Propionibacterium shermanii. The specific growth rate decreases rapidly for undissociated propionic acid concentrations above 5 mM. This effect is also demonstrated by Blanc et al. (1987, Bioproc. Eng., 2: 175-179) for P. acidi-propionici, where the growth rate is drastically reduced above a pseudo critical value of 4 mM propionic acid. This implies that in fermentations with a pH around 7.0 propionic acid concentrations above 40 g/l are only reached with very low growth rates. This maximum amount of propionic acid produced in such fermentations results in a maximum of 25-35 g/l biomass that can be reached. Propionic acid concentration is thus one limiting factor for biomass growth and thereby for high vitamin B12 yield.
Several Propionibacterium species are capable to produce vitamin B12 in large scale fermentation processes. The process is described as a two-stage fermentation with a 72-88 hours anaerobic fermentation followed by a 72-88 hours aerobic phase. The vitamin B12 concentration in the cells rapidly increases in the aerobic phase, with typical values of 25-40 mg vitamin B12/l (see e.g. DE 1 239 694, U.S. Pat. No. 3,411,991, or in: Biochemical engineering and biotechnology handbook, 1991, B. Atkinson ed., Macmillan Publishers Ltd, pp: 1213-1220). Anaerobic growth followed by an aerobic phase with limited growth is important for economic production of vitamin B12 using Propionibacterium species. This requirement, however, limits the amount of biomass to 25-35 g/l as described above. Several attempts have been made to overcome the barrier of propionic acid toxicity in order to increase biomass and thereby the yield of vitamin B12.
Alternated anaerobic-aerobic phases are e.g. suggested to reduce the amount of acids (Ye et al., 1996, J. Ferment. Bioeng. 85: 484-491). In the aerobic phase the propionic acid is converted to less toxic acetic acid, with simultaneous formation of vitamin B12. The relative yield of vitamin B12 has been increased, but the final titre is rather low. This is probably due to inhibition early in the synthesis of vitamin B12 and/or other oxygen related products limiting the synthesis of vitamin B12. The final vitamin B12 produced with this method is 9 mg/l compared to 4.5 mg/l with the fully separated anaerobic and aerobic phases. Both values are rather low for vitamin B12 production with Propionibacteria.
The suggestion to use immobilized cells is mainly focused on the production of propionic acid (Rickert et al., 1998, Enzyme Microb. Technol. 22: 409-414). The propionic acid production is greatly enhanced. Use of this option for vitamin B12 production (which is not mentioned by Rickert et al.) will imply harvesting of the vitamin B12-containing cells with the immobilization material. This is only feasible when the additional cost for the immobilization equipment as well as the immobilization material itself are competitive with the current technology. Yongsmith et al. presented the production of vitamin B12 with immobilised cells of Propionibacterium sp. strain arl AKU1251. The maximum vitamin B12 concentrations is in the range of 14-16 mg/kg, which is no improvement of the production with freely suspended cells, as described before (Yongsmith et al. 1983, J. Ferment. Technol. 61: 593-598).
Although Propionibacteria can grow under aerobic conditions, the production of corrinoids (i.e. the general name for vitamin B12 and its precursors) is absent above a dissolved oxygen concentration of 0.19 mM=6 mg O2/L. The lower the oxygen concentration the higher the corrinoid production is with a maximum corrinoid production under non-aerated conditions (Quesada-Chanto et al., 1998, Appl. Microbiol. Biotechnol. 49: 732-736). Oxygen concentration is a limiting factor for vitamin B12 synthesis.
A repeated fed-batch fermentation with an anaerobic phase followed by an aerobic phase and withdrawal of broth at the end of the aerobic phase is not possible. According to Quesada-Chanto et al. (1998), production of the corrinoids is optimal under anaerobic conditions, whereas small amounts of oxygen reduce the production of corrinoids. These findings are supported by the results obtained in example 1. A repeated fed-batch process with an aerobic and anaerobic phase in one fermenter therefore is, not economically feasible.
GB patent 846,149 describes a continuous process for the synthesis of vitamin B12. This process comprises fermenting Propionibacterium in a nutrient medium under anaerobic conditions in a first zone while adding nutrients to this zone, passing cell-containing medium from the first zone into a second zone which is under microaerobic conditions and withdrawing cell-containing medium containing vitamin B12 from this second zone. The concentration of cells and the volume of medium in both zones is maintained substantially constant by continuous fill and draw operations. This process leads to the synthesis of up to 12 mg/l of vitamin B12, which is no improvement compared with a more classical method of production.
There is thus still a need for Propionibacterium-based fermentation processes for the production of vitamin B12 with further improvements in efficiency and/or vitamin B12 yield.
The present invention provides a process for producing vitamin B12 (and precursors thereof having detectable vitamin B12 activity) which is not a continuous process and which comprises the steps of:
(a) culturing a strain of the genus Propionibacterium in a first fermenter under anaerobic conditions to obtain a culture of Propionibacterium,
(b) transferring at least part of the culture obtained in (a) to a second fermenter and subjecting this culture to oxygen,
(c) replacing in the first fermenter part of the volume transferred in (b) with fresh culture medium, and
(d) repeating steps (a), (b), and (c) at least once.
In this specification the term vitamin B12 should be attributed its broad meaning so as to include all the cobalt corrinoids of the cobalamin group, which include in particular cyanocobalamin, hydroxocobalamin, methylcobalamin and 5xe2x80x2desoxyadenosylcobalamin, characterised by a cyano, hydroxyl, methyl or 5xe2x80x2-desoxyadenosyl radical respectively. The term vitamin B12 further comprises any vitamin B12 precursor having vitamin B12 activity as detectable in the turbidimetric bioassay based on the growth response of Lactobacillus leichmanii ATCC 7830 as described in detail in: the United States Pharmacopoeia, The National Formulary, 1995, pp. 1719-1721, United States Pharmacopoeial Convention, Inc., Rockville, Md.
One aspect of the process of the invention concerns the relation between the fraction of the anaerobic culture which is transferred in (b) and replenished with fresh medium in (c) and, on the one hand, the growth rate of the anaerobic culture (in (a)) and, on the other hand, the time interval between the subsequent withdrawals. Preferably, the withdrawal volume (which is transferred in (b) and replaced in (c)) relates to the total working volume of the first fermenter as a function of growth rate of the culture in the first fermenter and time interval between each draw according to the equation:       ln              xe2x80x83                  (                        working                                xe2x80x83                              volume                                      working                                      xe2x80x83                                    volume                    -                      withdrawal                                      xe2x80x83                                    volume                              )        =      growthrate    *          (              time                          xe2x80x83                        interval                          xe2x80x83                        between                          xe2x80x83                        each                          xe2x80x83                        draw            )
In this equation the growth rate is expressed in hxe2x88x921. Typically, the growth rate may vary over the applied time interval and an average value may be applied in the formula. The time interval between each draw is expressed in hours. Preferably, the growth rate during the anaerobic phase is maintained in the range between 0.03 and 1 hxe2x88x921. The skilled person will appreciate that at constant growth rate, decreasing both the time interval and the withdrawal volume will approach a continuous process, which is not a preferred embodiment of the present invention.
One embodiment of the process of the present invention comprises the steps of:
(a) culturing a strain of the genus Propionibacterium in a first fermenter under anaerobic conditions,
(b) transferring at least 30 to 90%, preferably at least 40 to 90%, more preferably at least 50 to 90%,more preferably at least 60 to 90% and most preferably at least 70 to 90% of the culture volume obtained in (a) to a second fermenter and subjecting this culture to oxygen,
(c) replacing in the first fermenter the same volume as the one withdrawn in step (b) with fresh culture medium; and
(d) repeating steps (a), (b), and (c) at least once.
In another preferred embodiment of the process of the invention, the culture of a strain of the genus Propionibacterium under anaerobic conditions (step (a)) leads to at least 20 g/l dry biomass, preferably at least 30 g/l, preferably at least 40 g/l, preferably at least 50 g/l, preferably at least 60 g/l, preferably at least 70 g/l, preferably at least 80 g/l, more preferably at least 90 g/l and most preferably at least 100 g/l.
Knowing the withdrawal volume and the growth rate of the microorganism used, the skilled person can easily deduce from the formula the time interval between each draw and thus the duration of the whole process.
In another preferred embodiment of the process of the invention, the dissolved Oxygen concentration at inoculation of the anaerobic phase is less than 5% of air saturation, preferably less than 2.5%, and more preferably less than 1% of air saturation.
Preferably, the anaerobic conditions of the process of the invention are such that the oxygen uptake rate during the anaerobic phase (a) is no more than 2 mmol O2 lxe2x88x921hxe2x88x921, preferably no more than 1 mmol O2 lxe2x88x921hxe2x88x921, and most preferably approaches zero mmol O2 lxe2x88x921hxe2x88x921, as measured by mass-spectometry and gas flow analysis (see e.g. in: Basic Bioreactor Design, 1991, K. van""t Riet and J. Tramper, eds., Marcel Dekker Inc.).
In step (b) of the process of the invention, the culture is subjected to oxygen. Preferably, the oxygen uptake rate (OUR) during this aerobic phase of the process is at least 5 mmol O2 lxe2x88x921hxe2x88x921, more preferably at least 20 mmol O2 lxe2x88x921hxe2x88x921, still more preferably at least 40 mmol O2 lxe2x88x921hxe2x88x921, and most preferably at least 80 mmol O2 lxe2x88x921hxe2x88x921.
According to one embodiment of the invention there is provided a process wherein the aerobic second phase in (b) is performed in at least two serially connected aerobic fermenters. Most preferably the aerobic second phase in (b) is performed in plug flow mode, wherein e.g. the xe2x80x9csecondxe2x80x9d aerobic fermenter comprises a series of aerobic fermenters.
Suitable culture media for the production of vitamin B12 with Propionibacteria are well-known in the art (cf. Biochemical engineering and biotechnology handbook, 1991, B. Atkinson ed., Macmillan Publishers Ltd, pp: 1213-1220). In a preferred embodiment of the invention the culture medium is supplemented with 1-50 mM of one or more compounds selected from the group consisting of betaine, methionine and glutamine. Another preferred supplement for the culture medium is 5,6-dimethylbenzimidazole (DBI). DBI is preferably supplemented at 1-40 mg DBI per litre. Preferably, DBI is added to the culture medium at the start of the aerobic phase or during that phase.
In a preferred embodiment of the process of the invention the concentration of undissociated propionic acid is controlled such that it does not exceed 5 mM. This conveniently may be done by increasing the pH of the culture medium according to methods well known to the skilled person.
According to another embodiment of the invention, the temperature under anaerobic conditions is different from the temperature under aerobic conditions. Preferably, the temperature under anaerobic condition is higher than the temperature under aerobic conditions. More preferably, the temperature under anaerobic conditions is at least 2 degrees higher than the temperature under aerobic conditions, more preferably at least 4 degrees higher, more preferably at least 6 degrees higher, more preferably at least 8 degrees higher, more preferably at least 10 degrees higher and most preferably at least 12 degrees higher. For instance, the temperature under anaerobic conditions may be 36xc2x0 C. and under aerobic conditions 24xc2x0 C., or these temperatures may be 36xc2x0 C. and 30xc2x0 C., respectively.
In the process of the invention, preferably a strain of a Propionibacterium species is used which is selected from the group consisting of the classical or Dairy Propionibacteria as described in Bergey""s manual of systematic bacteriology, 1986, J. B. Butler, Williams and Wilkins, p 1346-1353. This group comprises inter alia the species P. freundenreichii with subspecies freudenreichii and shermanii, P. thoenii, P. jensenii and P. acidipropionici. More preferably the strain P. freundenreichii CBS 929.97 is used. P. freundenreichii CBS 929.97 was deposited Jul. 10, 1997 at the Centraal Bureau voor Schimmelcultures, Baarn, The Netherlands.
In one embodiment of the invention, the process of the invention is performed using Propionibacteria strains that are genetically modified by means of classical mutagenesis and/or recombinant DNA technology. Classically mutagenised strains can be propionic acid-resistant strains of the genus Propionibacterium, such as P. shermanii NOC 11012 and P. freudenreichii NOC 11013, as disclosed in U.S. Pat. No. 4,544,633. A propionic acid-resistant strain of Propionibacterium is herein defined as a strain which shows approximately equal (i.e. less than 10% difference) growth rates when compared in identical media with and without 20 g propionic acid/l.
Transformed Propionibacteria strains that have been genetically modified by recombinant DNA technology are exemplified in J 08-056673.
One of the advantages of the process of the invention is the throughput increase of the fermentation. The anaerobic phase is considerably reduced. For a growth rate of 0.06 hxe2x88x921 the output of the anaerobic phase is three fermenter volumes in 72 hours, compared to one fermenter volume for the classical process. In addition, the invention reduces the turnaround time of the fermentation, with ten consecutive fills and draws, to 20% of the classical process.
Another advantage of the process of the invention is that the size of the fill and draw volumes may be relatively large. Consequently, the growth inhibiton caused by high concentration of propionic acid under anaerobic conditions does not occur, leading to an increase in the biomass and thereby an increase in vitamin B12 yield. The amount of vitamin B12 formed using the process of the invention may be 20 to as high as 200 mg/kg mesh.

Process for the production of vitamin b12


In a display device which includes a back substrate, a face substrate, a support body which is interposed between both substrates and surrounds a display region, thus forming an inner space, and a sealing material is provided which hermetically seals the support body and both substrates, thereby to provide a display device having a long lifetime and in which the desired degree of vacuum can be ensured in the inner space. A partition wall body is arranged substantially in parallel at the outside of the display region and at the inside of the support body, and getters are arranged in a space defined between the partition wall body and the support body.

The present invention relates to a display device which utilizes an emission of electrons into a vacuum space, which is defined between a face substrate and a back substrate; and, more particularly, the invention relates to a display device in which those are cathode lines having electron sources and control electrodes which control a quantity of electrons led out or emitted from the electron sources, and, at the same time, to a display device which exhibits stable display characteristics by maintaining a vacuum between the front substrate and the back substrate.
As a display device which exhibits high brightness and high definition, color cathode ray tubes have been popularly used conventionally. However, with the recent demand for the production of higher quality images in information processing equipment or television broadcasting, there has been an increasing demand for planar displays (panel displays) which are light in weight and require a small space, while exhibiting a high brightness and a high definition.
As typical examples, liquid crystal display devices, plasma display devices and the like have been put into practice. Further, more particularly, as display devices which can realize a higher brightness, it is expected that various kinds of panel-type display devices, including a display device which utilizes an emission of electrons from electron sources into a vacuum and is referred to as an electron emission type display device or a field emission type display device and an organic EL display, which is characterized by low power consumption, will be commercialized.
Among such panel type display devices, as an example of the above-mentioned field emission type display device, a display device having an electron emission structure, which was developed by C. A. Spindt et al, a display device having an electron emission structure of a metal-insulator-metal (MIM) type, a display device having an electron emission structure which utilizes an electron emission phenomenon based on a quantum theory tunneling effect (also referred to as "surface conduction type electron source,), and a display device which utilizes an electron emission phenomenon having a diamond film, a graphite film and carbon nanotubes and the like have been known.
Among these panel type display devices, the field emission type display device is formed by laminating a front panel, in which an anode electrode and a fluorescent material layer on an inner surface thereof, and a back panel, in which electron emission type cathodes and grid electrodes, which constitute a control electrode, are formed on an inner surface thereof with a distance of not less than 0.5 mm, for example, therebetween, wherein a sealed space is formed between both panels and the sealed space is evacuated to a pressure lower than an ambient atmospheric pressure or to a vacuum.
Recently, the use of carbon nanotubes (CNT) as a field emission electron source, which constitutes the cathodes of this type of planar display, has been studied. Carbon nanotubes are an extremely thin needle-like compound (more particularly, a so-called graphene sheet in which carbon atoms are coupled in a hexagonal shape is formed in a cylindrical shape). A carbon nanotube assembly which is formed by collecting a large number of carbon nanotubes is fixed to a cathode electrode. By applying an electric field to the cathode electrode formed of the carbon nanotubes, it is possible to emit electrons of high density from the carbon nanotubes at a high efficiency, whereby it is possible to constitute a flat panel display which is capable of displaying images of high brightness by exciting a phosphor with these electrons.
FIG. 13 is a schematic diagram illustrating the basic structure of a field emission type display device. CNT indicates the carbon nanotubes that are formed on a cathode (cathode electrode) K, A indicates an anode (anode electrode), and a phosphor PH is formed on an inner surface of the anode A. A grid electrode G, which controls the emission of electrons, is formed in the vicinity of the cathode K, and a voltage Vs is applied between the cathode K and the grid electrode G so as to emit electrons from the carbon nanotubes CNT. By applying a high voltage Eb between the cathode K and the anode A, the electrons e that are emitted from the carbon nanotubes CNT are accelerated, and the phosphor PH is excited, whereby a colored light L, which is dependent on the composition of the phosphor PH, is irradiated. Then, by controlling the quantity of electrons which are emitted based on the modulation voltage Vs applied to the grid electrode G disposed in the vicinity of the cathode K, for example, the brightness of the colored light L can be controlled.
FIG. 14 is a diagrammatic cross-sectional view illustrating an example of a field emission type display device. In this field emission type display (FED) device, a back substrate 1 which is formed of a glass plate, and a face substrate 2, which is also formed of a glass plate, are laminated to each other by way of a frame-like support body 3, which is interposed between both substrates. The support body 3 has a height of approximately 1 mm, for example, and it surrounds a display region so as to maintain a given distance between both substrates 1, 2. Further, the inside hermetic space is evacuated and sealed. Cathode lines 13, insulation layers 14 and grid electrodes 15 are formed on an inner surface of the back substrate 1, while anode electrodes 11 and phosphors 12 are formed on the face substrate 2. Carbon nanotubes of electron sources (not shown in the drawing) are provided on the cathode lines 13.
FIG. 15 is a diagrammatic plan view as seen from the back substrate 1 side of the field emission type display shown in FIG. 14. In the inside of the effective display region AR on the inner surface of the face substrate 2, phosphors R, G, B of three colors are arranged. In this example, respective pixels are defined by partitions 16. In a monochromic display, all phosphors are formed to have the same color.
With respect to a panel display which is constituted of two panels, as described above, a plasma display (PDP) or a panel display (MIM-FED) having a metal-insulator-metal field emission source has the same constitution. Although the explanation of the present invention will be directed hereinafter to a FED device as an example, the present invention is also applicable to a PDM device and a MIM-FED device. Further, the present invention is also applicable to a display device using surface conductive elements.
As an example of this type of panel display device, patent literature 1 (Unexamined Published Patent Japanese Application No. 2000-149788) discloses a device in which a getter housing chamber is separately provided to make up for a small evacuation conductance. Further, a technique which prevents the absorption of gas into the getter by introducing an inert gas into a high-temperature exhaust gas is disclosed in patent literature 2 (Unexamined Published Japanese Patent Application No. 2002-75202). Further, a proposal which carries out sealing and evacuation in a vacuum chamber is disclosed in patent literature 3 (Unexamined Published Japanese Patent Application No. 2002-56777). Further, a device which is further provided with getter support members, which control the scattering direction of the getter flash, is disclosed in the patent literature 4 (Unexamined Published Japanese Patent Application No. 2002-42638).


The present invention is directed to formulations including a polymer and a plasticizer composition. The plasticizer composition is a blend of an alkyl ketal ester plasticizer and a second plasticizer selected from a cycloaliphatic compound, an ortho phthalate compound, a terephthalate compound, a benzoate ester compound, and a bio-based compound. The plasticizer composition is at least 10% by weight of the total of the polymer and the plasticizer composition.

Plasticizers derived from 1,2-propanediol ketals of oxocarboxylate esters are described in WO2010/151558 which is hereby incorporated by reference in its entirety for all purposes.
A number of known plasticizer compounds are derived from non-renewable, petroleum or natural gas derived feedstocks. Phthalate esters, particularly, dioctyl terephthalate ester, di(2-ethylhexyl) phthalate ester, and diisononyl phthalate ester are industrially significant plasticizers useful for plasticizing many formulations; more common formulations include those containing poly(vinyl chloride) (PVC). Recent regulatory pressure has targeted phthalates (United States Environmental Protection Agency Report: Phthalates Action Plan—Dec. 30, 2009) for replacement due to the risks associated with their use.


An ink including a water-soluble phthalocyanine compound, wherein in the spectral absorption curve of an aqueous solution of the phthalocyanine compound, the absorbance ratio b/a of the maximum absorbance b in the absorption band of 660 to 680 nm and the maximum absorbance a in the absorption band of 600 to 640 nm is less than 0.8 and the counter ion for the ionic hydrophilic group of the phthalocyanine compound is lithium ion. The ink can provide an image having excellent (color) hue and high fastness to light and ozone gas, can be used as an ink for an ink jet and can be used in an ink jet recording method.

In recent years, the image recording material is predominated particularly by a material for forming a color image. More specifically, a recording material using an ink jet system, a recording material using a heat-sensitive transfer system, a recording material using an electro-photographic system, a silver halide light-sensitive material using a transfer system, a printing ink, a recording pen and the like are popularly used. Also, a color filter for recording/reproducing a color image is used in an image pick-up element such as CCD of photographing equipment, or in LCD or PDP of display. In these color image recording materials or color filters, three primary color dyes (dyes or pigments) by a so-called additive or subtractive color mixing method are used for reproducing or recording a full color image, however, a dye having absorption properties capable of realizing a preferred color reproduction region and having fastness capable of enduring various use and environmental conditions is not found at present and improvements are keenly demanded.
The ink jet recording method has been abruptly spread and is further growing because the material cost is low, high-speed recording can be obtained, noises are less generated at the recording and color recording is easy. The ink jet recording method includes a continuous system of continuously jetting out a liquid droplet and an on-demand system of jetting out a liquid droplet according to image information signals, and the ejection system therefore includes a system of ejecting a liquid droplet by generating bubbles in ink using heat, a system of using an ultrasonic wave, and a system of ejecting a liquid droplet by suction using an electrostatic force. The ink used for ink jetting includes an aqueous ink, an oily ink and a solid (fusion-type) ink.
The dye used in the ink for ink jetting is required to have good solubility or dispersibility in a solvent, enable high-density recording, provide good (color) hue, have fastness to light, heat and active gas in environment (for example, oxidative gas such as NOx and ozone, and SOx), exhibit excellent resistance against water and chemicals, ensure good fixing property to an image-receiving material to cause less blurring, give an ink having excellent storability, have no toxicity and high purity and be available at a low cost.
In particular, the dye is strongly demanded to have good cyan color and fastness to light, humidity and heat and when printed on an image-receiving material having an ink-accepting layer containing a porous white inorganic pigment particle, be resistant against oxidative gas such as ozone in the environment.
A representative skeleton of the cyan dye used for ink is a phthalocyanine or triphenylmethane structure. Representative examples of the phthalocyanine compound which has been reported and is used over the widest range include phthalocyanine derivatives classified into the following (1) to (6):    (1) copper phthalocyanine compounds such as Direct Blue 86 and Direct blue 87 [for example, Cu-Pc-(SO3Na)m: a mixture of m=1 to 4] (hereinafter, Pc means a phthalocyanine skeleton);    (2) Direct Blue 199 and phthalocyanine dyes described in JP-A-62-190273 (the term "JP-A" as used herein means an "unexamined published Japanese patent application"), JP-A-63-28690, JP-A-63-306075, JP-A-63-306076, JP-A-2-131983, JP-A-3-122171, JP-A-3-200883, JP-A-7-138511, etc. [for example, Cu-Pc-(SO3Na)m(SO2NH2)n: a mixture of m+n=1 to 4];    (3) phthalocyanine-base dyes described in JP-A-63-210175, JP-A-63-37176, JP-A-63-304071, JP-A-5-171085, WO00/08102, etc. [for example, Cu-Pc-(CO2H)m(CONR1R2)n: a mixture of m+n=0 to 4];    (4) phthalocyanine-base dyes described in JP-A-59-30874, JP-A-1-126381, JP-A-1-190770, JP-A-6-16982, JP-A-7-82499, JP-A-8-34942, JP-A-8-60053, JP-A-8-113745, JP-A-8-310116, JP-A-10-140063, JP-A-10-298463, JP-A-11-29729, JP-A-11-320921, EP-A-173476, EP-A-468649, EP-A-559309, EP-A-596383, German Patent 3,411,476, U.S. Pat. No. 6,086,955, WO99/13009, British Patent Publication 2,341,868A, etc. [for example, Cu-Pc-(SO3H)m(SO2NR1R2)n: a mixture of m+n=0 to 4, and m≠0];    (5) phthalocyanine-base dyes described in JP-A-60-208365, JP-A-61-2772, JP-A-6-57653, JP-A-8-60052, JP-A-8-295819, JP-A-10-130517, JP-A-11-72614, Japanese Unexamined Published International Application Nos. 11-515047 and 11-515048, EP-A-196901, WO95/29208, WO98/49239, W098/49240, W099/50363, W099/67334, etc. [for example, Cu-Pc-(SO3H)l(SO2NH2)m(SO2NR1R2)n: a mixture of 1+m+n=0 to 4]; and    (6) phthalocyanine-base dyes described in JP-A-59-22967, JP-A-61-185576, JP-A-1-95093, JP-A-3-195783, EP-A-649881, WO00/08101, WO00/08103, etc. [for example, Cu-Pc-(SO2NR1R2)n: a mixture of n=1 to 5].
Phthalocyanine-base dyes widely used in general at present, represented by Direct Blue 87 and Direct Blue 199, are excellent in the light fastness as compared with generally known magenta dyes, yellow dyes and triphenylmethane-base cyanine dyes.
However, the phthalocyanine-base dyes provide a greenish (color) hue under acidic conditions and are improper for a cyan ink. In the case of using these dyes for a cyanine ink, these are most suitably used under conditions from neutral to alkaline. However, even if the ink is in the region from neutral to alkaline, when the material on which an image or the like is recorded is an acidic paper, the (color) hue of the printed matter may greatly change.
Furthermore, discoloration to a greenish (color) hue or decoloration occurs due to oxidative gases such as nitrogen oxide gas and ozone, which are often taken as a problem also from an environmental issue, and this simultaneously causes reduction in the printing density.
On the other hand, triphenylmethane-base dyes provide a good (color) hue but are very inferior in the light fastness, resistance against ozone gas and the like.
If the use field hereafter expands and the printed matter is widely used for exhibition such as advertisement, the case of being exposed to light or active gas in the environment increases and to cope with this, a dye and an ink composition having light fastness and excellent resistance against active gases (for example, oxidative gas such as NOx and ozone, and SOx) in the environment are more strongly demanded.
However, it is very difficult to find out a cyan dye (for example, phthalocyanine-base dye) and a cyan ink satisfying these requirements in a high level.
As for the ink for an ink jet recording system, an aqueous dye ink obtained by dissolving a water-soluble dye of various types in a liquid medium comprising water and a water-soluble organic solvent, an aqueous pigment ink obtained by dispersing a pigment of various types in a liquid medium comprising water and a water-soluble organic solvent, an oily dye ink obtained by dissolving an oil-soluble dye in an organic solvent, and the like are known. Among these inks, the aqueous ink obtained by dissolving an aqueous dye is excellent in the safety because the main solvent is water, enables good coloring of a color image and formation of a high-grade printed image because a dye is used, and also exhibits excellent ink storage stability. Therefore, this aqueous ink is predominating as an ink for ink jet recording.
The phthalocyanine-base dyes imparted with water solubility are heretofore disclosed, for example, in WO00/08102, JP-A-2000-303014 and JP-A-2000-313837, however, none of these dyes have succeeded in satisfying both the (color) hue and the fastness to light and oxidative gas. A cyan ink product fully satisfying the requirements on the market is not yet provided.
When a recorded image having a high optical density is formed, this is accompanied with a problem that as the image is dried, the dye crystal deposits on the surface of the recording material and the recorded image reflects light to cause a so-called bronze phenomenon of emitting metallic gloss. This phenomenon is considered to readily occur when the water solubility of dye is decreased so as to improve water resistance or an amino group of a hydrogen bond group is introduced into the dye structure, because the dye is elevated in the associating (aggregating) property. The generation of bronze phenomenon not only incurs decrease in the optical density of the recorded image but also causes great difference from the desired (color) hue of the recorded image. Therefore, it is one of important performances required of the ink for ink jetting to prevent the bronze phenomenon.
Known examples of the method for preventing the bronze phenomenon include a method of adding a specific nitrogen-containing compound (see, for example, JP-A-55-120676, JP-A-62-119280, JP-A-64-6072, JP-A-1-152176, JP-A-2-41369, JP-A-5-125311, JP-A-6-25575, JP-A-6-128515, JP-A-6-228476, JP-A-6-228483, JP-A-6-248212, JP-A-7-228810, JP-A-7-268261, JP-A-8-259865, JP-A-9-12944, JP-A-9-12946, JP-A-9-12949 and JP-A-10-36735) and a method of adding a specific titanium compound (see, JP-A-8-337745). The bronze phenomenon may be prevented from occurring by adding these compounds, however, there is a fear that the additives decrease various performances of ink and the quality of recorded image. For example, as described in JP-A-8-259865, when an alkanolamine is added to the ink, the bronze phenomenon can be prevented but by the addition only in a small amount, the pH of ink increases to 11 or more and the high pH ink not only adversely affects nozzles but also lacks in safety on erroneously contacting with a human body and moreover, decreases the printing grade or water resistance of the recorded image.
Other than these, examples of the method for improving the performance of ink for ink jetted by using an additive are described in JP-A-5-339532 and JP-A-2001-254040 where an anionic additive except for dyes, having lithium ion, quaternary ammonium ion or quaternary phosphonium ion as the counter cation is added and thereby, even when the counter ion of the dye is not such ion, an effect of preventing clogging is obtained because the solubility is improved. On the other hand, JP-A-7-26178 describes a technique where an alkali metal compound is added to ink and thereby, the production of an aggregate of dye is prevented, as a result, the viscosity of ink does not increase. However, in JP-A-1036735, it is pointed out that this improvement effect can be attained when the storage time is short, but when stored for a long period of time, the storage stability has a problem.
As such, various effects can be obtained by using additives, however, various performances can be hardly maintained if additives are used. Particularly, in the case where the solubility and aggregating property of dye must be taken account of, selection of the kind and amount of additive is difficult. In using an ionic additive, the effect thereof on the counter ion must also be taken into consideration. Accordingly, a substantial bronze phenomenon-inhibiting method not relying on additives is preferred.
Studies are being aggressively made with an attempt to improve various performances required of the ink for ink jetting by changing the counter ion for the ionic hydrophilic group of metal phthalocyanine compounds and examples thereof include JP-A-5-339532, JP-A-6-16982, JP-A-6-248212, JP-A-6-322286, JP-A-7-138511 and JP-A-10-130517.
For example, in JP-A-57-202358, JP-A-63-81179, JP-A-63-317568 and Japanese Patents 2581769 and 3163176, lithium ion is referred to as preferred counter ion for the ionic hydrophilic group of metal phthalocyanine dyes and it is stated that this ion is effective for providing an ink having high concentration, storage stability and jetting stability. On the other hand, JP-A-7-82499 states that lithium ion is not preferred as the counter cation, because the water resistance of the recorded image decreases due to high water solubility of the dye. From these, it is seen that the performances required of the ink for ink jetting cannot be easily satisfied merely by changing the counter salt.
As described above, an ink capable of satisfying all of various performances required of the water-soluble ink for ink jetting is not yet found at present.
Problems to be Solved by the Invention:
The present invention has been made to solve those problems in conventional techniques and achieve the following objects. That is, the objects of the present invention are
(1) to provide a novel ink having absorption properties ensuring excellent color reproduction as a dye for three primary colors and at the same time, having sufficiently high fastness to light, heat, humidity and active gas in the environment;
(2) to provide an ink of giving a colored image or colored material excellent in the (color) hue and the fastness, for example, an ink composition for printing such as ink jetting;
(3) to provide an ink for ink jet recording and an ink jet recording method, which can form an image having good (color) hue by the use of a phthalocyanine compound derivative, having high fastness particularly against ozone gas and free of generation of a bronze phenomenon; and
(4) to provide a method for forming an image having fastness by using the above-described ink jet recording method and thereby improving the ozone gas discoloration resistance of the image recorded material.
Means to Solve the Problems:
As a result of extensive investigations on phthalocyanine derivatives of providing good (color) hue, generating no bronze phenomenon and ensuring fastness to light and gas (particularly ozone gas), the present inventors have found that the above-described objects can be attained by a phthalocyanine compound where the counter cation of the ionic hydrophilic group is lithium ion, particularly a phthalocyanine compound represented by the following formula (I), having (1) a specific spectral absorption curve and (2) a specific dye structure (specific substituents are introduced into specific substitution sites in a specific number of substituents), more particularly, a phthalocyanine compound represented by formula (II) or (III).

This patent is subject to a terminal disclaimer.

Water-soluble phthalocyanine compound-containing ink for ink jetting, ink jet recording method and method for improving ozone gas discoloration of colored image material


This patent discloses a curbside mailbox assembly having a mailbox adapted to be attached to a post. The mailbox may include a base and a cover attached to the base to form a compartment. The mailbox additionally may include a platform attached to the mailbox base, a door attached to the platform, and a basket assembly. The basket assembly may include a basket, a first slide rail assembly, and a second slide rail assembly. The basket may be an openwork container having tabs.

1. Field of Endeavor
The information disclosed in this patent relates to a mailbox having movement that may aid in mail collection by both the user and postal carrier and aid in delivery by the postal carrier.
2. Background Information
In just about every country, postal mail is delivered to one type of receptacle or another. In the United States, mail receptacles may be broken down into (i) multiple compartment troughs such as those used with apartment houses, (ii) door slots for city delivery, (iii) wall-mounted centralized mailboxes for city delivery, and (iv) curbside mailboxes for rural, highway contract, and city delivery.
The United States Postal Services (USPS) maintains particular regulations regarding curbside mailbox sizes and installation. For example, "customer mail receptacles" (as they are antiseptically known by the USPS) must be placed so they can be safely and conveniently served by postal carriers without leaving their right-hand-side driven vehicles. Curbside mailbox should be installed with the bottom of the box at a vertical height of between 3½ to 4 feet from the road surface and with the mailbox door at a distance of six to eight inches from the front face of the curb.
While these regulations may meet the needs of the United States Postal Services, they do not address the needs of the rural and highway contract customer who desires to retrieve all the mail from a roadside mailbox while in a vehicle or while the mailbox is enclosed by a bank of snow. The elderly and people with physical disabilities particularly have such needs. Moreover, a mail carrier also may need additional assistance in delivering mail while the mailbox is enclosed by a bank of snow.
While inventors have proposed some solutions to these needs, each one fall short in one or more areas. Some are difficult to install and others are complicated or difficult to use. Many are inconvenient and unaffordable. What is needed is an apparatus and method to overcome these and other problems.


Exemplary embodiments are disclosed of socket adaptors for retaining impact sockets to impact tools.

This section provides background information related to the present disclosure which is not necessarily prior art.
FIG. 1 shows a conventional impact socket adaptor 1 on an anvil 5 of an impact tool 9. The conventional impact socket adaptor 1 includes a tool connection portion 13 having a first set of aligned side holes 17, and a socket connector portion 21 having a second set of aligned side holes 25 defining a passageway through the socket connector portion 21.
As shown in FIG. 1, the first set of aligned holes 17 of the adaptor 1 are aligned with corresponding holes 7 in the impact tool's anvil 5 for receiving a first keeper or retainer therethrough. The first keeper would be inserted through the aligned holes for retaining the adaptor 1 to the impact tool's anvil 5.
The second set of holes 25 of the adaptor 1 are configured to align with side holes in an impact socket when the impact socket is positioned on the socket connector portion 21 of the adaptor 1 for receiving a second keeper or retainer. The second keeper would be inserted through the aligned holes for retaining the socket to the adaptor 1.
FIG. 2 shows a conventional locking pin and retaining O-ring set 29 that may be used with the conventional adaptor 1 shown in FIG. 1. To retain the adaptor 1 to the anvil 5 of the impact tool 9, the locking pin 33 of a first locking pin and retaining O-ring set 29 would be inserted entirely through the aligned holes of the adaptor 1 and impact tool 9. To retain the adaptor 1 to a socket, a locking pin 33 of a second locking pin and retaining O-ring set 29 would be inserted entirely through the aligned holes of the adaptor 1 and the socket.
FIG. 3 shows a conventional socket adaptor 37 that relies upon magnets 41 for retaining an impact socket on the adaptor 37. As shown in FIG. 3, magnets have fallen out of the empty recess 45 and/or are falling apart, which is likely due to impact vibrations generated during use of the impact tool. As recognized by the inventor hereof, this failure of the magnets may allow the impact socket to dislodge and fall off the adaptor 37. The falling impact socket may causes catastrophic injury, death, and/or damage especially when falling from significant heights.
Corresponding reference numbers may indicate corresponding (but not necessarily identical) parts throughout the several views of the drawings.


An apparatus that recursively classifies packets includes a hierarchical set of classification engines that perform parallel classification of the packets in a packet processing queue. In particular, a first classification engine separates the packets based on physical-layer information and/or link-layer information in the packets. Then, second classification engines further separate the packets into multiple parallel pipelines based on layer information in the packets that is other than the physical-layer information and the link-layer information. The first classification engine and the second classification engines maintain a relative ordering of the packets in network sub-flows while allowing changes in relative ordering among different network flows.

1. Field
The disclosed embodiments generally relate to a packet-processing technique in communications networks. More specifically, the disclosed embodiments relate to a hierarchical technique for separating packets.
2. Related Art
Packet classification engines are used in many high-performance network processing systems to separate or classify packets into several parallel processing elements. This classification is usually performed to exploit the inherent parallelism present in network flows and associated applications, and to match this inherent parallelism to the parallelism provided by the processing elements.
As network speeds have increased and with virtualized applications, more of the offload classification is being handled in hardware. However, in the overall packet-processing path, a packet classification engine can become a potential bottleneck. Consequently, the packet classification engine typically needs to scale to match the speed and the amount of additional processing that it has to perform.
In a conventional classification framework, even though there may be multiple contexts with pipelines within the packet classification engine, the bottleneck usually is the time it takes to determine the processing queue where a given packet is sent. Note that the use of multiple pipelines within the packet classification engine may not always solve this problem. In particular, the depth of classification can vary from packet to packet based on the application. Furthermore, because pipelines are often unequal, scaling issues can occur. In addition, with some of the emerging tunneling standards, pipelined packet classification engines often do not scale.
Hence, what is needed is a packet classification engine that facilitates the separation of packets without the problems described above.

Parallelizing packet classification and processing engines


A retaining assembly includes a body and a retainer. The body includes a compartment defined in an end thereof. The compartment is defined by a perimeter wall and an end wall. A coupling hole is defined in the end wall for receiving a tool. The retainer is mounted in the compartment of the body and has a through-hole aligned with the coupling hole of the body. The retainer further includes at least one resilient positioning portion abutting against the perimeter wall of the body for retaining the retainer in the compartment of the body. The retainer further includes at least one resilient clamping portion extending into the coupling hole of the body for pressing against at least one face of the tool received in the coupling hole of the body.

1. Field of the Invention
The present invention relates to a retaining assembly and, more particularly, to a retaining assembly for retaining a driving member such as a screwdriver bit or the like.
2. Description of the Related Art
FIG. 6 of the drawings illustrates a conventional sleeve 1 having a compartment 2. An end of the sleeve 1 is coupled to a handle of a screwdriver. A member, such as a screwdriver bit is mounted into the compartment 2 and retained in place by a C-clip 3. In assembly, the C-clip 3 is compressed by a pair of pliers and placed into the compartment 2 in a position aligned with an annular groove 4 in a perimeter wall defining the compartment 2. Finally, the C-clip 3 is inserted into the annular groove 4 and then released. The resiliency of the C-clip 3 is not affected when the diameter of the compartment 2 is large enough, for the C-clip 3 deforms in an allowable extent during the assembling procedure. However, if the diameter of the compartment 2 is too small, the C-clip 3 is deformed beyond its tolerable limit such that permanent deformation occurs. As a result, the clamping force imparted by the C-clip 3 to the member received in the compartment 2 is not uniform or insufficient to reliably retain the member in place.
FIG. 7 shows a conventional shock-proof retainer 7 that is mounted into a bottom of a compartment 6 in a sleeve 5. However, undesired shift occurs easily while mounting the retainer 7 into the deepest portion of the compartment 6. The mounting procedure is more difficult when the compartment 6 is small in diameter. Further, the retainer 7 occupies a certain space in the compartment 6 and, thus, adversely affects the function and effect of retaining.


A sintered Ti alloy comprising: 4 to 6 wt. % iron; 1 to 4 wt. % aluminium or 1 to 3 wt. % copper; >0 to 0.5 wt. % silicon; >0 to 0.3 wt. % boron; >0 to 1 wt. % lanthanum, and the balance being titanium with incidental impurities. In the associated powder metallurgy formation process, the boron and lanthanum content is preferably introduced into a blended powder mixture in the form of lanthanum boride (LaB6).

The following discussion of the background to the invention is intended to facilitate an understanding of the invention. However, it should be appreciated that the discussion is not an acknowledgement or admission that any of the materials referred to was published, known or part of the common general knowledge as at the priority date of the application.
Titanium alloys are advanced structural materials possessing an array of desirable properties that are not readily achievable with any other material. These include excellent corrosion resistance to seawater environments, high specific strength and fracture toughness, good compatibility with composites, long durability with little or no maintenance, excellent biocompatibility, and the like. However, such alloys can have a very low yield because of production difficulties involved in conventional ingot metallurgy based methods. Powder metallurgy can overcome a number of these disadvantages by permitting the production of parts that need only a few finishing steps.
Of many powder metallurgy methods, the conventional press-and-sinter or cold-compaction-and-sinter powder metallurgy approach is technically the simplest and economically the most attractive near-net shape manufacturing process. This approach typically uses a mixed powder method involving the mixing of titanium powder with various alloying powders, followed by compacting and sintering. This method offers several advantages, including the flexibility of using inexpensive raw material powder, high yields, and simple production process, which can lead to a considerable cost saving compared to conventional ingot metallurgy based manufacturing methods.
Further cost reduction of powder metallurgy Ti components also depends on the availability of lower-cost powder metallurgy Ti alloys that can offer desired properties. From an alloy design perspective, a wide variety of alloying elements can be introduced to titanium for various alloying purposes. However, from a cost perspective it is preferable to use lower cost or inexpensive alloying elements, such as iron, aluminium, silicon, copper, and the like. It is probable that small amounts of higher cost alloying elements such as rare earth elements may be needed in order to enable the achievement of desired microstructures and/or mechanical properties.
Hydrogenated-dehydrogenated (HDH) titanium powder or hydrogenated titanium powder made directly from the titanium sponge offers an attractive basis for current powder metallurgy Ti alloy development due to its affordable price and manageable oxygen content. It is likely that both powders will continue to be major sources of cost-affordable Ti powder for the future powder metallurgy Ti market.
The oxygen content of HDH Ti powder products varies over a wide range. Inexpensive HDH Ti powder products normally contain ≥0.25 wt. % oxygen. Ti powder has high chemical affinity for oxygen (O) and each Ti powder particle is constantly enveloped with a surface oxide film. However, unlike other metal powders, owing to the high solubility of O in Ti (up to 14 wt. %), the surface titanium oxide film on each titanium powder particle will dissolve into the underlying Ti metal from temperatures above approximately 500° C. leading to an increased O content in solid solution. In addition, there is an unavoidable pick-up of oxygen during the powder handling process and especially the subsequent sintering process. Consequently, the oxygen content in solid solution of the as-sintered titanium components may readily exceed 0.33 wt. %, which is the critical oxygen content identified for powder metallurgy (PM) Ti-6Al-4V (wt. %) [see reference 1]. This critical oxygen content may vary for different PM Ti alloys [see reference 2]. However, it has been well established that the ductility of both unalloyed Ti and Ti alloys is sensitive to their O content. Being able to control the O content thus lies at the heart of the fabrication of cost affordable ductile Ti alloys from inexpensive powder for structural applications.
It is technically challenging to directly use such inexpensive HDH titanium powder for the production of structural titanium components. The two prime reasons are that:
(i) current commercial grade titanium alloys are not designed for powder metallurgy processing; it is therefore difficult to form these alloys to a near pore-free density (e.g. >99% theoretical density) by the simple press-and-sinter approach; and
(ii) the as-sintered titanium alloys are often not ductile enough (e.g. tensile elongation <4%) or are even lack of ductility due to resulting high oxygen content discussed previously and the existence of large pores.
It has proved to be demanding to address these two challenges. Although alloy design is only one aspect of the problem, having a low-cost, readily sinterable titanium alloy will serve as an important starting point to realize low-cost titanium powder metallurgy.
It would therefore be desirable to provide a new and/or alternative titanium alloy which can provide a low-cost alternative to existing press-and-sintered titanium alloys.


The present invention provides a polybutylene terephthalate resin composition, having performance of high durability and the like in a cold cycle environment, and having high strength. Specifically, relative to 100 parts by weight of a polybutylene terephthalate resin (A) having 30 meq/kg or less of the amount of terminal carboxyl groups, there are added a carbodiimide compound (B) in an amount of 0.3 to 1.5 equivalents of the carbodiimide functional group when the amount of carboxyl terminal group in the polybutylene terephthalate resin (A) is set as 1, 20 to 100 parts by weight of a fibrous filler (C), and 5 to 15 parts by weight of an elastomer (D).

Polybutylene terephthalte resins are used as engineering plastics in wide fields including automobile parts, electric and electronic parts, or the like owing to their excellent mechanical properties, electric properties, and other physical and chemical properties, and their good workability. In particular, since their heat resistance and strength can be increased by adding a fibrous filler such as glass fiber thereto, polybutylene terephthalte resins are often used by reinforcing thereof by the fibrous filler.
Specifically in the automobile field, polybutylene terephthalate is often used as the material of sensor for electric control and of ECU housing. In that case, for the parts (insert molded articles) being mounted in an environment of severe temperature increase/decrease, such as engine room of automobile, the toughness of the parts is often improved by adopting an elastomer and the like to prevent crack generation caused by strain resulting from the difference in linear expansion between metal and resin. Many kinds of compositions have been proposed for that purpose.
For example, JP-A 3-285945 discloses the improvement in the resistance to heat shock by adding an elastomer such as ethylene-alkyl acrylate to polybutylene terephthalate. The resin, however, does not exhibit satisfactory resistance to heat shock and does not exhibit satisfactory resistance to hot water, although the improvement effect of those resistances is recognized in comparison with that of non-additive resin.
JP-A 60-210659 discloses the improvement of the resistance to hot water by adding an elastomer such as ethylene-alkyl acrylate and carbodiimide to polybutylene terephthalate. That kind of composition, however, does not exhibit satisfactory resistance to heat shock, although the resistance to hot water is improved.
Furthermore, JP-A 2001-234046 discloses that a resin composition composed of polybutylene terephthalate, a material providing impact resistance, and an aromatic polyvalent carboxylic acid ester compound exhibits excellent resistance to heat shock. However, the addition of the aromatic polyvalent carboxylic acid ester compound raises a problem of deteriorating the strength and the toughness, and also raises a problem of inducing bleeding at high temperatures.
As described above, although the addition of elastomer in order to improve the toughness is known, the addition thereof at an amount necessary for improving the toughness raises a problem of deteriorating the strength.

Method for forming an insert injection-molded article exhibiting improved resistance to heat shock utilizing a specifically defined polybutylene terephthalate composition