An enterprise wide electronic commerce system allows trading partners to act as participants in a complex trading process. Participants communicate with one another by joining conversations that are hosted in a collaboration space and managed by a collaboration hub. In this manner, the enterprise workflow may have an effect on, or be affected by, local workflows. The invention provides an open market collaboration system for enterprise wide electronic commerce. An embodiment of the invention includes a collaboration system that allows the exchange of data between participants in an electronic commerce environment, comprising a collaboration hub for the transfer of data between participants, a collaboration space defining the rules governing said transfer of data and the role of said participants, and a hub transport that allows a participant to send and receive data from the collaboration hub in accordance with the definitions of the collaboration space.

To prosper in the Internet economy, a company must be able to streamline its business process, eliminate unnecessary cost, and react quickly to competitive pressures. To support this mandate, information technology (IT) organizations must have the ability to rapidly consolidate systems from newly created or incorporated divisions and, in many cases, to exchange mission-critical information with outsourced partners as a virtual enterprise. New Internet applications must be linked with each enterprise's core technologies to deliver accurate information, solid operational performance, and a satisfactory customer purchase experience. And, whether companies do business on the Web or not, customers expect all businesses to run on Internet time—a rapid pace that calls for seamless, high-performance business operations that can be accomplished only when applications are integrated with each other to create the zero latency enterprise.
The first business issue is the integration of critical business information and logic that reside in enterprise production and legacy systems. Multiple IT systems that are implemented as silos or standalone systems, each addressing particular business issues, should be integrated across the enterprise.
Traditionally, islands of individual applications that need to share data have been integrated in an adhoc manner, using homegrown integration and, more recently, Enterprise Application Integration (EAI) toolsets. These hard-coded and point-to-point solutions attempted to address the problem but created an IT nightmare of innumerable spaghetti-like connections between applications. EAI solutions that cobble together a combination of point-to-point interfaces, procedure calls, file transfers, and "e-mail-like" messaging to deliver enterprise-wide data transformation and routing are notoriously high risk.
Further, multiple point-to-point and ad hoc solutions are inherently difficult to deploy and maintain because they lack a centralized management and support for real-time change management. These features are desirable to the management of business processes and the goal of addressing the e-commerce integration environment.
The second business issue is the need to incorporate Web-based, e-commerce applications. The goal of getting on the Web, however, was not a simple one; only new businesses starting from scratch had the luxury of building from the ground up. With substantial IT infrastructures and investments in place, most businesses were faced with having to leverage current information systems and merge them into the e-commerce age. Businesses that are not able to integrate customer-facing Web applications with enterprise systems find that they simply cannot support today's competitive market and customer demands. This is because data is locked away in disparate systems that do not speak the same language, much less speak to each other.
The third business issue is taking full advantage of integrated e-commerce, including the integration of business processes with trading partners. E-Commerce enables companies to enjoy significant savings and increase revenue opportunities by (1) improving service to customers, (2) engaging in just-in-time production, (3) finding more competitive providers of operational goods and production materials, and (4) being able to create new markets quickly. These two objectives—reducing cost and increasing revenue—have always been driving business forces. However, to date, there has been no solution that has provided the key enablers for e-business. Electronic data interchange (EDI) emerged in the 1990s as a standard for exchanging data between companies. EDI is a highly structured, expensive, and time-consuming technology. Packaged solutions have also emerged that claim to solve business-to-business (B2B) dilemmas; however they also require heavy investment in proprietary application technology across all business partners, entail significant configuration expertise, and deliver a hard-coded, pre-packaged process that all parties must adopt. Packaged solutions and EDI deliver very little competitive advantage, are not customizable for differing business processes, and are expensive, time-consuming options.
Most people are familiar with the traditional EDI batch mode type of B2B, and with the more recent electronic store fronts of dot-coms, otherwise referred to as basic commerce. While both EDI and basic commerce provide companies with business advantages that were not previously available—the high costs and technical constraints of implementing EDI and the minimal transaction functionality of basic commerce have limited their adoption as long-term e-business strategies. Community commerce, the third type of B2B e-commerce, features the same characteristics of basic commerce—the simple matching of buyers and sellers online—with perhaps some added functionality, such as auction and search, and the sharing of common information with vertical or community groups. However, these three types of commerce share one common limitation—they do not involve real-time, dynamic conversations between businesses. The sharing of information is in the form of simple point-to-point messages that are not really conversations. While these types of commerce may be sufficient to do things like sharing simple inventory information with suppliers, or posting product catalogs for buyers, these types of commerce have, to date, done little more than simply take information and automate its distribution to participants.
Existing B2B models fall short in meeting modern day requirements. From EDI and outsourced procurement to supply chain management systems and first-generation online exchanges, companies are feverishly searching out technology that will enable them to quickly, efficiently, and reliably conduct business with trading partners over the Internet. Unfortunately, companies are discovering that most of these traditional B2B technologies meet only a fraction of their e-business IT requirements. A more comprehensive, powerful and flexible solution is required to successfully meet the challenges of collaborative B2B commerce today.
While EDI offers an advantage over paper-based business transactions, it has traditionally been restricted to large companies with substantial IT budgets and technical resources. EDI typically requires as much as 9-12 months to implement and can be quite costly. Finally, EDI is not real-time or process-driven. Data is batch transmitted, and transactions can be sent out of sequence without system oversight. In some cases, data may not be received at all—creating consternation and confusion on all sides.
Unlike EDI, new B2B solutions are designed to leverage the Internet and technologies such as Java, in order to lower the barriers to entry for trading partners of any size, reduce deployment cycles and cost, and power managed, real-time communication between partners. Recognizing that EDI will continue to be used by many of the world's largest companies because of familiarity and confidence in legacy systems, new Internet-based e-business platforms must also co-exist comfortably with EDI legacy systems. Nonetheless, as the real and opportunity costs of using EDI grow, companies are investing IT resources in Internet-based systems that make more financial and strategic sense.
Another commonly found form of B2B interaction is the use of outsourced e-procurement applications. Web-based purchasing of maintenance, repair, and operation (MRO) supplies—the goods required to run a company but not the materials used in the direct manufacture of a product or the provision of a service—is becoming more and more common every day. To deliver process efficiencies and cost savings, many companies have outsourced their MRO provisioning to third parties because these goods are non-strategic, low-cost items that can be intermittently purchased in bulk from a pre-established set of suppliers.
However, from a technology perspective, outsourced e-procurement is much like EDI in that it increases efficiency over paper-based processes but is also monolithic, inflexible, and requires all participants to adopt a single proprietary application. This does not enable customers to create competitive advantage by streamlining their mainstream purchasing process or doing business any differently than direct competitors. These serious limitations, combined with the fact that MRO vendors typically own all the data associated with using their exchange, mean that most companies are reluctant to consider e-procurement vendors for their core or strategic enterprise functions. In fact, some participants in MRO exchanges may consider e-procurement vendors as potential downstream competition and are careful to limit the scope of business conducted on these sites.
Given these factors, while many companies may continue using MRO procurement for a portion of their e-business portfolio, they must still acquire strategic technology that will encompass MRO exchanges but support larger and more strategic e-business objectives.
Some organizations have implemented B2B solutions as a first-generation online exchanges for e-markets and supply chain management. An e-market maker can be defined as an organization that develops a B2B, Internet-based, e-marketplace of buyers and sellers within a particular industry, geographic region or affinity group. The list of e-market makers is growing larger every day.
Although it is indisputable that e-marketplaces in general will power much of e-business tomorrow, supporting a broad variety of collaboration, purchasing sales and trading activities, the majority of them are not delivering on the B2B promise today. A recent research study found that of 600 surveyed exchanges, only 10 provided application integration. A primary goal of B2B and online marketplaces is to reduce human intervention. This goal cannot be achieved unless systems are integrated from end-to-end.
E-Markets without back-end integration to a company's enterprise systems significantly reduces the return on investment for e-market makers and participants, and limits that company's opportunities to satisfy customers in new and unique ways. Supply chain transparency, which occurs when e-market makers have increased visibility into a supplier's product availability and delivery information, enables B2C companies to better meet customer demands in real-time and represents a significant source of competitive advantage. The differentiating factor between two supply chains often boils down to which one is better at managing the information float—the time between when data is captured in one place and when it becomes available and actionable elsewhere.
As e-markets continue to proliferate—interconnecting with each other and growing into tomorrow's interconnected e-business "power grid"—they promise to super-charge the B2B network effect. E-businesses need to respond quickly to market demand, and as such look to build not just their own supply chains but also those of their customers and suppliers. These benefits will flow through entire industry segments as information improves, order processing becomes easier, and all parties can begin to rely on getting what they need to meet customer demands in a timely fashion.

Collaboration system for exchanging of data between electronic participants via collaboration space by using a URL to identify a combination of both collaboration space and business protocol


The elevator chair has a seat assembly mounted on a support frame which includes an occupant supporting seat having a rear seat section, a seat back connected to and extending upwardly from the rear seat section and a front seat section which extends substantially across the extent of the rear seat section and which is pivoted to the rear seat section. A seat drive unit drives the seat assembly from a first position where the front and rear seat sections extend in the same first plane to a second position where the rear seat section remains in a second plane parallel to said first plane while the front seat section angles downwardly and outwardly. Subsequently the seat drive unit drives the seat assembly to a third position where the rear seat section tilts forwardly toward the front seat section.

It is often desirable to provide assistance to a person who is attempting to move from a sitting position in a chair to a standing position. Age, infirmity, or various disabilities often render it difficult for persons to rise out of a chair from a sitting to a standing position without assistance.
In moving the occupant of a chair from a sitting to a free standing position, it is critical that both positions provide adequate and comfortable support if the chair is to function efficiently. The chair should be designed to distribute pressure to the back, buttocks and thighs of a user in the standing position. Also, as the chair moves an occupant from a sitting to a standing position, it is often critical that the chair backrest not apply shear stresses to the back of an occupant. It is very important that the upper leg of the occupant be positioned as the chair rises to support the weight of the occupant in the standing position as weight is transferred from the chair to the legs. Once the legs are properly positioned, then it is desirable for the chair to tilt forward to aid in transferring the weight of the occupant to the occupant's legs.
In the past, the design of chairs which have been developed to move occupants upwardly from a sitting position has been directed toward providing the upward movement and has not concentrated on positioning the legs and torso of the occupant and then tilting the chair for transition from the sitting to the standing position. U.S. Pat. No. 4,249,774 to Andreasson discloses a chair of this type which requires an occupant to slide forward over a projecting seat.
A number of wheelchairs have been developed to raise an occupant from a sitting to a standing position and to support the occupant in the standing position, but these chairs are designed for continued occupant support in a standing position and not to facilitate transition from the chair to a free standing, unsupported position. U.S. Pat. Nos. 5,211,414 and 5,401,044 to Galumbeck are illustrative of wheelchairs of this type.


There is provided a flaw detection testing method applied to a slot dovetail portion of a turbine generator rotor shaft. The flaw detection testing method includes an angle determining step of determining a slot angle of the slot dovetail portion using a variable-angle ultrasonic probe, a flaw detection performing step of, on the basis of a determination result in the angle determining step, using an angle ultrasonic probe or a phased array probe to perform flaw detection to detect a flaw in the slot dovetail portion, and a flaw depth measuring step of, when the flaw is detected in the flaw detection performing step, using an angle ultrasonic probe to measure a depth of the flaw from a surface of the slot dovetail portion.

1. Field of the Invention
The present invention relates to a flaw detection testing method applied to a slot dovetail portion of a turbine generator rotor shaft.
2. Description of the Related Art
While a turbine generator rotor is in operation, a fretting fatigue fracture may occur in a slot dovetail portion of a turbine generator rotor shaft, that is, a shaft side of the vicinity of a shoulder portion of a rotor coil wedge to be inserted.
Known methods for detecting the fretting fatigue fracture during a periodic inspection are magnetic particle testing and eddy current testing, in which surface flaw detection is performed with an end ring and the rotor coil wedge disassembled.
However, to allow the end ring and the rotor coil wedge to be disassembled, the rotor needs to be carried to a manufacturing plant. This increases a period during which a power plant needs to be shut down, placing a heavy burden on power companies. Thus, ultrasonic testing is often adopted, which is an internal flaw detection technique that can be performed at the site without the need for disassembling.
When ultrasonic testing is applied to the slot dovetail portion, the slot angle of the slot dovetail portion to an outer peripheral surface of the rotor shaft, which is a test surface, needs to be taken into account.
The slot angle is known if a manufacturing drawing of the rotor shaft 1 is available. Otherwise, the slot angle needs to be pre-measured in order to allow an ultrasonic probe to be selected.
Furthermore, to increase the accuracy of detection of flaws such as the fretting fatigue fracture, which generally have small opening widths and which are directional, a reflection angle at which an ultrasonic beam is reflected by the flaw needs to be adjusted so as to avoid mode conversion losses in spite of the constraint on the slot angle.
If any flaw is detected, the depth of the flaw needs to be measured in order to determine whether operation can be continued or repairs are required.


A 4-oxatricyclo[4.3.1.13,8]undecan-5-one derivative is shown by the following formula (1):

1. Field of the Invention
The present invention relates to 4-oxatricyclo[188.8.131.52,8]undecan-5-one derivatives which are useful as materials for photosensitive resins and other functional polymers and as materials for pharmaceuticals, agricultural chemicals, and other fine chemicals, and to a process for producing the derivative.
2. Description of the Related Art
A compound 4-oxatricyclo[22.214.171.124,8]undecan-5-one is known as an intermediate for organic synthesis (e.g., Synthesis, 1986, 741-743). This compound is obtained by introducing an oxygen atom to the adjacent position of a carbonyl group of 2-adamantanone. However, 4-oxatricyclo[18.104.22.168,8]undecan-5-one derivatives having a hydroxyl group or a (meth)acryloyloxy group bonded to a carbon atom at the 1-position are not known.
On the other hand, a lithography technique is used for the formation of fine patterns of semiconductor integrated circuits. The lithography technique includes the steps of covering a substrate having a thin film formed thereon (work) with a resist, subjecting the work to selective exposure to yield a latent image of a target pattern, subjecting the work to developing to form a patterned resist, dry-etching the work using the pattern as a mask, and then removing the resist to yield the target pattern. In the lithography technique, g-ray, i-ray, and other ultraviolet rays are used as light sources. However, with an increasing fineness of patterns, far ultraviolet rays, vacuum ultraviolet rays, excimer laser beams, electron beams, x-rays and other rays having a shorter wavelength are employed as the light sources. To form fine patterns using such a short-wavelength light source (e.g., ArF excimer laser), the resist used must have a satisfactory transparency at the wavelength of the light source, have a good adhesion to the substrate, be resistance to dry etching, and be satisfactorily soluble in a developer in development. As such resist materials, polymers of polymerizable monomers each having a bridged ring or a lactone ring have received attention in recent years (e.g., Japanese Unexamined Patent Application Publication No. 9-73173), but none of them sufficiently satisfies the above requirements.
Accordingly, an object of the invention is to provide a novel 4-oxatricyclo[220.127.116.11,8]undecan-5-one derivative having a hydroxyl group or a (meth)acryloyloxy group at the 1-position.
Another object of the invention is to provide a 4-oxatricyclo[126.96.36.199,8]undecan-5-one derivative which is useful as a monomeric material for photoresist resins.
A further object of the invention is to provide a process for efficiently producing the 4-oxatricyclo[220.127.116.11,8]undecan-5-one derivative.
After intensive investigations to achieve the above objects, the present inventors found that when a 4-adamantanone derivative having a hydroxyl group or a (meth)acryloyloxy group at the 1-position is oxidized with molecular oxygen by catalysis of an imide compound having a specific structure in the coexistence of a specific compound, a Baeyer-Villiger type reaction proceeds to efficiently yield a corresponding 4-oxatricyclo[18.104.22.168,8]undecan-5-one derivative. The present invention has been accomplished based on these findings.
Specifically, the invention provides, in an aspect, a 4-oxatricyclo[188.8.131.52,8]undecan-5-one derivative shown by the following formula (1):
wherein R is a hydrogen atom or a (meth)acryloyl group, and carbon atoms constituting a ring may have a substituent in addition to the substituents indicated in the formula. Preferred R includes a (meth)acryloyl group.
In another aspect, the invention provides a process for producing a 4-oxatricyclo[184.108.40.206,8]undecan-5-one derivative. This process includes the step of oxidizing an adamantanone derivative shown by the following formula (2):
wherein R is a hydrogen atom or a (meth)acryloyl group, and carbon atoms constituting a ring may have a substituent in addition to the substituents indicated in the formula, with molecular oxygen in the presence of an imide compound shown by the following formula (3):
wherein each of R1 and R2 is, identical to or different from each other, a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a cycloalkyl group, a hydroxyl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, or an acyl group, where R1 and R2 may be combined to form a double bond, or an aromatic or non-aromatic ring; X is an oxygen atom or a hydroxyl group; and one or two N-substituted cyclic imido groups indicated in the formula (3) may be further formed on the R1, R2, or on the double bond or aromatic or non-aromatic ring formed together by R1 and R2, and in the coexistence of an co-oxidizing agent to yield a 4-oxatricyclo[126.96.36.199,8]undecan-5-one derivative shown by the following formula (1):
wherein R is a hydrogen atom or a (meth)acryloyl group, and carbon atoms constituting a ring may have a substituent in addition to the substituents indicated in the formula. The co-oxidizing agent includes, for example, a primary or secondary alcohol.
The invention provides, in a further aspect, a process for producing a 4-oxatricyclo[22.214.171.124,8]undecan-5-one derivative. This process includes the step of allowing a compound of the following formula (1a):
wherein carbon atoms constituting a ring may have a substituent in addition to the substituents indicated in the formula, to react with (meth)acrylic acid or a reactive derivative thereof to yield a compound shown by the following formula (1b):
wherein Rd is a (meth)acryloyl group, and carbon atoms constituting a ring may have a substituent in addition to the substituents indicated in the formula.
In this specification, both acryloyl group and methacryloyl group are simply referred to as xe2x80x9c(meth)acryloyl groupxe2x80x9d.
In the 4-oxatricyclo[18.104.22.168,8]undecan-5-one derivative of the formula (1), R is a hydrogen atom or a (meth)acryloyl group. Carbon atoms constituting a ring may have a substituent in addition to the substituents (xe2x80x94OR group and oxo group) indicated in the formula. Such substituents include, but are not limited to, methyl group, ethyl group, isopropyl group, and other C1-C4 alkyl groups, hydroxyl group which may have a protective group, and carboxyl group which may have a protective group. As the protective groups, those conventionally used in the field of organic synthesis can be employed.
Typical 4-oxatricyclo[188.8.131.52,8]undecan-5-one derivatives of the formula (1) include, but are not limited to, 1-hydroxy-4-oxatricyclo[184.108.40.206,8]undecan-5-one, 1-(meth)acryloyloxy-4-oxatricyclo[18.104.22.168,8]undecan-5-one, 1-hydroxy-3,8-dimethyl-4-oxatricyclo[220.127.116.11,8]undecan-5-one, 1-(meth)acryloyloxy-3,8-dimethyl-4-oxatricyclo[126.96.36.199,8]undecan-5-one, 1-hydroxy-3,6-dimethyl-4-oxatricyclo[188.8.131.52,8]undecan-5-one, 1-(meth)acryloyloxy-3,6-dimethyl-4-oxatricyclo[126.96.36.199,8]undecan-5-one, 1,8-dihydroxy-4-oxatricyclo[126.96.36.199,8]undecan-5-one, 8-hydroxy-1-(meth)acryloyloxy-4-oxatricyclo[188.8.131.52,8]undecan-5-one, 1,6-dihydroxy-4-oxatricyclo[184.108.40.206,8]undecan-5-one, 6-hydroxy-1-(meth)acryloyloxy-4-oxatricyclo[220.127.116.11,8]undecan-5-one, 1,3-dihydroxy-4-oxatricyclo[126.96.36.199,8]undecan-5-one, 3-hydroxy-1-(meth)acryloyloxy-4-oxatricyclo[22.214.171.124,8]undecan-5-one, 8-carboxy-1-hydroxy-4-oxatricyclo[188.8.131.52,8]undecan-5-one, 8-carboxy-1-(meth)acryloyloxy-4-oxatricyclo[22.214.171.124,8]undecan-5-one, 6-carboxy-1-hydroxy-4-oxatricyclo[184.108.40.206,8]undecan-5-one, 6-carboxy-1-(meth)acryloyloxy-4-oxatricyclo[22.214.171.124,8]undecan-5-one, 3-carboxy-1-hydroxy-4-oxatricyclo[126.96.36.199,8]undecan-5-one, and 3-carboxy-1-(meth)acryloyloxy-4-oxatricyclo[126.96.36.199,8]undecan-5-one.
[Production of Compound of Formula (1)]
The 4-oxatricyclo[220.127.116.11,8]undecan-5-one derivative of the formula (1) can be obtained, for example, by oxidizing the adamantanone derivative of the formula (2) with molecular oxygen in the presence of the imide compound of the formula (3) and in the coexistence of a co-oxidizing agent. The term xe2x80x9cco-oxidizing agentxe2x80x9d used herein means and includes a compound which is oxidized together with the compound of the formula (2) under reaction conditions.
The substituents which carbon atoms constituting a ring may have in the formula (2) include the groups exemplified as substituents which carbon atoms constituting a ring may have in the formula (1).
Typical compounds of the formula (2) include, but are not limited to, 5-hydroxy-2-adamantanone, 5-(meth)acryloyloxy-2-adamantanone, 5-hydroxy-3,7-dimethyl-2-adamantanone, 5-(meth)acryloyloxy-3,7-dimethyl-2-adamantanone, 5-hydroxy-1,3-dimethyl-2-adamantanone, 5-(meth)acryloyloxy-1,3-dimethyl-2-adamantanone, 5,7-dihydroxy-2-adamantanone, 7-hydroxy-5-(meth)acryloyloxy-2-adamantanone, 1,5-dihydroxy-2-adamantanone, 1-hydroxy-5-(meth)acryloyloxy-2-adamantanone, 3,5-dihydroxy-2-adamantanone, 3-hydroxy-5-(meth)acryloyloxy-2-adamantanone, 7-carboxy-5-hydroxy-2-adamantanone, 7-carboxy-5-(meth) acryloyloxy-2-adamantanone, 1-carboxy-5-hydroxy-2-adamantanone, 1-carboxy-5-(meth)acryloyloxy-2-adamantanone, 3-carboxy-5-hydroxy-2-adamantanone, and 3-carboxy-5-(meth)acryloyloxy-2-adamantanone.
Of the substituents R1 and R2 in the imide compound of the formula (3), the halogen atom includes iodine, bromine, chlorine and fluorine atoms. The alkyl group includes, but is not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, hexyl, heptyl, octyl, decyl, and other straight- or branched-chain alkyl groups each having about 1 to 10 carbon atoms. Preferred alkyl groups are alkyl groups each having about 1 to 6 carbon atoms, of which lower alkyl groups each having about 1 to 4 carbon atoms are particularly preferred.
The aryl group includes phenyl, and naphthyl groups, for example. Illustrative cycloalkyl groups include cyclopentyl, and cyclohexyl groups. Illustrative alkoxy groups are methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, t-butoxy, pentyloxy, hexyloxy, and other alkoxy groups each having about 1 to 10 carbon atoms, and preferably having about 1 to 6 carbon atoms. Among them, lower alkoxy groups each having about 1 to 4 carbon atoms are especially preferred.
Examples of the alkoxycarbonyl group include methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, t-butoxycarbonyl, pentyloxycarbonyl, hexyloxycarbonyl, and other alkoxycarbonyl groups each having about 1 to 10 carbon atoms in the alkoxy moiety. Preferred alkoxycarbonyl groups are alkoxycarbonyl groups each having about 1 to 6 carbon atoms in the alkoxy moiety, of which lower alkoxycarbonyl groups each having about 1 to 4 carbon atoms in the alkoxy moiety are particularly preferred.
The illustrative acyl groups include, for example, formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl, isovaleryl, pivaloyl, and other acyl groups each having about 1 to 6 carbon atoms.
The substituents R1 and R2 may be identical to or different from each other. The substituents R1 and R2 in the formula (3) may be combined to form a double bond or an aromatic or non-aromatic ring. The preferred aromatic or non-aromatic ring has about 5 to 12 members, and particularly about 6 to 10 members. The ring may be a heterocyclic ring or condensed heterocyclic ring, but it is often a hydrocarbon ring. Such rings include, for example, non-aromatic alicyclic rings (e.g., cyclohexane ring and other cycloalkane rings which may have a substituent, cyclohexene ring and other cycloalkene rings which may have a substituent), non-aromatic bridged rings (e.g., 5-norbornene ring and other bridged hydrocarbon rings which may have a substituent), benzene ring, naphthalene ring, and other aromatic rings (including condensed rings) which may have a substituent. The ring is composed of an aromatic ring in many cases. The ring may have a substituent. Such substituents include, but are not limited to, alkyl groups, haloalkyl groups, hydroxyl group, alkoxy groups, carboxyl group, alkoxycarbonyl groups, acyl groups, nitro group, cyano group, amino group, and halogen atoms.
In the formula (3), X represents an oxygen atom or a hydroxyl group, and the bond between the nitrogen atom N and X is a single bond or a double bond.
One or two N-substituted cyclic imido groups indicated in the formula (3) may be further formed on R1, R2, or on the double bond or aromatic or non-aromatic ring formed together by R1 and R2. For example, when R1 or R2 is an alkyl group having two or more carbon atoms, the N-substituted cyclic imido group may be formed together with the adjacent two carbon atoms constituting the alkyl group. Likewise, when R1 and R2 are combined to form a double bond, the N-substituted cyclic imido group may be formed together with the double bond. In case that R1 and R2 are combined to form an aromatic or non-aromatic ring, the N-substituted cyclic imido group may be formed with the adjacent two carbon atoms constituting the ring.
Preferred imide compounds include compounds of the following formulae:
wherein R3 to R6 are each, identical to or different from each other, a hydrogen atom, an alkyl group, a haloalkyl group, a hydroxyl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, an acyl group, a nitro group, a cyano group, an amino group, or a halogen atom, where adjacent groups of R3 to R6 may be combined to form an aromatic or non-aromatic ring; in the formula (3f), A1 is a methylene group or an oxygen atom, and R1 and R2 have the same meanings as defined above, where one or two N-substituted cyclic imido groups indicated in the formula (3c) may be further formed on the benzene ring in the formula (3c); and X has the same meaning as defined above.
In the substituents R3 to R6, the alkyl group includes similar alkyl groups to those exemplified above, especially alkyl groups each having about 1 to 6 carbon atoms. The haloalkyl group includes trifluoromethyl group, and other haloalkyl groups each having about 1 to 4 carbon atoms, and the alkoxy group includes similar alkoxy groups to those mentioned above, and especially lower alkoxy groups each having about 1 to 4 carbon atoms. The alkoxycarbonyl group includes similar alkoxycarbonyl groups to those described above, particularly lower alkoxycarbonyl groups each having about 1 to 4 carbon atoms in the alkoxy moiety. The acyl group includes similar acyl groups to those described above, especially acyl groups each having about 1 to 6 carbon atoms. The illustrative halogen atoms include fluorine, chlorine and bromine atoms. Each of the substituents R3 to R6 is often a hydrogen atom, a lower alkyl group having about 1 to 4 carbon atoms, a carboxyl group, a nitro group, or a halogen atom. The ring formed together by R3 to R6 includes similar rings to the aforementioned rings which are formed together by R1 and R2. Among them, aromatic or non-aromatic 5- to 12-membered rings are particularly preferred.
Typically preferred imide compounds include N-hydroxysuccinimide, N-hydroxymaleimide, N-hydroxyhexahydrophthalimide, N,Nxe2x80x2-dihydroxycyclohexanetetracarboximide, N-hydroxyphthalimide, N-hydroxytetrabromophthalimide, N-hydroxytetrachlorophthalimide, N-hydroxychlorendimide, N-hydroxyhimimide, N-hydroxytrimellitimide, N,Nxe2x80x2-dihydroxypyromellitimide, and N,Nxe2x80x2-dihydroxynaphthalenetetracarboximide.
The imide compounds can be prepared by a conventional imidation process (a process for the formation of an imide), such as a process that comprises the steps of allowing a corresponding acid anhydride to react with hydroxylamine NH2OH for ring-opening of an acid anhydride group, and closing the ring to form an imide.
Such acid anhydrides corresponding to the imide compounds of the formula (3) include, but are not limited to, succinic anhydride, maleic anhydride, and other saturated or unsaturated aliphatic dicarboxylic anhydrides, tetrahydrophthalic anhydride, hexahydrophthalic anhydride (1,2-cyclohexanedicarboxylic anhydride), 1,2,3,4-cyclohexanetetracarboxylic 1,2-dianhydride, and other saturated or unsaturated non-aromatic cyclic polycarboxylic anhydrides (alicyclic polycarboxylic anhydrides), HET anhydride (chlorendic anhydride), himic anhydride, and other bridged cyclic polycarboxylic anhydrides (alicyclic polycarboxylic anhydrides), phthalic anhydride, tetrabromophthalic anhydride, tetrachlorophthalic anhydride, nitrophthalic anhydride, trimellitic anhydride, methylcyclohexenetricarboxylic anhydride, pyromellitic anhydride, mellitic anhydride, 1,8;4,5-naphthalenetetracarboxylic dianhydride, and other aromatic polycarboxylic anhydrides.
Typically preferred imide compounds include N-hydroxyimide compounds derived from alicyclic polycarboxylic anhydrides or aromatic polycarboxylic anhydrides, of which N-hydroxyphthalimide and other N-hydroxyimide compounds derived from aromatic polycarboxylic anhydrides are especially preferred.
Each of the imide compounds of the formula (3) can be used alone or in combination in the oxidation reaction. The imide compounds can be used as being supported on a carrier. As such carriers, activated carbon, zeolite, silica, silica-alumina, bentonite, and other porous carries are frequently employed.
The proportion of the imide compound can be selected within a wide range and is, for example, about 0.0001 to 1 mole, preferably about 0.001 to 0.5 mole, more preferably about 0.01 to 0.4 mole, and often about 0.05 to 0.35 mole, relative to 1 mole of the compound of the formula (2).
In the inventive process, a promoter (co-catalyst) can be used in combination with the catalyst of the formula (3) to improve or enhance the rate and selectivity of the reaction. Such promoters include, but are not limited to, (i) compounds each having a carbonyl group combined with an electron attractive group, (ii) metallic compounds, and (iii) organic salts each composed of a polyatomic cation or a polyatomic anion and its counter ion, which polyatomic cation or anion contains a Group 15 or Group 16 element of the Periodic Table of Elements having at least one organic group bonded thereto. Each of these promoters can be used alone or in combination.
In the compounds (i) each having a carbonyl group combined with an electron attractive group, the electron attractive group includes, but is not limited to, phenyl; fluoromethyl, trifluoromethyl, tetrafluoroethyl, fluorophenyl, pentafluorophenyl, and other hydrocarbon groups each substituted with a fluorine atom. Practical examples of the compounds (i) include, for example, hexafluoroacetone, trifluoroacetic acid, pentafluorophenyl methyl ketonxc3xa9, pentafluorophenyl trifluoromethyl ketone, and benzoic acid.
The use of these compounds can enhance the reaction rate of a Baeyer-Villiger type reaction. This is provably because these compounds are converted into highly reactive peroxides in a reaction system. The amount of the compound (i) is about 0.0001 to 1 mole, preferably about 0.01 to 0.7 mole, and more preferably about 0.05 to 0.5 mole, relative to 1 mole of the compound of the formula (2).
Metallic elements constituting the metallic compounds (ii) are not limited and can be any of metallic elements of the Groups 1 to 15 of the Periodic Table of Elements. The term xe2x80x9cmetallic elementxe2x80x9d as used herein also includes boron B. Examples of the metallic elements include, of the Periodic Table of Elements, Group 1 elements (e.g., Li, Na, K), Group 2 elements (e.g., Mg, Ca, Sr, Ba), Groups 3 elements (e.g., Sc, lanthanoid elements, actinoid elements), Group 4 elements (e.g., Ti, Zr, Hf), Group 5 elements (e.g., V), Group 6 elements (e.g., Cr, Mo, W), Group 7 elements (e.g., Mn), Group 8 elements (e.g., Fe, Ru), Group 9 elements (e.g., Co, Rh), Group 10 elements (e.g., Ni, Pd, Pt), Group 11 elements (e.g., Cu), Group 12 elements (e.g., Zn), Groups 13 elements (e.g., B, Al, In), Group 14 elements (e.g., Sn, Pb), and Group 15 elements (e.g., Sb, Bi). Preferred metallic elements include transition metal elements (elements of Groups 3 to 12 of the Periodic Table of Elements). Among them, elements of the Groups 5 to 11 of the Periodic Table of Elements are preferred, of which elements of Group 6, Group 7 and Group 9 are typically preferred. Especially, Mo, Co and Mn can be advantageously used. The valency of the metallic element is not particularly limited, and is about 0 to 6 in many cases.
The metallic compounds (ii) include, but are not limited to, elementary substances, hydroxides, oxides (including complex oxides), halides (fluorides, chlorides, bromides, and iodides), salts of oxoacids (e.g., nitrates, sulfates, phosphates, borates, and carbonates), oxoacids, isopolyacids, heteropolyacids, and other inorganic compounds of the aforementioned metallic elements; salts of organic acids (e.g., salts of acetic acid, propionic acid, hydrocyanic acid, naphthenic acid, or stearic acid), complexes, and other organic compounds of the metallic elements. Ligands for constituting the complexes include OH (hydroxo), alkoxy (e.g., methoxy, ethoxy, propoxy, and butoxy), acyl (e.g., acetyl and propionyl ), alkoxycarbonyl groups (e.g., methoxycarbonyl and ethoxycarbonyl), acetylacetonato, cyclopentadienyl group, halogen atoms (e.g., chlorine, and bromine atoms), CO, CN, oxygen atom, H2O (aquo), phosphines (triphenylphosphine and other triarylphosphines), and other phosphorus compounds, NH3 (ammine), NO, NO2 (nitro), NO3 (nitrato), ethylenediamine, diethylenetriamine, pyridine, phenanthroline, and other nitrogen-containing compounds. Each of the metallic compounds (ii) can be used alone or in combination.
The use of the metallic compounds (ii) improves the selectivity of the reaction in some cases. Particularly, the combination use of a compound containing V, Mo, Co, Mn or another transition metal element (excludingFe) with a compound containing a platinum group element (Ru, Rh, Pd, Os, Ir, or Pt) or Fe can markedly improve the selectivity to yield a target compound in a high yield. Especially, the combination use of a Co compound with Pt(dppb) (xcexc-OH)]2(BH4)2 or other platinum group metal-hydrogen complex compounds is preferred.
The proportion of the metallic compound (ii) is, for example, about 0.0001 to 0.7 mole, preferably about 0.001 to 0.5 mole, more preferably about 0.002 to 0.1 mole, and often about 0.005 to 0.05 mole, relative to 1 mole of the compound of the formula (2).
In the organic salts (iii), the Group 15 elements of the Periodic Table of Elements include N, P, As, Sb, and Bi, and the Group 16 elements of the Periodic Table of Elements include, for example, O, S, Se and Te. Preferred elements are N, P, As, Sb, and S, of which N, P, and S are typically preferred.
The organic groups to be bonded to atoms of the elements include, but are not limited to, hydrocarbon groups which may have a substituent, and substituted oxy groups. The hydrocarbon groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, hexyl, octyl, decyl, tetradecyl, hexadecyl, octadecyl, allyl, and other straight- or branched-chain aliphatic hydrocarbon groups (alkyl groups, alkenyl groups and alkynyl groups) each having about 1 to 30 carbon atoms (preferably about 1 to 20 carbon atoms); cyclopentyl, cyclohexyl, and other alicyclic hydrocarbon groups each having about 3 to 8 carbon atoms; and phenyl, naphthyl, and other aromatic hydrocarbon groups each having about 6 to 14 carbon atoms. Substituents which the hydrocarbon groups may have include, but are not limited to, halogen atoms, oxo group, hydroxyl group, substituted oxy groups (e.g., alkoxy groups, aryloxy groups, and acyloxy groups), carboxyl group, substituted oxycarbonyl groups, substituted or unsubstituted carbamoyl groups, cyano group, nitro group, substituted or unsubstituted amino groups, alkylgroups (e.g., methyl, ethyl, and other C1-C4 alkyl groups), cycloalkyl groups, aryl groups (e.g., phenyl, and naphthyl groups) , and heterocyclic groups. The preferred hydrocarbon groups include, for example, alkyl groups each having about 1 to 30 carbon atoms, and aromatic hydrocarbon groups (especially, phenyl or naphthyl group) each having about 6 to 14 carbon atoms. The substituted oxy groups include, but are not limited to, alkoxy groups, aryloxy groups and aralkyloxy groups.
The polyatomic cation is, for example, represented by the following formula (4). This polyatomic cation constitutes, with a counter anion, an organic onium salt represented by the following formula (5).
[RamA]+xe2x80x83xe2x80x83(4)
[RamA]xe2x88x92Yxe2x88x92xe2x80x83xe2x80x83(5)
In the above formulae, Ra is a hydrocarbon group or a hydrogen atom. The four Ras may be identical to or different from one another, and at least one Ra is a hydrocarbon group. The atom A is an atom of Group 15 or Group 16 element of the Periodic Table of Elements. Two Ras may be combined to form a ring with the adjacent A, or two Ras may together form a double bond as one with the atom A and be concurrently combined with another Ra to form a ring with the atom A. The numeral m denotes 3 or 4. Yxe2x88x92 is a counter anion, and Y is an acid radical. The above hydrocarbon group may have, for example, any of the aforementioned substituents.
The rings which are to be formed by two Ras with the adjacent A include, but are not limited to, pyrrolidine ring, piperidine ring, and other nitrogen-containing or phosphorus-containing heterocyclic rings each having about 3 to 8 members (preferably 5 or 6 members). Alternately, two Ras may together form a double bond as one with the atom A and be concurrently combined with another Ra to form a ring with the atom A. Such rings just mentioned above include pyridine ring, and other 5- to 8-membered nitrogen-containing heterocyclic rings. To these rings, a benzene ring or another ring may be condensed. Such a condensed ring includes, for example, quinoline ring. In many cases, m is 4 when A is an atom of Group 15 element of the Periodic Table of Elements, and, m is 3 when A is an atom of Group 16 element of the Periodic Table of Elements.
The atom A is preferably N, P, As, Sb or S, more preferably N, P or S, and particularly N or P. In the preferred polyatomic cations, all the four Ras are organic groups (including cases where a ring containing A is formed).
The acid radical Y includes, but is not limited to, fluorine, chlorine, bromine, iodine, and other halogen atoms;
nitrate radical (NO3), sulfate radical (SO4), phosphate radical (PO4), perchlorate radical (ClO4), and other inorganic acid radicals; acetate radical (CH3CO2), methanesulfonate radical, benzenesulfonate radical, and other organic acid radicals.
Preferred acid radicals include halogen atoms and inorganic acid radicals, of which chlorine atom, bromine atom and other halogen atoms are typically desirable.
Of the organic onium salts, organic ammonium salts, organic phosphonium salts, and organic sulfonium salts are typically preferred. Concrete examples of organic ammonium salts include tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, tetrahexylammonium chloride, trioctylmethylammonium chloride, triethylphenylammonium chloride, tributyl(hexadecyl)ammonium chloride, di(octadecyl) dimethylammonium chloride, and other quaternary ammonium chlorides, and corresponding quaternary ammonium bromides, and other quaternary ammonium salts each having four hydrocarbon groups bonded to its nitrogen atom; dimethylpiperidinium chloride, hexadecylpyridinium chloride, methylquinolinium chloride, and other cyclic quaternary ammonium salts.
Practical examples of the organic phosphonium salts include tetramethylphosphonium chloride, tetrabutylphosphonium chloride, tributyl(hexadecyl)phosphonium chloride, triethylphenylphosphonium chloride, and other quaternary phosphonium chlorides, and corresponding quaternary phosphonium bromides, and other quaternary phosphonium salts each having four hydrocarbon groups bonded to its phosphorus atom. Concrete examples of the organic sulfonium salts include triethylsulfonium iodide, ethyldiphenylsulfonium iodide, and other sulfonium salts each having three hydrocarbon groups bonded to its sulfur atom.
The polyatomic anion is represented by, for example, the following formula (6). This polyatomic anion constitutes, with a counter cation, an organic salt of the following formula (7).
[RbAO3]qxe2x88x92xe2x80x83xe2x80x83(6)
Zq+[RbAO3]qxe2x88x92xe2x80x83xe2x80x83(7)
In the above formulae, Rb is a hydrocarbon group or a hydrogen atom; A is an atom of Group 15 or Group 16 element of the Periodic Table of Elements; q denotes 1 or 2; and Zq+ is a counter cation.
Such hydrocarbon groups represented by Rb include, in addition to similar groups to the aforementioned hydrocarbon groups, resins (polymer chains or branched chains thereof). Preferred A includes, but is not limited to, S and P. The numeral q is 1 when A is S or the like, and q is 2 when A is P or the like. The atom Z includes, but is not limited to, sodium, potassium, and other alkali metals; magnesium, calcium, and other alkaline earth metals, of which alkali metals are preferred. The counter cation Zq+ may be the above-mentioned polyatomic cation.
Illustrative organic salts of the formula (7) include methanesulfonates, ethanesulfonates, octanesulfonates, dodecanesulfonates, and other alkyl-sulfonates; benzenesulfonates, p-toluenesulfonates, naphthalenesulfonates, decylbenzenesulfonates, dodecylbenzenesulfonates, and other aryl-sulfonates which may be substituted with an alkyl group; sulfonic acid type ion exchange resins (ion exchangers); and phosphonic acid type ion exchange resins (ion exchangers). Of these salts, a C6-C18 alkyl-sulfonate, or a C6-C18 alkyl-aryl sulfonate is often used.
The proportion of the organic salt (iii) is, for example, about 0.0001 to 0.7 mole, preferably about 0.001 to 0.5 mole, more preferably about 0.002 to 0.1 mole, and often about 0.005 to 0.05 mole, relative to 1 mole of the compound of the formula (2). The use of the organic salt (iii) in excess amounts may reduce the reaction rate.
The molecular oxygen for use in oxidation includes, but is not limited to, pure oxygen, and oxygen diluted with an inert gas such as nitrogen, helium, argon, or carbon dioxide. Air is preferably used as the oxygen from the viewpoints of operating property and safety, as well as cost efficiency.
The amount of the molecular oxygen is generally equal to or more than 0.5 mole (e.g., equal to or more than 1 mole), preferably about 1 to 100 moles, and more preferably about 2 to 50 moles, relative to 1 mole of the compound of the formula (2). The molecular oxygen is often employed in excess moles relative to the compound of the formula (2).
In the above process, for example a primary or secondary alcohol can be used as a co-oxidizing agent. Such primary or secondary alcohols include a wide variety of alcohols, and may be any of monohydric, dihydric or polyhydric alcohols. The primary or secondary alcohol may have a variety of substituents. Such substituents include, but are not limited to, halogen atoms, oxo group, hydroxyl group, mercapto group, substituted oxy groups (e.g., alkoxy groups, aryloxy groups, and acyloxy groups), substituted thio groups, carboxyl group, substituted oxycarbonyl groups, substituted or unsubstituted carbamoyl groups, cyano group, nitro group, substituted or unsubstituted amino groups, alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, cycloalkenyl groups, aryl groups (e.g., phenyl and naphthyl groups), aralkyl groups, and heterocyclic groups.
Such primary alcohols include, but are not limited to, methanol, ethanol, 1-propanol, 1-butanol, 2-methyl-1-propanol, 1-pentanol, 1-hexanol, 1-octanol, 1-decanol, 1-hexadecanol, 2-buten-1-ol, ethylene glycol, trimethylene glycol, hexamethylene glycol, pentaerythritol, and other saturated or unsaturated aliphatic primary alcohols each having about 1 to 30 (preferably about 1 to 20, and more preferably about 1 to 15) carbon atoms; cyclopentylmethyl alcohol, cyclohexylmethyl alcohol, 2-cyclohexylethyl alcohol, and other saturated or unsaturated alicyclic primary alcohols; benzyl alcohol, 2-phenylethyl alcohol, 3-phenylpropyl alcohol, cinnamyl alcohol, and other aromatic primary alcohols; and 2-hydroxymethylpyridine, and other heterocyclic alcohols. Preferred primary alcohols include aliphatic primary alcohols such as saturated aliphatic primary alcohols each having about 1 to 20 carbon atoms.
Illustrative secondary alcohols include 2-propanol, s-butyl alcohol, 2-pentanol, 3-pentanol, 2-hexanol, 2-octanol, 4-decanol, 2-hexadecanol, 2-penten-4-ol, and other saturated or unsaturated aliphatic secondary alcohols each having about 3 to 30 (preferably about 3 to 20, and more preferably about 3 to 15) carbon atoms; cyclobutanol, cyclopentanol, cyclohexanol, cyclooctanol, cyclododecanol, cyclopentadecanol, 2-cyclohexen-1-ol, 3,5,5-trimethyl-2-cyclohexen-1-ol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,4-cyclooctanediol, 2,2-bis(4-hydroxycyclohexyl)propane, bis(4-hydroxycyclohexyl)methane, 4-(4-hydroxycyclohexyl)cyclohexanol, and other saturated or unsaturated alicyclic secondary alcohols each having about 3 to 20 members (preferably about 3 to 15 members, more preferably about 5 to 15 members, and especially about 5 to 8 members); 1-phenylethanol, 1-phenylpropanol, 1-phenylmethylethanol, diphenylmethanol (benzhydrol), and other aromatic secondary alcohols; and 1-(2-pyridyl)ethanol, and other heterocyclic secondary alcohols.
Preferred primary or secondary alcohols include secondary alcohols (e.g., s-butyl alcohol, and other aliphatic secondary alcohols; cyclohexanol and other alicyclic secondary alcohols; I-phenylethanol, diphenylmethanol (benzhydrol) and other aromatic secondary alcohols). Each of these alcohols can be used singly or in combination.
The primary or secondary alcohol as the co-oxidizing agent is generally converted into an aldehyde, a carboxylic acid, or a ketone upon reaction.
In the invented process, other compounds than primary or secondary alcohols can be employed as co-oxidizing agents. Such compounds include a variety of compounds that can be oxidizable with the imide compound and oxygen (refer to Japanese Unexamined Patent Application Publications No. 8-38909 and No. 9-327626). Such co-oxidizing agents other than primary or secondary alcohols include, for example, compounds each having a carbon-hydrogen bond at the adjacent position to an unsaturated bond (e.g., toluene, ethylbenzene, tetralin, fluorene, and other aromatic compounds each having a methyl group or methylene group at the adjacent position to an aromatic ring), compounds each having a methine carbon atom (e.g., decalin, adamantane, and other bridged cyclic compounds each having a methine group; and isobutane, and other chain or alicyclic hydrocarbons each having a methine carbon atom), cycloalkanes (e.g., cyclohexane), and non-aromatic heterocyclic compounds each having a carbon-hydrogen bond at the adjacent position to a hetero atom (e.g., chroman, and isochroman)
Each of these co-oxidizing agents can be used alone or in combination. The amount of the co-oxidizing agent is, for example, about 0.1 to 200 moles, preferably about 0.5 to 100 moles, more preferably about 1 to 50 moles, and especially about 2 to 30 moles, relative to 1 mole of the compound of the formula (2). The co-oxidizing agent can also serve as a reaction solvent.
In the above process, the role of the co-oxidizing agent is supposed to be as follows. The co-oxidizing agent (e.g., a primary or secondary alcohol) is oxidized to yield a compound (e.g., a peroxide when the co-oxidizing agent is a primary or secondary alcohol), and this compound is involved in a reaction in which the compound of the formula (2) is converted into a corresponding lactone [the compound of the formula (1)].
The oxidation reaction is generally performed in an organic solvent. Such organic solvents include, but are not limited to, acetic acid, propionic acid, and other organic acids; acetonitrile, propionitrile, benzonitrile, and other nitrites; formamide, acetamide, dimethylformamide (DMF), dimethylacetamide, andotheramides; hexane, octane, andother aliphatic hydrocarbons; chloroform, dichloromethane, dichloroethane, carbon tetrachloride, chlorobenzene, trifluoromethylbenzene, and other halogenated hydrocarbons; nitrobenzene, nitromethane, nitroethane, and other nitro compounds; ethyl acetate, butyl acetate, and other esters; and mixtures of these solvents. In may cases, acetic acid and other organic acids, acetonitrile, benzonitrile, and other nitriles, trifluoromethylbenzene, and other halogenated hydrocarbons, ethyl acetate and other esters are used as the solvent.
A reaction temperature is, for example, about 0xc2x0 C. to 300xc2x0 C., preferably about 20xc2x0 C. to 200xc2x0 C., and more preferably about 30xc2x0 C. to 150xc2x0 C. The reaction is usually performed at a temperature of about 40xc2x0 C. to 100xc2x0 C. The reaction can be performed at atmospheric pressure or under a pressure (under a load). When the reaction is conducted under a pressure, the pressure is usually about 1 to 100 atm (e.g. 1.5 to 80 atm), and preferably about 2 to 70 atm. A reaction time can be appropriately selected within a range of, for example, about 30 minutes to 48 hours depending on the reaction temperature and pressure.
The reaction can be performed in a batch system, semi-batch system, continuous system or another conventional system, in the presence of, or under flow of, molecular oxygen.
After the completion of the reaction, reaction products can be easily separated and purified by a conventional technique such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography and other separation means, or any combination of these separation means.
Alternatively, the compound of the formula (1) can be also obtained upon an ordinary Baeyer-Villiger reaction, i.e., a reaction of the compound of the formula (2) with hydrogen peroxide or another peroxide, or with m-chloroperbenzoic acid or another peracid.
Of the 4-oxatricyclo[184.108.40.206,8]undecan-5-one derivatives of the formula (1), a compound where R is an acryloyl group or methacryloyl group [the compound of the formula (1b)] can be obtained by allowing the compound of the formula (1a) to react with (meth)acrylic acid or a reactive derivative thereof. The compound of the formula (1a) is a compound (an alcohol derivative) where R is a hydrogen atom among the 4-oxatricyclo[220.127.116.11,8]undecan-5-one derivatives of the formula (1).
In the formulae (1a) and (1b) , substituents which carbon atoms constituting the ring may have include the groups exemplified as substituents which carbon atoms consisting the ring in the formula (1) may have. Reactive derivatives of (meth)acrylic acid include, for example, acid halides, acid anhydrides, esters (e.g., C1-C4 alkyl esters, and active esters), and amides (e.g., active amides).
More practically, the compound of the formula (1b) can be obtained, for example, by the following process (i), (ii), or (iii). In the process (i), a compound (an alcohol derivative) where R is a hydrogen atom among the 4-oxatricyclo[220.127.116.11,8]undecan-5-one derivatives of the formula (1) is allowed to react with (meth)acrylic acid in the presence of an acid catalyst such as hydrochloric acid, sulfuric acid, or p-toluenesulfonic acid. In the process (ii), the alcohol derivative is allowed to react with a (meth)acrylic halide in the presence of a base such as triethylamine. In the process (iii), the alcohol derivative and a (meth)acrylic ester are subjected to transesterification in the presence of a transesterification catalyst. In the processes (i) and (ii), the reaction can be performed under usual esterification conditions. In the process (iii), the transesterification can be performed using a conventional transesterification catalyst such as sodium alkoxides, aluminium alkoxides, and titanates. However, a corresponding (meth)acryloyloxy derivative can be obtained in a high yield by using vinyl (meth)acrylate, propenyl (meth)acrylate, and another C2-C4 alkenyl (meth)acrylate as the (meth)acrylic ester and by using a compound of Group 3 element of the Periodic Table of Elements (e.g., samarium iodide, samarium triflate, samarium complexes, and other samarium compounds) as the transesterification catalyst.
[Production of Compound of Formula (2)]
Of the adamantanone derivatives of the formula (2) for use as materials in the process for producing the compound of the formula (1), a compound where R is a hydrogen atom can be obtained, for example, by the following process. Specifically, an adamantanone derivative shown by the following formula (8)
wherein Rc is a hydrogen atom, and the other carbon atoms than carbon atoms to which the oxo group or Rc indicated in the formula is bonded may have a substituent, is allowed to react with oxygen in the presence of the imide compound of the formula (3) and a vanadium compound and a manganese compound to yield an a damantanone derivative shown by the following formula (2a):
wherein the other carbon atoms than carbon atoms to which the oxo group or hydroxyl group indicated in the formula may have a substituent.
In the formula (8), the other carbon atoms than carbon atoms to which the oxo group or Rc indicated in the formula is bonded may have a substituent, and in the formula (2a), the other carbon atoms than carbon atoms to which the oxo group or hydroxyl group indicated in the formula may have a substituent. Such substituents include the groups exemplified as substituents which carbon atoms constituting the ring in the formula (1) may have.
Typical compounds of the formula (8) include, but are not limited to, 2-adamantanone, 3,7-dimethyl-2-adamantanone, 1,3-dimethyl-2-adamantanone, 7-hydroxy-2-adamantanone, 1-hydroxy-2-adamantanone, 7-carboxy-2-adamantanone, and 1-carboxy-2-adamantanone.
The compound of the formula (8) can be obtained, for example, by allowing a corresponding adamantane derivative to react with oxygen in. the presence of the imide compound of the formula (3), the metallic compound, and a strong acid (e.g., a concentrated sulfuric acid) to convert the adamantane derivative into an oxo derivative (refer to Japanese Unexamined Patent Application Publication No. 10-309469).
The proportion of the imide compound in the production of the adamantanone derivative of the formula (2a) can be selected within a wide range and is, for example, about 0.0001 to 1 mole, preferably about 0.001 to 0.5 mole, more preferably about 0.01 to 0.4 mole, and often about 0.05 to 0.35 mole, relative to 1 mole of the compound of the formula (8).
As the vanadium compound and manganese compound, a wide variety of compounds each containing a vanadium atom or a manganese atom can be employed. Each of these vanadium compounds and manganese compounds can be respectively used alone or in combination. The vanadium element in the vanadium compound has a valency of 2 to 5, and the manganese element in the manganese compound has a valency of 1 to 7.
Such vanadium compounds and manganese compounds include, but are not limited to, hydroxides, oxides (including complex oxides), halides (fluorides, chlorides, bromides, and iodides), salts of oxoacids (e.g., nirates, sulfates, phosphates, borates, and carbonates), oxoacids, isopolyacids, heteropolyacids, and other inorganic compounds of each element; salts of organic acids (e.g., salts of acetic acid, propionic acid, hydrocyanic acid, naphthenic acid, or stearic acid), complexes, and other organic compounds of each element. Ligands constituting the complexes include OH (hydroxo), alkoxy (e.g., methoxy, ethoxy, propoxy, andbutoxy), acyl (e.g., acetyl and propionyl), alkoxycarbonyl (e.g., methoxycarbonyl and ethoxycarbonyl), acetylacetonato, cyclopentadienyl group, halogen atoms (e.g., chlorine and bromine), CO, CN, oxygen atom, H2O (aquo), phosphines (e.g., triphenylphosphine and other triarylphosphines), and other phosphorus compounds, NH3 (ammine), NO, NO2 (nitro), NO3 (nitrato), ethylenediamine, diethylenetriamine, pyridine, phenanthroline, and other nitrogen-containing compounds.
Illustrative vanadium compounds include vanadium hydroxide, vanadium oxide, vanadium chloride, vanadyl chloride, vanadium sulfate, vanadyl sulfate, sodium vanadate, and other inorganic compounds; acetylacetonatovanadium, vanadyl acetylacetonato, and other complexes, and other vanadium compounds having a valency of 2 to 5. Typical manganese compounds include, but are not limited to, manganese hydroxide, manganese oxide, manganese chloride, manganese bromide, manganese nitrate, manganese sulfate, manganese phosphate, and other inorganic compounds; manganese acetate, manganese naphthenate, manganese stearate, and other salts of organic acids; and acetylacetonatomanganese, and other complexes, and other divalent or trivalent manganese compounds.
The total amount of the vanadium compound and the manganese compound is, for example, about 0.0001 to 0.7 mole, preferably about 0.001 to 0.5 mole, more preferably about 0.0015 to 0.1 mole, and often about 0.0015 to 0.05 mole (particularly, about 0.002 to 0.01 mole), relative to 1 mole of the compound of the formula (8).
The ratio (metallic atomic ratio) of the vanadium compound to the manganese compound is, for example, such that the former/the latter is about 99/1 to 1/99, preferably about 95/5 to 10/90, more preferably about 90/10 to 30/70, and often about 80/20 to 50/50.
The other metallic catalysts can be employed as co-catalysts in combination with the above compounds within a range not deteriorating the rate and selectivity of the reaction.
As the oxygen, either of molecular oxygen and nascent oxygen can be used. Such molecular oxygen includes, but is not limited to, pure oxygen, and oxygen diluted with an inert gas such as nitrogen, helium, argon or carbon dioxide. Air is preferably used as the oxygen from the viewpoints of operating property and safety, as well as cost efficiency.
The amount of the oxygen is, generally, equal to or more than about 0.5 mole (e.g., equal to or more than 1 mole), preferably about 1 to 100 moles, and more preferably about 2 to 50 moles, relative to 1 mole of the compound of the formula (8). The oxygen is often used in excess moles relative to the compound of the formula (8).
The reaction is generally performed in an organic solvent. The type of the organic solvent, reaction temperature, reaction pressure, and other reaction conditions are the same with the conditions described in the process for producing the compound of the formula (1) from the compound of the formula (2). The reaction can be performed in a batch system, semi-batch system, continuous system or another conventional system in the presence of, or under flow of oxygen. This process can introduce a hydroxyl group into a specific position of an adamantane ring to yield the compound of the formula (2a) in a high yield. After the completion of the reaction, reaction products can be easily separated and purified by a conventional technique such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, and other separation means, or any combination of these separation means.
Of the adamantanone derivatives of the formula (2), a compound where R is a (meth)acryloyl group c an b e produced, using the compound of the formula (2a), in accordance with any of the processes for producing the compound of the formula (1b) from the compound of the formula (1a) (e.g., the processes (i) (ii), and (iii)). The compound of the formula (1a) is a compound where R is a hydrogen atom among the compounds of the formula (1), and the compound of the formula (1b) is a compound where R is an acryloyl group or methacryloyl group among the compounds of the formula (1).
The invented 4-oxatricyclo[184.108.40.206,8]undecan-5-one derivatives of the formula (1) are useful as materials for photosensitive resins, and other functional polymers, and as materials for pharmaceuticals, agricultural chemicals, and other fine chemicals. Among them, when a compound where R is a (meth)acryloyl group is used as a monomeric component of a resist resin, the adamantane skeleton exhibits a higher dry etching resistance. In addition, this compound has a highly hydrophilic lactone ring and has a satisfactory solubility and a high adhesion to a substrate. Specifically, the compound in question is an ideal compound that can satisfy three requirements, i.e., dry etching resistance, solubility, and adhesion in one molecule.
As thus described, the invention can provide novel 4-oxatricyclo[18.104.22.168,8]undecan-5-one derivatives each having a hydroxyl group or (meth)acryloyloxy group at the 1-position, and a process for efficiently producing the derivatives. These compounds are useful, for example, as materials for photosensitive resins such as acid-sensitive polymers constituting photoresist resin compositions and as materials for fine chemicals.

4-oxatricyclo[4.3.1.1 3,8]undecan-5-one derivative and process for producing the same

Abstract: wherein R is a hydrogen atom or a (meth)acryloyl group, and carbon atoms constituting a ring may have a substituent in addition to the substituents indicated in the formula. This compound is a novel 4-oxatricyclo[4.3.1.13,8]undecan-5-one derivative having a hydroxyl group or a (meth)acryloyloxy group at the 1-position.


The present invention provides, in certain embodiments, a negatively charged microporous membrane comprising a porous substrate and a crosslinked coating having fixed negative charges. The crosslinked coating can be prepared, e.g., from a polymerized composition comprising an unsaturated monomer having an anionic group, an N-(hydroxymethyl)- and/or N-(alkoxymethyl)-acrylamide, a hydrophilic unsaturated monomer, and an initiator. The present invention further provides, in some embodiments, a negatively charged microporous membrane comprising a porous substrate and a crosslinked coating prepared from a polymerized composition comprising an unsaturated monomer having an anionic group, an N-(hydroxymethyl)- or N-(alkoxymethyl)-acrylamide, a polysaccharide, and an initiator. The membranes of the present invention are suitable for use in ion exchange chromatography, for example, in the separation and purification of positively charged species such as proteins.

Negatively charged ion-exchange membranes have been proposed for the separation and/or purification of biomolecules such as proteins, amino acids, and nucleic acids. For the ion exchange membrane to perform effectively in the above applications, the membrane should satisfy several important parameters. For example, the membrane should exhibit high rates of fluid flow. The membrane should have high dynamic binding capacity for biomolecules, and should be capable of selectively binding the biomolecules, which have different surface charges. The membrane should, therefore, have low non-specific binding, e.g., resulting from hydrophobic interactions. The membrane should withstand high treatment fluid velocities. The preparation of the membrane should not involve chemistries and processes that are cumbersome to practice. Some of the cation exchange membranes known heretofore suffer from the failure to satisfy one or more of the parameters set forth above.
Accordingly, there exists a need for a cation exchange membrane that exhibits high rates of fluid flow. There further exists a need for a cation exchange membrane that has high dynamic binding capacity and selectivity for biomolecules. There further exists a need for a membrane that has low non-specific binding or low binding that results from hydrophobic interactions. There further exists a need for a membrane that can withstand high fluid flow velocities. There further exists a need for a membrane that involves preparation chemistries and/or processes that are not cumbersome to practice.
These advantages of the present invention, as well as additional inventive features, will be apparent from the description of the invention provided herein.

This patent is subject to a terminal disclaimer.


A mobile communication system is provided that performs bi-directional communications between a mobile station and a wireless access network device. The mobile station includes a connection set-up signal reception timing calculation unit for calculating a reception timing of a connection set-up signal when a connection request signal is transmitted, and a connection set-up signal reception determination unit that determines, according to the reception timing, whether the connection set-up signal is received, and performs a signal reception operation based on the determination. The wireless access network device includes a connection set-up signal scheduling unit that, after receiving a connection request signal from the mobile station, performs a connection set-up signal transmission assignment based on a reception timing of the connection request signal, a connection set-up signal generation unit that generates a connection set-up signal to be sent to the mobile station; and a connection set-up signal transmission unit that transmits the connection set-up signal based on the connection set-up signal transmission assignment.

In a mobile communication system, setting up a connection between a mobile station and a wireless access network device is started upon a connection request from the mobile station or the wireless access network device.
FIG. 1 is a sequence diagram exemplifying a sequence of setting up a connection between a mobile station and a wireless access network device when the connection request is made from the side of the mobile station.
As shown in FIG. 1, first, the mobile station transmits a radio resource control (RRC) connection request signal through a random access channel (RACH), which is mapped into (namely, associated with) a physical random access channel (PRACH) (in other words, transmitting the random access channel (RACH), which is a transport channel, with the physical random access channel (PRACH), which is a physical channel.
After receiving the RRC connection request signal, the wireless access network device transmits a RRC connection set-up signal through a forward access channel (FACH), which is mapped into a secondary common control physical channel (SCCPCH).
Next, after receiving the RRC connection setup signal, the mobile station switches to a dedicated physical channel (DPCH), and transmits a RRC connection setup complete signal. After, that, signal transmission and reception are performed with the dedicated physical channel (DPCH).
As described above, in the related art, the mobile station and the wireless access network device need to switch, before the connection setup is completed, the physical channel for signal transmission and reception from the physical random access channel (PRACH), which is an uplink common physical channel, to the secondary common control physical channel (SCCPCH), which is a downlink shared channel, and further to the dedicated physical channel (DPCH).
In addition, after the mobile station transmits the radio resource control (RRC) connection request signal, if the mobile station fails to receive the RRC connection set-up signal from the wireless access network device within a time period T300, which is designated by the wireless access network device in advance, the mobile station needs to repeatedly execute the above connection operations up to the number of times (N300) designated by the wireless access network device.
For example, this technique is disclosed in "3GPP TS 25.331 v6.5.0".

Mobile station, wireless access network device, mobile communication system, and communication method


The invention is directed to a thermal addition curable solventless silicone release composition having a reduced coefficient of friction and improved slip characteristics. The invention is also directed to a method for producing a thermal addition curable solventless silicone release composition on a substrate by applying the thermal addition curable solventless release composition of the invention to a substrate and curing the coating on the substrate using heat. The invention is further directed to a thermal addition curable solventless silicone release coated article having a reduced coefficient of friction and improved slip characteristics.

Silicone release coatings or compositions are well known and the subject of many publications and patents. They are useful in many applications where one requires a relatively non-adherent surface. In such applications release compositions are coated onto a substrate, and are caused to be cured. A particularly useful application is the coating of paper, film, and other materials that are used among other applications by providing non-stick surfaces for pressure sensitive adhesive labels, decorative laminates, and transfer tapes.
Silicone release compositions have been used in large volumes for many years. Silicone polymers and copolymers have been used extensively in release compositions because they are inherently low in surface energy. The silicone polymers and copolymers (sometimes referred to as polyorganosiloxanes) used in the prior art for making release compositions can be radiation cured or thermally cured. In the beginning the silicone release composition of choice was the thermal solvent diluted condensation cured release coating system. Silicone technology has progressed from thermal condensation curable solvent-based release coating systems to thermal addition curable solvent-based release coating systems and then to thermal addition curable solventless release coating systems and radiation cured release coatings. The advantages of using solventless, radiation curable, or thermally curable release compositions are well known to the person skilled in the art of release coatings.
Thermal addition curable solventless compositions have become the dominant release coating compositions for delivering pressure sensitive adhesive products to the market place. These markets include pressure sensitive label, graphic arts, tapes, prepreg, and medical, to name a few. Accordingly, to be effective, a thermal addition curable solventless silicone release system must be versatile and meet minimum converter demands.
It is desirable that release coated papers and films have a release force which is low enough to enable the release backing sheet to be easily removed from the coated substrate, but not so low that the release backing sheet will become prematurely separated from the coated surface by forces normally encountered in handling and processing. "Release force" is defined as the amount of force required to peel or separate the release coated substrate from the adhesive or facing.
Conventional thermal addition curable solventless silicone release coatings have a high coefficient of friction compared to condensation curable solvent-based silicone release coatings. The higher coefficient of friction imparts a problematic characteristic referred to as "grab" wherein the coated substrate tends to stick or grab. Due to the differences in the both physical and functional chemistry between condensation curable solvent-based systems and thermal addition curable solventless systems, the thermal addition curable solventless system produces a tacky grabby feel as opposed to the waxy slippery feel of the condensation curable solvent system. It has been the desire of the Pressure Sensitive Adhesive (PSA) industry to have a thermal addition curable solventless system that gives the waxy slippery feel of a condensation curable solvent-based system.
In order to overcome the "grab" problem, associated with thermal addition curable solventless compositions, current technology uses very high molecular weight nonreactive polymers to reduce the coefficient of friction or grab. These high molecular weight polymers tend to bloom or migrate to the surface to impart additional slip however they also tend to cause converting problems.
During manufacture and storage of the coated sheets prior to use, the free nonreactive silicone oil that has bloomed to the surface is inevitably released from the coated sheet onto the surface of another coated or uncoated sheet leaving discrete patches of free nonreactive silicone oil on the sheet surface. When, for example, the coated sheet is stored in a front surface to back surface contact manner, as in a typical roll, some of the free nonreactive silicone oil (typically high molecular weight silicones) on the front silicone coated surface of the sheet will be transferred to the back (typically uncoated) surface of the roll.
In practice, this free nonreactive silicone oil contamination can be a drawback. For example, when the coated sheet traverses over idler rolls during subsequent processing steps (e.g., during label application), the idler rolls can develop a buildup. This can result in uneven tension on the sheet web or loss of alignment. Related problems arise when printing on the resulting release coated sheet or when labels are applied to the sheet. The ability of printing inks and solvents to adhere is impaired by the presence of free nonreactive silicone oil on the surface to be printed. Moreover, loss of alignment due to the sheet's slip characteristics can lead to a high reject rate during printing, particularly where multiple printing passes are used and in cases where proper alignment is critical for formation of an integrated image.
By having a thermal addition curable solventless system that produces a coefficient of friction similar to a condensation curable solvent-based system, a more complete cure off the coater will be achieved, thereby providing a more stable release coating when compared to thermal solvent condensation cured release coating systems.
Accordingly, there exists a need in the art to provide a thermal addition curable solventless silicone release composition with a lower coefficient of friction and lower slip. A need also exists to provide a thermal addition curable solventless silicone release compositions with similar slip and feel properties to a condensation curable solvent-based silicone release composition.

Reduction of coefficient of friction for thermal addition curable solventless silicone release coating systems


An electronic apparatus includes a component to which a pressure is applied or which provides vibration, a heat absorbing member, a heat dissipating member, an elastomer bag which receives a pressure or the vibration from the component, a first check valve connected to a port of the elastomer bag, a second check valve connected to another port of the elastomer bag, and a coolant which flows passing through the heat absorbing member, the first check valve, the elastomer bag, the second check valve, and said heat dissipating member.

With the recent increasing processing rates of notebook PCs, the amount of heat diffused from their heat producing components, such as CPUs, hard disk drives, and graphics chips has been increasing. Such heat producing components, however, cannot be sufficiently cooled by conventional components, such as a heat sink, a heat pipe, and a cooling fan.
Conventionally, it is known that a notebook PC employs a closed loop system constructed of a tube that efficiently cools the CPU by circulating a liquid coolant in the tube from a heat absorbing element to a heat dissipating element and back to the heat absorbing element by means of an electric motor.
In Japanese Patent Application Laid-Open Publication (JP-A) HEI 7-243738 published on Sep. 19, 1995, Takeda et al. disclose an electronic apparatus cooling device using a magnetic fluid vibration motor. In this cooling device, a tube forms a closed loop, and a spherical magnetic member is caused to vibrate along the tube by means of an external magnetic field formed by an exciting current flowing through a coil in a driving section of the tube, to cause the liquid coolant in the tube to flow back and forth between the heat absorbing element and the heat dissipating element, whereby efficient cooling is achieved. The spherical magnetic element has an outer diameter which is substantially equal to an inner diameter of the tube. In an alternative configuration, the cooling device includes a tube of a closed loop having a branch tube equipped with such a driving section, and a one-way valve is provided on each side or one side of the branching section of the closed loop tube, wherein the liquid coolant is circulated by causing the spherical magnetic element to vibrate along the branch tube.
Forced cooling in common electronic apparatuses requires electric energy. In a battery operated electronic apparatus, however, it is desirable to reduce electric energy consumption significantly.
The inventors have recognized the need for an efficient energy-saving cooling system for an electronic apparatus.
An object of the present invention is to provide energy-saving cooling in an electronic apparatus.
Another object of the invention is to provide cooling in an electronic apparatus by circulating a fluid coolant by means of an energy-saving driving power.

Electronic apparatus having energy-saving cooling system


A vibration isolator has four fluid filled variable volume load bearing chambers, with two arranged on one side of a core and the other two on the other side. The core and chambers are contained within a frame, with the chambers extending between the core and the frame, so that vibrating the core axially compresses or extends the chambers. Diagonally opposite pairs of chambers are each connected with a separate fluid track, and the two fluid tracks may be tuned to have different resonant frequencies or the same resonant frequency. The chambers are defined by elastomeric bodies which may be reinforced using a tubular shaped reinforcing element adjacent to the chamber, to help contain the pressures within the chamber without materially increasing the compression strength of the elastomeric bodies. A fluid expansion chamber communicates with the fluid envelope of the chambers and tracks through porous flow restriction elements which allow flow to or from the expansion chamber in response to temperature changes of the fluid but snub significant flow to or from the expansion chamber which may otherwise be caused by subjecting the isolator to vibrations.

Vibration isolators are well known and are commonly used to mount engines to a frame. For example, in an automobile, an elastomeric or other vibration isolator mounts the engine to the frame to curtail the transmission of vibrations from the engine to the frame. Similarly, aircraft engines are mounted to the air frame using vibration isolation mounts.
It is desirable for vibration isolation mounts to be strong and stiff when they are statically loaded so as to support the weight of the engine or other element they support and to counteract other static forces. As an engine is accelerated, it will typically reasonate at a certain speed, which is known as the resonant frequency. At the resonant frequency, the vibrations generated by the engine are at their highest amplitude and it is desirable to curtail their transmission to the automotive, aircraft or other frame to which the engine is mounted.
It is a characteristic of elastomeric isolators that they become stiffer when they are subjected to higher frequency vibrations. Thus, at the resonant frequency of an engine, an elastomeric isolator is stiffer than when the engine is static, which is exactly the opposite of the desired characteristic of the isolator.
Elasto-hydraulic isolators have also been developed in which fluid filled elastomeric isolation elements are employed in an effort to reduce the stiffness of the vibration isolator at the resonant frequency of the engine. Typically, one or two elastomeric chambers are provided and are filled with an incompressible fluid. In the single chamber type, fluid is pumped by the chamber as it is subjected to vibrations through an inertia fluid track, which is usually in communication with another variable volume chamber of a significantly lower volume stiffness. In the two chamber type, the fluid is pumped in an inertia fluid track which communicates with both chambers and the chambers are arranged so that as the volume of one increases, the volume of the other diminishes, and vice versa. The pumping of the fluid in the fluid track dissipates the energy of the vibrations, and the fluid track can be tuned, for example by varying its area and/or length, so that the energy dissipation is maximized at the vibration frequency sought to be isolated.
The frequency at which the stiffness of the vibration isolator is reduced is known as the notch frequency, because on a plot of stiffness versus frequency the stiffness curve dips there. It is desirable to make the notch as wide and as deep as possible, as well as to tune it to correspond with the resonant frequency of the engine, for the most effective vibration isolation.
Prior fluid filled vibration isolators have resulted in improvements in isolating higher frequency vibrations over elastomeric mounts. However, it still remains desirable to further reduce the ratio of dynamic stiffness to static stiffness in vibration isolation mounts, i.e., to increase the depth and bandwidth of the notch.
Moreover, in some applications, more than one frequency can be sought to be isolated. Prior isolators have been limited to isolating a single frequency, with a certain bandwidth spanning either side of the frequency. It is therefore desirable to be able to tune in more than one frequency, with the effect of increasing the overall bandwidth of vibration suppression.
In addition, a problem with fluid filled vibration isolation mounts has been that they can be extremely sensitive to fluctuations in temperature. Fluctuations in temperature cause the fluid in the chamber to expand or contract, which results in shifts in the fluid pressure that can greatly vary the stiffness of the vibration isolator. Pressure equalization of the fluid in response to temperature fluctuations has been provided in the prior art, but resulted in the fluid of the isolation chambers being in continuous communication with an equalization chamber of substantially lower volume stiffness, which adversely affected the stiffness of the load bearing chambers.

Vibration isolator with two pairs of fluid chambers with diagonal fluid communication


Disclosed is a new and improved, environmentally acceptable and negligibly corrosive deicing composition comprising steepwater solubles produced, for example, as by-products from a wet milling process of corn, which by-products are biodegradable. The invention also relates to the use of a deicing composition to reduce the buildup of snow and ice on roads, bridges and other outdoor surfaces.

It is well known that the ice and snow located on roads and bridges significantly slow traffic and pose increased danger to the general public. Mechanical snow removal is often used to alleviate some of the traffic problems. It is also known that chemical compounds, such as chloride salts, whether in solid form or in solution or in admixture with sand and other substances, are often used to treat the roadways to melt snow and ice. Most deicing compounds, however, are environmentally harmful, and therefore, municipalities are often restricted in the amounts and types of substances that they may use to help control the buildup of snow and ice.
Most chemicals used to treat roadways are detrimental for the following reasons: They damage the soil and surrounding vegetation by turning the soil alkaline and damaging the root systems of the plants; They damage freshwater streams, rivers and lakes and are often absorbed into underground water systems; and, The chemicals cause significant damage to vehicles, as well as concrete and metallic structures that are near roadways because of the corrosive effects of said chemicals. It is well known that many salts cause spalling in concrete structures, which significantly reduce the strength and life of such structures. For the foregoing reasons, many states have banned the use of salts and other chemicals, while others have placed significant restrictions on their usage.
It is known that it is desirable to replace the corrosive salts with non-corrosive substances, such as alcohols and glycols, but because of their flammability, toxicity and expense, these other substances have not been effectively and economically utilized to date. Therefore, a need has arisen for a minimally corrosive, environmentally acceptable, cost-effective, deicing composition.


A tilt apparatus and method for operating it is disclosed. The tilt apparatus for a cab of a construction vehicle comprises a support frame attached to a chassis of said vehicle, the horizontal plane of said support frame being parallel to that of said chassis, a mounting attached to said cab and connected with said support frame, and configured so that the horizontal plane of said mounting can tilt about any direction of said chassis, at least one actuator having one end connected with said support frame and the other end connected with said mounting, and operating so as to tilt said mounting, at least two inclination sensors comprising at least one top sensor installed on said mounting and at least one bottom sensor installed on said support frame or said chassis and a CPU installed in said cab and receiving the continual slope information from said top and bottom sensors and controlling the operation of said actuator on the basis of said continual slope information and the relative tilted angle information between the horizontal plane of said mounting and that of said support frame or chassis. The tilt apparatus of the invention is able automatically to level the cab of vehicle whilst the vehicle is in transit.

In particular, this invention relates to a tilt apparatus for the cab of an excavator/digger. However this should not be seen as limiting as the present invention may be applied to the cabs of the other vehicles.
For ease of reference only, the vehicle will now be referred to as being an excavator.
Existing tilt apparatus for leveling the cab of an excavator all suffer from a number of drawbacks.
U.S. Pat. No. 4,679,803 (US'803) provides a tilt apparatus for a cab, but this unit due to its construction, needs to be fitted to a purpose built chassis and this cannot be retrofitted to existing excavators.
PCT/NZ1998/00092 (PCT'00092) is an earlier patent application by the present inventor and describes a tilt apparatus which is capable of being retrofitted to an excavator.
However, this tilt apparatus is not configured to allow for substantially continuous adjustment of the tilt apparatus as inclination sensors are not employed. Furthermore, this tilt apparatus does not have the ability to detect and display the relative position of the track chassis to the cab.
Moreover, the inventor has discovered that both the inventions described in US'803 and PCT'00092 do not provide a tilt apparatus capable of automatically tilt leveling the cab whilst the excavator is in transit. In particular, they do not provide any indication as to whether a slope is too steep for the unit to operate. Therefore, the units described in these patent specifications are within a short period of time, prone to mechanical failure if operated when in transit. This is because there is no control over the hydraulics of the tilt apparatus when approaching the edge of the stroke limit of a ram. Accordingly, on steep slopes outside the range of the tilt apparatus' ability to level the cab the rams do not slow down as they reach their limit.
It is an object of the present invention to address the foregoing problems or at least to provide the public with a useful choice.
All references, including any patents or patent applications cited in this specification are hereby incorporated by reference. No admission is made that any reference constitutes prior art. The discussion of the references states what their authors assert, and the applicants reserve the right to challenge the accuracy and pertinency of the cited documents. It will be clearly understood that, although a number of prior art publications are referred to herein, this reference does not constitute an admission that any of these documents from part of the common general knowledge in the art, in New Zealand or in any other country.
It is acknowledged that the term 'comprise' may, under varying jurisdictions, be attributed with either an exclusive or an inclusive meaning. For the purpose of this specification, and unless otherwise noted, the term 'comprise' shall have an inclusive meaning—i.e. that it will be taken to mean an inclusion of not only the listed components it directly references, but also other non-specified components or elements. This rationale will also be used when the term 'comprised' or 'comprising' is used in relation to one or more steps in a method or process.
Further aspects and advantages of the present invention will become apparent from the ensuing description which is given by way of example only.

Tilt apparatus and method for operating it


Various technologies for continuous-variable quantum key distribution without transmitting a transmitter's local oscillator are described herein. A receiver on an optical transmission channel uses an oscillator signal generated by a light source at the receiver's location to perform interferometric detection on received signals. An optical reference pulse is sent by the transmitter on the transmission channel and the receiver computes a phase offset of the transmission based on quadrature measurements of the reference pulse. The receiver can then compensate for the phase offset between the transmitter's reference and the receiver's reference when measuring quadratures of received data pulses.

Quantum key distribution (QKD) enables generation of secured shared randomness between two communicating parties, which facilitates secure communications between the parties. Continuous-variable quantum key distribution (CV-QKD) is a method of QKD that encodes data on phase and amplitude quadratures of a continuous optical signal. When communicating using CV-QKD, interferometric detection is used to measure the phase or amplitude quadratures of a received signal. Conventional CV-QKD systems rely on a transmitter transmitting a local oscillator signal at a power that is orders of magnitude higher than a power of the data signal to be measured; this power discrepancy improves performance of the aforementioned interferometric detection. When transmitting the local oscillator, the transmitter physically separates the local oscillator and data signal prior to encoding the data signal. Separation of the local oscillator and data signal is undertaken to avoid contamination of the low-power data signal by the high-power local oscillator.

Self-referenced continuous-variable quantum key distribution


Embedding of digital incentive tokens within a digital image can occur cryptographically using a public key in some embodiments. An encrypted digital incentive token may be embedded within a digital image, including a variety of encrypted information. The digital image with the embedded digital incentive token may be sent to users via delivery mechanisms such as direct webpage embedding, email, text message, and social media sharing. An image recipient may be able to view the image and also take additional action including gaining access to the embedded digital incentive token. Digital incentive tokens can be embedded by altering image metadata so that the image itself is not changed in some embodiments, but data associated with the image is changed to identify the token. Pixel data can be altered to reflect a token for an image. Digital incentive tokens can also be tracked through different platforms to determine usage.

Digital image files typically use a certain amount of data to store a picture. Images may include stored information usable to render picture using a red/green/blue (RGB) value for each pixel within the image, for example.
Images are also frequently transferred on the Internet. Users may receive images via email, web pages, or other mechanisms.
Typically, however, when an Internet user receives an image, no additional information is conveyed. The recipient of an image is able to view the image, but generally only is able to appreciate artistry, text, and/or a real-world picture that is contained in the image.

Encryption of digital incentive tokens within images