A computer main body has a system bus. The system bus is connected to a PCI-DS bridge. A docking station has a plurality of expansion devices for expanding the functions of the computer main body. The computer main body is attached to the docking station by means of the DS-PCI/ISA bridge of the docking station and the PCI-DS bridge of the computer main body, while the expansion devices of the docking station are separated from the bus of the computer main body. The computer main body outputs to the docking station an instruction for starting power supply, after having been attached. After switching on of the docking station has been detected, gates in the bus sides of the DS-PCI/ISA bridge and the PCI-DS bridge are switched ON.

1. Field of the Invention
The present invention relates to a computer system having a main body and an expansion unit attached to/detached from the main body. More particularly, it relates to a computer system in which an expansion unit can be attached and detached in the main body which power is being supplied to the main body.
The invention also relates to a computer system which has a main body and an expansion unit driven by using the battery provided in the main body and in which the main body and the expansion unit can be connected to a connector having a small number of pins.
2. Description of the Related Art
In recent years, various personal portable computers of a laptop type and a notebook type easily carried and operable by a battery have been developed. The portable computer of this type is constructed such that an expansion unit can be attached so as to expand its functions, as necessary.
The expansion unit has a drive bay housing driving devices such as a hard disk drive and the like, and expansion slots through which various optional cards are placed. Therefore, by using the portable computer connected to this expansion unit as necessary, it is possible to easily expand the functions of the portable computer without losing its portability.
Recently, moreover, expansion units as a simple type expansion unit, for example a port replicator incorporating a PC card controller, have been developed. Thus, depending on purposes, the same portable computer is used being selectively connected to a plurality of expansion units.
Conventionally, while the power of the computer main body is turned ON, attaching and detaching of the expansion unit have involved the risk of destroying the optional card of the expansion unit, because of unexpected flowing of a current from the computer main body to the optional card due to hot swapping. As a result, it is necessary for a user manually that the power of the expansion unit and the main body is turned off, prior to attaching and detaching the main body to and from the expansion unit. The conventional type thus has a lack of convenience.
Where the portable replicator incorporating PC card controller is used, conventionally three kinds of driving power sources, 3.3V, 5V and 12V have all been supplied from the main body to PCMCIA slots. As a result, the number of pins used as power lines increase and the size of the connector, for connecting the computer main body with the expansion unit, increase. Also, power is always output into the connector in the main body side. Thus, if no expansion units are placed, the pins of the connector may be short-circuited for some reason, allowing an excessive current to flow. This excessive current may damage devices within the main body.
In the main body and the expansion unit, a connector for connecting such peripheral equipment as a mouse, a keyboard, a joystick and the like therewith is provided. Power is supplied from the main body to the peripheral equipment by this connector. A fuse is normally connected to a line for supplying power for the purpose of protection from an excessive current.
In such a method using the fuse, however, when the fuse is blown and needs to be replaced, the main body must be sent to a service center, etc., for repair. This is usually for the reason that it is far more difficult for the user to repair the portable computer of the notebook type and the like, than a desktop type. In order to deal with this problem, use of excessive current protection parts of automatic recovery type, for instance a breaker, may be considered. Being large in size, however, it is difficult for these to be actually used in the portable computer.
As described above, the expansion unit is important in order to expand the functions of the portable computer. Conventionally, however, attaching and detaching of the computer main body to and from the expansion unit, while power for the computer main body is turned ON, has resulted in destruction of the optional card and the computer hanging-up. There has also been a problem of supplying of a number of power lines from the main body to the expansion unit. Furthermore, in the conventional type, the fuse has been used for the purpose of protection from an excessive current and the main body must be sent for repair when the fuse is to be replaced.

Computer system having computer main body and expansion unit


The present invention includes aspects pertaining to enabling an IMS batch application program to temporarily release its access to IMS resources that it shares with an IMS database management system or other non-IMS system agent, without terminating the application program. The present invention identifies when the batch application program issues a call that generate a sync point, and disconnects the program's connection to the IMS resources. The batch application program retains access to any independently obtained non-IMS resources when the program is disconnected from the IMS resources. The IMS database management system or other non-IMS system agent has temporary exclusive access to the IMS resources after the batch application program connection is disconnected. After such temporary exclusive access is complete, the batch application program's connection to the IMS resources is reestablished, and the batch application receives a response to its original call that generated a sync point. In another embodiment of the present invention, a plurality of IMS batch application programs temporarily release their access to IMS resources. In this embodiment, the IMS database management system or other non-IMS system agent obtains temporary exclusive access to the IMS resources after all of said plurality of batch application program connections to IMS resources are disconnected.

1. Field of the Invention
The invention relates to suspending accesses by IMS batch application programs to shared IMS resources. The invention also relates to IMS batch application programs maintaining control of independently obtained resources while the IMS system temporarily obtains exclusive control of the shared IMS resources.
2. Description of the Related Art
IBM's Information Management System ("IMS") is a widely used database management system. IMS "implemented the hierarchical model tree structure to organize the collection of records in a one-to-many entity-relationship data model." K. R. Blackman, IMS Celebrates Thirty Years as an IBM Product, IBM Systems Journal, Vol. 37, No. 4, 596 (1998). Today, a large percentage of the top worldwide companies in the areas of manufacturing, finance, banking, retailing, aerospace, communications, government, insurance, high technology, and health care use IMS to run their day-to-day database operations. Id. at 597.
"The IMS database (DB) function provides a full-function resource manager and a fast path resource manager for hierarchical database management . . . . The data managed by IMS are organized in hierarchical database records. A database record is composed of segments, a segment being the smallest piece of information that IMS can store. A segment contains fields that are the smallest pieces of data an application program can manipulate. A field is identified as a unique key field that can be used to navigate the database to find a specific segment. The hierarchical structure of the segments establishes the structure of the database record. A root segment identifies a database record, and a database record cannot exist without a root segment. Dependent segments are the pieces of data that complete the rest of a database record. The IMS DB full-function resource manager provides sequential access, indexed sequential access, and direct access for database processing. The fast path DB resource manager provides the direct method for processing data by using direct access pointers to the segments." Id. at 597-98. An OS dataset is a physical device on which an IMS database is stored.
"The fundamental architecture of IMS consists of a control region, a DLI secondary address space (DLISAS), a DBRC address space, an IRLM address space, and one or more dependent regions [hereinafter "IMS Database Management System" or "IMS system"]. The control region is the execution environment for the IMS system software, the control blocks, and storage pools required for managing communication access and application program scheduling. The control region also contains the fast path system software for managing access to fast path databases. This isolates the IMS system functions from the customer's application programs to maintain the integrity of the IMS system. The DLISAS execution environment contains the IMS DB full-function system software, control blocks, and storage pools for managing access to the full-function databases. The dependent regions provide the execution environments for the application programs to process transactions." Id. at 599.
Periodically, IMS databases need to be taken offline for maintenance. For example, because IMS databases become physically disorganized as the database is utilized and modified, they periodically need to be reorganized. The degree of disorganization is usually a function of the number of segments added, deleted, or updated. Segments being added or split as the result of an update tend to be physically located in a block other than their root segment or hierarchical predecessor. Subsequent retrieval of these new or split segments require additional DASD read requests, thus degrading the performance of the database. If a database is not reorganized, its performance degrades, at least in part because more I/O operations are required to retrieve data. Unloading and reloading a complete database is a common technique used to reorganize a database. This technique requires that the entire database be offline and unavailable during the period of time that that database is being reorganized. When a database is reorganized, its primary and secondary indexes have to be updated as well.
Dependent regions are divided into short running thread and long running thread dependent regions. If only short running thread dependent regions are accessing the shared IMS resources (e.g., an IMS database) and IMS needs to access the shared IMS shared resources (e.g., to perform maintenance of a database), IMS will allow such access. However, processing by any and all IMS Batch Message Processing (BMP) regions, or Data Language 1 (DL1) regions including DBB regions (hereinafter "IMS batch regions"), which are long running thread dependent regions, must be terminated or abended to release control of the shared IMS resources to the IMS system.
By terminating processing of the IMS batch regions, business application programs become unavailable. This is perceived as an undesirable outage or period of downtime to users of the business application. Furthermore, if application programs are terminated or abended prematurely, this prevents application continuity. For example, an application may be terminated in the middle of printing a report, and a complete report may have to be printed in pieces. Furthermore, when application programs are terminated, resources need to be expended to restart such applications. In addition, there is greater risk of operational impact when applications are restarted, such as operator error. Also, to be able to restart an application program, it must implement, or be modified to implement, functional restart and repositioning programming.
On the other hand, if IMS batch regions are not terminated, and business applications are allowed to continue running, maintenance of the IMS resources (e.g., IMS database) cannot occur and less than optimum performance may result.
Thus, this has caused a dilemma in the prior art between the desirability of application program availability versus IMS resource maintenance.
BMC Software's Application Restart Control ("ARC") product allows IMS resources being utilized by an application program to be released without terminating the job step. However, the ARC product abends the application program and then must restart it for it to resume operations. Thus, the application program must include, or be modified to include, restart programming. Furthermore, the ARC product supports only BMP IMS application programs and not DL1 or DBB IMS application programs.
It should also be noted that IMS batch jobs can be running while the IMS system is offline. Nonetheless, even if these IMS batch jobs have exclusive access to IMS resources while the IMS system is offline, they may preclude tasks such as batch database reorganizations, and DASD management functions, such as volume defrag, database dataset moves from one DASD volume to another, and Disaster Recovery backups, and other general DASD management issues. These tasks and general DASD management issues are performed by a system hereinafter referred to as a "non-IMS system agent." Thus, there also is a need for such IMS batch jobs to temporarily suspend their access to IMS resources shared with such a non-IMS system agent.
Therefore, a need exists for the capability of suspending accesses by BMP, DL1, or DBB IMS application programs to shared IMS resources without terminating or abending the programs. A further need exists for enabling BMP, DL1, and DBB IMS application programs to resume their accesses to shared IMS resources, after suspension, without requiring the application programs to be restarted or for them to contain restart programming. Still another need exists for an external interface to such application program suspend and resume capability.

Facilitating suspension of batch application program access to shared IMS resources


The present invention provides a process for preparing a peptide of formula (I):Sub-[L]-[NH-A-C(O)]n+m—OH  (I)                comprising:        (a) reacting an immobilized compound of formula (II):Sub-(L)-[NH-A-C(O)]n—OH  (II)         with an amino acid ester or peptide derivative of formula (III):H—[NH-A-C(O)]m—O(tBu)  (III)         in the presence of a coupling agent to yield a peptide compound of general formula (IV):Sub-[L]-[NH-A-C(O)]n+m—O(tBu);  (IV)        (b) removing the tBu (t-butyl) group to produce a solid-support bound carboxylic acid or peptide derivative of general formula (I);wherein n is a positive integer, e.g., 1-10, preferably 1-5; m is a positive integer.

The standard methods for the solid phase synthesis of peptides (SPPS) on beaded resins in the normal C-to-N direction are well developed, as they must be if long peptides are to be synthesized (reviewed in M. Bodanszky et al., "Peptide Chemistry: A Practical Textbook," Springer-Verlag, N.Y. (2d ed., 1993) and M. Bodanszky et al., "The Practice of Peptide Synthesis," Springer-Verlag, N.Y. (2d ed., 1993)). These methods are based on attaching the carboxy terminus of an amino-protected amino acid to the resin. It essentially allows peptides to be synthesized without racemization when amino acids with Nα-protecting groups of the urethane (carbamate) type were coupled in stepwise fashion. The amino-protecting group is removed, and the next amino acid with a free carboxy group and protected amino group is then added using standard coupling conditions. Standard peptide chemistry has been used to prepare solid phase peptide libraries of tremendous diversity (H. M. Geysen et al., Molec. Immunol., 23, 709 (1986); R. A. Houghten et al., Nature, 354, 84 (1991); K. S. Lam et al., Nature, 354, 84 (1991)).
Peptide mimetic libraries (mimetic is used to indicate a modified peptide), based on the normal C-to-N direction of peptide synthesis, have been described. A peptide phosphinate library has been synthesized and used to find potent and selective inhibitors of zinc metalloproteases (J. Jiracek et al., J. Biol. Chem., 270, 21701 (1995); J. Jiracek et al., J. Biol. Chem., 271, 19606 (1996); V. Dive et al., PNAS USA, 96, 4330 (1999)). A (hydroxyethyl)amine library has also been synthesized and used to find inhibitors of the prototypical aspartyl protease Cathepsin D (E. R. Kick et al., Chem. Biol., 4, 297 (1997)).
However, combinatorial libraries of polypeptides representative of serine and cysteine proteases have not been synthesized. This can be attributed to the fact that virtually all the effective classes of serine and cysteine classes, such as peptide aldehydes (R. C. Thompson, Biochem., 12, 47 (1973)), chloromethyl ketones (CMKs) (G. Schoellmann et al., Biochem., 2, 252 (1963)), fluoromethyl ketones (FMKs) (M. H. Gelb et al., Biochem., 24, 1813 (1985); B. Imperiali et al., Biochem., 25, 3760 (1986)), and boronic acids (C. A. Kettner et al., J. Biol. Chem., 259, 15106 (1984); C. A. Kettner et al., J. Biol. Chem., 265, 18289 (1990)), are prepared by elaboration of a peptide at its C terminus. Thus, a need exists for the development of combinatorial peptide libraries representative of the serine and cysteine protease classes. Such libraries would greatly improve the ability to develop potent and specific inhibitors of these enzymes. This, in turn, requires a free C terminus of an immobilized oligopeptide, which, in turn, requires the ability to synthesize peptides in the N-to-C direction: or "reverse peptide synthesis."
Considering the importance of such C-terminally modified peptides and peptide libraries, relatively few reports have been devoted to the development of a direct method for peptide assembly in the inverse direction. See, for example, R. J. Broadbridge et al., Chem. Commun., 1449 (1998), K. H. Bleicher et al., Tett. Lett., 39, 4591 (1998); F. Bordusa et al., Angew Chim Int. Ed. Eng., 36, 1099 (1997); R. Leger et al., Tet. Lett., 39, 4147 (1998); R. Letsinger et al., J. Amer. Chem. Soc., 85, 5163 (1969); and 85, 3015 (1963).
Merrifield et al., J. Amer. Chem. Soc., 92, 1385 (1970), used protected amino acid hydrazides as building blocks for the C-terminal elongation of peptides, followed by deprotection and subsequent reaction of the hydrazide function with nitrite allowed the next building block to be coupled by the azide method. However, the procedure is elaborate, requiring activation and coupling at low temperature with moderate yields.
Later investigations, mainly by Bayer and co-workers, have included the use of base labile amino acid 9-fluorenylmethyl esters, which were coupled with N-hydroxybenzotriazole (HOBt)/diisopropylcarbodiimide (DIC) or N-[(1H-benzotriazole-1-yl)-(di-methylamino)methylene]-N-methylmethanaminium tetrafluoroborate N-oxide (TBTU)/N-methylmorpholine (NMM). B. Henkel et al., Liebigs Ann./Recieul, 2161 (1997). In both cases, a 30-min. preactivation step with a large excess of activator (8 equiv.) was included before addition of the amino acid ester. Using TBTU/NMM extensively racemized products were obtained, whereas coupling using HOBt/DIC gave moderate racemization but led to significant formation of other byproducts.
Sharma et al. have described a few C-terminally modified tetrapeptide HIV-1 protease inhibitors, generated in the inverse direction. For example, see, R. P. Sharma et al., published PCT applications WO 93/05065 (18 Mar. 1993) and WO 90/05738 (31 May 1990) and Chem. Commun., 1449 (1998). Sharma's approach relies on coupling of amino acid tri-tert-butoxysilyl (Sil) esters. More recently, A. Johannsson et al., J. Comb. Chem., 2, 496 (2000) described a modification of the method of Sharma et al. that involves the coupling of a photolabile resin-bound C-terminal amino acid with excess amounts of amino acid tri-tert-butoxysilyl (Sil) esters, using HATU as coupling reagent and 2,4,6-trimethylpyridine (TMP, collidine) as a base. Levels of epimerization were considerably lower than those reported for other N-to-C methods, usually ca. 5% and occasionally even below 1%. However, in unfavorable cases, as in the coupling of Ile to Ser, the level was higher (ca. 20%). Also, this method requires the synthesis of sensitive zwitterionic tris (t-butoxy silylesters) and familiarity with photolytic techniques.
Thus, a continuing need exists for simple and efficient methods for the reverse synthesis of peptides and peptide mimetics, particularly for the synthesis of oligopeptide mimetic libraries useful for high-throughput drug screening.

Method for inverse solid phase synthesis of peptides

The Curators of the University of Missouri


The present invention is directed to energy-efficient, photoinitiators having the general formula:

The present invention relates to novel photoinitiators and methods for generating a reactive species using the photoinitiators. The present invention further relates to methods of polymerizing or photocuring polymerizable material using the above-mentioned photoinitiators. The photoinitiators of the present invention find particular utility in photocurable inks as used in ink jet printers or on a printing press with and without nitrogen blanketing.
Polymers have served essential needs in society. For many years, these needs were filled by natural polymers. More recently, synthetic polymers have played an increasingly greater role, particularly since the beginning of the 20th century. Especially useful polymers are those prepared by an addition polymerization mechanism, i.e., free radical chain polymerization of unsaturated monomers, and include, by way of example only, coatings and adhesives. In fact, the majority of commercially significant processes are based on free-radical chemistry. That is, chain polymerization is initiated by a reactive species, which often is a free radical. The source of the free radicals is termed an initiator or photoinitiator.
Improvements in free radical chain polymerization have focused both on (1) more reactive monomer and pre-polymer materials and (2) the photoinitiator. Whether a particular unsaturated monomer can be converted to a polymer requires structural, thermodynamic, and kinetic feasibility. Even when all three exist, kinetic feasibility is achieved in many cases only with a specific type of photoinitiator. Moreover, the photoinitiator can have a significant effect on reaction rate which, in turn, may determine the commercial success or failure of a particular polymerization process or product.
A free radical-generating photoinitiator may generate free radicals in several different ways. For example, the thermal, homolytic dissociation of an initiator typically directly yields two free radicals per initiator molecule. A photoinitiator, i.e., an initiator which absorbs light energy, may produce free radicals by one of three pathways:
(1) the photoinitiator undergoes excitation by energy absorption with subsequent decomposition into one or more radicals;
(2) the photoinitiator undergoes excitation and the excited species interacts with a second compound (by either energy transfer or a redox reaction) to form free radicals from the latter and/or former compound(s); or
(3) the photoinitiator undergoes an electron transfer to produce a radical cation and a radical anion.
While any free radical chain polymerization process should avoid the presence of species which may prematurely terminate the polymerization reaction, prior photoinitiators present special problems. For example, absorption of the light by the reaction medium may limit the amount of energy available for absorption by the photoinitiator. Also, the often competitive and complex kinetics involved may have an adverse effect on the reaction rate. Moreover, some commercially available radiation sources, such as medium and high pressure mercury and xenon lamps, may emit over a wide wavelength range, thus producing individual emission bands of relatively low intensity. Many photoinitiators only absorb over a small portion of the emission spectra and, as a consequence, much of the lamps"" radiation remains unused. In addition, most known photoinitiators have only moderate xe2x80x9cquantum yieldsxe2x80x9d (generally less than 0.4) at these wavelengths, indicating that the conversion of light radiation to radical formation can be more efficient.
Many commercially available photoinitiators, including IRGACURE(copyright) 369, are presently used in ink compositions to accelerate ink drying in xe2x80x9cradiation-drying printing.xe2x80x9d As used herein, the term xe2x80x9cradiation-drying printingxe2x80x9d refers to any printing method which utilizes radiation as a drying means. Radiation-drying printing includes, for example, off-set printing operations, such as on a Heidelberg press, flexographic printing, and flat-bed printing. Commercially available photoinitiator systems have a number of shortcomings. First, most of the commercially available photoinitiator systems require a relatively large amount of photoinitiator in the ink composition to fully cure/dry the ink composition. This leads to undesirable extractables within the ink composition. Second, most of the commercially available photoinitiator systems require a high energy radiation source to induce photocuring. Moreover, even with the high energy radiation source, often the cure results are unsatisfactory. Third, many commercially available photoinitiator systems are highly reactive to oxygen and must be used under a nitrogen blanket. Fourth, even with a large amount of photoinitiator and a high energy light source, the commercially available photoinitiator systems require a dry/cure time only accomplished by multiple passes, as many as 15 passes, under a light source, which significantly limits the output of a radiation-drying printing press.
What is needed in the art is a new class of energy-efficient photoinitiators having unsurpassed photoreactivity even when exposed to a low energy light source, such as a 50 W excimer cold lamp. What is also needed in the art is a new class of energy-efficient photoinitiators that may be cured in air, as well as, a nitrogen atmosphere. Further, what is needed in the art is a class of photoinitiators having unsurpassed photoreactivity, for use in the radiation-drying printing industry, which will significantly increase the output of a radiation-drying printing press due to reduction in ink drying/curing time.
The present invention addresses some of the difficulties and problems discussed above by the discovery of energy-efficient photoinitiators having the following general formula:
wherein Z each independently represents
wherein R1, R2, R3 and R4 each independently represent hydrogen, an alkyl group having from one to six carbon atoms, an alkoxy group having from one to six carbon atoms, or a halogen-substituted alkyl group; R5, R6, R7 and R8 each independently represent an alkyl group having from one to six carbon atoms, an aryl group, or a halogen-substituted alkyl group having from one to six carbon atoms; wherein R9 represents (R10)2O or (R10)3N; wherein R10 represents H or an alkyl group having from one to eight carbon atoms; and wherein R11, represents H, an alkyl group having from one to eight carbon atoms, a benzyl group or an aralkyl group. By selecting particular xe2x80x9cRxe2x80x9d groups, photoinitiators are produced having a desired absorption maximum, which substantially corresponds to an emission band of a radiation source and selectively varies from less than about 290 nm to greater than about 350 nm.
The present invention is directed to the above-described photoinitiators, compositions containing the same, and methods for generating a reactive species which includes providing one or more of the photoinitiators and irradiating the one or more photoinitiators. One of the main advantages of the photoinitiators of the present invention is that they efficiently generate one or more reactive species under extremely low energy lamps, such as excimer lamps and mercury lamps, as compared to prior art photoinitiators. The photoinitiators of the present invention also efficiently generate one or more reactive species in air or in a nitrogen atmosphere. Unlike many prior photoinitiators, the photoinitiators of the present invention are not sensitive to oxygen. Further, the photoinitiators of the present invention are as much as ten times faster than the best prior art photoinitiators.
The present invention is further directed to a method of efficiently generating a reactive species by matching a photoinitiator having an absorption maximum to an emission band of a radiation source, which corresponds to the absorption maximum. By adjusting the substituents of the photoinitiator, one can shift the absorption maximum of the photoinitiator from less than about 290 nm to greater than about 350 nm.
The present invention is also directed to methods of using the above-described photoinitiators to polymerize and/or photocure a polymerizable material. The photoinitiators of the present invention result in rapid curing times in comparison to the curing times of prior art photoinitiators, even with relatively low output lamps. The present invention includes a method of polymerizing a polymerizable material by exposing the polymerizable material to radiation in the presence of the efficacious wavelength specific photoinitiator composition described above. When an unsaturated oligomer/monomer mixture is employed, curing is accomplished.
The present invention further includes a film and a method for producing a film, by drawing an admixture of polymerizable material and one or more photoinitiators of the present invention, into a film and irradiating the film with an amount of radiation sufficient to polymerize the composition. The admixture may be drawn into a film on a nonwoven web or on a fiber, thereby providing a polymer-coated nonwoven web or fiber, and a method for producing the same.
The present invention is also directed to an adhesive composition comprising a polymerizable material admixed with one or more photoinitiators of the present invention. Similarly, the present invention includes a laminated structure comprising at least two layers bonded together with the above-described adhesive composition, in which at least one layer is a nonwoven web or film. Accordingly, the present invention provides a method of laminating a structure wherein a structure having at least two layers with the above-described adhesive composition between the layers is irradiated to polymerize the adhesive composition.
The present invention is further directed to a method of printing, wherein the method comprises incorporating one or more photoinitiators of the present invention into an ink composition; printing the ink onto a substrate; and drying the ink with a source of radiation.
These and other features and advantages of the present invention will become apparent after a review of the following detailed description of the disclosed embodiments and the appended claims.
The present invention is directed to energy-efficient, reactive, photoinitiators and methods for utilizing the same. More particularly, the present invention is directed to new photoinitiators having the following general formula:
wherein Z each independently represents
wherein R1, R2, R3 and R4 each independently represent hydrogen, an alkyl group having from one to six carbon atoms, an alkoxy group having from one to six carbon atoms, or a halogen-substituted alkyl group; R5, R6, R7 and R8 each independently represent an alkyl group having from one to six carbon atoms, an aryl group, or a halogen-substituted alkyl group having from one to six carbon atoms; wherein R9 represents (R10)2O or (R10)3N; wherein R10 represents H or an alkyl group having from one to eight carbon atoms; and wherein R11, represents H, an alkyl group having from one to eight carbon atoms, a benzyl group or an aralkyl group.
The present invention is further directed to a method of efficiently generating a reactive species by matching a photoinitiator having an absorption maximum to an emission band of a radiation source, which corresponds to the absorption maximum. The present invention also includes a method of polymerizing a polymerizable material by exposing the polymerizable material to electromagnetic radiation in the presence of one or more of the photoinitiators described above. Further, the present invention is directed to a film and a method for producing a film, by drawing an admixture of polymerizable material and one or more of the photoinitiators described above, into a film and irradiating the film with an amount of electromagnetic radiation sufficient to polymerize the admixture.
The present invention is further directed to an adhesive composition comprising a polymerizable material admixed and one or more photoinitiators of the present invention. Similarly, the present invention includes a laminated structure comprising at least two layers bonded together with the above-described adhesive composition. The present invention further provides a method of laminating a structure wherein a structure having at least two layers with the above-described adhesive composition between the layers is irradiated with appropriate electromagnetic radiation to polymerize the adhesive composition.
Definitions
As used herein, the term xe2x80x9creactive speciesxe2x80x9d is used herein to mean any chemically reactive species including, but not limited to, free-radicals, cations, anions, nitrenes, and carbenes. Illustrated below are examples of several of such species. Examples of carbenes include, for example, methylene or carbene, dichlorocarbene, diphenylcarbene, alkylcarbonyl-carbenes, siloxycarbenes, and dicarbenes. Examples of nitrenes include, also by way of example, nitrene, alkyl nitrenes, and aryl nitrenes. Cations (sometimes referred to as carbocations or carbonium ions) include, by way of illustration, a proton; primary, secondary, and tertiary alkyl carbocations, such as methyl cation, ethyl cation, propyl cation, t-butyl cation, t-pentyl cation, t-hexyl cation; allylic cations; benzylic cations; aryl cations, such as triphenyl cation; cyclopropylmethyl cations; methoxymethyl cation; triarylsulphonium cations; and acyl cations. Cations also include those formed from various metal salts, such as tetra-n-butylammonium tetrahaloaurate(III) salts; sodium tetrachloroaurate(III); vanadium tetrachloride; and silver, copper(I) and (II), and thallium(I) triflates. Examples of anions (sometimes referred to as carbanions) include, by way of example, alkyl anions, such as ethyl anion, n-propyl anion, isobutyl anion, and neopentyl anion; cycloalkyl anions, such as cyclopropyl anion, cyclobutyl anion, and cyclopentyl anion; allylic anions; benzylic anions; aryl cations; and sulfur- or phosphorus-containing alkyl anions. Finally, examples of organometallic photoinitiators include titanocenes, fluorinated diaryltitanocenes, iron arene complexes, manganese decacarbonyl, and methylcyclopentadienyl manganese tricarbonyl. Organometallic photoinitiators generally produce free radicals or cations.
As used herein, the term xe2x80x9cquantum yieldxe2x80x9d is used herein to indicate the efficiency of a photochemical process. More particularly quantum yield is a measure of the probability that a particular molecule will absorb a quantum of light during its interaction with a photon. The term expresses the number of photochemical events per photon absorbed. Thus, quantum yields may vary from zero (no absorption) to 1.
As used herein, the term xe2x80x9cpolymerizationxe2x80x9d is used herein to mean the combining, e.g. covalent bonding, of a number of smaller molecules, such as monomers, to form large molecules, i.e., macromolecules or polymers. The monomers may be combined to form only linear macromolecules or they may be combined to form three-dimensional macromolecules, commonly referred to as crosslinked polymers.
As used herein, the term xe2x80x9ccuringxe2x80x9d means the polymerization of functional oligomers and monomers, or even polymers, into a crosslinked polymer network. Thus, curing is the polymerization of unsaturated monomers or oligomers in the presence of crosslinking agents.
As used herein, the terms xe2x80x9cunsaturated monomer,xe2x80x9d xe2x80x9cfunctional oligomer,xe2x80x9d and xe2x80x9ccrosslinking agentxe2x80x9d are used herein with their usual meanings and are well understood by those having ordinary skill in the art. The singular form of each is intended to include both the singular and the plural, i.e., one or more of each respective material.
As used herein, the term xe2x80x9cunsaturated polymerizable materialxe2x80x9d is meant to include any unsaturated material capable of undergoing polymerization. The term encompasses unsaturated monomers, oligomers, and crosslinking agents. Again, the singular form of the term is intended to include both the singular and the plural.
As used herein, the term xe2x80x9cfiberxe2x80x9d as used herein denotes a threadlike structure. The fibers used in the present invention may be any fibers known in the art. As used herein, the term xe2x80x9cnonwoven webxe2x80x9d as used herein denotes a web-like matter comprised of one or more overlapping or interconnected fibers in a nonwoven manner. It is to be understood that any nonwoven fibers known in the art may be used in the present invention.
Photoinitiators
The present invention is directed to new photoinitiators having the following general formula:
wherein Z each independently represents
wherein R1, R2, R3 and R4 each independently represent hydrogen, an alkyl group having from one to six carbon atoms, an alkoxy group having from one to six carbon atoms, or a halogen-substituted alkyl group; R5, R6, R7 and R8 each independently represent an alkyl group having from one to six carbon atoms, an aryl group, or a halogen-substituted alkyl group having from one to six carbon atoms; wherein R9 represents (R10)2O or (R10)3N; wherein R10 represents H or an alkyl group having from one to eight carbon atoms; and wherein R11, represents H, an alkyl group having from one to eight carbon atoms, a benzyl group or an aralkyl group.
Photoinitiators having the above formula include, but are not limited to, the following photoinitiators:
wherein R5, R6, R7, R8 and R9 are as described above.
The photoinitiators of the present invention may be associated with a variety of counterions. Suitable counterions possess a negative charge distribution, which is spread over a large anion, resulting in a diffused charge rather than a point charge. Examples of suitable counterions include, but are not limited to, tetraphenylboron, tetrachloroboron, tetrafluoroboron, hexafluorophosphate, and perchlorate. Desirably, the counterion comprises tetraphenylboron or tetrafluoroboron. More desirably, the counterion comprises tetrafluoroboron.
In one embodiment of the present invention, a photoinitiator system comprises the following photoinitiator and counterions:
The above-described photoinitiators of the present invention may be produced by the following reaction mechanism, shown for when R11 is hydrogen and Z is NC4H4O:
wherein one or more compounds react with the Zn-containing compound or complex to produce a photoinitiator of the present invention and one or more anions (Xxe2x88x92). Suitable Zn-containing compounds or complexes include, but are not limited to, Zn(OEt2)2Cl2, Zn(H2O)6(BF4)2, and Zn(H2O)6(BPh4)2. In the above mechanism, the use of a particular Zn-containing compound or complex results in a particular R9 group and anions as shown in the table below:
It should be understood that the above examples of suitable photoinitiators are only a few of the possible photoinitiators encompassed by the present invention. Any combination of photoinitiator having selected xe2x80x9cRxe2x80x9d groups and any of the above-mentioned counterions may be used in combination to form a photoinitiator system of the present invention. Further, the above reaction mechanism is only one example of many possible reaction mechanisms, which may include a variety of reactants, resulting in the photoinitiators of the present invention.
The resulting photoinitiators are relatively stable at room temperature (from about 15xc2x0 C. to 25xc2x0 C.) and normal room humidity (from about 5% to 60%; desirably from 5% to 30%). However, upon exposure to radiation at an appropriate wavelength, the photoinitiators efficiently produce one or more reactive species. The photoinitiators of the present invention have a high intensity of absorption. For example, the photoinitiators of the present invention have a molar extinction coefficient (absorptivity) greater than about 20,000 1 molexe2x88x921 cmxe2x88x921. As a further example, the photoinitiators of the present invention have a molar extinction coefficient greater than about 25,000 1 molexe2x88x921 cmxe2x88x921.
Method of Generating a Reactive Species and Applications Therefor
The present invention is further directed to a method of generating a reactive species. The method of generating a reactive species involves generating a reactive species by exposing one or more of the above-described photoinitiators to radiation. The exposure of the photoinitiators to a radiation source triggers a photochemical process. As stated above, the term xe2x80x9cquantum yieldxe2x80x9d is used herein to indicate the efficiency of a photochemical process. More particularly, quantum yield is a measure of the probability that a particular molecule (photoinitiator) will absorb a quantum of light during its interaction with a photon. The term expresses the number of photochemical events per photon absorbed. Thus, quantum yields may vary from zero (no absorption) to 1.
The photoinitiators of the present invention absorb photons having a relatively specific wavelength and transfers the absorbed energy to one or more excitable portions of the molecule. The excitable portion of the molecule absorbs enough energy to cause a bond breakage, which generates one or more reactive species. The efficiency with which a reactive species is generated with the photoinitiators of the present invention is significantly greater than that experienced with photoinitiators of the prior art as indicated by faster cure times. For example, the photoinitiators of the present invention desirably will have a quantum yield greater than about 0.8. More desirably, the quantum yield of the photoinitiators of the present invention will be greater than about 0.9. Even more desirably, the quantum yield of the photoinitiators of the present invention will be greater than about 0.95. Still more desirably, the quantum yield of the photoinitiators of the present invention will be greater than about 0.99, with the most desirable quantum yield being about 10.
In one embodiment of the present invention, the photoinitiators of the present invention are exposed to radiation at a desired wavelength, resulting in the generation of one or more reactive species, wherein an electron-donating solvent is used to generate one or more reactive species. Any solvent capable of donating an electron to the photoinitiators of the present invention may be used to generate one or more reactive species. Suitable electron-donating solvents include, but are not limited to, acrylates, methacylates, vinyl esters, enamines, and a combination thereof. Desirably, the electron-donating solvent comprises acrylic acid.
It is believed that the interaction between the photoinitiator of the present invention and the electron-donating solvent takes place as shown by the following reaction mechanism:
Donation of Electron
As shown above, donation of an electron from the electron-donating solvent generates a cationic free radical.
Electron Interaction With Photoinitiator:
The introduction of the electron into the structure of the photoinitiator results in the formation of a carbon-carbon double bond and cleavage of the carbon-nitrogen bond. The end result is a nitrogen-containing free radical.
The above mechanism generates a combination of free radicals, one of which is a cationic free radical and one of which is nitrogen radical species. In conventional electron transfer systems, an initiator generates a radical cation, which starts the polymerization process, and a radical anion, which is a chain terminator (i.e., stops polymerization). However, the method of generating a reactive species of the present invention generates a radical cation and a nitrogen radical species, both of which start the polymerization process, and neither of which act as a chain terminator (i.e., stop polymerization).
Exposing the photoinitiators of the present invention to radiation results in the generation of one or more reactive species as discussed above. Thus, the photoinitiators may be employed in any situation where reactive species are required, such as for the polymerization of an unsaturated monomer and the curing of an unsaturated oligomer/monomer mixture. The unsaturated monomers and oligomers may be any of those known to one having ordinary skill in the art. In addition, the polymerization and curing media also may contain other materials as desired, such as pigments, extenders, amine synergists, and such other additives as are well known to those having ordinary skill in the art.
By way of illustration only, examples of unsaturated monomers and oligomers include ethylene, propylene, vinyl chloride, isobutylene, styrene, isoprene, acrylonitrile, acrylic acid, methacylic acid, ethyl acrylate, methyl methacrylate, vinyl acrylate, allyl methacrylate, tripropylene glycol diacrylate, trimethylol propane ethoxylate acrylate, epoxy acrylates, such as the reaction product of a bisphenol A epoxide with acrylic acid; polyether acrylates, such as the reaction product of acrylic acid with an adipic acid/hexanediol-based polyether, urethane acrylates, such as the reaction product of hydroxypropyl acrylate with diphenylmethane-4,4xe2x80x2-diisocyanate, and polybutadiene diacrylate oligomer.
The types of reactions that various reactive species enter into include, but are not limited to, addition reactions, including polymerization reactions; abstraction reactions; rearrangement reactions; elimination reactions, including decarboxylation reactions; oxidation-reduction (redox) reactions; substitution reactions; and conjugation/deconjugation reactions.
Accordingly, the present invention also comprehends a method of polymerizing a polymerizable material, such as an unsaturated monomer or epoxy compound, by exposing the polymerizable material to radiation in the presence of the effacious photoinitiators of the present invention described herein. When an unsaturated oligomer/monomer mixture is employed in place of an unsaturated monomer, curing is accomplished. It is to be understood that the polymerizable material admixed with the photoinitiators of the present invention is to be admixed by means known in the art, and that the mixture will be irradiated with an amount of radiation sufficient to polymerize the material. The amount of radiation sufficient to polymerize the material is readily determinable by one of ordinary skill in the art, and depends upon the identity and amount of photoinitiators, the identity and amount of the polymerizable material, the intensity and wavelength of the radiation, and the duration of exposure to the radiation.
Polymer Films, Coated Fibers and Webs, and Adhesive Compositions
The present invention further includes a film and a method for producing a film, by drawing an admixture of a polymerizable material and one or more photoinitiators of the present invention, into a film and irradiating the film with an amount of radiation sufficient to polymerize the composition. When the polymerizable material is an unsaturated oligomer/monomer mixture, curing is accomplished. Any film thickness may be produced, as per the thickness of the admixture formed, so long as the admixture sufficiently polymerizes upon exposure to radiation. The admixture may be drawn into a film on a nonwoven web or on a fiber, thereby providing a polymer-coated nonwoven web or fiber, and a method for producing the same. Any method known in the art of drawing the admixture into a film may be used in the present invention. The amount of radiation sufficient to polymerize the material is readily determinable by one of ordinary skill in the art, and depends upon the identity and amount of photoinitiator, the identity and amount of the polymerizable material, the thickness of the admixture, the intensity and wavelength of the radiation, and duration of exposure to the radiation.
The present invention is further directed to coatings comprising a polymerizable material admixed with one or more photoinitiators of the present invention. The coatings may be applied to a substrate and then exposed to an amount of radiation sufficient to polymerize the polymerizable material of the coating. Any substrate may be used in the practice of the present invention. Particular applications of interest include, but are not limited to, coatings on textiles, coatings on fabrics, coatings on textile fibers, and coatings on optical fibers.
The present invention also includes an adhesive composition comprising a polymerizable material admixed with one or more photoinitiators of the present invention. Similarly, the present invention includes a laminated structure comprising at least two layers bonded together with the above-described adhesive composition. In one embodiment of the present invention, a laminate is produced wherein at least one layer is a cellulosic or polyolefin nonwoven web or film. Accordingly, the present invention provides a method of laminating a structure wherein a structure having at least two layers with the above-described adhesive composition between the layers is irradiated to polymerize the adhesive composition. When the unsaturated polymerizable material in the adhesive is an unsaturated oligomer/monomer mixture, the adhesive is irradiated to cure the composition.
It is to be understood that any layers may be used in the laminates of the present invention, on the condition that at least one of the layers allows sufficient radiation to penetrate through the layer to enable the admixture to polymerize sufficiently. Accordingly, any cellulosic or polyolefin nonwoven web or film known in the art may be used as one of the layers so long as they allow radiation to pass through. Again, the amount of radiation sufficient to polymerize the admixture is readily determinable by one of ordinary skill in the art, and depends upon the identity and amount of photoinitiator, the identity and amount of the polymerizable material, the thickness of the admixture, the identity and thickness of the layer, the intensity and wavelength of the radiation, and the duration of exposure to the radiation.
The radiation to which the photoinitiators of the present invention may be exposed generally will have a wavelength of from about 4 to about 1,000 nanometers. Thus, the radiation may be ultraviolet radiation, including near ultraviolet and far or vacuum ultraviolet radiation; visible radiation; and near infrared radiation. Desirably, the radiation will have a wavelength of from about 100 to about 900 nanometers. More desirably, the radiation will have a wavelength of from about 100 to 700 nanometers. Desirably, the radiation will be ultraviolet radiation having a wavelength of from about 4 to about 400 nanometers. More desirably, the radiation will have a wavelength of from about 100 to about 420 nanometers, and even more desirably will have a wavelength of from 290 to about 320 nanometers. The radiation desirably will be incoherent, pulsed ultraviolet radiation from a dielectric barrier discharge excimer lamp or radiation from a mercury lamp.
Excimers are unstable excited-state molecular complexes which occur only under extreme conditions, such as those temporarily existing in special types of gas discharge. Typical examples are the molecular bonds between two rare gaseous atoms or between a rare gas atom and a halogen atom. Excimer complexes dissociate within less than a microsecond and, while they are dissociating, release their binding energy in the form of ultraviolet radiation. The dielectric barrier excimers in general emit in the range of from about 125 nm to about 500 nm, depending upon the excimer gas mixture.
Dielectric barrier discharge excimer lamps (also referred to hereinafter as xe2x80x9cexcimer lampxe2x80x9d) are described, for example, by U. Kogelschatz, xe2x80x9cSilent discharges for the generation of ultraviolet and vacuum ultraviolet excimer radiation.xe2x80x9d Pure and Appl. Chem., 62, No. 9, pp. 16671674 (1990); and E. Eliasson and U. Kogelschatz, xe2x80x9cUV Excimer Radiation from Dielectric- Barrier Discharges.xe2x80x9d Appl. Phys. B. 46, pp. 299-303 (1988). Excimer lamps were developed by ABB Infocom Ltd., Lenzburg, Switzerland, and at the present time are available from Heraeus Noblelight GmbH, Kleinostheim, Germany.
The excimer lamp emits incoherent, pulsed ultraviolet radiation. Such radiation has a relatively narrow bandwidth, i.e., the half width is of the order of approximately 5 to 100 nanometers. Desirably, the radiation will have a half width of the order of approximately 5 to 50 nanometers, and more desirably will have a half width of the order of 5 to 25 nanometers. Most desirably, the half width will be of the order of approximately 5 to 15 nanometers.
The ultraviolet radiation emitted from an excimer lamp can be emitted in a plurality of wavelengths, wherein one or more of the wavelengths within the band are emitted at a maximum intensity. Accordingly, a plot of the wavelengths in the band against the intensity for each wavelength in the band produces a bell curve. The xe2x80x9chalf widthxe2x80x9d of the range of ultraviolet radiation emitted by an excimer lamp is defined as the width of the bell curve at 50% of the maximum height of the bell curve.
The emitted radiation of an excimer lamp is incoherent and pulsed, the frequency of the pulses being dependent upon the frequency of the alternating current power supply which typically is in the range of from about 20 to about 300 kHz. An excimer lamp typically is identified or referred to by the wavelength at which the maximum intensity of the radiation occurs, which convention is followed throughout this specification and the claims. Thus, in comparison with most other commercially useful sources of ultraviolet radiation which typically emit over the entire ultraviolet spectrum and even into the visible region, excimer lamp radiation is essentially monochromatic.
Although excimer lamps are highly desirable for use in the present invention, the source of radiation used with the photoinitiators of the present invention may be any radiation source known to those of ordinary skill in the art. In a further embodiment of the present invention, a mercury lamp with a D-bulb, which produces radiation having an emission peak of about 360 nm is used to produce free radicals from the above-described photoinitiators. This radiation source is particularly useful when matched with one or more photoinitiators of the present invention having an absorption maximum of about 360 nanometers, corresponding to the emission peak of the mercury lamp. Other specialty doped lamps, which emit radiation at about 420 nm, may be used with photoinitiators of the present invention which have an absorption maximum at about 420 nm. One lamp, the V-bulb available from Fusion Systems, is another suitable lamp for use in the present invention. In addition, specialty lamps having a specific emission band may be manufactured for use with one or more specific photoinitiators of the present invention. New lamp technology provides the following potential advantages:
(a) substantially single wavelength output;
(b) unique wavelength output;
(c) high intensity; and
(d) absence of radiation trapping.
As a result of the photoinitiators of the present invention absorbing radiation in the range of about 250 to about 390 nanometers, some of the photoinitiators of the present invention will generate one or more reactive species upon exposure to sunlight. Accordingly, these photoinitiators of the present invention provides a method for the generation of reactive species that does not require the presence of a special light source.
The photoinitiators of the present invention enable the production of adhesive and coating compositions that consumers can apply to a desired object and polymerize or cure upon exposure to sunlight. These photoinitiators also enable numerous industry applications wherein polymerizable materials may be polymerized merely upon exposure to sunlight. Therefore, depending upon how the photoinitiator is designed, the photoinitiator of the present invention can eliminate the cost of purchasing and maintaining light sources in numerous industries wherein such light sources are necessary without the photoinitiators of the present invention.
The effective tuning of the photoinitiators of the present invention for a specific wavelength band permits the photoinitiators of the present invention to more efficiently utilize the target radiation in the emission spectrum of the radiating source corresponding to the xe2x80x9ctunedxe2x80x9d wavelength band, even though the intensity of such radiation may be much lower than, for example, radiation from a narrow band emitter, such as an excimer lamp. For example, it may be desirable to utilize an excimer lamp, or other radiation emission source, that emits radiation having a wavelength of approximately 360 nm or 420 nm with the photoinitiators of the present invention. However, the effectiveness of the photoinitiators of the present invention is not necessarily dependent upon the availability or use of a narrow wavelength band radiation source.
Use of the Above-Described Photoinitiators in an Ink Composition
The above-described photoinitiators of the present invention may be incorporated into ink compositions. In one embodiment of the present invention, one or more of the photoinitiators are incorporated into an ink jet ink composition for use on ink jet ink printers. The ink composition may be used on commercially available ink jet printing machines alone or in combination with a radiation source in series with the ink jet printing machine for instantaneous curing of the ink jet ink composition. Any radiation source known to those of ordinary skill in the art may be used to cure the ink jet ink composition. Desirably, one of the above-described radiation sources is used to cure the ink composition.
Use of the Above-Described Photoinitiators in Other Radiation-Drying Printing Process
A further use of the above-described photoinitiators of the present invention involves the incorporation of one or more of the photoinitiators into an ink composition for use on a radiation-drying printing press. As discussed above, xe2x80x9cradiation-drying printingxe2x80x9d refers to any printing method which utilizes radiation as a drying means. Radiation-drying printing includes, for example, off-set printing operations, such as on a Heidelberg press, flexographic printing, and flat-bed printing.
The photoinitiators of the present invention enable increased press output due to the photoreactivity of the photoinitiators. Further, the increased output may be obtained while using a minimal amount of photoinitiator and a low energy light source. In one embodiment of the present invention, complete curing at an output rate of 10,000 printed sheets per hour may be obtained using a 50 W cold lamp as the light source.
Any of the above-described photoinitiators may be used in the printing processes disclosed herein. Desirably, the amount of photoinitiator added to the ink composition, adhesive composition or resin is less than about 4.0 wt % of the total weight of the composition. More desirably, the amount of photoinitiator added to the composition is from about 0.25 to about 3.0 wt % of the total weight of the composition. Most desirably, the amount of photoinitiator added to the composition is from about 0.25 to about 2.0 wt % of the total weight of the composition.
A major advantage of the photoinitiators of the present invention is that they enable rapid curing times of ink compositions, adhesive compositions and/or resins in comparison to the curing times of prior art photoinitiators. Ink compositions containing the photoinitiators of the present invention possess rapid curing times from 5-10 times faster than the curing times of ink compositions containing the best known photoinitiators. The use of the photoinitiators of the present invention in ink compositions, adhesive compositions or resins for printing presses enables print speeds, which were at one time thought to be unobtainable. For example, in an open air printing process using a Heidelberg print press and a 50 W excimer cold lamp for photocuring, desirably the printed sheet output is greater than 6,000 sheets per hour. More desirably, the printed sheet output is greater than 8,000 sheets per hour. Most desirably, the printed sheet output is greater than 10,000 sheets per hour.

Zinc-complex photoinitiators and applications therefor

Abstract: wherein Z each independently represent

Abstract: wherein R1, R2, R3, R4, R5, R6, R7, R8 are as defined in claim 1, and wherein R9 represents (R10)2O or (R10)3N; wherein R10 represents H or an alkyl group having from one to eight carbon atoms; and wherein R11 represents H, an alkyl group having from one to eight carbon atoms, a benzyl group or an aralkyl group. The present invention is also directed to a method of generating a reactive species, methods of polymerizing polymerizable materials, methods of curing an unsaturated oligomer/monomer mixture, and methods of laminating using the photoinitiators of the present invention. In addition, the present invention is directed to ink compositions, adhesive compositions and resins, and methods of printing using the above-described photoinitiators.


A plating jig for plating a corrugated tube includes a linear center rod, a circular rod helically formed with the center rod as its center axis, support rods each having a base fixed to the center rod and an end extended in the radial direction of the circular rod, and suspensions provided at the ends of the support rods respectively, extended in the same direction as the center rod and connected to the one-end side outer circumferential surface of the circular rod.

The present invention relates to a plating jig for holding a flexible pipe material having a slit in the lengthwise direction thereof and a plating method using the plating jig and, in particular, relates to a plating jig and a plating method adapted to the case where electroless plating is applied to a long-size corrugated tube formed of a resin material.
In recent years, electronic application to controllers has been developed in the field of cars, machine tools, office machines, etc. Measures counter to electromagnetic wave noise in these electronic appliances have become an important problem. Such electronic appliances require shielding measures for shielding internal conductors of wirings from external electric field because wirings connected to the electronic appliances are apt to absorb electromagnetic wave noise. The shielding of the internal conductors is performed by grounding external conductors covering the internal conductors. One of the external conductors used in this occasion is a shielded-plating corrugated tube obtained by applying plating to a bellows-like pipe material (corrugated tube) having flexibility and formed of a resin material. The shielded-plating corrugated tube is formed so as to have a shielding effect by applying plating to a tube used originally as a wiring protecting material. In the shielded-plating corrugated tube, a slit for inserting wiring therein is formed in the lengthwise direction in the same manner as in the conventional corrugated tube.
For plating the shielded-plating corrugated tube, an electroless plating method is used because the corrugated tube (to be plated) as a base is an electrically insulating material. In the electroless plating method, a material (to be plated) with a catalyst spread on the surface thereof is put into a bath containing a metal ion and a reducing agent, so that a metal coating is formed on the surface of the material (to be plated) by a catalytic reaction. Such electroless plating is classified by plating equipment into a hang-plating method (also called a rack type plating method), a barrel plating method, etc.
In the hang-plating method, as shown in FIGS. 19 and 20, a roll of long-size corrugated tube 3 is put into a resin-coated cage 1 and then a set of the corrugated tube 3 and the cage 1 is put into a plating tank 7 in which a plating solution 5 is stored. In another method, as shown in FIG. 21, short-cut corrugated tubes 3 may be put into a plating tank 7 while hung by a rack 9.
On the other hand, in the barrel plating method, as shown in FIG. 22, a roll of corrugated tube 3 put into a cylindrical wire net cage 11 is put into a plating tank 7, so that plating is performed while rotating or swinging the wire net cage 11.
In the plating method shown in FIG. 20, however, the slit formed in the lengthwise direction of the corrugated tube 3 is not disposed in a predetermined direction. Accordingly, in a portion in which the slit 3a is disposed downward as shown in FIG. 23(A), bubbles 13 of air remaining in the corrugated tube 3 without being discharged from the corrugated tube 3 or hydrogen gas or the like, generated in the plating solution remain in the inside in the form of a bubble reservoir, so that the portion does not touch the plating solution. As a result, there arises a problem that portions which are not plated may be generated. Further, in a portion in which the slit 3a is disposed upward as shown in FIG. 23(B), when the corrugated tube 3 is pulled up from the plating tank, some plating solution remains in the bottom portion, that is, so-called bailing of the plating solution occurs. As a result, there arises a problem that the remaining plating solution is mixed with the next plating solution so that deterioration of the plating solution makes proper plating impossible. If exchange of the plating solution to a new one is performed frequently in order to prevent the deterioration of the plating solution, production costs increase.
Further, in the plating method shown in FIG. 21, there arises a problem that not only the commercial value thereof is reduced because the corrugated tube 3 is cut into a short length, but also production costs are increased because large scale processing cannot be performed.
Further, in the plating method shown in FIG. 22, the slit 3a is not disposed in a predetermined direction in the same manner as in the method shown in FIG. 20. Accordingly, there arises a problem that not only plating failure due to the bubble reservoir and deterioration of the plating solution due to the bailing of the plating solution occur but also corrugated tubes 3 are apt to touch each other so that adhesion of plating in the contact portion is lowered.

Plating jig and plating method using the plating jig


A projectile (2) includes a cylindrical casing with the one (nose) end has a relatively non-penetrating front face (3) with an opening therein defining a cavity (5) extending longitudinally into the casing from said opening, and the other (tail) end (10) of the cylindrical casing is adapted to receive a propelling force; said projectile further comprises an implant (14) for penetrating a target on impact; wherein said implant is located at least in part within the cavity during flight and has longitudinal freedom of movement within the cavity towards the nose of the casing; whereby on impact said implant tends to penetrate said target whilst said relatively non-penetrating front face abuts at least momentarily said target.

When administering a medicament dosage, a marker or a tracking device to cattle it is often necessary to herd the cattle to a particular station for administrating a medicament dosage, a marker, or a tracking device. During this process the cattle goes through intense exertion which results in considerable weight loss which can only be recovered through intensive feeding of several thousands of calories. There is therefore a need to administer cattle with minimal herding requirement. There is also a requirement to implant a medicament or a tracking device through the hide and into the sub-cutaneous flesh at 2-3 inches whilst leaving less tissue and muscle damage than conventional administering methods.
The following prior art documents are acknowledged:
U.S. Pat. No. 6,807,908, GB2346201, U.S. Pat. No. 4,243,036, FR2800867 and U.S. Pat. No. 3,995,550.
U.S. Pat. No. 6,807,908 is concerned with retarding the velocity of a projectile impact to prevent excessive damage, injury or penetration at the target by using an inflatable membrane. The needle is fixed relative to the casing to the projectile so that the needle has no longitudinal freedom of movement within the cavity towards the nose of the casing.
GB2346201 discloses a marking projectile, which is of a non-penetrating kind. There is no implant member suggested for the delivery of a payload.
U.S. Pat. No. 4,243,036 incorporates a penetrating needle which is fixed relative to a syringe casing. This system employs a projectile brake to prevent excessive penetration of the needle.
FR2800867 fails to show any form of penetration since it is destined to project a liquid over an object rather than into an object.
U.S. Pat. No. 3,995,550 disclosed a spinning artillery projectile which has no relatively non-penetrating front face and has no implant of the kind in question for this invention.
An object of the invention is to provide a projectile, which serves to deliver and implant a payload with the minimum of damage and discomfort to an animal target.

Projectile for administering a medicament


A wafer stage including an electrostatic chuck and a method for dechucking a wafer using the wafer stage are provided, wherein, the wafer stage includes an electrostatic chuck support, an electrostatic chuck, a lifting means, and a grounding means including a device for connecting the interconnections for grounding the lifting means. According to the method for dechucking a wafer, when a lifting means is in contact with a rear side of the wafer, the lifting means is grounded. Then, an electrostatic chuck is neutralized by supplying power to electrostatic electrodes, and the wafer is neutralized by supplying plasma to the wafer.

1. Field of the Invention
The present invention relates to an apparatus for manufacturing a semiconductor device and a method for using the apparatus. More particularly, the present invention relates to a wafer stage including an electrostatic chuck, and to a method for dechucking a wafer using the wafer stage.
2. Description of the Related Art
Semiconductor devices are manufactured after performing many processes such as depositing a material layer on a wafer, patterning the deposited material layer, and removing unnecessary residuals on the wafer. To perform these processes repeatedly, a wafer is loaded on a wafer stage inside a chamber, the wafer is processed, and then unloaded.
In order to successively process a wafer, it is very important to chuck and fix the wafer in the chamber and to dechuck the wafer so that the wafer will not be damaged after processing. As semiconductor devices become highly integrated, the design rule becomes smaller, and the process margin becomes narrower. As a result, there is a greater need to chuck and fix the wafer without damaging the wafer during dechucking.
Methods for fixing the wafer to the wafer stage in the process chamber when the wafer is loaded on the wafer stage include using hardware structures such as clamps, using a vacuum to suction the rear side of the wafer (a vacuum chuck), using gravity, and using a piezoelectric effect. Various methods are available for dechucking the fixed wafer on the wafer stage after processing the wafer. The dechucking method used is chosen in accordance with the method used for fixing the wafer.
The most widely used method for fixing a wafer is the piezoelectric effect. In this method, an electrostatic chuck is used to fix the wafer, and the electrostatic chuck and a lifting means are used to dechuck the fixed wafer.
FIG. 1A illustrates a sectional view of a method for chucking a wafer using an electrostatic chuck according to the prior art. Referring to FIG. 1A, first, the structure of an electrostatic chuck 10 will be described, and then, a method for chucking a wafer 20 will be described. The electrostatic chuck 10 includes an upper insulating layer 2, an electrostatic electrode 4, a lower insulating layer 6, and a lower electrode 8. The lower electrode 8 controls the reaction speed of plasma when plasma is generated in the chamber (not shown). The electrostatic electrode 4 is connected to a DC generator (not shown), and positive charges or negative charges are distributed on the electrostatic electrode 4 by the DC generator. The electric charges on the electrostatic electrode 4 induce an electrostatic field such that the wafer 20 is chucked or dechucked. The electrostatic electrode 4 and the lower electrode 8 are insulated by the lower insulating layer 6, and the wafer 20 and the electrostatic electrode 4 are insulated by the upper insulating layer 2.
In a method for dechucking the wafer 20 according to the prior art, the wafer 20 is put on the electrostatic chuck 10, and an electrostatic field is induced by supplying power to the electrostatic electrode 4 under the upper insulating layer 2 on the upper surface of the electrostatic chuck 10. Positive charges accumulate on the electrostatic electrode 4 connected to the external DC generator (not shown), and negative charges accumulate on the lower surface of the wafer 20 by plasma generated on an upper portion of the wafer 20, thereby inducing an electrostatic field between the wafer 20 and the electrostatic electrode 4. When the upper surface of the electrostatic chuck 10 is completely in contact with the wafer 20, a clamping force is produced by the electrostatic field, and thus, the wafer 20 is chucked.
Meanwhile, some of the charges on the electrostatic electrode 4 of the electrostatic chuck 10 flow into the upper surface of the electrostatic chuck 10 through the upper insulating layer 2, and as time goes by, the electric charges accumulate. The clamping force between the wafer 20 and the electrostatic chuck 10 increases due to the accumulated electric charges. As a result, the magnitude of the clamping force grows larger than the voltage applied to the electrostatic electrode 4 of the electrostatic chuck 10. The wafer 20 and the electrostatic chuck 10 are stuck together by the increased clamping force when the wafer 20 and the electrostatic chuck 10 are dechucked.
FIG. 1B illustrates a sectional view of a method for dechucking a wafer 20 using an electrostatic chuck according to the prior art. When the wafer 20 is chucked, plasma formation on the upper portion of the wafer 20 stops, and the voltage supplied to the lower electrode 8 and the electrostatic electrode 4 of the electrostatic chuck 10 is turned off. As a result, the electric charges flow out and the clamping force is reduced. However, since a discharge time is necessary for the charges to flow when the clamping force is reduced, the wafer 20 becomes stuck to the electrostatic chuck 10.
When lift pins 12 are raised to dechuck a wafer 20 that is stuck to the electrostatic chuck 10, the force applied to the wafer 20 can easily damage the wafer 20. In order to prevent the sticking phenomenon, power is again supplied to the electrostatic electrode 4, in which positive charges remain, and negative charges flow into the electrostatic electrode 4. That is, electric charges having a charge opposite to those supplied to the electrostatic electrode 4 during chucking flow into the electrostatic electrode 4 during dechucking in order to neutralize the electrostatic electrode 4, thereby easily dechuck the wafer 20.
Subsequently, the lift pins 12 of the lifting means (not shown) are raised, and the wafer 20 is dechucked. However, in the method for supplying electric charges having an opposite polarity to the electrostatic electrode 4, the wafer 20 still possesses electric charges, and thus, the method is not of much help for dechucking.

Wafer stage including electrostatic chuck and method for dechucking wafer using the wafer stage


The present invention provides a contact lens cleaning solution which is capable of, simultaneously and in a simplified manner, rendering surfaces of the contact lens hydrophilic and cleaning the contact lens for removal of protein deposits, without suffering from reduction of the cleaning effect of a protease, and also provides a method of cleaning a contact lens which is capable of rendering the surfaces of the contact lens hydrophilic while, at the same time, cleaning the contact lens for removal of the protein deposits, by using the contact lens cleaning solution as described above.. A desired contact lens cleaning solution is prepared, which contains a protease in an amount effective for removing protein adhering or clinging to the contact lens and gum arabic as a hydrophilicity rendering component, wherein divalent metal ions in the gum arabic are removed or inactivated. The contact lens is immersed in such a contact lens cleaning solution, so as to remove the protein adhering or clinging to the contact lens and render the surfaces of the contact lens hydrophilic.

1. Field of the Art
The present invention relates to a contact lens cleaning solution and a method of cleaning a contact lens using the solution.
2. Discussion of the Related Art
As conventionally used non-water-absorbable contact lenses, there are known a hard contact lens of polymer made mainly of methyl methacrylate, a high-degree oxygen permeable hard contact lens of polymer made mainly of siloxanyl methacrylate, fluoroalkyl methacrylate, or the like, and a non-water-absorbable soft contact lens made mainly of a silicone rubber that contains polydimethylsiloxane as a major component, or a butyl rubber that contains butyl acrylate as a major component. The surfaces of these non-water-absorbable contact lenses are hydrophobic. In particular, the surfaces of the high-degree oxygen permeable contact lens which has recently attracted public attention exhibit a high degree of hydrophobic property. The hydrophobic property of the lens surfaces causes a problem that lipid deposits which derive from tear fluid and lipid of the eyes adhere to the lens surfaces when the non-water-absorbable contact lenses are worn on the eyes of a user, whereby the contact lens is clouded, leading to deteriorated eyesight of the lens user.
In an attempt to deal with the above-described problem, there are proposed various methods of rendering the hydrophobic surfaces of the contact lens hydrophilic. Examples of the proposed methods include a plasma surface treatment and a chemical treatment using an acid or an alkali. However, the contact lens treated by these methods does not exhibit satisfactory durability in its hydrophilic property at the surfaces thereof, and it is considerably cumbersome to repeat the treatment for rendering the lens surfaces hydrophilic. Thus, the proposed methods are not practical.
Further, there is known a method which uses a so-called wetting solution so as to improve the surfaces of the contact lens. In this method, the contact lens is immersed in a solution that contains a hydrophilic polymer, so that the polymer is fixed to the surfaces of the contact lens. This method permits the contact lens to be repeatedly subjected to the treatment for rendering the lens surfaces hydrophilic, by simply immersing the contact lens in the solution as needed. Thus, the hydrophilic property of the contact lens surfaces is comparatively easily maintained. For instance, JP-B-48-37910 discloses a solution for a contact lens containing polyvinyl alcohol and a water-soluble polymer such as hydroxyethyl cellulose and polyvinyl pyrrolidone.
Such a treatment solution is effective for a contact lens having a comparatively low degree of hydrophobic property, such as a high-degree oxygen permeable contact lens of polymer made mainly of methyl methacrylate. However, the solution is not effective for a contact lens having a high degree of hydrophobic property, such as a non-water-absorbable contact lens which contains a large amount of a silicone or fluorine component, since the water-soluble polymer included in the solution is not likely to adhere to the surfaces of the contact lens. Thus, the solution as described above is not capable of effectively rendering the surfaces of the contact lens hydrophilic.
JP-A-63-246718 discloses a surface treatment solution for a contact lens which consists of a polymeric material with an ionic charge. In effecting the treatment for rendering the surfaces of the contact lens hydrophilic by using the disclosed surface treatment solution, the surfaces of the contact lens need to have an ionic charge opposite to that of the solution. Further, the density of the opposite ionic charge of the lens surfaces needs to be higher than a certain level. For satisfying these requirements, it is necessary to effect a treatment for increasing the density of the ionic charge of the contact lens surfaces, prior to the treatment for rendering the lens surfaces hydrophilic, undesirably making the procedure cumbersome. Like the wetting solution as described above, the disclosed polymeric solution which contains the ionic group that gives the ionic charge as described above is not capable of giving a satisfactory degree of hydrophilic property to the non-water-absorbable contact lens which contains a large amount of the silicone or fluorine component.
JP-A-3-235914 discloses various contact lens solutions which contain gum arabic as a hydrophilicity rendering component. The gum arabic contained in the contact lens solutions is effectively adsorbed on the highly hydrophobic surfaces of the contact lens. Accordingly, the solutions disclosed in the publication are effective to give the hydrophilic property to the non-water-absorbable contact lens which contains a large amount of silicone or fluorine component. The contact lens whose surfaces are rendered hydrophilic by using these solutions assures the lens user of its comfortable wearing.
While the contact lenses are worn on the eyes, protein included in the tear fluid adheres or clings to the surfaces of the contact lenses. In view of this, there have been conventionally proposed various methods of cleaning and removing protein deposits adhering to the contact lenses by using a cleaning agent that contains a protease, for instance. JP-A-2-168224 and JP-A-6-9504 disclose methods of removing such protein deposits by decomposition using the protease.
The treatment for rendering the lens surfaces hydrophilic by the gum arabic and the treatment for removing the protein deposits by the protease are both necessary for the contact lenses to be worn on the eyes of the user. It would be considerably convenient to the user if the user can effect these treatments simultaneously in one step, rather than in different steps. In other words, the surfaces of the contact lens can be rendered hydrophilic while, at the same time, the protein adhering to the surfaces of the contact lens can be removed, in a single step of immersing the contact lens in a mixture of a solution containing the protease and a solution of the gum arabic which effectively gives the hydrophilic property to the contact lens.
However, a study by the inventors of the present invention revealed that such a contact lens solution containing the gum arabic and protease considerably deteriorates a cleaning effect to be exhibited by the protease, namely, an effect of the protease to remove the protein deposits by decomposition.

Contact lens cleaning solution and method for cleaning contact lenses using the same


In one embodiment, a PWM controller uses the input power of a power system to regulate a duty cycle of a switching PWM signal.

The present invention relates, in general, to electronics, and more particularly, to methods of forming semiconductor devices and structure.
In the past, the semiconductor industry utilized various methods and structures to form pulse width modulated (PWM) power supply controllers. PWM controllers generally were used in a power supply to regulate an output voltage to a desired value. In one configuration, the power supply controllers functioned as a voltage mode controller that used the value of the output voltage to form a closed loop regulation system. Some of these voltage mode controllers also incorporated voltage feed forward that utilized the value of the input voltage to assist in regulating the output voltage. One example of such a power supply controller was the UCC35701 that was supplied by Texas Instruments, Inc. of Dallas Tex. One problem was that these prior controllers only utilized the inductor current as a current limit in order to limit the maximum value of the current supplied to the inductor. Another problem was that oscillations or overshoots in the value of the output voltage may occur in response to transient conditions of the load current or transient conditions of the input voltage that was supplied to the power supply.
Accordingly, it is desirable to have a power supply controller which more accurately regulates the value of the output voltage in response to a change in the input voltage, in response to a change in the current required by the load, or in response to noise signals on the input voltage.
For simplicity and clarity of the illustration, elements in the figures are not necessarily to scale, and the same reference numbers in different figures denote the same elements. Additionally, descriptions and details of well-known steps and elements are omitted for simplicity of the description. As used herein current carrying electrode means an element of a device that carries current through the device such as a source or a drain of an MOS transistor or an emitter or a collector of a bipolar transistor or a cathode or anode of a diode, and a control electrode means an element of the device that controls current through the device such as a gate of an MOS transistor or a base of a bipolar transistor. Although the devices are explained herein as certain N-channel or P-Channel devices, a person of ordinary skill in the art will appreciate that complementary devices are also possible in accordance with the present invention. It will be appreciated by those skilled in the art that the words during, while, and when as used herein are not exact terms that mean an action takes place instantly upon an initiating action but that there may be some small but reasonable delay, such as a propagation delay, between the reaction that is initiated by the initial action.

Power supply controller and method therefor

Semiconductor Components Industries, L.L.C.


Methods and apparatus for protecting parts of a process chamber from thermal cycling effects of deposited materials. In some embodiments, a method of protecting the part of the process chamber includes wet etching the part with a weak alkali or acid, cleaning the part by bead blasting, coating at least a portion of a surface of the part with a stress relief layer. The stress relief layer forms a continuous layer that is approximately 50 microns to approximately 250 microns thick and is configured to preserve a structural integrity of the part from the thermal cycling of aluminum deposited on the part. The method may also include wet cleaning of the part with a heated deionized water rinse after formation of the stress relief layer.

Large scale integrated circuits (LSI) have long used aluminum as an interconnect material. When single layered wiring was used in LSI, the film thicknesses were about one micron. Advancements in technology, such as barrier metal layer use, allowed the film thicknesses to be reduced to about 0.3 micron to 0.6 micron. However, recently, the semiconductor industry has turned to requiring that the film thicknesses be increased from about 1.5 microns to about 6 microns or more in order to support advanced packaging technologies. As the film thicknesses increase, the target is depleted faster and process kit life is shortened, decreasing productivity. The inventors have observed that in aluminum deposition chambers producing increased film thicknesses, the process kit components required maintenance far more frequently than the target, causing additional downtime to replace the process kit components and then more downtime to replace the target at end of life.
Accordingly, the inventors have provided improved process kit component life, increasing production while reducing maintenance costs.

Methods and apparatus for prevention of component cracking using stress relief layer


The processor obtains a process time, which is a time taken for processing a control message when the control device requests that a target processing device, selected from among the plurality of processing devices, process a control message. When the process time has become longer than a first threshold, the processor determines which of a first and a second congestion has occurred based on whether the process time has become longer than a second threshold, which is greater than the first threshold. The first congestion occurs in the transfer devices used for a communication between the control device and the target processing device. The second congestion occurs in the target processing device. The network connection device transmits a request message requesting that a transfer route for which it has been determined that the control message is not processed in a device in which the congestion has occurred be set.

In recent years, Software Defined Networking (SDN), which is a technique used for constructing virtual network that uses software, has gathered attention. According to SDN, a device referred to as a controller controls devices (nodes) that transfer data in a network. For example, a node such as a switch in a network uses a transfer rule obtained from the controller so as to conduct a transfer process of a received packet. When an undefined packet, which it is not possible to process by using the transfer rule, has been received, the node reports the information of the received packet to the controller, and thereby obtains information for identifying the processing method for that packet from the controller. As described above, the controller controls transfer processes in a network in a centralized manner, sometimes making processes in the controller a bottleneck. Against this background, a controller system is proposed in which a plurality of controllers are included in a network and the plurality of controllers conduct processes as logically one controller.
FIG. 1 illustrates an example of a controller system. Nodes 6 (6a through 6i) included in a wide area network 3 conduct a transfer process of packets in accordance with a transfer rule obtained from a controller system 1. The wide area network 3 is connected to an arbitrary number of LANs such as Local Area Networks (LANs) 4a and 4b on an as-needed basis. The controller system 1 includes a controller cluster 8, a messaging system 5 and an application cluster 15. Control devices 2 (2a through 2d) include undefined packets received from the node 6 in control messages that are used in the controller system 1, and transfer the messages to a device in the messaging system 5. In the example illustrated in FIG. 1, the messaging system 5 includes transfer devices 10 (10a through 10c). Each of the transfer devices 10 transfers a message received from the control device 2 to processing devices 20 (20a through 20d) in the application cluster 15. The processing devices 20 process control messages and transmit the process results to the transfer devices 10 and the control devices 2, and the control devices control the nodes 6 in accordance with the process contents. Note that while the control device 2 is connected to the messaging system 5 in order to facilitate the understanding the illustration of FIG. 1, it is assumed that each control device 2 (2a through 2d) may access arbitrary transfer devices 10 in the messaging system 5. Similarly, it is assumed that each transfer device may access arbitrary processing device 20 in the application cluster 15. When it is assumed for example that the node 6a has transmitted an undefined packet to the control device 2a, the control device 2a includes the received undefined packet in a control message for internal processes and requests, via the transfer device 10a, that the processing device 20b conduct the process of the control message, and the processing device 20b transmits the process result to the control device 2a via the transfer device 10b. The control device 2a controls the node 6a based on the obtained process result, and the node 6a conducts a transfer process of the packet based on the control content.
Note that the controller system 1 illustrated in FIG. 1 is an example and the numbers of the control devices, the transfer devices and the processing devices included in the controller system 1 may change arbitrarily in accordance with implementations.
As related arts, the following documents are known.
[Non Patent Document 1] "Study of Distributed Network Controller and Development of Benchmark Tool for the Controller in SDN" by Shimizu Sho, Yamada Akiko and Somiya Toshio, The Institute of Electronics, Information and Communication Engineers, General Conference, Institute of Electronics, Information and Communication Engineers, BS-2-4, p. S130-131, March 2013[Non Patent Document 2] "Study on Scalable Messaging System for Distributed SDN Controller" by Shimizu Sho, Yamada Akiko and Somiya Toshio, IEICE Technical Report, The Institute of Electronics, Information and Communication Engineers, vol. 113, no. 472, NS2013-212, pp. 207-212, April 2014
In a controller system that uses a distributed network controller, transfer routes of messages and processing devices that process the messages are to be changed when congestion has occurred in a processing device or a transfer device included in the distributed network controller. However, because there is not a method of identifying the location at which congestion has occurred, it is not possible to resolve the congestion efficiently.

Route determination apparatus and transfer route determination method