This invention discloses a novel stable crystal form of imatinib mesylate, designated by us as α2 Form, which is stable at room temperature and even at higher temperatures up to 120° C. and accelerated stress conditions and, freely soluble in water. This invention also discloses a pharmaceutical composition containing the novel stable α2 form of Imatinib mesylate and other usually employed excipients, useful in the treatment of Chronic Myelogenous Leukemia (CML). This new α2 Form of imatinib mesylate is prepared by slurrying Imatinib base in isopropanol at room temperature followed by addition of methane sulfonic acid and maintaining 50-60 ° C. followed by filtration. This invention also discloses another process for the preparation of the novel, stable α2 crystalline form of Imatinib Mesylate by the conversion of Imatinib mesylate β-polymorphic modification by suspending it in water and organic solvents, distilling off water azeotropically, cooling and filtering to obtain the α2 crystal form.

Imatinib mesylate which is N-{5-[4-(4-methylpiperazino-methyl)-benzoylamido]-2-methylphenyl}-4-(3-pyridyl) 2-pyrimidine-amine, having the formula given above is approved under the trademark "Gleevec®" by the US Food and Drug Administration for the treatment of Chronic Myelogenous Leukemia before and after the failure of interferon alpha. It has also been approved for the treatment of patients with kit (CD117) positive unresectable and/or metastatic malignant Gastro Intestinal Stromal Tumors (GISTs). Recently it has been approved for the treatment of pediatric patients with Philadelphia chromosome positive (Ph+) Chronic Myeloid Leukemia (CML) in chronic phase. It is known that Imatinib mesylate exists in two polymorphic forms α and β (WO 99/03854).
In the said WO application it has been sated that the α form prepared is needle shaped and is hygroscopic. It has also been stated that in this form the crystals are not well suited for pharmaceutical formulations as solid dosage from because their physical properties for example, their flow characteristics are unfavorable. The applicants have also mentioned that under certain conditions however, it is possible to obtain a crystal form which is not needle shaped. This form, in the above patent is named as βform.
From the above given description regarding the α form it is very clear that the α form of Imatinib mesylate is not suitable for preparing formulations due to its: unsuitable physical characteristics and the form which is used is only the β form.
The said WO application also describes processes for the preparation of both the forms of Imatinib Mesylate. In the Examples 1 to 3 of the said patent the process for the preparation of Imatinib mesylate β-form has described using a maximum of 50 gms Imatinib base in solution.
In the Example-2 of the said patent a process has been described for the preparation of the β-form which involves suspending Imatinib base in methanol, adding methane sulfonic acid in methanol, heating to 50° C., followed by carbon treatment and distilling off methanol. Then dissolving the residue in minimum methanol and inoculation by some seeding crystals of Imatinib mesylate β-form.
The said WO application also describes processes for the preparation of both the forms of Imatinib Mesylate In the Example-1 of the said WTO application, the α-crystal form is prepared as follows:
Imatinib base was suspended in ethanol, methane sulfonic acid was added and heated under reflux for 20 minutes and than filtered at 65° C. The filtrate was evaporated down to 50% and the residue filtered off at 25° C. (filter material A). The mother liquor was evaporated to dryness. The residue and filter material A were suspended in ethanol dissolved under reflux with addition of water. Cooling overnight to 25° C., filtration and drying yielded Imatinib mesylate α-crystal form.
The above process for preparing α-crystal form suffers from the following disadvantages    a) In Examples 2 and 3 seed crystals of β-form are required to crystallize out the product    b) The process for preparing α-crystal form given under Example-1 is not reproducible. Repetition of the experiment exactly under identical conditions as reported in the above patent (WO 99/03854) resulted only in the α-form    c) Thus, there is currently no available process to prepare the α-crystal modification.
Important solid state properties of a pharmaceutical substance are its rate of dissolution in aqueous fluid. The rate of dissolution of an active ingredient in a patients stomach fluid may have therapeutic consequences because it imposes an upper limit on the rate at which an orally-administered active ingredient may reach the blood stream. The solid state form of a compound may also affect its behavior on compaction and its storage stability.
These practical physical characteristics are influenced by the conformation and orientation of molecules in the unit cell, which defines a particular polymorph form of a substance. The polymorphic form may give rise to thermal behavior different form that of the amorphous material (or) another polymorphic form.
Thermal behaviour is measured in the laboratory by such techniques as capillary melting point, Thermo Gravimetric Analysis (TGA) and Differential Scanning Calorimetry (DSC), and may be used to distinguish some polymorphic forms from others. A particular polymorphic form may also give rise to distinct properties that may be detectable by X-Ray Powder Diffraction (XRPD) solid state 13CNMR spectrometry and infrared spectrometry.
The various characteristics and properties of the polymorphic forms of a substance. e.g. shape, colour, density and the like, will make one polymorphic form preferable over the others for production and/or pharmaceutical compounding. As a result, a very first step in the processes of product development of a new pharmaceutical agent is the determination of whether it exists in polymorphic forms and if so which of such form possesses advantages for the eventual commercial pharmaceutical application. In the case of Imatinib mesylate, β form is offered commercially under the trade name Gleevec®/Glivec®.
In the patent mentioned above (WO 99/03854), β-form was selected over α-form based on the following observations and conclusions.    (i) β-form is thermodynamically stable at room temperature and at temperatures below 140° C. Greater stability of the β form is thus expected.    (ii) (β-crystal form is less hygroscopic than the α-crystal form.    (iii) α-crystal form is meta stable at room temperature    (iv) β-crystal has the advantage that its flow properties are substantially more favourable than those of that the α-crystal form.
Based on the above information, we undertook a detailed study of the solid state physical properties of the polymorphic forms of Imatinib mesylate. The presumption was that these properties may be influenced by controlling the conditions under which Imatinib mesylate is obtained in solid form.
Our detailed studies by carrying out research and development work on polymorphic forms of Imatinib Mesylate, and their processes for preparation surprisingly revealed the existence of another novel, stable polymorphic form of imatinib mesylate which we have designated as α2 form, having the below mentioned characteristics.
The novel α2 form of the present invention, can be prepared under certain specific conditions with improved physical properties such as greater stability and less hygroscopicity etc thereby making it suitable just like the β-form for commercial pharmaceutical applications.
Accordingly, we focussed our R&D efforts in taking up an elaborate study on the polymorphism of Imatinib Mesylate with particular reference to stable forms. Our detailed studies of the novel α2 form revealed that:    i. The novel α2-form is not meta stable and is stable at room temperature and even at higher temperatures like 120° C.    ii. The novel α2-form is stable at normal and accelerated stress conditions both in bulk and formulated capsule form.    iii. The novel α2-form is as freely soluble in water as is the β-form. The rate of dissolution of the α2-form in the formulation is comparable and even better than that of the β-form.    iv. The flow properties of the formulations prepared with the α2 form and β-forms are comparable as the same excipient composition is employed in both cases.
The above mentioned stable α2 form of imatinib Mesylate is not hither to known and is a novel polymorphic form. In addition, the form prepared by us now is also suitable for developing a pharmaceutical composition. Such a pharmaceutical composition containing α2 form is also not known and is novel.
Therefore, the main objective of the present invention is to provide a novel α2 crystalline form of Imatinib Mesylate which is stable at room temperature and even at higher temperatures like 120° C. and accelerated stress conditions, freely soluble in water and having the characteristics given in Table 1 given below
Another objective of the present invention is to provide a process for the preparation of novel α2 form of Imatinib Mesylate which is stable and less hygroscopic and water soluble having the characteristics given in Table 1
Yet another objective of the present invention is to provide a pharmaceutical composition useful for the treatment of Chronic Myeloid Leukemia containing the novel α2 form of Imatinib Mesylate which is stable and less hygroscopic and water soluble having the characteristics given in table 1.
Still another objective of the present invention is to provide an improved process for the preparation of β-polymorphic Imatinib mesylate.
Accordingly, the present invention provides a novel α2 crystalline form of Imatinib Mesylate which is stable at room temperature and even at higher temperatures up to 120° C. and accelerated stress conditions, freely soluble in water having the XRD characteristics given in the Table-I below.
TABLE IAngle[2-d-valueTheta]AngstromIntensity %4.84118.2405733.610.4108.49070100.011.1947.8977514.211.8567.4582719.912.8816.867096.813.8196.4032812.914.8605.9566367.716.4395.3878832.417.0495.196655.617.6235.0287058.618.0524.9100061.618.5674.7749198.819.0324.6592570.219.7724.4865715.321.2364.1805560.821.5824.1143159.422.5943.9321719.723.1373.8411221.823.6963.7517225.024.8513.5799358.626.2503.392269.127.3413.2593218.728.4753.1320442.431.8962.803479.032.5332.750056.643.4472.081176.4
According to another embodiment of the present invention there is provided a process for the preparation novel α2 crystalline form of Imatinib Mesylate which is stable at room temperature and even at higher temperatures like 120° C. and accelerated stress conditions, freely soluble in water and having the characteristics given in Table 1 which comprises suspending Imatinib base in isopropanol and adding methane sulfonic acid at room temperature and maintaining the reaction mixture at a temperature in the range of 40-80° C., for a period in the range of 20-30 minutes, cooling and filtering to obtain the α2 crystal form.
According to yet another embodiment of the invention there is provided another process for the preparation of novel α2 crystalline form of Imatinib Mesylate which comprises converting Imatinib mesylate β-polymorphic modification which comprises suspending β-polymorphic it in water and organic solvents like methanol, Isopropyl ether, toluene, cyclohexane and Isopropyl alcohol, distilling off water azeotropically and, cooling filtering to obtain the α2 crystal form.
According to stiff another embodiment of the present invention, there is provided a pharmaceutical composition useful for the treatment of Chronic Myeloid Leukemia which comprises novel α2 form of Imatinib Mesylate which is stable and less hygroscopic and water soluble having the characteristics given in table 1 and a commonly employed pharmaceutically acceptable excipients.
According to another embodiment of the present invention there is provided an improved process for the preparation of β-polymorphic form of Imatinib mesylate which comprises suspending Imatinib base in a solvent selected from acetone, acetonitrile, mixture of methanol and isopropanol and mixture of isopropanol and water and adding methane sulfonic acid to the resulting solution at room temperature and maintaining the solution at the reflux temperature of the solvent (or) at room temperature and filtering the β-crystal form.
It is to be noted that the α2 form of Imatinib mesylate prepared by the process of the present invention does not substantially convert over time to form β, either as such in bulk form or after formulation in the dosage form, upon storage at about 40° and about 75% relative humidity for at least about 6 months.
Determination of presence of imatinib mesylate form-β in Imatinib mesylate α2-form prepared by the process of the present invention may be made by analysis for the presence of various peaks associated with form-β particularly at 9.7, 13.9, 18.2, 20.0, 20.6, 21.1, 22.1, 22.7, 23.8, 29.8, 30.8±0.2 degree 2θ. (WO99/03854).
FIG. 1 of the drawings accompanying these specifications shows the X-Ray Powder Diffraction (XRPD) pattern which substantially depicts a typically pure sample of Imatinib Mesylate of α2-form prepared by the process disclosed in the Example-1 given below. The 2θ values and intensities are tabulated in Table-1.
The other figures correspond to the data as detailed below:—
FIG. - 1XRD spectrum of the novel α2 formFIG. - 2IR spectrum of the novel α2 formFIG. - 3DSC thermogram of the novel α2 formFIG. - 4XRD spectrum of the novel α2 form capsules stored for6 months at 40° ± 2°/75 ± 5% (Table-5)FIG. - 5XRD spectrum of β form prepared by he process of theinventionFIG. - 6XRD spectrum of β form form prepared by he process ofthe inventionFIG. - 7XRD spectrum of β form form prepared by he process ofthe inventionFIG. - 8XRD spectrum of β form form prepared by he process ofthe invention
The dosage form of the formulation containing the novel, stable α2 form prepared by the process of the present invention, preferably oral dosage form, may be a capsule containing the composition preferably a powdered on granulated solid composition, within either a hard (or) soft shell. The shell may be made from gelatine and optionally contains a plasticizer such as glycerin and sorbitol and an opacifying agent (or) colorant.
Methods known in the art, may be used to prepare the pharmaceutical composition containing Imatinib mesylate α2 form in the form of capsules. The excipients which may be employed include micro crystalline cellulose, lactose, crospovidone XL, colloidal silicondioxide magnesium stearate and talc
Table-2 shows suitable ranges of active ingredients and excipients (weight %) and the preferred amounts for the present pharmaceutical formulations.
TABLE 2Pharmaceutical compositions containing Imatinib Mesylate α2-formRange of %compositionPreferred %S. No.Material(w/w)compositionFunction1.Imatinib mesylate45-60%53Activeα2-formingredient2.Micro crystalline15-25%21Filler andcellulosedisintegrant3.Lactose10-20%13Diluent4.Crospovidone XL 5-10%8.7Disintegrant5.Magnesium stearate1-2%1.3Lubricant6.Talc0.5-1.0%0.80Glidant7.Colloidal Silicon1.5-2.5%2.20Glidantdioxide
Table-3 shows two typical examples of the capsule formulation containing Imatinib Mesylate α2-form and their dissolution and stability characteristics.
TABLE 3PHARMACEUTICAL COMPOSITIONS CONTAININGIMATINIB MESYLATE α2-FORMDissolution and stability characteristicsComposition (%)Composition (%)MaterialB. No. 001B. No. 002Imatinib mesylate α2-form5053Microcrystalline cellulose2521Lactose1213Crosporidone XL68.7Magnesium stearate1.51.3Tale0.50.80Colloidal silicon dioxide2.02.2Dissolution rate85% (10 min)85% (10 min)90% (20 min)90% (20 min)100% (45 min) 100% (45 min) Stability1. stable at1. stable at40° ± 2° C. and40° ± 2° C. and75 ± 5% RH75 ± 5% RH2. stable at2. stable at25° ± 2° C. and25° ± 2° C. and60 ± 5% RH60 ± 5% RH
Inference: Two typical batch formulations of Imatinib α2-form are prepared. The dissolution and stability characteristics indicate that α2-form has excellent formulation characteristics.
Table-4 shows the heat stability of α2 form over the temperature range 110-120° C. The α2 form is shown to be non-metastable and stable when heated at 120° C. for 6 hours.
Stability of α2-Crystal Form
Pure α2-crystal polymorph 1 gm prepared by the process described in Example 1 was taken in a boiling test tube and heated gradually in oil bath the substance was examined by XRPD. The results are tabulated below
TABLE 4PolymorphTime ofPolymorphcontent*heatingform detected*before hatingTemperature(hours)after heatingα2 form110° C.2α2 formα2 form110° C.4α2 formα2 form120° C.2α2 formα2 form120° C.4α2 formα2 form120° C.6α2 form*The presence of form-β was below the detection level in these examples.
Inference: The α2 form of Imatinib mesylate is not metastable.                It is fairly stable to heat even at 120° C./6 hours.
Table-5 shows the stability of α2 form under accelerated stress conditions (45±2° C., 75±5% RH, 6 months) in the bulk and capsule formulation
TABLE 5Stability of α2 form of Imatinib mesylate in bulk andformulated capsulePolymorph content* ofPolymorph content*imatinib mesylate inof bulkformulated capsuleimatinib mesylateDuration of storagePolymorph formPolymorph form(months) atdetecteddetected40 ± 2° C./75 ± 5% RHα2 formα2 form0 Month α2 formα2 form1 Month α2 formα2 form2 Monthsα2 formα2 form3 Monthsα2 formα2 form6 Months(XRPD FIG. - 4)*The presence of form-β was below the detection level in these examples showing that α2 form is not converted to β-form over a time period. The stability of α2 form in bulk and in the formulated capsule is thus established.
Table-6 shows comparative dissolution data of Imatinib capsule formulation containing α2 form and β-form. The formulation with α2 form is found to have better dissolution characteristics.
TABLE 6Comparative dissolution data for Imatinib mesylate capsules 100 mg*(α2 and β-forms)Test parameters1.Dissolution medium0.1 N HCl2.Dissolution volume900 ml3.RPM (Revolutions Per Minute)504.Wave length240 nm(for assay determination)Imatinib mesylateImatinib mesylate(β-crystal form)(α2 crystal form)Release profilecapsules 100 mgcapsules 100 mg 5 minutes32.6%61.3%10 minutes54.4%85.5%15 minutes69.4%90.5%20 minutes78.2%92.6%30 minutes95.8%98.0%45 minutes100.0%100.0%                The capsules contain Imatinib Mesylate equivalent of 100 mg of Imatinib base. The excipients are as per the Example-7
Inference: The release profile and dissolution data show that the capsule formulation with α2-form is better than the formulation with β-form.
Storage of capsule containing pure Imatinib mesylate α2 form prepared by the process of the present invention at about 40° C. and about 75% relative humidity for 6 months, does not show any significant conversion to β-polymorphic form of Imatinib mesylate preferably less than about 5%. The detection of Imatinib mesylate form-β in a pharmaceutical formulation to the extent about 1% w/w or more may be accomplished by use of x-ray powder diffraction.
The pharmaceutical formulations containing the novel, stable α2 form prepared by the process of the present invention are useful in the treatment of Chronic Myelogenous Leukemia. The oral pharmaceutical dosage forms preferably contain about 100 mg of the base equivalent.
The preparative aspects, physical and functional properties of novel Imatinib mesylate α2 form prepared by the process of the present invention are compared with the properties of α form described in the prior art (WO 99/03854) and tabulated in Table-7. The tabulated data clearly demonstrates the stability and functional superiority of the novel α2 polymorph of the present invention over the α polymorph described in WO 99/03854.
TABLE 7A COMPARATIVE ACCOUNT OF IMATINIB MESYLATE α-FORMKNOWN IN PRIOR ART AND THE NOVEL α2 FORM OF CURRENTINVENTIONLiterature α formPresent inventionS. No.PropertyWO 99/03854α2 form1.Method ofPreparation reported inThe method results in novel andpreparationethanol solvent. Howeverstable α2 form consistently inmethod not reproduciblehigh purity and yield.yielding β-form only2.Melting point226° C.223-227° C.3.Differential scanning226° C. (start of melting)225-227° C. Peak 227°thermogram4.XRDSpectrum scan given 2θSpectra given in FIGS. 1& 4values not listedPrincipal 2θ values 4.9, 10.4,14.9, 16.4, 17.6, 18.6, 19.1,21.2, 24.6, 24.9, 28.55.Crystal shapeNeedle shape (Not freeNon-needle shaped free-flowingflowing)crystals6.HygroscopicityHygroscopicNon-hygroscopic7.DissolutionNot mentionedDissolves freely in watercharacteristicDissolution of more than 95%during 30 min in capsuleformulation8.Flow propertiesNot well-suited toFound to be well suited forpharmaceutical solidpharmaceutical formulations asdosage formssolid dosage forms.9.StabilityMetastable at roomStable at room temperature andtemperatureeven at 120° C.
The details of the invention are provided in the Examples given below which are provided to illustrate the invention only and therefore they should not be construed to limit the scope of the invention.

Polymorphic form of imatinib mesylate and a process for its preparation


A method includes receiving a light beam propagating along an optical path, converting, using a first diffractive element, a first portion of the light beam into a first circularly polarized beam, and a second portion of the light beam into a second circularly polarized beam. The method also includes converting, using a second diffractive element, the first circularly polarized beam into a first circularly polarized output beam, and the second circularly polarized beam into a second circularly polarized output beam.

Image displays, including near-eye displays, have been utilized in virtual reality and augmented reality systems. Typically, the resolution and field of view of the image, as well as the eyebox size, are system parameters of interest. Despite the progress in the area of optical systems, there is a need in the art for improved methods and systems related to image display systems.

Method and system for eyebox expansion in display systems


A credit/service card with expanded surface area comprises a first card member, a second card member and a hinge connecting the two card members. The credit/service card also comprises a fastener for holding the first and second card member together when the credit/service card is in the closed position.

The present invention relates to credit/service cards and methods of use of credit/service cards. In particular, the present invention relates to credit/service cards with expanded surface area for the recording and displaying of information.
In today's world credit/service cards are in wide use. It is estimated that a typical American household may have as many as three or four different credit/service cards. Credit/service cards may be used for a variety of purposes including purchasing goods or services without using cash, charging a telephone call at a public telephone, or withdrawing money from, or depositing money into ones bank account.
Referring to FIGS. 1 and 2, there is depicted a prior art, or conventional, credit/service card 30. The credit/service card may contain on its front surface 32 various data including an account number 34, the holder's name 36, the expiration date 38, one or more reference numbers 40, 42, the name of the issuing company 44, and a logo or indication of the type of card 46. Some of this information may be embossed on the card's face. The credit/service card may also contain a hologram 48 to prevent tampering with or unauthorized duplication of the credit/service card. The back 50 of the credit/service card 30 may contain a variety of other information (including a photograph of the card holder) in any open space available 52. The credit/service card also may have a magnetic strip 54 that contains magnetically recorded information which is able to be read by magnetic card readers, telephones, and/or ATM machines at various locations for verification of credit, account balance/information, validity, or possibly obtaining other information about the user. The back of the credit/service card 38 may also contain a signature strip 56 with the holder's signature. The back surface 50 of the credit/service card may contain various important data 52, for example the account number, rules relating to use of the card, additional logos of the card type, telephone numbers and/or addresses to report loss of the card, telephone numbers and/or addresses for billing inquiries, other telephone numbers needed by the user, and/or instructions for use of the card.
A standard size credit/service card has a length of about 3.375 inches, a width of 2.125 inches and a thickness of approximately 0.030 .+-.10% inches. As can be seen this prior art credit/service card has only two faces or surfaces 32, 50 for the inclusion of information.
Similar credit/service cards are issued by telephone companies for charging telephone calls from remote locations. These cards may include some of the same elements, including the magnetic strip and the information on the front of the card. Additionally, the typical telephone charge card includes information on the back surface of the card for charging telephone calls and dialing information. In some public telephones, the user can slide the card through a slot in the telephone in order to charge calls on his telephone card. This type of telephone is capable of reading the magnetic strip, verifying the caller's credit/service, and charging the caller's account.
Typically, ATM machines use cards of the size and shape described for credit/service cards. These cards are used for snowing a user to withdraw money from, or deposit money into, and/or obtain balance information from her bank account. These cards may also be used to transfer money between accounts. As with the normal credit/service card, there is typically a magnetic strip placed along the back of the ATM card which is read upon placing the A.T.M. card into a bank teller machine. The bank teller machine may withdraw the card into the machine so that the card may totally disappear from the user's view while the transaction is being processed.
Increasingly, credit/service card companies are offering more and more services that can be charged on a single, credit/service card or services that are given complimentary for using the credit/service card. Some of these services may be termed "credit card enhancements" and may include for example, life/travel insurance, automobile servicing, automobile rental insurance, and/or replacement of lost items that are purchased with the credit/service card. Credit/service cards issuers may offer a combination of services to be used with one card such as charging longdistance calls, automobile club membership, and at the same time charging typical items, for example retail store purchases, purchases of services, and restaurant purchases. Combining the functions and benefits of many different cards into a single card may alleviate the need to carry multiple cards.
Also, membership and other types of cards may be combined with conventional credit/service cards and a photograph of the holder may be added for identification purposes. For example, a card may double as a membership card and a credit card, or a telephone card and a credit card, or a store charge card and a credit card, or any combination or all of the above. In order to effectuate these multipurpose cards, more surface area is needed on the card for the printing of information, such as telephone numbers, instructions, photographs, and other items needed to use the offered services. The additional information may include "800" telephone numbers, instructions for or codes needed to use certain services, and other essential data.
One solution to this problem might be to change the size and dimensions of the conventional credit/service card so that more information can be placed on the resultant expanded surface area. This solution may not be advantageous in that there exists hundreds of thousands of magnetic credit/service card readers at point of sale locations which read the magnetic strip by sliding the credit/service card through a slot in the credit/service card reader. Also, other equipment exists for other uses such as ATM machines and public telephones which may require a certain standard size card.
Typically, the merchant takes the card and runs it through a slot in a small machine that reads the magnetic strip, typically on the back surface of the credit/service card. In order to be able to be used in the machine, the credit/service card must be no greater than a predetermined maximum thickness so that it fits through the existing slot. Public telephones may have similar sized slots to read the card. And, as described above, ATM machines may withdraw the whole card into the machine for processing. Furthermore, current wallets and purses are made to hold conventional size credit/service cards. Therefore, it is highly desirable that any new type of credit/service card be able to fit and be read in the existing machines used for scanning and reading magnetic information on these cards.
Because of the increasing number of uses that a single credit/service card may have, a need exists for any improvement in the credit/service card to result in a product the same size as existing credit/service cards so that it may be read by existing machinery and held in existing holders and wallets, and which has the same dimensions as a typical credit/service card.
It is an object of the present invention to provide a credit/service card with qualities that are desirable among credit/service cards generally and that is also able to have more printed, readable, material placed thereon.
It is a further object to provide a credit/service card containing an increased amount of surface readable information and which is still able to be used in the existing credit/service card equipment.

Credit/service card with expanded surface area


A small-sized food chopper for chopping up foodstuffs, includes an outer case including a lower casing removably connected with an upper casing and a button mounted on the upper casing; a blade connection holder installed inside the outer case, the blade connection holder can move axially up and down in the outer case; a plurality of blades installed on the lower end of the blade connection holder; a reset spring sheathed on the blade connection holder which restores the blade connection holder axially up; a mechanism which makes the blade connection holder rotate a predetermined angle circumferential each time the blade connection holder operates axially; the button is configured such that it can slide up and down axially, and the button acts on the upper end of the blade connection holder to make the blade connection holder move axially downwardly.

1. Field of the Invention
This invention relates to a small-sized food chopper, and more particularly, to a small food chopper for chopping up foodstuff.
2. Description of the Related Art
Food choppers mainly use a handle to connect itself with a reset spring and further control a W-shaped blade, the foodstuff is repetitively cut by repetitively pushing down the handle, and each time the handle is pushed down, the handle, together with the W-shaped blade will rotate a certain angle so that the foodstuff is chopped up by the blade. There are two designs in the prior art technology: one is an apparatus with a stainless steel outer case completely wrapping the interior parts, comprising a reset spring, a W-shaped blade and a through shaft with inside sprocket. However, this design has a defect, for the whole food chopping apparatus is hidden in the stainless steel outer case, and thus it is rather difficult to cleanse it each time after chopping up the foodstuff. In addition, this known technical design has other defects, besides its large volume, which occupies a relatively large space, although the material of this design is mainly stainless steel, many interior parts are made of metal, therefore, after a long period of use, it contaminates the foodstuff due to the rusting problem, which is a problem that cannot be neglected.
Besides, another designing method is an apparatus with a plastic outer case wrapping the interior parts; comprising a lower half handle, a W-shaped blade and a through shaft with inside sprocket, whereas the upper half handle and the reset spring are exposed. However, this design has a defect: the exposed reset spring is more prone to damage, which renders the food chopper not durable enough; although the food chopper uses a plastic outer case instead, many other parts are still made of metal, and thus the rusting problem of the food chopper still exists; in addition, the principles of the rotation of the aforesaid two food choppers are both that: the handle which is on the through shaft with inside sprocket is pushed down, and when it is raised and returns to the original state, the pit lines on the handle of this portion will be shifted from one sprocket tooth inside the through shaft to another sprocket tooth next to it so as to achieve the rotation effect; however, this design will result in the parts in charge of rotation and the parts in charge of the pushing-down action locating at the same place and thus affecting each other, wherein the biggest problem is that when the handle is pushed down and when it begins to rotate and rise, the handle will readily be stuck and thus cannot successfully accomplish the whole chopping process.


The invention relates to a mask and a method of fabricating the same. When a mask pattern is formed using E-Beam, the size of the divisional region obtained by a fracturing process can not be formed equally. Therefore, the uniformity of the mask pattern is degraded. In order to form the divisional region to be of equal sizes, the method includes performing a fracturing process by adding a subsidiary pattern to divide a region except for mask pattern, thereby obtaining a mask pattern having excellent uniformity and reducing defects of semiconductor devices.

The invention relates generally to a method for fabricating a semiconductor device, and more specifically, to a method for performing a fracturing process by adding a subsidiary pattern to divide a region excluding a mask pattern.
In the case of semiconductor devices such as DRAM, a technique is required to add additional transistors in a limited region to improve integration. Accordingly, a vertical transistor as an element included in high integrated memory cells generally having an area of 4F2 has been suggested. The vertical transistor provides a surrounding gate structure that surrounds a vertical channel.
In order to form the surrounding gate in an area of 4F2, a channel region is selectively, isotropically-etched so that the channel region is formed to be thinner than source/drain regions, thereby obtaining excellent device characteristics. As a result, the vertical transistor can use the limited space more efficiently. The vertical transistor has been highlighted as a transistor for use in various applications such as DRAM where fabricating smaller transistors is optimal.
The vertical transistor is an effective means to improve a short channel effect because a given channel length can be maintained even in a reduced device area. Particularly, the surrounding gate can maximize controllability of the gate, thereby improving the short channel effect and providing excellent operating current characteristics because the current flowing area is broad. As a result, in order to increase the integration, the vertical transistor requires a thinner and longer structure.
In the memory cell having a Critical Dimension (CD) of less than 50 nm, the width of the CD of a pillar of the vertical transistor is narrow, so that it is difficult to fabricate a mask that defines the CD of the pillar.
FIG. 1 is a top view illustrating a conventional mask.
Referring to FIG. 1, a pillar pattern 20 is formed over a mask 10 including a transparent substrate 15. After forming a chrome layer over the transparent substrate 15, the pillar pattern 20 is obtained by removing a portion of the chrome layer by irradiation with electric beams into a region of the chrome layer excluding the pillar-pattern-expected region. This process is called a fracturing process. However, the CD uniformity of the pillar pattern 20 is remarkably reduced due to high-integration of semiconductor devices.
FIG. 2 is a top view illustrating a conventional method of fabricating a mask.
Referring to FIG. 2, divisional regions are numbered in order of the fracturing processes. The divisional region "1", the divisional region "2", the divisional region "3", and the divisional region "4" each have different shapes, which results in each having a different irradiation degree of E-Beam. As a result, the uniformity of the pillar pattern 20 is reduced.
Specifically, E-Beam is irradiated once on the left and right sides of the divisional region "2" of the chrome pattern element A. However, E-Beam is irradiated twice on the left and right sides, respectively, of the divisional region "2" of the chrome pattern element B. As a result, the lithography number is different in the peripheral divisional regions of the chrome pattern element A and the chrome pattern element B.
As a result, the non-uniformity of the pattern is generated by a difference in sizes of the divisional regions.
FIGS. 3 and 4 are micrographs illustrating defects of a semiconductor device formed using a conventional mask.
Referring to FIGS. 3 and 4, a photoresist pattern formed using a mask having reduced uniformity as shown in FIG. 2 shows multiple occurrences of a defect, that is, a bridge phenomenon between the photoresist patterns.
FIG. 5 is a simulation diagram illustrating the CD non-uniformity of the semiconductor device formed using the conventional mask.
Referring to FIG. 5, the diagram shows that the color is differentiated in each CD of the pillar pattern formed over the mask. A CD of the pillar pattern is changed depending on the exposed region.
FIG. 6 is a graph illustrating CD non-uniformity of a conventional mask.
Referring to FIG. 6, the graph shows the simulation results of FIG. 5 and compares the change in the CD of the pillar pattern 20 depending on locations of the pillar pattern 20 formed over the mask.
As mentioned above, when the divisional regions of the fracturing process are defined differently in formation of a mask for manufacturing a semiconductor device, the uniformity of the mask pattern that defines the semiconductor device is reduced. As a result, when a semiconductor device is manufactured with a mask having non-uniformity, defective patterns are generated, thereby degrading yield and reliability of the semiconductor device.


The data interface device accesses a memory operating in synchronization with a clock. A board clock and selective data capturing improve the operating rate of a memory interface and time-synchronize data flow from memory to memory controller with a internal clock produced by the memory controller; or time-synchronize data flow from the memory controller with the board clock. The internal clock is passed through a sequential path of an output pad of the memory controller, the memory, and an input pad of the memory controller and then re-inputted into the memory controller thereby the feedback clock is generated. The selective data capturing uses a register part for storing data inputted into the memory controller. The register part for storing the data is configured by double registers that are operated in an alternative manner according to a correlation between the inputted data and the feedback clock.

1. Field of the Invention
The present invention relates to a data interface device for accessing an SDRAM (Synchronous Dynamic Random Access Memory), and more particularly to a data interface device for accessing an SDRAM that can address a phase problem between a clock and data incurable at a high-speed SDRAM access time.
2. Description of the Related Art
FIG. 1 is a schematic diagram illustrating a typical connection state of a data bus and a clock for an SDRAM (Synchronous Dynamic Random Access Memory) interface. A timing diagram associated with FIG. 1 is shown in FIG. 2. Input PADs 3 and 5 and output PADs 4 and 6 are provided between an SDRAM 1 and a memory controller 2. As shown in FIG. 2, it can be seen that a board clock is measured between the PAD 3 of the SDRAM 1 and the PAD 6 of the memory controller 2, and that board DATA is measured between the PAD 4 of the SDRAM 1 and the PAD 5 of the memory controller 2. That is, when an internal clock is outputted from the PAD 6 of the memory controller 2, and then changed to a board level signal, it can be seen that data inputted to the memory controller 2 has larger delay in comparison with the internal clock produced by the memory controller 2. This delay can be different according to various elements such as voltage, temperature, board state, etc. FIG. 3 shows larger delay as compared with FIG. 2. The SDRAM 1 outputs data at a rising edge of the board clock. Here, the board clock is the same as the board level signal based on the internal clock. As shown in FIGS. 2 and 3, as a phase of the board clock for driving the SDRAM 1 is slower than a phase of the internal clock, data outputted from the SDRAM 1 synchronized with the board clock and then inputted to the memory controller 2, has larger delay in comparison with the internal clock.
When delay of a signal such as a clock or data is large, a time point of inputting internal DATA into the memory controller 2 can be the same as a time point of a rising edge of the internal clock as indicated by "V" in FIG. 3. That is, when the internal DATA is used with the internal clock, setup or hold violation can be incurred. To prevent this violation, there is present a method using a negative edge of the internal clock. However, the method has a problem in that data may be inputted at a time point of the negative edge of the internal clock as delay in the method is smaller than delay in FIG. 3.
That is, this phenomenon occurs because a relationship between the internal clock and the data input is asynchronous. When the phenomenon cannot be removed, an operating frequency must be lowered according to an operating state, such that the lowered operating frequency may have a negative effect on the performance of a device.
In many methods for preventing the negative effect, a DLL (Delay Locked Loop) circuit 7 is used as shown in FIG. 4. When the DLL circuit 7 is used, externally inputted data can be predicted to some degree because an external clock (i.e., a board clock) and an internal clock can be matched to each other. Consequently, the above-described asynchronous problem can be avoided. In particular, there are problem in that a design of the DLL circuit 7 requires complicated technology differently from general circuits and it is very difficult for replica delay in PADs, pins, etc. to be predicted.

Data interface device for accessing memory


The present invention provides a poker game playing method wherein multiple five-card hands from once previously shuffled 52-card poker deck can be played without increasing probabilities against a casino, while maintaining maximum entertainment value, and with immediate certainty of winning or losing. The method of the present invention maximizes entertainment value derived from the poker deck by rewarding a gambler with free five-card hands when there had been five-card hand winning combinations, wherein the rewarding free five-card hands are from the remaining un-played cards of said same poker deck, thus, without increasing chances against a casino or gaming house, and wherein a gambler may have a false impression of increased probabilities in his favor because of the rewarding free five-card hands, therefore increasing his gambling desire to start anew waging against newly shuffled 52-card poker decks.

1. Field of the Present Invention
The field of the present invention relates to a method of playing a poker game wherein a 52-card deck entertainment value is maximized without increasing the probabilities against a gaming house or casino.
2. Description of the Prior Art
Ways or methods to play a poker game are many. However, there is no description of playing multiple five-card hands from just one previously shuffled 52-card poker deck, wherein the probabilities against a casino do not increase, while maintaining maximum entertainment value.
By way of example, U.S. Pat. No. 6,638,163 to Moody describes a poker game that start with a poker deck, and an incentive component derived from a complete newly shuffled poker deck, thus, renewing or duplicating the gambler probabilities against a casino. Other examples are U.S. Patent Application No. 20060267283A1 by Jackson, U.S. Pat. No. 5,908,353 to Andrews, U.S. Pat. No. 5,845,907 to Wells, U.S. Patent Application No. 20060157936A1 by Moody, U.S. Pat. No. 6,131,907 to Nucifora, etc.
The present invention provides a poker game playing method that overcomes the mentioned limitations of the prior art.


Disclosed herein are a method of localization by synchronizing multi sensors and a robot implementing the same. The robot according to an embodiment includes a controller that, when a first sensor acquires first type information, generates first type odometry information using the first type information, that, at a time point when the first type odometry information is generated, acquires second type information by controlling a second sensor and then generates second type odometry information using the second type information, and that the robot by combining the first type odometry information and the second type odometry information.

A large-scale retail store, a department store, an airport, a golf course, and the like are places where exchange of goods and services takes place between people. Robots may be useful in the places to offer information or convenience to people.
Robots may be classified as guide robots, security robots, cleaning robots and the like. The robots move in a space, confirming their positions.
The robots are required to holding information on a space, on their current positions, on a path previously moved by the robots and the like such that the robots move confirming their positions and avoiding obstacles.
The robots may store maps to confirm a space and to move in the space. To generate a map, the robots may draw up a map using a variety of sensors, and may match and store various pieces of information in the map.
Additionally, after the robots store a map, comparison between information of the map and information acquired by the robots during movement of the robots is required to localize the robots using the map. That is, the robots may perform localization in which a position of a robot is estimated as a result of comparison between the information of the map and the information acquired by the robots during movement of the robots.
When multiple sensors are used to enhance accuracy of localizing the robot, it takes time to use information acquired by the sensors for localization. In this case, when it takes a long time to use the information for localization or when there is a difference in time between the sensors, accuracy of localization may be reduced. Accordingly, there is a growing need for a method of resolving the above-described problem.

Method of localization by synchronizing multi sensors and robot implementing same


A polymer comprising a structural unit represented by the formula (Ia) or (Ib):

A chemically amplified resist composition used for semiconductor microfabrication employing a lithography process contains an acid generator comprising a compound generating an acid by irradiation.
In semiconductor microfabrication, it is desirable to form patterns having high resolution and good pattern profile, and it is expected for a chemically amplified resist composition to give such patterns.
U.S. Pat. No. 5,968,713 A discloses a chemically amplified resist composition comprising a resin which comprises a structural unit derived from 2-methyl-2-adamantyl methacrylate.
U.S. Pat. No. 6,239,231 B1 discloses a chemically amplified resist composition comprising a resin which comprises a structural unit derived from 2-alkyl-2-adamantyl methacrylate and a structural unit derived from 3-hydroxy-1-adamantyl acrylate.
US 2005/0100819 A1 discloses a chemically amplified resist composition comprising a resin which comprises a structural unit derived from 2-isopropyl-2-adamantyl methacrylate, a structural unit derived from 3-hydroxy-1-adamantyl acrylate and a structural unit derived from 5-acryloyloxy-2,6-norbornenelactone.
WO 2007/046388 A1 discloses a chemically amplified resist composition comprising a resin which comprises a structural unit derived from 1-ethyl-1-cyclohexyl methacrylate, a structural unit derived from 3-tert-butoxycarbonyloxy-1-adamantyl acrylate and a structural unit derived from α-acryloyloxy-γ-butyrolactone.

Polymer and chemically amplified resist composition comprising the same

Abstract: wherein R1 represents a hydrogen atom etc., R2 represents a linear, branched chain or cyclic C1-C8 alkyl group, R3 represents a methyl group, n represents an integer of 0 to 14, Z1 represents a single bond etc., k represents an integer of 1 to 4, R4 and R5 each independently represents a hydrogen atom etc., and m represents an integer of 1 to 3, a structural unit represented by the formula (II):

Abstract: wherein R6 and R7 each independently represents a hydrogen atom etc., R8 represents a methyl group, R9 represents a hydrogen atom etc., n′ represents an integer of 0 to 12, Z2 represents a single bond etc., k′ represents an integer of 1 to 4, R21 and R22 each independently represents a hydrogen atom etc., and R23 represents a C1-C30 monovalent hydrocarbon group, andat least one structural unit selected from the group consisting of structural units represented by the formulae (IIIa), (IIIb), (IIIc), (IIId) and (IIIf)

Abstract: wherein R10 represents a hydrogen atom etc., R11 represents a methyl group, R12 is independently in each occurrence a carboxyl group etc., j represents an integer of 0 to 3, a represents an integer of 0 to 5, b represents an integer of 0 to 3, c represents an integer of 0 to (2j+2), Z3 represents a single bond etc., and k″ represents an integer of 1 to 4.


A conveying device having individually controllable grippers conveys the printed products in the conveying direction to a straightening station where the printed products are aligned. Subsequently, for opening, the folded printed products are fed to an opening device with their open edge leading and are then conveyed further to a transfer region, which is spaced apart from the opening device, for depositing on the rests. The separation of the different functions, i.e. the alignment, the opening and the depositing of the printed products allows simple setting to different formats of the printed products to be processed. Between the opening device and the transfer region, the open printed products are held open by a holding-open device.

This invention is related to U.S. patent application Ser. No. 07/895,081, entitled "Method And Apparatus For Processing Printed Products", filed concurrently herewith.
The present invention relates to a method and an apparatus for opening folded printed products and depositing them on a saddle-type rest and more particularly to a method and apparatus for opening folded printed products and depositing them on saddle-type rests wherein the products are conveyed by individually controllable grippers of a conveying device.
An apparatus of this type is described, for example, in Swiss Patent Specification 667,859. In the disclosed arrangement, each of the printed products are held securely against rotation in the central region of the fold by a gripper of a conveying device. The printed products are also compressed by means of a pusher element which acts on an end region of the fold. An opening strip is introduced between the halves of the printed products starting from the compressed fold. The opening strip is moved along the relevant side edge of the printed products to the region of the open edge opposite the fold to separate the two halves from one another. In order to hold the printed products securely against rotation, the grippers have two clamping fingers which are each controllable independently of one another and a clamping jaw which interacts with both clamping fingers. In order to further open the printed products which have previously been opened by means of the pusher element and the opening strip, the clamping finger closer to the pusher is moved into its open position. The relevant printed product is then rotated about the clamping point between the other gripper and the clamping due to the effect of the pusher element. The rotation thus causes printed product to be positioned obliquely. One half of the printed product is then introduced into an opening cam of an opening device in the region of the corner of the printed product which is now leading due to the oblique positioning. The opening cams are rotationally or circularly driven around a wheel which is rotatable about an axle and which runs perpendicular to the conveying direction of the printed products. By deflecting the opening cam around the wheel, the half of the printed product held by the relevant opening cam is separated from the other half starting at the open edge. During this separation, a saddle-type rest of a drum-type collecting device is introduced from below between the two halves of the printed product. After the relevant opening cam has opened, the two halves of the printed product grip around the saddle-type rest from above. The relevant gripper of the conveying device is then opened causing the printed product to drop astride this rest. The opening device of this arrangement is thus located in the transfer region of the printed products to the rests and is actively involved in the transfer.
Similar devices, in which the printed products, however, are not placed obliquely for introduction into the opening cams of the opening device, are disclosed in EP-A-0,341,425 or the corresponding U.S. Pat. No. 5,052,667, EP-A-0,208,081 or the corresponding U.S. Pat. No. 4,684,117 or DE-A-3,620,945 or the corresponding U.S. Pat. No. 4,684,116. The common factor in all of the devices disclosed in these references is that the opening devices are arranged in the transfer region of the printed products to the rests and, due to the opening of the printed products, are themselves actively involved in the depositing operation during the insertion of the rests between the opening printed products. When changing over to printed products of different formats, these known devices require considerable expenditure since all of the components involved in opening and depositing have to be coordinated with one another.
Therefore, a primary object of the present invention is to provide a method and apparatus of the type described above but wherein setting the printed products to be processed to other formats is greatly simplified.

Method and apparatus for opening folded printed products having distinct sheet opening and hold-open means


A white or whitish luminescent material for phosphorescence is provided by synthesizing an organometallic complex that is able to convert a triplet excited state into light emission. In particular, a white electroluminescent device that has a high luminous efficiency and can be manufactured easily is provided by using the organometallic complex to manufacture a white or whitish electroluminescent device. The electroluminescent device is used to provide a light-emitting device with low power consumption. A fluorescent and phosphorescent material represented by a general formula (2) is synthesized. Since this material can emit both components of fluorescence and phosphorescence in the region of visible light, white or whitish luminescence can be achieved, which is applied to an electroluminescent device or a light-emitting device

When light is absorbed by an organic compound (organic molecule), the organic compound (organic molecule) gets to have energy (an excited state). Through this excited state, various photochemical reactions may be developed or light emission (luminescence) may be generated, and various applications have been tried. In particular, as an application field of a light-emitting compound, an electroluminescent device (a device that emits light by applying electric field) can be given.
In the case of using an organic compound as a light emitter, the emission mechanism of an electroluminescent device is a carrier injection type. In other words, by applying a voltage with an electroluminescent layer sandwiched between electrodes, an electron injected from a cathode and a hole injected from an anode are recombined in the electroluminescent layer to form a molecule in an excited state (hereinafter, referred to as an exited molecule), and energy is released to emit light while the excited molecule moves back toward the ground state.
In the foregoing electroluminescent device, the electroluminescent layer is generally formed of a thin film about below 1 μm. Further, since the foregoing electroluminescent device is a self-luminous device, where the electroluminescent layer itself emits light, a backlight that is used for a conventional liquid crystal display is unnecessary. Therefore, a great advantage of using such devices is that it is possible to manufacture a significantly thin and a lightweight display.
In the case of an electroluminescent layer with a thickness approximately from 100 to 200 nm, for example, the time from an injection of carriers to their recombination is about several ten nanoseconds considering the carrier mobility of the electroluminescent layer. Even when processes from the recombination of the carriers to light emission are included, only time on the microsecond time scale is required to reach light emission. Thus, the fairly high response speed is also one of the features.
In addition, since the foregoing electroluminescent device is a carrier injection type light-emitting device, driving by DC voltage is possible, and it is unlikely that a noise is generated. As for the driving voltage, an uniform ultra thin film with a thickness of approximately 100 nm is first used as the electroluminescent layer, a material for an electrode is also selected to reduce a carrier injection barrier against the electroluminescent layer, and a heterostructure (two-layer structure) is additionally introduced. Accordingly, a sufficient luminance of 100 cd/m2 can be obtained at 5.5V (refer to Non-Patent Document 1, for example).
(Non-Patent Document 1)
C. W. Tang and S. A. Vanslyke, "Organic electroluminescent diodes", Applied Physics Letters, vol. 51, No. 12, 913-915 (1987)
The electroluminescent device has been attracting attention as a next-generation flat panel display in terms of the features such as the thin thickness and the lightweight, the high speed response, and the low DC voltage drive. In addition, relatively favorable visibility can be obtained since the electroluminescent device is a self-luminous device that has a wide viewing angle, and the electroluminescent device is considered to be effective as the device for a display screen of a portable device.
By the way, light emission observed in the foregoing electroluminescent device is a luminous phenomenon in an excited molecule moving back toward a ground state. When excited, the molecule formed from an organic molecule can take two kinds of state: a singlet excited state (S*) and a triplet excited state (T*). In addition, the statistic generation ratio in an electroluminescent device is considered to be S*:T*=1:3 (see Non-Patent Document 2, for example).
(Non-Patent Document 2)
Tetsuo TSUTSUI, Text of the third lecture meeting, Bulletin of Organic Molecular/Bioelectronics Subconirnittee, Society of Applied Physics, p. 31-37 (1993)
However, in the case of a general organic compound, luminescence from the triplet exited state (phosphorescence) is not observed at room temperature while only luminescence from the singlet exited state (fluorescence) is observed generally. This is because T* (S0 transition (phosphorescence process)) becomes a forbidden transition and S* (S0 transition (fluorescence process)) becomes an allowed transition since an organic compound generally has a ground state of a singlet state (S0). In other words, only the singlet excited state contributes to luminescence generally.
Consequently, the internal quantum efficiency (the ration of photons generated to injected carriers) in an electroluminescent device is assumed to have a theoretical limit of 25% in accordance with S*:T*=1:3.
Further, generated light is not all coupled out to the outside, and it is not possible to take a portion of the light out due to inherent refractive indexes of a constituent material of an electroluminescent device and a material of a substrate. The ratio of light taken out to the outside to generated light is referred at as a light-extraction efficiency, it is said that the light-extraction efficiency is only about 20% in an electroluminescent device that has a glass substrate.
Consequently, it is said that the ratio of photons that can be taken out finally to the outside to the number of the injected carriers (hereinafter, "external quantum efficiency") has a theoretical limit of 25%×20%=5% if injected carriers are all formed into excited molecules. In other words, if all of the carriers are recombined, it is conceivable that only 5% thereof can be taken out as light.
However, in these years, an electroluminescent device that is able to convert an energy released in moving back toward a ground state from a triplet excited state (T*) (hereinafter, referred to as "triplet excitation energy") into light emission has been made in public one after the other, and a high luminous efficiency thereof has been attracting attention (refer to Non-Patent Document 3 and Non-Patent Document 4, for example).
(Non-Patent Document 3)
D. F. O'Brien, M. A. Baldo, M. E. Thompson and S. R. Forrest, "Improved energy transfer in slctrophosphorescent devices", Applied Physics Letters, vol. 74, No. 3, 442-444 (1999)
(Non-Patent Document 4)
Tetsuo TSUTSUI, Moon-Jae YANG, Masayuki YAHIRO, Kenji NAKAMURA, Teruichi WATANABE, Taishi TSUJI, Yoshinori FUKUDA, Takeo WAKIMOTO and Satoshi MIYAGUCHI, "High Quantum Efficiency in Organic Light-Emitting Devices with Iridium-Complex as a Triplet Emissive center", Japanese Journal of Applied Physics Vol. 38, pp. L1502-L1504 (1999)
A porphyrin complex that has platinum as a central metal and an organometallic complex that has iridium as a central metal are respectively used in Non-Patent Document 3 and in Non-Patent Document 4, and both of the complexes are of a phosphorescent material that has a third-series transition element introduced as a central metal, which includes one that well exceeds the foregoing theoretical limit 5% of the external quantum efficiency. In other words, an electroluminescent device using a phosphorescent material can achieve a higher external efficiency than conventional one. Then, as the external efficiency is higher, the luminance is improved.
Therefore, an electroluminescent device using a phosphorescent material is considered to occupy an important position in a future development as a means for accomplishing luminescence with a high luminance and a high luminance efficiency.
As described above, a phosphorescent material is useful for being applied to electroluminescent devices, which is expected. However, it is still the case that the number thereof is small. The iridium complex that is used in Non-Paten Document 4 is one of organometallic complexes referred to as an orthometalated complex. Since this complex has a phosphorescence lifetime of several hundreds nanoseconds and a high phosphorescence quantum yield, the decrease in efficiency associated with an increase in luminance is small as compared to the porphyrin complex. From that viewpoint, the foregoing organometallic complex using the heavy metal is one of guidelines for synthesizing a phosphorescent material.
By the way, an electroluminescent device has been actively developed for being applied to displays. Above all, the development of a device that can emit white light has been distinctly attracting attention. This is because full color display is possible when a color filter is attached to a display device, in addition to applications as mono-color display and lighting such as a backlight.
Since a light-emitting device with a filter passed through has an usability of light lowered, a device that can achieve high-luminance while light emission with lower power consumption is strongly required. In addition, considering the application as lighting, it is no mistake that a higher luminance is required. Therefore, it can be said that the use of an electroluminescent device using a phosphorescent material for realizing white light emission is the most effective means.
In the case of a conventional electroluminescent device using a phosphorescent material for white light emission, a method such as a method of mixing materials that respectively emit R (red), G (green), and B (blue) to form a thin film, a method of laminating layers that respectively emit R (red), G (green), and B (blue), or a method of combining complementary colors (a blue-green color and an orange color, for example) (refer to Non-Patent Document 5, for example) is considered. However, since a plurality of luminescent materials that have different emission wavelengths are needed in any case in order to obtain a spectrum of white light, there is a problem that a driving voltage is increased. In addition, since it is necessary to combine a hole blocking layer in order to obtain a high luminous efficiency from an electroluminescent device using a phosphorescent material, a quite complicated device structure is required.
(Non-Patent Document 5)
Brian W. D'Andrade, Jason Brooks, Vadim Adamovich, Mark E. Thompson, and Stephen R. Forrest, "White Light Emission Using Triplet Excimers in Electrophosphorescent Organic Light-Emitting Device", Advanced Materials, 14, No. 15, 1032-1036 (2002)
As above, since a planar source for white light emission_is composed of a plurality of materials combined quite intricately, a manufacturing process is not only controlled with difficulty but also is made cumbersome and complicated.

Organic metallic complex and electroluminescent element using the same

Semiconductor Energy Laboratory Co., Ltd.


A lighting module comprising an elliptical collector for reflecting in the direction of an optical element a beam originating from a light source. The module comprises a screen assembled along the path of the light beam so as to form a cutoff edge. In accordance with the invention, the light source, the elliptical collector and the screen are assembled on an active surface of a support, which additionally comprises a referencing wall. Means for pressing the screen against said active surface and for pushing the front face of the screen, which comprises the cutoff edge, against said referencing wall are provided.

1. Field of the Invention
The present invention relates generally to motor vehicle headlamps. The invention more specifically relates to an illumination module with which these headlamps can be equipped and which comprises a light source, an elliptical collector which allows the reflection of a beam originating from this source, and a convergent lens in the direction of which the beam is reflected so as to be distributed and projected externally of the headlamp, in front of the vehicle. The light source is disposed substantially in line with the first focal point of the collector.
2. Description of the Related Art
Such modules comprising a light source, a collector and a convergent lens are known, in which, in order to meet standards aimed for example at preventing road users coming from the opposite direction from being dazzled, an lighting beam of the cutoff type is produced. A cutoff beam means a lighting beam which has a directional limit, that is to say the cutoff, beyond which the luminous intensity is reduced. To this end, these modules are equipped with a shield, which is disposed along the path of the light beam, substantially in line with the second focal point of the collector, so as to cut off the potentially dazzling part of the beam. It is therefore necessary to precisely position close to the second focal point the edge of the shield that will delimit the cutoff of the beam, this edge being referred to as the cutoff edge.
Conventionally, such a shield is placed in position in the module by the cooperation of indexing holes formed in the shield and indexing pieces interdependent with a component of the module and is fixed in place by screwing. It is therefore necessary during manufacture of the shield to ensure very precise positioning of the indexing holes in relation to the cutoff edge. In addition, the assembly play which arises with this type of assembly may hinder the precise positioning of the cutoff edge of the shield in the module. This results in a less precise cutting of the light beam exiting from the module. This impaired positioning hinders chromatism, inter alia.

Lighting module and method for assembling such a module


A joint implant assembly including a spherical shaped component adapted to securing to an end of a first joint defining bone and a recess shaped component adapted to securing to an end of a second joint defining bone. Each of the components establishes an opposing wear surface, at which microscopic sized particles build up over time resulting from prolonged use of the joint. At least one of the spherical and recess shaped components exhibits a plurality of interior entrapment chambers, each of which including a narrow-most entranceway location communicating with the wear surface. The entrapment chambers further exhibit outwardly widening capture profiles extending within the associated component for securing volumes of the microscopic particles away from a zone defined between the wear surfaces.

The prior art is documented with numerous examples of artificial implant assemblies, such as which are constructed in the attempt to facilitate ease of articulation as well as to reduce long term wear. Examples of such implants include the wear reducing acetabular component of Serbousek U.S. Pat. No. 5,916,269 and prosthetic component of Chan, U.S. Pat. No. 6,866,685, each of which incorporate interruptions in the inter-articulating joint faces. Also noted is the passive lubricating prosthetic joint of Heinz, US 2007/0179613, along with the prosthesis constructions in Taylor, US 2007/0270975 and the ball joint or cap implant for an artificial hip joint depicted in Grundei U.S. Pat. No. 7,771,485.
A further objective of such artificial implant assemblies is the attempt to remove or isolate debris resulting from abrading contact and associated wear between the articulating surfaces of the joint implant. An example of one such construction is depicted in the debris isolating prosthetic hip joint of Kwong, U.S. Pat. No. 5,702,483 and which, in relevant part, incorporates a capsule configured by first and second surface treatments and in turn defined by the acetabular and femoral components. Each of the surface treatments causes fibrous tissue to attach to the acetabular and femoral components such that any resulting debris particles resulting from wearing of the articulating surfaces is confined within the capsule.

This patent is subject to a terminal disclaimer.

Hip and knee joint assemblies incorporating debris collection architecture between the ball and seat interface


A new and distinct floricane fruiting red raspberry, Rubus idaeus L., variety is described. The variety results from selection among a population of seedlings derived from controlled pollination crossing of the raspberry varieties known as ‘Chilcotin’ (not patented) and ‘Waimea’ (not patented). The fruit of this new variety has an attractive appearance characterized by uniformly large berry size, good fruit firmness, and medium-red fruit color. The new variety is distinguished from others by its high yields of firm, attractive, uniformly sized, large, red berries that ripen in the mid season. The plant exhibits a semi spine-free upright growth habit, of strong vigor. In addition, the plant has displayed resistance to Raspberry Bushy Dwarf Virus (RBDV) under New Zealand conditions. Fruit of the new variety appears suitable for the fresh fruit market. The variety has been named ‘Korpiko’.

The new variety of red raspberry, Rubus idaeus L., was created in the course of a planned breeding program carried out at Nelson, Motueka, New Zealand. The parents used to make the cross in 1990, were the varieties 'Chilcotin' (seed parent) (unpatented) and 'Waimea' (pollen parent) (unpatented).
Seed from this cross was grown and the original plant of the new variety was selected during the 1993-94 summer (Southern Hemisphere) and was found to exhibit:                (a) a semi spine-free upright growth habit of strong vigor,        (b) the ability to form attractive large red fruit of good flavor in high yields on medium length fruiting laterals that ripen mid season, and        (c) resistance to Raspberry Bushy Dwarf Virus (RBDV).
The new variety was first asexually propagated in 1998, at Motueka, Nelson, New Zealand, being reproduced by vegetative cuttings arising from root cuttings. Cuttings developed this way in spring, root within a 3–4 week propagation period, and thus plants suitable for field planting are then ready in autumn of the same year. The resulting plants propagated true to type, demonstrating that the characteristics of the new cltivar are stable and are transmitted without change through succeeding generations. Since 2000, 'Korpiko' has been asexually propagated in vitro via tissue culture methods. The cultivar has propagaated true to type via these means.

The New Zealand Institute for Plant and Food Research Limited


Reducing transmission of electromagnetic waves through a barrel portion of an optical module. A barrel for optically coupling an optical device to an optical fiber within a fiber optic cable can include a plastic portion and a metallic shielding portion for reducing transmission through the barrel. An optical device can be coupled to the plastic portion. The metallic shielding portion can be coupled to the plastic portion and surround at least a portion of the plastic portion. The metallic shielding portion can be shaped and configured so as to reduce transmission of electromagnetic radiation through the barrel.

1. The Field of the Invention
Embodiments of the invention relate to improving fiber optic integrity within an optical component. More particularly, embodiments of the invention relate to optical devices that provide electromagnetic shielding.
2. The Relevant Technology
Fiber optic technology is increasingly employed in the transmission of data over communications networks. Networks employing fiber optic technology are known as optical communications networks, and are typically characterized by high bandwidth and reliable, high-speed data transmission.
To communicate over an optical communications network using fiber optic technology, fiber optic components such as fiber optic transceivers are used to send and receive optical data. Generally, a fiber optic transceiver includes optical subassemblies ("OSA") such as a transmit optical subassembly ("TOSA") for sending optical signals, and a receive optical subassembly ("ROSA") for receiving optical signals.
More particularly, the TOSA receives an electrical data signal and converts the electrical data signal into an optical data signal for transmission onto an optical network. The ROSA receives an optical data signal from the optical network and converts the received optical data signal to an electrical data signal for further use and/or processing. Both the ROSA and the TOSA include specific optical components for performing such functions.
A conventional TOSA includes an optical transmitter such as a light emitting diode (LED) or a laser diode. The optical transmitter generates an optical signal that is launched onto an optical fiber. A plastic barrel is typically used to align and couple the optical signal emission from the optical transmitter with the end of a fiber optic cable for transmission of the optical signal to a fiber optic network. The optical transmitter can be located within a header, such as a TO-Can package, and is typically covered by an at least partially transparent cap (or lid) that protects the optical transmitter and allows the optical transmitter to transmit the optical data signal to an optical fiber. The cap may include a lens for focusing the optical signal transmission.
A conventional ROSA includes an optical receiver, such as a PIN photodiode or avalanche photodiode ("APD"). A plastic barrel is typically used to align and couple the end of a fiber optic cable relative to the optical receiver. This facilitates transmission of the optical signal to the optical receiver. The optical receiver can be covered by a partially transparent cap that protects the optical receiver and allows the optical receiver to receive the optical data signal from the optical cable. The cap may also include a lens for focusing the optical signal transmission.
A typical optical fiber has a core of high refractive index material surrounded by a low-index cladding material. In order for an optical transmitter to transmit an optical signal to an optical fiber, the optical emission of the optical transmitter is aligned with the transmissive core of the optical fiber such that the core of the optical fiber receives a sufficient portion of the emission from the optical transmitter. Likewise, in order for an optical receiver to receive an optical signal from an optical fiber, the active surface of the optical receiver is aligned with the transmissive core of the optical fiber such that a sufficient portion of the optical signal is received by the optical receiver from the optical fiber.
Referring to FIG. 1, a conventional module 100 for coupling an optical device 101 to a fiber optic cable 102 is shown. As shown in FIG. 1, the module 100 has a plastic barrel 103 with an open end 104 that is sized and configured to receive a fiber optic end face 105 of the fiber optic cable 102 in alignment with the optical device 101 mounted on a header 106.
In the case of a ROSA, the optical device 101 includes an optical receiver for receiving an optical signal from the optical fiber 102 and converting the optical signal to an electronic signal. In the case of a TOSA, the optical device 101 includes an optical transmitter for receiving an electronic signal, converting the electronic signal to an optical signal, and transmitting the optical signal to the optical fiber 102. The header 106 has electrical leads 107, sometimes referred to as feed throughs, for providing power and data signals between an OSA printed circuit board ("PCB") (not shown) and any optical device(s) mounted on the header 106.
A cap 108 covers the optical device 101 mounted on the header 106 for protection of the optical device 101. The cap 106 can be made of an at least partially transparent plastic material, and may include a focusing lens or transmission window for allowing optical signals to travel to or from the optical device 101.
While the header 106 is partially fabricated with metal and provides some electromagnetic shielding, the electro magnetic shielding provided by both the header 106 and the plastic barrel 103 can be insufficient. In some instances, electromagnetic radiation 109A originating from inside the module 100 can be transmitted through the plastic barrel 103 and to the outside of the module. Similarly, electromagnetic radiation 109B may travel from the outside of the module 100 and through the plastic barrel 103 entering into the inside of the barrel causing interference. Such interference can disrupt communication, especially in compact products and products transferring data at high rates where the highest level of attenuation is desirable.
Therefore, what would be advantageous are optical components having additional electromagnetic shielding, thereby reducing, if not eliminating, the adverse effects of electromagnetic radiation on the reception or transmission of optical signals.

Optical barrels with electromagnetic shielding


A method and system is provided to automate many of the steps involved in processing restricted securities. Data can be received relating to restrictions associated with the trade of a security. Typically the data includes notification by a seller of their desire to transact a trade involving a restricted security as well as answers to a checklist of questions related to the restricted trade. In addition, the system can receive an electronic verification that the data is correct. The system can respond by automatically generating documentation supportive of the trade and receiving an electronic signature to execute the generated documents. Trade information can also be automatically forwarded to a clearing house. In addition, an instruction can be transmitted to a transfer agent to convert physical restricted securities into an electronic format. Notification that the securities have been converted can subsequently be received.

The present invention relates to a method and system for providing automated trading and processing of restricted securities. In particular the present invention relates to an automated system and process to transform restricted securities processing (RSP) from being a slow and inconsistent process into an industry benchmark, and possibly a competitive advantage as a distinct and significant source of value creation for a financial institution.
Several conditions can distinguish RSP from non-RSP and are the dominant root causes for process inefficiencies: RSP requires extra "legal" process steps that culminate with a Transfer Agent's review of a Legal Opinion from Company Counsel. A Broker's Letter and Seller's Letter can be inputs wherein the primary purpose of the letters is to facilitate the generation of a Legal Opinion by Company Counsel. The Legal Opinion typically states that Company Counsel believes a trade involving restricted securities meets regulations.
Restricted securities are almost always physical documents while non-restricted securities are almost always electronic. In addition, restricted securities uniquely require legends. In present markets, physical restricted securities can be replaced by electronic positions on the books and records of the Transfer Agent with a stop order, however, this does not usually happen.
The conditions of being restricted and being physical are not one and the same, they can be separated, such as via Transfer Agent (TA) books-and-records. However, both conditions require manually intensive, inefficient, non-standard processes with poor quality control and lagging status.
In general, the prior art has shown that when a Client desires to sell restricted stock the client will call their Broker to inform them of their desire. Typically, the associated restricted stock security will already be retained by the Broker in a vault and the Broker will have some indication of a restriction applying. The Broker will typically have a pre-signed Seller's Letter with blanks for the date, rule of sale, amount to be sold and potentially other transaction specific information. The Broker and the Client, who is now a Seller, will attempt to determine an appropriate rule for sale, and whether or not the Seller meets the requirements. If they are not able to do so, the Broker and/or Seller may call the Broker's internal Restriction Desk; the Client's Counsel, or the Company Counsel to determine the appropriate rule for sale.
When the appropriate rule of sale has been ascertained, the Broker will fill in the pre-signed Seller's Letter. If the Broker does not have a pre-signed Seller's Letter on hand, they will fax the filled in Letter to the Client for signature, and the Client will then fax the signed letter back to the Broker or directly to Company Counsel. The Broker will also fill out and sign a Broker's Letter. The Broker will then determine the identity of Company Counsel in order to fax both the Seller's and Broker's Letter. The Broker will also call Company Counsel to inform them of the impending fax and give a transaction overview, and then fax the letters. Upon receipt of the faxed letters, Company Counsel will review the letters to determine if the appropriate rule has been identified and that the conditions under the rule are met. If so, Company Counsel creates and signs a Legal Opinion stating that they believe conditions for sale have been met. Company Counsel will also identify the Transfer Agent, and fax the Legal Opinion to the Transfer Agent.
In the early part of the process when the Client first calls the Broker to place the sale, the Broker will also receive from the Seller an original signed document of negotiability to forward to the Transfer Agent. If the security is on deposit in the Broker's vault, typically the Broker will have had previously given the Client a stock power which if signed by the Client, can act as documentation of negotiability. During a call to the Broker, the Broker will inform the Client to sign the stock power and physically send it, typically via an overnight service, to the Broker. If the security is in the possession of the Client or another source, the Broker will typically inform the Client to sign the security itself. The signed security can be used as the document of negotiability and forward it to the Broker. However it is accomplished, both a signed document of negotiability and the security itself must be delivered to the Transfer Agent to complete the transfer. The Broker will put events into action to ensure both items are received into the Broker's possession to be forwarded to the Transfer Agent.
Typically, the Transfer Agent will not begin the transfer process until it has received either a faxed copy or original of the signed Legal Opinion. In addition the transfer agent will require an original security along with an original signed document of negotiability.
The Transfer Agent will sort through piles of packages of negotiability documentation which typically arrive through an overnight service, and stacks of faxes of Legal Opinions to match the appropriate Legal Opinion to the appropriate security package. Alternatively, some Transfer Agents request that the Broker take receipt of the fax from Company Counsel and package this letter with the security package to eliminate the laborious task of doing this themselves. Upon completing this task, the Transfer Agent will initiate the transfer process, which includes destroying the old certificate and either reissuing a new physical security or moving the security to electronic form in a trust company environment, such as the Depository Trust Company. The only way the Broker can identify that the transfer has been complete is to go into a trust company system and search, or call the transfer agent and inquire. Overall, this process may require from one to three weeks and occasionally even longer.
What is needed is a method and system to automate Restricted Securities Processing and provide a timely, secure, platform for trading restricted securities.


Methods for polymerization of phosphaalkenes using initiators are provided. Also provided are polymers and co-polymers in which the polymer backbone contains tracts of carbon and phosphorous atoms in approximately equimolar amounts. C—P bonds in the polymers of this invention may be predominantly in a head-to-tail arrangement or mixed arrangements. Co-polymers may comprise polyolefin monomer units.

Polymers comprising phosphorus atoms in the polymer backbone are desirable for a variety of applications, including use as polymeric supports for metal catalysts (i.e. Peckham, T. J., et al. (1999) Macromolecules 32:2830-37). Synthetic approaches to the production of such polymers have included ring-opening polymerization (i.e. Peckham, T. J., et al. [supra]; and Kobayashi, S., et al. (1984) Macromolecules 17:107-115), condensation or co-polymerization of aryl phosphines with alkyl radicals and alkylene moieties (i.e. Fox, M. A., et al. (1991) Macromolecules 24:4626; Lucht, B. L. and St. Onge, N. O. (2000) Chem. Commun. 2000:2097-8; Kanazawa, A., et al. (1993) J. of Polymer Science 31:3031-38; and JP6016508). These approaches have resulted in the production of oligomers or polymers of unspecified length comprising phosphine or phosphonium moieties in a chain which otherwise contains aryl groups and/or alkyl or alkene spacers. None of these approaches allow for the production of polymers containing C—P bonds and approximately equimolar amounts of carbon and phosphorus atoms in the polymer backbone.
It has been reported that unstable phosphaalkenes such as methylenephosphine can spontaneously polymerize into unspecified oligomers or polymers (Klebach, T. C., et al. (1978) J. Am. Chem. Soc. 100:4886-8; Pellerin, B., et al. (1987) Tetrahedron Letters 28:5811; Quin, L. D., et al. (1987) Tetrahedron Letters 28:5783-86; Chow, J. R. and Goldwhite, H. (1989) J. Phys. Chem. 93:421-6; and Gaumont, A. C., et al. (1994) J. Chem. Soc. Chem. Commun. 945-6; and Aitken, R. A., et al. (1997) Tetrahedron Letters 38:8417-20). In view of the instability of acyclic compounds containing carbon-phosphorus π bonds, researchers have focused on the development of thermally stable phosphaalkenes, phosphaallenes and phosphaalkynes which have been kinetically stabilized through the presence of bulky substituents on the phosphorus atom (i.e. Gaumont, A. C. and Denis, J. M. (1994) Chem. Rev. 94:1413-39). One of the first such thermally stable phosphaalkene with a localized P═C bond was P-mesityldiphenylmethylenephosphine, the structure of which is shown below in which Ph is phenyl and Mes is 2,4,6-trimethylphenyl (Klebach, T. C., et al. [supra]; Van der Knapp, T. A., et al. (1984) Tetrahedron 40:765-5; and Mundt, O., et al. (1986) Z. Anorg. Allg. Chem. 540/541:319-35).

Various thermally stable acyclic phosphaalkenes have been synthesized and reported (i.e. Appel, R. (1990) "Multiple Bonds and Low Coordination in Phosphorus Chemistry", Chapter 4; M. Regits and O. J. Scherer (eds), Thieme; Stuttgart) but there have been no reports of their use in polymerization reactions.


A method and composition for reducing the levels of hydrogen sulphide and mercaptans in hydrocarbon streams. The method comprises contacting the gas stream with a composition comprising the reaction product of mixing monoethanolamine, diglycolamine and formaldehyde. The use of the method and composition alleviates problems associated with crystalline dithiazine depost build-up associated with the use of triazine based scavengers.

A large number of compositions are known for removing or reducing the hydrogen sulphide content of and removing mercaptans from natural gas, crude oil, and other hydrocarbon streams. These compositions include those based on alkanolamine and aldehyde reaction products such as described in U.S. Pat. No. 4,978,512 which issued on Dec. 18, 1990 to Quaker Chemical Corporation. These reaction products include triazine compounds, and in particular 1,3,5 tri-(2-hydroxy-ethyl)-hexahydro-S-triazine.
While alkanolamine and aldehyde reaction products such described in U.S. Pat. No. 4,978,512 are effective hydrogen sulphide scavengers, they are known to form solids upon reaction with hydrogen sulphide. In particular, the reaction with hydrogen sulphide forms dithiazine which is not water soluble. Dithiazine forms a separate liquid phase or layer in gas processing equipment. In temperatures of about 20° C. or lower, solid dithiazine crystals form in this layer and precipitate out of solution.
Substantial amounts of dithiazine solid deposit buildup routinely occurs in gas processing equipment, particularly in colder weather applications. These dithiazine deposits are crystalline in nature and are particularly difficult to remove. For example, in bubble tower gas contactors, dithiazine crystals build up in the bottom of the tower and plug the lines through which the spent scavenger chemical is drawn off. Similarly, dithiazine forms a solid crystalline layer in the bottom of the spent scavenger chemical storage tanks located at the well site. Even for inline injection applications, dithiazine crystals tend to accumulate in areas of line restriction such as chokes and in dips or "dead spots" in the gas line. Further, crystallization can occur in bulk truck tanks used to haul away spent product and can cause plugging problems in produced water disposal wells. An enormous amount of effort continues to be expended simply in cleaning out gas processing equipment to remove dithiazine deposits. Often, the only practical solution is to manually chip away the deposits and/or dissolve the dithiazine deposits by steam or hot water. This is an expensive and time consuming process which requires the gas processing equipment to be shut down until treatment is complete.
There have been a number of attempts to improve the performance of triazine based scavengers. For example, there is disclosed in U.S. Pat. No. 5,347,004 and U.S. Pat. No. 5,554,349 (Rivers et al.), the use of a mixture of amines to scavenger hydrogen sulphide from natural gas, The mixture includes reaction products or blends of alkoxyalkylene amines, ammonia and dialkylamines with formaldehyde wherein the reaction product is a hexahydrotriazine having at least one substituent being an alkoxyalkylene group. While Rivers et al. discloses that the amine mixture may be employed without the need for antifreeze or polymerization inhibitors, there is no suggestion that the amine mixture will have any effect on the formation of dithiazine solids.
There is disclosed in PCT international application No. PCT/CA97/00826 (Warrender et al.) a scavenger composition which comprises a reaction product of formaldehyde. with aminoethylpiperazine (AEP) and a second or "enhancing" amine, which can be monoethanolamine. The reaction product is described as reacting with impurities in the natural gas to form a hydrophobic component which forms a second liquid phase so as to solubilize the hydrophobic reaction products to preclude the formation of solids. It would appear from the disclosure, that the solids referred to are not dithiazine solids. The test results in the disclosure indicate that solids formed slowly over time, presumably at room temperature, after the scavenger compositions were subjected to hydrogen sulphide breakthrough tests, i.e., by "overspending" the scavenger. These solids were apparently not observed when a sufficient amount of the enhancing amine was used. It has been found that solids that are produced at room temperature in conventional laboratory hydrogen sulphide breakthrough tests by continuing to overspend the scavenger composition until well after breakthrough are not of the type typically experienced in the field. It is believed that over spending a triazine based scavenger in a laboratory test causes the third ring nitrogen in the triazine molecule to be displaced by sulphur causing the ring to open and the resulting molecule to undergo a slow polymerization type reaction to produce an amorphous solid.
This type of solid is not typically encountered in field applications as the scavenger chemical must be replaced or regenerated at or before breakthrough in order to avoid production of non-merchantable gas. Moreover, dithiazine solids do not usually form at room temperature. The solidification point of pure dithiazine is about 46° C. However, residual methanol (typically present as part of the Formalin component) plus other components in reacted triazine based scavengers mixes with the dithiazine layer and lowers the solidification point below 20° C. Thus, solids formation observed in laboratory breakthrough tests at room temperature are typically not dithiazine. It is very difficult to form a dithiazine crystal in laboratory tests. In field applications, methanol is more readily lost and hence initiation of crystal formation is more apparent. There also may be other impurities in field gas streams or equipment which seed initial crystallization.
Accordingly, while the prior art teaches a number of possible solutions to solids buildup associated with triazine based hydrogen sulphide scavengers, none have effectively addressed the particular problem of dithiazine solids buildup in field applications. There remains a need for a scavenger composition that is effective at removing hydrogen sulphide and which avoids the problems of dithiazine deposit formation characteristic of alkanolamine/aldehyde scavenging products.

Method and composition for removing sulfides from hydrocarbon streams