WO2001051908A1 - Procede et appareil permettant d'appliquer des gouttelettes sur une lame test, par utilisation d'une imprimante a jet d'encre - Google Patents

Procede et appareil permettant d'appliquer des gouttelettes sur une lame test, par utilisation d'une imprimante a jet d'encre Download PDF

Info

Publication number
WO2001051908A1
WO2001051908A1 PCT/GB2001/000066 GB0100066W WO0151908A1 WO 2001051908 A1 WO2001051908 A1 WO 2001051908A1 GB 0100066 W GB0100066 W GB 0100066W WO 0151908 A1 WO0151908 A1 WO 0151908A1
Authority
WO
WIPO (PCT)
Prior art keywords
carrier
marker material
marker
droplets
layer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/GB2001/000066
Other languages
English (en)
Inventor
Michael John Fox
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Willett International Ltd
Original Assignee
Willett International Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Willett International Ltd filed Critical Willett International Ltd
Priority to AU2001225322A priority Critical patent/AU2001225322A1/en
Publication of WO2001051908A1 publication Critical patent/WO2001051908A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01L—CHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
    • B01L3/00—Containers or dishes for laboratory use, e.g. laboratory glassware; Droppers
    • B01L3/02—Burettes; Pipettes
    • B01L3/0241—Drop counters; Drop formers
    • B01L3/0268—Drop counters; Drop formers using pulse dispensing or spraying, eg. inkjet type, piezo actuated ejection of droplets from capillaries
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00—Sampling; Preparing specimens for investigation
    • G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
    • G01N1/30—Staining; Impregnating ; Fixation; Dehydration; Multistep processes for preparing samples of tissue, cell or nucleic acid material and the like for analysis
    • G01N1/31—Apparatus therefor
    • G01N1/312—Apparatus therefor for samples mounted on planar substrates

Definitions

  • the present invention relates to a method and apparatus, notably to a method for applying a fluid to a test slide and apparatus for carrying out the method.
  • a plurality of interactions can take place to provide a plurality of spectra whose combination provides a unique fingerprint to characterise the fluid being tested. In this way it is possible to determine whether an ink or other fluid is the authentic product of a given manufacturer.
  • the determination can be made sufficiently selective to be able to detect differences between batches of supposedly identical products from the same manufacturer or between products from different sites.
  • the manufacturer can provide a reference spectrum for that product.
  • the characteristic spectrum of that sample can be determined. Comparison of that spectrum with the reference spectrum obtained initially, will enable the manufacturer or his customer readily to determine whether the sample corresponds to the authentic material .
  • test method Such a method of authentification is described in the specification of US Patent No 5,753,115 and the subject matter of that specification is incorporated herein by reference and is denoted hereinafter as the test method.
  • a suitable marker material is applied to a suitable carrier.
  • the preferred carrier is a glass slide, since glass is usually substantially inert to any of the fluids to be assessed and will not generate extraneous spectra which could mask or distort the spectra from the marker material/sample interaction which it is desired to observe. It is also preferred to apply the marker material to a layer of an inert absorbent material applied to the surface of the carrier so that the amount of marker material carried by the carrier and its position on the carrier can be held to within specified tolerances.
  • the absorbent material is particulate silica, for example fumed silica, which is secured as a layer of predetermined thickness to the underlying glass slide by means of a film of gelatin or other inert binder/adhesive.
  • the marker material is applied to such a silica-coated slide to achieve the desired rate of application of the marker to a given area of the plan area of the slide.
  • the surface of the slide can be sub-divided into a plurality of discrete areas, for example by a grid of upstanding walls or ridges on the surface of the slide.
  • Each of the discrete areas carries a single selected marker material or mixture of marker materials.
  • An ink jet printer is a non-contact technique by which closely controlled droplets of a fluid can be accurately applied to a substrate. Prima facie, such a technique would seem suitable for applying the marker material to the slide or other carrier or to the absorbent layer on such a carrier.
  • a conventional continuous jet ink jet printer produces test slides which perform erratically. This would preclude the use of such printers to apply the marker materials to the slides or other carriers, especially where the carrier carries an absorbent layer.
  • the erratic performance is due to uneven application of the marker materials over the plan area of the slide and scattering of the re-radiated or reflected radiation.
  • this surface will usually be a non-absorbent surface and spattering and uneven film formation on the surface may occur. This will result in uneven application of the marker material and possible contamination of adjacent areas of the surface of the carrier to which different marker materials have been applied.
  • the marker material is carried in an absorbent layer applied to the carrier, we have found that the layer is disturbed by the application of the droplets of the marker material .
  • the present invention provides a method for applying a marker material as hereinbefore defined to a surface of a carrier so as to form deposits of a predetermined amount of one or more marker materials at one or more predetermined locations upon the surface of the carrier to which a sample of a product to be assessed can be applied so as to interact with the marker material in the deposit to provide a characteristic spectrum upon radiation of the predetermined location with IR, UV or other radiation, characterised in that a selected amount of the marker material is applied as a fluid to a selected area of the surface of the carrier or of a layer carried by the carrier using a drop on demand or impulse jet ink jet printer apparatus which has been selected and/or whose operation and/or design has been modified so that the droplets of fluid striking the surface or the surface layer do not cause an unacceptable level of disturbance of the layer and/or of scattering of the applied marker material upon the surface of the carrier.
  • the design and/or operation of the ink jet printer is such that the droplets striking the surface or surface layer or the carrier have a kinetic energy of less than about 40, preferably from 8 to 35, picojoules.
  • the kinetic energy of the droplets is notionally that of the droplet when it strikes the surface of the carrier or surface layer.
  • the kinetic energy for practical purposes will be that for the droplet as it is ejected from the nozzle orifice of the printer, since the kinetic energy lost during the flight of the droplet to the surface which it strikes is not significant.
  • the values for the kinetic energies quoted herein are those calculated for the droplets at the nozzle orifice of the printer .
  • the ability to use an ink jet printer to apply the marker material to the carrier enables the operator to apply many thousands of droplets of fluid containing the marker material per second accurately and rapidly. Since the positioning of the droplets onto the carrier can readily be controlled and varied, the invention enables a selected area of the surface or surface layer on the carrier to have the desired amount of marker material applied thereto rapidly, whereas other areas can have a different marker material applied thereto.
  • drop on demand ink jet printer is used herein to denote those non-contact printers in which ink or other fluid is applied under pressure, typically less than 1 bar, to a nozzle to eject droplets of ink from the nozzle orifice, the flow of ink to the nozzle being controlled by a valve mechanism.
  • An impulse ink jet printer is a variation of a drop on demand printer in which ink is applied at a slight negative pressure to the nozzle orifice so that flow of ink through the nozzle orifice is restrained by the surface tension effects at the meniscus of the ink at the nozzle orifice; and means, usually a piezo-electric driver, are provided for causing a change of volume or a rise in pressure in a chamber upstream of the nozzle orifice so as to eject a droplet of ink upon actuation of the driver.
  • Such printers are commercially available and may be used in their commercially available form without significant modification in the method of the invention.
  • the kinetic energy of the droplets can readily be reduced by reducing the nozzle orifice diameter and/or the open time of the valve controlling the flow of fluid through the nozzle or the change in volume of the ink chamber caused by the piezoelectric driver using known technology.
  • Another factor in the operation of the printer which can be modified to reduce the kinetic energy of the droplets formed is to reduce the pressure at which the fluid is fed to the nozzle of the printer. This will reduce the volume of fluid flowing per unit time through the nozzle orifice and hence the size of droplet formed.
  • the pressure required to form droplets successfully at the nozzle outlet is however dependent upon the viscosity, and hence the temperature and composition, of the fluid being ejected through the nozzle.
  • the optimum nozzle orifice bore diameter, ink pressure, viscosity and other factors of the operation of the ink jet printer can be established by simple trial and error tests. For present use it is desirable to select, design or modify the printer and/or its operation so that the kinetic energy of the droplets is less than 40, typically 8 to 35, notably 10 to 25, for example about 20, picojoules .
  • the invention can be applied to the application of a wide range of fluids containing a wide range of marker materials to a wide range of absorbent layers or carriers, depending upon the fluids to be sampled and the nature of the carrier and absorbent layer.
  • the optimum form of marker fluid can readily be determined from knowledge of the chemistry of the various components of the sample, the marker material and test slide using conventional chemical and physical techniques and ingredients .
  • Suitable marker materials and their uses are described in for example US Patent No 5,753,115 and other marker materials include those described in US Patents Noose 5,292,855, 5,336,714, 5,614,008 and 5,665,151.
  • Suitable fluid carrier media for the marker chemicals include water, lower alkanols, esters and ketones and mixtures thereof, notably those which are readily volatile and in which the alkyl moieties contain from 1 to 3 carbon atoms.
  • the marker materials can be dissolved, emulsified or suspended in the carrier medium.
  • the fluid compositions containing the marker materials can contain other ingredients to assist the jet- ability thereof and such other ingredients can be those conventionally used in ink jet formulations.
  • the composition can contain a film forming binder to aid formation of a deposit containing the marker material which is secured to the particles in the absorbent layer and thus reduce potential migration of the marker material within the absorbent layer or upon the surface of the slide or other carrier.
  • the carrier and the absorbent layer can be selected from a wide range, for example from amongst those described in US Patent No 5,753,115.
  • the carrier can be a planar glass strip, slip or slide as described above.
  • the plastic may comprise a laminate of materials, for example a colourless layer to discrete areas of which the marker material (s) is/are applied and an underlying white layer having apertures therein which are in register with the areas of the colourless layer to which the marker material (s) is/are applied.
  • the colourless layer may carry an apertured top layer to form recesses in the top face of the carrier to assist retention of the fluid composition containing the marker material in the desired location on the carrier whilst the composition gels, sets or cures.
  • the ability to use a drop on demand or impulse jet printer to apply the marker material to the surface of the slide or other carrier or to the absorbent layer on the carrier enables high speed of formation of a test square or other discrete area on the carrier to be achieved. Since the ink jet printer achieves accurate placement of individual droplets of the marker material on the surface of the carrier or the absorbent or other surface layer, the printer can readily be operated, for example under micro- processor control, to form a plurality of individual discrete areas on the surface of the carrier or the surface layer. Furthermore, since the print head of a drop on demand or impulse jet printer can be formed as a compact unit, it is possible to form a single assembly for present use which comprises an array of two, four or more individual print heads, each fed with a different marker fluid.
  • a print head of a drop on demand or impulse jet printer typically comprises and array of individual nozzle fed with ink from a reservoir.
  • the nozzles in such a print head can be fed with fluids from different reservoirs so that each nozzle or a combination of nozzles, can be used to apply one marker material to the surface of the carrier or absorbent layer.
  • Other nozzles in the print head can be fed with a different marker material from another reservoir, further enhancing the flexibility of the operator in designing the shape and location of the areas of each marker material on the carrier or absorbent layer.
  • a series of arrays of print heads can be passed over a static carrier to apply a plurality of marker materials to the carrier.
  • the carrier can be transported through a series of printer stations where arrays of print heads apply marker materials to different areas of the carrier successively.
  • Such a transport mechanism could be a rotary table or an x/y movement and can be operated under microprocessor control to provide an automated operation for the application of marker materials to a slide.
  • the invention has been described above in terms of the application of a single marker material to a single selected area of the surface of the absorbent layer on a carrier.
  • the surface to which the marker material is applied need not be absorbent, but may be structured in some other manner to define and retain the marker material within the confines of a selected area of the carrier surface, for example using the recessed top layer on the carrier as described above.
  • the surface of the carrier may be subdivided physically by walls or the like into separate cells or areas, as is the case with an analytical cell, and the marker material applied in a binder which forms a film of the marker material upon the floor or base of the cells or areas.
  • Such a form of construction may be desirable where the scanning of the test slide to which a sample of the fluid to be assessed is to be viewed in a conventional automated sample analysis machine.
  • the invention also provides an apparatus for applying a fluid containing a marker material for use in the test method, which apparatus comprises a mechanism for moving a carrier, upon which the marker material is to be applied, relative to an application mechanism by which a predetermined amount of the marker material is to be applied to a selected area of the carrier or a surface layer carried by the carrier, characterised in that the application mechanism comprises a drop on demand or impulse jet printer which has been selected and/or whose design and/or operation has been modified so that the kinetic energy of the droplets from the printer striking the carrier or surface is sufficiently low that no unacceptable spattering of the marker material or disturbance of the surface layer occurs.
  • the application mechanism comprises a drop on demand or impulse jet printer which has been selected and/or whose design and/or operation has been modified so that the kinetic energy of the droplets from the printer striking the carrier or surface is sufficiently low that no unacceptable spattering of the marker material or disturbance of the surface layer occurs.
  • the kinetic energy of the droplets is less than 40 picojoules, eg. 8 to 40 picojoules.
  • the ink jet printer for present use may have been manufactured ab initio specifically for use in the method of the invention.
  • the printer design and its operation will have been selected to ensure the desired low level of kinetic energy for the droplets.
  • the term selected as used herein is therefore to be construed to include printers which have been designed and manufactured ab initio to meet the requirements of the present invention as well as printers existing which have been selected as suitable for present use because, co-incidentally, they produce droplets having sufficiently low a kinetic energy for present use.
  • the term acceptable is used herein in relation to the spattering of the marker material and disturbance of the surface layer carried by the carrier to denote that any such spattering or disturbance which may occur does not produce spectral information from inspection of the sample which cannot be used in the test method.
  • the level of distortion which may be acceptable in any given case is readily determined by simple trial and error tests.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Biochemistry (AREA)
  • Immunology (AREA)
  • Molecular Biology (AREA)
  • Analytical Chemistry (AREA)
  • Biomedical Technology (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Physics & Mathematics (AREA)
  • Pathology (AREA)
  • Clinical Laboratory Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Ink Jet (AREA)

Abstract

La présente invention concerne un procédé permettant d'appliquer un matériau de marquage sur une surface d'un support, de manière à former une certaine quantité de dépôts d'un ou plusieurs matériaux de marquage, à un ou plusieurs emplacements sur ladite surface du support, sur laquelle peut être appliqué un échantillon d'un produit devant être évalué, de façon à interagir avec le matériau de marquage dans le dépôt, afin de fournir un spectre caractéristique se basant sur le rayonnement de l'emplacement prédéfini avec un rayonnement infrarouge, ultraviolet ou autre. Cette invention est caractérisée en ce que le matériau de marquage est appliqué à travers la buse d'une imprimante à jet d'encre goutte à la demande ou impulsionnel qui a été choisie et/ou dont le fonctionnement et/ou la conception à été modifié de façon que les gouttelettes de liquide frappant la surface ou la couche superficielle possèdent une énergie cinétique suffisamment faible, de préférence de 8 à 35 picojoules, pour qu'elles n'engendrent pas un niveau de perturbation inacceptable de la couche et/ou une dispersion du matériau de marquage sur la surface du support, notamment lorsque le support est une lame de verre plane qui présente une couche absorbante, comprenant de la silice sublimée dans un liant de gélatine, sur laquelle le matériau de marquage est appliqué. La présente invention concerne également un appareil utilisé pour la mise en oeuvre dudit procédé.
PCT/GB2001/000066 2000-01-14 2001-01-10 Procede et appareil permettant d'appliquer des gouttelettes sur une lame test, par utilisation d'une imprimante a jet d'encre Ceased WO2001051908A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2001225322A AU2001225322A1 (en) 2000-01-14 2001-01-10 Method and apparatus for applying droplets to a test slide using an ink jet printer

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB0000789A GB0000789D0 (en) 2000-01-14 2000-01-14 Apparatus
GB0000789.8 2000-01-14

Publications (1)

Publication Number Publication Date
WO2001051908A1 true WO2001051908A1 (fr) 2001-07-19

Family

ID=9883655

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB2001/000066 Ceased WO2001051908A1 (fr) 2000-01-14 2001-01-10 Procede et appareil permettant d'appliquer des gouttelettes sur une lame test, par utilisation d'une imprimante a jet d'encre

Country Status (3)

Country Link
AU (1) AU2001225322A1 (fr)
GB (1) GB0000789D0 (fr)
WO (1) WO2001051908A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7976906B2 (en) 2003-08-25 2011-07-12 DIPTech Ltd. Digital ink-jet glass printer
CN107824040A (zh) * 2016-06-28 2018-03-23 项敬来 一种石化工业废气的VOCs净化方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0172709A1 (fr) * 1982-08-09 1986-02-26 Willett International Limited Méthode pour appliquer des gouttelettes de colle en utilisant une imprimante à jet d'encre
US4835208A (en) * 1987-07-01 1989-05-30 Willett International Limited Method for applying a composition to a substrate and a composition for use therein
EP0352026A2 (fr) * 1988-07-19 1990-01-24 Ruby Pauline Bonderman Lamelle de contrôle ou d'étalonnage munie de plusieurs zones à niveaux ou types différents de composants à détecter et procédé et dispositif pour sa préparation
WO1993015404A2 (fr) * 1992-01-22 1993-08-05 Actimed Laboratories, Inc. Procede de fabrication concernant un dispositif de dosage mis en marche par echantillons
EP0798351A1 (fr) * 1996-03-29 1997-10-01 Willett International Limited Article imprimé et procédé

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0172709A1 (fr) * 1982-08-09 1986-02-26 Willett International Limited Méthode pour appliquer des gouttelettes de colle en utilisant une imprimante à jet d'encre
US4835208A (en) * 1987-07-01 1989-05-30 Willett International Limited Method for applying a composition to a substrate and a composition for use therein
EP0352026A2 (fr) * 1988-07-19 1990-01-24 Ruby Pauline Bonderman Lamelle de contrôle ou d'étalonnage munie de plusieurs zones à niveaux ou types différents de composants à détecter et procédé et dispositif pour sa préparation
WO1993015404A2 (fr) * 1992-01-22 1993-08-05 Actimed Laboratories, Inc. Procede de fabrication concernant un dispositif de dosage mis en marche par echantillons
EP0798351A1 (fr) * 1996-03-29 1997-10-01 Willett International Limited Article imprimé et procédé

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7976906B2 (en) 2003-08-25 2011-07-12 DIPTech Ltd. Digital ink-jet glass printer
US8603589B2 (en) 2003-08-25 2013-12-10 Dip Tech Ltd. Digital ink-jet glass printer
CN107824040A (zh) * 2016-06-28 2018-03-23 项敬来 一种石化工业废气的VOCs净化方法

Also Published As

Publication number Publication date
AU2001225322A1 (en) 2001-07-24
GB0000789D0 (en) 2000-03-08

Similar Documents

Publication Publication Date Title
US6399395B1 (en) Device and method of applying microdroplets to a substrate
US5658802A (en) Method and apparatus for making miniaturized diagnostic arrays
JP2524439B2 (ja) 生化学分析液体のタ―ゲットへの計量適用のための方法および装置
US8486715B2 (en) Dispensing of a diagnostic liquid onto a diagnostic reagent
US9616661B2 (en) Inkjet device and method for the controlled positioning of droplets of a substance onto a substrate
AU746828B2 (en) Apparatus for dispensing a predetermined volume of a liquid
AU755169B2 (en) Method and device for applying a plurality of microdroplets onto a substrate
EP3909678B1 (fr) Dispositif de distribution numérique et procédé associé
US20080252679A1 (en) Ink Jet Device for the Controlled Positioning of Droplets of a Substance Onto a Substrate, Method for the Controlled Positioning of Droplets of a Substrate, and Use of an Ink Jet Device
US20080309701A1 (en) Ink Jet Device for Releasing Controllably a Plurality of Substances Onto a Substrate, Method of Discrimination Between a Plurality of Substances and Use of an Ink Jet Device
WO2001051908A1 (fr) Procede et appareil permettant d'appliquer des gouttelettes sur une lame test, par utilisation d'une imprimante a jet d'encre
US20060183261A1 (en) Method of forming a biological sensor
Gutmann et al. Non-contact production of oligonucleotide microarrays using the highly integrated TopSpot nanoliter dispenser
Gutmann et al. Impact of medium properties on droplet release in a highly parallel nanoliter dispenser
TW517015B (en) Multi-reagent inkjet cartridge
WO2001051219A2 (fr) Procede et appareil
Gutmann et al. Droplet release in a highly parallel, pressure driven nanoliter dispenser
US11820140B2 (en) Dispense modes for multi-mode capable device
JP7595783B2 (ja) キャリア上に液体を滴下するための装置及び方法
Müller et al. Manufacturing of 2-D arrays by pin-printing technologies
EP1069941A2 (fr) Procede et dispositif pour realiser des series de syntheses et d'analyses
JP2004506184A (ja) インクジェットプリントヘッドによるマイクロアレイの高度平行構成体
JP2006145224A (ja) プローブ担体製造用の液体吐出装置及び製造装置

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CR CU CZ DE DK DM DZ EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT TZ UA UG US UZ VN YU ZA ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE TR BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: JP