[go: up one dir, main page]

WO2012115369A2 - Mésogène réactif à base de triphénylène contenant de l'acétylène - Google Patents

Mésogène réactif à base de triphénylène contenant de l'acétylène Download PDF

Info

Publication number
WO2012115369A2
WO2012115369A2 PCT/KR2012/000955 KR2012000955W WO2012115369A2 WO 2012115369 A2 WO2012115369 A2 WO 2012115369A2 KR 2012000955 W KR2012000955 W KR 2012000955W WO 2012115369 A2 WO2012115369 A2 WO 2012115369A2
Authority
WO
WIPO (PCT)
Prior art keywords
scheme
triphenylene
acetylene
arh
reactive mesogen
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/KR2012/000955
Other languages
English (en)
Korean (ko)
Other versions
WO2012115369A3 (fr
Inventor
가재원
이미혜
정혜인
박정신
김진수
이계형
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.)
Korea Research Institute of Chemical Technology KRICT
Original Assignee
Korea Research Institute of Chemical Technology KRICT
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 Korea Research Institute of Chemical Technology KRICT filed Critical Korea Research Institute of Chemical Technology KRICT
Publication of WO2012115369A2 publication Critical patent/WO2012115369A2/fr
Publication of WO2012115369A3 publication Critical patent/WO2012115369A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C237/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups
    • C07C237/02—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atoms of the carboxamide groups bound to acyclic carbon atoms of the carbon skeleton
    • C07C237/20—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atoms of the carboxamide groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton containing six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/88—Carboxylic acid amides having nitrogen atoms of carboxamide groups bound to an acyclic carbon atom and to a carbon atom of a six-membered aromatic ring wherein at least one ortho-hydrogen atom has been replaced
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/32—Non-steroidal liquid crystal compounds containing condensed ring systems, i.e. fused, bridged or spiro ring systems
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/13363—Birefringent elements, e.g. for optical compensation
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/32—Non-steroidal liquid crystal compounds containing condensed ring systems, i.e. fused, bridged or spiro ring systems
    • C09K2019/328—Non-steroidal liquid crystal compounds containing condensed ring systems, i.e. fused, bridged or spiro ring systems containing a triphenylene ring system
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/13363—Birefringent elements, e.g. for optical compensation
    • G02F1/133633—Birefringent elements, e.g. for optical compensation using mesogenic materials

Definitions

  • the present invention relates to a disk-shaped mesogen compound containing a photoreactive group capable of film formation through photocrosslinking reaction by ultraviolet (UV) irradiation and containing acetylene for high birefringence, and a method for preparing the same.
  • UV ultraviolet
  • CTR cathod ray tube
  • LCD which combines liquid crystal and semiconductor technology, is widely applied to large TVs, PC monitors, display devices of various measuring devices, PMP or mp3 devices, car navigation devices, mobile phones, etc. due to its thin, light and low power consumption.
  • TN twisted nematic
  • STN super twisted nematic
  • VA Very alignment
  • IPS Intelligent alignment switching
  • the rod-shaped liquid crystal molecules used in such LCDs are oriented in one direction on the polymer alignment layer, and this orientation causes a change in the apparent ⁇ nd of the liquid crystals according to the viewing angle in each LCD, thereby limiting the optical viewing angle in the LCD.
  • the traveling light meets the liquid crystal molecules at different angles, thereby causing a difference in the polarization state of the transmitted light.
  • some of the light leaks when the transmitted light passes through the polarizer on the LCD surface.
  • Compensation film is a principle of compensating using a film having an opposite direction while having a change value of a phase difference with increasing viewing angle.
  • Compensation films for wide viewing angles which are currently used in LCDs in TN mode, have been commercialized as film-forming mixtures containing discotic reactive liquid crystals having negative birefringence, but have a low birefringence value and a thick film.
  • the present invention provides an acetylene-containing triphenylene-based reactive mesogen compound capable of producing a compensation film, which is a core material, for a large-screen wide viewing angle liquid crystal display, and provides a compensation film prepared by including the acetylene-containing triphenylene-based reactive mesogen compound. do.
  • the present invention provides an electronic device, particularly a liquid crystal display device having a compensation film manufactured using the acetylene-containing triphenylene-based reactive mesogen compound.
  • the present invention provides an acetylene-containing triphenylene-based reactive mesogen compound of the general formula (1) having a photoreactive group capable of film formation by photocrosslinking and including acetylene for high birefringence.
  • X is any one selected from O, NH, S,
  • Z is , , , , , , Is any one selected from
  • the acetylene-containing triphenylene-based reactive mesogen compound may be exemplified by the acetylene-containing triphenylene-based reactive mesogen compound represented by the following formula (2) or (3).
  • R is a linear or branched C 1 -C 12 alkylene group
  • Ar is acetylene containing phenylene, naphthylene, anthracenylene, benzopyrenylene, pyrenylene, phenanthryl or fluorenylene
  • Triphenylene-based reactive mesogen compounds may be exemplified, but this does not limit the compound of the present reaction.
  • the present invention provides a compensation film comprising a liquid crystal composition comprising an acetylene-containing triphenylene-based reactive mesogen compound represented by the formula (1).
  • the present invention also provides a liquid crystal display device having the compensation film.
  • the present invention provides an acetylene-containing triphenylene-based reactive mesogen compound by introducing acetylene for high birefringence and side branches for liquid crystal phase temperature control.
  • Example 1 is a polarization optical microscope photograph observed after aligning a triphenylene-based reactive mesogen compound containing acetylene prepared in Example 2 on the alignment layer and film formation.
  • FIG. 2 shows a birefringence measuring apparatus (PEM) of a film produced by photocuring in Preparation Example 3, and description of each reference is as follows.
  • PEM birefringence measuring apparatus
  • Figure 3 shows the birefringence value measured according to the thickness of the film produced by the photocuring of Preparation Example 3.
  • the present invention provides an acetylene-containing triphenylene-based reactive mesogen compound capable of producing a compensation film, which is a core material of a liquid crystal display.
  • the acetylene-containing triphenylene-based reactive mesogen compound of the present invention includes acetylene for high birefringence around triphenylene and can be crosslinked by photoreaction at the terminal side of the compound with acryloyl group, methacryloyl group, and phenyl Acryloyl group (cinnamoyl group) or furyl acryloyl group was introduced.
  • the acetylene-containing triphenylene-based reactive mesogen compound of the present invention is characterized by the following formula (1).
  • X is any one selected from O, NH, S,
  • Z is , , , , , , Is any one selected from
  • the acetylene-containing triphenylene-based reactive mesogen compound may be exemplified by the acetylene-containing triphenylene-based reactive mesogen compound represented by the following formula (2) or (3).
  • R is a linear or branched C 1 -C 12 alkylene group
  • Ar is acetylene containing phenylene, naphthylene, anthracenylene, benzopyrenylene, pyrenylene, phenanthryl or fluorenylene
  • Triphenylene-based reactive mesogen compounds may be exemplified, but this does not limit the compound of the present reaction.
  • the present invention provides a liquid crystal composition comprising an acetylene-containing triphenylene-based reactive mesogen compound represented by Formula 1, and the liquid crystal composition comprising an acetylene-containing triphenylene-based reactive mesogen compound is not particularly limited, but a liquid crystal display device It can be usefully used as a liquid crystal medium, a liquid crystal organic semiconductor material layer, etc. in various modes including a compensation film, IPS.
  • the present invention provides a compensation film including the liquid crystal composition, and the compensation film has a high birefringence and the liquid crystal display device having the same has an advantage of realizing a wide viewing angle of a large screen.
  • acetylene-containing triphenylene-based reactive mesogen compound of Chemical Formula 1 of the present invention can be produced by the reactions described in Schemes 1 to 221 below.
  • the acetylene-containing side branches for the high birefringence disc-shaped mesogen can be prepared through the reaction schemes 25 to 112.
  • a photocrosslinkable acetylene-containing triphenylene-based reactive mesogen compound including a symmetric or asymmetric acetylene group may be prepared.
  • Acetylene-containing triphenylene-based reactive mesogen compound of the present invention is a symmetric or asymmetric triphenylene acetylene group for the center and high birefringence, side branches for various liquid crystal phase temperature control, the compound of the crosslinking to enable a variety of conditions
  • the acryloyl group, the methacryloyl group, the phenyl acryloyl group (cinnamoyl group), or the furyl acryloyl group was introduce
  • a compensation film of a liquid crystal display device can be manufactured in a thin film, and a liquid crystal device employing such a compensation film has an advantage of realizing a wide viewing angle. have.
  • Example 3 Film preparation containing acetylene-containing triphenylene-based reactive mesogen prepared in Example 2
  • Example 2 compound in anisole when preparing a 1000 nm thick film using an acetylene-containing triphenylene-based reactive mesogen compound prepared in Example 2 on the rubbed alignment layer Example 2 compound in anisole when preparing a film of 24wt%, 250 nm thick A liquid crystal solution in which 7 wt% was dissolved was prepared.
  • Triphenylene-based reactive mesogen (2,3,6,7,10,11-hexakis [4- (6-acryloyloxyhexyloxy) benzoyloxy] containing no acetylene in place of the acetylene-containing triphenylene-based reactive mesogen compound of Preparation Example 2 Except for using triphenylene) to prepare a film in the same manner as in Example 3.
  • Example 3 Before the alignment of the liquid crystal compound synthesized through Example 2 can confirm the image of the liquid crystal under a polarization optical microscope, if the film is formed as in Example 3 after the alignment, as shown in the polarization optical microscope picture of Figure 1, the film is a polarizer When placed between 0 degrees and 45 degrees, black and white single phases were observed.
  • Example 3 PEM equipment was used as shown in FIG. 2 to measure the phase difference of the compensation film obtained in Example 3.
  • the orientation of the liquid crystal was fixed to the polarizing axis of the polarizer and the analyzer between the 90 ° orthogonal polarizer and the analyzer so as to be 45 ° , and then rotated 360 ° on the plane to measure the transmittance of light as a voltage change amount. This experiment was repeated five times.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Nonlinear Science (AREA)
  • Mathematical Physics (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Polarising Elements (AREA)
  • Liquid Crystal Substances (AREA)

Abstract

La présente invention concerne un composé à cristaux liquides destiné à un film de compensation pour un dispositif d'affichage à cristaux liquides, et plus particulièrement un mésogène réactif à base de triphénylène contenant de l'acétylène. Selon la présente invention, le mésogène réactif à base de triphénylène contenant de l'acétylène peut être formé en couche mince pour un film de compensation en raison de la biréfringence élevée de celui-ci, et un dispositif à cristaux liquides utilisant ledit film de composition est avantageux en ce qu'il peut produire un angle de vision large pour un grand écran.
PCT/KR2012/000955 2011-02-24 2012-02-09 Mésogène réactif à base de triphénylène contenant de l'acétylène Ceased WO2012115369A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR1020110016412A KR101260235B1 (ko) 2011-02-24 2011-02-24 아세틸렌 함유 트리페닐렌계 반응성 메조겐
KR10-2011-0016412 2011-02-24

Publications (2)

Publication Number Publication Date
WO2012115369A2 true WO2012115369A2 (fr) 2012-08-30
WO2012115369A3 WO2012115369A3 (fr) 2012-10-18

Family

ID=46721290

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2012/000955 Ceased WO2012115369A2 (fr) 2011-02-24 2012-02-09 Mésogène réactif à base de triphénylène contenant de l'acétylène

Country Status (2)

Country Link
KR (1) KR101260235B1 (fr)
WO (1) WO2012115369A2 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI501042B (zh) * 2012-12-26 2015-09-21 Cheil Ind Inc 硬遮罩組成物用單體及包含該單體之硬遮罩組成物，以及使用該硬遮罩組成物形成圖案的方法

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI409509B (zh) 2005-09-07 2013-09-21 Fujifilm Corp 光學補償膜、其製法、及使用它之偏光板與液晶顯示裝置
JP2007233082A (ja) 2006-03-01 2007-09-13 Fujifilm Corp 重合性液晶化合物を用いた光学補償フィルム、および偏光板、液晶表示装置
JP2009098662A (ja) 2007-09-28 2009-05-07 Fujifilm Corp 液晶表示装置
JP2010262098A (ja) * 2009-05-01 2010-11-18 Fujifilm Corp 光学補償フィルム、光学補償フィルムの製造方法、偏光板、及び液晶表示装置
KR100997544B1 (ko) 2009-05-29 2010-11-30 한국화학연구원 아마이드기를 포함하는 내열성 트리페닐렌계 반응성 메조겐
CN102211973A (zh) * 2011-04-11 2011-10-12 北京科技大学 一种取向可控苯并菲类盘状液晶分子及其制备方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI501042B (zh) * 2012-12-26 2015-09-21 Cheil Ind Inc 硬遮罩組成物用單體及包含該單體之硬遮罩組成物，以及使用該硬遮罩組成物形成圖案的方法
US9513546B2 (en) 2012-12-26 2016-12-06 Cheil Industries, Inc. Monomer, hard mask composition comprising said monomer, and method for forming pattern using said hard mask composition

Also Published As

Publication number Publication date
KR20120115606A (ko) 2012-10-19
KR101260235B1 (ko) 2013-05-03
WO2012115369A3 (fr) 2012-10-18

Similar Documents

Publication Publication Date Title
WO2022216094A1 (fr) Agoniste du récepteur glp-1, composition pharmaceutique le comprenant et son procédé de préparation
WO2013105747A1 (fr) Composé pour élément électronique organique, élément électronique organique l'utilisant et dispositif électronique associé
WO2014058232A2 (fr) Matériau organique de type spiro et dispositif électroluminescent organique le mettant en œuvre
WO2018066830A1 (fr) Dispositif électroluminescent organique à longue durée de vie, faible tension et efficacité élevée
WO2022107992A1 (fr) Mxene bidimensionnel modifié en surface et procédé permettant de le produire
WO2013081315A1 (fr) Composé pour un dispositif électronique organique, dispositif électronique organique comprenant celui-ci et dispositif électronique comprenant le dispositif électronique organique
WO2018066872A1 (fr) Dérivé de 3-phényl -2,3,4,8,9,10-hexahydropyrano [2,3-f] chromène et procédé de synthèse d'un isomère optique de celui-ci
WO2015016456A1 (fr) Film de retardement et dispositif d'affichage d'images présentant un tel film
WO2019212183A1 (fr) Composé de cristaux liquides polymérisable, composition de cristaux liquides pour élément optique, polymère, corps optiquement anisotrope et élément optique pour dispositif d'affichage
WO2021101003A1 (fr) Procédé de synthèse de gliflozine à l'aide d'un intermédiaire de méthanesulfonylation dans un procédé de réaction en continu
WO2019212184A1 (fr) Composé de cristaux liquides polymérisable, composition de cristaux liquides pour élément optique, polymère, corps optiquement anisotrope et élément optique pour dispositif d'affichage
WO2013051831A2 (fr) Composition de formation d'une couche d'alignement et couche d'alignement et film de différence de phase fabriqués à l'aide de celle-ci
WO2019074241A1 (fr) Inhibiteur de l'interaction entre pd-1 et pd-l1, comprenant un dérivé de phénylacétylène
WO2023243864A1 (fr) Composé de cristaux liquides pour film de retard, film de retard le comprenant, dispositif d'affichage le comprenant, et son procédé de fabrication
WO2012115369A2 (fr) Mésogène réactif à base de triphénylène contenant de l'acétylène
WO2020036382A1 (fr) Procédé de production d'intermédiaire utile pour la synthèse d'un inhibiteur de sglt
WO2020149574A1 (fr) Composition d'alignement de cristaux liquides, procédé de préparation d'un film d'alignement de cristaux liquides l'utilisant, et film d'alignement de cristaux liquides et affichage à cristaux liquides l'utilisant
WO2016085087A9 (fr) Composés (méth)acryliques ayant un indice de réfraction élevé, leur procédé de préparation, feuille optique les comprenant, et dispositif d'affichage optique l'utilisant
WO2018097630A1 (fr) Composé polymérisable et composition de cristaux liquides le comprenant
WO2020105933A1 (fr) Composition d'agent d'alignement de cristaux liquides, procédé de préparation de film d'alignement de cristaux liquides l'utilisant, et film d'alignement de cristaux liquides et dispositif d'affichage à cristaux liquides l'utilisant
WO2020080625A1 (fr) Film polarisant à revêtement utilisant un mélange cristallin liquide lyotrope à base de diacétylène contenant des iodes, et procédé de fabrication associé
WO2020080784A1 (fr) Composé et film de conversion de couleur le comprenant
WO2022065938A1 (fr) Composé pour une émission induite par agrégation, composition pour imagerie cellulaire l'utilisant et utilisation en tant qu'agent de contraste pour imagerie cellulaire
WO2019088747A1 (fr) Matériau électrochromique présentant une excellente solubilité et dispositif électrochromique le comprenant
WO2022045737A1 (fr) Composition de résine photosensible positive

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 12749811

Country of ref document: EP

Kind code of ref document: A2

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 12749811

Country of ref document: EP

Kind code of ref document: A2