WO2012044867A1 - Patterned retarder - Google Patents
Patterned retarder Download PDFInfo
- Publication number
- WO2012044867A1 WO2012044867A1 PCT/US2011/054091 US2011054091W WO2012044867A1 WO 2012044867 A1 WO2012044867 A1 WO 2012044867A1 US 2011054091 W US2011054091 W US 2011054091W WO 2012044867 A1 WO2012044867 A1 WO 2012044867A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- stripes
- retardation
- type
- organic compound
- list
- Prior art date
Links
- 0 CC(C=C1)(C=CC(Oc2c3)=C1Nc2cc(C=C1)c3C=C*1S(O)(=O)=O)S(O)(=O)=O Chemical compound CC(C=C1)(C=CC(Oc2c3)=C1Nc2cc(C=C1)c3C=C*1S(O)(=O)=O)S(O)(=O)=O 0.000 description 2
- WRVJUMWFAIFFQF-UHFFFAOYSA-N CC(C=C1)(C=CC(C(c2ccc(C(C=C3)=C4C=CC3(C)S(O)(=O)=O)c3c22)=O)=C1c2ccc3C4=O)S(O)(=O)=O Chemical compound CC(C=C1)(C=CC(C(c2ccc(C(C=C3)=C4C=CC3(C)S(O)(=O)=O)c3c22)=O)=C1c2ccc3C4=O)S(O)(=O)=O WRVJUMWFAIFFQF-UHFFFAOYSA-N 0.000 description 1
- MXLNEUAAMYZJDP-UHFFFAOYSA-N OC(c(cc1)cc(S(O)(=O)=O)c1-c(ccc(C(O)=O)c1)c1S(O)(=O)=O)=O Chemical compound OC(c(cc1)cc(S(O)(=O)=O)c1-c(ccc(C(O)=O)c1)c1S(O)(=O)=O)=O MXLNEUAAMYZJDP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/08—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of polarising materials
-
- 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
- C09K19/38—Polymers
- C09K19/3804—Polymers with mesogenic groups in the main chain
-
- 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
- C09K19/38—Polymers
- C09K19/3804—Polymers with mesogenic groups in the main chain
- C09K19/3809—Polyesters; Polyester derivatives, e.g. polyamides
-
- 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
- C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
- C09K19/60—Pleochroic dyes
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B30/00—Optical systems or apparatus for producing three-dimensional [3D] effects, e.g. stereoscopic images
- G02B30/20—Optical systems or apparatus for producing three-dimensional [3D] effects, e.g. stereoscopic images by providing first and second parallax images to an observer's left and right eyes
- G02B30/22—Optical systems or apparatus for producing three-dimensional [3D] effects, e.g. stereoscopic images by providing first and second parallax images to an observer's left and right eyes of the stereoscopic type
- G02B30/25—Optical systems or apparatus for producing three-dimensional [3D] effects, e.g. stereoscopic images by providing first and second parallax images to an observer's left and right eyes of the stereoscopic type using polarisation techniques
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3016—Polarising elements involving passive liquid crystal elements
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3083—Birefringent or phase retarding elements
-
- H—ELECTRICITY
- H04—ELECTRIC COMMUNICATION TECHNIQUE
- H04N—PICTORIAL COMMUNICATION, e.g. TELEVISION
- H04N13/00—Stereoscopic video systems; Multi-view video systems; Details thereof
- H04N13/30—Image reproducers
- H04N13/332—Displays for viewing with the aid of special glasses or head-mounted displays [HMD]
- H04N13/337—Displays for viewing with the aid of special glasses or head-mounted displays [HMD] using polarisation multiplexing
-
- 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
- C09K2019/0488—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a special bonding
- C09K2019/0496—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a special bonding the special bonding being a specific pi-conjugated group
Definitions
- the present invention relates generally to the field of organic chemistry and particularly to the optical retardation films particularly for application in 3D liquid crystal displays.
- Two images can be projected onto a screen using polarized (linear or circular) light.
- Suitable viewing devices enable the viewer to reconstruct the 3-D image.
- Many devices are described as LCD shutter devices. These use liquid crystalline materials to provide a filter to each eye. The device is electronically controlled so that the shutters are activated sequentially. This allows the viewer to see the first image through the left eye and later the other image through the right eye.
- the present invention provides a patterned retarder comprising at least one retardation plate comprising a substrate substantially transparent in visible spectral range and having front and rear surfaces and a set of parallel stripes located on front surface of the substrate and possessing in-plane retardation.
- the present invention provides a method of producing a patterned retardation plate, comprising the steps of a) preparation of a lyotropic liquid crystal solution of a composition comprising at least one organic compound of a first type, and/or at least one organic compound of a second type, wherein the organic compound of the first type has the general structural formula I
- Core is a conjugated organic unit capable of forming a rigid rod-like
- n is a number of the conjugated organic units in the rigid rod-like macromolecule
- Gk is a set of ionogenic side-groups
- k is a number of the side-groups in the set Gk; wherein the ionogenic side-groups and the number k provide solubility of the organic compound of the first type in a solvent and give rigidity to the rod-like
- the number n provides molecule anisotropy that promotes self-assembling of macromolecules in a solution of the organic compound or its salt, and wherein the organic compound of the second type has the eneral structural formula II
- Sys is an at least partially conjugated substantially planar polycyclic molecular system
- X, Y, Z, Q and R are substituents; substituent X is a carboxylic group -COOH, m is 0, 1, 2, 3 or 4; substituent Y is a sulfonic group -SO 3 H, h is 0, 1, 2, 3 or 4; substituent Z is a carboxamide -CONH 2 , p is 0, 1, 2, 3 or 4; substituent Q is a sulfonamide S0 2 NH 2 , v is 0, 1, 2, 3 or 4; wherein the organic compound of the second type is capable of forming board- like supramolecules via ⁇ - ⁇ -interaction, b) coating of a liquid layer of the solution onto a substrate, c) application of an external alignment action onto said liquid layer, d) drying to form a solid optical retardation layer, and e) forming of a set of parallel retardation stripes.
- Figure 1 schematically shows one embodiment of a retardation plate according to the present invention.
- Figure 2 schematically shows another embodiment of a retardation plate according to the present invention.
- Figure 3 schematically shows one embodiment of a patterned retarder according to the present invention.
- Figures 4a and 4b schematically show another embodiment of a patterned retarder according to the present invention.
- FIGS 5 a and 5b schematically show yet another embodiment of a patterned retarder according to the present invention.
- visible spectral range refers to a spectral range having the lower boundary approximately equal to 400 nm, and upper boundary approximately equal to 700 nm.
- retardation layer refers to an optically anisotropic layer which is characterized by three principal refractive indices (n x , n y and n z ), wherein two principal directions for refractive indices n x and n y belong to xy-plane coinciding with a plane of the retardation layer and one principal direction for refractive index (n z ) coincides with a normal line to the retardation layer.
- optically anisotropic retardation layer of Ac-type refers to an optical layer which principal refractive indices n x , n y , and n z obey the following condition in the visible spectral range: n z ⁇ n y ⁇ n x .
- optically anisotropic retardation layer of B A -type refers to an optical layer which principal refractive indices n x , n y , and n z obey the following condition in the visible spectral range: n x ⁇ n z ⁇ n y .
- the present invention provides a patterned retarder as disclosed hereinabove.
- the stripes possess B A -type retardation and characterized by two principal refractive indices (n x and n y ) corresponding to two mutually perpendicular directions in the plane of the stripes and one principal refractive index (n z ) in the normal direction to the stripes, which satisfy the following condition: n x ⁇ n z ⁇ n y .
- the fast optical axis corresponding to the principal refractive index n x is directed in a parallel way with respect to stripes.
- the fast optical axis corresponding to the principal refractive index n x is directed perpendicularly with respect to stripes.
- the fast optical axis corresponding to the principal refractive index n x is directed at 45 degrees in respect to the stripes.
- the fast optical axis corresponding to the principal refractive index n x is directed in a parallel way with respect to the stripes.
- the fast optical axis corresponding to the principal refractive index n x is directed perpendicularly with respect to the stripes.
- the fast optical axis corresponding to the principal refractive index n x is directed at 45 degrees in respect to the stripes.
- the stripes possess positive A-type retardation and are characterized by two principal refractive indices (n x and n y )
- the slow optical axis corresponding to the principal refractive index n x is directed in a parallel way with respect to the stripes.
- the slow optical axis corresponding to the principal refractive index n x is directed perpendicularly with respect to the stripes.
- the slow optical axis corresponding to the principal refractive index n x is directed at 45 degrees in respect to the stripes.
- the stripes possess Ac-type retardation and characterized by two principal refractive indices (n x and n y ) corresponding to two mutually perpendicular directions in the plane of the stripes and one principal refractive index (n z ) in the normal direction to the stripes, which satisfy the following condition: n z ⁇ n y ⁇ n x .
- the slow optical axis n z ⁇ n y ⁇ n x .
- the slow optical axis corresponding to the principal refractive index n x is directed in a parallel way with respect to the stripes.
- the slow optical axis corresponding to the principal refractive index n x is directed is directed perpendicularly with respect to the stripes.
- the slow optical axis corresponding to the principal refractive index n x is directed at 45 degrees in respect to the stripes.
- the stripes further comprise at least one organic compound of a first type or its salt, and/or at least one organic compound of a second type.
- the organic compound of the first type has the general structural formula I
- Core is a conjugated organic unit capable of forming a rigid rod-like
- n is a number of the conjugated organic units in the rigid rod-like macromolecule which is equal to integers in the range from 10 to 10000
- G k is a set of ionogenic side-groups
- k is a number of the side-groups in the set G k
- k is a number of the side-groups in the set G k i which is equal to 0, 1, 2, 3, 4, 5, 6, 7, or 8.
- the organic compound of the second type has the general structural formula II
- Sys is an at least partially conjugated substantially planar polycyclic molecular system
- X, Y, Z, Q and R are substituents
- substituent X is a carboxylic group -COOH, m is 0, 1, 2, 3 or 4
- substituent Y is a sulfonic group -SO 3 H, h is 0, 1, 2, 3 or 4
- substituent Z is a carboxamide -CONH 2 , p is 0, 1, 2, 3 or 4
- substituent Q is a sulfonamide -S0 2 NH 2 , v is 0, 1, 2, 3 or 4.
- the organic compound of the second type forms board-like
- composition comprising the compounds of the first and the second types forms lyotropic liquid crystal in a solution with a suitable solvent.
- the organic compound of the first type is selected from the structures 1 to 20 shown in Table 1.
- R is a side-group selected from the list comprising Alkil, (CH 2 ) m S0 3 H, (CH 2 ) m Si(0 Alkyl) 3 , CH 2 Phenyl, (CH 2 ) m OH and M is counterion selected from the list comprising H + , Na + , K + , Li + , Cs + , Ba 2+ , Ca 2+ , Mg 2+ , Sr 2+ , Pb 2+ , Zn 2+ , La 3+ , Ce 3+ , Y 3+ , Yb 3+ , Gd 3+ , Zr 4+ and NH 4 _ k Q k + , where Q is selected from the list comprising linear and branched (C 1-C20) alkyl, (C2-C20) alkenyl, (C2-C20) alkinyl, and (C6-C20)arylalkyl, and k
- the organic compound of the first type further comprises additional side-groups independently selected from the list comprising linear and branched (Ci- C 2 o)alkyl, (C 2 -C 2 o)alkenyl, and (C 2 -C 2 o)alkinyl.
- at least one of the additional side-groups is connected with the conjugated organic unit Core via a bridging group A selected from the list comprising -C(O)-, -C(0)0-, -C(0)-NH-, -(S0 2 )NH-, -0-, -CH 2 0-, -NH-, >N-, and any combination thereof.
- the salt of the organic compound of the first type is selected from the list comprising ammonium and alkali-metal salts.
- the organic compound of the second type has at least partially conjugated substantially planar polycyclic molecular system Sys selected from the structures of the general formulas 21 to 34 shown in Table 2.
- the organic compound of the second type is selected from structures 35 to 43 shown in Table 3, where the molecular system Sys is selected from the structures 21 and 28 to 34, the substituent is a sulfonic group -SO 3 H, and ml, pi, and vl are equal to 0.
- the organic compound of the second type further comprises at least one substituent selected from the list comprising CH 3 , C 2 H 5 , CI, Br, N0 2 , F, CF 3 , CN, OH, OCH 3 , OC 2 H 5 , OCOCH 3 , OCN, SCN, and NHCOCH 3 .
- the substrate is made of a polymer. In another embodiment of a patterned retarder, the substrate is made of a glass. In yet another embodiment of a patterned retardation plate, the substrate is made of a birefringent material substantially transparent to electromagnetic radiation in the visible spectral range and possesses an anisotropic property of a positive A-type retarder.
- the birefringent material is selected from the list comprising poly ethylene terephtalate (PET), poly ethylene naphtalate (PEN), polyvinyl chloride (PVC), polycarbonate (PC), poly propylene (PP), poly ethylene (PE), polyimide (PI), and poly ester.
- a patterned retarder further comprises planarization layer located on top of the set of the stripes.
- a patterned retarder further comprises an additional transparent adhesive layer.
- a patterned retarder further comprises a retardation panel.
- the retardation panel comprises a panel substrate substantially transparent in visible spectral range and having front and rear surfaces and a panel retardation layer located on the front surface of the panel substrate, wherein the retardation plate is located on the panel retardation layer so that the front surface of the panel substrate is facing the front surface of the substrate of the retardation plate.
- the panel retardation layer further comprise at least one organic compound of a first type or its salt, wherein the organic compound of the first type has the general structural formula I
- Core is a conjugated organic unit capable of forming a rigid rod-like
- n is a number of the conjugated organic units in the rigid rod-like macromolecule which is equal to integers in the range from 10 to 10000
- G k is a set of ionogenic side-groups
- k is a number of the side-groups in the set G k
- k is a number of the side-groups in the set G k i which is equal to 0, 1 , 2, 3, 4, 5, 6, 7, or 8; and/or at least one organic compound of a second type, wherein the organic compound of the second type has the general structural formula II
- Sys is an at least partially conjugated substantially planar polycyclic molecular system
- X, Y, Z, Q and R are substituents
- substituent X is a carboxylic group -COOH, m is 0, 1, 2, 3 or 4
- substituent Y is a sulfonic group -SO 3 H, h is 0, 1, 2, 3 or 4
- substituent Z is a carboxamide -CONH 2 , p is 0, 1, 2, 3 or 4
- substituent Q is a sulfonamide -S0 2 NH 2 , v is 0, 1, 2, 3 or 4;
- the organic compound of the second type forms board-like supramolecules via ⁇ - ⁇ -interaction
- a composition comprising the compounds of the first and the second types forms lyotropic liquid crystal in a solution with a suitable solvent.
- the stripes of the retardation plate possess in-plane retardation equal to ⁇ /2 and the additional retardation panel possesses in-plane retardation equal to ⁇ /4, where ⁇ is central wave-length of a working wave-band.
- a patterned retarder comprises two retardation plates.
- the first retardation plate comprises a first substrate having a front surface and a rear surface and the second retardation plate comprises a second substrate having a front surface and a rear surface.
- the first retardation plate comprises a first set of parallel stripes located on the front surface of the first substrate and the second retardation plate comprises a second set of parallel stripes located on the front surface of the second substrate.
- the first retardation plate is located on the second retardation plate so that the front surface of the first substrate is faced to the front surface of the second substrate.
- the stripes of the first set are located between the stripes of the second set and the stripes of both sets are mostly parallel to each other.
- the in-plane retardation of the stripes of the first retardation plate and the in-plane retardation of the stripes of the second retardation plate are equal to ⁇ /4, where ⁇ is central wave-length of a working wave-band, wherein the fast optical axis of the first retardation plate is directed perpendicularly with respect to the fast optical axis of the second retardation plate, and wherein the optical axes are located in the plane of the stripes.
- the in-plane retardations of the first patterned retardation plate is equals to ⁇ /4 and the in-plane retardations of the second patterned retardation plate is equals to 3 ⁇ /4, where ⁇ is central wave-length of a working wave-band.
- the present invention also provides a method of producing a patterned retardation plate as disclosed hereinabove.
- the forming of the set of parallel retardation stripes is carried out by different methods selected from the list comprising skiving, plasma-assisted etching and laser ablation method.
- the disclosed method further comprises a post- treatment step comprising a treatment with a solution of any inorganic salt with a cation selected from the list comprising H + , Ba 2+ , Pb 2+ , Ca 2+ , Mg 2+ , Sr 2+ , La 3+ , Zn 2+ , Zr 4+ , Ce 3+ , Y 3+ , Yb 3+ , Gd 3+ and any combination thereof soluble in water or any solvent mixable with water.
- the application of an external alignment action c) and the forming of the set of parallel retardation stripes e) are carried out simultaneously.
- the drying d) and the forming of the set of parallel retardation stripes e) are carried out sequentially.
- the external alignment action is directed in a parallel way with respect to the retardation stripes.
- the external alignment action is directed perpendicularly with respect to the retardation stripes.
- the organic compound of the first type is selected from the structures 1 to 20 shown in Table 1.
- the organic compound of the first type further comprises additional side-groups independently selected from the list comprising linear and branched (C ⁇ - C2o)alkyl, (C 2 - C 2 o)alkenyl, and (C 2 -C 2 o)alkinyl.
- At least one of the additional side-groups is connected with the conjugated organic unit Core via a bridging group A selected from the list comprising -C(O)-, -C(0)0-, -C(0)-NH-, - (S0 2 )NH-, -0-, -CH 2 0-, -NH-, >N-, and any combination thereof.
- the salt of the organic compound of the first type is selected from the list comprising ammonium and alkali-metal salts.
- the organic compound of the second type has at least partially conjugated substantially planar polycyclic molecular system Sys selected from the structures 21 to 34 shown in Table 2.
- the organic compound of the second type is selected from structures 35 to 43 shown in Table 3, where the molecular system Sys is selected from the structures 21 and 28 to 34, the substituent is a sulfonic group -SO 3 H, and ml , pi , and vl , are equal to 0.
- the organic compound of the second type further comprises at least one substituent selected from the list comprising CH 3 , C2H5, CI, Br, NO2, F, CF 3 , CN, OH, OCH 3 , OC 2 H 5 , OCOCH 3 , OCN, SCN, and NHCOCH 3 .
- the stripes possess BA-type retardation and are characterized by two principal refractive indices (n x and n y ) corresponding to two mutually perpendicular directions in the plane of the stripes and one principal refractive index (n z ) in the normal direction to the stripes, which satisfy the following condition: n x ⁇ n z ⁇ n y .
- the fast optical axis corresponding to the principal refractive index n x coincides with coating direction.
- the stripes possess Ac-type retardation and characterized by two principal refractive indices (n x and n y ) corresponding to two mutually perpendicular directions in the plane of the stripes and one principal refractive index (n z ) in the normal direction to the stripes, which satisfy the following condition: n z ⁇ n y ⁇ n x .
- the slow optical axis corresponding to the principal refractive index n x coincides with coating direction.
- FIG. 1 schematically shows a retardation plate according one embodiment of the present invention.
- This retardation plate comprises a set of parallel stripes (1) coated on a substrate (2).
- the stripes possess positive A-type retardation and characterized by in-plane retardation equal to ⁇ /2 and the substrate possess positive A-type retardation also and characterized by in-plane retardation equal to ⁇ /4.
- the slow optical axes of the substrate (3) and stripes (4) mostly parallel to each other.
- the stripes (1) are made in parallel to coating direction (5).
- This retardation plate is intended for circular polarizer for 3D LCD.
- the retardation plate is attached to LCD front polarizer with slow optical axis at 45 degree to polarizer absorption axis.
- the manufacturing process is: 1) roll of polarizer is cut in diagonal pieces with -30% losses (standard process); 2) roll of retarder is made with stripes in parallel to roll axis; 3) roll of retarder is cut in rectangular pieces without losses; 4) sheets of retarder are laminated to polarizer sheets.
- FIG. 2 schematically shows a retardation plate according another embodiment of the present invention.
- This retardation plate comprises a set of parallel stripes (6) coated on a substrate (7).
- the stripes possess B A -type retardation and characterized by in-plane retardation equal to ⁇ /2 and the substrate possess positive A-type retardation and characterized by in-plane retardation equal to ⁇ /4.
- the fast optical axes of the substrate (8) and stripes (9) mostly parallel to each other.
- the stripes (6) are made perpendicular to coating direction (10).
- This retardation plate is intended for circular polarizer for 3D LCD.
- the retardation plate is attached to LCD front polarizer with slow optical axis at 45 degree to polarizer absorption axis.
- FIG. 3 schematically shows a patterned retarder according yet another embodiment of the present invention.
- This patterned retarder comprises a set of the parallel stripes (11) coated on a substrate (12) made of TAC or glass.
- the stripes possess positive A-type retardation and are characterized by in-plane retardation equal to ⁇ /2.
- the patterned retarder comprises a retardation layer (14) located on a substrate (13) made of TAC or glass.
- the retardation layer (14) possesses positive A-type retardation and is characterized by in-plane retardation equal to ⁇ /4.
- the stripes and the retardation layer are glued together with an adhesive layer (15).
- the slow optical axes of the substrate (12) and the stripes (11) are substantially parallel to each other.
- This patterned retardation plate can be used as a circular polarizer for 3D LCD.
- the patterned retarder is attached to the LCD front polarizer with slow optical axis at 45 degree to a polarizer absorption axis.
- the stripes (11) and the retardation layer (14) possess positive B A -type retardation.
- FIGS 4a and 4b schematically show a patterned retarder according to another embodiment of the present invention.
- This patterned retarder comprises a first retardation plate (16) having a set of parallel stripes (17) coated on a substrate (18) made of TAC or glass.
- the stripes possess positive A-type retardation and are characterized by in-plane retardation equal to ⁇ /4. These stripes are directed at 45 degree to coating direction (19).
- the slow optical axes (20) of the stripes (17) and coating direction (19) are substantially parallel to each other.
- the patterned retarder comprises a second retardation plate (21) having a set of parallel stripes (22) coated on a substrate (23) made of TAC or glass.
- the stripes possess positive A-type retardation and are characterized by in-plane retardation equal to ⁇ /4. These stripes are made at 45 degree to coating direction (19).
- the slow optical axes (25) of the stripes (22) and coating direction (19) are substantially
- FIGs 5 a and 5b schematically show a patterned retarder according to another embodiment of the present invention.
- the patterned retarder comprises a first retardation plate (26) having a set of parallel stripes (27) coated on a substrate (28) made of TAC or glass.
- the stripes possess positive A-type retardation and are characterized by in-plane retardation equal to 3 ⁇ /4. These stripes are covered with the adhesive stripes (29).
- the patterned retarder comprises a second retardation plate (30) having a set of parallel stripes (31) coated on a substrate (32) made of TAC or glass.
- the stripes possess positive A-type retardation and are characterized by in-plane retardation equal to ⁇ /4.
- the first (16) and second (21) retardation plates are glued together with the adhesive stripes (29).
- Figure 5b schematically shows a final design of the disclosed patterned retarder.
- This Example describes synthesis of poly(2,2'-disulfo-4,4'-benzidine terephthalamide) cesium salt (structure 1 in Table 1).
- the emulsion was diluted with 40 ml of water, and the stirring speed was reduced to 100 rpm. After the reaction mass has been homogenized the polymer was precipitated via adding 250 ml of acetone. Fibrous sediment was filtered and dried.
- GPC Gel permeation chromatography
- triphenylphosphine 20 g of Lithium chloride and 50 ml of pyridine were dissolved in 200 ml of N-methylpyrrolidone in a 500 ml three-necked flask. The mixture was stirred at
- This Example describes synthesis of poly(/?ara-phenylene sulfoterephthalamide) (structure 3 in Table 1).
- This Example describes synthesis of poly(2-sulfo-l,4-phenylene sulfoterephthalamide) (structure 4 in Table 1).
- This Example describes synthesis of poly(2,2'-disulfo-4,4' -benzidine naphthalene- 2,6-dicarboxamide) cesium salt (structure 5 in Table 1).
- Example 6 This Example describes synthesis of 4,4'-(5,5-dioxidodibenzo[b,d]thiene-3,7- diyl)dibenzenesulfonic acid (structure 32 in Table 3).
- l,l ' :4',l":4",l"'-quarerphenyl (lOg) was charged into 0%-20% oleum (100ml). Reaction mass was agitated for 5 hours at heating to 50°C. After that the reaction mixture was diluted with water (170 ml). The final sulfuric acid concentration became approximately 55%. The precipitate was filtered and rinsed with glacial acetic acid (-200 ml). The filter cake was dried in an oven at 110°C.
- This example describes synthesis of Poly(disulfobiphenylene-l,2-ethylene-2,2 '- disulfobiphenylene) (structure 6 in Table 1).
- a solution of 70 g of sodium hydroxide in 300 ml of water is added, the solution evaporated to a total volume of 400 ml, diluted with 2500 ml of methanol to precipitate the inorganic salts and filtered.
- the methanol is evaporated to 20-30 ml and 3000 ml of isopropanol is added.
- the precipitate is washed with methanol on the filter and recrystallized from methanol. Yield of 4,4'-dibromo-2,2'-biphenyldisulfonic acid is 10.7 g.
- the polymerization is carried out under nitrogen. 2.7 g of 4,4'-Dihydroxy-2,2'- biphenyldisulfonic acid and 2.0 g of dipropyleneglycol ester of bibenzyl 4,4'-diboronic acid are dissolved in a mixture of 2.8 g of sodium hydrocarbonate, 28.5 ml of tetrahydrofuran and 17 ml of water. Tetrakis(triphenylphosphine)palladium(0) is added (5 xlO " molar equivalent compared to dipropyleneglycol ester of bibenzyl 4,4'-diboronic acid). The resulting suspension is stirred for 20 hrs. 0.04 g of bromobenzene is then added.
- the polymer is precipitated by pouring it into 150 ml of ethanol.
- the product is washed with water, dried, and dissolved in toluene.
- the filtered solution is concentrated and the polymer precipitated in a 5 -fold excess of ethanol and dried.
- the yield of polymer is 2.7 g.
- This example describes synthesis of poly(2,2 '-disulfobiphenyl-dioxyterephthaloyl) (structure 7 in Table 1).
- This example describes synthesis of poly(2,2 '-disulfobiphenyl-2- sulfodioxyterephthaloyl) (structure 8 in Table 1).
- This example describes synthesis of poly(sulfophenylene-l,2-ethylene-2,2 '- disulfobiphenylene) (structure 9 in Table 1).
- a solution of 23.6 g of 1 ,4-dibromobenzene in 90 ml of dry tetrahydrofuran is prepared. 10 ml of the solution is added with stirring to 5.0 g of magnesium chips and iodine (a few crystals) in 60 ml of dry tetrahydrofuran, and the mixture is heated until reaction starts. Boiling conditions are maintained by the gradual addition of the remained dibromobenzene solution. Then the reaction mixture is boiled for 8 hours and left overnight under argon at room temperature.
- the mixture is transferred through a hose to a dropping funnel by means of argon pressure and added to a solution of 24 ml of trimethylborate in 40 ml of dry tetrahydrofuran during 3 hours at -78-70°C (a solid carbon dioxide/acetone bath) and vigorous stirring.
- the mixture is stirred for 2 hrs, then allowed to heat to room temperature with stirring overnight under argon.
- the mixture is diluted with 20 ml of ether and poured to a stirred mixture of crushed ice (200 g) and cone. H 2 SO 4 (6 ml).
- 20 ml of ether and 125 ml of water are added and the mixture is filtered.
- the aqueous layer is extracted with ether (4x40 ml), the combined organic extracts are washed with 50 ml of water, dried over sodium sulfate and evaporated to dryness.
- the light brown solid is dissolved in 800 ml of chloroform and clarified.
- the polymerization is carried out under nitrogen.
- 2.7 g of 4,4'-dibromo-2,2'-bibenzyl and 1.9 g of dipropyleneglycol ester of benzyne 1 ,4-diboronic acid are added to in a mixture of 2.8 g of sodium hydrocarbonate, 28.5 ml of tetrahydrofuran and 17 ml of water.
- Tetrakis(triphenylphosphine)palladium(0) is added (5 xlO " molar equivalent compared to dipropyleneglycol ester of benzyne 1 ,4-diboronic acid).
- the resulting suspension is stirred for 20 hrs. 0.04 g of Bromobenzene is then added.
- the polymer is precipitated by pouring it into 150 ml of ethanol.
- the product is washed with water, dried, and dissolved in toluene.
- the filtered solution is concentrated and the polymer precipitated in a 5-fold excess of ethanol and dried.
- the yield of polymer is 2.5 g.
- Example 11 This example describes synthesis of poly(2-sulfophenylene-l,2-ethylene-2 '- sulfophenylene) (structure 10 in Table 1).
- Polymerization is carried out under nitrogen. 10.2 g of 2,2'-[ethane-l,2- diylbis(4,l-phenylene)]bis-l,3,2-dioxaborinane, 10.5 g of l,l'-ethane-l,2-diylbis(4- bromobenzene) and 1 g of tetrakis(triphenylphosphine)palladium(0) are mixed under nitrogen. Mixture of 50 ml of 2.4 M solution of potassium carbonate and 300 ml of tetrahydrofuran is degassed by nitrogen bubbling. Obtained solution is added to the first mixture. After that reaction mixture is agitated at ⁇ 40°C for 72 hours. The polymer is precipitated by pouring it into 150 ml of ethanol. The product is washed with water and dried. The yield of polymer is 8.7 g.
- Example 12 This example describes synthesis of poly(2,2 '-disulfobiphenyl-2-sulfo-l,4- dioxymethylphenylene) (structure 11 in Table 1).
- a mixture of 35 ml of carbon tetrachloride, 2.5 g of p-xylene sulfonic acid, 4.8 g of N-bromosuccinimide and 0.16 g of benzoyl peroxide is heated with agitation to boiling and held at temperature for 60 min. Then additional 0.16 g of benzoyl peroxide is added, and the mixture is kept boiling for additional 60 min. After cooling the product is extracted with 45 ml of water and recrystallized form 20% hydrochloric acid. The yield of 2,5-bis(bromomethyl) benzene sulfonic acid is approximately 1 g.
- This example describes synthesis of a rigid rod-like macromolecule of the structural formula 12 in Table 1, wherein Ri is CH 3 and M is Cs.
- Maisch GmbH ReproSil - Pur Basic C18 column by use of a linear gradient prepared from acetonitrile (component A), water-solution of tetra-n-butylammonium bromide 0.01M (component B), and phosphate buffer 0.005M with pH 6.9-7.0 (component C).
- the gradient was: A-B-C 20:75:5 (v/v) to A-B-C 35:60:5 (v/v) in 20 min.
- the flow rate was 1.5 mL min "1 , the column temperature 30 °C, and effluent was monitored by diode array detector at 230 and 300 nm.
- This Example describes synthesis of natrium salt of the polymer shown with structure 20 in Table 1.
- This Example describes synthesis of natrium salt of the polymer shown with structure 18 in Table 1.
- 2-iodo-5-methylbenzenesulfonic acid 46 g, 137 mmol was placed into a two-neck flask (volume 500 mL) and water (200 mL) was added. Blue copperas copper sulfate (0.25 g, 1 mmol) in water (40 mL) was added to a resultant solution and the mixture was then heated to 85°C for 15 min. Copper powder was added (14 g, 227 mmol) to a resultant dark solution. Temperature was raised to 90° C, and then the reaction mixture was stirred for 3 h at 80-85°.
- 4,4'-dimethylbiphenyl-2,2'-disulfonic acid (30.0 g, 71.7 mmol) was dissolved in water (600 mL), and sodium hydroxide was added (12 g, 300 mmol). Resultant solution was heated to 45-50° C and potassium permanganate was added (72 g, 45 mmol) in portions for 1 h 30 min. The resultant mixture was stirred for 16 h at 50-54°C then cooled to 40° C, methanol was added (5 mL), temperature was raised to 70° C. Mixture was cooled to 40° C, filtered from manganese oxide, a clear colorless solution was concentrated to 100 mL acidified with hydrochloric acid (50 mL).
- 2,2'-disulfobiphenyl-4,4'-dicarboxylic acid (7.5 g, 18.6 mmol) was mixed with n-pentanol (85 mL, 68 g, 772 mmol) and sulfuric acid (0.5 mL) and heated under reflux with Dean- Stark trap for 3 h more. Reaction mixture was cooled to 50° C, diluted with hexane (150 mL), stirred at the same temperature for 10 min, precipitate was filtered off and washed with hexane (3x50 mL) and then dried at 50° C for 4 h. Weight 8.56 g (84%) as a white solid.
- Anhydrous tetrahydrofuran 400 mL was placed into a flask supplied with condenser, magnetic stirrer, thermometer and argon T-tube. Lithium alumohydride (3.5 g, 92 mmol) was added to tetrahydrofuran, the resultant suspension was heated to 50° C, and 4,4'- bis[(pentyloxy)carbonyl]biphenyl-2,2'-disulfonic acid was added in portions for 10 min with efficient stirring (20.0 g, 37 mmol). The resultant suspension was mildly boiled under reflux (63-64° C) for 1.5 h.
- the resultant weight is 30 g, white powder.
- Calculated product content is approx 1.25 mmol/g (50%) of diol in the mixture of inorganic salts (AICI 3 , LiCl) and solvating water.
- This Example describes synthesis of natrium salt of the polymer shown with structure 19 in Table 1.
- lOOmg of 4,4'-bis(bromomethyl)biphenyl-2-sulfonic acid, 83mg of 4,4'- dihydroxybiphenyl-2,2'-disulfonic acid and 80mg of tetra-n- butylammonium bromide were dissolved in 2ml of abs. N- methylpyrrolidone.
- 50mg of 60% sodium hydride (5.1eq.) was added by small portions to this solution, and the mixture was stirred for 4 days at 50°C. After that, the mixture was poured into 20ml of ethanol and filtered off. The precipitate was dissolved in water ( ⁇ 2-3ml) and precipitated into 50ml of ethanol and filtered off again.
- 2-Sulfo-/?-toluidine 50 g, 267 mmol was mixed with water (100 mL) and hydrochloric acid 36% (100 mL). The mixture was stirred and cooled to 0° C. A solution of sodium nitrite (20 g, 289 mmol) in water (50 mL) was added slowly (dropping funnel, 1.25 h) keeping temperature at 3-5° C.
- Powdered 2-sulfobiphenyl-4,4'-dicarboxylic acid (7.5 g, 23.3 mmol) was mixed with anhydrous (dist. over magnesium) methanol (100 mL) and sulfuric acid (d 1.84, 2.22 mL, 4.0 g, 42.6 mmol). Resultant suspension was left with stirring and mild boiling for 2 days. Sodium carbonate (5.01 g, 47.7 mmol) was added to methanol solution and stirred for 45 min then evaporated on a rotary evaportator.
- Residue (white powder) was mixed with tetrahydrofuran to remove any big particles (100 mL) and resultant suspension was dried on a rotary evaporator, then in a desiccator over phosphorus oxide under reduced pressure overnight. Resultant residue was used in further transformation as it is.
- a one -neck flask (volume 250 mL) containing dried crude 4,4'- bis(methoxycarbonyl)biphenyl-2-sulfonic acid and magnetic stirrer and closed with a stopper was filled with tetrahydrofuran (anhydrous over sodium, 150 mL).
- White suspension was stirred for 20 min at r.t. to insure its smoothness then lithium alumohydride was added in portions (0.2-0.3 g) for 40 min. Exothermic effect was observed.
- Temperature was raised to 45-50° C.
- joints were cleaned with soft tissue and flask was equipped with condenser and argon bubble T-counter. Resultant suspension was heated with stirring (bath 74° C) for 3 h.
- Reaction mixture was cooled to 10° C on ice, and water was added drop wise until hydrogen evolution (handle with caution) seized (4 mL).
- Hydrobromic acid (48%) was added in small portions until suspension became milky (43 g, acid reaction of indicator paper).
- the suspension was transferred to flask of 0.5 L volume and it was taken to almost to dryness on a rotary evaporator.
- Hydrobromic acid 48% was added to the flask (160 mL), resultant muddy solution was filtered (PALL) and flask was equipped with h-tube with a thermometer and argon inlet tube. Apparatus was flashed with argon and placed on an oil bath. Stirring was carried out while temperature (inner) was raised to 75° C for 15 min.
- 4,4'-(5,5-Dioxidodibenzo[b,d]thiene-3,7-diyl)dibenzenesulfonic acid (structure 25) was prepared by sulfonation of l,r:4',l":4",r"-quaterphenyl. 1,1':4', ⁇ :4", ⁇ '- Quaterphenyl (10 g) was charged into 20% oleum (100 ml). Reaction mass was agitated for 5 hours at ambient conditions. After that the reaction mixture was diluted with water (170 ml). The final sulfuric acid concentration became -55%. The precipitate was filtered and rinsed with glacial acetic acid (-200 ml). Filter cake was dried in oven at -110°C.
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Multimedia (AREA)
- Signal Processing (AREA)
- Polarising Elements (AREA)
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201180056748.8A CN103354912B (en) | 2010-10-02 | 2011-09-29 | Patterned retarders |
JP2013531892A JP2013541735A (en) | 2010-10-02 | 2011-09-29 | Patterned retarder |
KR1020137011160A KR20130114667A (en) | 2010-10-02 | 2011-09-29 | Patterned retarder |
EP11776040.5A EP2622392A1 (en) | 2010-10-02 | 2011-09-29 | Patterned retarder |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US38920710P | 2010-10-02 | 2010-10-02 | |
US61/389,207 | 2010-10-02 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2012044867A1 true WO2012044867A1 (en) | 2012-04-05 |
Family
ID=44872595
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2011/054091 WO2012044867A1 (en) | 2010-10-02 | 2011-09-29 | Patterned retarder |
Country Status (6)
Country | Link |
---|---|
US (2) | US20120081784A1 (en) |
EP (1) | EP2622392A1 (en) |
JP (1) | JP2013541735A (en) |
KR (1) | KR20130114667A (en) |
CN (1) | CN103354912B (en) |
WO (1) | WO2012044867A1 (en) |
Families Citing this family (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5588443B2 (en) * | 2008-08-19 | 2014-09-10 | クリスオプティクス株式会社 | Composition of organic compound, optical film and method for producing the same |
WO2012052950A1 (en) * | 2010-10-21 | 2012-04-26 | Crysoptix Kk | Retarder and liquid crystal display comprising the same |
WO2014120505A2 (en) * | 2013-01-29 | 2014-08-07 | Crysoptix Kk | Optical film |
US9360596B2 (en) | 2013-04-24 | 2016-06-07 | Light Polymers Holding | Depositing polymer solutions to form optical devices |
WO2015162495A1 (en) * | 2014-04-23 | 2015-10-29 | Light Polymers B.V. | Liquid crystal article and fabrication thereof |
US9829617B2 (en) | 2014-11-10 | 2017-11-28 | Light Polymers Holding | Polymer-small molecule film or coating having reverse or flat dispersion of retardation |
US9856172B2 (en) | 2015-08-25 | 2018-01-02 | Light Polymers Holding | Concrete formulation and methods of making |
US10403435B2 (en) | 2017-12-15 | 2019-09-03 | Capacitor Sciences Incorporated | Edder compound and capacitor thereof |
US10962696B2 (en) | 2018-01-31 | 2021-03-30 | Light Polymers Holding | Coatable grey polarizer |
US11370914B2 (en) | 2018-07-24 | 2022-06-28 | Light Polymers Holding | Methods of forming polymeric polarizers from lyotropic liquid crystals and polymeric polarizers formed thereby |
EP3753446A1 (en) | 2019-06-21 | 2020-12-23 | The Procter & Gamble Company | Cleaning element carrier and toothbrush head comprising it |
EP3753448A1 (en) | 2019-06-21 | 2020-12-23 | The Procter & Gamble Company | Method for producing a toothbrush head |
EP3753447A1 (en) | 2019-06-21 | 2020-12-23 | The Procter & Gamble Company | Method for producing a toothbrush head or a part thereof |
JP2023115445A (en) * | 2022-02-08 | 2023-08-21 | 日東電工株式会社 | optical laminate |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0887667A2 (en) * | 1997-06-28 | 1998-12-30 | Sharp Kabushiki Kaisha | Method of making a patterned retarder, patterned retarder and illumination source |
US6055103A (en) * | 1997-06-28 | 2000-04-25 | Sharp Kabushiki Kaisha | Passive polarisation modulating optical element and method of making such an element |
US20100085521A1 (en) * | 2008-08-19 | 2010-04-08 | Crysoptix Kk | Composition of Organic Compounds, Optical Film and Method of Production Thereof |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5327285A (en) * | 1990-06-11 | 1994-07-05 | Faris Sadeg M | Methods for manufacturing micropolarizers |
US5113285A (en) * | 1990-09-28 | 1992-05-12 | Honeywell Inc. | Full color three-dimensional flat panel display |
TW336999B (en) * | 1996-07-03 | 1998-07-21 | Sumitomo Kagaku Kk | Phase retarder and liquid crystal display device using the same |
JP2004004150A (en) * | 2002-05-13 | 2004-01-08 | Sumitomo Chem Co Ltd | Laminated phase differential film and liquid crystal display device using the same |
JP2007304375A (en) * | 2006-05-12 | 2007-11-22 | Dainippon Printing Co Ltd | Retardation film |
TWI381191B (en) * | 2007-12-03 | 2013-01-01 | Au Optronics Corp | Three-dimensional display device and fabricating method thereof |
-
2011
- 2011-09-29 KR KR1020137011160A patent/KR20130114667A/en not_active Application Discontinuation
- 2011-09-29 JP JP2013531892A patent/JP2013541735A/en not_active Withdrawn
- 2011-09-29 WO PCT/US2011/054091 patent/WO2012044867A1/en active Application Filing
- 2011-09-29 US US13/249,165 patent/US20120081784A1/en not_active Abandoned
- 2011-09-29 CN CN201180056748.8A patent/CN103354912B/en not_active Expired - Fee Related
- 2011-09-29 EP EP11776040.5A patent/EP2622392A1/en not_active Withdrawn
-
2014
- 2014-04-07 US US14/247,001 patent/US20140334002A1/en not_active Abandoned
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0887667A2 (en) * | 1997-06-28 | 1998-12-30 | Sharp Kabushiki Kaisha | Method of making a patterned retarder, patterned retarder and illumination source |
US6055103A (en) * | 1997-06-28 | 2000-04-25 | Sharp Kabushiki Kaisha | Passive polarisation modulating optical element and method of making such an element |
US20100085521A1 (en) * | 2008-08-19 | 2010-04-08 | Crysoptix Kk | Composition of Organic Compounds, Optical Film and Method of Production Thereof |
Also Published As
Publication number | Publication date |
---|---|
JP2013541735A (en) | 2013-11-14 |
US20120081784A1 (en) | 2012-04-05 |
EP2622392A1 (en) | 2013-08-07 |
CN103354912B (en) | 2016-09-07 |
CN103354912A (en) | 2013-10-16 |
US20140334002A1 (en) | 2014-11-13 |
KR20130114667A (en) | 2013-10-17 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2012044867A1 (en) | Patterned retarder | |
EP2638126A1 (en) | Negative dispersion retardation plate and achromatic circular polarizer | |
EP2331655B1 (en) | Composition of organic compounds, optical film and method of production thereof | |
WO2012052950A1 (en) | Retarder and liquid crystal display comprising the same | |
WO2013003780A1 (en) | Three-dimensional circular polarization eyeglasses | |
WO2012008981A2 (en) | Polarizer and liquid crystal display comprising the same | |
US7026019B2 (en) | Anisotropic films based on 1,8-naphthoylene-1′,2′-benzimidazole sulfonates and lyotropic liquid crystal systems and methods for making | |
EP2279233B1 (en) | Organic compound, optical film and method of production thereof | |
EP2373761B1 (en) | Organic polymer compound, optical film and method of production thereof | |
KR102432583B1 (en) | Polarizer and image display device | |
US8865313B2 (en) | Optical retardation film and method of production thereof | |
WO2021200978A1 (en) | Composition, optically anisotropic film, circularly polarizing plate, and display device |
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: 11776040 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2013531892 Country of ref document: JP Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 20137011160 Country of ref document: KR Kind code of ref document: A |
|
REEP | Request for entry into the european phase |
Ref document number: 2011776040 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2011776040 Country of ref document: EP |