WO2018003359A1 - Filtre coloré stratifié, kit, procédé de fabrication de filtre coloré stratifié et capteur optique - Google Patents

Filtre coloré stratifié, kit, procédé de fabrication de filtre coloré stratifié et capteur optique Download PDF

Info

Publication number
WO2018003359A1
WO2018003359A1 PCT/JP2017/019483 JP2017019483W WO2018003359A1 WO 2018003359 A1 WO2018003359 A1 WO 2018003359A1 JP 2017019483 W JP2017019483 W JP 2017019483W WO 2018003359 A1 WO2018003359 A1 WO 2018003359A1
Authority
WO
WIPO (PCT)
Prior art keywords
color filter
group
wavelength region
liquid crystal
independently
Prior art date
Application number
PCT/JP2017/019483
Other languages
English (en)
Japanese (ja)
Inventor
亮司 後藤
嶋田　和人
Original Assignee
富士フイルム株式会社
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 富士フイルム株式会社 filed Critical 富士フイルム株式会社
Priority to JP2018524961A priority Critical patent/JP6641009B2/ja
Publication of WO2018003359A1 publication Critical patent/WO2018003359A1/fr

Links

Images

Classifications

    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/26—Reflecting filters
    • H—ELECTRICITY
    • H04—ELECTRIC COMMUNICATION TECHNIQUE
    • H04N—PICTORIAL COMMUNICATION, e.g. TELEVISION
    • H04N23/00—Cameras or camera modules comprising electronic image sensors; Control thereof
    • H04N23/10—Cameras or camera modules comprising electronic image sensors; Control thereof for generating image signals from different wavelengths
    • H04N23/12—Cameras or camera modules comprising electronic image sensors; Control thereof for generating image signals from different wavelengths with one sensor only

Definitions

  • the present invention relates to a laminated color filter in which an absorption color filter and a filter having a reflective color filter are laminated, a kit, a method for producing the laminated color filter, and an optical sensor having the laminated color filter, and more particularly to an absorptive color filter.
  • Layered color filter, kit, method for producing layered color filter, and optical having layered color filter having a number of species in the wavelength region that exceeds the total number of species in the wavelength region and the number of species in the reflective color filter It relates to sensors.
  • Patent Document 1 includes a color filter used to reproduce blue formed on a photodiode that receives blue among photodiodes in order to improve color reproducibility, and reproduces red. At least one of a color filter used to reproduce or a color filter used to reproduce green or a color filter used to reproduce blue is a red filter, a green filter, a blue filter, a cyan filter, or a yellow filter.
  • a solid-state imaging device formed by stacking at least two is described.
  • a color filter used for reproducing red is formed by stacking a red filter and a first yellow filter
  • a color filter used for reproducing green is a second yellow filter and a first yellow filter.
  • the color filter used for reproducing blue is formed by laminating a second cyan filter and a blue filter.
  • Patent Document 2 discloses a blue, green color by superimposing layer patterns (20) and (30) indicating two subtractive color mixture primary hue patterns and an example pattern of a single pixel blue filter B3, a green filter G3, and a red filter R3. And a red filter array is described.
  • the layer array (20) consists of two layers Y3 and M3, each containing a yellow dye and a magenta dye.
  • the layer array (30) consists of two layers M4 and C5, each containing cyan and magenta dyes.
  • Layer Y3 is limited to the region that forms filters G3 and R3.
  • Layer C5 is limited to the area where filters G3 and B3 are formed.
  • the layer M3 is limited to the region where the filter B3 is formed, but the layer M4 is limited to the region where the filter R3 is formed.
  • Patent Document 2 describes a color filter array that enables precise control of layer hue, that is, spectral absorption and transmission profiles.
  • JP 2009-289768 A Japanese Patent No. 2664154
  • Patent Document 1 color reproducibility is improved using a plurality of filters
  • Patent Document 2 it is described that the hue of a layer is accurately controlled using a plurality of filters.
  • the purpose is to acquire RGB color information in accordance with human visibility, and information in a specific wavelength range is not acquired.
  • An object of the present invention is to provide a multilayer color filter, a kit, a method for manufacturing a multilayer color filter, and an optical sensor for solving the above-described problems based on the prior art and acquiring information in a specific wavelength range. It is in.
  • the present invention has at least one absorption color filter and at least one reflection color filter, and the absorption color filter and the reflection color filter are laminated to absorb each other.
  • P> m ⁇ 2 where m is the number of species in the wavelength region of the color filter, n is the number of species in the wavelength region of the reflective color filter, and p is the number of species in the wavelength region of the multilayer color filter.
  • the present invention provides a multilayer color filter, wherein p> n ⁇ 2.
  • the reflective color filter has a circularly polarized light reflection characteristic. Moreover, it is preferable to have at least one or more layers of a reflective color filter having right circular polarization reflection characteristics and a reflective color filter having left circular polarization reflection characteristics.
  • the reflective color filter is preferably one obtained by curing a polymerizable cholesteric liquid crystal composition.
  • the polymerizable cholesteric liquid crystal composition preferably contains at least one polymerizable liquid crystal compound and at least one photoreactive chiral agent.
  • the photoreactive chiral agent is preferably represented by the following general formulas (1) to (5).
  • a 11 and A 12 each independently represent —C ( ⁇ O) — or —C ( ⁇ O) —Ar 11 —
  • Ar 11 represents an optionally substituted aromatic carbocycle or Represents an optionally substituted aromatic heterocycle
  • R 11 and R 13 each independently represents a hydrogen atom, a C 1 to C 12 alkyl group, or an optionally substituted aromatic carbocycle Represents an optionally substituted aromatic heterocyclic ring, a cyano group, or a C 1 to C 12 alkyloxycarbonyl group
  • R 12 and R 14 each independently represents a hydrogen atom or C 1 to C 12.
  • B 11 and B 12 each independently represents —C ( ⁇ O) — (Ar 12 ) n 11 — or —C ( ⁇ O) —Ar 13 —N ⁇ X 11 —Ar 14 —.
  • X 11 represents N or CH
  • Ar 12 Ar 13 and Ar 14 represents an aromatic heterocycle optionally having independently an aromatic carbocyclic ring which may have a substituent or substituents
  • n 11 represents an integer of 0 to 2
  • n 11 represents 2
  • a plurality of Ar 12 may be the same or different
  • Z 11 and Z 12 are each independently a hydrogen atom, a C 1 -C 12 alkyl group, a C 1 -C 12 alkoxy group, Represents a C 1 -C 12 alkylcarbonyloxy group, a C 1 -C 12 alkylamino group, or a C 1 -C 12 alkylamide group
  • Z 11 and Z 12 may have a polymerizable group.
  • a 21 and A 22 each independently represent —C ( ⁇ O) — or —C ( ⁇ O) —Ar 21 —, wherein Ar 21 represents an optionally substituted aromatic carbocycle or Represents an optionally substituted aromatic heterocycle, wherein R 21 and R 23 each independently represents a hydrogen atom, a C 1 -C 12 alkyl group, or an optionally substituted aromatic carbocycle Represents an optionally substituted aromatic heterocyclic ring, a cyano group, or a C 1 to C 12 alkyloxycarbonyl group, and R 22 and R 24 each independently represent a hydrogen atom or C 1 to C 12.
  • B 21 and B 22 each independently represents —C ( ⁇ O) — (Ar 22 ) n 21 — or —C ( ⁇ O) —Ar 23 —N ⁇ X 21 —Ar 24 —.
  • X 21 represents N or CH
  • Ar 22 Ar 23 and Ar 24 represents an aromatic heterocycle optionally having independently an aromatic carbocyclic ring which may have a substituent or substituents
  • n 21 represents an integer of 0 to 2
  • n 21 represents 2
  • a plurality of Ar 22 may be the same or different
  • Z 21 and Z 22 are each independently a hydrogen atom, a C 1 -C 12 alkyl group, a C 1 -C 12 alkoxy group, Represents a C 1 -C 12 alkylcarbonyloxy group, a C 1 -C 12 alkylamino group, or a C 1 -C 12 alkylamide group
  • Z 21 and Z 22 may have a polymerizable group.
  • a 31 and A 32 each independently represent a single bond, —O—C ( ⁇ O) — or —O—C ( ⁇ O) —Ar 31 —, and Ar 31 has a substituent.
  • R 31 and R 33 each independently represents a hydrogen atom, a C 1 to C 12 alkyl group, or a substituent.
  • a 41 and A 42 each independently represent —C ( ⁇ O) — or —C ( ⁇ O) —Ar 41 —
  • Ar 41 represents an aromatic carbocyclic ring which may have a substituent or Represents an optionally substituted aromatic heterocycle
  • R 41 and R 43 each independently represent a hydrogen atom, a C 1 -C 12 alkyl group, or an optionally substituted aromatic carbocycle Represents an optionally substituted aromatic heterocyclic ring, a cyano group, or a C 1 to C 12 alkyloxycarbonyl group
  • R 42 and R 44 each independently represents a hydrogen atom or C 1 to C 12.
  • B 41 and B 42 each independently represents —C ( ⁇ O) — (Ar 42 ) n 41 — or —C ( ⁇ O) —Ar 43 —N ⁇ X 41 —Ar 44 —.
  • X 41 represents N or CH
  • Ar 42 Ar 43 and Ar 44 represents an aromatic heterocycle optionally having independently an aromatic carbocyclic ring which may have a substituent or substituents
  • n 41 represents an integer of 0 to 2
  • n 41 is 2
  • a plurality of Ar 42 may be the same or different
  • Z 41 and Z 42 each independently represent a hydrogen atom, a C 1 -C 12 alkyl group, a C 1 -C 12 alkoxy group, Represents a C 1 -C 12 alkylcarbonyloxy group, a C 1 -C 12 alkylamino group, or a C 1 -C 12 alkylamide group
  • Z 41 and Z 42 may have a polymerizable group.
  • Z 41 and R 42 and Z 42 and R 44 may form a ring with each other, and multiple molecules of Z 41 and Z 42 may be polymerized via a covalent bond, and R 45 and R 46 are C 1 to C 30 And may form a ring with each other. * Represents an asymmetric carbon.
  • P 51 represents a polymerizable group
  • Sp 51 represents an alkylene group of a single bond or C 1 ⁇ 12
  • plurality of carbon atoms may be replaced by an oxygen atom or a carbonyl group
  • X 51 represents a single bond Or an oxygen atom
  • Ar 51 and Ar 52 each independently represent an optionally substituted aromatic carbocyclic ring or an optionally substituted aromatic heterocyclic ring
  • L 51 represents a single bond Or, it represents a divalent linking group
  • n 51 represents an integer of 1 to 3 and when n 51 is 2 or more, a plurality of Ar 51 and L 51 may be the same or different from each other, and R 52 is asymmetric. Represents a side chain containing carbon.
  • a photo-alignment film in contact with a reflective color filter having a right circular polarization reflection characteristic or a reflection color filter having a left circular polarization reflection characteristic, which is obtained by curing the polymerizable cholesteric liquid crystal composition.
  • the refractive index anisotropy ⁇ n of the polymerizable liquid crystal compound is preferably 0.2 or more.
  • the present invention relates to a polymerizable liquid crystal composition
  • a polymerizable liquid crystal composition comprising at least one or more polymerizable liquid crystal compounds, a photoreactive chiral agent having right-handed twist characteristics and a polymerization initiator, at least one or more polymerizable liquid crystal compounds, left-twisted characteristics.
  • a kit comprising a polymerizable liquid crystal composition containing a photoreactive chiral agent having a polymerization initiator and a polymerization initiator is provided.
  • a photoreactive chiral agent having a right twist property is represented by the following general formula (1) or general formula (3)
  • a photoreactive chiral agent having a left twist property is represented by the following general formula (2) or general formula ( It is preferable that it is represented by 3).
  • a 11 and A 12 each independently represent —C ( ⁇ O) — or —C ( ⁇ O) —Ar 11 —
  • Ar 11 represents an optionally substituted aromatic carbocycle or Represents an optionally substituted aromatic heterocycle
  • R 11 and R 13 each independently represents a hydrogen atom, a C 1 to C 12 alkyl group, or an optionally substituted aromatic carbocycle Represents an optionally substituted aromatic heterocyclic ring, a cyano group, or a C 1 to C 12 alkyloxycarbonyl group
  • R 12 and R 14 each independently represents a hydrogen atom or C 1 to C 12.
  • B 11 and B 12 each independently represents —C ( ⁇ O) — (Ar 12 ) n 11 — or —C ( ⁇ O) —Ar 13 —N ⁇ X 11 —Ar 14 —.
  • X 11 represents N or CH
  • Ar 12 Ar 13 and Ar 14 represents an aromatic heterocycle optionally having independently an aromatic carbocyclic ring which may have a substituent or substituents
  • n 11 represents an integer of 0 to 2
  • n 11 represents 2
  • a plurality of Ar 12 may be the same or different
  • Z 11 and Z 12 are each independently a hydrogen atom, a C 1 -C 12 alkyl group, a C 1 -C 12 alkoxy group, Represents a C 1 -C 12 alkylcarbonyloxy group, a C 1 -C 12 alkylamino group, or a C 1 -C 12 alkylamide group
  • Z 11 and Z 12 may have a polymerizable group.
  • a 21 and A 22 each independently represent —C ( ⁇ O) — or —C ( ⁇ O) —Ar 21 —, wherein Ar 21 represents an optionally substituted aromatic carbocycle or Represents an optionally substituted aromatic heterocycle, wherein R 21 and R 23 each independently represents a hydrogen atom, a C 1 -C 12 alkyl group, or an optionally substituted aromatic carbocycle Represents an optionally substituted aromatic heterocyclic ring, a cyano group, or a C 1 to C 12 alkyloxycarbonyl group, and R 22 and R 24 each independently represent a hydrogen atom or C 1 to C 12.
  • B 21 and B 22 each independently represents —C ( ⁇ O) — (Ar 22 ) n 21 — or —C ( ⁇ O) —Ar 23 —N ⁇ X 21 —Ar 24 —.
  • X 21 represents N or CH
  • Ar 22 Ar 23 and Ar 24 represents an aromatic heterocycle optionally having independently an aromatic carbocyclic ring which may have a substituent or substituents
  • n 21 represents an integer of 0 to 2
  • n 21 represents 2
  • a plurality of Ar 22 may be the same or different
  • Z 21 and Z 22 are each independently a hydrogen atom, a C 1 -C 12 alkyl group, a C 1 -C 12 alkoxy group, Represents a C 1 -C 12 alkylcarbonyloxy group, a C 1 -C 12 alkylamino group, or a C 1 -C 12 alkylamide group
  • Z 21 and Z 22 may have a polymerizable group.
  • a 31 and A 32 each independently represent a single bond, —O—C ( ⁇ O) — or —O—C ( ⁇ O) —Ar 31 —, and Ar 31 has a substituent.
  • R 31 and R 33 each independently represents a hydrogen atom, a C 1 to C 12 alkyl group, or a substituent.
  • the present invention is also a method for producing a laminated color filter having at least one absorption color filter and at least one reflection color filter, wherein the absorption color filter and the reflection color filter are laminated.
  • the present invention provides a method for producing a laminated color filter, wherein the reflective color filter is formed by patterning regions having different spectral characteristics by exposure.
  • the reflective color filter forming step includes a right circularly polarized reflective layer forming step for forming a right circularly polarized reflective layer having a plurality of wavelength regions in the surface, and a left circularly polarized reflective layer having a plurality of wavelength regions in the surface. It is preferable to comprise a left circularly polarized light reflecting layer forming step to be formed.
  • the right circularly polarized light reflecting layer forming step was applied in a coating step and a coating step in which a polymerizable liquid crystal composition containing at least one polymerizable liquid crystal compound, a photoreactive chiral agent having a right twist characteristic and a polymerization initiator was applied.
  • An alignment process in which the polymerizable liquid crystal composition is heated to form a cholesteric alignment state, and a part of the polymerizable liquid crystal composition that has been converted into a cholesteric alignment state in the alignment process is subjected to an exposure treatment, whereby the reflection wavelength region of the exposed portion And a fixing step for fixing the alignment state of the polymerizable liquid crystal composition by performing an exposure treatment on the entire surface of the polymerizable liquid crystal composition whose partial alignment state has been converted in the conversion step.
  • a step of forming a left circularly polarized light reflecting layer the step of applying a polymerizable liquid crystal composition comprising at least one polymerizable liquid crystal compound, a photoreactive chiral agent having left-twisting properties, and a polymerization initiator;
  • the polymerizable liquid crystal composition applied in the cloth process was heated to be an cholesteric alignment state, and an exposure process was performed on a part of the polymerizable liquid crystal composition that was converted into a cholesteric alignment state in the alignment process.
  • a conversion step for converting the partial reflection wavelength region, and an immobilization step for fixing the cholesteric alignment state by performing an exposure process on the entire surface of the polymerizable liquid crystal composition in which a part of the alignment state is converted in the conversion step. It is preferable to include.
  • the right circularly polarized light reflecting layer forming step is a coating step and a coating step in which a polymerizable liquid crystal composition containing at least one polymerizable liquid crystal compound, a photoreactive chiral agent having right-twisting characteristics, and a polymerization initiator is applied.
  • a polymerizable liquid crystal composition containing at least one polymerizable liquid crystal compound, a photoreactive chiral agent having right-twisting characteristics, and a polymerization initiator is applied.
  • the first fixing process to be fixed, the conversion process for converting the reflection wavelength region of the exposed part by performing an exposure process on the unexposed part in the first fixing process, and the orientation state was converted in the conversion process Including a second fixing step of fixing the alignment state of the polymerizable liquid crystal composition by performing an exposure treatment on the polymerizable liquid crystal composition, wherein the left circularly polarized light reflecting layer forming step includes at least one kind A coating process for applying a polymerizable liquid crystal composition comprising a compatible liquid crystal compound, a photoreactive chiral agent having left-handed twisting properties and a polymerization initiator, and heating the polymerizable liquid crystal composition applied in the coating process to produce a cholesteric alignment state
  • the cholesteric alignment state in the exposed portion is fixed by performing an exposure process on a part of the polymerizable liquid crystal composition in the cholesteric alignment state.
  • the conversion process of converting the reflection wavelength region of the exposed part, and the polymerizable liquid crystal composition whose orientation state has been converted in the conversion process is subjected to an exposure process. It is preferable to include a second fixing step for fixing the alignment state of the liquid crystal composition.
  • the alignment layer applying step for applying the photo-alignment film, and the photo-alignment film formed by coating are exposed with polarized light. It is preferable to include an orientation regulating step for providing an orientation regulating force.
  • the present invention also provides an optical sensor having the multilayer color filter of the present invention.
  • a multilayer color filter a kit, a method for producing a multilayer color filter, and an optical sensor of the present invention will be described in detail based on preferred embodiments shown in the accompanying drawings.
  • “to” indicating a numerical range includes numerical values written on both sides.
  • ⁇ is a numerical value ⁇ to a numerical value ⁇
  • the range of ⁇ is a range including the numerical value ⁇ and the numerical value ⁇ , and expressed by mathematical symbols, ⁇ ⁇ ⁇ ⁇ ⁇ .
  • the angle or the like includes a generally allowable error range unless otherwise specified.
  • FIG. 1 is a schematic cross-sectional view showing an optical sensor having a laminated color filter according to an embodiment of the present invention.
  • FIG. 2 is a schematic diagram showing a reflective color filter of a multilayer color filter according to an embodiment of the present invention
  • FIG. 3 is a schematic diagram showing an absorption color filter of the multilayer color filter according to an embodiment of the present invention.
  • FIG. 4 is a schematic view showing a laminated color filter according to an embodiment of the present invention.
  • the optical sensor 10 illustrated in FIG. 1 includes a sensor unit 12 and a stacked color filter 14.
  • the sensor unit 12 includes a substrate 20, a wiring layer 22, and a photodiode 24.
  • the sensor unit 12 is generally called a charge coupled device (CCD) or a complementary metal oxide semiconductor (CMOS) including a photodiode 24.
  • CCD charge coupled device
  • CMOS complementary metal oxide semiconductor
  • an image corresponding to the stacked color filter 14 can be acquired. For example, a color image represented by three primary colors of red, blue, and green can be obtained.
  • the color image is not limited to the one represented by the above three primary colors as long as it is represented by a plurality of colors.
  • the wiring layer 22 is for electrically connecting the sensor unit 12 to the outside, and has a wiring (not shown) made of a conductive material.
  • the signal charge obtained by the photodiode 24 is output to the outside.
  • a configuration having a readout circuit (not shown) for amplifying the signal charge obtained by the photodiode 24 may be used.
  • the photodiode 24 detects light and functions as a light receiving element. For light detection, for example, photoelectric conversion is used. A plurality of photodiodes 24 are two-dimensionally arranged, and a specific number of photodiodes 24 constitute one pixel.
  • the photodiode 24 is made of, for example, silicon or germanium.
  • the photodiode 24 is not particularly limited as long as it can detect light, and a PN junction type, a PIN junction type, a Schottky type, or an avalanche type can be used.
  • An insulating film 25 is formed on the photodiode 24, and a light shielding film 26 is formed on the insulating film 25 between the adjacent photodiodes 24.
  • the insulating film 25 is made of, for example, BPSG (Boron Phosphorus Silicon Glass), but is not limited thereto.
  • the light shielding film 26 is made of metal such as tungsten (W), aluminum (Al), copper (Cu), titanium (Ti), molybdenum (Mo), and nickel (Ni), but is not limited thereto. It is not a thing.
  • the multilayer color filter 14 includes at least one absorption color filter 30 and at least one reflection color filter 32.
  • the absorption color filter 30 and the reflection color filter 32 are laminated.
  • the number of species in the wavelength region of the absorption color filter 30 is m
  • the number of species in the wavelength region of the reflective color filter 32 is n
  • the number of species in the wavelength region of the multilayer color filter 14 is p, p> m ⁇ 2 and p> n ⁇ 2.
  • the absorption color filter 30 has two or more wavelength regions, and each wavelength region has different spectral characteristics as described later.
  • the reflective color filter 32 has two or more wavelength regions, and each wavelength region has different spectral characteristics as will be described later.
  • the absorption color filter 30 is provided on the insulating film 25, and the wavelength region is disposed on the photodiode 24.
  • the absorption color filter 30 is provided with a plurality of microlenses 28.
  • a planarizing layer 29 is provided on the plurality of microlenses 28.
  • a reflective color filter 32 is provided on the planarizing layer 29.
  • the multilayer color filter 14 preferably further has a near-infrared cut layer (not shown) that blocks part or the whole of the near-infrared region.
  • the arrangement position of the near infrared cut layer may be above or below the laminated color filter 14.
  • the near-infrared region is a wavelength region having a wavelength of 650 to 1200 nm.
  • As the near-infrared cut layer a known layer that can block light in the above-described near-infrared region can be appropriately used. Since the multilayer color filter 14 has a near infrared cut layer, the optical sensor 10 can perform photometry with the near infrared light removed, thereby reducing noise during photometry.
  • the microlens 28 is a convex lens whose center is thicker than the edge, and collects light on the photodiode 24.
  • the plurality of microlenses 28 have the same shape, and a microlens 28 is provided for each photodiode 24.
  • the microlens 28 is formed of a resin material such as a styrene resin, an acrylic resin, a styrene-acrylic copolymer resin, or a siloxane resin, but is not limited thereto.
  • the planarization layer 29 planarizes the microlens 28 that is a convex lens, and is made of, for example, an acrylic resin material, a styrene resin material, or an epoxy resin material.
  • a conventional RGB color filter can be used as the absorption color filter 30 .
  • the production can be performed using a known method, and is also useful in that it is not necessary to start a new production process.
  • color filters with spectral characteristics other than RGB may be used, complementary color (YMC) color filters having transmitted light spectra in the cyan, magenta and yellow regions, and near-infrared light transmitted by cutting visible light.
  • YMC complementary color
  • a visible light cut filter is also included. Visible light is light having a wavelength of about 380 nm to 780 nm.
  • the reflective color filter 32 is preferably a cholesteric liquid crystal layer in which a cholesteric liquid crystal phase having circular polarization reflection characteristics is fixed. That is, the reflective color filter 32 preferably has a circularly polarized light reflection characteristic.
  • the cholesteric liquid crystal layer has a property of reflecting either left or right circularly polarized light.
  • the cholesteric liquid crystal layer can be obtained by fixing the cholesteric liquid crystal phase as described above.
  • the structure in which the cholesteric liquid crystal phase is fixed may be any structure as long as the orientation of the liquid crystal compound in the cholesteric liquid crystal phase is maintained. Thus, any structure may be used as long as it is polymerized and cured by ultraviolet irradiation, heating, or the like to form a layer having no fluidity, and at the same time, the orientation is not changed by an external field or an external force.
  • the cholesteric liquid crystal phase it is sufficient that the optical properties of the cholesteric liquid crystal phase are maintained, and the liquid crystal compound may not exhibit liquid crystallinity.
  • the polymerizable liquid crystal compound may have a high molecular weight by a curing reaction and lose liquid crystallinity.
  • a liquid crystal composition containing a liquid crystal compound can be given.
  • the liquid crystal compound is preferably a polymerizable liquid crystal compound.
  • the liquid crystal composition containing the liquid crystal compound used for forming the cholesteric liquid crystal layer preferably further contains a surfactant.
  • the liquid crystal composition used for forming the cholesteric liquid crystal layer may further contain a chiral agent and a polymerization initiator.
  • the liquid phase composition having right circularly polarized light reflection property is preferably a polymerizable cholesteric liquid crystal composition containing a polymerizable liquid crystal compound, a chiral agent that induces right twist, or a polymerization disclosure agent.
  • the liquid phase composition having left circularly polarized light reflection property is preferably a polymerizable cholesteric liquid crystal composition containing a polymerizable liquid crystal compound, a chiral agent that induces left twist, or a polymerization disclosure agent.
  • the polymerizable cholesteric liquid crystal composition preferably contains one or more polymerizable liquid crystal compounds having a refractive index anisotropy ⁇ n of 0.2 or more.
  • the polymerizable liquid crystal compound may be a rod-like liquid crystal compound or a disk-like liquid crystal compound, but is preferably a rod-like liquid crystal compound.
  • Examples of the rod-like polymerizable liquid crystal compound that forms the cholesteric liquid crystal phase include a rod-like nematic liquid crystal compound.
  • rod-like nematic liquid crystal compounds examples include azomethines, azoxys, cyanobiphenyls, cyanophenyl esters, benzoic acid esters, cyclohexanecarboxylic acid phenyl esters, cyanophenylcyclohexanes, cyano-substituted phenylpyrimidines, alkoxy-substituted phenylpyrimidines.
  • Phenyldioxanes, tolanes and alkenylcyclohexylbenzonitriles are preferably used. Not only low-molecular liquid crystal compounds but also high-molecular liquid crystal compounds can be used.
  • the polymerizable liquid crystal compound can be obtained by introducing a polymerizable group into the liquid crystal compound.
  • the polymerizable group include an unsaturated polymerizable group, an epoxy group, and an aziridinyl group, preferably an unsaturated polymerizable group, and more preferably an ethylenically unsaturated polymerizable group.
  • the polymerizable group can be introduced into the molecule of the liquid crystal compound by various methods.
  • the number of polymerizable groups possessed by the polymerizable liquid crystal compound is preferably 1 to 6, more preferably 1 to 3. Examples of polymerizable liquid crystal compounds are described in Makromol. Chem. 190, 2255 (1989), Advanced Materials 5, 107 (1993), US Pat. No.
  • polymerizable liquid crystal compound examples include compounds represented by the following formulas (1) to (14).
  • X 1 is 2 to 5 (integer).
  • ⁇ n at 30 ° C. of the liquid crystal compound is preferably 0.25 or more, more preferably 0.3 or more, and further preferably 0.35 or more.
  • the upper limit is not particularly limited, but is often 0.6 or less.
  • a method for measuring the refractive index anisotropy ⁇ n a method using a wedge-shaped liquid crystal cell described in page 202 of a liquid crystal handbook (edited by the Liquid Crystal Handbook Editorial Committee, published by Maruzen Co., Ltd.) is generally used. In this case, the evaluation can be performed by using a mixture with another liquid crystal and estimated from the extrapolated value.
  • liquid crystal compound exhibiting a high ⁇ n examples include, for example, US Pat.
  • liquid crystal compound exhibiting a high ⁇ n examples include, for example, US Pat.
  • examples thereof include compounds described in Japanese Patent Publication No. 5705465, Japanese Patent No. 5721484, and Japanese Patent No. 5723641.
  • liquid crystal compound having a polymerizable group is a compound represented by the general formula (6).
  • a 1 to A 4 each independently represents an aromatic carbocyclic ring or heterocyclic ring which may have a substituent.
  • the aromatic carbocycle include a benzene ring and a naphthalene ring.
  • the heterocyclic ring furan ring, thiophene ring, pyrrole ring, pyrroline ring, pyrrolidine ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, imidazole ring, imidazoline ring, imidazolidine ring, pyrazole ring, pyrazoline ring, Pyrazolidine ring, triazole ring, furazane ring, tetrazole ring, pyran ring, thiyne ring, pyridine ring, piperidine ring, oxazine ring, morpholine ring, thiazine ring, pyridazine
  • A1 to A4 are preferably aromatic carbocycles, and more preferably benzene rings.
  • the type of substituent that may be substituted on the aromatic carbocycle or heterocyclic ring is not particularly limited, and examples thereof include a halogen atom, a cyano group, a nitro group, an alkyl group, a halogen-substituted alkyl group, an alkoxy group, an alkylthio group, and an acyloxy group.
  • a single bond, —COO—, —CONH—, —NHCO— or —C ⁇ C— is preferable.
  • Sp 1 and Sp 2 each independently represents a single bond or a carbon chain having 1 to 25 carbon atoms.
  • the carbon chain may be linear, branched, or cyclic.
  • a so-called alkyl group is preferable. Of these, an alkyl group having 1 to 10 carbon atoms is more preferable.
  • P 1 and P 2 each independently represent a hydrogen atom or a polymerizable group, and at least one of P 1 and P 2 represents a polymerizable group.
  • a polymeric group the polymeric group which the liquid crystal compound which has a polymeric group mentioned above has is illustrated.
  • n 1 and n 2 each independently represents an integer of 0 to 2, and when n 1 or n 2 is 2, a plurality of A 1 , A 2 , X 1 and X 2 may be the same or different Good.
  • Specific examples of the compound represented by the general formula (6) include compounds represented by the following formulas (2-1) to (2-30).
  • cyclic organopolysiloxane compounds having a cholesteric phase as disclosed in JP-A-57-165480 can be used.
  • the above-mentioned polymer liquid crystal compound includes a polymer in which a mesogenic group exhibiting liquid crystal is introduced into the main chain, a side chain, or both the main chain and the side chain, and a polymer cholesteric in which a cholesteryl group is introduced into the side chain
  • a liquid crystalline polymer as disclosed in JP-A-9-133810, a liquid crystalline polymer as disclosed in JP-A-11-293252, or the like can be used.
  • the addition amount of the polymerizable liquid crystal compound in the liquid crystal composition is preferably 75 to 99.9% by mass with respect to the solid content mass (mass excluding the solvent) of the liquid crystal composition, and preferably 80 to 99. More preferably, it is more preferably 85% to 90% by weight.
  • the chiral agent has a function of inducing a helical structure of a cholesteric liquid crystal phase.
  • the chiral agent may be selected according to the purpose because the twist direction or the spiral pitch of the spiral induced by the compound is different. That is, a chiral agent that induces right-handed twist is used when it has right-circularly polarized light reflection characteristics, and a chiral agent that induces left-handed twist is used when it has left-handed circularly polarized light reflection characteristics.
  • the chiral agent is not particularly limited, and is a known compound (for example, liquid crystal device handbook, Chapter 3-4, chiral agent for TN (twisted nematic), STN (Super Twisted Nematic), 199 pages, Japan Science Foundation) 142), 1989), isosorbide and isomannide derivatives can be used.
  • a chiral agent generally contains an asymmetric carbon atom, but an axially asymmetric compound or a planar asymmetric compound that does not contain an asymmetric carbon atom can also be used as the chiral agent.
  • the axial asymmetric compound or the planar asymmetric compound include binaphthyl, helicene, paracyclophane, and derivatives thereof.
  • the chiral agent may have a polymerizable group.
  • both the chiral agent and the liquid crystal compound have a polymerizable group, they are derived from the repeating unit derived from the polymerizable liquid crystal compound and the chiral agent by a polymerization reaction between the polymerizable chiral agent and the polymerizable liquid crystal compound.
  • a polymer having repeating units can be formed.
  • the polymerizable group possessed by the polymerizable chiral agent is preferably the same group as the polymerizable group possessed by the polymerizable liquid crystal compound.
  • the polymerizable group of the chiral agent is also preferably an unsaturated polymerizable group, an epoxy group or an aziridinyl group, more preferably an unsaturated polymerizable group, and an ethylenically unsaturated polymerizable group. Further preferred.
  • the chiral agent may be a liquid crystal compound.
  • the chiral agent has a photoisomerization group
  • a pattern having a desired reflection wavelength corresponding to the emission wavelength can be formed by irradiation with a photomask such as actinic rays after coating and orientation.
  • a photomask such as actinic rays after coating and orientation.
  • an isomerization site of a compound exhibiting photochromic properties an azo group, an azoxy group, or a cinnamoyl group is preferable.
  • Specific examples of the compound include JP 2002-80478, JP 2002-80851, JP 2002-179633, JP 2002-179668, JP 2002-179669, and JP 2002-2002. No. 179670, JP-A No. 2002-179681, JP-A No.
  • photoreactive chiral agent compounds represented by the following general formulas (1) to (5) can be used.
  • a 11 and A 12 each independently represent —C ( ⁇ O) — or —C ( ⁇ O) —Ar 11 —
  • Ar 11 represents an optionally substituted aromatic carbocycle or Represents an optionally substituted aromatic heterocycle
  • R 11 and R 13 each independently represents a hydrogen atom, a C 1 to C 12 alkyl group, or an optionally substituted aromatic carbocycle Represents an optionally substituted aromatic heterocyclic ring, a cyano group, or a C 1 to C 12 alkyloxycarbonyl group
  • R 12 and R 14 each independently represents a hydrogen atom or C 1 to C 12.
  • B 11 and B 12 each independently represents —C ( ⁇ O) — (Ar 12 ) n 11 — or —C ( ⁇ O) —Ar 13 —N ⁇ X 11 —Ar 14 —.
  • X 11 represents N or CH
  • Ar 12 Ar 13 and Ar 14 represents an aromatic heterocycle optionally having independently an aromatic carbocyclic ring which may have a substituent or substituents
  • n 11 represents an integer of 0 to 2
  • Z 11 and Z 12 are each independently a hydrogen atom, a C 1 -C 12 alkyl group, a C 1 -C 12 alkoxy group, Represents a C 1 -C 12 alkylcarbonyloxy group, a C 1 -C 12 alkylamino group, or a C 1 -C 12 alkylamide group, and Z 11 and Z 12 may have a polymerizable group.
  • Z 11 and R 12 and Z 12 and R 14 may form a ring with each other, and a plurality of molecules of Z 11 and Z 12 may be polymerized via a covalent bond.
  • the compound represented by the general formula (1) includes, for example, JP-A-2002-080851, JP-A-2002-179681, JP-A-2002-179682, JP-A-2002-338575, JP-A-2002-338668, JP-A-2003-306490, JP-A-2003-306491, JP-A-2003-313187, JP-A-2003-313189, JP-A-2003-313292 ing.
  • a 21 and A 22 each independently represent —C ( ⁇ O) — or —C ( ⁇ O) —Ar 21 —, wherein Ar 21 represents an optionally substituted aromatic carbocycle or Represents an optionally substituted aromatic heterocycle, wherein R 21 and R 23 each independently represents a hydrogen atom, a C 1 -C 12 alkyl group, or an optionally substituted aromatic carbocycle Represents an optionally substituted aromatic heterocyclic ring, a cyano group, or a C 1 to C 12 alkyloxycarbonyl group, and R 22 and R 24 each independently represent a hydrogen atom or C 1 to C 12.
  • B 21 and B 22 each independently represents —C ( ⁇ O) — (Ar 22 ) n 21 — or —C ( ⁇ O) —Ar 23 —N ⁇ X 21 —Ar 24 —.
  • X 21 represents N or CH
  • Ar 22 Ar 23 and Ar 24 represents an aromatic heterocycle optionally having independently an aromatic carbocyclic ring which may have a substituent or substituents
  • n 21 represents an integer of 0 to 2
  • Z 21 and Z 22 are each independently a hydrogen atom, a C 1 -C 12 alkyl group, a C 1 -C 12 alkoxy group, Represents a C 1 -C 12 alkylcarbonyloxy group, a C 1 -C 12 alkylamino group, or a C 1 -C 12 alkylamide group
  • Z 21 and Z 22 may have a polymerizable group.
  • Z 21 and R 22 and Z 22 and R 24 may form a ring with each other, and a plurality of molecules of Z 21 and Z 22 may be polymerized via a covalent bond. More specifically, the compound represented by the general formula (2) is described in JP-A Nos. 2002-080478 and 2003-313188.
  • a 31 and A 32 each independently represent a single bond or —O—C ( ⁇ O) — or —O—C ( ⁇ O) —Ar 31 —, and Ar 31 has a substituent.
  • R 31 and R 33 each independently represents a hydrogen atom, a C 1 to C 12 alkyl group, or a substituent.
  • N X 31 —Ar 34 —, where X 31 is N or Or CH 32 , Ar 32 , Ar 33 and Ar 34 each independently represent an optionally substituted aromatic carbocyclic ring or an optionally substituted aromatic heterocyclic ring, and n 31 Represents an integer of 0 to 2, and when n 31 is 2, a plurality of Ar 32 may be the same or different, Z 31 and Z 32 are each independently a hydrogen atom, a C 1 to C 12 alkyl group, Represents a C 1 -C 12 alkoxy group, a C 1 -C 12 alkylcarbonyloxy group, a C 1 -C 12 alkylamino group, or a C 1 -C 12 alkylamide group, and Z 31 and Z 32 represent , May have a polymerizable group, Z 31 and R 32 and Z 32 and R 34 may form a ring with each other, and a plurality of molecules of Z 31 and Z 32 are polymerized via a covalent bond.
  • L is It represents the valence of the group.
  • the binaphthyl moiety has either (R) or (S) axial asymmetry. More specifically, compounds represented by the general formula (3) are described in JP-A Nos. 2002-179668, 2002-179669, 2002-179670, and 2002-302487. Are listed.
  • a 41 and A 42 each independently represent —C ( ⁇ O) — or —C ( ⁇ O) —Ar 41 —
  • Ar 41 represents an aromatic carbocyclic ring which may have a substituent or Represents an optionally substituted aromatic heterocycle
  • R 41 and R 43 each independently represent a hydrogen atom, a C 1 -C 12 alkyl group, or an optionally substituted aromatic carbocycle Represents an optionally substituted aromatic heterocyclic ring, a cyano group, or a C 1 to C 12 alkyloxycarbonyl group
  • R 42 and R 44 each independently represents a hydrogen atom or C 1 to C 12.
  • B 41 and B 42 each independently represents —C ( ⁇ O) — (Ar 42 ) n 41 — or —C ( ⁇ O) —Ar 43 —N ⁇ X 41 —Ar 44 —.
  • X 41 represents N or CH
  • Ar 42 Ar 43 and Ar 44 represents an aromatic heterocycle optionally having independently an aromatic carbocyclic ring which may have a substituent or substituents
  • n 41 represents an integer of 0 to 2
  • n 41 is 2
  • a plurality of Ar 42 may be the same or different
  • Z 41 and Z 42 each independently represent a hydrogen atom, a C 1 -C 12 alkyl group, a C 1 -C 12 alkoxy group, Represents a C 1 -C 12 alkylcarbonyloxy group, a C 1 -C 12 alkylamino group, or a C 1 -C 12 alkylamide group
  • Z 41 and Z 42 may have a polymerizable group.
  • Z 41 and R 42 and Z 42 and R 44 may form a ring with each other, and multiple molecules of Z 41 and Z 42 may be polymerized via a covalent bond, and R 45 and R 46 are C 1 to C 30 And may form a ring with each other.
  • * Represents an asymmetric carbon. More specifically, the compound represented by the general formula (4) is described in JP-A No. 2002-179633.
  • P 51 represents a polymerizable group
  • Sp 51 represents an alkylene group of a single bond or C 1 ⁇ 12
  • plurality of carbon atoms may be replaced by an oxygen atom or a carbonyl group
  • X 51 represents a single bond Or an oxygen atom
  • Ar 51 and Ar 52 each independently represent an optionally substituted aromatic carbocyclic ring or an optionally substituted aromatic heterocyclic ring
  • L 51 represents a single bond
  • it represents a divalent linking group
  • n 51 represents an integer of 1 to 3
  • n 51 is 2 or more, a plurality of Ar 51 and L 51 may be the same or different from each other
  • R 52 is asymmetric.
  • the content of the chiral agent in the liquid crystal composition is preferably 0.01 mol% to 200 mol%, more preferably 1 mol% to 30 mol%, based on the amount of the polymerizable liquid crystal compound.
  • the content of the chiral agent in the liquid crystal composition is preferably 0.01 mol% to 200 mol%, more preferably 1 mol% to 30 mol%, based on the amount of the polymerizable liquid crystal compound.
  • the cholesteric liquid crystal composition of the present invention may contain two or more kinds of chiral agents.
  • Torsional strength HTP (Helical Twisting Power)
  • photoisomerization ability can be adjusted.
  • the liquid crystal composition contains a polymerizable compound, it preferably contains a polymerization initiator.
  • the polymerization initiator to be used is preferably a photopolymerization initiator that can start the polymerization reaction by ultraviolet irradiation.
  • photopolymerization initiators include ⁇ -carbonyl compounds (described in US Pat. Nos. 2,367,661 and 2,367,670), acyloin ether (described in US Pat. No. 2,448,828), ⁇ -hydrocarbon substituted aromatics.
  • Group acyloin compounds described in US Pat. No.
  • the content of the photopolymerization initiator in the liquid crystal composition is preferably 0.1 to 20% by mass, more preferably 0.5 to 12% by mass with respect to the content of the polymerizable liquid crystal compound. .
  • the liquid crystal composition may optionally contain a crosslinking agent in order to improve the film strength after curing and improve the durability.
  • a crosslinking agent one that can be cured by ultraviolet rays, heat, moisture, or the like can be suitably used.
  • polyfunctional acrylate compounds such as a trimethylol propane tri (meth) acrylate and pentaerythritol tri (meth) acrylate
  • Glycidyl (meth) acrylate Epoxy compounds such as ethylene glycol diglycidyl ether; aziridine compounds such as 2,2-bishydroxymethylbutanol-tris [3- (1-aziridinyl) propionate], 4,4-bis (ethyleneiminocarbonylamino) diphenylmethane; hexa Isocyanate compounds such as methylene diisocyanate and biuret type isocyanate; polyoxazoline compounds having an oxazoline group in the side chain; vinyltrimethoxysilane, N- (2-aminoethyl) 3-aminopropylto Alkoxysilane compounds such as methoxy silane.
  • a well-known catalyst can be used according to the reactivity of a crosslinking agent, and productivity can be improved in addition to membrane strength and durability improvement. These may be used individually by 1 type and may use 2 or more types together.
  • the content of the crosslinking agent is preferably 3 to 20% by mass and more preferably 5 to 15% by mass with respect to the solid content mass of the liquid crystal composition. When the content of the crosslinking agent is within the above range, the effect of improving the crosslinking density is easily obtained, and the stability of the cholesteric liquid crystal phase is further improved.
  • Polymerization inhibitor-- The polymerization inhibitor is added to the liquid crystal composition for the purpose of improving the storage stability.
  • the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, phenothiazine, benzoquinone, hindered amine (HALS), and derivatives thereof. These may be added in an amount of 0 to 10% by mass with respect to the liquid crystalline compound. Preferably, 0 to 5% by mass is added.
  • the liquid crystal composition is preferably used as a liquid when forming a cholesteric liquid crystal layer.
  • the liquid crystal composition may contain a solvent.
  • a solvent There is no restriction
  • the organic solvent is not particularly limited and may be appropriately selected depending on the intended purpose.
  • ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and cyclopentanone, alkyl halides, amides, sulfoxides, hetero Examples thereof include ring compounds, hydrocarbons, esters, ethers and the like. These may be used individually by 1 type and may use 2 or more types together. Among these, ketones are preferable in consideration of environmental load.
  • the above-described components such as the above-described monofunctional polymerizable monomer may function as a solvent.
  • the kit of the present invention comprises at least one polymerizable liquid crystal compound, a polymerizable liquid crystal composition comprising a photoreactive chiral agent having right-handed twisting properties and a polymerization initiator, at least one polymerizable liquid crystal compound, left It consists of a polymerizable liquid crystal composition containing a photoreactive chiral agent having twisting properties and a polymerization initiator.
  • the photoreactive chiral agent having a right-twist characteristic is represented by, for example, the above general formula (1) or general formula (3).
  • the photoreactive chiral agent which has the left twist characteristic is represented by the above-mentioned general formula (2) or general formula (3), for example.
  • the above-mentioned polymerizable liquid crystal composition may be divided into a plurality of parts instead of one.
  • a cholesteric layer having a right circular polarization reflection characteristic includes a liquid crystal composition having a right circular polarization reflection characteristic containing a chiral agent that induces right twist as a substrate. What is necessary is just to form by performing the process of apply
  • a cholesteric layer having a left-circularly polarized reflection characteristic (hereinafter, also simply referred to as a left-circularly polarized cholesteric layer) is, for example, a liquid crystal composition having a left-circularly polarized reflection characteristic containing a chiral agent that induces left-handed twist.
  • coating of a liquid-crystal composition, drying, and irradiation of an ultraviolet-ray may all be performed by a well-known method.
  • a chiral agent having a moiety (photoisomerization group) that isomerizes with light such as a cinnamoyl group
  • photoisomerization group a chiral agent having a photoisomerizable group
  • the photoisomerization group may be isomerized and then irradiated with ultraviolet rays for fixing the cholesteric liquid crystal phase.
  • the photoisomerization group is isomerized by irradiating weak UV light to the unexposed part or the entire surface, Thereafter, irradiation with ultraviolet rays for fixing the cholesteric liquid crystal phase may be performed.
  • the right circularly polarized cholesteric layer and the left circularly polarized cholesteric layer can have a plurality of reflective regions that reflect light in different wavelength regions in the plane.
  • the right circularly polarized cholesteric layer and the left circularly polarized cholesteric layer are preferably laminated in the same position in the plane direction with reflection regions that reflect light in the same wavelength region.
  • the reflection wavelength region can be adjusted by adjusting the temperature at the time of ultraviolet irradiation.
  • the right circularly polarized cholesteric layer and the left circularly polarized cholesteric layer have a plurality of reflective regions that reflect light in different wavelength regions in the plane. it can.
  • a transmission region having no reflection characteristics in any wavelength region can be formed in the plane.
  • the right circularly polarized cholesteric layer or the left circularly polarized cholesteric layer may be a single layer, or the right circularly polarized cholesteric layer and the left circularly polarized cholesteric layer may each have at least one layer.
  • Widening the wavelength range of reflected light that is, the wavelength range of light to be blocked, can be realized by sequentially laminating layers with different selective reflection center wavelengths ⁇ .
  • Also known is a technique of expanding the wavelength range by a method of stepwise changing the spiral pitch in the layer called the pitch gradient method, specifically, Nature 378, 467-469 (1995), Examples include the methods described in Japanese Patent No. 281814 and Japanese Patent No. 4990426.
  • the reflection wavelength region of the right circularly polarized cholesteric layer and the left circularly polarized cholesteric layer in the present invention should be set in any range of visible light (wavelength of about 380 nm to 780 nm) and near infrared light (wavelength of about 780 nm to 2000 nm).
  • the setting method is as described above.
  • the reflective color filter forming step includes, for example, a right circular polarized reflective layer forming step for forming a right circular polarized reflective layer having a plurality of wavelength regions in the plane, and a left circular polarized reflective layer having a plurality of wavelength regions in the plane.
  • the left circularly polarized light reflecting layer forming step includes, for example, a right circular polarized reflective layer forming step for forming a right circular polarized reflective layer having a plurality of wavelength regions in the plane, and a left circular polarized reflective layer having a plurality of wavelength regions in the plane.
  • the right circularly polarized light reflection layer forming step includes, as an example, a coating step and a coating step in which a polymerizable liquid crystal composition including at least one polymerizable liquid crystal compound, a photoreactive chiral agent having right-twisting characteristics, and a polymerization initiator is applied.
  • the polymerizable liquid crystal composition applied in step 1 is heated to form a cholesteric alignment state, and a portion of the exposed portion of the polymerizable liquid crystal composition that has been converted to a cholesteric alignment state in the alignment step is exposed to light.
  • a conversion step for converting the reflection wavelength region, and a fixing for fixing the alignment state of the polymerizable liquid crystal composition by performing an exposure process on the entire surface of the polymerizable liquid crystal composition whose partial alignment state has been converted in the conversion step.
  • the conversion process may be performed.
  • the left circularly polarized light reflection layer forming step is, as an example, a coating step and a coating step in which a polymerizable liquid crystal composition including at least one polymerizable liquid crystal compound, a photoreactive chiral agent having left-twisting characteristics, and a polymerization initiator is applied.
  • the polymerizable liquid crystal composition applied in step 1 is heated to form a cholesteric alignment state, and a portion of the exposed portion of the polymerizable liquid crystal composition that has been converted to a cholesteric alignment state in the alignment step is exposed to light.
  • a conversion process for converting the reflection wavelength region, and What is necessary is just to perform the fixing process which fixes a cholesteric alignment state by performing the exposure process to the whole surface of the polymeric liquid crystal composition which converted some alignment states at the conversion process.
  • the right circularly polarized light reflecting layer forming step includes, as another example, a coating step of applying a polymerizable liquid crystal composition containing at least one polymerizable liquid crystal compound, a photoreactive chiral agent having a right twist property and a polymerization initiator,
  • the polymerizable liquid crystal composition applied in the coating process is heated to form an cholesteric alignment state, and an exposure process is performed on a part of the polymerizable liquid crystal composition in the cholesteric alignment state, thereby exposing the cholesteric portion of the exposed portion.
  • a second fixing step for fixing the alignment state of the polymerizable liquid crystal composition may be performed by performing an exposure treatment on the polymerizable liquid crystal composition converted from the above.
  • the left circularly polarized light reflection layer forming step is a coating step of applying a polymerizable liquid crystal composition containing at least one polymerizable liquid crystal compound, a photoreactive chiral agent having left-handed twist characteristics, and a polymerization initiator,
  • the polymerizable liquid crystal composition applied in the coating process is heated to form an cholesteric alignment state, and an exposure process is performed on a part of the polymerizable liquid crystal composition in the cholesteric alignment state, thereby exposing the cholesteric portion of the exposed portion.
  • a second fixing step for fixing the alignment state of the polymerizable liquid crystal composition may be performed by performing an exposure treatment on the polymerizable liquid crystal composition converted from the above.
  • the alignment layer coating step for coating the photo-alignment film, and the photo-alignment film formed by coating with light is exposed with polarized light and the alignment is regulated. It is preferable to perform an orientation regulating step that applies force.
  • the essence of the present invention is to easily obtain a color filter having a large number of spectral characteristics by combining the absorption type color filter 30 and the reflection type color filter 32, and the combination method is not limited at all. Absent.
  • the present invention is not limited to the following configuration, and the configuration can be freely changed without departing from the gist of the present invention.
  • the spectral characteristic diagram illustrated below is a conceptual diagram for explaining changes in spectral characteristics due to the combination of the absorption color filter and the reflective color filter, and is different from the actual spectral shape.
  • the absorption color filter 30 is, for example, a color filter of three primary colors of red, blue, and green. As shown in FIG. 3, the absorption color filter 30 has a red wavelength region 30R, a green wavelength region 30G, and a blue wavelength region 30B arranged in a Bayer array. The red wavelength region 30R, the green wavelength region 30G, and the blue wavelength region 30B have different spectral characteristics.
  • the absorption color filter 30 has a plurality of first sections 31. In the first section 31, two green wavelength regions 30G, one red wavelength region 30R, and one blue wavelength region 30B are arranged.
  • the absorptive color filter 30 has three wavelength regions of a red wavelength region 30R, a green wavelength region 30G, and a blue wavelength region 30B having different spectral characteristics. Any device having a region may be used.
  • the spectral characteristics of the absorption color filter 30 are shown in FIG. As shown in FIG. 6, the red wavelength region 30R has a spectral characteristic 33R, the green wavelength region 30G has a spectral characteristic 33G, and the blue wavelength region 30B has a spectral characteristic 33B, and the spectral characteristics are different.
  • both the ultraviolet region (that is, the left side of the blue wavelength region) and the infrared region (that is, the right side of the red wavelength region) have low transmittance.
  • an ultraviolet absorber and an infrared absorber are contained in each of the red, blue and green regions of an ordinary color filter, or an ordinary absorption color filter and an ultraviolet absorption layer are included.
  • wavelength cut filters used in combination do not necessarily have to be integrated with the absorption type cut filter, but between the measurement object in the optical sensor using the laminated color filter of the present invention and the image sensor that detects light. What is necessary is just to be arrange
  • the red wavelength region 30R transmits, for example, red light having a wavelength of 570 nm to 700 nm in the long wavelength region of the visible light region, and absorbs light other than red light.
  • the green wavelength region 30G for example, transmits green light having a wavelength of 480 nm to 600 nm in the middle wavelength region of the visible light region and absorbs light other than green light.
  • the blue wavelength region 30B transmits blue light having a wavelength of 400 nm to 500 nm in the short wavelength region of the visible light region, and absorbs light other than blue light.
  • the multilayer color filter 14 is configured by the reflective color filter 32 and the absorption color filter 30.
  • the reflective color filter 32 is disposed on the planarizing layer 29.
  • the reflective color filter 32 has a plurality of second sections 32a.
  • the absorption type color filter 30 and the reflection type color filter 32 are laminated such that the first section 31 (see FIG. 3) and the second section 32a (see FIG. 2) coincide.
  • a microlens 28 is provided between the absorption color filter 30 and the reflection color filter 32, and the absorption color filter 30 and the reflection color filter 32 are laminated. Instead, the absorption color filter 30 and the reflection color filter 32 may be laminated in direct contact with each other. As shown in FIGS.
  • the reflective color filter 32 has two wavelength regions of a first wavelength region 34 and a second wavelength region 35 having different spectral characteristics.
  • the first wavelength region 34 or the second wavelength region 35 is arranged for each second section 32 a of the reflective color filter 32.
  • the same wavelength region is not arranged in the adjacent second section 32a.
  • FIG. 5 shows spectral characteristics of the first wavelength region 34 and the second wavelength region 35 of the reflective color filter 32.
  • the first wavelength region 34 has a spectral characteristic 34a. As shown in the spectral characteristics 34a, the first wavelength region 34 includes a part of the light transmitted through the blue wavelength region 30B, including a region where light transmitted through the blue wavelength region 30B and light transmitted through the green wavelength region 30G overlap. And part of the light transmitted through the green wavelength region 30G is not transmitted.
  • the second wavelength region 35 has a spectral characteristic 35a.
  • the second wavelength region 35 does not transmit light on the longer wavelength side than the first wavelength region 34.
  • the second wavelength region 35 includes a part of light that passes through the green wavelength region 30G, including a region where light that passes through the green wavelength region 30G and light that passes through the red wavelength region 30R overlap. And part of the light transmitted through the red wavelength region 30R is not transmitted.
  • the reflective color filter 32 is preferably one obtained by curing a polymerizable cholesteric liquid crystal composition.
  • the multilayer color filter 14 is as shown in FIG. 4 when viewed from the incident light side.
  • the laminated color filter 14 shown in FIG. 4 is a composite of the absorption color filter 30 and the reflection color filter 32. 7 and 8 show the spectral characteristics of the multilayer color filter 14.
  • the multilayer color filter 14 includes a first green wavelength region 30G 1 two, one pixel region in the first blue wavelength region 30B 1, the first red wavelength region 30R 1 31a is configured. Further, two second green wavelength region 30G 2, and second blue wavelength region 30B 2, 1 single pixel area 31b is composed of a second red wavelength region 30R 2. Thus, it has two types of pixel regions 31a and 31b.
  • the first blue wavelength region 30B 1 has a spectral characteristic 36B 1.
  • the first green wavelength region 30G 1 has the spectral characteristics 36G 1.
  • the first red wavelength region 30R 1 has the spectral characteristics 36R 1.
  • Spectral characteristics of the pixel region 31b of the multilayer color filter 14, as shown in FIG. 8, a second blue wavelength region 30B 2 has the spectral characteristics 36B 2.
  • Second green wavelength region 30G 2 has a spectral characteristic 36G 2.
  • the second red wavelength region 30R 2 has a spectral characteristic 36R 2.
  • the laminated color filter 14 has a red wavelength region, a green wavelength region, and a blue wavelength region as compared with the color filters of the three primary colors of red, blue, and green.
  • Light in different wavelength regions can be transmitted. That is, multi-gradation can be achieved.
  • the absorptive color filter 30 has three types of wavelength regions
  • the reflective type color filter 32 has two types of wavelength regions
  • the laminated color filter 14 has six gradations.
  • the number of species of the multilayer color filter 14 is larger than the total of the species of the wavelength region of the absorption color filter 30 and the species of the reflective color filter 32.
  • the absorption color filter 30 having m types of wavelength regions and the reflection type color filter 32 having n types of wavelength regions are overlapped with each other in different combinations, whereby the absorption type color filter 30 is obtained.
  • the maximum value of the species p of the wavelength region generated at this time is m ⁇ n.
  • the band that can be shielded by the reflective color filter is limited to about 150 nm. Therefore, when the multilayer color filter 14 is a combination of a reflective color filter and a reflective color filter, a region other than a specific wavelength is used. It is necessary to shield everything. In a reflection type color filter, it is necessary to stack a considerable number of layers in order to block a region other than a specific wavelength, which is complicated in terms of configuration and production.
  • the absorptive color filter 30 is, for example, a color filter of three primary colors, and can be manufactured by a manufacturing method similar to that used for an image pickup device such as a CCD (Charge Coupled Device), and therefore a detailed description thereof Omitted.
  • a method for manufacturing the reflective color filter 32 will be described with reference to FIGS. 9 to 16 are schematic perspective views showing the method of manufacturing the multilayer color filter according to the embodiment of the present invention in the order of steps.
  • a base layer 42 is formed on a substrate 40, and a reflective layer 44, that is, a polymerizable liquid crystal composition containing a right-twisted chiral agent having a photoisomerizable group is formed on the base layer 42, that is, A liquid crystal composition layer is prepared.
  • an exposure mask 46 having a predetermined pattern is disposed on the reflective layer 44.
  • the light L 1 is irradiated onto the reflective layer 44 from above the exposure mask 46 to expose the exposure region 45.
  • region 45 the photoisomerization of a chiral agent occurs and the wavelength of the light reflected changes in connection with it.
  • FIG. 10 schematically shows the patterning process.
  • an i-line stepper or the like is used to form a micropattern, so that there is a gap between the exposure mask 46 and the reflective layer 44.
  • the cholesteric liquid crystal composition is polymerized and fixed, the wavelength of the light reflected by the reflective layer 44 is fixed, and the first region 47 and the second region having different wavelengths of the reflected light as shown in FIG.
  • a right circularly polarized light reflection type color filter 49 a having 48 is obtained.
  • the light L 1 and the light L 2 are both ultraviolet light, and the light L 2 has higher light intensity than the light L 2 .
  • the underlayer 42 is a layer for horizontally aligning the cholesteric liquid crystal composition.
  • the base layer 42 is preferably a photo-alignment film.
  • a left circular polarized light reflective type having a first region 47a (see FIG. 16) and a second region 48a (see FIG. 16) having different wavelengths of reflected light.
  • a color filter 49b (see FIG. 16) is produced on the right circularly polarized light reflective color filter 49a.
  • the left circularly polarized reflective color filter 49b has a configuration other than the point that the reflective layer 44a is formed using a polymerizable liquid crystal composition containing a left-twisted chiral agent having an isomerization group. Can be produced in the same manner as the right circular polarization reflection type color filter 49a.
  • the above-described exposure mask 46 is disposed on the reflective layer 44a. Then, the light L 1 is irradiated on a reflective layer 44a from above the exposure mask 46 to expose the exposure area 45a. Thereby, in the exposure area
  • the exposure mask 46 is disposed at the same position as the right circular polarization reflection type color filter 49a, and the exposure area 45a is on the above-described exposure area 45.
  • FIG. 16 schematically shows the patterning as in FIG. 10, and an optical system including a plurality of lenses and the like exists between the exposure mask 46 and the reflective layer 44 as described above.
  • the cholesteric liquid crystal composition is polymerized and fixed, the wavelength of light reflected by the reflective layer 44a is fixed, and the first region 47a and the second region having different wavelengths of reflected light as shown in FIG.
  • a left circularly polarized reflective color filter 49b having 48a is obtained.
  • the first region 47a is formed on the first region 47 of the right circular polarization reflection type color filter 49a, and the second region 48a is formed on the second region 48 of the right circular polarization reflection type color filter 49a.
  • the light L 1 and the light L 2 are ultraviolet light, and the light L 2 has higher light intensity than the light L 2 .
  • it is preferably performed in a nitrogen atmosphere.
  • the left circular polarization reflection type color filter 49b is laminated on the right circular polarization reflection type color filter 49a, and the reflection type color filter 32 can be obtained.
  • the reflective color filter 32 can obtain various spectral characteristics with the same material by using optical HTP (Helical Twisting Power) conversion technology, and develops corresponding dyes like an absorption color filter. Save time and effort.
  • optical HTP Helical Twisting Power
  • the reflective color filter 32 is not limited to the configuration shown in FIG. 2, but may be the configuration shown in FIG.
  • the reflective color filter 50 shown in FIG. 17 has a plurality of second sections 52 and four types of wavelength regions having different spectral characteristics. That is, the reflective color filter 50 has a first wavelength region 34, a second wavelength region 35, a third wavelength region 53, and a fourth wavelength region 54 that have different spectral characteristics.
  • the same components as those of the reflective color filter 32 shown in FIG. 2 are denoted by the same reference numerals, and detailed description thereof is omitted.
  • the reflective color filter 50 is also laminated with the first section 31 of the absorption color filter 30 and the second section of the reflective color filter 50 matched to each other as in the above-described reflective color filter 32.
  • the reflective color filter 50 has two sets of wavelength regions that are selected from four different wavelength regions having different spectral characteristics without overlapping, and are configured by two types of wavelength regions, respectively.
  • the two sets of wavelength regions include a first set composed of a first wavelength region 34 and a third wavelength region 53, and a second wavelength region 35 and a fourth wavelength region 54. Two sets of the second set. One of the first group and the second group described above is arranged for each second section 52 of the reflective color filter 50.
  • the first wavelength region 34 is disposed at a position corresponding to the blue wavelength region 30B
  • the third wavelength region 53 is disposed at a position corresponding to the green wavelength region 30G and the red wavelength region 30R.
  • the second wavelength region 35 is disposed at a position corresponding to the blue wavelength region 30B and the green wavelength region 30G
  • the fourth wavelength region 54 is disposed at a position corresponding to the red wavelength region 30R.
  • FIG. 18 shows spectral characteristics of the first wavelength region 34 to the fourth wavelength region 54 of the reflective color filter 50.
  • the same components as those of the spectral characteristics of the reflective color filter 32 shown in FIG. 5 are denoted by the same reference numerals, and detailed description thereof is omitted.
  • the first wavelength region 34 has a spectral characteristic 34a.
  • the first wavelength region 34 does not transmit part of the light transmitted through the blue wavelength region 30B.
  • the second wavelength region 35 has a spectral characteristic 35a.
  • the second wavelength region 35 transmits part of the light transmitted through the blue wavelength region 30B and the green wavelength region 30G, including the region where the light transmitted through the blue wavelength region 30B and the light transmitted through the green wavelength region 30G overlap. Do not transmit part of the light.
  • the third wavelength region 53 has a spectral characteristic 53a.
  • the third wavelength region 53 transmits a part of the light transmitted through the green wavelength region 30G and the red wavelength region 30R including the region where the light transmitted through the green wavelength region 30G and the light transmitted through the red wavelength region 30R overlap.
  • the fourth wavelength region 54 has a spectral characteristic 54a. The fourth wavelength region 54 does not transmit light on the longer wavelength side of the light transmitted through the red wavelength region 30R than the third wavelength region 53.
  • the multilayer color filter 14 using the reflective color filter 50 and the above-described absorption color filter 30 has two third green wavelength regions 30G 3 and a first blue wavelength region 30B 1. If, one pixel region 31c is composed of the third red wavelength region 30R 3. Further, two second green wavelength region 30G 2, and second blue wavelength region 30B 2, 1 single pixel region 31d is formed in the fourth red wavelength region 30R 4. Thus, it has two types of pixel regions 31c and 31d.
  • a first blue wavelength region 30B 1 has a spectral characteristic 36B 1.
  • the second blue wavelength region 30B 2 has the spectral characteristics 36B 2. It found the following second blue wavelength region 30B 2, and transmits light having a shorter wavelength than the first blue wavelength region 30B 1.
  • Second green wavelength region 30G 2 has a spectral characteristic 36G 2.
  • the third green wavelength region 30G 3 has the spectral characteristics 36G 3. Towards the third green wavelength region 30G 3 is, to transmit light having a shorter wavelength than the second green wavelength region 30G 2.
  • the third red wavelength region 30R 3 has the spectral characteristics 36R 3.
  • Fourth red wavelength region 30R 4 has the spectral characteristics 36R 4.
  • fourth red wavelength region 30R transmits light of a shorter wavelength side than the third red wavelength region 30R 3.
  • Second green wavelength region 30G 2 has a spectral characteristic 36G 2.
  • Fourth red wavelength region 30R 4 has the spectral characteristics 36R 4.
  • the multilayer color filter 14 is different in the red wavelength region, the green wavelength region, and the blue wavelength region, respectively, as compared with the color filters of the three primary colors of red, blue, and green.
  • Light in the wavelength region can be transmitted. That is, multi-gradation can be achieved.
  • the laminated color filter 14 has 6 gradations. Thereby, for example, a specific wavelength region can be detected in the blue wavelength region. A specific wavelength region can be detected in the green wavelength region. A specific wavelength region can be detected in the red wavelength region.
  • the reflective color filter 32 is not limited to the configuration shown in FIG. 2, but may be the configuration shown in FIG.
  • a reflective color filter 51 shown in FIG. 21 has a plurality of second sections 52 and eight wavelength regions having different spectral characteristics.
  • the same components as those of the reflective color filter 32 shown in FIG. 2 are denoted by the same reference numerals, and detailed description thereof is omitted.
  • the reflection type color filter 51 shown in FIG. 21 is also laminated in such a manner that the first section 31 of the absorption color filter 30 and the second section 52 of the reflection type color filter 50 coincide with each other like the reflection color filter 32 described above. Is done.
  • the reflection type color filter 51 has four sets of wavelength regions that are selected without overlapping from eight wavelength regions having different spectral characteristics, and are configured by two types of wavelength regions, respectively.
  • FIG. 21 includes a first set including a first wavelength region 34 and a fifth wavelength region 55.
  • the first wavelength region 34 is a blue wavelength region 30B.
  • the fifth wavelength region 55 is disposed at a position corresponding to the green wavelength region 30G and the red wavelength region 30R.
  • it has a second set composed of a second wavelength region 35 and a sixth wavelength region 56.
  • the second wavelength region 35 is disposed at a position corresponding to the blue wavelength region 30B, and Six wavelength regions 56 are arranged at positions corresponding to the green wavelength region 30G and the red wavelength region 30R.
  • the third wavelength region 53 and the seventh wavelength region 57 have a third set.
  • the seventh wavelength region 57 is disposed at a position corresponding to the red wavelength region 30R
  • 7 wavelength region 57 is arranged at a position corresponding to blue wavelength region 30B and green wavelength region 30G.
  • the fourth set includes a fourth wavelength region 54 and an eighth wavelength region 58.
  • the eighth wavelength region 58 is disposed at a position corresponding to the red wavelength region 30R.
  • the eight wavelength regions 58 are arranged at positions corresponding to the blue wavelength region 30B and the green wavelength region 30G.
  • the spectral characteristics of the first to eighth wavelength regions 34 to 58 of the reflective color filter 51 are shown in FIGS. 22 and 23, the same components as those of the spectral characteristics of the reflective color filter 32 shown in FIG. 5 are denoted by the same reference numerals, and detailed description thereof is omitted.
  • the first wavelength region 34 has a spectral characteristic 34a.
  • the first wavelength region 34 does not transmit part of the light transmitted through the blue wavelength region 30B.
  • the third wavelength region 53 has a spectral characteristic 53a.
  • the third wavelength region 53 includes a part of the light transmitted through the blue wavelength region 30B and the light transmitted through the green wavelength region 30G, including a region where the light transmitted through the blue wavelength region 30B and the light transmitted through the green wavelength region 30G overlap. It does not transmit part of.
  • the fifth wavelength region 55 has a spectral characteristic 55a.
  • the fifth wavelength region 55 transmits a part of the light transmitted through the green wavelength region 30G and the red wavelength region 30R, including a region where the light transmitted through the green wavelength region 30G and the light transmitted through the red wavelength region 30R overlap. Do not transmit part of the light.
  • the seventh wavelength region 57 has spectral characteristics 57a. The seventh wavelength region 57 does not transmit part of the light transmitted through the red wavelength region 30R.
  • the second wavelength region 35 has a spectral characteristic 35a.
  • the second wavelength region 35 does not transmit light on the longer wavelength side of the light transmitted through the blue wavelength region 30B than the first wavelength region 34.
  • the fourth wavelength region 54 has a spectral characteristic 54a.
  • the fourth wavelength region 54 includes a portion of the light transmitted through the blue wavelength region 30B and the light transmitted through the green wavelength region 30G, including a region where light transmitted through the blue wavelength region 30B and light transmitted through the green wavelength region 30G overlap. It does not transmit part of.
  • the fourth wavelength region 54 does not transmit light longer than the third wavelength region 53.
  • the sixth wavelength region 56 has spectral characteristics 56a.
  • the sixth wavelength region 56 transmits a part of the light transmitted through the green wavelength region 30G and the red wavelength region 30R including the region where the light transmitted through the green wavelength region 30G and the light transmitted through the red wavelength region 30R overlap. Do not transmit part of the light.
  • the sixth wavelength region 56 does not transmit light on the longer wavelength side than the fifth wavelength region 55.
  • the eighth wavelength region 58 has spectral characteristics 58a.
  • the eighth wavelength region 58 transmits part of the light transmitted through the red wavelength region 30R.
  • the eighth wavelength region 58 transmits light longer than the seventh wavelength region 57.
  • the multilayer color filter 14 using the reflective color filter 51 and the above-described absorption color filter 30 includes two fifth green wavelength regions 30G 5 and a first blue wavelength region 30B 1. If, one pixel region 31e is composed of a red wavelength region 30R 5 of the fifth. Further, two of the sixth green wavelength region 30G 6 of a second blue wavelength region 30B 2, 1 single pixel area 31f is composed of a red wavelength region 30R 6 sixth. And two third green wavelength region 30G 3, and the third the blue wavelength region 30B 3, 1 single pixel area 31g is constituted by a red wavelength region 30R 7 of the seventh. And two fourth green wavelength region 30G 4, the fourth blue wavelength region 30B 4, 1 single pixel area 31h is composed of a red wavelength region 30R 8 of the eighth. Thus, it has four types of pixel regions 31e, 31f, 31g, and 31h.
  • the third the blue wavelength region 30B 3 has a spectral characteristic 36B 3.
  • the third green wavelength region 30G 3 has the spectral characteristics 36G 3.
  • Spectral characteristics of the pixel region 31h of the multilayer color filter 14, as shown in FIG. 26, the fourth blue wavelength region 30B 4 has a spectral characteristic 36B 4.
  • the laminated color filter 14 has a red wavelength region, a green wavelength region, and a blue wavelength region, as compared with the color filters of the three primary colors of red, blue and green. , Light in different wavelength regions can be transmitted. That is, multi-gradation can be achieved.
  • the laminated color filter 14 has 12 gradations. Also in this case, the number of species of the multilayer color filter 14 is larger than the total of the species of the wavelength region of the absorption color filter 30 and the species of the reflective color filter 51. Thereby, for example, a specific wavelength region can be detected in the blue wavelength region. A specific wavelength region can be detected in the green wavelength region. A specific wavelength region can be detected in the red wavelength region.
  • the optical sensor 10 shown in FIG. 1 uses the absorption color filter 30 of the three primary colors as described above.
  • the present invention is not limited to this, and infrared light is detected like the optical sensor 11 shown in FIG. It may be possible.
  • the same components as those of the optical sensor 10 shown in FIG. 27 is a schematic cross-sectional view showing another configuration of the optical sensor having the color filter according to the embodiment of the present invention
  • FIG. 28 shows another configuration of the absorption type color filter of the color filter according to the embodiment of the present invention.
  • FIG. 29 is a schematic diagram showing another configuration of the reflective color filter of the color filter according to the embodiment of the present invention.
  • FIG. 30 is a graph showing spectral characteristics of the absorption type color filter of the color filter according to the embodiment of the present invention
  • FIG. 31 is a graph showing spectral characteristics of the reflective color filter of the color filter according to the embodiment of the present invention.
  • the optical sensor 11 is different from the optical sensor 10 shown in FIG. 1 in that infrared light can be detected, and the photodiode 24 has sensitivity to infrared light.
  • the optical sensor 11 is different in the configuration of the absorption color filter 30 and the reflection color filter 32 from the optical sensor 10 shown in FIG.
  • the absorption color filter 30 has four strip-shaped first sections 31. In the first section 31, a blue wavelength region 30B, a green wavelength region 30G, a red wavelength region 30R, and an infrared wavelength region 30IR are arranged in this order.
  • the infrared wavelength region 30IR has a spectral characteristic 33IR shown in FIG.
  • the light in the blue wavelength region 30B, the light in the green wavelength region 30G, and the light in the red wavelength region 30R are not transmitted, but only light on the longer wavelength side than the red wavelength region 30R is transmitted.
  • the infrared light transmitted through the infrared wavelength region 30IR reaches the photodiode 24 below the infrared wavelength region 30IR, and the infrared light is detected by the photodiode 24.
  • the optical sensor 11 can obtain a color image of three primary colors and an infrared light image.
  • the infrared wavelength region 30IR can be composed of a visible light cut filter that cuts visible light and transmits near infrared light.
  • the visible light cut filter contains a plurality of dyes for absorbing the entire visible light region.
  • Near-infrared light is light having a wavelength of about 780 nm to 2000 nm.
  • an infrared absorber is contained only in the blue wavelength region 30B, the green wavelength region 30G, and the red wavelength region 30R, or the infrared absorption layer is included in the blue wavelength region 30B, green wavelength. It is necessary to arrange so as to overlap only the region 30G and the red wavelength region 30R.
  • the infrared absorbing layer is disposed so as to overlap only the blue wavelength region 30B, the green wavelength region 30G, and the red wavelength region 30R, the infrared absorbing layer is formed by some method so that the infrared absorbing layer does not overlap the infrared wavelength region 30IR.
  • wavelength conversion patterning using the photoreactive chiral agent used in the present invention can be used in addition to techniques such as lithography and etching.
  • the reflective color filter 32 has ten wavelength regions of a first wavelength region 34 to a tenth wavelength region 60.
  • the first wavelength region 34 and the second wavelength region 35 are arranged at positions corresponding to the blue wavelength region 30 ⁇ / b> B of the absorption color filter 30.
  • the third wavelength region 53 and the fourth wavelength region 54 are disposed at positions overlapping and overlapping the blue wavelength region 30B and the green wavelength region 30G of the absorption color filter 30.
  • the fifth wavelength region 55 and the sixth wavelength region 56 are disposed at positions that overlap and overlap the green wavelength region 30G and the red wavelength region 30R of the absorption color filter 30.
  • the seventh wavelength region 57 and the eighth wavelength region 58 are disposed at positions that overlap and overlap the red wavelength region 30R and the infrared wavelength region 30IR of the absorption color filter 30.
  • the ninth wavelength region 59 and the tenth wavelength region 60 are disposed at positions overlapping the blue wavelength region 30B of the absorption color filter 30.
  • the first wavelength region 34 has a spectral characteristic 34a.
  • the first wavelength region 34 does not transmit part of the light transmitted through the blue wavelength region 30B.
  • the third wavelength region 53 has a spectral characteristic 53a.
  • the third wavelength region 53 transmits part of the light transmitted through the blue wavelength region 30B and the green wavelength region 30G, including the region where the light transmitted through the blue wavelength region 30B and the light transmitted through the green wavelength region 30G overlap. Do not transmit part of the light.
  • the fifth wavelength region 55 has a spectral characteristic 55a.
  • the fifth wavelength region 55 transmits a part of the light transmitted through the green wavelength region 30G and the red wavelength region 30R, including a region where the light transmitted through the green wavelength region 30G and the light transmitted through the red wavelength region 30R overlap.
  • the seventh wavelength region 57 has spectral characteristics 57a.
  • the seventh wavelength region 57 does not transmit part of the light transmitted through the red wavelength region 30R and part of the light transmitted through the infrared wavelength region 30IR.
  • the ninth wavelength region 59 has a spectral characteristic 59a. The ninth wavelength region 59 does not transmit part of the light transmitted through the infrared wavelength region 30IR.
  • the second wavelength region 35 has a spectral characteristic 35a.
  • the second wavelength region 35 does not transmit part of the light transmitted through the blue wavelength region 30B.
  • the fourth wavelength region 54 has a spectral characteristic 54a.
  • the fourth wavelength region 54 transmits part of the light transmitted through the blue wavelength region 30B and the green wavelength region 30G, including a region where the light transmitted through the blue wavelength region 30B and the light transmitted through the green wavelength region 30G overlap. Do not transmit part of the light.
  • the sixth wavelength region 56 has spectral characteristics 56a.
  • the sixth wavelength region 56 transmits a part of the light transmitted through the green wavelength region 30G and the red wavelength region 30R including the region where the light transmitted through the green wavelength region 30G and the light transmitted through the red wavelength region 30R overlap.
  • the eighth wavelength region 58 has spectral characteristics 58a.
  • the eighth wavelength region 58 does not transmit part of the light transmitted through the red wavelength region 30R and part of the light transmitted through the infrared wavelength region 30IR.
  • the tenth wavelength region 60 has a spectral characteristic 60a. The tenth wavelength region 60 does not transmit part of the light transmitted through the infrared wavelength region 30IR.
  • the laminated color filter 14 using the absorption color filter 30 and the reflection color filter 32 is 1 in the first blue wavelength region 30B 1 to the fourth blue wavelength region 30B 4 .
  • One pixel region 37a is configured, and one pixel region 37b is configured by the third blue wavelength region 30B 3 to the sixth blue wavelength region 30B 6 , and the fifth red wavelength region 30R 5 to the eighth red wavelength region.
  • one pixel region 37c at 30R 8 is formed, one pixel region 37d in the infrared wavelength region 30IR 10 of the seventh infrared wavelength region 30IR7 ⁇ tenth is constructed.
  • a first blue wavelength region 30B 1 of the laminated color filter 14 has a spectral characteristic 36B 1.
  • Third blue wavelength region 30B 3 has a spectral characteristic 36B 3.
  • the third green wavelength region 30G 3 has the spectral characteristics 36G 3.
  • Green wavelength region 30G 5 of the fifth has a spectral characteristic 36G 5.
  • Red wavelength region 30R 5 of the fifth has a spectral characteristic 36R 5.
  • the ninth infrared wavelength region 30IR 9 has a spectral characteristic 36IR 9 .
  • a second blue wavelength region 30B 2 of the laminated color filter 14 has a spectral characteristic 36B 2.
  • Fourth blue wavelength region 30B 4 has a spectral characteristic 36B 4.
  • Green wavelength region 30G 6 sixth having spectral characteristics 36G 6.
  • Red wavelength region 30R 6 of the sixth having spectral characteristics 36R 6.
  • Red wavelength region 30R 8 of the eighth having spectral characteristics 36R 8.
  • Infrared wavelength region 30IR 8 of the eighth having spectral characteristics 36IR 8 have a spectral characteristic 36IR 10.
  • the laminated color filter 14 has a red wavelength region, a blue wavelength region, and a color filter in the three primary colors of red, blue, and green and an infrared wavelength region. Further, light in different wavelength regions can be transmitted for the green wavelength region and the infrared wavelength region. That is, multi-gradation can be achieved.
  • the laminated color filter 14 has 16 gradations. Also in this case, the number of species of the multilayer color filter 14 is larger than the total of the species of the wavelength region of the absorption color filter 30 and the species of the reflective color filter 32. Thereby, for example, a specific wavelength region can be detected in the blue wavelength region. A specific wavelength region can be detected in the green wavelength region. A specific wavelength region can be detected in the red wavelength region. Even in the infrared wavelength region, a specific wavelength region can be detected.
  • the reflective color filter 50 shown in FIG. 17 is composed of a first reflective filter 50a shown in FIG. 36 and a second reflective filter 50b shown in FIG. 37, and the first reflective filter 50a.
  • the second reflective filter 50b may be laminated.
  • the first reflective filter 50a has a right circular polarization reflection characteristic
  • the second reflection filter 50b has a left circular polarization reflection characteristic.
  • the first reflective filter 50a in FIG. 36 has the second wavelength region 35 and the third wavelength region 53 of the reflective color filter 50 shown in FIG. 17, and has a plurality of wavelength regions.
  • the first reflective filter 50 a has a plurality of second sections 62, and the second wavelength region 35 or the third wavelength region 53 is arranged for each second section 62.
  • the second reflective filter 50b shown in FIG. 37 has the first wavelength region 34 and the fourth wavelength region 54 of the reflective color filter 50 shown in FIG. Even in this case, the second reflective filter 50 b has a plurality of second sections 64, and the first wavelength region 34 or the fourth wavelength region 54 is arranged for each second section 64. .
  • the first reflective filter 50a and the second reflective filter 50b are stacked such that the second compartment 62 of the first reflective filter 50a and the second compartment 64 of the second reflective filter 50b are matched.
  • the same configuration as that of the reflective color filter 50 shown in FIG. 17 is obtained, and the same function as that of the reflective color filter 50 is provided.
  • the first reflective filter 50a and the second reflective filter 50b are used, the first reflective filter 50a and the second reflective filter 50b have a small number of species in the wavelength region. The number of exposures can be reduced, and the manufacturing process can be simplified.
  • the present invention is basically configured as described above.
  • the color filter, kit, color filter manufacturing method, and optical sensor of the present invention have been described in detail above.
  • the present invention is not limited to the above-described embodiment, and various improvements can be made without departing from the gist of the present invention. Of course, changes may be made.
  • a coating solution (L2) was prepared with the same composition except that the photoreactive right-turning chiral agent 1 in the preparation of the coating solution R1 was changed to the photoreactive left-turning chiral agent 1 described below.
  • a coating solution 1 for a photo-alignment film was prepared.
  • the prepared coating liquid 1 for photo-alignment film was applied by a spin coating method to form the photo-alignment film-forming film 1.
  • the coating liquid R1 was spin-coated on the glass substrate P1 with a photo-alignment film to form a coating film so as to have a film thickness of 5 ⁇ m.
  • the glass substrate P1 with a photo-alignment film on which the coating film is arranged is heated on a hot plate at 80 ° C. for 1 minute to dry and remove the solvent and form a cholesteric alignment state, and then using EXECURE 3000-W manufactured by HOYA-SCHOTT Then, UV (ultraviolet) light with an illuminance of 30 mW / cm 2 was irradiated for 10 seconds through a photomask at room temperature in a nitrogen atmosphere to fix the orientation of the region F1.
  • UV light with an illuminance of 2 mW / cm 2 was irradiated for 50 seconds (100 mJ / cm 2 ) under air, and then heated on an 80 ° C. hot plate for 1 minute to be immobilized.
  • UV light having an illuminance of 30 mW / cm 2 is irradiated again for 10 seconds through a photomask in a nitrogen atmosphere at room temperature, and the region F2 different from the region F1 is irradiated.
  • the orientation was fixed.
  • UV light with an illuminance of 2 mW / cm 2 was irradiated for 50 seconds (100 mJ / cm 2 ) under air, and then heated on an 80 ° C. hot plate for 1 minute to be immobilized.
  • UV light with an illuminance of 30 mW / cm 2 is again irradiated for 10 seconds through a photomask at room temperature in a nitrogen atmosphere, which is different from the regions F1 and F2.
  • the orientation of the region F3 was fixed.
  • UV light with an illuminance of 2 mW / cm 2 was irradiated for 50 seconds (100 mJ / cm 2 ) under air, and then heated on an 80 ° C. hot plate for 1 minute to be immobilized.
  • UV light having an illuminance of 30 mW / cm 2 is irradiated again for 10 seconds at room temperature in a nitrogen atmosphere, and the region F4 different from the region F1, the region F2, and the region F3
  • the reflection type color filter RCF1 was produced by fixing the orientation of the color filter.
  • Region F1 the area F2, the dose for the spectral transform in the area F3, and area F4, respectively 0mJ / cm 2, 100mJ / cm 2, 200mJ / cm 2 and 300 mJ / cm 2, and the reflection at the respective portions centered
  • the wavelengths were 426 nm, 496 nm, 572 nm, and 640 nm.
  • ⁇ Production of reflective color filter (LCF1)> A reflective color filter LCF1 was produced in the same manner except that the coating liquid in the production process of the reflective color filter RCF1 was changed to L1.
  • the reflection center wavelengths in the respective parts of the region F1, the region F2, the region F3, and the region F4 were 426 nm, 496 nm, 572 nm, and 640 nm.
  • RLCF1> A laminated reflective color filter RLCF1 was produced in the same manner except that the substrate in the production process of the reflective color filter LCF1 was changed to the reflective color filter RCF1 produced above.
  • the position of the region F1, the region F2, the region F3, and the region F4 of the RCF1 and the region F1, the region F2, the region F3, and the region F4 of the LCF1 overlap each other. Combined and exposed.
  • the reflection center wavelengths in the respective portions of the region F1, the region F2, the region F3, and the region F4 of the laminate were 426 nm, 496 nm, 572 nm, and 640 nm.
  • ⁇ Lamination with absorption color filter> Spectroscopy by stacking the multilayer reflective color filter RLCF1 and the color filters of the three primary colors red (R), green (G), and blue (B) used for the absorption color filter was measured.
  • the spectrum in the region F1 of the multilayer reflective color filter RLCF1 cuts the short wavelength side of the blue wavelength region
  • the spectrum in the region F2 cuts the long wavelength side of the blue wavelength region and the short wavelength side of the green wavelength region
  • region F3 It was found that the spectrum in Fig. 4 cuts the long wavelength side in the green wavelength region and the short wavelength side in the red wavelength region
  • the spectrum in the region F4 can cut the long wavelength side in the red wavelength region. That is, a stacked color filter having spectral characteristics divided into 6 wavelength regions can be realized by superimposing specific wavelength regions of the stacked reflective color filter RLCF1 and the absorption RGB color filter.
  • a red filter (R), a green filter (G), and a blue filter (B) are formed on the image sensor array by a known method, and further, a microlens and a flattening layer are formed. 3 and FIG. 17, the photo-alignment film and the laminated reflective color filter are formed on the stacked layers, and the above-described regions F1, F2, F3, and F4 and the RGB color filters are shown in FIGS.
  • the optical sensor according to the present invention can be manufactured by forming a known near-infrared cut layer that is formed as shown and further blocks a wavelength range of 650 to 1200 nm.

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Engineering & Computer Science (AREA)
  • Multimedia (AREA)
  • Signal Processing (AREA)
  • Polarising Elements (AREA)
  • Solid State Image Pick-Up Elements (AREA)
  • Optical Filters (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention porte également sur un filtre coloré pour acquérir des informations de régions de longueurs d'onde spécifiques, sur un kit, sur un procédé de fabrication de filtre coloré et sur un capteur optique. Ce filtre coloré stratifié comprend au moins un filtre coloré absorbant et au moins un filtre coloré réfléchissant. Le filtre coloré absorbant et le filtre coloré réfléchissant sont empilés les uns sur les autres. Définissant n en tant que nombre de types de régions de longueur d'onde du filtre coloré absorbant, n étant le nombre de types de régions de longueur d'onde du filtre coloré réfléchissant, et p étant le nombre de types de régions de longueur d'onde du filtre coloré stratifié, est maintenu que p > m ≧ 2 et p > n ≧ 2.
PCT/JP2017/019483 2016-07-01 2017-05-25 Filtre coloré stratifié, kit, procédé de fabrication de filtre coloré stratifié et capteur optique WO2018003359A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2018524961A JP6641009B2 (ja) 2016-07-01 2017-05-25 積層型カラーフィルター、積層型カラーフィルターの製造方法、および光学センサ

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2016-131975 2016-07-01
JP2016131975 2016-07-01
JP2016-166721 2016-08-29
JP2016166721 2016-08-29

Publications (1)

Publication Number Publication Date
WO2018003359A1 true WO2018003359A1 (fr) 2018-01-04

Family

ID=60787151

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2017/019483 WO2018003359A1 (fr) 2016-07-01 2017-05-25 Filtre coloré stratifié, kit, procédé de fabrication de filtre coloré stratifié et capteur optique

Country Status (3)

Country Link
JP (1) JP6641009B2 (fr)
TW (1) TW201803097A (fr)
WO (1) WO2018003359A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020202876A1 (fr) * 2019-03-29 2020-10-08 ソニーセミコンダクタソリューションズ株式会社 Élément d'imagerie à semi-conducteurs et dispositif d'imagerie
WO2023032644A1 (fr) * 2021-08-30 2023-03-09 富士フイルム株式会社 Film décoratif, corps moulé et article
JP7472182B2 (ja) 2018-03-23 2024-04-22 富士フイルム株式会社 コレステリック液晶層の製造方法、コレステリック液晶層、液晶組成物、硬化物、光学異方体、反射層

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10705026B2 (en) * 2018-10-26 2020-07-07 Kla Corporation Scanning differential interference contrast in an imaging system design

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000258760A (ja) * 1999-03-12 2000-09-22 Toshiba Corp 液晶表示装置
JP2008502936A (ja) * 2004-06-17 2008-01-31 コーニンクレッカ フィリップス エレクトロニクス エヌ ヴィ 光学分離フィルタ
WO2014097895A1 (fr) * 2012-12-17 2014-06-26 富士フイルム株式会社 Cristaux liquides cholestériques à plusieurs couches, procédé de fabrication associé et stratifié de cristaux liquides cholestériques à plusieurs couches
JP2016076682A (ja) * 2014-10-06 2016-05-12 采▲ぎょく▼科技股▲ふん▼有限公司ＶｉｓＥｒａ Ｔｅｃｈｎｏｌｏｇｉｅｓ Ｃｏｍｐａｎｙ Ｌｉｍｉｔｅｄ イメージセンサーとその形成方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4287598B2 (ja) * 2000-06-27 2009-07-01 富士フイルム株式会社 光反応型カイラル剤、液晶組成物、液晶カラーフィルタ、光学フィルム、記録媒体、及び液晶の捻れ構造を変化させる方法
JP4287599B2 (ja) * 2000-06-27 2009-07-01 富士フイルム株式会社 光反応型光学活性化合物、光反応型カイラル剤、液晶組成物、液晶カラーフィルタ、光学フィルム、記録媒体、及び液晶の捻れ構造を変化させる方法
JP2002267830A (ja) * 2001-03-12 2002-09-18 Fuji Photo Film Co Ltd カラーフィルター、その製造方法および液晶表示装置
JP2002309256A (ja) * 2001-04-13 2002-10-23 Fuji Photo Film Co Ltd 液晶組成物、カラーフィルターおよび液晶表示装置
JP6149006B2 (ja) * 2014-06-18 2017-06-14 富士フイルム株式会社 反射フィルムおよび反射フィルムを有するディスプレイ

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000258760A (ja) * 1999-03-12 2000-09-22 Toshiba Corp 液晶表示装置
JP2008502936A (ja) * 2004-06-17 2008-01-31 コーニンクレッカ フィリップス エレクトロニクス エヌ ヴィ 光学分離フィルタ
WO2014097895A1 (fr) * 2012-12-17 2014-06-26 富士フイルム株式会社 Cristaux liquides cholestériques à plusieurs couches, procédé de fabrication associé et stratifié de cristaux liquides cholestériques à plusieurs couches
JP2016076682A (ja) * 2014-10-06 2016-05-12 采▲ぎょく▼科技股▲ふん▼有限公司ＶｉｓＥｒａ Ｔｅｃｈｎｏｌｏｇｉｅｓ Ｃｏｍｐａｎｙ Ｌｉｍｉｔｅｄ イメージセンサーとその形成方法

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7472182B2 (ja) 2018-03-23 2024-04-22 富士フイルム株式会社 コレステリック液晶層の製造方法、コレステリック液晶層、液晶組成物、硬化物、光学異方体、反射層
WO2020202876A1 (fr) * 2019-03-29 2020-10-08 ソニーセミコンダクタソリューションズ株式会社 Élément d'imagerie à semi-conducteurs et dispositif d'imagerie
WO2023032644A1 (fr) * 2021-08-30 2023-03-09 富士フイルム株式会社 Film décoratif, corps moulé et article

Also Published As

Publication number Publication date
JPWO2018003359A1 (ja) 2019-05-16
TW201803097A (zh) 2018-01-16
JP6641009B2 (ja) 2020-02-05

Similar Documents

Publication Publication Date Title
TWI733845B (zh) 影像感測器用彩色濾光片、影像感測器及影像感測器用彩色濾光片的製造方法
WO2018003359A1 (fr) Filtre coloré stratifié, kit, procédé de fabrication de filtre coloré stratifié et capteur optique
JP6650526B2 (ja) イメージセンサー用カラーフィルター、イメージセンサーおよびイメージセンサー用カラーフィルターの製造方法
US6800220B2 (en) Optically active polyester, photoreactive chiral agent, liquid crystal composition, liquid crystal color filter, optical film, recording medium, method of changing the helical structure of a liquid crystal, and method of fixing the helical structure of a liquid crystal
KR102089668B1 (ko) 중합성 화합물, 중합성 조성물, 고분자, 및 광학 이방체
JP2018036314A (ja) 偏光イメージセンサーおよび偏光イメージセンサーの製造方法
KR100739420B1 (ko) 액정성 조성물, 컬러필터, 및 광학필름
JP2003313292A (ja) 光学活性ポリエステル／アミド、光反応型キラル剤、液晶組成物、液晶カラーフィルター、光学フィルム及び記録媒体、並びに液晶の螺旋構造を変化させる方法、液晶の螺旋構造を固定化する方法
WO2019142707A1 (fr) Film, stratifié, dispositif d'imagerie, capteur et dispositif d'affichage tête haute
WO2019073974A1 (fr) Feuille réfléchissante, feuille décorative et procédé de production de feuille réfléchissante
JP2002179670A (ja) 光学活性化合物、光反応型キラル剤、液晶組成物、液晶の螺旋構造を変化させる方法、液晶の螺旋構造を固定化する方法、液晶カラーフィルタ、光学フィルムおよび記録媒体
KR102442596B1 (ko) 중합성 화합물, 혼합물, 중합성 액정 조성물, 고분자, 광학 필름, 광학 이방체, 편광판, 표시 장치 및 반사 방지 필름
CN110382471B (zh) 聚合性化合物、聚合性液晶混合物、高分子、光学膜、光学各向异性体、偏振片、显示装置、防反射膜和化合物
CN1636164A (zh) 复合非线性光学薄膜、其制造方法及其应用
JP7440845B2 (ja) 偏光撮像装置
JP7416798B2 (ja) フィルターおよび撮像装置
WO2021261541A1 (fr) Dispositif d'imagerie de polarisation
JP2002179633A (ja) 光学活性化合物、光反応型キラル剤、液晶組成物、液晶の螺旋構造を変化させる方法、液晶の螺旋構造を固定化する方法、液晶カラーフィルタ、光学フィルム、及び記録媒体
JP7433435B2 (ja) 液晶組成物、光学素子および導光素子
JP2002180051A (ja) 液晶キラル剤、液晶組成物、液晶カラーフィルター、光学フイルム及び記録媒体
US20240004116A1 (en) Liquid crystal composition, optical element, and light guide element
JP7465968B2 (ja) 光学素子、導光素子および液晶組成物
JP7200383B2 (ja) 光学素子
JP7173914B2 (ja) 画像表示装置
WO2023085398A1 (fr) Élément optique et dispositif d'affichage d'image

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: 17819726

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2018524961

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 17819726

Country of ref document: EP

Kind code of ref document: A1