WO2005080529A9 - 光学素子用液晶材料および光変調素子 - Google Patents
光学素子用液晶材料および光変調素子Info
- Publication number
- WO2005080529A9 WO2005080529A9 PCT/JP2005/002742 JP2005002742W WO2005080529A9 WO 2005080529 A9 WO2005080529 A9 WO 2005080529A9 JP 2005002742 W JP2005002742 W JP 2005002742W WO 2005080529 A9 WO2005080529 A9 WO 2005080529A9
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- WIPO (PCT)
- Prior art keywords
- liquid crystal
- compound
- blue phase
- light
- chiral agent
- Prior art date
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Classifications
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/137—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells characterised by the electro-optical or magneto-optical effect, e.g. field-induced phase transition, orientation effect, guest-host interaction or dynamic scattering
- G02F1/13731—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells characterised by the electro-optical or magneto-optical effect, e.g. field-induced phase transition, orientation effect, guest-host interaction or dynamic scattering based on a field-induced phase transition
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/02—Liquid crystal materials characterised by optical, electrical or physical properties of the components, in general
- C09K19/0275—Blue phase
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/42—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
- C09K19/58—Dopants or charge transfer agents
- C09K19/586—Optically active dopants; chiral dopants
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/137—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells characterised by the electro-optical or magneto-optical effect, e.g. field-induced phase transition, orientation effect, guest-host interaction or dynamic scattering
- G02F1/13718—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells characterised by the electro-optical or magneto-optical effect, e.g. field-induced phase transition, orientation effect, guest-host interaction or dynamic scattering based on a change of the texture state of a cholesteric liquid crystal
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/137—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells characterised by the electro-optical or magneto-optical effect, e.g. field-induced phase transition, orientation effect, guest-host interaction or dynamic scattering
- G02F1/13775—Polymer-stabilized liquid crystal layers
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/137—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells characterised by the electro-optical or magneto-optical effect, e.g. field-induced phase transition, orientation effect, guest-host interaction or dynamic scattering
- G02F1/13793—Blue phases
Definitions
- Liquid crystal material for optical element and light modulation element Liquid crystal material for optical element and light modulation element
- the present invention relates to a liquid crystal material for an optical element that has a large dielectric anisotropy and a large refractive index anisotropy and has a high light transmittance.
- the present invention relates to a light modulation element using liquid crystal that modulates the spectrum, polarization state, wavefront, and the like of transmitted light or reflected light.
- Optical information processing technology is a promising information processing technology that can utilize the characteristics of light, such as high-speed signal transmission, spatial parallelism of transmission and processing, wide bandwidth, and frequency band.
- an optical element that controls light intensity, polarization state, etc. at high speed and with high precision is indispensable, and a small and inexpensive optical element using liquid crystal is attracting attention.
- a blue phase which is one of liquid crystal phases, appears immediately before the transition from the cholesteric phase to the isotropic phase.
- the blue phase is considered to be a state where a double-twisted structure in which liquid crystals are twisted and arranged and a linear defect in a state close to an isotropic phase coexist, and a body-centered cubic lattice with a lattice constant on the order of several hundred nm. It is known to form three-dimensional periodic structures such as (blue phase I) and simple cubic lattice (blue phase II).
- the liquid crystal in the blue phase has both the properties of a cubic crystal and the property of a cholesteric liquid crystal, exhibiting optical rotation with respect to visible light, and Bragg diffraction is observed.
- the crystal plane on which Bragg diffraction is observed (hereinafter referred to as the Bragg diffraction plane) is blue phase II, such as (110) plane, (200) plane, (211) plane, etc.
- the Bragg diffraction plane is blue phase II, such as (110) plane, (200) plane, (211) plane, etc.
- the cubic structure it is known that they are (100) plane, (110) plane, (210) plane, and the like.
- the blue phase is a number just below the temperature at which the isotropic phase appears. Since it appears only in the temperature range (temperature range) of C (generally 1 to 3 ° C), extremely precise temperature control is required, making practical application difficult.
- the temperature range (temperature range) of the blue phase is improved by polymerizing a liquid crystal composition containing a liquid crystal exhibiting a blue phase and a polymerizable monomer! /, Ru (see Patent Document 1).
- Patent Document 1 Japanese Patent Application Laid-Open No. 2003-327966
- Patent Document 1 has a problem of high drive voltage. Also, since the refractive index anisotropy is small, there is a problem that the phase difference force becomes small when applied to an element. Further, according to the study by the present inventors, the material has a problem that the transmittance after driving is large and a problem that the transmittance of light used is low, and it is recognized that the material is insufficient for practical use. It was.
- the optical element has different optical characteristics for each region by a simple configuration and a simple manufacturing method. There is a problem that it is difficult to realize an optical modulation element that can maintain the optical characteristics of each region without an external field and can be controlled by the external field.
- the present invention has been made to solve the above-described problems, and can be driven at a low voltage, and has a low value of transmittance loss due to driving with a large value of refractive index anisotropy.
- a liquid crystal / polymer composite obtained by polymerizing a liquid crystal composition comprising a liquid crystal compound, a chiral agent, a monofunctional polymerizable monomer, and a polyfunctional polymerizable monomer,
- the combination of the liquid crystal compound and the chiral agent has a dielectric anisotropy ( ⁇ 8) of 30 or more and a refractive index anisotropy ( ⁇ ⁇ ) of 0.13 or more.
- a liquid crystal / polymer composite obtained by polymerizing a liquid crystal composition comprising a liquid crystal compound, a chiral agent, a monofunctional polymerizable monomer, and a polyfunctional polymerizable monomer,
- the liquid crystal compound includes at least one compound represented by the following formula (1), and includes at least one compound represented by the following formula (2) as the chiral agent.
- R 2 an alkyl group having 48 carbon atoms having an asymmetric carbon atom, an alkyl group having 28 carbon atoms having an asymmetric carbon atom substituted with an aryl group, or an alkoxy group having 48 carbon atoms having an asymmetric carbon atom Group.
- a 2 Independently, 1, 4 phenylene group or trans 1, 4-cyclohexylene group.
- the hydrogen atom bonded to the carbon atom in these groups may be substituted with a fluorine atom.
- ⁇ 2 ⁇ 4 each independently, COO— — OCO—, single bond, or — c ⁇ c X 1 X 2 X 3 X 4 : each independently a hydrogen atom or a fluorine atom, and X 3 and X 4 At least one is a fluorine atom.
- X 5 , X 6 , X 7 , X 8 each independently a hydrogen atom or a fluorine atom, and at least one of X 7 and X 8 is a fluorine atom.
- n, m 0 or 1 independently.
- a liquid crystal / polymer composite obtained by polymerizing a liquid crystal composition comprising a liquid crystal compound, a chiral agent, a compound represented by the following formula (3), and a polyfunctional polymerizable monomer.
- a liquid crystal material for an optical element, wherein the combination of the liquid crystal compound and the chiral agent in the composite has a blue phase.
- R in the formula represents a linear alkyl group having 10 to 30 carbon atoms in which an etheric oxygen atom may be inserted between carbon-carbon bonds.
- liquid crystal material for an optical element according to any one of the above ;! to 3 above, characterized by exhibiting a blue phase in a temperature range covering at least ⁇ 10 to + 30 ° C.
- a light modulation element comprising a pair of substrates, at least one of which is translucent, and a liquid crystal layer sandwiched between the pair of substrates and selectively reflecting incident light,
- the liquid crystal layer includes the liquid crystal material for an optical element according to any one of the above ;! to 4, and includes an angular force S formed between a Bragg diffraction surface of the blue phase and a substrate normal, and light incident on the substrate surface.
- a light modulation element characterized in that it varies depending on the position.
- the angular force formed by the Bragg diffraction surface in the blue phase and the substrate normal differs depending on the incident position of the light in the substrate surface. It is possible to realize a light modulation element that has different optical characteristics for each region, maintains the optical characteristics of each region without an external field, and can be controlled by the external field.
- an electrode is provided so that the effective refractive index of the liquid crystal layer or the molecular orientation of the liquid crystal material contained in the liquid crystal layer can be controlled.
- a light modulation element can be realized.
- a pair of substrates, a transparent electrode provided on each of the pair of substrates, and the pair of substrates A light modulation element comprising a liquid crystal layer sandwiched between substrates,
- the liquid crystal layer is composed of a first liquid crystal layer and a second liquid crystal layer containing the liquid crystal material for optical elements according to any one of the above;! To 4,
- the first liquid crystal layer selectively reflects the clockwise circularly polarized component of two incident lights having different wavelengths
- the second liquid crystal layer selectively reflects the counterclockwise circularly polarized component of the two incident lights. Is to shoot,
- a light modulation element wherein the transmittance of the two incident lights is changed by a voltage applied to the transparent electrode from the outside.
- the liquid crystal layer includes the first liquid crystal layer that selectively reflects the clockwise circular polarization component of the two incident lights, and the second liquid crystal layer that selectively reflects the counterclockwise circular polarization component of the two incident lights. Therefore, the transmittance of two incident lights can be changed by applying an electric field to the liquid crystal layer and changing the reflectance of the selective reflection by the liquid crystal.
- a light modulation element comprising a polarization selection means that transmits the light
- the liquid crystal layer includes the liquid crystal material for an optical element according to any one of the above;! To 4, and has a clockwise circular polarization component or a counterclockwise circular polarization component of two incident lights having different wavelengths. Selective reflection,
- a light modulation element wherein the transmittance of the two incident lights is changed by a voltage applied to the transparent electrode from the outside.
- the liquid crystal layer selectively reflects the right-handed circularly polarized light component or the left-handed circularly polarized light component of the two incident lights, and the polarization selection means transmits only the linearly polarized light in the predetermined polarization direction.
- the reflectivity we can change the transmittance of the two incident lights with the force S.
- the light modulation element of 5 to 8 is most preferably an optical element liquid crystal material described in any one of the above;! To 4; however, at least the liquid crystal layer exhibits a blue phase. If there is, the liquid crystal material for an optical element described in any one of the above; The invention's effect
- liquid crystal material for an optical element of the present invention it is possible to reduce the driving voltage of an optical element composed of a liquid crystal in a blue phase state. In addition, a large phase difference can be obtained and repeated use is possible. Furthermore, the light utilization efficiency can be improved.
- FIG. 1 is a schematic cross-sectional view of a first light modulation element in the present invention.
- FIG. 2 is a diagram showing an example of a reflection spectrum obtained by the first light modulation element in the present invention.
- FIG. 3 is a schematic cross-sectional view of a second light modulation element in the present invention.
- FIG. 4 is a schematic cross-sectional view of another example of a light modulation element using a liquid crystal material applicable to the second light modulation element in the present invention.
- FIG. 5 is a schematic cross-sectional view of another example of a light modulation element using a liquid crystal material applicable to the second light modulation element in the present invention.
- the compound represented by the formula (1) is also referred to as a compound (1).
- a group represented by the formula (Q) is also referred to as a group (Q).
- the dielectric anisotropy is abbreviated as ⁇ 8, and the refractive index anisotropy is abbreviated as ⁇ . Even if the oscillation wavelength from the light source is described as a single value, it shall include the range of 10 nm.
- the liquid crystal composition in the present invention is a composition containing a liquid crystal compound, a chiral agent, a monofunctional polymerizable monomer, and a polyfunctional polymerizable monomer.
- the combination of the liquid crystalline compound and the chiral agent in the present invention is a combination consisting of only the liquid crystalline compound and the chiral agent.
- a combination of a liquid crystal compound and a chiral agent is treated as a cholesteric liquid crystal in a broad sense, and a liquid crystal phase represented by the combination is referred to as a cholesteric liquid crystal phase.
- the physical properties ( ⁇ and ⁇ ) of the combination of the liquid crystal compound and the chiral agent refer to the physical properties of the mixture when a mixture of only the liquid crystal compound and the chiral agent is prepared.
- the combination of a liquid crystal compound and a chiral agent is also simply referred to as “liquid crystal” hereinafter.
- liquid crystal compound examples include nematic liquid crystal compounds, smectic liquid crystal compounds, discotic liquid crystal compounds, and the like.
- the compound is preferred.
- One or more liquid crystal compounds may be used, or two or more liquid crystal compounds may be used. When two or more kinds are used, it is preferable to show a nematic liquid crystal phase after mixing.
- the chiral agent in the present invention may be a liquid crystalline compound or a non-liquid crystalline compound.
- the configuration of the asymmetric carbon atom present in the structure of the chiral agent may be either R or S. Only one kind of chiral agent may be used, or two or more kinds may be used. When two or more chiral agents are used, it is preferable to use a combination of chiral agents having the same induced spiral direction.
- the chiral agent preferably has a similar structure to the liquid crystal compound. This ensures compatibility between the liquid crystal compound and the chiral agent. This can be improved, and the phenomenon that the chiral agent is precipitated after the liquid crystal / polymer composite is formed can be prevented, and the blue phase can be further stabilized.
- the combination of the liquid crystal compound and the chiral agent is preferably a combination showing a cholesteric liquid crystal phase.
- the helical pitch in the cholesteric liquid crystal phase is preferably 500 nm or less.
- the pitch is over 500 nm, the blue phase does not appear or becomes unstable.
- the blue phase can be confirmed by observation with a polarizing microscope and measurement of the reflection spectrum. In other words, when the blue phase is expressed, platelets characteristic of the blue phase are observed with a polarizing microscope. When the reflection spectrum is measured, a peak is observed near the wavelength corresponding to platelets.
- ⁇ of the liquid crystal is 30 or more, preferably 30 to 80 force S, particularly preferably 30 to 70.
- Equation 1 It is considered that the relationship between the driving voltage and ⁇ required to shift the liquid crystal in the blue phase to the homeotopic picked state is approximately the relationship shown in equation ( ⁇ ).
- the liquid crystal exhibiting a blue phase can be driven at a low voltage when ⁇ is large. Also, depending on the type of liquid crystal compound or chiral agent, the power that can have various values can be obtained. If the ⁇ force of liquid crystal is more than 3 ⁇ 40, an electric field of about 10V / am is generated even if the power value increases. The force S is used to transfer the blue phase to the homeo-mouth pick state at the generated low voltage.
- ⁇ II represents the refractive index in the molecular axis (long axis) direction
- ⁇ represents the refractive index in the direction perpendicular to the molecular axis.
- the thickness of the optical element can be reduced when ⁇ is large.
- the cell gap is required to be 10 m or less.
- ⁇ of the liquid crystal is 0.13 or more, preferably 0.15 to 0.4, and preferably 0.15 to 0.25 is particularly preferable, and 0.15 to 0.2 is particularly preferable.
- the liquid crystal having such values of ⁇ and ⁇ preferably includes a liquid crystalline compound having a structure represented by the following formulas (al) to (a4) and a chiral agent.
- the left-hand bond of Q is bonded to an alkyl group having 8 or less carbon atoms and an alkyl group having 8 or less carbon atoms substituted with an alkyl group, alkenyl group, alkoxy group, or aryl group. That power S favored.
- Q in the formula is also selected from the following groups (Q ;!) to (Q8) force! /, Any of the groups (wherein 1 to L 4 are each independently a hydrogen atom or a fluorine atom) And T is a group selected from the following groups (T1) to (T4)! /. [0030] [Chemical 2]
- the liquid crystalline compound preferably has a structure represented by the above formulas (al) to (a4), and has good compatibility with other compounds having a large ⁇ value. It is particularly preferable to have the structure represented by (a2).
- the group (T) in the liquid crystal compound the group ( ⁇ 3) or the group ( ⁇ 4) is preferable from the viewpoint that the ⁇ value can be increased. Among these, the group ( ⁇ 3) is particularly preferable in view of good liquid crystallinity and good compatibility with other compounds.
- the groups (Q2) to (Q7) are preferable, and the groups (Q2) to (Q5) and (Q7) are particularly preferable.
- All l ⁇ L 4 as group (Q5) is preferably a group where L 3 and L 4 is a hydrogen atom as a group preferred tool group in the case where a hydrogen atom (Q 7).
- a liquid crystal compound having a monocyclic structure (group (Q2), etc.) and a polycyclic structure (group (Q7), etc.) It is preferable to use in combination with a liquid crystal compound which is
- the chiral agent preferably has a structure represented by the above formulas (al) to (a3). From the viewpoint of good compatibility with other compounds having a large ⁇ value, It is particularly preferable to have the structure represented by (a2).
- the group (T) in the chiral agent In view of the above, the group (T3) or the group (T4) is preferable, and the group (T4) is particularly preferable!
- the group (Q) is preferably the group (Q2).
- the number of fluorine atoms in the group (Q) in the chiral agent may cause disorder in the alignment of the liquid crystal if the number of fluorine atoms substituted in the 1,4-phenylene group is too large. It is preferable to adjust appropriately according to other components.
- the liquid crystalline compound preferably has a structure represented by the following formula (al-1), the following formula (a2-1), or the following formula (a2-5)!
- the chiral agent preferably has a structure represented by the following formula (al-2) or the following formula (a2-2).
- the present invention also provides a liquid crystal / polymer composite having a blue phase, wherein the liquid crystalline compound is the following compound (1) and the chiral agent is a compound represented by the following formula (2): An optical element liquid crystal material is provided.
- R 1 is an alkyl group having 1 to 8 carbon atoms, 2 to 8 carbon atoms ( nyl group, or an alkoxy group having 1 to 8 carbon atoms).
- alkyl group having 1 to 8 carbon atoms a linear alkyl group having 3 to 6 carbon atoms is preferable.
- alkenyl group having 2 to 8 carbon atoms a straight chain alkenyl group having 2 to 6 carbon atoms is preferable! / 'Especially, since the elastic constant ratio (K / K) is large, the number of carbon atoms is even.
- H—CH— or CH—CH ⁇ CH is particularly preferred.
- alkoxy group having 1 to 8 carbon atoms a straight-chain alkoxy group having 2 to 6 carbon atoms is preferable, and an ethoxy group, an n propyloxy group, an n butyloxy group, or an n pentyloxy group is particularly preferable.
- R 1 includes n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, ethoxy group, n-propyloxy group, n-butyloxy group, or CH 2 —CH ⁇ CH—CH
- a 1 is a 1,4 phenylene group or a trans 1,4-cyclohexylene group. These groups are preferably unsubstituted groups, which may be unsubstituted groups or hydrogen atoms bonded to carbon atoms in the groups may be substituted with fluorine atoms. A 1 is preferably a non-substituted trans 1,4-cyclohexylene group.
- Y is COO OCO, a single bond, CH CH or one C ⁇ C—
- Y 2 is COO——OCO—, a single bond, or c ⁇ c, preferably COO or a single bond.
- X 1 X 2 X 3 and X 4 are each independently a hydrogen atom or a fluorine atom, and at least one of X 3 and X 4 is a fluorine atom.
- X 3 is a fluorine atom
- X 1 X 2 and X 4 are all preferably hydrogen atoms.
- n 0 or 1.
- R 2 is an alkyl group having 48 carbon atoms having an asymmetric carbon atom, and having 28 carbon atoms having an asymmetric carbon atom substituted by an aryl group.
- the alkyl group having 48 carbon atoms having an asymmetric carbon atom the following group (W1) in which a branched alkyl group having 46 carbon atoms is preferable is particularly preferable.
- the carbon atom to which the symbol “*” in the formula is attached means an asymmetric carbon atom.
- R 2 is an alkyl group having 28 carbon atoms having an asymmetric carbon atom substituted with an aryl group
- carbon number 28 means that the alkyl group moiety has 28 carbon atoms.
- the alkyl group portion preferably has a linear structure, and an n-propyl group is particularly preferable.
- the aryl group is preferably a phenyl group or an m tolyl group. The number of aryl groups to be substituted is preferably one.
- a group represented by the following formula (W2) is preferable.
- the C 4 8 alkoxy group having an asymmetric carbon atom includes a C 4 6 branch.
- R 2 is preferably a group represented by the formula (Wl) or a group represented by the formula (W2).
- a 2 is the same group as A 1 and is preferably an unsubstituted 1,4-phenylene group.
- Y 3 is the same group as Y 1 and is preferably a single bond.
- Y 4 is the same group as Y 2, and preferably -coo or a single bond.
- X 5 , X 6 X 7 , and X 8 are each independently a hydrogen atom or a fluorine atom, and at least one of X 7 and X 8 is a fluorine atom.
- X 5 x 8 , X 5 and X 6 are preferably hydrogen atoms, and X 7 and X 8 are preferably fluorine atoms.
- m 0 or 1.
- the following compounds (1K) to (; IN) are preferable.
- the compound (2) is preferably used in combination of two or more.
- the compound (1K) and the compound (1L) or the compound (1K) and the compound (1M) are used in combination.
- the compound (1) and the compound (2) in the present invention have the following group (T3) or the following group (T4), so that the response speed with low viscosity can be increased.
- the compound having the following group (T1) has a force S effective for reducing the driving voltage when the content in the liquid crystal composition is small, and the compound cancels the dipole moment when the content is large. Since such a dimer is formed, the driving voltage reduction effect tends to be small.
- the compound of the formula (1) and the compound of the formula (2) have a fluorine atom-containing group (T3) or group (T4), it is difficult to form the dimer.
- ⁇ is not easily saturated, it is effective in reducing drive voltage.
- the ratio of the liquid crystal compound such as the compound (1) contained in the liquid crystal composition of the present invention is preferably 50 to 75 mass% with respect to the liquid crystal composition.
- the ratio of the chiral agent such as the compound of the formula (2) is preferably 17 to 45% by mass with respect to the liquid crystal composition.
- a combination of a liquid crystal compound such as compound (1) and a chiral agent such as compound (2) is used.
- the ratio of the liquid crystal compound is preferably 20 to 80 mol% with respect to the total of both.
- the ratio of the chiral agent is preferably 20 to 80 mol% with respect to the total of both.
- the total amount of both is 85 to 96 mol% with respect to the total amount of the liquid crystal compound, the chiral agent, the monofunctional polymerizable monomer described later, and the polyfunctional polymerizable monomer. preferable.
- the total amount of the liquid crystal compound and the chiral agent is particularly preferably 92 to 95% by mass, preferably 85 to 95% by mass with respect to the liquid crystal composition.
- the liquid crystal composition of the present invention contains a monofunctional polymerizable monomer and a polyfunctional polymerizable monomer described later in addition to the liquid crystal compound and the chiral agent.
- a monofunctional polymerizable monomer in a liquid crystal composition together with a polyfunctional polymerizable monomer and performing a polymerization reaction, the temperature range in which the liquid crystal exhibits a blue phase can be improved.
- the monofunctional polymerizable monomer in the present invention is a non-liquid crystalline or liquid crystalline compound having one polymerizable functional group.
- the polymerizable functional group an allyloyl group or a methacryloyl group is preferable.
- monofunctional polymerizable monomers acrylic acid alkyl esters are particularly preferred, with acrylic acid esters or methacrylic acid esters being preferred.
- a compound represented by the following formula (3) as a monofunctional polymerizable monomer.
- R in the formula (3) is a linear alkyl group having 10 to 30 carbon atoms in which an etheric oxygen atom may be inserted between carbon and carbon bonds, and R is a group having 12 to 24 carbon atoms. I like it.
- the carbon number of the group is in the range of 10 to 30, more appropriate compatibility with the liquid crystal for stabilizing the blue phase can be realized.
- the number of carbon atoms in the group is more than 30, the compatibility with the liquid crystal is insufficient, and when the optical element is formed, the light transmittance may be lowered.
- the step of injecting the liquid crystal composition into the cell is preferably carried out by injection under reduced pressure in order to avoid the adverse effects of oxygen, moisture, etc. on the liquid crystal composition.
- the liquid crystal composition does not volatilize at the time of injection under reduced pressure. Since compound (3) has 10 or more carbon atoms, it does not volatilize when injected under reduced pressure, and the blue phase stabilization effect is not impaired! /.
- R may have an etheric oxygen atom.
- the number of oxygen atoms is; Is preferred.
- the number of carbon atoms present between the etheric oxygen atom and the etheric oxygen atom is preferably !!-5, and 2 or 4 is particularly preferred. It is particularly preferable that R has no etheric oxygen atom.
- p, q, r, and s have the following meanings, respectively, and become an integer of [10 (30p + 4q) X r) + s] and the direct force S10-30.
- p represents — (CH 2 CH 2 O) —the number of units, 0 to; an integer of 15; an integer of 0 to 5 is preferred
- r is one [(CH CH O) ⁇ (CH CH CH CH O)] —the number of units
- s represents one (CH 3) —the number of units and is an integer from 0 to 30
- s is preferably an integer of 12 to 24.
- An integer of 12 to 20 is particularly preferable.
- the values of p, q, and s in the case of r force SI can be changed as appropriate in the range where the value of [((2p + 4q) X r) + s] is an integer of 10 to 30.
- It may be a unit or a (CH 2 CH 2 CH 2 O) unit. -(CH CH O)
- the arrangement of the two units is preferably block-like or block-like.
- Examples of the compound (3A) include the following compounds (3Aa) to (3Ap). From the viewpoint of compatibility with the liquid crystal, the following compounds (3Aa) to (3Ae), the following compounds (3Ah) to (3Aj), and The following compound (3Am) is preferred!
- the proportion of the monofunctional polymerizable monomer such as the compound (3) contained in the liquid crystal composition is excellent in the effect of stabilizing the blu-phase, so that it is based on the liquid crystal composition; 1.5 to 3.5% by mass is particularly preferable, and 2 to 3% by mass is particularly preferable. If the amount of the compound (3) is less than 1% by mass with respect to the liquid crystal composition, the effect of stabilizing the blue phase is insufficient when a liquid crystal / polymer composite is produced by carrying out a polymerization reaction described later 4% by mass If the amount is more than the blue phase, the blue phase does not appear, or even if it appears, the regularity of the three-dimensional periodic structure is disturbed during polymerization, which may cause phenomena such as scattering.
- the polyfunctional polymerizable monomer in the present invention is a compound capable of forming a network structure by bonding molecules of a monofunctional polymerizable monomer such as the compound (3).
- a compound having two polymerizable functional groups is preferred.
- Examples of the polymerizable functional group include the same groups as the polymerizable functional group in the monofunctional polymerizable monomer.
- Examples of the polyfunctional polymerizable monomer include diatalate, dimetatalylate, etc., and the structure of the monofunctional polymerizable monomer, the strength and characteristics required for the liquid crystal / polymer composite, etc. It is preferable to select accordingly. Moreover, it is preferable that the polymerizable functional group in both is the same.
- the polyfunctional polymerizable monomer may be either a liquid crystal compound or a non-liquid crystal compound, and needs to have good compatibility with the liquid crystal, and therefore preferably has a mesogenic structure.
- diatalates such as liquid crystalline diacrylate (manufactured by Merck, product number: RM-257) are preferable.
- a polymer part in which a monofunctional polymerizable monomer such as compound (3) and a polyfunctional polymerizable monomer are polymerized is used.
- the crosslinking density is important. When the crosslink density is low, the blue phase does not appear, or even if the blue phase appears, the onset temperature range becomes narrow. Therefore, it is necessary to use an appropriate amount of a monofunctional polymerizable monomer and a polyfunctional polymerizable monomer so as to form a highly continuous network structure.
- the total amount of the monofunctional polymerizable monomer and the polyfunctional polymerizable monomer is 4 to 15 with respect to the total amount of the liquid crystalline compound, the chiral agent, the monofunctional and polyfunctional polymerizable monomer; It is preferable that it is mol%.
- the total amount of the monofunctional polymerizable monomer and the polyfunctional polymerizable monomer is preferably 5 to 8% by mass based on the liquid crystal composition! /.
- the mixing ratio of the monofunctional polymerizable monomer and the polyfunctional polymerizable monomer can be adjusted as appropriate depending on the structure of each, the liquid crystal compound, the structure of the chiral agent, etc., but the monofunctional polymerizable monomer / Multifunctional polymerizable monomer (mass ratio), preferably 1 / ;! to 1/4
- the temperature range of the blue phase in the liquid crystal composition of the present invention is preferably 3 to 7 ° C. If the temperature range of the blue phase in the liquid crystal composition is 3 to 7 ° C, the blue phase can be stably maintained during the polymerization reaction described later from the start to the end of the polymerization reaction. The structural change of the complex can be suppressed.
- the difference ( ⁇ ) between T and the clearing point (T) of the liquid crystal composition is 4 ° C or more and 10 ° C or less, and the temperature range ( ⁇ ) in which the liquid crystal composition exhibits a blue phase is 3 It is preferable that the temperature is not lower than ° C and not higher than 6 ° C.S
- the liquid crystal clearing point (Tc 1 ) is the blue phase isotropic phase transition of liquid crystal
- the clearing point ( ⁇ ) of the liquid crystal composition is the blue phase isotropic phase transition point of the liquid crystal composition c
- the blue phase stabilization effect is reduced. If the ⁇ BP force is less than ° C, the blue phase may not be stabilized even if the polymerization reaction is performed. If the ⁇ BP is greater than 6 ° C, the compound (3) is concentrated in the defective part. This is considered to be a state, and interface scattering between the compound (3) present in the defect and the liquid crystal may occur, leading to a decrease in transmittance.
- the upper limit temperature at which the blue phase of the liquid crystal in the composite disappears is substantially the same as T of the liquid crystal composition. Therefore, it is preferable to increase the T of the liquid crystal composition by 5 ° C. or more than the temperature used as the optical element, and it is particularly preferable to increase it by 1 ° C. or more.
- the guideline for the minimum temperature at which the blue phase disappears is (T 60) ° C, and this temperature is 10 ° C or more lower than the minimum use temperature of the optical element.
- Tc of the liquid crystal composition it is preferable to set Tc of the liquid crystal composition. Furthermore, when the liquid crystal composition is stored under low temperature conditions, if crystal precipitation occurs, the characteristics of the element may deteriorate when used as an optical element, so it has excellent storage stability at low temperatures! /, That power S favored.
- the liquid crystal composition is polymerized to obtain a liquid crystal / polymer composite.
- the polymerization reaction is preferably performed in a state where the liquid crystal composition is injected into a cell and the combination of the liquid crystal compound and the chiral agent contained in the liquid crystal composition retains a blue phase.
- the liquid crystal in the liquid crystal / polymer composite can have a blue phase.
- “having a blue phase” means a combination of the liquid crystalline compound and the chiral agent in the liquid crystal / polymer complex S in a temperature range that covers at least ⁇ 10 to + 30 ° C. It means that the blue phase is stably expressed in a temperature range that preferably covers 10 ° C to Tc of the liquid crystal composition.
- the photopolymerization reaction by ultraviolet rays is preferred, and the photopolymerization reaction by ultraviolet rays is particularly preferred. Yes.
- the temperature at which the blue phase is maintained does not necessarily match the polymerization temperature (heating temperature), and thus it may be difficult to carry out the polymerization reaction while maintaining the blue phase.
- the structure of the liquid crystal / polymer composite may be changed by heating.
- a photopolymerization initiator In the photopolymerization reaction, it is preferable to use a photopolymerization initiator.
- the photopolymerization initiator it can be appropriately selected from acetofenones, benzophenones, benzoins, benzyls, Michler ketones, benzoin alkyl ethers, benzyl dimethyl ketals, thixanthones, and the like.
- the amount of the photopolymerization initiator is preferably 0.0;! To 1% by mass based on the liquid crystal composition, and 0.05 to 0.5% by mass is particularly preferable.
- the liquid crystal material for an optical element of the present invention exhibits a blue phase in a temperature range covering at least 10 to + 30 ° C. It is useful for optical elements because it exhibits a stable blue phase in a temperature range suitable for practical use! Since this material does not change the selective reflection wavelength or precipitate crystals, it can maintain the blue phase stably over a long period of time.
- the transmittance of light at the wavelength used is 80% or more, preferably 90% or more, and the transmittance after driving is 80% or more, preferably 90% or more of the initial transmittance.
- the liquid crystal material for an optical element of the present invention stably develops a blue phase in a temperature range suitable for practical use, has a transmittance of a laser beam having a wavelength of 400 to 420 nm of 80% or more, and the driven optical material.
- the transmittance of laser light is as high as 80% or more of the initial transmittance, it is useful for optical elements used for laser light of the wavelength.
- the optical element include a light modulation element, a diffraction element, a phase plate, and a liquid crystal lens.
- FIG. 1 is a cross-sectional view showing a conceptual configuration of a first form (hereinafter referred to as a first light modulation element) of a light modulation element using the liquid crystal material for an optical element of the present invention.
- the first light modulation element is an optical wavelength filter that selectively reflects light having different wavelengths according to the incident position of light.
- an optical modulation element 100 is composed of a pair of substrates 1 and 2 made into a cell by a seal 3 and the liquid crystal material 4 for an optical element of the present invention filled in the cell.
- An alignment film 5 for aligning the liquid crystal material 4 and electrodes 6 and 7 for applying a voltage to the liquid crystal material 4 are formed on the surfaces of the substrates 1 and 2, and the electrodes 6 and 7 are external power sources.
- At least one of the substrates 1 and 2 is a transparent material, and an organic material such as polycarbonate or glass may be used.
- an organic material such as polycarbonate or glass
- glass is preferable in terms of heat resistance and durability, and alkali-free glass is particularly preferable. .
- thermosetting resin such as an epoxy resin, an ultraviolet curable resin, or the like can be used.
- a spacer such as a glass fiber is used.
- mass% for example, about 5 mass% may be mixed.
- the electrodes 6 and 7 are made of a transparent conductive film made of ITO (Indium-Tin-Oxide), tin oxide, zinc oxide or the like, or a metal conductive film containing gold, silver, aluminum, chromium, or the like as a component. It is formed by sputtering or vapor deposition.
- the electrode When using a metal conductive film, prevent reflection by sandwiching it with a transparent oxide film such as zinc oxide, tin oxide, or titanium oxide in order to increase the transmittance or improve various durability and handleability. Is preferred.
- the electrode may be divided into a plurality of regions by etching or the like, or a composite electrode of a high resistance film and a low resistance film.
- the alignment film 5 may be a film made of polyimide which is rubbed or a silicon oxide film or the like formed by vapor deposition or the like in order to align liquid crystal molecules in the vicinity of the alignment film 5 in the horizontal or vertical direction. It is provided.
- the electrodes 6 and 7 are formed in order to change the optical characteristics of the light modulation element 100 by applying a voltage from the external power supply 8, but there is no need to change the optical characteristics.
- the electrodes 6 and 7 need not be formed.
- the alignment film 5 may be formed on only one of the substrates 1 and 2 according to need! /, And may not be formed on the substrate with V or displacement! /.
- the selective reflection of the optical element using the liquid crystal material for an optical element of the present invention is caused by Bragg diffraction by a blue phase regular grating, and the selective reflection wavelength is the blue phase lattice constant, surface index, and selective reflection. It depends on the angle between the surface and the incident light. Therefore, the selective reflection wavelength is selected and adjusted for the chiral agent content in the liquid crystal composition, the selective reflection surface, the angle formed by the selective reflection surface with respect to the light incident surface, and the light incident angle on the incident surface. Especially Therefore, it can be designed and adjusted arbitrarily.
- the direction of the lattice plane of the blue phase refers to the normal direction of the plane. In other words, the (110) plane of the blue phase is oriented perpendicular to the substrate surface. The normal direction force s of the (110) plane of the blue phase is aligned with the normal direction of the substrate surface. The state is! /.
- the (211) surface is preferably used in addition to the (110) surface and the (200) surface in the blue phase I, and the (100) surface, the (110) surface, ( 210) surface is preferably used
- the amount of the chiral agent used in the preparation of the liquid crystal composition is adjusted so that the selective reflection wavelength power in the optical element becomes a desired wavelength. At this time, if a chiral agent having a positive temperature dependency and a chiral agent having a negative temperature dependency are mixed and added to the liquid crystal composition, the temperature characteristics of the torsional force are reduced. This is preferable because changes in the reflected wavelength due to temperature can be suppressed.
- the liquid crystal layer using the liquid crystal material for optical elements of the present invention and having a predetermined selective reflection wavelength is formed, for example, as follows.
- the liquid crystal composition described above is filled in a cell, heated to a temperature higher than the clearing point of the liquid crystal composition, for example, a liquid crystal composition having a clearing point of about 50 ° C., to 70 ° C. When things become isotropic.
- the liquid crystal composition is gradually cooled to a temperature at which it exhibits blue phase I, and maintained at that temperature using a temperature controller,
- the entire liquid crystal is a monodomain in which the (110) plane of blue phase I is aligned perpendicular to the substrate.
- UV light (wavelength 365nm) with an irradiation intensity of 5mW / cm 2 or less is irradiated to photopolymerize the polymerizable monomer, and the liquid crystal / polymer A composite is formed (hereinafter, the liquid crystal layer thus formed is also referred to as a polymer-stabilized blue phase liquid crystal layer).
- the liquid crystal layer thus formed is also referred to as a polymer-stabilized blue phase liquid crystal layer.
- ultraviolet light for photopolymerization may be irradiated intermittently.
- the voltage is applied to the liquid crystal composition before photopolymerization in order to align the (110) plane of the blue phase perpendicular to the substrate.
- the AC voltage to be applied is preferably a rectangular wave of 0.5 to 10 kHz, but is not limited to this, and a sine wave may be used.
- the appropriate width of the applied voltage value is determined by the size of the cell gap and the physical properties of the liquid crystal composition used. Although it cannot be said, for example, in the present invention, an applied voltage higher than 20 V may not be preferable because the blue phase collapses and does not show selective reflection, or a light scattering phase appears.
- the alignment film on the substrate a horizontal alignment film is provided on any substrate, and the alignment process direction in each substrate is the same, and the pretilt angle of the liquid crystal molecules is in a non-parallel state. Orientation is preferred because it makes it easier to form a monodomain polymer-stabilized blue phase liquid crystal layer.
- the first light modulation element 100 is configured such that the plane orientation of the Bragg diffraction surface varies depending on the incident position of the light on the substrate 1.
- FIG. 1 shows an example in which three domain regions 10 to 12 having different plane orientations are formed in one light modulation element 100.
- the lattice lines shown in the domain regions 10 to 12 schematically show the crystal orientation of the blue phase, and the thick line shows the Bragg diffraction surface of interest in this embodiment!
- phase indicated by the liquid crystal material 4 is the blue phase I and the Bragg diffraction surface indicated by the thick line in the domain regions 10 to 12 is the (110) plane will be described as an example.
- the phase indicated by 4 may be blue phase II, and the Bragg diffraction surface may be the (200) plane of blue phase II.
- Incident light is efficiently reflected if the Bragg diffraction surface is a plane orientation with a low index, such as the (110) plane, (200) plane with a body-centered cubic structure, or the (100) plane with a simple cubic structure. It can be made easy.
- the plane orientation of the (110) plane is parallel to the normal direction of the substrate, and in the domain regions 11 and 12, the inclination angle increases in order.
- an external field such as an electric field or a magnetic field to which the liquid crystal responds is applied with an inclination with respect to the normal direction of the substrate (hereinafter referred to as this external field).
- the field is referred to as an inclined field).
- the (110) plane orientation can be more easily inclined by partially weakening the alignment regulating force of the alignment film or by partially applying the vertical alignment force.
- domain regions 11 and 12 having an inclined (110) plane orientation as shown in FIG. 1 can be formed by applying an inclined external field to photopolymerization only in the domain regions 11 and 12.
- the first light modulation element 100 separates the light multiplexed with wavelengths,, and ⁇ into a single wavelength for each domain region
- the Bragg diffraction wavelength changes according to the incident angle ⁇ to the Bragg diffraction surface, and is expressed by the following equation:
- d is a surface interval of the Bragg diffraction surface.
- the angle between the Bragg surface with respect to the normal direction of the substrate, ⁇ , and the light incident angle ⁇ and the Bragg incident angle ⁇ are given by the following equation (5).
- n is an effective refractive index of the liquid crystal material 4.
- Figure 2 shows the spectrum of reflected light from the domain regions 10-12.
- Each spectrum indicated by A, B, and C in FIG. 2 corresponds to each reflection spectrum from the domain region 10 to 12;
- the substrate distance of the light modulation element is about 10 m, when an AC voltage of about 100 V and ⁇ is applied to the liquid crystal material 4 by the power source 8, the liquid crystal material 4 becomes homeo-picted orientation, and the symbol A in FIG.
- the reflection spectra indicated by, B, and C are no longer observed.
- the electrodes 6 and 7 configured as shown in Fig. 1 are divided so that different voltages can be applied to the domain regions 10 to 12; thus, the Bragg diffraction wavelength is switched only in one domain region by switching the applied voltage. The light can be selectively reflected or transmitted.
- the light modulation element 100 shown in FIG. 1 has a force configured to have three domain regions. Even if the light modulation device 100 is configured to have two domain regions, it has four or more domain regions. It may be configured to have.
- FIG. 3 is a cross-sectional view showing a conceptual configuration of a second form (hereinafter referred to as a second light modulation element) of a light modulation element using the liquid crystal material for optical elements of the present invention.
- the second light modulator is 2 It is an optical attenuator that changes the transmittance of incident light having two different wavelengths.
- the light modulation element 200 is composed of a pair of transparent substrates 25 and 26 which are sealed into cells by a seal 22 and formed into a cell, and a liquid crystal layer 21 sandwiched between the cells. .
- Transparent electrodes 23 and 24 for applying an external signal to the liquid crystal layer 21 are formed on the surfaces of the transparent substrates 25 and 26. It is preferable to provide an alignment film (not shown) on the surface of the substrate in contact with the liquid crystal so that the liquid crystal molecules in the vicinity of the alignment film are aligned horizontally or vertically. With respect to the substrate, electrodes, alignment film, and seal, the same structure as the first light modulation element can be adopted.
- the liquid crystal layer 21 includes the first liquid crystal layer 21a and the second liquid crystal layer 21b containing the liquid crystal material for an optical element of the present invention.
- the liquid crystal layer 21a selectively reflects the clockwise circular polarization component of two incident lights having different wavelengths, and the second liquid crystal layer 21b selects the counterclockwise circular polarization component of the two incident lights. It is a reflection.
- the first liquid crystal layer and the second liquid crystal layer are preferably laminated.
- a third transparent substrate 33 made of glass or the like is disposed between the first liquid crystal layer 21a and the second liquid crystal layer 21b, and the force, Transparent electrodes 31 and 32 such as ITO are provided on both sides of the third transparent substrate 33, and an external signal voltage is applied between each of the two electrodes sandwiching the first liquid crystal layer 21a and the second liquid crystal layer 21b.
- the device can be driven at a lower voltage than the configuration shown in FIG. 3 without the third transparent substrate 33.
- the same parts as those in FIG. 3 are denoted by the same reference numerals as those in FIG.
- the polarization selection means 28 that transmits only linearly polarized light in a predetermined polarization direction is disposed on the light exit surface side of the light modulation element 200, and the liquid crystal layer 21 includes The liquid crystal material for an optical element of the present invention is included, and the right-handed circularly polarized light component or the left-handed circularly polarized light component of two incident lights having different wavelengths are selectively reflected.
- the light modulation element 200 that functions as an optical attenuator for incident light having two different wavelengths. 4
- the same parts as those in FIG. 3 are indicated by the same reference numerals as those in FIG.
- polarization using absorption in which a pigment is dispersed in a transparent film or the like A polarizer that transmits only polarized light in a specific direction, such as a polarizer that uses diffraction using a birefringent material or a polarizer that uses total reflection such as an inorganic material such as a Glan-Thompson prism, is used.
- an antireflection film for preventing reflection of the two wavelengths on the incident surface and / or the exit surface of the light modulation element in order to suppress light loss due to interface reflection.
- a composition obtained by adding 1, 2, or 4% by mass of a mixture to nematic liquid crystal (Merck, product number: ZLI-1565) was injected into a cell with an ITO electrode and an alignment film (cell gap 4 Hm).
- voltage was applied using an AC power supply with a frequency of 1 kHz, and the values of ( ⁇
- ⁇ ⁇ was calculated by the following equation (C), and ⁇ ⁇ was obtained from the outer shell (where ( ⁇ II) represents the dielectric constant in the molecular axis (major axis) direction, and ( ) Represents the dielectric constant perpendicular to the molecular axis.
- a composition obtained by adding 1, 2, or 4% by mass of a mixture to a nematic liquid crystal was poured into a wedge-shaped cell.
- a nematic liquid crystal Merck, product number: “ZLI-1565”
- ZLI-1565 nematic liquid crystal
- a liquid crystal compound, a chiral agent, a monofunctional polymerizable monomer, and a polyfunctional polymerizable monomer were mixed in the ratios shown in Tables 1 to 3, and liquid crystal compositions of Examples 1 to 12 were obtained.
- the ratio of each component constituting the liquid crystal composition is expressed by mass% with respect to the entire liquid crystal composition.
- compound (1) monofunctional polymerizable monomer
- 2-ethylhexyl ateryl Aldrich hereinafter abbreviated as 2EHA.
- N-lauryl acrylate Aldrich, hereinafter abbreviated as C acrylate
- n-stearyl acrylate Aldrich, hereafter
- liquid crystalline diatalylate manufactured by Merck, product number:
- DMPMP DMPMP.
- Tables !! to 3 show the composition ratios of the liquid crystal compositions of Examples;! To 12, and the values of ⁇ and ⁇ of the mixture of the liquid crystal compound and the chiral agent. Table 1 also shows the value of ⁇ (temperature range in which the liquid crystal composition exhibits a blue phase) of the liquid crystal compositions of Examples 1 to 5.
- Example 1 Example 2 Example 3
- Example 4 Example 5 Liquid crystal group Liquid crystal group Liquid crystal group Liquid crystal composition 1 Composition 2 Composition 3
- Composition 4 Composition 5 Liquid crystalline compound (1 A) 51. 9 22. 01 ⁇ 47 83-Compound (61. 62) (27. 22) (56. 70)
- Example 6 Example 7 Example 8
- Example 9 Example 1 0 Liquid crystal composition Liquid crystal composition Liquid crystal composition Liquid crystal composition Liquid crystal composition 6 articles 7 articles 8 articles 9 articles 1 0 Liquid crystalline compounds (1 ⁇ ) 4 7. 8 4 7. 8---Compounds Compound (1C-4) 5. 3 5. 3---
- the liquid crystal composition of [1];! To 12 was injected into a sandwich cell having an electrode and an alignment film and a cell gap of 10 m.
- Liquid crystal compositions 6, 7, 10, and 11 were injected under reduced pressure in an isotropic phase at 60 ° C. and IhPa.
- Liquid crystal compositions 6, 7, and 10 can be injected under reduced pressure. Possible force In the liquid crystal composition 11, the monofunctional polymerizable monomer volatilized during the injection under reduced pressure.
- the liquid crystal compositions;! To 5, 8, 9, and 12 were injected into the cell in an isotropic phase at atmospheric pressure.
- Table 4 shows ⁇ ⁇ ⁇ and selective reflection length after cell injection for the liquid crystal compositions of Examples 6 to 12, and Tables 5 and 6 show polymer / liquid crystal composites; The phase transition temperature of the liquid crystal, the temperature range of the blue phase, and the selective reflection wavelength in 10 and 12 are shown. As shown in Table 5 and Table 6, the liquid crystal compositions of Examples;! To 10, 12 are blue in the temperature range covering at least one 10 to + 30 ° C by being a polymer / liquid crystal composite. It was confirmed that a phase was developed.
- Example 6 Example 7
- Example 8 Example 9
- Example 1 Example 1 1
- Example 1 2 Example 1
- the polymer / liquid crystal composite obtained in [2];! ⁇ 10, 12 was applied at 25 ° C using a sine wave, 1 kHz frequency AC power supply, and changed from the blue phase to the homeopic state.
- the drive voltage required to make the transition was measured.
- laser light (wavelength 407 nm) was irradiated using a semiconductor laser diode (manufactured by Nichia Kagaku Kogyo Co., Ltd., product number: NDHV310APC), and the transmittance of the laser light before and after voltage application was measured.
- a Si photodiode manufactured by Hamamatsu Photonics, product number: S2281 was used.
- the measurement results are shown in Tables 7 and 8.
- the transmittance change (%) is a ratio to the transmittance before application.
- the method for manufacturing the light modulation element 200 will be specifically described with reference to the cross-sectional view shown in FIG.
- transparent electrodes 23 and 24 made of ITO on one side by sputtering, and SiO and TiO layers on the other side.
- An anti-reflection coating (not shown) is formed respectively.
- transparent electrodes 31 and 32 made of ITO are formed on both surfaces by sputtering.
- the polyimide film surface is rubbed in one direction with a cloth to form a horizontal alignment film (not shown). At this time, the rubbing direction of the opposing surface is such that the orientation of the liquid crystal molecules is antiparallel. The process is performed so as to be suitable.
- a seal 22 made of a thermosetting adhesive mixed with 5% by mass of a glass fiber spacer with a diameter of 10 ⁇ m was printed and applied around the electrode forming surfaces of the transparent substrates 25 and 26.
- the liquid crystal cells are formed by stacking two layers of the first liquid crystal cell and the second liquid crystal cell, both of which are 10 m apart from each other.
- a liquid crystal composition to be injected into the first and second liquid crystal cells is prepared.
- the liquid crystal group composition as to form a polymer-stabilized blue-phase liquid crystal layer exhibiting a right twist as nematic liquid crystal JC- 1041XX (44. 6 mass 0/0) and 5CB ( 33.1 mass 0/0), as a chiral agent showing a right twist ZLI- 4572 (9. 7 wt%), 2EHA monofunctional polymerizable monomer (4.0 wt%), as a polyfunctional polymerizable monomer RM257 (8.2% by mass) and photopolymerization initiator (0.4% by mass) are respectively weighed and mixed.
- the blending ratio of each component is the ratio of each component to the total amount of nematic liquid crystal, chiral agent, monofunctional polymerizable monomer, polyfunctional polymerizable monomer, and photopolymerization initiator.
- a liquid crystal composition for forming a polymer-stabilized blue phase liquid crystal layer exhibiting a left twist that is injected into the second liquid crystal cell is a chiral agent in the liquid crystal composition injected into the first liquid crystal cell. It is prepared in the same manner using a chiral agent exhibiting counter-twist left twist instead of ZLI-4572.
- the transition temperature (clearing point) to the isotropic phase of these liquid crystal compositions is about 53 ° C, and the addition amount of the chiral agent is such that when a polymer-stabilized blue phase is formed by the operation described later,
- the selective reflection wavelengths for vertically incident light by the (110) plane and the (101) plane are determined to be 570 nm and 290 nm, respectively.
- Such a liquid crystal composition is filled into a liquid crystal cell from an inlet (not shown) provided in a part of the seal 22, and the inlet is sealed with an adhesive.
- the temperature of the liquid crystal cell is raised to 70 ° C to make the liquid crystal composition an isotropic phase, and a 10 V, 1 kHz rectangular wave AC voltage is applied between the transparent electrodes 23 and 31 and 24 and 32.
- a 10 V, 1 kHz rectangular wave AC voltage is applied between the transparent electrodes 23 and 31 and 24 and 32.
- the entire liquid crystal has a (1 10) plane perpendicular to the substrate. Change the phase so that it becomes a domain blue phase.
- the polymer-stabilized blue phase liquid crystal layer has light of oblique incidence at a selective reflection wavelength of (110) plane and (101) plane of 570 nm and 290 nm with respect to normal incident light and an incident angle of 25 °. 515 nm and 430 nm, the first liquid crystal layer 21 a emits clockwise circularly polarized light having a wavelength, and the second liquid crystal layer 21b emits counterclockwise circularly polarized light having such a wavelength. Selective reflection.
- a 0-160V, 1kHz square wave AC voltage was applied to the electrode for the light modulation element of Reference Example 1 produced in the above-described process, linearly polarized light with wavelengths of 515nm and 430nm, clockwise Circularly polarized light or counterclockwise circularly polarized light is incident on the polymer-stabilized blue phase liquid crystal layer at an incident angle of 25 ° to measure the optical characteristics of the light modulation element.
- Table 9 when the applied voltage is 0 V, all incident light other than partially scattered or transmitted light is reflected for any wavelength and polarization state.
- the reflectance decreases and the transmittance increases regardless of the difference in wavelength and polarization state, and the reflected light becomes substantially 0% at an applied voltage of 160 V, and is partially scattered. All incident light is transmitted through the element
- the light modulation element of Reference Example 1 has incident light of 515 nm and 430 nm incident on the (110) plane of the polymer-stabilized blue phase liquid crystal layer at an incident angle of 25 °, depending on the wavelength and polarization state.
- the transmittance is modulated in the same way, it is possible to produce a squeezing force.
- the response speed of the light modulation element in Reference Example 1 is around lms, which is about an order of magnitude faster than before.
- Transparent substrates 25 and 26 made of non-alloyed glass are prepared, and transparent electrodes 23 and 24 made of ITO are formed on one surface by sputtering, and the transparent substrate 26 is opposite to the surface on which the transparent electrode 24 is formed.
- An anti-reflective coating (not shown) is applied.
- an anti-parallel horizontal alignment film (not shown) is formed on the surface of the transparent electrodes 23 and 24 by the same procedure as in Reference Example 1, and the transparent substrates 25 and 26 are overlapped by the single 22
- a liquid crystal cell 210 having a cell spacing of 10 mm is formed.
- the wavelength of 515 nm and 4 consisting of multiple layers of SiO and TiO layers on the light exit surface side.
- a light modulation element of Reference Example 2 having a 30 nm antireflection film, which is a polarizer that transmits only linearly polarized light in a single polarization direction (polarization selection means 28) is bonded and laminated with an ultraviolet curable adhesive.
- the light modulation element of Reference Example 2 is not transmittance-modulated regardless of the wavelength.
- Table 11 even for linearly polarized light having a wavelength parallel to or orthogonal to the polarizing plate, the transmittance can be modulated by changing the reflectance according to the applied voltage. That is, when no voltage is applied, a circularly polarized light component having a high transmittance is incident on the polarizing plate among the incident linearly polarized light, so that the polarization direction of the incident linearly polarized light is perpendicular to the polarization axis direction of the polarizing plate. Even so, the light modulation element is transmitted.
- the incident linearly polarized light is transmitted while maintaining its polarization direction. Therefore, when the polarization direction of the incident linearly polarized light is perpendicular to the polarization axis direction of the polarizing plate, it is transmitted through the light modulation element. Disappear.
- the response speed of the light modulation element in Reference Example 2 is around lms, and it responds approximately one digit faster than the conventional light modulation element.
- the reflectance is 100 at the applied voltage OV for light of any wavelength of 515 nm and 430 nm. %, The transmittance is 0%, the applied voltage is 160V, the reflectance is 0%, and the transmittance is 100%.
- the characteristic values shown in the above table are the values of the polymer-stabilized blue phase. Crystal This is thought to be due to imperfections in orientation and orientation. Also, in Reference Example 1 and Reference Example 2, the values of reflectivity and transmittance for incident light at wavelengths of 515 nm and 430 nm differ between wavelengths for the same reason.
- the driving voltage can be reduced and the phase difference can be increased. Further, since the light transmittance is good and the decrease in transmittance before and after voltage application is small, it is suitable for repeated use. In addition, the blue phase can be kept stable. Therefore, it can be useful for optical elements that control the wavefront state and / or polarization state of transmitted light and reflected light, optical elements that control the reflection wavelength, and the like.
- the characteristics as the wavelength filter can be maintained without an external field and can be controlled by the external field.
- the light modulation element using the liquid crystal material for an optical element according to the present invention is used as an optical attenuator, it does not exhibit incident wavelength dependency at two wavelengths of incident light, and further exhibits incident polarization dependency. Therefore, it can be preferably used as an optical modulation element as an optical attenuator in an optical pickup using light of a plurality of wavelengths or an optical communication system.
- the liquid crystal light modulation device according to the present invention is used in an optical system using a semiconductor laser, and can be suitably used for optical communication and an optical head device.
- the specification of the present invention includes Japanese patent application No. 2004-044741 (filed on February 20, 2004), which is the basis for claiming priority of this application, and No. 2004-227050 (issued in 2004). 3)), Japanese Patent Application No. 2004-260080 (filed Sep. 7, 2004) and Special Specification of Tsujimoto No. 2004-371369 (No. 22 Dec. 2004) It is cited here and incorporated as a disclosure of the invention.
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JP2004-227050 | 2004-08-03 | ||
JP2004260080 | 2004-09-07 | ||
JP2004-260080 | 2004-09-07 | ||
JP2004371369 | 2004-12-22 | ||
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