JP6428977B1 - Optical element - Google Patents

Abstract

The present invention has been made to solve the above-mentioned problems, and is a polymer-dispersed liquid crystal element that controls the alignment state of a liquid crystal composition with light, a diffusion plate for a liquid crystal display element using the same, a window, and the like The purpose is to provide.
The present invention provides the photoresponse by irradiating a photoresponsive composition containing at least a light-responsive substance having a threshold value and an anisotropic molecule with light having a light intensity equal to or greater than the threshold value. Provided is a polymer-dispersed liquid crystal device characterized in that the alignment state of the composition is changed, and provides a window or the like using the device.
The present invention also includes a diffusion plate for a liquid crystal display element including the polymer dispersed liquid crystal element, or a photoresponsive substance having a threshold value in response light intensity, an anisotropic molecule, a monomer, an oligomer, and / or a polymer. A window is provided in which the photoresponsive composition is irradiated with light having a light intensity equal to or higher than a threshold to change the orientation state of the photoresponsive composition.

Description

  The present invention relates to an optical element using a polymer dispersed liquid crystal (polymer dispersed optical element), and a member utilizing transmission and scattering of light, such as a diffusion plate and a window for liquid crystal display using the same.

The polymer-dispersed liquid crystal element does not require a polarizing plate, so it has the advantage of achieving brighter display compared to TN, STN, IPS or VA mode liquid crystal display elements using conventional polarizing plates. Since the structure is simple, it is applied to optical shutter applications such as light control glass and segment display applications such as watches.

  There are several types of polymer dispersed liquid crystal elements, for example, a type called NCAP (Patent Document 1), a type called PDLC (Polymer Dispersed LC) (Patent Document 2, Patent Document 3), PNLC ( A type called “Polymer Network LC” (Patent Document 4) has been proposed.

  Among polymer dispersed liquid crystals, types called PDLC and PNLC will be briefly described. These liquid crystal compositions for polymer-dispersed liquid crystal elements are usually composed of a non-polymerizable nematic liquid crystal composition, one or more polymerizable compounds, and a photopolymerization initiator, and a mixture thereof (polymer The liquid crystal composition for the dispersion type liquid crystal element) is made uniform, sandwiched between glass cells or plastic films, and irradiated with ultraviolet rays to polymerize the polymerizable compound or the composition, and at the same time, the polymerized polymer and the liquid crystal composition To form a structure in which a liquid crystal composition forms a continuous layer in a three-dimensional network structure of a polymer, a structure in which droplets of a liquid crystal composition are dispersed in a polymer, or a structure in which both are mixed . This liquid crystal composition for a polymer dispersed liquid crystal device is divided into a liquid crystal rich phase and a monomer rich phase below Tnm (nematic-isotropic transition point of the liquid crystal composition for polymer dispersed liquid crystal device) and is in a uniform state. In order to achieve this, the temperature must be equal to or higher than Tnm. Although it may be experimentally heated to obtain a uniform state, practically, it is required that Tnm be set to room temperature or lower and that the film can be handled without heating. The Tnm of the liquid crystal composition for polymer dispersed liquid crystal elements is proportionally decreased from the Tni of the liquid crystal composition itself (nematic-isotropic transition point of the liquid crystal composition) as the polymerizable compound or the composition is added. Therefore, in order to bring the Tnm of the liquid crystal composition for polymer dispersed liquid crystal elements to room temperature or lower, the Tni of the liquid crystal composition itself and the amount of the polymerizable compound or the composition added are appropriately controlled. I need it.

  This liquid crystal composition for a polymer-dispersed liquid crystal device can be obtained by sandwiching a glass or film and irradiating with ultraviolet rays. In the polymer-dispersed liquid crystal element, the liquid crystal composition takes a random alignment state when no voltage is applied, and light is generated by a difference in refractive index between the cured polymer and the liquid crystal composition, or by random alignment of the liquid crystal composition itself. In a normal mode and a state where no voltage is applied, the liquid crystal composition is oriented in the direction of the electric field when a sufficient voltage is applied, and the liquid crystal composition itself becomes non-scattering. When the product is aligned in a certain direction and the liquid crystal composition itself is not scattered, that is, in a transparent state, when a sufficient voltage is applied, the liquid crystal composition itself scatters light by random alignment, That is, there is a reverse mode that becomes cloudy.

  These cloudiness may differ depending on the application, but generally, the cloudiness tends to be preferred. In order to obtain high turbidity, the Δn (refractive index anisotropy) of the liquid crystal composition should be large, and there is an optimum size for the polymer network structure or the particle size of the liquid crystal droplets. On the other hand, if the difference between the refractive index of the polymer and the no (ordinary refractive index) of the liquid crystal composition is sufficiently small when the liquid crystal composition is aligned in a certain direction, light scattering does not occur and a transparent state is obtained. Therefore, in order to obtain high transparency, it is necessary to match the refractive index of the polymer with the no of the liquid crystal composition.

  Regarding the driving voltage, the Δε (dielectric anisotropy) of the liquid crystal, the anchoring force between the liquid crystal composition and the polymer interface, the size of the polymer network structure, or the particle size of the liquid crystal droplets are the dominant factors. Become. Naturally, the larger the Δε of the liquid crystal, the lower the driving voltage, and the smaller the anchoring force between the liquid crystal composition and the polymer interface, the lower the driving voltage. In addition, a smaller driving voltage is obtained when the size of the polymer network structure or the particle size of the liquid crystal droplets is larger and uniform.

  As described above, in general, polymer dispersion type liquid crystal elements control the alignment state of the liquid crystal composition by applying a voltage, but the method for controlling the alignment state of the liquid crystal with light has not been studied. .

US Pat. No. 4,435,047 US Pat. No. 4,688,900 U.S. Pat. No. 4,834,509 US Pat. No. 5,304,323

  The present invention has been made to solve the above-described problems, and an optical element using a polymer-dispersed liquid crystal that controls the alignment state of a liquid crystal composition with light, and a diffusion for a liquid crystal display element using the same. The purpose is to provide boards, windows, etc.

The present inventors have found that it is possible to control the alignment of liquid crystal with light by doping a liquid crystal composition of a polymer-dispersed liquid crystal element with a dye that interacts strongly with light. By using a photoresponsive composition containing a photoresponsive substance having a threshold value in response light intensity and an anisotropic molecule such as a liquid crystal composition, the threshold value of the light intensity at which the anisotropic molecule is aligned is set. The inventors have found that it can be lowered, and have reached the present invention.

  That is, the present invention irradiates a light-responsive composition containing at least a light-responsive substance having a threshold value and an anisotropic molecule with light having a light intensity equal to or greater than the threshold value. Provided is a polymer-dispersed liquid crystal element characterized in that the alignment state of the photoresponsive composition is changed.

  The present invention also includes a diffusion plate for a liquid crystal display element including the polymer dispersed liquid crystal element, or a photoresponsive substance having a threshold value in response light intensity, an anisotropic molecule, a monomer, an oligomer, and / or a polymer. A window is provided in which the photoresponsive composition is irradiated with light having a light intensity equal to or higher than a threshold to change the orientation state of the photoresponsive composition.

  According to the present invention, by using a photoresponsive composition containing at least a photoresponsive substance having a threshold value in response light intensity and an anisotropic molecule, the threshold value of the light intensity at which the anisotropic molecule is aligned is set. Thus, the transparent state and the scattering state of the polymer dispersed liquid crystal element can be controlled by light.

It is a schematic sectional drawing which shows a polymer dispersion type liquid crystal element as one Embodiment of the optical element of this invention. It is a schematic sectional drawing which shows a polymer dispersion type liquid crystal element as one Embodiment of the optical element of this invention.

Embodiments of the optical element and the manufacturing method thereof according to the present invention will be described.
Note that this embodiment is specifically described for better understanding of the gist of the invention, and does not limit the present invention unless otherwise specified.
(Optical element)
The optical element of the present invention emits light by irradiating a photoresponsive composition containing a photoresponsive substance having a threshold value in response light intensity and an anisotropic molecule with light having a light intensity equal to or greater than the threshold value. The orientation of the responsive composition is changed, and the optical element is a polymer dispersed liquid crystal element.
The optical element of the present invention expresses an optical function by controlling orienting anisotropic molecules with light so that the refractive index of the photoresponsive composition is modulated or distributed spatially and regionally. It is. The optical element of the present invention can be applied to optical elements (for example, lenses, prisms, mirrors, filters, etc.) using a refractive index distribution without any particular limitation, and also includes liquid crystal display elements, hologram elements, retardation films, etc. Although it can be used as a phase difference element, a 3D printer element, a liquid crystal display element diffusion, a window, etc., it is a polymer-dispersed liquid crystal element, so from an optical shutter lens, optical mirror, optical filter, liquid crystal display It is preferably applied to a diffusion plate for an element or a window.

  Here, a polymer dispersed liquid crystal element 10 shown in FIG. 1 is illustrated as an optical element of the present invention.

  The polymer-dispersed liquid crystal element 10 includes two base materials 11 and 12 and a photoresponsive substance 13 and an anisotropic molecule 14 encapsulated between these substrates. The photoresponsive substance 13 and anisotropic molecules 14 are roughly configured in a state of being dispersed in a polymer network 15. In addition, an alignment film 16 that has been subjected to a vertical alignment process or a horizontal alignment process is provided on a surface 11 a of the one substrate 11 that faces the other substrate 12. Similarly, an alignment film 17 subjected to a vertical alignment process or a horizontal alignment process is provided on a surface 12a of the other substrate 12 facing the one substrate 11.

  The substrate is not particularly limited as long as it is a transparent material. Examples of such base materials include glass base materials, metal base materials, plastic base materials, and organic materials such as paper (cellulose nanofibers). In particular, cellulose derivatives, polyolefins, polyesters, polyolefins, polycarbonates, polyacrylates, polyarylates, polyethersulfones, polyimides, polyphenylene sulfides, polyphenylene ethers, nylons, polystyrenes, and the like can be given. Of these, plastic substrates such as polyester, polystyrene, polyolefin, cellulose derivatives, polyarylate, and polycarbonate are preferable. As a shape of a base material, you may have a curved surface other than a flat plate.

  The thickness of the substrate is not particularly limited as long as the transparency is not lost, but is preferably 0.01 to 1 mm, more preferably 0.02 to 0.5 mm, and 0.03 to 0.00. 2 mm is particularly preferable.

  The alignment film subjected to the vertical alignment treatment is not particularly limited as long as the alignment film itself or the anisotropic molecules are vertically aligned by the alignment treatment. Examples of such alignment films include SiO2 oblique vapor deposition film, transparent metal oxide sputtering film, polyimide, polysiloxane, polyamide, polyvinyl alcohol, polycarbonate, polystyrene, polyphenylene ether, polyarylate, polyethylene terephthalate, and polyethersulfone. , Epoxy resin, epoxy acrylate resin, acrylic resin, azo compound, coumarin compound, chalcone compound, cinnamate compound, fulgide compound, anthraquinone compound, azo compound, arylethene compound, calixarene compound, silane coupling agent, or And a coating film of a polymer or copolymer of the above compound. In the case of performing the alignment treatment, it is preferable to perform polarized ultraviolet visible light irradiation treatment, ion beam treatment or the like.

  Moreover, you may perform surface treatment of these base materials in order to improve the adhesiveness of a base material and an oriented film. Examples of the surface treatment include ozone treatment, plasma treatment, corona treatment, silane coupling treatment, and the like. In order to adjust light transmittance and reflectance, an organic thin film, an inorganic oxide thin film, a metal thin film, or the like may be provided on the surface of the substrate by a method such as vapor deposition.

  As the photoresponsive substance, a compound having a threshold value for the light intensity to be used is used. Specifically, the photoresponsive substance is not particularly limited as long as it has a molecular structure having anisotropy in light absorption. As the photoresponsive substance, a substance that does not cause a photochemical reaction or has a small influence on the orientation of the anisotropic substance even when the photochemical reaction is caused is preferable. For example, a visible light region or a visible light region A compound having a threshold value in the intensity of the light that absorbs the light and responds to light emitted from any region outside is used. In the present invention, the photoresponsive substance responds when irradiated with light, and the photoresponsive substance is oriented when irradiated with light. More specifically, the photoresponsive substance is oriented such that the long axis direction of the photoresponsive substance is parallel to the vibration direction of light (electric field vector of polarized light).

  As such a photoresponsive substance, for example, a dichroic dye is used as a substance that responds to light in the visible light region. The dichroic dye is not particularly limited, and anthraquinone, merocyanine, styryl, azomethine, quinone, quinophthalone, perylene, indigo, tetrazine, stilbene, benzidine, etc. Can be mentioned. Oligothiophene is also preferably used.

  As the photoresponsive substance, for example, the following general formula (I-1)

Wherein R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 14 carbon atoms, an alkenyl group having 2 to 14 carbon atoms, an alkynyl group having 2 to 14 carbon atoms, carbon Represents an alkoxy group having 1 to 14 atoms, a cyano group (—CN), a nitro group (—NO ₂ ), and one or two or more CH ₂ groups in the alkyl group are not directly adjacent to each other. In addition, it may be substituted with -O-, -CO-, -OCO-, or -COO-, and one or more hydrogen atoms in the alkyl group, alkenyl group, alkynyl group, alkoxy group are (It may be optionally substituted with a halogen atom, and n represents 1 to 8.)
And an oligothiophene compound represented by the formula:
R ¹ and R ² are each independently an alkyl group having 1 to 10 carbon atoms (—C _n H _{2n + 1} ), —OC _n H _{2n + 1} , —N (C _n H _{2n + 1} ) ₂ , —COOC _n H _{2n + 1} , A cyano group (—CN) and a nitro group (—NO ₂ ) are preferable, and an alkyl group having 2 to 5 carbon atoms (—C _n H _{2n + 1} ), —OC _n H _{2n + 1} , —N (C _n H) _{2n + 1} ) ₂ and -COOC _n H _{2n + 1} are more preferable.
n is preferably 1 to 5, and more preferably 1 to 3.
The general formula (I-1) is represented by the following general formula (I-2)

(Wherein, ^{R 1} and ^{R 2} have the same meanings as ^{R 1} and ^{R 2} in the general formula (I-1).)
It is preferable that it is a compound represented by these.
As the compound represented by the general formula (I-2), specifically, as a compound having symmetry, the following formula (I-3)

A compound represented by the following general formula (I-4)

And compounds in which R ¹ and R ² represent —C ₄ H ₉ , —OC ₄ H ₉ , —N (C ₄ H ₉ ) ₂ , —COOC ₄ H ₉ , and —CN, respectively. It is done.
The compound represented by the general formula (I-2), as a compound having an asymmetric, ^{R 1} is _-C 4 _{H 9, or, -N (C 4 H 9)} 2, R 2 is - A compound representing CN or —NO ₂ is exemplified.
The general formula (I-1) is a compound represented by the following formula (I-5):

And a compound represented by the following formula (I-6):

And a non-colored compound represented by the formula:
As other oligothiophene compounds, the following general formula (I-7)

(Wherein, ^{R 1} and ^{R 2} represent the same meanings as ^{R 1} and ^{R 2} in the general formula (I-1), n represents 0 or 1.)
The compound represented by these is mentioned.
Examples of the compound represented by the general formula (I-7) include the following formula (I-8)

(In the formula, n represents 0 or 1.)
The compound represented by these is mentioned.
Moreover, as a photoresponsive substance, the following general formula (I-9)

(Wherein, ^{R 1} and ^{R 2} have the same meanings as ^{R 1} and ^{R 2} in the general formula (I-1).)
The compound represented by these is mentioned.
Examples of the compound represented by the general formula (I-9) include the following formula (I-10)

The compound represented by these is mentioned.
Moreover, as a photoresponsive substance, the following general formula (I-11)

(In the formula, A ¹ and A ² each independently represent a 1,4-phenylene group, a 2,5-thiophene group, or a naphthalene-2,6-diyl group, and R ′ and R ″ each represent Independently, —CH═CH— group and —C≡C— group are represented, and R ¹ and R ² represent the same meaning as R ¹ and R ^{2 in} formula (I-1), and n ₁ and n ₂ independently represents 0 to 8, and n ₃ and n ₄ each independently represents 0 or 1.)
The compound represented by these is mentioned.
n ₁ and _{n 2} is preferably 0-6, more preferably 0-4.
Specific examples of the compound represented by the general formula (I-11) include compounds represented by the following formulas (I-12) to (I-19).

(Wherein, ^{R 1} and ^{R 2} represent the same as ^{R 1} and ^{R 2} in the general formula (I-1).)

(Wherein, ^{R 1} and ^{R 2} represent the same as ^{R 1} and ^{R 2} in the general formula (I-1).)

(Wherein, ^{R 1} and ^{R 2} represent the same as ^{R 1} and ^{R 2} in the general formula (I-1).)

(Wherein, ^{R 1} and ^{R 2} represent the same as ^{R 1} and ^{R 2} in the general formula (I-1).)

(Wherein, ^{R 1} and ^{R 2} represent the same as ^{R 1} and ^{R 2} in the general formula (I-1).)

(Wherein, ^{R 1} and ^{R 2} represent the same as ^{R 1} and ^{R 2} in the general formula (I-1).)

(Wherein, ^{R 1} and ^{R 2} represent the same as ^{R 1} and ^{R 2} in the general formula (I-1).)
Moreover, as a photoresponsive substance, the following general formula (I-19)

Wherein R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 14 carbon atoms, an alkenyl group having 2 to 14 carbon atoms, an alkynyl group having 2 to 14 carbon atoms, carbon Represents an alkoxy group having 1 to 14 atoms, a cyano group (—CN), a nitro group (—NO ₂ ), and one or two or more CH ₂ groups in the alkyl group are not directly adjacent to each other. In addition, it may be substituted with -O-, -CO-, -OCO-, or -COO-, and one or more hydrogen atoms in the alkyl group, alkenyl group, alkynyl group, alkoxy group are Optionally substituted with a halogen atom,
B ¹ and B ² are each independently a hydrogen atom, an alkyl group having 1 to 14 carbon atoms, an alkenyl group having 2 to 14 carbon atoms, an alkynyl group having 2 to 14 carbon atoms, or 1 to 1 carbon atom. 14 alkoxy groups, a cyano group (—CN), a nitro group (—NO ₂ ), an optionally substituted phenyl group (one or more —C═ present in this group is Which may be substituted), a naphthyl group which may have a substituent, a cyclohexyl group which may have a substituent (one or more —C— present in this group is —O—). Or may be substituted with -S-), and any one of the following groups (a), (b), or (c), and one or more CH ₂ in the alkyl group: The group is -O-, -CO-, -OCO-, or COO- may be substituted with the alkyl group, an alkenyl group, an alkynyl group, one or more hydrogen atoms in the alkoxy group may be optionally substituted halogen atom. )

(In the formula, R ⁵ represents a hydrogen atom, an alkyl group having 1 to 14 carbon atoms, an alkenyl group having 2 to 14 carbon atoms, an alkynyl group having 2 to 14 carbon atoms, or an alkoxy group having 1 to 14 carbon atoms. , A cyano group (—CN), a nitro group (—NO ₂ ), and one or more CH ₂ groups in the alkyl group are —O—, —CO, so that oxygen atoms are not directly adjacent to each other. -, -OCO-, or -COO- may be substituted, and one or more hydrogen atoms in the alkyl group, alkenyl group, alkynyl group, and alkoxy group are optionally substituted with a halogen atom. May be.)
The coumarin type compound represented by these is mentioned.
When R ³ and R ⁴ represent an alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable, an alkyl group having 1 to 5 carbon atoms is more preferable, and when B ¹ and B ² represent an alkyl group, carbon An alkyl group having 1 to 10 atoms is preferable, and an alkyl group having 1 to 5 carbon atoms is more preferable.
Examples of the compound represented by the general formula (I-20) include compounds represented by the following formulas (I-22) to (I-24).

(In the formula, R ³ and R ⁴ represent the same meaning as R ³ and R ^{4 in} formula (I-20)).

(In the formula, R ³ and R ⁴ represent the same meaning as R ³ and R ^{4 in} formula (I-20)).

(In the formula, R ³ and R ⁴ represent the same meaning as R ³ and R ^{4 in} formula (I-20)).
As other coumarin compounds, the following general formula (I-23)

(Wherein, ^{B 1} and ^{B 2} have the same meanings as ^{B 1} and ^{B 2} in the general formula (I-20).)
The compound represented by these is mentioned.

When B ¹ and B ² represent an alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 5 carbon atoms is more preferable.
Examples of the compound represented by the general formula (I-25) include compounds represented by the following formulas (I-26) to (I-30).

  Moreover, as a photoresponsive substance, the following general formula (I-29)

(Wherein R ⁶ and R ⁷ are each independently a hydrogen atom, an alkyl group having 1 to 14 carbon atoms, an alkenyl group having 2 to 14 carbon atoms, an alkynyl group having 2 to 14 carbon atoms, carbon, Represents an alkoxy group having 1 to 14 atoms, a cyano group (—CN), a nitro group (—NO ₂ ), and one or two or more CH ₂ groups in the alkyl group are not directly adjacent to each other. In addition, it may be substituted with -O-, -CO-, -OCO-, or -COO-, and one or more hydrogen atoms in the alkyl group, alkenyl group, alkynyl group, alkoxy group are Optionally substituted with a halogen atom,
B ³ is a hydrogen atom, an alkyl group having 1 to 14 carbon atoms, an alkenyl group having 2 to 14 carbon atoms, an alkynyl group having 2 to 14 carbon atoms, an alkoxy group having 1 to 14 carbon atoms, a cyano group (- CN), a nitro group (—NO ₂ ), an optionally substituted phenyl group (one or more —C═ present in this group may be substituted with —N═), A naphthyl group which may have a substituent, a cyclohexyl group which may have a substituent (one or more —C— present in this group is substituted with —O— or —S—). And one or more CH ₂ groups in the alkyl group may be —O—, —CO—, —OCO—, or —COO— so that the oxygen atoms are not directly adjacent. The alkyl group, alkenyl group, alkynyl group, One or more hydrogen atoms in the xy group may be optionally substituted with a halogen atom. )
The compound represented by these is mentioned.
When R ⁶ , R ⁷ and B ³ each independently represent an alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 5 carbon atoms is more preferable. Moreover, when R < ⁶ >, R < ⁷ > and B < ³ > represent an alkenyl group each independently, a C2-C10 alkenyl group is preferable and a C2-C5 alkenyl group is more preferable. B ³ is preferably a phenyl group which may have a substituent. Examples of the substituent include an alkyl group having 1 to 14 carbon atoms, an alkenyl group having 2 to 14 carbon atoms, and 1 carbon atom. -14 alkoxy groups are preferable, and alkyl groups having 1 to 10 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, and alkoxy groups having 1 to 10 carbon atoms are more preferable.

  The compound represented by the general formula (I-29) includes the following formula (I-30):

(In the formula, R ⁶ represents the same meaning as R ^{6 in the} general formula (I-29).)
A compound represented by formula (I-31):

(Wherein R ⁸ and R ⁹ are each independently a hydrogen atom, an alkyl group having 1 to 14 carbon atoms, an alkenyl group having 2 to 14 carbon atoms, an alkynyl group having 2 to 14 carbon atoms, Represents an alkoxy group having 1 to 14 carbon atoms, a cyano group (—CN), a nitro group (—NO ₂ ), and one or two or more CH ₂ groups in the alkyl group are not directly adjacent to each other with an oxygen atom. As described above, one or two or more hydrogen atoms in the alkyl group, alkenyl group, alkynyl group or alkoxy group, which may be substituted with -O-, -CO-, -OCO-, or -COO- May be optionally substituted with a halogen atom.)
The compound represented by these is mentioned.
Moreover, as a photoresponsive substance, the following general formula (I-32)

(In the formula, R ^{20 to} R ²³ are each independently a hydrogen atom, an alkyl group having 1 to 14 carbon atoms, an alkenyl group having 2 to 14 carbon atoms, an alkynyl group having 2 to 14 carbon atoms, or carbon. Represents an alkoxy group having 1 to 14 atoms, a cyano group (—CN), or a nitro group (—NO 2), and one or more CH ₂ groups in the alkyl group are not directly adjacent to each other. , -O-, -CO-, -OCO-, or -COO-, one or two or more hydrogen atoms in the alkyl group, alkenyl group, alkynyl group, and alkoxy group may be any May be substituted with a halogen atom.)
The compound represented by these is mentioned.
R ^{20 to} R ¹³ each independently preferably represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms in which a CH 2 group in the alkyl group is substituted with —COO— or —OCO—. More preferably, it represents an alkyl group having 1 to 5 carbon atoms in which the CH ₂ group in the atom or alkyl group is substituted with —COO— or —OCO—.
Examples of the compound represented by the general formula (I-34) include the following formula (I-33)

(In the formula, R ²⁴ and R ²⁵ each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.)
A compound represented by formula (I-34):

(Wherein R ^{24 to} R ²⁷ each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.)
The compound represented by these is mentioned.
Moreover, as a photoresponsive substance, the following general formula (I-35)

(In the formula, B ₄ is a hydrogen atom, an alkyl group having 1 to 14 carbon atoms, an alkenyl group having 2 to 14 carbon atoms, an alkynyl group having 2 to 14 carbon atoms, or an alkoxy group having 1 to 14 carbon atoms. , A cyano group (—CN), a nitro group (—NO 2), an optionally substituted phenyl group (one or more —C═ present in this group may be substituted with —N═) ), A naphthyl group which may have a substituent, a cyclohexyl group which may have a substituent (one or more —C— present in this group may be —O— or —S—). NR28R29 (R28 and R29 each independently represents a hydrogen atom, an alkyl group having 1 to 14 carbon atoms, an alkenyl group having 2 to 14 carbon atoms, or 2 to 14 carbon atoms). An alkynyl group, an alkoxy group having 1 to 14 carbon atoms, Represents a cyano group (—CN), a nitro group (—NO 2), and one or more CH 2 groups in the alkyl group are —O—, —CO—, — It may be substituted with OCO-, or -COO-, may be substituted with a 1,4-phenylene group, and one or more of the alkyl group, alkenyl group, alkynyl group, alkoxy group The hydrogen atom may be optionally substituted with a halogen atom.))
The compound represented by these is mentioned.
R ²⁸ and R ^{29 in} formula (I-35) are preferably an alkyl group having 1 to 14 carbon atoms, an alkenyl group having 2 to 14 carbon atoms which may have a substituent, or a phenyl group. .
Examples of the compound represented by the general formula (I-35) include the following formula (I-36)

(In the formula, R ²⁸ and R ²⁹ represent the same meaning as R ²⁸ and R ^{29 in} formula (I-35)).
A compound represented by formula (I-37):

(In the formula, R ³⁰ represents a hydrogen atom or an alkyl group having 1 to 14 carbon atoms.)
A compound represented by formula (I-38):

(In the formula, R ³¹ represents a hydrogen atom or an alkyl group having 1 to 14 carbon atoms.)
The compound represented by these is mentioned.
Moreover, as a photoresponsive substance, the following general formula (I-39)

(Wherein, X ₁ and X ₂ each independently represent a hydrogen atom, a fluorine atom or a chlorine atom, and B5 to B8 each independently represent a hydrogen atom, an alkyl group having 1 to 14 carbon atoms, Having an alkenyl group having 2 to 14 carbon atoms, an alkynyl group having 2 to 14 carbon atoms, an alkoxy group having 1 to 14 carbon atoms, a cyano group (—CN), a nitro group (—NO ₂ ), and a substituent. An optionally substituted phenyl group (one or more -C = present in this group may be substituted by -N =), an optionally substituted naphthyl group, and a substituted group. An cyclohexyl group (one or more —C— present in this group may be substituted by —O— or —S—), and one or two of the alkyl groups One or more CH2 groups may be -O-, so that the oxygen atoms are not directly adjacent. -CO-, -OCO-, or -COO- may be substituted, and one or more hydrogen atoms in the alkyl group, alkenyl group, alkynyl group, and alkoxy group are optionally substituted with a halogen atom. And n ⁶ and n ⁷ each independently represents 1 to 14.)
The dioxazine type compound represented by these is mentioned.
B _{5 to} B ₈ each independently have an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a phenyl group which may have a substituent, or a substituent. May be.
A cyclohexyl group is preferable, and as the substituent, an alkyl group having 1 to 10 carbon atoms and an alkoxy group having 1 to 10 carbon atoms are preferable.
Examples of the compound represented by the general formula (I-39) include the following formula (I-40)

A compound represented by formula (I-41):

The compound represented by these is mentioned.
Moreover, as a photoresponsive substance, the following general formula (I-42)

(In the formula, each of B ^{9 to} B ¹² is independently a hydrogen atom, a hydroxy group, an alkyl group having 1 to 14 carbon atoms, an alkenyl group having 2 to 14 carbon atoms, or an alkynyl group having 2 to 14 carbon atoms. Group, an alkoxy group having 1 to 14 carbon atoms, a cyano group (—CN), a nitro group (—NO ₂ ), an optionally substituted phenyl group (one or more — C = may be substituted with -N =), a naphthyl group which may have a substituent, a cyclohexyl group which may have a substituent (one or more present in this group). -C- may be substituted by -O- or ^{-S-.), NR 28 R 29} (R 28 and ^{R 29} are each independently a hydrogen atom, an alkyl group having 1 to 14 carbon atoms , An alkenyl group having 2 to 14 carbon atoms, and 2 to 14 carbon atoms Rukiniru group, an alkoxy group having 1 to 14 carbon atoms, a cyano group (-CN), nitro group (-NO _2), one or more CH2 groups in the alkyl group, directly oxygen atom In order not to be adjacent to each other, it may be substituted with —O—, —CO—, —OCO—, or —COO—, may be substituted with a 1,4-phenylene group, and the alkyl group, alkenyl group, One or two or more hydrogen atoms in the alkynyl group or alkoxy group may be optionally substituted with a halogen atom)
R ^{32 to} R ³⁵ are each independently a hydrogen atom, an alkyl group having 1 to 14 carbon atoms, an alkenyl group having 2 to 14 carbon atoms, an alkynyl group having 2 to 14 carbon atoms, or 1 to 1 carbon atom. 14 represents an alkoxy group, a cyano group (—CN), a nitro group (—NO ₂ ), and one or more CH 2 groups in the alkyl group are —O— so that the oxygen atom is not directly adjacent to each other. , -CO-, -OCO-, or -COO-, and one or more hydrogen atoms in the alkyl group, alkenyl group, alkynyl group, and alkoxy group may be optionally substituted with a halogen atom. May be substituted. )
The anthraquinone type compound represented by these is mentioned.

  Examples of the compound represented by the general formula (I-42) include the following formula (I-43)

A compound represented by formula (I-44):

A compound represented by formula (I-47):

The compound represented by these is mentioned.
As other anthraquinone compounds, the following general formula (I-46)

(In the formula, B _{9 to} B ₁₂ each independently represent the same meaning as B _{9 to} B _{12 of the} general formula (I-42),
R ₃₂ , R ₃₃ and R ₃₆ are each independently a hydrogen atom, an alkyl group having 1 to 14 carbon atoms, an alkenyl group having 2 to 14 carbon atoms, an alkynyl group having 2 to 14 carbon atoms, or a carbon atom. Represents an alkoxy group of formula 1 to 14, a cyano group (—CN), a nitro group (—NO ₂ ), and one or two or more CH ₂ groups in the alkyl group are not directly adjacent to each other. , -O-, -CO-, -OCO-, or -COO-, one or two or more hydrogen atoms in the alkyl group, alkenyl group, alkynyl group, and alkoxy group may be any May be substituted with a halogen atom. )
The compound represented by these is mentioned.
As the compound represented by the general formula (I-46), the following formula (I-48)

The compound represented by these is mentioned.
Furthermore, as the photoresponsive substance, the following formula (I-48)

(In the formula, R ₃₇ represents a hydrogen atom, an alkyl group having 1 to 14 carbon atoms, an alkenyl group having 2 to 14 carbon atoms, an alkynyl group having 2 to 14 carbon atoms, or an alkoxy group having 1 to 14 carbon atoms. , A cyano group (—CN), a nitro group (—NO ₂ ), and one or two or more CH 2 groups in the alkyl group are —O—, —CO— so that an oxygen atom is not directly adjacent to each other. , -OCO-, or -COO-, and one or two or more hydrogen atoms in the alkyl group, alkenyl group, alkynyl group, or alkoxy group are optionally substituted with a halogen atom. May be good.)
A compound represented by the following formula (I-49):

(Wherein R _{38 to} R ₄₀ are each independently a hydrogen atom, an alkyl group having 1 to 14 carbon atoms, an alkenyl group having 2 to 14 carbon atoms, an alkynyl group having 2 to 14 carbon atoms, carbon Represents an alkoxy group having 1 to 14 atoms, a cyano group (—CN), or a nitro group (—NO 2), and one or more CH ₂ groups in the alkyl group are not directly adjacent to each other. , -O-, -CO-, -OCO-, or -COO-, one or two or more hydrogen atoms in the alkyl group, alkenyl group, alkynyl group, and alkoxy group may be any May be substituted with a halogen atom.)
A compound represented by formula (I-50):

A compound represented by formula (I-51):

A compound represented by formula (I-52):

Wherein R ₄₁ and R ₄₂ are each independently a hydrogen atom, an alkyl group having 1 to 14 carbon atoms, an alkenyl group having 2 to 14 carbon atoms, an alkynyl group having 2 to 14 carbon atoms, carbon Represents an alkoxy group having 1 to 14 atoms, a cyano group (—CN), a nitro group (—NO ₂ ), and one or two or more CH ₂ groups in the alkyl group are not directly adjacent to each other. In addition, it may be substituted with -O-, -CO-, -OCO-, or -COO-, and one or more hydrogen atoms in the alkyl group, alkenyl group, alkynyl group, alkoxy group are It may be optionally substituted with a halogen atom.)
A compound represented by formula (I-53):

Wherein Y ₁ and Y ₂ are each independently a hydrogen atom, a fluorine atom, an alkyl group having 1 to 14 carbon atoms, an alkenyl group having 2 to 14 carbon atoms, or an alkynyl group having 2 to 14 carbon atoms. Group, an alkoxy group having 1 to 14 carbon atoms, a cyano group (—CN), a nitro group (—NO ₂ ), and one or two or more CH ₂ groups in the alkyl group have a direct oxygen atom It may be substituted with —O—, —CO—, —OCO—, or —COO— so as not to be adjacent to each other, and one or more of the alkyl group, alkenyl group, alkynyl group, and alkoxy group may be substituted. (The hydrogen atom may be optionally substituted with a halogen atom.)
A compound represented by formula (I-54):

Wherein R ₄₃ and R ₄₄ are each independently a hydrogen atom, an alkyl group having 1 to 14 carbon atoms, an alkenyl group having 2 to 14 carbon atoms, an alkynyl group having 2 to 14 carbon atoms, carbon Represents an alkoxy group having 1 to 14 atoms, a cyano group (—CN), a nitro group (—NO ₂ ), and one or two or more CH ₂ groups in the alkyl group are not directly adjacent to each other. In addition, it may be substituted with -O-, -CO-, -OCO-, or -COO-, and one or more hydrogen atoms in the alkyl group, alkenyl group, alkynyl group, alkoxy group are It may be optionally substituted with a halogen atom.)
A compound represented by formula (I-55):

Wherein R _{45 to} R ₄₈ are each independently a hydrogen atom, an alkyl group having 1 to 14 carbon atoms, an alkenyl group having 2 to 14 carbon atoms, an alkynyl group having 2 to 14 carbon atoms, carbon Represents an alkoxy group having 1 to 14 atoms, a cyano group (—CN), a nitro group (—NO ₂ ), and one or two or more CH ₂ groups in the alkyl group are not directly adjacent to each other. In addition, it may be substituted with -O-, -CO-, -OCO-, or -COO-, and one or more hydrogen atoms in the alkyl group, alkenyl group, alkynyl group, alkoxy group are It may be optionally substituted with a halogen atom.)
The compound represented by these is mentioned.
In the above formula (I-49), formula (I-52), formula (I-54) and formula (I-55), R38 to R48 are each an alkyl group having 1 to 10 carbon atoms, and 2 to 2 carbon atoms. 10 alkenyl groups are preferable, and an alkyl group having 1 to 5 carbon atoms and an alkenyl group having 2 to 5 carbon atoms are more preferable.
Specific examples of the compound represented by the formula (I-54) include those in which R ₄₃ and R ₄₄ are each a C ₂ H ₅ group.
Specific examples of the compound represented by the formula (I-55) include those in which R _{45 to} R ₄₈ are each a C ₂ H ₅ group.
Among these compounds, an oligothiophene compound is preferable because the threshold value of the light intensity for response is low.
Further, a conjugated liquid crystal compound can also be used as the photoresponsive substance. As the liquid crystal compound that can function as such a photoresponsive substance, a rod-like liquid crystal compound is preferable.
Liquid crystal is used as the anisotropic molecule.
The liquid crystal preferably contains a compound represented by the following general formula (LC).

(In the general formula (LC), R ^LC represents an alkyl group having 1 to 15 carbon atoms, and one or two or more CH ₂ groups in the alkyl group are not directly adjacent to each other. -O-, -CH = CH-, -CO-, -OCO-, -COO- or C≡C- may be substituted, and one or more hydrogen atoms in the alkyl group are optionally May be substituted with a halogen atom,
A ^LC1 and A ^LC2 are each independently
(A) trans-1,4-cyclohexylene group (one CH ₂ group present in this group or two or more non-adjacent CH ₂ groups may be substituted with an oxygen atom or a sulfur atom) Good),
(B) 1,4-phenylene group (one CH group present in this group or two or more CH groups not adjacent to each other may be substituted with a nitrogen atom), and (c) 1,4-bicyclo (2.2.2) octylene group, naphthalene-2,6-diyl group, decahydronaphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6- A diyl group or a group selected from the group consisting of a chroman-2,6-diyl group, but one or more hydrogen atoms contained in the group (a), group (b) or group (c) The atoms may be substituted with F, Cl, CF ₃ or OCF ₃ respectively.
Z ^LC is a single bond, —CH═CH—, —CF═CF—, —C≡C—, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —OCH ₂ —, —CH ₂ O—, _{-OCF 2 -, - CF 2 O} -, - COO- or OCO- represent,
Y ^LC represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, or an alkyl group having 1 to 15 carbon atoms, and one or two or more CH ₂ groups in the alkyl group are directly bonded to an oxygen atom. May be substituted with —O—, —CH═CH—, —CO—, —OCO—, —COO—, —C≡C—, —CF ₂ O—, —OCF ₂ — so as not to be adjacent, One or more hydrogen atoms in the alkyl group may be optionally substituted by halogen atoms;
a represents an integer of 1 to 4, but when a represents 2, 3 or 4, and there are a plurality of A ^LC1 , the plurality of A ^LC1 may be the same or different, and Z ^LC is When there are a plurality of Z ^LCs , the plurality of Z ^LCs may be the same or different. )
The compounds represented by the general formula (LC) are represented by the following general formula (LC1) and general formula (LC2).

( ^Wherein R ^LC11 and R ^LC21 each independently represents an alkyl group having 1 to 15 carbon atoms, and one or more CH ₂ groups in the alkyl group are directly adjacent to each other with an oxygen atom. Not optionally substituted with —O—, —CH═CH—, —CO—, —OCO—, —COO— or C≡C—, wherein one or more of the alkyl groups hydrogen atom may be optionally substituted by a halogen atom, a ^LC11, and a ^LC21 are each independently any of the following structures

(In the structure, one or more CH ₂ groups in the cyclohexylene group may be substituted with an oxygen atom, and one or more CH groups in the 1,4-phenylene group are And one or more hydrogen atoms in the structure may be substituted with F, Cl, CF ₃ or OCF ₃ . ^{LC11, X LC12, X LC21 ~X} LC23 each independently represent a hydrogen atom, Cl, F, and CF _3, or OCF ^{_3, Y LC11} and ^{Y LC21} are each independently a hydrogen atom, Cl, F , CN, CF ₃ , OCH ₂ F, OCHF ₂ or OCF ₃ , Z ^LC11 and Z ^LC21 each independently represent a single bond, —CH═CH—, ^{—CF═CF—} , ^—C≡C— , _-CH 2 CH _{2 -, - (CH 2)} 4 -, - OCH 2 -, - CH 2 O -, - OCF 2 -, - CF 2 O -, - represents COO- or ^{OCO-, m LC11} and ^{m LC21} are each Independently, it represents an integer of 1 to 4, and when there are a plurality of A ^LC11 , A ^LC21 , Z ^LC11 and Z ^LC21 , they may be the same or different. )
It is preferable that it is 1 type, or 2 or more types of compounds chosen from the compound group represented by these.
R ^LC11 and R ^LC21 are each independently preferably an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, or an alkenyl group having 2 to 7 carbon atoms, and 1 to 5 carbon atoms. An alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms is more preferable, and a straight chain is more preferable, and the alkenyl group most preferably represents the following structure. .

(In the formula, it shall be bonded to the ring structure at the right end.)
A ^LC11 and A ^LC21 each independently preferably have the following structure.

Y ^LC11 and Y ^LC21 are each independently preferably F, CN, CF ₃ or OCF ₃ , preferably F or OCF ₃ , and particularly preferably F.
Z ^LC11 and Z ^LC21 are preferably a single bond, —CH ₂ CH ₂ —, ^—COO— , ^—OCO— , —OCH ₂ —, —CH ₂ O—, —OCF ₂ — or CF ₂ O—, , —CH ₂ CH ₂ —, —OCH ₂ —, —OCF ₂ — or CF ₂ O— are preferred, and a single bond, —OCH ₂ — or CF ₂ O— is more preferred.
m ^LC11 and m ^LC21 are preferably 1, 2 or 3, preferably 1 or 2 when emphasizing storage stability at low temperature and response speed, and 2 or 2 for improving the upper limit of the nematic phase upper limit temperature. 3 is preferred.
The general formula (LC1) is represented by the following general formula (LC1-a) to general formula (LC1-c).

^(Wherein, R ^LC11, Y ^{LC11, X LC11} and ^{X LC12} each independently represents the same meaning as ^{R LC11,} Y ^{LC11, X} LC11 and ^{X LC12} in the general formula ^{(LC1), A LC1a1, A LC1a2} and ^ALC1b1 represent a trans-1,4-cyclohexylene group, a tetrahydropyran-2,5-diyl group, and a 1,3-dioxane-2,5-diyl group, and ^XLC1b1 , ^XLC1b2 , ^XLC1c1 to X ^LC1c4 each independently represents a hydrogen atom, Cl, F, CF ₃ or OCF ₃ ), and is preferably one or more compounds selected from the group consisting of compounds represented by:
R ^LC11 is independently preferably an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, or an alkenyl group having 2 to 7 carbon atoms, and an alkyl group having 1 to 5 carbon atoms. And an alkoxy group having 1 to 5 carbon atoms and an alkenyl group having 2 to 5 carbon atoms are more preferable.
X ^{LC11 to} X ^LC1c4 are each independently preferably a hydrogen atom or F.

Y ^LC11 is preferably each independently F, CF ₃ or OCF ₃ .

  The general formula (LC1) is changed from the following general formula (LC1-d) to the general formula (LC1-m).

^(Wherein, R ^LC11, Y ^{LC11, X LC11} and ^{X LC12} each independently represents the same meaning as ^{R LC11,} Y ^{LC11, X} LC11 and ^{X LC12} in the general formula ^{(LC1), A LC1d1, A LC1f1} , ^ALC1g1 , ^ALC1j1 , ^ALC1k1 , ^ALC1k2 , ^{ALC1m1 to ALC1m3} are 1,4-phenylene group, trans-1,4-cyclohexylene group, tetrahydropyran-2,5-diyl group, 1, It represents 3-dioxane-2,5-diyl ^{group, X LC1d1, X LC1d2, X} LC1f1, X LC1f2, X LC1g1, X LC1g2, X LC1h1, X LC1h2, X LC1i1, X LC1i2, X LC1j1 ~X LC1j4, X ^LC1k1 , X ^LC1k2 , X ^LC1m1 and ^{X LC1m2} are each independently a hydrogen atom, Cl, F, and CF _3, or _{^{OCF 3, Z LC1d1, Z LC1e1}} , Z LC1j1, Z LC1k1, Z LC1m1 are each independently a single bond, —CH═CH—, —CF═CF—, —C≡C—, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —OCH ₂ —, —CH ₂ O—, —OCF ₂ —, — CF ₂ O—, —COO— or OCO— is preferred), and it is preferably one or more compounds selected from the group consisting of compounds represented by:
R ^LC11 is independently preferably an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, or an alkenyl group having 2 to 7 carbon atoms, and an alkyl group having 1 to 5 carbon atoms. And an alkoxy group having 1 to 5 carbon atoms and an alkenyl group having 2 to 5 carbon atoms are more preferable.
X ^{LC11 to} X ^LC1m2 are each independently preferably a hydrogen atom or F.
Y ^LC11 is preferably each independently F, CF ₃ or OCF ₃ .
Z ^{LC1d1 to} Z ^LC1m1 are each independently preferably —CF ₂ O— or —OCH ₂ —.
The general formula (LC2) is represented by the following general formula (LC2-a) to general formula (LC2-g).

^{(Wherein, R LC21, Y LC21, X LC21} ~X LC23 each independently represents the same meaning as ^{R LC21, Y LC21, X LC21} ~X LC23 in the general formula ^{(LC2), X LC2d1} ~X ^{LC2d4, X LC2e1 ~X LC2e4, X} LC2f1 ~X LC2f4 and ^X LC2g1 ^{~X LC2g4} each independently represent a hydrogen atom, Cl, F, and CF _3, or _{^{OCF 3, Z LC2a1, Z LC2b1}} , Z LC2c1, Z ^LC2d1 , Z ^LC2e1 , Z ^LC2f1 and Z ^LC2g1 are each independently a single bond, —CH═CH—, ^{—CF═CF—} , ^—C≡C— , —CH ₂ CH ₂ —, — (CH ₂ ) ₄ −, —OCH ₂ —, —CH ₂ O—, —OCF ₂ —, —CF ₂ O—, —COO— Or OCO-.) It is preferably one or more compounds selected from the group consisting of compounds represented by:
R ^LC21 is each independently preferably an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, or an alkenyl group having 2 to 7 carbon atoms, and an alkyl group having 1 to 5 carbon atoms. And an alkoxy group having 1 to 5 carbon atoms and an alkenyl group having 2 to 5 carbon atoms are more preferable.
X ^{LC21 to} X ^LC2g4 are each independently preferably a hydrogen atom or F,
Y ^LC21 is preferably each independently F, CF ₃ or OCF ₃ .
Z ^{LC2a1 to} Z ^LC2g4 are each independently preferably —CF ₂ O— or —OCH ₂ —.
The compounds represented by the general formula (LC) are represented by the following general formula (LC3) to general formula (LC5).

^{(Wherein, R LC31, R LC32, R} LC41, R LC42, R LC51 and ^{R LC52} each independently represent an alkyl group having 1 to 15 carbon atoms, one or two in the alkyl group The above CH ₂ groups may be substituted with —O—, —CH═CH—, —CO—, —OCO—, —COO— or C≡C— so that oxygen atoms are not directly adjacent to each other, one or more hydrogen atoms in the alkyl group may be optionally substituted by a halogen ^{atom, a LC31, a LC32, a} LC41, a LC42, a LC51 and ^{a LC52} are each independently , Any of the following structures

(In the structure, one or more CH ₂ groups in the cyclohexylene group may be substituted with an oxygen atom, and one or more CH groups in the 1,4-phenylene group are Z may be substituted with a nitrogen atom, and one or more hydrogen atoms in the structure may be substituted with Cl, CF ₃ or OCF ₃ ) ^{LC31, Z LC32, Z LC41,} Z LC42, Z LC51 and ^{Z LC51} are each independently a single bond, -CH = CH -, - C≡C -, - CH 2 CH 2 -, - (CH 2) _{4 -, - COO -, -} OCH 2 -, - CH 2 O -, - OCF 2 - or _CF 2 O-to represent, ^{Z 5} represents a CH ₂ group or an oxygen ^{atom, X LC41} is a hydrogen atom or It represents a fluorine ^{atom, m LC31,} m ^{C32, m LC41, m LC42,} m LC51 and ^{m LC52} each independently represent ^{0~3, m LC31 + m LC32,} m LC41 + m LC42 and ^m LC51 ^{+ m LC52} is 1, 2 or 3, When a plurality of A ^{LC31 to} A ^LC52 and Z ^{LC31 to} Z ^LC52 are present, they may be the same or different. It is preferable that it is 1 type, or 2 or more types of compounds chosen from the compound group represented by this.
R ^{LC31 to} R ^LC52 are each independently preferably an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, or an alkenyl group having 2 to 7 carbon atoms. Most preferably,

(In the formula, it shall be bonded to the ring structure at the right end.)
A ^{LC31 to} A ^LC52 each independently preferably have the following structure:

Z ^{LC31 to} Z ^LC51 each independently represent a single bond, —CH ₂ O—, —COO—, ^—OCO— , —CH ₂ CH ₂ —, —CF ₂ O—, —OCF ₂ — or OCH ₂ —. Is preferred.
The general formula (LC3) is represented by the following general formula (LC3-a) and general formula (LC3-b).

(Wherein R ^LC31 , R ^LC32 , A ^LC31 and Z ^LC31 each independently represent the same meaning as R ^LC31 , R ^LC32 , A ^LC31 and Z ^LC31 in the general formula (LC3), and X ^{LC3b1 to} X ^{LC3 LC3b6} represents a hydrogen atom or a fluorine atom, but at least one of X ^LC3b1 and X ^LC3b2 or X ^LC3b3 and X ^LC3b4 represents a fluorine atom, and m ^LC3a1 is 1, 2 or 3. m ^LC3b1 represents 0 or 1, and when a plurality of A ^LC31 and Z ^LC31 are present, they may be the same or different.) One or two selected from the compound group represented by The above compounds are preferable.
R ^LC31 and R ^LC32 each independently represent an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, or an alkenyl group having 2 to 7 carbon atoms. It preferably represents an oxy group.
A ^LC31 preferably represents a 1,4-phenylene group, a trans-1,4-cyclohexylene group, a tetrahydropyran-2,5-diyl group, or a 1,3-dioxane-2,5-diyl group. , 4-phenylene group and trans-1,4-cyclohexylene group are more preferable.
Z ^LC31 is a single _{bond, -CH 2 O -, - COO} -, - OCO -, - CH 2 CH 2 - is preferred to represent, and more preferably a single bond.
The general formula (LC3-a) preferably represents the following general formula (LC3-a1) to general formula (LC3-a4).

(In the formula, R ^LC31 and R ^LC32 each independently represent the same meaning as R ^LC31 and R ^LC32 in General Formula (LC3).)
R ^LC31 and R ^LC32 are each independently preferably an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, or an alkenyl group having 2 to 7 carbon atoms, and R ^LC31 is the number of carbon atoms. More preferably, it represents an alkyl group having 1 to 7 and R ^LC32 represents an alkoxy group having 1 to 7 carbon atoms.
The general formula (LC3-b) preferably represents the following general formula (LC3-b1) to general formula (LC3-b12). The following general formula (LC3-b1) and the following general formula (LC3-b6) The following general formula (LC3-b8) and the following general formula (LC3-b11) are more preferable, the following general formula (LC3-b1) and the general formula (LC3-b6) are more preferable. Most preferably, it represents the formula (LC3-b1).

(In the formula, R ^LC31 and R ^LC32 each independently represent the same meaning as R ^LC31 and R ^LC32 in General Formula (LC3).)
R ^LC31 and R ^LC32 are each independently preferably an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, or an alkenyl group having 2 to 7 carbon atoms, and R ^LC31 is the number of carbon atoms. More preferably, it represents 2 or 3 alkyl groups, and R ^LC32 represents an alkyl group having 2 carbon atoms.
The general formula (LC4) is represented by the following general formula (LC4-a) to general formula (LC4-c), and the general formula (LC5) is represented by the following general formula (LC5-a) to general formula (LC5-c).

^{(Wherein, R LC41,} R ^LC42 and ^{X LC41} each independently represents the same meaning as ^{R LC41, R LC42} and ^{X LC41} in the general formula ^{(LC4), R LC51} and ^{R LC52} are each independently Te represents the same meaning as ^{R LC51} and ^{R LC52} in the general formula ^{(LC5), Z LC4a1, Z} LC4b1, Z LC4c1, Z LC5a1, Z LC5b1 and ^{Z LC5c1} are each independently a single bond, -CH = CH—, —C≡C—, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —COO—, —OCH ₂ —, —CH ₂ O—, —OCF ₂ — or CF ₂ O— is represented. It is more preferable that it is 1 type, or 2 or more types of compounds selected from the group consisting of compounds represented by.
^{R LC41,} R LC42, R ^LC51 and ^{R LC52} are each independently an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group or a carbon atom of 2 to 7 carbon atoms It preferably represents an alkenyloxy group having a number of 2 to 7.
Z ^{LC4a1 to} Z ^LC5c1 each independently preferably represent a single bond, —CH ₂ O—, ^—COO— , ^—OCO— , —CH ₂ CH ₂ —, and more preferably represent a single bond.
The compound represented by the general formula (LC) is represented by the following general formula (LC6).

(In the formula, R ^LC61 and R ^LC62 each independently represent an alkyl group having 1 to 15 carbon atoms, and one or two or more CH ₂ groups in the alkyl group are directly adjacent to each other with an oxygen atom. Not optionally substituted with —O—, —CH═CH—, —CO—, —OCO—, —COO— or C≡C—, wherein one or more of the alkyl groups The hydrogen atom may be optionally halogen-substituted, and A ^{LC61 to} A ^LC63 are each independently described below.

(In the structure, one or more CH ₂ CH ₂ groups in the cyclohexylene group may be substituted with —CH═CH—, —CF ₂ O—, —OCF ₂ —, One or two or more CH groups in the 4-phenylene group may be substituted with a nitrogen atom), and Z ^LC61 and Z ^LC62 each independently represent a single bond, —CH ═CH—, —C≡C—, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —COO—, —OCH ₂ —, —CH ₂ O—, —OCF ₂ — or CF ₂ O—. ^Miii1 represents 0-3. However, the compound represented by the general formula (LC1) to the general formula (LC5) is excluded. A liquid crystal composition containing one or more compounds represented by formula (1) is preferred.
R ^LC61 and R ^LC62 are each independently preferably an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, or an alkenyl group having 2 to 7 carbon atoms. Most preferably,

(In the formula, it shall be bonded to the ring structure at the right end.)
A ^{LC61 to} A ^LC63 each independently preferably have the following structure:

Z ^LC61 and Z ^LC62 are each independently ^preferably a single bond, —CH ₂ CH ₂ —, ^—COO— , —OCH ₂ —, —CH ₂ O—, —OCF ₂ — or CF ₂ O—.
The general formula (LC6) is represented by the following general formula (LC6-a) to general formula (LC6-m).

(In the formula, R ^LC61 and R ^LC62 each independently represent an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, or 2 carbon atoms. It is more preferable that it is 1 type, or 2 or more types of compounds chosen from the group which consists of a compound represented by -7 alkenyloxy group.
Further, the liquid crystal may be any of a rod-like liquid crystal (nematic liquid crystal, smectic liquid crystal), a disk-like (discotic) liquid crystal, a bent liquid crystal (banana liquid crystal), and a liquid crystal obtained by adding chirality thereto.
The shape of the liquid crystal (bar-shaped, disk-shaped, or bent-type) is appropriately selected in order to obtain a desired refractive index anisotropy. When fast response is required, nematic liquid crystal that is liquid crystal close to liquid is preferable. When stable orientation is required, it is preferable to use smectic liquid crystal close to solid. A liquid crystal phase peculiar to a chiral liquid crystal can also be used. In that case, a part or all of the liquid crystal may be chiral, or a liquid crystal and a chiral non-liquid crystal may be mixed. The liquid crystal may be any of a monomer, a dimer, a multimer (oligomer) of trimer or higher, and a polymer (polymer). Monomers are preferred when quick responsiveness is required, and dimers, multimers higher than trimers (oligomers), and polymers (polymers) are preferred when stable orientation is required.

  The ratio of the photoresponsive substance to the total of the photoresponsive substance, the liquid crystal composition, and the polymer of the polymerizable compound in the polymer dispersed liquid crystal element of the present invention is 0.01% by weight or more and 35% by weight or less. Is preferable, and more preferably 0.05 wt% or more and 15 wt% or less.

If the ratio of the photoresponsive substance to the total is within the above range, the photoresponsive composition is irradiated with light having a light intensity equal to or higher than a threshold value, so that the photoresponsive substance is aligned with the orientation of the photoresponsive substance. The anisotropic molecules contained in the conductive composition can be easily oriented in any direction.
Here, the arbitrary direction in which the photoresponsive substance and the liquid crystal composition are aligned is a direction in which the major axis direction of these substances (molecules) is parallel to the vibration direction of light. The photoresponsive composition can contain oligomers and / or polymers to reduce the light intensity threshold.

  In this case, the oligomer and / or polymer may be mixed with the mixture of the photoresponsive substance and the liquid crystal composition, or the low molecular compound having a polymerizable group may be mixed before polymerization.

Examples of the oligomer and / or polymer include polyacrylate, polymethacrylate, polyacrylamide, polymethacrylamide, polymethyl methacrylate and the like. The degree of polymerization or the presence or absence of liquid crystallinity may be determined in consideration of the solubility in the mixture.
The low molecular compound having a polymerizable group may or may not have liquid crystallinity, but preferably has liquid crystallinity. Note that “showing liquid crystallinity” means having a rigid portion called a mesogen and showing orientation. Examples of the polymerizable compound exhibiting liquid crystallinity include, for example, Handbook of Liquid Crystals (D. Demus, JW Goodby, GW Gray, HW Spies, V. Vill, edited by Wiley-VCH, 1998), Quarterly Chemical Review No. 22, Liquid Crystal Chemistry (Edited by Chemical Society of Japan, 1994), or JP-A-7-294735, JP-A-8-3111, JP-A-8-29618, JP-A-11-80090, 1,4-phenylene group, 1,4-cyclohexene, as described in Kaihei 11-148079, JP-A 2000-178233, JP-A 2002-308831, and JP-A 2002-145830. A rod-like polymerizable liquid crystal compound having a rigid site called a mesogen in which a plurality of structures such as a silene group are connected, and a polymerizable functional group such as a (meth) acryloyloxy group, a vinyloxy group, and an epoxy group, or JP-A-2004-2373 And a rod-like polymerizable liquid crystal compound having a maleimide group as described in JP 2004-99446 A Alternatively, a rod-like polycyclic liquid crystal compound having an allyl ether group as described in JP-A-2004-149522, or, for example, Handbook of Liquid Crystals (D. Demus, JW Goodbye, G. W. Gray, H. W. Spiess, edited by V. Vill, published by Wiley-VCH, 1998), Quarterly Chemical Review No. 22. Liquid crystal chemistry (edited by Chemical Society of Japan, 1994) and discotic polymerizable compounds described in JP-A-07-146409.

  The polymerizable compound may or may not have liquid crystallinity. Specific examples include compounds represented by general formula (2) to general formula (8).

In the above formula, P ^{11 to} P ⁷⁴ each independently represent a polymerizable group,
S ^{11 to} S ⁷² each independently represent a spacer group or a single bond, but when there are a plurality of S ^{11 to} S ^72, they may be the same or different,
X ^{11 to} X ⁷² are each independently —O—, —S—, —OCH ₂ —, —CH ₂ O—, —CO—, —COO—, —OCO—, —CO—S—, —S—. CO -, - O-CO- O -, - CO-NH -, - NH-CO -, - SCH 2 -, - CH 2 S -, - CF 2 O -, - OCF 2 -, - CF 2 S- _{, -SCF 2 -, - CH =} CH-COO -, - CH = CH-OCO -, - COO-CH = CH -, - OCO-CH = CH -, - COO-CH 2 CH 2 -, - OCO- _{CH 2 CH 2 -, - CH} 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - COO-CH 2 -, - OCO-CH 2 -, - CH 2 -COO -, - CH 2 -OCO —, —CH═CH—, —N═N—, —CH═N—N═CH—, —CF═CF—, —C≡C— or a single bond. Represents
When a plurality of X ^{11 to} X ⁷² are present, they may be the same or different from each other (however, each P— (S—X) — bond does not include —O—O—).
M ¹¹ , M ²¹ , M ³¹ , M ⁵¹ , and M ⁷¹ each represent a divalent organic group having 1 to 30 carbon atoms, M ³¹ is a trivalent organic group having 1 to 30 carbon atoms, and M ⁶¹ is Represents a tetravalent organic group having 1 to 30 carbon atoms,
R ¹¹ and R ³¹ are each a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfuranyl group, a cyano group, a nitro group, an isocyano group, a thioisocyano group, or a group having 1 to 20 carbon atoms. Represents an alkyl group, the alkyl group may be linear or branched, and any hydrogen atom in the alkyl group may be substituted with a fluorine atom. number of -CH ₂ - or nonadjacent two or more -CH ₂ - each independently -O is -, - S -, - CO -, - COO -, - OCO -, - CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO- or -C≡C- may be substituted,
m1 to m7, n2 to n7, l4 to l6, and k6 each independently represent an integer of 0 to 5.

The spacer group represented by S ^{11 to} S ⁷² represents an alkylene group having 1 to 18 carbon atoms (the alkylene group is one or more halogen atoms, CN group, alkyl group having 1 to 8 carbon atoms, Alternatively, it may be substituted by an alkyl group having 1 to 8 carbon atoms having a polymerizable functional group, and one CH ₂ group present in this group or two or more CH ₂ groups not adjacent to each other are mutually bonded. Independently, in a form in which oxygen atoms are not directly bonded to each other, —O—, —S—, —NH—, —N (CH ₃ ) —, —CO—, —CH (OH) —, CH (COOH) ), -COO-, -OCO-, -OCOO-, -SCO-, -COS- or -C≡C-, and among these spacer groups, from the viewpoint of orientation, a carbon atom A linear alkylene group of 2 to 8 and a fluorine atom Conversion alkylene group having 2 to 6 carbon atoms, an alkylene group having a carbon number of 5 to 14 which partially replaced by -O- alkylene groups are preferred.
The polymerizable groups represented by P ^{11 to} P ⁷⁴ are represented by the following formulas (P-1) to (P-20).

Of these polymerizable groups, from the viewpoint of enhancing the polymerizability and storage stability, the formula (P-1), the formula (P-2), the formula (P-7), the formula (P-12), Or Formula (P-13) is preferable, and Formula (P-1), Formula (P-7), and Formula (P-12) are more preferable.
In the divalent organic group represented by M ¹¹ , M ²¹ , M ³¹ , M ⁵¹ , M ⁷¹ , one —CH ₂ — or two or more non-adjacent —CH ₂ — are each independently -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO -, -CH = CH-, -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -CH = CH-, -CF = CF ^{-, - N = N -,} - CR 1 = N-N = CR 1 -, or -C≡C- linear good having 1 to 20 carbon atoms which may be substituted by a branched alkylene group, carbon atoms A group having an alicyclic structure of several 3 to 20, for example, 1,2-cyclopropylene group, 1,3-cyclobutylene group, 2,5-cyclopentylene Group, octahydro-4,7-methano-1H-indene-1,5-diyl group, octahydro-4,7-methano-1H-indene-1,6-diyl group, octahydro-4,7-methano-1H- Indene-2,5-diyl group, tricyclo [3.3.1.1 ^3,7 ] -1,3-diyl group, 1,4-phenylene group, 1,4-cyclohexylene group, 1,4-cyclo Hexenyl group, tetrahydropyran-2,5-diyl group, 1,3-dioxane-2,5-diyl group, tetrahydrothiopyran-2,5-diyl group, 1,4-bicyclo (2,2,2) octylene Group, decahydronaphthalene-2,6-diyl group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, pyrazine-2,5-diyl group, thiophene-2,5-diyl group, 1,2,3,4 Trahydronaphthalene-2,6-diyl group, naphthylene-1,4-diyl group, naphthylene-1,5-diyl group, naphthylene-1,6-diyl group, naphthylene-2,6-diyl group, phenanthrene-2 , 7-diyl group, 9,10-dihydrophenanthrene-2,7-diyl group, benzothiazole group, 1,2,3,4,4a, 9,10a-octahydrophenanthrene-2,7-diyl group, benzo [1,2-b: 4,5-b ′] dithiophene-2,6-diyl group, benzo [1,2-b: 4,5-b ′] diselenophen-2,6-diyl group, [1] Selected from benzothieno [3,2-b] thiophene-2,7-diyl group, [1] benzoselenopheno [3,2-b] selenophene-2,7-diyl group, or fluorene-2,7-diyl group Preferred group These groups may be unsubstituted or substituted with one or more L ¹ .
The trivalent organic group represented by M ³¹ and the tetravalent organic group represented by M ⁶¹ are trivalent and tetravalent organic groups, respectively, and are the same groups as the divalent organic group. Is preferred.
In addition, the divalent to tetravalent organic group represented by M ^{11 to} M ⁷¹ is a group represented by the following formula (9-a).

(A ⁹¹ and A ⁹² A ⁹³ are each independently a divalent group having at least one ring structure, and the divalent group includes a 1,2-cyclopropylene group, a 1,3-cyclobutylene group, 2,5-cyclopentylene group, octahydro-4,7-methano-1H-indene-1,5-diyl group, octahydro-4,7-methano-1H-indene-1,6-diyl group, octahydro-4 , 7-methano-1H-indene-2,5-diyl group, tricyclo [3.3.1.1 ^3,7 ] -1,3-diyl group, 1,4-phenylene group, 1,4-cyclohexylene Group, 1,4-cyclohexenyl group, tetrahydropyran-2,5-diyl group, 1,3-dioxane-2,5-diyl group, tetrahydrothiopyran-2,5-diyl group, 1,4-bicyclo ( 2,2,2) Octylene Group, decahydronaphthalene-2,6-diyl group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, pyrazine-2,5-diyl group, thiophene-2,5-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, naphthylene-1,4-diyl group, naphthylene-1,5-diyl group, naphthylene-1,6-diyl group, naphthylene-2,6 -Diyl group, phenanthrene-2,7-diyl group, 9,10-dihydrophenanthrene-2,7-diyl group, benzothiazole group, 1,2,3,4,4a, 9,10a-octahydrophenanthrene-2 , 7-diyl group, benzo [1,2-b: 4,5-b ′] dithiophene-2,6-diyl group, benzo [1,2-b: 4,5-b ′] diselenophen-2,6 A diyl group, [1] Selected from zothieno [3,2-b] thiophene-2,7-diyl group, [1] benzoselenopheno [3,2-b] selenophene-2,7-diyl group, or fluorene-2,7-diyl group These groups may be unsubstituted or substituted with one or more L ¹ groups, but when a plurality of A ⁹¹ , A ⁹² and / or A ⁹³ appear, they may be the same or different. It ’s okay,
Z ⁹¹ and Z ⁹² are each independently —O—, —S—, —OCH ₂ —, —CH ₂ O—, —CH ₂ CH ₂ —, —CO—, —COO—, —OCO—, —CO. -S -, - S-CO - , - O-CO-O -, - CO-NH -, - NH-CO -, - SCH 2 -, - CH 2 S -, - CF 2 O -, - OCF 2 _{-, - CF 2 S -,} - SCF 2 -, - CH = CH-COO -, - CH = CH-OCO -, - COO-CH = CH -, - OCO-CH = CH -, - COO-CH 2 _{CH 2 -, - OCO-CH} 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - COO-CH 2 -, - OCO-CH 2 -, - CH 2 -COO _{-, - CH 2 -OCO -,} - CH = CH -, - N = N -, - CH = N -, - N = CH -, - CH = N- N═CH—, —CF═CF—, —C≡C— or a single bond, and when a plurality of Z ⁹¹ and / or Z ⁹² appear, they may be the same or different,
L ¹ is a fluorine atom, chlorine atom, bromine atom, iodine atom, pentafluorosulfuranyl group, nitro group, isocyano group, amino group, hydroxyl group, mercapto group, methylamino group, dimethylamino group, diethylamino group, diisopropylamino. Group, trimethylsilyl group, dimethylsilyl group, thioisocyano group, or one —CH ₂ — or two or more non-adjacent —CH ₂ — are each independently —O—, —S—, —CO—. , -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH = CH-COO-,- CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -CH = CH-, -CF = CF-, -N = N-, -CR ¹ = N-N = CR ¹ -, or -C≡C- Therefore, a linear or branched alkyl group having 1 to 20 carbon atoms that may be substituted, an aromatic group that may have a substituent, a heterocyclic group that may have a substituent, or the spacer group A hydrogen atom in the alkyl group may be substituted with a fluorine atom (wherein R ¹ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms). The alkyl group may be linear or branched, and any hydrogen atom in the alkyl group may be substituted with a fluorine atom, and one alkyl group in the alkyl group —CH ₂ — or two or more non-adjacent —CH ₂ — are each independently —O—, —S—, —CO—, —COO—, —OCO—, —CO—S—, —S. -CO-, -O-CO-O-, -CO-NH-, -NH-CO- or -C≡C- Is preferred).

  Specific examples of the compound represented by the general formula (2) include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl acrylate, propyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, Butyl (meth) acrylate, isobutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, Stearyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyloxylethyl (meth) acrylate, isobornyloxylethyl (meth) acrylate, isobornyl (meth) acrylate, ada Nthyl (meth) acrylate, dimethyladamantyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, methoxyethyl (meth) acrylate, ethyl carbitol (meth) acrylate, tetrahydrofurfuryl (meth) ) Acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, 2-phenoxydiethylene glycol (meth) acrylate, 2-hydroxy-3-phenoxyethyl (meth) acrylate, (2-methyl-2-ethyl-1,3) -Dioxolan-4-yl) methyl (meth) acrylate, (3-ethyloxetane-3-yl) methyl (meth) acrylate, o-phenylphenol ethoxy (meth) acrylate, dimethylamino (Meth) acrylate, diethylamino (meth) acrylate, 2,2,3,3,3-pentafluoropropyl (meth) acrylate, 2,2,3,4,4,4-hexafluorobutyl (meth) acrylate, 2 , 2,3,3,4,4,4-heptafluorobutyl (meth) acrylate, 2- (perfluorobutyl) ethyl (meth) acrylate, 2- (perfluorohexyl) ethyl (meth) acrylate, 1H, 1H , 3H-tetrafluoropropyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) acrylate, 1H, 1H, 7H-dodecafluoroheptyl (meth) acrylate, 1H-1- (trifluoromethyl) trifluoro Ethyl (meth) acrylate, 1H, 1H, 3H-hexafluorobutyl ( (Meth) acrylate, 1,2,2,2-tetrafluoro-1- (trifluoromethyl) ethyl (meth) acrylate, 1H, 1H-pentadecafluorooctyl (meth) acrylate, 1H, 1H, 2H, 2H-tri Decafluorooctyl (meth) acrylate, 2- (meth) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, glycidyl (meth) acrylate, 2- (meth) acryloyloxyethyl phosphoric acid, acryloyl Morpholine, dimethylacrylamide, dimethylaminopropylacrylamide, isopropylpropylacrylamide, diethylacrylamide, hydroxyethylacrylamide, cyclohexylacrylamide, N-acryloyloxyethylhexahydrophthalimi Mono (meth) acrylates such as, acrylic acid, hydroxyethyl acrylate, hydroxybutyl acrylate, hydroxyl group-containing acrylates such as 1,4-cyclohexanedimethanol monoacrylate, or the following formula (2-1) to formula (2-39) ) Is preferred.

  Specific examples of the compound represented by the general formula (3) include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and 1,9-nonanediol di (meth). ) Acrylate, neopentyldiol di (meth) acrylate, tripropylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, trichlorodecane dimethanol di Acrylate, adamantane di (meth) acrylate, bisphenol A di (meth) acrylate, hydrogenated bisphenol A di (meth) acrylate, bisphenol F di (meth) acrylate, ethylene oxide modified bisphenol A di (meth) Chryrate, tricyclodecane dimethanol di (meth) acrylate, 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene, glycerin di (meth) acrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate 1,6-hexanediol diglycidyl ether acrylic acid adduct, 1,4-butanediol diglycidyl ether acrylic acid adduct, etc., diacrylate, 4- and 2,6-tolylene diisocyanate (TDI), Orthotoluidine diisocyanate (TODI), naphthylene diisocyanate (NDI), xylylene diisocyanate (XDI), 4,4′-diphenylmethane diisocyanate (MDI), isophorone diisocyanate, and carbodiimide modified MDI, Various urethane acrylates obtained by reacting diisocyanate, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, Epoxy compounds such as bisphenol A diglycidyl ether, or compounds represented by the following formulas (3-1) to (3-53) are preferable.

  Specifically, the compounds represented by the general formula (4) are preferably compounds represented by the following formulas (4-1) to (4-9).

Specific examples of the compound represented by the general formula (5) include trimethylolpropane tri (meth) acrylate, ethoxylated isocyanuric acid triacrylate, pentaerythritol tri (meth) acrylate, ε-caprolactone-modified tris- (2- Tri (meth) acrylates such as (acryloyloxyethyl) isocyanurate, or compounds represented by the following formulas (5-1) to (5-23) are preferred.

Specifically, the compounds represented by the general formula (6) are preferably compounds represented by the following formulas (6-1) to (6-11).

Specific examples of the compound represented by the general formula (7) include tetra (meth) acrylates such as pentaerythritol tetra (meth) acrylate and ditrimethylolpropane tetra (meth) acrylate, or the following formula (7- Compounds represented by formula (7-14) from 1) are preferred.

Specifically, the compound represented by the general formula (8) is preferably a compound represented by the following formula (8-1) to formula (8-10).

(In the formula, k, l, m and n each independently represent an integer of 1 to 10. R, R ¹ and R ² each independently represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms. , An alkoxy group having 1 to 6 carbon atoms, or a cyano group When these groups are alkyl groups having 1 to 6 carbon atoms or alkoxy groups having 1 to 6 carbon atoms, they are all unsubstituted or 1 These may be substituted by one or two or more halogen atoms.) These polymerizable compounds may be used alone or in combination of two or more.

  In addition, as the polymerizable compound and polymerizable oligomer other than the polymerizable compound, specifically, dipentaerythritol hexa (meth) acrylate, oligomer type (meth) acrylate, polyether polyol, polyester polyol, polycarbonate polyol, Various urethane acrylates obtained by reacting polyisocyanates such as polybutadiene polyol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polytetramethylene ether glycol and the like, polymethylene polyphenyl isocyanate, polymeric polyisocyanate and the like, various macromonomers, Examples include maleimide. These can be used alone or in combination of two or more.

  The total content of the polymer of the polymerizable compound in the total of the photoresponsive substance, the liquid crystal composition, and the polymer of the polymerizable compound in the polymer dispersed optical element of the present invention is 1% by weight or more and 70% by weight. It is preferably 3% by weight or more and 50% by weight or less, more preferably 5% by weight or more and 35% by weight or less. If it is in the said range, the threshold value of the light intensity of light can be reduced.

  In the case where an oligomer is added to the mixture of the photoresponsive substance, liquid crystal composition, and polymerizable compound in the polymer dispersed optical element of the present invention, the polymerization proceeds even in the absence of a polymerization initiator, but the polymerization is accelerated. In order to do so, a polymerization initiator may be contained. Examples of the polymerization initiator include benzoin ethers, benzophenones, acetophenones, benzyl ketals, acylphosphine oxides, and the like.

For example, diphenyl- (2,4,6-trimethylbenzoyl) phosphine oxide, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2 -Methyl-1-phenyl-propan-1-one, benzophenone, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy- 1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2-methyl-propan-1-one, phenylglyoxylic acid methyl ester, 2-methyl-1- [4- (Methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4 -Morpholinophenyl) -butanone-1,2-dimethylamino-2- (4-methyl-benzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one, bis (2, 4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 1,2-octanedione, 1- [4- (phenylthio)-, 2- ( O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), benzophenone, methylbenzoyl formate , Oligo {2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone, 2,4,6 trimethylbenzo Phenone, 4-methylbenzophenone, 2-ethoxy-1,2-diphenylethane-1-one, 2- (1-methylethoxy) -1,2-diphenylethane-1-one, 2-isobutoxy-2-phenylacetophenone Etc.
Among these, 2,2-dimethoxy-1,2-diphenylethane-1-one and 2-hydroxy-2-methyl-1-phenyl-propan-1-one are more preferable.

The threshold value (minimum value) of light intensity required for the polymer dispersed optical element having such a configuration to respond is preferably 10 W / cm ² or less in order to make the light intensity to be irradiated smaller. It is more preferably 5 W / cm ² or less, and further preferably 1 W / cm ² or less. Further, in order to control to be oriented at a specific light intensity, it is preferable to adjust the required light intensity threshold value to be in a specific range.

  Note that the threshold value of light intensity necessary for the polymer dispersion type optical element to respond is necessary for aligning the alignment direction of the liquid crystal molecules in the liquid crystal composition along with the alignment of the photoresponsive substance. It is the minimum value of light intensity.

  That is, in the polymer-dispersed optical element of the present invention, the liquid crystal molecules in the liquid crystal composition respond as the photoresponsive substance is aligned by light irradiation.

  Further, the thickness of the optical element itself excluding the substrate and alignment film in the polymer dispersed optical element of the present invention is preferably 3 μm or more and 100 μm, more preferably 5 μm or more and 75 μm or less, More preferably, it is 10 μm or more and 50 μm or less.

If the thickness of the optical element itself is within the above range, the threshold value of light intensity required for making the liquid crystal molecules in the liquid crystal composition respond can be lowered.
When the polymer dispersion type optical element of the present invention is irradiated with light to a mixture of a photoresponsive substance, a liquid crystal composition, and a polymer of a polymerizable compound, the photoresponsive substance has an oscillation of light in the long axis direction. The liquid crystal molecules in the liquid crystal composition are aligned so that the major axis direction thereof is parallel to the vibration direction of light. The amount of transmitted light is controlled by utilizing the birefringence difference between the liquid crystal molecules and the polymer of the polymerizable compound, or the alignment of the liquid crystal molecules becomes random due to the alignment regulating force of the polymer of the polymerizable compound. This is applied to a liquid crystal display element or the like that controls the amount of transmitted light.

  As liquid crystal display elements, AM-LCD (active matrix liquid crystal display element), TN (twisted nematic liquid crystal display element), STN-LCD (super twisted nematic liquid crystal display element), OCB-LCD, IPS-LCD (in-plane switching) Although it is useful for liquid crystal display elements) and FFS (fringe field switching mode liquid crystal display elements), it is particularly useful for AM-LCDs having an active matrix addressing device, and for scattering, reflection type, or transmission type liquid crystal display elements. Can be used.

  When the optical element is the liquid crystal display element 10, the two substrates of the liquid crystal cell used in the liquid crystal display element 10 can be made of a transparent material having flexibility such as glass or plastic. One of the two substrates may be an opaque material such as silicon.

  The color filter can be produced by, for example, a pigment dispersion method, a printing method, an electrodeposition method, or a dyeing method. A method for producing a color filter by a pigment dispersion method will be described as an example. A curable coloring composition for a color filter is applied onto the transparent substrate, subjected to patterning treatment, and cured by heating or light irradiation. By performing this process for each of the three colors red, green, and blue, a pixel portion for a color filter can be manufactured. In addition, a pixel electrode provided with an active element such as a TFT, a thin film diode, or a metal insulator metal specific resistance element may be provided on the substrate.

  Moreover, the said board | substrate may be made to oppose so that a transparent electrode layer may become an inner side, and you may adjust the space | interval of a board | substrate through a spacer. In this case, the thickness of the obtained liquid crystal layer is preferably 1 μm or more and 500 μm or less, more preferably 3 μm or more and 250 μm or less, and further preferably 5 μm or more and 200 μm or less. When a polarizing plate is used, it is preferable to adjust the product of the refractive index anisotropy Δn of the liquid crystal and the cell thickness d so that the contrast is maximized. In addition, when there are two polarizing plates, the polarizing axis of each polarizing plate can be adjusted so that the viewing angle and contrast are good. Furthermore, a retardation film for widening the viewing angle can also be used. Examples of the spacer include columnar spacers made of glass particles, plastic particles, alumina particles, photoresist materials, and the like. Thereafter, a sealing agent such as an epoxy thermosetting composition is screen-printed on the substrates in a form provided with a liquid crystal injection port, the substrates are bonded to each other, heated, and the sealing agent is thermally cured.

  When the polymer dispersed optical element is the liquid crystal display element 10, the liquid crystal molecules in the liquid crystal composition are on the first substrate surface (FIG. 1) on the first substrate (for example, substrate 11 in FIG. 1) side. In FIG. 1, the substrate 11 is oriented parallel to the surface 11a facing the substrate 12, and on the second substrate (for example, the substrate 12 in FIG. 1) side, the second substrate surface (the substrate 12 in FIG. It is preferably oriented perpendicular to the surface 12a) facing the substrate 11 in FIG.

Thus, the threshold value of the light intensity necessary for making the liquid crystal molecules respond is made different by changing the alignment direction of the liquid crystal molecules in the liquid crystal composition between the first substrate side and the second substrate side. Can be lowered.
According to the polymer-dispersed optical element of the present invention, a photo-responsive substance is contained in a mixture containing a photo-responsive substance having a threshold in response light intensity, a liquid crystal composition, and a polymer of a polymerizable compound. The photoresponsive substance contained in the mixture is aligned by irradiating light having a light intensity equal to or higher than a threshold value to which the liquid crystal responds, and accordingly, the liquid crystal molecules in the liquid crystal composition respond, so that the liquid crystal molecules respond. Therefore, the threshold value of the light intensity necessary for this can be lowered.
[Method for Manufacturing Optical Element]
A method for producing a polymer-dispersed optical element of the present invention comprises a mixture containing a photoresponsive substance having a threshold value in response light intensity, a liquid crystal composition, and a polymer of a polymerizable compound (hereinafter, the mixture, This is a method comprising a step of causing liquid crystal molecules in the liquid crystal composition to respond by irradiating light having a light intensity equal to or higher than a threshold value on the polymerization sample).
In the method for producing an optical element of the present invention, first, a photoresponsive composition is sandwiched between two substrates.
As a method for sandwiching the mixture between two substrates, a normal vacuum injection method, a drop injection (ODF: One Drop Fill) method, or the like can be used.
After sandwiching the mixture between two substrates, the mixture is irradiated with light having a light intensity equal to or greater than a threshold of light intensity necessary for orienting the photoresponsive substance contained in the mixture, By aligning the photoresponsive substance so that the major axis direction thereof is parallel to the vibration direction of light, the major axis direction of the liquid crystal molecules in the liquid crystal composition is parallel to the vibration direction of light. Oriented as follows. Preferably, the polymerizable compound is polymerized by light irradiated to the mixture, and when the mixture is irradiated with light, the light applied to the mixture is irradiated with respect to the normal direction of the layer containing the photoresponsive composition. It is preferable to irradiate at an angle.
By irradiating the light irradiating the mixture at an angle with respect to the normal direction of the layer containing the mixture, for example, before the light irradiation, the photoresponsive substance has its long axis direction in the light axis direction. Even when oriented so as to be perpendicular to the vibration direction, light can be irradiated from an oblique direction with respect to the major axis direction of the photoresponsive substance. Thereby, the photoresponsive substance can be efficiently oriented so that the long axis direction is parallel to the vibration direction of light. Furthermore, when the mixture is irradiated with light, the angle of the layer containing the mixture with respect to the normal direction is set to 20 degrees or less, so that the photoresponsive substance can be more efficiently reflected in the long axis direction. It can be oriented parallel to the vibration direction.
The temperature at which the mixture is irradiated with light is preferably within a temperature range in which the liquid crystal state of the liquid crystal molecules contained in the mixture is maintained. It is preferable to irradiate light at a temperature close to room temperature, that is, typically at a temperature of 15 to 35 ° C.
A metal halide lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, an LED lamp, or the like can be used as a light source that generates light for irradiating the mixture.
In addition, the intensity of light applied to the mixture is a threshold value of light intensity (light intensity required for the photoresponsive substance contained in the mixture to align its long axis direction parallel to the vibration direction of light. Minimum intensity), preferably 10 W / cm ² or less, more preferably 5 W / cm 2 or less, further preferably 1 W / cm 2 or less. It is appropriately selected depending on the intensity of the light to be emitted, preferably 10 to 3600 seconds, more preferably 10 to 600 seconds.
When the polymer dispersed optical element is the liquid crystal display element 10, the mixture is placed on the first substrate surface (in FIG. 1, for example, the substrate 11) side on the first substrate surface (in FIG. 1, on the substrate 11). Oriented parallel to the surface 11a facing the substrate 12 and facing the second substrate surface (for example, the substrate 12 in FIG. 1) on the second substrate surface (the substrate 12 in FIG. 1). It is preferable to irradiate the mixture with light having a light intensity equal to or higher than a threshold value after being oriented perpendicular to the surface 12a). Thus, it is necessary to make liquid crystal molecules in the liquid crystal composition contained in the mixture respond by making the orientation direction of the mixture different between the first substrate side and the second substrate side. The light intensity threshold can be lowered.
In the case where the mixture is oriented on the first substrate side or the second substrate side either perpendicularly or parallel to the substrate surface, an alignment film in contact with the mixture (for example, 11a, 12a in FIG. 1). It is preferable to irradiate the mixture with light having a light intensity equal to or higher than a threshold value, after the orientation is performed so that a certain angle is obtained in the normal direction of the layer containing the mixture.
According to the method for producing a polymer-dispersed optical element of the present invention, a mixture containing a photoresponsive substance having a threshold value in response light intensity, a liquid crystal composition, and a polymer of a polymerizable compound is used. By irradiating light having the above light intensity, the liquid crystal molecules in the liquid crystal composition are caused to respond, so that the threshold value of the light intensity to which the liquid crystal molecules respond can be lowered.
(Diffusion plate)
The diffusion plate of the present invention is similar to a diffusion plate for a liquid crystal display element that is generally used, and the light emitted from a backlight light source such as an LED is locally uniform according to the location where the light is emitted, and An optical member having a function for increasing the front luminance. In order to obtain a backlight using the diffusing plate of the present invention, a plurality of point light sources such as LED arrays are arranged at the end of the polymer dispersed optical element of the present invention, and the optical element is disposed on one substrate side. A reflector is provided. On the other substrate side, an optical member for increasing luminance, such as a prism sheet, a microlens sheet, and a multilayer sheet having birefringence, is provided. Thereby, only the part which is radiate | emitted from the light source of a specific location and has the light intensity more than the threshold value of the said photoresponsive substance makes the liquid crystal molecule in a liquid crystal composition respond, and light comes to be scattered. In other cases, the light intensity is less than the threshold value, so that the light is not scattered. As a result, only the portion where the light is scattered can enter the liquid crystal display element with the same luminance as the backlight unit having a general light guide plate or diffuser plate. Light to the optical member for increasing the luminance is blocked. That is, the contrast of the liquid crystal display element can be improved on the backlight unit side by using the diffusion plate of the present invention.
(window)
The window of the present invention is an application of the effects of the polymer dispersed optical element of the present invention. The window of the present invention responds to the portion of the liquid crystal molecules corresponding to the incident part when outdoor light or laser light or the like exceeding the threshold at which the photoresponsive substance responds is incident on the polymer dispersed optical element of the present invention. And light is scattered. The other parts remain transparent and function as normal windows. That is, by using the window of the present invention, the human body can be protected from a powerful light source.

  In addition, the window of the present invention includes an ultraviolet absorber and a light stabilizer in the liquid crystal composition in order to prevent deterioration of the liquid crystal composition and the polymer of the polymerizable compound contained in the polymer dispersed optical element of the present invention. Or an ultraviolet cut film can be provided outside the optical element. As a result, the durability of the optical element can be improved.

EXAMPLES Hereinafter, although an Example is given and this invention is further explained in full detail, this invention is not limited to these Examples.
(Example 1)
The following formula (LC7)

80 parts by weight of a composition represented by the following formula, 13 parts by weight of an acrylate monomer represented by the following formula (III), 1 part of UN-6300 (manufactured by Negami Kogyo Co., Ltd., molecular weight 13000), and morpholine A composition (A-1) was prepared by mixing 6% by weight of acrylate.

  The composition (A-1) 99.3% by weight, the photoresponsive substance represented by the following formula (IV) (oligothiophene TR5, manufactured by Merck Ltd.) 0.2% by weight, and absorption only in the ultraviolet region. A photopolymerization initiator (trade name: Irgacure 651, manufactured by BASF Japan) 0.5 wt% was added to prepare a sample for polymerization.

  Next, a polyimide solution for a vertical alignment film was applied to a 0.7 mm thick glass substrate using a spin coating method, dried at 100 ° C. for 10 minutes, and then baked at 200 ° C. for 60 minutes to obtain a coating film. . The obtained coating film was subjected to orientation treatment by rubbing. The rubbing treatment was performed using a commercially available rubbing apparatus.

  The two glass substrates subjected to the vertical alignment treatment are bonded so that the rubbing direction is opposite and the surface subjected to the alignment treatment is inside, and the thickness (cell gap) is 100 μm. A glass cell was prepared.

Next, the prepared polymerization sample was sealed in the glass cell (between two glass substrates), and photopolymerized in a state of being kept at room temperature (25 ° C.). Photopolymerization was performed by taking out a bright line of a high-pressure mercury lamp having a wavelength of 366 nm with a filter and irradiating it with light having a light intensity of 10.0 mW / cm ² for 6 minutes.

  After photopolymerization, the sample was gradually cooled to room temperature (25 ° C.) to obtain Sample 1-1 of Example 1.

  When the sample 1-1 was observed with a polarizing microscope (trade name: Olympus BX50, manufactured by Olympus), a cross isogyre was confirmed in the conoscopic image, and a dark field was confirmed in the orthoscope image. Therefore, it has been found that in the polymer-dispersed liquid crystal containing a dye, the molecular orientation is homeotropic orientation perpendicular to the glass substrate.

  In addition, the photoresponse behavior was measured.

For this observation, an Ar ⁺ laser having a beam diameter of 2.0 mm and a wavelength of 488 nm was used as pump light. The pump light is converted into vertical vertical polarization using a Glan-Thompson prism, condensed with a lens having a focal length of 15 cm, irradiated onto the sample 1-1, and the light transmitted through the sample 1-1 is projected onto a screen and observed. .

  Here, the principle of measurement will be described.

  When light having a Gaussian intensity distribution is incident on the polymer-dispersed optical element, the molecules do not change their orientation at a light intensity lower than the threshold value, and the incident light is transmitted as it is. However, when light having an intensity equal to or higher than the threshold is irradiated, the molecular orientation of the liquid crystal changes depending on the light intensity, and a Gaussian-type refractive index gradient is formed. Here, since the liquid crystal plays a role as a lens, first, phase modulation is performed by the refractive index gradient created by the incident light itself, and the self-convergence effect and the self-phase modulation effect appear, and the light transmitted through the liquid crystal has a different phase. The light interferes and shows interference fringes. Further, when the molecular orientation of the liquid crystal changes, the liquid crystal starts to be scattered by the polymer network.

  Here, the pump light transmitted through the sample was projected on a distant screen, and the change from interference fringes to scattered light was observed.

  As a result, it has been found that interference fringes occur in the vicinity where the pump light intensity exceeds the threshold value, but when the pump light intensity further increases, scattered light is generated and the area of the projected light increases. Moreover, the scattered light disappeared reversibly when the light intensity was lowered.

Moreover, when the light intensity (threshold value) at which scattered light appears was measured for the sample 1-1 using a beam profiler, it was 1.3 W / cm ² , which was greatly reduced compared to the result of Comparative Example 1 below. I found out.
(Comparative Example 1)
Instead of the polymerization sample prepared in Example 1, 99.8% by weight of the composition represented by the above formula (LC7) was added 0.2% by weight of the photoresponsive substance represented by the above formula (IV). In addition, a cell was produced in the same manner as in Example 1 except that the prepared sample was used, and Sample 1′-1 of Comparative Example 1 was obtained.

When the sample 1′-1 was observed with a polarizing microscope in the same manner as in Example 1, it was confirmed that a cross isogyre was observed in the conoscopic image and a dark field was observed in the orthoscope image.
Moreover, when the light intensity (threshold value) at which scattered light appears was measured using a beam profiler in the same manner as in Example 1, it was 20 W / cm ² .
(Example 2)
80 parts by weight of the composition represented by the above formula (LC7), 13% by weight of an acrylate monomer represented by the following formula (III), and UN-6300 (molecular weight 13000, manufactured by Negami Kogyo Co., Ltd.) which is a urethane acrylate oligomer. And 6 weight% of OXE-10 (made by Osaka Organic Chemical Co., Ltd.) which is oxetane acrylate was mixed, and the composition (B-1) was prepared.
The composition (B-1) 99.3% by weight, the photoresponsive substance represented by the following formula (IV) (oligothiophene TR5, manufactured by Merck Ltd.) 0.2% by weight, and absorption only in the ultraviolet region. A photopolymerization initiator (trade name: Irgacure 651, manufactured by BASF Japan) 0.5 wt% was added to prepare a sample for polymerization.
Next, a polyimide solution for a vertical alignment film was applied to a 0.7 mm thick glass substrate using a spin coating method, dried at 100 ° C. for 10 minutes, and then baked at 200 ° C. for 60 minutes to obtain a coating film. . The obtained coating film was subjected to orientation treatment by rubbing. The rubbing treatment was performed using a commercially available rubbing apparatus. Further, a polyimide solution for a horizontal alignment film was applied to a 0.7 mm glass substrate by a spin coating method, dried at 80 ° C. for 10 minutes, and then baked at 230 ° C. for 60 minutes to obtain a coating film. The obtained coating film was subjected to orientation treatment by rubbing.
The glass substrate subjected to the vertical alignment treatment and the glass substrate subjected to the horizontal alignment treatment are bonded so that the rubbing direction is opposite and the surface subjected to the alignment treatment is inward. A glass cell having a cell gap of 50 μm was produced.
Next, the prepared polymerization sample was sealed in the glass cell (between two glass substrates), and photopolymerized in a state of being kept at room temperature (25 ° C.). Photopolymerization was performed by taking out a bright line of a high-pressure mercury lamp having a wavelength of 366 nm with a filter and irradiating it with light having a light intensity of 10.0 mW / cm ² for 6 minutes.
After photopolymerization, the sample was slowly cooled to room temperature (25 ° C.) to obtain a sample 2-1 of Example 2 which was hybrid-oriented.
The sample 2-1 was irradiated with Ar ⁺ laser light having a beam diameter of 2.0 mm and a wavelength of 488 nm as pump light so that the polarization direction was parallel to the homogeneous alignment processing direction from the homeotropic alignment processing substrate side. The light response behavior was measured in the same manner as in Example 1. As a result, when the light intensity (threshold value) at which scattered light appeared was measured, it was found to be very low as 0.48 W / cm ² . . That is, it was found that a hybrid alignment cell using a glass substrate subjected to vertical alignment treatment and a glass substrate subjected to horizontal alignment treatment has an effect of reducing the threshold value of light intensity.
Example 3
80 parts by weight of the composition represented by the above formula (LC7), 13% by weight of an acrylate monomer represented by the following formula (III), and UN-6300 (molecular weight 13000, manufactured by Negami Kogyo Co., Ltd.) which is a urethane acrylate oligomer. And 6 weight% of OXE-10 (made by Osaka Organic Chemical Co., Ltd.) which is oxetane acrylate was mixed, and the composition (C-1) was prepared.
The composition (C-1) 99.3% by weight, the photoresponsive substance represented by the following formula (IV) (oligothiophene TR5, manufactured by Merck) 0.2% by weight, and absorption only in the ultraviolet region A photopolymerization initiator (trade name: Irgacure 651, manufactured by BASF Japan) 0.5 wt% was added to prepare a sample for polymerization.
Next, the polyimide solution for a horizontal alignment film was applied to a 0.7 mm glass substrate using a spin coating method, dried at 80 ° C. for 10 minutes, and then baked at 230 ° C. for 60 minutes to obtain a coating film. The obtained coating film was subjected to orientation treatment by rubbing.
The two glass substrates that have been subjected to the horizontal alignment treatment are bonded together so that the rubbing treatment direction is opposite (anti-parallel direction), and the orientation treatment surface is on the inside, Cell gap) A glass cell of 50 μm was produced.
Next, the prepared polymerization sample was sealed in the glass cell (between two glass substrates), and photopolymerized in a state of being kept at room temperature (25 ° C.). Photopolymerization was performed by taking out a bright line of a high-pressure mercury lamp having a wavelength of 366 nm with a filter and irradiating it with light having a light intensity of 10.0 mW / cm ² for 6 minutes.
After photopolymerization, the sample was gradually cooled to room temperature (25 ° C.) to obtain a sample 3-1 of Example 3 substantially homogeneously oriented. The tilt angle of the liquid crystal component in the obtained sample 3-1 was measured with a liquid crystal evaluation apparatus and found to be 10 °.
The sample 3-1 was irradiated with Ar ⁺ laser light having a beam diameter of 2.0 mm and a wavelength of 488 nm as pump light, and the optical response behavior was measured in the same manner as in Example 1. As a result, when the light intensity (threshold value) at which scattered light appears was measured, it was found to be as low as 0.08 W / cm ² . That is, it has been found that a homogeneously oriented cell using a glass substrate subjected to a horizontal alignment treatment has an effect of reducing the threshold value of light intensity.
(Example 4)
75 parts by weight of the composition represented by the above formula (LC7), 14 parts by weight of an acrylate monomer represented by the following formula (III), UN-6300 (molecular weight 13000, manufactured by Negami Kogyo Co., Ltd.) which is a urethane acrylate oligomer , Morpholine acrylate ACMO 8.98% by weight and 2-methacryloyloxyethyl acid phosphate 0.02% by weight of light ester P-2M (manufactured by Kyoeisha Chemical Co., Ltd.) Was prepared.
The composition (D-1) 99.3% by weight, the photoresponsive substance represented by the following formula (IV) (oligothiophene TR5, manufactured by Merck) 0.2% by weight, and absorption only in the ultraviolet region A photopolymerization initiator (trade name: Irgacure 651, manufactured by BASF Japan) 0.5 wt% was added to prepare a sample for polymerization.
Next, a polyimide solution for a horizontal alignment film was applied to a 0.7 mm glass substrate using a spin coating method, dried at 100 ° C. for 10 minutes, and then baked at 200 ° C. for 60 minutes to obtain a coating film. The obtained coating film was subjected to orientation treatment by rubbing.
The two glass substrates subjected to the vertical alignment treatment are bonded so that the rubbing treatment directions are opposite and the orientation-treated surface is inside, and the thickness (cell gap) is 50 μm. A glass cell was prepared.
Next, the prepared polymerization sample was sealed in the glass cell (between two glass substrates), and photopolymerized in a state of being kept at room temperature (25 ° C.). Photopolymerization was performed by taking out a bright line of a high-pressure mercury lamp having a wavelength of 366 nm with a filter and irradiating it with light having a light intensity of 10.0 mW / cm ² for 6 minutes.
After photopolymerization, the sample was gradually cooled to room temperature (25 ° C.) to obtain Sample 4-1 of Example 4.
The sample 4-1 was irradiated with Ar ⁺ laser light having a beam diameter of 2.0 mm and a wavelength of 488 nm as pump light, and the optical response behavior was measured in the same manner as in Example 1. As a result, when the light intensity (threshold value) at which scattered light appears was measured, it was found to be 1.8 W / cm ² (Example 5).
75% by weight of the composition represented by the above formula (LC7), 14% by weight of an acrylate monomer represented by the following formula (III), UN-6300 which is a urethane acrylate oligomer (manufactured by Negami Industrial Co., Ltd., molecular weight 13000) 98 parts, 5% by weight of morpholine acrylate ACMO, 4% by weight of OXE-10 (Osaka Organic Chemical Co., Ltd.) which is oxetane acrylate, and light ester P-2M which is 2-methacryloyloxyethyl acid phosphate (Kyoeisha) Chemical Co., Ltd.) (0.02% by weight) was mixed to prepare a composition (E-1).
The composition (E-1) 99.3% by weight, the photoresponsive substance represented by the following formula (IV) (oligothiophene TR5, manufactured by Merck & Co.) 0.2% by weight, and absorption only in the ultraviolet region. A photopolymerization initiator (trade name: Irgacure 651, manufactured by BASF Japan) 0.5 wt% was added to prepare a sample for polymerization.
Next, a polyimide solution for a vertical alignment film was applied to a 0.7 mm thick glass substrate using a spin coating method, dried at 100 ° C. for 10 minutes, and then baked at 200 ° C. for 60 minutes to obtain a coating film. . The obtained coating film was subjected to orientation treatment by rubbing. The rubbing treatment was performed using a commercially available rubbing apparatus. Further, a polyimide solution for a horizontal alignment film was applied to a 0.7 mm glass substrate by a spin coating method, dried at 80 ° C. for 10 minutes, and then baked at 230 ° C. for 60 minutes to obtain a coating film. The obtained coating film was subjected to orientation treatment by rubbing.
The glass substrate subjected to the vertical alignment treatment and the glass substrate subjected to the horizontal alignment treatment are bonded so that the rubbing direction is opposite and the surface subjected to the alignment treatment is inward. A glass cell having a cell gap of 20 μm was produced.
Next, the prepared polymerization sample was sealed in the glass cell (between two glass substrates), and photopolymerized in a state of being kept at room temperature (25 ° C.). Photopolymerization was performed by taking out a bright line of a high-pressure mercury lamp having a wavelength of 366 nm with a filter and irradiating it with light having a light intensity of 10.0 mW / cm ² for 6 minutes.
After photopolymerization, the sample was gradually cooled to room temperature (25 ° C.) to obtain a sample 5-1 of Example 5 which was hybrid-oriented.
The sample 5-1 is irradiated with Ar ⁺ laser light having a beam diameter of 2.0 mm and a wavelength of 488 nm as pump light so that the polarization direction is parallel to the homogeneous alignment processing direction from the homeotropic alignment processing substrate side. The light response behavior was measured in the same manner as in Example 1. As a result, when the light intensity (threshold value) at which scattered light appeared was measured, it was found to be as low as 0.51 W / cm ² . .
(Example 6)
87% by weight of the composition represented by the above formula (LC7), 9% by weight of an acrylate monomer represented by the following formula (V), UN-6300 which is a urethane acrylate oligomer (manufactured by Negami Kogyo Co., Ltd., molecular weight 13000). 4 parts and 3.6% by weight of morpholine acrylate ACMO were mixed to prepare a composition (F-1).

The composition (F-1) 99.3% by weight, the photoresponsive substance represented by the following formula (IV) (oligothiophene TR5, manufactured by Merck) 0.2% by weight, and absorption only in the ultraviolet region A photopolymerization initiator (trade name: Irgacure 651, manufactured by BASF Japan) 0.5 wt% was added to prepare a sample for polymerization.
Next, a polyimide solution for a vertical alignment film was applied to a 0.7 mm thick glass substrate using a spin coating method, dried at 100 ° C. for 10 minutes, and then baked at 200 ° C. for 60 minutes to obtain a coating film. . The obtained coating film was subjected to orientation treatment by rubbing. The rubbing treatment was performed using a commercially available rubbing apparatus. Further, a polyimide solution for a horizontal alignment film was applied to a 0.7 mm glass substrate by a spin coating method, dried at 80 ° C. for 10 minutes, and then baked at 230 ° C. for 60 minutes to obtain a coating film. The obtained coating film was subjected to orientation treatment by rubbing.
The glass substrate subjected to the vertical alignment treatment and the glass substrate subjected to the horizontal alignment treatment are bonded so that the rubbing direction is opposite and the surface subjected to the alignment treatment is inward. A glass cell having a cell gap of 20 μm was produced.
Next, the prepared polymerization sample was sealed in the glass cell (between two glass substrates), and photopolymerized in a state of being kept at room temperature (25 ° C.). Photopolymerization was performed by taking out a bright line of a high-pressure mercury lamp having a wavelength of 366 nm with a filter and irradiating it with light having a light intensity of 10.0 mW / cm ² for 6 minutes.
After photopolymerization, the sample was gradually cooled to room temperature (25 ° C.) to obtain a sample 6-1 of Example 6 which was hybrid-oriented.
This test 65-1 is irradiated with Ar ⁺ laser light having a beam diameter of 2.0 mm and a wavelength of 488 nm as pump light so that the polarization direction is parallel to the homogeneous alignment processing direction from the homeotropic alignment processing substrate side. The light response behavior was measured in the same manner as in Example 1. As a result, when the light intensity (threshold value) at which scattered light appeared was measured, it was found to be as low as 0.37 W / cm ² . .
(Example 7)
87% by weight of the composition represented by the above formula (LC7), 10% by weight of the acrylate monomer represented by the following formula (V), UN-6300 which is a urethane acrylate oligomer (manufactured by Negami Kogyo Co., Ltd., molecular weight 13000). 3 parts and 2.7 wt% of OXE-10 (Osaka Organic Chemical Co., Ltd.) which is oxetane acrylate were mixed to prepare a composition (G-1).
This composition (G-1) 99.3% by weight, a photoresponsive substance represented by the following formula (IV) (oligothiophene TR5, manufactured by Merck & Co., Inc.) 0.2% by weight, and absorbs only in the ultraviolet region. A photopolymerization initiator (trade name: Irgacure 651, manufactured by BASF Japan) 0.5 wt% was added to prepare a sample for polymerization.
Next, the polyimide solution for a horizontal alignment film was applied to a 0.7 mm glass substrate using a spin coating method, dried at 80 ° C. for 10 minutes, and then baked at 230 ° C. for 60 minutes to obtain a coating film. The obtained coating film was subjected to orientation treatment by rubbing.
The two glass substrates that have been subjected to the horizontal alignment treatment are bonded together so that the rubbing treatment direction is opposite (anti-parallel direction), and the orientation treatment surface is on the inside, Cell gap) A 20 μm glass cell was prepared.
Next, the prepared polymerization sample was sealed in the glass cell (between two glass substrates), and photopolymerized in a state of being kept at room temperature (25 ° C.). Photopolymerization was performed by taking out a bright line of a high-pressure mercury lamp having a wavelength of 366 nm with a filter and irradiating it with light having a light intensity of 10.0 mW / cm ² for 6 minutes.
After photopolymerization, the sample was gradually cooled to room temperature (25 ° C.) to obtain a sample 7-1 of Example 7 substantially homogeneously oriented. It was 8 degrees when the tilt angle of the liquid-crystal component in the obtained sample 7-1 was measured with the liquid-crystal evaluation apparatus.
The sample 7-1 was irradiated with Ar ⁺ laser light having a beam diameter of 2.0 mm and a wavelength of 488 nm as pump light, and the optical response behavior was measured in the same manner as in Example 1. As a result, when the light intensity (threshold value) at which scattered light appears was measured, it was found to be as low as 0.09 W / cm ² . That is, it has been found that a homogeneously oriented cell using a glass substrate subjected to a horizontal alignment treatment has an effect of reducing the threshold value of light intensity.
(Example 8)
Formula (LC8)

And 75 parts by weight of a composition represented by formula (14), 14 parts by weight of an acrylate monomer represented by the following formula (VI), 4 parts of UN-6300 (manufactured by Negami Kogyo Co., Ltd., molecular weight 13000), and morpholine The composition (H-1) was prepared by mixing 4% by weight of acrylate ACMO and 3% by weight of OXE-10 (Osaka Organic Chemical Co., Ltd.), which is oxetane acrylate.

The composition (H-1) 99.3% by weight, the photoresponsive substance represented by the following formula (IV) (oligothiophene TR5, manufactured by Merck Ltd.) 0.2% by weight, and absorption only in the ultraviolet region. A photopolymerization initiator (trade name: Irgacure 651, manufactured by BASF Japan) 0.5 wt% was added to prepare a sample for polymerization.
Next, a polyimide solution for a vertical alignment film was applied to a 0.7 mm thick glass substrate using a spin coating method, dried at 100 ° C. for 10 minutes, and then baked at 200 ° C. for 60 minutes to obtain a coating film. . The obtained coating film was subjected to orientation treatment by rubbing. The rubbing treatment was performed using a commercially available rubbing apparatus. Further, a polyimide solution for a horizontal alignment film was applied to a 0.7 mm glass substrate by a spin coating method, dried at 80 ° C. for 10 minutes, and then baked at 230 ° C. for 60 minutes to obtain a coating film. The obtained coating film was subjected to orientation treatment by rubbing.
The glass substrate subjected to the vertical alignment treatment and the glass substrate subjected to the horizontal alignment treatment are bonded so that the rubbing direction is opposite and the surface subjected to the alignment treatment is inward. A glass cell having a cell gap of 50 μm was produced.
Next, the prepared polymerization sample was sealed in the glass cell (between two glass substrates), and photopolymerized in a state of being kept at room temperature (25 ° C.). Photopolymerization was performed by taking out a bright line of a high-pressure mercury lamp having a wavelength of 366 nm with a filter and irradiating it with light having a light intensity of 10.0 mW / cm ² for 6 minutes.
After photopolymerization, the sample was slowly cooled to room temperature (25 ° C.) to obtain a sample 8-1 of Example 8 which was hybrid-oriented.
The sample 8-1 is irradiated with Ar ⁺ laser light having a beam diameter of 2.0 mm and a wavelength of 488 nm as pump light so that the polarization direction is parallel to the homogeneous alignment processing direction from the homeotropic alignment processing substrate side. The light response behavior was measured in the same manner as in Example 1. As a result, when the light intensity (threshold value) at which scattered light appeared was measured, it was found to be as low as 0.28 W / cm ² . .
From the above results, it was possible to obtain a polymer-dispersed liquid crystal capable of being transmitted and scattered by light by using a photoresponsive substance. Moreover, compared with the sample of Comparative Example 1, the samples of Examples 1 to 8 were able to reduce the light intensity threshold. In addition, by increasing the thickness of the vertically aligned molecules and weakening the initial alignment regulating force, it was possible to reduce the light intensity threshold as compared with the sample of Comparative Example 1. Further, the samples of Examples 1 to 8 are compared with the sample of Comparative Example 1 by tilting the sample with respect to the direction parallel to the polarization plane of incident light and tilting the initial orientation of the dye with respect to the electric field. The light intensity threshold could be reduced.

 The present invention can be used, for example, as a liquid crystal display element and a manufacturing method thereof.

10 ... Liquid crystal display element,
11, 12 ... substrate, 11a, 12a ... alignment film 13 ... photoresponsive substance,
14: anisotropic molecules,
DESCRIPTION OF SYMBOLS 15 ... Photoresponsive composition 16 ... The optical element which provides a polymer network, and its manufacturing method are provided.

Claims (11)

A first substrate;
A second substrate facing the first substrate;
An optical element comprising a layer having a photoresponsive composition provided between the first substrate and the second substrate,
The layer having the photoresponsive composition includes a photoresponsive substance having a threshold value in response light intensity, a liquid crystal composition, and a polymer of a polymerizable compound .
The polymer of the polymerizable compound is a polymer of a polymerizable compound including a liquid crystal polymerizable compound and a non-liquid crystal polymerizable compound,
An alignment film is provided on a surface of the first substrate and the second substrate that faces the other substrate, and the alignment of the liquid crystal molecules in the liquid crystal composition is controlled by the alignment film. An optical element in which a polymer network is formed . 2. The polymer network according to claim 1, wherein the liquid crystal molecules form a network of the polymer in a state of homeotropic alignment, homogeneous alignment, or hybrid alignment with respect to the first substrate or the second substrate. Optical element. The photoresponsive substance is an anisotropic substance that does not cause a photochemical reaction. By irradiating light having a light intensity equal to or higher than the threshold, the major axis direction of the photoresponsive substance is changed to the vibration direction of light. the optical element according to claim 1 or 2 oriented parallel against. The optical element according to any one of claims 1 to 3, wherein the threshold value of the light intensity is 10 W / cm ² or less. The liquid crystal composition, the polymerizable compound, among the total of the polymers of oligomers and the polymerizable compound of the polymerizable compound, the polymerizable compound, containing a total of oligomers and polymers of the polymerizable compound of the polymerizable compound The optical element according to any one of claims 1 to 4 , wherein the amount is 2 to 70 mass %. The thickness of the layer to have a photoresponsive composition, optical element according to any one of claims 1 to 5, at 3μm or more. Layer having the photoresponsive composition, and characterized by exhibiting a transparent state upon irradiation with light having a light intensity of less than the threshold value, and exhibits a scattering state at the time of irradiation of the light having the threshold value or more light intensity The optical element according to any one of claims 1 to 6 . The optical element according to claim 7, wherein the transparent state and the scattering state are reversibly controlled.   A diffusion plate for a liquid crystal display element using the optical element according to claim 1.   A window using the optical element according to claim 1. A first substrate, a second substrate facing the first substrate, an alignment film provided on a surface facing the other substrate of the first and second substrates, and the first substrate; A layer having a photoresponsive composition provided between the second substrate and
The layer having the photoresponsive composition includes a photoresponsive material having a threshold value in response light intensity, a liquid crystal composition, and a polymer of a polymerizable compound; and
A method for producing an optical element capable of reversibly controlling a transmission state and a scattering state of a layer having the photoresponsive composition by light irradiation,
Encapsulating a photoresponsive composition between the first substrate and the second substrate to form a layer having the photoresponsive composition; and
The polymerizable compound comprising a liquid crystalline compound and a non-liquid crystalline compound in a state in which the liquid crystal molecules in the liquid crystal composition are aligned and controlled by the alignment film by irradiating the layer having the photoresponsive composition with light. A method for producing an optical element, comprising the step of polymerizing a polymer.

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