WO2016113931A1 - Liquid crystal alignment agent using non-photoreactive hydrogen-bonding polymer liquid crystal, and liquid crystal alignment film - Google Patents
Liquid crystal alignment agent using non-photoreactive hydrogen-bonding polymer liquid crystal, and liquid crystal alignment film Download PDFInfo
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- WO2016113931A1 WO2016113931A1 PCT/JP2015/070766 JP2015070766W WO2016113931A1 WO 2016113931 A1 WO2016113931 A1 WO 2016113931A1 JP 2015070766 W JP2015070766 W JP 2015070766W WO 2016113931 A1 WO2016113931 A1 WO 2016113931A1
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- JHOMRDSMJKYMIV-FMIVXFBMSA-N CC(C(OCCCCCCOc1ccc(/C=C/C(O)=O)cc1)=O)=C Chemical compound CC(C(OCCCCCCOc1ccc(/C=C/C(O)=O)cc1)=O)=C JHOMRDSMJKYMIV-FMIVXFBMSA-N 0.000 description 1
- HYDAAXXVYRPEKY-UHFFFAOYSA-N c(cc1)ccc1C1=[O]OC(c2ccccc2)=[O]O1 Chemical compound c(cc1)ccc1C1=[O]OC(c2ccccc2)=[O]O1 HYDAAXXVYRPEKY-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
- C08L101/06—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
- C08L101/08—Carboxyl groups
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
- C09K19/54—Additives having no specific mesophase characterised by their chemical composition
- C09K19/56—Aligning agents
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
- G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
Definitions
- the present invention relates to a liquid crystal alignment agent, a liquid crystal alignment film, a liquid crystal display element using the same, and a polymer film suitable for the production of an optical element with controlled molecular alignment such as a retardation film and a polarization diffraction element. .
- the liquid crystal display element is known as a light, thin, and low power consumption display device and has been remarkably developed in recent years.
- the liquid crystal display element is configured, for example, by sandwiching a liquid crystal layer between a pair of transparent substrates provided with electrodes.
- an organic film made of an organic material is used as the liquid crystal alignment film so that the liquid crystal is in a desired wrinkle alignment state between the substrates.
- the liquid crystal alignment film is a component of the liquid crystal display element, and is formed on the surface of the substrate that holds the liquid crystal in contact with the liquid crystal, and plays a role of aligning the liquid crystal in a certain direction between the substrates.
- the liquid crystal alignment film may be required to play a role of controlling the pretilt angle of the liquid crystal in addition to the role of aligning the liquid crystal in a certain direction such as a direction parallel to the substrate.
- alignment control ability is given by performing an alignment treatment on the organic film constituting the liquid crystal alignment film.
- the rubbing method is a method of rubbing (rubbing) the surface of an organic film such as polyvinyl alcohol, polyamide or polyimide on a substrate with a cloth such as cotton, nylon or polyester in the rubbing direction (rubbing direction).
- This is a method of aligning liquid crystals. Since this rubbing method can easily realize a relatively stable alignment state of liquid crystals, it has been used in the manufacturing process of conventional liquid crystal display elements.
- an organic film used for the liquid crystal alignment film a polyimide-based organic film excellent in reliability such as heat resistance and electrical characteristics has been mainly selected.
- Anisotropy is formed in the organic film constituting the liquid crystal alignment film by linearly polarized light or collimated light, and the liquid crystal is aligned according to the anisotropy.
- the main alignment methods are “photolytic type” that causes anisotropic decomposition of the molecular structure by irradiation with polarized UV light, and polyvinyl cinnamate is used to irradiate polarized UV light, and two sides parallel to the polarized light.
- the polymer film obtained by this alignment amplification method exhibits birefringence due to molecular orientation, it can be used as various optical elements such as a retardation film in addition to the use of a liquid crystal alignment film. it can.
- the optimal irradiation dose of polarized ultraviolet rays for introducing highly efficient anisotropy into liquid crystal alignment films used in alignment amplification methods is the irradiation dose of polarized ultraviolet rays that optimizes the amount of photoreactive reaction of photosensitive groups in the coating film.
- the amount of photoreaction will not be sufficient. In that case, sufficient self-organization does not proceed even after heating.
- the photoreactive side-chain photosensitive group becomes excessive, the resulting film may become rigid and hinder the progress of self-assembly by subsequent heating.
- liquid crystal alignment films used in the alignment amplification method have a narrow range of the optimal amount of polarized ultraviolet light irradiation because of the high sensitivity of the photoreactive group in the polymer used. is there. As a result, a decrease in manufacturing efficiency of the liquid crystal display element is a problem.
- the reliability of the liquid crystal display element may be lowered due to the influence of the residual solvent, etc., but the liquid crystal aligning agent obtained by the alignment amplification method is not suitable for polymer liquid crystals. Since baking cannot be performed at a temperature equal to or higher than the liquid crystal expression temperature, the baking temperature is generally low, and the residual solvent contributes to a decrease in reliability.
- an object of the present invention is to provide a liquid crystal alignment film having a wide process margin that can be adjusted to an optimum polarized ultraviolet ray irradiation amount and an optimum baking temperature, with high efficiency and orientation control ability.
- T may be any carbon atom other than Q or X bonded to an oxygen atom, nitrogen atom or sulfur atom, and a hydrogen atom on any carbon atom other than Q or X bonded
- X represents a single bond, an alkylene having 1 to 12 carbon atoms, a disubstituted alkene in which a hydrogen atom on carbon may be substituted with a monovalent organic group, or a disubstituted alkyne
- Y represents a single bond, ether,
- a hydrogen atom on any carbon atom other than T in Formula (1) bonded to Q or X is substituted with a monovalent organic group. It may represent an aromatic ring having any structure of benzene, biphenyl, terphenyl, naphthalene, anthracene, pyrene, pyridine, furan, pyrrole, or thiophene.
- a hydrogen atom on any carbon atom other than T in Formula (1) bonded to Q or X is a monovalent organic group. It may represent an aromatic ring having any structure of benzene, biphenyl, terphenyl, naphthalene, anthracene, or pyrene, which may be substituted.
- the component (A) preferably does not contain a photoreactive group in the structure.
- the component (B) is 0.5% by weight to 70% by weight with respect to the weight of the polymer of the component (A). It should be contained.
- the component (A) is a polymer having a side chain containing a carboxylic acid group structure represented by the following formula (2). Is good.
- A represents a group selected from a single bond, —O—, —COO—, —CONH—, and —NH—
- B represents a group selected from a single bond, —O—, —COO—, —CONH—, —NH—, and —CH ⁇ CH—COO—
- Ar 1 and Ar 2 each independently represent a phenyl group or a naphthyl group, l and m are each independently an integer of 0 to 12.
- the component (B) may be at least one compound selected from the following.
- R represents an alkyl group having 1 to 36 carbon atoms in which any non-adjacent carbon atom may be substituted with an oxygen atom; n represents an integer of 2 to 5, R ′ represents oxygen, sulfur, or a nitrogen atom in which a hydrogen atom on nitrogen may be substituted with a monovalent organic group, and the monovalent organic group in R ′ is optional unless adjacent to each other Represents an alkyl group having 1 to 10 carbon atoms or a phenyl group, in which the carbon atom may be replaced by an oxygen atom].
- a liquid crystal aligning agent comprising the optically active composition according to any one of ⁇ 1> to ⁇ 7>.
- a liquid crystal display device comprising the liquid crystal alignment film according to ⁇ 9>.
- an optically active composition a liquid crystal aligning agent containing the composition, a liquid crystal aligning film obtained from the liquid crystal aligning agent, a substrate having the liquid crystal aligning film, and a horizontal having the substrate
- An electric field drive type liquid crystal display element can be provided.
- a polymer film having a wide process margin polarized ultraviolet ray irradiation amount or baking temperature
- 6 is a graph showing changes in absorbance with respect to an exposure dose at 262 nm when the optically active composition (B2-10) prepared in Example 2 is used. 6 is a graph showing a change in dichroism with respect to an exposure amount at 262 nm when the optically active composition (B2-10) prepared in Example 2 is used. It is a graph showing the change in absorbance with respect to the exposure dose at 262 nm when the optically active composition (B4-10) is used. It is a graph showing the dichroic change with respect to the exposure amount in 262 nm at the time of using an optically active composition (B4-10).
- 6 is a graph showing an in-plane order parameter (S) at each irradiation amount (exposure amount) obtained from Example 11 and Comparative Example 3.
- 6 is a graph showing in-plane orientation degree S before and after non-polarized UV irradiation obtained from Example 12 and Comparative Example 4.
- the optically active composition of the present invention contains the following components (A) and (B), the component (B) contains a photoreactive group, and the components (A) and (B). And form liquid crystalline supramolecules through hydrogen bonds.
- T may be any carbon atom other than Q or X bonded to an oxygen atom, nitrogen atom or sulfur atom, and a hydrogen atom on any carbon atom other than Q or X bonded
- X represents a single bond, an alkylene having 1 to 12 carbon atoms, a disubstituted alkene in which a hydrogen atom on carbon may be substituted with a monovalent organic group, or a disubstituted alkyne
- Y represents a single bond, ether,
- the polymer having a side chain containing a carboxylic acid group structure which is the component (A) in the present invention, is said to exhibit supramolecular liquid crystals due to hydrogen bonds between carboxylic acids.
- the structure of the aromatic ring-carboxylic acid-carboxylic acid-aromatic ring forming a hydrogen bond has a mesogenic structure as shown below. It is considered that the absorption band is almost determined by this mesogen site.
- the aromatic carboxylic acid which is the component (B) of the present invention is present, a carboxylic acid-carboxylic acid hydrogen bond between different kinds of molecules is formed with the component (A), and it consists only of the component (A). Physical properties different from the composition are given. As a result, the temperature range exhibiting liquid crystallinity, the ultraviolet absorption band, and the like change. In the present invention, by freely selecting these combinations, it is possible to adjust the temperature range of the liquid crystal, the sensitivity to ultraviolet rays, and the like in an arbitrary range. Note that these are theories and do not restrict the present invention.
- the component (A) is a polymer having a side chain containing a carboxylic acid group structure. According to one preferable aspect of the present invention, the component (A) does not contain a photoreactive group in the structure. That is, a preferable component (A) contains a carboxylic acid group in one side chain structure and does not contain a photoreactive group in the structure.
- a non-carboxylic acid component may be copolymerized together with a side chain component having a carboxylic acid structure at the terminal, but in order to obtain good anisotropy (uniaxial orientation), a component having a terminal carboxylic acid structure Is preferably contained at least 50 mol% or more.
- A represents a group selected from a single bond, —O—, —COO—, —CONH—, and —NH—, and among them, —O— and —COO— are from the viewpoint of liquid crystallinity. preferable.
- B represents a group selected from a single bond, —O—, —COO—, —CONH—, —NH—, —CH ⁇ CH—COO—, and among them, —O—, —COO— from the viewpoint of liquid crystalline expression. Is preferred.
- Ar 1 and Ar 2 each independently represent a phenyl group or a naphthyl group.
- L and m are each independently an integer of 0 to 12, preferably an integer of 2 to 12. Among them, an integer of 2 to 8 is preferable from the viewpoint of liquid crystalline expression.
- p represents an integer of 0 to 12.
- the polymer of component (A) can be obtained by the polymerization reaction of the monomer containing the specific side chain described above. It can also be obtained by copolymerization of a monomer having a side chain containing a photoreactive group and a monomer having a side chain containing a carboxylic acid group. Furthermore, it can be copolymerized with other monomers as long as the liquid crystallinity is not impaired.
- Examples of other monomers include industrially available monomers capable of radical polymerization reaction.
- monomers include unsaturated carboxylic acid, acrylic ester compound, methacrylic ester compound, maleimide compound, acrylonitrile, maleic anhydride, styrene compound and vinyl compound.
- unsaturated carboxylic acid examples include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid and the like.
- acrylic ester compound examples include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, 2,2,2-trifluoroethyl acrylate, tert-butyl.
- methacrylic acid ester compound examples include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl.
- (Meth) acrylate compounds having a cyclic ether group such as glycidyl (meth) acrylate, (3-methyl-3-oxetanyl) methyl (meth) acrylate, and (3-ethyl-3-oxetanyl) methyl (meth) acrylate are also used. be able to.
- vinyl compound examples include vinyl ether, methyl vinyl ether, benzyl vinyl ether, 2-hydroxyethyl vinyl ether, phenyl vinyl ether, and propyl vinyl ether.
- styrene compound examples include styrene, methyl styrene, chlorostyrene, bromostyrene, and the like.
- maleimide compounds include maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.
- the method for producing the polymer of the component (A) is not particularly limited, and a general-purpose method that is handled industrially can be used. Specifically, it can be produced by cationic polymerization, radical polymerization, or anionic polymerization using a vinyl group of a specific side chain monomer. Among these, radical polymerization is particularly preferable from the viewpoint of ease of reaction control.
- RAFT reversible addition-cleavage chain transfer
- a radical thermal polymerization initiator is a compound that generates radicals when heated to a decomposition temperature or higher.
- radical thermal polymerization initiators include ketone peroxides (methyl ethyl ketone peroxide, cyclohexanone peroxide, etc.), diacyl peroxides (acetyl peroxide, benzoyl peroxide, etc.), hydroperoxides (peroxidation).
- the radical photopolymerization initiator is not particularly limited as long as it is a compound that initiates radical polymerization by light irradiation.
- examples of such radical photopolymerization initiators include benzophenone, Michler's ketone, 4,4′-bis (diethylamino) benzophenone, xanthone, thioxanthone, isopropylxanthone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2-hydroxy -2-methylpropiophenone, 2-hydroxy-2-methyl-4'-isopropylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, isopropyl benzoin ether, isobutyl benzoin ether, 2,2-diethoxyacetophenone, 2,2 -Dimethoxy-2-phenylacetophenone, camphorquinone, benzanthrone, 2-methyl-1- [4- (
- the radical polymerization method is not particularly limited, and an emulsion polymerization method, suspension polymerization method, dispersion polymerization method, precipitation polymerization method, bulk polymerization method, solution polymerization method and the like can be used.
- the organic solvent used for the polymerization reaction is not particularly limited as long as the generated polymer is soluble. Specific examples are given below.
- organic solvents may be used alone or in combination. Furthermore, even if it is a solvent which does not dissolve the polymer
- the polymerization temperature at the time of radical polymerization can be selected from any temperature of 30 ° C. to 150 ° C., but is preferably in the range of 50 ° C. to 100 ° C.
- the reaction can be carried out at any concentration, but if the concentration is too low, it is difficult to obtain a high molecular weight polymer, and if the concentration is too high, the viscosity of the reaction solution becomes too high and uniform stirring is difficult. Therefore, the monomer concentration is preferably 1% by mass to 50% by mass, more preferably 5% by mass to 30% by mass.
- the initial stage of the reaction is carried out at a high concentration, and then an organic solvent can be added.
- the molecular weight of the obtained polymer is decreased when the ratio of the radical polymerization initiator is large relative to the monomer, and the molecular weight of the obtained polymer is increased when the ratio is small, the ratio of the radical initiator is
- the content is preferably 0.1 mol% to 10 mol% with respect to the monomer to be polymerized. Further, various monomer components, solvents, initiators and the like can be added during the polymerization.
- the reaction solution is poured into a poor solvent to precipitate the polymer.
- the poor solvent used for precipitation include methanol, acetone, hexane, heptane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, diethyl ether, methyl ethyl ether, and water.
- the polymer deposited in a poor solvent and precipitated can be recovered by filtration and then dried at normal temperature or under reduced pressure at room temperature or by heating.
- the polymer collected by precipitation is redissolved in an organic solvent and reprecipitation and collection is repeated 2 to 10 times, impurities in the polymer can be reduced.
- the poor solvent at this time include alcohols, ketones, hydrocarbons and the like, and it is preferable to use three or more kinds of poor solvents selected from these because purification efficiency is further improved.
- the molecular weight of the polymer of the component (A) of the present invention was measured by a GPC (Gel Permeation Chromatography) method in consideration of the strength of the obtained coating film, workability during coating film formation, and coating film uniformity.
- the weight average molecular weight is preferably from 2,000 to 1,000,000, more preferably from 5,000 to 100,000.
- the optically active composition of the present invention contains a compound represented by the following formula (1) as the component (B).
- Q represents a single bond, an alkylene having 1 to 12 carbon atoms, a disubstituted alkene in which a hydrogen atom on carbon may be substituted with a monovalent organic group, or a disubstituted alkyne.
- the alkylene having 1 to 12 carbon atoms is preferably alkylene having 2 to 6 carbon atoms, more preferably alkylene having 2 to 4 carbon atoms, and specific examples thereof include ethylene, propylene, butylene and the like. As mentioned.
- the “disubstituted alkene in which the hydrogen atom on carbon may be substituted with a monovalent organic group” in Q means that the hydrogen atom on the carbon of the disubstituted alkene is substituted with a certain monovalent organic group.
- a monovalent organic group include an alkyl group such as a methyl group and an ethyl group, a fluorine atom, and a cyano group, preferably a methyl group or a cyano group. More preferably a cyano group.
- the “disubstituted alkene” refers to a disubstituted alkene having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms, and specific examples include an ethenyl group, a propenyl group, and a butenyl group.
- the “disubstituted alkyne” in Q means a disubstituted alkene having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms, and specific examples thereof include an ethynyl group, a pyropinyl group, a butynyl group, and the like. .
- T is an arbitrary carbon atom other than that bonded to Q or X may be substituted with an oxygen atom, a nitrogen atom or a sulfur atom, and any other than bonded to Q or X
- 5- or 6-membered carbocyclic or heterocyclic ring means a 5- or 6-membered carbocyclic ring or a 5- or 6-membered heterocyclic ring.
- a structure in which 2 to 4 of these rings are bonded or condensed means any 2 to 4 rings that can be selected from 5-membered or 6-membered carbon rings, 5-membered or 6-membered heterocycles Have a structure in which they are directly bonded to the binding site of the substituent, or the aforementioned 2 to 4 rings are condensed to form a 2 to 4 cyclic group structure.
- Any carbon atom other than those bonded to Q or X may be substituted with an oxygen atom, a nitrogen atom or a sulfur atom, or a 5- or 6-membered carbocyclic or heterocyclic ring, or 2 of these rings
- the aromatic ring having a structure in which ⁇ 4 are bonded or condensed include benzene, biphenyl, terphenyl, naphthalene, anthracene, pyrene, pyridine, furan, pyrrole, thiophene, pyrazine, pyrimidine and the like.
- the substitution when an arbitrary carbon atom other than Q or X is substituted with an oxygen atom, a nitrogen atom or a sulfur atom, the substitution is 1 or 2 or more, preferably 1 or 2, more preferably 1 carbon. Can be replaced with an atom.
- the compound of formula (1) excludes compounds containing one or more pyrazine structures, naphthyridine structures, or phenazine structures.
- the compound of formula (1) excludes compounds containing two or more pyridine structures, compounds containing one or more pyrazine structures, naphthyridine structures, and phenazine structures. When substituted with a child, the substitution can be substituted with 1 or 2 carbon atoms, preferably 1 or 2, more preferably 1 carbon atom.
- the compound of formula (1) excludes compounds containing two or more pyridine structures.
- containing two or more pyridine structures here means one containing two pyridine structures (bipyridine) or one containing two or more.
- the pyridine structure is a carboxyl group in both ends of the compound (formula (1)). The one that comes to both ends after the group).
- at least a is 2 and T is pyridine.
- T is a benzene, biphenyl, terphenyl, naphthalene in which a hydrogen atom on any carbon atom other than Q or X may be substituted with a monovalent organic group
- T is a benzene, biphenyl, terphenyl, naphthalene, anthracene, or pyrene in which a hydrogen atom on any carbon atom other than bonded to X may be substituted with a monovalent organic group.
- An aromatic ring having any structure is represented.
- the “monovalent organic group” in which a hydrogen atom on any carbon atom other than that bonded to Q or X may be substituted is preferably an alkyl group such as a methyl group or an ethyl group, Alkoxy groups such as methoxy group and ethoxy group, nitro group, cyano group, dimethylamino group, halogen atoms such as fluorine atom, more preferably methyl group, methoxy group, fluorine, cyano group, nitro group, or dimethylamino More preferably a methyl group, a methoxy group, or a cyano group.
- X represents a single bond, an alkylene having 1 to 12 carbon atoms, a disubstituted alkene in which a hydrogen atom on carbon may be substituted with a monovalent organic group, or a disubstituted alkyne.
- the alkylene having 1 to 12 carbon atoms is preferably alkylene having 2 to 6 carbon atoms, more preferably alkylene having 2 to 4 carbon atoms, and specific examples thereof include ethylene, propylene, butylene and the like. It is done.
- the “disubstituted alkene in which the hydrogen atom on carbon may be substituted with a monovalent organic group” in X means that the hydrogen atom on the carbon of the disubstituted alkene is substituted with a certain monovalent organic group.
- a monovalent organic group include an alkyl group such as a methyl group and an ethyl group, a fluorine atom, and a cyano group, preferably a methyl group or a cyano group. More preferably a cyano group.
- the “disubstituted alkene” refers to a disubstituted alkene having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms, and specific examples include an ethenyl group, a propenyl group, and a butenyl group.
- the “disubstituted alkyne” in X means a disubstituted alkene having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms. Specific examples thereof include an ethynyl group, a pyropinyl group, and a butynyl group. .
- Y represents a single bond, an ether, an azo, a thioether, or an ester, and preferably a single bond (where Q is a hydrogen atom on carbon substituted with a monovalent organic group).
- Q is a hydrogen atom on carbon substituted with a monovalent organic group.
- Z has 1 to 36 carbon atoms in which any hydrogen atom may be substituted with fluorine, and any non-adjacent carbon atom may be substituted with an oxygen atom.
- A represents 1 or 2.
- Z is a hydrogen atom on hydrogen, fluorine, iodine, bromine, chlorine, hydroxyl group, nitro group or nitrogen atom. May be optionally substituted with one or two alkyl groups having 1 to 36 carbon atoms and optionally substituted with an amino group or cyano group, preferably Z is substituted with fluorine, hydroxyl group or cyano group May be.
- At least one of Q and X always includes a disubstituted alkene or a disubstituted alkyne in which a hydrogen atom on carbon may be substituted with a monovalent organic group.
- formula (1) When a is 1, Q is a disubstituted alkene or disubstituted alkyne, in which a hydrogen atom on carbon may be substituted with a monovalent organic group, or Y is azo; -When a is 2, Q is a disubstituted alkene or a disubstituted alkyne, in which a hydrogen atom on carbon may be substituted with a monovalent organic group.
- R represents an alkyl group having 1 to 36 carbon atoms in which any non-adjacent carbon atom may be substituted with an oxygen atom, preferably an alkyl group having 1 to 10 carbon atoms. . n represents an integer of 2 to 5.
- R ′ represents an oxygen atom, a sulfur atom, or a nitrogen atom in which a hydrogen atom on nitrogen may be substituted with a monovalent organic group, and preferably represents an oxygen atom or a nitrogen atom.
- the “monovalent organic group” in R ′ represents an alkyl group having 1 to 10 carbon atoms in which any carbon atom may be replaced with an oxygen atom unless they are adjacent to each other, or a phenyl group. Examples include a methyl group, an ethyl group, a methoxyethyl group, and a phenyl group.
- the component (B) is preferably contained in an amount of 0.5% to 70% by weight, more preferably 5% to 30% by weight, based on the weight of the polymer of the component (A). .
- the optically active composition used in the present invention is preferably prepared as a coating solution so as to be suitable for forming a coating film. That is, it is preferably prepared as a solution in which the component (A), the component (B), and various additives that will be described later are added in an organic solvent.
- the content of the component (A), the component (B) and the various additives added as necessary (hereinafter also referred to as a resin component) is preferably 1% by mass to 20% by mass, More preferably, the content is 3% by mass to 15% by mass, and particularly preferably 3% by mass to 10% by mass.
- Organic solvent used in the optically active composition of the present invention is not particularly limited as long as it is an organic solvent that dissolves the resin component. Specific examples are given below.
- the polymer contained in the optically active composition of the present invention may be a polymer having all of the side chains containing the carboxylic acid group structure described above, but as long as the liquid crystal expression ability and the photosensitive performance are not impaired. Other polymers other than these may be mixed. In that case, the content of the other polymer in the resin component is 0.5 to 80% by mass, preferably 1 to 50% by mass.
- polymers examples include polymers that are made of poly (meth) acrylate, polyamic acid, polyimide, and the like and are not photosensitive side chain polymers that can exhibit liquid crystallinity.
- the optically active composition of the present invention may contain components other than the components (A) and (B). Examples thereof include solvents and compounds that improve the film thickness uniformity and surface smoothness when a solution of the optically active composition is applied, and compounds that improve the adhesion between the coating film and the substrate. However, it is not limited to this.
- solvents that improve film thickness uniformity and surface smoothness include the following.
- solvents may be used alone or in combination.
- it is preferably 5% by mass to 80% by mass with respect to the entire solvent so as not to significantly reduce the solubility of the entire solvent contained in the optically active composition of the present invention. More preferably, it is 20% by mass to 60% by mass.
- Examples of compounds that improve film thickness uniformity and surface smoothness include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants.
- Ftop (registered trademark) 301, EF303, EF352 (manufactured by Tochem Products), MegaFac (registered trademark) F171, F173, R-30 (manufactured by DIC), Florard FC430, FC431 (Manufactured by Sumitomo 3M), Asahi Guard (registered trademark) AG710 (manufactured by Asahi Glass Company), Surflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Seimi Chemical Co., Ltd.) It is done.
- the use ratio of these surfactants is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the resin component contained in the polymer composition. Part by mass.
- Specific examples of the compound for improving the adhesion between the coating film and the substrate include the following functional silane-containing compounds.
- additives such as the following phenoplasts and epoxy group-containing compounds are used for the purpose of preventing deterioration of electrical characteristics due to the backlight when a liquid crystal display element is constructed. May be contained in the optically active composition of the present invention. Specific phenoplast additives are shown below, but are not limited to this structure.
- Specific epoxy group-containing compounds include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N, N, N ′, N ′,-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ′, N ′,-tetraglycidyl- , 4'-diaminodip
- the amount used is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the resin component contained in the optically active composition. More preferably, it is 1 to 20 parts by mass. If the amount used is less than 0.1 parts by mass, the effect of improving the adhesion cannot be expected, and if it exceeds 30 parts by mass, the orientation of the liquid crystal may deteriorate.
- a photosensitizer can also be used as an additive. Colorless and triplet sensitizers are preferred.
- Aromatic 2-hydroxyketones (2-hydroxybenzophenone, mono- or di-p- (dimethylamino) -2-hydroxybenzophenone), acetophenone, anthraquinone, xanthone, thioxanthone, benzanthrone, thiazoline (2-benzoylmethylene-3 -Methyl- ⁇ -naphthothiazoline, 2- ( ⁇ -naphthoylmethylene) -3-methylbenzothiazoline, 2- ( ⁇ -naphthoylmethylene) -3-methylbenzothiazoline, 2- (4-biphenoylmethylene)- 3-methylbenzothia Phosphorus, 2- ( ⁇ -nap
- aromatic 2-hydroxyketone (benzophenone), coumarin, ketocoumarin, carbonyl biscoumarin, acetophenone, anthraquinone, xanthone, thioxanthone, and acetophenone ketal.
- a dielectric or conductive material is used for the purpose of changing the electrical properties such as the dielectric constant and conductivity of the coating film as long as the effects of the present invention are not impaired.
- a crosslinkable compound may be added for the purpose of increasing the hardness and density of the substance and, further, the film when formed into a coating film.
- the coating film obtained by coating and baking the optically active composition described above on a substrate can be used as a liquid crystal alignment film, for example.
- the method for applying the liquid crystal aligning agent containing the optically active composition of the present invention onto a substrate having a conductive film for driving a lateral electric field is not particularly limited.
- the application method is generally industrially performed by screen printing, offset printing, flexographic printing, or an inkjet method.
- Other coating methods include a dipping method, a roll coater method, a slit coater method, a spinner method (rotary coating method), or a spray method, and these may be used depending on the purpose.
- a liquid crystal display device using a liquid crystal aligning agent containing the optically active composition of the present invention is represented by the following steps [I] to [IV]. That is, first, a substrate having a liquid crystal alignment film can be produced by a method including the following [I] to [III].
- Step [I] is a process of applying the liquid crystal aligning agent of the present invention on a substrate having a conductive film.
- the solvent can be evaporated at 50 to 200 ° C., preferably 50 to 150 ° C. by a heating means such as a hot plate, a heat circulation oven or an IR (infrared) oven, and a coating film can be obtained.
- the drying temperature at this time is preferably lower than the liquid crystal phase expression temperature of the side chain polymer. If the thickness of the coating film is too thick, it will be disadvantageous in terms of power consumption of the liquid crystal display element, and if it is too thin, the reliability of the liquid crystal display element may be lowered.
- it is preferably 5 nm to 300 nm, more preferably 10 nm to 150 nm. It is. In addition, it is also possible to provide the process of cooling the board
- step [II] the coating film obtained in step [I] is irradiated with polarized ultraviolet rays.
- the substrate is irradiated with polarized ultraviolet rays through a polarizing plate from a certain direction.
- ultraviolet rays to be used ultraviolet rays having a wavelength in the range of 100 nm to 400 nm can be used.
- the optimum wavelength is selected through a filter or the like depending on the type of coating film to be used.
- ultraviolet light having a wavelength in the range of 290 nm to 400 nm can be selected and used so that the photocrosslinking reaction can be selectively induced.
- the ultraviolet light for example, light emitted from a high-pressure mercury lamp can be used.
- the irradiation amount of polarized ultraviolet rays depends on the coating film used.
- the amount of irradiation is polarized ultraviolet light that realizes the maximum value of ⁇ A (hereinafter also referred to as ⁇ Amax), which is the difference between the ultraviolet light absorbance in a direction parallel to the polarization direction of polarized ultraviolet light and the ultraviolet light absorbance in a direction perpendicular to the polarization direction of the polarized ultraviolet light.
- the amount is preferably in the range of 1% to 70%, more preferably in the range of 1% to 50%.
- step [III] the ultraviolet-irradiated coating film polarized in step [II] is heated.
- An orientation control ability can be imparted to the coating film by heating.
- Heating can be performed using a heating means such as a hot plate, a heat circulation type oven, or an IR (infrared) type oven.
- the heating temperature can be determined in consideration of the temperature at which the liquid crystallinity of the coating film used is developed.
- the heating temperature is preferably within the temperature range of the temperature at which the side chain polymer exhibits liquid crystallinity (hereinafter referred to as liquid crystal expression temperature).
- the liquid crystal expression temperature on the coating film surface is expected to be lower than the liquid crystal expression temperature when a photosensitive side chain polymer that can exhibit liquid crystallinity is observed in bulk.
- the heating temperature is more preferably within the temperature range of the liquid crystal expression temperature on the coating film surface. That is, the temperature range of the heating temperature after irradiation with polarized ultraviolet rays is 10 ° C. lower than the lower limit of the temperature range of the liquid crystal expression temperature of the side chain polymer used, and 10 ° C.
- the temperature of the range which makes an upper limit If the heating temperature is lower than the above temperature range, the anisotropic amplification effect due to heat in the coating film tends to be insufficient, and if the heating temperature is too higher than the above temperature range, the state of the coating film Tends to be close to an isotropic liquid state (isotropic phase), and in this case, self-organization may make it difficult to reorient in one direction.
- the liquid crystal expression temperature is not less than the glass transition temperature (Tg) at which the side chain polymer or coating film surface undergoes a phase transition from the solid phase to the liquid crystal phase, and from the liquid crystal phase to the isotropic phase (isotropic phase). It means a temperature below the isotropic phase transition temperature (Tiso) that causes a phase transition.
- the thickness of the coating film formed after heating is preferably 5 nm to 300 nm, more preferably 50 nm to 150 nm, for the same reason described in the step [I].
- the production method of the present invention can realize highly efficient introduction of anisotropy into the coating film. And a board
- a substrate having a liquid crystal alignment film obtained in [III] is disposed oppositely so that both liquid crystal alignment films face each other through liquid crystal, and a liquid crystal cell is produced by a known method. And a step of manufacturing a liquid crystal display element.
- liquid crystal cell or a liquid crystal display element two sheets of the above-mentioned substrate are prepared, spacers are dispersed on the liquid crystal alignment film of one substrate, and the liquid crystal alignment film surface is on the inside
- Examples include a method in which the other substrate is bonded and liquid crystal is injected under reduced pressure, or a method in which liquid crystal is dropped on the liquid crystal alignment film surface on which spacers are dispersed, and then the substrate is bonded and sealed. can do.
- the diameter of the spacer at this time is preferably 1 ⁇ m to 30 ⁇ m, more preferably 2 ⁇ m to 10 ⁇ m. This spacer diameter determines the distance between the pair of substrates that sandwich the liquid crystal layer, that is, the thickness of the liquid crystal layer.
- a polymer composition is applied on a substrate to form a coated film, and then irradiated with polarized ultraviolet rays. Next, by heating, high-efficiency anisotropy is introduced into the side chain polymer film, and a substrate with a liquid crystal alignment film having a liquid crystal alignment control ability is manufactured.
- the coating film used in the present invention realizes the introduction of highly efficient anisotropy into the coating film by utilizing the principle of molecular reorientation induced by the side chain photoreaction and liquid crystallinity. .
- polarized ultraviolet rays are formed. After irradiation and then heating, a liquid crystal display element is formed.
- the liquid crystal display element provided by the present invention exhibits high reliability against external stresses such as light and heat.
- the lateral electric field drive type liquid crystal display element substrate manufactured by the method of the present invention or the lateral electric field drive type liquid crystal display element having the substrate has excellent reliability, large screen and high definition. It can be suitably used for LCD TVs.
- tetrahydrofuran is 10 ml / L
- Flow rate 1.0 ml / standard curve preparation standard sample: Tosoh TSK standard polyethylene oxide (molecular weight about 9,000,150,000, 100,000, 30,000) and polymer laboratory polyethylene glycol ( Molecular weight about 12,000, 4,000 1,000).
- Example 1 M6BA (15.32 g, 50.0 mmol) was dissolved in THF (141.6 g), deaerated with a diaphragm pump, then AIBN (0.411 g, 2.5 mmol) was added and deaerated again. It was. Thereafter, the mixture was reacted at 60 ° C. for 30 hours to obtain a polymer solution of methacrylate. This polymer solution was added dropwise to diethyl ether (1500 ml), and the resulting precipitate was filtered. This precipitate was washed with diethyl ether and dried under reduced pressure in an oven at 40 ° C. to obtain a methacrylate polymer powder (B). This polymer had a number average molecular weight of 13,000 and a weight average molecular weight of 31,000.
- NMP 29.29 g was added to the obtained methacrylate polymer powder (B) (6.0 g), and the mixture was dissolved by stirring at room temperature for 5 hours. NMP (14.7.5 g) and BC (50.0 g) were added to this solution and stirred for 5 hours to obtain a liquid crystal aligning agent (B1).
- cinnamic acid-based additive 4MCA (5% by mass with respect to the solid content) is added to 10.0 g of the liquid crystal aligning agent (B1), and the mixture is stirred and dissolved at room temperature for 3 hours.
- An aligning agent (B2-5) was prepared.
- liquid crystal aligning agents B2-10 to B6-50 in which the type and amount of cinnamic acid additive were changed were adjusted.
- Example 2 A liquid crystal cell was prepared using the liquid crystal aligning agent (B2-5) obtained in Example 1, and the orientation of the low molecular liquid crystal was confirmed. The conditions for obtaining the optimum orientation were confirmed by varying the irradiation amount of polarized UV in the alignment treatment and the heating temperature after polarized UV irradiation.
- the substrate used was a glass substrate having a size of 30 mm ⁇ 40 mm and a thickness of 0.7 mm, on which comb-like pixel electrodes formed by patterning an ITO film were arranged.
- the pixel electrode has a comb-like shape configured by arranging a plurality of dog-shaped electrode elements whose central portion is bent. The width in the short direction of each electrode element is 10 ⁇ m, and the distance between the electrode elements is 20 ⁇ m. Since the pixel electrode forming each pixel is formed by arranging a plurality of bent-shaped electrode elements in the central portion, the shape of each pixel is not rectangular, but in the central portion like the electrode elements.
- Each pixel has a shape that bends and resembles a bold-faced koji.
- Each pixel is divided into upper and lower portions with a central bent portion as a boundary, and has a first region on the upper side of the bent portion and a second region on the lower side.
- the formation directions of the electrode elements of the pixel electrodes constituting them are different. That is, when the alignment processing direction of the liquid crystal alignment film described later is used as a reference, the electrode element of the pixel electrode is formed to form an angle of + 15 ° (clockwise) in the first region of the pixel, and in the second region of the pixel.
- the electrode elements of the pixel electrode are formed so as to form an angle of ⁇ 15 ° (clockwise). That is, in the first region and the second region of each pixel, the directions of the rotation operation (in-plane switching) of the liquid crystal induced by the voltage application between the pixel electrode and the counter electrode are mutually in the substrate plane. It is comprised so that it may become a reverse direction.
- the liquid crystal aligning agent (A2) obtained in Example 1 was spin-coated on the prepared substrate with electrodes. Subsequently, it dried for 90 second with a 70 degreeC hotplate, and formed the liquid crystal aligning film with a film thickness of 100 nm.
- the coating surface was irradiated with 3 to 13 mJ / cm 2 of 313 nm ultraviolet rays via a polarizing plate and then heated on a hot plate at 140 to 170 ° C. for 10 minutes to obtain a substrate with a liquid crystal alignment film. Further, a coating film was similarly formed on a glass substrate having a columnar spacer having a height of 4 ⁇ m on which no electrode was formed as a counter substrate, and an orientation treatment was performed. A sealant (XN-1500T manufactured by Kyoritsu Chemical Co., Ltd.) was printed on the liquid crystal alignment film of one substrate.
- a liquid crystal cell having a configuration of an IPS (In-Plane Switching) mode liquid crystal display element was prepared by injecting liquid crystal MLC-2041 (manufactured by Merck Co., Ltd.) into the empty cell by a reduced pressure injection method, sealing the injection port. Obtained.
- IPS In-Plane Switching
- the obtained liquid crystal cell was placed between polarizing plates made of crossed Nicols, and the orientation of the liquid crystal was confirmed. Further, an AC voltage of 8 Vpp was applied between the electrodes, and it was confirmed whether or not the liquid crystal in the pixel portion was driven.
- the table below shows the results of the liquid crystal orientation depending on the irradiation amount of polarized UV and the subsequent heating temperature.
- X indicates that alignment failure such as fluid alignment is confirmed after liquid crystal injection
- ⁇ indicates that liquid crystal alignment is confirmed without alignment failure.
- Example 3 A liquid crystal cell was produced using the liquid crystal aligning agent (B2-10) in the same manner as in Example 2, and the orientation of the obtained liquid crystal cell was confirmed. Table 3 below shows the results of the liquid crystal alignment of the liquid crystal cell.
- Example 4 A liquid crystal cell was produced in the same manner as in Example 2 using the liquid crystal aligning agent (B2-30), and the orientation of the obtained liquid crystal cell was confirmed. Table 4 below shows the results of the liquid crystal alignment of the liquid crystal cell.
- Example 5 A liquid crystal cell was produced using the liquid crystal aligning agent (B2-50) in the same manner as in Example 2, and the orientation of the obtained liquid crystal cell was confirmed. Table 5 below shows the results of liquid crystal alignment of the liquid crystal cell.
- Example 6 A liquid crystal cell was produced using the liquid crystal aligning agent (B3-10) in the same manner as in Example 2, and the orientation of the obtained liquid crystal cell was confirmed. Table 6 below shows the results of the liquid crystal alignment of the liquid crystal cell.
- Example 7 A liquid crystal cell was prepared using the liquid crystal aligning agent (B4-10) in the same manner as in Example 2, and the orientation of the obtained liquid crystal cell was confirmed. Table 7 below shows the results of the liquid crystal orientation of the liquid crystal cell.
- Example 8 A liquid crystal cell was produced in the same manner as in Example 3 using the liquid crystal aligning agent (B5-10), and the orientation of the obtained liquid crystal cell was confirmed. Table 8 below shows the results of the liquid crystal alignment of the liquid crystal cell.
- Example 9 A liquid crystal cell was produced using the liquid crystal aligning agent (B6-5) in the same manner as in Example 2, and the orientation of the obtained liquid crystal cell was confirmed. Table 9 below shows the results of the liquid crystal alignment of the liquid crystal cell.
- the heating temperature there is a concern about deterioration of the electrical characteristics of the liquid crystal display element due to the influence of the residual solvent and the like, and thus it is required to perform firing at as high a temperature as possible.
- the ability to arbitrarily select the heating conditions to be obtained leads to a wider range of material selection.
- Example 10 The optically active composition (B2-10) produced in Example 1 was applied to a 1.1 mm quartz substrate by spin coating so as to have a film thickness of 100 nm, and dried on a hot plate at 70 ° C. This coating film was irradiated with 313 nm polarized UV light from 0 J / cm 2 to 30 J / cm 2 , and then subjected to a heat treatment for 10 minutes on a hot plate at 170 ° C. (so-called orientation amplification process by self-organization of polymer liquid crystal). It was. The change in absorbance at 262 nm before and after heating at 170 ° C. (FIG. 1) and dichroism (FIG. 2) were traced with respect to the polarized UV irradiation substrate. The change in absorbance and dichroism ⁇ A were measured by measuring the polarized UV-vis absorption spectrum and calculated by the following formula.
- Dichroism ⁇ A A
- the absorbance is a value of absorbance at 262 nm.
- LPUV represents the result for the polarized UV irradiated substrate before heating at 170 ° C.
- anneal represents the result for the polarized UV irradiated substrate after 170 ° C. heating.
- Exposure energy on the horizontal axis in the figure means the exposure amount.
- UV-3100 manufactured by Shimadzu Corporation was used for measurement of polarized UV-vis absorption spectrum.
- Example 11 The same treatment as in Example 10 was performed on the optically active composition (B2-5, B2-30, B2-50), and in-plane order parameter (in-plane) in each thin film was combined with B-2-10.
- In-plane orientation S (A ⁇ A
- FIG. 5 shows the in-plane orientation degree S at each irradiation dose obtained from Example 11 and Comparative Example 3.
- FIG. 5 since all take positive values, it can be seen that they are oriented in the direction perpendicular to the light irradiation axis. In the figure, the larger the numerical value, the higher the degree of orientation.
- Example 10 From the evaluation of Example 10 and Comparative Example 2, by adding a cinnamic acid-based additive, changes in absorbance and dichroism that are not manifested only by the liquid crystal aligning agent (B1) occur. It was confirmed that the dichroic size can be changed.
- Example 11 and Comparative Example 3 by adding a cinnamic acid-based additive, an in-plane alignment degree that is not manifested only by the liquid crystal aligning agent (B1) can be produced. It has been clarified that the optimum irradiation region for increasing the degree of in-plane orientation can be changed according to the added amount of the agent.
- Example 12 On the coated substrate of the optically active composition (B2-5, B-2-10, B2-30, B2-50) after the In-plane order parameter (degree of in-plane orientation S) measurement used in Example 11 On the other hand, 313 nm non-polarized UV light was irradiated at 1 J / cm 2, and a confirmation experiment was conducted on the light resistance stability of the coating film from the change in the UV absorption spectrum before and after irradiation with 313 nm non-polarized UV light.
- An optically active composition (B7) having the same solid content concentration was obtained using a polymer prepared in the same manner by replacing M6BA in Example 1 with M6CA (number average molecular weight is 11000, weight average molecular weight is 26000).
- a coating film was prepared in the same manner as in Example 10, irradiated with 313 nm polarized UV light at 6 mJ / cm 2 and then heated on a hot plate at 170 ° C. for 10 minutes. A treated substrate was produced.
- this substrate was irradiated with 1 J / cm 2 of 313 nm non-polarized UV light, and the light stability of the coating film was confirmed from the change in the UV absorption spectrum before and after 313 nm non-polarized UV light irradiation. Went.
- Example 12 and Comparative Example 4 The in-plane orientation degree S before and after non-polarized UV irradiation obtained from Example 12 and Comparative Example 4 is shown in FIG.
- “after annealed” represents the result for the polarized UV-irradiated substrate after heat treatment at 170 ° C.
- “after exposed” represents the result for the polarized UV-irradiated substrate after irradiation with 313 nm non-polarized UV light.
- Example 12 and Comparative Example 4 From the evaluation of Example 12 and Comparative Example 4, the orientation-treated coating film (B-2-30: FIG. 6a) produced by the method of the present invention was irradiated before and after irradiation even with non-polarized UV light irradiation of 313 nm. There was no spectral change at all. On the other hand, in the coating film (B7: FIG. 6b) made of pM6CA produced in Comparative Example 4, the anisotropy disappeared after irradiation with non-polarized UV light of 313 nm, and therefore, it was sensitive to light and low in light resistance. Became clear.
Abstract
Description
(A)カルボン酸基構造を含有する側鎖を有する重合体、及び
(B)下記式(1)で表される化合物から選ばれる少なくとも1種の化合物。
[式中、
Qは、単結合、炭素原子数1~12のアルキレン、炭素上の水素原子が一価の有機基で置換されていても良い二置換アルケン、又は、二置換アルキンを表し、
Tは、QもしくはXと結合する以外の任意の炭素原子が酸素原子、窒素原子又は硫黄原子で置換されていても良くて、かつQもしくはXと結合する以外の任意の炭素原子上の水素原子が一価の有機基で置換されていても良い、5もしくは6員の炭素環もしくは複素環、又はそれらの環の2~4つが結合もしくは縮環した構造を有する芳香族環を表し、
Xは、単結合、炭素原子数1~12のアルキレン、炭素上の水素原子が一価の有機基で置換されていても良い二置換アルケン、又は、二置換アルキンを表し、
Yは、単結合、エーテル、アゾ、チオエーテル、又はエステルを表し、
Zは、任意の水素原子がフッ素に置換されていても良く、かつ、任意の隣り合わない炭素原子が酸素原子に置換されていても良い炭素原子数1~36のアルキレン基を表し、
aは1または2を表し、
ただし、XとYが共に単結合で、かつaが1である場合には、Zは水素、フッ素、ヨウ素、臭素、塩素、水酸基、ニトロ基、窒素原子上の水素原子が任意に1または2つの炭素原子数1~36のアルキル基で置換されていても良いアミノ基、又はシアノ基で置換されていても良く、かつ
QもしくはXの少なくとも一方には必ず、炭素上の水素原子が一価の有機基で置換されていても良い二置換アルケン、又は、二置換アルキンが含まれる]。 <1> The following (A) component and (B) component are contained, the (B) component contains a photoreactive group, and the (A) component and the (B) component are bonded to each other via a hydrogen bond. An optically active composition characterized by forming a molecule.
(A) a polymer having a side chain containing a carboxylic acid group structure, and (B) at least one compound selected from compounds represented by the following formula (1).
[Where:
Q represents a single bond, an alkylene having 1 to 12 carbon atoms, a disubstituted alkene in which a hydrogen atom on carbon may be substituted with a monovalent organic group, or a disubstituted alkyne,
T may be any carbon atom other than Q or X bonded to an oxygen atom, nitrogen atom or sulfur atom, and a hydrogen atom on any carbon atom other than Q or X bonded Represents a 5- or 6-membered carbocyclic or heterocyclic ring which may be substituted with a monovalent organic group, or an aromatic ring having a structure in which 2 to 4 of these rings are bonded or condensed,
X represents a single bond, an alkylene having 1 to 12 carbon atoms, a disubstituted alkene in which a hydrogen atom on carbon may be substituted with a monovalent organic group, or a disubstituted alkyne,
Y represents a single bond, ether, azo, thioether, or ester;
Z represents an alkylene group having 1 to 36 carbon atoms in which any hydrogen atom may be substituted with fluorine, and any non-adjacent carbon atom may be substituted with an oxygen atom;
a represents 1 or 2,
However, when X and Y are both a single bond and a is 1, Z is hydrogen, fluorine, iodine, bromine, chlorine, hydroxyl group, nitro group, or a hydrogen atom on the nitrogen atom is optionally 1 or 2 May be substituted with an amino group or a cyano group which may be substituted with one alkyl group having 1 to 36 carbon atoms, and at least one of Q and X must be a monovalent hydrogen atom on carbon. A disubstituted alkene or a disubstituted alkyne optionally substituted with an organic group of
[式(2)中、
Aは、単結合、-O-、-COO-、-CONH-、及び-NH-から選ばれる基を表し、
Bは、単結合、-O-、-COO-、-CONH-、-NH-、及び-CH=CH-COO-から選ばれる基を表し、
Ar1及びAr2はそれぞれ独立にフェニル基またはナフチル基を表し、
l及びmはそれぞれ独立に0~12の整数である]。
[In Formula (2),
A represents a group selected from a single bond, —O—, —COO—, —CONH—, and —NH—,
B represents a group selected from a single bond, —O—, —COO—, —CONH—, —NH—, and —CH═CH—COO—.
Ar 1 and Ar 2 each independently represent a phenyl group or a naphthyl group,
l and m are each independently an integer of 0 to 12.]
[式中、
Rは、任意の隣り合わない炭素原子が酸素原子に置換されていても良い炭素原子数1~36のアルキル基を表し、
nは、2~5の整数を表し、
R’は、酸素、または硫黄、または窒素上の水素原子が一価の有機基に置換されていても良い窒素原子を表し、前記R’中の一価の有機基は、隣り合わなければ任意の炭素原子が酸素原子に置き換えられていても良い炭素原子数1~10のアルキル基、またはフェニル基を表す]。
[Where:
R represents an alkyl group having 1 to 36 carbon atoms in which any non-adjacent carbon atom may be substituted with an oxygen atom;
n represents an integer of 2 to 5,
R ′ represents oxygen, sulfur, or a nitrogen atom in which a hydrogen atom on nitrogen may be substituted with a monovalent organic group, and the monovalent organic group in R ′ is optional unless adjacent to each other Represents an alkyl group having 1 to 10 carbon atoms or a phenyl group, in which the carbon atom may be replaced by an oxygen atom].
<9> 前記<8>に記載の液晶配向剤から得られる、液晶配向膜。
<10> 前記<9>に記載の液晶配向膜を具備する、液晶表示素子。 <8> A liquid crystal aligning agent comprising the optically active composition according to any one of <1> to <7>.
<9> A liquid crystal alignment film obtained from the liquid crystal aligning agent according to <8>.
<10> A liquid crystal display device comprising the liquid crystal alignment film according to <9>.
本発明の光学活性組成物は、前記したように、下記(A)成分及び(B)成分を含有し、(B)成分に光反応性基を含有し、(A)成分と(B)成分とが水素結合を介して、液晶性超分子を形成することを特徴とする。
(A)カルボン酸基構造を含有する側鎖を有する重合体、及び
(B)下記式(1)で表される芳香族化合物から選ばれる少なくとも1種の化合物。 <Optically active composition>
As described above, the optically active composition of the present invention contains the following components (A) and (B), the component (B) contains a photoreactive group, and the components (A) and (B). And form liquid crystalline supramolecules through hydrogen bonds.
(A) a polymer having a side chain containing a carboxylic acid group structure, and (B) at least one compound selected from aromatic compounds represented by the following formula (1).
[式中、
Qは、単結合、炭素原子数1~12のアルキレン、炭素上の水素原子が一価の有機基で置換されていても良い二置換アルケン、又は、二置換アルキンを表し、
Tは、QもしくはXと結合する以外の任意の炭素原子が酸素原子、窒素原子又は硫黄原子で置換されていても良くて、かつQもしくはXと結合する以外の任意の炭素原子上の水素原子が一価の有機基で置換されていても良い、5もしくは6員の炭素環もしくは複素環、又はそれらの環の2~4つが結合もしくは縮環した構造を有する芳香族環を表し、
Xは、単結合、炭素原子数1~12のアルキレン、炭素上の水素原子が一価の有機基で置換されていても良い二置換アルケン、又は、二置換アルキンを表し、
Yは、単結合、エーテル、アゾ、チオエーテル、又はエステルを表し、
Zは、任意の水素原子がフッ素に置換されていても良く、かつ、任意の隣り合わない炭素原子が酸素原子に置換されていても良い炭素原子数1~36のアルキレン基を表し、
aは1または2を表し、
ただし、XとYが共に単結合で、かつaが1である場合には、Zは水素、フッ素、ヨウ素、臭素、塩素、水酸基、ニトロ基、窒素原子上の水素原子が任意に1または2つの炭素原子数1~36のアルキル鎖で置換されていても良いアミノ基、又はシアノ基で置換されていても良く、
QもしくはXの少なくとも一方には必ず、炭素上の水素原子が一価の有機基で置換されていても良い二置換アルケン、又は、二置換アルキンが含まれる]。
[Where:
Q represents a single bond, an alkylene having 1 to 12 carbon atoms, a disubstituted alkene in which a hydrogen atom on carbon may be substituted with a monovalent organic group, or a disubstituted alkyne,
T may be any carbon atom other than Q or X bonded to an oxygen atom, nitrogen atom or sulfur atom, and a hydrogen atom on any carbon atom other than Q or X bonded Represents a 5- or 6-membered carbocyclic or heterocyclic ring which may be substituted with a monovalent organic group, or an aromatic ring having a structure in which 2 to 4 of these rings are bonded or condensed,
X represents a single bond, an alkylene having 1 to 12 carbon atoms, a disubstituted alkene in which a hydrogen atom on carbon may be substituted with a monovalent organic group, or a disubstituted alkyne,
Y represents a single bond, ether, azo, thioether, or ester;
Z represents an alkylene group having 1 to 36 carbon atoms in which any hydrogen atom may be substituted with fluorine, and any non-adjacent carbon atom may be substituted with an oxygen atom;
a represents 1 or 2,
However, when X and Y are both a single bond and a is 1, Z is hydrogen, fluorine, iodine, bromine, chlorine, hydroxyl group, nitro group, or a hydrogen atom on the nitrogen atom is optionally 1 or 2 An amino group which may be substituted with one alkyl chain having 1 to 36 carbon atoms, or a cyano group,
At least one of Q or X always includes a disubstituted alkene or a disubstituted alkyne in which a hydrogen atom on carbon may be substituted with a monovalent organic group.
本発明における(A)成分であるカルボン酸基構造を含有する側鎖を有する重合体はカルボン酸同士の水素結合によって超分子液晶を示すと言われている。このような超分子液晶では水素結合を形成している芳香環-カルボン酸-カルボン酸-芳香環の構造が下記に示すようなメソゲン構造になっており、液晶性を示す温度範囲や、紫外線の吸収帯などはほとんどこのメソゲン部位で決定されると考えられる。 Although it is not certain whether a composition that satisfies the above-described constituents can solve the problems of the present invention, it is generally considered as follows.
The polymer having a side chain containing a carboxylic acid group structure, which is the component (A) in the present invention, is said to exhibit supramolecular liquid crystals due to hydrogen bonds between carboxylic acids. In such a supramolecular liquid crystal, the structure of the aromatic ring-carboxylic acid-carboxylic acid-aromatic ring forming a hydrogen bond has a mesogenic structure as shown below. It is considered that the absorption band is almost determined by this mesogen site.
(A)成分は、カルボン酸基構造を含有する側鎖を有する重合体である。本発明の一つの好ましい態様によれば、前記(A)成分は、構造中に光反応性基を含まないものである。すなわち、好ましい(A)成分は、1つの側鎖構造中にカルボン酸基を含有し、かつ構造中に光反応性基を含有しないものである。 << (A) component >>
The component (A) is a polymer having a side chain containing a carboxylic acid group structure. According to one preferable aspect of the present invention, the component (A) does not contain a photoreactive group in the structure. That is, a preferable component (A) contains a carboxylic acid group in one side chain structure and does not contain a photoreactive group in the structure.
(A)成分の重合体は、上述した特定側鎖を含有するモノマーの重合反応により得ることができる。また、光反応性基を含有する側鎖を有するモノマーと、カルボン酸基を含有する側鎖を有するモノマーとの共重合によっても得ることができる。さらに、液晶性の発現能を損なわない範囲でその他のモノマーと共重合することができる。 << Method for producing polymer >>
The polymer of component (A) can be obtained by the polymerization reaction of the monomer containing the specific side chain described above. It can also be obtained by copolymerization of a monomer having a side chain containing a photoreactive group and a monomer having a side chain containing a carboxylic acid group. Furthermore, it can be copolymerized with other monomers as long as the liquid crystallinity is not impaired.
上述の反応により得られた、重合体の反応溶液から、生成した高分子を回収する場合には、反応溶液を貧溶媒に投入して、それら重合体を沈殿させれば良い。沈殿に用いる貧溶媒としては、メタノール、アセトン、ヘキサン、ヘプタン、ブチルセルソルブ、ヘプタン、メチルエチルケトン、メチルイソブチルケトン、エタノール、トルエン、ベンゼン、ジエチルエーテル、メチルエチルエーテル、水等を挙げることができる。貧溶媒に投入して沈殿させた重合体は、濾過して回収した後、常圧あるいは減圧下で、常温あるいは加熱して乾燥することができる。また、沈殿回収した重合体を、有機溶媒に再溶解させ、再沈殿回収する操作を2回~10回繰り返すと、重合体中の不純物を少なくすることができる。この際の貧溶媒として、例えば、アルコール類、ケトン類、炭化水素等が挙げられ、これらの中から選ばれる3種類以上の貧溶媒を用いると、より一層精製の効率が上がるので好ましい。 [Recovery of polymer]
When the produced polymer is recovered from the polymer reaction solution obtained by the above-described reaction, the reaction solution is poured into a poor solvent to precipitate the polymer. Examples of the poor solvent used for precipitation include methanol, acetone, hexane, heptane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, diethyl ether, methyl ethyl ether, and water. The polymer deposited in a poor solvent and precipitated can be recovered by filtration and then dried at normal temperature or under reduced pressure at room temperature or by heating. In addition, when the polymer collected by precipitation is redissolved in an organic solvent and reprecipitation and collection is repeated 2 to 10 times, impurities in the polymer can be reduced. Examples of the poor solvent at this time include alcohols, ketones, hydrocarbons and the like, and it is preferable to use three or more kinds of poor solvents selected from these because purification efficiency is further improved.
本発明の光学活性組成物は、(B)成分として下記式(1)で表される化合物を含有する。 << B component >>
The optically active composition of the present invention contains a compound represented by the following formula (1) as the component (B).
本発明のさらに一つの好ましい態様によれば、式(1)の化合物は、ピラジン構造、ナフチリジン構造、又はフェナジン構造を1以上含む化合物を除く。本発明の一つのより好 ましい態様によれば、式(1)の化合物は、ピリジン構造を2以上含む化合物、ピラジン構造、ナフチリジン構造、及びフェナジン構造を1以上含む化合物を除く。
子で置換される場合、置換は、1又は2以上、好ましくは1又は2、より好ましくは1の炭素原子と置換されることができる。 Any carbon atom other than those bonded to Q or X may be substituted with an oxygen atom, a nitrogen atom or a sulfur atom, or a 5- or 6-membered carbocyclic or heterocyclic ring, or 2 of these rings Examples of the aromatic ring having a structure in which ˜4 are bonded or condensed include benzene, biphenyl, terphenyl, naphthalene, anthracene, pyrene, pyridine, furan, pyrrole, thiophene, pyrazine, pyrimidine and the like. Here, when an arbitrary carbon atom other than Q or X is substituted with an oxygen atom, a nitrogen atom or a sulfur atom, the substitution is 1 or 2 or more, preferably 1 or 2, more preferably 1 carbon. Can be replaced with an atom.
According to yet another preferred embodiment of the present invention, the compound of formula (1) excludes compounds containing one or more pyrazine structures, naphthyridine structures, or phenazine structures. According to one more preferred embodiment of the present invention, the compound of formula (1) excludes compounds containing two or more pyridine structures, compounds containing one or more pyrazine structures, naphthyridine structures, and phenazine structures.
When substituted with a child, the substitution can be substituted with 1 or 2 carbon atoms, preferably 1 or 2, more preferably 1 carbon atom.
- aが1の場合、Qは、炭素上の水素原子が一価の有機基で置換されていても良い二置換アルケン、又は、二置換アルキンであり、または、Yがアゾであり、
- aが2の場合、Qは、炭素上の水素原子が一価の有機基で置換されていても良い二置換アルケン、又は、二置換アルキンである。 According to one preferred embodiment of the present invention, in formula (1):
When a is 1, Q is a disubstituted alkene or disubstituted alkyne, in which a hydrogen atom on carbon may be substituted with a monovalent organic group, or Y is azo;
-When a is 2, Q is a disubstituted alkene or a disubstituted alkyne, in which a hydrogen atom on carbon may be substituted with a monovalent organic group.
nは、2~5の整数を表す。
R’は、酸素原子、または硫黄原子、または窒素上の水素原子が一価の有機基に置換されていても良い窒素原子を表し、好ましくは、酸素原子、または窒素原子を表す。また前記R’中「一価の有機基」は、隣り合わなければ任意の炭素原子が酸素原子に置き換えられていても良い炭素原子数1~10のアルキル基、またはフェニル基を表し、好ましい具体例としては、メチル基、エチル基、メトキシエチル基、フェニル基なとが挙げられる。 In the above formula, R represents an alkyl group having 1 to 36 carbon atoms in which any non-adjacent carbon atom may be substituted with an oxygen atom, preferably an alkyl group having 1 to 10 carbon atoms. .
n represents an integer of 2 to 5.
R ′ represents an oxygen atom, a sulfur atom, or a nitrogen atom in which a hydrogen atom on nitrogen may be substituted with a monovalent organic group, and preferably represents an oxygen atom or a nitrogen atom. The “monovalent organic group” in R ′ represents an alkyl group having 1 to 10 carbon atoms in which any carbon atom may be replaced with an oxygen atom unless they are adjacent to each other, or a phenyl group. Examples include a methyl group, an ethyl group, a methoxyethyl group, and a phenyl group.
本発明に用いられる光学活性組成物は、塗膜の形成に好適となるように塗布液として調製されることが好ましい。すなわち、(A)成分、(B)成分及び後述する、必要に応じて添加される各種添加剤を有機溶媒に溶解した溶液として調製されることが好ましい。その際、(A)成分、(B)成分及び必要に応じて添加される各種添加剤を合計した成分(以下、樹脂成分とも称する)の含有量は、1質量%~20質量%が好ましく、より好ましくは3質量%~15質量%、特に好ましくは3質量%~10質量%である。 <Preparation of optically active composition>
The optically active composition used in the present invention is preferably prepared as a coating solution so as to be suitable for forming a coating film. That is, it is preferably prepared as a solution in which the component (A), the component (B), and various additives that will be described later are added in an organic solvent. At that time, the content of the component (A), the component (B) and the various additives added as necessary (hereinafter also referred to as a resin component) is preferably 1% by mass to 20% by mass, More preferably, the content is 3% by mass to 15% by mass, and particularly preferably 3% by mass to 10% by mass.
本発明の光学活性組成物に用いる有機溶媒は、樹脂成分を溶解させる有機溶媒であれば特に限定されない。その具体例を以下に挙げる。 <Organic solvent>
The organic solvent used in the optically active composition of the present invention is not particularly limited as long as it is an organic solvent that dissolves the resin component. Specific examples are given below.
-β-ナフトチアゾリン、2-(4-ビフェノイルメチレン)-3-メチル-β-ナフトチアゾリン、2-(p-フルオロベンゾイルメチレン)-3-メチル-β-ナフトチアゾリン)、オキサゾリン(2-ベンゾイルメチレン-3-メチル-β-ナフトオキサゾリン、2-(β-ナフトイルメチレン)-3-メチルベンゾオキサゾリン、2-(α-ナフトイルメチレン)-3-メチルベンゾオキサゾリン、2-(4-ビフェノイルメチレン)-3-メチルベンゾオキサゾリン、2-(β-ナフトイルメチレン)-3-メチル-β-ナフトオキサゾリン、2-(4-ビフェノイルメチレン)-3-メチル-β-ナフトオキサゾリン、2-(p-フルオロベンゾイルメチレン)-3-メチル-β-ナフトオキサゾリン)、ベンゾチアゾール、ニトロアニリン(m-もしくはp-ニトロアニリン、2,4,6-トリニトロアニリン)またはニトロアセナフテン(5-ニトロアセナフテン)、(2-[(m-ヒドロキシ-p-メトキシ)スチリル]ベンゾチアゾール、ベンゾインアルキルエーテル、N-アルキル化フタロン、アセトフェノンケタール(2,2-ジメトキシフェニルエタノン)、ナフタレン、アントラセン(2-ナフタレンメタノール、2-ナフタレンカルボン酸、9-アントラセンメタノール、および9-アントラセンカルボン酸)、ベンゾピラン、アゾインドリジン、メロクマリン等がある。 As photosensitizers, aromatic nitro compounds, coumarins (7-diethylamino-4-methylcoumarin, 7-hydroxy4-methylcoumarin), ketocoumarins, carbonyl biscoumarins, aromatic 2-hydroxyketones, and amino-substituted Aromatic 2-hydroxyketones (2-hydroxybenzophenone, mono- or di-p- (dimethylamino) -2-hydroxybenzophenone), acetophenone, anthraquinone, xanthone, thioxanthone, benzanthrone, thiazoline (2-benzoylmethylene-3 -Methyl-β-naphthothiazoline, 2- (β-naphthoylmethylene) -3-methylbenzothiazoline, 2- (α-naphthoylmethylene) -3-methylbenzothiazoline, 2- (4-biphenoylmethylene)- 3-methylbenzothia Phosphorus, 2- (β-naphthoylmethylene) -3-methyl-β-naphthothiazoline, 2- (4-biphenoylmethylene) -3-methyl-β-naphthothiazoline, 2- (p-fluorobenzoylmethylene)- 3-methyl-β-naphthothiazoline), oxazoline (2-benzoylmethylene-3-methyl-β-naphthoxazoline, 2- (β-naphthoylmethylene) -3-methylbenzoxazoline, 2- (α-naphthoylmethylene) ) -3-methylbenzoxazoline, 2- (4-biphenoylmethylene) -3-methylbenzoxazoline, 2- (β-naphthoylmethylene) -3-methyl-β-naphthoxazoline, 2- (4-biphenoyl) Methylene) -3-methyl-β-naphthoxazoline, 2- (p-fluorobenzoylmethylene) -3-methyl-β- Ftoxazoline), benzothiazole, nitroaniline (m- or p-nitroaniline, 2,4,6-trinitroaniline) or nitroacenaphthene (5-nitroacenaphthene), (2-[(m-hydroxy-p -Methoxy) styryl] benzothiazole, benzoin alkyl ether, N-alkylated phthalone, acetophenone ketal (2,2-dimethoxyphenylethanone), naphthalene, anthracene (2-naphthalenemethanol, 2-naphthalenecarboxylic acid, 9-anthracenemethanol And 9-anthracenecarboxylic acid), benzopyran, azoindolizine, melocoumarin and the like.
本発明の光学活性組成物を含有する液晶配向剤を用いた液晶表示素子の製造は、以下の工程[I]から[IV]で表される。
すなわち、まず、下記[I]~[III]を含む方法によって、液晶配向膜を有する基板を製造することができる。
[I] 本発明の光学活性組成物を含有する液晶配向剤を、導電膜を有する基板上に塗布して塗膜を形成する工程;
[II] [I]で得られた塗膜に偏光した紫外線を照射する工程;及び
[III] [II]で得られた塗膜を加熱する工程;
次いで、得られた、液晶配向膜を有する基板を下記工程[IV]を含む方法によって、液晶表示素子を製造することができる。
[IV] [III]で得られた、液晶配向膜を有する基板を、液晶を介して、双方の液晶配向膜が相対するように対向配置して、液晶表示素子を得る工程である。 << Manufacture of liquid crystal display elements >>
Production of a liquid crystal display device using a liquid crystal aligning agent containing the optically active composition of the present invention is represented by the following steps [I] to [IV].
That is, first, a substrate having a liquid crystal alignment film can be produced by a method including the following [I] to [III].
[I] The process of apply | coating the liquid crystal aligning agent containing the optically active composition of this invention on the board | substrate which has an electrically conductive film, and forming a coating film;
[II] a step of irradiating the coating film obtained in [I] with polarized ultraviolet rays; and [III] a step of heating the coating film obtained in [II];
Subsequently, a liquid crystal display element can be manufactured by the method of including the obtained process [IV] for the board | substrate which has a liquid crystal aligning film.
[IV] In this step, the substrate having the liquid crystal alignment film obtained in [III] is disposed to face each other with the liquid crystal alignment films facing each other through the liquid crystal.
工程[I]は、導電膜を有する基板上に本発明の液晶配向剤を塗布する過程である。塗布した後は、ホットプレート、熱循環型オーブンまたはIR(赤外線)型オーブンなどの加熱手段により50~200℃、好ましくは50~150℃で溶媒を蒸発させて塗膜を得ることができる。このときの乾燥温度は、側鎖型高分子の液晶相発現温度よりも低いことが好ましい。
塗膜の厚みは、厚すぎると液晶表示素子の消費電力の面で不利となり、薄すぎると液晶表示素子の信頼性が低下する場合があるので、好ましくは5nm~300nm、より好ましくは10nm~150nmである。
尚、[I]工程の後、続く[II]工程の前に塗膜の形成された基板を室温にまで冷却する工程を設けることも可能である。 <Process [I]>
Step [I] is a process of applying the liquid crystal aligning agent of the present invention on a substrate having a conductive film. After coating, the solvent can be evaporated at 50 to 200 ° C., preferably 50 to 150 ° C. by a heating means such as a hot plate, a heat circulation oven or an IR (infrared) oven, and a coating film can be obtained. The drying temperature at this time is preferably lower than the liquid crystal phase expression temperature of the side chain polymer.
If the thickness of the coating film is too thick, it will be disadvantageous in terms of power consumption of the liquid crystal display element, and if it is too thin, the reliability of the liquid crystal display element may be lowered. Therefore, it is preferably 5 nm to 300 nm, more preferably 10 nm to 150 nm. It is.
In addition, it is also possible to provide the process of cooling the board | substrate with which the coating film was formed to room temperature after the [I] process and before the following [II] process.
工程[II]では、工程[I]で得られた塗膜に偏光した紫外線を照射する。塗膜の膜面に偏光した紫外線を照射する場合、基板に対して一定の方向から偏光板を介して偏光された紫外線を照射する。使用する紫外線としては、波長100nm~400nmの範囲の紫外線を使用することができる。好ましくは、使用する塗膜の種類によりフィルター等を介して最適な波長を選択する。そして、例えば、選択的に光架橋反応を誘起できるように、波長290nm~400nmの範囲の紫外線を選択して使用することができる。紫外線としては、例えば、高圧水銀灯から放射される光を用いることができる。 <Process [II]>
In step [II], the coating film obtained in step [I] is irradiated with polarized ultraviolet rays. When irradiating the surface of the coating film with polarized ultraviolet rays, the substrate is irradiated with polarized ultraviolet rays through a polarizing plate from a certain direction. As the ultraviolet rays to be used, ultraviolet rays having a wavelength in the range of 100 nm to 400 nm can be used. Preferably, the optimum wavelength is selected through a filter or the like depending on the type of coating film to be used. For example, ultraviolet light having a wavelength in the range of 290 nm to 400 nm can be selected and used so that the photocrosslinking reaction can be selectively induced. As the ultraviolet light, for example, light emitted from a high-pressure mercury lamp can be used.
工程[III]では、工程[II]で偏光した紫外線の照射された塗膜を加熱する。加熱により、塗膜に配向制御能を付与することができる。 <Step [III]>
In step [III], the ultraviolet-irradiated coating film polarized in step [II] is heated. An orientation control ability can be imparted to the coating film by heating.
[IV]工程は、[III]で得られた、液晶配向膜を有する基板を、液晶を介して、双方の液晶配向膜が相対するように対向配置して、公知の方法で液晶セルを作製し、液晶表示素子を作製する工程である。 <Process [IV]>
In the step [IV], a substrate having a liquid crystal alignment film obtained in [III] is disposed oppositely so that both liquid crystal alignment films face each other through liquid crystal, and a liquid crystal cell is produced by a known method. And a step of manufacturing a liquid crystal display element.
(メタクリルモノマー)
M6BA: 4’-((6-(メタクリロイロキシ)ヘキシル)オキシ)-[1,1’-ビフェニル]-4-カルボン酸 Abbreviations used in the examples are as follows.
(Methacrylic monomer)
M6BA: 4 ′-((6- (methacryloyloxy) hexyl) oxy)-[1,1′-biphenyl] -4-carboxylic acid
THF:テトラヒドロフラン
NMP:N-メチル-2-ピロリドン
BC:ブチルセロソルブ (Organic solvent)
THF: Tetrahydrofuran NMP: N-methyl-2-pyrrolidone BC: Butyl cellosolve
AIBN:2,2’-アゾビスイソブチロニトリル (Polymerization initiator)
AIBN: 2,2′-azobisisobutyronitrile
装置:センシュー科学社製 常温ゲル浸透クロマトグラフィー(GPC)装置(SSC―7200)、
カラム:Shodex社製カラム(KD-803、KD-805)
カラム温度:50℃
溶離液:N,N’-ジメチルホルムアミド(添加剤として、臭化リチウム-水和物(Li
Br・H2O)が30mmol/L、リン酸・無水結晶(o-リン酸)が30mmol/
L、テトラヒドロフラン(THF)が10ml/L)
流速:1.0ml/分
検量線作成用標準サンプル:東ソー社製 TSK 標準ポリエチレンオキサイド(分子量
約9000,000、150,000、100,000、30,000)、および、ポリ
マーラボラトリー社製 ポリエチレングリコール(分子量 約12,000、4,000
、1,000)。 Conditions for measuring the molecular weight of the polymer are as follows.
Apparatus: Room temperature gel permeation chromatography (GPC) apparatus (SSC-7200) manufactured by Senshu Scientific Co., Ltd.
Column: Column made by Shodex (KD-803, KD-805)
Column temperature: 50 ° C
Eluent: N, N′-dimethylformamide (as additive, lithium bromide-hydrate (Li
Br.H2O) is 30 mmol / L, phosphoric acid / anhydrous crystal (o-phosphoric acid) is 30 mmol / L.
L, tetrahydrofuran (THF) is 10 ml / L)
Flow rate: 1.0 ml / standard curve preparation standard sample: Tosoh TSK standard polyethylene oxide (molecular weight about 9,000,150,000, 100,000, 30,000) and polymer laboratory polyethylene glycol ( Molecular weight about 12,000, 4,000
1,000).
M6BA(15.32g、50.0mmol)をTHF(141.6g)中に溶解し、ダイアフラムポンプで脱気を行なった後、AIBNを(0.411g、2.5mmol)を加え再び脱気を行なった。この後60℃で30時間反応させメタクリレートのポリマー溶液を得た。このポリマー溶液をジエチルエーテル(1500ml)に滴下し、得られた沈殿物をろ過した。この沈澱物をジエチルエーテルで洗浄し、40℃のオーブン中で減圧乾燥しメタクリレートポリマー粉末(B)を得た。このポリマーの数平均分子量は13000、重量平均分子量は31000であった。 <Example 1>
M6BA (15.32 g, 50.0 mmol) was dissolved in THF (141.6 g), deaerated with a diaphragm pump, then AIBN (0.411 g, 2.5 mmol) was added and deaerated again. It was. Thereafter, the mixture was reacted at 60 ° C. for 30 hours to obtain a polymer solution of methacrylate. This polymer solution was added dropwise to diethyl ether (1500 ml), and the resulting precipitate was filtered. This precipitate was washed with diethyl ether and dried under reduced pressure in an oven at 40 ° C. to obtain a methacrylate polymer powder (B). This polymer had a number average molecular weight of 13,000 and a weight average molecular weight of 31,000.
実施例1で得られた液晶配向剤(B2-5)を用いて液晶セルを作成し、低分子液晶の配向性を確認した。配向処理における偏光UVの照射量、偏光UV照射後の加熱温度の条件を振り、最適な配向性が得られる条件を確認した。 <Example 2>
A liquid crystal cell was prepared using the liquid crystal aligning agent (B2-5) obtained in Example 1, and the orientation of the low molecular liquid crystal was confirmed. The conditions for obtaining the optimum orientation were confirmed by varying the irradiation amount of polarized UV in the alignment treatment and the heating temperature after polarized UV irradiation.
基板は、30mm×40mmの大きさで、厚さが0.7mmのガラス基板であり、ITO膜をパターニングして形成された櫛歯状の画素電極が配置されたものを用いた。画素電極は、中央部分が屈曲したくの字形状の電極要素を複数配列して構成された櫛歯状の形状を有する。各電極要素の短手方向の幅は10μmであり、電極要素間の間隔は20μmである。各画素を形成する画素電極が、中央部分の屈曲したくの字形状の電極要素を複数配列して構成されているため、各画素の形状は長方形状ではなく、電極要素と同様に中央部分で屈曲する、太字のくの字に似た形状を備える。そして、各画素は、その中央の屈曲部分を境にして上下に分割され、屈曲部分の上側の第1領域と下側の第2領域を有する。各画素の第1領域と第2領域とを比較すると、それらを構成する画素電極の電極要素の形成方向が異なるものとなっている。すなわち、後述する液晶配向膜の配向処理方向を基準とした場合、画素の第1領域では画素電極の電極要素が+15°の角度(時計回り)をなすように形成され、画素の第2領域では画素電極の電極要素が-15°の角度(時計回り)をなすように形成されている。すなわち、各画素の第1領域と第2領域とでは、画素電極と対向電極との間の電圧印加によって誘起される液晶の、基板面内での回転動作(インプレーン・スイッチング)の方向が互いに逆方向となるように構成されている。実施例1で得られた液晶配向剤(A2)を、準備された上記電極付き基板にスピンコートした。次いで、70℃のホットプレートで90秒間乾燥し、膜厚100nmの液晶配向膜を形成した。次いで、塗膜面に偏光板を介して313nmの紫外線を3~13mJ/cm2照射した後に140~170℃のホットプレートで10分間加熱し、液晶配向膜付き基板を得た。また、対向基板として電極が形成されていない高さ4μmの柱状スペーサーを有するガラス基板にも、同様に塗膜を形成させ、配向処理を施した。一方の基板の液晶配向膜上にシール剤(協立化学製XN-1500T)を印刷した。次いで、もう一方の基板を、液晶配向膜面が向き合い配向方向が0°になるようにして張り合わせた後、シール剤を熱硬化させて空セルを作製した。この空セルに減圧注入法によって、液晶MLC-2041(メルク株式会社製)を注入し、注入口を封止して、IPS(In-Planes Switching)モード液晶表示素子の構成を備えた液晶セルを得た。 [Production of liquid crystal cell]
The substrate used was a glass substrate having a size of 30 mm × 40 mm and a thickness of 0.7 mm, on which comb-like pixel electrodes formed by patterning an ITO film were arranged. The pixel electrode has a comb-like shape configured by arranging a plurality of dog-shaped electrode elements whose central portion is bent. The width in the short direction of each electrode element is 10 μm, and the distance between the electrode elements is 20 μm. Since the pixel electrode forming each pixel is formed by arranging a plurality of bent-shaped electrode elements in the central portion, the shape of each pixel is not rectangular, but in the central portion like the electrode elements. It has a shape that bends and resembles a bold-faced koji. Each pixel is divided into upper and lower portions with a central bent portion as a boundary, and has a first region on the upper side of the bent portion and a second region on the lower side. When the first region and the second region of each pixel are compared, the formation directions of the electrode elements of the pixel electrodes constituting them are different. That is, when the alignment processing direction of the liquid crystal alignment film described later is used as a reference, the electrode element of the pixel electrode is formed to form an angle of + 15 ° (clockwise) in the first region of the pixel, and in the second region of the pixel. The electrode elements of the pixel electrode are formed so as to form an angle of −15 ° (clockwise). That is, in the first region and the second region of each pixel, the directions of the rotation operation (in-plane switching) of the liquid crystal induced by the voltage application between the pixel electrode and the counter electrode are mutually in the substrate plane. It is comprised so that it may become a reverse direction. The liquid crystal aligning agent (A2) obtained in Example 1 was spin-coated on the prepared substrate with electrodes. Subsequently, it dried for 90 second with a 70 degreeC hotplate, and formed the liquid crystal aligning film with a film thickness of 100 nm. Next, the coating surface was irradiated with 3 to 13 mJ / cm 2 of 313 nm ultraviolet rays via a polarizing plate and then heated on a hot plate at 140 to 170 ° C. for 10 minutes to obtain a substrate with a liquid crystal alignment film. Further, a coating film was similarly formed on a glass substrate having a columnar spacer having a height of 4 μm on which no electrode was formed as a counter substrate, and an orientation treatment was performed. A sealant (XN-1500T manufactured by Kyoritsu Chemical Co., Ltd.) was printed on the liquid crystal alignment film of one substrate. Next, the other substrate was bonded so that the liquid crystal alignment film faces each other and the alignment direction was 0 °, and then the sealing agent was thermally cured to produce an empty cell. A liquid crystal cell having a configuration of an IPS (In-Plane Switching) mode liquid crystal display element was prepared by injecting liquid crystal MLC-2041 (manufactured by Merck Co., Ltd.) into the empty cell by a reduced pressure injection method, sealing the injection port. Obtained.
なお、液晶注入後に流動配向などの配向不良が確認されたものを「×」、配向不良が無く良好な液晶配向性が確認されたものを「○」と表示する。 The table below shows the results of the liquid crystal orientation depending on the irradiation amount of polarized UV and the subsequent heating temperature.
In addition, “X” indicates that alignment failure such as fluid alignment is confirmed after liquid crystal injection, and “◯” indicates that liquid crystal alignment is confirmed without alignment failure.
実施例2と同様な方法で、液晶配向剤(B2-10)を用いて液晶セルを作製し、得られた液晶セルの配向性を確認した。
以下の表3に液晶セルの液晶配向性の結果を示す。 <Example 3>
A liquid crystal cell was produced using the liquid crystal aligning agent (B2-10) in the same manner as in Example 2, and the orientation of the obtained liquid crystal cell was confirmed.
Table 3 below shows the results of the liquid crystal alignment of the liquid crystal cell.
実施例2と同様な方法で、液晶配向剤(B2-30)を用いて液晶セルを作製し、得られた液晶セルの配向性を確認した。
以下の表4に液晶セルの液晶配向性の結果を示す。 <Example 4>
A liquid crystal cell was produced in the same manner as in Example 2 using the liquid crystal aligning agent (B2-30), and the orientation of the obtained liquid crystal cell was confirmed.
Table 4 below shows the results of the liquid crystal alignment of the liquid crystal cell.
実施例2と同様な方法で、液晶配向剤(B2-50)を用いて液晶セルを作製し、得られた液晶セルの配向性を確認した。
以下の表5に液晶セルの液晶配向性の結果を示す。 <Example 5>
A liquid crystal cell was produced using the liquid crystal aligning agent (B2-50) in the same manner as in Example 2, and the orientation of the obtained liquid crystal cell was confirmed.
Table 5 below shows the results of liquid crystal alignment of the liquid crystal cell.
実施例2と同様な方法で、液晶配向剤(B3-10)を用いて液晶セルを作製し、得られた液晶セルの配向性を確認した。
以下の表6に液晶セルの液晶配向性の結果を示す。 <Example 6>
A liquid crystal cell was produced using the liquid crystal aligning agent (B3-10) in the same manner as in Example 2, and the orientation of the obtained liquid crystal cell was confirmed.
Table 6 below shows the results of the liquid crystal alignment of the liquid crystal cell.
実施例2と同様な方法で、液晶配向剤(B4-10)を用いて液晶セルを作製し、得られた液晶セルの配向性を確認した。
以下の表7に液晶セルの液晶配向性の結果を示す。 <Example 7>
A liquid crystal cell was prepared using the liquid crystal aligning agent (B4-10) in the same manner as in Example 2, and the orientation of the obtained liquid crystal cell was confirmed.
Table 7 below shows the results of the liquid crystal orientation of the liquid crystal cell.
実施例3と同様な方法で、液晶配向剤(B5-10)を用いて液晶セルを作製し、得られた液晶セルの配向性を確認した。
以下の表8に液晶セルの液晶配向性の結果を示す。 <Example 8>
A liquid crystal cell was produced in the same manner as in Example 3 using the liquid crystal aligning agent (B5-10), and the orientation of the obtained liquid crystal cell was confirmed.
Table 8 below shows the results of the liquid crystal alignment of the liquid crystal cell.
実施例2と同様な方法で、液晶配向剤(B6-5)を用いて液晶セルを作製し、得られた液晶セルの配向性を確認した。
以下の表9に液晶セルの液晶配向性の結果を示す。 <Example 9>
A liquid crystal cell was produced using the liquid crystal aligning agent (B6-5) in the same manner as in Example 2, and the orientation of the obtained liquid crystal cell was confirmed.
Table 9 below shows the results of the liquid crystal alignment of the liquid crystal cell.
実施例2と同様な方法で、液晶配向剤(B1)を用いて液晶セルを作成し、得られた液晶セルの配向性を確認した。
以下の表10に液晶セルの液晶配向性の結果を示す。 <Comparative Example 1>
In the same manner as in Example 2, a liquid crystal cell was prepared using the liquid crystal aligning agent (B1), and the orientation of the obtained liquid crystal cell was confirmed.
Table 10 below shows the results of the liquid crystal alignment of the liquid crystal cell.
<実施例10>
上記実施例1で作製した光学活性組成物(B2-10)を、1.1mmの石英基板に膜厚100nmとなるようにスピンコート法により塗布し、70℃のホットプレートで乾燥した。
この塗膜に313nmの偏光UVを0J/cm2から30J/cm2まで照射し、その後、170℃のホットプレートで10分加熱処理(高分子液晶の自己組織化による所謂配向増幅処理)を行った。偏光UV照射基板に対して、170℃加熱前後の262nmにおける吸光度変化(図1)、及び二色性(図2)を追跡した。なお吸光度変化、及び二色性△Aの測定は偏光UV-vis吸収スペクトルを測定して以下の式により算出した。 [Evaluation as a polymer film]
<Example 10>
The optically active composition (B2-10) produced in Example 1 was applied to a 1.1 mm quartz substrate by spin coating so as to have a film thickness of 100 nm, and dried on a hot plate at 70 ° C.
This coating film was irradiated with 313 nm polarized UV light from 0 J / cm 2 to 30 J / cm 2 , and then subjected to a heat treatment for 10 minutes on a hot plate at 170 ° C. (so-called orientation amplification process by self-organization of polymer liquid crystal). It was. The change in absorbance at 262 nm before and after heating at 170 ° C. (FIG. 1) and dichroism (FIG. 2) were traced with respect to the polarized UV irradiation substrate. The change in absorbance and dichroism ΔA were measured by measuring the polarized UV-vis absorption spectrum and calculated by the following formula.
(A||は照射した偏光UVに対して平行方向の吸光度、A⊥は照射した偏光UVに対して⊥方向の吸光度を表す。吸光度は262nmにおける吸光度の値である。) Dichroism ΔA = A || -A⊥
(A || represents the absorbance in the direction parallel to the irradiated polarized UV, and A⊥ represents the absorbance in the tilted direction with respect to the irradiated polarized UV. The absorbance is a value of absorbance at 262 nm.)
また図2及び図4において、二色性(ΔA)が負の値ということは、照射軸に対して垂直方向(面内)に異方性が存在することを意味する。 From FIG. 1 and FIG. 3, there is almost no change after polarized UV irradiation. However, after heating (annealing), the vertical component increased and the parallel component decreased, so the absorption component in the parallel direction was reoriented. It was found that they were rearranged in the direction perpendicular to the light irradiation axis.
In FIGS. 2 and 4, the negative value of dichroism (ΔA) means that anisotropy exists in the direction perpendicular to the irradiation axis (in-plane).
実施例10と同様の方法で、液晶配向剤(B1)の二色性も算出したが、いずれの照射領域においても顕著な二色性の発現は認められなかった。 <Comparative example 2>
The dichroism of the liquid crystal aligning agent (B1) was also calculated in the same manner as in Example 10, but no significant dichroism was observed in any irradiation region.
実施例10と同様の処理を光学活性組成物(B2-5、B2-30、B2-50)に対しても行い、B-2-10と合わせて各薄膜におけるIn-plane order parameter (面内配向度S)を追跡した。なお面内配向度Sの測定は偏光UV-vis吸収スペクトルを測定して以下の式により算出した。
面内配向度 S=(A⊥-A||)/(A⊥+2A||)
(ここで、A⊥は熱処理後の薄膜の吸光度測定における偏光UV照射軸に対して垂直成分の吸光度、A||は平行成分の吸光度を表す)。
なお、A⊥及びA||はいずれも314nmにおける吸光度の値を使用した。 <Example 11>
The same treatment as in Example 10 was performed on the optically active composition (B2-5, B2-30, B2-50), and in-plane order parameter (in-plane) in each thin film was combined with B-2-10. The degree of orientation S) was followed. The in-plane orientation degree S was measured by measuring a polarized UV-vis absorption spectrum and calculated by the following equation.
In-plane orientation S = (A⊥−A ||) / (A⊥ + 2A ||)
(Here, A⊥ represents the absorbance of the component perpendicular to the polarized UV irradiation axis in the absorbance measurement of the thin film after the heat treatment, and A || represents the absorbance of the parallel component).
For A 吸 光 and A ||, the absorbance value at 314 nm was used.
同様の方法で液晶配向剤(B1)を用いた場合の面内配向度Sも算出した。 <Comparative Example 3>
The degree of in-plane orientation S when the liquid crystal aligning agent (B1) was used was also calculated by the same method.
図5では、いずれも正の値をとっていることから、光照射軸に対して垂直方向に配向していることがわかる。なお図では数値が大きいほど、配向度が高いことを意味する。 FIG. 5 shows the in-plane orientation degree S at each irradiation dose obtained from Example 11 and Comparative Example 3.
In FIG. 5, since all take positive values, it can be seen that they are oriented in the direction perpendicular to the light irradiation axis. In the figure, the larger the numerical value, the higher the degree of orientation.
実施例11で用いたIn-plane order parameter (面内配向度S)測定後の光学活性組成物(B2-5、B-2-10、B2-30、B2-50)の塗膜付基板に対して、313nmの非偏光UV光を1J/cm2照射し、313nmの非偏光UV光照射前後のUV吸収スペクトル変化から塗膜の耐光安定性について確認実験を行った。 <Example 12>
On the coated substrate of the optically active composition (B2-5, B-2-10, B2-30, B2-50) after the In-plane order parameter (degree of in-plane orientation S) measurement used in Example 11 On the other hand, 313 nm non-polarized UV light was irradiated at 1 J / cm 2, and a confirmation experiment was conducted on the light resistance stability of the coating film from the change in the UV absorption spectrum before and after irradiation with 313 nm non-polarized UV light.
使用したM6CA((E)-3-(4-((6-(メタクリロイロキシ)ヘキシル)オキシ)フェニル)アクリル酸)の構造式を下記に示す。 <Comparative example 4>
The structural formula of M6CA ((E) -3- (4-((6- (methacryloyloxy) hexyl) oxy) phenyl) acrylic acid) used is shown below.
この光学活性組成物(B-7)を用いて実施例10と同様の方法で塗膜を作製し、313nmの偏光UVを6mJ/cm2照射し、その後、170℃のホットプレートで10分加熱処理した基板を作製した。この基板に対しても実施例12と同様に、313nmの非偏光UV光を1J/cm2照射し、313nmの非偏光UV光照射前後のUV吸収スペクトル変化から塗膜の耐光安定性について確認実験を行った。 An optically active composition (B7) having the same solid content concentration was obtained using a polymer prepared in the same manner by replacing M6BA in Example 1 with M6CA (number average molecular weight is 11000, weight average molecular weight is 26000).
Using this optically active composition (B-7), a coating film was prepared in the same manner as in Example 10, irradiated with 313 nm polarized UV light at 6 mJ / cm 2 and then heated on a hot plate at 170 ° C. for 10 minutes. A treated substrate was produced. Similarly to Example 12, this substrate was irradiated with 1 J / cm 2 of 313 nm non-polarized UV light, and the light stability of the coating film was confirmed from the change in the UV absorption spectrum before and after 313 nm non-polarized UV light irradiation. Went.
なお、図中、「after annealed」は、170℃加熱処理後の偏光UV照射基板についての結果を表し、「after exposed」は、313nmの非偏光UV光照射後の偏光UV照射基板についての結果を表す。 The in-plane orientation degree S before and after non-polarized UV irradiation obtained from Example 12 and Comparative Example 4 is shown in FIG.
In the figure, “after annealed” represents the result for the polarized UV-irradiated substrate after heat treatment at 170 ° C., and “after exposed” represents the result for the polarized UV-irradiated substrate after irradiation with 313 nm non-polarized UV light. To express.
一方、比較例4で作製したpM6CAからなる塗膜(B7:図6b)では、313nmの非偏光UV光照射後に異方性が消失したことから、光に対して感受性があり耐光性が低いことが明らかとなった。 From the evaluation of Example 12 and Comparative Example 4, the orientation-treated coating film (B-2-30: FIG. 6a) produced by the method of the present invention was irradiated before and after irradiation even with non-polarized UV light irradiation of 313 nm. There was no spectral change at all.
On the other hand, in the coating film (B7: FIG. 6b) made of pM6CA produced in Comparative Example 4, the anisotropy disappeared after irradiation with non-polarized UV light of 313 nm, and therefore, it was sensitive to light and low in light resistance. Became clear.
In addition, in other coating films (B2-5, B-2-10, B2-50) with different amounts of 4MCA added, even when 313 nm non-polarized UV light was irradiated, the spectrum was completely changed before and after irradiation. Not confirmed.
Claims (10)
- 下記(A)成分及び(B)成分を含有し、(B)成分に光反応性基を含有し、(A)成分と(B)成分とが水素結合を介して、液晶性超分子を形成することを特徴とする光学活性組成物。
(A)カルボン酸基構造を含有する側鎖を有する重合体、及び
(B)下記式(1)で表される化合物から選ばれる少なくとも1種の化合物。
[式中、
Qは、単結合、炭素原子数1~12のアルキレン、炭素上の水素原子が一価の有機基で置換されていても良い二置換アルケン、又は、二置換アルキンを表し、
Tは、QもしくはXと結合する以外の任意の炭素原子が酸素原子、窒素原子又は硫黄原子で置換されていても良くて、かつQもしくはXと結合する以外の任意の炭素原子上の水素原子が一価の有機基で置換されていても良い、5もしくは6員の炭素環もしくは複素環又はそれらの環の2~4つが結合もしくは縮環した構造を有する芳香族環を表し、
Xは、単結合、炭素原子数1~12のアルキレン、炭素上の水素原子が一価の有機基で置換されていても良い二置換アルケン、又は、二置換アルキンを表し、
Yは、単結合、エーテル、アゾ、チオエーテル、又はエステルを表し、
Zは、任意の水素原子がフッ素に置換されていても良く、かつ、任意の隣り合わない炭素原子が酸素原子に置換されていても良い炭素原子数1~36のアルキレン基を表し、
aは1または2を表し、
ただし、XとYが共に単結合で、かつaが1である場合には、Zは水素、フッ素、ヨウ素、臭素、塩素、水酸基、ニトロ基、窒素原子上の水素原子が任意に1または2つの炭素原子数1~36のアルキル基で置換されていても良いアミノ基、又はシアノ基で置換されていても良く、かつ
QもしくはXの少なくとも一方には必ず、炭素上の水素原子が一価の有機基で置換されていても良い二置換アルケン、又は、二置換アルキンが含まれる]。 The following (A) component and (B) component are contained, the (B) component contains a photoreactive group, and the (A) component and the (B) component form liquid crystalline supramolecules through hydrogen bonds. An optically active composition characterized by comprising:
(A) a polymer having a side chain containing a carboxylic acid group structure, and (B) at least one compound selected from compounds represented by the following formula (1).
[Where:
Q represents a single bond, an alkylene having 1 to 12 carbon atoms, a disubstituted alkene in which a hydrogen atom on carbon may be substituted with a monovalent organic group, or a disubstituted alkyne,
T may be any carbon atom other than Q or X bonded to an oxygen atom, nitrogen atom or sulfur atom, and a hydrogen atom on any carbon atom other than Q or X bonded Represents a 5- or 6-membered carbocyclic or heterocyclic ring which may be substituted with a monovalent organic group, or an aromatic ring having a structure in which 2 to 4 of these rings are bonded or condensed,
X represents a single bond, an alkylene having 1 to 12 carbon atoms, a disubstituted alkene in which a hydrogen atom on carbon may be substituted with a monovalent organic group, or a disubstituted alkyne,
Y represents a single bond, ether, azo, thioether, or ester;
Z represents an alkylene group having 1 to 36 carbon atoms in which any hydrogen atom may be substituted with fluorine, and any non-adjacent carbon atom may be substituted with an oxygen atom;
a represents 1 or 2,
However, when X and Y are both a single bond and a is 1, Z is hydrogen, fluorine, iodine, bromine, chlorine, hydroxyl group, nitro group, or a hydrogen atom on the nitrogen atom is optionally 1 or 2 May be substituted with an amino group or a cyano group which may be substituted with one alkyl group having 1 to 36 carbon atoms, and at least one of Q and X must be a monovalent hydrogen atom on carbon. A disubstituted alkene or a disubstituted alkyne optionally substituted with an organic group of - 式(1)中のTが、QもしくはXと結合する以外の任意の炭素原子上の水素原子が一価の有機基で置換されていても良い、ベンゼン、ビフェニル、ターフェニル、ナフタレン、アントラセン、ピレン、ピリジン、フラン、ピロール、又はチオフェンのいずれかの構造を有する芳香族環を表す、請求項1に記載の光学活性組成物。 Benzene, biphenyl, terphenyl, naphthalene, anthracene, in which hydrogen in any carbon atom other than T in formula (1) is bonded to Q or X may be substituted with a monovalent organic group, The optically active composition according to claim 1, which represents an aromatic ring having a structure of any one of pyrene, pyridine, furan, pyrrole, or thiophene.
- 式(1)中のTが、QもしくはXと結合する以外の任意の炭素原子上の水素原子が一価の有機基で置換されていても良い、ベンゼン、ビフェニル、ターフェニル、ナフタレン、アントラセン、又はピレンのいずれかの構造を有する芳香族環を表す、請求項1又は2に記載の光学活性組成物。 Benzene, biphenyl, terphenyl, naphthalene, anthracene, in which hydrogen in any carbon atom other than T in formula (1) is bonded to Q or X may be substituted with a monovalent organic group, Or the optically active composition of Claim 1 or 2 showing the aromatic ring which has a structure of either pyrene.
- 前記(A)成分が、構造中に光反応性基を含まないものである、請求項1~3のいずれか一項に記載の光学活性組成物。 The optically active composition according to any one of claims 1 to 3, wherein the component (A) does not contain a photoreactive group in the structure.
- 前記(B)成分が、前記(A)成分の重合体の重量に対して0.5重量%~70重量%含有される、請求項1~4のいずれか一項に記載の光学活性組成物。 The optically active composition according to any one of claims 1 to 4, wherein the component (B) is contained in an amount of 0.5 wt% to 70 wt% based on the weight of the polymer of the component (A). .
- 前記(A)成分が、下記式(2)のカルボン酸基構造を含有する側鎖を有する重合体である、請求項1~5のいずれか一項に記載の光学活性組成物。
[式(2)中、
Aは、単結合、-O-、-COO-、-CONH-、及び-NH-から選ばれる基を表し、
Bは、単結合、-O-、-COO-、-CONH-、-NH-、及び-CH=CH-COO-から選ばれる基を表し、
Ar1及びAr2はそれぞれ独立に、フェニル基またはナフチル基を表し、
l及びmはそれぞれ独立に、0~12の整数である]。 The optically active composition according to any one of claims 1 to 5, wherein the component (A) is a polymer having a side chain containing a carboxylic acid group structure represented by the following formula (2).
[In Formula (2),
A represents a group selected from a single bond, —O—, —COO—, —CONH—, and —NH—,
B represents a group selected from a single bond, —O—, —COO—, —CONH—, —NH—, and —CH═CH—COO—.
Ar 1 and Ar 2 each independently represent a phenyl group or a naphthyl group,
l and m are each independently an integer of 0 to 12.] - 前記(B)成分が、下記から選ばれる少なくとも1種の化合物である、請求項1~6のいずれか一項に記載の光学活性組成物。
[式中、
Rは、任意の隣り合わない炭素原子が酸素原子に置換されていても良い炭素原子数1~36のアルキル基を表し、
nは、2~5の整数を表し、
R’は、酸素原子、硫黄原子、または窒素上の水素原子が一価の有機基に置換されていても良い窒素原子を表し、前記R’中の一価の有機基は、隣り合わなければ任意の炭素原子が酸素原子に置き換えられていても良い炭素原子数1~10のアルキル基、またはフェニル基を表す]。 The optically active composition according to any one of claims 1 to 6, wherein the component (B) is at least one compound selected from the following.
[Where:
R represents an alkyl group having 1 to 36 carbon atoms in which any non-adjacent carbon atom may be substituted with an oxygen atom;
n represents an integer of 2 to 5,
R ′ represents an oxygen atom, a sulfur atom, or a nitrogen atom in which a hydrogen atom on nitrogen may be substituted with a monovalent organic group, and the monovalent organic group in R ′ must be adjacent to each other. An arbitrary carbon atom is an alkyl group having 1 to 10 carbon atoms in which an oxygen atom may be substituted, or a phenyl group]. - 請求項1~7のいずれか一項に記載の光学活性組成物を含有する、液晶配向剤。 A liquid crystal aligning agent comprising the optically active composition according to any one of claims 1 to 7.
- 請求項8に記載の液晶配向剤から得られる、液晶配向膜。 A liquid crystal alignment film obtained from the liquid crystal alignment agent according to claim 8.
- 請求項9に記載の液晶配向膜を具備する、液晶表示素子。
A liquid crystal display device comprising the liquid crystal alignment film according to claim 9.
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WO2022176555A1 (en) * | 2021-02-19 | 2022-08-25 | 株式会社フジクラ | Optical diffractive element, optical computing device, and method for producing optical diffractive element |
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