Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B5/00—Optical elements other than lenses
  • G02B5/30—Polarising elements

Definitions

• the present invention relates to compounds, liquid crystal compositions, and liquid crystal films.
• the liquid crystal layer formed by using a liquid crystal compound is used for an optical film used in the display field.
• a method for forming a liquid crystal layer a method using a photo-alignment layer containing a photo-alignment component is known (Reference 1). Specifically, there is known a method of forming a liquid crystal layer by forming a photo-alignment layer having an orientation-regulating force and then applying a liquid crystal layer-forming composition on the photo-alignment layer.
• the present inventors applied a liquid crystal composition containing a photoalignment compound and a liquid crystal compound described in Patent Document 1 on a substrate, and attempted to form a liquid crystal layer in a single coating operation. It was found that the orientation of the compound was not sufficient and there was room for improvement.
• the compound according to (1) which comprises a repeating unit A having a photo-oriented group and a repeating unit B having at least one of the groups represented by the formulas (A) to (D).
• the repeating unit B includes the repeating unit represented by the formula (1) or the repeating unit represented by the formula (2), the content of the repeating unit B is the total amount of the repeating unit A and the repeating unit B.
• the repeating unit B includes the repeating unit represented by the formula (3)
• the content of the repeating unit B is 15 to 40% by mass with respect to the total amount of the repeating unit A and the repeating unit B.
• the repeating unit B includes the repeating unit represented by the formula (4)
• the content of the repeating unit B is 40 to 80% by mass with respect to the total amount of the repeating unit A and the repeating unit B (3).
• a liquid crystal composition containing the compound according to any one of (1) to (5) and a liquid crystal compound.
• (7) A liquid crystal film formed by using the liquid crystal composition according to (6).
• a compound capable of forming a liquid crystal layer having excellent orientation of the liquid crystal compound when the liquid crystal layer is formed in combination with the liquid crystal compound it is also possible to provide a compound capable of forming a liquid crystal layer having excellent orientation of the liquid crystal compound when the liquid crystal layer is formed in combination with the liquid crystal compound. Further, according to the present invention, a liquid crystal composition and a liquid crystal film can also be provided.
• Re ( ⁇ ) and Rth ( ⁇ ) represent in-plane retardation and thickness direction retardation at wavelength ⁇ , respectively. Unless otherwise specified, the wavelength ⁇ is 550 nm.
• Re ( ⁇ ) and Rth ( ⁇ ) are values measured at a wavelength ⁇ in AxoScan and Axometrics.
• Slow phase axial direction (°) Re ( ⁇ ) R0 ( ⁇ )
• Rth ( ⁇ ) ((nx + ny) /2-nz) ⁇ d Is calculated.
• R0 ( ⁇ ) is displayed as a numerical value calculated by AxoScan, it means Re ( ⁇ ).
• cellulose acylate (1.48), cycloolefin polymer (1.52), polycarbonate (1.59), polymethylmethacrylate (1.49), And polystyrene (1.59).
• light means active light or radiation, for example, the emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV light: Extreme Ultraviolet), X-rays, ultraviolet rays, and the like. And, it means an electron beam (EB: Electron Beam) and the like. Of these, ultraviolet rays are preferable.
• the bonding direction of the divalent group (for example, -O-CO-) described in the present specification is not particularly limited, and for example, L 2 is-in the bonding of "L 1- L 2- L 3".
• L 2 is * 1-O-CO- * 2. It may be * 1-CO-O- * 2.
• a feature of the compound of the present invention is that it has at least one group represented by the formulas (A) to (D) described later.
• the groups represented by the formulas (A) to (D) easily interact with the base material and make it easy for the compound to be unevenly distributed on the base material side.
• the groups represented by the formulas (A) to (D) are also collectively referred to as an interacting group. Therefore, when a coating film is formed on a base material using a liquid crystal composition containing a specific compound and a liquid crystal compound, the specific compounds in the coating film tend to be unevenly distributed on the base material side.
• the compound of the present invention has a photo-oriented group and at least one of the groups represented by the formulas (A) to (D).
• the compound may be a polymer.
• the polymer may have a photooriented group and at least one of the groups represented by the formulas (A) to (D) in the same repeating unit or in different repeating units. May have in. That is, the polymer may contain a repeating unit having a photo-oriented group and at least one of the groups represented by the formulas (A) to (D), or the repeating unit having a photo-oriented group and the formula ( It may contain two kinds of repeating units with a repeating unit having at least one of the groups represented by A) to (D).
• the specific compound will be described in detail.
• a photo-oriented group is a group having a photo-alignment function in which rearrangement or an heterogeneous chemical reaction is induced by irradiation with anisotropic light (for example, planar polarization), and the uniformity of orientation.
• anisotropic light for example, planar polarization
• a photo-oriented group that produces at least one of dimerization and isomerization by the action of light is preferable because it is excellent in heat stability or chemical stability.
• Examples of photo-oriented groups that dimerize by the action of light include cinnamic acid derivatives (M. Schadt et al., J. Appl. Phys., Vol. 31, No. 7, page 2155 (1992)) and coumarins.
• Derivatives M. Schadt et al., Nature., Vol. 381, page 212 (1996)
• coumarin derivatives Toshihiro Ogawa et al. (YK Jang et al., SID Int. Symposium Digest, P-53 (1997)
• examples of photo-oriented groups that are isomerized by the action of light include azobenzene compounds (K.
• the photooriented group is preferably selected from the group consisting of a cinnamoyl group, an azobenzene group, a chalconyl group, and a coumarin group.
• the specific compound is preferably a polymer in that a liquid crystal layer having an excellent orientation of the liquid crystal compound can be obtained (hereinafter, also simply referred to as "a point where the effect of the present invention is more excellent").
• the specific compound preferably contains a repeating unit A having a photo-oriented group.
• the structure of the main chain of the repeating unit A is not particularly limited, and known structures can be mentioned, including (meth) acrylic type, styrene type, siloxane type, cycloolefin type, methylpentene type, amide type, and aromatic ester type.
• a skeleton selected from the group consisting of is preferred.
• a skeleton selected from the group consisting of (meth) acrylic-based, siloxane-based, and cycloolefin-based skeletons is more preferable, and (meth) acrylic-based skeletons are even more preferable.
• the repeating unit A the repeating unit represented by the formula (W) is preferable.
• RW1 represents a hydrogen atom or a methyl group.
• L W represents a single bond or a divalent linking group. Preferred embodiments of the divalent linking group are the same as preferred embodiment of the divalent linking group represented by L 1 to be described later.
• RW2 , RW3 , RW4 , RW5 and RW6 each independently represent a hydrogen atom or substituent. Of R W2, R W3, R W4 , R W5 and R W6, may form a ring by bonding two groups adjacent.
• the type of the above-mentioned substituent is not particularly limited, and examples thereof include the groups exemplified by the substituents that the groups represented by Ra and R b described later may have. Of these, an alkoxy group having 1 to 20 carbon atoms is preferable.
• the content of the repeating unit A in the specific compound is not particularly limited, but is preferably 15 to 98% by mass, preferably 30 to 95% by mass, based on all the repeating units in the specific compound, in that the effect of the present invention is more excellent. Is more preferable.
• the specific compound has at least one of the groups represented by the formulas (A) to (D). As described above, these groups easily interact with the base material and make it easy for the specific compound to be unevenly distributed on the base material side.
• * represents the bond position.
• X + represents an organic cation group.
• the organic cation group is an organic group having a positive charge.
• the organic cation group is not particularly limited, and examples thereof include a quaternary ammonium group and a pyridinium group. Of these, a quaternary ammonium group is preferable.
• Y - represents an anion. The type of anion is not particularly limited, and known anions can be mentioned.
• halogen ions F -, Cl -, Br -, I -
• inorganic anions such as SO 4 2-, CH 3 OSO 3 -, C 2 H 5 OSO 3 -
• halogen ions halogen anions
• halogen anions are preferable because the effects of the present invention are more excellent.
• D - represents an anion group.
• An anionic group is a group having a negative charge.
• Anionic group is not particularly limited, -COO -, and, -SO 3 - and the like.
• E + represents an organic cation.
• the organic cation is not particularly limited, and examples thereof include an organic ammonium cation, an organic sulfonium cation, an organic iodonium cation, and an organic phosphonium cation. Of these, organic ammonium cations are preferable.
• the organic ammonium cation is a cation represented by N + (R) 4.
• R represents an alkyl group which may independently have a hydrogen atom or a substituent.
• the number of carbon atoms of the alkyl group is not particularly limited, but is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 5.
• the alkyl group may be linear, branched or cyclic, or may have a structure in which these are combined.
• R a and R b are independently hydrogen atoms, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a hetero which may have a substituent. Representing an aryl group, either Ra or R b is a hydrogen atom.
• the number of carbon atoms of the alkyl group is not particularly limited, and is preferably 1 to 10, and more preferably 1 to 5.
• the alkyl group may be linear, branched or cyclic, or may have a structure in which these are combined.
• the aryl group may have a monocyclic structure or a polycyclic structure.
• the hetero atom contained in the heteroaryl group is not particularly limited, and examples thereof include a nitrogen atom, an oxygen atom, and a sulfur atom.
• the type of substituent that the group represented by Ra and R b (alkyl group, aryl group, heteroaryl group) may have is not particularly limited, and known substituents can be mentioned.
• substituents include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an amino group, an alkoxy group, an aryloxy group, an aromatic heterocyclic oxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group and an acyloxy group.
• R c represents an alkyl group having 1 to 20 carbon atoms.
• the number of carbon atoms of the alkyl group is preferably 1 to 10, and more preferably 1 to 5.
• the alkyl group may be linear, branched or cyclic, or may have a structure in which these are combined.
• R c is an alkyl group having 2 to 20 carbon atoms
• one or more of -CH 2- constituting the alkyl group is -O-, -S-, -N (Q)-, and -CO-O.
• -, -O-CO- or -CO- may be substituted.
• Q represents a substituent.
• the type of the substituent is not particularly limited, and examples thereof include known substituents, and examples thereof include the groups exemplified by the substituents that the groups represented by Ra and R b may have. * Represents the bond position.
• the specific compound is preferably a polymer.
• the specific compound preferably contains a repeating unit B having at least one of the groups represented by the formulas (A) to (D).
• the repeating unit B contains at least one of the repeating units represented by the formulas (1) to (4).
• the specific compound is a repeating unit represented by the formula (1), a repeating unit represented by the formula (2), or a repeating unit represented by the formula (4). It is preferable to include a unit.
• the specific compound may have a plurality of repeating units represented by the formulas (1) to (4). For example, a repeating unit represented by the formula (1), a repeating unit represented by the formula (2), or a unit represented by the formula (4) and a repeating unit represented by the formula (3). It can also be included.
• R 1 , R 2 , R 3 and R 4 each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may have a substituent.
• the number of carbon atoms of the alkyl group is preferably 1 to 10, and more preferably 1 to 5.
• the alkyl group may be linear, branched or cyclic, or may have a structure in which these are combined.
• the type of substituent that the alkyl group may have is not particularly limited, and known substituents are mentioned, and the groups exemplified by the substituents represented by Ra and R b may have. Can be mentioned.
• L 1 , L 2 , L 3 and L 4 each independently represent a single bond or a divalent linking group.
• the divalent linking group is not particularly limited, and for example, a divalent hydrocarbon group which may have a substituent (for example, an alkylene group having 1 to 10 carbon atoms, an alkenylene group having 1 to 10 carbon atoms, and an alkenylene group having 1 to 10 carbon atoms).
• a divalent aliphatic hydrocarbon group such as an alkynylene group having 1 to 10 carbon atoms, and a divalent aromatic hydrocarbon group such as an arylene group
• a divalent heterocycle which may have a substituent.
• R d represents a hydrogen atom or an alkyl group.
• the type of substituent that the divalent hydrocarbon group and the divalent heterocyclic group may have is not particularly limited, and known substituents are mentioned, and there are groups represented by Ra and R b. Examples thereof include the groups exemplified by the substituents which may be used.
• the repeating unit B preferably contains at least one of the repeating units represented by the formulas (5) to (7) in that the effect of the present invention is more excellent.
• R 5 , R 6 and R 7 each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may have a substituent.
• the alkyl group preferably has 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms.
• the alkyl group may be linear, branched or cyclic, or may have a structure in which these are combined.
• the type of substituent that the alkyl group may have is not particularly limited, and known substituents are mentioned, and the groups exemplified by the substituents represented by Ra and R b may have. Can be mentioned.
• L 5 , L 6 and L 7 each independently represent a divalent linking group.
• the divalent linking group include the groups exemplified by the divalent linking groups represented by L 1 , L 2 , L 3 and L 4 described above.
• Y - represents an anion.
• Y in the formula (5) - is, Y in the formula (1) - synonymous.
• E + represents an organic cation.
• E + in equation (6) is synonymous with E + in equation (2).
• R 8 , R 9 and R 10 each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may have a substituent.
• the alkyl group preferably has 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms.
• the alkyl group may be linear, branched or cyclic, or may have a structure in which these are combined.
• the type of the substituent that the alkyl group may have is not particularly limited, and known substituents are mentioned, and the substituents that the alkyl groups represented by Ra and R b may have are exemplified. The group is mentioned.
• the content of the repeating unit B in the specific compound is not particularly limited.
• the content of the repeating unit B is determined. It is preferably 5 to 30% by mass with respect to the total amount of the repeating unit A and the repeating unit B.
• the repeating unit B includes the repeating unit represented by the formula (3)
• the content of the repeating unit B shall be 15 to 40% by mass with respect to the total amount of the repeating unit A and the repeating unit B. Is preferable.
• the repeating unit B includes the repeating unit represented by the formula (4)
• the content of the repeating unit B is 40 to 80% by mass with respect to the total amount of the repeating unit A and the repeating unit B. Is preferable.
• the specific compound preferably contains the repeating unit A and the repeating unit B described above.
• the specific compound may contain other repeating units other than the repeating unit A and the repeating unit B.
• the specific compound may contain a repeating unit having a crosslinkable group.
• the structure of the main chain of the repeating unit having a crosslinkable group is not particularly limited, and known structures include known structures such as (meth) acrylic, styrene, siloxane, cycloolefin, methylpentene, amide, and.
• a skeleton selected from the group consisting of aromatic esters is preferred. Of these, a skeleton selected from the group consisting of (meth) acrylic-based, siloxane-based, and cycloolefin-based skeletons is more preferable, and (meth) acrylic-based skeletons are even more preferable.
• repeating unit having a crosslinkable group the repeating unit represented by the formula (Z) is preferable.
• R 11 represents a hydrogen atom or a methyl group.
• L 8 represents a single bond or a divalent linking group.
• Examples of the divalent linking group include the groups exemplified by the divalent linking groups represented by L 1 , L 2 , L 3 and L 4 described above.
• Z represents a crosslinkable group.
• the type of the crosslinkable group is not particularly limited, and examples thereof include known crosslinkable groups, such as a radical polymerizable group and a cationically polymerizable group.
• As the crosslinkable group any of the groups represented by the formulas (Z1) to (Z4) is preferable.
• Re represents a hydrogen atom, a methyl group, or an ethyl group.
• R f represents a hydrogen atom or a methyl group. * Represents the bond position.
• the content of the repeating unit having a crosslinkable group in the specific compound is not particularly limited, but all repetitions in the specific compound are obtained in that the effect of the present invention is more excellent.
• the unit 20 to 80% by mass is preferable, and 30 to 70% by mass is more preferable.
• repeating units include a repeating unit A, a repeating unit B, and a repeating unit having an alkyl group, which is different from the repeating unit having a crosslinkable group.
• the number of carbon atoms of the alkyl group is not particularly limited, and is preferably 1 to 20 and more preferably 1 to 15.
• the alkyl group may be linear, branched or cyclic, or may have a structure in which these are combined.
• a cyclic alkyl group is preferable because it can suppress the relaxation of the orientation of the specific compound due to heat. Examples of the cyclic alkyl group include adamantane and the like.
• the content of the repeating unit having an alkyl group in the specific compound is not particularly limited, but all the repeating units in the specific compound are more excellent in the effect of the present invention. On the other hand, 20 to 80% by mass is preferable, and 30 to 70% by mass is more preferable.
• the weight average molecular weight (Mw) of the specific compound is not particularly limited, but 10,000 to 500,000 is preferable, and 20,000 to 300,000 is more preferable, in that the effect of the present invention is more excellent.
• the weight average molecular weight and the number average molecular weight in the present invention are values measured by a gel permeation chromatography (GPC) method under the following conditions.
• the photo-aligned compound can be synthesized by a known method.
• the liquid crystal compound of the present invention includes the above-mentioned specific compound and the liquid crystal compound.
• the specific compound is as described above, and the description thereof will be omitted.
• liquid crystal compound The type of the liquid crystal compound is not particularly limited, and examples thereof include compounds capable of any of homeotropic orientation, homogeneous orientation, hybrid orientation, and cholesteric orientation.
• liquid crystal compounds can be classified into rod-shaped type and disk-shaped type according to their shapes.
• a polymer generally refers to a polymer having a degree of polymerization of 100 or more (Polymer Physics / Phase Transition Dynamics, Masao Doi, p. 2, Iwanami Shoten, 1992).
• any liquid crystal compound can be used, but a rod-shaped liquid crystal compound or a discotic liquid crystal compound (disk-shaped liquid crystal compound) is preferable.
• a liquid crystal compound which is a monomer or has a relatively low molecular weight having a degree of polymerization of less than 100 is preferable.
• the liquid crystal compound preferably has a polymerizable group. That is, the liquid crystal compound is preferably a polymerizable liquid crystal compound.
• the polymerizable group contained in the polymerizable liquid crystal compound include an acryloyl group, a methacryloyl group, an epoxy group, and a vinyl group.
• the rod-shaped liquid crystal compound for example, those described in claim 1 of JP-A No. 11-513019 or paragraphs [0026] to [0098] of JP-A-2005-289980 are preferable, and the discotic liquid crystal compound is preferably a discotic liquid crystal compound.
• the discotic liquid crystal compound is preferably a discotic liquid crystal compound.
• those described in paragraphs [0020] to [0067] of JP2007-108732 or paragraphs [0013] to [0108] of JP2010-2404038 are preferable.
• the polymerizable liquid crystal compound a liquid crystal compound having a reverse wavelength dispersibility can be used.
• the liquid crystal compound having "reverse wavelength dispersibility” means that the in-plane retardation (Re) value at a specific wavelength (visible light range) of a retardation film produced using this compound is measured. In this case, it means that the Re value becomes equal or higher as the measurement wavelength becomes larger.
• the reverse wavelength dispersible liquid crystal compound is not particularly limited as long as it can form a reverse wavelength dispersive film as described above, and is represented by, for example, the general formula (I) described in JP-A-2008-297210. (In particular, the compounds described in paragraphs [0034] to [0039]), and the compounds represented by the general formula (1) described in JP-A-2010-084032 (particularly, paragraphs [0067] to [0073]. ], And compounds represented by the general formula (1) described in JP-A-2016-081035 (particularly, compounds described in paragraphs [0043] to [0055]).
• the content of the photoalignment compound in the liquid crystal composition is not particularly limited, but is preferably 0.01 to 30% by mass, preferably 0.1 to 30% by mass, based on the content of the liquid crystal compound in that the effect of the present invention is more excellent. 10% by mass is more preferable.
• the content of the liquid crystal compound in the liquid crystal composition is not particularly limited, but is preferably 50% by mass or more, more preferably 70% by mass or more, based on the total solid content in the composition, in that the effect of the present invention is more excellent. It is preferable, and 90% by mass or more is more preferable.
• the upper limit is not particularly limited, but in many cases it is 99% by mass or less.
• the total solid content in the liquid crystal composition is intended to be a component constituting the liquid crystal layer, and does not contain a solvent.
• the liquid crystal composition may contain a compound other than the liquid crystal compound and the photoalignment compound described above.
• the liquid crystal composition may contain a leveling agent.
• the leveling agent preferably has a fluorine atom or a silicon atom. That is, as the leveling agent, a fluorine-based leveling agent or a silicon-based leveling agent is preferable, and a fluorine-based leveling agent is more preferable.
• the leveling agent include the compounds described in paragraphs [0079] to [0102] of JP-A-2007-069471, and the compounds represented by the general formula (I) described in JP-A-2013-047204.
• the content of the leveling agent in the liquid crystal composition is preferably 0.01 to 5% by mass, more preferably 0.05 to 1% by mass, based on the total solid content in the liquid crystal composition.
• the liquid crystal composition may contain a polymerization initiator.
• the polymerization initiator used is selected according to the type of polymerization reaction, and examples thereof include a thermal polymerization initiator and a photopolymerization initiator.
• examples of the photopolymerization initiator include ⁇ -carbonyl compounds, acyloin ethers, ⁇ -hydrocarbon-substituted aromatic acyloin compounds, polynuclear quinone compounds, and combinations of triarylimidazole dimers and p-aminophenyl ketones. Be done.
• the content of the polymerization initiator in the liquid crystal composition is preferably 0.01 to 20% by mass, more preferably 0.3 to 10% by mass, based on the total solid content of the liquid crystal composition.
• the liquid crystal composition may contain a thermoacid generator.
• a thermoacid generator when the specific compound has a cationically polymerizable group, a liquid crystal film having excellent heat resistance can be obtained by polymerizing the cationically polymerizable group using a thermoacid generator when forming the liquid crystal film.
• the content of the thermoacid generator in the liquid crystal composition is preferably 0.01 to 20% by mass, more preferably 0.3 to 10% by mass, based on the total solid content of the liquid crystal composition.
• the liquid crystal composition may contain a polymerizable monomer.
• the polymerizable monomer include radically polymerizable or cationically polymerizable compounds. Of these, a polyfunctional radically polymerizable monomer is preferable.
• a monomer copolymerizable with the above-mentioned liquid crystal compound having a polymerizable group is preferable.
• the content of the polymerizable monomer in the liquid crystal composition is preferably 1 to 50% by mass, more preferably 2 to 30% by mass, based on the total mass of the liquid crystal compound.
• the liquid crystal composition may contain a solvent.
• a solvent an organic solvent is preferable.
• Organic solvents include amines (eg diisopropylethylamine), amides (eg N, N-dimethylformamide), sulfoxides (eg dimethyl sulfoxide), heterocyclic compounds (eg pyridine, 1,3-dioxolane), hydrocarbons.
• benzene, hexane, toluene alkyl halides (eg, chloroform, dichloromethane), esters (eg, methyl acetate, ethyl acetate, butyl acetate), ketones (eg, acetone, methyl ethyl ketone, cyclopentanone), and ethers.
• alkyl halides eg, chloroform, dichloromethane
• esters eg, methyl acetate, ethyl acetate, butyl acetate
• ketones eg, acetone, methyl ethyl ketone, cyclopentanone
• ethers eg, tetrahydrofuran, 1,2-dimethoxyethane
• Two or more kinds of organic solvents may be used in combination.
• the liquid crystal composition may contain various orientation control agents such as a vertical alignment agent and a horizontal alignment agent. These orientation control agents are compounds capable of horizontally or vertically controlling the orientation of the liquid crystal compound on the interface side.
• the liquid crystal composition may contain a polymerization inhibitor, an adhesion improver, and a plasticizer in addition to the above components.
• the liquid crystal composition may contain a polymerization inhibitor for the purpose of suppressing the polymerization of the liquid crystal compound in step 2 described later.
• the liquid crystal film of the present invention is formed by using the above-mentioned liquid crystal composition.
• the method for producing the liquid crystal film of the present invention is not particularly limited, and any method using the above-mentioned liquid crystal composition may be used, and it is preferable to have the following steps 1 to 3. More specifically, a production method having the following steps 1 to 3 is preferable.
• Step 1 A liquid crystal composition containing a specific compound and a polymerizable liquid crystal compound is applied onto a substrate to form a coating film.
• Step 2 The formed coating film is irradiated with polarized light.
• Step 3 A step of orienting the polymerizable liquid crystal compound in the coating film obtained in step 2 and then performing a curing treatment to form a liquid crystal film.
• the procedures of steps 1 to 3 will be described in detail below.
• Step 1 is a step of applying a liquid crystal composition containing a specific compound and a polymerizable liquid crystal compound onto a substrate to form a coating film.
• a liquid crystal composition containing a specific compound and a polymerizable liquid crystal compound onto a substrate to form a coating film.
• the liquid crystal composition used is as described above.
• the base material may be an organic base material (a base material composed of an organic material) or an inorganic base material (a base material composed of an inorganic material), and an organic base material is preferable.
• a resin base material is preferable.
• Materials for the resin substrate include cellulose-based polymers; polymethylmethacrylate and acrylic polymers such as acrylate ring-containing polymers, acrylic acid ester polymers; thermoplastic norbornene-based polymers; polycarbonate-based polymers; polyethylene terephthalates, and , Polyester-based polymers such as polyethylene naphthalate; Polystyrene and styrene-based polymers such as acrylonitrile styrene copolymers; Polyethylene-based polymers such as polyethylene, polypropylene, and ethylene-propylene copolymers; , And amide-based polymers such as aromatic polyamides; imide-based polymers; sulfone-based polymers; polyether sulfone-based polymers; polyether ether ketone-based polymers; polyphenylene sulfide-based polymers; vinylidene chloride-based polymers; vinyl alcohol-based polymers; vinyl
• Examples of the inorganic base material include a glass base material.
• the base material is preferably transparent. That is, as the base material, a transparent base material is preferable.
• the transparent base material is intended to be a base material having a visible light transmittance of 60% or more, and the transmittance is preferably 80% or more, more preferably 90% or more.
• the base material preferably has a hydrogen-bonding group on its surface.
• the hydrogen-bonding group include a hydroxy group, a thiol group, a carboxy group, an amino group, an amide group, a urea group, and a urethane group, and a hydroxy group or a carboxy group is preferable in that the effect of the present invention is more excellent. ..
• the method for introducing a hydrogen-bonding group onto the surface of the base material is not particularly limited, and examples thereof include known surface treatment methods such as corona treatment and ultraviolet irradiation treatment. Further, the material (for example, polymer) itself constituting the base material may have a hydrogen-bonding group.
• the base material may contain an additive having a hydrogen-bonding group in addition to the main component constituting the base material.
• the base material contains a compound that is decomposed by heat or light to generate a hydrogen-bonding group, and the surface of the base material is subjected to a predetermined treatment (for example, light irradiation treatment or heat treatment). Hydrogen-bonding groups may be introduced.
• the water contact angle on the surface of the base material is not particularly limited, but 80 ° or less is preferable, and 70 ° or less is more preferable, because the effect of the present invention is more excellent.
• the lower limit is not particularly limited, but it is often 1 ° or more.
• the method for measuring the water contact angle on the surface of the base material is as follows. First, a 3 ⁇ L liquid using a contact angle meter [“CA-X” type contact angle meter, manufactured by Kyowa Interface Science Co., Ltd.] in a dry state (20 ° C./65% RH) and using pure water as a liquid. Droplets are made on the tip of the needle and brought into contact with the surface of the substrate to form droplets on the substrate. The angle formed by the tangent to the liquid surface and the surface of the base material at the point where the base material and the liquid come into contact with each other 15 seconds after the dropping is measured, and the angle on the side containing the liquid is measured and used as the water contact angle.
• the base material may have a single-layer structure or a multi-layer structure.
• the base material may have a support and an optically anisotropic layer arranged on the support.
• the optically anisotropic layer include an optically anisotropic layer having a phase difference in the in-plane direction and an optically anisotropic layer having a phase difference in the thickness direction.
• the thickness of the base material is not particularly limited, and is preferably 5 to 200 ⁇ m, more preferably 10 to 100 ⁇ m, and even more preferably 20 to 90 ⁇ m.
• the method of applying the liquid crystal composition onto the substrate is not particularly limited, and is a curtain coating method, a dip coating method, a spin coating method, a print coating method, a spray coating method, a slot coating method, a roll coating method, a slide coating method, and a blade.
• Examples include a coating method, a gravure coating method, and a wire bar method.
• the coating film may be heat-treated after the coating film is formed and before the step 2 described later. By performing the heat treatment, the specific compound is more likely to be unevenly distributed on the base material side.
• the heating temperature during the heat treatment is preferably 50 to 250 ° C., more preferably 50 to 150 ° C., and preferably 10 seconds to 10 minutes as the heating time because the effect of the present invention is more excellent. ..
• Step 2 is a step of irradiating the formed coating film with polarized light.
• the specific compound unevenly distributed in the coating film is oriented in a predetermined direction, and a part of the region in the coating film can easily function as a photoalignment film.
• the polarization applied to the coating film is not particularly limited, and examples thereof include linearly polarized light, circularly polarized light, and elliptically polarized light, and linearly polarized light is preferable.
• the wavelength of polarized light is not particularly limited, and examples thereof include ultraviolet rays, near ultraviolet rays, and visible light. Of these, near-ultraviolet rays of 250 to 450 nm are preferable.
• the light source for irradiating polarized light include a xenon lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, and a metal halide lamp.
• an interference filter, a color filter, or the like for ultraviolet rays or visible rays obtained from such a light source the wavelength range to be irradiated can be limited.
• linearly polarized light can be obtained by using a polarizing filter or a polarizing prism for the light from these light sources.
• the irradiation direction of polarized light is not particularly limited, and irradiation may be performed from the coating film side or from the base material side. Irradiation from the base material side is preferable because the effect of the present invention is more excellent.
• the integrated light amount of polarized light is not particularly limited , but is preferably 1 to 300 mJ / cm 2 and more preferably 2 to 100 mJ / cm 2 .
• Step 3 is a step of orienting the polymerizable liquid crystal compound in the coating film obtained in step 2 and then performing a curing treatment to form a liquid crystal film.
• the polymerizable liquid crystal compound is oriented based on the orientation restricting force of the specific compound oriented in the predetermined direction obtained in step 2, and the oriented polymerizable liquid crystal compound is cured.
• a liquid crystal film formed by immobilizing the oriented liquid crystal compound is formed.
• Examples of the method for orienting the polymerizable liquid crystal compound include heat treatment.
• the conditions for heating the coating film are not particularly limited, but the heating temperature is preferably 50 to 250 ° C, more preferably 50 to 150 ° C, and the heating time is preferably 10 seconds to 10 minutes. Further, after heating the coating film, the coating film may be cooled, if necessary, before the curing treatment described later.
• the cooling temperature is preferably 20 to 200 ° C, more preferably 30 to 150 ° C.
• the coating film in which the polymerizable liquid crystal compound is oriented is subjected to a curing treatment.
• the method of curing treatment performed on the coating film on which the polymerizable liquid crystal compound is oriented is not particularly limited, and examples thereof include light irradiation treatment and heat treatment. Among them, the light irradiation treatment is preferable, and the ultraviolet irradiation treatment is more preferable from the viewpoint of manufacturing suitability.
• the irradiation conditions of the light irradiation treatment are not particularly limited, but an irradiation amount of 50 to 1000 mJ / cm 2 is preferable.
• the atmosphere during the light irradiation treatment is not particularly limited, but a nitrogen atmosphere is preferable.
• the liquid crystal film formed when the liquid crystal composition contains a leveling agent is a liquid crystal film having two main surfaces formed by using the liquid crystal compound, the specific compound, and the liquid crystal composition containing the leveling agent.
• the leveling agent is unevenly distributed on the main surface side of one surface and the specific compound is unevenly distributed on the main surface side of the other surface in the liquid crystal film.
• the thickness of the liquid crystal film is not particularly limited, but is preferably 0.1 to 10 ⁇ m, more preferably 0.5 to 5 ⁇ m.
• the in-plane retardation of the liquid crystal film is not particularly limited, but for example, when used for an antireflection film application, the in-plane retardation of the liquid crystal film at a wavelength of 550 nm is preferably 110 to 160 nm.
• the liquid crystal film can be applied to various uses.
• an image display device including a display element and a liquid crystal film can be mentioned.
• the display element used in the image display device of the present invention is not particularly limited, and examples thereof include a liquid crystal cell, an organic electroluminescence (hereinafter abbreviated as "EL") display panel, and a plasma display panel, and the liquid crystal cell or An organic EL display panel is preferred. That is, as the image display device of the present invention, a liquid crystal display device using a liquid crystal cell as a display element or an organic EL display device using an organic EL display panel as a display element is preferable.
• the liquid crystal cell used in the liquid crystal display device is preferably a VA (Vertical Element) mode, an OCB (Optically Compensated Bend) mode, an IPS (In-Plane-Switching) mode, or a TN (Twisted Nematic) mode. ..
• VA Vertical Element
• OCB Optically Compensated Bend
• IPS In-Plane-Switching
• TN Transmission Nematic
• the organic EL display device which is an example of the image display device of the present invention, for example, it is preferable to have a polarizer, a liquid crystal film, and an organic EL display panel in this order from the visual side.
• the polarizer is not particularly limited as long as it is a member having a function of converting light into specific linearly polarized light, and conventionally known absorption type polarizers and reflection type polarizers can be used.
• absorption type polarizer an iodine-based polarizer, a dye-based polarizer using a dichroic dye, a polyene-based polarizer, and the like are used.
• the iodine-based polarizer and the dye-based polarizer include a coating type polarizing element and a stretching type polarizing element, and both of them can be applied.
• Japanese Patent No. 5048120 Japanese Patent No. 5143918, Japanese Patent No. 46910205, and Japanese Patent No.
• the methods described in Japanese Patent No. 4751481 and Japanese Patent No. 4751486 can be mentioned, and known techniques for these polarizers can also be preferably used.
• the reflective polarizer include a polarizer in which thin films having different birefringences are laminated, a wire grid polarizer, and a polarizer in which a cholesteric liquid crystal having a selective reflection region and a 1/4 wave plate are combined.
• a polymer containing a polyvinyl alcohol-based resin (-CH 2- CHOH- as a repeating unit.
• a polyvinyl alcohol-based resin (-CH 2- CHOH- as a repeating unit.
• a polarizer containing (1) is preferable.
• the thickness of the polarizer is not particularly limited, and is preferably 3 to 60 ⁇ m, more preferably 5 to 30 ⁇ m.
• the organic EL display panel is a member in which a light emitting layer or a plurality of organic compound thin films including a light emitting layer are formed between a pair of electrodes of an anode and a cathode.
• the organic EL display panel may have a hole injection layer, a hole transport layer, an electron injection layer, an electron transport layer, a protective layer, and the like in addition to the light emitting layer, and each of these layers has other functions. It may be provided.
• reaction solution was stirred at 50 ° C. for 6 hours.
• the reaction mixture was cooled to room temperature, washed separately with water, and the obtained organic phase was dried over anhydrous magnesium sulfate. Magnesium sulfate was filtered off, and the obtained solution was concentrated to obtain a yellowish white solid.
• the obtained yellowish white solid was dissolved by heating in methyl ethyl ketone (400 g) and recrystallized to obtain 76 g of the following monomer mA-1 as a white solid (yield 40%).
• Me represents a methyl group.
• the reaction solution was stirred while maintaining the reaction solution. After completion of the reaction, the reaction solution was allowed to cool to room temperature, and dimethylacetamide (60 g) was added to the reaction solution for dilution to obtain a polymer solution having a polymer concentration of about 20% by mass.
• the obtained polymer solution is poured into a large excess of methanol to precipitate the polymer, the precipitate is filtered off, the obtained solid content is washed with a large amount of methanol, and then air-dried at room temperature for 24 hours. As a result, polymer P-1 was obtained.
• Me represents a methyl group.
• each repeating unit in the following structural formula represent the content (mass%) of each repeating unit with respect to all the repeating units, and below, 91% by mass and 9% by mass from the repeating unit on the left side. Met.
• the weight average molecular weight of the polymer P-1 measured by the above method was 58,000.
• reaction solution was allowed to cool to room temperature, and cyclohexanone (30 g) was added to the reaction solution for dilution to obtain a polymer solution having a polymer concentration of about 20% by mass.
• the obtained polymer solution is poured into a large excess of methanol to precipitate the polymer, the precipitate is filtered off, the obtained solid content is washed with a large amount of methanol, and then air-dried at room temperature for 24 hours. As a result, a polymer of monomer mA-1 and methacrylic acid was obtained.
• the obtained polymer of monomer mA-1 and methacrylic acid (1.0 g) was added to a mixed solvent (4.0 g) of cyclohexanone / isopropyl alcohol (2/1) and dissolved at 50 ° C. Then, diisopropylethylamine (418 ⁇ L) was added to the obtained solution, and the mixture was stirred at 50 ° C. for 30 minutes to obtain a polymer P-4 (solid content concentration: 20%).
• the numerical values described in each repeating unit in the following structural formula represent the content (mass%) of each repeating unit with respect to all the repeating units, and below, 79% by mass and 21% by mass from the repeating unit on the left side. Met.
• ⁇ Preparation of specific base material> By corona-treating one side of a cycloolefin polymer film (ZF-14, manufactured by Zeon Corporation) once under the conditions of an output of 0.3 kW and a processing speed of 7.6 m / min using a corona treatment apparatus. A specific substrate was obtained.
• the specific base material had a hydrogen-bonding group such as a hydroxy group on the corona-treated surface.
• the water contact angle of the corona-treated surface was 63 °. The method for measuring the water contact angle is as described above.
• composition 1 for forming a liquid crystal layer was applied to the surface of the specific base material on the corona-treated side using a bar coater.
• the coating film formed on the specific substrate is dried at room temperature for 30 seconds, and then is passed through a bandpass filter (BPF313, manufactured by Asahi Spectroscopy Co., Ltd.) having a wavelength of 313 nm and a wire grid polarizer using a high-pressure mercury lamp.
• BPF313 bandpass filter
• Polarized ultraviolet rays were irradiated from the surface side opposite to the surface on which the coating film of the specific substrate was formed (the side opposite to the coating film forming surface) (50 mJ / cm 2 at a wavelength of 313 nm).
• the obtained film was heated with warm air at 120 ° C. for 1 minute, then cooled to 60 ° C., and then irradiated with ultraviolet rays of 80 mJ / cm 2 at a wavelength of 365 nm using a high-pressure mercury lamp in a nitrogen atmosphere. Irradiation was performed from the coating film side, and then ultraviolet rays of 300 mJ / cm 2 were irradiated from the coating film side while heating at 120 ° C.
• An optical film 1 having a specific base material and a liquid crystal film 1 (thickness 2.7 ⁇ m) was produced by the above procedure.
• the following polymerizable liquid crystal compound L-6 15.0 parts by mass ⁇
• the following polymerization Sex compound A-2 5.0 parts by mass, polymerization initiator (Irgacure2959, manufactured by Ciba Specialty Chemicals) 4.0 parts by mass ⁇
• Example 2 An optical film 2 having a liquid crystal film 2 was produced according to the same procedure as in Example 1 except that the polymer P-2 was used instead of the polymer P-1.
• Example 3 An optical film 3 having a liquid crystal film 3 was produced according to the same procedure as in Example 1 except that the polymer P-4 was used instead of the polymer P-1.
• Example 4 An optical film 4 having a liquid crystal film 4 was produced according to the same procedure as in Example 1 except that the polymer P-5 was used instead of the polymer P-1.
• Example 5 An optical film 5 having a liquid crystal film 5 was produced according to the same procedure as in Example 1 except that the polymer P-6 was used instead of the polymer P-1.
• Example 6 An optical film 6 having a liquid crystal film 6 was produced according to the same procedure as in Example 1 except that the polymer P-7 was used instead of the polymer P-1.
• Example 7 An optical film 7 having a liquid crystal film 7 was produced according to the same procedure as in Example 1 except that the polymer P-3 was used instead of the polymer P-1.
• Example 8 An optical film 8 having a liquid crystal film 8 was produced according to the same procedure as in Example 1 except that the polymer P-8 was used instead of the polymer P-1.
• the "interacting group” represents which of the groups represented by the formulas (1) to (4) is possessed.
• unit content (mass%) represents the content of the repeating unit B with respect to the total amount of the repeating unit A and the repeating unit B in the specific compound.
• the desired effect was obtained by using the compound of the present invention.
• the specific compound has a repeating unit represented by the formula (1), a repeating unit represented by the formula (2), or a unit represented by the formula (4).
• the repeating unit B is based on the total amount of the repeating unit A and the repeating unit B in the specific compound. It was confirmed that when the content was 30% by mass or less (preferably 5 to 30% by mass), a more excellent effect could be obtained.

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