TW201238980A - Composition for photoaligned film and optically anisotropic film - Google Patents

Abstract

A composition for a photoaligned film or an optically anisotropic film containing a photo-alignment compound assuring quite high flexibility of selection of a material is provided. The present invention provides a composition for a photoaligned film or a composition for an optically anisotropic film comprising a photo-reactive polymer having a repeating unit represented by the general formula (I): wherein M is a monomer unit forming a main chain of a homopolymer or a copolymer; SPCR is a spacer unit; Ring A is an unsubstituted or substituted alicyclic hydrocarbon or an unsubstituted or substituted aromatic ring; Ring B is an unsubstituted or substituted aromatic ring; and Z is an alkyl group, an alkoxy group, cyano group, nitro group, a halogen atom, -CH=CHZ1, -C=CZ1 (wherein Z1 is an alkyl group, an alkoxy group, an alkoxycarbonyl group, an alkoxysulfonyl group, cyano group, nitro group or a halogen atom), -COOZ2 or -SO3 Z2 (wherein Z2 is an alkyl group).

Description

201238980 6. Technical Field of the Invention The present invention relates to a novel composition for a photo-alignment film and an optical anisotropic composition; and various optical differences obtained by using the composition Square film, optical material and liquid crystal cell. [Prior Art] In recent years, in the field of displays (including liquid crystal displays, etc.), the phase difference of the viewing angle raising film, the brightness improving film, and the polarizing film are utilized in various forms. Various optical materials such as various types of light, such as a film, a conductive material, a nonlinear optical material, and a photoreactive device. Such an optical anisotropic film or optical material is produced by a layer having an alignment energy (film, substrate surface, etc.), a liquid crystal θ pigment, an electric compound, or the like, but is preferably θ. The method of the alignment layer is known to treat the surface chemically or physically. As such a method, for example, it is known that, in a certain direction, the rubbing treatment of a polymer resin film such as polyimide or the like which is coated on the surface of the substrate is rubbed by a cloth temple, and is used in the liquid crystal day and day. Formation of a film or the like. 1 疋 'In this method, the production of 魄η, micro, and the dust of the field caused by the occurrence of the dust of the liquid crystal living room line, dyed or ώ crystal) has a TFT due to static electricity (film electric day) Body) The damage of the pieces is good. ', has become the cause of the manufacturing process of the liquid crystal panel. - 疋 谷 谷 控制 控制 控制 控制 控制 控制 控制 控制 控制 易 易 易 易 易 易 易 易 易 易 谷 易 谷 谷 谷 谷 谷 谷 谷 谷 谷 谷 谷 谷 谷 谷 谷 谷 谷 谷 谷 光 光 光 光 光 光 谷 光 光 光 光 光 光;, there is a liquid alignment film with a liquid Ba to replace the friction treatment. For example, a azobenzene compound having an azo group is known as a cinnamic acid bacterium having a cinnamyl group as a compound which causes photo-analysis (Non-Patent Document 2). A coumarin derivative having a fragrant sulphate group (Non-Patent Document 3), an aryl propylene fluorene aromatic hydrocarbon derivative having an aryl olefin aryl hydrocarbon group (Non-Patent Document 4) ^ 光 is a photodecomposition of a compound which causes photolysis Polyimine (Non-Patent Document 5) and the like. ^疋, like this, “ww, 兴, 二, or quantitative”, in the manufacture of optical alignment films, there is a problem that the degree of freedom of material selection becomes lower. The so-called Fnes (Folly) The transformation is carried out by benzene vinegar to form a transition reaction between —-: and/or phenyl-p- ketone. ###################################################################### ί : The reaction mechanism that is particularly called the light Fries transition is considered to pass through free radicals as follows.

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〇^G— ..〇心~Ια ^ [Prior Art Literature] [Non-patent Literature]

Langmuir, vol. 4 [Non-Patent Document 1] K. Ichimura et al 201238980 page 1214 (1 988) [Non-Patent Document 2] M. Schadt et al., J. Appl. Phys., vol. 31, No. 7 , page 21 55 (1 992) [Non-Patent Document 3] M. Schadt et al., Nature., vol. 381, Page 21 2 (1 996) [Non-Patent Document 4] Ogawa Junbo et al. Manuscript, 2AB03 (1 997) [Non-Patent Document 5] The 22nd Liquid Crystal Symposium Presentation Pre-Collection, 1672 Pages A1 7 (1 996) [Non-Patent Document 6] THE MERCK INDEX FOURTEENTH EDITION, Organic Name Reactions 150 SUMMARY OF THE INVENTION [Problems to be Solved by the Invention] In view of the foregoing, the present invention provides a composition for a photo-alignment film comprising a photoreactive compound having a very high degree of freedom in material selection. In addition, the present invention provides a photo-alignment film using the composition for a photo-alignment film. Further, the present invention provides a retardation film, a film for viewing angle enhancement, a film for brightness enhancement, and a polarizing film using the photo-alignment film. Various optical materials such as various optical anisotropic films and conductive materials, nonlinear optical materials, photoreactive actuators, and the like, and liquid crystal cells using the photoalignment film. Further, the present invention provides a light-dried, square film-containing composition comprising the photoreactive compound and an optical anisotropic film using the composition. [Means for Solving the Problem] 6 201238980 The inventors of the present invention conducted a thorough study and found that if it is at the end of the side chain of the polymer, it is represented by the following chemical formula and bonded with a benzene vinegar group. The photoreactive group photoreactive polymer can solve the above problems as a photoreactive compound, and the present invention can be completed by repeating the review.

Storage (in the chemical ^ towel ' & A line unsubstituted or substituted alicyclic hydrocarbons or unsubstituted or substituted aromatic ring, ring B system unsubstituted or substituted aromatic ring.) This month's photoreactive polymer is The phenolic ester group in the side chain is subjected to irradiation of light 'by photolysis' to become a decomposition product via a radical. In addition, in the state in which the ortho (or para) of the hydroxyl group in the ring B is unsubstituted, the part of these radicals causes the Μα (Friss) transformation to form o-benzone ( Or p-benzene (four)). Therefore, the photo-alignment film or the optical anisotropic film composition containing the photoreactive polymer is applied to the substrate, and in the state of the irradiation light, linear polarized light is used as the cause of the series. At the time of the reaction light, only the polarized light relative to the linearly polarized light is gp X, , . The phenolic ester group present in the axis of the axis selectively causes photocleavage or photocleavage on the polarizing axis and A Fries is a light-aligning film or an optical anisotropic film which imparts an alignment energy to a liquid crystal or the like by & The present invention has been completed on the basis of such knowledge. 201238980

Fine one 3? Surveying Lang means that 'this invention is related to [1]: a composition for optical alignment film, which will have the formula (丨). m^PCr_〇--^WP (j) thousand W \〇^^z [In the chemical formula, the lanthanide forms the monomer unit of the main chain of the homopolymer or copolymer, the SPCR system spacer unit, the cyclic oxime unsubstituted or substituted alicyclic hydrocarbon or the unsubstituted or substituted aromatic Ring, ring B is an unsubstituted or substituted aromatic ring, Z series alkyl, alkoxy, cyano, nitro, dentate atom, _ch=chzi, -CeCZ1 (but 'Ζι钱基, alkoxy, courtyard oxygen (4), oxooxysulfonyl, fluorenyl, nitro or _ atom.), __c〇〇Z2 or -so"2 (however, Z2 is a sleek base.). 1 * Qian Xi tongue visit. „ j indicates that the photoreactive polymer in the early position is included and composed; [2]: the composition for the photoalignment film of the above [1], the substituent of the ring a and the substituent of the ring B respectively Independently selected from the group consisting of an alkyl group, an alkoxy group, a cyano group, a nitro group and a dentate atom, or two or more groups; [3]. The light alignment film of the above [1] is used for the daytime private pancreas With the composition, the ruthenium is made of acrylate, mercapto acrylate, 2 - teaches the lack of acrylate, 2 ~ styrene acrylate, 8 201238980 propylene decyl benzene, acrylamide, methyl Acrylamide, 2-propene decylamine, 2-phenylpropene decylamine, vinyl ether, stupid ethylene derivative, vinyl ester, maleic acid derivative, fumaric acid derivative, decane, epoxy One or more monomer units selected from the group consisting of compounds, and spCR is composed of —(CH2) p (but 疋, any integer of ph 1 to 12), 1 2 to propylene, 1, 3—butene, cyclopentene monodecene, 2—bifluorene, cyclopentene-1” 2-diindole, cyclohexene-indole, 3 dioxin, cyclohexene-fluorene, 4-diindole, piperazine Acridine~1 The group consisting of 4-12, piperazine-1,4-diindole, 1,2-phenylene, 1,3_phenylene, 1'4 support, and the ring unit is selected by :

[But the 'X' ~ Π is independently a gas atom, a hospital base, a hospital oxy group, a halogen atom or a cyano group.] Any one of the groups represented by the ring B is:

A dentate atom or a cyano group, an X-type nitrogen atom, an oxygen atom, or a sulfur atom. Any of the groups of 201238980; [4] The composition for a photo-alignment film of the above [3], which is at least one of X1B and ΛI, at least one of X5B and ΧΙ2β, and at least one of Χ2, χ At least one of Chuanhe, at least one of Χ3丨Β and X3〇, and Β Λ is a gas atom; [5]: a composition for a photo-alignment film, which has the formula a):

And each of X1B to X4B is independently a hydrogen atom, an alkyl group, an alkoxy group, a dentate atom or a cyano group, a Z-based alkyl group, an alkoxy group, a cyano group, a nitro group, a hydroxyl atom, or -CH= CHZ1, -Csczl (however, 21 is an alkyl group, an oxy group, an alkoxy group, an alkoxysulfonyl group, a murine group, a nitro group or a hydroxyl atom.), -c〇ns〇3Z2 (however, 22 Department bases.), any integer of the p system 12 is called a repeating unit of the photoreactive polymer to be included and composed. [6] The composition for a photo-alignment film according to the above [5], wherein at least one of the ruthenium and the ruthenium is a hydrogen atom; : a photo-alignment film prepared by coating the surface of the substrate] [6] The middle-item light-aligning film core is composed of a linearly polarized light in this illumination; 10 201238980 [8] . An optical anisotropic film or optical material, which is the light alignment film of the above [7], Oriented by a liquid crystal compound, a dye or a conductive compound; [9] : a liquid crystal cell which is opposite to the light alignment film of the above [7], and which causes a linear polarization of the edge of the film to the film The direction of the polarization axis and the direction of the polarization axis when the linear alignment of the light-aligning medium of the other side is 'formed at a predetermined angle to each other' is formed by filling the liquid crystal compound between the opposite photo-alignment films; The composition of the optical anisotropic film of the formula [10]. will have a monomer which is formed by (I) M-spcr-〇- [in the chemical formula, the main chain of the homopolymer or copolymer Unit 'SPCR line spacing unit, ring U non-substituted or substituted alicyclic smoke or unsubstituted or substituted aromatic , anthracycline unsubstituted or substituted aromatic ring, fluorene, alkoxy, cyano, nitro, _ atom, _CH=CHZ1, -CSCZ1 (but 'Z1 alkyl, alkoxy, alkoxy a photoreactive polymer of a repeating unit represented by a carbonyl group, an alkoxy fluorenyl group, a cyano group, a nitro group or a dentate atom 〇, —(10)z^_s〇3z2 (but 'Z2 minus group.). And the composition; π 1 ]-- an optical anisotropic film, which is prepared by coating the surface of the substrate with the composition of the optical anisotropic film described in [10], after which the linearly polarized light is irradiated The liquid crystal compound of the composition for an optical anisotropic film is heated to a temperature higher than the temperature at which the liquid crystal state is displayed, and the liquid crystal compound is further cooled to a temperature at which the liquid crystal state is not displayed. 11 201238980 [Effect of the invention] The present invention Provided by a composition for a light film which utilizes a novel generation mechanism called a conversion, a phenolic ester group which is not dependent on a conventional ruthenium base, an aryl propylene fluorene base, and a simple structure, and a photoreactive polymer is designed. The strength of the degree of freedom of sex. In addition, this hair Since the optical film is provided with an alignment film, it has the characteristic photocleavage and optical Fries of the optically anisotropic film (Flies aligning film composition and optical anisotropic photo-alignment group (for example, azo, meat, Since the coumarin group or the like is used as a photo-alignment group, it is not necessary to be simple and further low-cost, and it is not necessary to further improve the material selection method. [Embodiment of the Invention] In the photoreactive polymer (I) of the present invention, the batch-», 1" is not particularly preferred in the following. A photoreactive polymer has a general formula (work_a) )

[In the chemical formula, the symbol system has the same meaning as described above. ] Repeated units indicated. In the state of the general formula (I) (in the state also suitable for the general formula (!-a), 12 201238980 forms a homopolymer in the field also includes the general formula (I-a). The same applies hereinafter.), m system Or the monomer unit of the main chain of the copolymer, if it is a monomer unit, can be used moderately. As such a monomer unit series, for example, acrylic acid, mercapto acrylate, 2 __ chloropropane @ ^ 2 - phenyl acrylate, acrylamide, methacryl oxime, ^ ^ ^ ~ Propylene amide, 2-phenylpropenylamine, vinyl ether, styrene derivatives (eg, fluorenyl styrene, ρ-styrene sulfonate), maleic acid derivatives (eg, cis-butane) a group consisting of a enedic acid ester, a phenyl maleic anhydride imide, a cyclohexyl maleic anhydride imide, a fumaric acid derivative (for example, a fumarate), an arsine, and an epoxide One or more types of green body units to be selected. In the state in which the ruthenium is composed of one type of monomer unit, the photoreactive polymer-based homopolymer of the formula (work) is in a state in which ruthenium is composed of two or more monomer units, and the formula ( A photoreactive polymer copolymer of I). In the state where the photoreactive polymer of the present invention is a copolymer, such a copolymer system also includes any of an interactive type, a random type, a graft type and the like. Among these monomer units, an acrylate or a mercapto acrylate is preferable. The SPCR system is an interval unit between a monomer unit and a photoreactive group, and can be suitably used if it is used in the field. As such a series of intervals, for example, -(CH2) (but, any one of ρ, Bu 12), i, 2 propylene, j, 3-butene, cyclopentene, 2 - 2 Anthraquinone, cyclopentene-1,3-dioxene, cyclohexene-κ3-diindole, cyclohexene-1,4-dioxin, piperidine-h4-dihydrazine, piperazine- 14-dioxin, ^ = phenylene, 1,3 - stupid or bismuth, 4 phenylene, etc. Among these interval units, it is preferable that one (CH2) ρ ~ (however, ρ is any integer of i to 丨2). 13 201238980 As the P system, it is preferable to use any integer of 3 to 9, wherein it is more desirable to be any integer of 5 to 7, and the best ideal is 6. The ring A is an unsubstituted or substituted alicyclic hydrocarbon or an unsubstituted or substituted aromatic, wherein an unsubstituted or substituted aromatic ring is preferred, and an unsubstituted aromatic ring is more preferred. The ring B is an unsubstituted or substituted aromatic ring, and among them, an unsubstituted aromatic ring is preferred. Both the ring A and the ring B are divalent groups as represented by the formula (1). However, in the present specification, the ring A or the ring B is "unsubstituted" and means a bond forming these divalent groups. The key hand other than the hand becomes "non-replacement". Further, in the present specification, in the state in which the ring A and the ring B are exemplified by the structural formula, the bond hands on the main chain side reach the left side side chain end when the bond hands forming the divalent group are formed. The key hand on the side reaches the right side. The substituent of the ring A (Χ1Α~Γ2Α) and the substituent of the ring B (χ1Β to X) are each independently selected from the group consisting of an alkyl group, an alkoxy group, a cyano group, a nitro group and a south atom, wherein Most preferably an alkoxy group. Each of the ring Α or the ring B has one or two or more substituents. The number of substituents which are ideal for ring A or ring B is 1. As the Z series, alkyl, alkoxy 'cyano, nitro, dentate atom, -•Ci^CHZ1, one C^CZ1 (however, Z1 alkyl, alkoxy, alkoxycarbonyl, alkoxy A sulfonyl group, a cyano group, a nitro group or a dentate atom.), or a S〇3Z2 (however, a Z2 alkyl group), wherein an alkoxy group is preferred. In the above description of the Z1 system, an alkoxy group is preferred. The R series is a hydrogen atom, a methyl group, a stupid group, or a gas atom, and among them, a hydrogen atom and a methyl group are preferred. In the present specification, the alkyl group is a carbon number of 1 to 12, which is 14 201238980. 'It is best to list the carbon number 1 to 6, and it is more desirable to enumerate the carbon number 1 to 4. The ideal is to cite the methyl group. As the alkane, among them, #################################################################### Helmet ^ _ prime atom series of fluorine atoms, gas atoms, > stinky atoms, shirts, of which, preferably, the atom. The photoreactive polymer (1 or solvent) of the present invention is polymerized by the formula (n): (9) Μ-SPCR-ο

, 0 m [In the chemical formula, the symbol 1 千夕i 神工" has the meaning of the face-to-face description.] The table ^ ... In the state where M represents one type of monomer unit, each is obtained by la The first reactive polymer in (1) is a uniform =, and in the state where M represents two or more monomer units, the photoreactive polymer is a copolymer which polymerizes the early monomers of the plurality of monomers.聚干# Ink can be implemented by using light or heat. There is no particular limitation on the method of loading the monomer in the polymerization process, and it is possible to pre-inject all A in I5. After 廿4 to the reaction vessel, start the polymerization, and then start the polymerization on the monomer or the sputum, and then start the polymerization.浐λ哲 residual. The second J technique is added in stages. In addition, when the monomer (π) can contain other... I, there is no need to 'but' the body, such early system is only limited to have The unsaturated bond of polymerizability (for example, the aspect of 7 p is not particularly limited, and can be > f f,,. The compound of the saturated bond) may be a compound having liquid crystallinity other than this, or a compound having no liquid crystallinity may be used as a monomer of 201238980. As such a monomer series, for example, a mercapto (mercapto) acrylate, t — Butyl (meth) acrylate, stearin (meth) acrylate, cyclohexyl (meth) acrylate, ethoxyethyl (meth) acrylate, ethyl (meth) acrylate Dilute ester, phenyl (meth) acrylate, N, n-dimethyl acrylamide, etc. (mercapto) propylene monomer, styrene, fluorenyl styrene, ρ - stupid vinyl sulfonic acid, ethyl Vinyl ether, hydrazine-vinylimidazole, vinyl acetate 'vinyl pyridine, 2-vinyl naphthalene, vinyl chloride, vinyl fluoride, fluorene vinyl carbazole, vinyl amine, vinyl phenol, hydrazine - ethylene a vinyl monomer such as 2-pyrrolidone, 4-allyl-indole, 2-monooxybenzene, 4-allylphenol, 4-monooxyallyl, etc. Maleic anhydride imide, such as allyl monomer, phenyl maleic anhydride imide, cyclohexyl maleic anhydride, or the like Any one of these single-systems may be used alone or in combination of two or more. In the state of being polymerized in a solution, a general-purpose organic solvent can be used without particular limitation. As a specific example of the solvent, ethanol and C are used. Alcohol oxime solvent such as alcohol or butanol, ketone solvent such as acetone, mercaptoethyl fluorenone, methyl isobutyl ketone, f hexyl or cyclopentanone, ethyl acetate, butyl acetate, propylene glycol An ester-based solvent such as mercaptoacetate, diethyl ether or diethylene glycol: an ether solvent such as methyl, cyclohexane, cyclohexane, methylcyclohexane, toluene, toluene or the like The oxime solvent, a nitrile-based solvent such as acetonitrile, or a guanamine-based solvent such as N-methylpyrrole = acetylamine. These solvents may be used alone or in combination of two or more. A photopolymerization initiator can be used in the above polymerization. As the light 16 201238980, a polymerization initiator is used to form a uniform film by irradiation with a small amount of light, and therefore, a generally known photopolymerization agent can be used. As a specific example, for example, 2,2, azobisazobutyronitrile (AIBN), 2,2'-azobis(2,4-dimethyl phthalonitrile)-specific azonitrile-based photopolymerization Starting agent,

Α-amino ketone photopolymerization initiator, 4 _phenoxy dichloro acetophenone, 4 butyl butyl hydride, etc., Irgacure 907 (manufactured by Ciba Specialty Chemicals Co., Ltd.), Irgacure 369 (manufactured by Ciba Specialty Chemicals Co., Ltd.)醯乙醯, diethoxyethyl benzene, 1_(4-isopropylphenyl)-2-hydroxy-2-indolyl propyl 1-keto, 1-hydroxycyclohexyl phenyl ketone, 2 — Ethyl benzene photopolymerization initiator, benzoin, benzoin methyl ether, etc., benzyl 2- 2 - decylamino 1 - (4 morpholinyl phenyl) 1-butane-1-one , benzoin ethyl ether, benzoin isopropyl ether, benzyl dimethyl ketal, the exclusive photoinitiator, diphenyl sulfonium, benzoquinone benzoic acid, benzoquinone benzoic acid Dibenzophenone photopolymerization of methyl ester, 4-phenylbenzophenone, hydroxybenzophenone, propylene dicumenone, 4-alum, 4'-mercaptodiphenyl sulfide a thioxanthone-based photopolymerization initiator, a starting agent, a 2-oxothioxanthone, a 2-mercaptothioxanthone, an isopropylthioxanthone, a 2,4-diisopropylthioxanthone, 2, 4, 6 — three gas and one s Triazine, 2-phenyl- 4,6-bis(tris-methyl)~s-triazine, 2-(p-decyloxy)- 4,6-bis(dichloromethyl)-s —三0秦, 2_(p-甲笨基)-4,6 — bis(trimethylmethyl)-s-triazine, 2-pipeline--4,6-bis(tri-methyl)-5- 2°Q, 2,4-bis(trichloroindenyl)-6-styrene-s-triazine, 2-(naphtho-1)- 4,6-bis(tri-methyl) a s-triazine, 2-(4-methoxy-naphtho-indole-indole)-4,6-double (III 17 201238980 chloropurinyl)-s--tris-, 2,4-tris-methyl a triazine-based photopolymerization initiator, oxadiazole-based light, such as (pipeney-based)-6-triazine, 2,4-trichloromethyl (4'-fluorenyloxy) vinyl-6-triazine a polymerization initiator, an imidazole photopolymerization initiator, etc.; and a decyloxy ester, a mercaptophosphine oxide, a methylphenylglyoxylate, a benzyl group, a 9,10-phenanthrenequinone, a camphorquinone, a Base, 4, 4'-diethylisophthalonitrile, 3, 3', 4,4'-tetra(t-butylperoxycarbonyl)benzophenone, 4, 4 -Diethyl amino benzophenone, Ming, etc. thiazol ° Dayton photopolymerization initiator. The photopolymerization initiator may be used singly or in combination of two or more kinds. The temperature at the time of the polymerization differs depending on the kind of the monomer (jj), the type of the polymerization solvent, the type of the initiator, and the like, but it is preferably 4 〇 15 15 ° ° C, and more preferably 50 to 2 〇 t range. The photoreactive polymer (T) of the present invention obtained in this manner can be used in addition to a photopolymerization initiator, a surfactant, a solvent, etc., and can be appropriately added, and the addition of $& The polymerizable component component ' becomes a composition for a photo-alignment film. The content of these optional components is particularly limited. However, it is usually preferred to include the photopolymerization initiator in an amount of from about 1 to about 1 with respect to the total weight of the polymer (I). The % by weight of the surfactant is about 5% by weight of 〇 7η ' °·1, and the solvent becomes from 70 to about 99. The foregoing can be used similarly as a photopolymerization initiator. In order to form a uniform film, the α Φ activating agent 11 is used for sulfuric acid: two-purpose: a surfactant. As a specific example series, for example, the moon, the sulphuric acid, the lauryl sulfate, the triethanolamine, the poly 18 201238980, the sulphate, the sulphur-based sulphuric acid vinegar, the naphtha Ananiline surfactant such as potassium myristate, coconut oil fatty acid potassium, sodium laurel sarcosinate; polyethylene glycol monolaurate, sorbitan stearate, myristate, dioleic acid a nonionic surfactant such as glyceride sorbitan stearate or sorbitan oleate; stearic acid trimethylammonium vapor, gasified camellyl trimethylammonium, gasification hard a cationic surfactant such as decyl dimethyl benzyl ammonium or cetyl trimethyl ammonium chloride; lauryl betaine, alkyl sulfobetaine, coconut amidinopropyl betaine, alkyl di An amphoteric surfactant such as an alkylbetaine such as decylaminoacetic acid betaine, a sodium alkyl laurate, a sodium citrate, and a sodium amphoteric acid sodium acetate; and ΒΥΚ-361, ΒΥΚ-306, BYK-3 〇7 (Japan Βγκ Chemical Company illusion, Fluorad F_ (manufactured by Sumitomo 3), FI 71. A surfactant such as R〇8 (manufactured by Dainippon Ink Chemicals Co., Ltd.). These surfactants may be used singly or in combination of two or more kinds. Solvent in this field, as

In the case of the bright-light aligning film composition, it is also possible to use two kinds of the present invention, and the present invention 19 201238980 can be applied to the substrate as needed to distill off the solvent. 'Become a light alignment film. Examples of the substrate constituting the substrate include a glass substrate such as quartz glass, glass, and alkali-free glass, polyimide, polyamide, acrylic resin, polyethylene glycol, triethyl cellulose, and polyethylene. a resin substrate such as a terephthalic acid (tetra), a ring-shaped dilute hydrocarbon, a polyethylene, a polyethylene carbonate, a tetraphenyl ether, a polyfluorinated ethylene, or the like, and a metal substrate such as iron, aluminum or copper. More desirable is a glass substrate. As a method generally known as a composition for a photo-alignment film, a coating method of a method, a die coating method, or a screen printing method may be, for example, a spin coating method, a bar coating method, or a spray coating method in the field. Method and so on. The drying process can be carried out by any of the methods generally used in the field, and is not particularly limited as long as it is a film forming a resin layer. The linear polarizing system may be irradiated by any of the direction perpendicular to the crucible or the direction of the tilt, but it is preferable to irradiate it in the vertical direction. In the present invention, the linear polarization system includes a surface of a vibration direction of an electric field (or a magnetic field) to be specified in the __ 夕 夕. The first linear light system of the soil and the species can be used by the light source, the polarized light sheet or the polarized prism light system. If it is infrared light or visible light, the line is stupid, v, and outside (near ultraviolet light, far When purple is irradiated with a chemical reaction such as a ray, a ray, a charge, or a charged particle beam (for example, an electron beam), there is no particular limitation. Usually, the illuminating line has two illuminating lines. From the point of view of the wavelength of nm to 500, and the point of view of the four sexes, it is best to use near ultraviolet rays of coffee (10) to 45 〇 nm 20 201238980. As the light source series, for example, a xenon lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal toothed lamp, or the like can be cited. The ultraviolet light or visible light obtained by such a light source can be used to limit the wavelength range of the irradiation using an interference filter or a color filter. The irradiation energy differs depending on the type or film thickness of the photoreactive polymer (丨), but is usually about 10 mJ/cn] 2 to 5 μm J/cm 2 . For example, in the polymerization comprising the poly(丨-[β _ [ 4 —[ 4 —(methoxy)phenoxycarbonyl]]oxy]hexyloxycarbonyl]-indenylmethyl] synthesized by the examples] In the state of a film having a thickness of about 100 nm, it is about 250 to 4000 mJ/cm 2 . Further, when a linear ray is irradiated, if a reticle is used, the alignment energy of the liquid crystal or the like can be generated in a pattern in the direction of the photoalignment film in two or more directions. Specifically, after coating and drying the composition for a photo aligning film of the present invention, the reticle is covered thereon, and the linearly polarized light is irradiated, and only the exposed portion is imparted with the alignment & Xiao, repeating this complex two owes, and generating the aligning energy in a pattern in a plurality of directions. In the case of the photoalignment film of the present invention, the film thickness is preferably from about 1 Å to about 50 Å, more preferably from about 1 Torr to about 5 Å, even more preferably from about 100 Å to about 200 nm. The scope. By coating a liquid alignment film obtained in this manner, it is possible to apply a liquid crystal) biochemical alpha substance (including a liquid crystal compound which is a dye or a liquid crystal compound which becomes a conductive I·biochemical substance), and heat this to the liquid crystal. The compound is not more than the temperature of the liquid crystal state, and after being aligned with the 21 201238980 of the m compound, it is cooled until the liquid crystal compound shows that the temperature of the liquid crystal state is not full, and the alignment state of the liquid crystal compound is fixed. The retardation film, the viewing angle improvement m, the brightness enhancement film, the polarizing film, and the like, various optical anisotropic films, conductive materials, nonlinear optical materials, photoreactive actuators, and the like Various optical materials. The coating may be carried out by dissolving in a solvent in the state of applying a liquid crystal compound as required. As such a solvent system, a solvent which is generally used in the field can be used. Specifically, the foregoing, that is, toluene 'ethylbenzene, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, propylene glycol methyl ether, dibutyl ether, acetone, methyl ethyl fluorenone, SI, propanol, cyclohexane, cyclopentanone, methylcyclohexane, tetrahydrofuran, dioxins, cyclohexanone, n-hexane, ethyl acetate, butyl acetate, propylene glycol methyl ether Acetic acid cool, methoxybutyl acetic acid (a) - methyl port ratio (tetra), dimethyl ethyl ugly amine and the like. Any of these may be used alone or in combination of two or more. Further, even if these dyes, conductive compounds, and liquid crystal compounds are mixed in a state in which a dye or a conductive compound of a liquid crystal compound is not present, the same as the description of the kneading surface, or these colors: or The conductive compound 'dissolved in the solvent' is applied to the optical alignment crucible and dried, and various optical anisotropy (IV) or optical material can be produced. Here, the liquid crystal compound, the dye, and the conductive compound can be suitably used. Use is usually used in the field. For example, as a liquid crystal compound, a cyanobiphenyl nematic liquid crystal or the like is used. The dye is a dichroic dye such as an azo-based dye (a polyazo-based dye or a diazo-based dye) or a window I-based product. As a series of conductive compounds, for example, 22 201238980 porphin and the like. Further, the above-mentioned solvent can be used in the same manner as the solvent in the case of applying the liquid crystalline compound. + The optical anisotropic film and the optical material of the present invention obtained in the same manner are different in thickness, and in general, it is preferably in the range of 0.1 to 20·0 Å, and more preferably i Further, if the photo-alignment film of the present invention is used, a liquid crystal cell comprising the photo-alignment film can be produced. For example, the photo-alignment film can be aligned to form one side. The direction of the polarization axis when the linear alignment film is irradiated with the polarized light and the direction of the polarization axis when the linear alignment light of the other side of the light alignment film is irradiated to each other to form an angle (for example, Μ., 18 〇. Any one of the angles, etc., is filled with a liquid crystal compound between the opposite photoalignment films to produce a liquid crystal cell. The photoreactive polymer (!) of the present invention is in addition to a photopolymerization initiator, interface activity. In addition to the agent, the solvent, and the like, a component which is contained in the polymerizable composition which is polymerized by light and heat, and which is a composition for an optical anisotropic film, may be added as appropriate. Special limit However, it is usually preferred that the photopolymerization initiator is included in a large amount, from about i to about 5% by weight based on the total weight of the polymer, the surfactant is from about 0.1 to about 1% by weight, and the solvent is about 50%. Any of the components of the photopolymerization initiator, the surfactant, the solvent, and the like may be similarly used in the above-mentioned composition for a photo-alignment film. However, the photoreactive polymer (Ϊ) The liquid crystal compound is usually a liquid crystal compound, and in the state of production, when the other monomer added during the polymerization of the monomer is a compound having no liquid crystal property, the addition of the other monomer 23 201238980 can be used. The amount of the polymer (i AU JA ^ ^ becomes a compound exhibiting no liquid crystallinity. Thus, in the case where the polymer (z) ^ UL. At _ is a compound having no liquid crystallinity, When the τ., the use, and the preparation of the product are modulated, one part of the polymer (I) is replaced with the liquid s + and replaced with a liquid crystal compound, and the photonic heterojunction film is integrated as a whole. 15 - No LCD As an additive such as coupled-based liquid crystal compounds can all, generally used for people to swallow for use in the field

For example, it is preferably a liquid crystal compound composed of a knife of the skin of the skin, or a nematic liquid crystal. By preparing the optical anisotropic film of the present invention obtained as described above and applying it to the substrate by the article, after the linearly polarized light is irradiated, the package 3 is applied to the composition of the anisotropic optical film. The liquid crystal compound is heated to a temperature higher than the temperature at which the liquid crystal is not present, and is aligned with the liquid crystal compound, and the liquid crystal compound is cooled to a temperature at which the liquid crystal state is not formed, and the alignment state is fixed to produce an optical heterodyne. Sex film. The substrate constituting the substrate, the coating method, the irradiation of the linearly polarized light, and the like are all the same as those of the above-described photoalignment film. Further, the thickness range of the obtained optical anisotropic film is the same as that of the above-mentioned optical anisotropic film. In the following, the present invention will be specifically described by way of examples, but the present invention is not limited to the following examples at all. [Example 1] Synthesis of 4-(6-hydroxyhexyloxy)benzoic acid:

In water 400. 〇g, dissolved 4 by benzoic acid 100. 〇g (0.7 Mo 24 201238980 er) and hydroxide needle 105.1 g (i. 6 Mohr). In the solution, 6-air hexanol i 8.8 g (〇.8 mole) was dropped over 1 hour. Then, heating and refluxing were carried out at 100 °C. After the lapse of 20 hours, the reaction mixture was cooled, and the mixture was vigorously stirred, and 34.5 ml of hydrochloric acid was added dropwise at room temperature, 34. 6 g (1.7 mol). The precipitated solid was taken up and recrystallized by 400 g of tetrahydrofurfuryl (THF) to give 4 - (6-pyridyloxy)benzoic acid 12 0 · 〇g (0.5 mil) and became white. crystallization. The yield is 69.5%, and the melting point is 135~14 (TC. 2. 4- [6-(2-Mercaptopropenyloxy)hexyloxy] benzoic acid.

In 480. Og of THF, 40.0 g (0.5 mole) of 4-(6-hydroxyhexyloxy)benzoic acid and 815 g (0-8 mole) of triethylamine were dissolved. 2 g (〇·8 莫尔) was added dropwise to the solution of the thioglycolic acid chloride after 1 hour. Then, it was heated to 4 (TC. After 4 hours, the reaction liquid was cooled, and water 240. 〇g was added. In the separated organic layer, 1% hydrochloric acid 367. (1 mol) was added and stirred, and concentrated. The organic layer is recrystallized from the residue by a 笨g. 〇g to obtain 4-(6-(2-methylpropanyloxy)hexyloxy]benzoic acid 96.〇g ( 0.3 moles and white crystals. The yield is 62.2% and the melting point is 81〇c. 3. 4:[6-(2-mercaptopropenyloxy)hexyloxy]benzoic acid 4 ~ (decyloxy) Synthesis of stupyl esters:

201238980 In the second gas methane 960g, dissolved 4 ~ [6 - (2 - methacryloxy) hexyloxy] benzoic acid 96.0g (0.3 mole), methoxyhydroquinone 38.9g ((). 3 Mo And N,N-didecylamino group 0 to pyridine 7·7g (〇·i moir). In the solution, dicyclohexylcarbodiimide (DCC) 71. lg (〇. 3 moor) was added. After reacting at room temperature for 2 hours, 288 g of water was added. The separated organic layer was concentrated, and the residue was recrystallized from toluene (100 g) to give 4-(6-(2-mercaptopropenyloxy)hexyloxy]benzoic acid 4-(methoxy)phenyl ester. 〇3g (〇.2 moir) becomes white crystal. The yield was 79.6% and the melting point was 52. Hey. 4. Synthesis of poly[H6-[4-[4~(methoxy)phenyloxy]phenoxy]hexyloxycarbonyl]-1-methylethene]:

Dissolved in cyclohexanone 412g' 4-[6_(2-methylpropionyloxy 3 hexyloxy)benzoic acid 4-(methoxy) stupid vinegar 1〇3g (〇2mol: 〇.8g ( 5 millimoles of coffee. In this solution, i is small for nitrogen and then 'heated to 8 ° C. After 10 hours, the cooling reaction is vigorously stirred vigorously, and 'at room temperature, drip until it is simmered = The separated polymer was taken under reduced pressure, and dried to obtain 83.4 g of the labeled polymer. The yield was 81%. (Measurement of Weight Average Molecular Weight (MW)) Using gel chromatography ( The weight average molecular weight (.) of the polymer described above was determined by GPC. The weight average score obtained was 26 201238980 (MW) was 31 000. (Measurement of phase transition temperature) Determination using differential scanning calorimetry (~ % When the phase transition temperature of the polymer obtained as described above is measured, it becomes 7 〇 to i3 〇 c > c. 5. The preparation of the photo-alignment composition is dissolved in the polymer 5g' obtained as described above. As a result, it becomes a composition for a photo-alignment film 1. 6. Fabrication of a photo-alignment film on a quartz glass substrate Using a spin coating > this bismuth, coated with the film of the photoalignment film obtained by the above description, i ^ 叩 叩 大约 about 100 nm thick film. On the obtained substrate, use Gran Taylor.稜鏡, will be converted into linear polarized ultraviolet (1) mW / em2), (d) in the direction of the substrate in the vertical direction, 2 hrs of exposure, on the violent pull on the 'making light alignment 臈. (Phenyl phthalate backbone light cracking, etc. Confirmation)

It is confirmed by linear polarized light irradiation that the light cleavage of the benzoic acid vinegar is confirmed to produce a light Fries transition, and therefore, the same; the description is observed by polarized microscopic infrared spectroscopy. The film changes when the spring is polarized. The results are shown in the chart below. The same watch system measures the absorption in the same direction (coaxial spectrum: Abs 1 ) and the absorption in the vertical axis direction (vertical = axis light 4. Abs2) with respect to the polarization axis of the linearly polarized ultraviolet light to be irradiated, and the former is represented by a solid line. The latter is represented by a dotted line. In addition, for comparison, therefore, the value of AbS2 is subtracted from Absl to be 5 times the value (difference spectrum: Absl - Abs2 (X 27 201238980 5). It is known that if the difference spectrum is used, then The axis of the polarized ultraviolet light relative to the Zhao line is coaxial with the coaxial direction, .line -1 „ /χ* v 1 260cm 1 and the peak near 1196cm, increase by 1 727, see the peak. The peak of the reduction is by stupid The hydroxyl group of the formate skeleton and the absorption peak of the double, the peak of the increase is caused by a few bases (Fig. 2). Therefore, the reduction of the absorption peak is 'read relative to the linear polarized ultraviolet light. The polarizing axis is coaxially present in the benzoic acid s|bone system, causing the solution to disappear and partially disappear. In addition, by the force of the absorption peak, the ester which is coaxially present with respect to the polarization axis of the linearly polarized ultraviolet light is read ( The carbonyl group of the benzoic acid ester is converted into a carbonyl group of a ketone by photocleavage or light FriM f & flashing, and the carbonyl group of the ketone. (Evaluation of optical alignment) Knowing that it forms light Of the substrate film 2 to such that the form of greenish upon irradiation of linearly polarized ultraviolet rays become parallel, a liquid crystal cell, the liquid crystal cell "fill f Disperse dispersion dichroic Xingse

Liquid No. E7 (manufactured by Merck Co., Ltd.) of Bluel 4 (Aldrich Co., Ltd.) was heated to 8 Torr until the liquid crystal was in an isotropic phase, and then cooled to room temperature. When the liquid crystal cell was observed by a polarizing microscope, it was confirmed that the liquid crystal alignment was perpendicular to the polarization axis of the linearly polarized light which was irradiated. 7. Production of liquid crystal cell The two substrates which form the photoalignment film obtained in the above-mentioned 6 are opposed to each other such that the polarizing axis of the linear polarizing material line is orthogonal, and a liquid crystal cell is produced, and the liquid crystal cell is filled with liquid crystal E7. , making tn type liquid crystal. 28 201238980 It is confirmed that the liquid crystal cell is correctly driven by applying a voltage between the two substrates of the TN type liquid crystal cell. 8. Preparation of composition for optical anisotropic film 5 g of the polymer obtained in the above 4 was dissolved in 5 g of THF to form an optical anisotropic film composition 1. 9. Production of optical anisotropic film On the glass substrate, the optical anisotropic composition 1 was applied by a spin coater to a thickness of about i. 2 " m, and dried. On the obtained substrate, Glan Taylor was used to convert the ultraviolet light (10 mW/cm) into a linearly polarized light, and the substrate was irradiated for 2 (10) seconds in a direction perpendicular to the substrate. After heating the substrate at 80 C for 20 minutes, it was cooled to room temperature. When the film formed on the substrate was observed by a polarizing microscope, the brightness and darkness were observed to confirm that the optical film was already produced. When the double refractive index of the optical anisotropic film produced was measured using a polarizing analyzer OPTIPR (manufactured by SYMTEC Co., Ltd.), the values of Δη υ 5 and 126 nm were displayed, and it was confirmed that it can be used as a retardation film. [Industrial Applicability] . . . (4) The photo-alignment film or optical anisotropic film produced by using this, and the alignment of the liquid crystal compound on the photo-alignment film. And a, the phase of the film, the film for the viewing angle, the film for brightness enhancement, the film for brightness enhancement, and various j-shaped films, or conductive materials, non-linear materials, and optical Materials for various optical materials such as actuators, ^ m β wei and 'photon anisotropic film or optical material system can be used as a variety of optical month 29 201238980 'special use in computers Or the floor of a fax machine, etc.. Display of the thief, mobile phone, electronic notebook, LCD TV, video recorder, etc. [Simplified description of the drawing] Fig. 1 is a light alignment film to be used in the embodiment 1. The film composed of the composition , is shown by a polarizing micro-infrared spectroscopy method as a result of observing the change of the film when the linearly polarized light is irradiated. Fig. 2 is a view showing the photoreactive polymer of Example 1. Showing absorption signals of 1 260cnTi and 1196^" About hydroxy benzoate skeleton of 'absorption peak of about 1727CHT1 carbonyl group. The main element 30 None REFERENCE NUMERALS

Claims (1)

201238980 VII. Patent application scope: 1. A photo-aligning composition, which will have the formula (丨): α) '~|~~^ Ο~~{μέπ-Ζ [in the chemical formula] a monomer unit of a main chain of a homopolymer or a copolymer, an SPCR-based spacer unit, a cyclic oxime-based unsubstituted or substituted alicyclic hydrocarbon or an unsubstituted or substituted aromatic ring, a ring B-based unsubstituted or substituted aromatic ring, z-system Alkyl, alkoxy, cyano, nitro, halogen atom, -, -C tri CZ1 (however, ζι is alkyl, alkoxy, alkoxycarbonyl, alkoxysulfonyl, cyano, nitrate A photoreactive polymer having a repeating unit represented by a group or a halogen atom), _C00Z2 or -S0J2 (but 疋, Z-based 9 group) is contained. 2. The composition for a photo-alignment film according to claim 1, wherein the substituent of the % A and the substituent of the ring B are independently independently composed of an alkyl group, an alkoxy group, a cyano group, a nitro group and a nitro group. One or more than one selected from the prime atom. 3. The composition for a photo-alignment film according to the first aspect of the patent application, wherein the lanthanide is an acrylate, a methacrylate, a 2- oxy acrylate, a 2-phenyl acrylate, an acrylonitrile phenylene, or a propylene. Indoleamine, mercapto acrylamide 2 apocreamide, 2-phenyl propyl amide, ethyl sulphate, styrene, bioethene, maleic acid derivatives, fumaric acid derivatives One or more monomer units selected from the group consisting of oxime and epoxide, the SPCR system consists of one (CH2) ρ_ (however, ρ is i~12 of 31 201238980 any integer) 1,2 ~ propylene, 1, 3 - butene, cyclopentene - 1, 2 - 2 - brewed, cyclopentene - 1 . —二醯,cyclohexene-1,3—biquinone,cyclohexene-1,4—two brewed, a 疋—15 4 one or two brewed, british one 1,4—two brewed, 1,2 benzene The group consisting of the building, 1, 3, a stupid, 1, 4 - benzene support to select the interval unit, the ring A is by. [However, Xu~X42A is a system in which the argon is independently a hydrogen atom, an alkyl group or an alkoxy group, and the ring B is: Halogen atom or sulfhydryl group] [ [ [However, Χ1Β~ χ4β Β is an eight-w γ dentate atom or an aryl group; 7 is a hydrogen atom, a pyridyl group, an alkoxy group, any kind of money atom, an oxygen atom, 4. The sulfur atom is represented by 4. As disclosed in the patent specification, the composition of the light alignment film of the broadening to the w, _, the at least one of the species, the Χ5β and at least one, the χ|3Β and the p 32 201238980 A hydrogen atom of at least one of χ25β and at least one of χ3〇 and χ39Β. 5. A composition for a photo-alignment film having a formula (][-a) (I_a) [In the chemical formula, R is a hydrogen atom, a methyl group, a phenyl group or a chlorine atom, and each of χΐΑ~ρ and X~X is independently a hydrogen atom, an alkyl group, an alkoxy group, or a dentate. Atom or cyano group, Z-based alkyl group, alkoxy group, aryl group, nitro group, elemental proton, -CH=CHZ1, - (5), but Z* system, alkoxy, alkoxy Base, oxyalkyl, cyano, nitro or i atom), -C00Z2 or -S〇3Z2 (but 'z2 alkyl),? The photoreactive polymer of the repeating unit represented by any one of the integers of 12 is composed of. 6. The light of the fifth aspect of the patent application, particularly for a film composition, wherein at least one of X and X4B is a hydrogen atom. /, 7. - A kind of light alignment film, prepared for # # # ^ # , , , , # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # It consists of a linear polarized light. 8. An optical anisotropic film or optical material „ E is composed of a light alignment film according to item 7 of the scope of the patent, which is composed of a liquid crystal compound. Pigment or conductive compound 9. A liquid crystal cell, the scope of patent application The first alignment film 2 pieces 33 201238980 is opposite, and the direction of the polarization axis when the linear alignment light of one side of the light alignment film is irradiated with the direction of the polarization axis when the linear alignment light of the other side of the light alignment film is irradiated is mutually Forming a predetermined angle, and composing a liquid crystal compound between the opposing photo-alignment films. 10. A composition for optical anisotropic film, which has a general formula [In the chemical formula, the lanthanide forms a monomer of a main chain of a homopolymer or a copolymer, such as a position, a SPCR-based spacer unit, and the ring a is an unsubstituted or substituted aromatic ring, a ring-based alkyl 'alkoxy group, a cyano group, - CeCZ1 (however, the Z1 is a thiol group, a cyano group, a nitro group or a dentate (but a Z2 group)) is represented by inclusion. It is an unsubstituted or substituted alicyclic hydrocarbon or a B-based non- a photoreactive polymer substituted or substituted for an aromatic ring, a z-group, a ii-atom atom, a -CHsCHZ1, an alkoxy group, an alkoxycarbonyl group, an alkoxy atom, or a C00Z2 or -s〇3z2 repeating unit. An optical anisotropic film, car damage force feces. m + is prepared on the surface of the substrate to apply for a patent. The optical anisotropic film of the 10th item is used for the composition of the torsion film. After the irradiation is linearly polarized, 'the liquid crystal compound of the composition of the L-ray-drying film is heated to a temperature higher than the temperature at which the liquid crystal state is displayed, and the liquid crystal compound is cooled to no more. It is composed of the temperature of the liquid crystal state. 34