CN105705497B - Polymerizable liquid crystal compound, liquid-crystalline polymer, liquid crystalline composition and single coating type horizontal alignment film - Google Patents

Polymerizable liquid crystal compound, liquid-crystalline polymer, liquid crystalline composition and single coating type horizontal alignment film Download PDF

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CN105705497B
CN105705497B CN201480060544.5A CN201480060544A CN105705497B CN 105705497 B CN105705497 B CN 105705497B CN 201480060544 A CN201480060544 A CN 201480060544A CN 105705497 B CN105705497 B CN 105705497B
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polymer
horizontal alignment
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CN105705497A (en
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丹尼尔安东尼奥樱叶汀
后藤耕平
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Nissan Chemical Corp
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    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/20—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers
    • C09K19/2007—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers the chain containing -COO- or -OCO- groups
    • C09K19/2014—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers the chain containing -COO- or -OCO- groups containing additionally a linking group other than -COO- or -OCO-, e.g. -CH2-CH2-, -CH=CH-, -C=C-; containing at least one additional carbon atom in the chain containing -COO- or -OCO- groups, e.g. -(CH2)m-COO-(CH2)n-
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    • C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
    • C09K19/3402—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom
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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
    • G02B5/305—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
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    • C09K2019/0444—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group
    • C09K2019/0448—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group the end chain group being a polymerizable end group, e.g. -Sp-P or acrylate
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    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/20—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers
    • C09K19/2007—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers the chain containing -COO- or -OCO- groups
    • C09K2019/2042—Ph-Ph-COO-Ph
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    • C09K2219/00—Aspects relating to the form of the liquid crystal [LC] material, or by the technical area in which LC material are used
    • C09K2219/03—Aspects relating to the form of the liquid crystal [LC] material, or by the technical area in which LC material are used in the form of films, e.g. films after polymerisation of LC precursor

Abstract

The present invention provides the polymerizable liquid crystal compound represented by formula [1] and liquid-crystalline polymer, the liquid crystalline composition containing the liquid-crystalline polymer and the single coating type horizontal alignment film obtained by said composition containing the repeat unit represented by formula [2a] and [2b].Formula [1] (in formula, p is 2~9 integer)；[in formula, X is the group of formula [3] or [4] expression to formula [2a] [2b]；M is the group that formula [5] represents；M and n is 0≤m of satisfaction ＜ 100,0 ＜ n≤100, the number of m+n≤100；P and q is each independently 2~9 integer.Formula [3] [4] (in formula, R1For hydrogen or methyl；Dotted line is bonding key)；(in formula, s1 and s2 are 1 or 2 to formula [5]；G1For singly-bound, COO or OCO；R2For hydrogen, halogen, cyano group, alkyl or alkoxy；Dotted line is bonding key.)].

Description

Polymerizable liquid crystal compound, liquid-crystalline polymer, liquid crystalline composition and individual layer apply Cloth type horizontal alignment film
Technical field
The present invention relates to the painting of polymerizable liquid crystal compound, liquid-crystalline polymer, the composition containing the polymer and individual layer Cloth type horizontal alignment film.In detail, it is related to suitable be used in the optics for being suitable to the purposes such as display device or recording materials The polymerizable liquid crystal chemical combination of the material of characteristic, the particularly optical compensation films such as the Polarizer of liquid crystal display and polarizer Thing, liquid-crystalline polymer, the composition containing the polymer and the single coating type horizontal alignment film obtained by said composition.
Background technology
For the display grade for improving liquid crystal display device and the requirement of lightweight etc., as Polarizer or polarizer etc. Optical compensation films, increasingly increase to controlling the requirement of polymeric membrane of Molecular orientational structure of inside.Will in order to tackle this Ask, develop the optically anisotropic film having using polymerizable liquid crystal compound.
Polymerizable liquid crystal compound used herein is usually (with interval with polymerizable group and liquid crystal structure position Portion and the structure position in mesomorphic portion) liquid-crystal compounds, widely use acrylic as the polymerizable group.
Method that such polymerizable liquid crystal compound is polymerize generally by the irradiation radioactive ray such as ultraviolet is made Into polymer (film).
For example, as it is known that between the specific aggregation liquid-crystal compounds with acrylic is carried on into supporter, while will The compound is maintained at mesomorphic state, while irradiating radioactive ray to obtain the method for polymer (patent document 1)；And having There is in the mixture of 2 kinds of polymerizable liquid crystal compounds of acrylic or is mixed with the mixture the composition of chiral liquid crystal Middle addition Photoepolymerizationinitiater initiater, ultraviolet is irradiated to obtain the method for polymer (patent document 2).
In addition, there is reported in literature, it is not required to liquid crystal orientation film and uses the alignment films of polymerizable liquid crystal compound or polymer (patent document 3,4) or use the various single coatings such as the alignment films (patent document 5,6) of the polymer containing photo-crosslinking position Type alignment films.But the dissolubility of the polymer due to being used in above-mentioned film is low, N- methyl -2- must be used as solvent The excellent solvent of the dissolving powers such as pyrrolidones, chloroform, chlorobenzene, accordingly, there exist the refractive index of the film obtained by these solution is each Anisotropy (the problems such as characteristic such as Δ n), haze value deteriorates.
In addition, do not find just obtain the material of the alignment films of display low haze valus using simple technique so far.
Prior art literature
Patent document
Patent document 1：JP 62-70407 publications
Patent document 2：Unexamined Patent 9-208957 publications
Patent document 3：European Patent application discloses No. 1090325 specification
Patent document 4：International Publication No. 2008/031243
Patent document 5：JP 2008-164925 publications
Patent document 6：Unexamined Patent 11-189665 publications
The content of the invention
Invent problem to be solved
The present invention is to complete in view of the above problems, its object is to, there is provided it can be made by simpler technique Show the polymerizable liquid crystal compound of single coating type horizontal alignment film of low haze valus, liquid-crystalline polymer, contain the liquid crystal The liquid crystalline composition of property polymer and the single coating type horizontal alignment film obtained by said composition.
Means for solving the problems
The present inventor etc. further investigate repeatedly in order to solve above-mentioned problem, as a result find, by using main chain contain γ- Butyrolactone skeleton, and there is the liquid-crystalline polymer of cinnamic acid structure on the side chain extended the γ positions by lactonic ring, may It is due to form stable network structure after the polarized ultraviolet exposure of low light exposure, therefore, can be without using liquid The horizontal alignment film with Δ n is obtained in the case of brilliant alignment films, and then, the display low haze can be made under cryogenic The horizontal alignment film of value, so far completes the present invention.
That is, the present invention provides following polymerizable liquid crystal compound, liquid-crystalline polymer, liquid crystalline composition and individual layers Application type horizontal alignment film.
1st, polymerizable liquid crystal compound, it is characterised in that it is represented by following formula [1]：
[changing 1]
In formula, p represents 2~9 integer.
2nd, liquid-crystalline polymer, it is characterised in that wherein contain the repeat unit represented by following formula [2a] and [2b]：
[changing 2]
In formula, X is the group represented by following formula [3] or [4]：
[changing 3]
In formula, R1For hydrogen atom or methyl, dotted line is bonding key；
M is the group represented by following formula [5]：
[changing 4]
In formula, s1 and s2 are each independently 1 or 2；G1For singly-bound ,-COO- or-OCO-； R2For hydrogen atom, halogen atom, The alkoxy of cyano group, the alkyl of carbon number 1~10 or carbon number 1~10；Dotted line is bonding key；
M and n is to meet 0≤m ＜ 100,0 ＜ n≤100 and the number of m+n≤100 respectively；
P and q is each independently 2~9 integer.
3rd, liquid crystalline composition, wherein containing polymer and organic solvent described in 2.
4th, single coating type horizontal alignment film, its be by the way that the liquid crystalline composition described in 3 is coated on into substrate, then according to Penetrate polarised light, make its solidify obtained from.
5th, the single coating type horizontal alignment film described in 4, wherein, above-mentioned polarised light is rectilinearly polarized light ultraviolet.
6th, optical component, it possesses the single coating type horizontal alignment film described in 4 or 5.
The effect of invention
The liquid-crystalline polymer of the present invention contains gamma-butyrolacton skeleton on main chain.Therefore, the polymerization is contained by coating The composition of thing, in the rectilinearly polarized light of room temperature irradiation low light exposure, the technique dried after progress, make the list for showing low haze valus Layer application type horizontal alignment film is possible.
Embodiment
[polymerizable liquid crystal compound]
The polymerizable liquid crystal compound of the present invention is represented by following formula [1].
[changing 5]
In formula, the integer of p expressions 2~9, preferably 3~6.
The synthetic method of the polymerizable liquid crystal compound represented for formula [1], carry out aftermentioned.
[liquid-crystalline polymer]
The liquid-crystalline polymer of the present invention contains the repeat unit by following formula [2a] and [2b] expression.
[changing 6]
In formula [2a], X is the group of following formula [3] or [4] expression.
[changing 7]
(in formula, R1For hydrogen atom or methyl.Dotted line is bonding key.)
In formula [2a], M is the group represented by following formula [5].
[changing 8]
(in formula, s1 and s2 are each independently 1 or 2.G1For singly-bound ,-COO- or-OCO-, R2It is former for hydrogen atom, halogen Son, cyano group, the alkoxy of the alkyl of carbon number 1~10 or carbon number 1~10.Dotted line is bonding key.)
Herein, as halogen atom, fluorine, chlorine, bromine, iodine atom can be enumerated, in the present invention, preferred fluorine atom.
As alkyl, it can be any of straight-chain, branched, ring-type, be also not particularly limited for its carbon number. As the concrete example of abovementioned alkyl, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, normal-butyl, isobutyl group, Zhong Ding can be enumerated Base, the tert-butyl group, cyclobutyl, n-pentyl, cyclopenta, n-hexyl, cyclohexyl, n-heptyl, n-octyl, n-nonyl, positive decyl etc..Its In, the preferred alkyl, particularly preferred methyl, ethyl etc. of the alkyl, more preferably carbon number 1~3 of the carbon number 1~10 of straight-chain.
Can be any of straight-chain, branched, ring-type, for its carbon number also without special limit as alkoxy It is fixed.As the concrete example of above-mentioned alkoxy, methoxyl group, ethyoxyl, positive propoxy, isopropoxy, n-butoxy, isobutyl can be enumerated Epoxide, sec-butoxy, tert-butoxy, n-pentyloxy, positive hexyloxy, positive epoxide in heptan, n-octyloxy, positive nonyl epoxide, n-decyloxy Deng.Wherein, the alkoxy of the alkoxy, more preferably carbon number 1~3 of the carbon number 1~10 of preferably straight-chain, particularly preferred methoxyl group, Ethyoxyl etc..
It is explained, in abovementioned alkyl, alkoxy, some or all of its hydrogen atom can also use the halogen such as fluorine atom Atom substitutes.
As R2, particularly preferably hydrogen atom, fluorine atom, cyano group, methyl, methoxyl group etc..
As G1, preferably-COO- or-OCO-.
In formula [2a] and [2b], m and n represent the containing ratio (mol%) of each repeat unit, for meet respectively 0≤m ＜ 100, 0 ＜ n≤100 and the number of m+n≤100, consider from the viewpoint such as Δ n raising and the deliquescent raising of polymer, preferably divide Do not meet 0 ＜ m≤90,10≤n ＜ 100 number, more preferably meet 0 ＜ m≤50,50≤n ＜ 100 number.
In addition, in formula [2a] and [2b], p and q are each independently 2~9 integer, preferably 3~6, particularly as Q, more preferably 5 or 6.
The weight average molecular weight (Mw) of the liquid-crystalline polymer of the present invention is preferably 3,000~200,000, more preferably 4, 000~150,000, more preferably 5,000~100,000.If Mw is more than 200,000, then dissolubility in a solvent Reduce, make operational reduction sometimes；And if Mw is less than 3,000, then solidification becomes deficiency during heat cure, makes solvent tolerance sometimes Reduced with heat resistance.
It is explained, Mw is the polystyrene scaled value determined with gel permeation chromatography (GPC).
As long as in addition, do not damage the present invention effect, liquid-crystalline polymer of the invention can also contain formula [2a] and Other repeat units beyond [2b].As the polymerizable compound that can provide other above-mentioned repeat units, propylene can be enumerated Ester compound, methacrylate compound, maleimide compound, acrylamide compound, acrylonitrile, maleic acid Acid anhydride, distyryl compound etc..
In whole repeat units, the containing ratio of other above-mentioned repeat units is preferably 0~10mol%.If it is above-mentioned its His containing ratio of repeat unit is excessive, then characteristic, the characteristic such as liquid crystal liquid crystal property of polymer of the invention reduce sometimes.
It is explained, liquid-crystalline polymer of the invention can be in random copolymer, alternate copolymer, block copolymer It is any.
[synthesis of liquid-crystalline polymer]
The liquid-crystalline polymer of the present invention can be represented by the polymerizable liquid crystal compound and formula [6] for making formula [1] expression Polymerizable compound polymerize to obtain.
[changing 9]
[in formula, R2、G1, p, q, s1 and s2 it is as described above；The polymerizable group that X' is following formula [7] or [8] represent.
[changing 10]
(in formula, R1As described above.)]
The polymerizable compound that the polymerizable liquid crystal compound and formula [6] that formula [1] represents represent can be by by organic conjunction It is combined into the method in chemistry to synthesize, its synthetic method is not particularly limited.
It is for instance possible to use Talaga etc. (P.Talaga, M.Schaeffer, C.Benezra and J.L.Stampf, Synthesis, 530 (1990)) method that proposes synthesizes.This method is to use SnCl as shown in following synthetic schemes A12 The method for making 2- (bromomethyl) acrylic acid be reacted with aldehydes or ketones.It is explained, 2- (bromomethyl) acrylic acid can use The method of the propositions such as Ramarajan obtains (K.Ramarajan, K.Kamalingam, D.J.O'Donnell and K.D.Berlin,Organic Synthesis,vol.61, pp.56-59(1983))。
[changing 11]
Flow A1
(in formula, R' represents 1 valency organic group；Amberlyst (registration mark) 15 is Rhom and Hass's ion exchange Resin；THF represents tetrahydrofuran；Et represents ethyl.)
In addition, using SnCl22- (bromomethyl) acrylic acid reaction in, instead of aldehydes or ketones using corresponding Acetal or ketal are reacted, and can also obtain alpha-methylene-gamma-butyrolacton structure.As acetal or ketal, can enumerate Those have dimethylacetal base, diethyl acetal base, 1,3- bis-The compound of alkyl, 1,3- dioxolanyls etc..It is following The synthetic method and protection group being shown with synthesis flow A2 in the case of acetal or ketal.
[changing 12]
Flow A2
(in formula, R' is as described above.)
, can be with synthesis type by following synthesis flow B of the method that applies above-mentioned synthesis flow A1 or A2 method [1] compound represented.
[changing 13]
Flow B
(in formula, p is as described above.)
The polymerizable compound that formula [6] represents is prepared using for example following methods.
Work as G1For-COO- when, as shown in following flows, pass through make formula [9] represent benzoic acid derivative and phenol derivative Thing is condensed to prepare in a solvent, in the presence of condensing agent.
[changing 14]
(in formula, R2, X', q, s1 and s2 it is as described above；DCC represents N, N'- dicyclohexylcarbodiimides；DMAP represents N, N- dimethyl -4-aminopyridine.)
Work as G1For-OCO- when, as shown in following flows, derived by the phenol derivatives and the benzoic acid that represent formula [10] Thing is condensed to prepare in a solvent, in the presence of condensing agent.
[changing 15]
(in formula, R2, X', q, s1 and s2 it is as described above.)
When X' is the group that formula [7] represents, the compound of formula [9] and [10] expression can be used as SYNTHON Chemicals societies or Midori chemical (strain) commercially available product are bought.
In addition, when X' is the group that formula [8] represents, the compound represented by formula [9] and [10] can be by applying Following synthesis flow C or D of above-mentioned synthesis flow A1 or A2 method method synthesizes.
[changing 16]
Flow C
(in formula, q and s1 are as described above；Me represents methyl；PCC represents pyridine chlorochromateSalt.)
[changing 17]
Flow D
(in formula, q and s1 are as described above.)
As the method for the liquid-crystalline polymer of the synthesis present invention, it is not particularly limited, radical polymerization, the moon can be used Ionic polymerization, cationic polymerization etc..Wherein, particularly preferred radical polymerization, specifically, can draw in a solvent, in polymerization In the presence of sending out agent, above-mentioned polymerizable compound is heated so that it polymerize.
, can the suitably selection use from known polymerization initiator as polymerization initiator.Can enumerate for example, The peroxide such as benzoyl peroxide, cumene hydroperoxide, TBHP；Sodium peroxydisulfate, potassium peroxydisulfate, ammonium persulfate Deng persulfate；Azos such as azodiisobutyronitrile (AIBN), azobis methylbutyronitrile, AMBN etc..It Can be used alone, or two or more is applied in combination.
Relative to polymerizable compound 1mol, the usage amount of polymerization initiator is preferably 0.01~0.05mol or so.
Reaction temperature can from 0 DEG C to suitably set in boiling spread using solvent, preferably 20~100 DEG C of left sides It is right.Reaction time is preferably 0.1~30 hour or so.
As the solvent used in polymerisation, it is not particularly limited, as long as typically used from above-mentioned polymerisation Use is suitably selected in various solvents.Specifically, can enumerate：Water；Methanol, ethanol, 1- propyl alcohol, 2- propyl alcohol, n-butyl alcohol, 2- butanol, isobutanol, the tert-butyl alcohol, 1- amylalcohols, 2- amylalcohols, 3- amylalcohols, isoamyl alcohol, tert-pentyl alcohol, 1- hexanols, 1-heptanol, 2- heptan The alcohol such as alcohol, 3- enanthol, sec-n-octyl alcohol, 2- ethyl -1- hexanols, benzylalcohol, cyclohexanol；Anaesthetie Ether, Di Iso Propyl Ether, dibutyl ethers, Cyclopentyl-methyl ether, tetrahydrofuran, 1,4- bis-The ethers such as alkane；The halos such as chloroform, dichloromethane, dichloroethanes, carbon tetrachloride Hydrocarbon；The ether alcohols such as methyl cellosolve, ethyl cellosolve, ispropyl cellosolve, butyl cellosolve, diethylene glycol monobutyl ehter；Acetone, first The ketone such as base ethyl ketone, methyl iso-butyl ketone (MIBK), cyclohexanone；The esters such as ethyl acetate, butyl acetate, ethyl propionate, cellosolve acetate； Pentane, n-hexane, normal heptane, normal octane, n -nonane, n-decane, pentamethylene, methyl cyclopentane, hexamethylene, methyl cyclohexane The aliphatic hydrocarbons such as alkane, benzene,toluene,xylene, ethylbenzene, methyl phenyl ethers anisole or aromatic hydrocarbon；The acetals such as dimethoxym ethane, diethyl acetal；Formic acid, The aliphatic acid such as acetic acid, propionic acid；Nitropropane, nitrobenzene, dimethylamine, MEA, pyridine, METHYLPYRROLIDONE (NMP), N,N-dimethylformamide, dimethyl sulfoxide, acetonitrile etc..They be can be used alone, or two or more is mixed Use.
When the liquid-crystalline polymer of the present invention contains other repeat units beyond formula [2a] and [2b], as its synthesis Method, when carrying out above-mentioned polymerization, as long as in the bar that the polymerizable compound of other above-mentioned repeat units of offer can coexist It is polymerize under part.
[liquid crystalline composition]
The liquid crystalline composition of the present invention can be by by least a kind in above-mentioned liquid-crystalline polymer and organic solvent Mix to obtain.
As organic solvent, can include for example, tetrahydrofuran, twoThe ethers such as alkane；The aromatic hydrocarbon such as benzene,toluene,xylene； N,N-dimethylformamide, METHYLPYRROLIDONE polar solvent；The esters such as ethyl acetate, butyl acetate, ethyl lactate； 3- methoxy methyl propionates, 2- methoxy methyl propionates, 3- methoxypropionates, 2- methoxypropionates, 3- ethyoxyls The alkoxy esters such as ethyl propionate, 2- ethoxyl ethyl propionates；The glycol dialkyl group such as ethylene glycol dimethyl ether, propylene glycol dimethyl ether Ether；The diethylene glycol (DEG)s two such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol (DEG) methyl ethyl ether, dipropylene glycol dimethyl ether Alkyl ether；The glycol list alkane such as ethylene glycol single methyl ether, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl Base ether；The diethylene glycol (DEG)s such as diethylene glycol monomethyl ether, carbiphene, DPGME, dihydroxypropane single-ethyl ether Monoalky lether；The glycol monoalkyl ether-ether such as propylene glycol monomethyl ether, carbitol acetate, ethyl cellosolve acetate； Ketone such as cyclohexanone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), 2-HEPTANONE etc..These organic solvents can be used alone, or Two or more is used in mixed way.
Wherein, preferably propylene glycol monomethyl ether, propylene glycol monomethyl ether, ethyl lactate, cyclohexanone etc..
The usage amount of organic solvent, preferably it is in the composition 60~95 mass % or so.
In addition, to improve the purpose with the compatibility of substrate, surface can be added in the liquid crystalline composition of the present invention Activating agent.As surfactant, be not particularly limited, can include fluorine system surfactant, silicone type surface active agent, Nonionic surfactants etc..Wherein, the fluorine system surfactant high preferably with the compatibility improvement of substrate.
As the concrete example (being below trade name) of fluorine system surfactant, can include：Eftop (registration mark) EF301, EF303, EF352 (Mitsubishi's Materials electronics chemical conversion (strain)), Megafuck (registration mark) F171, F173, R- 30 (DIC (strain) systems), FLUORAD (registration mark) FC430, FC431 (3M societies system), Asahiguard (registration mark) AG710 (Asahi Glass (strain) system), Surflon (registration mark) S-382, SC101, SC102, SC103, SC104, SC105, SC106 (AGC Seimichemical (strain) systems) etc., but it is not limited to these.It is explained, surfactant can be used alone 1 Kind, two or more can also be applied in combination, relative to the mass parts of polymer 100, the addition of surfactant is preferably 5 matter Measure below part.
And then in order to improve the adaptation with substrate, closely sealed promotion can also be added in liquid crystalline composition of the invention Agent.
As closely sealed accelerator, trim,ethylchlorosilane, dimethyl vinyl chlorosilane, methyldiphenyl base chlorine silicon can be included The chlorosilane cpds such as alkane, CMDMCS chloromethyl dimethyl chlorosilane；Trimethylmethoxysilane, dimethyldiethoxysilane, methyl The alcoxyls such as dimethoxysilane, Vinyldimethylethoxysilane, dimethoxydiphenylsilane, phenyl triethoxysilane Base silane compound；HMDS, N, double (trimethyl silyl) ureas of N'-, dimethyl trimethyl silyl amine, The silicon nitrogen silane compounds such as trimethyl-silyl-imidazole；Vinyl trichlorosilane, 3- r-chloropropyl trimethoxyl silanes, 3- aminopropans Ethyl triethoxy silicane alkane, 3- methacryloxypropyl trimethoxy silanes, 3- glycidoxypropyltrime,hoxysilanes, The silane compounds such as 3- (N- piperidyls) propyl trimethoxy silicane；BTA, benzimidazole, indazole, imidazoles, 2- sulfydryls Benzimidazole, 2-mercaptobenzothiazole, 2- sulfydryl benzosThe heterocycles such as azoles, urazole, thiouracil, mercaptoimidazole, mercaptopyrimidine Formula compound；The carbamide compounds such as 1,1- dimethyl ureas, 1,3- dimethyl ureas；Thiourea compound etc..
Closely sealed accelerator can be used alone, and two or more can also be applied in combination, relative to the mass of polymer 100 Part, the addition of closely sealed accelerator is preferably below 1 mass parts.
[single coating type horizontal alignment film]
Pass through rod coating, spin coating, flow coat, roller coat, slot coated, the spin coating for following slot coated closely, ink-jet method, print process etc. Method, present invention mentioned above liquid crystalline composition is coated on substrate (for example, silicon/silicon dioxide is substrate coated, silicon nitride Substrate, be coated with substrate of the metal such as aluminium, molybdenum, chromium, glass substrate, quartz base plate, ito substrate etc.) or film (for example, three Acetylcellulose (TAC) film, cyclo-olefin-polymer films, polyethylene terephthalate film, acrylic resin film etc. are set Adipose membrane) etc. on and form film, then, be thermally dried by heating plate or baking oven etc., so as to form film.
As the condition of heat drying, it can use and be selected from 40~100 DEG C of temperature, in the range of 0.1~60 minute time Heating-up temperature and the heat time.Above-mentioned heating-up temperature and heat time are preferably 40~80 DEG C, 0.1~2 minute.
To the film so formed, by being dried after carrying out linear polarization light irradiation and progress, single coating type level can obtain Alignment films.
, generally can be by using 150~450nm of wavelength ultraviolet~visible as the illuminating method of rectilinearly polarized light Light, carried out in room temperature or the state of heating irradiation rectilinearly polarized light.Illuminated line amount is different according to the light used, preferably approximately 1~500mJ/cm2。
In addition, as long as rear dry is heated by heating plate or baking oven etc., its temperature and time is preferably 90~ 200 DEG C, 2~20 minutes, more preferably 90~150 DEG C, 5~20 minutes.
The thickness of the single coating type horizontal alignment film of the present invention can pass through the segment difference and optics of the substrate for considering to use , the property of electricity suitably selects, such as is suitably 0.1~3 μm.
The single coating type horizontal alignment film of the invention so obtained is with suitable for display device or recording materials etc. The material of the optical characteristics of purposes, the optical compensation particularly suitable as the Polarizer of liquid crystal display and polarizer etc. Film.
Embodiment
Hereinafter, synthesis example, embodiment and comparative example are enumerated, further illustrates the present invention, still, the present invention does not limit In following embodiments.It is explained, in embodiment, the assay method and condition determination of each physical property are as described below.
[1]1H-NMR
Compound is set to be dissolved in deuterochloroform (CDCl3) in, using nuclear magnetic resonance device (300MHz, JEOL society system), survey It is fixed1H-NMR。
[2] mean molecule quantity determines
Shodex GPC-101 (the solvents made using Showa electrician (strain)：Tetrahydrofuran, calibration curve：Standard polyphenyl second Alkene), measure number-average molecular weight (Mn), weight average molecular weight (Mw).
[3] haze value
Using the Spectral Haze Meter (TC-1800H) of Tokyo electricity color, the haze value of film is determined.
[4] length of delay (Δ nd) of film
Use length of delay measure device (RETS-100, Otsuka electronics (strain) system), measure wavelength 550nm Δ nd.
[5] polarized light microscope observing
The identification of liquid crystalline phase, by heating sample in thermal station (MATS-2002S, (strain) East Sea Hit systems), shown with polarisation Micro mirror (E600-Pol, (strain) Nikon systems) is observed.
The synthesis of [synthesis example 1] polymerizable compound (M2)
[changing 18]
Make 4- (6- acryloxy -1- hexyloxies) benzoic acid (SYNTHON Chemicals company systems) 29.2g (100mmol), 4- xenols 17.0g (100mmol), DMAP 0.6g and a small amount of BHT are stirred lower suspension in room temperature In dichloromethane 200mL, add what is be dissolved in dichloromethane 100mL by DCC 24.0g (116mmol) and formed thereto Solution, it is stirred overnight.The DCC ureas separated out are filtered, the filtrate is used to 0.5mol/L hydrochloric acid 150mL, saturated sodium bicarbonate successively Aqueous solution 150mL, saturated aqueous common salt 150mL respectively washing 2 times, after being dried with magnesium sulfate, are distilled off solvent, and weight is carried out with ethanol Crystallize to refine, obtain polymerizable compound (M2) 39.6g (yield 89%) of target.NMR measurement result is as follows.
1H-NMR(CDCl3)δ:1.57(m,4H),1.70(m,2H),1.86(m,2H), 4.00(m,2H),4.19(m, 2H),5.82(m,1H),6.12(m,1H),6.39(m,1H), 6.97(d,2H),7.29(m,2H),7.36(m,1H),7.47 (m,2H),7.62(m,4H), 8.18(m,2H).
The synthesis of [synthesis example 2] polymerizable compound (M3)
(1) synthesis of midbody compound (P2)
[changing 19]
Xenol 18.6g (100mmol), 2- (the bromo- 1- fourths of 4- are added in the 500mL eggplant type flasks with condenser pipe Base)-DOX 10.0g (48mmol), potassium carbonate 13.8g (100mmol) and acetone 200mL, mixture is made, 64 DEG C while stir 24 hours, while making its reaction.After reaction terminates, reaction solution is injected into pure water 500mL, obtains white Solid.The solid is mixed with methanol, filtered, and solvent is distilled off, as a result obtains white solid.Then, this is consolidated Body mixes with chloroform, is filtered, and solvent is distilled off, and obtains white solid 7.2g.The result of the solid is determined with NMR such as Shown in lower.By the results verification, the white solid is midbody compound (P2) (yield 48%).
1H-NMR(CDCl3)δ:1.62(m,2H),1.76(m,2H),1.87(m,2H), 3.85(m,2H),4.00(m, 4H),4.90(m,1H),6.87(m,4H),7.42(m,4H).
(2) synthesis of midbody compound (Q2)
[changing 20]
Then, in the 300mL eggplant type flasks with condenser pipe add midbody compound (P2) 7.2g (23mmol), 2- (bromomethyl) acrylic acid 4.1g (25mmol), THF 60mL, stannic chloride (II) 4.7g (25mmol) and 10 mass %HCl are water-soluble Liquid 19mL, is made mixture, makes its reaction within 5 hours in 70 DEG C of stirrings.After reaction terminates, reaction solution is injected into pure water 200mL In, obtain white solid 6.1g.The result that the solid is determined by NMR is as follows.By the results verification, during the white solid is Intermediate compounds therefor (Q2) (yield 78%).
1H-NMR(CDCl3)δ:1.60-1.95(m,6H),2.64(m,1H),3.11(s, 1H),4.02(t,2H),4.60 (m,1H),4.82(s,1H),5.64(s,1H),6.24(s, 1H),6.88(d,2H),6.94(d,2H),7.44(m,4H).
(3) synthesis of polymerizable compound (M3)
[changing 21]
Make midbody compound (Q2) 3.4g (10mmol), 4- methoxy cinnamic acids 1.8g (10mmol), DMAP 0.08g It is being suspended in dichloromethane 30mL, is adding thereto by DCC 2.6g (13mmol) under room temperature is stirred with a small amount of BHT The solution formed in dichloromethane 15mL is dissolved in, is stirred overnight.The DCC ureas separated out are filtered, the filtrate is used successively 0.5mol/L hydrochloric acid 50mL, saturated sodium bicarbonate aqueous solution 50mL, saturated aqueous common salt 50mL respectively washing 2 times, are done with magnesium sulfate After dry, solvent is distilled off, polymerizable compound (M3) 4.3g (yields for refine, obtaining target are recrystallized with ethanol 86%).NMR measurement result is as follows.
1H-NMR(CDCl3)δ:1.60-1.90(m,6H),2.63(m,1H),3.09(m, 1H),3.87(s,3H),4.03 (m,2H),4.57(m,1H),5.64(m,1H),6.24 (d,1H),6.54(d,1H),6.95(m,4H),7.26(m,2H), 7.44(m,2H), 7.57(m,4H),7.86(d,1H).
The synthesis of [embodiment 1] polymerizable liquid crystal compound (M1)
(1) synthesis of midbody compound (P1)
[changing 22]
4- hydroxy-methyl cinnamates 3.6g (20.0mmol), 2- are added in the 100mL eggplant type flasks with condenser pipe (the bromo- 1- butyl of 4-)-DOX 4.2g (20.0mmol), potassium carbonate 5.5g (40mmol) and acetone 50mL, is made mixed Compound, stirred at 64 DEG C 24 hours while making its reaction.After reaction terminates, reaction solution is injected into pure water 500mL, Obtain white solid 6.0g.The result that the solid is determined by NMR is as follows.By the results verification, the white solid is centre Body compound (P1) (yield 98%).
1H-NMR(CDCl3)δ:1.62(m,2H),1.76(m,2H),1.87(m,2H), 3.79(s,3H),3.85(m, 2H),4.00(m,4H),4.90(m,1H),6.29(d,1H), 6.90(d,2H),7.45(d,2H),7.64(d,1H).
(2) synthesis of midbody compound (Q1)
[changing 23]
Then, in the 200mL eggplant type flasks with condenser pipe add midbody compound (P1) 6.0g (20mmol), 2- (bromomethyl) acrylic acid 3.3g (20mmol), THF 55.0mL, stannic chloride (II) 4.3g (23mmol) and 10 mass % HCl Aqueous solution 17.0mL, is made mixture, makes its reaction within 20 hours in 70 DEG C of stirrings.After reaction terminates, reaction solution is filtered under diminished pressure, Mixed with pure water 40mL, add chloroform 50mL thereto, extracted.Extraction is carried out 3 times.
Anhydrous magnesium sulfate is added into the organic layer after extraction, is dried, is distilled off in the solution after being filtered under diminished pressure molten Agent, obtain liquid of vicidity 4.3g.The result that the liquid of vicidity is determined by NMR is as follows.By the results verification, this is sticky Property liquid is midbody compound (Q1) (yield 65%).
1H-NMR(CDCl3)δ:1.5-1.9(m,6H),2.63(m,1H),3.07(s,1H), 3.80(s,3H),4.03(t, 2H),4.58(m,1H),5.64(m,1H),6.23(m,1H), 6.30(d,1H),6.90(d,2H),7.45(d,2H),7.64 (d,1H).
(3) synthesis of polymerizable liquid crystal compound (M1)
[changing 24]
Ethanol 60mL, midbody compound (Q1) 4.3g are added in the 200mL eggplant type flasks with condenser pipe (13mmol) and 10 mass % sodium hydrate aqueous solution 15mL, are made mixture, make its reaction within 5 hours in 85 DEG C of stirrings.Reaction After end, water 300mL and reaction solution are added into 500mL beaker, after being stirred at room temperature 30 minutes, instills 10 mass % After HCl aqueous solution 15mL, filtering, white solid is obtained.
Then, white solid, the 10 mass %HCl for adding to obtain in the 50mL eggplant type flasks with condenser pipe are water-soluble Liquid 15mL and tetrahydrofuran 60.0mL, is made mixture, makes its reaction within 5 hours in 70 DEG C of stirrings.After reaction terminates, by reaction solution It is injected into pure water 500mL, obtains white solid.The white solid is refined by recrystallizing (hexane/tetrahydrofuran=2/1) Afterwards, white solid 3.0g is obtained.The result that the solid is determined by NMR is as follows.By the results verification, the white solid is mesh Target polymerizable liquid crystal compound (M1) (yield 73%).
1H-NMR(DMSO-d6)δ:1.45(m,2H),1.53(m,2H),1.74(m,2H), 2.62(m,1H),3.12(m, 1H),4.04(m,2H),4.60(m,1H),5.70(s,1H), 6.03(s,1H),6.97(d,2H),7.52(d,1H),7.63 (d,2H),12.22(s, 1H).
It is explained, the result of the liquid crystalline phase of observation polymerizable liquid crystal compound (M1), during heating, at 85 DEG C towards nematic Phase in version has mutually been carried out (in 113 DEG C of thermal polymerizations).
The synthesis of [embodiment 2] polymer (1)
[changing 25]
Obtained polymerizable liquid crystal compound (M1) 0.64g is added in embodiment 1 in the flask equipped with condenser pipe (2.0mmol), NMP 6.0g and AIBN 4mg, with after nitrogen displacement, its reaction will be made within 20 hours in 60 DEG C of stirrings in flask.Will Obtained reaction solution is put into 300mL methanol, precipitates white powder.After the white powder is filtered, enter at room temperature Row vacuum drying, obtains polymer (1) 0.35g (yield 55%).
The Mn of obtained polymer (1) is 18,640, Mw 35,975 (Mw/Mn=1.93).
The synthesis of [embodiment 3] polymer (2)
[changing 26]
Obtained polymerizable liquid crystal compound (M1) 0.50g is added in embodiment 1 in the flask equipped with condenser pipe Polymerizable compound (M2) 0.36g (0.8mmol), NMP 9.0g and the AIBN 4mg obtained in (1.6mmol), synthesis example 1, , with after nitrogen displacement, its reaction will be made within 20 hours in 60 DEG C of stirrings in flask.Obtained reaction solution is put into 600mL methanol In, precipitate white powder.After the white powder is filtered, it is dried in vacuo in room temperature, obtains polymer (2) 0.65g and (receive Rate 76%).
The Mn of obtained polymer (2) is 10,162, Mw 30,786 (Mw/Mn=3.0).
The synthesis of [embodiment 4] polymer (3)
[changing 27]
Obtained polymerizable liquid crystal compound (M1) 0.32g is added in embodiment 1 in the flask equipped with condenser pipe Polymerizable compound (M2) 0.44g (1.0mmol), NMP 8.0g and the AIBN 3mg obtained in (1.0mmol), synthesis example 1, , with after nitrogen displacement, its reaction will be made within 20 hours in 60 DEG C of stirrings in flask.Obtained reaction solution is put into 600mL methanol In, precipitate white powder.After the white powder is filtered, it is dried in vacuo in room temperature, obtains polymer (3) 0.6g and (receive Rate 79%).
The Mn of obtained polymer (3) is 3,271, Mw 4,907 (Mw/Mn=1.5).
The synthesis of [embodiment 5] polymer (4)
[changing 28]
Obtained polymerizable liquid crystal compound (M1) 0.30g is added in embodiment 1 in the flask equipped with condenser pipe Polymerizable compound (M2) 0.98g (2.2mmol), the NMP 12.0g and AIBN obtained in (0.95mmol), synthesis example 1 5mg, with after nitrogen displacement, its reaction will be made within 20 hours in 60 DEG C of stirrings in flask.Obtained reaction solution is put into 600mL's In methanol, precipitate white powder.After the white powder is filtered, it is dried in vacuo in room temperature, obtains polymer (4) 1.1g (yield 86%).
The Mn of obtained polymer (4) is 7,539, Mw 16,586 (Mw/Mn=2.2).
The synthesis of [comparative example 1] polymer (5)
[changing 29]
Obtained polymerizable compound (M2) 0.62g is added in synthesis example 1 in the flask equipped with condenser pipe Polymerizable compound (M3) 0.30g (0.6mmol), NMP 8.3g and the AIBN 17mg obtained in (1.4mmol), synthesis example 2, , with after nitrogen displacement, its reaction will be made within 20 hours in 60 DEG C of stirrings in flask.Obtained reaction solution is put into 200mL methanol In, precipitate white powder.After the white powder is filtered, it is dried in vacuo in room temperature, obtains polymer (5) 0.65g and (receive Rate 71%).
The Mn of obtained polymer (5) is 10,975, Mw 19,206 (Mw/Mn=1.75).
[preparation of composition and the making of film and evaluation]
Composition is prepared using the polymer obtained in above-described embodiment, comparative example, film is made according to following conditions, visits Beg for its characteristic.
The manufacturing conditions of film：
Spin coating：300rpm/5 seconds, 1000rpm/20 seconds
Preliminary drying：55 DEG C/30 seconds (heating plate)
Exposure：Rectilinearly polarized light ultraviolet, vertical irradiation, wavelength 313nm
[embodiment 6]
Polymer (2) 150mg and R-30 (DIC (strain) control surface activating agent, similarly hereinafter) 0.3mg is set to be dissolved in cyclohexanone In 850mg, the solution of polymer (2) is obtained.
By spin coating by the solution coating on the glass substrate, after preliminary drying, let cool to room temperature.Now, obtained on substrate Film is transparent.
Then, make to be formed film on the glass substrate with illuminated line amount 5mJ/cm2Exposure, then carry out 140 DEG C/15 points Clock (in heating plate) dries afterwards.The thickness of obtained film is 1.0 μm, it is observed with petrographic microscope, results verification, film is relative In real estate in horizontal alignment.Also, its Δ nd is 36nm, haze value 0.07%.
[embodiment 7]
Polymer (3) 150mg and R-30 0.3mg is dissolved in cyclohexanone 850mg, obtain the solution of polymer (3).
By spin coating by the solution coating on the glass substrate, after preliminary drying, let cool to room temperature.Now, obtained on substrate Film is transparent.
Then, make to be formed film on the glass substrate with illuminated line amount 5mJ/cm2Exposure, then carry out 110 DEG C/15 points Clock (in heating plate) dries afterwards.The thickness of obtained film is 0.8 μm, it is observed with petrographic microscope, results verification, film is relative In real estate in horizontal alignment.Also, its Δ nd is 58nm, haze value 0.06%.
[embodiment 8]
Polymer (4) 150mg and R-30 0.3mg is dissolved in cyclohexanone 850mg, obtain the solution of polymer (4).
By spin coating by the solution coating on the glass substrate, after preliminary drying, let cool to room temperature.Now, obtained on substrate Film is transparent.
Then, make to be formed film on the glass substrate with illuminated line amount 5mJ/cm2Exposure, then carry out 110 DEG C/15 points Clock (in heating plate) dries afterwards.The thickness of obtained film is 0.8 μm, it is observed with petrographic microscope, results verification, film is relative In real estate in horizontal alignment.Also, its Δ nd is 33nm, haze value 0.34%.
[comparative example 2]
Polymer (5) 150mg and R-30 0.3mg is dissolved in cyclohexanone 850mg, obtain the solution of polymer (5).
By spin coating by the solution coating on the glass substrate, after preliminary drying, let cool to room temperature.Now, obtained on substrate Film is transparent.
Then, make to be formed film on the glass substrate with illuminated line amount 500mJ/cm2Exposure, then carry out 100 DEG C/10 Minute (in heating plate) dries afterwards.The thickness of obtained film is 0.8 μm, it is observed with petrographic microscope, results verification, film phase For real estate in horizontal alignment.Also, its Δ nd is 62nm, haze value 2.1%.
Result above is summarized in table 1 below.
[table 1]
Polymer Thickness (μm) Δnd(nm) Haze value (%)
Embodiment 6 (2) 1.0 36 0.07
Embodiment 7 (3) 0.8 58 0.06
Embodiment 8 (4) 0.8 33 0.34
Comparative example 2 (5) 0.8 62 2.1

Claims (6)

1. polymerizable liquid crystal compound, it is characterised in that it is represented by following formula [1]：
[changing 1]
In formula, p represents 2~9 integer.
2. liquid-crystalline polymer, it is characterised in that it contains the repeat unit by following formula [2a] and [2b] expression：
[changing 2]
In formula, X is the group represented by following formula [3] or [4]：
[changing 3]
In formula, R1For hydrogen atom or methyl, dotted line is bonding key；
M is the group represented by following formula [5]：
[changing 4]
In formula, s1 and s2 are each independently 1 or 2；G1For singly-bound ,-COO- or-OCO-；R2For hydrogen atom, halogen atom, cyano group, The alkyl of carbon number 1~10 or the alkoxy of carbon number 1~10；Dotted line is bonding key；
M and n is to meet 0≤m ＜ 100,0 ＜ n≤100 and the number of m+n≤100 respectively；
P and q is each independently 2~9 integer.
3. liquid crystalline composition, it contains the polymer and organic solvent described in claim 2.
4. single coating type horizontal alignment film, it is by the way that the liquid crystalline composition described in claim 3 is coated on into substrate, connect Irradiation polarised light, make its solidify obtained from.
5. the single coating type horizontal alignment film described in claim 4, wherein, above-mentioned polarised light is rectilinearly polarized light ultraviolet.
6. optical component, it possesses the single coating type horizontal alignment film described in claim 4 or 5.
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Citations (4)

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Publication number Priority date Publication date Assignee Title
TW201206964A (en) * 2010-07-28 2012-02-16 Osaka Organic Chemical Ind Ltd Copolymerized (meth) acrylate polymer, photo-alignment film and phase difference film
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6270407A (en) 1985-09-25 1987-03-31 Fuji Photo Film Co Ltd Preparation of orientated film
JPH09208957A (en) 1996-01-31 1997-08-12 Teijin Ltd Production of optical isomer
JP3945790B2 (en) 1997-12-25 2007-07-18 林テレンプ株式会社 Birefringent film and manufacturing method thereof
JP5462628B2 (en) 2006-09-13 2014-04-02 ロリク アーゲー Volume light aligned retarder
JP2008164925A (en) 2006-12-28 2008-07-17 Hayashi Telempu Co Ltd Retardation film and method for producing the same
KR101090325B1 (en) 2009-03-18 2011-12-07 동방에프티엘(주) Industrial process of high purity olmesartan medoxomil
KR102162192B1 (en) * 2012-10-05 2020-10-06 닛산 가가쿠 가부시키가이샤 Manufacturing method for substrate having liquid crystal alignment film for in-plane switching-type liquid crystal display element

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103080152A (en) * 2010-06-30 2013-05-01 日产化学工业株式会社 Liquid crystal-aligning agent, liquid crystal-aligning film, liquid crystal display element and method for producing liquid crystal display elements
CN103080823A (en) * 2010-06-30 2013-05-01 日产化学工业株式会社 Liquid crystal aligning agent, liquid crystal alignment film, liquid crystal display element, manufacturing method for liquid crystal display element, and polymerisable compound
TW201206964A (en) * 2010-07-28 2012-02-16 Osaka Organic Chemical Ind Ltd Copolymerized (meth) acrylate polymer, photo-alignment film and phase difference film
WO2013133078A1 (en) * 2012-03-09 2013-09-12 日産化学工業株式会社 Polymer, composition containing said polymer, and single-layer-coated horizontally oriented film

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