CN101792391A - Polymerizable biphenyl compound - Google Patents
Polymerizable biphenyl compound Download PDFInfo
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- CN101792391A CN101792391A CN201010003321A CN201010003321A CN101792391A CN 101792391 A CN101792391 A CN 101792391A CN 201010003321 A CN201010003321 A CN 201010003321A CN 201010003321 A CN201010003321 A CN 201010003321A CN 101792391 A CN101792391 A CN 101792391A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/612—Esters of carboxylic acids having a carboxyl group bound to an acyclic carbon atom and having a six-membered aromatic ring in the acid moiety
- C07C69/618—Esters of carboxylic acids having a carboxyl group bound to an acyclic carbon atom and having a six-membered aromatic ring in the acid moiety having unsaturation outside the six-membered aromatic ring
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- 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
Abstract
The problem that the invention object to resolve is to provide a polymerizable compound, which has excellent solubility with other liquid crystal compounds during constituting a polymerizable liquid crystal composition, and displays excellent heat-resistant quality and mechanical intensity during curing the polymerizable liquid crystal composition. The invention provides a polymerizable compound represented by formula (I), and a liquid crystal composition taking the compound as the constitution material, and further provides an optical anisotropy body or liquid crystal device using the liquid crystal composition. As the inventive polymerizable compound has excellent solubility with other liquid crystal compounds, it is useful as the constitution material of the polymerizable compound. In addition, the polymerizable composition containing the inventive polymerizable compound has wide liquid crystal phase temperature range; the optical anisotropy body of the polymerism composition has high heat-resistant quality, and is useful in phase difference plates and the like applications.
Description
Technical field
The present invention relates to a kind of polymerizable biphenyl compound, contain the liquid-crystal composition of this compound and as the optically anisotropic body or the liquid-crystal apparatus of the cured article of this liquid-crystal composition.
Background technology
In recent years, be accompanied by the progress of informationized society, the importance that is used for the optical compensation films of polaroid necessary concerning liquid-crystal display, polarizer etc. improves day by day, with regard to the optical compensation films that requires weather resistance height, multifunction, report makes polymerizable liquid crystal compound polymeric example.Be used for the optically anisotropic body of optical compensation films etc., the light transmission of the polymerization velocity of not only optical characteristics, and compound, solvability, fusing point, second-order transition temperature, polymkeric substance, physical strength, surface hardness and thermotolerance etc. also become important factor.And then adding polymerizable compound in liquid crystal media also has report with the example that improves display characteristic.
As the compound that constitutes polymerizable liquid crystal compound, proposed in the past to have by ester bond and connected 1, the compound of the structure of 4-phenylene (with reference to patent documentation 1), have the compound (with reference to patent documentation 2) of fluorenyl.But there are problems such as solvability is low in the polymerizable compound of this citing document record.On the other hand, the polymerizable compound (patent documentation 3) that adopts unsymmetric structure in order to improve solvability is disclosed, compared with former polymerizable compound, though aspect solvability, be improved and insufficient, and have problems such as thermotolerance and physical strength are low.
The prior art document
Patent documentation 1: the flat 10-513457 communique of Japanese Unexamined Patent Application Publication
Patent documentation 2: TOHKEMY 2005-60373 communique
Patent documentation 3: the flat 2001-527570 communique of Japanese Unexamined Patent Application Publication
Summary of the invention
Invent problem to be solved
Problem to be solved by this invention is, a kind of polymerizable compound is provided, it has excellent solvability with other liquid crystalline cpds when constituting polymerizable liquid crystal compound, demonstrate the thermotolerance and the physical strength of excellence when solidifying aforementioned polymerizable liquid crystal compound.
The means of dealing with problems
Present inventors study all substituting groups in the polymerizable compound, found that, the polymerizable compound with ad hoc structure can solve foregoing problems, has finished the present invention thus.
The invention provides the polymerizable compound shown in a kind of general formula (I):
[changing 1]
Wherein, R
1And R
2Represent any one in the following formula (R-1)～(R-15) independently of one another,
[changing 2]
X
1And X
2Represent hydrogen atom, alkyl, haloalkyl, alkoxyl group, halogenated alkoxy, halogen, cyano group or nitro independently of one another; S
1And S
2Expression independently of one another, according to the mode carbon atom that does not directly link to each other between the Sauerstoffatom by Sauerstoffatom ,-COO-,-OCO-or-OCOO-replaces the alkylidene group of also passable carbonatoms 2～12, perhaps singly-bound; L
1Expression-CH=CH-COO-or-C
2H
4COO-; L
2, L
3Represent independently of one another singly-bound ,-O-,-S-,-OCH
2-,-CH
2O-,-CO-,-C
2H
4-,-COO-,-OCO-,-OCOOCH
2-,-CH
2OCOO-,-CO-NR
11-,-NR
11-CO-,-SCH
2-,-CH
2S-,-CH=CH-COO-,-OOC-CH=CH-,-COOC
2H
4-,-OCOC
2H
4-,-C
2H
4OCO-,-C
2H
4COO-,-OCOCH
2-,-CH
2COO-,-CH=CH-,-CF=CH-,-CH=CF-,-CF
2-,-CF
2O-,-OCF
2-,-CF
2CH
2-,-CH
2CF
2-,-CF
2CF
2-or-C ≡ C-(in the formula, R
11The alkyl of expression carbonatoms 1～4); M
1Expression 1,4-phenylene, 1,4-cyclohexylidene, pyridine-2,5-two bases, pyrimidine-2,5-two bases, naphthalene-2,6-two bases, naphthane-2,6-two bases or 1,3-diox-2,5-two bases; M
2Expression 1,4-phenylene, 1,4-cyclohexylidene, pyridine-2,5-two bases, pyrimidine-2,5-two bases, naphthalene-2,6-two bases, naphthane-2,6-two bases, 1,3-diox-2,5-two bases, 1,3,5-benzene three bases, 1,3,4-benzene three bases, 1,3,4,5-benzene four bases, 1,3,5-hexanaphthene three bases or 1,3,4-hexanaphthene three bases; M
1And M
2Can not be substituted independently of one another or be replaced by alkyl, haloalkyl, alkoxyl group, halogen, cyano group or nitro, p represents 0 or 1, and q represents 0,1,2 or 3, and q is 0 o'clock ,-(L
3-S
2-R
2)
0The expression hydrogen atom, q represents 2 or at 3 o'clock, 2 or 3 L of existence
3, S
2And R
2Can be the same or different.It is the liquid-crystal composition of constituent material with this compound that the present invention also provides a kind of, and a kind of optically anisotropic body or liquid-crystal apparatus that uses this liquid-crystal composition further is provided.
The effect of invention
Polymerizable compound of the present invention because and other liquid crystalline cpd have excellent solvability, so be useful as the constituent material of Polymerizable composition.In addition, contain the Polymerizable composition of polymerizable compound of the present invention, liquid crystal phase temperature range is wide; Use the optically anisotropic body of this Polymerizable composition, the thermotolerance height is useful for purposes such as polaroid, polarizers.
Embodiment
In general formula (I), R
1And R
2Represent polymerizable group independently of one another,, can enumerate structure as follows as the concrete example of polymerizable group:
[changing 2]
These polymerizable groups solidify by radical polymerization, radical addition polymerization, cationoid polymerisation and anionoid polymerization.Particularly be that polymerization process carries out the polymeric situation with the polymerizable ultraviolet, preferred formula (R-1), formula (R-2), formula (R-4), formula (R-5), (R-7), formula (R-11), formula (R-13) or (R-15), more preferably formula (R-1), formula (R-2), formula (R-7), formula (R-11) or (R-13), further preferred formula (R-1), formula (R-2).
S
1And S
2Represent spacer groups or singly-bound independently of one another, as spacer groups, preferred carbonatoms is 2～6 alkylidene group or singly-bound; For this alkylidene group, under not direct-connected prerequisite between the Sauerstoffatom, carbon atom can by Sauerstoffatom ,-COO-,-OCO-,-OCOO-replaces.
L
1Expression-CH=CH-COO-or-C
2H
4COO-in the occasion that requires bigger absorbancy, more preferably has the conjugated-CH=CH-COO-with biphenyl backbone conjugated carbon-carbon double bond, expansion πDian Zi; For L
2, L
3, be preferably independently of one another singly-bound ,-OCH
2-,-C
2H
4-,-CH
2O-,-COO-,-OCO-,-OCOOCH
2-,-CH
2OCOO-,-CH=CH-COO-,-OOC-CH=CH-,-COOC
2H
4-,-OCOC
2H
4-,-C
2H
4OCO-,-C
2H
4COO-,-CF
2O-, from the viewpoint of cheapness manufacturing, liquid crystal aligning, more preferably singly-bound ,-COO-,-OCO-or-OCH
2-,-CH
2O-.
M
1Be preferably 1,4-phenylene, pyridine-2,5-two bases, pyrimidine-2,5-two bases, naphthalene-2,6-two bases; M
2Be preferably 1,4-phenylene, 1,4-cyclohexylidene, pyridine-2,5-two bases, pyrimidine-2,5-two bases, naphthalene-2,6-two bases, naphthane-2,6-two bases, 1,3-diox-2,5-two bases, 1,3,5-benzene three bases, 1,3,4-benzene three bases, 1,3,4,5-benzene four bases, 1,3,5-hexanaphthene three bases or 1,3,4-hexanaphthene three bases.P represents 0 or 1, and q represents 0,1,2 and 3, is preferably p=0, q=1 or 2 especially.
The compound of general formula (I) expression, more specifically, the compound shown in preferably following general formula (I-1)～general formula (I-24).
[changing 3]
[changing 4]
[changing 5]
Compound of the present invention can be synthetic by the synthetic method of putting down in writing below.
The manufacturing of compound shown in (method for making 1) general formula (I-1)
Utilize 4-bromo-4 '-xenol and tert-butyl acrylate, and palladium catalyst, obtain biphenyl derivatives (S-1) by ditch Lv Mu-He Ke reaction.Further, the esterification of utilization and methacrylic chloride obtains having the biphenyl derivatives (S-2) of methacryloyl.Further, utilize trifluoroacetic acid, make the tertiary butyl remove to be transformed into carboxyl to obtain biphenyl derivatives (S-3).
[changing 6]
Then, utilize dehydrating condensation agents such as 4-(2-acryloxy) ethylphenol and dicyclohexylcarbodiimide, just can access target compound (I-1) by esterification.
[changing 7]
The manufacturing of compound shown in (method for making 2) general formula (1-7)
Utilize 4-bromo-4 '-xenol and tert-butyl acrylate, and palladium catalyst, obtain biphenyl derivatives (S-1) by ditch Lv Mu-He Ke reaction.Further, under the condition that alkali such as salt of wormwood exist, carry out etherification reaction, obtain containing the biphenyl derivatives (S-4) of acryl with 6-chlorine ethylhexyl acrylate.Further, utilize trifluoroacetic acid, make the tertiary butyl remove to be transformed into carboxyl to obtain biphenyl derivatives (S-5).
[changing 8]
Then, utilize dehydrating condensation agents such as 4-(2-acryloxy) ethylphenol and dicyclohexylcarbodiimide, can access target compound (I-7) by esterification.
[changing 9]
The manufacturing of compound shown in (method for making 3) general formula (I-16)
Utilize 4-bromo-4 '-xenol and tert-butyl acrylate, and palladium catalyst, obtain biphenyl derivatives (S-1) by ditch Lv Mu-He Ke reaction.Further, by with the esterification of acrylate chloride, obtain containing the biphenyl derivatives (S-6) of acryl.Further, utilize trifluoroacetic acid, make the tertiary butyl remove to be transformed into carboxyl to obtain biphenyl derivatives (S-7).
[changing 10]
Then,, use 2 moles acrylate chloride, carry out esterification, obtain containing the phenol derivatives (S-8) of 2 acryls for 1 mole Phloroglucinol.Further, use dehydrating condensation agents such as biphenyl derivatives (S-7) and dicyclohexylcarbodiimide, just can access target compound (I-16) by esterification.
[changing 11]
The manufacturing of compound shown in (method for making 4) general formula (I-14)
Use 2-fluoro-4-bromo biphenyl and Acetyl Chloride 98Min. and aluminum chloride to carry out Knut Fridell-Kerafyrm thatch reaction (Friedel-Crafts reaction), further, utilization obtains the xenol compound (S-10) that is replaced by fluorine atom by the peroxyformic acid that formic acid and hydrogen peroxide generate.Further, utilize tert-butyl acrylate and palladium catalyst, obtain biphenyl derivatives (S-11), further,, obtain biphenyl derivatives (S-12) by using the contact hydrogen reduction of palladium carbon by ditch Lv Mu-He Ke reaction.Then, under the condition that alkali such as salt of wormwood exist, carry out etherification reaction, obtain containing the biphenyl derivatives (S-13) of acryl with 6-chlorine ethylhexyl acrylate.Further, utilize trifluoroacetic acid, make the tertiary butyl remove to be transformed into carboxyl to obtain biphenyl derivatives (S-14).
[changing 12]
Then, with 4 '-xenol carboxylic acid and Hydroxyethyl Acrylate, with dehydrating condensation agents such as dicyclohexylcarbodiimide,, obtain having the biphenyl derivatives (S-15) of acryl by esterification.Further, with biphenyl derivatives (S-14) and (S-15),,, just can access target compound (I-14) by esterification with dehydrating condensation agents such as dicyclohexyl carbodiimides.
[changing 13]
The preparation of compound shown in (method for making 5) general formula (I-21)
Make 3-ethyl-3-methylol trimethylene oxide (trade(brand)name EOXA, East Asia Synesis Company system) and 1-bromo-3-chloropropane, under the condition that alkali such as sodium hydroxide exist, carry out etherification reaction, obtain trimethylene oxide derivative (S-16).Further, obtain biphenyl derivatives (S-12).Then, make biphenyl derivatives (S-1) and trimethylene oxide derivative (S-16), under the condition that alkali such as salt of wormwood exist, carry out etherification reaction, further, make the tertiary butyl remove, obtain containing the biphenyl derivatives (S-18) of oxetanyl and carboxyl by trifluoroacetic acid.
[changing 14]
Then; make as Resorcinol and 3; the Resorcinol list THP trtrahydropyranyl ether of the reaction product of 4-dihydro-2H-pyrans and trimethylene oxide derivative (S-16); under the condition that alkali such as salt of wormwood exist, carry out etherification reaction; remove the protecting group of phenol further with hydrochloric acid, obtain phenol derivatives (S-19).Further, make biphenyl derivatives (S-18) and (S-19), utilize dehydrating condensation agents such as dicyclohexylcarbodiimide,, just can access target compound (1-21) by esterification.
[changing 15]
The manufacturing of compound shown in (method for making 6) general formula (I-9)
Use 4-benzyloxy M-nitro benzoic acid and 4-(3-chlorination propionyloxy) ethylphenol, reach dehydrating condensation agents such as dicyclohexylcarbodiimide,, obtain Pheyl benzoate derivatives (S-20) by esterification.By using the contact hydrogen reduction of palladium carbon, obtain phenol derivatives (S-21) then.Further, use excessive triethylamine, obtain containing the phenol derivatives (S-22) of acryl by taking off the HCl reaction.
[changing 16]
Then, use biphenyl derivatives (S-14) and contain the dehydrating condensation agents such as dicyclohexylcarbodiimide of the phenol derivatives (S-22) of acryl, can access target compound (I-9) by esterification.
[changing 17]
Compound of the present invention can be used in nematic liquid crystal, smectic liquid crystal, Chinrally nematic liquid crystal, chiral smectic type liquid crystal and cholesteric liquid crystal compositions.Liquid-crystal composition of the present invention except using more than one compounds of the present invention, can add other polymerizable compound in any range.For the polymerizable liquid crystal compound that contains in the polymerizable liquid crystal compound of the present invention, be preferably especially and contain as the acryloxy of polymerizability functional group, the compound of methacryloxy.Further, as polymerizable liquid crystal compound, preferred intramolecularly has the compound of plural polymerizability functional group.In addition, liquid-crystal composition of the present invention is the occasion of cholesteryl liquid crystal, preferably adds chipal compounds.Further, also can add the liquid-crystal composition that does not have polymerizable group, particularly for the useful material of polymer-stabilized liquid-crystal apparatus.
Object lesson as the polymerizable compound beyond the present invention has no particular limits except containing the represented compound of general formula (I); As the polymerizable liquid crystal compound that is used in combination, contain acryloxy (R-1) or methacryloxy (R-2) in the preferred compound, more preferably intramolecularly contains plural polymerizability functional group.
As the polymerizable liquid crystal compound that is used in combination, be in particular the represented compound of general formula (II).
[changing 18]
Wherein, A is H, F, Cl, CN, SCN, OCF in the formula
3, contain the alkyl of 1～12 carbon atom, under the situation that Sauerstoffatom does not directly link to each other each other, carbon atom also can by Sauerstoffatom, sulphur atom ,-CO-,-COO-,-OCO-,-OCOO-,-CH=CH-,-C ≡ C-replaces, perhaps be-L
6-S
4-R
4R
3And R
4Be polymerizable group; S
3And S
4Represent singly-bound independently of one another or contain the alkylidene group of 1～12 carbon atom, for more than one-CH herein
2-, under the situation that Sauerstoffatom does not directly link to each other each other, carbon atom can by Sauerstoffatom ,-COO-,-OCO-,-OCOO-replaces; L
4, L
5And L
6Represent independently of one another singly-bound ,-O-,-S-,-OCH
2-,-CH
2O-,-CO-,-COO-,-OCO-,-OCOOCH
2-,-CH
2OCOO-,-CO-NR
11-,-NR
11-CO-,-SCH
2-,-CH
2S-,-CH=CH-COO-,-OOC-CH=CH-,-COOC
2H
4-,-OCOC
2H
4-,-C
2H
4OCO-,-C
2H
4COO-,-OCOCH
2-,-CH
2COO-,-CH=CH-,-C
2H
4-,-CF=CH-,-CH=CF-,-CF
2-,-CF
2O-,-OCF
2-,-CF
2CH
2-,-CH
2CF
2-,-CF
2CF
2-or-C ≡ C-(in the formula, R
11The expression carbonatoms is 1～4 alkyl); M
3And M
4Represent 1 independently of one another, 4-phenylene, 1,4-cyclohexylidene, pyridine-2,5-two bases, pyrimidine-2,5-two bases, naphthalene-2,6-two bases, naphthane-2,6-two bases or 1,3-diox-2,5-two bases; M
3And M
4Can not be substituted independently of one another or be replaced by alkyl, haloalkyl, alkoxyl group, halogenated alkoxy, halogen, cyano group or nitro; N represents 0,1,2 or 3.N represents 2 or at 3 o'clock, 2 or 3 L of existence
5And M
4Can be the same or different.
As particularly preferred compound, be preferably such compound: L
4, L
5And L
6Represent independently of one another singly-bound ,-O-,-COO-or-OCO-, M
3And M
4Represent 1 independently of one another, 4-phenylene, 1,4-cyclohexylidene, pyridine-2,5-two bases, pyrimidine-2,5-two bases, naphthalene-2,6-two bases.
The represented compound of general formula (II) particularly, is preferably general formula (II-1)～represented compound of general formula (II-22).
[changing 19]
[changing 20]
[changing 21]
In the formula, m and l represent 0～12 integer, just when for 0 the time, remove and aromatic nucleus bonded Sauerstoffatom.In addition, as the polymerizable liquid crystal compound that is used for liquid-crystal composition of the present invention,, preferably cooperate general formula (III-1)～general formula (III-11) in order to regulate liquid crystal temperature range and degree of birefringence, reduction viscosity.
[changing 22]
[changing 23]
In the formula, m and l represent 0～12 integer, just when for 0 the time, remove and aromatic nucleus bonded Sauerstoffatom.Liquid-crystal composition of the present invention is the occasion of cholesteryl liquid crystal, adds chipal compounds usually, as concrete compound shown in general formula (IV-1)～(IV-7).With respect to liquid-crystal composition, the use level of chipal compounds is preferably 0.5～30 weight %, more preferably 2～20 weight %.
[changing 24]
In addition, can add the liquid-crystal composition that does not have polymerizable group in the liquid-crystal composition of the present invention; Can enumerate at common the liquid-crystal apparatus for example nematic liquid crystal composition of use, ferroelectric liquid crystals composition etc. in STN (supertwist to row) liquid crystal, TN (twisted-nematic) liquid crystal, TFT (thin film transistor) liquid crystal etc.
In addition, also can add the compound that has polymerizability functional group and do not show liquid crystal liquid crystal property.As such compound, usually, form oligomers as long as in this technical field, be considered to can be used as polymer formation property monomer or polymer, just can use with being not particularly limited, need adjust in order to make composition exhibiting go out its addition of liquid crystal liquid crystal property.
Liquid-crystal composition of the present invention, owing to have the extensive conjugated biphenyl backbone of πDian Zi, thus even do not add polymerization starter, also can come polymerization by light and heat, but the preferred Photoepolymerizationinitiater initiater that adds.The concentration of the Photoepolymerizationinitiater initiater that adds is preferably 0.1～10 quality %, and more preferably 0.2～10 quality % is preferably 0.4～5 quality % especially.As light trigger, can enumerate st-yrax ethers, benzophenone, acetophenones, dibenzoyl ketal class, acylphosphine oxide class etc.
In addition, in order to improve the storage stability of liquid-crystal composition of the present invention, also can add stablizer therein.As the stablizer that can use, can enumerate for example hydroquinone type, Resorcinol monoalkyl ethers, tert-butyl catechol class, pyrogallol class, thiophenol class, nitro-compound class, beta-naphthylamine class, 2-Naphthol class, nitroso compound etc.Addition under the situation of use stablizer with respect to liquid-crystal composition, is preferably the scope of 0.005～1 quality %, and more preferably 0.02～0.5 quality % is preferably 0.03～0.1 quality % especially.
In addition; at the raw material that liquid-crystal composition of the present invention is used for phase retardation film, polarizing coating, alignment films; the perhaps occasion of the purposes of printing-ink and coating, protective membrane etc.; according to its purpose, also can add metal oxides such as metal, metal complex, dyestuff, pigment, pigment, fluorescent material, phosphor material, tensio-active agent, flow agent, thixotropic agent, jelling agent, polyose, UV light absorber, infrared absorbent, antioxidant, ion exchange resin, titanium dioxide.
Next describe about optically anisotropic body of the present invention.Optically anisotropic body by polymerization liquid-crystal composition of the present invention is made can be used in various uses.For example, the situation of polymerization polymerizable liquid crystal compound of the present invention under non-state of orientation can be used as light diffuser plate, depolarization sheet, Moire fringe and prevent plate.In addition, polymerization polymerizable liquid crystal compound of the present invention under state of orientation and the optically anisotropic body made has optical anisotropy aspect physical properties is useful.Such optically anisotropic body can be by the method manufacturing below for example: polymerizable liquid crystal compound area load of the present invention on the substrate that carried out friction treatment with cloth etc. or the substrate surface that formed organic film was carried out on the substrate of friction treatment with cloth etc. or the SiO that had oblique evaporation
2The substrate of alignment films on, be clamped between substrate after, make polymerizable mesogenic of the present invention.
Method when loading on polymerizable liquid crystal compound on the substrate can be enumerated spin-coating method, mouthful mould coating method, extrusion coated method, rolling method, line rod and be coated with method, intaglio plate coating method, spraying method, dip coating, seal Tu Fa etc.In addition, in the time of coating, polymerizable liquid crystal compound can be directly used, also organic solvent can be added.As organic solvent, can enumerate ethyl acetate, tetrahydrofuran (THF), toluene, hexane, methyl alcohol, ethanol, dimethyl formamide, methylene dichloride, Virahol, acetone, methylethylketone, acetonitrile, cellosolve, pimelinketone, gamma-butyrolactone, acetoxyl-2-Ethoxyethane, propylene glycol methyl ether acetate, N-Methyl pyrrolidone class.They can use separately also and can be used in combination, and suitably select to get final product according to the solvability of its vapour pressure and polymerizable liquid crystal compound.In addition, its addition is preferably below the 90 weight %.As making the organic solvent evaporable method of adding, can use seasoning, heat drying, drying under reduced pressure, decompression heat drying.In order further to improve the coating of polymerizable liquid crystal material, middle layers such as Kapton are set on substrate, it all is effective perhaps adding flow agent in the polymerizable liquid crystal material.Middle layers such as Kapton are set on substrate, and the optically anisotropic body that obtains at the polymerization liquid crystal material and the bad occasion of cementability of substrate also are effective as the means that improve cementability.
As holding liquid crystal method for compositions between substrate, can enumerate the injection method that utilizes capillary phenomenon.Reduce pressure for the space that forms between substrate, the means of injecting liquid crystal material then also are effective.
As friction treatment or SiO
2Oblique evaporation beyond orientation process, can enumerate the flow orientation of utilizing liquid crystal material, utilize electric field or magnetic field.These orientation means may be used alone, can also be used in combination.Further, instead Mo Ca method for orientation treatment also can use optical alignment method.This method is, for example, has on the organic films such as the organic film of photodimerization reactive functionality, organic film or polyimide the formation alignment films at intramolecularly by the preferred polarized UV rays of polarized light being radiated at poly-vinyl cinnamate etc. with light opposite sexization functional group.Since in this optical alignment method by selecting for use optical mask can realize orientation pattern easily, so molecular orientation that also can accurate control optically anisotropic body inside.
As the shape of substrate, except flat board, also can be curved surface as component part.Organic materials, inorganic materials constitute the material of substrate, no matter all can use.As the organic materials that constitutes baseplate material; can enumerate for example polyethylene terephthalate, polycarbonate, polyimide, polymeric amide, polymethylmethacrylate, polystyrene, polyvinyl chloride, tetrafluoroethylene, voltalef, polyarylate, polysulfones, tri acetyl cellulose, Mierocrystalline cellulose, polyether-ether-ketone etc.; in addition; as inorganic materials, can enumerate for example silicon, glass, calcite etc.
By can not obtaining under the situation of suitable orientation, also can form at substrate surface behind the organic films such as Kapton or PVA (PVOH) FILM with frictions such as cloth according to known method with these substrates of frictions such as cloth.In addition, the Kapton that tilt angle is provided that in common TN liquid-crystal apparatus or stn liquid crystal device, uses, because can be the further accurate molecular orientation structure of controlling optically anisotropic body inside, so be preferred.
In addition, in occasion, use substrate with electrode layer by the electric field controls state of orientation.In such occasion, preferably on electrode, form organic films such as aforesaid Kapton.
As the method for polymerization liquid-crystal composition of the present invention, because polymerization is rapidly carried out in expectation, so preferably carry out the polymeric method by irradiation ultraviolet radiation or electron rays isoreactivity energy-ray.Use ultraviolet occasion, can use polarized light source, also can use unpolarized light source.In addition, liquid-crystal composition is clamped under two states between the substrate carries out the polymeric occasion, the substrate of shadow surface side must have suitable light transmission for active energy beam at least.In addition, also can use such means: only after the polymerization specific part,, change the not state of orientation of polymeric part with mask during rayed, further shine active energy beam and carry out polymerization by conditions such as changing electric field, magnetic field or temperature.In addition, the temperature during irradiation is in the temperature range of mesomorphic state keeping liquid-crystal composition of the present invention preferably.Especially, make the occasion of optically anisotropic body by photopolymerization in desire, preferred from the angle of the thermopolymerization of avoiding causing non-expectation as much as possible near the temperature of room temperature, that is, typically, polymerization under 25 ℃ temperature.The intensity of active energy beam is preferably 0.1mW/cm
2～2W/cm
2Intensity is at 0.1mW/cm
2Under the following situation, finishing photopolymerization needs the long time, and productivity worsens, at 2W/cm
2Under the above situation, polymerizable liquid crystal compound or polymerizable liquid crystal compound have the danger that becomes deterioration.
The optically anisotropic body of the present invention that obtains by polymerization for the characteristic variations at the initial stage of alleviating, show stable properties, also can be implemented thermal treatment.Heat treated temperature is 50～250 ℃ a scope, and preferred heat treatment time is 30 seconds～12 hours a scope.
The optically anisotropic body of making by this method of the present invention can be peeled off and uses separately from substrate, also can not peel off and uses.In addition, stacked or be fitted in to use on other the substrate and all be fine the optically anisotropic body that obtains.
[embodiment]
Below, provide embodiment and be described in further detail the present invention, but the present invention is not subjected to the qualification of these embodiment.In addition, " % " meaning is " quality % " in the composition of the following examples and comparative example.
(embodiment 1)
In the reaction vessel that possesses whipping appts, water cooler and thermometer, pack into 4-bromo-4 '-xenol 10g (40.1 mmole), tertiary butyl acrylate 6.2g (48.2 mmole), triethylamine 4.8g (48 mmole), acid chloride 530mg, dimethyl formamide 300ml, under nitrogen atmosphere, reactor is heated to 100 ℃, reacts.After reaction finishes, add ethyl acetate, THF, clean organic layer with 10% aqueous hydrochloric acid, pure water, saturated aqueous common salt then.Distillation is made with extra care the compound 11g shown in the formula of obtaining (1) with the silicagel column of 2 times of amounts (weight ratio) after removing and desolvating.
[changing 25]
Then, compound 3g shown in the above-mentioned formula of in the reaction vessel that possesses whipping appts, water cooler and thermometer, packing into (1) (10.1 mmole), acrylate chloride 1g (11 mmole), methylene dichloride 50ml, under nitrogen atmosphere below the reactor cooling to 5 ℃.Then, slowly splash into triethylamine 1.2g (12 mmole).Splash into finish after, below 20 ℃ the reaction 3 hours.After reaction is finished, add methylene dichloride, clean organic layer with 10% aqueous hydrochloric acid, pure water, saturated aqueous common salt then.Distillation is made with extra care the compound 3.6g shown in the formula of obtaining (2) with the silicagel column of 2 times of amounts (weight ratio) after removing and desolvating.
[changing 26]
Then, in the reaction vessel that possesses whipping appts, water cooler and thermometer, the compound 3.6g shown in the above-mentioned formula (2) is dissolved in after the methylene dichloride of 10ml, splashes into trifluoroacetic acid 10ml, at room temperature stirred 30 fens.Subsequently, add ethyl acetate 200ml, and clean organic layer with pure water, saturated aqueous common salt.Distillation removes and desolvates, and obtains the compound 2.4g shown in the formula (3).
[changing 27]
Then, compound 2.4g shown in the above-mentioned formula of packing in the reaction vessel that possesses whipping appts, water cooler and thermometer (3) (8.1 mmole), vinylformic acid-2-(4-hydroxy phenyl) ethyl ester 1.7g (9 mmole), dimethyl aminopyridine 120mg, methylene dichloride 100ml keep reaction vessel below 5 ℃ in ice bath.Under nitrogen atmosphere, slowly splash into DIC 1.2g (9.7 mmole).Splash into finish after, reaction vessel is returned back to room temperature, reacted 5 hours.After the filtering reacting liquid, in filtrate, add methylene dichloride 200ml, clean, further clean, use the anhydrous sodium sulfate drying organic layer with saturated aqueous common salt with 10% aqueous hydrochloric acid.Distillation is made with extra care with the silicagel column of 2 times of amounts (weight ratio) after removing and desolvating, and by the methylene chloride recrystallize, obtains the target compound 3g shown in the formula (1).This compound, from 113 ℃ in very wide temperature range, showing as mesomorphic phase more than 200 ℃.
[changing 28]
(physics value)
H-NMR (solvent: deuterochloroform): δ: 2.98 (t, 2H), 4.36 (t, 2H), 5.82 (d, 1H), 6.03-6.18 (m, 2H), 6.32-6.44 (m, 2H), 6.62-6.66 (m, 2H), 7.12 (d, 2H), 7.22-7.33 (m, 4H), 7.65 (m, 6H), 7.88 (d, 1H) C-NMR (solvents: deuterochloroform): δ: 34.6,64.8,117.0,121.5,127.4,127.9,128.2,128.6,129.7,130.7,132.7,133.0,135.1,137.6,142.3,145.7,149.2,150.2,165.2
Infrared absorption spectrum (IR) is (KBr): 2925,2855,1760, and 1652-1622,809cm
-1Fusing point: 113 ℃
(embodiment 2)
In possessing the autoclave vessel of whipping appts, embodiment 1 synthetic intermediate 4.5g (15.2 mmole) shown in the loading type (1), 5% palladium carbon 250mg, tetrahydrofuran (THF) 50ml, ethanol 5ml carry out reduction reaction (room temperature, 8 hours) in the hydrogen of 0.3MPa.After the filtering reacting liquid, reaction solvent is removed in distillation, obtains the compound 4.5g shown in the formula (5).
[changing 29]
Then, compound 4.5g shown in the above-mentioned formula of in the reaction vessel that possesses whipping appts, water cooler and thermometer, packing into (5) (15.1 mmole), acrylate chloride 1.6g (18 mmole), methylene dichloride 50ml, under nitrogen atmosphere below the reactor cooling to 5 ℃.Then, slowly splash into triethylamine 1.8g (18 mmole).Splash into finish after, below 20 ℃ the reaction 3 hours.After reaction is finished, add methylene dichloride, clean organic layer with 10% aqueous hydrochloric acid, pure water, saturated aqueous common salt then.Distillation is made with extra care the compound 4.7g shown in the formula of obtaining (6) with the silicagel column of 2 times of amounts (weight ratio) after removing and desolvating.
[changing 30]
Then, in the reaction vessel that possesses whipping appts, water cooler and thermometer, the compound 4.7g shown in the above-mentioned formula (6) is dissolved in after the methylene dichloride of 10ml, splashes into trifluoroacetic acid 10ml, at room temperature stirred 30 minutes.Subsequently, add ethyl acetate 200ml, and clean organic layer with pure water, saturated aqueous common salt.Distillation removes and desolvates, and obtains the compound 2.7g shown in the formula (7).
[changing 31]
Then, compound 2.7g shown in the above-mentioned formula of packing in the reaction vessel that possesses whipping appts, water cooler and thermometer (7) (9.1 mmole), vinylformic acid-2-(4-hydroxy phenyl) ethyl ester 1.9g (10 mmole), dimethyl aminopyridine 120mg, methylene dichloride 100ml keep reaction vessel below 5 ℃ in ice bath.Under nitrogen atmosphere, slowly splash into DIC 1.4g (11 mmole).Splash into finish after, reaction vessel is returned back to room temperature, reacted 5 hours.After the filtering reacting liquid, in filtrate, add methylene dichloride 200ml, clean, further clean, use the anhydrous sodium sulfate drying organic layer with saturated aqueous common salt with 10% aqueous hydrochloric acid.Distillation is made with extra care with the silicagel column of 2 times of amounts (weight ratio) after removing and desolvating, and by the methylene chloride recrystallize, obtains the target compound 2.5g shown in the formula (8).This compound shows as mesomorphic phase in very wide temperature range till 87 ℃～123 ℃.
[changing 26]
(physics value)
H-NMR (solvent: deuterochloroform): δ: 2.89-2.98 (m, 4H), 3.11 (t, 2H), 4.33 (t, 2H), 5.80 (dd, 1H), 6.02-6.12 (m, 2H), 6.32-6.40 (m, 2H), 6.61 (dd, 1H), 6.95 (d, 2H), 7.20-7.28 (m, 4H), 7.32 (d, 2H), 7.52 (d, 2H), 7.59 (d, 2H)
13C-NMR (solvent: deuterochloroform): δ: 30.6,34.5,35.9,64.8,121.4,121.6,127.1,127.7,128.2,128.7,129.7,130.7,132.5,135.2,138.3,139.1,149.0,149.7,164.3,165.8,171.1
Infrared absorption spectrum (IR) is (KBr): 2925,2855,1760, and 1652-1622,809cm
-1Fusing point: 87 ℃
(embodiment 3)
In the reaction vessel that possesses whipping appts, water cooler and thermometer, add aluminum chloride 12.8g (96 mmole), methylene dichloride 100ml, stir.Slowly splashed into Acetyl Chloride 98Min. 8.4g (110 mmole) with 90 minutes then, further, with the dichloromethane solution 80ml that slowly splashed into 4-bromo-2-fluorine biphenyl 20g (80 mmole) in 2 hours.Splash into after the end, restir 2 hours is finished reaction.Reaction solution is slowly injected the frozen water of 500ml, use dichloromethane extraction, clean organic layer with pure water, saturated aqueous common salt.Distillation is carried out drying after removing and desolvating, and has obtained introducing the compound 23g of ethanoyl.Next, the compound 23g, the formic acid 300ml that in the reaction vessel that possesses whipping appts, water cooler and thermometer, pack into and introduced ethanoyl, the hydrogen peroxide 20ml of adding 34.5%, reflux 6 hours.After reaction is finished, add 10% aqueous solution of sodium bisulfite 450ml, decompose hydroperoxide filters the solid of separating out, and uses acetic acid ethyl dissolution, and water, saturated aqueous common salt are cleaned organic layer.Distillation is made with extra care with the silicagel column of 2 times of amounts (weight ratio) after removing and desolvating, and obtains the compound 18g shown in the formula (9).
[changing 27]
4-bromo-3-fluorine biphenyl 10g (37.4 mmole), tertiary butyl acrylate 5.7g (44.8 mmole), triethylamine 5.6g (56 mmole), acid chloride 410mg, dimethyl formamide 300ml pack in the reaction vessel that possesses whipping appts, water cooler and thermometer, under nitrogen atmosphere, reactor is heated to 100 ℃, reacts.Behind the reaction terminating, add ethyl acetate, THF, clean organic layer with 10% aqueous hydrochloric acid, pure water, saturated aqueous common salt then.Distillation is made with extra care the compound 10.5g shown in the formula of obtaining (10) with the silicagel column of 2 times of amounts (weight ratio) after removing and desolvating.
[changing 28]
Then, compound 10.5g shown in the above-mentioned formula of in the reaction vessel that possesses whipping appts, water cooler and thermometer, packing into (10) (33.4 mmole), acrylate chloride 3.6g (40 mmole), methylene dichloride 100ml, under nitrogen atmosphere below the reactor cooling to 5 ℃.Then, slowly splash into triethylamine 4g (40 mmole).Splash into finish after, below 20 ℃ the reaction 3 hours.After reaction is finished, add methylene dichloride, clean organic layer with 10% aqueous hydrochloric acid, pure water, saturated aqueous common salt then.Distillation is made with extra care the compound 10.5g that obtains having acryl after removing and desolvating with the silicagel column of 2 times of amounts (weight ratio).
Next, in the reaction vessel that possesses whipping appts, water cooler and thermometer, the compound 10.5g with acryl is dissolved in after the methylene dichloride 20ml, splashes into trifluoroacetic acid 30ml, at room temperature stirred 30 minutes.Subsequently, add ethyl acetate 200ml, clean organic layer with pure water, saturated aqueous common salt.Distillation removes and desolvates, and obtains the compound 8.9g shown in the formula (11).
[changing 29]
Then, compound 8g shown in the above-mentioned formula of packing in the reaction vessel that possesses whipping appts, water cooler and thermometer (11) (25.6 mmole), 4-xenol 4.36g (25.6 mmole), dimethyl aminopyridine 300mg, methylene dichloride 150ml keep reaction vessel below 5 ℃ in ice bath.Under nitrogen atmosphere, slowly splash into DIC 3.8g (30 mmole).Splash into finish after, reaction vessel is returned back to room temperature, reacted 5 hours.After the filtering reacting liquid, in filtrate, add methylene dichloride 200ml, clean, further clean, use the anhydrous sodium sulfate drying organic layer with saturated aqueous common salt with 10% aqueous hydrochloric acid.Distillation is made with extra care with the silicagel column of 2 times of amounts (weight ratio) after removing and desolvating, and by the methylene chloride recrystallize, obtains the target compound 9.5g shown in the formula (12).This compound shows as mesomorphic phase since 164 ℃ in very wide temperature range till more than 200 ℃.
[changing 32]
(physics value)
H-NMR (solvent: deuterochloroform): δ: 6.04 (d, 1H), 6.32-6.44 (m, 1H), 6.62-6.67 (m, 2H), 7.25-7.28 (m, 4H), 7.34-7.49 (m, 6H), 7.61-7.65 (m, 6H), 7.88 (d, 1H)
13C-NMR (solvent: deuterochloroform): δ: 115.2,118.2,121.4,121.5,126.8,127.0,127.4,127.8,128.4,129.7,132.5,132.0,135.1,142.3,145.7,149.2,150.2,165.2
Infrared absorption spectrum (IR) is (KBr): 1760, and 1652-1622,809cm
-1
Fusing point: 164 ℃
(embodiment 4)
The polymerizable liquid crystal compound of forming shown in below the preparation (composition 1).
[changing 33]
Polymerizable liquid crystal compound has the good stability that mixes, and shows the nematic liquid crystal phase.In said composition, add 3% Photoepolymerizationinitiater initiater Irgacure 907 (Ciba corporate system), preparation polymerizable liquid crystal compound (composition 2).The pimelinketone solution of said composition 2 be spin-coated on have the on glass of polyimide, with high voltage mercury lamp 4mW/cm
2Uviolizing 120 seconds result thereon, composition 2 carries out polymerization and has obtained optically anisotropic body under the state of orientation that keeps homogeneous.The surface hardness of this optically anisotropic body (according to JIS-S-K-5400) is H.Phase differential before the heating of the optically anisotropic body that obtains is 100% o'clock, and the phase differential of 240 ℃ of heating after 1 hour is 85%, and the phase differential decrement is 15%.
(comparative example 1)
The polymerizable liquid crystal compound of forming shown in below the preparation (composition 3).
[changing 34]
Polymerizable liquid crystal compound, though be shown as the nematic liquid crystal phase, poorly soluble, room temperature promptly had crystallization to separate out in following 1 hour.
(comparative example 2)
The polymerizable liquid crystal compound of forming shown in below the preparation (composition 4).
[changing 35]
Polymerizable liquid crystal compound has the good stability that mixes, and shows the nematic liquid crystal phase.In said composition, add 3% Photoepolymerizationinitiater initiater Irgacure 907 (Ciba corporate system), preparation polymerizable liquid crystal compound (composition 5).The pimelinketone solution of said composition 5 be spin-coated on have the on glass of polyimide, with high voltage mercury lamp 4mW/cm
2Uviolizing 120 seconds result thereon, composition 5 polymerization and obtained optically anisotropic body under the state of orientation that keeps homogeneous.The surface hardness of this optically anisotropic body (according to JIS-S-K-5400) is 2B.Phase differential before the heating of the optically anisotropic body that obtains is 100% o'clock, and the phase differential of 240 ℃ of heating after 1 hour is 75%, and the phase differential decrement is 25%.
As seen, the composition 5 of comparative example 2 is compared with composition 2 of the present invention, and the phase differential decrement of the optically anisotropic body that can make is bigger, poor heat resistance.And surface hardness is 2B, and is abundant inadequately.
Claims (9)
1. polymerizable compound, shown in general formula (I):
Wherein, R
1And R
2Represent any one in the following formula (R-1)～(R-15) independently of one another,
X
1And X
2Represent hydrogen atom, alkyl, haloalkyl, alkoxyl group, halogenated alkoxy, halogen, cyano group or nitro independently of one another; S
1And S
2Expression independently of one another, according between the Sauerstoffatom directly bonded mode carbon atom by Sauerstoffatom ,-COO-,-OCO-or-OCOO-replaces the alkylidene group of also passable carbonatoms 2～12, perhaps singly-bound; L
1Expression-CH=CH-COO-or-C
2H
4COO-; L
2, L
3Represent independently of one another singly-bound ,-O-,-S-,-OCH
2-,-CH
2O-,-CO-,-C
2H
4-,-COO-,-OCO-,-OCOOCH
2-,-CH
2OCOO-,-CO-NR
11-,-NR
11-CO-,-SCH
2-,-CH
2S-,-CH=CH-COO-,-OOC-CH=CH-,-COOC
2H
4-,-OCOC
2H
4-,-C
2H
4OCO-,-C
2H
4COO-,-OCOCH
2-,-CH
2COO-,-CH=CH-,-CF=CH-,-CH=CF-,-CF
2-,-CF
2O-,-OCF
2-,-CF
2CH
2-,-CH
2CF
2-,-CF
2CF
2-or-C ≡ C-(in the formula, R
11The alkyl of expression carbonatoms 1～4); M
1Expression 1,4-phenylene, 1,4-cyclohexylidene, pyridine-2,5-two bases, pyrimidine-2,5-two bases, naphthalene-2,6-two bases, naphthane-2,6-two bases or 1,3-diox-2,5-two bases; M
2Expression 1,4-phenylene, 1,4-cyclohexylidene, pyridine-2,5-two bases, pyrimidine-2,5-two bases, naphthalene-2,6-two bases, naphthane-2,6-two bases, 1,3-diox-2,5-two bases, 1,3,5-benzene three bases, 1,3,4-benzene three bases, 1,3,4,5-benzene four bases, 1,3,5-hexanaphthene three bases or 1,3,4-hexanaphthene three bases; M
1And M
2Can not be substituted independently of one another or be replaced by alkyl, haloalkyl, alkoxyl group, halogen, cyano group or nitro, p represents 0 or 1, and q represents 0,1,2 or 3; Q is 0 o'clock ,-(L
3-S
2-R
2)
0The expression hydrogen atom, q represents 2 or at 3 o'clock, 2 or 3 L of existence
3, S
2And R
2Can be the same or different.
2. according to the polymerizable compound of claim 1 record, wherein, in general formula (I), L
2And L
3Independently of one another expression-O-,-OCH
2-,-CH
2O-,-COO-,-OCO-,-C
2H
4-,-C ≡ C-or singly-bound; M
1Expression 1,4-cyclohexylidene, 1,4-phenylene, naphthalene-2,6-two bases or naphthane-2,6-two bases; M
2Expression 1,4-phenylene, 1,4-cyclohexylidene, naphthalene-2,6-two bases, naphthane-2,6-two bases, 1,3-diox-2,5-two bases, 1,3,5-benzene three bases, 1,3,4-benzene three bases, 1,3,4,5-benzene four bases, 1,3,5-hexanaphthene three bases or 1,3,4-hexanaphthene three bases; M
1And M
2Can be replaced by alkyl, haloalkyl, alkoxyl group, halogenated alkoxy, halogen, cyano group or nitro independently of one another; Q represents 1 or 2.
According to claim 1 or 2 the record polymerizable compounds, wherein, in general formula (I), M
2Expression is not substituted or by alkyl, haloalkyl, alkoxyl group, halogenated alkoxy, halogen, cyano group or nitro replaced 1,4-phenylene, 1,3,5-benzene three bases, 1,3,4-benzene three bases or 1,3,4,5-benzene four bases.
According to claim 1,2 or 3 the record polymerizable compounds, wherein, in general formula (I), R
1And R
2Expression (R-1) or formula (R-2) independently of one another.
5. according to the polymerizable compound of claim 1,2,3 or 4 records, wherein, p represents 0.
According to claim 1,2,3,4 or 5 the record polymerizable compounds, wherein, S
1The expression singly-bound.
7. liquid-crystal composition contains the polymerizable compound of any record in the claim 1～6.
8. optically anisotropic body is made of the polymkeric substance of the liquid-crystal composition that contains polymerizable compound of claim 7 record.
9. a liquid crystal display device is characterized in that, uses the optically anisotropic body of claim 8 record.
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| KR101563574B1 (en) | 2015-10-27 |
| CN101792391B (en) | 2015-02-04 |
| KR20100086922A (en) | 2010-08-02 |
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