CN103725291A - Polymerizable liquid crystal composition, optical anisotropy film and liquid crystal display element - Google Patents

Polymerizable liquid crystal composition, optical anisotropy film and liquid crystal display element Download PDF

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CN103725291A
CN103725291A CN201310291308.1A CN201310291308A CN103725291A CN 103725291 A CN103725291 A CN 103725291A CN 201310291308 A CN201310291308 A CN 201310291308A CN 103725291 A CN103725291 A CN 103725291A
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liquid crystal
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formula
carbon number
polymerizable liquid
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CN103725291B (en
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大槻大辅
奈良和美
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JNC Corp
JNC Petrochemical Corp
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Chisso Petrochemical Corp
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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
    • C09K19/42—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40
    • C09K19/46—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40 containing esters
    • 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
    • C09K19/12—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings at least two benzene rings directly linked, e.g. biphenyls
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • 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
    • C09K19/32—Non-steroidal liquid crystal compounds containing condensed ring systems, i.e. fused, bridged or spiro ring systems
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • 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
    • C09K19/38—Polymers
    • 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
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/13363—Birefringent elements, e.g. for optical compensation

Abstract

The invention provides a polymerizable liquid crystal composition, an optical anisotropy film and a liquid crystal display element. The polymerizable liquid crystal composition can be coated on a base material in the case of not using an organic solvent and has great refractive index anisotropy performance. The polymerizable liquid crystal composition is characterized by comprising the compound represented by a formula (1-1). In the formula (1-1)(img file= 'DDA00003497991600011. TIF 'wi= '1672 he ='328 '/), R is a hydrogen or a methyl, W1 and W2 are respectively a hydrogen, a fluorine, a methyl and a methoxy group , and R2 is an alkyl with the carbon number from 1-10 or an alkoxy with the carbon number from 1-10, wherein at least one -CH2- of the alkyl and the alkoxy can be replaced by -O-.

Description

Polymerizable liquid crystal compound, optical anisotropic film and liquid crystal display device
Technical field
The liquid crystal display device that the present invention relates to a kind of polymerizable liquid crystal compound that contains polymerizable liquid crystal compound, uses the optically anisotropic film of having of this composition gained (optical anisotropic film) and contain this optical anisotropic film.
Background technology
In the optical anisotropic film of Polarizer, reflection polarizing plate, polarizer etc., can utilize polymerizable liquid crystal compound (patent documentation 1).Its reason is: this compound demonstrates optical anisotropy under mesomorphic state, and by polymerization, this anisotropy is fixed.The necessary optical characteristics of optical anisotropic film according to object and difference, therefore needs to have the compound of the characteristic corresponding with target.The compound using in the purposes of optically anisotropic body, in the situation that using separately, is difficult to control described anisotropy mostly, therefore sometimes with various compound combinations with the form utilization of composition.
Polymerizable liquid crystal compound sometimes in order to adjust its coating with added organic solvent ink (ink) form use.When thering is optically anisotropic film with polymerizable liquid crystal compound manufacture, polymerizable liquid crystal compound, photopolymerization initiator, interfacial agent etc. are dissolved in organic solvent, the ink of soltion viscosity, levelling property etc. has been adjusted in preparation.This ink is applied on the transparency carrier of orientation processing, makes solvent seasoning, make polymerizable liquid crystal compound orientation on substrate.Then irradiation ultraviolet radiation carries out polymerization, and orientation state is fixed.
In recent years, proposed to show at stereo-picture the method (patent documentation 2) of using lens pillar (lenticular lens) in purposes.So-called lens pillar, refers to fine half-terete convex lens, by these lens being arranged on to the surface of image, can be separated into right eye identification use, left eye identification use, can realize the stereoscopic vision of naked eyes.And then, in order to improve optical characteristics or the visibility of lens pillar, proposed to utilize the technology (non-patent literature 1) of polymerizable liquid crystal compound.By using the high material of optical anisotropy, also there is advantages such as can making lens attenuation.
In the situation that making lens pillar with polymerizable liquid crystal compound, polymerizable liquid crystal compound is flow in the mould with half-terete depressed part, and make it orientation, by uviolizing, fixed.Now, if the ink that contains organic solvent needs to make the step of solvent seasoning, worry the obvious variation of productivity.Therefore, for polymerizable liquid crystal compound not being flow in mould with an organic solvent in the situation that, the material that demand liquid crystal lower limit temperature is low.
In addition, in the situation that making the optical anisotropic films such as lens pillar with polymerizable liquid crystal compound, must be after polymerizable liquid crystal compound be applied on base material, utilizing uviolizing to keep mesomorphic state before being fixed and non-crystallizable.Due to manufacture view, sometimes after being applied on base material, before fixing, place for a long time, it is desirable at room temperature keep mesomorphic state within the long as far as possible time.
As the low material of liquid crystal lower limit temperature, two ring phenylene system's (methyl) acrylate monomers (patent documentation 3, non-patent literature 2) have been proposed.But, this material is because the liquid crystal lower limit temperature of described monomer is more than 40 ℃, therefore in the case of with the relatively high material of liquid crystal lower limit temperature composition composition, be difficult at room temperature keep for a long time the possibility of mesomorphic state high, further the low material of demand liquid crystal lower limit temperature.In addition, the material that contains cyclohexane ring is also known to the low material of liquid crystal lower limit temperature (patent documentation 4).But this material, because optical anisotropy is low, therefore in order to obtain required optical characteristics, must increase the thickness of optical anisotropic film, is difficult to be referred to as to give full play to the advantage of polymerizable liquid crystal compound.Known in addition, having the substituent compound of the large volumes such as chain alkyl is also the low material (patent documentation 5) of liquid crystal lower limit temperature.But may there is situation about being reduced by the optical characteristics due to orientation lack of homogeneity in this material.
[prior art document]
[patent documentation]
[patent documentation 1] Japanese Patent Laid-Open 2002-372623 communique
[patent documentation 2] Japanese patent laid-open 6-214323 communique
[patent documentation 3] Japanese patent laid-open 10-195138 communique
[patent documentation 4] Japanese patent laid-open 9-316032 communique
[patent documentation 5] Japanese Patent Laid-Open 2009-184974 communique
[non-patent literature]
[non-patent literature 1] international display technology symposial (Internationa] Display Workshop, IDW) ' 04,1495 page～1496 pages
[non-patent literature 2] molecular crystal and liquid crystal (Mol.Cryst.Liq.Cryst.), 261,593-603 (1995)
Summary of the invention
The 1st object of the present invention is to provide the polymerizable liquid crystal compound that a kind of liquid crystal lower limit temperature is low, optical anisotropy is high.The 2nd object is to provide a kind of orientation that comprises described polymerizable liquid crystal compound, film evenly and the optical anisotropic film corresponding with purposes.The 3rd object is to provide a kind of liquid crystal display device that contains described optical anisotropic film.
The inventor has carried out making great efforts research repeatedly, found that, by use, containing two fluorine-containing ring phenylenes is the polymerizable liquid crystal compound of polymerizable liquid crystal compound, can solve described problem, thereby complete the present invention.Polymerizable liquid crystal compound of the present invention is shown in following [1].
[1] polymerizable liquid crystal compound, is characterized in that containing the represented compound of formula (1),
Figure BDA00003497991500031
In formula (1), R 1for hydrogen or methyl; Z 1for-COO-or-OCO-; W 1and W 2independent is respectively the alkyl of hydrogen, halogen, carbon number 1～5 or the alkoxyl group of carbon number 1～5; R 2for the alkyl of carbon number 1～20 or the alkoxyl group of carbon number 1～20, in described alkyl and alkoxyl group at least one-CH 2-can be replaced by-O-; N is 1 or 2.
[effect of invention]
Having fluorine can make liquid crystal lower limit temperature reduce as substituent phenylene.And then, not only liquid crystal lower limit temperature is low for the compound of the formula (1) that is polymerizable liquid crystal compound as fluorine-containing two ring phenylenes, and have and the characteristics such as the intermiscibility excellence of other liquid crystalline cpds, orientation excellent in uniformity, therefore as the constituent of polymerizable liquid crystal compound and useful.The optical anisotropic film that comprises polymerizable liquid crystal compound of the present invention for example can be for the polarizer of the integrant as liquid crystal display device, polarization element, choice reflective film, luminance raising film and compensation film for angular field of view.
Embodiment
The using method of the term in this specification sheets is as follows.Liquid crystalline cpd is to have the compound of mesomorphic phase and do not have mesomorphic phase but as the composition of liquid-crystal composition and the general name of useful compound.Mesomorphic phase is that nematic phase, smectic phase, cholesterol equate, mostly in situation, refers to nematic phase.Liquid crystal lower limit temperature is the lower limit temperature that demonstrates mesomorphic phase, is the temperature from mesomorphic phase to crystalline transition.Polymerizability refers to by means such as light, heat, catalyzer and makes monomer polymerization, forms the ability of polymkeric substance.Sometimes compound statement represented formula (1) is made to compound (1).About the represented compound of other formulas, sometimes also according to identical short cut technique, carry out appellation.The connotation of term " liquid crystal liquid crystal property " is not limited to only has mesomorphic phase.Even if himself does not have mesomorphic phase, but the characteristic that can be used as the composition of liquid-crystal composition while mixing with other liquid crystalline cpds is also included within the connotation of liquid crystal liquid crystal property.When the structure of compound is described, term " at least one " used refers to that not only position but also number are also at least one.For example, the statement of " at least one A can be replaced by B, C or D " refers to following connotation: not only comprise the situation that situation that at least one A replaced by B, situation that at least one A is replaced by C and at least one A are replaced by D, and comprise that multiple A are by least 2 situations about being replaced of B～D.But, at least one-CH 2in-the definition that can be replaced by-O-, do not comprise that result generates in conjunction with the replacement as base-O-O-.In addition, at least one-CH 2in the situation that-quilt-O-replaces, carbon number does not exceed the scope of record.For example, the R in formula (1) 2for the alkylidene group of carbon number 1～20, in this alkylidene group at least one-CH 2-can be replaced by-O-, but comprise by the carbon number of the alkylidene group of the replacement of-O-, be no more than in this case 20.This rule (rule) is also identical for other definition.
Sometimes the optically active compound with polymerizability base is called to polymerizable optically-active compound, optically active compound or referred to as compound.Polymerizable liquid crystal compound too, is sometimes referred to as liquid-crystal composition or referred to as composition.The situation sometimes compound to 1 polymerizability base is called simple function.In addition, in the situation that compound has multiple polymerizability base, sometimes with multi-functional or claim to come appellation with exhale corresponding with the number of polymerizability base.
Here, in formula (1)-(F) connotation of n describes.It represents that any hydrogen of 2,3,5,6 on Isosorbide-5-Nitrae-phenylene can be replaced to fluorine, in addition, with n, represents that it replaces number.That is, the in the situation that of n=1, represent that any hydrogen of 2,3,5,6 on Isosorbide-5-Nitrae-phenylene is replaced by fluorine, the in the situation that of n=2, represent that any two hydrogen of 2,3,5,6 on Isosorbide-5-Nitrae-phenylene are replaced by fluorine.
The present invention consists of following [1] item～[11] institute.
[1] polymerizable liquid crystal compound, is characterized in that containing the represented compound of formula (1),
Figure BDA00003497991500051
In formula (1), R 1for hydrogen or methyl; Z 1for-COO-or-OCO-; W 1and W 2independent is the alkyl of hydrogen, halogen, carbon number 1～5 or the alkoxyl group of carbon number 1～5; R 2for the alkyl of carbon number 1～20 or the alkoxyl group of carbon number 1～20, in this alkyl and alkoxyl group at least one-CH 2-can be replaced by-O-; N is 1 or 2.
[2] polymerizable liquid crystal compound of recording according to [1] item, its Chinese style (1) is the compound of formula (1-1),
Figure BDA00003497991500052
In formula (1-1), R 1for hydrogen or methyl; W 1and W 2independent is hydrogen, fluorine, methyl or methoxy; R 2for the alkyl of carbon number 1～10 or the alkoxyl group of carbon number 1～10, in this alkyl and alkoxyl group at least one-CH 2-can be replaced by-O-.
[3] polymerizable liquid crystal compound that basis [1] item or [2] item are recorded, it contains at least one compound in the represented compound of the formula of being selected from (M1), formula (M2) and formula (M3),
Figure BDA00003497991500053
In formula (M1), formula (M2) and formula (M3), R 1for hydrogen or methyl; A 1independent is respectively Isosorbide-5-Nitrae-phenylene, Isosorbide-5-Nitrae-cyclohexylidene or naphthalene-2,6-bis-bases, and in described Isosorbide-5-Nitrae-phenylene, at least one hydrogen can be replaced by the alkoxyl group of the alkyl of fluorine, carbon number 1～5 or carbon number 1～5; A 2be 1,4-phenylene, 1,4-cyclohexylidene, naphthalene-2,6-bis-bases or fluorenes-2,7-bis-bases, described 1, in 4-phenylene, at least one hydrogen can be replaced by the alkyl ester of the alkoxyl group of the alkyl of fluorine, chlorine, cyano group, hydroxyl, formyl radical, acetoxyl group, ethanoyl, trifluoromethyl, carbon number 1～5, carbon number 1～5 or carbon number 1～5, in fluorenes-2, in 7-bis-bases, the hydrogen of 9 can be replaced by the alkyl of carbon number 1～5; Z 2independent is respectively singly-bound ,-C 2h 4-,-COO-,-OCO-,-C ≡ C-,-CH=CHCOO-,-OCOCH=CH-,-COOC 2h 4-,-C 2h 4oCO-,-C 2h 4cOO-or-OCOC 2h 4-; W 1and W 2independent is respectively hydrogen, fluorine, methyl or methoxy; Y is the alkyl of cyano group, carbon number 1～10 or the alkoxyl group of carbon number 1～10, at least one CH in described alkyl and alkoxyl group 2-can be replaced by-O-; Q be singly-bound ,-O-,-COO-,-OCO-or-OCOO-; P is 1～12 integer; R is independent is respectively the integer of O～12; A is 1 or 2; B is 0～2 integer, and c and d are independently 0～2 integer, and meets 1≤c+d≤3.
[4] polymerizable liquid crystal compound of recording according to any one in [1] to [3], it contains the represented compound of formula (1) and is selected from least one compound in the represented compound of formula (M2-1),
In formula (M2-1), R 1for hydrogen or methyl; Z 2independent is respectively singly-bound ,-COO-,-OCO-,-C ≡ C-,-CH=CHCOO-,-OCOCH=CH-,-C 2h 4cOO-or-OCOC 2h 4-; W 1and W 2independent is respectively hydrogen, fluorine, methyl or methoxy; W 3independent is the alkyl of hydrogen or carbon number 1～5; Q is-O-,-COO-,-OCO-or-OCOO-; R is 1～12 integer.
[5] polymerizable liquid crystal compound of recording according to any one in [1] to [4], the represented compound of its Chinese style (1) is the represented compound of formula (1-1-a),
Figure BDA00003497991500071
In formula (1-1-a), R 2for the alkyl of carbon number 2～10, at least one CH in this alkyl 2-can be replaced by-O-.
[6] polymerizable liquid crystal compound of recording according to any one in [1] to [5], it is at room temperature nematic phase.
[7] polymerizable liquid crystal compound of recording according to any one in [1] to [6], wherein total amount 100 % by weight of the compound represented with respect to formula (1), formula (M1), formula (M2) and formula (M3), the formula (M1) of the compound that the formula that contains 10 % by weight～50 % by weight (1) is represented and 50 % by weight～90 % by weight and the represented compound of formula (M2).
[8] polymerizable liquid crystal compound of recording according to any one in [1] to [7], it can not use solvent and be applied on substrate.
[9] optical anisotropic film, it is that polymerizable liquid crystal compound by making to record according to any one in [1] to [8] carries out polymerization and obtains.
[10] optical anisotropic film of recording according to [9] item, its specific refractory power anisotropy is more than 0.15.
[11] liquid crystal display device, it has the optical anisotropic film of recording according to [9] or [10] item.
At least one compound in the cohort that composition of the present invention contains the represented compound of the formula of being selected from (1) is as (A) composition.
Figure BDA00003497991500081
In formula (1),
R 1for hydrogen or methyl, preferably hydrogen.
Z 1for-COO-or-OCO-, preferably-COO-.
W 1and W 2independent is respectively the alkyl of hydrogen, halogen, carbon number 1～5 or the alkoxyl group of carbon number 1～5, preferably hydrogen, fluorine, methyl or methoxy, and then preferred hydrogen.
R 2for the alkyl of carbon number 1～20 or the alkoxyl group of carbon number 1～20, in this alkyl and alkoxyl group at least one-CH 2-can be replaced by-O-the preferably alkyl of carbon number 1～10 or the alkoxyl group of carbon number 1～10, and then the preferred alkyl of carbon number 2～10.
N is 1 or 2, preferably 1.
At least one compound in the cohort that composition of the present invention contains the represented compound of the formula of being selected from (M1), formula (M2) and formula (M3) is as (B) composition.
In formula (M1),
Figure BDA00003497991500082
R 1for hydrogen or methyl.
A 1independent is Isosorbide-5-Nitrae-phenylene, Isosorbide-5-Nitrae-cyclohexylidene or naphthalene-2,6-bis-bases, and in this Isosorbide-5-Nitrae-phenylene, at least one hydrogen can be replaced by the alkoxyl group of the alkyl of fluorine, carbon number 1～5 or carbon number 1～5.
Z 2independent is singly-bound ,-C 2h 4-,-COO-,-OCO-,-C ≡ C-,-CH=CHCOO-,-OCOCH=CH-,-COOC 2h 4-,-C 2h 4oCO-,-C 2h 4cOO-or-OCOC 2h 4-.
W 1and W 2independent is respectively hydrogen, fluorine, methyl or methoxy.
Y is the alkyl of cyano group, carbon number 1～10 or the alkoxyl group of carbon number 1～10, in this alkyl and alkoxyl group at least one-CH 2-can be replaced by-O-.
P is 1～12 integer.
A is 1 or 2.
In formula (M2),
Figure BDA00003497991500091
R 1for hydrogen or methyl.
A 2be 1; 4-phenylene, 1; 4-cyclohexylidene, naphthalene-2,6-bis-bases or fluorenes-2,7-bis-bases; this 1; in 4-phenylene, at least one hydrogen can be replaced by the alkyl ester of the alkoxyl group of the alkyl of fluorine, chlorine, cyano group, hydroxyl, formyl radical, acetoxyl group, ethanoyl, trifluoromethyl, carbon number 1～5, carbon number 1～5 or carbon number 1～5, in fluorenes-2; in 7-bis-bases, the hydrogen of 9 can be replaced by the alkyl of carbon number 1～5.
Z 2independent is singly-bound ,-C 2h 4-,-COO-,-OCO-,-C ≡ C-,-CH=CHCOO-,-OCOCH=CH-,-COOC 2h 4-,-C 2h 4oCO-,-C 2h 4cOO-or-OCOC 2h 4-.
W 1and W 2independent is respectively hydrogen, fluorine, methyl or methoxy.
Q be singly-bound ,-O-,-COO-,-OCO-or-OCOO-.
R is independently 0～12 integer.
B is 0～2 integer.
In formula (M3),
Figure BDA00003497991500092
R 1for hydrogen or methyl.
A 1independent is Isosorbide-5-Nitrae-phenylene, Isosorbide-5-Nitrae-cyclohexylidene or naphthalene-2,6-bis-bases, and in this Isosorbide-5-Nitrae-phenylene, at least one hydrogen can be replaced by the alkoxyl group of the alkyl of fluorine, carbon number 1～5 or carbon number 1～5.
Z 2independent is singly-bound ,-C 2h 4-,-COO-,-OCO-,-C ≡ C-,-CH=CHCOO-,-OCOCH=CH-,-COOC 2h 4-,-C 2h 4oCO-,-C 2h 4cOO-or-OCOC 2h 4-.
Q be singly-bound ,-O-,-COO-,-OCO-or-OCOO-.
R is independently 0～12 integer.
C and d are independently respectively 0～2 integer, and meet 1≤c+d≤2.
More preferably contain at least one compound in the cohort of the represented compound of the formula of being selected from (M2-1) as (B) composition.
R 1for hydrogen or methyl.
Z 1independent is respectively singly-bound ,-COO-,-OCO-,-C ≡ C-,-CH=CHCOO-,-OCOCH=CH-,-C 2h 4cOO-or-OCOC 2h 4-.
W 1and W 2independent is respectively hydrogen, fluorine, methyl or methoxy.
W 3independent is the alkyl of hydrogen or carbon number 1～5.
Q is-O-,-COO-,-OCO-or-OCOO-.
R is 1～12 integer.
Composition of the present invention preferably contains the represented compound of formula (1) as (A) composition, and at least one compound in the cohort that contains the represented compound of the formula of being selected from (M1), formula (M2) and formula (M3) is as (B) composition.
In addition, with respect to (A) composition and (B) total amount 100 % by weight of composition, (B) composition of (A) composition that contains 10 % by weight～50 % by weight and 50 % by weight～90 % by weight.
Composition of the present invention also can further contain non-ionic surfactant.The example of non-ionic surfactant is fluorine system, silicone-based or hydrocarbon system.Non-ionic surfactant is improved the effect of the smoothness of coated film.
Composition of the present invention at room temperature has the mesomorphic phase of nematic phase or smectic phase.In the case of composition of the present invention is applied on the plastic base of the orientation processing such as friction treatment or supporting substrate that surface is covered by the film of plastics on be filmed, become horizontal direction matching (homogeneous alignment) or mixed orientation (hybrid alignment).In addition, in composition of the present invention, add the optically active compound of non-polymerization or polymerizability, become and reverse orientation (twist alignment).If add and there is the compound of phenolphthalein structure (cardo structure) or the polymerizable liquid crystal compound of simple function in composition of the present invention, easily obtain vertical orientation (homeotropic alignment).
Compound used in composition of the present invention is illustrated.
Compound (1) is using following two ring structures as liquid crystal former (mesogen), and have (methyl) acrylic as polymerizability base, described two ring structures comprise and have fluorine as substituent phenylene and another phenylene.This compound demonstrates liquid crystal liquid crystal property near room temperature, and demonstrates the relatively large optical anisotropy that exceedes Δ n=0.1.
Compound (M1) is simple function polymerizable liquid crystal compound, but different from compound (1), at polymerizability base and liquid crystal, has spacer (spacer) between former.Compound (M2) is two sense polymerizable liquid crystal compounds, and this polymkeric substance becomes three-dimensional structure, therefore, with the Compound Phase comparison with 1 polymerizability base, becomes harder polymkeric substance.Compound (M3) is trifunctional polymerizable liquid crystal compound, and this polymkeric substance can further form firmly network (network), and the Compound Phase comparison with having 1 and 2 polymerizability base, becomes harder polymkeric substance.Below, sometimes by compound (M1), compound (M2) and compound (M3) or be generically and collectively referred to as compound (M) by the derivative compound of those compounds.
Composition of the present invention also can contain other polymerizable compounds different from compound (1), compound (M1), compound (M2), compound (M3) and non-ionic surfactant.Said composition also can contain silane coupling agent in order to improve the adhesion of film and support base material.Said composition also can contain and is suitable for the additives such as the polymerization initiator, light sensitizer of polyreaction.Said composition also can contain in order to improve the characteristic of polymkeric substance the additives such as UV light absorber, antioxidant, free radical scavenger, photostabilizer, chain-transfer agent.Said composition also can contain organic solvent.
Add preferred proportion during non-ionic surfactant take with respect to (A) composition and (B) the total weight of composition weight ratio and as 0.0001～0.03.The scope of preferred weight ratio is 0.0001～0.005.
Add preferred proportion during silane coupling agent take with respect to (A) composition and (B) the total weight of composition weight ratio and as 0.01～0.15.The scope of preferred weight ratio is 0.03～0.10.
While adding other polymerizable compounds, its preferred proportion take with respect to (A) composition and (B) the total weight of composition weight ratio and as 0.01～0.50, more preferably 0.03～0.30.When using the additives such as polymerization initiator, as long as its usage quantity is the minimum for achieving the goal.
Then, next illustrates the preference of compound (1).
Figure BDA00003497991500121
Next illustrates the preference of compound (M1).
Figure BDA00003497991500131
Figure BDA00003497991500141
In formula (M1-1)～formula (M1-15), R 1independent is hydrogen or methyl, and p is independently 1～12 integer.
Next illustrates the preference of compound (M2).
Figure BDA00003497991500161
Figure BDA00003497991500171
In formula (M2-1-1)～formula (M2-1-10) and formula (M2-2-1)～formula (M2-2-22), R 1independent be hydrogen or methyl, and r is independently 1～12 integer, when in formula, exist more than 2 r time, any 2 r can be identical also can difference.
Next illustrates the preference of compound (M3).
Figure BDA00003497991500181
In formula (M3-1)～formula (M3-10), R 1independent be hydrogen or methyl, and r is independently 1～12 integer, when in formula, exist more than 2 r time, any 2 r can be identical also can difference.
Secondly illustrate non-ionic surfactant.
The example of the non-ionic surfactant of silicone-based is not Lip river (Polyflow) ATF-2 of Pohle that the common prosperity society chemistry (thigh) using unmodified silicone or modified silicone as principal constituent is manufactured, Ge Lanuo (Glanol) 100, Ge Lanuo (Glanol) 115, Ge Lanuo (Glanol) 400, Ge Lanuo (Glanol) 410, Ge Lanuo (Glanol) 435, Ge Lanuo (Glanol) 440, Ge Lanuo (Glanol) 450, Ge Lanuo (Glanol) B-1484, Pohle is Lip river (Polyflow) KL-250 not, Pohle is Lip river (Polyflow) KL-260 not, Pohle is Lip river (Polyflow) KL-270 not, Pohle is Lip river (Polyflow) KL-280 not, Bi Ke (BYK)-300, Bi Ke (BYK)-302, Bi Ke (BYK)-306, Bi Ke (BYK)-307, Bi Ke (BYK)-310, Bi Ke (BYK)-315, Bi Ke (BYK)-320, Bi Ke (BYK)-322, Bi Ke (BYK)-323, Bi Ke (BYK)-325, Bi Ke (BYK)-330, Bi Ke (BYK)-331, Bi Ke (BYK)-333, Bi Ke (BYK)-337, Bi Ke (BYK)-341, Bi Ke (BYK)-342, Bi Ke (BYK)-344, Bi Ke (BYK)-345, Bi Ke (BYK)-346, Bi Ke (BYK)-347, Bi Ke (BYK)-348, Bi Ke (BYK)-370, Bi Ke (BYK)-375, Bi Ke (BYK)-377, Bi Ke (BYK)-378, Bi Ke (BYK)-3500, Bi Ke (BYK)-3510 and Bi Ke (BYK)-3570.
Fluorine is that the example of non-ionic surfactant is Bi Ke (BYK)-340, Fu Jite (Ftergent) 251, Fu Jite (Ftergent) 221MH, Fu Jite (Ftergent) 250, FTX-215M, FTX-218M, FTX-233M, FTX-245M, FTX-290M, FTX-209F, FTX-213F, Fu Jite (Ftergent) 222F, FTX-233F, FTX-245F, FTX-208G, FTX-218G, FTX-240G, FTX-206D, Fu Jite (Ftergent) 212D, FTX-218, FTX-220D, FTX-230D, FTX-240D, FTX-720C, FTX-740C, FTX-207S, FTX-211S, FTX-220S, FTX-230S, KB-L82, KB-L85, KB-L97, KB-L109, KB-L110, KB-F2L, KB-F2M, KB-F2S, KB-F3M and KB-FaM.
The example of hydrocarbon system non-ionic surfactant is not Lip river (Polyflow) No.3 of Pohle using acrylic acid polymer as principal constituent, Pohle is Lip river (Polyflow) No.50EHF not, Pohle is Lip river (Polyflow) No.54N not, Pohle is Lip river (Polyflow) No.75 not, Pohle is Lip river (Polyflow) No.77 not, Pohle is Lip river (Polyflow) No.85HF not, Pohle is Lip river (Polyflow) No.90 not, Pohle is Lip river (Polyflow) No.95 not, Pohle is Lip river (Polyflow) No.99C not, Bi Ke (BYK)-350, Bi Ke (BYK)-352, Bi Ke (BYK)-354, Bi Ke (BYK)-355, Bi Ke (BYK)-358N, Bi Ke (BYK)-361N, Bi Ke (BYK)-380N, Bi Ke (BYK)-381, Bi Ke (BYK)-392 and Bi Ke (BYK)-Xi Keli (Silclean) 3700.
In addition, not Lip river (Polyflow's described Pohle) passes that to draw promise (Glanol) be all the title of the commodity sold by common prosperity society chemistry (thigh).The serve as reasons title of the commodity that Japanese Bi Ke chemistry (BYK Chemie Japan) (thigh) sells of Bi Ke (BYK).The title of the commodity that Fu Jite (Ftergent), FTX and KB sell Wei You Ni Aosi (Neos) (thigh).
Described interfacial agent can be used alone, and also can mix use two or more.
Secondly, illustrate other polymerizable compounds, additive, organic solvent.These compounds can be also commercially available product.The example of other polymerizable compounds is the compound with 1 polymerizability base, have the compound of 2 polymerizability bases and have the polyfunctional compound of 3 above polymerizability bases.
The example with the compound of 1 polymerizability base is vinylbenzene, core substituted phenylethylene, vinyl cyanide, vinylchlorid, vinylidene chloride, vinyl pyridine (vinylpyridine), NVP (N-vinylpyrrolidone), vinyl sulfonic acid, vinyl fatty ester (for example vinyl-acetic ester), α, β-ethene unsaturated carboxylic acid (for example vinylformic acid, methacrylic acid, toxilic acid, fumaric acid, methylene-succinic acid etc.), (methyl) acrylic acid alkyl ester (carbon number of alkyl is 1～18), (methyl) acrylic acid hydroxyalkyl acrylate (carbon number of hydroxyalkyl is 1～18), (methyl) acrylic acid aminoalkyl ester (carbon number of aminoalkyl group is 1～18), (carbon number of the alkyl that contains ether oxygen is 3～18 to (methyl) acrylic acid alkyl ester that contains ether oxygen, for example methoxyl group ethyl ester, ethoxy ethyl ester, methoxyl group propyl ester, methyl Sheep's-parsley ester (methyl carvyl ester), ethyl Sheep's-parsley ester and butyl Sheep's-parsley ester), N-vinyl acetamide, p-p t butylbenzoic acid vinyl acetate, N, N-dimethylaminobenzoic acid vinyl acetate, vinyl benzoate, trimethylacetic acid vinyl acetate, 2,2-dimethyl butyrate vinyl acetate, 2,2-dimethyl-penten vinyl acetate, 2-methyl-2-vinyl butyrate, propionate, stearic acid vinyl ester, 2-Ethyl-2-Methyl vinyl butyrate, (methyl) vinylformic acid two cyclopentyloxy ethyl esters, (methyl) vinylformic acid iso-borneol oxygen base ethyl ester, (methyl) isobornyl acrylate, (methyl) vinylformic acid diamantane ester, (methyl) vinylformic acid dimethyladamantane ester, (methyl) vinylformic acid two encircles pentyl ester, (methyl) vinylformic acid two cyclopentenes esters, 2-acryloxy ethyl succsinic acid, 2-acryloxy ethyl hexahydrophthalic acid, 2-acryloxy ethyl phthalic acid, 2-acryloxy ethyl-2-hydroxyethyl phthalic acid, 2-acryloxy ethyl phosphate ester acid (2-acryloyloxyethyl acid phosphate), 2-methacryloxyethyl phosphate ester acid, the polyoxyethylene glycol that the polymerization degree is 1～100, polypropylene glycol, list (methyl) acrylate or two (methyl) acrylate of the polyalkylene glycols such as the multipolymer of oxyethane and propylene oxide, or the end polyoxyethylene glycol that is 1～100 by the polymerization degree of alkyl-blocked (cap) of carbon number 1～6, polypropylene glycol, and list (methyl) acrylate of the polyalkylene glycol such as the multipolymer of oxyethane and propylene oxide.
The example with the compound of 2 polymerizability bases is 1, 4-butylene glycol diacrylate, 1, 6-hexanediyl ester, 1, 9-nonanediol diacrylate, neopentylglycol diacrylate, dihydroxymethyl tristane diacrylate, triethylene glycol diacrylate, propylene glycol diacrylate, tripropylene glycol diacrylate, tetraethylene glycol diacrylate, oxyethane (the Ethylene Oxide of dihydroxyphenyl propane, EO) addition diacrylate, dihydroxyphenyl propane glycidyl diacrylate (Wei Sike (Viscoat) V#700), the methacrylate compound of polyethyleneglycol diacrylate and these compounds.
The example with the compound of 3 above polymerizability bases is: tetramethylolmethane three (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, trishydroxymethyl EO addition three (methyl) acrylate, tricresyl phosphate (methyl) acryloxy ethyl ester, isocyanuric acid three ((methyl) acryloxy ethyl) ester, alkyl-modified Dipentaerythritol three (methyl) acrylate, EO modification trimethylolpropane tris (methyl) acrylate, propylene oxide (Propylene Oxide, PO) modification trimethylolpropane tris (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, alkyl-modified Dipentaerythritol four (methyl) acrylate, two TriMethylolPropane(TMP) four (methyl) acrylate, Dipentaerythritol six (methyl) acrylate, Dipentaerythritol monohydroxy five (methyl) acrylate, alkyl-modified Dipentaerythritol five (methyl) acrylate, Wei Sike (Viscoat) V#802 (sense radix=8), Wei Sike (Viscoat) V#1000 (sense radix=average 14)." Wei Sike (Viscoat) " is the trade(brand)name of Osaka organic chemistry limited-liability company.Functional group for more than 16 compounds be to obtain in the following manner: Bolton (Boltorn) H20 that Bai Situo specialty chemical (Perstorp Specialty Chemicals) is sold (16 officials can), Bolton (Boltorn) H30 (32 officials can), Bolton (Boltorn) H40 (64 officials can), as raw material, carry out acrylated to these raw materials.
In addition, also can contain the polymerizability bisphenol fluorene derivative with phenolphthalein structure.The hardenability that these compounds are suitable for controlling alignment direction or further improve polymkeric substance.The example of the polymerizability bisphenol fluorene derivative with phenolphthalein structure is shown in to formula (α-1)～formula (α-6).
Figure BDA00003497991500221
In order to make the polymerization velocity optimizing of polymerizable liquid crystal compound, also can use well-known optical free radical polymerization initiator.About the preferred addition of optical free radical polymerization initiator, take with respect to (A) composition and (B) the total weight of composition weight ratio and as 0.0001～0.20.The preferred scope of this weight ratio is 0.001～0.15.And then preferred scope is 0.01～0.15.The example of optical free radical polymerization initiator is 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone (Da Luoka (Darocur) 1173), 1-hydroxycyclohexylphenylketone, 2,2-dimethoxy-1,2-diphenylethane-1-ketone (Yi Luka (Irgacure) 651), 1-hydroxyl-cyclohexyl-phenyl-one (Yi Luka (Irgacure) 184), Yi Luka (Irgacure) 127, Yi Luka (Irgacure) 500 (mixture of Yi Luka (Irgacure) 184 and benzophenone), Yi Luka (Irgacure) 2959, Yi Luka (Irgacure) 907, Yi Luka (Irgacure) 369, Yi Luka (Irgacure) 379, Yi Luka (Irgacure) 754, Yi Luka (Irgacure) 1300, Yi Luka (Irgacure) 819, Yi Luka (Irgacure) 1700, Yi Luka (Irgacure) 1800, Yi Luka (Irgacure) 1850, Yi Luka (Irgacure) 1870, Da Luoka (Darocur) 4265, Da Luoka (Darocur) MBF, Da Luoka (Darocur) TPO, Yi Luka (Irgacure) 784, Yi Luka (Irgacure) 754, Yi Luka (Irgacure) OXE01 and Yi Luka (Irgacure) OXE02.All the serve as reasons title of the commodity that Japanese BASF (BASF Japan) (thigh) sells of described Da Luoka (Darocur) and Yi Luka (Irgacure).Also can in these optical free radical polymerization initiators, add well-known sensitizing agent (isopropyl thioxanthone, diethyl thioxanthone, ethyl-4-dimethylaminobenzoic acid ester (Da Luoka (Darocur) EDB), 2-ethylhexyl-4-dimethylaminobenzoic acid ester (Da Luoka (Darocur) EHA) etc.).
Also can use following optical free radical polymerization initiator as optical free radical polymerization initiator.
P-methoxyphenyl-2, two (trichloromethyl) triazine (p-methoxyphenyl-2 of 4-, 4-bis (trichloromethyl) triazine), 2-(to butyl phenyl ether vinyl)-5-trichloromethyl-1, 3, 4-oxadiazoles, 9-phenylacridine, 9, 10-benzo coffee piperazine (9, 10-benzphenazine), benzophenone/ meter Qi Le alcohol/ketone mixtures, six aryl bisglyoxaline/mercaptobenzimidazole mixtures, 1-(4-isopropyl phenyl)-2-hydroxy-2-methyl propane-1-ketone, benzil dimethyl ketal, 2-methyl isophthalic acid-[4-(methylthio group) phenyl]-2-morpholinyl propane-1-ketone, 2, 4-diethyl xanthone (2, 4-diethyl xanthone)/ESCAROL 507 methyl mixture, benzophenone/methyl trolamine mixture.
One or more chain-transfer agent can be added in polymerizable liquid crystal compound, control the mechanical characteristics of polymkeric substance.By using chain-transfer agent, can control the length of 2 cross-linked polymer chains in length or the polymeric film of polymer chain.Also can control these length simultaneously.If increase the amount of chain-transfer agent, the length of polymer chain reduces.Preferred chain-transfer agent is mercaptan compound.The example of simple function mercaptan is dodecyl mercaptans, 2-ethylhexyl-(3-mercaptopropionic acid ester).The example of multi-functional mercaptan is trimethylolpropane tris (3-mercaptopropionic acid ester), tetramethylolmethane four (3-mercaptopropionic acid ester), 1, two (the 3-sulfydryl butyryl acyloxy) butane (Ka Lanci (Karenz) MT BD1) of 4-, tetramethylolmethane four (3-sulfydryl butyric ester) (Ka Lanci (Karenz) MT PE1) and 1,3,5-tri-(3-sulfydryl butoxyethyl group)-1,3,5-triazine-2,4,6 (1H, 3H, 5H)-triketone (Ka Lanci (Karenz) MT NR1)." Ka Lanci (Karenz) " is clear and trade(brand)name electrician limited-liability company.
In polymerizable liquid crystal compound, in order to prevent starting polymerization when preserving, can add anti-polymerizing agent.Can use well-known anti-polymerizing agent, its preference is 2,5-bis-(tertiary butyl) hydroxytoluene (2,5-di (t-butyl) hydroxy toluene, BHT), Resorcinol (hydroquinone), Methylene blue, phenylbenzene picric acid hydrazides (diphenyl picric acid hydrazide, DPPH), benzothiazine (benzothiazine), 4-nitrosodimethylaniline (4-nitroso dimethyl aniline, NIDI), O-hydroxyl-diphenyl ketone.
In order to improve the keeping quality of polymerizable liquid crystal compound, also can add polymerization retarder.The in the situation that of having produced free radical in composition or composition solution, the polyreaction of polymerizable compound is promoted.In order to prevent this situation, preferably add polymerization retarder.It is that antioxidant, sulphur are that antioxidant, phosphoric acid are antioxidant that polymerization retarder can utilize phenol.
In order further to improve the weathering resistance of polymerizable liquid crystal compound, also can add UV light absorber, photostabilizer (free radical scavenger) and antioxidant etc.The example of UV light absorber is ground slave refined (Tinuvin) PS, ground slave refined (Tinuvin) P, ground slave refined (Tinuvin) 99-2, refined (Tinuvin) 109 of ground slave, refined (Tinuvin) 213 of ground slave, refined (Tinuvin) 234 of ground slave, refined (Tinuvin) 326 of ground slave, refined (Tinuvin) 328 of ground slave, refined (Tinuvin) 329 of ground slave, ground slave refined (Tinuvin) 384-2, refined (Tinuvin) 571 of ground slave, refined (Tinuvin) 900 of ground slave, refined (Tinuvin) 928 of ground slave, refined (Tinuvin) 1130 of ground slave, refined (Tinuvin) 400 of ground slave, refined (Tinuvin) 405 of ground slave, refined (Tinuvin) 460 of ground slave, refined (Tinuvin) 479 of ground slave, refined (Tinuvin) 5236 of ground slave, Ai Di Coase tower ripple (Adeka Stab) LA-32, Ai Di Coase tower ripple (Adeka Stab) LA-34, Ai Di Coase tower ripple (Adeka Stab) LA-36, Ai Di Coase tower ripple (Adeka Stab) LA-31, Ai Di Coase tower ripple (Adeka Stab) 1413 and Ai Di Coase tower ripple (Adeka Stab) LA-51." slave refined (Tinuvin) " is the trade(brand)name of Japanese BASF (BASF Japan) (thigh), and " Ai Di Coase tower ripple (Adeka Stab) " is the trade(brand)name of Ai Dike (ADEKA).
The example of photostabilizer is ground slave refined (Tinuvin) 111FDL, refined (Tinuvin) 123 of ground slave, refined (Tinuvin) 144 of ground slave, refined (Tinuvin) 152 of ground slave, refined (Tinuvin) 292 of ground slave, refined (Tinuvin) 622 of ground slave, refined (Tinuvin) 770 of ground slave, refined (Tinuvin) 765 of ground slave, refined (Tinuvin) 780 of ground slave, refined (Tinuvin) 905 of ground slave, refined (Tinuvin) 5100 of ground slave, refined (Tinuvin) 5050 of ground slave, 5060, refined (Tinuvin) 5151 of ground slave, intelligence agate rope (Chimassorb) 119FL, intelligence agate rope (Chimassorb) 944FL, intelligence agate rope (Chimassorb) 944LD, Ai Di Coase tower ripple (Adeka Stab) LA-52, Ai Di Coase tower ripple (Adeka Stab) LA-57, Ai Di Coase tower ripple (Adeka Stab) LA-62, Ai Di Coase tower ripple (Adeka Stab) LA-67, Ai Di Coase tower ripple (Adeka Stab) LA-63P, Ai Di Coase tower ripple (Adeka Stab) LA-68LD, Ai Di Coase tower ripple (Adeka Stab) LA-77, Ai Di Coase tower ripple (Adeka Stab) LA-82, Ai Di Coase tower ripple (Adeka Stab) LA-87, (Cyasorb) UV-3346 of Sai Yasuo portion that Cytec (cyanogen spy) company manufactures and Gourde(G) Lai Te (Goodrite) UV-3034 of Goodrich (Goodrich) company." intelligence agate rope (Chimassorb) " is the trade(brand)name of Japanese BASF (BASF Japan) (thigh).
The example of antioxidant is Ai Di Coase tower ripple (Adeka Stab) AO-20 of Ai Dike (ADEKA), Ai Di Coase tower ripple (Adeka Stab) AO-30, Ai Di Coase tower ripple (Adeka Stab) AO-40, Ai Di Coase tower ripple (Adeka Stab) AO-50, Ai Di Coase tower ripple (Adeka Stab) AO-60, Ai Di Coase tower ripple (Adeka Stab) AO-80, Si Milaize (Sumilizer) BHT being sold by Sumitomo Chemical (thigh), Si Milaize (Sumilizer) BBM-S and Si Milaize (Sumilizer) GA-80, and the Yi Lunuosi (Irganox) 1076 being sold by Japanese BASF (BASF Japan) (thigh), Yi Lunuosi (Irganox) 1010, Yi Lunuosi (Irganox) 3114 and Yi Lunuosi (Irganox) 245.Also can use these commercially available products.
In polymerizable liquid crystal compound, in order to control and the adhesion of substrate, also can further add silane coupling agent.Be specially vinyl trialkyl oxysilane, 3-isocyanic ester propyl-triethoxysilicane (3-isocyanatopropyl triethoxy silane), N-(2-amino-ethyl) 3-aminopropyl trialkoxy silane, N-(1,3-dimethyl butylidene)-3-(trialkoxy silane base)-1-propane amine, 3-glycidoxypropyl trialkoxy silane, 3-chlorine trialkoxy silane, 3-acryl propyl trimethoxy silicane, 3-methacryloyl propyl trialkoxy silane etc.Other examples for to be substituted by by one in alkoxyl group (3) the dialkoxy methyl-monosilane that methyl forms in these compounds.
Polymerizable liquid crystal compound of the present invention, because liquid crystal lower limit temperature is low, therefore can be coated directly onto on real estate.But, in order to make coating easily, also can dilute polymerizable liquid crystal compound with solvent, or each composition of polymerizable liquid crystal compound is dissolved in solvent, the solution of the polymerizable liquid crystal compound that preparation comprises polymerizable liquid crystal compound and solvent, and be coated with this solution.This solvent can be used separately, also can mix in addition use two or more.The example of solvent is ester series solvent, acid amides series solvent, alcohol series solvent, ether series solvent, glycol monoalkyl ether series solvent, aromatic hydrocarbons series solvent, halogenated aromatic hydrocarbon system solvent, aliphatic hydrocarbon series solvent, halogenation aliphatic hydrocarbon series solvent, ester ring type hydrocarbon system solvent, ketone series solvent and acetic ester series solvent.
The preference of ester series solvent is alkyl acetate (for example methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butylacetate, acetic acid-3-methoxyl group butyl ester, isobutyl acetate, pentyl acetate and Isoamyl Acetate FCC), Trifluoroacetic Acid Ethyl Ester, alkyl propionates (for example methyl propionate, 3-methoxy methyl propionate, ethyl propionate, propyl propionate and butyl propionate), butyric acid alkyl ester (for example methyl-butyrate, ethyl butyrate, butyl butyrate, isobutyl butyrate and propyl butyrate), dialkyl malonate (for example diethyl malonate), glycolic acid alkyl ester (for example glycolic acid methyl esters and glycolic acid ethyl ester), lactic acid alkyl ester (for example methyl lactate, ethyl lactate, isopropyl lactate, lactic acid n-propyl ester, n-Butyl lactate and lactic acid ethylhexyl), glyceryl monoacetate (monoacetin), gamma-butyrolactone and γ-valerolactone.
The preference of acid amides series solvent is METHYLPYRROLIDONE, N, N-N,N-DIMETHYLACETAMIDE, N-methyl propanamide, N, dinethylformamide, N, N-diethylformamide, N, N-diethyl acetamide, N,N-dimethylacetamide dimethyl-acetal, N-methyl caprolactam and methylimidazole pyridine ketone (dimethyl imidazolidinone).
The preference of alcohol series solvent is methyl alcohol, ethanol, 1-propyl alcohol, 2-propyl alcohol, 1-methoxy-2-propanol, the trimethyl carbinol, sec-butyl alcohol, butanols, 2-ethyl butanol, n-hexyl alcohol, n-Heptyl alcohol, n-Octanol, 1-lauryl alcohol, ethylhexanol, 3, 5, 5-trimethyl hexanol, Pentyl alcohol (n-amyl alcohol), hexafluoro-2-propyl alcohol, glycerine, ethylene glycol, Diethylene Glycol, triethylene glycol, TEG, propylene glycol, dipropylene glycol, tripropylene glycol, hexylene glycol, 1, 3-butyleneglycol, 1, 4-butyleneglycol, 2, 3-butyleneglycol, 1, 5-pentanediol, 2, 4-pentanediol, 2, 5-hexylene glycol, 3-methyl-3-methoxybutanol, hexalin and methyl-cyclohexanol.
The preference of ether series solvent is glycol dimethyl ether, diethylene glycol dimethyl ether, two (2-propyl group) ether, Isosorbide-5-Nitrae-dioxan and tetrahydrofuran (THF) (Tetrahydrofuran, THF).
The preference of glycol monoalkyl ether series solvent is ethylene glycol monoalkyl ether (for example ethylene glycol monomethyl ether and ethylene glycol monobutyl ether), Diethylene Glycol monoalky lether (for example diethylene glycol monoethyl ether), triethylene glycol monoalky lether, propylene-glycol monoalky lether (for example propylene glycol monobutyl ether), dipropylene glycol monoalky lether (for example dipropylene glycol monomethyl ether), ethylene glycol monoalkyl ether acetate (for example ethylene glycol monobutyl ether acetic ester), Diethylene Glycol monoalky lether acetic ester (for example diethylene glycol monoethyl ether acetic ester), triethylene glycol monoalky lether acetic ester, propylene-glycol monoalky lether acetic ester (for example propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate and propylene glycol monobutyl ether acetic ester), dipropylene glycol monoalky lether acetic ester (for example dipropylene glycol monomethyl ether acetic ester) and diethylene glycol methyl ethyl ether.
The preference of aromatic hydrocarbons series solvent is benzene,toluene,xylene, sym-trimethylbenzene (mesitylene), ethylbenzene, diethylbenzene, isopropyl benzene, n-propylbenzene, tert.-butylbenzene, sec-butylbenzene, n-butylbenzene and naphthane (tetralin).The preference of halogenated aromatic hydrocarbon system solvent is chlorobenzene.The preference of aliphatic hydrocarbon series solvent is hexane and heptane.The preference of halogenation aliphatic hydrocarbon series solvent is chloroform, methylene dichloride, tetracol phenixin, ethylene dichloride, trieline and zellon.The preference of ester ring type hydrocarbon system solvent is hexanaphthene and perhydronaphthalene (dacalin).
The preference of ketone series solvent is acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), pimelinketone, cyclopentanone and methyl propyl ketone.
The preference of acetic ester series solvent is ethylene glycol monomethyl ether acetate, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, methyl acetoacetate and 1-methoxyl group-2-propyl-acetic acid ester.
From the deliquescent viewpoint of polymerizable liquid crystal compound, preferably use acid amides series solvent, aromatic series hydrocarbon system, ketone series solvent, if consider the boiling point of solvent, also preferably also with ester series solvent, alcohol series solvent, ether series solvent, glycol monoalkyl ether series solvent.About the selection of solvent, there is no particular restriction, in the situation that using plastic base as support base material, in order to prevent the distortion of substrate, must reduce drying temperature, and make solvent not corrode substrate.The solvent that can preferably use is in this case aromatic hydrocarbons series solvent, ketone series solvent, ester series solvent, ether series solvent, alcohol series solvent, acetic ester series solvent, glycol monoalkyl ether series solvent.
About the ratio of the solvent in the solution of polymerizable liquid crystal compound, take the gross weight of this solution as benchmark is as 10%～95%.The preferable range of this ratio is 10%～70%, and preferred scope is 10%～50%.
In the following description, sometimes the polymkeric substance (optical anisotropic film) that makes polymerizable liquid crystal compound polymerization gained is called to liquid crystal film.Liquid crystal film can obtain as below.First, polymerizable liquid crystal compound is applied on supporting substrate under the state with mobility, forms film.In the case of having prepared the solution of polymerizable liquid crystal compound, to supporting substrate, and make it dry and form film this solution coat.This film is carried out rayed and makes polymerizable liquid crystal compound polymerization, and what the composition in film was formed under mesomorphic state fixes to row orientation.Operable supporting substrate is glass and plastic film.The example of plastic film is polyimide, polyamidoimide, polymeric amide, polyetherimide, polyether-ether-ketone, polyetherketone, polyketone thioether, polyethersulfone, polysulfones, polyphenylene sulfide, polyphenylene oxide (polyphenylene oxide), polyethylene terephthalate, polybutylene terephthalate, Polyethylene Naphthalate, poly-acetal, polycarbonate, polyarylester, acrylic resin, polyvinyl alcohol, polypropylene, Mierocrystalline cellulose, triacetyl cellulose and partly-hydrolysed thing thereof, epoxy resin, the film of phenol resins and cyclic olefine resin etc.
Cyclic olefine resin can be enumerated norbornene resin, Dicyclopentadiene (DCPD) is resin etc., but is not limited to these resins.In these resins, can preferably use and not there is the resin that unsaturated link(age) or unsaturated link(age) are hydrogenated.For example can enumerate: the hydrogenated products of open loop (being total to) polymkeric substance of one or more norborneol alkene monomer, addition (being total to) polymkeric substance of one or more norborneol alkene monomer, norborneol alkene monomer and ethylene series monomer (ethene, alpha-olefin etc.) addition copolymer, norborneol alkene monomer and cyclic olefine monomer (cyclopentenes, cyclooctene, 5, 6-dihydro Dicyclopentadiene (DCPD) etc.) addition copolymer and the modifier of these polymkeric substance etc., specifically can enumerate: auspicious naphthalene gram this (ZEONEX), Rui Nuo (ZEONOR) (manufacture of Japanese auspicious father-in-law (Zeon) company), Ya Dun (ARTON) (manufacture of JSR company), holder Paasche (TOPAS) (manufacture of Ticona (Ticona) company), A Peier (APEL) (Mitsui Chemicals, Inc.'s manufacture), Ai Si happiness Na (Escena) (manufacture of ponding chemical industrial company), Ao Putuolaici (OPTOREZ) (Hitachi changes into company and manufactures).
These plastic films can be uniaxial extension film, also can be biaxial stretchable film.These plastic films for example also can be for having implemented the surface-treated films such as the hydrophilicity-imparting treatment such as corona treatment or plasma body (plasma) processing or hydrophobization processing.There is no particular restriction for the method for hydrophilicity-imparting treatment, preferably corona treatment or Cement Composite Treated by Plasma, and particularly preferred method is Cement Composite Treated by Plasma.Cement Composite Treated by Plasma also can be used the method for recording in Japanese Patent Laid-Open 2002-226616 communique, Japanese Patent Laid-Open 2002-121648 communique etc.In addition, in order to improve the adhesion of liquid crystal film and plastic film, also can form tackifier coating (anchor coat layer).This tackifier coating, as long as improve the adhesion of liquid crystal film and plastic film, is the equal no problem of any material of inorganic system, organic system.In addition, plastic film also can be laminated film.Also can replace plastic film with following article: formed from the teeth outwards the metal substrate of aluminium, iron, copper of the groove of slit-shaped etc., or effects on surface has carried out glass substrates such as the alkali glass, pyrex, flint glass (fliht glass) of etching and processing etc. with slit-shaped.
On the supporting substrates such as these glass, plastic film, before forming the film of polymerizable liquid crystal compound, form the liquid crystal film of horizontal direction matching and mixed orientation, by friction etc., carry out the mechanical surface treatment of physics mode.In the case of forming the liquid crystal film of vertical orientation, the surface treatment such as scarcely rub, but in order to prevent orientation defect etc., also can carry out friction treatment.In friction treatment, can adopt method arbitrarily, conventionally adopt following methods: comprising the raw-material friction cloth such as artificial silk (rayon), cotton, polymeric amide, to be wound up into metallic roll etc. upper, the method that makes the rotation of roller one side simultaneously move under state contact with supporting substrate or polymkeric substance tunicle; The method etc. that keeps having fixed the state of roller and make supporting substrate side shifting.Friction treatment can be directly implemented supporting substrate, or also can on supporting substrate, set in advance the polymkeric substance tunicle of the polyimide etc. that is commonly called alignment film, and this polymkeric substance tunicle is implemented to friction treatment.The method of friction treatment as described above.Depending on the kind difference of supporting substrate, also can tilt in its surface evaporation silicon oxide and give orientation ability.
In addition, in the case of forming the liquid crystal film of horizontal direction matching and mixed orientation, except being undertaken the mechanical surface treatment of physics mode by friction etc., also can on supporting substrate, set in advance the polymkeric substance tunicle that is commonly called the polyimide of light alignment film or polyacrylic ester etc., and this polymkeric substance tunicle is implemented to polarisation ultraviolet ray (Ultraviolet, UV) and process.
When coating polymerizable liquid crystal compound or its solution, the example of the coating process that is used for obtaining homogeneous film thickness is method of spin coating (spin coat method), nick version coating method (microgravure coat method), intaglio plate coating method (gravure coat method), line rod coating method (wire bar coat method), dip coated method (dip coat method), spraying coating method (spray coat method), meniscus coating method (meniscus coat method) and die coating method (die coat method).Especially can be by the line rod coating method etc. that in when coating, liquid-crystal composition is applied shear-stress for following situation: in the surface-treated situation of not carrying out substrate by friction etc., control the orientation of liquid-crystal composition.
While being coated with the solution of polymerizable liquid crystal compound of the present invention, for after coating, on supporting substrate, form the polymerizable liquid crystal layer of uniform film thickness, polymerizable liquid crystal compound layer, also can heat-treat.Thermal treatment can utilize blowing of hot plate (hot plate) or drying oven, warm air or hot blast attached etc.
Light wavelength used, the light quantity of irradiating from light source etc. when temperature and time when film is heat-treated, rayed, depending on the kind of compound used in polymerizable liquid crystal compound and ratio of components, photopolymerization initiator be added with without or the difference of its addition etc., preferable range difference.Therefore,, the condition of light wavelength used and the light quantity of irradiating from light source only represents scope roughly during by the heat treated temperature and time about film, the rayed of explanation.
The thermal treatment of film is preferably carried out under the condition of even regiospecific that can obtain polymerizable liquid crystal.Also can more than the liquid crystal phase transition point of polymerizable liquid crystal compound, carry out.One example of heat treating method is for following methods: till film is warmed to the temperature that described polymerizable liquid crystal compound demonstrates nematic liquid crystal phase, the polymerizable liquid crystal compound in film is formed to row orientation.The temperature variation that also can make film in polymerizable liquid crystal compound demonstrates the temperature range of nematic liquid crystal phase, forms thus to row orientation.The method is following methods: till film being warmed to the high temperature range of described temperature range, make thus roughly to complete to row orientation in film, then reduce temperature, form thus more orderly orientation.In the situation that adopting described arbitrary heat treating method, thermal treatment temp is room temperature～120 ℃.The preferable range of this temperature is room temperature～80 ℃, and preferred scope is room temperature～60 ℃.Heat treatment time is 5 seconds～2 hours.The preferable range of this time is 10 seconds～40 minutes, and preferred scope is 20 seconds～20 minutes.For make to comprise polymerizable liquid crystal compound layer temperature rise till both fixed temperatures preferably heat treatment time is set as more than 5 seconds.In order not make productivity reduce, preferably heat treatment time was set as in 2 hours.Obtain like this polymerizable liquid crystal layer of the present invention.
The polymerizable liquid crystal compound forming in polymerizable liquid crystal layer to row orientation state, be to fix in the following manner: by rayed, make polymerizable liquid crystal compound carry out polymerization.Light wavelength used during rayed is not particularly limited.Can utilize electron beam, ultraviolet ray, visible rays, infrared rays (hot line) etc.Conventionally as long as use ultraviolet ray or visible rays.The scope of wavelength is 150nm～500nm.Preferable range is 250nm～450nm, and preferred scope is 300nm～400nm.The example of light source is Cooper-Hewitt lamp (sterilizing lamp, fluorescence chemical lamp, black lamp), high-pressure discharge lamp (high pressure mercury vapour lamp, metal halide lamp), short arc discharge lamp (extra-high-pressure mercury vapour lamp, xenon lamp, mercury xenon lamp).The preference of light source is metal halide lamp or xenon lamp, extra-high-pressure mercury vapour lamp and high pressure mercury vapour lamp.Wave filter etc. also can be set between light source and polymerizable liquid crystal layer and only make specific wavelength region pass through, carrying out whereby the wavelength region of Selective irradiation light source.The light quantity of irradiating from light source is 2mJ/cm when arriving coated surface 2～5000mJ/cm 2.The preferable range of light quantity is 10mJ/cm 2～3000mJ/cm 2, preferred scope is 100mJ/cm 2～2000mJ/cm 2.Temperature condition during rayed is preferably similarly set with described thermal treatment temp.In addition, the atmosphere surrounding of polymerization environment can be any of nitrogen environment, inert gas environment, air ambient, from improving indurative viewpoint, preferred nitrogen environment or inert gas environment.
In the case of by polymerizable liquid crystal layer of the present invention and make its by liquid crystal films of being polymerized such as light or heat for various optical elements, or in the situation of application as optical compensatory element used in liquid crystal indicator, it is very important that the control of the distribution at the pitch angle on thickness direction becomes.
The method of the kind that one of the method at control pitch angle is liquid crystalline cpd used in adjustment polymerizable liquid crystal compound or ratio of components etc.Also can, by add other compositions in this polymerizable liquid crystal compound, control pitch angle.The pitch angle of liquid crystal film also can be controlled by the kind of the kind of the solvent in polymerizable liquid crystal compound or solute concentration, the interfacial agent that adds as one of other compositions or addition etc.Also can control by the drying conditions of the film of the kind of supporting substrate or polymkeric substance tunicle or friction condition, polymerizable liquid crystal compound or heat-treat condition etc. the pitch angle of liquid crystal film.And then the temperature when irradiation environment in the photopolymerization step after orientation or irradiation etc. also impacts the pitch angle of liquid crystal film.That is, can think that in the manufacture processing procedure of liquid crystal film, nearly all condition more or less all impacts pitch angle.Therefore, by the optimized while at polymerizable liquid crystal compound, suitably select each condition of the manufacture processing procedure of liquid crystal film, can be set as pitch angle arbitrarily.
During horizontal direction matching (homogeneous alignment), pitch angle as one man distributes to approach 0 degree, particularly 0 degree～5 degree to free interface from substrate interface.This orientation state is to obtain in the following manner: polymerizable liquid crystal compound of the present invention is applied on surface-treated supporting substrate surfaces such as having carried out friction, forms film.
In composition of the present invention, also can contain the liquid crystal compounds without polymerizability base.The example of the liquid crystal compounds of this non-polymerization is the < < liquid crystal > > (LiqCryst that is recorded in the database (data base) as liquid crystal compounds, the GmbH of LCI press (Publisher), hamburger (Hamburg), Germany (Germany)) etc. in.The concrete example without the liquid crystal compounds of polymerizability base be recorded in Japanese Patent Laid-Open 2011-148762 communique p.66～p.69 in.Polymerizable liquid crystal compound of the present invention has the good intermiscibility with other liquid crystal compounds.This polymerizable liquid crystal compound also can further contain the additives such as dichroism pigment or fluorochrome.By making this polymerizable liquid crystal compound polymerization, can obtain and the matrix material (composite materials) of liquid crystal compounds without polymerizability base.
In composition of the present invention, also can add optically active compound.The preference of optically active compound is the represented compound of formula (Op-1)～formula (Op-25).In these formulas, Ak represents the alkyl of carbon number 1～15 or the alkoxyl group of carbon number 1～15, and Me, Et and Ph represent respectively methyl, ethyl and phenyl.P 2for the group of polymerizability, preferably contain the group of (methyl) acryloxy, vinyloxy group, oxa-cyclopropyl or oxa-cyclobutyl.Composition of the present invention is following by the raw material of the polymkeric substance of explanation except being used as, and also can be used as liquid crystal, the integrant that this liquid crystal is liquid crystal display device.
Figure BDA00003497991500321
Concrete example has the compound of recording in the paragraph 0170 of the paragraph p.70 0159 of Japanese Patent Laid-Open 2011-148762 communique～p.81.
By the polymerizable liquid crystal compound with optically active compound that contains appropriate amount or the polymerizable liquid crystal compound with optically active polymerizable compound that contains appropriate amount are applied on the substrate of orientation processing and carry out polymerization, can obtain the phase retardation film that demonstrates spirane structure (torsion structure).By the polymerization of polymerizable liquid crystal compound, this spirane structure is fixed.The characteristic of the liquid crystal film of gained exists with ... the helix pitch of the spirane structure of gained.This helix pitch length can be adjusted by the kind of optically active compound and addition.The optically active compound adding can be one, but in order to offset the temperature dependency of helix pitch, also can use multiple optically active compound.In addition,, in polymerizable liquid crystal compound, except optically active compound, also can contain other polymerizable compounds.
Selection reflection as the visible ray of the characteristic of liquid crystal film is as described above that spirane structure acts on incident light, makes rotatory polarization or elliptical polarized light reflection.Selecting reflection characteristic is that (λ is the centre wavelength of selecting reflection by λ=nPitch, n is mean refractive index, Pitch is helix pitch) represented, can suitably adjust centre wavelength (λ) and wavelength width (Δ λ) by changing n or Pitch.In order to improve purity of color (color purity), as long as reduce wavelength width (Δ λ), or as long as increase wavelength width (Δ λ) at the reflex time that needs wide band.And then this selection reflection is also subject to the considerable influence of the thickness of polymkeric substance.In order to keep purity of color, must not become too small mode with thickness and set.In order to keep uniform regiospecific, must set in the constant mode too much of thickness.Therefore, must be adjusted into suitable thickness, preferably 0.5 μ m～25 μ m, more preferably 1 μ m～10 μ m.
By helix pitch is set shortlyer than visible ray, can prepare the middle minus C plate (Negative C plate) of recording of physical properties (Physical Properties of Liquid Crystalline Materials) > > (Gordon and Bu Ritchie press (Gordon and Breach), New York (NewYork) (1980)) of the < < liquid crystal material of W.H.de Jeu work.In order to shorten helix pitch, can reach by using the optically active compound that twisting resistance (screw twisted power (Helical Twisting Power, HTP)) is large and further increasing its addition.Specifically, by λ is set as below 350nm, preferably, below 200nm, can prepare minus C plate.This minus C plate becomes the vertical orientation being suitable in liquid crystal display device to row (Vertical Aligned Nematic, VAN) type, vertical orientation cholesterol (Vertical Aligned Cholesteric, VAC) optical compensation films of the display element of type, optical compensation birefringence (Optically Compensated Birefringence, OCB) type etc.
Liquid crystal film, can be for the reflectance coating that reflected wavelength range is set as near infrared range (wavelength is 800nm～2500nm) as recording in Japanese Patent Laid-Open 2004-333671 communique by helix pitch is set longlyer than visible ray.In order to make helix pitch elongated, can be by reaching with the addition of the little optically active compound of twisting resistance or minimizing optically active compound.
As long as described optically active compound brings out spirane structure and can suitably mix with the polymerizable liquid crystal compound that becomes matrix (base), can use any optically active compound.In addition, any of polymerizable compound, non-polymerization compound all can, can add best compound according to object.In the situation that considering thermotolerance and solvent resistance, preferred polymeric compound.
And then in described optically active compound, the compound that twisting resistance (screw twisted power (HTP)) is large is preferred aspect shortening helix pitch.The typical example of the compound that twisting resistance is large is open in GB2298202 communique, DE10221751 communique.
About the thickness (thickness) of liquid crystal film, depending on different, the suitable thickness difference of degree of birefringence (optically anisotropic value) of the delay corresponding from object component (retardation) or liquid crystal film.Therefore, the scope of thickness is looked each object and difference, and its standard is 0.05 μ m～100 μ m.Preferred scope is 0.1 μ m～50 μ m, and then preferred scope is 0.5 μ m～20 μ m.The preferred mist value of liquid crystal film is below 1.5%, and preferred transmission rate is more than 80%.Preferred mist value is below 1.0%, and preferred transmissivity is more than 95%.About transmissivity, preferably in visible-range, meet these conditions.
The degree of birefringence (optically anisotropic value) of liquid crystal film is higher, more can make thickness attenuation.There are the optical characteristics such as thickness thinner mist value or transmissivity more to become good tendency.(Δ is n) preferably more than 0.15, more preferably more than 0.2 for the degree of birefringence of liquid crystal film of the present invention.
Liquid crystal film as the optical compensatory element of application in liquid crystal display device (the particularly liquid crystal display device of active matrix (active matrix) type and passive matrix (passive matrix) type) and effectively.Being suitable for using this liquid crystal film is coplanar switch type (In-Plain Switching as the example of the liquid crystal display device type of optical compensation films, IPS), optical compensation birefringence type (Optically Compensated Birefringence, OCB), stable twisted nematic (Twisted Nematic, TN), STN Super TN type (Super Twisted Nematic, STN), electrically controlled birefringence mode (Electrically Controlled Birefringence, ECB), phase distortion type arranged vertically (deformation of vertical aligned phases, DAP), colored super vertical-type (color super homeostropic, CSH), vertical orientation is to row/vertical orientation cholesterol type (Vertical Aligned Nematic/Vertical Aligned Cholesteric, VAN/VAC), optical mode interfere type (Optical Mode Interference, OMI), super birefringence effect type (the Supertwisted Birefringent Effect that reverses, SBE) etc.And then, the phase delay device (phase retarder) that also can use this liquid crystal film to use as the display element of guest-master (guest-host) type, ferroelectric sexual type, antiferroelectric sexual type etc.In addition, the isoparametric optimum value of the distribution of the thickness direction at the required pitch angle of liquid crystal film or thickness exists with ... kind and the optical parametric thereof of liquid crystal display device that needs compensation consumingly, therefore looks the kind of element and difference.
Liquid crystal film also can be used as and the integrated optical elements that form such as Polarizer, in this situation, is configured in the outside of liquid crystal cells.On the other hand, as the liquid crystal film of optical compensatory element, due to few to the stripping of the liquid crystal of filling in unit pure stripping or impurity, therefore also can be configured in the inside of liquid crystal cells.If for example disclosed method in application Japanese Patent Laid-Open 2008-01943 communique can form polymerizable liquid crystal layer of the present invention on colored filter, further improve thus the function of colored filter.The liquid crystal film of the horizontal direction matching being composited with dichroism pigment also can be used as absorption-type Polarizer.The liquid crystal film of the horizontal direction matching being composited with fluorochrome in addition, also can be used as polarisation light emitting-type film.
[embodiment]
Below, by embodiment, the present invention is described in detail, but the present invention is not limited to these embodiment.Evaluation assessment in embodiment is below shown.
< polymerizing condition >
Under nitrogen environment, at room temperature using the extra-high-pressure mercury vapour lamp (oxtail (Ushio) motor company manufactures, many light (Multilight)-250) of 250W is 30mW/cm by intensity 2(365nm) 30 seconds of rayed.
The evaluation > of < orientation
(1) with the making of the glass substrate of the alignment film through friction treatment
On the glass substrate that is 1.1mm at thickness, for the low tilt angle of rotary coating (horizontal direction matching pattern), polyamic acid (is made every effort to overcome loose alignment machine (Lixon Aligner): PIA-5370, JNC (thigh) manufactures), on the hot plate of 80 ℃ by after solvent seasoning, at 230 ℃, in baking oven, calcine 30 minutes, to gained article, utilize artificial silk cloth to carry out friction treatment.
(2) observational technique of range estimation
Between 2 Polarizers that are configured to cross-polarized light (crossed Nicol), clamping has formed the substrate of phase retardation film and has observed, and substrate is rotated in horizontal plane, confirms the state of light and shade.The substrate that has formed phase retardation film is carried out to polarized light microscope observing, confirm to have or not orientation defect.
(3) utilize the mensuration of polarisation analytical equipment
Ao Pudipuluo (OPTIPRO) the polarisation analytical equipment that uses prosperous Deco (Shintec) (thigh) to manufacture, to having formed the light that the substrate illumination wavelength of phase retardation film is 550nm.The incident angle that one side makes this light reduces since 90 ° with respect to face, and one side is measured and postponed.Postpone (retardation; Also referred to as phase delay, postpone (retardation)) be represented by Δ n × d.Mark Δ n is optical anisotropy value, the thickness that mark d is polymeric film.
< determining film thickness >
The layer of the liquid crystal film of the glass substrate with liquid crystal film is cut out, use fine shape determinator (KLA-Tencor (KLA TENCOR) (thigh) is manufactured, α rank (α-Step) IQ) to measure its jump.
< optical anisotropy (Δ evaluation > n)
According to the delay that the liquid crystal film with horizontal direction matching is obtained and film thickness value, (Δ n) with the form of postpone/thickness, to calculate optical anisotropy.
The compound using in embodiment and comparative example is below shown.
[synthesis example 1]
Compound (1-1-a-1) is to utilize following methods to synthesize.
Figure BDA00003497991500381
(first stage)
Fluoro-2-4-HBA 100g and pyridine 55.8g are added in tetrahydrofuran (THF) (THF) 400mL, under nitrogen environment, at 10 ℃, stir below.Drip wherein diacetyl oxide 78.5g.After dropping, at room temperature stir 4 hours.Adding ethyl acetate and water extracts.Utilize saturated aqueous common salt to clean organic layer, utilize anhydrous magnesium sulfate to be dried.Under reduced pressure, solvent distillation is removed, utilize ethyl acetate to carry out recrystallize to the residue of gained, obtain thus compound (ex-1) 94.0g.
(subordinate phase)
Compound (ex-1) 30g and pyridine 0.1g are added in toluene 150mL, under nitrogen environment, at 60 ℃, stir.Drip wherein thionyl chloride 19.9g.After dropping, at 60 ℃, stir 4 hours, under reduced pressure, solvent distillation is removed.In the residue of gained, add toluene 300mL, under nitrogen environment, at 10 ℃, stir below.The toluene solution 50mL that drips wherein 4-amyl phenol 25g, then drips triethylamine 23.1g.After dropping, at room temperature stir 4 hours.Add water and extract, utilize 1N aqueous sodium hydroxide solution and water to clean organic layer.Utilize anhydrous magnesium sulfate to be dried, under reduced pressure, solvent distillation is removed.In the residue of gained, add THF100mL and methyl alcohol 50mL, under nitrogen environment, at 10 ℃, stir below.Drip wherein 28% ammonia soln 18mL, at room temperature stir 8 hours.Add ethyl acetate and water and extract, utilize saturated aqueous common salt to clean organic layer, utilize anhydrous magnesium sulfate to be dried.Under reduced pressure, solvent distillation is removed, utilize toluene to carry out recrystallize to the residue of gained, obtain thus compound (ex-2) 39.2g.
(phase III)
Compound (ex-2) 39.2g and triethylamine 19.7g are added in methylene dichloride 400mL, under nitrogen environment, at 10 ℃, stir below.Drip wherein acrylate chloride 12.9g, at room temperature stir 8 hours.Add water and extract, utilize 1N aqueous sodium hydroxide solution and water to clean organic layer.Utilize anhydrous magnesium sulfate to be dried, under reduced pressure, solvent distillation is removed.Utilize tubing string chromatography (column chromatography) by residue purifying, utilize methyl alcohol to carry out recrystallize, obtain thus described compound (1-1-a-1) 27.3g.The phase transition temperature of the compound (1-1-a-1) of gained is as follows.
Phase transition temperature: C30N48I
1H-NMR(500MHz，CDCl 3；δppm)：8.15(t，1H)，7.24(d，2H)，7.15-7.07(m，4H)，6.65(d，1H)，6.36-6.28(m，1H)，6.09(d，1H)，2.62(t，2H)，1.67-1.59(m，2H)，1.39-1.28(m，4H)，0.90(t，3H).
19F-NMR(500MHz，CDCl 3；δppm)：-104.98.
[synthesis example 2]
Compound (1-1-a-3) is to utilize following methods to synthesize.
Figure BDA00003497991500391
(first stage)
Compound (ex-1) 30g and pyridine 0.1g are added in toluene 150mL, under nitrogen environment, at 60 ℃, stir.Drip wherein thionyl chloride 19.9g.After dropping, at 60 ℃, stir 4 hours, under reduced pressure, solvent distillation is removed.In the residue of gained, add toluene 300mL, under nitrogen environment, at 10 ℃, stir below.The toluene solution 50mL that drips wherein 4-(2-methoxy ethyl) phenol 23g, drips triethylamine 23.1g then.After dropping, at room temperature stir 4 hours.Add water and extract, utilize 1N aqueous sodium hydroxide solution and water to clean organic layer.Utilize anhydrous magnesium sulfate to be dried, under reduced pressure, solvent distillation is removed.In the residue of gained, add THF100mL and methyl alcohol 50mL, under nitrogen environment, at 10 ℃, stir below.Drip wherein 28% ammonia soln 18mL, at room temperature stir 8 hours.Add ethyl acetate and water and extract, utilize saturated aqueous common salt to clean organic layer, utilize anhydrous magnesium sulfate to be dried.Under reduced pressure, solvent distillation is removed, utilize toluene to carry out recrystallize to the residue of gained, obtain thus compound (ex-3) 37.2g.
(subordinate phase)
Compound (ex-3) 37.2g and triethylamine 19.4g are added in methylene dichloride 400mL, under nitrogen environment, at 10 ℃, stir below.Drip wherein acrylate chloride 12.8g, at room temperature stir 8 hours.Add water and extract, utilize 1N aqueous sodium hydroxide solution and water to clean organic layer.Utilize anhydrous magnesium sulfate to be dried, under reduced pressure, solvent distillation is removed.Utilize tubing string chromatography by residue purifying, utilize methyl alcohol to carry out recrystallize, obtain thus described compound (1-1-a-3) 25.6g.The phase transition temperature of the compound (1-1-a-3) of gained is as follows.
Phase transition temperature: C34 (N-19) I
1H-NMR(500MHz，CDCl 3；δppm)：8.15(t，1H)，7.27(d，2H)，7.16(d，2H)，7.11(d，2H)，6.66(d，1H)，6.36-6.28(m，1H)，6.09(d，1H)，3.61(t，2H)，3.37(s，3H)，2.91(t，2H).
19F-NMR(500MHz，CDCl 3；δppm)：-104.95.
[synthesis example 3]
Compound (M2-1-4-1) is to utilize following methods to synthesize.
Figure BDA00003497991500401
(first stage)
Trans P-coumaric acid (trans-p-coumaric acid) 400g and vitriol oil 10mL are added in methyl alcohol 1200mL, under the condition of reflux, stir 5 hours.Under reduced pressure, solvent distillation is removed.The residue of gained is injected in frozen water, adds ethyl acetate and extract.Utilize saturated sodium bicarbonate, then utilize water to clean organic layer, utilize anhydrous magnesium sulfate to be dried.Under reduced pressure, solvent distillation is removed.Utilize ethanol to carry out recrystallize to residue, obtain thus compound (ex-3) 384.3g.
(subordinate phase)
Compound (ex-3) 100g, sodium hydroxide 24.7g and sodium iodide 8.4g are added in DMF (DMF) 1000mL, under nitrogen environment, at 60 ℃, stir.Drip wherein 6-Mecoral 84.3g.After dropping, at 80 ℃, stir 8 hours.In reaction solution, add ethyl acetate and water extracts.Utilize water to clean gained organic layer, utilize anhydrous magnesium sulfate to be dried.Under reduced pressure, solvent distillation is removed.The residue of gained, sodium hydroxide 24.7g are added in the mixing solutions of water 500ml and methyl alcohol 500ml, under the condition of reflux, stir 3 hours.Under reduced pressure, solvent distillation is removed, the residue of gained is injected into and in 3N hydrochloric acid, carries out redeposition.By crystallization filtering separation, utilize ethanol to carry out recrystallize, obtain thus compound (ex-4) 94.1g.
(phase III)
Compound (ex-4) 80.0g, xylidine 66.8g are added in toluene 400mL, at room temperature under nitrogen environment, stir.Drip wherein acrylate chloride 31.5g.After dropping, at 50 ℃, stir 4 hours.Reaction solution is injected in frozen water, adds ethyl acetate and extract, utilize anhydrous magnesium sulfate to be dried.Under reduced pressure, solvent distillation is removed.Utilize toluene to carry out recrystallize to the residue of gained, obtain thus compound (ex-5) 37.6g.
(fourth stage)
By compound (ex-5) 20g, 9-methyl-2,7-dihydroxyl fluorenes 6.6g and 4-dimethylaminopyridine (4-dimethylaminopyridine, DMAP) 1.6g add in methylene dichloride 200ml, under nitrogen environment, stir.Drip wherein the dichloromethane solution 30mL of 1,3-dicyclohexylcarbodiimide (1,3-dicyclohexylcarbodiimide, DCC) 13.6g.After dropping, at room temperature stir 8 hours.By the throw out filtering separation of separating out, utilize water to clean organic layer, utilize anhydrous magnesium sulfate to be dried.Under reduced pressure, solvent distillation is removed, utilize tubing string chromatography by residue purifying, utilize ethanol to carry out recrystallize, obtain thus described compound (M2-1-4-1) 16.3g.The phase transition temperature of the compound (M2-1-4-1) of gained is as follows.
Phase transition temperature: C74N250 < I
1H-NMR(500MHz，CDCl 3；δppm)：7.85(d，2H)，7.73(d，2H)，7.55(d，4H)，7.31(s，2H)，7.16(d，2H)，6.93(d，4H)，6.53(d，2H)，6.41(d，2H)，6.16-6.09(m，2H)，5.83(d，2H)，4.18(t，4H)，4.04-3.96(m，5H)，1.87-1.80(m，4H)，1.76-1.69(m，4H)，1.57-1.43(m，11H).
Compound (M2-1-1-1) is to synthesize according to the method for recording in Japanese Patent Laid-Open 2003-238491 communique and Japanese Patent Laid-Open 2006-307150 communique.
Compound (M2-2-2-1) is to utilize < < polymer chemistry (Makromol.Chem.) > >, the method of recording in 190,2255-2268 (1989) is synthesized.
Compound (M2-2-2-2) is to utilize < < polymer chemistry (Makromol.Chem.) > >, the method of recording in 192,59-74 (1991) is synthesized.
Compound (M2-2-7-1) is to utilize the method for recording in Japanese Patent the 4063873rd to synthesize.
Compound (M1-7-1) is to utilize < < giant molecule (Macromolecules) > >, 3938-3943, (23) method of, recording in 1990. is synthesized.
Compound (M1-2-1) is to utilize < < polymer chemistry (Makromol.Chem.) > > 183,2311-2321, the method for recording in (1982) is synthesized.
Compound (C-1) is to utilize < < molecular crystal and liquid crystal (Mol.Cryst.Liq.Cryst.) > >, the method of recording in 261,593-603 (1995) is synthesized.
Compound (C-2) is to utilize the method for recording in Japanese patent laid-open 9-316032 communique to synthesize.
[embodiment 1]
[preparation of polymerizable liquid crystal compound (1)]
With compound (1-1-a-1): compound (M2-1-1-1): compound (M2-2-2-2): compound (M2-1-4-1)=25: 25: 25: 25 weight ratio is by these compound.In said composition, adding weight ratio is that 0.06 polymerization initiator Yi Luka (Irgacure) Oxe01 (Japanese BASF (BASF Japan) manufacture), the fluorine that weight ratio is 0.005 are the anti-polymerizing agent 2 that non-ionic surfactant FTX-218 (Ni Aosi (Neos) (thigh) manufacture) and weight ratio are 0.005,5-bis-(tertiary butyl) hydroxytoluene (BHT).Said composition is warmed to 60 ℃, evenly mixes, make thus polymerizable liquid crystal compound (1).Polymerizable liquid crystal compound (1), even if at room temperature place and also keep mobility in 1 day, judges that it is room temperature liquid crystal composition.
Then, by rotary coating, polymerizable liquid crystal compound (1) is applied on the glass substrate with the alignment film through friction treatment.This substrate is heated 5 minutes at 80 ℃, at room temperature cooling 2 minutes, by ultraviolet ray, under nitrogen gas stream, make to be coated with membrane fussion and obtain liquid crystal film.The substrate with liquid crystal film of gained is put between 2 Polarizers that are configured to cross-polarized light, substrate is set as to the state of dark field, now confirm and there is no light leak, be judged as orientation evenly and there is horizontal direction matching.This delay with the substrate of liquid crystal film is measured, and it is 621nm that result becomes the delay measured value of 90 degree with respect to face, and thickness is 3.45 μ m, and calculating thus Δ n is 0.18.
[embodiment 2]
[preparation of polymerizable liquid crystal compound (2)]
With compound (1-1-a-1): compound (M2-1-1-1): compound (M1-7-1): compound (M2-1-4-1)=25: 25: 25: 25 weight ratio is by these compound.In said composition, adding weight ratio is that 0.06 polymerization initiator Yi Luka (Irgacure) Oxe01 (Japanese BASF (BASF Japan) manufacture), the fluorine that weight ratio is 0.002 are the anti-polymerizing agent 2 that non-ionic surfactant FTX-218 (Ni Aosi (Neos) (thigh) manufacture) and weight ratio are 0.005,5-bis-(tertiary butyl) hydroxytoluene (BHT).Said composition is warmed to 60 ℃, and evenly mixes, make thus polymerizable liquid crystal compound (2).Polymerizable liquid crystal compound (2), even if at room temperature place and also keep mobility in 1 day, judges that it is room temperature liquid crystal composition.
Then, by rotary coating, polymerizable liquid crystal compound (2) is applied on the glass substrate with the alignment film through friction treatment.This substrate is heated 5 minutes at 80 ℃, at room temperature cooling 2 minutes, by ultraviolet ray, under nitrogen gas stream, make to be coated with membrane fussion and obtain liquid crystal film.The substrate with liquid crystal film of gained is put between 2 Polarizers that are configured to cross-polarized light, substrate is set as to the state of dark field, now confirm and there is no light leak, be judged as orientation evenly and there is horizontal direction matching.This delay with the substrate of liquid crystal film is measured, and it is 894nm that result becomes the delay measured value of 90 degree with respect to face, and thickness is 3.44 μ m, and calculating thus Δ n is 0.26.
[embodiment 3]
[preparation of polymerizable liquid crystal compound (3)]
With compound (1-1-a-1): compound (M1-2-1): the weight ratio of compound (M2-2-2-1)=20: 30: 50 is by these compound.In said composition, adding weight ratio is that 0.06 polymerization initiator Yi Luka (Irgacure) Oxe01 (Japanese BASF (BASF Japan) manufacture), the fluorine that weight ratio is 0.002 are the anti-polymerizing agent 2 that non-ionic surfactant FTX218 (Ni Aosi (Neos) (thigh) manufacture) and weight ratio are 0.005,5-bis-(tertiary butyl) hydroxytoluene (BHT).Said composition is warmed to 60 ℃, evenly mixes, make thus polymerizable liquid crystal compound (3).Polymerizable liquid crystal compound (3), even if at room temperature place and also keep mobility in 1 day, judges that it is room temperature liquid crystal composition.
Then, by rotary coating, polymerizable liquid crystal compound (3) is applied on the glass substrate with the alignment film through friction treatment.This substrate is heated 5 minutes at 80 ℃, at room temperature cooling 2 minutes, by ultraviolet ray, under nitrogen gas stream, make to be coated with membrane fussion and obtain liquid crystal film.The substrate with liquid crystal film of gained is put between 2 Polarizers that are configured to cross-polarized light, substrate is set as to the state of dark field, now confirm and there is no light leak, be judged as orientation evenly and there is horizontal direction matching.This delay with the substrate of liquid crystal film is measured, and it is 504nm that result becomes the delay measured value of 90 degree with respect to face, and thickness is 3.15 μ m, and calculating thus Δ n is 0.16.
[embodiment 4]
[preparation of polymerizable liquid crystal compound (4)]
With compound (1-1-a-1): compound (M2-2-7-1): the weight ratio of compound (M2-1-1-1)=50: 20: 30 is by these compound.In said composition, add weight ratio and be the non-ionic surfactant FTX-218 (Ni Aosi (Neos) (thigh) manufacture) of 0.06 polymerization initiator Yi Luka (Irgacure) Oxe01 (Japanese BASF (BASF Japan) manufacture), fluorine system that weight ratio is 0.002 and the anti-polymerizing agent 2 that weight ratio is 0.005,5-bis-(tertiary butyl) hydroxytoluene (BHT).Said composition is warmed to 60 ℃, evenly mixes, make thus polymerizable liquid crystal compound (4).Polymerizable liquid crystal compound (4), even if at room temperature place and also keep mobility in 1 day, judges that it is room temperature liquid crystal composition.
Then, by rotary coating, polymerizable liquid crystal compound (4) is applied on the glass substrate with the alignment film through friction treatment.This substrate is heated 5 minutes at 80 ℃, at room temperature cooling 2 minutes, by ultraviolet ray, under nitrogen gas stream, make to be coated with membrane fussion and obtain liquid crystal film.The substrate with liquid crystal film of gained is put between 2 Polarizers that are configured to cross-polarized light, substrate is set as to the state of dark field, now confirm and there is no light leak, be judged as orientation evenly and there is horizontal direction matching.This delay with the substrate of liquid crystal film is measured, and it is 700nm that result becomes the delay measured value of 90 degree with respect to face, and thickness is 3.89 μ m, and calculating thus Δ n is 0.18.
[embodiment 5]
[preparation of polymerizable liquid crystal compound (5)]
With compound (1-1-a-1): compound (1-1-a-3): the weight ratio of compound (M2-1-4-1)=30: 20: 50 is by these compound.In said composition, add weight ratio and be the anti-polymerizing agent 2 that 0.06 polymerization initiator Yi Luka (Irgacure) Oxe01 (Japanese BASF (BASF Japan) manufacture), hydrocarbon system non-ionic surfactant Bi Ke (BYK)-361N (Japanese Bi Ke chemistry (BYK Chemie Japan) manufacture) that weight ratio is 0.002 and weight ratio are 0.005,5-bis-(tertiary butyl) hydroxytoluene (BHT).Said composition is warmed to 60 ℃, evenly mixes, make thus polymerizable liquid crystal compound (5).Polymerizable liquid crystal compound (5), even if at room temperature place and also keep mobility in 1 day, judges that it is room temperature liquid crystal composition.
Then, by rotary coating, polymerizable liquid crystal compound (5) is applied on the glass substrate with the alignment film through friction treatment.This substrate is heated 5 minutes at 80 ℃, at room temperature cooling 2 minutes, by ultraviolet ray, under nitrogen gas stream, make to be coated with membrane fussion and obtain liquid crystal film.The substrate with liquid crystal film of gained is put between 2 Polarizers that are configured to cross-polarized light, substrate is set as to the state of dark field, now confirm and there is no light leak, be judged as orientation evenly and there is horizontal direction matching.This delay with the substrate of liquid crystal film is measured, and it is 568nm that result becomes the delay measured value of 90 degree with respect to face, and thickness is 3.55 μ m, and calculating thus Δ n is 0.16.
[comparative example 1]
With compound (C-1): compound (M2-1-1-1): compound (M2-2-2-2): compound (M2-1-4-1)=25: 25: 25: 25 weight ratio is by these compound, in addition, mixing cpd similarly to Example 1.Said composition is prepared to polymerizable liquid crystal compound (6) similarly to Example 1.Polymerizable liquid crystal compound (6) is if place 1 day under room temperature, crystallization and losing flowability.In addition, even if be warmed to 40 ℃, also cannot obtain mobility, cannot form liquid crystal film.
[comparative example 2]
With compound (C-2): compound (M2-2-7-1): the weight ratio of compound (M2-1-1-1)=50: 20: 30 is these compound, in addition, mixing cpd similarly to Example 4.Said composition is prepared to polymerizable liquid crystal compound (7) similarly to Example 4.Polymerizable liquid crystal compound (7), even if at room temperature place and within 1 day, also keep mobility, is room temperature liquid crystal composition.
Then, by rotary coating, polymerizable liquid crystal compound (7) is applied on the glass substrate with the alignment film through friction treatment.This substrate is heated 5 minutes at 80 ℃, at room temperature cooling 2 minutes, by ultraviolet ray, under nitrogen gas stream, make to be coated with membrane fussion and obtain liquid crystal film.This delay with the substrate of liquid crystal film is measured, and it is 536nm that result becomes the delay measured value of 90 degree with respect to face, and thickness is 4.12 μ m, and calculating thus Δ n is 0.13.
[utilizability in industry]
The polymerizable liquid crystal compound of the application of the invention can obtain the liquid crystal film with uniform orientation form in the situation that not using solvent, and the specific refractory power anisotropy of gained liquid crystal film is relatively large.

Claims (11)

1. a polymerizable liquid crystal compound, is characterized in that containing the represented compound of formula (1),
Figure FDA00003497991400011
In formula (1), R 1for hydrogen or methyl; Z 1for-COO-or-OCO-; W 1and W 2independent is the alkyl of hydrogen, halogen, carbon number 1～5 or the alkoxyl group of carbon number 1～5; R 2for the alkyl of carbon number 1～20 or the alkoxyl group of carbon number 1～20, in described alkyl and alkoxyl group at least one-CH 2-can be replaced by-O-; N is 1 or 2.
2. polymerizable liquid crystal compound according to claim 1, is characterized in that: the compound that formula (1) is formula (1-1),
Figure FDA00003497991400012
In formula (1-1), R 1for hydrogen or methyl; W 1and W 2independent is hydrogen, fluorine, methyl or methoxy; R 2for the alkyl of carbon number 1～10 or the alkoxyl group of carbon number 1～10, in described alkyl and alkoxyl group at least one-CH 2-can be replaced by-O-.
3. polymerizable liquid crystal compound according to claim 1, is characterized in that: contain at least one compound in the represented compound of the formula of being selected from (M1), formula (M2) and formula (M3),
Figure FDA00003497991400021
In formula (M1), formula (M2) and formula (M3), R 1for hydrogen or methyl; A 1independent is respectively Isosorbide-5-Nitrae-phenylene, Isosorbide-5-Nitrae-cyclohexylidene or naphthalene-2,6-bis-bases, and in described Isosorbide-5-Nitrae-phenylene, at least one hydrogen can be replaced by the alkoxyl group of the alkyl of fluorine, carbon number 1～5 or carbon number 1～5; A 2be 1,4-phenylene, 1,4-cyclohexylidene, naphthalene-2,6-bis-bases or fluorenes-2,7-bis-bases, described 1, in 4-phenylene, at least one hydrogen can be replaced by the alkyl ester of the alkoxyl group of the alkyl of fluorine, chlorine, cyano group, hydroxyl, formyl radical, acetoxyl group, ethanoyl, trifluoromethyl, carbon number 1～5, carbon number 1～5 or carbon number 1～5, in fluorenes-2, in 7-bis-bases, the hydrogen of 9 can be replaced by the alkyl of carbon number 1～5; Z 2independent is respectively singly-bound ,-C 2h 4-,-COO-,-OCO-,-C ≡ C-,-CH=CHCOO-,-OCOCH=CH-,-COOC 2h 4-,-C 2h 4oCO-,-C 2h 4cOO-or-OCOC 2h 4-; W 1and W 2independent is respectively hydrogen, fluorine, methyl or methoxy; Y is the alkyl of cyano group, carbon number 1～10 or the alkoxyl group of carbon number 1～10, at least one CH in described alkyl and alkoxyl group 2-can be replaced by-O-; Q be singly-bound ,-O-,-COO-,-OCO-or-OCOO-; P is 1～12 integer; R is independently respectively 0～12 integer; A is 1 or 2; B is 0～2 integer, and c and d are independently 0～2 integer, and meets 1≤c+d≤3.
4. polymerizable liquid crystal compound according to claim 1, is characterized in that: contains the represented compound of formula (1) and is selected from least one compound in the represented compound of formula (M2-1),
Figure FDA00003497991400022
In formula (M2-1), R 1for hydrogen or methyl; Z 2independent is respectively singly-bound ,-COO-,-OCO-,-C ≡ C-,-CH=CHCOO-,-OCOCH=CH-,-C 2h 4cOO-or-OCOC 2h 4-; W 1and W 2independent is respectively hydrogen, fluorine, methyl or methoxy; W 3independent is the alkyl of hydrogen or carbon number 1～5; Q is-O-,-COO-,-OCO-or-OCOO-; R is 1～12 integer.
5. polymerizable liquid crystal compound according to claim 1, is characterized in that: the represented compound of formula (1) is the represented compound of formula (1-1-a),
Figure FDA00003497991400031
In formula (1-1-a), R 2for the alkyl of carbon number 2～10, at least one CH of described alkyl 2-can be replaced by-O-.
6. polymerizable liquid crystal compound according to claim 1, is characterized in that being at room temperature nematic phase.
7. polymerizable liquid crystal compound according to claim 3, it is characterized in that: total amount 100 % by weight of the compound represented with respect to formula (1), formula (M1), formula (M2) and formula (M3), the formula (M1) of the compound that the formula that contains 10 % by weight～50 % by weight (1) is represented and 50 % by weight～90 % by weight and the represented compound of formula (M2).
8. polymerizable liquid crystal compound according to claim 1, is characterized in that: can not use solvent and be applied on substrate.
9. an optical anisotropic film, is characterized in that: it is to obtain by making polymerizable liquid crystal compound according to claim 1 carry out polymerization.
10. optical anisotropic film according to claim 9, is characterized in that: specific refractory power anisotropy is more than 0.15.
11. 1 kinds of liquid crystal display device, is characterized in that: have optical anisotropic film according to claim 9.
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