CN106467750A - The manufacture method of polymerizable liquid crystal compound, compositionss and its polymer, polaroid, display element and optical anisotropic film - Google Patents

The manufacture method of polymerizable liquid crystal compound, compositionss and its polymer, polaroid, display element and optical anisotropic film Download PDF

Info

Publication number
CN106467750A
CN106467750A CN201610694069.8A CN201610694069A CN106467750A CN 106467750 A CN106467750 A CN 106467750A CN 201610694069 A CN201610694069 A CN 201610694069A CN 106467750 A CN106467750 A CN 106467750A
Authority
CN
China
Prior art keywords
liquid crystal
compound
polymerizable liquid
carbon number
formula
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201610694069.8A
Other languages
Chinese (zh)
Inventor
大槻大辅
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
JNC Corp
JNC Petrochemical Corp
Original Assignee
JNC Corp
Chisso Petrochemical Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by JNC Corp, Chisso Petrochemical Corp filed Critical JNC Corp
Publication of CN106467750A publication Critical patent/CN106467750A/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • C09K19/38—Polymers
    • 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
    • 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
    • C09K19/32—Non-steroidal liquid crystal compounds containing condensed ring systems, i.e. fused, bridged or spiro ring systems
    • 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
    • C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
    • C09K19/3402—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom
    • 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
    • C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
    • C09K19/3491—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having sulfur as hetero atom
    • 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
    • C09K19/38—Polymers
    • C09K19/3804—Polymers with mesogenic groups in the main chain
    • C09K19/3809—Polyesters; Polyester derivatives, e.g. polyamides
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3016—Polarising elements involving passive liquid crystal elements
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Nonlinear Science (AREA)
  • Mathematical Physics (AREA)
  • Polarising Elements (AREA)
  • Liquid Crystal (AREA)
  • Liquid Crystal Substances (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

It is an object of the invention to provide a kind of polymerizable liquid crystal compound that can control wavelength dispersion characteristics, the aspect of the polymerizable liquid crystal compound represented by formula (1) can be illustrated.And polymerizable liquid crystal compound and its manufacture method of polymer, polaroid, display element and optical anisotropic film are provided.In formula (1), A1For Isosorbide-5-Nitrae phenylene or Isosorbide-5-Nitrae cyclohexylidene, Z1And Y1For concatenating group, X1For singly-bound, CH2Or hetero atom, T1With T2Alkylthio group for carbon number 1～12 or be bonded each other and form the base of ring, m is 0～3 integer, Q1For sept, PG is polymerism base.The liquid crystal polymer of the increase of wavelength with visible region and the increase low degree of the delay of liquid crystal polymer according to the present invention, can be manufactured.

Description

Polymerizable liquid crystal compound, compositionss and its polymer, polaroid, display element and The manufacture method of optical anisotropic film
Technical field
The present invention relates to a kind of polymerizable liquid crystal chemical combination with indone or man-α-naphthylketone or the skeleton similar with them Thing, the compositionss comprising described polymerizable liquid crystal compound, the polymer with described polymerizable liquid crystal compound as raw material, polarization The manufacture method of piece, display element and optical anisotropic film.
Background technology
Sometimes purpose is turned to the wide area of the angle of visual field or high-contrast and built-in polarizer in a liquid crystal display.Have When for the purpose of effective antireflection in organic electroluminescent (Electroluminescence, EL) display built-in bag Circular polarizing disk containing polarizer and polarizer.
Show that the liquid crystal polymer of birefringence can be used as polarizer.
The polymerizable liquid crystal compound comprising polymerizable liquid crystal compound shows birefringence.Polymerizable liquid crystal compound Orientation is fixed by polymerization.So, polymerizable liquid crystal compound becomes the raw material of liquid crystal polymer.
If phase place as the conventional liquid crystal polymer that show positive wavelength dispersion characteristics is used in a liquid crystal display , then there is polarization state and change according to wavelength, and the problem of the form and aspect being intended to reach cannot be obtained in difference plate.
If being used in organic el display as the conventional liquid crystal polymer, the bag that show positive wavelength dispersion characteristics , then there is polarization state and change according to wavelength in the circular polarizing disk containing polarizer and polarizer, and cannot obtain to can See that total wavelength in region carries out the problem of antireflecting function effectively.
In order to solve described two problems, need the delay of the increase of wavelength with visible region and liquid crystal polymer Increase low degree liquid crystal polymer.Liquid crystal polymer is as optical anisotropic film in patent documentation 1～patent documentation 5 In on the books.
[prior art literature]
[patent documentation]
[patent documentation 1] Japanese Patent Laid 2010-522893 publication
[patent documentation 2] Japanese Patent Laid-Open 2009-179563 publication
[patent documentation 3] International Publication No. 2012/060011
[patent documentation 4] Japanese Patent Laid-Open 2005-289980 publication
[patent documentation 5] Japanese Patent Laid-Open 2010-31223 publication
Content of the invention
[inventing problem to be solved]
The problem of the present invention is to provide a kind of polymerizable liquid crystal compound, and it becomes the wavelength with visible region Increase and the raw material of the liquid crystal polymer of increase low degree of the delay of liquid crystal polymer.
[solving the technological means of problem]
Invention is it has been found that have the polymerizable liquid crystal chemical combination of the skeleton of indone or man-α-naphthylketone or their derivant The polymer of thing with the increase of the wavelength of visible region and the increase low degree of the delay of liquid crystal polymer, thus completing Invention.
[1] polymerizable liquid crystal compound represented by a kind of formula (1),
[changing 1]
In formula (1),
A1Independently be Isosorbide-5-Nitrae-phenylene or Isosorbide-5-Nitrae-cyclohexylidene, in described Isosorbide-5-Nitrae-phenylene, at least one hydrogen can through fluorine, Chlorine, trifluoromethyl, the alkyl of carbon number 1～5, the alkoxyl of carbon number 1～5, the alkoxy carbonyl of carbon number 1～5 or carbon number 1～5 Alkanoyl replaces,
Z1It independently is singly-bound ,-OCH2-、-CH2O-、-COO-、-OCO-、-CF2O-、-OCF2-、-CH2CH2-、- CF2CF2-、-OCH2CH2O-、-CH2CH2COO-、-OCOCH2CH2-、-CH2CH2OCO- or-COOCH2CH2-,
X1For singly-bound ,-CH2-、-O-、-S-、-NR2- or-CO-, R2For the alkyl of hydrogen or carbon number 1～5,
W1And W2It independently is hydrogen, the fluoroalkyl of fluorine, the alkyl of carbon number 1～5 or carbon number 1～5,
T1And T2Independently be hydrogen, the aromatic rings of electron number 6～18 of non-localized, the alkyl of carbon number 1～12, carbon number 1～ 12 alkoxyl or the alkylthio group of carbon number 1～12, in described alkyl, described alkoxyl and described alkylthio group, at least one-CH2- Can replace through-O- or-S-, at least one hydrogen can be fluorine-substituted, T1With T2Can be bonded each other and form ring,
M independently is 0～3 integer, and m's and be more than 1,
Y1It independently is singly-bound ,-O- ,-COO- ,-OCO- or-OCOO-,
Q1It independently is singly-bound or the alkylidene of carbon number 1～20, in described alkylidene, at least one-CH2- can through-O- ,- COO- ,-OCO- ,-CH=CH- or-CH ≡ CH- replace,
PG independently is alkyl or any one represented polymerism base of formula (PG-1)～formula (PG-9).
[changing 2]
In formula (PG-1)～formula (PG-9), R1It independently is hydrogen, halogen, methyl, ethyl or trifluoromethyl.
[2] polymerizable liquid crystal compound according to [1], wherein, T1And T2One of them be non-localization electronics The aromatic rings of number 6～18, and T1And T2Another be hydrogen, methyl or non-localized electron number 6～18 aromatic rings.
[3] polymerizable liquid crystal compound according to [1] or [2], wherein, T1And T2One be formula (G-1)～formula (G-9) functional group,
[changing 3]
In formula (G-1)～formula (G-9), X2For-O- or-S-, at least one-CH=can be substituted by-N=, at least one Hydrogen can be through fluorine, chlorine, cyano group, trifluoroacetyl group, trifluoromethyl, the alkyl of carbon number 1～5, the alkoxyl of carbon number 1～5, carbon number 1～5 Alkoxy carbonyl or carbon number 1～5 alkanoyl replace.
[4] polymerizable liquid crystal compound according to [1], wherein, T1And T2It independently is the alkylthio group of carbon number 1～12, In described alkylthio group, at least one-CH2- can replace through-O- or-S-, in described alkylthio group, at least one hydrogen can be fluorine-substituted.
[5] polymerizable liquid crystal compound according to [1], wherein, T1And T2It is bonded each other and formed and there is at least one The monocyclic or condensed ring of the carbon number 4～11 of sulphur atom.
[6] polymerizable liquid crystal compound according to [1] or [5], wherein, T1And T2Be bonded each other and formed dithiane, Dithiolane, two mercaptan or benzo two mercaptan.
[7] according to [1] polymerizable liquid crystal compound any one of to [6], wherein, PG is formula (PG-1)～formula (PG-9) functional group.
[8] according to [1] polymerizable liquid crystal compound any one of to [6], wherein, PG is the sense of formula (PG-1) Base, R1For hydrogen or methyl.
[9] according to [1] polymerizable liquid crystal compound any one of to [8], wherein, A1At least one of be 1, 4- cyclohexylidene, Z1At least one of be-CH2CH2COO- or-OCOCH2CH2-, m is 2.
[10] according to [1] polymerizable liquid crystal compound any one of to [9], wherein, X1For singly-bound.
[11] a kind of polymerizable liquid crystal compound, it is poly- any one of to [10] according to [1] that it contains at least one Conjunction property liquid-crystal compoundss.
[12] polymerizable liquid crystal compound according to [11], it contains the basis [1] of 4 weight %～50 weight % extremely [10] polymerizable liquid crystal compound any one of.
[13] a kind of liquid crystal polymer, it is to be hardened according to the polymerizable liquid crystal compound described in [11] or [12] to form.
[14] liquid crystal polymer according to [13], wherein, the identical state of orientation immobilization of liquid crystal molecule.
[15] liquid crystal polymer according to [13] or [14], wherein, (the light to face vertical incidence wavelength 450nm When delay)/(delay to during the light of face vertical incidence wavelength 550nm) be less than 1.05.
[16] a kind of polaroid, it has according to [13] liquid crystal polymer any one of to [15].
[17] a kind of display element, it has according to [13] liquid crystal polymer any one of to [15].
[18] display element according to [17], it has more polaroid.
[19] a kind of manufacture method of liquid crystal polymer, it includes making the polymerizable liquid crystal group according to [11] or [12] The step of compound polymerization.
[The effect of invention]
The increase journey of the increase of wavelength with visible region and the delay of liquid crystal polymer according to the present invention, can be manufactured Spend low liquid crystal polymer.
Brief description
No
Specific embodiment
In the present invention, so-called " wavelength dispersion characteristics " refer to the two-fold of the liquid crystal polymer under each wavelength of visible region Penetrate the distribution of rate.
In the present invention, so-called " positive wavelength dispersion characteristics " refer to the increase of wavelength and polymerizable mesogenic with visible region The increase of the delay of body is big.
In the present invention, " Δ n " refers to the birefringence of liquid crystal polymer.
In the present invention, so-called " Δ n (550) " refer to the birefringence of the liquid crystal polymer under wavelength 550nm.
In the present invention, so-called " Re450nm" refer to face vertical incidence wavelength 450nm light when delay.
In the present invention, so-called " Re550nm" refer to face vertical incidence wavelength 550nm light when delay.
In the present invention, so-called " Re650nm" refer to face vertical incidence wavelength 650nm light when delay.
In the present invention, so-called " aromatic rings " refer to the ring knot having including condensed ring or ring set (ring assemblies) Structure, and be relatively to suppose that by the non-localized of valency electron energy during the localization of valency electron becomes the official of more stable state Energy portion.Described sense portion also comprises with oxygen atom, nitrogen-atoms or sulphur atom.
In the present invention, so-called " compound (X) " refers to the compound represented by formula (X).Herein, the X in " compound (X) " Refer to text line, numeral, symbol etc..
Wherein, in the present invention, so-called " compound (M) " be compound (M1), compound (M2) and compound (M3) and The general name of their derivant.
In the present invention, so-called " liquid-crystal compoundss " refer to the compound with liquid crystalline phase, even and if in compound monomer There is no liquid crystalline phase, but when mixing with other liquid-crystal compoundss it is also possible to make the total of the compound of the composition of liquid-crystal composition Claim.
In the present invention, so-called " polymerizable compound " refers to following compound, and described compound has by light, heat, urges The methods such as agent are polymerized and are become and turn to the high molecular ability containing more macromolecule.
In the present invention, so-called " polymerizable liquid crystal compound " refers to as liquid-crystal compoundss and polymerizable compound.
In the present invention, so-called " monofunctional compound " refers to the compound with a following functional group, described functional group Have by light, heat, catalyst and additive method and become and turn to the high molecular ability containing more macromolecule.
In the present invention, so-called " polyfunctional compound " refers to the compound with multiple following functional groups, described functional group Have by light, heat, catalyst and additive method and become and turn to the high molecular ability containing more macromolecule.
In the present invention, so-called " X functional compound " refers to the compound with X following functional group, described functional group's tool Have by light, heat, catalyst and additive method and become and turn to the high molecular ability containing more macromolecule.Herein, " X sense X in compound " is integer.
In the present invention, so-called " polymerizable liquid crystal compound " refers to comprise the combination of polymerizable compound and liquid-crystal compoundss Thing and the compositionss comprising " polymerizable liquid crystal compound ".
In the present invention, so-called " liquid crystal polymer with substrate " refers to the polymerizable liquid crystal compound polymerization on substrate And obtain.
In the present invention, so-called " the not liquid crystal polymer of belt substrate " refers to remove from " liquid crystal polymer with substrate " Obtained by substrate.
In the present invention, so-called " liquid crystal polymer " refers to " liquid crystal polymer with substrate " and " the not liquid crystal of belt substrate The general name of polymer ".
In the present invention, so-called " inclination angle " refers to the angle between the differently- oriented directivity of liquid crystal molecule and the face supporting base material.
In the present invention, so-called " parallel-oriented " refers to that inclination angle is 0 degree to 5 degree.
In the present invention, so-called " vertical orientated " refers to that inclination angle is 85 degree to 90 degree.
In the present invention, so-called " tilted alignment " refers to the differently- oriented directivity of the major axis with liquid crystal molecule away from base material, from phase Parallel and rise to vertical state for base material.
In the present invention, so-called " twisted-oriented " refers to that the differently- oriented directivity of the long axis direction of liquid crystal molecule is put down with respect to base material OK, and with away from base material, the state of stepped torsion and centered on helical axis.
In the present invention, so-called " room temperature " refers to 15 DEG C to 35 DEG C.
In chemical formula, in the case that the binding site being expressed as with the carbon constituting ring and chemical bond intersect, refer to its official The binding site of energy base can arbitrarily be replaced on the atom constituting described ring.
In the case that the number of described functional group is 0, represent the replacement having no described functional group.
In addition, in the case that there is in chemical formula the record of following functional groups, being set to wave line part and refer to described functional group Binding site.Herein, following C is arbitrary atom or sense portion.
[changing 4]
Polymerizable liquid crystal compound
The polymerizable liquid crystal compound inclusion compound (1) of the present invention.The species of the compound (1) in compositionss can be one Kind, alternatively multiple.By using the polymerizable liquid crystal compound represented by formula (1), light for wavelength 450nm can be manufactured Birefringence Δ n (450) with for wavelength 550nm light birefringence Δ n (550) meet Δ n (450)/Δ n (550)≤ The optical anisotropic film of 1.05 relation, i.e. the positive low liquid crystal polymer of wavelength dispersion characteristics.
Therefore, sometimes with the increase of the wavelength of visible region, the delay of described liquid crystal polymer reduces.
Thinking using the polymerizable liquid crystal compound represented by formula (1) becomes the low polymerizable mesogenic of the long dispersing characteristic of positive wave The reason body is following reason.The wavelength dispersion characteristics of refractive index are as shown in Lao Lunci-Lorenz (Lorentz-Lorenz) formula Like that, there is close relationship with the absorption waveform of material.
Import the substituent group of absorption visible ray in the short-axis direction of liquid crystal molecule and absorb the long wave in short-axis direction vibration Long light.The substituent group absorbing visible ray has aromatic rings with electron conjugated system etc..The major axis of liquid crystal molecule imports not Absorb the substituent group of visible ray and do not absorb the light of the long wavelength in long axis direction vibration.The substituent group not absorbing visible ray has not There is cycloaliphatic ring of electron conjugated system etc..If the wavelength of the incident illumination near the very big wavelength band of the light absorbs of material changes, Then the refractive index of material is increased dramatically.Refractive index changes with the change postponing for wavelength for wavelength.Therefore, liquid crystal Polymeric positive wavelength dispersion characteristics can be controlled by design of the liquid crystal molecule in liquid crystal polymer etc..
Even if the polymerizable liquid crystal compound of the present invention contains substantial amounts of polymerizable liquid crystal compound, solvent is being removed Afterwards, crystallization will not also be produced in polymerizable liquid crystal compound.If using described polymerizable liquid crystal compound, can obtain and no take Liquid crystal polymer to defect.Therefore, the incidence point postponing will not to depend in the plane of incidence of liquid crystal polymer can be obtained and produce Change dynamic liquid crystal polymer.
[changing 5]
In described formula (1), A1It independently is Isosorbide-5-Nitrae-phenylene or Isosorbide-5-Nitrae-cyclohexylidene.In order that under positive wavelength dispersion characteristics Fall, more preferably A1For Isosorbide-5-Nitrae-cyclohexylidene, in order to have bigger birefringence, more preferably A1For Isosorbide-5-Nitrae-phenylene. In described Isosorbide-5-Nitrae-phenylene, at least one hydrogen can through fluorine, chlorine, trifluoromethyl, the alkyl of carbon number 1～5, carbon number 1～5 alcoxyl The alkanoyl of base, the alkoxy carbonyl of carbon number 1～5 or carbon number 1～5 replaces.
When described Isosorbide-5-Nitrae-phenylene is unsubstituted, birefringence is high.
In formula (1), Z1It independently is singly-bound ,-OCH2-、-CH2O-、-COO-、-OCO-、-CF2O-、-OCF2-、- CH2CH2-、-CF2CF2-、-OCH2CH2O-、-CH2CH2COO-、-OCOCH2CH2-、-CH2CH2OCO- or-COOCH2CH2-.In Z1 For-COO- ,-OCO- ,-CH2CH2COO- or-OCOCH2CH2- in the case of, the liquid crystalline phase of described compositionss easily manifests, and can It is manufactured inexpensively compound.In addition, in Z1At least one of be-CH2CH2COO- or-OCOCHHCH2- in the case of, described group Other liquid-crystal compoundss in compound and organic solvent are not susceptible to be separated, and the brocken spectrum of described compositionss declines.
Independently be 0～3 integer in m, and m's and for more than 1 when, compound (1) easily shows described compositionss Liquid crystalline phase, other liquid-crystal compoundss in described compositionss and organic solvent are not susceptible to be separated.In addition, the feelings being 2 in m Under condition, even if the concentration of the organic solvent in described compositionss rises, also can not occur to be separated and maintain liquid crystalline phase.
In X1For singly-bound ,-CH2-、-O-、-S-、-NR2- or-CO-, and R2For hydrogen or carbon number 1～5 alkyl when, compound (1) positive wavelength dispersion characteristics are low.
In W1And W2Separately be hydrogen, fluorine or carbon number 1～5 alkyl when, the positive wavelength dispersion characteristics of compound (1) Low.In W1And W2When being hydrogen, the liquid crystalline phase of compositionss easily manifests.In W1And W2At least one be fluorine or carbon number 1～5 In the case of alkyl, other liquid-crystal compoundss in described compositionss and organic solvent are not susceptible to be separated.
In formula (1), T1And T2It independently is hydrogen, the aromatic rings of electron number 6～18 of non-localized, the alkane of carbon number 1～12 The alkylthio group of base, the alkoxyl of carbon number 1～12 or carbon number 1～12, in described alkyl, described alkoxyl or described alkylthio group, extremely A few-CH2- can replace through-O- or-S-, at least one hydrogen can be fluorine-substituted, and then, T1With T2Can be bonded each other and be formed Ring.
Furthermore, in the present invention, so-called " electron number of non-localized " refer to by
(a) constitute described structural formula in the number of the double bond of conjugated double bond and
B (i) nitrogen-atoms that the atom group of the conjugated double bond in () and described structural formula adjoins, (ii) oxygen atom and (iii) The number that is total and being multiplied by twice gained of the number of sulphur atom.
(A) the positive wavelength dispersion characteristics of described compositionss are low and for described compositionss, its in described compositionss His liquid-crystal compoundss and organic solvent are not susceptible to be separated, therefore preferably following compound (1)：T1And T2Independently be hydrogen, The aromatic rings of electron number 6～18 of methyl or non-localized and any one be non-localization electron number 6～18 aromatic rings.Just For the aspect of low cost of manufacture, more preferably described aromatic rings are the compound (1) of formula (G-1)～formula (G-9).
[changing 6]
In formula (G-1)～formula (G-9), X2For-O- or-S-, at least one-CH=can be substituted by-N=, at least one Hydrogen can be through fluorine, chlorine, cyano group, trifluoroacetyl group, trifluoromethyl, the alkyl of carbon number 1～5, the alkoxyl of carbon number 1～5, carbon number 1～5 Alkoxy carbonyl or carbon number 1～5 alkanoyl replace.
(B) the positive wavelength dispersion characteristics of described compositionss are low and for described compositionss, its in described compositionss His liquid-crystal compoundss and organic solvent are not susceptible to be separated, therefore preferably following compound (1)：T1And T2It independently is carbon The alkylthio group of number 1～12.Herein, at least one-CH of described alkylthio group2- can replace through-O- or-S-, described alkylthio group is extremely Few hydrogen can be fluorine-substituted.
(C) the positive wavelength dispersion characteristics of described compositionss are low and for described compositionss, its in described compositionss His liquid-crystal compoundss and organic solvent are not susceptible to be separated, therefore preferably T1And T2It is bonded each other and formed and have at least one The monocyclic or condensed ring of the carbon number 4～11 of individual sulphur atom, specifically, preferably described ring structure is to have at least one sulphur atom 5 yuan of rings, the compound (1) of 6 yuan of rings or 5 yuan of rings and the condensed ring of 6 yuan of rings.For the aspect of low cost of manufacture, more preferably Described ring structure is dithiane, the compound (1) of dithiolane, two mercaptan or benzo two mercaptan.
In formula (1), Y1It independently is singly-bound ,-O- ,-COO- ,-OCO- or-OCOO-, Q1It is separately singly-bound or carbon The alkylidene of number 1～20, in described alkylidene, at least one-CH2- can replace through-O- ,-COO- or-OCO-.In Q1For carbon number 1 In the case of～20 alkylidene, the liquid crystalline phase of compositionss easily manifests, and other liquid-crystal compoundss and organic solvent are susceptible to It is separated.
PG independently is alkyl or any one represented polymerism base of formula (PG-1)～formula (PG-9).The carbon number of alkyl 1～12 can be enumerated.
[changing 7]
In formula (PG-1)～formula (PG-9), R1It independently is hydrogen, halogen, methyl, ethyl or trifluoromethyl.Described halogen can Illustrate fluorine, chlorine, bromine or iodine.When making film, it is however preferred to have the compound of polymerism base, therefore PG preferably formula (PG-1)～ Any one represented polymerism base of formula (PG-9).
The selection of the polymerism base represented by formula (PG-1)～formula (PG-9) can be selected by the manufacturing condition of film suitably 's.However, in the case of using commonly used photo-hardening to make film, with regard to high hardening, the dissolubility to solvent, behaviour For making the aspect of easiness, preferably select the formula (PG-1) of acrylic or methacrylic acid group etc..
The preference of the polymerizable liquid crystal compound represented by formula (1) is next shown.But it is not limited to shown below.
[changing 8]
[changing 9]
[changing 10]
[changing 11]
In formula (1-1-1)～formula (1-1-8), formula (1-2-1)～formula (1-2-10) or formula (1-3-1)～formula (1-3-15), Y1It independently is singly-bound ,-O- ,-COO- ,-OCO- or-OCOO-, Q1It independently is singly-bound or the alkylidene of carbon number 1～20, described In alkylidene, at least one-CH2- can replace through-O- ,-COO- or-OCO-, PG independently be alkyl or described formula (PG-1)～ Any one polymerism base represented by formula (PG-9).
Compound (1) can be synthesized by being combined the method for known Synthetic Organic Chemistry.In initial substance The method importing target terminal groups, ring and bond base is recorded in：《Hou Ben-Huai Er》(Houben-Wyle, organic chemistry procedures (Methods of Organic Chemistry), George-Di Mu publishing house (Georg Thieme Verlag), Stuttgart (Stuttgart))、《Organic synthesiss》(Organic Syntheses, John Wei Li father and son publishing company (John Wily＆ Sons, Inc.)),《Organic reaction》(Organic Reactions, John Wei Li father and son publishing company (John Wily＆Sons, Inc.))、《Comprehensive organic synthesiss》(Comprehensive Organic Synthesis, Pei Geman publishing company (Pergamon Press)) and in new experimental chemistry lecture (ball is apt to).
Compound (1) can be synthesized by following reactions steps.
[changing 12]
The nuclear skeleton structure of compound (1) can by as dimethoxy indone, dimethoxy-man-α-naphthylketone or dimethoxy- The compound of active methylene as man-α-naphthylketone derivant and synthesize.The X of described formula1For-CH2-、-O-、-S-、- NR2- or-CO- ,-NR2- R2Alkyl for hydrogen or carbon number 1～5.Specifically, 4,7- dimethoxy -1- indone and two can be made Nitric sulfid and iodide react and methylene-bis- (methyl mercapto) structure are directed into 2 of indone.Deprotection is carried out simultaneously to it In addition class, thus can synthesize the compound of the synthesis for compound (1).
And then, by iodide is substituted by Bromofume, also into dithiolane structure.
The aromatic rings aldehyde such as benzaldehyde and methoxyl group indone, dimethoxy-man-α-naphthylketone or dimethoxy-man-α-naphthylketone can be made The compound of the active methylene of derivant etc. is had an effect, and to import styryl structures.
By using 4- hydroxy cyclohexane carboxylic and its derivant, Isosorbide-5-Nitrae-cyclohexylidene can be imported.
[changing 13]
In described formula, r is 2～20 integer.
The structure of synthesized compound can by proton magnetic resonance (PMR) (Nuclear Magnetic Resonance, NMR) spectrum is confirming.
Polymerizable liquid crystal compound
The polymerizable liquid crystal compound of the present invention contains more than one compound (1).The polymerizable liquid crystal group of the present invention Compound has nematic phase or the liquid crystalline phase of disk like phase at relatively low temperatures.Apply in the polymerizable liquid crystal compound by the present invention Spread on the plastic bases of orientation process such as rubbed process or by masking on the support substrate on the film coated surface of plastics In the case of, become parallel-oriented or tilted alignment.In addition, add described later non-in the polymerizable liquid crystal compound to the present invention In the case of the optically active compound of polymerism or polymerism, become twisted-oriented.If the polymerizable liquid crystal group in the present invention The compound with card many (cardo) structure described later or end is added to have the compound of polar group, then easily in compound Obtain vertical orientated.Described polar group has hydroxyl, carboxyl, amino, mercapto, sulfonic group, ester group, amide groups and ammonium.
For controlling the viewpoint of wavelength dispersion characteristics, if the gross weight of polymerizable liquid crystal compound is set to 100%, The polymerizable liquid crystal compound of the present invention is preferably the compound (1) containing 4 weight %～50 weight %.
Also can be containing the liquid-crystal compoundss beyond compound (1) in the polymerizable liquid crystal compound of the present invention.
Described liquid-crystal compoundss can be from the data base's as liquid-crystal compoundss《Liquid crystal》(LiqCryst, LCI publishing house stock Part company limited (LCI Publisher GmbH), hamburger (Hamburg), German (Germany)) in described compound Select.Wherein it is preferably compound (LC).
[changing 14]
In formula (LC), A2It independently is selected from Isosorbide-5-Nitrae-phenylene, Isosorbide-5-Nitrae-cyclohexylidene, pyridine -2,5- diyl (pyridine-2,5-diyl), 1,3- dioxanes -2,5- diyl and naphthalene -2, any one of 6- diyl bilvalent radical, described bivalence In base, at least one oxygen can be through fluorine, chlorine, cyano group, hydroxyl, formoxyl, trifluoroacetyl group, difluoromethyl, trifluoromethyl, carbon number 1 ～5 alkyl, the alkanoyl of the alkoxyl of carbon number 1～5, the alkoxy carbonyl of carbon number 1～5 or carbon number 1～5 replace,
Z2It is separately the alkylidene of singly-bound or carbon number 1～20, in described alkylidene, at least one-CH2- can through- O- ,-CO- ,-COO- ,-OCO- ,-CH=CH- ,-CF=CF- or-C ≡ C- replace, and in described alkylidene, at least one oxygen can be through Halogen substiuted,
B is 1～5 integer,
R3It independently is hydrogen, fluorine, chlorine, cyano group, hydroxyl, formoxyl, trifluoroacetyl group, difluoromethyl, trifluoromethyl, carbon number 1～10 alkyl or the alkoxyl of carbon number 1～10, at least one-CH in described alkyl2- can replace through-CH=CH-.
Hereinafter, the concrete example of the compound represented by compound (LC) is shown.
[changing 15]
[changing 16]
[changing 17]
The content of the compound (LC) in the polymerizable liquid crystal compound of the present invention is preferably below 50 weight %.
Following compounds (M1), compound (M2) and compound can be contained in the polymerizable liquid crystal compound of the present invention (M3).
[changing 18]
In formula (M1), formula (M2) and formula (M3),
AMIt independently is selected from Isosorbide-5-Nitrae-phenylene, Isosorbide-5-Nitrae-cyclohexylidene, Isosorbide-5-Nitrae-cyclohexadienylidene, pyridine -2,5- diyl, 1, 3- dioxanes -2,5- diyl, naphthalene -2,6- diyl or fluorenes -2, any one of 7- diyl bilvalent radical, in described bilvalent radical, at least One hydrogen can through fluorine, chlorine, cyano group, hydroxyl, formoxyl, trifluoroacetyl group, difluoromethyl, trifluoromethyl, the alkyl of carbon number 1～5, The alkanoyl of the alkoxyl of carbon number 1～5, the alkoxy carbonyl of carbon number 1～5 or carbon number 1～5 replaces,
ZMIt independently is singly-bound ,-OCH2-、-CH2O-、-COO-、-OCO-、-COS-、-SCO-、-OCOO-、-CONH-、- NHCO-、-CF2O-、-OCF2-、-CH2CH2-、-CF2CF2- ,-CH=CHCOO- ,-OCOCH=CH- ,-CH2CH2COO-、- OCOCH2CH2- ,-CH=CH- ,-N=CH- ,-CH=N- ,-N=C (CH3)-、-C(CH3)=N- ,-N=N- or-C ≡ C-,
XMFor hydrogen, fluorine, chlorine, trifluoromethyl, trifluoromethoxy, cyano group, the alkyl of carbon number 1～20, carbon number 1～20 alkene The alkoxy carbonyl of base, the alkoxyl of carbon number 1～20 or carbon number 1～20,
Q is 1～4 integer,
C and d independently is 0～3 integer, and the relation for 1≤c+d≤4,
A independently is 0～20 integer,
RMIt independently is hydrogen or methyl,
yMIt independently is singly-bound ,-O- ,-COO- ,-OCO- or-OCOO-,
QMIt independently is singly-bound ,-O- or-COO-.
The positive wavelength dispersion characteristics of described compositionss are low, and described compositionss easily manifest liquid crystalline phase, i.e. toilet at room temperature State the lowering of concentration of the organic solvent in compositionss, also can not occur to be separated and maintain liquid crystalline phase, and the manufacture of compound Cheap and easily, the A of at least one of therefore preferably compound (M1) and compound (M2)MFor Isosorbide-5-Nitrae-cyclohexylidene, and remove A beyond thisMFor Isosorbide-5-Nitrae-phenylene or Isosorbide-5-Nitrae-cyclohexylidene.
The positive wavelength dispersion characteristics of described compositionss are low, and described compositionss easily manifest liquid crystalline phase, i.e. toilet at room temperature State the lowering of concentration of the organic solvent in compositionss, also can not occur to be separated and maintain liquid crystalline phase, and the manufacture of compound Cheap and easily, the Z of therefore preferably compound (M1) and compound (M2)MFor singly-bound ,-OCH2-、-CH2O-、-COO-、- OCO-、-CH2CH2-、-CH2CH2COO- or-OCOCH2CH2-.
Compound (M1) is monofunctional compound, therefore adds the liquid-crystal composition having compound (M1) to be easily controlled liquid crystal Temperature range, optical characteristics and orientation.If in addition, increasing the addition of compound (M1), having the tendency of inclination angle and uprising, And it is readily available vertical orientated.
Compound (M2) is difunctional's compound, therefore adds the polymerization of the polymerizable liquid crystal compound having compound (M2) Body becomes three dimensional structure.Described polymer is become compared with the polymer of polymerizable liquid crystal compound being had compound (M1) with addition Hard polymer for relatively.
Compound (M3) is trifunctional compound, therefore adds the polymerization of the polymerizable liquid crystal compound having compound (M3) Body becomes has the comparatively speaking hard polymer of the polymer of the polymerizable liquid crystal compound of compound (M2) with addition.
Hereinafter, the preference of the compound represented by formula (M1) is shown.
[changing 19]
[changing 20]
In formula (M1-1)～formula (M1-24), RMIt independently is hydrogen or methyl, a independently is 1～12 integer.
Hereinafter, the preference of compound (M2) is shown.
Change 21]
[changing 22]
[changing 23]
In formula (M2-1)～formula (M2-31), RMIt independently is hydrogen or methyl, a independently is 1～12 integer.
Hereinafter, the preference of compound (M3) is shown.
[changing 24]
[changing 25]
In formula (M3-1)～formula (M3-10), RMSolely shield ground is hydrogen or methyl, and a independently is 1～12 integer.
Easily manifest liquid crystalline phase at room temperature, be easily adjusted the wavelength dispersion characteristics of birefringence, and there is good painting Cloth, therefore when the gross weight of the gross weight of compound (1) and compound (M) is set to 100 weight %, polymerizable liquid crystal group The content of the compound (M) in compound is preferably 1 weight %～70 weight %.
Compound adding in polymerizable liquid crystal compound etc.
The compound adding in the polymerizable liquid crystal compound of the present invention can only add one kind according to each function, also can add Plus it is two or more.
Surfactant can be divided into ionic surfactant or nonionic surfactant.Nonionic surfactant Agent can make the flatness of liquid crystal polymer improve.Nonionic surfactant has the Air Interface side of suppression liquid crystal polymer Tilted alignment effect.It is therefore preferable that being the interpolation nonionic surfactant in polymerizable liquid crystal compound.Silicone-based Nonionic surfactant, fluorine system nonionic surfactant, ethylene base system nonionic surfactant, hydrocarbon system non-from Sub- property surfactant etc. is nonionic surfactant.
Due to having the effect integrated with other polymerizable liquid crystal compounds, therefore it is preferably and adds as polymerism The surfactant of compound.With regard to the viewpoint of the reactivity of polymerizable liquid crystal compound for, described surfactant is preferably Start the surfactant of polyreaction using ultraviolet.
It is uniformly directed because liquid crystal polymer easily becomes, and because the coating of polymerizable liquid crystal compound improves, Surfactant therefore in polymerizable liquid crystal compound is preferably 0.0001 weight %～0.1 weight %, more preferably 0.0001 weight %～0.005 weight %.
Ionic surfactant can enumerate：Titanate based compound, imidazoline, quarternary ammonium salt, oxidation of alkyl amine, polyamine Derivant, polyethylene glycol oxide-polypropylene oxide condensation substance, Polyethylene Glycol and its ester, sodium lauryl sulfate, ammonium lauryl sulfate, Lauryl sulfate amine, alkyl substituent aromatic sulfonate, alkylphosphonic, aliphatic or aromatic sulphonic acid formaldehyde condensation products, Lauryl amidopropyl betaine, lauryl amino acetic acid glycine betaine, cithrol class, polyoxyethylene allylic alkylation Amine, fluorinated alkyl sulfonate, perfluoroalkyl carboxylate etc..
Silicone-based nonionic surfactant can be enumerated：Po Lifuluo (Polyflow) KL-400HF, Po Lifuluo (Polyflow) KL-401, Po Lifuluo (Polyflow) KL-402, Po Lifuluo (Polyflow) KL-403, Po Lifuluo (Polyflow)KL-404、BYK-300、BYK-302、BYK-306、BYK-307、BYK-310、BYK-315、BYK-320、BYK- 322、BYK-323、BYK-325、BYK-330、BYK-331、BYK-333、BYK-337、BYK-341、BYK-342、BYK-344、 BYK-345、BYK-346、BYK-347、BYK-348、BYK-349、BYK-370、BYK-371、BYK-375、BYK-377、BYK- 378th, BYK-3455, BYK-3500, BYK-3510, BYK-3530, BYK-3570, BYK- wish crin (Silclean) 3720, enlightening Gao Fuluo (TEGOFlow) 425 etc..
Fluorine system nonionic surfactant can be enumerated：BYK-340, Fu Jiete (Ftergent) 251, Fu Jiete (Ftergent) 212M, Fu Jiete (Ftergent) 215M, Fu Jiete (Ftergent) 250, Fu Jiete (Ftergent) 222F, Good fortune Ztel (Ftergent) 245F, Fu Jiete (Ftergent) 208G, Fu Jiete (Ftergent) 240G, Fu Jiete (Ftergent) 220P, Fu Jiete (Ftergent) 228P, Fu Jiete (Ftergent) FTX-218, Fu Jiete (Ftergent) DFX-18, Fu Jiete (Ftergent) 710FL, Fu Jiete (Ftergent) 710FM, Fu Jiete (Ftergent) 710FS, Fu Jie Special (Ftergent) 730LM, Mei Jiafa (Megafac) F-251, Mei Jiafa (Megafac) F-410, Mei Jiafa (Megafac) F- 430th, Mei Jiafa (Megafac) F-444, Mei Jiafa (Megafac) F-477, Mei Jiafa (Megafac) F-551, Mei Jiafa (Megafac) F-553, Mei Jiafa (Megafac) F-554, Mei Jiafa (Megafac) F-556, Mei Jiafa (Megafac) F- 557th, Mei Jiafa (Megafac) F-558, Mei Jiafa (Megafac) F-559, Mei Jiafa (Megafac) F-562, Mei Jiafa (Megafac) F-563, Mei Jiafa (Megafac) F-565, Mei Jiafa (Megafac) F-570, Mei Jiafa (Megafac) R-40, Mei Jiafa (Megafac) R-41, Mei Jiafa (Megafac) R-43, Mei Jiafa (Megafac) R-94 etc..
Ethylene base system nonionic surfactant can be enumerated：Po Lifuluo (Polyflow) No.7, Po Lifuluo (Polyflow) No.50EHF, Po Lifuluo (Polyflow) No.54N, Po Lifuluo (Polyflow) No.75, Po Lifuluo (Polyflow) No.77, Po Lifuluo (Polyflow) No.85HF, Po Lifuluo (Polyflow) No.90, Po Lifuluo (Polyflow) No.95, Po Lifuluo (Polyflow) No.99C, BYK-350, BYK-352, BYK-354, BYK-355, BYK- 358N, BYK-361N, BYK-380N, BYK-381, BYK-392, BYK-399, BYK- wish crin (Silclean) 3700, enlightening height Fu Luo (TEGOFlow) 300, Di Gaofuluo (TEGOFlow) 370, Di Gaofuluo (TEGOFlow) ZFS460 etc..
Can be enumerated using the surfactant that ultraviolet starts polyreaction：Good fortune Ztel (Ftergent) 601AD, Fu Jiete (Ftergent) 602A, Fu Jiete (Ftergent) 650A, Mei Jiafa (Megafac) RS-55, Mei Jiafa (Megafac) RS- 56th, Mei Jiafa (Megafac) RS-72-K, Mei Jiafa (Megafac) RS-75, Mei Jiafa (Megafac) RS-78, Mei Jiafa (Megafac) RS-90 etc..
Wetting agent can be enumerated：KL-100, KL-700, LE-604, LE-605 and LE-606 of Po Lifuluo (Polyflow), Twin (Twin) 4000 of enlightening height (TEGO), moistening (Wet) series KL245 of enlightening height (TEGO), 250,260,265,270, 280th, 500,505 and 510 and 3000 series 3277,3700 and 3770 that manufacture of angstrom husband's Kona (AFCONA) company etc..
Additionally, Po Lifuluo (Polyflow), BYK, enlightening height (TEGO), Fu Jiete (Ftergent), Mei Jiafa (Megafac) it is registered trade mark.
In the present invention, so-called " non-liquid crystal polymerizable compound " refers to be not the polymerism of polymerizable liquid crystal compound Compound.
The polymerizable liquid crystal compound of the present invention also can contain non-liquid crystal polymerizable compound.In order to maintain liquid crystalline phase, With total weight ratio meter of the polymerizable compound in described polymerizable liquid crystal compound, in described polymerizable liquid crystal compound Total weight of non-liquid crystal polymerizable compound is preferably less than 0.1.
Adding multifunctional polymerizable compound in liquid-crystal composition can make mechanical strength or the chemically-resistant of liquid crystal polymer Moral character or both raisings described.
Non-liquid crystal polymerizable compound as monofunctional compound can be enumerated：Styrene, core substituted phenylethylene, propylene Nitrile, vinyl chloride, vinylidene chloride, vinylpyridine, NVP, vinyl sulfonic acid, fatty acid vinyl ester, α, β- Ethylene unsaturated carboxylic acid, the carbon number of alkyl be 1～18 (methyl) acrylic acid Arrcostab, hydroxy alkyl carbon number be 1～ 18 (methyl) acrylic acid hydroxyalkyl acrylate, the carbon number of aminoalkyl be 1～18 (methyl) acrylic acid aminoalkyl ester, The carbon number of the alkyl containing ether oxygen be 3～18 (methyl) acrylic acid Arrcostab containing ether oxygen, N- vinyl acetamide, to tertiary fourth Benzoate, N, N- dimethylaminobenzoic acid vinyl acetate, vinyl benzoate, pivalic acid vinyl acetate, 2,2- diformazan Base vinyl butyrate, 2,2- dimethyl-penten vinyl acetate, 2- methyl -2- vinyl butyrate, propionate, vinyl stearate Ester, 2- Ethyl-2-Methyl vinyl butyrate, (methyl) acrylic acid two cyclopentyloxy ethyl ester, (methyl) isobomyl acrylate base oxygen Base ethyl ester, (methyl) isobornyl acrylate, (methyl) acrylic acid adamantane esters, (methyl) acrylic acid dimethyladamantane base Ester, (methyl) acrylic acid bicyclo- pentyl ester, (methyl) acrylic acid dicyclopentenyl ester, 2- acryloyloxyethylsuccinic acid, 2- propylene Trimethylammonium hexahydrophthalic acid, 2- acryloyl-oxyethyl phthalic acid, 2- acryloyl-oxyethyl -2- hydroxyl second Base phthalic acid, acid phosphate 2- acryloyloxyethyl ester, acid phosphate 2- methacryloyloxyethyl, the degree of polymerization are 1 List (methyl) acrylic acid of the poly- alkane glycol such as copolymer of～100 Polyethylene Glycol, polypropylene glycol, oxirane and expoxy propane Polyethylene Glycol that ester or two (methyl) acrylate or end are 1～100 by the degree of polymerization that the alkyl of carbon number 1～6 to block, Polypropylene glycol and list (methyl) acrylate of copolymer poly- alkane glycol as oxirane and expoxy propane etc..This place " fatty acid vinyl ester " stated can enumerate vinyl acetate etc.." α, β-ethylene unsaturated carboxylic acid " described herein can be enumerated： Acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid etc.." the carbon of the alkyl containing ether oxygen described herein Number (methyl) acrylic acid Arrcostab containing ether oxygen for 3～18 " can be enumerated：Methoxy acrylate, ethoxy ethyl ester, methoxy propyl Ester, methyl Apium graveolenss base ester, ethyl Apium graveolenss base ester and butyl Apium graveolenss base ester etc..
Non-liquid crystal polymerizable compound as difunctional's compound can be enumerated：Isosorbide-5-Nitrae-butanediol diacrylate, 1,6- hexane diol diacrylate, 1,9- nonane omega-diol diacrylate, neopentylglycol diacrylate, dihydroxymethyl three ring Dimethylol tricyclo decane diacrylate ester, triethylene glycol diacrylate, propylene glycol diacrylate, tripropylene glycol diacrylate, tetrem Omega-diol diacrylate, bisphenol-A epoxy ethane (ethylene oxide, EO) addition diacrylate, bisphenol A dimethacrylate contracting Water glyceride, polyethyleneglycol diacrylate, methacrylate compound of these compounds etc..
Bisphenol A dimethacrylate ethylene oxidic ester is also referred to as Bi Si bandit spy (Viscoat) V#700.
It is not that the non-liquid crystal polymerizable compound of the polyfunctional compound of difunctional's compound can be enumerated：Tetramethylolmethane Triacrylate, trimethylolpropane trimethacrylate, trihydroxy methyl EO addition triacrylate, phosphoric acid triacryl epoxide Ethyl ester, isocyanuric acid three (acryloyl group epoxide ethyl) ester, alkyl-modified dipentaerythritol triacrylate, EO modification three hydroxyl first Base propane triacrylate, expoxy propane (propylene oxide, PO) modification trimethylolpropane trimethacrylate, season penta Tetra-acrylate, alkyl-modified dipentaerythritol tetraacrylate, two-trimethylolpropane tetra-acrylate, two seasons penta Tetrol six acrylate, dipentaerythritol monohydroxypentaacryande, alkyl-modified Dipentaerythritol Pentaacrylate, Ji Wusi Alcohol trimethyl acrylic ester, trimethylol-propane trimethacrylate, trihydroxy methyl EO addition trimethyl acrylic ester, phosphoric acid Trimethacrylate acyl group epoxide ethyl ester, isocyanuric acid three (methylacryloyl epoxide ethyl) ester, alkyl-modified dipentaerythritol Trimethyl acrylic ester, EO modification trimethylol-propane trimethacrylate, PO modification trimethylol propane trimethyl propylene Acid esters, pentaerythritol tetramethylacrylate, alkyl-modified dipentaerythritol tetramethyl acrylate, two-trimethylolpropane Tetramethyl acrylate, dipentaerythritol hexamethacrylate, dipentaerythritol monohydroxy pentamethacrylates, alkyl change Property dipentaerythritol pentamethacrylates, Bi Si bandit spy (Viscoat) V#802 and Bi Si bandit spy (Viscoat) V#1000 etc.. Herein, Bi Si bandit spy (Viscoat) is registered trade mark.
Add the non-liquid crystal polymerizable compound that there is bis-phenol structure or block many structures in polymerizable liquid crystal compound Polymeric hardenability can be improved and induce the vertical orientated of liquid crystal polymer.
The polymerism fluorene derivative with the many structures of card can enumerate compound (α -1)～compound (α -3) etc..
[changing 26]
In formula (α -1)～formula (α -3), RαIt independently is hydrogen or methyl, s independently is 0～4 integer.
In order that polymerization speed optimization, the polymerizable liquid crystal compound of the present invention can contain polymerization initiator.Polymerization is drawn Sending out agent has optical free radical initiator etc..
Described optical free radical initiator can be enumerated：1- hydroxy-cyclohexyl-phenyl -one, 2- hydroxy-2-methyl -1- phenyl third Alkane -1- ketone, 1- hydroxycyclohexylphenylketone, 2,2- dimethoxy -1,2- diphenylethane -1- ketone, p-methoxyphenyl -2,4- Double (trichloromethyl) triazine, 2- (to butyl phenyl ether vinyl) -5- trichloromethyl -1,3,4- oxadiazoles, 9- phenylacridine, 9, 10- phenonaphthazine, benzophenone (benzophenone)/ meter Qi Le alcohol/ketone mixtures, six aryl bisglyoxalines/mercaptobenzimidazole mix Compound, 1- (4- isopropyl phenyl) -2- hydroxy-2-methyl propane -1- ketone, benzyl dimethyl ketal, 2- methyl isophthalic acid-[4- (first sulfur Base) phenyl] -2- morpholinopropane -1- ketone, 2,4- diethyl xanthone/ESCAROL 507 mixtures of methyl esters, two Benzophenone/methyl triethanol amine blends, Ai Dike Otto horse (Adeka optomer) N-1919, Ai Dike Cruise (Adeka cruise) NCI-831, Ai Dike Cruise (Adeka cruise) NCI-930, gorgeous good solid (Irgacure) 127, Gorgeous good solid (Irgacure) 369, gorgeous good solid (Irgacure) 379, gorgeous good solid (Irgacure) 500, gorgeous good solid (Irgacure) 754th, gorgeous good solid (Irgacure) 784, gorgeous good solid (Irgacure) 819, gorgeous good solid (Irgacure) 907, gorgeous good solid (Irgacure) 1300, gorgeous good solid (Irgacure) 1700, gorgeous good solid (Irgacure) 1800, gorgeous good solid (Irgacure) 1850th, gorgeous good solid (Irgacure) 1870, gorgeous good solid (Irgacure) 2959, gorgeous good solid (Irgacure) OXE01, gorgeous good solid (Irgacure) OXE02, moral firmly (Darocure) 4265, moral firmly (Darocure) MBF, moral firmly (Darocure) TPO Deng.Herein, firmly (Darocure) is registered trade mark for Ai Dike (Adeka), gorgeous good solid (Irgacure) and moral.
The weight that always contains of the optical free radical polymerization initiator in polymerizable liquid crystal compound is preferably polymerizable liquid crystal group The 0.0001～0.20 of the total content of the polyfunctional compound in compound, more preferably 0.001～0.15, and then preferably 0.01 ～0.15.
Sensitizer can be made an addition in polymerizable liquid crystal compound together with optical free radical polymerization initiator.Sensitizer can arrange Lift；Isopropyl thioxanthone, diethyl thioxanthone, ethyl -4- dimethyl aminobenzoate, 2- ethylhexyl -4- diformazan Base Aminobenzoate etc..
Chain-transferring agent in polymerizable liquid crystal compound adjust gained the response rate of the liquid crystal polymer of not belt substrate and Polymeric chain length in the liquid crystal polymer of not belt substrate of gained.
The amount increase of described chain-transferring agent can make described response rate decline.The amount increasing described chain-transferring agent can make described gathering Fit chain length reduces.
For playing the aspect of described effect, chain-transferring agent is preferably thiol derivative and styrene dimer syntaxy Thing.
Thiol derivative has mono-functional's thiol derivative and multi-functional thiol derivative.
Mono-functional's thiol derivative can be enumerated：Dodecyl mercaptans, 2- ethylhexyl-(3- sulfydryl) propionic ester etc..Many officials Can enumerate property thiol derivative：Trimethylolpropane tris (3-thiopropionate), tetramethylolmethane four (3-thiopropionate), 1, 4- double (3- sulfydryl bytyry epoxide) butane, tetramethylolmethane four (3- mercaptobutylate), 1,3,5- tri- (3- mercaptobutyl epoxide second Base) -1,3,5-triazines -2,4,6 (1H, 3H, 5H)-triketones etc..
Described styrene dimer tethers transfer agent can be enumerated：2,4- diphenyl -4-methyl-1-pentene, 2,4- diphenyl - 1-butylene etc..
To in polymerizable liquid crystal compound, interpolation polymerization preventing agent can prevent the gathering during preservation of polymerizable liquid crystal compound Run the beginning jointly.Polymerization preventing agent can be enumerated：(1) as having 2,5- bis- (tert-butyl group) hydroxy-methylbenzene of nitroso compound, right Benzodiazepiness, methylene blue, diphenyl picric acid hydrazides, phenothiazine, N, N- dimethyl -4- nitrosoaniline etc. and (2) conduct The O-hydroxyl-diphenyl ketone of benzothiazine derivative, 2H-1,3- benzothiazine -2,4 (3H) diketone etc..
Add polymerization Inhibitorses can suppress by the free radical in polymerizable liquid crystal compound in polymerizable liquid crystal compound The polyreaction producing in caused polymerizable liquid crystal compound.The interpolation of polymerization Inhibitorses can make polymerizable liquid crystal combine The keeping quality of thing improves.
Described polymerization Inhibitorses can be enumerated：(1) phenol antioxidant, (2) sulfur system antioxidant, (3) phosphate antioxidation Agent etc..
Adding UV absorbent in polymerizable liquid crystal compound can make the weatherability of polymerizable liquid crystal compound improve.
Described UV absorbent can be enumerated：Supreme Being slave refined (Tinuvin) PS, Supreme Being slave refined (Tinuvin) P, Supreme Being slave are refined (Tinuvin) refined (Tinuvin) 109 of 99-2, Supreme Being slave, refined (Tinuvin) 213 of Supreme Being slave, refined (Tinuvin) 234 of Supreme Being slave, Supreme Being slave are refined (Tinuvin) 326, refined (Tinuvin) 328 of Supreme Being slave, refined (Tinuvin) 329 of Supreme Being slave, Supreme Being slave refined (Tinuvin) 384-2, Supreme Being slave Refined (Tinuvin) 571, refined (Tinuvin) 900 of Supreme Being slave, refined (Tinuvin) 928 of Supreme Being slave, refined (Tinuvin) 1130 of Supreme Being slave, Supreme Being slave Refined (Tinuvin) 400, refined (Tinuvin) 405 of Supreme Being slave, refined (Tinuvin) 460 of Supreme Being slave, refined (Tinuvin) 479 of Supreme Being slave, Supreme Being slave Refined (Tinuvin) 5236, Ai Di Coase tower cloth (Adekastab) LA-32, Ai Di Coase tower cloth (Adekastab) LA-34, Chinese mugwort Enlightening Coase tower cloth (Adekastab) LA-36, Ai Di Coase tower cloth (Adekastab) LA-31, Ai Di Coase tower cloth (Adekastab) 1413, Ai Di Coase tower cloth (Adekastab) LA-51 etc..Herein, Supreme Being slave refined (Tinuvin) and Ai Di Coase Tower cloth (Adekastab) is registered trade mark.
Adding light stabilizer in polymerizable liquid crystal compound can make the weatherability of polymerizable liquid crystal compound improve.
Described light stabilizer can be enumerated：Supreme Being slave refined (Tinuvin) 111FDL, refined (Tinuvin) 123 of Supreme Being slave, Supreme Being slave are refined (Tinuvin) 144, refined (Tinuvin) 152 of Supreme Being slave, refined (Tinuvin) 292 of Supreme Being slave, refined (Tinuvin) 622 of Supreme Being slave, Supreme Being slave are refined (Tinuvin) 770, refined (Tinuvin) 765 of Supreme Being slave, refined (Tinuvin) 780 of Supreme Being slave, refined (Tinuvin) 905 of Supreme Being slave, Supreme Being slave are refined (Tinuvin) 5100, refined (Tinuvin) 5050 of Supreme Being slave, refined (Tinuvin) 5060 of Supreme Being slave, refined (Tinuvin) 5151 of Supreme Being slave, neat Ma Subu (Chimassorb) 119FL, neat Ma Subu (Chimassorb) 944FL, neat Ma Subu (Chimassorb) 944LD, Ai Di Coase tower cloth (Adekastab) LA-52, Ai Di Coase tower cloth (Adekastab) LA-57, Ai Di Coase tower cloth (Adekastab) LA-62, Ai Di Coase tower cloth (Adekastab) LA-67, Ai Di Coase tower cloth (Adekastab) LA-63P, Ai Di Coase tower cloth (Adekastab) LA-68LD, Ai Di Coase tower cloth (Adekastab) LA-77, Ai Di Coase tower cloth (Adekastab) Xin Subu that LA-82, Ai Di Coase tower cloth (Adekastab) LA-87, cyanogen spy (Cytec) company manufacture (Cyasorb) Gourde(G) Lai Te (Goodrite) UV-3034 of UV-3346 and Goodrich (Goodrich) company etc..Herein, Supreme Being slave refined (Tinuvin), neat Ma Subu (Chimassorb) and Ai Di Coase tower cloth (Adekastab) are registered trade mark.
Adding antioxidant in polymerizable liquid crystal compound can make the weatherability of polymerizable liquid crystal compound improve.
Described antioxidant can be enumerated：Ai Di Coase tower cloth (Adekastab) AO-20, AO-30, AO-40, AO-50, AO- 60th, AO-80, Si Milaize (Sumilizer) BHT, Si Milaize (Sumilizer) BBM-S and Si Milaize (Sumilizer) GA-80, easy fine jade Northey (Irganox) 1076, easy fine jade Northey (Irganox) 1010, easy fine jade Northey (Irganox) 3114, Yi Lu Northey (Irganox) 245 etc..Herein, Ai Di Coase tower cloth (Adekastab), Si Milaize (Sumilizer) and easy fine jade Northey (Irganox) it is registered trade mark.
Add in polymerizable liquid crystal compound silane coupler can improve substrate and not belt substrate liquid crystal polymer it Between adhesion.
Described silane coupler can be enumerated：Vinyl trialkyl oxysilane, 3- NCO propyl-triethoxysilicane, N- (2- amino-ethyl) 3- aminopropyltrialkoxy silanes, N- (1,3- dimethylbutylene) -3- (trialkoxy silane base) - 1- propane amine, 3- glycidyloxypropyl silane, 3- chlorine trialkoxy silane, 3- acryloxypropyl front three TMOS, 3- methacryloxypropyl trialkoxy silane etc..In addition, adding institute in polymerizable liquid crystal compound State the alkoxysilane group in silane coupler be substituted by more than one methyl silane coupler also can improve described Adhesion.
In order to easily be coated, add solvent preferably in polymerizable liquid crystal compound.
The composition of solvent can be enumerated：Ester, amide based compound, alcohol, ether, glycol monoalkyl ether, aromatic hydrocarbon, halogenation fragrance Race's hydrocarbon, aliphatic hydrocarbon, halogenated aliphatic hydrocarbons, ester ring type hydrocarbon, ketone, acetic acid ester series solvent etc..
So-called amide based compound refers to the compound of composition having amide groups and becoming solvent.So-called acetass system is molten Agent refers to the compound of composition having acetic acid ester structure and becoming solvent.
Described ester can be enumerated：Alkyl acetate, Trifluoroacetic Acid Ethyl Ester, alkyl propionates, alkyl butyrate, malonic acid dioxane Base ester, glycol acid alkyl ester, lactic acid alkyl ester, acetin, gamma-butyrolacton, gamma-valerolactone etc..
" alkyl acetate " described herein can be enumerated：Methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, second Acid butyl ester, acetic acid 3- methoxybutyl, isobutyl acetate, pentyl acetate, isoamyl acetate etc.." propanoic acid alkyl described herein Ester " can be enumerated：Methyl propionate, 3- methoxy methyl propionate, ethyl propionate, propyl propionate, butyl propionate etc..Described herein " alkyl butyrate " can be enumerated：Methyl butyrate, ethyl n-butyrate., butyl butyrate, isobutyl isobutyrate (IBIB), propyl butyrate etc..Described herein " dialkyl malonate " diethyl malonate etc. can be enumerated." glycol acid alkyl ester " described herein can enumerate two alkyd first Ester, two ethyl glycolates etc.." lactic acid alkyl ester " described herein can be enumerated：Methyl lactate, ethyl lactate, isopropyl lactate, breast Sour n-propyl, butyl lactate, lactic acid Octyl Nitrite etc..
Described amide based compound can be enumerated：METHYLPYRROLIDONE, N,N-dimethylacetamide, N- methyl propionyl Amine, DMF, N, N- diethylformamide, N, N- diethyl acetamide, N,N-dimethylacetamide dimethyl Acetal, N- methyl caprolactam, methylimidazole alkanone etc..
Described alcohol can be enumerated：Methanol, ethanol, 1- propanol, 2- propanol, 1- methoxy-2-propanol, the tert-butyl alcohol, sec-butyl alcohol, fourth Alcohol, 2-ethyl butanol, hexanol, n-heptanol, n-octyl alcohol, DODECANOL, 1-, ethyl hexanol, 3,5,5- trimethyl hexanols, positive penta Alcohol, hexafluoro -2- propanol, glycerol, ethylene glycol, diethylene glycol, triethylene glycol, TEG, propylene glycol, dipropylene glycol, 3 third Glycol, hexanediol, 1,3 butylene glycol, BDO, 2,3-butanediol, 1,5-PD, 2,4- pentanediol, 2,5- oneself two Alcohol, 3- methyl -3- methoxybutanol, Hexalin, methyl cyclohexanol etc..
Described ether can be enumerated：Glycol dimethyl ether, diethylene glycol dimethyl ether, double (2- propyl group) ether, Isosorbide-5-Nitrae-dioxanes, tetrahydrochysene Furan (tetrahydrofuran, THF) etc..
Described glycol monoalkyl ether can be enumerated：Ethylene glycol monoalkyl ether, diethylene glycol monoalky lether, triethylene glycol monoalkyl Ether, propylene-glycol monoalky lether, dipropylene glycol monoalkylether, ethylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate Ester, triethylene glycol monoalkyl ether acetate, propylene-glycol monoalky lether acetass, dipropylene glycol monoalkylether acetass, diethyl two Alcohol MEE etc..
" ethylene glycol monoalkyl ether " described herein can be enumerated：Glycol monoethyl ether, ethylene glycol monobutyl ether etc..Described herein " diethylene glycol monoalky lether " diethylene glycol monoethyl ether etc. can be enumerated." propylene-glycol monoalky lether " described herein can enumerate third Glycol monobutyl ether etc.." dipropylene glycol monoalkylether " described herein can enumerate dipropylene glycol monomethyl ether etc.." second described herein Glycol monoalkyl ether acetass " can enumerate ethylene glycol monomethyl ether acetate etc.." diethylene glycol monoalkyl ether acetate described herein Ester " can enumerate diethylene glycol monoethyl ether acetic acid esters etc.." propylene-glycol monoalky lether acetass " described herein can be enumerated：Propylene glycol Methyl ether acetate, propylene glycol monoethyl ether acetate and propylene glycol monobutyl ether acetass etc.." dipropylene glycol list alkane described herein Base ether acetic acid ester " can enumerate dipropylene glycol monomethyl ether acetass etc..
Described aromatic hydrocarbon can be enumerated：Benzene,toluene,xylene, sym-trimethylbenzene., ethylo benzene, diethylbenzene, cumene, N-propylbenzene, tert-butyl benzene, sec-butylbenzene, n-butylbenzene, naphthane.
Described halogenated aromatic hydrocarbon can enumerate chlorobenzene etc..Described aliphatic hydrocarbon can enumerate hexane, heptane etc..Halogenated aliphatic Hydrocarbon can be enumerated：Chloroform, dichloromethane, carbon tetrachloride, dichloroethanes, trichloro ethylene, tetrachloroethylene etc..Ester ring type hydrocarbon can enumerate ring Hexane, decahydronaphthalene etc..
Described ketone can be enumerated：Acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), Ketohexamethylene, Ketocyclopentane, methyl propyl ketone etc..
Acetic acid ester series solvent can be enumerated：Ethylene glycol monomethyl ether acetate, propylene glycol methyl ether acetate, dihydroxypropane single-ether Acetass, methyl acetoacetate, acetic acid 1- methoxyl group -2- propyl ester etc..
With regard to the viewpoint of the intermiscibility of polymerizable liquid crystal compound for, the solvent in polymerizable liquid crystal compound is preferably 30 weight %～96 weight %, more preferably 50 weight %～90 weight %, and then preferably 60 weight %～80 weight %.
The liquid crystal polymer of the present invention can contain there is optically active compound.Multiple with having optically active compound The liquid crystal polymer of combination shows twisted-oriented.Described liquid crystal polymer can be used as in the wavelength region of 300nm～2000nm Choice reflective film and minus C plate (Negative C plate).
There is optically active compound can enumerate：There is asymmetric carbon compound, there is binaphthyl structure and helicene knot The axle asymmetric compound of structure etc. and there is face asymmetric compound of ring sweet smell structure etc. etc..Just by between the spiral of twisted-oriented For immobilized viewpoint, described in the case of optically active compound that has be preferably polymerizable compound.
The liquid crystal polymer of the present invention can contain dichroism pigment.Can use with the liquid crystal polymer of dichroism pigment Composite Make absorption-type polaroid.
Dichroism pigment is preferably has maximum absorption ripple elder in the range of 300nm～700nm.Dichroism pigment can Using acridine pigment, oxazines pigment, anthocyanidin, naphthalene pigment, azopigment, anthraquinone pigment etc..Azopigment can be enumerated：Single even Nitrogen pigment, bisazo pigment, trisazo- pigment, four azopigments, stilbene azopigment etc..
The liquid crystal polymer of the present invention can contain fluorochrome.Can be used as partially with the liquid crystal polymer of fluorochrome Composite Shake light emitting-type film and wavelength converting film.
Substrate
The material of substrate can be enumerated：Glass, plastics, metal etc..Slit-shaped can be implemented to described glass or metallic surface Processing.With regard to described plastics, the surface treatment such as prolonged treatment and hydrophilicity-imparting treatment and silicic acid anhydride can be implemented.
The substrate of described glass has alkali glass, pyrex, flint glass (flint glass) etc..
The substrate of described plastics can be enumerated：Polyimides, polyamidoimide, polyamide, Polyetherimide, polyethers ether Ketone, polyether-ketone, polyketone sulfide, polyether sulfone, polysulfones, polyphenylene sulfide, polyphenylene oxide, polyethylene terephthalate, poly- terephthaldehyde Sour fourth diester, PEN, polyacetals, Merlon, polyarylate, acrylic resin, polyvinyl alcohol, polypropylene, Cellulose, tri acetyl cellulose, the partly-hydrolysed thing of tri acetyl cellulose, epoxy resin, phenol resin, cyclic olefine resin Deng.
Described cyclic olefine resin can enumerate norbornene resin, bicyclopentadiene system resin etc..
Sticky end coating (anchor coat) is formed on substrate and can improve the close of substrate and the liquid crystal polymer of not belt substrate Connecing property.Described sticky end coating comprises inorganic matters, Organic substance or its mixture.
The substrate of described metal can enumerate aluminum, ferrum, copper etc..
In the case that the parallel-oriented and liquid crystal polymer of tilted alignment is formed on substrate, coating polymerization on substrate Property liquid-crystal composition before, substrate is surface-treated, induction liquid crystal polymer orientation.Described surface treatment can be enumerated： A () is rubbed to substrate, (b) enters line tilt evaporation silicon oxide to substrate, and (c) arranges polymer envelope and to described to substrate Polymer envelope irradiates the methods such as polarisation ultraviolet (Ultra Violet, UV).
Following order is of described friction.
(1) friction cloth comprising the raw materials such as artificial silk, cotton, polyamide is wound in metallic roll etc.,
(2) described roller is made to contact with substrate,
(3) make described roller while rotation, so that described roller and substrate surface is moved parallel to, or described roller is solid Substrate is made to move in the state of fixed.
Also polymeric envelope can be arranged on substrate, described envelope is rubbed before friction.
By friction, defect of the orientation of liquid crystal polymer etc. can be prevented.
<Liquid crystal polymer>
The liquid crystal polymer with substrate of the present invention is obtained using below step.
(1) it is coated with polymerizable liquid crystal compound on substrate, so that it is dried and form film.
(2) in order that liquid crystal molecular orientation is identical state, film is remained the temperature of display liquid crystalline phase.
(3) make described polymerizable liquid crystal compound polymerization using methods such as light, heat, catalyst, obtain the liquid with substrate Brilliant polymer.
Thus, the immobilization under mesomorphic state of the polymerizable liquid crystal compound in film.
For the viewpoint of the uniformity of the thickness of the polymerizable liquid crystal compound on substrate, coating process is preferably：Rotation Coating, micro gravure coating method, gravure coating process, bar rubbing method, Dipcoat method, spraying coating method, meniscus coating (meniscus coat) method and mould rubbing method.
If in order to apply shear stress while being coated with polymerizable liquid crystal compound and using bar rubbing method, being not required to Carry out the friction of the liquid crystal polymer in order to parallel-oriented and tilted alignment to be formed on substrate.
In order to form the liquid crystal polymer of not belt substrate on substrate, the method for described drying is preferably heat treatment.Can profit Attached etc. carry out described heat treatment with blowing of hot plate, drying oven and warm air or hot blast.
For coating polymerizable liquid crystal compound, various rubbing methods can be used.
In order to obtain the liquid crystal polymer of the present invention, the method such as available electron beam, ultraviolet, luminous ray, infrared ray. In order to obtain liquid crystal polymer, the scope of the wavelength of the light being irradiated is 150nm～500nm.Preferably scope be 250nm～ 450nm, preferred scope is 300nm～400nm.
The light source of described light can utilize low pressure mercury lamp, high-pressure discharge lamp, short arc discharge lamp.Described low pressure mercury lamp can arrange Lift：Germicidal lamp, fluorescence chemical lamp, black light lamp etc..Described high-pressure discharge lamp can enumerate high-pressure mercury-vapor lamp, metal halide lamp etc.. Described short orphan's discharge lamp can be enumerated：Extra-high-pressure mercury vapour lamp, xenon lamp, mercury xenon etc..
According to calculated delay or calculated birefringence, determine the thickness of liquid crystal polymer.Liquid crystal polymer Thickness is preferably 0.05 μm～100 μm, more preferably 0.1 first～50 μm, and then preferably 0.5 first～20 μm.Liquid crystal polymer Haze value be preferably less than 2.0%, more preferably less than 1.0%.The transmitance of the visible region of liquid crystal polymer is preferred For more than 80%, more preferably more than 90%.
The raising of the birefringence of liquid crystal polymer can reduce the thickness of liquid crystal polymer.The subtracting of the thickness of liquid crystal polymer I haven't seen you for ages improves the optical characteristics of haze value, transmitance etc..Accordingly, it would be desirable to the raising of the birefringence of liquid crystal polymer.
Liquid crystal polymer is configured in the inside and outside of the liquid crystal cells of liquid crystal display cells.Liquid crystal caused by thermal history gathers The variation of fit delay is few and few to the impurity of liquid crystal dissolution from liquid crystal polymer, and therefore liquid crystal polymer is configured in liquid The inside of brilliant unit.
Polaroid is formed liquid crystal polymer as substrate, thus can manufacture the polarization with functions such as optical compensations Piece.For example, the liquid crystal polymer with the delay of 1/4 wavelength plate is combined with polaroid, circular polarizing disk can be manufactured.
Described polaroid can enumerate absorption-type polaroid and the wiregrating (wire grid) of adulterate iodine or dichroism pigment The reflection type polarizers such as polaroid.
In organic el display, for the purpose of preventing external light reflection, and comprising 1/4 wavelength plate and polarization depending on recognizing side use The circular polarizing disk of piece.In order to show the total wavelength to visibility region carry out effectively antireflecting function it is necessary to 1/4 wavelength The wavelength dispersion characteristics of plate are controlled.
In order to improve the visibility such as mottle or angle of visual field characteristic, liquid crystal polymer is used as 1/4 wavelength plate or 1/2 wavelength plate Wavelength dispersion characteristics during equiphase difference plate are preferably Re450nm/Re550nm≤1.05.In addition, in order to set for green Most preferably postpone, and the angle of visual field characteristic of blueness does not deteriorate, wavelength dispersion characteristics of liquid crystal polymer and then preferably For 0.75≤Re450nm/Re550nm≤1.05.
In addition, most preferably postponing for green to set, and the angle of visual field characteristic of redness does not deteriorate, The wavelength dispersion characteristics of liquid crystal polymer and then preferably Re650nm/Re550nm≥1.00.
[embodiment]
The present invention is not only restricted in the disclosed embodiments.
In embodiments of the invention, " Al2O3- KL " refers to the immobilized fluorine made using the method described in this specification Change the aluminium oxide of potassium.
In embodiments of the invention, " DCC " refers to 1,3- dicyclohexylcarbodiimide.
In embodiments of the invention, " DMAP " refers to 4-dimethylaminopyridine.
In embodiments of the invention, " pTSA " refers to p-methyl benzenesulfonic acid.
In embodiments of the invention, " IPA " refers to 2- propanol.
In embodiments of the invention, it is gorgeous good solid that " Irg-907 " refers to that Japanese BASF (BASF Japan) (stock) manufactures (Irgacure) (trade mark) 907 (Irg-907).
In embodiments of the invention, " NCI-930 " refers to the Ai Dike Cruise that Ai Dike (ADEKA) (stock) manufactures (Adeka cruise) (trade mark) NCI-930.
In embodiments of the invention, " FTX-218 " refers to the Fu Jiete (Ftergent) that Ni Ousi (Neos) (stock) manufactures (trade mark) FTX-218.
In embodiments of the invention, " Di Gaofuluo (TEGOFlow) 370 " refers to that Japan wins wound (Evonik Japan) The Di Gaofuluo (TEGOFlow) (trade mark) 370 of (stock).
In embodiments of the invention, " Po Lifuluo (POLYFLOW) No.75 " refers to the Po Lifu of common prosperity society chemistry (stock) Lip river (POLYFLOW) (trade mark) No.75.
In embodiments of the invention, " PIA-5370 " refers to the vertical news aligner (LIXON Aligner) that JNC (stock) manufactures PIA-5370.
<Polymerizing condition>
Film irradiation light is made with the extra-high-pressure mercury vapour lamp (oxtail using 250W for the light source of polymerizable liquid crystal compound polymerization (Ushio) Motor Corporation manufactures, multiple light courcess lamp (Multi-Light) -250).Polymerization is to enter under room temperature in a nitrogen environment OK.Irradiation light is 30mW/em2(365nm), irradiation time is 30 seconds.
<The structural confirmation of compound>
The structure of compound is the mensure of the proton NMR of the 500MHz of the DRX-500 being manufactured by Brooker (Bruker) And confirm.The unit of described numerical value is ppm.S represents unimodal, and d represents bimodal, and t represents three peaks, and m represents multimodal.
<Phase transition temperature>
Sample is placed on the hot plate of melting point apparatus, measures transition temperature using polarizing microscope.While with 3 DEG C/ The speed of min heats up while carrying out the mensure of transition temperature.When representing transition temperature, crystalline phase, nematic phase, disk like phase, each It is expressed as " C ", " N ", " S ", " I " to same sex liquid respectively.Numeral between respective phase refer to degree Celsius come to represent turn Temperature." C 50 N 63 I " represent at 50 DEG C from crystalline transition be nematic phase, at 63 DEG C from nematic Phase for each to Same sex liquid.The liquid crystalline phase of monotropic (monotropic) is represented in parantheses.
<Observational technique by visual observation>
Between the two panels polaroid being configured to cross Nicols, clamping is formed with the substrate of phase retardation film to observe.Make institute State substrate to rotate in the horizontal plane, confirm the state of light and shade.Polarizing microscope observation is carried out to the substrate being formed with phase retardation film, Confirm the presence or absence of orientation defect.When there is light transmission in the dark state and visible position or cannot simultaneously confirm bright state And during dark state, it is set to " there is orientation defect ".When being not " there is orientation defect ", it is set to " there is not orientation defect ".
<Film thickness measuring>
The glass substrate that the part of liquid crystal polymer is come with liquid crystal film cuts out.Measure device by the use of as fine shape Alpha's step instrument (Alpha Step) IQ that manufactures of KLA-Tencor (KLA TENCOR) (stock) measuring the jump of described part.
<Mensure using polarization analyses device>
Postponing (retardation) is Austria Lip river (OPIPRO) polarization analyses being manufactured using masterstroke (Shintee) (stock) Device measures.So that the angle of incidence of light is reduced from 90 ° with respect to the surface of liquid crystal polymer while to postpone into Row measurement.The wavelength of the light used in measurement is 450nm, 550nm and 650nm.
<The evaluation of birefringence Δ n>
Calculate the birefringence Δ n under each wavelength using delay/thickness.
<The evaluation of wavelength dispersion characteristics>
In order to evaluate wavelength dispersion characteristics, and obtain Re450nm/Re550nmAnd Re650nm/Re550nm.
<Pencil hardness>
The hardness of liquid crystal polymer is in addition to beyond the part described in this specification, using JIS standard " JIS-K-5400 8.4 pencil tests " are measuring.The pencil Uni (trade mark) being manufactured using Rhizoma Sparganii pencil (stock).Manufactured using lucky light essence machine Pencil hardometer C-221.Core using the pencil fixing with 45 ° of angle streaks liquid crystal polymer.Measure liquid crystal polymer The middle hardness producing the scar core of pencil the lightest.
<The evaluation of orientation>
The thickness of the glass using as the glass substrate of the alignment films finishing with friction treatment is 1.1mm.Vertical news Aligner (LIXON Aligner) is the vertical news school that polyamic acid is the low tilt angle polyamic acid towards horizontal alignment pattern Quasi- device PIA-5370.
The glass substrate of the alignment films finishing with friction treatment is to be made using following steps.
(1) polyamic acid is spun on to make film on glass.
(2) solvent is removed from described film on 80 DEG C of hot plate.
(3) described film is calcined 30 minutes in 230 DEG C of baking oven.
(4) using rayon cloth, friction treatment is carried out to described film.
<The synthesis of the aluminium oxide of immobilized potassium fluoride>
The column chromatography (Column Chromatography) of the potassium fluoride of 20g, 30g is added with neutral alumina To the water of 200mL, it is stirred at room temperature 1 hour.Under reduced pressure water is distilled and remove.The crystallization of gained is forged at 110 DEG C Burn 3 hours, be derived from the aluminium oxide of immobilized potassium fluoride.
[embodiment 1]
To synthesize compound (1-3-1-1) in the following order.
[changing 27]
The aluminium oxide of 4, the 7- dimethoxy -1- indone of 10.0g, the immobilized potassium fluoride of 40.0g is added to the second of 100mL In nitrile, in a nitrogen environment, it is stirred under room temperature.It is added to the Carbon bisulfide of 4.8g, be stirred at room temperature 1 hour. Thereafter, add the glycol dibromide of 10.3g, and then be stirred at room temperature 16 hours.Water and dichloromethane is added in reactant liquor Contaminant filter is separated by alkane using kieselguhr.Filtrate is extracted, utilizes water to organic layer is carried out, and utilize Anhydrous magnesium sulfate is dried.Equal solvent distillation under reduced pressure removes, and using column chromatography to carry out purification to residue, goes forward side by side Row drying under reduced pressure, is derived from the product of 6.7g, and is named as compound (ex-1).
Herein, the packing material of column chromatography is silica dioxide gel, and eluat is toluene-ethyl acetate mixture v/ V=2/1.
The compound (ex-1) of 6.7g is added to the dichloromethane of 133mL, in a nitrogen environment, at -78 DEG C Cooling is while stir.The Boron tribromide of Deca 12.5g thereto.After Deca, stir 1 hour at -78 DEG C, thereafter, in room temperature Lower stirring 16 hours.Reactant liquor is injected into carry out quenching in frozen water, and by precipitate filtration separation.Utilize water to crystallization Fully cleaned, and carried out drying under reduced pressure, be derived from the product of 5.5g, and be named as compound (ex-2).
The triethylamine of the trans -4- hydroxy cyclohexane carboxylic of 25.0g and 26.3g is added to the N of 125mL, N- dimethyl In Methanamide (dimethylformamide, DMF), in a nitrogen environment, less than 10 DEG C cool down and stir.Thereto It is slowly added dropwise the chloromethyl methyl ether of 14.7g.After Deca, it is stirred at room temperature 8 hours.Ethyl acetate and water is added to come to organic layer Extracted, using saturated sodium bicarbonate water and water, organic layer is carried out, and is dried using anhydrous magnesium sulfate.? Under decompression, ethyl acetate is distilled and remove, using column chromatography, purification is carried out to residue, and carry out drying under reduced pressure, thus obtain Obtain the product of 25.2g, and be named as compound (ex-3).Herein, the packing material of column chromatography is silica dioxide gel, molten Chaotropic is toluene-ethyl acetate mixture v/v=2/1.
By the compound (ex-3) of 25.2g, the compound (ex-4) of 42.9g and the 4-dimethylaminopyridine (4- of 3.3g Dimethylaminopyridine, DMAP) add to the dichloromethane of 430mL, cool down in a nitrogen environment and stir Mix.Thereto Deca make 29.0g 1,3- dicyclohexylcarbodiimide (1,3-dicyclohexylcarbodiimide, DCC the 60mL dichloromethane solution) dissolving.After Deca, it is stirred at room temperature 16 hours.The precipitate filtration separation that will separate out, Using saturated sodium bicarbonate water and water, organic layer is carried out, and is dried using anhydrous magnesium sulfate.Under reduced pressure will Dichloromethane distillation removes, and carries out purification using column chromatography to residue, and carries out drying under reduced pressure.By the residue of gained and The p-methyl benzenesulfonic acid (p-toluenesulfonic acid, pTSA) of 2.1g adds mixing of the IPA of THF and 55mL to 110mL Close in solution, heated and stirred 8 hours at 40 DEG C.Ethyl acetate and water is added organic layer is extracted, using saturation food Saline organic layer is carried out, and is dried using anhydrous magnesium sulfate.Under reduced pressure solvent is distilled and remove, and utilize The mixed solution of ethyl acetate and heptane residue is recrystallized, and is derived from the product of 31.8g, and is named as compound (ex-5).Herein, the packing material of column chromatography is silica dioxide gel, and eluat is toluene-ethyl acetate mixture v/v =2/1.
The DMAP of the compound (ex-2) of 1.5g, the compound (ex-5) of 5.0g and 0.3g is added to the dichloro of 50mL In methane, cool down in a nitrogen environment and stir.Deca makes the dichloromethane of the 5mL that the DCC of 2.4g dissolves thereto Solution.After Deca, it is stirred at room temperature 16 hours.The precipitate filtration separation that will separate out, utilizes water to organic layer is carried out clearly Wash, and be dried using anhydrous magnesium sulfate.Under reduced pressure dichloromethane is distilled and remove, using column chromatography come to residue Carry out purification, and recrystallized using methanol, be derived from the compound (1-3-1-1) of 4.6g.Herein, column chromatography Packing material is silica dioxide gel, and eluat is toluene-ethyl acetate mixture v/v=8/1.
The phase transition temperature of compound (1-3-1-1) and NMR assay value are as described below.
Phase transition temperature：C 122 I
1H-NMR(CDCl3；δppm)：7.24 (d, 1H), 7.11 (d, 4H), 6.99 (d, 1H), 6.82 (d, 4H), 6.40 (d, 2H), 6.16-6.08 (m, 2H), 5.82 (d, 2H), 4.82-4.74 (m, 2H), 4.17 (t, 4H), 3.94 (t, 4H), 3.54 (t, 2H), 3.49 (s, 2H), 3.42 (t, 2H), 2.89 (t, 4H), 2.77-2.69 (m, 1H), 2.66-2.56 (m, 5H), 2.37- 2.28 (m, 2H), 2.26-2.18 (m, 2H), 2.13-2.05 (m, 4H), 1.84-1.67 (m, 12H), 1.55-1.41 (m, 12H).
[embodiment 2]
The glycol dibromide of embodiment 1 is changed to 1,3- dibromopropane, in addition, using described in embodiment 1 Method synthesizing compound (1-3-2-1).
[changing 28]
The phase transition temperature of compound (1-3-2-1) and NMR assay value are as described below.
Phase transition temperature：C 126 I
1H-NMR(CDCl3；δppm)：7.21 (d, 1H), 7.11 (d, 4H), 6.97 (d, 1H）, 6.82 (d, 4H), 6.40 (d, 2H), 6.16-6.08 (m, 2H), 5.82 (d, 2H), 4.82-4.74 (m, 2H), 4.17 (t, 4H), 3.93 (t, 4H), 3.46 (s, 2H), 3.07 (t, 2H), 3.00 (t, 2H), 2.89 (t, 4H), 2.76-2.68 (m, 1H), 2.65-2.55 (m, 5H), 2.36- 2.17 (m, 6H), 2.12-2.04 (m, 4H), 1.83-1.67 (m, 12H), 1.56-1.49 (m, 12H).
[embodiment 3]
To synthesize compound (1-2-1-1) in the following order.
[changing 29]
Al by 4,7- dimethoxy -1- indone skill 24g of 6.0g2O3- KF adds to the acetonitrile of 60mL, in nitrogen ring Under border, it is stirred under room temperature.It is added to the Carbon bisulfide of 3.3g, be stirred at room temperature 1 hour.Thereafter, add 9.8g Iodide, and then be stirred at room temperature 16 hours.Add water and ethyl acetate in reactant liquor, will be miscellaneous using kieselguhr Matter filtration separation.Filtrate is extracted, utilizes water to organic layer is carried out, and be dried using anhydrous magnesium sulfate. Under reduced pressure solvent is distilled and remove, using column chromatography, purification is carried out to residue, and carry out drying under reduced pressure, be derived from The product of 5.7g, and it is named as compound (ex-6).Herein, the packing material of column chromatography be silica dioxide gel, molten from Liquid is toluene-ethyl acetate mixture v/v=4/1.
The compound (ex-6) of 5.7g is added to the dichloromethane of 114mL, in a nitrogen environment, at -78 DEG C Cooling is while stir.The Boron tribromide of Deca 10.6g thereto.After Deca, stir 1 hour at -78 DEG C, thereafter, in room temperature Lower stirring 16 hours.Reactant liquor is injected into carry out quenching in frozen water, adds ethyl acetate to be extracted.Using unsaturated carbonate Hydrogen sodium water, is then utilized water to organic layer is carried out, and is dried using anhydrous magnesium sulfate.Under reduced pressure solvent is steamed Evaporate and remove, be derived from the product of 5.0g, and be named as compound (ex-7).
The DMAP of the compound (ex-8) of 1.5g, the compound (ex-5) of 5.0g and 0.3g is added to the dichloro of 50mL In methane, cool down in a nitrogen environment and stir.Deca makes the dichloromethane of the 5mL that the DCC of 24g dissolves molten thereto Liquid.After Deca, it is stirred at room temperature 16 hours.The precipitate filtration separation that will separate out, utilizes water to organic layer is carried out, And be dried using anhydrous magnesium sulfate.Under reduced pressure dichloromethane is distilled and remove, using column chromatography, residue is entered Row purification, and recrystallized using methanol, it is derived from the compound (1-2-1-1) of 3.3g.Herein, the filling out of column chromatography Filling material is silica dioxide gel, and eluat is toluene-ethyl acetate mixture v/v=8/1.
The phase transition temperature of compound (1-2-1-1) and NMR assay value are as described below.
Phase transition temperature：C 103(N 84)I
1H-NMR(CDCl3；δppm)：7.25 (d, 1H), 7.11 (d, 4H), 6.98 (d, 1H), 6.82 (d, 4H), 6.40 (d, 2H), 6.16-6.08 (m, 2H), 5.82 (d, 2H), 4.82-4.74 (m, 2H), 4.17 (t, 4H), 3.94 (t, 4H), 3.64 (s, 2H), 2.88 (t, 4H), 2.76-2.68 (m, 1H), 2.66-2.57 (m, 5H), 2.54 (s, 3H), 2.51 (s, 3H), 2.35- 2.28 (m, 2H), 2.25-2.18 (m, 2H), 2.13-2.04 (m, 4H), 1.84-1.67 (m, 12H), 1.56-1.41 (m, 12H).
[embodiment 4]
The iodide of embodiment 1 is changed to base in iodate, in addition, using the method described in embodiment 1 Lai Synthesis compound (1-2-2-1).
[changing 30]
The phase transition temperature of compound (1-2-2-1) and NMR assay value are as described below.
Phase transition temperature：C 78(N 52)I
1H-NMR(CDCl3；δppm)：7.23 (d, 1H), 7.11 (d, 4H), 6.97 (d, 1H), 6.82 (d, 4H), 6.40 (d, 2H), 6.16-6.08 (m, 2H), 5.82 (d, 2H), 4.83-4.74 (m, 2H), 4.17 (t, 4H), 3.93 (t, 4H), 3.64 (s, 2H), 3.03-2.95 (m, 4H), 2.89 (t, 4H), 2.77-2.69 (m, 1H), 2.67-2.57 (m, 5H), 2.35-2.28 (m, 2H), 2.25-2.18 (m, 2H), 2.13-2.04 (m, 4H), 1.84-1.63 (m, 16H), 1.56-1.41 (m, 12H), 1.05- 0.99 (m, 6H).
[embodiment 5]
To synthesize compound (1-1-1-1) in the following order.
[changing 31]
The benzaldehyde of 4, the 7- dimethoxy -1- indone of 3.0g and 1.7g is added to the ethanol of 24mL, in nitrogen ring Under border, less than 10 DEG C cool down while stirring.40 weight % sodium hydrate aqueous solutions of Deca 1.7mL thereto, in room temperature Lower stirring 16 hours.Add water by precipitate filtration separation in reactant liquor.Using ethanol, the crystallization of gained is carried out again Crystallization, is derived from the product of 4.0g, and is named as compound (ex-8).
The compound (ex-8) of 4.0g is added to the dichloromethane of 40mL, in a nitrogen environment, cold at -78 DEG C But while stirring.The BBr of Deca 7.9g thereto3.After Deca, stir 1 hour at -78 DEG C, thereafter, be stirred at room temperature 16 Hour.Reactant liquor is injected into carry out quenching in frozen water, adds ethyl acetate organic layer is extracted.Using saturated carbon Sour oxygen sodium water and water organic layer is carried out, and are dried using anhydrous magnesium sulfate.Under reduced pressure solvent distillation is gone Remove, and recrystallized using ethanol/heptane, be derived from 2.4g and be named as compound (ex-9).
The DMAP of the compound (ex-9) of 1.4g, the compound (ex-5) of 5.0g and 0.3g is added to the dichloromethane of 50mL In alkane, cool down in a nitrogen environment and stir.Deca makes the dichloromethane solution 5mL that the DCC of 2.4g dissolves thereto. After Deca, it is stirred at room temperature 16 hours.The precipitate filtration separation that will separate out, utilizes water to organic layer is carried out, and It is dried using anhydrous magnesium sulfate.Under reduced pressure dichloromethane is distilled and remove, using column chromatography, residue is carried out Purification, is recrystallized using methanol, is derived from the compound (1-1-1-1) of 3.0g.Herein, the filling material of column chromatography Expect for silica dioxide gel, eluat is toluene-ethyl acetate mixture v/v=8/1.
The phase transition temperature of compound (1-1-1-1) and NMR assay value are as described below.
Phase transition temperature：C 101(N 100)I
1H-NMR(CDCl3；δppm)：7.63-7.57 (m, 3H), 7.50-7.40 (m, 3H), 7.33 (d, 1H), 7.11 (d, 4H), 7.05 (d, 1H), 6.83 (d, 4H), 6.40 (d, 2H), 6.16-6.08 (m, 2H), 5.82 (d, 2H), 4.85-4.77 (m, 2H), 4.17 (t, 4H), 3.94 (t, 4H), 3.84 (s, 2H), 2.94-2.88 (m, 4H), 2.75-2.57 (m, 6H), 2.37- 2.30 (m, 2H), 2.28-2.21 (m, 2H), 2.15-2.08 (m, 4H), 1.88-1.68 (m, 12H), 1.55-1.41 (m, 12H).
[embodiment 6]
To synthesize compound (1-3-10-1) in the following order.
[changing 32]
The 60 weight % sodium hydrides of 5.5g are added to the toluene of 150mL, in a nitrogen environment, is stirred under room temperature Mix.The phosphoryl 3-acetic acid methyl ester (Phosphonoacetic acid trimethyl ester) of Deca 25.0g thereto, Stir 1 hour under room temperature.Thereafter, Deca makes the 2 ' of 19g, the toluene solution of the 40mL of 5 '-dimethoxy-acetophenone dissolving, is adding Stir 8 hours under hot reflux.Add saturated ammonium chloride solution and extracted in reactant liquor.Utilize water to organic layer is carried out Cleaning, and be dried using anhydrous magnesium sulfate.Under reduced pressure solvent is distilled and remove, and carry out drying under reduced pressure, be derived from The product of 17.3g, and it is named as compound (ex-10).
10 weight % palladium carbons of the compound (ex-10) of 17.3g, 1.2g are added to the ethanol of 300mL, using high pressure Kettle, stirs 24 hours under the hydrogen environment under 7MPa, under room temperature.Make reactant liquor pass through kieselguhr, under reduced pressure solvent is steamed Evaporate and remove.The water of the residue of gained, the sodium hydroxide of 4.9g and 72mL is added to the methanol of 72mL, under being heated to reflux Stirring 3 hours.Add the aqueous hydrochloric acid solution of 3N.Add toluene and extracted, utilize water to organic layer is carried out, and profit It is dried with anhydrous magnesium sulfate.Under reduced pressure solvent is distilled and remove, recrystallized using heptane, be derived from 14.8g Product, and be named as compound (ex-11).
The DMF of the compound (ex-11) of 14.8g and 0.1g is added to the toluene of 100mL, in a nitrogen environment, 60 It is stirred at DEG C.Deca thionyl chloride 9.4g thereto, stirs 4 hours at 60 DEG C.Thereafter, under reduced pressure by reactant liquor Solvent distillation removes, and obtains residue.The aluminum chloride of 9.2g is added to the dichloromethane of 180mL, in a nitrogen environment, 10 Cool down below DEG C while stirring.Deca makes the dichloromethane solution of the 50mL of described residue dissolving thereto.After Deca, Stir 24 hours under room temperature.Reactant liquor is injected into carry out quenching in frozen water, and is extracted.Using saturated sodium bicarbonate Water, is then utilized water to organic layer is carried out, and is dried using anhydrous magnesium sulfate.Under reduced pressure solvent distillation is gone Remove, using column chromatography, purification is carried out to residue, and carry out drying under reduced pressure, be derived from the product of 10.4g, and be named as Compound (ex-12).The packing material of column chromatography is silica dioxide gel, and eluat is toluene-ethyl acetate mixture V/v=3/1.
The compound (ex-12) of 10.4g is added to the DMF of 200mL, in a nitrogen environment, is stirred under room temperature. It is added to the 60 weight % sodium hydrides of 5.3g.And then the Carbon bisulfide of interpolation 4.8g, it is stirred at room temperature 1 hour.Thereafter, Add the glycol dibromide of 10.9g, and then be stirred at room temperature 1 hour.1N aqueous hydrochloric acid solution and second is added in reactant liquor Acetoacetic ester, and extracted.Utilize water to organic layer is carried out, and be dried using anhydrous magnesium sulfate.Under reduced pressure Solvent is distilled and removes, using column chromatography, purification is carried out to residue, and carry out drying under reduced pressure, be derived from 11.5g's Product, and it is named as compound (ex-13).The packing material of column chromatography is silica dioxide gel, and eluat is toluene-second Acetoacetic ester mixture v/v=4/1.
The compound (ex-13) of 11.5g is added to the dichloromethane of 115mL, in a nitrogen environment, -78 DEG C next Side cooling is while stir.The Boron tribromide of Deca 20.5g thereto.After Deca, stir 1 hour at -78 DEG C, thereafter, in room The lower stirring of temperature 16 hours.Reactant liquor is injected into carry out quenching in frozen water, and by precipitate filtration separation.Utilize water to knot Crystalline substance is fully cleaned, and carries out drying under reduced pressure, is derived from the product of 10.3g, and is named as compound (ex-14).
The DMAP of the compound (ex-14) of 1.5g, the compound (ex-5) of 5.0g and 0.3g is added to the dichloro of 50mL In methane, cool down in a nitrogen environment and stir.Deca makes the dichloromethane of the 5mL that the DCC of 2.4g dissolves thereto Solution.After Deca, it is stirred at room temperature 16 hours.The precipitate filtration separation that will separate out, utilizes water to organic layer is carried out clearly Wash, and be dried using anhydrous magnesium sulfate.Under reduced pressure dichloromethane is distilled and remove, using column chromatography come to residue Carry out purification, and recrystallized using methanol, be derived from the compound (1-3-10-1) of 3.7g.The filling of column chromatography Material is silica dioxide gel, and eluat is toluene-ethyl acetate mixture v/v=8/1.
The phase transition temperature of compound (1-3-10-1) and NMR assay value are as described below.
Phase transition temperature：C 137 I
1H-NMR(CDCl3；δppm)：7.23 (d, 1H), 7.11 (d, 4H), 6.99 (d, 1H), 6.82 (d, 4H), 6.40 (d, 2H), 6.16-6.08 (m, 2H), 5.82 (d, 2H), 4.82-4.74 (m, 2H), 4.17 (t, 4H), 3.94 (t, 4H), 3.80- 3.75 (m, 1H), 3.52-3.36 (m, 4H), 2.89 (t, 4H), 2.76-2.69 (m, 1H), 2.65-2.56 (m, 5H), 2.36- 2.18 (m, 4H), 2.13-2.04 (m, 4H), 1.84-1.68 (m, 12H), 1.55-1.41 (m, 12H).
[embodiment 7]
To synthesize compound (1-3-12-1) as follows.
[changing 33]
The Michaelis acid of 2, the 5- dimethoxy benzaldehyde of 27.7g and 24g is added to the water of 700mL, in nitrogen environment Under, stir 2 hours at 75 DEG C.Reactant liquor is placed cooling, and by precipitate filtration separation.Recrystallized using methanol, by This obtains the product of 31.0g, and is named as compound (ex-15).
(trifluoromethyl) trimethyl silane of the compound (ex-15), the sodium acetate of 12.6g and 21.9g of 30.0g is added Enter to the DMF of 150mL, in a nitrogen environment, stir 2 hours at 50 DEG C.Thereafter, add the concentrated hydrochloric acid of 7.5mL, in nitrogen ring Stir 1 hour under border, at 110 DEG C.Water and ethyl acetate are added to reactant liquor, and is extracted.Utilize water to organic Layer is carried out, and is dried using anhydrous magnesium sulfate.Under reduced pressure solvent is distilled and remove, tied again using heptane Crystalline substance, is derived from the product of 18.1g, and is named as compound (ex-16).
The DMF of the compound (ex-16) of 18.1g, 0.1g is added to the toluene of 100mL, in a nitrogen environment, 60 DEG C Under be stirred.The thionyl chloride of Deca 9.3g thereto, stirs 4 hours at 60 DEG C.Thereafter, under reduced pressure by reactant liquor Solvent distillation removes, and obtains residue.The aluminum chloride of 9.1g is added to the dichloromethane of 220mL, in a nitrogen environment, 10 Cool down below DEG C while stirring.Deca makes the dichloromethane solution 50mL of described residue dissolving thereto.After Deca, in room The lower stirring of temperature 24 hours.Reactant liquor is injected into carry out quenching in frozen water, and is extracted.Using saturated sodium bicarbonate water, Then utilize water to organic layer is carried out, and be dried using anhydrous magnesium sulfate.Under reduced pressure solvent is distilled and removes, Using column chromatography, purification is carried out to residue, and carry out drying under reduced pressure, be derived from the product of 7.0g, and be named as chemical combination Thing (ex-17).The packing material of column chromatography is silica dioxide gel, and eluat is toluene-ethyl acetate mixture v/v= 9/1.
The compound (ex-17) of 7.0g is added to the DMF of 30mL, in a nitrogen environment, is stirred under room temperature.To Wherein add the 60 weight % sodium hydrides of 2.3g, be stirred at room temperature 1 hour.And then the Carbon bisulfide of interpolation 2.3g, in room temperature Lower stirring 1 hour.Thereafter, add the glycol dibromide of 5.2g, and then be stirred at room temperature 1 hour.Add in reactant liquor 1N aqueous hydrochloric acid solution and ethyl acetate, and extracted.Utilize water to organic layer is carried out, and entered using anhydrous magnesium sulfate Row drying.Under reduced pressure solvent is distilled and removes, using column chromatography, purification is carried out to residue, and carry out drying under reduced pressure, It is derived from the product of 7.1g, and be named as compound (ex-18).The packing material of column chromatography is silica dioxide gel, Eluat is toluene-ethyl acetate mixture v/v=9/1.
The compound (ex-18) of 7.1g is added to the dichloromethane of 70mL, in a nitrogen environment, at -78 DEG C Cooling is while stir.The Boron tribromide of Deca 10.7g thereto.After Deca, stir 1 hour at -78 DEG C, thereafter, in room temperature Lower stirring 16 hours.Reactant liquor is injected into carry out quenching in frozen water, and by precipitate filtration separation.Utilize water to crystallization Fully cleaned, and carried out drying under reduced pressure, be derived from the product of 5.9g, and be named as compound (ex-19).
The DMAP of the compound (ex-19) of 1.9g, the compound (ex-5) of 5.0g and 0.3g is added to the dichloro of 50mL In methane, cool down in a nitrogen environment and stir.Deca makes the dichloromethane of the 5mL that the DCC of 2.4g dissolves thereto Solution.After Deca, it is stirred at room temperature 16 hours.The precipitate filtration separation that will separate out, utilizes water to organic layer is carried out clearly Wash, and be dried using anhydrous magnesium sulfate.Under reduced pressure dichloromethane is distilled and remove, using column chromatography come to residue Carry out purification, and recrystallized using methanol, be derived from the compound (1-3-12-1) of 3.8g.The filling of column chromatography Material is silica dioxide gel, and eluat is toluene-ethyl acetate mixture v/v=9/1.
The phase transition temperature of compound (1-3-12-1) and NMR assay value are as described below.
Phase transition temperature：C 150 I
1H-NMR(CDCl3；δppm)：7.30 (d, 1H), 7.14-7.09 (m, 5H), 6.81 (d, 4H), 6.40 (d, 2H), 6.16-6.08 (m, 2H), 5.81 (d, 2H), 4.82-4.74 (m, 2H), 4.52-4.46 (m, 1H), 4.17 (t, 4H), 3.94 (t, 4H), 3.57-3.50 (m, 3H), 3.33-3.26 (m, 1H), 2.89 (t, 4H), 2.76-2.68 (m, 1H), 2.62-2.56 (m, 5H), 2.34-2.27 (m, 2H), 2.25-2.16 (m, 2H), 2.12-2.05 (m, 4H), 1.84-1.68 (m, 12H), 1.55- 1.40 (m, 12H).
<The making of polymerizable liquid crystal compound>
[embodiment 8]
The compound (M2-7-1) of the composition as polymerizable liquid crystal compound described below, compound (M2-1-1), change Compound (M2-1-2) and the structure of compound (M1-24-1).
[changing 34]
In embodiments of the invention shown in table 1 and table 2 confirm polymerizable liquid crystal compound in compound with contain Amount." 0 " expression of table 1 and table 2 does not contain.
[table 1]
[comparative example 1]
The structure of the compound (C-1) of the composition as polymerizable liquid crystal compound described below.
[changing 35]
Herein, (C-1) synthesis order as described below.
[changing 36]
Compound (cex-1) is according to described in organic chemistry periodical (J.Org.Chem.) 69,2164-2177 (2004) Method and synthesize.
The Ketocyclopentane of the compound (cex-1) of 5.0g and 6.4g is added to the DMF of 50mL, in a nitrogen environment, 100 Stir 8 hours at DEG C.Place cooling, add ethyl acetate and water and extracted.Using 1N aqueous hydrochloric acid solution, then using full Organic layer is carried out with saline solution, and be dried using anhydrous magnesium sulfate.Under reduced pressure solvent is distilled and remove, profit With column chromatography, purification is carried out to residue, and carry out drying under reduced pressure, be derived from compound (cex-2) 1.2g.Tubing string color The packing material of spectrometry is silica dioxide gel, and eluat is toluene-methanol mixture v/v=10/1.
Compound (cex-3) is to synthesize according to the method described in Japanese Patent Laid-Open 2011-231098 publication.
The DMAP of the compound (cex-2) of 1.2g, the compound (cex-3) of 5.0g and 0.3g is added to the two of 50mL In chloromethanes, cool down in a nitrogen environment and stir.Deca makes the dichloromethane of the 5mL that the DCC of 2.4g dissolves thereto Alkane solution.After Deca, it is stirred at room temperature 16 hours.The precipitate filtration separation that will separate out, utilizes water to organic layer is carried out Cleaning, and be dried using anhydrous magnesium sulfate.Under reduced pressure dichloromethane is distilled and remove, using column chromatography come to residual Slag carries out purification, and is recrystallized using methanol, is derived from the compound (C-1) of 2.9g.
The packing material of column chromatography is silica dioxide gel, and eluat is toluene-ethyl acetate mixture v/v=9/ 1.
[table 2]
<The making of liquid crystal polymer>
[embodiment 9]
Make liquid crystal polymer (F-1) in the following order.
(1) pass through spin coating, liquid-crystal composition (S-1) is coated the glass substrate of the alignment films finishing with friction treatment On.
(2) use hot plate, described substrate is heated 2 minutes at 80 DEG C～100 DEG C.
(3) then, using hot plate, described substrate is kept 1 minute at 50 DEG C～60 DEG C.
(4) then, described substrate is cooled down 1 minute at room temperature,
(5) utilize ultraviolet to irradiate, so that described substrate is polymerized in atmosphere.
There is not orientation defect in liquid crystal polymer (F-1).
[embodiment 10]
According to the order described in embodiment 9, replace liquid using liquid-crystal composition (S-2)～liquid-crystal composition (S-8) Crystal composite (S-1), and obtain liquid crystal polymer (F-2)～liquid crystal polymer (F-8) respectively.Liquid crystal polymer (F-2)～liquid There is not orientation defect in brilliant polymer (F-8).
[comparative example 2]
According to the order described in embodiment 9, replaced using liquid-crystal composition (SC-1) and liquid-crystal composition (SC-2) Liquid-crystal composition (S-1), and obtain liquid crystal polymer (CF-1) and liquid crystal polymer (CF-2) respectively.Liquid crystal polymer (CF-1) There is not orientation defect in～liquid crystal polymer (CF-2).
Using the method described in embodiment 9, obtained by liquid-crystal composition (SC-1) and liquid-crystal composition (SC-2) respectively Obtain liquid crystal polymer (CF-1) and liquid crystal polymer (CF-2).
It is being intended to using the method described in embodiment 9, when liquid crystal polymer is obtained by liquid-crystal composition (SC-3), (2) in stage, crystallization separates out.Accordingly, it is difficult to be obtained the polymerizable mesogenic that there is not orientation defect by liquid-crystal composition (SC-3) Body.According to described result：Compared with compound (C-1), compound (1), even if being more contents, also can obtain and not deposit Liquid crystal polymer in orientation defect.
<The optical characteristics of optical anisotropic film>
By being relatively shown in Table 3 of the wavelength dispersion characteristics of liquid crystal polymer.Re450nm、Re550nmAnd Re650nmUnit be nm.The unit of the thickness of liquid crystal polymer be μm.
[table 3]
According to table 3, the Re of liquid crystal polymer (F-1)～liquid crystal polymer (F-8)450/Re550With liquid crystal polymer (CF-1) And the Re of liquid crystal polymer (CF-2)450/Re550Comparatively speaking significant low.On the other hand, liquid crystal polymer (F-1)～liquid crystal The Re of polymer (F-8)650/Re550Re with liquid crystal polymer (CF-1) and liquid crystal polymer (CF-2)650/Re550Compare and Say significant height.
Recognize accordingly, the increase of the wavelength with visible region can be obtained by the polymerizable liquid crystal compound of the present invention And the few liquid crystal polymer of increase of the delay of liquid crystal polymer.
[industrial utilizability]
Liquid crystal polymer with the polymerizable liquid crystal compound of the present invention as raw material can be used for phase retardation film, optical compensation Film, reflectance coating, choice reflective film, anti-reflective film, visual field angle compensation film, liquid crystal orientation film, polarizer, circular polarization element, ellipse Film or the display element with element that circular polarization element etc. comprises optical anisotropic film.

Claims (19)

1. a kind of polymerizable liquid crystal compound is it is characterised in that represented with formula (1)：
In formula (1),
A1Independently be Isosorbide-5-Nitrae-phenylene or Isosorbide-5-Nitrae-cyclohexylidene, in described Isosorbide-5-Nitrae-phenylene, at least one hydrogen can through fluorine, chlorine, three Methyl fluoride, the alkyl of carbon number 1～5, the alkanoyl of the alkoxyl of carbon number 1～5, the alkoxy carbonyl of carbon number 1～5 or carbon number 1～5 Replace,
Z1It independently is singly-bound ,-OCH2-、-CH2O-、-COO-、-OCO-、-CF2O-、-OCF2-、-CH2CH2-、-CF2CF2-、- OCH2CH2O-、-CH2CH2COO-、-OCOCH2CH2-、-CH2CH2OCO- or-COOCH2CH2-,
X1For singly-bound ,-CH2-、-O-、-S-、-NR2- or-CO-, R2For the alkyl of hydrogen or carbon number 1～5,
W1And W2It independently is hydrogen, the fluoroalkyl of fluorine, the alkyl of carbon number 1～5 or carbon number 1～5,
T1And T2It independently is hydrogen, the aromatic rings of electron number 6～18 of non-localized, the alkyl of carbon number 1～12, carbon number 1～12 Alkoxyl or the alkylthio group of carbon number 1～12, in described alkyl, described alkoxyl and described alkylthio group, at least one-CH2- can Replace through-O- or-S-, at least one hydrogen can be fluorine-substituted, T1With T2Can be bonded each other and form ring,
M independently is 0～3 integer, and m's and be more than 1,
Y1It independently is singly-bound ,-O- ,-COO- ,-OCO- or-OCOO-,
Q1It independently is singly-bound or the alkylidene of carbon number 1～20, in described alkylidene, at least one-CH2- can through-O- ,- COO- ,-OCO- ,-CH=CH- or-CH ≡ CH- replace；
PG independently is alkyl or any one represented polymerism base of formula (PG-1)～formula (PG-9),
In formula (PG-1)～formula (PG-9), R1It independently is hydrogen, halogen, methyl, ethyl or trifluoromethyl.
2. polymerizable liquid crystal compound according to claim 1 it is characterised in that：T1And T2One of them be non-localized The aromatic rings of the electron number 6～18 changed, and T1And T2Another be hydrogen, methyl or non-localized electron number 6～18 fragrance Ring.
3. polymerizable liquid crystal compound according to claim 1 and 2 it is characterised in that：T1And T2One of be formula (G-1) functional group of～formula (G-9),
In formula (G-1)～formula (G-9), X2For-O- or-S-, at least one-CH=can be substituted by-N=, and at least one hydrogen can be through Fluorine, chlorine, cyano group, trifluoroacetyl group, trifluoromethyl, the alkyl of carbon number 1～5, the alkoxyl of carbon number 1～5, the alcoxyl of carbon number 1～5 The alkanoyl of base carbonyl or carbon number 1～5 replaces.
4. polymerizable liquid crystal compound according to claim 1 it is characterised in that：T1And T2It independently is carbon number 1～12 Alkylthio group, in described alkylthio group, at least one-CH2- can replace through-O- or-S-, in described alkylthio group, at least one hydrogen can be through Fluorine replaces.
5. polymerizable liquid crystal compound according to claim 1 it is characterised in that：T1And T2It is bonded each other and formed and have The monocyclic or condensed ring of the carbon number 4～11 of at least one sulphur atom.
6. according to claim 1 or 5 polymerizable liquid crystal compound it is characterised in that：T1And T2It is bonded each other and form two Thiophene alkane, dithiolane, two mercaptan or benzo two mercaptan.
7. polymerizable liquid crystal compound according to claim 1 and 2 it is characterised in that：PG is formula (PG-1)～formula (PG- 9) functional group.
8. polymerizable liquid crystal compound according to claim 1 and 2 it is characterised in that：PG is the functional group of formula (PG-1), R1For hydrogen or methyl.
9. polymerizable liquid crystal compound according to claim 1 and 2 it is characterised in that：A1At least one of be Isosorbide-5-Nitrae-Asia Cyclohexyl, Z1At least one of be-CH2CH2COO- or-OCOCH2CH2-, m is 2.
10. polymerizable liquid crystal compound according to claim 1 and 2 it is characterised in that：X1For singly-bound.
A kind of 11. polymerizable liquid crystal compounds it is characterised in that：Containing at least one according to any one of claim 1 to 10 Described polymerizable liquid crystal compound.
12. polymerizable liquid crystal compounds according to claim 11 it is characterised in that：Containing 4 weight %～50 weight % Described polymerizable liquid crystal compound.
A kind of 13. liquid crystal polymers it is characterised in that：It is that polymerizable liquid crystal compound according to claim 11 or 12 is hard Change forms.
14. liquid crystal polymers according to claim 13 it is characterised in that：The identical state of orientation of liquid crystal molecule is fixed Change.
15. liquid crystal polymers according to claim 13 or 14 it is characterised in that：Re450nm/Re550nmFor less than 1.05, its Middle Re450nmIt is the delay during light to face vertical incidence wavelength 450nm, Re550nmIt is to face vertical incidence wavelength 550nm Light when delay.
A kind of 16. polaroids it is characterised in that：There is the liquid crystal polymer according to any one of claim 13 to 15.
A kind of 17. display elements it is characterised in that：There is the polymerizable mesogenic according to any one of claim 13 to 15 Body.
18. display elements according to claim 17 it is characterised in that：With more polaroid.
A kind of 19. manufacture methods of optical anisotropic film it is characterised in that：Including making according to claim 11 or 12 The step of polymerizable liquid crystal compound polymerization.
CN201610694069.8A 2015-08-21 2016-08-19 The manufacture method of polymerizable liquid crystal compound, compositionss and its polymer, polaroid, display element and optical anisotropic film Pending CN106467750A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2015-163350 2015-08-21
JP2015163350 2015-08-21

Publications (1)

Publication Number Publication Date
CN106467750A true CN106467750A (en) 2017-03-01

Family

ID=58206307

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610694069.8A Pending CN106467750A (en) 2015-08-21 2016-08-19 The manufacture method of polymerizable liquid crystal compound, compositionss and its polymer, polaroid, display element and optical anisotropic film

Country Status (4)

Country Link
JP (1) JP6729106B2 (en)
KR (1) KR20170022894A (en)
CN (1) CN106467750A (en)
TW (1) TWI685559B (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109207162A (en) * 2017-07-07 2019-01-15 捷恩智株式会社 Polymerizable liquid crystal compound, polymerizable mesogenic film, phase difference film, polarizer and display element
CN111712744A (en) * 2018-02-14 2020-09-25 富士胶片株式会社 Optical film, polarizing plate and image display device
CN112961086A (en) * 2021-02-05 2021-06-15 齐鲁工业大学 2-methylene-1-indanone derivative and synthesis method thereof

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3725764A1 (en) * 2017-12-12 2020-10-21 JNC Corporation Polymerizable compound having methoxymethyl acrylic group, liquid crystal composition, and liquid crystal display device

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101470227A (en) * 2007-12-28 2009-07-01 住友化学株式会社 Optical film
JP2009242718A (en) * 2008-03-31 2009-10-22 Fujifilm Corp Liquid crystal composition comprising polymerizable liquid crystal compound and stabilizer
CN101838264A (en) * 2009-03-16 2010-09-22 住友化学株式会社 The manufacture method of compound, blooming and blooming
WO2010150693A1 (en) * 2009-06-25 2010-12-29 チッソ株式会社 Retardation film composed of photo-aligned liquid crystalline polyimide and optical element
CN101937114A (en) * 2009-06-26 2011-01-05 住友化学株式会社 Phase difference board, display device containing the phase difference board and method for producing the phase difference board
JP2011246365A (en) * 2010-05-25 2011-12-08 Jnc Corp Polymerizable liquid crystal compound, composition, and polymer thereof
CN104136947A (en) * 2012-02-22 2014-11-05 柯尼卡美能达株式会社 Optical film, circularly polarizing plate, and image display device
WO2015098702A1 (en) * 2013-12-25 2015-07-02 Dic株式会社 Compound containing mesogenic group, and mixture, composition, and optically anisotropic body using said compound
CN104769463A (en) * 2012-10-15 2015-07-08 柯尼卡美能达株式会社 Phase difference film, circular polarization plate and organic EL display manufactured using phase difference film

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4606195B2 (en) 2004-03-08 2011-01-05 富士フイルム株式会社 Liquid crystal compound, liquid crystal composition, polymer, retardation plate, and elliptically polarizing plate
JP5401032B2 (en) * 2006-12-15 2014-01-29 富士フイルム株式会社 Optically anisotropic film, brightness enhancement film, retardation plate, and liquid crystal display device
ATE487777T1 (en) 2007-03-30 2010-11-15 Merck Patent Gmbh DOUBLE REFRACTION POLYMER FILM WITH NEGATIVE OPTICAL DISPERSION
JP5391682B2 (en) 2007-12-28 2014-01-15 住友化学株式会社 Compound, optical film and method for producing optical film
JP5373293B2 (en) 2008-01-29 2013-12-18 富士フイルム株式会社 Compound, liquid crystal composition and anisotropic material
WO2012060011A1 (en) 2010-11-05 2012-05-10 富士通株式会社 Disconnect program, embedding program, disconnect method, and embedding method

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101470227A (en) * 2007-12-28 2009-07-01 住友化学株式会社 Optical film
JP2009242718A (en) * 2008-03-31 2009-10-22 Fujifilm Corp Liquid crystal composition comprising polymerizable liquid crystal compound and stabilizer
CN101838264A (en) * 2009-03-16 2010-09-22 住友化学株式会社 The manufacture method of compound, blooming and blooming
CN104592219A (en) * 2009-03-16 2015-05-06 住友化学株式会社 Compound, optical film and method for making optical film
WO2010150693A1 (en) * 2009-06-25 2010-12-29 チッソ株式会社 Retardation film composed of photo-aligned liquid crystalline polyimide and optical element
CN101937114A (en) * 2009-06-26 2011-01-05 住友化学株式会社 Phase difference board, display device containing the phase difference board and method for producing the phase difference board
JP2011246365A (en) * 2010-05-25 2011-12-08 Jnc Corp Polymerizable liquid crystal compound, composition, and polymer thereof
CN104136947A (en) * 2012-02-22 2014-11-05 柯尼卡美能达株式会社 Optical film, circularly polarizing plate, and image display device
CN104769463A (en) * 2012-10-15 2015-07-08 柯尼卡美能达株式会社 Phase difference film, circular polarization plate and organic EL display manufactured using phase difference film
WO2015098702A1 (en) * 2013-12-25 2015-07-02 Dic株式会社 Compound containing mesogenic group, and mixture, composition, and optically anisotropic body using said compound

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109207162A (en) * 2017-07-07 2019-01-15 捷恩智株式会社 Polymerizable liquid crystal compound, polymerizable mesogenic film, phase difference film, polarizer and display element
CN111712744A (en) * 2018-02-14 2020-09-25 富士胶片株式会社 Optical film, polarizing plate and image display device
CN111712744B (en) * 2018-02-14 2022-04-29 富士胶片株式会社 Optical film, polarizing plate and image display device
CN112961086A (en) * 2021-02-05 2021-06-15 齐鲁工业大学 2-methylene-1-indanone derivative and synthesis method thereof
CN112961086B (en) * 2021-02-05 2022-10-21 齐鲁工业大学 2-methylene-1-indanone derivative and synthesis method thereof

Also Published As

Publication number Publication date
TW201708519A (en) 2017-03-01
JP6729106B2 (en) 2020-07-22
KR20170022894A (en) 2017-03-02
TWI685559B (en) 2020-02-21
JP2017039907A (en) 2017-02-23

Similar Documents

Publication Publication Date Title
CN105384723B (en) Liquid crystal compounds, liquid-crystal composition, condensate and its application
CN105936828A (en) Polymerizable liquid crystal composition, optically anisotropic film, polarizing film, display element and compound
JP6597244B2 (en) Liquid crystal compound, liquid crystal composition and polymer thereof
TWI730022B (en) Polymerizable liquid crystal compounds, compositions, liquid crystal polymer films and their production methods and their uses
JP6497241B2 (en) Polymerizable liquid crystal compound, composition and polymer thereof
TWI476174B (en) Chemical compound
JP5987623B2 (en) Polymerizable liquid crystal composition and optically anisotropic film
JP6015988B2 (en) Polymerizable liquid crystal composition and optical anisotropic body
CN106467750A (en) The manufacture method of polymerizable liquid crystal compound, compositionss and its polymer, polaroid, display element and optical anisotropic film
WO2015080219A1 (en) Polymerizable compound, composition, polymer, optical anisotropic body, liquid crystal display element, and organic el element
JP5545518B2 (en) Polymerizable biphenyl compound
CN109563408A (en) Polymerizable liquid crystal compound and liquid crystal polymer
JP6107441B2 (en) Liquid crystal compound, liquid crystal composition and polymer thereof
CN107794056A (en) Polymerizable liquid crystal compound, polymerizable liquid crystal compound, liquid crystal polymer, phase retardation film and display element
TW200819521A (en) Unsaturated fatty acid esters, and polymerizable liquid crystal compositions, optically anisotropic materials and optical elements, made by using the esters
KR101855525B1 (en) Polymerizable liquid crystal composition and optical anisotropic body
CN106256874A (en) Polymerizable liquid crystal compound, polymerizable liquid crystal layer, liquid crystal film, optical compensatory element and optical element
CN108018047A (en) Polymerizable liquid crystal compound, polymerizable liquid crystal compound, polymerizable mesogenic film class, phase difference film, polarization plates and display element
JP2019206677A (en) Polymerizable liquid crystal compound, composition and polymer thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication

Application publication date: 20170301

RJ01 Rejection of invention patent application after publication