CN104903764A - Photopolymerizable liquid crystal composition, optical compensation film, optical compensataion laminate film, electrode substrate, substrate for liquid crystal display devices, and liquid crystal display device - Google Patents

Photopolymerizable liquid crystal composition, optical compensation film, optical compensataion laminate film, electrode substrate, substrate for liquid crystal display devices, and liquid crystal display device Download PDF

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Publication number
CN104903764A
CN104903764A CN201480004428.1A CN201480004428A CN104903764A CN 104903764 A CN104903764 A CN 104903764A CN 201480004428 A CN201480004428 A CN 201480004428A CN 104903764 A CN104903764 A CN 104903764A
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liquid crystal
optical polymerism
nitrae
isosorbide
optical
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冈田悟史
中村清久
田原慎哉
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AGC Inc
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Asahi Glass Co Ltd
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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
    • G02B5/305—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/13356—Structural association of cells with optical devices, e.g. polarisers or reflectors characterised by the placement of the optical elements
    • G02F1/133565—Structural association of cells with optical devices, e.g. polarisers or reflectors characterised by the placement of the optical elements inside the LC elements, i.e. between the cell substrates
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/13363—Birefringent elements, e.g. for optical compensation
    • G02F1/133633—Birefringent elements, e.g. for optical compensation using mesogenic materials
    • 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
    • G02F2413/00—Indexing scheme related to G02F1/13363, i.e. to birefringent elements, e.g. for optical compensation, characterised by the number, position, orientation or value of the compensation plates
    • G02F2413/02—Number of plates being 2

Abstract

The invention discloses a photopolymerizable liquid crystal composition, an optical compensation film, an optical compensataion laminate film, an electrode substrate, a substrate for liquid crystal display devices, and a liquid crystal display devic. The photopolymerizable liquid crystal composition is capable of forming a positive A plate that has improved wavelength dispersion characteristics of birefringence and exhibits good heat resistance to the production process of a liquid crystal display device. The photopolymerizable liquid crystal composition for forming an optical compensation film with positive uniaxial anisotropy contains (A) a first photopolymerizable liquid crystal having an aliphatic ring but not having an aromatic ring, and (B) a second photopolymerizable liquid crystal having an aromatic ring, and wherein the amount of the first photopolymerizable liquid crystal (A) is 50 percent by mass or more but less than 100 percent by mass and the amount of the second photopolymerizable liquid crystal (B) is more than 0 percent by mass but 50 percent by mass or less relative to the total amount of the photopolymerizable liquid crystals. An optical compensation laminate film (12) is provided with an optical compensation film with negative uniaxial anisotropy (12A) and an optical compensation film with positive uniaxial anisotropy (12B) which is produced using the above-described composition.

Description

The stacked film of optical polymerism liquid-crystal composition, optical compensation films, optical compensation, electrode base board, base plate for liquid crystal display device and liquid crystal indicator
Technical field
The present invention relates to optical polymerism liquid-crystal composition and use the stacked film of the optical compensation films of this optical polymerism liquid-crystal composition, optical compensation, electrode base board, base plate for liquid crystal display device and liquid crystal indicator.
Background technology
In liquid crystal indicator, use the optical compensation films (also referred to as phase retardation film) with the phase place of the control light of birefringence to expand visual angle etc.Especially, vertical orientated (below sometimes referred to as " VA ".) pattern liquid crystal indicator in there is the narrow tendency of field-of-view angle, optical compensation films is necessary constitutive requirements.In patent documentation 5 grade, disclose and use positive A plate as phase difference compensation in the liquid crystal indicator of VA pattern, light when suppressing field-of-view angle to increase leaks.
In the past, above-mentioned optical compensation films and light polarizing film were attached to outside to liquid crystal cell, and the thickness of optical compensation films is about 50 ~ 150 μm.
On the other hand, in recent years, have studied and the stacked film of optical compensation is set in the inside of liquid crystal cell, make liquid crystal indicator and carried electronic equipment slimization of this device.
As the form of the stacked film of optical compensation, the stacked film (i) of following optical compensation ~ (iv) etc. can be exemplified.
I () is laminated with the stacked film of optical compensation of two axillares in the alignment films such as polyimide.
(ii) the stacked film of optical compensation of the optical compensation films (hereinafter referred to as positive A plate) being laminated with the positive uniaxial anisotropy of display in the alignment films such as polyimide successively and the optical compensation films (hereinafter referred to as negative C plate) showing negative uniaxial anisotropy.
(iii) on negative C plate, the stacked film of optical compensation of positive A plate is laminated with via alignment films.
(iv) on the negative C plate worked as alignment films, be directly laminated with the stacked film of optical compensation of positive A plate.
In patent documentation 1,2, disclose the base plate for liquid crystal display device possessing the stacked film of above-mentioned optical compensation (iii) or (iv).
In the embodiment 1,2 of patent documentation 1, coated polyester on substrate, is carrying out heat drying and is implementing friction treatment after burning till to the coated film obtained, and forms the negative C plate of the effect had as alignment films.Afterwards, negative C plate is coated with optical polymerism liquid crystal, after carrying out heat drying, implements photopolymerization, form positive A plate (paragraph 0025,0026).
The embodiment 1,2 of patent documentation 1 all only uses a kind of optical polymerism liquid crystal optical polymerism liquid crystal as positive A plate material with aromatic ring.
In the embodiment 8 of patent documentation 2, substrate is coated with polyimide, heat drying is carried out to the coated film obtained and burns till, form negative C plate.This negative C plate forms alignment films, is coated with optical polymerism liquid crystal after implementing friction treatment, implements photopolymerization after the drying, form positive A plate (paragraph 0098 ~ 0100).
The embodiment 1 ~ 12 of patent documentation 2 all only uses a kind of optical polymerism liquid crystal optical polymerism liquid crystal as positive A plate material with aromatic ring.
Prior art document
Patent documentation
Patent documentation 1: Japanese Patent Laid-Open 2010-230823 publication
Patent documentation 2: Japanese Patent Laid-Open 2009-223304 publication
Patent documentation 3: No. 2009/148142nd, International Publication
Patent documentation 4: No. 2011/004826th, International Publication
Patent documentation 5: Japanese Patent Laid-Open 11-258605 publication
Summary of the invention
Invent technical matters to be solved
In the positive A plate of color liquid crystal display arrangement, require the wavelength dispersion of the delay Re as shown in the profile I of Fig. 5.But, in positive A plate in the past, as patent documentation 1,2, use the optical polymerism liquid crystal with aromatic ring, be difficult to due to the light absorption of aromatic ring obtain expected wavelength dispersion.Specifically, use the positive A plate in the past with the optical polymerism liquid crystal of aromatic ring as shown in the profile II of Fig. 5, along with wavelength is elongated, Re diminishes.In addition, Re is the birefringent index of x-y plane, its definition aftermentioned.
For this reason, positive A plate is designed to specific wavelength, green light that specifically visual sense degree is the highest is positioned at center and carries out phase difference compensation.In positive A plate in the past, owing to demonstrating the wavelength dispersion of the profile II of Fig. 5, when showing black when field-of-view angle increases, fully can not reduce the leakage of red and blue light component.
In patent documentation 3,4, disclose the optical polymerism liquid crystal (with reference to the claim 1 of patent documentation 3 and the claim 1 of patent documentation 4) that there is aliphatics ring, not there is aromatic ring.
Above-mentioned patent documentation mainly using the purposes of optical information recording regenerator as object, do not have to record for the application of the optical compensation films of liquid crystal cell inside.But it is on the occasion of (with reference to the table 2 of patent documentation 3 and the table 2 of patent documentation 4) that above-mentioned material all shows Δ n, can use as positive A plate material.Herein, Δ n is refractive anisotrop.
Think use do not have in the positive A plate of the optical polymerism liquid crystal of aromatic ring, the wavelength dispersion characteristics of Re can be improved.
When the inside of liquid crystal cell arranges optical compensation films, to the requirement of the thermotolerance that the manufacturing process after film forming has the optical characteristics of optical compensation films not change.But its thermotolerance of optical polymerism liquid crystal without aromatic ring recorded in patent documentation 3,4 is poorer than the optical polymerism liquid crystal with aromatic ring.
A kind of can formation is the object of the present invention is to provide to improve birefringent wavelength dispersion characteristics and the optical polymerism liquid-crystal composition manufacturing process of liquid crystal indicator to the positive A plate of good thermotolerance.
" improve birefringent wavelength dispersion characteristics " and refer to as liquid crystal indicator used time birefringent wavelength dispersion characteristics close to perfect condition.
The object of the present invention is to provide a kind of by improving birefringent wavelength dispersion characteristics and the optical compensation films formed the positive A plate that the manufacturing process of liquid crystal indicator has good thermotolerance.
The object of the present invention is to provide and a kind ofly comprise negative C plate and positive A plate, improve birefringent wavelength dispersion characteristics and the manufacturing process of liquid crystal indicator is had to the optical compensation films of good thermotolerance.
The object of the present invention is to provide a kind of optical characteristics good and can the electrode base board of slimming and cost degradation, base plate for liquid crystal display device and liquid crystal indicator.
The technical scheme that technical solution problem adopts
The invention provides the optical polymerism liquid-crystal composition of the formation with following [1] ~ [15], optical compensation films, the stacked film of optical compensation, electrode base board, base plate for liquid crystal display device and liquid crystal indicator.
The present inventor find by by having aliphatics ring, not there is the first optical polymerism liquid crystal (A) of aromatic ring and there is the second optical polymerism liquid crystal (B) of aromatic ring and use, the birefringent wavelength dispersion characteristics of improvement can be formed and the manufacturing process of liquid crystal indicator is had to the positive A plate of good thermotolerance.
[1] an optical polymerism liquid-crystal composition, it is the optical polymerism liquid-crystal composition of the optical compensation films for the formation of the positive uniaxial anisotropy of display,
Containing there is aliphatics ring, not there is the first optical polymerism liquid crystal (A) of aromatic ring, and there is the second optical polymerism liquid crystal (B) of aromatic ring,
Relative to the total amount of optical polymerism liquid crystal, the amount of the first optical polymerism liquid crystal (A) is at more than 50 quality % and lower than 100 quality %, and the amount of the second optical polymerism liquid crystal (B) is more than 0 quality % and at below 50 quality %.
[2] the optical polymerism liquid-crystal composition as described in [1], wherein, the first optical polymerism liquid crystal (A) is containing including the simple function optical polymerism liquid crystal of 1 photopolymerization reaction group at 1 molecule and/or including two sense optical polymerism liquid crystal of 2 photopolymerization reaction groups at 1 molecule.
[3] the optical polymerism liquid-crystal composition as described in [2], wherein, the simple function optical polymerism liquid crystal that the first optical polymerism liquid crystal (A) represents containing following formula (11).
CH 2＝CR 11-COO-(L 1) a1-E 11-(S 1) b1-E 12-(T 1) c1-(E 13) d1-R 12···(11)
(in formula, symbol represents following implication.R 11: hydrogen atom or methyl.R 12: the alkyl of carbon number 1 ~ 8 or fluorine atom (wherein, when for alkyl, can between carbon-carbon bond or with the end of cyclic group bonding on there is the oxygen atom of ehter bond, part or all of hydrogen atom can be replaced by fluorine atoms.)。L 1: the oxygen atom can between carbon-carbon bond with ehter bond, part or all of hydrogen atom can be replaced by fluorine atoms, with E 11the position of bonding can have the alkyl of the carbon number 1 ~ 8 of COO, OCO or O.E 11, E 12and E 13: be separately trans-Isosorbide-5-Nitrae-cyclohexylidene or trans-2,6-decahydronaphthalene naphthyls (wherein, in group can by fluorine atom or methyl substituted with the hydrogen atom of carbon atom bonding.)。S 1and T 1: be separately-OCO-,-COO-,-(CH 2) 2-,-CH 2o-,-OCH 2-or singly-bound.A1, b1, c1 and d1: be separately 0 or 1.)
[4] the optical polymerism liquid-crystal composition as described in [2], wherein, the two sense optical polymerism liquid crystal that the first optical polymerism liquid crystal (A) represents containing following formula (12).
CH 2＝CR 21-COO-(L 2) a2-E 21-(S 2) b2-E 22-(T 2) c2-(E 23) d2-(M 2) e2-OCO-CR 22＝CH 2···(12)
(in formula, symbol represents following implication.R 21and R 22: be separately hydrogen atom or methyl; L 2: the oxygen atom can between carbon-carbon bond with ehter bond, part or all of hydrogen atom can be replaced by fluorine atoms, with E 21the position of bonding can have the alkyl of the carbon number 1 ~ 8 of COO, OCO or O.M 2: the oxygen atom can between carbon-carbon bond with ehter bond, part or all of hydrogen atom can be replaced by fluorine atoms, with E 23the position of bonding can have the alkyl of the carbon number 1 ~ 8 of COO, OCO or O.E 21, E 22and E 23: be separately trans-Isosorbide-5-Nitrae-cyclohexylidene or trans-2,6-decahydronaphthalene naphthyls (wherein, in group can by fluorine atom or methyl substituted with the hydrogen atom of carbon atom bonding.)。S 2and T 2: be separately-OCO-,-COO-,-(CH 2) 2-,-CH 2o-,-OCH 2-or singly-bound.A2, b2, c2 and d2: be separately 0 or 1.)
[5] the optical polymerism liquid-crystal composition according to any one of [1] ~ [4], wherein, the second optical polymerism liquid crystal (B) represents with following formula (20).
Q 1-Z 1-A 1-Z 3-M-Z 4-A 2-Z 2-Q 2···(20)
(in formula, symbol represents following implication.Q 1and Q 2: be separately photopolymerization reaction group.Z 1, Z 2, Z 3and Z 4: be separately singly-bound or divalent linker.A 1and A 2: the interval base being separately carbon number 2 ~ 20.M: the mesomorphic group containing aromatic ring)
[6] the optical polymerism liquid-crystal composition as described in [5], wherein, the optical polymerism liquid crystal that the second optical polymerism liquid crystal (B) represents containing following formula (21).
CH 2＝CR 41-COO-(E 41) m4-Cy-Y 4-Cy-(E 42) n4-OCO-CR 42＝CH 2···(21)
(in formula, symbol represents following implication.R 41and R 42: be separately hydrogen atom or methyl.Y 4:-OCO-or-COO-.M4 and n4: be separately 0 or 1 (wherein, both sides are except the situation of 0).E 41and E 42: be separately Isosorbide-5-Nitrae-phenylene or trans-Isosorbide-5-Nitrae-cyclohexylidene.Wherein, E 41and E 42middle at least one party is Isosorbide-5-Nitrae-phenylene.Cy: trans-Isosorbide-5-Nitrae-cyclohexylidene.Wherein, the hydrogen atom in above-mentioned Isosorbide-5-Nitrae-phenylene and trans-Isosorbide-5-Nitrae-cyclohexylidene can by fluorine atom, chlorine atom or methyl substituted.)
[7] the optical polymerism liquid-crystal composition as described in [5], wherein, the optical polymerism liquid crystal that the second optical polymerism liquid crystal (B) represents containing following formula (22).
CH 2＝CR 51-COO-(L 5) k5-E 51-E 52-E 53-E 54-(M 5) n5-OCO-CR 52＝CH 2···(22)
(in formula, symbol represents following implication.R 51and R 52: be separately hydrogen atom or methyl, k5 and n5: be separately 0 or 1.L 5:-(CH 2) p5o-or-(CH 2) p5-(here, p5 is the integer of 2 ~ 8.)。M 5:-O (CH 2) p5-or-(CH 2) p5-(here, p5 is the integer of 2 ~ 8.)。E 51: Isosorbide-5-Nitrae-phenylene.E 52, E 53, E 54: be separately Isosorbide-5-Nitrae-phenylene or trans-Isosorbide-5-Nitrae-cyclohexylidene, and E 52and E 53in at least one party be trans-Isosorbide-5-Nitrae-cyclohexylidene.In described Isosorbide-5-Nitrae-phenylene and trans-Isosorbide-5-Nitrae-cyclohexylidene can by fluorine atom, chlorine atom or methyl substituted with the hydrogen atom of carbon atom bonding.)
[8] the optical polymerism liquid-crystal composition as described in [5], wherein, the optical polymerism liquid crystal that the second optical polymerism liquid crystal (B) represents containing following formula (23).
CH 2＝CR 61-COO-(L 6) k6-E 61-E 62-E 63-(M 6) n6-OCO-CR 62＝CH 2···(23)
(in formula, symbol represents following implication.R 61and R 62: be separately hydrogen atom or methyl.K6 and n6: be separately 0 or 1.L 6:-(CH 2) p6(Cy is trans-Isosorbide-5-Nitrae-cyclohexylidene for O-,-Cy-COO-.) or-Cy-OCO-(here, p6 is the integer of 2 ~ 8.)。M 6:-O (CH 2) p6-, (Cy is trans-Isosorbide-5-Nitrae-cyclohexylidene to-OCO-Cy-.) or-COO-Cy-(here, p6 is the integer of 2 ~ 8.)。E 61, E 62and E 63: be separately Isosorbide-5-Nitrae-phenylene or trans-Isosorbide-5-Nitrae-cyclohexylidene.Wherein, E 61, E 62and E 63in at least 1 be Isosorbide-5-Nitrae-phenylene, and at least 1 is trans-Isosorbide-5-Nitrae-cyclohexylidene.In addition, L 6for E during-Cy-OCO- 61for trans-Isosorbide-5-Nitrae-cyclohexylidene, L 6for-(CH 2) p6e when O-or k6 is 0 61and E 63be respectively Isosorbide-5-Nitrae-phenylene, E 62for trans-Isosorbide-5-Nitrae-cyclohexylidene).Wherein, in above-mentioned Isosorbide-5-Nitrae-phenylene and trans-Isosorbide-5-Nitrae-cyclohexylidene can by fluorine atom, chlorine atom or methyl substituted with the hydrogen atom of carbon atom bonding.)
[9] the optical polymerism liquid-crystal composition as described in [5], wherein, the optical polymerism liquid crystal that the second optical polymerism liquid crystal (B) represents containing following formula (24).
CH 2＝CR 71-COO-(L 7) k7-Ph-(X 7)-Ph-(Y 7)-Ph-(M 7) n7-OCO-CR 72＝CH 2···(24)
(in formula, symbol represents following implication.R 71and R 72: be separately hydrogen atom or methyl.X 7and Y 7: be separately-OCO-or-COO-.L 7:-(CH 2) p7o-,-(CH 2) p7o-COO-,-(CH 2) p7oCO-or-(CH 2) p7(here, p7 is the integer of 2 ~ 8 to COO-.)。M 7:-O (CH 2) p7-, OCO-O (CH 2) p7-,-OCO-(CH 2) p7or-COO (CH 2) p7-(here, p7 is the integer of 2 ~ 8.)。K7 and n7: be separately 0 or 1.Ph:1,4-phenylene.Wherein, in above-mentioned Isosorbide-5-Nitrae-phenylene can by fluorine atom, chlorine atom or methyl substituted with the hydrogen atom of carbon atom bonding.)
[10] optical compensation films, wherein, the optical polymerism liquid-crystal composition according to any one of [1] ~ [9] and obtaining, described optical compensation films shows positive uniaxial anisotropy.
[11] the stacked film of optical compensation, wherein, possesses the optical compensation films of the negative uniaxial anisotropy of display, and the optical compensation films of the positive uniaxial anisotropy of the display as described in [10] of lamination on this optical compensation films.
[12] the stacked film of the optical compensation as described in [11], wherein, the optical compensation films of the uniaxial anisotropy that above-mentioned display is born contains the polyimide in skeleton with aliphatics ring.
[13] electrode base board, wherein, electrode substrate possessing the stacked film of optical compensation as described in [12] and is formed on the stacked film of this optical compensation.
[14] base plate for liquid crystal display device, wherein, the alignment films possessing the electrode base board as described in [13] and be formed on this electrode base board.
[15] liquid crystal indicator, wherein, possess the liquid crystal substrate as described in [14], subtend substrate, by the liquid crystal layer of this liquid crystal substrate and subtend substrate clamping.
The effect of invention
Optical polymerism liquid-crystal composition of the present invention can be formed and improve birefringent wavelength dispersion characteristics and the optical polymerism liquid-crystal composition manufacturing process of liquid crystal indicator to the positive A plate of good thermotolerance.
The optical compensation films be made up of positive A plate of the present invention improves birefringent wavelength dispersion characteristics and has good thermotolerance to the manufacturing process of liquid crystal indicator.
The stacked film of optical compensation of the present invention comprises negative C plate and positive A plate, improves birefringent wavelength dispersion characteristics and have good thermotolerance to the manufacturing process of liquid crystal indicator.
The optical characteristics possessing the electrode base board of the present invention of the stacked film of above-mentioned optical compensation, base plate for liquid crystal display device and liquid crystal indicator is good.Electrode base board of the present invention, base plate for liquid crystal display device and liquid crystal indicator owing to possessing the stacked film of optical compensation in liquid crystal cell, therefore, it is possible to carry out slimming and cost degradation.
Accompanying drawing explanation
Fig. 1 is the exploded pictorial sectional view of the liquid crystal indicator of an example of the present invention.
Fig. 2 is the exploded pictorial sectional view representing design alteration example.
Fig. 3 is the constructed profile of the structure of the stacked film of optical compensation representing an example of the present invention.
Fig. 4 A is the mensuration wavelength (nm) of the stacked film of optical compensation of representation case 21 gained and the figure of Re relation.
Fig. 4 B is the mensuration wavelength (nm) of the stacked film of optical compensation of representation case 22 gained and the figure of Re relation.
Fig. 4 C is the mensuration wavelength (nm) of the stacked film of optical compensation of representation case 23 gained and the figure of Re relation.
Fig. 4 D is the mensuration wavelength (nm) of the stacked film of optical compensation of representation case 24 gained and the figure of Re relation.
Fig. 5 is the schematic diagram of the relation representing the desired wavelength (nm) of positive A plate and wavelength in the past (nm) and Re.
Embodiment
In this instructions, the group that formula (x) represents is sometimes referred to as group (x).
In this instructions, the compound that formula (y) represents is sometimes referred to as compound (y).
Here, formula (x), formula (y) represent arbitrary formula.
In this instructions, face that will be parallel with the face of optical compensation films (the stacked film of optical compensation is also identical) is as x-y plane, and using film thickness direction as z direction, the refractive index in x direction, y direction, z direction is respectively nx, ny, nz.
As the material of optical compensation films, use the optical polymerism liquid crystal with rodlike molecule structure, described rodlike molecule structure has rectilinearity.In optical compensation films, rodlike molecule is in the long axis direction state parallel or close with it with face.X-axis direction is the long axis direction of rodlike molecule.
In negative C plate, nx=ny > nz.
In positive A plate, nx > ny=nz.
As the delay Rth of the birefringent index in the z direction in negative C plate and defined by following formula as the delay Re of the birefringent index of the x-y plane in positive A plate.
Rth＝P×da
(here, da is the thickness of negative C plate, P=((nx+ny)/2-nz).)
Re＝Δn×db
(here, Δ n is refractive anisotrop, Δ n=nx-ny.Db is the thickness of positive A plate.)
Below, embodiments of the present invention are described.
In this instructions, unless otherwise specified, " % " represents quality %.
[optical polymerism liquid-crystal composition]
Optical polymerism liquid-crystal composition of the present invention is (hereinafter referred to as composition (Y).) be the material of optical compensation films (positive A plate) for the formation of the positive uniaxial anisotropy of display.
Composition (Y) comprises the first optical polymerism liquid crystal (A) having aliphatics ring, do not have aromatic ring, and has the second optical polymerism liquid crystal (B) of aromatic ring.
Optical polymerism liquid-crystal composition of the present invention is applicable to the stacked film of optical compensation, and the stacked film of described optical compensation is that optical compensation films (negative C plate) the upper lamination of the uniaxial anisotropy born in the display of working as alignment films shows the optical compensation films (positive A plate) of positive uniaxial anisotropy.
Aromatic ring has light absorption, and this light absorption depends on wavelength.Therefore, have in the positive A plate in the past of the second optical polymerism liquid crystal of aromatic ring only using, as shown in the profile II of Fig. 5, contrary with desired, along with wavelength is elongated, Re diminishes.
Postpone the wavelength dispersion of Re, such as using the delay Re in certain any wavelength X as Re (λ) time, the ratio by the delay Re of green light and red light is evaluated.That is, Re (450)/Re (590) < 1 in desirable positive A plate, but when use in the past material Re (450)/Re (590) > 1.
By using the first optical polymerism liquid crystal (A) without aromatic ring, the wavelength dispersion characteristics of Re can be improved, Re (450)/Re (590) can be made to diminish.But the material without aromatic ring, compared with the material with aromatic ring, has the tendency of poor heat resistance.For this reason, when only use there is aliphatics ring, do not have the first optical polymerism liquid crystal (A) of aromatic ring form positive A plate, likely can not present the thermotolerance good for the manufacturing process of liquid crystal indicator.Such as, in the manufacturing process of liquid crystal indicator, optical characteristics may change.
Therefore, by and with the first optical polymerism liquid crystal (A) and the second optical polymerism liquid crystal (B), can be formed and improve birefringent wavelength dispersion characteristics, and there is the positive A plate for the good thermotolerance of the manufacturing process of liquid crystal indicator.
In composition (Y), relative to the total amount of optical polymerism liquid crystal, the amount of the first optical polymerism liquid crystal (A) is at more than 50 quality % and lower than 100 quality %, and the amount of the second optical polymerism liquid crystal (B) is more than 0 quality % and at below 50 quality %.
If contain the first optical polymerism liquid crystal (A) of more than 50 quality % and the second optical polymerism liquid crystal (B) containing below 50 quality %, then can form the positive A plate of the suitable wavelength dispersion of display.In addition, if containing lower than 100 quality % the first optical polymerism liquid crystal (A) and containing the second optical polymerism liquid crystal (B) more than 0 quality %, then can form the positive A plate with good thermotolerance.
In composition (Y), relative to the total amount of optical polymerism liquid crystal, amount preferably 50 ~ 90 quality % of the first optical polymerism liquid crystal (A), amount preferably below 50 ~ 10 quality % of the second optical polymerism liquid crystal (B).In composition (Y), relative to the total amount of optical polymerism liquid crystal, the amount of the first optical polymerism liquid crystal (A) preferred 70 ~ 90 quality % further, the amount of the second optical polymerism liquid crystal (B) preferred 30 ~ 10 quality % further.
Use composition (Y) and Re (the 450)/Re (590) of positive A plate that obtains preferably less than 1.07, more preferably less than 1.05.
To when using composition (Y) and the positive A plate that obtain to carry out at 230 DEG C 30 minutes burning till, the rate of change burning till the Re (590) of front and back preferably less than 5%.
In order to form the positive A plate of display wavelength dispersion, the first optical polymerism liquid crystal (A) can contain one kind or two or more simple function optical polymerism liquid crystal and/or two sense optical polymerism liquid crystal.
First optical polymerism liquid crystal (A) is preferably made up of a kind or 2 kinds of simple function optical polymerism liquid crystal and/or two sense optical polymerism liquid crystal, is more preferably made up of a kind of simple function optical polymerism liquid crystal or two sense optical polymerism liquid crystal.
As the simple function optical polymerism liquid crystal being suitable for the first optical polymerism liquid crystal (A), the compound that following formula (11) represents can be exemplified.
CH 2＝CR 11-COO-(L 1) a1-E 11-(S 1) b1-E 12-(T 1) c1-(E 13) d1-R 12···(11)
In optical polymerism liquid crystal (11), R 11for hydrogen atom or methyl, be preferably hydrogen atom.If R 11for hydrogen atom, then when making the composition containing optical polymerism liquid crystal (11) (Y) photopolymerization, polymerization can be made to carry out rapidly.In addition, the optical characteristics of the optical compensation films obtained in addition is not subject to the impact of the external environment conditions such as temperature, can reduces the advantage of the delay Re deviation of optical compensation films.
In optical polymerism liquid crystal (11), R 12for alkyl or the fluorine atom of carbon number 1 ~ 8.At R 12during for alkyl, between carbon-carbon bond or with the end of cyclic group bonding on can have the oxygen atom of ehter bond, part or all of hydrogen atom can be replaced by fluorine atoms.
By making R 12for above-mentioned group, the fusing point (T of the composition (Y) containing optical polymerism liquid crystal (11) can be reduced m: crystallization phase-nematic phase phase transfer point).R 12the alkyl of preferred carbon number 2 ~ 6 or fluorine atom.And, show the temperature range of liquid crystal liquid crystal property due to optical polymerism liquid crystal (11) can be widened, at R 12during for alkyl, preferred linear chain structure.
In optical polymerism liquid crystal (11), L 1be the alkyl of carbon number 1 ~ 8, the alkyl of described carbon number 1 ~ 8 can have the oxygen atom of ehter bond between carbon-carbon bond, and part or all of hydrogen atom can be replaced by fluorine atoms, with E 11the position of bonding can have COO, OCO or O.L 1preferably-(CH 2) p1cOO-,-(CH 2) p1oCO-,-(CH 2) p1o-or-(CH 2) p1-, p1 preferably 1 ~ 8 integer.L 1more preferably-(CH 2) p1cOO-, p1 more preferably 1 ~ 8 integer.
Usually, if make optical polymerism polymerizable mesogenic, then there is the tendency of decline in the value of the front and back refractive anisotrop Δ n of polymerization.But, at L 1for above-mentioned there is the group of polymethylene time, the decline of the Δ n value of the front and back of being polymerized can be suppressed.And, from the view point of guarantee be polymerized before liquid crystal liquid crystal property, p1 preferably 2 ~ 4 integer.
In optical polymerism liquid crystal (11), E 11, E 12and E 13be separately trans-Isosorbide-5-Nitrae-cyclohexylidene or trans-2,6-decahydronaphthalene naphthyls.E 11, E 12and E 13in with the hydrogen atom of carbon atom bonding can by fluorine atom or methyl replace.But, in the present invention, trans-Isosorbide-5-Nitrae-cyclohexylidene and trans-2,6-decahydronaphthalene naphthyls be preferably in these groups with the hydrogen atom of carbon atom bonding not the non-substituted group that replaces by other groups.
In optical polymerism liquid crystal (11), S 1and T 1be independently-OCO-,-COO-,-(CH 2) 2-,-CH 2o-,-OCH 2-or singly-bound.From the view point of the liquid crystal liquid crystal property embodying compound, preferred singly-bound.
In optical polymerism liquid crystal (11), a1, b1, c1 and d1 are separately 0 or 1.
Optical polymerism liquid crystal (11) preferably has following radicals (I) or group (II) in molecule.
[changing 1]
As the concrete example of optical polymerism liquid crystal (11) with group (I), following compound (11A) can be exemplified.Symbol in compound (11A) as previously mentioned.In addition, the alkyl in formula exists the group of isomery, comprise wherein all groups, preferred straight chained alkyl.
[changing 2]
In compound (11A), R 11preferred hydrogen atom, a1 preferably 0 or 1, R 12the straight chained alkyl of preferred carbon number 2 ~ 6 or fluorine atom.Due to wider liquid crystal liquid crystal property can be guaranteed, L 1preferably-(CH 2) p1cOO-or-(CH 2) p1oCO-.And, due to the process number of synthesis can be reduced, L 1particularly preferably-(CH 2) p1cOO-.In addition, p1 particularly preferably 2 ~ 4 integer.
As compound (11A), compound shown below can be exemplified.Symbol in these compounds as previously mentioned.P1 preferably 2 ~ 4 integer.Trans-2,6-decahydronaphthalene naphthyls are from the viewpoint of embodying liquid crystal liquid crystal property, preferred trans-2,6-anti-decahydronaphthalene naphthyls.R 12being applicable to is the straight chained alkyl of carbon number 2 ~ 6.
[changing 3]
For the synthetic method of above-claimed cpd (11A-1) and (11A-2), hope the paragraph 0050-0056 with reference to patent documentation 3.
As the concrete example of optical polymerism liquid crystal (11) with group (II), following compound (11B) ~ (11D) can be exemplified.Symbol in compound as previously mentioned.In addition, the alkyl in formula exists the group of isomery, comprise wherein all groups, preferred straight chained alkyl.
[changing 4]
In compound (11B) ~ (11D), R 11preferred hydrogen atom, a1 preferably 0 or 1, R 12the straight chained alkyl of preferred carbon number 2 ~ 6 or fluorine atom.Due to wider liquid crystal liquid crystal property can be guaranteed, L 1preferably-(CH 2) p1cOO-or-(CH 2) p1oCO-.Here, p1 particularly preferably 2 ~ 4 integer.
As compound (11B) ~ (11D), compound shown below can be exemplified.Symbol in these compounds as previously mentioned.P1 preferably 2 ~ 4 integer.R 12being applicable to is the straight chained alkyl of carbon number 2 ~ 6.In addition, the alkyl in formula exists the group of isomery, comprise wherein all groups, preferred straight chained alkyl.
[changing 5]
Above-claimed cpd (11B) ~ (11D) also can be identical with compound (11A), uses known synthetic method to manufacture.
As the two sense optical polymerism liquid crystal being suitable for the first optical polymerism liquid crystal (A), the compound that following formula (12) represents can be exemplified.
CH 2＝CR 21-COO-(L 2) a2-E 21-(S 2) b2-E 22-(T 2) c2-(E 23) d2-(M 2) e2-OCO-CR 22＝CH 2···(12)
In optical polymerism liquid crystal (12), R 21and R 22be separately hydrogen atom or methyl, preferred hydrogen atom.If R 21and R 22for hydrogen atom, then, when making the composition containing optical polymerism liquid crystal (12) (Y) photopolymerization, can be polymerized rapidly.In addition, the advantage that optical characteristics is not subject to the impact of the external environment conditions such as temperature, the delay Re deviation of optical compensation films reduces of the optical compensation films obtained in addition.
In optical polymerism liquid crystal (12), L 2be the alkyl of carbon number 1 ~ 8, the alkyl of described carbon number 1 ~ 8 can have the oxygen atom of ehter bond between carbon-carbon bond, and part or all of hydrogen atom can be replaced by fluorine atoms, with E 21the position of bonding can have COO, OCO or O.L 2preferably-(CH 2) p2cOO-,-(CH 2) p2oCO-,-(CH 2) p2o-or-(CH 2) p2-, p2 preferably 1 ~ 8 integer.L 2from the view point of the liquid crystal liquid crystal property embodying compound, more preferably-(CH 2) p2cOO-, p2 more preferably 1 ~ 8 integer.
In optical polymerism liquid crystal (12), M 2be the alkyl of carbon number 1 ~ 8, the alkyl of described carbon number 1 ~ 8 can have the oxygen atom of ehter bond between carbon-carbon bond, and part or all of hydrogen atom can be replaced by fluorine atoms, with E 23the position of bonding can have COO, OCO or O.M 2preferably-OCO (CH 2) q2-,-COO (CH 2) q2-,-O (CH 2) q2-or-(CH 2) q2-, q2 preferably 1 ~ 8 integer.M 2from the view point of the liquid crystal liquid crystal property embodying compound, more preferably-OCO (CH 2) q2-or-(CH 2) q2-, q2 more preferably 1 ~ 8 integer; Particularly preferably-OCO (CH 2) q2-, q2 particularly preferably 1 ~ 8 integer.
Usually, if make optical polymerism polymerizable mesogenic, then there is the tendency of decline in the value of the front and back refractive anisotrop Δ n of polymerization.But, at L 2and M 2for above-mentioned there is the group of polymethylene time, the decline of the Δ n value of the front and back of being polymerized can be suppressed.And, from guaranteeing the aspect of liquid crystal liquid crystal property before being polymerized, p2 and q2 separately preferably 2 ~ 4 integer.
In optical polymerism liquid crystal (12), E 21, E 22and E 23be separately trans-Isosorbide-5-Nitrae-cyclohexylidene or trans-2,6-decahydronaphthalene naphthyls.E 21, E 22and E 23in with the hydrogen atom of carbon atom bonding can by fluorine atom or methyl replace.But, in the present invention, trans-Isosorbide-5-Nitrae-cyclohexylidene and trans-2,6-decahydronaphthalene naphthyls be preferably in these groups with the hydrogen atom of carbon atom bonding not the non-substituted group that replaces by other groups.
In optical polymerism liquid crystal (12), S 2and T 2be independently-OCO-,-COO-,-(CH 2) 2-,-CH 2o-,-OCH 2-or singly-bound.From the view point of the liquid crystal liquid crystal property embodying compound, preferred singly-bound.
In optical polymerism liquid crystal (12), a2, b2, c2, d2 and e2 are separately 0 or 1.
Optical polymerism liquid crystal (12) preferably has following radicals (I) or group (II) in molecule.
[changing 6]
As the concrete example of optical polymerism liquid crystal (12) with group (I), following compound (12A) can be exemplified.Symbol in compound (12A) as previously mentioned.In addition, the alkyl in formula exists the group of isomery, comprise wherein all groups, preferred straight chained alkyl.
[changing 7]
In compound (12A), R 21and R 22preferred hydrogen atom, a2 and e2 separately preferably 0 or 1.From the view point of guaranteeing liquid crystal liquid crystal property, p2 and q2 separately particularly preferably 2 ~ 4 integer.
As compound (12A), compound shown below can be exemplified.Symbol in these compounds as previously mentioned.P2 and q2 separately preferably 2 ~ 4 integer.Trans-2,6-decahydronaphthalene naphthyls are from the viewpoint of embodying liquid crystal liquid crystal property, preferred trans-2,6-anti-decahydronaphthalene naphthyls.
[changing 8]
For the synthetic method of above-claimed cpd (12A-1) and (12A-2), hope the paragraph 0055-0057 with reference to patent documentation 4.
As the concrete example of optical polymerism liquid crystal (12) with group (II), following compound (12B) can be exemplified.Symbol in compound (12B) as previously mentioned.In addition, the alkyl in formula exists the group of isomery, comprise wherein all groups, preferred straight chained alkyl.
[changing 9]
In compound (12B), R 21and R 22preferred hydrogen atom, a2 and e2 separately preferably 0 or 1.From the view point of guaranteeing liquid crystal liquid crystal property, p2 and q2 separately particularly preferably 2 ~ 4 integer.
As compound (12B), compound shown below can be exemplified.Symbol in these compounds as previously mentioned.P2 and q2 separately preferably 2 ~ 4 integer.
[changing 10]
Above-claimed cpd (12B) also can be identical with compound (12A), uses known synthetic method to manufacture.
Second optical polymerism liquid crystal (B) can contain one kind or two or more simple function optical polymerism liquid crystal and/or two sense optical polymerism liquid crystal.Second optical polymerism liquid crystal (B), from the view point of raising thermotolerance, preferably contains two one kind or two or more sense optical polymerism liquid crystal.
As the second optical polymerism liquid crystal (B), the compound that preferred following formula (20) represents.
Q 1-Z 1-A 1-Z 3-M-Z 4-A 2-Z 2-Q 2···(20)
Symbol in formula represents following implication.
Q 1and Q 2it is separately photopolymerization reaction group.
Z 1, Z 2, Z 3and Z 4be separately singly-bound or divalent linker.
A 1and A 2it is separately the interval base of carbon number 2 ~ 20.
M is the mesomorphic group containing aromatic ring.
As the second optical polymerism liquid crystal (B), the compound that preferred following formula (21), (22), (23) or (24) represent.
CH 2＝CR 41-COO-(E 41) m4-Cy-Y 4-Cy-(E 42) n4-OCO-CR 42＝CH 2···(21)
In optical polymerism liquid crystal (21), R 41and R 42be separately hydrogen atom or methyl, preferred hydrogen atom.If R 41and R 42for hydrogen atom, then, when making the composition containing optical polymerism liquid crystal (21) (Y) photopolymerization, can be polymerized rapidly.In addition, the optical characteristics of the optical compensation films obtained in addition is not subject to the advantage that the delay Re deviation in the impact of the external environment conditions such as temperature, optical compensation face reduces.
Y 4for-OCO-or-COO-.From reducing fusing point (T m) aspect to set out preferably-OCO-, when as optical compensation films, from the viewpoint of presenting larger Δ n, preferred-COO-.
M4 and n4 is separately 0 or 1, and at least one party is 1.
E 41and E 42be separately Isosorbide-5-Nitrae-phenylene (Ph) or trans-Isosorbide-5-Nitrae-cyclohexylidene (Cy).Wherein, E 41and E 42middle at least one party is Isosorbide-5-Nitrae-phenylene.
Hydrogen atom in above-mentioned Isosorbide-5-Nitrae-phenylene (Ph) and trans-Isosorbide-5-Nitrae-cyclohexylidene (Cy) can by fluorine atom, chlorine atom or methyl substituted.
CH 2＝CR 51-COO-(L 5) k5-E 51-E 52-E 53-E 54-(M 5) n5-OCO-CR 52＝CH 2···(22)
In optical polymerism liquid crystal (22), R 51and R 52be separately hydrogen atom or methyl, preferred hydrogen atom.
K5 and n5 is separately 0 or 1, preferably 1.
L 5:-(CH 2) p5o-or-(CH 2) p5-(here, p5 is the integer of 2 ~ 8.)。
M 5:-O (CH 2) p5-or-(CH 2) p5-(here, p5 is the integer of 2 ~ 8.)。
Usually, if make optical polymerism polymerizable mesogenic, then the value of rear Δ n has the tendency of decline before polymerization, but at L 5and M 5for above-mentioned there is the group of polymethylene when, the decline of the Δ n value before and after being polymerized can be suppressed.
E 51preferred Isosorbide-5-Nitrae-phenylene (Ph).
E 52, E 53, E 54be separately Isosorbide-5-Nitrae-phenylene (Ph) or trans-Isosorbide-5-Nitrae-cyclohexylidene (Cy), and E 52and E 53in at least one party be trans-Isosorbide-5-Nitrae-cyclohexylidene (Cy).
In above-mentioned Isosorbide-5-Nitrae-phenylene (Ph) and trans-Isosorbide-5-Nitrae-cyclohexylidene (Cy) can by fluorine atom, chlorine atom or methyl substituted with the hydrogen atom of carbon atom bonding.
CH 2＝CR 61-COO-(L 6) k6-E 61-E 62-E 63-(M 6) n6-OCO-CR 62＝CH 2···(23)
In optical polymerism liquid crystal (23), R 61and R 62be separately hydrogen atom or methyl, preferred hydrogen atom.
K6 and n6 is separately 0 or 1, preferably 1.
L 6:-(CH 2) p6(Cy is trans-Isosorbide-5-Nitrae-cyclohexylidene for O-,-Cy-COO-.) or-Cy-OCO-(here, p6 is the integer of 2 ~ 8.)。
M 6:-O (CH 2) p6-, (Cy is trans-Isosorbide-5-Nitrae-cyclohexylidene to-OCO-Cy-.) or-COO-Cy-(here, p6 is the integer of 2 ~ 8.)。
E 61, E 62and E 63be separately Isosorbide-5-Nitrae-phenylene or trans-Isosorbide-5-Nitrae-cyclohexylidene.Wherein, E 61, E 62and E 63in at least 1 be Isosorbide-5-Nitrae-phenylene, and at least 1 is trans-Isosorbide-5-Nitrae-cyclohexylidene.In addition, L 6for E during-Cy-OCO- 61for trans-Isosorbide-5-Nitrae-cyclohexylidene, L 6for-(CH 2) p6e when O-or k6 is 0 61and E 63be respectively Isosorbide-5-Nitrae-phenylene, E 62for trans-Isosorbide-5-Nitrae-cyclohexylidene.
In above-mentioned Isosorbide-5-Nitrae-phenylene (Ph) and trans-Isosorbide-5-Nitrae-cyclohexylidene (Cy) can by fluorine atom, chlorine atom or methyl substituted with the hydrogen atom of carbon atom bonding.
CH 2＝CR 71-COO-(L 7) k7-Ph-(X 7)-Ph-(Y 7)-Ph-(M 7) n7-OCO-CR 72＝CH 2···(24)
In optical polymerism liquid crystal (24), R 71and R 72be separately hydrogen atom or methyl, preferred hydrogen atom.
X 7and Y 7be separately-OCO-or-COO-.
L 7:-(CH 2) p7o-,-(CH 2) p7o-COO-,-(CH 2) p7oCO-or-(CH 2) p7(here, p7 is the integer of 2 ~ 8 to COO-.)。
M 7:-O (CH 2) p7-, OCO-O (CH 2) p7-,-OCO-(CH 2) p7or-COO (CH 2) p7-(here, p7 is the integer of 2 ~ 8.)。
K7 and n7 is separately 0 or 1.
Ph is Isosorbide-5-Nitrae-phenylene.
In above-mentioned Isosorbide-5-Nitrae-phenylene can by fluorine atom, chlorine atom or methyl substituted with the hydrogen atom of carbon atom bonding.
Composition (Y) can containing known Photoepolymerizationinitiater initiater (C), known surfactant (D), known solvent (E) or other any compositions beyond the first optical polymerism liquid crystal (A) and the second optical polymerism liquid crystal (B).
As Photoepolymerizationinitiater initiater (C), oxime ester class, acetophenone class, Benzophenones, acylphosphine oxide class, benzoin class, benzil class, Michler's keton class, benzoin alkyl ethers and benzil dimethyl ketal class etc. can be exemplified.These can suitably select one kind or two or more use.
As oxime ester class; 1,2-acetyl caproyl, 1-[4-(thiophenyl)-, 2-(o-benzoyl oxime)] and ethyl ketone can be exemplified; 1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-base]-, 1-(o-acetyl-oxime).
As acetophenone class, can 2 be exemplified, 2-dimethoxy-1, 2-diphenyl-1-ethyl ketone, 1-hydroxy-cyclohexyl-phenyl-one, 2-hydroxy-2-methyl-1-phenyl-1-acetone, 1-[4-(2-hydroxyl-oxethyl)-phenyl]-2-hydroxy-2-methyl-1-acetone, 2-benzyl-2-dimethylamino-1-(4-morphlinophenyl)-1-butanone-12-(dimethylamino)-2-[(4-aminomethyl phenyl) methyl]-1-[4-(4-morpholinyl) phenyl]-1-butanone, 2-hydroxyl-1-{4-[4-(2-hydroxy-2-methyl-propiono)-benzyl] phenyl }-2-methyl isophthalic acid-acetone, 2-methyl isophthalic acid-(4-methyl mercapto phenyl)-2-morpholino-1-acetone and 2-hydroxyl-1-{4-[4-(2-hydroxy-2-methyl-propiono)-benzyl]-phenyl }-2-methyl isophthalic acid-acetone etc.
As acylphosphine oxide class, 2,4,6-trimethylbenzoy-dipheny-phosphine oxide and two (2,4,6-trimethylbenzoyl)-diphenyl-phosphineoxide etc. can be exemplified.
As surfactant (D), the surfactant of following anionic surface active agent, non-ionics, cationic surfactant, amphoteric surfactant etc. can be exemplified.
Anionic surface active agent: NaLS, Texapon Special, triethanolamine lauryl sulfate, polyoxyethylene alkyl ether sulfate salt, alkyl ether phosphate, oleoyl sodium succinate, potassium myristate, coco-nut oil fatty acid potassium, sodium lauroyl sarcosine etc.
Non-ionics: polyethylene glycol monolaurate, stearic acid sorbitan ester, myristic acid glyceride, glyceryl dioleate, sorbitan stearate, sorbitanoleate etc.
Cationic surfactant: chlorination stearyl trimethyl ammonium, chlorination behenyl ammonium, chlorination stearalkonium, cetyltrimethylammonium chloride etc.
Amphoteric surfactant: the alkyl betaines such as lauryl betaine, alkyl sulfo betaines, Cocoamidopropyl betaine and alkyl dimethyl oxyneurine, alkyl imidazoline, sodium lauroyl sarcosine, cocounut oil acyl both sexes guanidine-acetic acid sodium etc.
These surfactants can be used alone any one, also can two or more also use.
As solvent (E); cyclohexanone, ethyl cellosolve acetate, butyl cellosolve acetate, 1-methoxyl-2-propyl acetate, diethylene glycol dimethyl ether, ethylbenzene can be exemplified, ethylene glycol diethyl ether, dimethylbenzene, ethyl cellosolve, methyl-n acyl group ketone, propylene glycol monomethyl ether, toluene, MEK, ethyl acetate, methyl alcohol, ethanol, isopropyl alcohol, butanols and isobutyl ketone etc.
These solvents can be used alone any one, also can two or more also use.
As other any compositions, antioxidant, ultraviolet light absorber, silane coupling agent and light stabilizer etc. can be exemplified.
When using the total of material beyond solvent (E) in composition (Y) as 100 quality %, the first optical polymerism liquid crystal (A) in composition (Y) and the total amount of the second optical polymerism liquid crystal (B) preferably more than 80 quality % and lower than 100 quality %, particularly preferably more than 90 quality % and lower than 100 quality %.
[optical compensation films]
Optical compensation films of the present invention is formed by the coated film photocuring of above-mentioned optical polymerism liquid-crystal composition of the present invention, is the optical compensation films (positive A plate) showing positive uniaxial anisotropy.
Re (the 450)/Re (590) of positive A plate of the present invention preferably less than 1.07, more preferably less than 1.05.
When to carry out at 230 DEG C 30 minutes burn till to positive A plate of the present invention, the rate of change of the Re (590) before and after burning till preferably less than 5%.
[the stacked film of optical compensation]
The stacked film of optical compensation of the present invention is by carrying out lamination by the optical compensation films (positive A plate) of uniaxial anisotropy positive to the optical compensation films (negative C plate) and above-mentioned display of the present invention that show negative uniaxial anisotropy and obtain.
In the stacked film of optical compensation of the present invention, the laminated order of optical compensation films is not limited.In addition, alignment films can be set between negative C plate and positive A plate.That is, optical compensation films of the present invention any one form of above-mentioned (i) ~ (iv) can form the stacked film of optical compensation.Wherein, from the viewpoint of the filming of the stacked film of optical compensation, the preferably form of (iv), the i.e. form of the direct positive A plate of lamination on the negative C plate with orientation.
As for the formation of there is the composition of material of negative C plate of orientation (hereinafter sometimes referred to composition (X).), preferably containing polyimide (PI) or its precursor polyamic acid (PAA).From the birefringent aspect embodying thickness direction during hot-imide, composition (X) is preferably containing polyamic acid (PAA).
Here, polyimide film all has orientation substantially.Therefore, preferably select to make negative C plate, namely embody the birefringent material of thickness direction in the polyimide (PI) or polyamic acid (PAA) of the alignment films for the formation of liquid crystal indicator.
The equal thermotolerance of polyimide is good.Therefore, if use polyimide as negative C plate, then because the thermotolerance as optical compensation films is well preferred.
Polyimide is obtained by the polyreaction of acid anhydrides and diamines.From the view point of the light transmission improving polyimide, preferably there is in skeleton aliphatics ring.In this case, as long as select acid anhydrides or the diamines in skeleton with aliphatics ring.
When acid anhydrides has aliphatics ring, can 1 be exemplified as acid anhydrides, 2,3,4-butane tetracarboxylic acid dianhydride, 1,3-dimethyl-1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic dianhydride, 2,3,5-tricarboxylic cyclopentyl acetic acid dianhydride, 1,2,4,5-cyclopentanetetracarboxylic dianhydride and 3,3', 4,4'-bicyclohexane tetracarboxylic dianhydrides etc., can exemplify 2,2'-two (trifluoromethyl) biphenylamine and p-phenylenediamines etc. as diamines.
When diamines has aliphatics ring, can to illustrate 3,3' as acid anhydrides, 4,4'-biphenyl tetracarboxylic dianhydride, 2,3,3', 4'-biphenyl tetracarboxylic dianhydride and 1,2,5,6-naphthalene tetracarboxylic acid dianhydrides etc., can exemplify trans-1 as diamines, 4-diamino-cyclohexane, cis-1,4-diamino-cyclohexane and 4,4'-diaminostilbene, 1'-bis cyclohexane etc.
Composition (X) can contain one kind or two or more known solvent, or other one kind or two or more any compositions.
Overall relative to composition (X), content preferably 10 ~ 30 quality % of polyimide (PI) or polyamic acid (PAA).
The formation process with the negative C plate of orientation such as comprises
Substrate contains preferably by coatings such as spin-coating methods the composition (X) of polyamic acid (PAA) and solvent, forms the operation (S1) of the first coated film, and
The operation (S2) of the solvent in the first coated film is removed by the heat dryings of about 150 DEG C (baking and banking up with earth in advance), drying under reduced pressure or heating under reduced pressure drying etc., and
Polyamic acid in coated film is carried out under about 230 DEG C burn till (post-baking), generate the operation (S3) of polyimide film, and
Polyimide film is implemented to the operation (S4) of friction treatment.
The formation process of positive A plate such as comprises
On above-mentioned negative C plate, coating contains the above-mentioned optical polymerism liquid-crystal composition (Y) of the present invention of the first optical polymerism liquid crystal (A) and the second optical polymerism liquid crystal (B), form the operation (S5) of the second coated film, and
The operation (S6) of the solvent in the second coated film is removed by the heat dryings of about 80 DEG C (baking and banking up with earth in advance), drying under reduced pressure or heating under reduced pressure drying etc., and
To light such as the second coated film irradiating ultraviolet light (UV), photopolymerisable operation (S7) is carried out to optical polymerism liquid crystal (A), (B).
Sometimes only carry out illumination to penetrate, the optical polymerism liquid crystal (A) of meeting remained unreacted, (B).In this case, after operation (S7), firing process (S8) can be implemented under about 230 DEG C.
The stacked film of optical compensation of the present invention is applicable to the liquid crystal indicator of vertical orientated (VA) pattern.
In the stacked film of optical compensation, as the delay Rth preferably 100 ~ 500nm of the birefringent index in z direction, particularly preferably 200 ~ 300nm.
In the stacked film of optical compensation, super and at below 100nm preferably greater than 0nm as the delay Re of the birefringent index of x-y plane, particularly preferably 40 ~ 60nm.
The stacked film of optical compensation of the present invention owing to not needing base material film, therefore, it is possible to realize the slimming of liquid crystal indicator.
Especially, in the stacked film of optical compensation be made up of the negative C plate and direct lamination positive A plate thereon with orientation, do not need alignment films in the stacked film of optical compensation, further slimming can be realized.In addition, if reduce film number, then worker ordinal number tails off, and can realize the reduction of manufacturing cost.
In the present invention, thickness d a, the db all preferably less than 10 μm of negative C plate and positive A plate, further, more preferably less than 5 μm.Therefore, the thickness d of the stacked film of optical compensation can be made into less than 20 μm, can be made into less than 10 μm further.
In the stacked film of optical compensation of the present invention, the average transmittance of wavelength 400nm ~ 800nm preferably more than 80%, more preferably more than 85%.In this instructions, " average transmittance " is the value measured for benchmark with JISK 7361-1.
The stacked film of optical compensation of the present invention improves the wavelength dispersion characteristics of Re, and optical characteristics is good.Further, the manufacturing process of its optical characteristics for liquid crystal indicator has good thermotolerance.
[liquid crystal indicator]
The liquid crystal indicator of an example of the present invention is the color, transmissive TFT liquid crystal indicator of VA pattern.
This example can be applicable to other source matrix types such as liquid crystal indicator, TFD liquid crystal indicator of Unicolor LCD, reflection-type or Transflective, or passive matrix.
As shown in Figure 1, the liquid crystal indicator 1 of this example has liquid crystal cell 1A, is attached to the polariton 51,52 outside it, and backlight BL.
Liquid crystal cell 1 possess color filter substrate 10, as subtend substrate TFT substrate 20 and by this pair substrate the liquid crystal layer 30 of seizing on both sides by the arms.
Color filter substrate (electrode base board, base plate for liquid crystal display device) 10 possesses light-transmitting substrate 11, black matrix layer BM, colour filter CF in this liquid crystal layer 30 side successively lamination, the stacked film 12 of optical compensation, common electrode 13 and alignment films 14.
TFT substrate 20 possesses in liquid crystal layer 30 side of light-transmitting substrate and is formed as rectangular pixel electrode substrate 21 using multiple pixel electrode with as multiple TFT (thin film transistor (TFT)) of the on-off element of pixel electrode, and is formed in the alignment films 22 of this liquid crystal layer 30 side.
As the light-transmitting substrate for color filter substrate 10 and TFT substrate 20, preferred glass substrate.
In transmissive liquid crystal display device 1, as the material of common electrode 13 and pixel electrode, use the transparent conductive materials such as ITO (indium tin oxide).
Black matrix layer BM is the light shield layer to carrying out shading between the pixel adjoined each other.
Colour filter CF such as comprises the dyed layer of red (R), green (G) and blue (B).In this case, the dyed layer of 3 pixel electrodes and 3 colors forms 1 pixel (1 pixel=3 pixel).
The stacked film of optical compensation 12 is above-mentioned stacked films of optical compensation of the present invention, as shown in Figure 3, and the stacked film of preferred negative C plate 12A and positive A plate 12B.
In this example, and then the stacked film 12 of optical compensation forms common electrode 13, form alignment films 14 thereon.
The laminated structure of color filter substrate 10 can carry out suitable design alteration.
Such as, shown in the color filter substrate 40 of design alteration as shown in Figure 2, liquid crystal cell 2A and liquid crystal indicator 2, the stacked film 12 of optical compensation, black matrix layer BM, colour filter CF, common electrode 13 and alignment films 14 can be set gradually form on light-transmitting substrate 11.
The color filter substrate (electrode base board, base plate for liquid crystal display device) 10 of this example and the optical characteristics of liquid crystal indicator 1 and thermotolerance good.The color filter substrate 10 of this example and liquid crystal indicator 1 owing to possessing the stacked film 12 of optical compensation in liquid crystal cell 1A, therefore, it is possible to carry out slimming and cost degradation.
Embodiment
Below, based on embodiment, the present invention will be described, but the present invention is not limited to these embodiments.Example 11,12 and example 21,22 are embodiment, and example 13,14 and example 23,24 are comparative example.
As the optical polymerism liquid crystal of positive A plate, prepare following compound (A1), (A2), (B1).
[changing 11]
The other materials of positive A plate is as follows.
Photoepolymerizationinitiater initiater (C1): BASF AG (BASF society) system " Irgacure907 ".
Surfactant (D1): AGC Agc Seimi Chemical Co., Ltd. (AGC セ イ ミ ケ ミ カ Le society) fluorine class non-ionic surfactant " Surflon S420 " processed.
Solvent (E1): cyclopentanone.
[example 11: the positive A plate preparation of coating fluid (Y1)]
Optical polymerism liquid crystal (A1) 0.75g, optical polymerism liquid crystal (B1) 0.25g are mixed, obtains liquid-crystal composition.Weighing is the Photoepolymerizationinitiater initiater (C1) of 5 quality % and the surfactant (D1) of 1 quality % relative to said composition respectively, mixes.Afterwards, add solvent (E1) and mix, making 15 quality % solution.Used the filtrator in 0.5 μm, opening footpath to filter, obtained coating fluid (Y1).
Proportioning composition is shown in table 1.
[example 12: the positive A plate preparation of coating fluid (Y2)]
Except cooperation composition is as shown in table 1, obtain coating fluid (Y2) in the mode identical with example 11.
[example 13,14: the preparation of positive A plate coating fluid (Z1), (Z2)]
Except cooperation composition is as shown in table 1, obtain coating fluid (Z1), (Z2) in the mode identical with example 11.
[example 21: the making of the stacked film of optical compensation]
< bears the film forming > of C plate (NC1)
Trans-Isosorbide-5-Nitrae-diamino-cyclohexane 1.14g is dissolved in METHYLPYRROLIDONE 17.44g, adds 3,3', 4,4'-biphenyl tetracarboxylic dianhydride 2.83g and METHYLPYRROLIDONE 4.00g, stir 3 hours at 60 DEG C.Then, after adding phthalic anhydride 0.12g, stir 3 hours at 60 DEG C, obtain polyamic acid (PAA1) solution.Used the filtrator in 0.5 μm, opening footpath to filter, obtained coating fluid (X1).By this coating fluid with spin-coating method coating on the glass substrate (3000rpm, 30 seconds), with heating plate at 90 DEG C dry 2 minutes.Carry out friction treatment carry out the heating of 30 minutes again at 230 DEG C after, film forming is carried out to the negative C plate (NC1) of the function with alignment films.Thickness is 3.1 μm, and the birefraction P under the 590nm of thickness direction is 0.090, Rth=279nm.
The film forming > of the positive A plate (PA1) of <
On above-mentioned negative C plate (NC1), be coated with above-mentioned coating fluid (Y1) with spin-coating method, carry out 80 DEG C of dryings in 2 minutes, direction of adjustment.Afterwards, from vertical direction to real estate irradiation ultraviolet radiation 60 seconds, coated film is solidified, forms positive A plate (PA1).Illumination for the high-pressure sodium lamp of photocuring counts 190mW/cm with wavelength 365nm 2.
As above the stacked film of optical compensation is obtained.
Main manufacturing condition is shown in table 1.
[example 22: the making of the stacked film of optical compensation]
In the mode identical with example 21, film forming is carried out to negative C plate (NC1).
Except replacing except coating fluid (Y1) at the upper above-mentioned coating fluid (Y2) that uses of above-mentioned negative C plate (NC1), aligning A plate (PA2) in the mode identical with example 21 and carrying out film forming, obtaining the stacked film of optical compensation.
The main manufacturing condition of each example is shown in table 1.
[example 23,24: the making of the stacked film of optical compensation]
In the mode identical with example 21, film forming is carried out to negative C plate (NC1).
Except replacing except coating fluid (Y1) at above-mentioned negative C plate (NC1) the above-mentioned coating fluid of upper use (Z1), (Z2), align A plate (PA3) in the mode identical with example 21, (PA4) carry out film forming, obtain the stacked film of optical compensation.
The main manufacturing condition of each example is shown in table 1.
[evaluation]
(mensuration of Re)
Re when wavelength being changed in visible-range (400 ~ 800nm) is determined to the stacked film of the optical compensation obtained.The value of Re (450)/Re (590) is obtained according to the data obtained.
(thermotolerance)
30 minutes burning till is carried out at 230 DEG C to the stacked film of the optical compensation obtained, obtains the rate of change of the Re (590) before and after burning till.Evaluate based on following benchmark.Good (zero): 0 ~ 5%, can (△): 5 ~ 10%, can not (×): more than 10%.
[result]
The mensuration figure of the Re relative to wavelength in the stacked film of the optical compensation of example 21 ~ example 24 has been shown in Fig. 4 A ~ Fig. 4 D.
The evaluation result of Re (450)/Re (590) and thermotolerance is shown in table 1.
Only using the second optical polymerism liquid crystal (B) with aromatic ring as in the stacked film of optical compensation of the example 23 of the optical polymerism liquid crystal of positive A plate material, relative to the increase of wavelength, the minimizing level of Re is high, and Re (450)/Re (590) is 1.10.
Only using the first optical polymerism liquid crystal (A) without aromatic ring as in the stacked film of optical compensation of the example 24 of the optical polymerism liquid crystal of positive A plate material, relative to the increase of wavelength, the minimizing of Re is suppressed, and Re (450)/Re (590) is 1.02.But 230 DEG C of rate of change burning till the Re (590) of front and back are 5 ~ 10%, and thermotolerance is not enough.
In the stacked film of optical compensation also using the first optical polymerism liquid crystal (A) without aromatic ring and the second optical polymerism liquid crystal (B) with aromatic ring as the example 21,22 of the optical polymerism liquid crystal of positive A plate material, relative to the increase of wavelength, the minimizing of Re is suppressed, and Re (450)/Re (590) is 1.04.In addition, 230 DEG C burn till before and after the rate of change of Re (590) be within 5%, thermotolerance is also good.
[table 1]
The concentration of (note 1) composition (C), (D) is the concentration of the total amount relative to composition (A), (B), the concentration of composition (E) is concentration relative to coating fluid entirety 100%.
Here the announcement of full content as instructions of the present invention of the instructions of No. 2013-002538, the Japanese patent application that on January 10th, 2013 files an application, claims, accompanying drawing and summary is quoted.
Symbol description
1,2: liquid crystal indicator; 1A, 2A: liquid crystal cell; 10,40: color filter substrate (electrode base board, base plate for liquid crystal display device); 11: light-transmitting substrate; 12: the stacked film of optical compensation; 12A: negative C plate (optical compensation films of the uniaxial anisotropy that display is negative); 12B: positive A plate (showing the optical compensation films of positive uniaxial anisotropy); 13: common electrode; 14: alignment films; 20:TFT substrate; 21: pixel electrode substrate; 22: alignment films; 30: liquid crystal layer; 51,52: polariton; BM: black matrix; CF: colour filter; BL: backlight.

Claims (15)

1. an optical polymerism liquid-crystal composition, it is the optical polymerism liquid-crystal composition of the optical compensation films for the formation of the positive uniaxial anisotropy of display, it is characterized in that,
Containing there is aliphatics ring, not there is the first optical polymerism liquid crystal (A) of aromatic ring, and there is the second optical polymerism liquid crystal (B) of aromatic ring,
Relative to the total amount of optical polymerism liquid crystal, the amount of the first optical polymerism liquid crystal (A) is at more than 50 quality % and lower than 100 quality %, and the amount of the second optical polymerism liquid crystal (B) is more than 0 quality % and at below 50 quality %.
2. optical polymerism liquid-crystal composition as claimed in claim 1, it is characterized in that, the first optical polymerism liquid crystal (A) is containing including the simple function optical polymerism liquid crystal of 1 photopolymerization reaction group at 1 molecule and/or including two sense optical polymerism liquid crystal of 2 photopolymerization reaction groups at 1 molecule.
3. optical polymerism liquid-crystal composition as claimed in claim 2, is characterized in that, the simple function optical polymerism liquid crystal that the first optical polymerism liquid crystal (A) represents containing following formula (11);
CH 2＝CR 11-COO-(L 1) a1-E 11-(S 1) b1-E 12-(T 1) c1-(E 13) d1-R 12···(11)
In formula, symbol represents following implication:
R 11: hydrogen atom or methyl;
R 12: the alkyl of carbon number 1 ~ 8 or fluorine atom, wherein, when for alkyl, can between carbon-carbon bond or with the end of cyclic group bonding on there is the oxygen atom of ehter bond, part or all of hydrogen atom can be replaced by fluorine atoms;
L 1: the oxygen atom can between carbon-carbon bond with ehter bond, part or all of hydrogen atom can be replaced by fluorine atoms, with E 11the position of bonding can have the alkyl of the carbon number 1 ~ 8 of COO, OCO or O;
E 11, E 12and E 13: be separately trans-Isosorbide-5-Nitrae-cyclohexylidene or trans-2,6-decahydronaphthalene naphthyls, wherein, in group can by fluorine atom or methyl substituted with the hydrogen atom of carbon atom bonding;
S 1and T 1: be separately-OCO-,-COO-,-(CH 2) 2-,-CH 2o-,-OCH 2-or singly-bound;
A1, b1, c1 and d1: be separately 0 or 1.
4. optical polymerism liquid-crystal composition as claimed in claim 2, is characterized in that, the two sense optical polymerism liquid crystal that the first optical polymerism liquid crystal (A) represents containing following formula (12);
CH 2＝CR 21-COO-(L 2) a2-E 21-(S 2) b2-E 22-(T 2) c2-(E 23) d2-(M 2) e2-OCO-CR 22＝CH 2···(12)
In formula, symbol represents following implication:
R 21and R 22: be separately hydrogen atom or methyl;
L 2: the oxygen atom can between carbon-carbon bond with ehter bond, part or all of hydrogen atom can be replaced by fluorine atoms, with E 21the position of bonding can have the alkyl of the carbon number 1 ~ 8 of COO, OCO or O;
M 2: the oxygen atom can between carbon-carbon bond with ehter bond, part or all of hydrogen atom can be replaced by fluorine atoms, with E 23the position of bonding can have the alkyl of the carbon number 1 ~ 8 of COO, OCO or O;
E 21, E 22and E 23: be separately trans-Isosorbide-5-Nitrae-cyclohexylidene or trans-2,6-decahydronaphthalene naphthyls, wherein, in group can by fluorine atom or methyl substituted with the hydrogen atom of carbon atom bonding;
S 2and T 2: be separately-OCO-,-COO-,-(CH 2) 2-,-CH 2o-,-OCH 2-or singly-bound;
A2, b2, c2 and d2: be separately 0 or 1.
5. the optical polymerism liquid-crystal composition according to any one of Claims 1 to 4, is characterized in that, the second optical polymerism liquid crystal (B) represents with following formula (20);
Q 1-Z 1-A 1-Z 3-M-Z 4-A 2-Z 2-Q 2···(20)
In formula, symbol represents following implication:
Q 1and Q 2: be separately photopolymerization reaction group;
Z 1, Z 2, Z 3and Z 4: be separately singly-bound or divalent linker;
A 1and A 2: the interval base being separately carbon number 2 ~ 20;
M: the mesomorphic group containing aromatic ring.
6. optical polymerism liquid-crystal composition as claimed in claim 5, is characterized in that, the optical polymerism liquid crystal that the second optical polymerism liquid crystal (B) represents containing following formula (21);
CH 2＝CR 41-COO-(E 41) m4-Cy-Y 4-Cy-(E 42) n4-OCO-CR 42＝CH 2···(21)
In formula, symbol represents following implication:
R 41and R 42: be separately hydrogen atom or methyl;
Y 4:-OCO-or-COO-;
M4 and n4: be separately 0 or 1, wherein, both sides are except the situation of 0;
E 41and E 42: be separately Isosorbide-5-Nitrae-phenylene or trans-Isosorbide-5-Nitrae-cyclohexylidene, wherein, E 41and E 42middle at least one party is Isosorbide-5-Nitrae-phenylene;
Cy: trans-Isosorbide-5-Nitrae-cyclohexylidene;
Hydrogen atom in described Isosorbide-5-Nitrae-phenylene and trans-Isosorbide-5-Nitrae-cyclohexylidene can by fluorine atom, chlorine atom or methyl substituted.
7. optical polymerism liquid-crystal composition as claimed in claim 5, is characterized in that, the optical polymerism liquid crystal that the second optical polymerism liquid crystal (B) represents containing following formula (22);
CH 2＝CR 51-COO-(L 5) k5-E 51-E 52-E 53-E 54-(M 5) n5-OCO-CR 52＝CH 2···(22)
In formula, symbol represents following implication:
R 51and R 52: be separately hydrogen atom or methyl;
K5 and n5: be separately 0 or 1;
L 5:-(CH 2) p5o-or-(CH 2) p5-, here, p5 is the integer of 2 ~ 8;
M 5:-O (CH 2) p5-or-(CH 2) p5-, here, p5 is the integer of 2 ~ 8;
E 51: Isosorbide-5-Nitrae-phenylene;
E 52, E 53, E 54: be separately Isosorbide-5-Nitrae-phenylene or trans-Isosorbide-5-Nitrae-cyclohexylidene, and E 52and E 53in at least one party be trans-Isosorbide-5-Nitrae-cyclohexylidene; In described Isosorbide-5-Nitrae-phenylene and trans-Isosorbide-5-Nitrae-cyclohexylidene can by fluorine atom, chlorine atom or methyl substituted with the hydrogen atom of carbon atom bonding.
8. optical polymerism liquid-crystal composition as claimed in claim 5, is characterized in that, the optical polymerism liquid crystal that the second optical polymerism liquid crystal (B) represents containing following formula (23);
CH 2＝CR 61-COO-(L 6) k6-E 61-E 62-E 63-(M 6) n6-OCO-CR 62＝CH 2···(23)
In formula, symbol represents following implication:
R 61and R 62: be separately hydrogen atom or methyl;
K6 and n6: be separately 0 or 1;
L 6:-(CH 2) p6o-,-Cy-COO-or-Cy-OCO-, wherein Cy is trans-Isosorbide-5-Nitrae-cyclohexylidene, and p6 is the integer of 2 ~ 8;
M 6:-O (CH 2) p6-,-OCO-Cy-or-COO-Cy-, wherein Cy is trans-Isosorbide-5-Nitrae-cyclohexylidene, and p6 is the integer of 2 ~ 8;
E 61, E 62and E 63: be separately Isosorbide-5-Nitrae-phenylene or trans-Isosorbide-5-Nitrae-cyclohexylidene, wherein, E 61, E 62and E 63in at least 1 be Isosorbide-5-Nitrae-phenylene, and at least 1 is trans-Isosorbide-5-Nitrae-cyclohexylidene; In addition, L 6for E during-Cy-OCO- 61for trans-Isosorbide-5-Nitrae-cyclohexylidene, L 6for-(CH 2) p6e when O-or k6 is 0 61and E 63be respectively Isosorbide-5-Nitrae-phenylene, E 62for trans-Isosorbide-5-Nitrae-cyclohexylidene; Wherein, in described Isosorbide-5-Nitrae-phenylene and trans-Isosorbide-5-Nitrae-cyclohexylidene can by fluorine atom, chlorine atom or methyl substituted with the hydrogen atom of carbon atom bonding.
9. optical polymerism liquid-crystal composition as claimed in claim 5, is characterized in that, the optical polymerism liquid crystal that the second optical polymerism liquid crystal (B) represents containing following formula (24);
CH 2＝CR 71-COO-(L 7) k7-Ph-(X 7)-Ph-(Y 7)-Ph-(M 7) n7-OCO-CR 72＝CH 2···(24)
In formula, symbol represents following implication:
R 71and R 72: be separately hydrogen atom or methyl;
X 7and Y 7: be separately-OCO-or-COO-;
L 7:-(CH 2) p7o-,-(CH 2) p7o-COO-,-(CH 2) p7oCO-or-(CH 2) p7cOO-, here, p7 is the integer of 2 ~ 8;
M 7:-O (CH 2) p7-, OCO-O (CH 2) p7-,-OCO-(CH 2) p7or-COO (CH 2) p7-, here, p7 is the integer of 2 ~ 8;
K7 and n7: be separately 0 or 1; Ph:1,4-phenylene; Wherein, in described Isosorbide-5-Nitrae-phenylene can by fluorine atom, chlorine atom or methyl substituted with the hydrogen atom of carbon atom bonding.
10. an optical compensation films, is characterized in that, carry out photocuring to the coated film of the optical polymerism liquid-crystal composition according to any one of claim 1 ~ 9 and obtain, described optical compensation films shows positive uniaxial anisotropy.
11. 1 kinds of stacked films of optical compensation, is characterized in that, possess the optical compensation films of the negative uniaxial anisotropy of display, and the optical compensation films of the positive uniaxial anisotropy of the as claimed in claim 10 display of lamination on this optical compensation films.
The stacked film of 12. optical compensation as claimed in claim 11, it is characterized in that, the optical compensation films of the uniaxial anisotropy that described display is born contains the polyimide in skeleton with aliphatics ring.
13. 1 kinds of electrode base boards, is characterized in that, substrate possesses the stacked film of optical compensation as claimed in claim 12 and is formed at the electrode on the stacked film of this optical compensation.
14. 1 kinds of base plate for liquid crystal display device, is characterized in that, possess electrode base board as claimed in claim 13 and are formed at the alignment films on this electrode base board.
15. 1 kinds of liquid crystal indicators, is characterized in that, possess liquid crystal substrate as claimed in claim 14, subtend substrate, by the liquid crystal layer of this liquid crystal substrate and subtend substrate clamping.
CN201480004428.1A 2013-01-10 2014-01-09 Photopolymerizable liquid crystal composition, optical compensation film, optical compensataion laminate film, electrode substrate, substrate for liquid crystal display devices, and liquid crystal display device Pending CN104903764A (en)

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