CN110651208B - Optically anisotropic layer and method for producing same, optically anisotropic laminate, transfer multilayer, polarizing plate, and image display device - Google Patents
Optically anisotropic layer and method for producing same, optically anisotropic laminate, transfer multilayer, polarizing plate, and image display device Download PDFInfo
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- CN110651208B CN110651208B CN201880033980.1A CN201880033980A CN110651208B CN 110651208 B CN110651208 B CN 110651208B CN 201880033980 A CN201880033980 A CN 201880033980A CN 110651208 B CN110651208 B CN 110651208B
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- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
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- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
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- 125000002883 imidazolyl group Chemical group 0.000 description 1
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- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
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- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- SKTCDJAMAYNROS-UHFFFAOYSA-N methoxycyclopentane Chemical compound COC1CCCC1 SKTCDJAMAYNROS-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- KKFHAJHLJHVUDM-UHFFFAOYSA-N n-vinylcarbazole Chemical compound C1=CC=C2N(C=C)C3=CC=CC=C3C2=C1 KKFHAJHLJHVUDM-UHFFFAOYSA-N 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Chemical group C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
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- 125000002971 oxazolyl group Chemical group 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
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- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- LFSXCDWNBUNEEM-UHFFFAOYSA-N phthalazine Chemical group C1=NN=CC2=CC=CC=C21 LFSXCDWNBUNEEM-UHFFFAOYSA-N 0.000 description 1
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- 230000010287 polarization Effects 0.000 description 1
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- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
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- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid group Chemical group C(CCC(=O)O)(=O)O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
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Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/13363—Birefringent elements, e.g. for optical compensation
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/02—Details
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/80—Constructional details
- H10K59/8791—Arrangements for improving contrast, e.g. preventing reflection of ambient light
Landscapes
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- General Physics & Mathematics (AREA)
- Nonlinear Science (AREA)
- Mathematical Physics (AREA)
- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Polarising Elements (AREA)
- Devices For Indicating Variable Information By Combining Individual Elements (AREA)
- Electroluminescent Light Sources (AREA)
- Laminated Bodies (AREA)
- Liquid Crystal (AREA)
Abstract
The invention provides an optically anisotropic layer comprising a polymer of a positive C polymer and a mesogenic compound, wherein the mesogenic compound is a compound having a mesogenic skeleton and an acrylate structure, and the optically anisotropic layer satisfies 0.073 & ltAC‑H/AC＝O(mesogenic compound) < 0.125. A. theC‑HIs an infrared absorption of an out-of-plane bending vibration of the C-H bond of the acrylate structure in the infrared absorption spectrum of the optically anisotropic layer, AC＝OThe (mesogenic compound) is a sum of infrared absorption of stretching vibration of the C ═ O bond of the acrylate structure and infrared absorption of stretching vibration of the C ═ O bond derived from the C ═ O bond of the acrylate structure in the infrared absorption spectrum of the optically anisotropic layer. The invention also provides the manufacture and use of the optically anisotropic layer.
Description
Technical Field
The present invention relates to an optically anisotropic layer and a method for producing the same; an optically anisotropic laminate having the optically anisotropic layer; and a transfer multilayer article, a polarizing plate and an image display device each having the optically anisotropic layer.
Background
Image display devices such as liquid crystal display devices and organic electroluminescence display devices are provided with various optical films. Hereinafter, "organic electroluminescence" is sometimes referred to as "organic EL" as appropriate. Conventionally, techniques relating to such optical films have been studied (for example, patent documents 1 and 2).
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2015-14712;
patent document 2: japanese patent laid-open publication No. 2015-57646 (corresponding publication: U.S. patent application publication No. 2015/041051).
Disclosure of Invention
Problems to be solved by the invention
A circularly polarizing plate may be provided on the display surface of the image display device. As the circularly polarizing plate, an optical film having a linear polarizer and an optically anisotropic layer is generally used. By providing the circularly polarizing plate on the display surface of the image display device, when the display surface is viewed from the front direction, reflection of external light is suppressed, and light for displaying an image can be transmitted through the polarized sunglasses, whereby the visibility of the image can be improved.
When the display surface is viewed from an oblique direction, the effect of the circularly polarizing plate described above may be impaired. In order to improve the effect when the display surface is viewed from an oblique direction, it is conceivable to provide a positive C film in combination with a circularly polarizing plate. The positive C film for such use is preferably a film exhibiting reverse wavelength dispersion in retardation Rth in the thickness direction thereof. It is conceivable to produce such a positive C film by a production method using a liquid crystal compound as described in patent documents 1 and 2, for example.
However, it is not easy to produce a positive C film having retardation Rth in the thickness direction showing reverse wavelength dispersion in the conventional art. For example, in a method using an alignment film, such as a method for producing a liquid crystal compound described in patent documents 1 and 2, it is necessary to adjust the compatibility between the alignment film and the liquid crystal compound, and therefore, the adjustment is troublesome. Further, since the number of steps for applying the alignment film to the substrate is increased, the use of the alignment film may increase the cost. In addition, various properties are required for optical films used in image display devices in addition to wavelength dispersion properties. For example, an optical film is required to have high durability and a good color tone. In the conventional positive C film having reverse wavelength dispersibility Rth, such durability and color tone are sometimes poor. For example, an optical film is generally required to be less deteriorated by long-term use in an environment at high temperature, but a conventional positive C film having a reverse wavelength dispersibility Rth is likely to have problems such as an increase in haze and white turbidity by long-term use in a high-temperature environment. In addition, although the optical film is generally required to have nearly colorless color tone without variation in transmittance and reflectance depending on the wavelength of light, the conventional positive C film having the reverse wavelength dispersibility Rth may have a color tone of yellow or the like instead of colorless.
Accordingly, an object of the present invention is to provide an optically anisotropic layer which can be produced without using an alignment film, has high durability in a positive C-plate in which retardation Rth in the thickness direction exhibits reverse wavelength dispersibility, and has a good color tone, an optically anisotropic laminate having the optically anisotropic layer, a method for producing the same, and an optically anisotropic laminate, a transfer multilayer, a polarizing plate, and an image display device each having the optically anisotropic layer.
Means for solving the problems
The present invention is as follows.
[1] An optically anisotropic layer, comprising: n-C polymers, mesogenic (mesogen) compounds, and polymers of mesogenic compounds,
when the n-C polymer is formed into a film of the n-C polymer by a coating method using a solution of the n-C polymer, the film is a polymer satisfying formula (1),
the mesogenic compound is a compound having a mesogenic skeleton and an acrylate structure,
the optically anisotropic layer satisfies formula (2) and formula (3):
nz (P) > nx (P) ≧ ny (P) formula (1)
nz (A) > nx (A) ≧ ny (A) formula (2)
0.073＜AC-H/AC＝O(mesogenic compound) < 0.125 formula (3)
Wherein,
nx (P), ny (P) and nz (P) are the principal refractive indices of the film,
nx (A), ny (A) and nz (A) are principal refractive indices of the optically anisotropic layer,
AC-His infrared absorption of out-of-plane bending vibration of the C-H bond of the acrylate structure of the mesogenic compound in the infrared absorption spectrum of the optically anisotropic layer,
AC＝Othe (mesogenic compound) is a sum of infrared absorption of stretching vibration of the C ═ O bond of the acrylate structure of the mesogenic compound and infrared absorption of stretching vibration of the C ═ O bond derived from the C ═ O bond of the acrylate structure of the mesogenic compound in the infrared absorption spectrum of the optically anisotropic layer.
[2] The optically anisotropic layer according to [1], wherein the mesogenic compound is a compound which exhibits an in-plane retardation of inverse wavelength dispersibility when aligned in parallel.
[3] The optically anisotropic layer according to [1] or [2], wherein formulae (4) and (5) are satisfied:
0.50 < Rth (A450)/Rth (A550) < 1.00 formula (4)
1.00. ltoreq. Rth (A650)/Rth (A550) < 1.25 formula (5)
Wherein,
rth (A450) is a retardation in the thickness direction of the optically anisotropic layer at a wavelength of 450nm,
rth (A550) is a retardation in the thickness direction of the optically anisotropic layer at a wavelength of 550nm,
rth (A650) is the retardation in the thickness direction of the optically anisotropic layer at a wavelength of 650 nm.
[4] The optically anisotropic layer according to any one of [1] to [3], wherein the mesogenic compound is represented by the following formula (I):
[ chemical formula 1]
(in the above-mentioned formula (I),
Y1～Y8each independently represents a chemical single bond, -O-, or,-S-、-O-C(＝O)-、-C(＝O)-O-、-O-C(＝O)-O-、-NR1-C(＝O)-、-C(＝O)-NR1-、-O-C(＝O)-NR1-、-NR1-C(＝O)-O-、-NR1-C(＝O)-NR1-、-O-NR1-, or-NR1-O-. Herein, R is1Represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
G1And G2Each independently represents a divalent aliphatic group having 1 to 20 carbon atoms which may have a substituent. In the above aliphatic group, 1 or more of-O-, -S-, -O-C- (O) -, -C- (O) -O-, -O-C- (O) -O-, -NR-, may be inserted into each aliphatic group2-C(＝O)-、-C(＝O)-NR2-、-NR2-, or-C (═ O) -. However, except for the case where more than 2 adjacent insertions of-O-or-S-respectively are present. Herein, R is2Represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
Z1And Z2Each independently represents an alkenyl group having 2 to 10 carbon atoms which may be substituted with a halogen atom.
AxThe aromatic ring is an organic group having 2 to 30 carbon atoms and having at least one aromatic ring selected from an aromatic hydrocarbon ring and an aromatic heterocyclic ring.
AyRepresents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, a cycloalkyl group having 3 to 12 carbon atoms which may have a substituent, an alkynyl group having 2 to 20 carbon atoms which may have a substituent, -C (═ O) -R3、-SO2-R4、-C(＝S)NH-R9Or an organic group having 2 to 30 carbon atoms and having at least one aromatic ring selected from an aromatic hydrocarbon ring and an aromatic heterocyclic ring. Herein, R is3Represents an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, a cycloalkyl group having 3 to 12 carbon atoms which may have a substituent, or an aromatic hydrocarbon ring group having 5 to 12 carbon atoms. R4Represents an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a phenyl group, or a 4-methylphenyl group. R9The representation can haveThe substituent is an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, a cycloalkyl group having 3 to 12 carbon atoms which may have a substituent, or an aromatic group having 5 to 20 carbon atoms which may have a substituent. A abovexAnd AyThe aromatic ring may have a substituent. Further, the above-mentioned AxAnd AyMay together form a ring.
A1Represents a trivalent aromatic group which may have a substituent.
A2And A3Each independently represents a divalent alicyclic hydrocarbon group having 3 to 30 carbon atoms which may have a substituent.
A4And A5Each independently represents a divalent aromatic group having 6 to 30 carbon atoms which may have a substituent.
Q1Represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent.
m and n each independently represent 0 or 1.
Wherein Z is1-Y7-and-Y8-Z2One or both of which are acryloxy groups. )
[5] The optically anisotropic layer according to any one of [1] to [4], wherein the mesogenic compound contains in its molecular structure: at least one selected from the group consisting of a benzothiazole ring, and a combination of a cyclohexyl ring and a phenyl ring.
[6] The optically anisotropic layer according to any one of [1] to [5], wherein the positive C polymer is at least one polymer selected from polyvinylcarbazole, polyfumarate and cellulose derivatives.
[7] The optically anisotropic layer according to any one of [1] to [6], wherein a ratio of the mesogenic compound and the polymer thereof in a total solid content of the optically anisotropic layer is 20% by weight or more and 60% by weight or less.
[8] The optically anisotropic layer according to any one of [1] to [7], wherein the following formulas (6) and (7) are satisfied:
re (A590) is less than or equal to 10nm type (6)
Rth (A590) of 200nm or more and 10nm or less as formula (7)
Wherein,
re (A590) is an in-plane retardation of the optically anisotropic layer at a wavelength of 590nm,
rth (A590) is the retardation in the thickness direction of the optically anisotropic layer at a wavelength of 590 nm.
[9] A transfer multilayer article comprising: a substrate, and the optically anisotropic layer according to any one of [1] to [8 ].
[10] An optically anisotropic laminate comprising: [1] the optically anisotropic layer and the retardation layer according to any one of [1] to [8],
the retardation layer satisfies formula (8):
nx (B) ny (B) nz (B) formula (8)
Wherein nx (B), ny (B) and nz (B) are the principal refractive indices of the retardation layer.
[11] The optically anisotropic laminate according to [10], wherein the retardation layer satisfies formula (9) and formula (10):
0.75 < Re (B450)/Re (B550) < 1.00 formula (9)
1.01 < Re (B650)/Re (B550) < 1.25 formula (10)
Wherein,
re (B450) is an in-plane retardation of the retardation layer at a wavelength of 450nm,
re (B550) is an in-plane retardation of the retardation layer at a wavelength of 550nm,
re (B650) is an in-plane retardation of the retardation layer at a wavelength of 650 nm.
[12] The optically anisotropic laminate according to [11], wherein the retardation layer comprises a liquid crystal compound for retardation layer represented by the following formula (II):
[ chemical formula 2]
(in the above-mentioned formula (II),
Y1～Y8are respectively and independentlyRepresents a single chemical bond, -O-, -S-, -O-C (═ O) -, -C (═ O) -O-, -O-C (═ O) -O-, -NR1-C(＝O)-、-C(＝O)-NR1-、-O-C(＝O)-NR1-、-NR1-C(＝O)-O-、-NR1-C(＝O)-NR1-、-O-NR1-, or-NR1-O-. Herein, R is1Represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
G1And G2Each independently represents a divalent aliphatic group having 1 to 20 carbon atoms which may have a substituent. In addition, in the above aliphatic group, 1 or more of — O-, -S-, -O-C (═ O) -, -C (═ O) -O-, -O-C (═ O) -O-, -NR can be inserted into each aliphatic group2-C(＝O)-、-C(＝O)-NR2-、-NR2-, or-C (═ O) -. However, except for the case where more than 2 adjacent insertions of-O-or-S-respectively are present. Herein, R is2Represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
Z1And Z2Each independently represents an alkenyl group having 2 to 10 carbon atoms which may be substituted with a halogen atom.
AxThe aromatic ring is an organic group having 2 to 30 carbon atoms and having at least one aromatic ring selected from an aromatic hydrocarbon ring and an aromatic heterocyclic ring.
AyRepresents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, a cycloalkyl group having 3 to 12 carbon atoms which may have a substituent, an alkynyl group having 2 to 20 carbon atoms which may have a substituent, -C (═ O) -R3、-SO2-R4、-C(＝S)NH-R9Or an organic group having 2 to 30 carbon atoms and having at least one aromatic ring selected from an aromatic hydrocarbon ring and an aromatic heterocyclic ring. Herein, R is3Represents an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, a cycloalkyl group having 3 to 12 carbon atoms which may have a substituent, or an aromatic hydrocarbon ring group having 5 to 12 carbon atoms. R4Represents an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a phenyl group, or a 4-methylphenyl group. R9Represents an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, a cycloalkyl group having 3 to 12 carbon atoms which may have a substituent, or an aromatic group having 5 to 20 carbon atoms which may have a substituent. A abovexAnd AyThe aromatic ring may have a substituent. And, the above-mentioned AxAnd AyMay together form a ring.
A1Represents a trivalent aromatic group which may have a substituent.
A2And A3Each independently represents a divalent alicyclic hydrocarbon group having 3 to 30 carbon atoms which may have a substituent.
A4And A5Each independently represents a divalent aromatic group having 6 to 30 carbon atoms which may have a substituent.
Q1Represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent.
m and n each independently represent 0 or 1. )
[13] A polarizing plate, comprising:
a linear polarizer; and
[1] the optically anisotropic layer according to any one of [1] to [8], the transfer multilayer object according to [9], or the optically anisotropic laminate according to any one of [10] to [12 ].
[14] An image display device having the polarizing plate of [13 ].
[15] An image display device, comprising in order: [10] the optically anisotropic laminate according to any one of [1] to [12],
A linear polarizer,
And an image display element, and a display element,
the image display element is a liquid crystal cell or an organic electroluminescent element.
[16] A method for producing an optically anisotropic layer according to any one of [1] to [8], comprising:
preparing a coating liquid containing a positive C polymer, a mesogenic compound, a solvent, a photopolymerization initiator, and a crosslinking agent;
applying the coating liquid to a support surface to obtain a coating liquid layer;
and curing the coating liquid layer by irradiating the coating liquid layer with light.
[17] The method for producing an optically anisotropic layer according to item [16], wherein a ratio of the photopolymerization initiator to 100 parts by weight of the mesogenic compound in the coating liquid is 1 to 10 parts by weight,
the ratio of the crosslinking agent to 100 parts by weight of the mesogenic compound is 1 to 10 parts by weight.
[18]According to [16]Or [17]]The manufacturing method described above, wherein the cumulative quantity of the irradiated light is 600mJ/cm2～5000mJ/cm2。
Effects of the invention
According to the present invention, there can be provided an optically anisotropic layer which can be produced without using an alignment film, has high durability in a positive C-plate in which retardation Rth in the thickness direction exhibits reverse wavelength dispersibility, and has a good color tone, and an optically anisotropic laminate, a transfer multilayer, a polarizing plate, and an image display device each having the optically anisotropic layer.
Detailed Description
The present invention will be described in detail below with reference to embodiments and examples. However, the present invention is not limited to the embodiments and examples described below, and may be implemented by arbitrarily changing the embodiments and examples without departing from the scope and range of equivalents of the claims.
In the following description, unless otherwise specified, the front direction of a certain plane refers to the normal direction of the plane, and specifically, refers to the direction in which the polar angle of the plane is 0 ° and the azimuth angle is 0 °.
In the following description, unless otherwise specified, the direction of inclination of a certain plane means a direction neither parallel nor perpendicular to the plane, and specifically means a direction in which the polar angle of the above-mentioned plane is in a range of more than 0 ° and less than 90 °.
In the following description, unless otherwise specified, the in-plane retardation Re of a certain layer represents a value represented by Re { (nx-ny) × d, and the retardation Rth in the thickness direction of a certain layer represents a value represented by Rth [ { (nx + ny)/2} -nz ] × d. Here, nx represents a refractive index in a direction giving the largest refractive index among in-plane directions of the layer, ny represents a refractive index in a direction perpendicular to the nx direction among the in-plane directions of the layer, nz represents a refractive index in a thickness direction of the layer, and d represents a thickness of the layer. In addition, the in-plane direction means a direction perpendicular to the thickness direction.
In the following description, the measurement wavelength of the refractive index is 590nm unless otherwise specified.
In the following description, a "long" member is a member having a length of usually 5 times or more, preferably 10 times or more, with respect to the width, and more specifically, a member having a length enough to be stored or transported in a roll shape. The upper limit of the length of the elongated member is not particularly limited, and may be, for example, 10 ten thousand times or less of the width.
In the following description, the "polarizing plate" and the "wave plate" include not only rigid members but also members having flexibility such as a resin film.
In the following description, "(meth) acrylic acid" is a term including "acrylic acid", "methacrylic acid", and a combination thereof unless otherwise specified.
In the following description, unless otherwise specified, the directions of the elements "parallel" and "perpendicular" may include an error in the range of ± 5 °, for example, within a range not to impair the effects of the present invention.
In the following description, a resin having a positive intrinsic birefringence value means a resin having a refractive index in the stretching direction larger than a refractive index in a direction perpendicular thereto. The resin having a negative intrinsic birefringence value is a resin having a refractive index in the stretching direction smaller than that in the direction perpendicular thereto. The intrinsic birefringence value can be calculated from the dielectric constant distribution.
In the following description, the principal refractive index of a layer or film means a refractive index nx in the direction giving the largest refractive index among the in-plane directions of the layer, a refractive index ny in the direction perpendicular to the direction giving the nx among the in-plane directions of the layer, and a refractive index nz in the thickness direction of the layer. In the present application, the refractive indices corresponding to these nx, ny, and nz are denoted by symbols including the strings "nx", "ny", "nz", respectively. For example, of the principal refractive indices nx (a), ny (a), and nz (a) of the optically anisotropic layer, nx (a) is the refractive index in the direction giving the maximum refractive index among the in-plane directions of the optically anisotropic layer, ny (a) is the refractive index in the direction perpendicular to the direction giving nx (a) among the in-plane directions of the optically anisotropic layer, and nz (a) is the refractive index in the thickness direction of the optically anisotropic layer.
In the following description, the in-plane retardation Re of a layer exhibiting reverse wavelength dispersibility means that the in-plane retardations Re (450) and Re (550) of the layer at wavelengths of 450nm and 550nm satisfy Re (450)/Re (550) < 1.00. Preferably, Re has reverse wavelength dispersibility, and in-plane retardations Re (550) and Re (650) at wavelengths of 550nm and 650nm of the layer satisfy Re (550)/Re (650) < 1.00.
The retardation Rth in the thickness direction of a layer exhibiting reverse wavelength dispersion means that the retardation Rth (450) and Rth (550) in the thickness direction at the wavelength of 450nm and 550nm of the layer satisfy Rth (450)/Rth (550) < 1.00. Rth has reverse wavelength dispersibility and further the in-plane retardation Rth (550) and Rth (650) at wavelengths of 550nm and 650nm of the layer satisfy Rth (550)/Rth (650) < 1.00.
[1. optically Anisotropic layer ]
The optically anisotropic layer of the present invention comprises a positive C polymer, a mesogenic compound, and a polymer of a mesogenic compound, and has specific optical characteristics.
[1.1. Positive C Polymer ]
The n-C polymer is a polymer satisfying formula (1) when a polymer film is formed by a coating method using a solution of the polymer.
nz (P) > nx (P) ≧ ny (P) formula (1)
Wherein nx (P), ny (P), and nz (P) are the principal refractive indices of the film. By using such a positive C polymer in combination with a mesogenic compound, an optically anisotropic layer which can be produced without using an alignment film and can be used as a positive C film exhibiting reverse wavelength dispersion in retardation Rth in the thickness direction can be realized.
Whether a polymer is a positive C polymer or not can be confirmed by the following method.
First, a polymer as a sample is added to a solvent such as Methyl Ethyl Ketone (MEK), 1, 3-dioxolane, N-methylpyrrolidone (NMP) so that the concentration of the polymer becomes 10 to 20 wt%, and the mixture is dissolved at room temperature to obtain a polymer solution.
This polymer solution was applied to an unstretched film made of a resin using a film coater to form a layer of the polymer solution. Thereafter, the film was dried in an oven at 85 ℃ for about 10 minutes to evaporate the solvent, thereby obtaining a polymer film having a thickness of about 10 μm.
Then, whether or not the refractive index nx (p), the refractive index ny (p), and the refractive index nz (p) of the polymer film satisfy the formula (1) is evaluated, and if so, it is judged that the polymer as the sample belongs to a positive C polymer.
It is particularly preferred that the refractive index nx (P) is the same as or similar to the value of the refractive index ny (P). Specifically, the difference nx (P) -ny (P) between the refractive index nx (P) and the refractive index ny (P) is preferably 0.00000 to 0.00100, more preferably 0.00000 to 0.00050, and particularly preferably 0.00000 to 0.00020. The optically anisotropic layer of the present invention can be easily obtained by controlling the refractive index difference nx (P) -ny (P) to the above range.
As the positive C polymer, any polymer having a refractive index satisfying the above formula (1) when a film of the positive C polymer is formed by a coating method using a solution of the positive C polymer can be used. Among them, the n-C polymer is preferably at least 1 polymer selected from polyvinylcarbazole, polyfumarate, and cellulose derivatives. By using these polymers as the positive C polymer, an optically anisotropic layer having a large retardation Rth in the thickness direction can be easily obtained by coating.
Examples of the polyvinylcarbazole include polymers containing a polymerization unit obtained by polymerizing 9-vinylcarbazole.
Examples of the polyfumarates include copolymers of diisopropyl fumarate with 3-ethyl-3-oxetanyl methyl acrylate; and copolymers of diisopropyl fumarate and cinnamate.
The n-C polymer may be used alone in 1 kind, or may be used in combination in 2 or more kinds at an arbitrary ratio.
The proportion of the positive C polymer in the total solid content of the optically anisotropic layer is preferably 30% by weight or more, more preferably 35% by weight or more, most preferably 40% by weight or more, preferably 60% by weight or less, more preferably 55% by weight or less, most preferably 50% by weight or less. When the ratio of the positive C polymer is equal to or more than the lower limit of the above range, the mesogenic compound can be uniformly dispersed in the optically anisotropic layer to improve the mechanical strength of the optically anisotropic layer, and when the ratio is equal to or less than the upper limit of the above range, the wavelength dispersion of the retardation Rth in the thickness direction of the optically anisotropic layer can be easily brought close to the reverse dispersion. Here, the solid content of a certain layer means a component remaining when the layer is dried.
[1.2. mesogenic Compound ]
In the present application, a mesogenic compound is a compound having a mesogenic skeleton and an acrylate structure.
The mesogenic skeleton of the mesogenic compound is a molecular skeleton that substantially contributes to the generation of a liquid crystal phase in a low molecular weight or high molecular weight substance due to anisotropy of interaction between attraction force and repulsion force. The mesogenic compound containing a mesogenic skeleton may not have liquid crystallinity itself which can cause a phase transition to a liquid crystal phase. Thus, the mesogenic compound may be a liquid crystal compound which alone undergoes a phase transition to a liquid crystal phase, or may be a non-liquid crystal compound which alone does not undergo a phase transition to a liquid crystal phase. Examples of mesogenic frameworks include rigid rod-like or disk-like shaped units. For mesogenic frameworks, see Pure appl. chem.2001, volume 73 (No. 5), page 888 and c.tschieske, g.pelzl, s.diele, angelw.chem.2004, volume 116, pages 6340-6368.
In the optically anisotropic layer, the orientation state of the mesogenic compound can be fixed. For example, the mesogenic compound may fix the orientation state of the mesogenic compound by polymerization. In general, the mesogenic compound can be polymerized while maintaining the oriented state of the mesogenic compound by polymerization, and thus the oriented state of the mesogenic compound is fixed by the polymerization. Thus, the term "mesogenic compound with fixed orientation state" includes polymers of mesogenic compounds. Therefore, in the case where the mesogenic compound is a liquid crystal compound having liquid crystallinity, the liquid crystal compound may exhibit a liquid crystal phase in the optically anisotropic layer, or may not exhibit a liquid crystal phase because the alignment state is fixed.
As the mesogenic compound, an inverse wavelength dispersion liquid crystal compound, an inverse wavelength mesogenic compound, or a combination thereof can be used.
Here, the inverse wavelength dispersion liquid crystal compound refers to a compound satisfying all of the following requirements (i) and (ii).
(i) The inverse wavelength dispersion liquid crystal compound exhibits liquid crystallinity.
(ii) The inverse wavelength dispersion liquid crystal compound exhibits an in-plane retardation of inverse wavelength dispersibility when aligned in parallel.
The inverse wavelength mesogenic compound is a compound satisfying all of the following requirements (iii), (iv), and (v).
(iii) The inverse wavelength mesogenic compound alone does not exhibit liquid crystallinity.
(iv) The specific evaluation mixture containing the inverse wavelength mesogenic compound exhibited liquid crystallinity.
(v) When the above-described evaluation mixture is aligned in parallel, the inverse wavelength mesogenic compound exhibits an in-plane retardation of inverse wavelength dispersibility.
The mixture for evaluation is a mixture in which the reverse wavelength mesogenic compound is mixed in at least any proportion of 30 to 70 parts by weight based on 100 parts by weight of the total of the liquid crystal compound for evaluation and the reverse wavelength mesogenic compound in a liquid crystal compound for evaluation which exhibits a positive in-plane retardation of dispersibility when aligned in parallel.
By using such a mesogenic compound in combination with the positive C polymer, an optically anisotropic layer which can be produced without using an alignment film and can be used as a positive C film exhibiting reverse wavelength dispersion in retardation Rth in the thickness direction can be realized.
Hereinafter, the inverse wavelength dispersion liquid crystal compound will be described.
The inverse wavelength dispersion liquid crystal compound exhibits an in-plane retardation of inverse wavelength dispersion when aligned in parallel. Here, the term "parallel alignment of the liquid crystal compound" means that a layer containing the liquid crystal compound is formed and the long axis direction of the mesomorphic skeleton of the molecules of the liquid crystal compound in the layer is aligned in any direction parallel to the surface of the layer. When the liquid crystal compound includes a plurality of kinds of mesogenic frameworks having different alignment directions, the direction in which the longest kind of mesogen among them is aligned is the above-described alignment direction. Whether or not the liquid crystal compound is aligned in parallel and the alignment direction thereof can be determined by measurement of the slow axis direction using a retardation meter such as AxoScan (manufactured by axomicics) and measurement of retardation distribution in the slow axis direction according to the incident angle.
When a liquid crystal layer containing a reverse wavelength dispersion liquid crystal compound is formed and the long axis direction of the mesogenic skeleton of the molecules of the liquid crystal compound in the liquid crystal layer is aligned in any one direction parallel to the plane of the liquid crystal layer, the in-plane retardations Re (L450) and Re (L550) of the liquid crystal layer at wavelengths of 450nm and 550nm usually satisfy Re (L450)/Re (L550) < 1.00.
Further, from the viewpoint of more favorably exhibiting the desired effects of the present invention, it is more preferable that the in-plane retardations Re (L450), Re (L550) and Re (L650) of the above-mentioned liquid crystal layer having wavelengths of 450nm, 550nm and 650nm satisfy Re (L450) < Re (L550). ltoreq.Re (L650).
As the inverse wavelength dispersion liquid crystal compound, for example, a compound containing a main chain mesogenic skeleton and a side chain mesogenic skeleton bonded to the main chain mesogenic skeleton in the molecule of the inverse wavelength dispersion liquid crystal compound can be used. The above-mentioned inverse wavelength dispersion liquid crystal compound comprising a main chain mesogenic skeleton and a side chain mesogenic skeleton can be oriented in a direction different from that of the main chain mesogenic skeleton in a state where the inverse wavelength dispersion liquid crystal compound is oriented. In this case, since birefringence appears as a difference between a refractive index corresponding to the mesogenic skeleton of the main chain and a refractive index corresponding to the mesogenic skeleton of the side chain, as a result, when the inverse wavelength dispersion liquid crystal compound is aligned in parallel, in-plane retardation of inverse wavelength dispersion can be exhibited.
For example, as in the above-mentioned compounds having a main chain mesogenic skeleton and a side chain mesogenic skeleton, the reverse wavelength dispersion liquid crystal compound generally has a specific steric shape different from that of a normal positive wavelength dispersion liquid crystal compound. Here, the "positive wavelength dispersion liquid crystal compound" refers to a liquid crystal compound that can exhibit an in-plane retardation exhibiting positive wavelength dispersion when aligned in parallel. The in-plane retardation of positive wavelength dispersion means an in-plane retardation in which the larger the measurement wavelength is, the smaller the in-plane retardation is. It is presumed that the specific three-dimensional shape of the inverse wavelength dispersion liquid crystal compound is one of the reasons for obtaining the effects of the present invention.
The CN point of the reverse wavelength dispersion liquid crystal compound is preferably 25 ℃ or higher, more preferably 45 ℃ or higher, particularly preferably 60 ℃ or higher, preferably 120 ℃ or lower, more preferably 110 ℃ or lower, and particularly preferably 100 ℃ or lower. Here, the "CN point" means a crystallization-nematic phase transition temperature. By using the reverse wavelength dispersion liquid crystal compound having a CN point in the above range, the optically anisotropic layer can be easily manufactured.
In the case of the monomer, the molecular weight of the reverse wavelength dispersion liquid crystal compound is preferably 300 or more, more preferably 700 or more, particularly preferably 1000 or more, preferably 2000 or less, more preferably 1700 or less, particularly preferably 1500 or less. When the inverse wavelength dispersion liquid crystal compound has a molecular weight as described above, the coating properties of the coating liquid for forming the optically anisotropic layer can be particularly improved.
The above-mentioned inverse wavelength dispersion liquid crystal compounds may be used alone in 1 kind, or may be used in combination in 2 or more kinds at an arbitrary ratio.
Examples of the inverse wavelength dispersion liquid crystal compound include those described in Japanese patent laid-open publication No. 2014-123134. Examples of the inverse wavelength dispersion liquid crystal compound include compounds exhibiting liquid crystallinity among compounds represented by the following formula (Ia). In the following description, the compound represented by the formula (Ia) is sometimes referred to as "compound (Ia)", as appropriate.
[ chemical formula 3]
In the above formula (Ia), A1aRepresents: an aromatic hydrocarbon ring group having an organic group having 1 to 67 carbon atoms as a substituent, the organic group having 1 to 67 carbon atoms having at least 1 aromatic ring selected from an aromatic hydrocarbon ring and an aromatic heterocyclic ring; or an aromatic heterocyclic group having an organic group having 1 to 67 carbon atoms as a substituent, wherein the organic group having 1 to 67 carbon atoms has at least 1 aromatic ring selected from an aromatic hydrocarbon ring and an aromatic heterocyclic ring.
As A1aSpecific examples of (3) include: is of the formula-RfC(＝N-N(Rg)Rh) or-RfC(＝N-N＝C(Rg1)Rh) Phenylene substituted with the group represented; 4, 7-diyl-benzothiazol substituted with 1-benzofuran-2-yl; benzothiazole-4, 7-diyl substituted with 5- (2-butyl) -1-benzofuran-2-yl; 4, 6-dimethyl-1-benzofuran-2-yl-substituted benzothiazole-4, 7-diyl; benzothiazole-4, 7-diyl substituted with 6-methyl-1-benzofuran-2-yl; 4, 7-diyl-benzothiazol substituted with 4,6, 7-trimethyl-1-benzofuran-2-yl; 4, 7-diyl benzothiazole substituted with 4,5, 6-trimethyl-1-benzofuran-2-yl; benzothiazole-4, 7-diyl substituted with 5-methyl-1-benzofuran-2-yl; benzothiazole-4, 7-diyl substituted with 5-propyl-1-benzofuran-2-yl; benzothiazole-4, 7-diyl substituted with 7-propyl-1-benzofuran-2-yl; benzothiazole-4, 7-diyl substituted with 5-fluoro-1-benzofuran-2-yl; phenyl-substituted benzothiazole-4, 7-diyl; 4-fluorophenyl substituted benzothiazole-4, 7-diyl; 4-nitrophenyl substituted benzothiazole-4, 7-diyl; 4-trifluoromethylphenyl-substituted benzothiazole-4, 7-diyl; 4-cyanophenyl substituted benzothiazole-4, 7-diyl(ii) a 4-methanesulfonylphenyl-substituted benzothiazole-4, 7-diyl; benzothiazol-4, 7-diyl substituted with thiophen-2-yl; benzothiazol-4, 7-diyl substituted with thiophen-3-yl; benzothiazole-4, 7-diyl substituted with 5-methylthiophen-2-yl; benzothiazole-4, 7-diyl substituted with 5-chlorothien-2-yl; by thieno [3,2-b]Thiophen-2-yl substituted-benzothiazol-4, 7-diyl; 4, 7-diyl benzothiazole substituted with 2-benzothiazolyl; 4-biphenyl substituted benzothiazole-4, 7-diyl; 4-propylbiphenyl substituted benzothiazole-4, 7-diyl; 4-thiazolyl-substituted benzothiazole-4, 7-diyl; 4, 7-diyl benzothiazole substituted with 1-phenylethen-2-yl; 4-pyridyl substituted benzothiazole-4, 7-diyl; benzothiazole-4, 7-diyl substituted with 2-furyl; is naphtho [1,2-b ]]Furan-2-yl substituted benzothiazole-4, 7-diyl; 1H-isoindole-1, 3(2H) -dione-4, 7-diyl substituted with 5-methoxy-2-benzothiazolyl; 1H-isoindole-1, 3(2H) -dione-4, 7-diyl substituted with phenyl; 1H-isoindole-1, 3(2H) -dione-4, 7-diyl substituted with 4-nitrophenyl; or 1H-isoindole-1, 3(2H) -dione-4, 7-diyl substituted with 2-thiazolyl, and the like. Herein, R isfIs shown in the following description with Q1The same meaning is used. RgAnd Rg1Each independently represents A described laterySame meaning as RhIs shown in the following description of AxThe same meaning is used.
In the above formula (Ia), Y1a～Y8aEach independently represents a single chemical bond, -O-, -S-, -O-C (═ O) -, -C (═ O) -O-, -O-C (═ O) -O-, -NR1-C(＝O)-、-C(＝O)-NR1-、-O-C(＝O)-NR1-、-NR1-C(＝O)-O-、-NR1-C(＝O)-NR1-、-O-NR1-, or-NR1-O-. Herein, R is1Represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
In the above formula (Ia), G1aAnd G2aEach independently represents a divalent aliphatic group having 1 to 20 carbon atoms which may have a substituent. In addition, in the above aliphatic group, 1 or more of — O-, -S-, -O-C (═ O) -, -C (═ O) -O-, -O-C (═ O) -O-, -NR can be inserted into each aliphatic group2-C(＝O)-、-C(＝O)-NR2-、-NR2-, or-C (═ O) -. However, except for the case where more than 2 adjacent insertions of-O-or-S-respectively are present. Herein, R is2Represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
In the above formula (Ia), Z1aAnd Z2aEach independently represents an alkenyl group having 2 to 10 carbon atoms which may be substituted with a halogen atom.
In the above formula (Ia), A2aAnd A3aEach independently represents a divalent alicyclic hydrocarbon group having 3 to 30 carbon atoms which may have a substituent.
In the above formula (Ia), A4aAnd A5aEach independently represents a divalent aromatic group having 6 to 30 carbon atoms which may have a substituent.
In the formula (Ia), k and I each independently represent 0 or 1.
Wherein, in the formula (Ia), Z1a-Y7a-and-Y8a-Z2aOne or both of which are acryloxy groups.
Particularly preferred specific examples of the inverse wavelength dispersion liquid crystal compound include compounds exhibiting liquid crystallinity among compounds represented by the following formula (I). In the following description, the compound represented by the formula (I) may be referred to as "compound (I)" as appropriate.
[ chemical formula 4]
The compound (I) is generally represented by the following formula and comprises a group represented by the formula-Y5-A4-Y3-(A2-Y1)n-A1-(Y2-A3)m-Y4-A5-Y6A main chain mesogenic skeleton 1a formed, and a structure of > A1-C(Q1)＝N-N(Ax)AySide chain mesogenic frameworks 1b formed 2 mesogenic frameworks. These main chain mesogenic skeleton 1a and side chain mesogenic skeleton 1b intersect with each other. The main chain mesogenic skeleton 1a and the side chain mesogenThe crystal skeletons 1b can be combined as 1 mesogenic skeleton, but in the present invention, they are separately labeled as 2 mesogenic skeletons.
[ chemical formula 5]
The refractive index in the major axis direction of the main chain mesogenic skeleton 1a was n1, and the refractive index in the major axis direction of the side chain mesogenic skeleton 1b was n 2. At this time, the absolute value of the refractive index n1 and the wavelength dispersibility generally depend on the molecular structure of the main chain mesogenic skeleton 1 a. In addition, the absolute value of the refractive index n2 and the wavelength dispersibility generally depend on the molecular structure of the side chain mesogenic skeleton 1 b. Here, since the compound (I) in the liquid crystal phase generally rotates about the major axis direction of the main chain mesogenic skeleton 1a as a rotation axis, the refractive indices n1 and n2 herein represent refractive indices of a rotating body.
The absolute value of the refractive index n1 is larger than the absolute value of the refractive index n2 due to the molecular structures of the main chain mesogenic skeleton 1a and the side chain mesogenic skeleton 1 b. Further, the refractive indices n1 and n2 generally exhibit positive wavelength dispersion. Here, the refractive index of positive wavelength dispersion means a refractive index whose absolute value is smaller as the measurement wavelength is larger. The refractive index n1 of the main chain mesogenic skeleton 1a exhibits positive wavelength dispersion to a small extent. Therefore, the refractive index n1 measured at a long wavelength is smaller than that measured at a short wavelength, but the difference therebetween is small. On the other hand, the refractive index n2 of the side chain mesogenic skeleton 1b exhibits a large degree of positive wavelength dispersion. Therefore, the refractive index n2 measured at a long wavelength is smaller than the refractive index n2 measured at a short wavelength, and the difference therebetween is large. Therefore, when the measurement wavelength is short, the difference Δ n between the refractive index n1 and the refractive index n2 is small, and when the measurement wavelength is long, the difference Δ n between the refractive index n1 and the refractive index n2 is large. As described above, the main chain mesogenic skeleton 1a and the side chain mesogenic skeleton 1b allow the compound (I) to exhibit an in-plane retardation of inverse wavelength dispersibility when they are aligned in parallel.
In the above formula (I), Y1～Y8Each independently represents a single chemical bond, -O-, -S-, -O-C (═ O) -, -C (═ O) -O-, -O-C (═ O) -O-, -NR1-C(＝O)-、-C(＝O)-NR1-、-O-C(＝O)-NR1-、-NR1-C(＝O)-O-、-NR1-C(＝O)-NR1-、-O-NR1-, or-NR1-O-. Herein, R is1Represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
In the above formula (1), G1And G2Each independently represents a divalent aliphatic group having 1 to 20 carbon atoms which may have a substituent. In addition, in the above aliphatic group, 1 or more of — O-, -S-, -O-C (═ O) -, -C (═ O) -O-, -O-C (═ O) -O-, -NR can be inserted into each aliphatic group2-C(＝O)-、-C(＝O)-NR2-、-NR2-, or-C (═ O) -. However, except for the case where more than 2 adjacent insertions of-O-or-S-respectively are present. Herein, R is2Represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
In the above formula (I), Z1And Z2Each independently represents an alkenyl group having 2 to 10 carbon atoms which may be substituted with a halogen atom.
In the above formula (I), AxThe organic group has 2-30 carbon atoms and has at least one aromatic ring selected from aromatic hydrocarbon rings and aromatic heterocyclic rings. The "aromatic ring" refers to a cyclic structure having a broad aromaticity conforming to Huckel's rule, that is, a cyclic conjugated structure having (4n +2) pi electrons, and a cyclic structure in which a lone pair of electrons of a hetero atom such as sulfur, oxygen, and nitrogen represented by thiophene, furan, and benzothiazolyl participate in a pi electron system to exhibit aromaticity.
Examples of the aromatic hydrocarbon ring include: benzene rings, naphthalene acid rings, anthracene rings, and the like. Examples of the aromatic heterocyclic ring include: monocyclic aromatic heterocyclic rings such as pyrrole rings, furan rings, thiophene rings, pyridine rings, pyridazine rings, pyrimidine rings, pyrazine rings, pyrazole rings, imidazole rings, oxazole rings, and thiazole rings; fused-ring aromatic heterocycles such as a benzothiazole ring, a benzoxazole ring, a quinoline ring, a phthalazine ring, a benzimidazole ring, a benzopyrazole ring, a benzofuran ring, a benzothiophene ring, a thiazolopyridine ring, an oxazolopyridine ring, a thiazolopyridazine ring, an oxazolopyrimidine ring, and an oxazolopyrimidine ring.
In the above formula (I), AyRepresents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, a cycloalkyl group having 3 to 12 carbon atoms which may have a substituent, an alkynyl group having 2 to 20 carbon atoms which may have a substituent, -C (═ O) -R3、-SO2-R4、-C(＝S)NH-R9Or an organic group having 2 to 30 carbon atoms and having at least one aromatic ring selected from an aromatic hydrocarbon ring and an aromatic heterocyclic ring. Herein, R is3Represents an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, a cycloalkyl group having 3 to 12 carbon atoms which may have a substituent, or an aromatic hydrocarbon ring group having 5 to 12 carbon atoms. R4Represents an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a phenyl group, or a 4-methylphenyl group. R9Represents an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, a cycloalkyl group having 3 to 12 carbon atoms which may have a substituent, or an aromatic group having 5 to 20 carbon atoms which may have a substituent. Above-mentioned has AxAnd AyThe aromatic ring of (c) can have a substituent. And, the above-mentioned AxAnd AyMay together form a ring.
In the above formula (I), A1Represents a trivalent aromatic group which may have a substituent.
In the above formula (I), A2And A3Each independently represents a divalent alicyclic hydrocarbon group having 3 to 30 carbon atoms which may have a substituent.
In the above formula (I), A4And A5Each independently represents a divalent aromatic group having 6 to 30 carbon atoms which may have a substituent.
In the following formula (I), Q1Represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent.
In the formula (I), m and n independently represent 0 or 1.
Wherein, in the following formula (I), Z1-Y7-and-Y8-Z2One or both of which are acryloxy groups.
Specific examples of the compound (I) include compounds described in International publication Nos. 2016/171169, 2017/057005 and 2016/190435. The compound (I) can be produced by the methods described in these documents.
Next, the inverse wavelength mesogenic compound will be explained.
The counter wavelength mesogenic compound is a compound which does not exhibit liquid crystallinity by itself and exhibits liquid crystallinity in a mixture for evaluation which is mixed with a liquid crystalline compound for evaluation at a specific mixing ratio. As the liquid crystal compound for evaluation, a positive wavelength dispersion liquid crystal compound, which is a liquid crystal compound exhibiting in-plane retardation of positive wavelength dispersion in the case of parallel alignment, was used. By using a positive wavelength dispersion liquid crystal compound as the liquid crystal compound for evaluation, the evaluation of the wavelength dispersion property of the in-plane retardation of the reverse wavelength mesogenic compound in the case of parallel alignment of the mixture for evaluation can be easily performed. The liquid crystal compound for evaluation is particularly preferably a liquid crystal compound having a rod-like structure which can be brought into a liquid crystal phase at 100 ℃. Specific examples of particularly preferable liquid crystal compounds for evaluation include: a positive wavelength dispersion liquid crystal compound having a structure represented by the following formula (E1) (Palioc color (registered trademark) LC242 (manufactured by BASF corporation)), a positive wavelength dispersion liquid crystal compound having a structure represented by the following formula (E2), and the like. In the following formula, Me represents a methyl group.
[ chemical formula 6]
[ chemical formula 7]
The mixing ratio of the inverse wavelength mesogenic compound mixed with the liquid crystal compound for evaluation to obtain the above-mentioned mixture for evaluation is usually at least any one of 30 to 70 parts by weight relative to 100 parts by weight of the total of the liquid crystal compound for evaluation and the inverse wavelength mesogenic compound. Therefore, if the mixture for evaluation exhibiting liquid crystallinity is obtained by mixing the inverse wavelength mesogenic compound at least at any mixing ratio included in the range of 30 parts by weight to 70 parts by weight with respect to 100 parts by weight of the total of the liquid crystal compound for evaluation and the inverse wavelength mesogenic compound, the mixture obtained by mixing the inverse wavelength mesogenic compound at other mixing ratios included in the range of 30 parts by weight to 70 parts by weight with respect to 100 parts by weight of the total of the liquid crystal compound for evaluation and the inverse wavelength mesogenic compound may not exhibit liquid crystallinity.
The mixture for evaluation was confirmed to exhibit liquid crystallinity by the following method.
The mixture for evaluation was applied to a substrate and dried to obtain a sample film having a layer of the substrate and the mixture for evaluation. The sample film was set on a hot stage. The temperature of the sample film was raised while observing the sample film with a polarizing microscope. When the phase transition from the layer of the mixture for evaluation to the liquid crystal phase was observed, it was judged that the mixture for evaluation exhibited liquid crystallinity.
When the above-described evaluation mixture is aligned in parallel, the inverse wavelength mesogenic compound in the evaluation mixture exhibits an in-plane retardation of inverse wavelength dispersibility. Here, the term "parallel alignment of the mixture for evaluation" means that a layer of the mixture for evaluation is formed and the liquid crystal compound for evaluation in the layer is aligned in parallel. Therefore, in the mixture for evaluation of parallel alignment, the long axis direction of the mesogenic skeleton of the molecules of the liquid crystal compound for evaluation is generally aligned in any one direction parallel to the layer.
In addition, the in-plane retardation in which the inverse wavelength mesogenic compound in the parallel-oriented mixture for evaluation exhibits inverse wavelength dispersibility means that in-plane retardations Re (450) and Re (550) at wavelengths of 450nm and 550nm of the inverse wavelength mesogenic compound contained in the mixture for evaluation satisfy Re (450)/Re (550) < 1.00.
However, in the layer of the mixture for evaluation, it is difficult to selectively measure the in-plane retardation of the inverse wavelength mesogenic compound. Then, by utilizing the fact that the liquid crystal compound for evaluation is a positive wavelength dispersion liquid crystal compound, the in-plane retardation in which the reverse wavelength mesogenic compound in the mixture for evaluation exhibits reverse wavelength dispersion can be confirmed by the following confirmation method.
A liquid crystal layer containing a liquid crystal compound for evaluation as a positive wavelength dispersion liquid crystal compound is formed, and the liquid crystal compound for evaluation is aligned in parallel in the liquid crystal layer. Then, the liquid crystal layer was measured for the ratio Re (X450)/Re (X550) of in-plane retardations Re (X450) and Re (X550) at wavelengths of 450nm and 550 nm.
Further, a layer of the evaluation mixture containing the evaluation liquid crystal compound and the inverse wavelength mesogenic compound is formed, and the evaluation mixture is aligned in parallel in the layer of the evaluation mixture. Then, the ratio Re (Y450)/Re (Y550) of in-plane retardations Re (Y450) and Re (Y550) at wavelengths of 450nm and 550nm of the layer of the evaluation mixture was measured.
When the measurement result shows that the retardation ratio Re (Y450)/Re (Y550) of the layer of the evaluation mixture containing the inverse wavelength mesogenic compound is smaller than the retardation ratio Re (X450)/Re (X550) of the liquid crystal layer not containing the inverse wavelength mesogenic compound, it can be judged that the inverse wavelength mesogenic compound exhibits the in-plane retardation of the inverse wavelength dispersibility.
In addition, from the viewpoint of more favorably exhibiting the desired effects of the present invention, in the above-described confirmation method, it is preferable that the ratio Re (Y650)/Re (Y550) of the in-plane retardations Re (Y550) and Re (Y650) at wavelengths of 550nm and 650nm of the layer of the evaluation mixture is larger than the ratio Re (X650)/Re (X550) of the in-plane retardations Re (X550) and Re (X650) at wavelengths of 550nm and 650nm of the liquid crystal layer.
As the inverse wavelength mesogenic compound, for example, a compound having a main chain mesogenic skeleton and a side chain mesogenic skeleton bonded to the main chain mesogenic skeleton in a molecule of the inverse wavelength mesogenic compound can be used.
Further, the inverse wavelength mesogenic compound preferably has polymerizability. Therefore, the inverse wavelength mesogenic compound preferably has a polymerizable group. If the inverse wavelength mesogenic compound having polymerizability as described above is used, the orientation state of the inverse wavelength mesogenic compound can be easily fixed by polymerization. Therefore, an optically anisotropic layer having stable optical characteristics can be easily obtained.
In the case of the monomer, the molecular weight of the inverse wavelength mesogenic compound is preferably 300 or more, more preferably 700 or more, particularly preferably 1000 or more, preferably 2000 or less, more preferably 1700 or less, particularly preferably 1500 or less. The inverse wavelength mesogenic compound has a molecular weight as described above, and thus the coating properties of the coating liquid for forming the optically anisotropic layer can be particularly excellent.
The above-mentioned inverse wavelength mesogenic compounds may be used alone in 1 kind, or may be used in combination in 2 or more kinds at an arbitrary ratio.
Examples of the inverse wavelength mesogenic compound include compounds which do not exhibit liquid crystallinity among the compounds represented by the above formula (Ia). Preferred examples of the inverse wavelength mesogenic compound include compounds having liquid crystallinity which does not appear in the compounds represented by the above formula (I). Among them, particularly preferred counter wavelength mesogenic compounds include the following compounds.
[ chemical formula 8]
Among the above mesogenic compounds, from the viewpoint of finding the desired effects of the present invention more favorably, the molecule of the mesogenic compound preferably contains at least one selected from the group consisting of a benzothiazolyl ring (the ring of formula (10A) below) and a combination of a cyclohexyl ring (the ring of formula (10B) below) and a phenyl ring (the ring of formula (10C) below).
[ chemical formula 9]
By polymerizing the mesogenic compound, a polymer of the mesogenic compound can be obtained. The specific method of polymerization is not particularly limited, and any method may be used. Specifically, the coating can be performed by irradiating a coating liquid containing a mesogenic compound with light. The details of this method are described later.
In the optically anisotropic layer, a mesogenic compound may be contained in combination with the polymers of the positive C polymer and the mesogenic compound. Specifically, in the optically anisotropic layer, in addition to the polymer of the mesogenic compound, an unreacted mesogenic compound remaining without polymerization may be contained. The ratio of the mesogenic compounds is such that the degree of cure a is within the specific range specified in the present application.
The ratio of the mesogenic compound and the polymer thereof in the total solid content of the optically anisotropic layer is preferably 20% by weight or more, more preferably 30% by weight or more, further preferably 35% by weight or more, particularly preferably 40% by weight or more, preferably 60% by weight or less, more preferably 55% by weight or less, further preferably 50% by weight or less, and particularly preferably 45% by weight or less. When the ratio of the mesogenic compound and the polymer thereof is equal to or more than the lower limit of the above range, the wavelength dispersion of the retardation Rth in the thickness direction of the optically anisotropic layer can be easily brought close to the inverse dispersion, and when the ratio is equal to or less than the upper limit of the above range, the polymer of the mesogenic compound can be uniformly dispersed in the optically anisotropic layer, and the mechanical strength of the optically anisotropic layer can be improved.
[1.3. optional Components ]
The optically anisotropic layer may further contain an arbitrary component in combination with the polymer of the positive C polymer, the mesogenic compound, and the mesogenic compound.
The optically anisotropic layer may contain a plasticizer. In the case where the optically anisotropic layer contains a cellulose derivative as the positive C polymer, the optically anisotropic layer particularly preferably contains a plasticizer in combination with the cellulose derivative. Examples of plasticizers include: comprising xylitol pentaacetate, xylitol pentapropionate, arabitol pentapropionate, triphenyl phosphate, polyesters comprising succinic acid residues and diethylene glycol residues, and polyesters comprising adipic acid residues and diethylene glycol residues. The proportion of the plasticizer in the n-C polymer and the plasticizer is preferably 2.5% by weight or more, more preferably 10% by weight or more, preferably 25% by weight or less, and more preferably 20% by weight or less, based on 100% by weight in total.
[1.4 ] characteristics of optically anisotropic layer: refractive index ]
The optically anisotropic layer satisfies formula (2).
nz (A) > nx (A) ≧ ny (A) formula (2)
nx (A), ny (A) and nz (A) are the principal refractive indices of the optically anisotropic layer. The optically anisotropic layer having such refractive indices nx (a), ny (a), and nz (a) can be used as the positive C film. Therefore, when the optically anisotropic layer is incorporated in a circularly polarizing plate and applied to an image display device, reflection of external light is suppressed in a direction inclined to the display surface of the image display device, and light energy of a displayed image can be transmitted through the polarizing sunglasses. Further, in the case where the image display device is a liquid crystal display device, the viewing angle can be generally enlarged. Therefore, when the display surface of the image display device is viewed from an oblique direction, the visibility of the image can be improved.
It is particularly preferable that the values of the refractive index nx (A) and the refractive index ny (A) of the optically anisotropic layer are the same or close to each other. Specifically, the difference nx (A) -ny (A) between the refractive index nx (A) and the refractive index ny (A) is preferably 0.00000 to 0.00100, more preferably 0.00000 to 0.00050, and particularly preferably 0.00000 to 0.00020. By controlling the refractive index difference nx (a) -ny (a) to be within the above range, the optical design in the case where the optically anisotropic layer is provided in an image display device can be simplified, and the bonding direction does not need to be adjusted when bonding to another phase difference film.
[1.5. characteristics of optically anisotropic layer: degree of curing ]
The optically anisotropic layer of the present invention satisfies formula (3).
0.073＜AC-H/AC＝O(mesogenic compound) < 0.125 formula (3)
In the formula (3), AC-HIs the infrared absorption of the out-of-plane bending vibrations of the C-H bond of the acrylate structure of the mesogenic compound in the infrared absorption spectrum of the optically anisotropic layer, AC＝O(Mesogenic Compound) as a Mesogenic Compound in the Infrared absorption Spectrum of an optically Anisotropic layerThe sum of the infrared absorption of stretching vibration of the C ═ O bond in the acrylate structure of (a) and the infrared absorption of stretching vibration of the C ═ O bond in the acrylate structure of (a) from the mesogenic compound. In the present application, a ═ aC-H/AC＝OThe value represented by (mesogenic compound) is sometimes referred to as the degree of cure a of the mesogenic compound.
The degree of cure a is a value determined depending on the amount of an unreacted acrylate structure contained in the optically anisotropic layer, and is a large value when the progress of the polymerization reaction is insufficient, and is a small value when the progress of the polymerization reaction is high. The degree of cure a is preferably greater than 0.073, more preferably greater than 0.076, and most preferably greater than 0.079. Furthermore, it is preferably less than 0.125, more preferably less than 0.122, most preferably less than 0.119. When the degree of curing a in the optically anisotropic layer is not less than the lower limit value, a favorable color tone of the optically anisotropic layer can be realized. On the other hand, when the degree of curing a of the optically anisotropic layer is not more than the upper limit value, high durability of the optically anisotropic layer can be achieved.
The infrared absorption spectrum of the optically anisotropic layer can be measured by, for example, total reflection measurement (ATR method).
As a measuring apparatus, Nicolet iS 5N manufactured by Thermo Fisher SCIENTIFIC can be used. The infrared absorption spectrum is obtained as a graph showing the relationship between the wave number and the absorbance.
When the acrylate of the mesogenic compound is polymerized, the vinyl group of the acrylate structure is converted into an ethylene group, and the carbonyl group bonded to the vinyl group is converted into a carbonyl group bonded to the ethylene group. The "C ═ O bond derived from the C ═ O bond of the acrylate structure of the mesogenic compound" means a C ═ O bond bonded to the carbonyl group of the ethylene group which appears after polymerization of the acrylate. For convenience of explanation, the "C-H bond of the acrylate structure of the mesogenic compound" is abbreviated as C-H in the followingMThe phrase "C ═ O bond in the acrylate structure of the mesogenic compound" is abbreviated as C ═ OMThe phrase "C ═ O bond derived from C ═ O bond of acrylate structure of mesogenic compound" is abbreviated as C ═ OMD。
In the case of C ═ OMPeak of stretching vibration and C ═ OMDWhen the peak of stretching vibration of (2) is not separated but becomes a single peak, the infrared absorption of the single peak may be regarded as C ═ OMInfrared absorption of stretching vibration and C ═ OMDThe sum of infrared absorption of the stretching vibration.
As AC-H/AC＝OAs the value of (mesogenic compound), C-H may be usedMArea of the peak of out-of-plane bending vibration (area)C-H) By C ═ OMC ═ O, and the area of the peak of stretching vibrationMDThe sum of the areas of the peaks of the stretching vibration (area)C＝O) Value of (area)C-H/areaC＝O)。
In the infrared absorption spectrum, C-HMThe peak of the out-of-plane bending vibration of (1) generally occurs at 810cm-1Nearby. Further, C ═ OMStretching vibration and C ═ OMDThe peak of stretching vibration of (2) is usually at 1720cm-1Nearby.
The composition in the optically anisotropic layer is other than C ═ OMDWhen the compound has a C ═ O bond similar to that of the compound, they may not be distinguished from each other in the infrared absorption spectrum. In this case, a plurality of optically anisotropic layers having different ratios of components may be prepared, and quantitative analysis may be performed to exclude the influence of similar C ═ O bonds by measuring the degree of influence of the ratio of each component on infrared absorption.
As a specific example of this quantitative analysis, polymers with a similarity to C ═ O for positive C are obtainedMDThe case of (C) is explained.
In this example, when the infrared absorption spectrum of the optically anisotropic layer is measured, the infrared absorption a of stretching vibration of C ═ O bond in the spectrumC＝OObtained as the sum of the following values.
AC＝O(Polymer): infrared absorption of stretching vibration of C ═ O bond of n-C polymer.
AC＝O(mesogenic compound): unreacted C ═ OMThe infrared absorption of stretching vibration and the C ═ O bond (i.e., C ═ O) of the polymer of the mesogenic compound of (a)MD) The sum of infrared absorption of the stretching vibration.
That is, the following formula (a1) is established.
AC＝O＝AC＝O(Polymer) + AC＝O(mesogenic Compound) formula (A1)
Can be regarded as AC＝OValue of (Polymer) and AC＝OThe value of (mesogenic compound) is proportional to their weight ratio in the optically anisotropic layer. Therefore, the following formula (a2) holds for the ratio of each component in the optically anisotropic layer and the stretching vibration infrared absorption of C ═ O bonds.
AC＝OW (polymer) × aC＝O(Polymer) + W (mesogenic Compound). times.aC＝O(mesogenic Compound) (A2)
In the formula:
w (polymer) is the ratio of the weight of the positive C polymer to the total of the weight of the positive C polymer and the weight of the mesogenic compound and its polymer in the optically anisotropic layer.
W (mesogenic compound) is the ratio of the weight of the mesogenic compound and its polymer to the total of the weight of the positive C polymer and the weight of the mesogenic compound and its polymer in the optically anisotropic layer. That is, W (polymer) + W (mesogenic compound) ═ 1.
aC＝OThe (polymer) is a coefficient, which is the infrared absorption of stretching vibration of C ═ O bonds per unit weight ratio of the positive C polymer.
aC＝OThe (mesogenic compound) is a coefficient which is the sum of the infrared absorption of stretching vibration of the C ═ O bond possessed by the acrylate structure and the infrared absorption of stretching vibration of the C ═ O bond derived from the C ═ O bond of the acrylate structure per unit weight ratio of the mesogenic compound and the polymer thereof.
aC＝O(Polymer) and aC＝OThe value of (mesogenic compound) can be determined as follows: a plurality of optically anisotropic layers having different ratios of the weight of the positive C polymer to the weight of the mesogenic compound and the polymer thereof were prepared, and the infrared absorption spectrum was measured for each of the optically anisotropic layers. Specifically, A was measured for each of a plurality of optically anisotropic layers of different W (polymer) and W (mesogenic compound)C＝O. Thus, W (polymer) and W (mesomorphism) in many casesCompound) and AC＝OThe value of (d) is known. From these values and the formula (A2), A is calculated by the least square methodC＝OA is the smallest difference between the measured value and the theoretical valueC＝O(Polymer) and aC＝O(mesogenic compounds). According to the calculated aC＝O(Mesogenic Compound) and known W (Mesogenic Compound) can be used to determine AC＝O(mesogenic compounds).
In the production process of the optically anisotropic layer, the value of the degree of curing a can be controlled by adjusting the irradiation intensity and time of the irradiated active energy ray.
[1.6 ] characteristics of optically anisotropic layer: others ]
The optically anisotropic layer generally satisfies formula (4) and formula (5).
0.50 < Rth (A450)/Rth (A550) < 1.00 formula (4)
1.00. ltoreq. Rth (A650)/Rth (A550) < 1.25 formula (5)
Where Rth (a450) is a retardation in the thickness direction of the optically anisotropic layer at a wavelength of 450nm, Rth (a550) is a retardation in the thickness direction of the optically anisotropic layer at a wavelength of 550nm, and Rth (a650) is a retardation in the thickness direction of the optically anisotropic layer at a wavelength of 650 nm.
When the above formula (4) is explained in detail, Rth (a450)/Rth (a550) is usually more than 0.50, preferably more than 0.60, more preferably more than 0.65, and usually less than 1.00, preferably less than 0.90, more preferably less than 0.85.
Further, when the above formula (5) is described in detail, Rth (a650)/Rth (a550) is usually 1.00 or more, preferably 1.01 or more, more preferably 1.02 or more, usually less than 1.25, preferably less than 1.15, more preferably less than 1.10.
An optically anisotropic layer having retardation in the thickness direction Rth (a450), Rth (a550) and Rth (a650) satisfying the above-mentioned formulas (4) and (5), wherein retardation in the thickness direction Rth exhibits reverse wavelength dispersibility. When the optically anisotropic layer exhibiting reverse wavelength dispersibility at retardation Rth in the thickness direction is incorporated in a circularly polarizing plate and applied to an image display device, the optically anisotropic layer can exhibit a function of suppressing reflection of external light in a wide wavelength range and transmitting light for displaying an image through a polarizing sunglass in an oblique direction of a display surface of the image display device. Further, in the case where the image display device is a liquid crystal display device, the viewing angle can be effectively enlarged in general. This can particularly effectively improve the visibility of the image displayed on the display surface.
The optically anisotropic layer preferably satisfies formula (6).
Re (A590) is less than or equal to 10nm type (6)
Wherein Re (A590) is an in-plane retardation of the optically anisotropic layer at a wavelength of 590 nm.
In the case of the above formula (6), Re (A590) is preferably 0 to 10nm, more preferably 0 to 5nm, particularly preferably 0 to 2 nm. By controlling Re (a590) in the above range, the optical design in the case where the optically anisotropic layer is provided in an image display device can be simplified, and the bonding direction does not need to be adjusted when bonding to another retardation film.
The optically anisotropic layer preferably satisfies formula (7).
Rth (A590) of 200nm or more and 10nm or less as formula (7)
Wherein Rth (a590) is a retardation in the thickness direction of the optically anisotropic layer with a wavelength of 590 nm.
When the above formula (7) is described in detail, Rth (A590) is preferably at least-200 nm, more preferably at least-130 nm, particularly preferably at least-100 nm, preferably at most-10 nm, more preferably at most-30 nm, and particularly preferably at most-50 nm. When the optically anisotropic layer having such Rth (a590) is incorporated in a circularly polarizing plate and applied to an image display device, reflection of external light is suppressed in the oblique direction of the display surface of the image display device, color change of reflected light is reduced, and light of a displayed image can be transmitted through the polarizing sunglasses. Further, when the image display device is a liquid crystal display device, the viewing angle is generally increased. Therefore, when the display surface of the image display device is viewed from an oblique direction, the visibility of the image can be improved.
The total light transmittance of the optically anisotropic layer is preferably 80% or more, more preferably 85% or more, and particularly preferably 90% or more. The total light transmittance can be measured in the wavelength range of 400nm to 700nm by using an ultraviolet/visible spectrometer.
The haze of the optically anisotropic layer is preferably 5% or less, more preferably 3% or less, particularly preferably 1% or less, and ideally 0%. The haze can be measured by a haze meter (for example, Toyo Seiki Seisakusho Co., Ltd. "haze-gard II" manufactured by Ltd.) according to JIS K7136: 2000.
The optically anisotropic layer can reduce the change in haze caused by heating by satisfying the requirements such as the degree of curing. Specifically, for example, the change ratio of the haze before and after heating at 85 ℃ for 500 hours (haze value after heating/initial haze value) can be made smaller. The haze ratio is preferably 5.0 or less, more preferably 4.0 or less, and still more preferably 3.0 or less. The change in haze caused by heating is generally a change in increase in haze, but sometimes the haze is also reduced. The lower limit of the change ratio of the haze may be set to 0.3 or more, 0.4 or more, or 0.5 or more.
The optically anisotropic layer can be colorless or a color tone close thereto by satisfying the requirements such as the degree of curing. Specifically, the positive C film having the reverse wavelength dispersibility Rth in the related art often has a yellow color tone, but the optically anisotropic layer of the present invention can make the yellow color tone low. More specifically, the value of b in the color system of la × b in the optically anisotropic layer of the present invention is preferably 2.5 or less, more preferably 2.2 or less, and still more preferably 2.0 or less. The lower limit of b is ideally 0. The b value can be observed by measuring the optically anisotropic layer with a spectrophotometer (for example, "V-550" manufactured by JASCO Corporation).
The thickness of the optically anisotropic layer can be appropriately adjusted in order to obtain a desired retardation. The specific thickness of the optically anisotropic layer is preferably 1.0 μm or more, more preferably 3.0 μm or more, preferably 50 μm or less, more preferably 40 μm or less, and particularly preferably 30 μm or less.
[1.7. method for producing optically anisotropic layer ]
The optically anisotropic layer can be produced by a production method comprising:
a step (a): preparing a coating liquid containing a n-C polymer, a mesogenic compound, and a solvent;
a step (b): coating the coating liquid on the support surface to obtain a coating liquid;
and a step (c): and curing the coating liquid by irradiating the coating liquid layer with light. This production method will be described below as a method for producing an optically anisotropic layer of the present invention.
[1.7.1. Process (a): preparation of coating liquid
The step of preparing the coating liquid is performed by mixing the n-C polymer, the mesogenic compound, and the solvent. The ratio of the positive C polymer of the entire solid content of the coating liquid and the ratio of the mesogenic compound of the entire solid content of the coating liquid may be adjusted to be in the same range as the ratio of the positive C polymer of the optically anisotropic layer and the ratio of the mesogenic compound of the optically anisotropic layer, respectively. When the production method of the present invention is performed, a part of the mesogenic compound in the coating liquid may remain in the optically anisotropic layer in an unreacted state without being polymerized. However, in case the degree of curing a is within the range specified in the present application, the proportion of the unreacted mesogenic compound is small.
As the solvent, an organic solvent is generally used. Examples of such organic solvents include: hydrocarbon solvents such as cyclopentane and cyclohexane; ketone solvents such as cyclopentanone, cyclohexanone, methyl ethyl ketone, acetone, methyl isobutyl ketone, and N-methylpyrrolidone; acetate solvents such as butyl acetate and amyl acetate; halogenated hydrocarbon solvents such as chloroform, dichloromethane, dichloroethane and the like; ether solvents such as 1, 4-dioxane, cyclopentylmethyl ether, tetrahydrofuran, tetrahydropyran, 1, 3-dioxolane, 1, 2-dimethoxyethane, and the like; aromatic hydrocarbon solvents such as toluene, xylene, mesitylene, and the like; and mixtures thereof. The boiling point of the solvent is preferably 60 to 250 ℃, more preferably 60 to 150 ℃ from the viewpoint of excellent handling properties. Further, 1 kind of solvent may be used alone, or 2 or more kinds may be used in combination at an arbitrary ratio.
The amount of the solvent is preferably adjusted so that the solid content concentration of the coating liquid can be in a desired range. The solid content concentration of the coating liquid is preferably 6% by weight or more, more preferably 8% by weight or more, particularly preferably 10% by weight or more, preferably 20% by weight or less, more preferably 18% by weight or less, and particularly preferably 15% by weight or less. By controlling the solid content concentration of the coating liquid in the above range, an optically anisotropic layer having desired optical characteristics can be easily formed.
The coating liquid for forming the optically anisotropic layer may contain any component in combination with the n-C polymer, the mesogenic compound and the solvent. In addition, any of the components can be used alone 1, also can be any ratio of combination of 2 or more.
The coating liquid may contain a polymerization initiator as an arbitrary component. The type of the polymerization initiator can be appropriately selected depending on the type of the polymerizable group of the polymerizable compound in the coating liquid. Here, the polymerizable compound is a generic term for compounds having polymerizability. In particular, a photopolymerization initiator is preferable. Examples of the photopolymerization initiator include: a radical polymerization initiator, an anionic polymerization initiator, a cationic polymerization initiator, and the like. Specific examples of commercially available photopolymerization initiators include: trade name manufactured by BASF Corporation: irgacure907, trade name: irgacure184, trade name: irgacure369, trade name: irgacure651, trade name: irgacure819, trade name: irgacure907, trade name: irgacure379, trade name: irgacure379EG, trade name: irgacure OXE02, and trade name: irgacure OXE 04; trade name manufactured by ADEKA corporation: ADEKA OPTOM ER N1919, and the like. Further, 1 kind of polymerization initiator may be used alone, or 2 or more kinds may be used in combination at an arbitrary ratio.
The amount of the polymerization initiator such as a photopolymerization initiator in the coating liquid can be adjusted to obtain a desired degree of curing a. The ratio of the polymerization initiator is preferably 1 part by weight or more, more preferably 2 parts by weight or more, preferably 10 parts by weight or less, and more preferably 8 parts by weight or less, relative to 100 parts by weight of the mesogenic compound in the coating liquid.
The coating liquid may contain a crosslinking agent as an arbitrary component. The type of the polymerization initiator is appropriately selected depending on the type of the polymerizable compound in the coating liquid. Examples of the crosslinking agent include trade names: A-TMPT (trimethylolpropane triacrylate, Shin-Nakamura Chemical Co., Ltd., manufactured by Ltd.). The crosslinking agent can be used alone in 1, also can be arbitrary ratio combination use 2 or more.
The amount of the crosslinking agent in the coating liquid can be adjusted to obtain an optically anisotropic layer having desired physical properties. The ratio of the crosslinking agent is preferably 1 part by weight or more, more preferably 2 parts by weight or more, preferably 10 parts by weight or less, and more preferably 8 parts by weight or less, relative to 100 parts by weight of the mesogenic compound in the coating liquid.
The coating liquid may contain, as an optional component, any additive such as a metal, a metal complex, a dye, a pigment, a fluorescent material, a phosphorescent material, a leveling agent, a thixotropic agent, a gelling agent, a polysaccharide, a surfactant, an ultraviolet absorber, an infrared absorber, an antioxidant, an ion exchange resin, a metal oxide such as titanium oxide, and the like. The proportion of the optional additives is preferably 0.1 to 20 parts by weight each per 100 parts by weight of the n-C polymer.
The coating liquid preferably does not exhibit liquid crystallinity. By using a coating liquid that does not exhibit liquid crystallinity, the dispersion of the positive C polymer and the mesogenic compound in the optically anisotropic layer can be made good. Further, by using a coating liquid having no liquid crystallinity, the occurrence of non-uniformity in the orientation of the mesogenic compound due to the influence of air fluctuations such as dry air can be suppressed.
[1.7.2 ] Process (b): coating ]
In the step of applying the coating liquid to the support surface to obtain the coating liquid layer, any surface capable of forming the coating liquid layer may be used as the support surface. As the supporting surface, a flat surface without a concave portion and a convex portion is generally used from the viewpoint of improving the surface condition of the optically anisotropic layer. The support surface is preferably a surface of a long substrate. When a long substrate is used, the coating liquid can be continuously applied to the continuously conveyed substrate. Therefore, the optically anisotropic layer can be continuously produced by using a long substrate, and thus the productivity can be improved.
As the substrate, a substrate film can be generally used. As the substrate film, a film used as a substrate of an optical laminate can be suitably selected and used. In particular, a transparent film is preferable as the base film from the viewpoint that a multilayer film having a base film and an optically anisotropic layer can be used as the optical film and that the optically anisotropic layer does not need to be peeled off from the base film. Specifically, the base film preferably has a total light transmittance of 80% or more, more preferably 85% or more, and particularly preferably 88% or more.
The material of the base material is not particularly limited, and various resins can be used. Examples of the resin include resins containing various polymers. Examples of the polymer include: alicyclic structure containing polymers, cellulose esters, polyvinyl alcohols, polyimides, UV transmissive acrylics, polycarbonates, polysulfones, polyethersulfones, epoxy polymers, polystyrenes, and combinations thereof. Among them, from the viewpoints of transparency, low hygroscopicity, dimensional stability, and lightweight property, the alicyclic structure-containing polymer and the cellulose ester are preferable, and the alicyclic structure-containing polymer is more preferable.
The alicyclic structure-containing polymer is a polymer having an alicyclic structure in a repeating unit, and is usually an amorphous polymer. The alicyclic structure-containing polymer may be any of a polymer having an alicyclic structure in the main chain and a polymer having an alicyclic structure in the side chain.
Examples of the alicyclic structure include a cycloalkane structure and a cycloalkene structure, and a cycloalkane structure is preferable from the viewpoint of thermal stability and the like.
The number of carbon atoms of the repeating unit constituting 1 alicyclic structure is not particularly limited, but is preferably 4 or more, more preferably 5 or more, particularly preferably 6 or more, preferably 30 or less, more preferably 20 or less, and particularly preferably 15 or less.
The proportion of the repeating unit having an alicyclic structure in the alicyclic structure-containing polymer may be suitably selected depending on the purpose of use, and is preferably 50% by weight or more, more preferably 70% by weight or more, and particularly preferably 90% by weight or more. By increasing the number of the repeating units having an alicyclic structure as described above, the heat resistance of the base film can be improved.
Examples of the alicyclic structure-containing polymer include: (1) norbornene polymer, (2) monocyclic cyclic olefin polymer, (3) cyclic conjugated diene polymer, (4) vinyl alicyclic hydrocarbon polymer, and hydrogenated products thereof. Among them, norbornene polymers are more preferable from the viewpoint of transparency and moldability.
Examples of the norbornene polymer include: a ring-opened polymer of a norbornene monomer, a ring-opened copolymer of a norbornene monomer and another monomer capable of ring-opening copolymerization, and a hydrogenated product thereof; addition polymers of norbornene monomers, addition copolymers of norbornene monomers and other monomers copolymerizable therewith, and the like. Among them, the hydrogenated ring-opening polymer of norbornene monomer is particularly preferable from the viewpoint of transparency.
The above-mentioned alicyclic structure-containing polymer can be selected from known polymers such as the polymers disclosed in Japanese patent laid-open publication No. 2002-321302.
In the case of using a resin containing an alicyclic structure-containing polymer as a material of the base film, the thickness of the base film is preferably 1 μm to 1000 μm, more preferably 5 μm to 300 μm, and particularly preferably 30 μm to 100 μm, from the viewpoint of facilitating improvement in productivity, reduction in thickness, and weight reduction.
The resin containing the alicyclic structure-containing polymer may be formed only of the alicyclic structure-containing polymer, and may contain any compounding agent as long as the effects of the present invention are not significantly impaired. The proportion of the alicyclic structure-containing polymer in the resin containing the alicyclic structure-containing polymer is preferably 70% by weight or more, and more preferably 80% by weight or more.
Preferable specific examples of the resin containing the alicyclic structure-containing polymer include "ZEONOR 1420" and "ZEONOR 1420R" manufactured by ZEON corporation.
Examples of the coating method of the coating liquid include: curtain coating method, extrusion coating method, roll coating method, spin coating method, dip coating method, bar coating method, spray coating method, slide coating method, print coating method, gravure coating method, die coating method, slit coating method, and dipping method. The thickness of the coating liquid to be applied is appropriately set in accordance with a desired thickness required for the optically anisotropic layer.
[1.7.3. drying ]
After the step (b), before the step (c), a step of drying the coating liquid layer is performed as necessary. By drying, the solvent can be removed from the coating liquid layer, and the orientation of the solid component of the coating liquid can be stabilized. As a result, the step (c) can be performed in a state where the solid content of the coating liquid is stable. As a specific method of drying, any method such as heat drying, drying under reduced pressure, drying under heat and reduced pressure, natural drying, or the like can be used.
In the method for producing an optically anisotropic layer of the present invention, an optically anisotropic layer can be produced by a simple operation of applying and curing a coating liquid containing a combination of a positive C polymer and a mesogenic compound. Therefore, an alignment film as described in patent document 1 is not required. Therefore, the adjustment of the compatibility of the inverse wavelength dispersion liquid crystal and the alignment film and the formation of the alignment film are not required, and therefore the optically anisotropic layer can be easily produced.
Further, the combination of the coating liquid containing the positive C polymer and the mesogenic compound can suppress the occurrence of the orientation unevenness of the mesogenic compound due to the influence of the fluctuation of air at the time of drying. Therefore, an optically anisotropic layer having a uniform orientation state in a wide range in the in-plane direction can be easily obtained, and therefore an optically anisotropic layer having an excellent surface state can be easily obtained. Therefore, white turbidity due to the alignment unevenness of the optically anisotropic layer can be suppressed.
[1.7.4 ] Process (c): light irradiation
By the step of irradiating with light, a part of the acrylate structure of the mesogenic compound is polymerized to become a polymer of the mesogenic compound. By this polymerization, an optically anisotropic layer of a polymer comprising a positive C polymer and a mesogenic compound can be formed. The method of irradiating the coating liquid layer with light can be appropriately selected according to the properties of the components contained in the coating liquid, such as the polymerizable compound and the polymerization initiator. The light to be irradiated may include visible light, ultraviolet light, infrared light, and the like. The method of irradiating ultraviolet rays is particularly preferable because of its easy operation.
The ultraviolet irradiation intensity is preferably 0.1mW/cm2～1000mW/cm2More preferably 0.5mW/cm2～600mW/cm2The range of (1). The ultraviolet irradiation time is preferably in the range of 1 second to 300 seconds, and more preferably in the range of 3 seconds to 100 seconds. Cumulative amount of ultraviolet light (mJ/cm)2) By ultraviolet irradiation intensity (mW/cm)2) The x irradiation time (sec). The preferred cumulative light amount is 600mJ/cm2～5000mJ/cm2. As the ultraviolet radiation light source, a high-pressure mercury lamp, a metal halide lamp, or a low-pressure mercury lamp can be used. Since the residual monomer ratio tends to decrease, the step (c) is preferably performed in an inert gas atmosphere such as a nitrogen atmosphere.
The method for producing the optically anisotropic layer may include any process other than the above-described process. For example, a step of peeling the optically anisotropic layer from the substrate may be included.
[2. transfer multilayer article ]
The transfer multilayer object of the present invention has a substrate and the above optically anisotropic layer. Here, the transfer multilayer material is a member including a plurality of layers, and transfers a part of the layers of the plurality of layers to manufacture a product including the part of the layers. In the transfer multilayer object of the present invention, the optically anisotropic layer is used for the production of the above-mentioned products.
As the substrate, the same substrate as described in the method for producing an optically anisotropic layer can be used. In particular, a peelable substrate is preferable as the substrate. The transfer multilayer article having such a base material can be produced by the above-described method for producing an optically anisotropic layer using a base material.
The transfer multilayer article can be used for producing an optical film. For example, an optical film having an optically anisotropic layer and a resin film can be produced by bonding the optically anisotropic layer of the transfer multilayer product to the resin film and then peeling the substrate.
[3. optically anisotropic laminate ]
The optically anisotropic laminate of the present invention has the optically anisotropic layer and the retardation layer.
[3.1. optically anisotropic layer in optically anisotropic laminate ]
The optically anisotropic layer is used as an optically anisotropic layer in an optically anisotropic laminate. Among them, the optically anisotropic layer of the optically anisotropic laminate preferably satisfies the following formulae (12) and (13).
Re (A590) is less than or equal to 10nm type (12)
Rth (A590) of ≤ 110nm and ≤ 20nm, and (13)
Re (A590) and Rth (A590) are as defined above.
In the case of the formula (12) described in detail above, Re (A590) is preferably 0nm to 10nm, more preferably 0nm to 5nm, and particularly preferably 0nm to 2 nm. By controlling Re (a590) in the above range, the optical design in the case of providing the optically anisotropic laminate in an image display device can be simplified.
In addition, when the above formula (13) is described in detail, Rth (A590) is preferably-110 nm or more, more preferably-100 nm or more, preferably-20 nm or less, more preferably-40 nm or less, and particularly preferably-50 nm or less. When an optically anisotropic laminate including an optically anisotropic layer having such Rth (a590) is incorporated in a circularly polarizing plate and applied to an image display device, the optically anisotropic laminate can effectively exhibit the function of suppressing reflection of external light in the oblique direction of the display surface of the image display device and transmitting light of a displayed image through a polarizing sunglass. Therefore, when the display surface of the image display device is viewed from an oblique direction, the visibility of the image can be effectively improved.
[3.2. retardation layer in optically anisotropic laminate ]
[3.2.1. optical characteristics of retardation layer ]
The phase difference layer is a layer satisfying formula (8).
nx (B) ny (B) nz (B) formula (8)
Wherein nx (B), ny (B) and nz (B) are the principal refractive indices of the retardation layer. The optically anisotropic laminate having such a retardation layer can be used to produce a circular polarizing plate by combining with a linear polarizer. The circularly polarizing plate is provided on the display surface of the image display device, and when the display surface is viewed from the front, the circularly polarizing plate can suppress reflection of external light and transmit light energy of a displayed image through the polarized sunglasses, thereby improving the visibility of the image.
It is particularly preferable that the values of the refractive index ny (B) and the refractive index nz (B) of the phase difference layer are the same or close to each other. Specifically, the absolute value of the difference between the refractive index ny (B) and the refractive index nz (B) | ny (B) -nz (B) | is preferably 0.00000 to 0.00100, more preferably 0.00000 to 0.00050, and particularly preferably 0.00000 to 0.00020. By controlling the absolute value of the refractive index difference | ny (b) -nz (b) | in the above range, the optical design in the case of providing the optically anisotropic laminate in the image display device can be simplified.
The retardation layer preferably satisfies formula (11).
Re (B590) of 110nm or less and 170nm or less formula (11)
Wherein Re (B590) is an in-plane retardation of the retardation layer having a wavelength of 590 nm.
When formula (11) is defined in detail, Re (B590) is preferably 110nm or more, more preferably 120nm or more, particularly preferably 130nm or more, preferably 170nm or less, more preferably 160nm or less, and particularly preferably 150nm or less. An optically anisotropic laminate comprising such a retardation layer having Re (B590) can be combined with a linear polarizer to obtain a circularly polarizing plate. By providing the circularly polarizing plate on the display surface of the image display device, when the display surface is viewed from the front direction, reflection of external light is suppressed, and light for displaying an image can be transmitted through the polarized sunglasses, thereby improving the visibility of the image.
The retardation layer preferably satisfies formula (9) and formula (10).
0.75 < Re (B450)/Re (B550) < 1.00 formula (9)
1.01 < Re (B650)/Re (B550) < 1.25 formula (10)
Wherein Re (B450) is an in-plane retardation of the retardation layer at a wavelength of 450nm, Re (B550) is an in-plane retardation of the retardation layer at a wavelength of 550nm, and Re (B650) is an in-plane retardation of the retardation layer at a wavelength of 650 nm.
When formula (9) above is specified, Re (B450)/Re (B550) is preferably greater than 0.75, more preferably greater than 0.78, and particularly preferably greater than 0.80, and is preferably less than 1.00, more preferably less than 0.95, and particularly preferably less than 0.90.
When the above formula (10) is specified, Re (B650)/Re (B550) is preferably more than 1.01, preferably more than 1.02, particularly preferably more than 1.04, and further preferably less than 1.25, more preferably less than 1.22, particularly preferably less than 1.19.
A retardation layer having in-plane retardations Re (B450), Re (B550) and Re (B650) satisfying the above-mentioned expressions (9) and (10) exhibits reverse wavelength dispersibility of the in-plane retardation Re. When the optically anisotropic laminate having such a retardation layer in which the in-plane retardation Re exhibits reverse wavelength dispersibility is incorporated in a circularly polarizing plate and applied to an image display device, the optically anisotropic laminate can exhibit a function of suppressing reflection of external light in a wide wavelength range in the front direction of the display surface of the image display device and transmitting light for displaying an image through a polarizing sunglass. Therefore, the visibility of the image displayed on the display surface can be particularly effectively improved.
The slow axis direction in the plane of the retardation layer is arbitrary, and can be arbitrarily set according to the application of the optically anisotropic laminate. In particular, when the optically anisotropic laminate is a long film, the angle formed between the slow axis of the retardation layer and the film width direction is preferably more than 0 ° and less than 90 °. In addition, in a certain state, the angle formed by the slow axis in the plane of the phase difference layer and the film width direction is preferably set to a specific range of 15 ° ± 5 °, 22.5 ° ± 5 °, 45 ° ± 5 °, or 75 ° ± 5 °, more preferably 15 ° ± 4 °, 22.5 ° ± 4 °, 45 ° ± 4 °, or 75 ° ± 4 °, and still more preferably 15 ° ± 3 °, 22.5 ° ± 3 °, 45 ° ± 3 °, or 75 ° ± 3 °. By having such an angular relationship, the optically anisotropic laminate can be roll-to-roll bonded to a long linear polarizer, and a circularly polarizing plate can be efficiently produced.
The total light transmittance of the retardation layer is preferably 80% or more, more preferably 85% or more, and particularly preferably 90% or more. The haze of the retardation layer is preferably 5% or less, more preferably 3% or less, particularly preferably 1% or less, and ideally 0%.
[3.2.2. stretched film layer as retardation layer ]
As the retardation layer, a stretched film layer can be used. In the case where a stretched film layer is used as the retardation layer, the stretched film layer may include a resin as a material of the base film described in the production method of the optically anisotropic layer. The film layer containing such a resin can exhibit optical properties such as retardation by being subjected to a stretching treatment. In particular, the stretched film described above preferably contains a polymer having an alicyclic structure.
The stretching direction of the stretched film layer is arbitrary. Therefore, the stretching direction may be the longitudinal direction, the width direction, or the oblique direction. Further, in these stretched squares, stretching is also applied in 2 or more directions. Here, the oblique direction means an in-plane direction of the film which is not parallel to both the longitudinal direction and the width direction.
In particular, the stretched film layer is preferably a diagonal stretched film layer. That is, the stretched film layer is preferably a long film, and is a film stretched in a direction not parallel to both the longitudinal direction and the width direction of the film. Specifically, the angle formed between the film width direction and the stretching direction in the case of the obliquely-stretched film layer may be more than 0 ° and less than 90 °. By using such an obliquely stretched film layer as a retardation layer, a circularly polarizing plate can be efficiently produced by laminating an optically anisotropic laminate to a long linear polarizer by a roll-to-roll method.
The angle formed between the stretching direction and the film width direction is preferably set to a specific range of 15 ° ± 5 °, 22.5 ° ± 5 °, 45 ° ± 5 °, or 75 ° ± 5 °, more preferably 15 ° ± 4 °, 22.5 ° ± 4 °, 45 ° ± 4 °, or 75 ° ± 4 °, and further preferably 15 ° ± 3 °, 22.5 ° ± 3 °, 45 ° ± 3 °, or 75 ° ± 3 °. By having such an angular relationship, the optically anisotropic laminate can be made into a material capable of efficiently producing a circularly polarizing plate.
Further, the stretched film layer preferably has a multilayer structure including a plurality of layers. The stretched film layer having a multilayer structure can exhibit various characteristics by a combination of functions of the respective layers included in the stretched film layer. For example, the stretch film layer preferably has, in order: the ultraviolet absorber includes a first outer layer formed of a resin including a polymer, an intermediate layer formed of a resin including a polymer and an ultraviolet absorber, and a second outer layer made of a resin including a polymer. In this case, the polymers contained in the respective layers may be different, but may be the same. The stretched film layer having the first outer layer, the intermediate layer and the second outer layer suppresses transmission of ultraviolet rays. Further, since the first outer layer and the second outer layer are provided on both sides of the intermediate layer, the ultraviolet absorber can be inhibited from bleeding out.
The amount of the ultraviolet absorber in the resin included in the intermediate layer is preferably 3 wt% or more, more preferably 4 wt% or more, particularly preferably 5 wt% or more, preferably 20 wt% or less, more preferably 18 wt% or less, and particularly preferably 16 wt% or less. When the amount of the ultraviolet absorber is not less than the lower limit of the above range, the ability of the stretched film layer to block the transmission of ultraviolet rays can be particularly improved, and when the amount is not more than the upper limit of the above range, the transparency of the stretched film layer to visible light can be improved.
The thickness of the intermediate layer is preferably set so that the ratio of "thickness of intermediate layer"/"total thickness of stretched film layer" is controlled within a specific range. The above specific range is preferably 1/5 or more, more preferably 1/4 or more, particularly preferably 1/3 or more, preferably 80/82 or less, more preferably 79/82 or less, and particularly preferably 78/82 or less. When the ratio is equal to or less than the lower limit of the above range, the ability of the stretched film layer to block the transmission of ultraviolet rays can be particularly improved, and when the ratio is equal to or less than the upper limit of the above range, the thickness of the stretched film layer can be reduced.
The thickness of the stretched film layer as the retardation layer is preferably 10 μm or more, more preferably 13 μm or more, particularly preferably 15 μm or more, preferably 60 μm or less, more preferably 58 μm or less, and particularly preferably 55 μm or less. When the thickness of the stretched film layer is not less than the lower limit of the above range, a desired retardation can be exhibited, and when the thickness is not more than the upper limit of the above range, the film can be thinned.
The stretched film layer can be produced, for example, by a method including a step of preparing a pre-stretch film layer and a step of stretching the prepared pre-stretch film layer.
The film layer before stretching can be produced by, for example, molding a resin as a material of the stretched film layer by an appropriate molding method. Examples of the molding method include: a cast molding method, an extrusion molding method, a blow molding method, and the like. In particular, from the viewpoint of efficiently reducing the amount of residual volatile components, environmental protection, and working environment, and from the viewpoint of excellent production efficiency, a melt extrusion method using no solvent is preferred. The melt extrusion method includes a blow molding method using a die, and a method using a T die is particularly preferable in terms of excellent productivity and thickness accuracy.
In the case of producing a stretched film layer having a multilayer structure, a stretch front film layer having a multilayer structure is generally prepared as a stretch front film layer. The stretched front film layer having a multilayer structure can be produced by molding a resin corresponding to each layer included in the multilayer structure by a moldability method such as a coextrusion method or a co-casting method. Among these molding methods, the coextrusion method is preferable because it is excellent in production efficiency and it is difficult to leave volatile components in the film. Examples of the coextrusion method include: a co-extrusion T-die method, a co-extrusion inflation molding method, a co-extrusion lamination method, and the like. Among them, the coextrusion T die method is preferable. The coextrusion T-die method includes a feedblock method and a multi-manifold method, and the multi-manifold method is particularly preferable in terms of reducing variations in thickness.
By forming the resin as described above, a long film before stretching is obtained. By stretching the pre-stretched film, a stretched film layer can be obtained. Stretching is usually performed continuously while conveying the film before stretching in the longitudinal direction. In this case, the stretching direction may be the longitudinal direction or the width direction of the film, and is preferably an oblique direction. The stretching may be free uniaxial stretching in which no constraining force is applied in the direction other than the stretching direction, or may be stretching in which a constraining force is applied in the direction other than the stretching direction. These stretching can be performed by using any stretching machine such as a roll stretching machine and a tenter stretching machine.
The stretching ratio is preferably 1.1 times or more, more preferably 1.15 times or more, particularly preferably 1.2 times or more, more preferably 3.0 times or less, more preferably 2.8 times or less, and particularly preferably 2.6 times or less. By setting the stretch ratio to be equal to or higher than the lower limit of the above range, the refractive index in the stretch direction can be increased. Further, by setting the upper limit value or less, the slow axis direction of the stretched film layer can be easily controlled.
The stretching temperature is preferably Tg-5 ℃ or higher, more preferably Tg-2 ℃ or higher, particularly preferably Tg or higher, preferably Tg +40 ℃ or lower, more preferably Tg +35 ℃ or lower, and particularly preferably Tg +30 ℃ or lower. Here, "Tg" means the highest temperature among the glass transition temperatures of the polymers contained in the film layer before stretching. By setting the stretching temperature in the above range, the molecules contained in the film layer before stretching can be reliably oriented, and therefore a stretched film layer that can function as a retardation layer having desired optical properties can be easily obtained.
[3.2.3. liquid Crystal layer as retardation layer ]
As the retardation layer as described above, a liquid crystal layer containing a liquid crystal compound whose alignment state can be fixed (hereinafter, may be referred to as "liquid crystal compound for retardation layer" as appropriate) can be used. In this case, the liquid crystal compound for the retardation layer is preferably the above-mentioned inverse wavelength dispersion liquid crystal compound aligned in parallel. Thus, the same advantages as those described in the item of the optically anisotropic layer can be obtained also in the retardation layer. In particular, the liquid crystal layer as the retardation layer preferably contains a liquid crystal compound represented by the following formula (II) whose alignment state can be fixed.
[ chemical formula 10]
In the above formula (II), Y1～Y8、G1、G2、Z1、Z2、Ax、Ay、A1～A5、Q1M and n have the same meanings as in the formula (I). Accordingly, the liquid crystal compound represented by the formula (II) represents the same compound as the liquid crystal compound represented by the formula (I).
However, in the formula (I), Z1-Y7-and-Y8-Z2One or more ofIn contrast to the case where both are acryloxy groups, in the formula (II), both of them may be groups other than acryloxy groups.
The thickness of the liquid crystal layer as the retardation layer is not particularly limited, and can be appropriately adjusted so that the characteristics such as retardation fall within a desired range. The specific thickness of the liquid crystal layer is preferably 0.5 μm or more, more preferably 1.0 μm or more, preferably 10 μm or less, more preferably 7 μm or less, and particularly preferably 5 μm or less.
The liquid crystal layer as the retardation layer can be produced, for example, by a method including: a step of preparing a liquid crystal composition containing a liquid crystal compound for a retardation layer; a step of applying a liquid crystal composition to a support to obtain a layer of the liquid crystal composition; and a step of aligning the liquid crystal compound for the retardation layer included in the layer of the liquid crystal polymer.
In the step of preparing the liquid crystal composition, the liquid crystal compound for a retardation layer and optional components to be used as needed are usually mixed to obtain the liquid crystal composition.
The liquid crystal composition may contain a polymerizable monomer as an optional component. The "polymerizable monomer" is specifically a compound other than the liquid crystal compound for retardation layer, among compounds usable as monomers having polymerizability. As the polymerizable monomer, for example, a monomer having 1 or more polymerizable groups per molecule can be used. When the polymerizable monomer is a crosslinkable monomer having 2 or more polymerizable groups per molecule, crosslinkable polymerization can be achieved. Examples of the polymerizable group include the group Z in the compound (I)1-Y7-and Z2-Y8Or a group which is the same as a part thereof, more specifically, for example, there are mentioned: acryl, methacryl, and epoxy. The polymerizable monomers may be used alone in 1 kind, or may be used in combination in 2 or more kinds at an arbitrary ratio.
In the liquid crystal composition, the proportion of the polymerizable monomer is preferably 1 to 100 parts by weight, more preferably 5 to 50 parts by weight, based on 100 parts by weight of the liquid crystal compound for retardation layer.
The liquid crystal composition may contain a photopolymerization initiator as an optional component. Examples of the polymerization initiator include the same polymerization initiators that the coating liquid used for producing the optically anisotropic layer may contain. Further, 1 kind of polymerization initiator may be used alone, or 2 or more kinds may be used in combination at an arbitrary ratio.
The proportion of the polymerization initiator in the liquid crystal composition is preferably 0.1 to 30 parts by weight, more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the polymerizable compound.
The liquid crystal composition may contain a surfactant as an arbitrary component. The surfactant is preferably a nonionic surfactant. Commercially available nonionic surfactants can be used. For example, an oligomer nonionic surfactant having a molecular weight of about several thousands can be used. As specific examples of these surfactants, "PF-151N", "PF-636", "PF-6320", "PF-656", "PF-6520", "PF-3320", "PF-651", "PF-652" of OMNOVA PolyFox; "FTX-209F", "FTX-208G", "FTX-204D", "601 AD" of FTERGENT of Neos, Inc.; "KH-40", "S-420", etc., of Surflon, Seimichematic corporation. Further, 1 kind of surfactant may be used alone, or 2 or more kinds may be used in combination at an arbitrary ratio.
The proportion of the surfactant in the liquid crystal composition is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 2 parts by weight, based on 100 parts by weight of the polymerizable compound.
The liquid crystal composition may contain a solvent as an arbitrary component. Examples of the solvent include the same solvents as those that can be contained in the coating liquid for producing the optically anisotropic layer. Further, 1 kind of solvent may be used alone, or 2 or more kinds may be used in combination at an arbitrary ratio.
The proportion of the solvent in the liquid crystal composition is preferably 100 to 1000 parts by weight based on 100 parts by weight of the polymerizable compound.
The liquid crystal composition may further contain, as an optional component, an additive such as a metal, a metal complex, a dye, a pigment, a fluorescent material, a phosphorescent material, a leveling agent, a thixotropic agent, a gelling agent, a polysaccharide, an ultraviolet absorber, an infrared absorber, an antioxidant, an ion exchange resin, a metal oxide such as titanium oxide, or the like. The proportion of such additives is preferably 0.1 to 20 parts by weight, respectively, based on 100 parts by weight of the polymerizable compound.
After preparing the liquid crystal composition as described above, the following steps are performed: and a step of applying the liquid crystal composition to a support to obtain a layer of the liquid crystal composition. The support is preferably an elongated support. In the case of using a long support, the liquid crystal composition can be continuously applied to a continuously conveyed support. Therefore, by using a long support, a liquid crystal layer as a retardation layer can be continuously produced, and thus productivity can be improved.
When the liquid crystal composition is applied to a support, it is preferable to apply the liquid crystal composition to the support while maintaining planarity by applying an appropriate tension (usually, 100 to 500N/m) to the support to reduce unstable conveyance of the support. The planarity is an amount of vibration in the vertical direction perpendicular to the width direction and the transport direction of the support, and is preferably 0mm, and usually 1mm or less.
As the support, a support film is generally used. As the support film, a film that can be used as a support of the optical layered body can be appropriately selected and used. In particular, a transparent film is preferable as the support film from the viewpoint that an optically anisotropic laminate having the support film, the retardation layer and the optically anisotropic layer can be used as the optical film and peeling of the support film is not necessary. Specifically, the total light transmittance of the support film is preferably 80% or more, more preferably 85% or more, and particularly preferably 88% or more.
The material of the support film is not particularly limited, and various resins can be used. Examples of the resin include the following resins: which comprises the polymer described as a material useful for forming a substrate of an optically anisotropic layer. Among them, from the viewpoint of transparency, low hygroscopicity, dimensional stability, and lightweight property, the alicyclic structure-containing polymer and the cellulose ester are preferable as the polymer contained in the resin, and the alicyclic structure-containing polymer is more preferable.
As the support, a support having an orientation controlling force can be used. The alignment controlling force of the support refers to a property of the support that can align the liquid crystal compound for the retardation layer in the liquid crystal composition applied on the support.
The orientation controlling force may be applied by applying a treatment for applying the orientation controlling force to a member such as a film as a material of the support. Examples of the treatment include a stretching treatment and a rubbing treatment.
In a preferred embodiment, the support is a stretched film. By providing the stretched film, the support can be provided with an orientation controlling force corresponding to the stretching direction.
The stretching direction of the stretched film is arbitrary. Therefore, the stretching direction may be the longitudinal direction, the width direction, or the oblique direction. Further, stretching may be applied in 2 or more of these stretching directions. The stretch ratio may be appropriately set in a range in which the orientation controlling force is generated on the surface of the support. When the material of the support is a resin having a positive intrinsic birefringence value, the molecules are oriented in the stretching direction, and a slow axis appears in the stretching direction. The stretching may be performed using a known stretching machine such as a tenter stretching machine.
In a more preferred embodiment, the support is an obliquely stretched film. In the case where the support is an obliquely stretched film, the angle formed between the stretching direction and the width direction of the stretched film may be, specifically, more than 0 ° and less than 90 °. By using the support as such an obliquely stretched film, the optically anisotropic laminate can be made into a material that enables efficient production of a circularly polarizing plate.
In one embodiment, the angle formed between the stretching direction and the width direction of the stretched film is preferably set to a specific range of 15 ° ± 5 °, 22.5 ° ± 5 °, 45 ° ± 5 °, or 75 ° ± 5 °, more preferably 15 ° ± 4 °, 22.5 ° ± 4 °, 45 ° ± 4 °, or 75 ° ± 4 °, and still more preferably 15 ° ± 3 °, 22.5 ° ± 3 °, 45 ° ± 3 °, or 75 ° ± 3 °. By having such an angular relationship, the optically anisotropic laminate can be made into a material that enables efficient production of the circularly polarizing plate.
Examples of the method for applying the liquid crystal composition include: curtain coating method, extrusion coating method, roll coating method, spin coating method, dip coating method, bar coating method, spray coating method, slide coating method, print coating method, gravure coating method, die coating method, slit coating method, dipping method. The thickness of the layer of the liquid crystal composition to be applied can be appropriately set according to a desired thickness required for the liquid crystal layer as the phase difference layer.
After the liquid crystal composition is applied to the support to obtain a layer of the liquid crystal composition, a step of aligning the liquid crystal compound for the retardation layer included in the layer of the liquid crystal composition is performed. Thus, the liquid crystal compound for retardation layer contained in the layer of the liquid crystal composition is aligned in the alignment direction according to the alignment controlling force of the support. For example, when a stretched film is used as the support, the liquid crystal compound for the retardation layer contained in the layer of the liquid crystal composition is aligned in parallel to the stretching direction of the stretched film.
Although the alignment of the liquid crystal compound for retardation layer may be achieved immediately by coating, it may be achieved by applying an alignment treatment such as heating after coating, if necessary. The conditions for the alignment treatment may be set as appropriate depending on the properties of the liquid crystal composition to be used, and for example, the treatment may be carried out at a temperature of 50 to 160 ℃ for 30 seconds to 5 minutes.
By aligning the liquid crystal compound for the retardation layer in the liquid crystal composition layer as described above, a liquid crystal layer that can function as a retardation layer can be obtained since desired optical characteristics are exhibited in the layer of the liquid crystal composition.
The method for producing a liquid crystal layer of the retardation layer may further include any step. The method for producing the liquid crystal layer may be, for example, a step of drying the layer of the liquid crystal composition or the liquid crystal layer. The drying can be realized by natural drying, heating drying, reduced pressure heating drying, etc.
In addition, as a method for producing a liquid crystal layer of a retardation layer, for example, a step of aligning a liquid crystal compound for a retardation layer contained in a liquid crystal composition and then fixing the alignment state of the liquid crystal compound for a retardation layer may be performed. In this step, generally, the alignment state of the liquid crystal compound for retardation layer is fixed by polymerizing the liquid crystal compound for retardation layer. Further, by polymerizing the liquid crystal compound for retardation layer, the rigidity of the liquid crystal layer can be improved and the mechanical strength can be improved.
The polymerization of the liquid crystal compound for the retardation layer can be appropriately selected according to the properties of the components of the liquid crystal composition. For example, a method of irradiating light is preferable. In particular, a method of irradiating ultraviolet rays is preferable because of its easy operation. Irradiation conditions such as ultraviolet irradiation intensity, ultraviolet irradiation time, ultraviolet accumulated light amount, and ultraviolet irradiation light source can be adjusted in the same range as the irradiation conditions of the method for producing an optically anisotropic layer.
In the polymerization, the liquid crystal compound for retardation layer is usually polymerized as it is while maintaining the molecular orientation. Therefore, by the above polymerization, a liquid crystal layer containing a polymer of a liquid crystal compound for retardation layer, which is aligned in a direction parallel to the alignment direction of the liquid crystal compound for retardation layer contained in the liquid crystal composition before polymerization, can be obtained. Therefore, for example, in the case where a stretched film is used as the support, a liquid crystal layer having an alignment direction parallel to the stretching direction of the stretched film can be obtained. Here, the term "parallel" means that the deviation between the stretching direction of the stretched film and the orientation direction of the polymer of the liquid crystal compound for retardation layer is usually ± 3 °, preferably ± 1 °, and ideally 0 °.
In the liquid crystal layer as the retardation layer produced by the above production method, the molecules of the polymer obtained from the liquid crystal compound for retardation layer preferably have an alignment order of horizontal alignment with respect to the support film. For example, when a support film having an alignment controlling force is used as the support film, the molecules of the polymer of the liquid crystal compound for the retardation layer can be aligned in the liquid crystal layer in a horizontal direction. Here, the term "horizontal alignment" of the molecules of the polymer of the liquid crystal compound for retardation layer with respect to the support film means that the average direction of the long axis direction of the mesogenic skeleton derived from the constitutional units of the liquid crystal compound for retardation layer contained in the polymer is aligned in any one direction parallel or nearly parallel to the film surface (for example, the angle with the film surface is within 5 °). When a plurality of mesogenic frameworks having different orientation directions are present in a liquid crystal layer as in the case where the compound represented by the formula (II) is used as a liquid crystal compound for a retardation layer, the orientation direction is usually the direction in which the long axis direction of the longest mesogenic framework among them is oriented.
Further, the method for producing a liquid crystal layer as a retardation layer may include a step of obtaining the liquid crystal layer and then peeling off the support.
[3.3. optional layers in optically anisotropic laminate ]
The optically anisotropic laminate may further have any layer, and may be combined with the optically anisotropic layer and the retardation layer. Examples of the optional layer include an adhesive layer and a hard coat layer.
[3.4. method for producing optically anisotropic laminate ]
The optically anisotropic laminate can be produced, for example, by the following production method 1 or 2.
Production method 1:
a method of manufacturing, comprising:
a step of manufacturing a retardation layer; and
and a step of forming an optically anisotropic layer on the retardation layer by performing the above-mentioned method for producing an optically anisotropic layer using the retardation layer as a substrate to obtain an optically anisotropic laminate.
When the coating liquid is applied to the retardation layer as in production method 1, the optically anisotropic layer is formed on the retardation layer by drying the coating liquid layer, thereby obtaining an optically anisotropic laminate.
In the production method 2, the reaction mixture is,
a method of manufacturing, comprising:
a step of manufacturing a retardation layer;
a step of manufacturing a transfer multilayer object;
a step of obtaining an optically anisotropic laminate by bonding the optically anisotropic layer of the transfer multilayer object and the retardation layer; and
and a step of peeling off the base material of the transfer multilayer object.
In the case of producing an optically anisotropic laminate by laminating an optically anisotropic layer and a retardation layer as in production method 2, an appropriate adhesive can be used for lamination. As the adhesive, for example, the same adhesive as used for a polarizing plate described later can be used.
The method for producing the optically anisotropic laminate described above may include any process other than the above-described process. For example, the above-described manufacturing method may include a step of providing an arbitrary layer such as a hard coat layer.
[4. polarizing plate ]
The polarizing plate of the present invention has a linear polarizer, and the optically anisotropic layer, the transfer multilayer object, or the optically anisotropic laminate. By providing such a polarizing plate in an image display device, the visibility of an image can be improved when the image display device is viewed from an oblique direction.
As the linear polarizer, known linear polarizers used for devices such as liquid crystal display devices and other optical devices can be used. Examples of linear polarizers include: a film obtained by subjecting a polyvinyl alcohol film to uniaxial stretching in a boric acid bath after adsorbing iodine or a dichroic dye; the film is obtained by adsorbing iodine or a dichroic dye to a polyvinyl alcohol film, stretching the film, and modifying a part of polyvinyl alcohol units in a molecular chain into a polyvinylidene unit. Further, as other examples of the linear polarizer, there may be mentioned: a grid polarizer, a multilayer polarizer, a cholesteric liquid crystal polarizer, or the like has a function of separating polarized light from reflected light and transmitted light. Among them, as the linear polarizer, a polarizer containing polyvinyl alcohol is preferable.
When natural light is made incident on a linear polarizer, only one polarized light is transmitted. The degree of polarization of the linear polarizer is not particularly limited, but is preferably 98% or more, and more preferably 99% or more.
The thickness of the linear polarizer is preferably 5 to 80 μm.
The polarizing plate may further include an adhesive layer for bonding the linear polarizer, the optically anisotropic layer, the transfer multilayer body, or the optically anisotropic laminate. As the adhesive layer, a layer obtained by curing a curable adhesive can be used. As the curable adhesive, a thermosetting adhesive can be used, but a photocurable adhesive is preferably used. As the photocurable adhesive, a photocurable adhesive containing a polymer or a reactive monomer can be used. The adhesive may contain a solvent, a photopolymerization initiator, other additives, and the like as necessary.
The photocurable adhesive is an adhesive that is curable when irradiated with light such as visible light, ultraviolet light, and infrared light. In particular, an adhesive curable by ultraviolet rays is preferable because of its easy handling.
The thickness of the adhesive layer is preferably 0.5 μm or more, more preferably 1 μm or more, preferably 30 μm or less, more preferably 20 μm or less, and further preferably 10 μm or less. By setting the thickness of the adhesive layer within the above range, good adhesion can be achieved without losing the optical properties of the optically anisotropic layer.
In addition, in the case where the polarizing plate has an optically anisotropic laminate, the polarizing plate may function as a circular polarizing plate. Here, the term "circularly polarizing plate" includes not only a circularly polarizing plate in a narrow sense but also an elliptically polarizing plate. Such a circularly polarizing plate may have a linear polarizer, an optically anisotropic layer, and a retardation layer in this order. Such a circularly polarizing plate may have a linear polarizer, a retardation layer, and an optically anisotropic layer in this order.
In the circularly polarizing plate as described above, the angle formed by the slow axis of the retardation layer and the absorption axis of the polarizing film of the linear polarizer is preferably 45 ° or an angle close thereto. The angle is, specifically, preferably 45 ° ± 5 °, more preferably 45 ° ± 4 °, and particularly preferably 45 ° ± 3 °.
The polarizing plate described above may further include an arbitrary layer. As an arbitrary layer, for example, a polarizer protective film layer can be cited. As the polarizer protective film layer, any transparent film layer may be used. In particular, a resin film layer excellent in transparency, mechanical strength, thermal stability, moisture resistance, and the like is preferable. Examples of such a resin include: an acetate resin such as triacetyl cellulose, a polyester resin, a polyether sulfone resin, a polycarbonate resin, a polyamide resin, a polyimide resin, a chain olefin resin, a cyclic olefin resin layer, a (meth) acrylic resin, and the like. Further, as an optional layer that the polarizing plate may include, for example, a hard coat layer such as an impact-resistant polymethacrylate resin layer, a matte layer for improving the smoothness of the film, a reflection suppressing layer, an antifouling layer, and the like. These arbitrary layers may be provided in only 1 layer, or 2 or more layers.
The polarizing plate can be produced by bonding a linear polarizer, an optically anisotropic layer, a transfer multilayer material, or an optically anisotropic laminate using an adhesive as needed.
[5. image display device ]
The image display device of the present invention has the polarizing plate of the present invention described above. The image display device of the present invention generally further includes an image display element. In an image display device, a polarizing plate is generally provided on the viewing side of an image display element. In this case, the orientation of the polarizing plate can be arbitrarily set according to the use of the polarizing plate. Therefore, the image display device may have, in order: an optically anisotropic layer, a transfer multilayer material, or an optically anisotropic laminate; a polarizer; an image display element. Further, the image display device may have, in order: a polarizer; an optically anisotropic layer, a transfer multilayer material, or an optically anisotropic laminate; an image display element.
There are various image display devices depending on the kind of image display element, and representative examples thereof include: a liquid crystal display device having a liquid crystal cell as an image display element, and an organic EL display device having an organic EL element as an image display element.
The image display device of the present invention includes the optically anisotropic layer of the present invention as a structural element, and thereby can suppress reflection of external light and transmit light for displaying an image through a polarizing sunglass. Further, a display device having such an effect, high durability, and a good color tone can be obtained.
[ examples ]
The present invention will be specifically described below with reference to examples. However, the present invention is not limited to the examples described below, and can be implemented by arbitrarily changing the examples without departing from the scope and the equivalent scope of the claims of the present invention. In the following description, "%" and "part" of the amounts are by weight unless otherwise specified. Unless otherwise stated, the operations described below were performed at normal temperature and normal pressure.
[ evaluation method ]
[ optical Properties of film ]
The optical properties (retardation, and inverse wavelength dispersion characteristics) of a sample layer (an optically anisotropic layer, a retardation layer, etc.) formed on a certain film (a base film, etc.) were measured by the following methods.
The sample layer to be evaluated was attached to a glass slide with an adhesive (adhesive "CS 9621T" manufactured by Nitto Denko Corporation). Thereafter, the film was peeled off to obtain a sample having a slide glass and a sample layer. The sample was set on a stage of a phase difference meter (manufactured by Axmetrics Co., Ltd.) and the wavelength dispersion of the in-plane retardation Re of the sample layer was measured. The chromatic dispersion of the in-plane retardation Re is a graph showing the in-plane retardation Re corresponding to the wavelength, and is, for example, a graph in which the horizontal axis is the wavelength and the vertical axis is the coordinate of the in-plane retardation Re. The in-plane retardations Re (450), Re (550), Re (590) and Re (650) of the sample layers having wavelengths of 450nm, 550nm, 590nm and 650nm were determined from the wavelength dispersion of the in-plane retardation Re of the sample layer thus obtained.
The stage was tilted by 40 ° about the slow axis of the sample layer as a rotation axis, and the wavelength dispersion of the retardation Re40 of the sample layer was measured in a tilt direction at an angle of 40 ° to the thickness direction of the sample layer. Here, the wavelength dispersion of the retardation Re40 is a graph indicating the retardation Re40 corresponding to the wavelength, and is, for example, a graph in which the abscissa axis represents the wavelength and the ordinate axis represents the coordinates of the retardation Re 40.
Further, the refractive index nx in the in-plane direction giving the maximum refractive index in the sample layer, the refractive index ny in the in-plane direction perpendicular to the direction of the nx, and the refractive index nz in the thickness direction were measured at wavelengths of 407nm, 532nm, and 633nm using a prism coupler (manufactured by Metricon corporation), and Cauchy fitting was performed to obtain wavelength dispersions of the refractive indices nx, ny, and nz. Here, the wavelength dispersion of the refractive index is a graph showing the refractive index according to the wavelength, and for example, the graph is shown with the horizontal axis as the wavelength and the vertical axis as the coordinate of the refractive index.
Then, the chromatic dispersion of the retardation Rth in the thickness direction of the sample layer was calculated based on the data of the retardation Re40 and the chromatic dispersion of the refractive index. Here, the chromatic dispersion of the retardation Rth in the thickness direction means the retardation Rth in the thickness direction corresponding to the wavelength, and is shown as a graph in which the abscissa represents the wavelength and the ordinate represents the coordinate of the retardation Rth in the thickness direction. Then, the in-plane retardations Rth (450), Rth (550), Rth (590) and Rth (650) of the sample layers at the wavelengths of 450nm, 550nm, 590nm and 650nm are determined from the wavelength dispersion of the retardation Rth in the thickness direction of the sample layer thus determined.
[ thickness ]
The thickness of a sample layer (optical anisotropic layer, retardation layer, etc.) formed on a film (base film, support film, multilayer film made of support film and retardation layer, etc.) was measured using a film thickness measuring apparatus ("films metrics" manufactured by FILMETRICS Co.).
[ haze Change ratio ]
A plate glass with an optical system adhesive (CS 9621 manufactured by Nitto Denko Corporation) was prepared. The optically anisotropic layer of the transfer multilayer article was transferred to the plate glass to prepare a laminate for haze measurement. Using this laminate for haze measurement, the haze of the optically anisotropic layer was measured by a haze meter (Toyo Seiki Seisakusho Co., Ltd., "haze gurdII" manufactured by Ltd., the same shall apply hereinafter) in accordance with JIS K7136: 2000 to obtain an initial haze value.
Next, the laminate for haze measurement was placed in an oven and heated. The heating temperature was 85 ℃ and the heating time was 100 hours. After the heating was completed, the haze was measured again by the haze meter, and the haze value after the heating was obtained. The haze change ratio (haze value after heating/initial haze value) was calculated from the initial haze value and the haze value after heating.
[ degree of curing ]
The optically anisotropic layer for measuring the degree of curing was prepared by peeling the optically anisotropic layer from the substrate.
The infrared absorption spectrum of the optically anisotropic layer in the optically anisotropic layer for measuring the degree of curing was measured by the ATR method. Specifically, the infrared absorption spectrum of the optically anisotropic layer exposed on the surface of the laminate for measuring the degree of curing was measured by using ZeSe as a prism under the condition of 1-time reflection using an ATR measuring device ("Nicolet iS 5N" manufactured by Thermo Fisher SCIENTIFIC). The infrared absorption spectrum is obtained as a relationship between the wave number and the absorbance. Measured as AC-HAppear at 810cm-1The area of the nearby peak is taken as AC＝OAppear at 1720cm-1Area of nearby peaks. In the examples and comparative examples of the present application, since the n-C polymer has a structure similar to that of C ═ OMDSince C ═ O bond(s) of (a), quantification was performed to exclude the influence of the analogous C ═ O bond (reference example 3). Based on these measurement results, A was obtainedC-H/AC＝OValue of (mesogenic compound).
[b*]
The optical anisotropic layer of the transfer multilayer article was transferred to a plate glass by the same procedure as in the preparation of the laminate for haze measurement, to prepare a laminate for hue measurement. The transmittance in the visible range (from 380nm to 780nm) of the laminate for hue measurement was measured by a spectrophotometer ("V-550" manufactured by JASCO Corporation) at intervals of 1.0 nm. Based on the measurements obtained, the hue b is calculated. The observation conditions at this time were a field of view of 2 °, a light source D65, and a data interval of 2 nm.
[ example 1]
The solvent was prepared by mixing 1, 3-Dioxolane (DOL) and methyl isobutyl ketone (MIBK). The mixing ratio of DOL and MIBK (DOL/MIBK, weight ratio) was 80/20.
55 parts by weight of a photopolymerizable reverse wavelength dispersion liquid crystal compound represented by the following formula (B1) (CN point 96 ℃ C.), 45 parts by weight of a copolymer of diisopropyl fumarate and cinnamate as a normal C polymer, 1.65 parts by weight of a polymerization initiator (trade name "Irgacure Oxe 04", manufactured by BASF Corporation), and 1.65 parts by weight of a crosslinking agent (trade name "A-TMPT", trimethylolpropane triacrylate, Shin-Nakamura Chemical Co., Ltd., manufactured by Ltd.) were dissolved in a solvent so that the solid content concentration became 12%, to prepare a coating liquid.
[ chemical formula 11]
The copolymer of diisopropyl fumarate and cinnamate used for the preparation of the coating liquid was a polyfumarate (weight average molecular weight 72000) having a repeating unit represented by the following formula (P1) and a repeating unit represented by the following formula (P2). In the following formulae (P1) and (P2), R represents an isopropyl group, and the ratio of the number of repeating units, m and n, is 85: 15.
[ chemical formula 12]
[ chemical formula 13]
As a base film, an unstretched film (made of ZEON CORPORATION, glass transition temperature (Tg) of resin 163 ℃ C., thickness 100 μm) made of a resin containing an alicyclic structure-containing polymer was prepared. The coating liquid was applied to the surface of the base film using a coating knife to form a coating liquid layer. The thickness of the coating liquid layer was adjusted so that the thickness of the obtained optically anisotropic layer became about 10 μm.
Then, the coating liquid layer was dried in an oven at 85 ℃ for 5 minutes, and the solvent in the coating liquid layer was evaporated to obtain a multilayer having a layer structure of (dried coating liquid layer)/(substrate film).
And then toThe dried coating liquid layer is irradiated with ultraviolet rays. The ultraviolet irradiation was performed as follows: using an irradiation apparatus having a high-pressure mercury light source, at an illuminance of 300mW/cm2Cumulative light amount 600mJ/cm2Under the conditions (3) above, the surface of the multilayer object on the side of the dry coating liquid layer is irradiated with ultraviolet rays from a light source. The dried coating liquid layer was cured by the irradiation with ultraviolet rays to form an optically anisotropic layer, thereby obtaining a transfer multilayer having a layer structure of (optically anisotropic layer)/(base film). The optically anisotropic layer of the transfer multilayer obtained was measured for optical properties, and nx (A), ny (A), nz (A), Rth (A450)/Rth (A550), Rth (A650)/Rth (A550), Re (A590) and Rth (A590) were determined. Further, the degree of cure A, b ×, and the haze change ratio of the optically anisotropic layer were measured.
Examples 2 to 4 and comparative examples 1 to 4
A multilayer for evaluation transfer was obtained and evaluated in the same manner as in example 1, except that the cumulative light amount was changed to the values shown in table 1.
The results of the examples and comparative examples are summarized in tables 1 and 2.
[ Table 1]
TABLE 1
[ Table 2]
TABLE 2
From the results of the examples and the comparative examples, it is understood that the optically anisotropic layer of the example having the specific degree of cure a defined in the present application has high durability because the increase in haze due to heating is reduced. It is found that the optically anisotropic layer of the example also has a good color tone with b × of 2.2 or less.
[ reference example 1: confirmation of wavelength Dispersion of reverse wavelength Dispersion liquid Crystal Compound represented by the formula (B1) ]
100 parts by weight of a photopolymerizable inverse wavelength dispersion liquid crystal compound represented by the above formula (B1), 3 parts by weight of a photopolymerization initiator ("Irgacure 379 EG" manufactured by BASF Corporation), and 0.3 part by weight of a surfactant (DIC, "MEGAFACE F-562" manufactured by inc.), a mixed solvent of cyclopentanone and 1, 3-dioxolane (the weight ratio of cyclopentanone: 1, 3-dioxolane is 4: 6) as a diluting solvent was added so that the solid content became 22% by weight, and the mixture was heated to 50 ℃ to be dissolved. The resulting mixture was filtered through a membrane filter having a pore size of 0.45 μm to obtain a liquid crystal composition.
An unstretched film made of a resin containing a polymer having an alicyclic structure ("ZEONORFILM" manufactured by ZEON CORP formation) was prepared. By applying a rubbing treatment to the unstretched film, an oriented base material was prepared.
The liquid crystal composition was applied to the above alignment substrate by a bar coater to form a layer of the liquid crystal composition. The thickness of the layer of the liquid crystal composition was adjusted so that the thickness of the optically anisotropic layer obtained after curing became about 2.3 μm.
Then, the layer of the liquid crystal composition is dried in an oven at 110 ℃ for about 4 minutes to evaporate the solvent in the liquid crystal composition while parallelly aligning the inverse wavelength dispersion liquid crystal compound contained in the liquid crystal composition.
Then, the layer of the liquid crystal composition is irradiated with ultraviolet rays using an ultraviolet irradiation apparatus. The irradiation with ultraviolet rays was performed in a nitrogen atmosphere in a state where the alignment base material was fixed to the SUS plate with a tape. The layer of the liquid crystal composition was cured by irradiation with ultraviolet rays, and a sample film having an optically anisotropic layer and an alignment substrate was obtained.
The wavelength dispersion of in-plane retardation of the sample film was measured by a phase difference meter (manufactured by Axmetrics). Since the alignment base material does not have in-plane retardation, the in-plane retardation obtained by the above measurement represents the in-plane retardation of the optically anisotropic layer. As a result of the measurement, in-plane retardations Re (450), Re (550) and Re (650) at wavelengths of 450nm, 550nm and 650nm satisfied Re (450) < Re (550) < Re (650). Therefore, it was confirmed that the photopolymerizable reverse wavelength dispersion liquid crystal compound represented by the formula (B1) exhibited a reverse wavelength dispersion in-plane retardation in the case of parallel alignment.
[ reference example 2: confirmation that the copolymer of diisopropyl fumarate and cinnamate is a Positive C Polymer
A copolymer of diisopropyl fumarate and cinnamate was added to N-methylpyrrolidone so that the solid content concentration became 12 wt%, and the mixture was dissolved at room temperature to obtain a polymer solution.
An unstretched film (ZEONORFILM, manufactured by ZEON CORP formation) made of a resin containing a polymer having an alicyclic structure was prepared. The polymer solution was applied to the unstretched film using a film coater to form a layer of the polymer solution. Thereafter, the film was dried in an oven at 85 ℃ for about 10 minutes, and the solvent was evaporated to obtain a sample film having a thickness of about 10 μm and an unstretched film.
The sample film was set on a stage of a phase difference meter (manufactured by Axmetrics Co., Ltd.), and the in-plane retardation Re0 of the sample film was measured at a measurement wavelength of 590 nm. Since the unstretched film was an optically isotropic film, the in-plane retardation Re0 measured was the in-plane retardation Re0 of the polymer film. As a result of the measurement, it was confirmed that nx (P) ≧ ny (P) since the in-plane retardation Re0 was Re 0. ltoreq.1 nm, and they were the same or similar values.
Then, the stage was tilted by 40 ° with the slow axis of the polymer film as the rotation axis of the stage, and the retardation Re40 in the tilt direction at an angle of 40 ° to the thickness direction of the sample film was measured. Then, by this measurement, the slow axis direction of the polymer film was measured. If the "slow axis direction" is perpendicular to the "rotation axis of the table", it can be judged that nz (P) > nx (P), whereas if the "slow axis direction" is parallel to the "rotation axis of the table", it can be judged that ny (P) > nz (P). As a result of the measurement, the slow axis direction was perpendicular to the rotation axis of the stage, and therefore, it was found that the refractive indices nx (P) and nz (P) of the polymer film satisfy nz (P) > nx (P).
Therefore, when a polymer film is formed by a coating method using a solution of the copolymer, it is confirmed that the refractive index of the polymer film satisfies nz (P) > nx (P) > ny (P). Therefore, it was confirmed that the copolymer of diisopropyl fumarate and cinnamate belongs to the n-C polymer.
[ reference example 3]
A plurality of transfer multilayer articles were obtained in the same manner as in example 3, except that the amounts of the microcrystalline compound and the n-C polymer in the coating liquid were changed. The infrared absorption spectrum of each optically anisotropic layer of the obtained transfer multilayer article was measured by the ATR method. 1720cm of the obtained infrared absorption spectrum-1The peak area of the peak appearing in the vicinity was regarded as AC＝O. As a result, the results shown in Table 3 were obtained. The constant a is calculated from these values by the least squares methodC＝O(mesogenic compounds). As a result, aC＝O(mesogenic compound) ═ 12.93, aC＝O(polymer) ═ 21.42. Based on these values, A in examples and comparative examples was determinedC＝OThe value of (mesogenic compound) is used for the calculation of the degree of curing A.
[ Table 3]
TABLE 3
| W (Polymer) | W (mesogenic compound) | AC＝O |
| 0.35 | 0.65 | 15.89 |
| 0.45 | 0.55 | 16.78 |
| 0.55 | 0.45 | 17.59 |
Claims (18)
1. An optically anisotropic layer, comprising: polymers of n-C, mesogenic compounds, and polymers of mesogenic compounds,
the n-C polymer is a polymer satisfying formula (1) when a film of the n-C polymer is formed by a coating method using a solution of the n-C polymer,
the mesogenic compound is a compound with a mesogenic skeleton and an acrylate structure,
the optically anisotropic layer satisfies formula (2) and formula (3):
nz (P) > nx (P) ≧ ny (P) formula (1)
nz (A) > nx (A) ≧ ny (A) formula (2)
0.073＜AC-H/AC＝O(mesogenic compound) < 0.125 formula (3)
Wherein,
nx (P), ny (P), and nz (P) are the principal refractive indices of the film,
nx (A), ny (A) and nz (A) are principal refractive indices of the optically anisotropic layer,
AC-His an infrared absorption of an out-of-plane bending vibration of a C-H bond possessed by the acrylate structure of the mesogenic compound in an infrared absorption spectrum of the optically anisotropic layer,
AC＝O(mesogenic compound) is the sum of infrared absorption of stretching vibration of the C ═ O bond possessed by the acrylate structure of the mesogenic compound and infrared absorption of stretching vibration of the C ═ O bond derived from the C ═ O bond of the acrylate structure of the mesogenic compound in the infrared absorption spectrum of the optically anisotropic layer,
the C ═ O bond derived from the C ═ O bond of the acrylate structure of the mesogenic compound is a C ═ O bond bonded to a carbonyl group of an ethylene group which appears after polymerization of an acrylate.
2. The optically anisotropic layer of claim 1, wherein the mesogenic compound is a compound that exhibits in-plane retardation of inverse wavelength dispersion with parallel orientation.
3. The optically anisotropic layer according to claim 1 or 2, wherein formula (4) and formula (5) are satisfied:
0.50 < Rth (A450)/Rth (A550) < 1.00 formula (4)
1.00. ltoreq. Rth (A650)/Rth (A550) < 1.25 formula (5)
Wherein,
rth (A450) is a thickness-direction retardation of the optically anisotropic layer at a wavelength of 450nm,
rth (a550) is a thickness direction retardation of the optically anisotropic layer at a wavelength of 550nm,
rth (a650) is a retardation in the thickness direction of the optically anisotropic layer at a wavelength of 650 nm.
4. The optically anisotropic layer according to claim 1 or 2, wherein the mesogenic compound is represented by the following formula (I),
in the above-mentioned formula (I),
Y1～Y8each independently represents a single chemical bond, -O-, -S-, -O-C (═ O) -, -C (═ O) -O-, -O-C (═ O) -O-, -NR1-C(＝O)-、-C(＝O)-NR1-、-O-C(＝O)-NR1-、-NR1-C(＝O)-O-、-NR1-C(＝O)-NR1-、-O-NR1-, or-NR1-O-where R1Represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,
G1and G2Each independently represents a divalent aliphatic group having 1 to 20 carbon atoms which may have a substituent, and each aliphatic group in the aliphatic groups may1 or more of-O-, -S-, -O-C- (O) -, -C- (O) -O-, -O-C- (O) -O-, -NR-, and the like2-C(＝O)-、-C(＝O)-NR2-、-NR2-, or-C (═ O) -, except for the case where 2 or more of, -O-or-S-are inserted adjacently, respectively, where R is2Represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,
Z1and Z2Each independently represents an alkenyl group having 2 to 10 carbon atoms which may be substituted with a halogen atom,
Axan organic group having 2 to 30 carbon atoms and having at least one aromatic ring selected from an aromatic hydrocarbon ring and an aromatic heterocyclic ring,
Ayrepresents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, a cycloalkyl group having 3 to 12 carbon atoms which may have a substituent, an alkynyl group having 2 to 20 carbon atoms which may have a substituent, -C (═ O) -R3、-SO2-R4、-C(＝S)NH-R9Or an organic group having 2 to 30 carbon atoms and having at least one aromatic ring selected from an aromatic hydrocarbon ring and an aromatic heterocyclic ring, wherein R is3Represents an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, a cycloalkyl group having 3 to 12 carbon atoms which may have a substituent, or an aromatic hydrocarbon ring group having 5 to 12 carbon atoms, R4Represents an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a phenyl group or a 4-methylphenyl group, R9Represents an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, a cycloalkyl group having 3 to 12 carbon atoms which may have a substituent, or an aromatic group having 5 to 20 carbon atoms which may have a substituent, wherein A isxAnd AyThe aromatic ring may have a substituent, and A isxAnd AyMay be formed together into a ring,
A1represents a trivalent aromatic group capable of having a substituent,
A2and A3Each independently represents a divalent alicyclic hydrocarbon group having 3 to 30 carbon atoms which may have a substituent,
A4and A5Each independently represents a divalent aromatic group having 6 to 30 carbon atoms which may have a substituent,
Q1represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent,
m and n each independently represent 0 or1,
wherein Z is1-Y7-and-Y8-Z2One or both of which are acryloxy groups.
5. Optically anisotropic layer according to claim 1 or 2, wherein the mesogenic compound contains in its molecular structure: at least 1 selected from the group consisting of a cyclohexyl ring in combination with a phenyl ring, and a benzothiazolyl ring.
6. The optically anisotropic layer of claim 1 or 2, wherein the positive C polymer is at least 1 polymer selected from polyvinylcarbazole, polyfumarate and cellulose derivatives.
7. The optically anisotropic layer according to claim 1 or 2, wherein a ratio of the mesogenic compound and the polymer thereof in a total solid content of the optically anisotropic layer is 20 wt% or more and 60 wt% or less.
8. The optically anisotropic layer according to claim 1 or 2, wherein formula (6) and formula (7) are satisfied:
re (A590) is less than or equal to 10nm type (6)
Rth (A590) of 200nm or more and 10nm or less as formula (7)
Wherein,
re (A590) is an in-plane retardation of the optically anisotropic layer at a wavelength of 590nm,
rth (a590) is a retardation in the thickness direction of the optically anisotropic layer at a wavelength of 590 nm.
9. A transfer multilayer article comprising the optically anisotropic layer according to any one of claims 1 to 8 and a substrate.
10. An optically anisotropic laminate comprising the optically anisotropic layer according to any one of claims 1 to 8 and a phase difference layer,
the phase difference layer satisfies formula (8):
nx (B) ny (B) nz (B) formula (8)
Wherein nx (B), ny (B) and nz (B) are the main refractive indexes of the phase difference layer.
11. The optically anisotropic laminate according to claim 10, wherein the phase difference layer satisfies formula (9) and formula (10):
0.75 < Re (B450)/Re (B550) < 1.00 formula (9)
1.01 < Re (B650)/Re (B550) < 1.25 formula (10)
Wherein,
re (B450) is an in-plane retardation of the retardation layer at a wavelength of 450nm,
re (B550) is an in-plane retardation of the retardation layer at a wavelength of 550nm,
re (B650) is an in-plane retardation of the retardation layer at a wavelength of 650 nm.
12. The optically anisotropic laminate according to claim 11, wherein the retardation layer comprises a liquid crystal compound for retardation layer represented by the following formula (II),
in the above-mentioned formula (II),
Y1～Y8each independently represents a single chemical bond, -O-, -S-, -O-C (═ O) -, -C (═ O) -O-, -O-C (═ O) -O-, -NR1-C(＝O)-、-C(＝O)-NR1-、-O-C(＝O)-NR1-、-NR1-C(＝O)-O-、-NR1-C(＝O)-NR1-、-O-NR1-, or-NR1-O-where R1Represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,
G1and G2Each independently represents a divalent aliphatic group having 1 to 20 carbon atoms which may have a substituent, and 1 or more-O-, -S-, -O-C (═ O) -, -C (═ O) -O-, -O-C (═ O) -O-, -NR can be inserted into each aliphatic group2-C(＝O)-、-C(＝O)-NR2-、-NR2-, or-C (═ O) -, except for the case where 2 or more of, -O-or-S-are inserted adjacently, respectively, where R is2Represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,
Z1and Z2Each independently represents an alkenyl group having 2 to 10 carbon atoms which may be substituted with a halogen atom,
Axan organic group having 2 to 30 carbon atoms and having at least one aromatic ring selected from an aromatic hydrocarbon ring and an aromatic heterocyclic ring,
Ayrepresents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, a cycloalkyl group having 3 to 12 carbon atoms which may have a substituent, an alkynyl group having 2 to 20 carbon atoms which may have a substituent, -C (═ O) -R3、-SO2-R4、-C(＝S)NH-R9Or an organic group having 2 to 30 carbon atoms and having at least one aromatic ring selected from an aromatic hydrocarbon ring and an aromatic heterocyclic ring, wherein R is3Represents an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, a cycloalkyl group having 3 to 12 carbon atoms which may have a substituent, or an aromatic hydrocarbon ring group having 5 to 12 carbon atoms, R4Represents an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a phenyl group or a 4-methylphenyl group, R9Represents an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, a cycloalkyl group having 3 to 12 carbon atoms which may have a substituent, or a cycloalkyl group having 5 to up to three carbon atoms which may have a substituent20, said AxAnd AyThe aromatic ring may have a substituent, and the A isxAnd AyMay be formed together into a ring,
A1represents a trivalent aromatic group capable of having a substituent,
A2and A3Each independently represents a divalent alicyclic hydrocarbon group having 3 to 30 carbon atoms which may have a substituent,
A4and A5Each independently represents a divalent aromatic group having 6 to 30 carbon atoms which may have a substituent,
Q1represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent,
m and n each independently represent 0 or 1.
13. A polarizing plate, comprising:
a linear polarizer; and
the optically anisotropic layer according to any one of claims 1 to 8, the transfer multilayer according to claim 9, or the optically anisotropic laminate according to any one of claims 10 to 12.
14. An image display device having the polarizing plate according to claim 13.
15. An image display device, comprising in order:
an optically anisotropic laminate according to any one of claims 10 to 12;
a linear polarizer; and
an image display element is provided on the substrate,
the image display element is a liquid crystal cell or an organic electroluminescent element.
16. A method for producing an optically anisotropic layer according to any one of claims 1 to 8, comprising the steps of:
preparing a coating liquid containing a positive C polymer, a mesogenic compound, a solvent, a photopolymerization initiator, and a crosslinking agent;
applying the coating liquid to a support surface to obtain a coating liquid layer; and
and curing the coating liquid layer by irradiating the coating liquid layer with light.
17. The method for producing an optically anisotropic layer according to claim 16,
the ratio of the photopolymerization initiator to 100 parts by weight of the mesogenic compound in the coating liquid is 1 to 10 parts by weight,
the ratio of the crosslinking agent to 100 parts by weight of the mesogenic compound is 1 to 10 parts by weight.
18. The manufacturing method according to claim 16 or 17, wherein a cumulative light amount of the irradiated light is 600mJ/cm2～5000mJ/cm2。
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| PCT/JP2018/021402 WO2019003812A1 (en) | 2017-06-30 | 2018-06-04 | Optically anisotropic layer and method for producing same, optically anisotropic laminate, multi-layered article for transfer use, polarizing plate, and image display device |
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| CN111752034A (en) * | 2019-03-28 | 2020-10-09 | 夏普株式会社 | Liquid crystal panel manufacturing method and liquid crystal panel |
| KR20220070429A (en) * | 2019-09-30 | 2022-05-31 | 니폰 제온 가부시키가이샤 | Optically anisotropic multilayer and manufacturing method |
| CN113004729A (en) * | 2021-02-25 | 2021-06-22 | 张家港莱拓新材料科技有限公司 | Novel polymerizable mesogenic mixture coating and application thereof in near-infrared band |
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| TW520449B (en) * | 1999-07-29 | 2003-02-11 | Teijin Ltd | Retardation film, composite retardation film, and liquid crystal display device using same |
| JP3832301B2 (en) * | 2001-10-03 | 2006-10-11 | チッソ株式会社 | Liquid crystalline fumaric acid diester and its polymer |
| JP4201171B2 (en) * | 2002-11-08 | 2008-12-24 | 日本化薬株式会社 | Liquid crystalline compounding composition and retardation film using the same |
| DE602006012969D1 (en) * | 2005-06-10 | 2010-04-29 | Merck Patent Gmbh | LIQUID CRYSTALLINE MATERIAL WITH HOMEOTROPER ORIENTATION |
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| CN101622219A (en) * | 2007-03-01 | 2010-01-06 | 日本瑞翁株式会社 | Polymerizable liquid crystal compound, polymerizable liquid crystal composition, liquid crystal polymer and optically anisotropic substance |
| JP2010020269A (en) * | 2007-09-28 | 2010-01-28 | Fujifilm Corp | Liquid crystal display device |
| KR101115075B1 (en) * | 2007-12-26 | 2012-02-28 | 주식회사 엘지화학 | Retardation film and polarizing plate and liquid crystal display comprising the same |
| JP2012224734A (en) * | 2011-04-19 | 2012-11-15 | Asahi Glass Co Ltd | Polymer compound, composition for alignment film, alignment film, optical element, and optical head device |
| CN102304365B (en) * | 2011-05-23 | 2014-06-11 | 西安彩晶光电科技股份有限公司 | Ultralow optical anisotropy mixed liquid crystal material |
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| WO2014069515A1 (en) * | 2012-10-30 | 2014-05-08 | 日本ゼオン株式会社 | Liquid crystal composition, retardation plate, image display device, and method for controlling wavelength dispersion in optically anisotropic layer |
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| WO2017170455A1 (en) * | 2016-03-30 | 2017-10-05 | 日本ゼオン株式会社 | Optically anisotropic layer and production method therefor, optically anisotropic laminate and production method therefor, optically anisotropic transfer body, polarization plate, and image display device |
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