CN116113858A - Method for producing optically anisotropic layer - Google Patents
Method for producing optically anisotropic layer Download PDFInfo
- Publication number
- CN116113858A CN116113858A CN202180057967.1A CN202180057967A CN116113858A CN 116113858 A CN116113858 A CN 116113858A CN 202180057967 A CN202180057967 A CN 202180057967A CN 116113858 A CN116113858 A CN 116113858A
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- China
- Prior art keywords
- liquid crystal
- crystal compound
- optically anisotropic
- composition layer
- anisotropic layer
- Prior art date
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Abstract
The present invention provides a simple method for manufacturing an optically anisotropic layer in which the alignment state of a liquid crystal compound is fixed and a plurality of regions in which the alignment states of the liquid crystal compound are different are provided in the thickness direction. The method for producing an optically anisotropic layer of the present invention comprises: a step 1 of forming a composition layer containing a liquid crystal compound having a polymerizable group; step 2, in the stepSubjecting the composition layer to a heat treatment to orient the liquid crystal compound in the composition layer; step 3 of forming a composition layer at 300mJ/cm under the condition that the oxygen concentration is 1% by volume or more after step 2 2 The irradiation with light is performed for 50 seconds or less; step 4 of performing a heat treatment on the composition layer at a temperature higher than that at the time of light irradiation after step 3; and a step 5 of forming an optically anisotropic layer having a plurality of regions in which the alignment state of the liquid crystal compound is different in the thickness direction by subjecting the composition layer to a curing treatment after the step 4.
Description
Technical Field
The present invention relates to a method for producing an optically anisotropic layer.
Background
The retardation layer (optically anisotropic layer) having refractive index anisotropy is suitable for various applications such as an antireflection film of a display device and an optical compensation film of a liquid crystal display device.
As an optically anisotropic layer, as described in patent document 1, a laminated optically anisotropic layer composed of a plurality of layers is disclosed.
Technical literature of the prior art
Patent literature
Patent document 1: japanese patent No. 5960743
Disclosure of Invention
Technical problem to be solved by the invention
Conventionally, when an optically anisotropic layer as described in patent document 1 is produced, a laminated optically anisotropic layer is formed by coating each layer, and therefore there is a problem that productivity is low and cost is high.
In addition, in the case of repeated coating, the coating liquid may repel each other, and a desired optically anisotropic layer may not be formed.
In view of the above, an object of the present invention is to provide a simple method for producing an optically anisotropic layer in which the alignment state of a liquid crystal compound is fixed and a plurality of regions in which the alignment states of the liquid crystal compound are different in the thickness direction are provided.
Means for solving the technical problems
As a result of intensive studies on the problems of the prior art, the present inventors have found that the above problems can be solved by the following configuration.
(1) A method of manufacturing an optically anisotropic layer, comprising:
a step 1 of forming a composition layer containing a liquid crystal compound having a polymerizable group;
a step 2 of subjecting the composition layer to a heat treatment to orient the liquid crystal compound in the composition layer;
step 3 of forming a composition layer at 300mJ/cm under the condition that the oxygen concentration is 1% by volume or more after step 2 2 The irradiation with light is performed for 50 seconds or less;
step 4 of performing a heat treatment on the composition layer at a temperature higher than that at the time of light irradiation after step 3; a kind of electronic device with high-pressure air-conditioning system
And step 5 of forming an optically anisotropic layer having a plurality of regions in which the alignment state of the liquid crystal compound is different in the thickness direction by subjecting the composition layer to a curing treatment after step 4.
(2) The method for producing an optically anisotropic layer according to (1), wherein the composition layer contains a photosensitive material selected from the group consisting of photopolymerization initiators and photosensitizers,
the molar absorptivity of the photosensitive material at the wavelength of light irradiation in step 3 is 5000L/(mol cm) or less.
(3) The method for producing an optically anisotropic layer according to (1) or (2), wherein the composition layer contains a chiral agent,
The chiral agent includes a photosensitive chiral agent whose helical twisting power is changed by light irradiation.
(4) The method for producing an optically anisotropic layer according to (3), wherein the total content of chiral agents is 5.0 mass% or less relative to the total mass of the liquid crystal compound.
(5) The method for producing an optically anisotropic layer according to (3), wherein the total content of chiral agents exceeds 5.0 mass% relative to the total mass of the liquid crystal compound.
(6) The method for producing an optically anisotropic layer according to (1) or (2), wherein the composition layer contains a photosensitive compound whose polarity is changed by light irradiation.
(7) The method for producing an optically anisotropic layer according to (6), wherein the photosensitive compound is a photosensitive compound hydrophilized by light irradiation.
(8) The method for producing an optically anisotropic layer according to (1) or (2), wherein the temperature of the heat treatment in step 4 is a temperature equal to or higher than the temperature at which the liquid crystal compound becomes an isotropic phase.
Effects of the invention
According to the present invention, a simple method for producing an optically anisotropic layer in which the alignment state of a liquid crystal compound is fixed and a plurality of regions in which the alignment states of the liquid crystal compound are different in the thickness direction can be provided.
Drawings
Fig. 1 is a cross-sectional view of a composition layer illustrating an example of step 1A of embodiment 1 of the method for producing an optically anisotropic layer of the present invention.
Fig. 2 is a cross-sectional view of a composition layer illustrating an example of step 3A in embodiment 1 of the method for producing an optically anisotropic layer of the present invention.
Fig. 3 is a cross-sectional view of a composition layer for explaining an example in the step 4A of embodiment 1 of the method for producing an optically anisotropic layer according to the present invention.
FIG. 4 is a graph plotting the helical twisting power (HTP: helical Twisting Power) (μm) for each of chiral reagent A and chiral reagent B -1 ) X concentration (mass%) and light irradiation amount (mJ/cm) 2 ) Schematic diagram of the relationship of (a).
FIG. 5 is a graph plotting the weighted average helical twisting power (. Mu.m) in a system in which chiral agent A and chiral agent B are used simultaneously -1 ) And the light irradiation amount (mJ/cm) 2 ) Schematic diagram of the relationship of (a).
Fig. 6 is a cross-sectional view of a composition layer illustrating another example of step 1A of embodiment 1 of the method for producing an optically anisotropic layer of the present invention.
Fig. 7 is a cross-sectional view of a composition layer for explaining another example in the step 4A of embodiment 1 of the method for producing an optically anisotropic layer according to the present invention.
Fig. 8 is a cross-sectional view of a composition layer illustrating an example of step 3B in embodiment 2 of the method for producing an optically anisotropic layer of the present invention.
Fig. 9 is a cross-sectional view of a composition layer illustrating an example of step 4B of embodiment 2 of the method for producing an optically anisotropic layer of the present invention.
FIG. 10 is a graph plotting the helical twisting power (. Mu.m) with respect to chiral agent A -1 ) And the light irradiation amount (mJ/cm) 2 ) Schematic diagram of the relationship of (a).
Fig. 11 is a cross-sectional view of a composition layer illustrating an example of step 3C of embodiment 3 of the method for producing an optically anisotropic layer of the present invention.
Fig. 12 is a cross-sectional view of a composition layer illustrating an example of step 4C in embodiment 3 of the method for producing an optically anisotropic layer of the present invention.
Fig. 13 is a cross-sectional view of a composition layer illustrating an example of step 3D of embodiment 4 of the method for producing an optically anisotropic layer of the present invention.
Fig. 14 is a cross-sectional view of a composition layer illustrating an example of step 4D of embodiment 4 of the method for producing an optically anisotropic layer of the present invention.
Fig. 15 is a cross-sectional view showing an embodiment of the laminate of the present invention.
Fig. 16 is a cross-sectional view showing an embodiment of the polarizer-equipped optically anisotropic layer of the present invention.
Detailed Description
The present invention will be described in detail below. In the present specification, a numerical range indicated by "to" means a range including numerical values described before and after "to" as a lower limit value and an upper limit value. First, terms used in the present specification will be described.
Unless otherwise specifically stated, the slow axis is defined at 550nm.
In the present invention, re (λ) and Rth (λ) represent in-plane retardation at wavelength λ and retardation in the thickness direction, respectively. Unless otherwise specifically stated, the wavelength λ is set to 550nm.
In the present invention, re (λ) and Rth (λ) are values obtained by measurement at wavelength λ using AxoScan (manufactured by Axometrics). The average refractive index ((nx+ny+nz)/3) and film thickness (d (μm)) were calculated by inputting into AxoScan
Slow axis direction (°)
Re(λ)＝R0(λ)
Rth(λ)＝((nx+ny)/2-nz)×d。
In addition, R0 (λ) is shown as a numerical value calculated using AxoScan, but represents Re (λ).
In this specification, regarding refractive indices nx, ny, and nz, an abbe refractometer (NAR-4T, ATAGO co., ltd. System) was used, and a sodium lamp (λ=589 nm) was used as a light source for measurement. In the case of measuring the wavelength dependence, the measurement can be performed by using a combination of a multi-wavelength Abbe refractometer DR-M2 (manufactured by ATAGO CO., LTD.) and an interference filter.
And, the polymer manual (JOHN WILEY & SONS, INC) and the values of the catalogues of various optical films can be used. The values of the average refractive index of the primary optical film are exemplified below: cellulose acylate (1.48), cycloolefin polymer (1.52), polycarbonate (1.59), polymethyl methacrylate (1.49) and polystyrene (1.59).
The term "light" in the present specification means an activating light or radiation, and means, for example, an open line spectrum of a mercury lamp, extreme ultraviolet rays typified by excimer laser, extreme ultraviolet rays (EUV light: extreme Ultraviolet), X-rays, ultraviolet rays, electron beams (EB: electron Beam), and the like. Among them, ultraviolet rays are preferable.
In the present specification, "visible light" means light of 380 to 780 nm. In this specification, the measurement wavelength is 550nm unless otherwise specifically described.
In this specification, in the case where the liquid crystal compound is twist-aligned in the optically anisotropic layer, the twist angle thereof is preferably more than 0 ° and less than 360 °. The cholesteric liquid crystal phase described later is a phase having a periodic structure in which a liquid crystal compound is spirally aligned, and has a twist angle of 360 ° or more.
As a characteristic point of the method for producing an optically anisotropic layer of the present invention, a predetermined step is performed.
As will be described in detail later, in the present invention, first, the liquid crystal compound in the composition layer is aligned. The oxygen concentration is low in a region of a part of the substrate side of the formed composition layer, and is high in other regions of the surface side opposite to the substrate side. Therefore, when such a composition layer is irradiated with light under a predetermined condition, it is difficult to polymerize the liquid crystal compound in a region having a high oxygen concentration, and it is easy to polymerize the liquid crystal compound in a region having a low oxygen concentration. In a region where polymerization of the liquid crystal compound is easy, the alignment state of the liquid crystal compound is fixed. In addition, when the heat treatment is performed after the light irradiation, the alignment state of the liquid crystal compound does not change in the region where the polymerization of the liquid crystal compound is performed, but the alignment state of the liquid crystal compound changes in the region where the polymerization of the liquid crystal compound is difficult to perform, and the alignment state that changes in the curing treatment is fixed. As a result, an optically anisotropic layer having a plurality of regions in which the alignment state of the fixed liquid crystal compound is different in the thickness direction can be manufactured.
The method for producing an optically anisotropic layer of the present invention comprises:
A step 1 of forming a composition layer containing a liquid crystal compound having a polymerizable group;
a step 2 of subjecting the composition layer to a heat treatment to orient the liquid crystal compound in the composition layer;
step 3 of forming a composition layer at 300mJ/cm under the condition that the oxygen concentration is 1% by volume or more after step 2 2 The irradiation with light is performed for 50 seconds or less;
step 4 of performing a heat treatment on the composition layer at a temperature higher than that at the time of light irradiation after step 3; a kind of electronic device with high-pressure air-conditioning system
And step 5 of forming an optically anisotropic layer having a plurality of regions in which the alignment state of the liquid crystal compound is different in the thickness direction by subjecting the composition layer to a curing treatment after step 4.
In addition, by performing the above step 5, the alignment state of the liquid crystal compound is immobilized.
As described later, examples of the mode of having the regions in which the alignment states of the liquid crystal compounds are different from each other include a mode in which the helical pitches of the cholesteric liquid crystal phases of the plurality of regions are different from each other, a mode in which the tilt angles of the alignment directions of the liquid crystal compounds with respect to the layer surface are different in the plurality of regions, and a mode in which one of the 2 regions is a region in which the state in which the liquid crystal compound exhibits an isotropic phase is fixed and the other region is a region in which the alignment state in which the liquid crystal compound is aligned is fixed.
Hereinafter, each preferred embodiment of the method for producing an optically anisotropic layer of the present invention will be described in detail.
Embodiment 1
Embodiment 1 of the method for producing an optically anisotropic layer of the present invention includes the following steps 1A to 5A. As described later, in embodiment 1, an optically anisotropic layer having a region in which the alignment state of a liquid crystal compound that is twist-aligned along a helical axis extending in the thickness direction is fixed is formed.
Step 1A: the step of forming a composition layer containing a chiral agent containing at least a photosensitive chiral agent whose helical twisting power is changed by light irradiation and a liquid crystal compound having a polymerizable group
Step 2A: in this step, the composition layer is subjected to a heat treatment to orient the liquid crystal compound in the composition layer
Step 3A: the step of forming a composition layer at 300mJ/cm under the condition that the oxygen concentration is 1% by volume or more after the step 2A 2 The following procedure of light irradiation for 50 seconds or less
Step 4A: the step of heating the composition layer at a temperature higher than that during light irradiation after the step 3A
Step 5A: in this step, after step 4A, the composition layer is subjected to a curing treatment to form an optically anisotropic layer having a plurality of regions in which the alignment states of the liquid crystal compounds are different in the thickness direction, as will be described later, and in order to produce the optically anisotropic layer having the above-described characteristics, in embodiment 1, the total content of chiral agents (total content of all chiral agents) in the composition layer is preferably 5.0 mass% or less with respect to the total mass of the liquid crystal compounds.
The steps of the above steps will be described in detail below.
< procedure 1A >
Step 1A is a step of forming a composition layer containing a chiral agent including at least a photosensitive chiral agent whose helical twisting power is changed by light irradiation and a liquid crystal compound having a polymerizable group. By performing this step, a composition layer subjected to a light irradiation treatment described later can be formed.
Hereinafter, first, the materials used in this step will be described in detail, and then, the steps of the step will be described in detail.
(chiral agent)
The composition layer of step 1A contains a chiral agent containing at least a photosensitive chiral agent whose helical twisting power is changed by light irradiation. First, a photosensitive chiral agent whose helical twisting power is changed by light irradiation will be described in detail.
The Helical Twisting Power (HTP) of the chiral reagent is a factor indicating the helical orientation ability represented by the following formula (a).
Htp=1/(length of helical pitch (unit: μm) ×concentration of chiral agent relative to liquid crystal compound (mass%)) [ μm -1 ]
The length of the helical pitch refers to the length of the pitch P (=period of helix) of the helical structure of the cholesteric liquid crystal phase, and can be measured by the method described in page 196 of liquid crystal review (published by MARUZEN GROUP).
The photosensitive chiral agent (hereinafter, also simply referred to as "chiral agent a") whose helical twisting power is changed by light irradiation may be liquid crystalline or non-liquid crystalline. Chiral agent a often contains asymmetric carbon atoms. The chiral agent a may be an axially asymmetric compound or a surface asymmetric compound containing no asymmetric carbon atom.
The chiral reagent a may be a chiral reagent having an increased helical twisting power by irradiation with light, or may be a chiral reagent having a decreased helical twisting power. Among them, chiral agents whose helical twisting power is reduced by light irradiation are preferable.
In the present specification, the term "increase or decrease in the helical twisting force" means an increase or decrease when the initial helical direction of the chiral reagent a (before light irradiation) is set to "positive". Therefore, even when the spiral twisting force is reduced by light irradiation and exceeds 0 and the spiral direction becomes "negative" (that is, when the spiral in the spiral direction opposite to the original (before light irradiation) spiral direction is twisted), the chiral reagent corresponds to "a chiral reagent having reduced spiral twisting force".
The chiral reagent a may be a so-called photoreactive chiral reagent. The photoreactive chiral agent is the following compound: the liquid crystal compound has a chiral region and a photoreactive region whose structure is changed by light irradiation, and for example, the twisting power of the liquid crystal compound is significantly changed according to the irradiation amount.
Examples of the photoreaction site whose structure is changed by light irradiation include photochromic compounds (in Tian Xinwu, jiang Zhenghao, chemical industry, vol.64, 640p,1999, in Tian Xinwu, jiang Zhenghao, fine chemistry, vol.28 (9), 15p, 1999), and the like. The structural change means decomposition, addition reaction, isomerization, racemization, [2+2] photocyclization, dimerization reaction, and the like caused by irradiation of light to the photoreaction site, and the structural change may be irreversible. Further, as chiral sites, for example, chemical general theory corresponding to field Ping Bo, chemistry of liquid crystal No.22, 73p: asymmetric carbons described in 1994, and the like.
As the chiral reagent A, for example, a photoreactive chiral reagent described in paragraphs 0044 to 0047 of Japanese patent application laid-open No. 2001-15979, an optically active compound described in paragraphs 0019 to 0043 of Japanese patent application laid-open No. 2002-179669, an optically active compound described in paragraphs 0020 to 0044 of Japanese patent application laid-open No. 2002-179633, an optically active compound described in paragraphs 0016 to 0040 of Japanese patent application laid-open No. 2002-179670, an optically active compound described in paragraphs 0017 to 0050 of Japanese patent application laid-open No. 2002-179668, an optically active compound described in paragraphs 0018 to 0044 of Japanese patent application laid-open No. 2002-180051, an optically active isosorbide derivative described in paragraphs 0016 to 00575 of Japanese patent application laid-open No. 2002-170023 to 0032, an optically active compound described in paragraphs 0016 to 00470, an optically active compound described in paragraphs 0016 to 0040 of Japanese patent application laid-open No. 2002-open No. 0017, an optically active compound described in terms of Japanese patent application laid-open No. 0019 to 0019, an optically active derivative described in terms of Japanese patent application laid-0019 to 0019, an optically active compound described in Japanese patent application laid-open No. 0019 to 0019, an optically active compound described in Japanese patent application laid-open No. 0019 to be placed-0019, an optically active compound described in Japanese patent application laid-open publication No. 0019 to be placed-open No. 0019-open publication, an optically active derivative, and an optically active derivative described in Japanese patent application laid-active publication to be placed application laid-open publication No. 0011 to be placed application-equipped with a publication, and a publication to be optically active substance, and a publication to be placed application-active and prepared, an optically active isosorbide derivative described in paragraphs 0015 to 0049 of JP-A-2003-313187, an optically active isomannide derivative described in paragraphs 0015 to 0057 of JP-A-2003-313188, an optically active isosorbide derivative described in paragraphs 0015 to 0049 of JP-A-2003-313189, an optically active polyester/amide described in paragraphs 0015 to 0052 of JP-A-2003-313292, an optically active compound described in paragraphs 0012 to 0053 of WO2018/194157, an optically active compound described in paragraphs 0020 to 0049 of JP-A-2002, and the like.
Among these chiral reagents a, a compound having at least a photoisomerization site is preferable, and the photoisomerization site more preferably has a double bond capable of photoisomerization. The photoisomerization moiety having a double bond capable of photoisomerization is preferably a cinnamoyl moiety, a chalcone moiety, an azobenzene moiety, or a stilbene moiety from the viewpoint of easiness of photoisomerization and a large difference in helical twisting power between before and after light irradiation, and is more preferably a cinnamoyl moiety, a chalcone moiety, or a stilbene moiety from the viewpoint of small absorption of visible light. The photoisomerization site corresponds to the photoreaction site whose structure is changed by light irradiation.
Further, from the viewpoints of high initial (before irradiation of light) helical twisting power and more excellent variation in helical twisting power due to irradiation of light, chiral reagent a preferably has a trans-form double bond capable of undergoing photoisomerization.
Further, from the viewpoints of low initial (before irradiation of light) helical twisting power and more excellent variation in helical twisting power due to irradiation of light, chiral reagent a preferably has a cis double bond capable of photoisomerization.
The chiral agent a preferably has any one of a binaphthyl moiety, an isosorbide moiety (isosorbide-derived moiety) and an isomannide moiety (isomannide-derived moiety). The binaphthyl moiety, the isosorbide moiety and the isomannide moiety are the following structures, respectively.
The portion of the binaphthyl moiety structure where the solid line and the dashed line are parallel represents a single bond or a double bond. In the structure shown below, the bonding position is represented.
[ chemical formula 1]
The chiral agent a may have a polymerizable group. The kind of the polymerizable group is not particularly limited, and is preferably a functional group capable of undergoing addition polymerization, more preferably a polymerizable ethylenically unsaturated group or a ring-polymerizable group, and further preferably a (meth) acryloyl group, vinyl group, styryl group or allyl group.
The chiral agent a is preferably a compound represented by the formula (C).
Formula (C) R-L-R
R each independently represents a group having at least 1 moiety selected from the group consisting of a cinnamoyl moiety, a chalcone moiety, an azobenzene moiety, and a stilbene moiety.
L represents a 2-valent linking group (a 2-valent linking group formed by removing 2 hydrogen atoms from the structure represented by the formula (D)) a 2-valent linking group represented by the formula (E) (a 2-valent linking group formed by the isosorbide moiety), or a 2-valent linking group represented by the formula (F) (a 2-valent linking group formed by the isomannide moiety).
In the formula (E) and the formula (F), the bonding position is represented.
[ chemical formula 2]
In step 1A, at least the chiral reagent a may be used. The step 1A may be a method using 2 or more chiral reagents a, or a method using at least 1 chiral reagent a and at least 1 chiral reagent (hereinafter, also simply referred to as "chiral reagent B") whose helical twisting power does not change by light irradiation.
The chiral agent B may be liquid crystalline or non-liquid crystalline. Chiral agent B often contains asymmetric carbon atoms. The chiral agent B may be an axially asymmetric compound or a surface asymmetric compound containing no asymmetric carbon atom.
The chiral agent B may have a polymerizable group. Examples of the polymerizable group include polymerizable groups that chiral agent a may have.
As the chiral reagent B, a known chiral reagent can be used.
The chiral reagent B is preferably a chiral reagent having a spiral twisted in the opposite direction to the chiral reagent a. That is, for example, in the case where the helix twisted by the chiral agent a is to the right, the helix twisted by the chiral agent B is to the left.
The molar absorptivity of chiral reagent a and chiral reagent B is not particularly limited, but the molar absorptivity at the wavelength of light (e.g., 365 nm) irradiated in step 3A described later is preferably 100 to 100,000 l/(mol·cm), more preferably 500 to 50,000L/(mol·cm).
The respective contents of the chiral agent a and chiral agent B in the composition layer can be appropriately set according to the characteristics (for example, retardation or wavelength dispersion) of the optically anisotropic layer to be formed. Further, the twist angle of the liquid crystal compound in the optically anisotropic layer depends largely on the types of chiral agent a and chiral agent B and the addition concentrations thereof, and thus the alignment state of the liquid crystal compound can be controlled by adjusting these.
In embodiment 1, the total content of chiral agents (total content of all chiral agents) in the composition layer is not particularly limited, but is preferably 5.0 mass% or less, more preferably 4.0 mass% or less, and still more preferably 2.0 mass% or less, relative to the total mass of the liquid crystal compound, from the viewpoint of easy control of the alignment state of the liquid crystal compound. The lower limit is not particularly limited, but is preferably 0.01 mass% or more, more preferably 0.02 mass% or more, and still more preferably 0.05 mass%.
The content of chiral agent a in the chiral agent is not particularly limited, but is preferably 5 to 95 mass%, more preferably 10 to 90 mass% with respect to the total mass of the chiral agent, from the viewpoint of easy control of the alignment state of the liquid crystal compound.
(liquid Crystal Compound)
The composition layer of step 1A contains a liquid crystal compound having a polymerizable group.
The type of the liquid crystal compound is not particularly limited. Generally, liquid crystal compounds can be classified into a rod type (rod-like liquid crystal compound) and a discotic type (discotic liquid crystal compound) according to their shapes. Also, liquid crystal compounds can be classified into low molecular type and high molecular type. The polymer is usually a compound having a polymerization degree of 100 or more (physical/phase transition kinetics of polymer, soil well, 2 pages, rock bookstore, 1992). In the present invention, any liquid crystal compound can be used, but a rod-like liquid crystal compound or a discotic liquid crystal compound is preferably used, and a rod-like liquid crystal compound is more preferably used. 2 or more rod-like liquid crystal compounds, 2 or more discotic liquid crystal compounds, or a mixture of rod-like liquid crystal compounds and discotic liquid crystal compounds may be used.
As the rod-like liquid crystal compound, for example, the rod-like liquid crystal compound described in paragraphs 0026 to 0098 of claim 1 of JP-A-11-513019 or JP-A-2005-289980 can be preferably used.
As the discotic liquid crystal compound, for example, those described in paragraphs 0020 to 0067 of japanese patent application laid-open No. 2007-108732 or 0013 to 0108 of japanese patent application laid-open No. 2010-244038 can be preferably used.
The type of the polymerizable group included in the liquid crystal compound is not particularly limited, and is preferably a functional group capable of undergoing addition polymerization, more preferably a polymerizable ethylenically unsaturated group or a ring-polymerizable group, and further preferably a (meth) acryloyl group, vinyl group, styryl group or allyl group.
In addition, the optically anisotropic layer produced in the present invention is a layer formed by fixing a liquid crystal compound having a polymerizable group (a rod-like liquid crystal compound or a discotic liquid crystal compound having a polymerizable group) by polymerization or the like, and after formation into a layer, it is no longer necessary to exhibit liquid crystallinity.
The content of the liquid crystal compound in the composition layer is not particularly limited, but is preferably 60 mass% or more, more preferably 70 mass% or more, relative to the total mass of the composition layer, from the viewpoint of easy control of the alignment state of the liquid crystal compound. The upper limit is not particularly limited, but is preferably 99 mass% or less, more preferably 97 mass% or less.
(other Components)
The composition layer may contain other components than the chiral agent and the liquid crystal compound.
For example, the composition layer may contain a polymerization initiator. In the case where the composition layer contains a polymerization initiator, polymerization of the liquid crystal compound having a polymerizable group proceeds more efficiently.
The polymerization initiator may be a known polymerization initiator, for example, a photopolymerization initiator or a thermal polymerization initiator, and preferably a photopolymerization initiator. In particular, a polymerization initiator that sensitizes light irradiated in step 5A described later is preferable.
The polymerization initiator preferably has a molar absorptivity of not more than 0.1 times the molar absorptivity of the maximum of the wavelengths of the light irradiated in step 3A, relative to the molar absorptivity of the maximum of the wavelengths of the light irradiated in step 5A.
Further, from the viewpoint of ease of forming a predetermined optically anisotropic layer, the molar absorption coefficient of the polymerization initiator at the wavelength of light irradiation in step 3A is preferably 5000L/(mol·cm) or less, more preferably 4000L/(mol·cm) or less, and still more preferably 3000L/(mol·cm) or less. The lower limit is not particularly limited, but is preferably 0L/(mol.cm), but 30L/(mol.cm) or more is often used.
The content of the polymerization initiator in the composition layer is not particularly limited, but is preferably 0.01 to 20 mass%, more preferably 0.5 to 10 mass% with respect to the total mass of the composition layer.
The composition layer may comprise a photosensitizer.
The type of the photosensitizer is not particularly limited, and known photosensitizers can be used.
In addition, from the viewpoint of ease of forming a predetermined optically anisotropic layer, the molar absorption coefficient of the photosensitizer at the wavelength of light irradiation in step 3A is preferably 5000L/(mol·cm) or less, more preferably 4800L/(mol·cm) or less, and still more preferably 4500L/(mol·cm) or less. The lower limit is not particularly limited, but is preferably 0L/(mol.cm), but 30L/(mol.cm) or more is often used.
The content of the photosensitizer in the composition layer is not particularly limited, but is preferably 0.01 to 20 mass%, more preferably 0.5 to 10 mass%, relative to the total mass of the composition layer.
The composition layer may contain a polymerizable monomer different from the liquid crystal compound having a polymerizable group. The polymerizable monomer may be a radical polymerizable compound or a cation polymerizable compound, and is preferably a polyfunctional radical polymerizable monomer. Examples of the polymerizable monomer include those described in paragraphs 0018 to 0020 of JP-A-2002-296423.
The content of the polymerizable monomer in the composition layer is not particularly limited, but is preferably 1 to 50% by mass, more preferably 5 to 30% by mass, relative to the total mass of the liquid crystal compound.
The composition layer may comprise a surfactant. The surfactant may be a conventionally known compound, and is preferably a fluorine-based compound. Specifically, examples thereof include compounds described in paragraphs 0028 to 0056 of Japanese patent application laid-open No. 2001-330725 and compounds described in paragraphs 0069 to 0126 of Japanese patent application laid-open No. 2003-295212.
The composition layer may comprise a polymer. Examples of the polymer include cellulose esters. As the cellulose ester, there may be mentioned the cellulose ester described in paragraph 0178 of JP-A-2000-155216.
The content of the polymer in the composition layer is not particularly limited, but is preferably 0.1 to 10 mass%, more preferably 0.1 to 8 mass% with respect to the total mass of the liquid crystal compound.
In addition to the above, the composition layer may contain an additive (alignment controlling agent) that promotes horizontal alignment or vertical alignment to bring the liquid crystal compound into a horizontal alignment state or a vertical alignment state.
(substrate)
As described later, when forming the composition layer, the composition layer is preferably formed on the substrate.
The substrate is a plate supporting the composition layer.
As the substrate, a transparent substrate is preferable. The transparent substrate is a substrate having a transmittance of 60% or more of visible light, and the transmittance is preferably 80% or more, more preferably 90% or more.
The retardation value (Rth (550)) in the thickness direction at a wavelength of 550nm of the substrate is not particularly limited, but is preferably-110 to 110nm, more preferably-80 to 80nm.
The retardation value (Re (550)) in the plane of the substrate at a wavelength of 550nm is not particularly limited, but is preferably 0 to 50nm, more preferably 0 to 30nm, and still more preferably 0 to 10nm.
The material for forming the substrate is preferably a polymer excellent in optical transparency, mechanical strength, thermal stability, moisture barrier property, isotropy, and the like.
Examples of the polymer film that can be used as the substrate include cellulose acylate films (for example, triacetate cellulose films (refractive index 1.48), diacetate cellulose films, acetate butyrate cellulose films, acetate propionate cellulose films), polyolefin films such as polyethylene and polypropylene, polyester films such as polyethylene terephthalate and polyethylene naphthalate, polyether sulfone films, polypropylene films such as polymethyl methacrylate, polyurethane films, polycarbonate films, polysulfone films, polyether films, polymethylpentene films, polyetherketone films, (meth) acrylonitrile films, and films of polymers having an alicyclic structure (norbornene resins (ARTON: product name, manufactured by JSR corporation, amorphous polyolefin (ZEONEX: product name, manufactured by Zeon Corporat ion)).
Among them, as a material of the polymer film, triacetyl cellulose, polyethylene terephthalate, or a polymer having an alicyclic structure is preferable, and triacetyl cellulose is more preferable.
The substrate may contain various additives (e.g., an optical anisotropy adjuster, a wavelength dispersion adjuster, fine particles, a plasticizer, an ultraviolet inhibitor, a degradation inhibitor, a peeling agent, etc.).
The thickness of the substrate is not particularly limited, but is preferably 10 to 200. Mu.m, more preferably 10 to 100. Mu.m, and still more preferably 20 to 90. Mu.m. The substrate may be formed by stacking a plurality of substrates. In order to improve adhesion of the substrate to a layer provided on the substrate, a surface treatment (for example, glow discharge treatment, corona discharge treatment, ultraviolet (UV) treatment, flame treatment) may be performed on the surface of the substrate.
Further, an adhesive layer (primer layer) may be provided on the substrate.
In order to impart slidability in the conveying step to the substrate or to prevent adhesion of the back surface to the front surface after winding, a polymer layer may be disposed on one side of the substrate, wherein the polymer layer is formed by mixing inorganic particles having an average particle diameter of about 10 to 100nm in a solid content mass ratio of 5 to 40 mass%.
The substrate may be a so-called dummy support. That is, after the manufacturing method of the present invention is carried out, the substrate may be peeled from the optically anisotropic layer.
Further, the rubbing treatment may be directly performed on the surface of the substrate. That is, a substrate subjected to a rubbing treatment may be used. The direction of the rubbing treatment is not particularly limited, and the optimum direction is appropriately selected according to the direction in which the liquid crystal compound is to be aligned.
The rubbing treatment can be applied to a treatment method widely used as a liquid crystal alignment treatment step for an LCD (liquid crystal display: liquid crystal display). That is, a method of rubbing the surface of the substrate in a certain direction using paper, gauze, felt, rubber, nylon fiber, polyester fiber, or the like to obtain orientation can be used.
An alignment film may be disposed on the substrate.
The alignment film can be formed using a rubbing treatment of an organic compound (preferably, a polymer), oblique evaporation of an inorganic compound, formation of a layer having micro grooves, or a method of accumulating an organic compound (for example, ω -ditridecanoic acid, dioctadecyl methyl ammonium chloride, methyl stearate) based on the langmuir-blodgett method (LB film).
Further, an alignment film that generates an alignment function by applying an electric field, a magnetic field, or light irradiation (preferably polarized light) is also known.
The alignment film is preferably formed by a rubbing treatment of a polymer.
Examples of the polymer contained in the alignment film include a methacrylate copolymer, a styrene copolymer, a polyolefin, a polyvinyl alcohol, a modified polyvinyl alcohol, a poly (N-methylolacrylamide), a polyester, a polyimide, a vinyl acetate copolymer, carboxymethyl cellulose, and a polycarbonate described in paragraph 0022 of JP-A-8-338913. Also, a silane coupling agent can be used as the polymer.
Among them, water-soluble polymers (e.g., poly (N-methylolacrylamide), carboxymethyl cellulose, gelatin, polyvinyl alcohol, modified polyvinyl alcohol) are preferable, gelatin, polyvinyl alcohol or modified polyvinyl alcohol are more preferable, and polyvinyl alcohol or modified polyvinyl alcohol are further preferable.
As described above, the alignment film can be formed by applying a solution containing the polymer as an alignment film forming material and an optional additive (for example, a crosslinking agent) to a substrate, and then performing heat drying (crosslinking) and rubbing treatment.
(step of Process 1A)
In step 1A, a composition layer containing the above components is formed, but the procedure is not particularly limited. For example, a method in which a composition containing the chiral agent and a liquid crystal compound having a polymerizable group is applied to a substrate and, if necessary, a drying treatment is performed (hereinafter, also simply referred to as "application method") and a method in which a composition layer is formed separately and transferred to the substrate are exemplified. Among them, the coating method is preferable from the viewpoint of productivity.
Hereinafter, the coating method will be described in detail.
The composition used in the coating method contains the chiral agent, the liquid crystal compound having a polymerizable group, and other components (e.g., a polymerization initiator, a polymerizable monomer, a surfactant, a polymer, etc.) that are used as necessary in addition to the chiral agent.
The content of each component in the composition is preferably adjusted to the content of each component in the composition layer.
The coating method is not particularly limited, and examples thereof include a bar coating method, an extrusion coating method, a direct gravure coating method, a reverse gravure coating method, and a die coating method.
Further, if necessary, after the composition is applied, a treatment of drying the coating film applied on the substrate may be performed. The solvent can be removed from the coating film by performing the drying treatment.
The film thickness of the coating film is not particularly limited, but is preferably 0.1 to 20. Mu.m, more preferably 0.2 to 15. Mu.m, and still more preferably 0.5 to 10. Mu.m.
< procedure 2A >
The step 2A is as follows: the composition layer is subjected to a heat treatment to orient the liquid crystal compound in the composition layer. By performing this step, the liquid crystal compound in the composition layer is brought into a predetermined alignment state.
As the conditions of the heat treatment, the optimum conditions are selected according to the liquid crystal compound used.
Among them, the heating temperature is usually 25 to 250℃and 40 to 150℃and 50 to 130 ℃.
As the heating time, there are many cases of 0.1 to 60 minutes, and many cases of 0.2 to 5 minutes.
The alignment state of the liquid crystal compound obtained in step 2A changes according to the helical twisting power of the chiral agent.
For example, as will be described later, in order to form an optically anisotropic layer having a 1 st region in which the alignment state of a liquid crystal compound that is twist-aligned along a helical axis extending in the thickness direction is fixed and a 2 nd region in which the alignment state of a uniformly aligned liquid crystal compound is fixed, the absolute value of the weighted average helical twisting force of the chiral agent in the composition layer formed by step 1A is preferably 0.0 to 1.9 μm -1 More preferably 0.0 to 1.5. Mu.m -1 More preferably 0.0 to 1.0. Mu.m -1 Particularly preferably 0.0 to 0.5. Mu.m -1 More particularly, 0.0 to 0.02 μm -1 Most preferably zero.
When the absolute value of the weighted average helical twisting power of the chiral agent in the composition layer is within the above range, the liquid crystal compound in the composition is uniformly aligned or the liquid crystal compound in the composition layer is twisted and aligned along the helical axis extending in the thickness direction when step 2A is performed.
In addition, the weighted average helical twisting power of the chiral agent means a total value obtained by dividing the product of the helical twisting power of each chiral agent contained in the composition layer and the concentration (mass%) of each chiral agent in the composition layer by the total concentration (mass%) of the chiral agents in the composition layer when the composition contains 2 or more chiral agents. For example, when 2 chiral reagents (chiral reagent X and chiral reagent Y) are used simultaneously, the chiral reagent is represented by the following formula (B).
Formula (B) weighted average helical twisting power (μm) -1 ) = (helical twisting force (μm) of chiral reagent X -1 ) Concentration of chiral agent X in composition layer (% by mass) + chiral agent Y helical twisting power (μm) -1 ) X concentration of chiral agent Y in composition layer (% by mass)/(concentration of chiral agent X in composition layer (% by mass) + concentration of chiral agent Y in composition layer (% by mass))
In the above formula (B), when the chiral reagent is spirally wound right, the spiral torque is set to a positive value. When the chiral reagent is spirally wound on the left side, the spiral torque is set to be negative. Namely, for example, when the helical twisting force is 10. Mu.m -1 In the case of the chiral reagent of (2), when the direction of the helix twisted by the chiral reagent is right-handed, the helical twisting force is expressed as 10. Mu.m -1 . On the other hand, when the direction of the helix twisted by the chiral agent is left-handed, the helical twisting force is represented as-10. Mu.m -1 。
When the absolute value of the weighted average helical twisting power of the chiral agent in the composition layer formed in step 1A is 0, as shown in fig. 1, a composition layer 12 in which the liquid crystal compound LC is uniformly aligned can be formed on the substrate 10. Fig. 1 is a schematic view of a cross section of the substrate 10 and the composition layer 12. In the composition layer 12 shown in fig. 1, the chiral agent a and the chiral agent B are present at the same concentration, and the helix twisted by the chiral agent a is rotated to the left and the helix twisted by the chiral agent B is rotated to the right. The absolute value of the helical twisting force of the chiral reagent a is the same as that of the chiral reagent B.
In the present specification, the uniform alignment means a state in which molecular axes of the liquid crystal compound (for example, corresponding to long axes in the case of a rod-shaped liquid crystal compound) are aligned horizontally and in the same orientation with respect to the surface of the composition layer (optical uniaxiality).
Wherein the level is not strictly required to be horizontal but means an orientation in which the average molecular axis of the liquid crystal compound in the composition layer forms an inclination angle of less than 20 degrees with the surface of the composition layer.
The same azimuth is not strictly required to be the same azimuth, but indicates that when the azimuth of the slow axis is measured at any 20 positions in the plane, the maximum difference in azimuth of the slow axis at 20 (the difference in azimuth of 2 slow axes having the largest difference in azimuth of 20 slow axes) is smaller than 10 °.
Although the liquid crystal compound LC is uniformly aligned in fig. 1, the liquid crystal compound LC is not limited to this method as long as the liquid crystal compound LC is in a predetermined alignment state, and may be twisted and aligned along a helical axis extending in the thickness direction of the composition layer, for example, as will be described in detail later.
< procedure 3A >
The step 3A is as follows: after the step 2A, the composition layer was subjected to a treatment at 300mJ/cm under conditions such that the oxygen concentration was 1% by volume or more 2 The light irradiation was performed for 50 seconds or less. The mechanism of this step will be described below with reference to the drawings. In the following, a typical example will be described in which the composition layer 12 shown in fig. 1 is subjected to the step 3A.
As shown in fig. 2, in step 3A, light irradiation is performed from the opposite side of the substrate 10 from the composition layer 12 side (the direction of the open arrow in fig. 2) under the condition that the oxygen concentration is 1% by volume or more. In fig. 2, the light irradiation is performed from the substrate 10 side, but may be performed from the composition layer 12 side.
At this time, when the lower region 12A of the composition layer 12 on the substrate 10 side is compared with the upper region 12B on the opposite side to the substrate 10 side, the surface of the upper region 12B is on the air side, and thus the oxygen concentration in the upper region 12B is high and the oxygen concentration in the lower region 12A is low. Therefore, when the composition layer 12 is irradiated with light, polymerization of the liquid crystal compound is easily performed in the lower region 12A, and the alignment state of the liquid crystal compound is fixed. In addition, a chiral agent a is also present in the lower region 12A, and the chiral agent a is also sensitized and the helical twisting force is changed. However, since the alignment state of the liquid crystal compound is fixed in the lower region 12A, even if the step 4A of performing the heat treatment on the composition layer irradiated with light, which will be described later, is performed, no change in the alignment state of the liquid crystal compound occurs.
Further, since the oxygen concentration is high in the upper region 12B, even when light irradiation is performed, polymerization of the liquid crystal compound is hindered by oxygen, and polymerization is difficult. Further, since the chiral reagent a is also present in the upper region 12B, the chiral reagent a is sensitized and the helical twisting force is changed. Therefore, when step 4A described later is performed, the alignment state of the liquid crystal compound changes along the changed helical twisting force.
That is, by performing step 3A, immobilization of the alignment state of the liquid crystal compound is easily performed in the substrate-side region (lower region) of the composition layer. In addition, the alignment state of the liquid crystal compound is difficult to be fixed in a region (upper region) of the composition layer on the side opposite to the substrate side, and the helical twisting power is changed according to the photosensitive chiral agent a.
Step 3A is performed under conditions in which the oxygen concentration is 1% by volume or more. Among them, in the optically anisotropic layer, the oxygen concentration is preferably 2% by volume or more, more preferably 5% by volume or more, from the viewpoint of easy formation of regions in which the alignment state of the liquid crystal compound is different. The upper limit is not particularly limited, but may be exemplified by 100% by volume.
The time of light irradiation in step 3A is 50 seconds or less, preferably 30 seconds or less, more preferably 10 seconds or less, from the viewpoint of easy formation of a predetermined optically anisotropic layer and productivity. The lower limit is not particularly limited, but from the viewpoint of curing the liquid crystal compound, it is preferably 0.1 seconds or more, more preferably 0.2 seconds or more.
The irradiation amount of the light irradiation in the step 3A was 300mJ/cm 2 Hereinafter, from the viewpoint of easy formation of a predetermined optically anisotropic layer and productivity, it is preferably 250mJ/cm 2 Hereinafter, more preferably 200mJ/cm 2 The following is given. The lower limit is not particularly limited, but is preferably 1mJ/cm from the viewpoint of curing of the liquid crystal compound 2 The above is more preferably 5mJ/cm 2 The above.
When the time and the irradiation amount of light do not satisfy the above-described requirements, a predetermined optically anisotropic layer cannot be formed.
The light irradiation in step 3A of embodiment 1 is preferably performed at 15 to 70 ℃ (preferably 25 to 50 ℃).
The light used for the light irradiation may be light to which the chiral agent a is exposed. That is, the light to be used for the light irradiation is not particularly limited as long as it is an activating light or a radiation for changing the helical twisting power of the chiral reagent a, and examples thereof include an open-line spectrum of a mercury lamp, extreme ultraviolet rays typified by excimer laser, extreme ultraviolet rays, X-rays, ultraviolet rays, and electron beams. Among them, ultraviolet rays are preferable.
< procedure 4A >
The step 4A is as follows: after step 3A, the composition layer is subjected to a heat treatment at a higher temperature than that at the time of light irradiation. By performing this step, the alignment state of the liquid crystal compound changes in the region where the helical twisting power of the chiral agent a changes in the composition layer subjected to light irradiation. More specifically, the present process is the following process: the composition layer after step 3A is subjected to a heat treatment at a temperature higher than that at the time of irradiation to orient the liquid crystal compound in the composition layer that is not fixed in step 3A.
The mechanism of this step will be described below with reference to the drawings.
As described above, when step 3A is performed on the composition layer 12 shown in fig. 1, the alignment state of the liquid crystal compound is fixed in the lower region 12A, and the polymerization of the liquid crystal compound is difficult in the upper region 12B, and the alignment state of the liquid crystal compound is not fixed. In the upper region 12B, the helical twisting force of the chiral agent a changes. When the helical twisting power of the chiral agent a changes, the force for twisting the liquid crystal compound in the upper region 12B changes compared with the state before the light irradiation. This will be described in more detail.
As described above, in the composition layer 12 shown in fig. 1, the chiral agent a and the chiral agent B are present at the same concentration, and the helical direction twisted by the chiral agent a is left-handed and the helical direction twisted by the chiral agent B is right-handed. The absolute value of the helical twisting force of the chiral reagent a is the same as that of the chiral reagent B. Therefore, the weighted average helical twisting power of the chiral agent in the composition layer before light irradiation was 0.
The above manner is shown in fig. 4. In FIG. 4, the vertical axis represents "the helical twisting force (μm) of the chiral agent -1 ) The farther from zero the value of ×concentration of chiral agent (% by mass) ", the greater the helical torque. First, the relationship between the chiral agent a and the chiral agent B in the composition layer before the irradiation of light corresponds to the point in time when the amount of light irradiation is 0, and corresponds to "the helical twisting power (μm) of the chiral agent a -1 ) The absolute value of x concentration of chiral reagent A (% by mass) "and the helical twisting force of chiral reagent B (μm) -1 ) The absolute values of ×chiral agent B concentration (% by mass) "are equal. That is, the helical twisting forces of both the chiral reagent a causing the left hand and the chiral reagent B causing the right hand cancel each other.
When light irradiation is performed in the upper region 12B in this state, as shown in fig. 4, if the helical twisting power of the chiral reagent a decreases according to the light irradiation amount, the weighted average helical twisting power of the chiral reagent in the upper region 12B increases, and the helical twisting power of the right hand increases, as shown in fig. 5. That is, the larger the irradiation amount is, the larger the helical twisting force for twisting the helix of the liquid crystal compound is in the direction (+) of the helix twisted by the chiral agent B.
Therefore, when the composition layer 12 after the step 3A in which the weighted average helical twisting force is changed is subjected to a heat treatment to promote the reorientation of the liquid crystal compound, the liquid crystal compound LC is twisted and oriented along the helical axis extending in the thickness direction of the composition layer 12 in the upper region 12B as shown in fig. 3.
On the other hand, as described above, in the lower region 12A of the composition layer 12, polymerization of the liquid crystal compound is performed at the time of step 3A, and the alignment state of the liquid crystal compound is fixed, so that the reorientation of the liquid crystal compound is not performed.
As described above, by performing step 4A, a plurality of regions in which the alignment states of the liquid crystal compounds are different are formed in the thickness direction of the composition layer.
In addition, in fig. 4 and 5, the description has been given of the method using the chiral reagent having a reduced helical twisting power by light irradiation as the chiral reagent a, but the method is not limited thereto. For example, a chiral agent whose helical twisting power is increased by light irradiation can be used as the chiral agent a. At this time, the helical twisting force by which the chiral agent a is twisted by light irradiation increases, and the liquid crystal compound is twisted and aligned in the rotation direction in which the chiral agent a is twisted.
In fig. 4 and 5, the mode of using the chiral reagent a and the chiral reagent B simultaneously has been described, but the mode is not limited thereto. For example, 2 chiral agents a may be used. Specifically, the chiral reagent A1 that causes a left-handed operation and the chiral reagent A2 that causes a right-handed operation may be used together. The chiral reagent A1 and the chiral reagent A2 may be each independently a chiral reagent having an increased helical twisting power or a chiral reagent having a decreased helical twisting power. For example, a chiral agent that causes a left-hand rotation and increases a helical twisting force by light irradiation and a chiral agent that causes a right-hand rotation and decreases a helical twisting force by light irradiation may be used simultaneously.
The heat treatment is performed at a higher temperature than when light is irradiated.
The difference between the temperature of the heat treatment and the temperature at the time of light irradiation is preferably 5 ℃ or higher, more preferably 10 to 110 ℃, and still more preferably 20 to 110 ℃.
The temperature of the heat treatment is preferably higher than the temperature at the time of light irradiation and the temperature at which the liquid crystal compound not fixed in the composition layer is aligned, more specifically, 35 to 250 ℃ is more often, 50 to 150 ℃ is more often, more than 50 ℃ and 150 ℃ or less is more often, and 60 to 130 ℃ is particularly often.
As the heating time, there are many cases of 0.01 to 60 minutes, and many cases of 0.03 to 5 minutes.
The absolute value of the weighted average screw torque of the chiral agent in the composition layer after light irradiation is not particularly limited, but the absolute value of the difference between the weighted average screw torque of the chiral agent in the composition layer after light irradiation and the weighted average screw torque before light irradiation is preferably 0.05. Mu.m -1 The above is more preferably 0.05 to 10.0. Mu.m -1 More preferably 0.1 to 10.0. Mu.m -1 。
< procedure 5A >
The step 5A is as follows: after step 4A, the composition layer is subjected to a curing treatment to form an optically anisotropic layer having a plurality of regions in which the alignment state of the liquid crystal compound is different in the thickness direction. By performing this step, the alignment state of the liquid crystal compound in the composition layer is fixed, and as a result, a predetermined optically anisotropic layer can be formed. In addition, for example, when the composition layer 12 shown in fig. 3 is subjected to a curing treatment, an optically anisotropic layer having a 1 st region in which the alignment state of the liquid crystal compound twist-aligned along the helical axis extending in the thickness direction is fixed and a 2 nd region in which the alignment state of the uniformly aligned liquid crystal compound is fixed can be formed.
The method of the curing treatment is not particularly limited, and examples thereof include a photo-curing treatment and a heat-curing treatment. Among them, the light irradiation treatment is preferable, and the ultraviolet irradiation treatment is more preferable.
Ultraviolet irradiation uses a light source such as an ultraviolet lamp.
The irradiation amount of light (for example, ultraviolet rays) is not particularly limited, but is generally preferably 100 to 800mJ/cm 2 Left and right.
The environment at the time of light irradiation is not particularly limited, and light irradiation may be performed under air or under an inactive environment. In particular, the light irradiation is preferably performed under the condition that the oxygen concentration is less than 1% by volume.
In the case of performing the photo-curing treatment as the curing treatment, the temperature condition at the time of photo-curing is not particularly limited as long as the temperature is a temperature at which the alignment state of the liquid crystal compound in the step 4A is maintained, and the difference between the temperature of the heating treatment in the step 4A and the temperature at the time of the photo-curing treatment is preferably within 100 ℃, more preferably within 80 ℃.
The temperature of the heat treatment in step 4A is preferably the same as or lower than the temperature of the photo-curing treatment.
In the optically anisotropic layer obtained by performing the curing treatment, the alignment state of the liquid crystal compound is fixed.
In the present specification, the "fixed" state is the most typical and preferable mode in which the alignment of the liquid crystal compound is maintained. More specifically, the state is preferably one in which the layer has no fluidity in a temperature range of-30 to 70 ℃ under a generally 0 to 50 ℃ and more severe condition, and the fixed orientation state can be stably maintained without changing the orientation state by an external field or an external force.
In addition, in the optically anisotropic layer, the composition in the final layer is no longer required to exhibit liquid crystallinity.
The thickness of the optically anisotropic layer is not particularly limited, but is preferably 0.05 to 10. Mu.m, more preferably 0.1 to 8.0. Mu.m, and still more preferably 0.2 to 6.0. Mu.m.
In the embodiment shown in fig. 3, the optically anisotropic layer having the 1 st region where the alignment state of the liquid crystal compound which is twist-aligned rightward along the helical axis extending in the thickness direction is fixed and the 2 nd region where the alignment state of the uniformly aligned liquid crystal compound is fixed is produced in the thickness direction, but the present invention is not limited to the embodiment described above.
For example, the twist orientation of the liquid crystal compound may be left twist. That is, the liquid crystal compound may be twisted in a left direction (counterclockwise direction) or a right direction (clockwise direction).
The alignment state of the liquid crystal compound in the 2 nd region may be other than uniform alignment, and in the case where the liquid crystal compound is a rod-like liquid crystal compound, examples of the alignment state include nematic alignment (a state in which a nematic phase is formed), smectic alignment (a state in which a smectic phase is formed), cholesteric alignment (a state in which a cholesteric phase is formed), and hybrid alignment. In the case where the liquid crystal compound is a discotic liquid crystal compound, examples of the alignment state include nematic alignment, columnar alignment (state in which columnar phase is formed), and cholesteric alignment.
In addition, a known method is given as a specific method of the alignment state of the liquid crystal compound. For example, a method of determining the alignment state of a liquid crystal compound by observing the cross section of an optically anisotropic layer by a polarized light microscope is mentioned.
In the embodiment shown in fig. 3, the optically anisotropic layer has 2 regions in which the alignment states of the liquid crystal compounds are different, but the present invention is not limited to the embodiment described above, and the optically anisotropic layer may have 3 or more regions in which the alignment states of the liquid crystal compounds are different.
In the case where the optically anisotropic layer has 2 regions in which the alignment states of the liquid crystal compounds are different, the ratio of the thickness of the region having a thick thickness among the 2 regions to the thickness of the region having a thin thickness among the 2 regions is not particularly limited, but is preferably more than 1 and 9 or less, more preferably more than 1 and 4 or less.
When the thicknesses of the 2 regions are the same, the ratio is 1.
The optically anisotropic layer in embodiment 1 may be an optically anisotropic layer having, in the thickness direction, a 1 st region in which the alignment state of the liquid crystal compound twist-aligned along the helical axis extending in the thickness direction is fixed and a 2 nd region in which the alignment state of the liquid crystal compound twist-aligned along the helical axis extending in the thickness direction is fixed at a different twist angle from that of the 1 st region.
As a method for forming the regions having different angles of twist angle of the liquid crystal compound as described above, for example, there may be mentioned a method for increasing the absolute value of the weighted average helical twisting power of the chiral agent in the composition layer formed by the above-mentioned step 1A (for example, more than 0 μm -1 ) Is a method of (2). When the absolute value of the weighted average helical twisting power of the chiral agent in the composition layer formed in step 1A is large, first, as shown in fig. 6, the liquid crystal compound is twisted and aligned along the helical axis extending in the thickness direction in the composition layer 120 in which step 2 is performed. When such a composition layer is subjected to the above-described step, the twist orientation of the liquid crystal compound is directly fixed in the region (lower region 120A in fig. 7) in the composition layer having a low oxygen concentration, and the twist force of the helix is changed in the region (upper region 120B in fig. 7) in the composition layer having a high oxygen concentration, so that, as a result, a region having a different twist angle of the liquid crystal compound can be formed after the step 5A is performed.
The optical characteristics of the optically anisotropic layer in embodiment 1 are not particularly limited, and the optimum value is selected according to the application. Hereinafter, as an example, a case of the optically anisotropic layer produced by the above-described steps will be described in detail, the optically anisotropic layer having, in the thickness direction, a 1 st region in which the alignment state of the liquid crystal compound twist-aligned along the helical axis extending in the thickness direction is fixed and a 2 nd region in which the alignment state of the uniformly aligned liquid crystal compound is fixed.
When the thickness of the 1 st region of the optically anisotropic layer is d1 and the refractive index anisotropy of the 1 st region measured at a wavelength of 550nm is Δn1, the 1 st region preferably satisfies the following formula (1A-1) from the viewpoint that the optically anisotropic layer can be preferably applied to a circularly polarizing plate.
The formula (1A-1) is 100nm less than or equal to delta n1d1 less than or equal to 240nm
Of these, the formula (1A-2) is more preferably satisfied, and the formula (1A-3) is more preferably satisfied.
The formula (1A-2) is 120 nm-deltan 1d 1-220 nm
Formula (1A-3) 140nm is less than or equal to delta n1d1 is less than or equal to 200nm
The absolute value of the twist angle of the liquid crystal compound in the 1 st region is not particularly limited, but is preferably 50 to 110 °, more preferably 60 to 100 °, from the viewpoint that the optically anisotropic layer can be preferably applied to a circularly polarizing plate.
First, the liquid crystal compound twist alignment means that the liquid crystal compound is twisted from one surface (the surface on the substrate 10 side in fig. 3) to the other surface (the surface on the opposite side from the substrate 10 side in fig. 3) of the 1 st region with the thickness direction of the 1 st region as an axis. Therefore, the twist angle indicates an angle formed by a molecular axis (long axis in the case of a rod-like liquid crystal compound) of the liquid crystal compound on one surface of the 1 st region and a molecular axis of the liquid crystal compound on the other surface of the 1 st region.
As for the method of measuring the twist angle, axoscan from Axometrics was used, and the measurement was performed using device analysis software from Axometrics.
When the thickness of the 2 nd region of the optically anisotropic layer is d2 and the refractive index anisotropy of the 2 nd region measured at a wavelength of 550nm is Δn2, the 2 nd region preferably satisfies the following formula (2A-1) from the viewpoint that the optically anisotropic layer can be preferably applied to a circularly polarizing plate.
The formula (2A-1) is 100nm less than or equal to delta n2d2 less than or equal to 240nm
Of these, the formula (2A-2) is more preferably satisfied, and the formula (2A-3) is more preferably satisfied.
The formula (2A-2) is 120 nm-delta n2d 2-220 nm
Formula (2A-3) 140nm is less than or equal to delta n2d2 is less than or equal to 200nm
The 2 nd region is a region in which the alignment state of the uniformly aligned liquid crystal compound is fixed. The definition of uniform orientation is as described above.
The difference between Δn1d1 and Δn2d2 is not particularly limited, but is preferably-50 to 50nm, more preferably-30 to 30nm, from the viewpoint that the optically anisotropic layer can be preferably applied to a circularly polarizing plate.
In addition, in the optically anisotropic layer in embodiment 1, 2 regions in which the alignment state of the liquid crystal compound twisted and aligned along the helical axis extending in the thickness direction is fixed are included, and when one region is defined as a region a and the other region is defined as a region B, when the thickness of the region a is defined as dA and the refractive index anisotropy of the region a measured at a wavelength of 550nm is defined as Δna, the region a preferably satisfies the following formula (3A-1) from the viewpoint that the optically anisotropic layer can be preferably applied to a circularly polarizing plate.
Formula (3A-1) 205 nm.ltoreq.delta nADA.ltoreq.345 nm
Of these, the formula (3A-2) is more preferably satisfied, and the formula (3A-3) is more preferably satisfied.
Formula (3A-2) 225 nm.ltoreq.delta nADA.ltoreq.325 nm
The formula (3A-3) is 245nm or less and delta nA A or less and 305nm or less
The absolute value of the twist angle of the liquid crystal compound in the region a is not particularly limited, but is preferably more than 0 ° and 60 ° or less, more preferably 10 to 50 ° from the viewpoint that the optically anisotropic layer can be preferably applied to a circularly polarizing plate.
When the thickness of the region B is d2 and the refractive index anisotropy of the region B measured at a wavelength of 550nm is Δnb, the region B preferably satisfies the following formula (4A-1) from the viewpoint that the optically anisotropic layer can be preferably applied to a circularly polarizing plate.
Formula (4A-1) 70nm is less than or equal to delta nBdB is less than or equal to 210nm
Of these, the formula (4A-2) is more preferably satisfied, and the formula (4A-3) is more preferably satisfied.
Formula (4A-2) is 90 nm-190 nm
Formula (4A-3) 110nm is less than or equal to delta nBdB is less than or equal to 170nm
The absolute value of the twist angle of the liquid crystal compound in the region B is not particularly limited, but is preferably 50 to 110 °, more preferably 60 to 100 °, from the viewpoint that the optically anisotropic layer can be preferably applied to a circularly polarizing plate.
In the case where the optically anisotropic layer formed by the 1 st embodiment of the method for producing an optically anisotropic layer according to the present invention has 2 regions in which the alignment states of the liquid crystal compounds are different in the thickness direction (hereinafter, 2 regions are referred to as a region X and a region y.), the slow axis on the surface of the region X on the region Y side is often parallel to the slow axis on the surface of the region Y on the region X side.
The optical characteristics of the optically anisotropic layer in embodiment 1 are not limited to the above, and for example, when the optically anisotropic layer has 2 regions in which the alignment states of the liquid crystal compounds are different in the thickness direction, it is preferable that the 2 regions satisfy the optical characteristics (relationship of twist angle, Δnd, re B, slow axis of the liquid crystal compounds) of the 1 st optically anisotropic layer and the 2 nd optically anisotropic layer described in japanese patent No. 5960743, respectively.
In addition, as another embodiment, when the optically anisotropic layer has 2 regions in the thickness direction, it is preferable that the 2 regions satisfy the optical characteristics (relationship of twist angle, Δn1d1, Δn2d2, slow axis of the liquid crystal compound) of the 1 st optically anisotropic layer and the 2 nd optically anisotropic layer described in japanese patent No. 5753922.
The optically anisotropic layer in embodiment 1 preferably exhibits inverse wavelength dispersion.
That is, it is preferable that Re (450) is an in-plane retardation measured at a wavelength of 450nm of the optically anisotropic layer, re (550) is an in-plane retardation measured at a wavelength of 550nm of the optically anisotropic layer, and Re (650) is an in-plane retardation measured at a wavelength of 650nm of the optically anisotropic layer, and Re (450). Ltoreq.Re (550). Ltoreq.Re (650) is a relationship.
The optical properties of the optically anisotropic layer in embodiment 1 are not particularly limited, but preferably function as a λ/4 plate.
The λ/4 plate is a plate having a function of converting linearly polarized light of a certain specific wavelength into circularly polarized light (or converting circularly polarized light into linearly polarized light), and refers to a plate (optically anisotropic layer) whose in-plane retardation Re (λ) at a specific wavelength λnm satisfies Re (λ) =λ/4.
The expression may be realized at any wavelength (e.g., 550 nm) in the visible light region, but it is preferable that the in-plane retardation Re (550) at a wavelength of 550nm satisfies a relationship of 110 nm.ltoreq.Re (550). Ltoreq.180 nm.
Embodiment 2
Embodiment 2 of the method for producing an optically anisotropic layer of the present invention includes the following steps 1B to 5B. As described later, in embodiment 2, an optically anisotropic layer having a region where a cholesteric liquid crystal phase is fixed is formed.
Step 1B: a step of forming a composition layer containing a chiral agent including at least a photosensitive chiral agent whose helical twisting power is changed by light irradiation and a liquid crystal compound having a polymerizable group
Step 2B: a step of heating the composition layer to orient the liquid crystal compound in the composition layer and form a cholesteric liquid crystal phase
Step 3B: after the step 2B, the composition layer was subjected to a treatment at 300mJ/cm under conditions such that the oxygen concentration was 1% by volume or more 2 The following procedure of light irradiation for 50 seconds or less
Step 4B: a step of performing a heat treatment on the composition layer at a higher temperature than the light irradiation step after the step 3B
Step 5B: after step 4B, a step of forming an optically anisotropic layer having a plurality of regions having different alignment states of the liquid crystal compound in the thickness direction by subjecting the composition layer to a curing treatment
As described later, in embodiment 2, in order to produce the optically anisotropic layer having the above characteristics, the total content of chiral agents (total content of all chiral agents) in the composition layer is preferably more than 5.0 mass% with respect to the total mass of the liquid crystal compound.
The difference between embodiment 1 and embodiment 2 is mainly the content of chiral agent.
The steps of the above steps will be described in detail below.
< procedure 1B >
Step 1B is a step of forming a composition layer containing a chiral agent including at least a photosensitive chiral agent whose helical twisting power is changed by light irradiation and a liquid crystal compound having a polymerizable group. By performing this step, a composition layer subjected to a light irradiation treatment described later can be formed.
The chiral agent (chiral agent a and chiral agent B) and the liquid crystal compound contained in the composition layer are as described in step 1A.
As described in step 1A, the composition layer may contain components other than the chiral agent and the liquid crystal compound.
In step 1B, a chiral agent is included in the composition layer to form a cholesteric liquid crystal phase in step 2B described later.
In embodiment 2, the total content of chiral agents (total content of all chiral agents) in the composition layer is not particularly limited, but is preferably more than 5.0 mass%, more preferably 5.5 mass% or more, and still more preferably 6.0 mass% or more with respect to the total mass of the liquid crystal compound, from the viewpoint of easy control of the alignment state of the liquid crystal compound. The upper limit is not particularly limited, but is preferably 25% by mass or less, more preferably 20% by mass or less, and still more preferably 15% by mass or less.
The content of chiral agent a in the chiral agent is not particularly limited, but is preferably 5 to 95 mass%, more preferably 10 to 90 mass% with respect to the total mass of the chiral agent, from the viewpoint of easy control of the alignment state of the liquid crystal compound.
The absolute value of the helical twisting power of the chiral agent in the composition layer formed by step 1B is preferably 10. Mu.m -1 The above is more preferably 15. Mu.m -1 The above is more preferably 20. Mu.m -1 The above. The upper limit is not particularly limited, but 250. Mu.m -1 The following is more often the case, 200. Mu.m -1 The following is more the case.
When the composition contains 2 or more chiral agents, the absolute value of the weighted average helical twisting power of the chiral agents in the composition layer formed in step 1B is preferably within the above range.
When the helical twisting power or the absolute value of the helical twisting power of the chiral agent in the composition layer is within the above range, the liquid crystal compound in the composition is aligned cholesterol by step 2B.
The definition of the weighted average helical twisting force is as described above.
The method for forming the composition layer in step 1B is the same as the method for forming the composition layer in step 1A.
< procedure 2B >
The step 2B is as follows: the composition layer is subjected to a heat treatment to orient the liquid crystal compound in the composition layer to form a cholesteric liquid crystal phase. By performing this step, the liquid crystal compound in the composition layer is brought into a predetermined alignment state.
As the conditions of the heat treatment, the optimum conditions are selected according to the liquid crystal compound used.
Among them, the heating temperature is usually 25 to 250℃and 40 to 150℃and 50 to 130 ℃.
As the heating time, there are many cases of 0.1 to 60 minutes, and many cases of 0.2 to 5 minutes.
< procedure 3B >
The step 3B is as follows: after the step 2B, the composition layer was subjected to a treatment at 300mJ/cm under conditions such that the oxygen concentration was 1% by volume or more 2 The light irradiation was performed for 50 seconds or less. The mechanism of this step will be described below with reference to the drawings. The pattern shown in fig. 8 corresponds to a pattern in which the liquid crystal compound forms a cholesteric liquid crystal phase.
As shown in fig. 8, in step 3B, light irradiation is performed from the opposite side of the substrate 10 from the composition layer 220 side (the direction of the open arrow in fig. 8) under the condition that the oxygen concentration is 1% by volume or more. In fig. 8, the light irradiation is performed from the substrate 10 side, but may be performed from the composition layer 220 side.
At this time, when the lower region 220A of the composition layer 220 on the substrate 10 side is compared with the upper region 220B on the opposite side to the substrate 10 side, the surface of the upper region 220B is on the air side, and thus the oxygen concentration in the upper region 220B is high and the oxygen concentration in the lower region 220A is low. Therefore, when the composition layer 220 is irradiated with light, polymerization of the liquid crystal compound is easily performed in the lower region 220A, and the alignment state of the liquid crystal compound is fixed. In addition, a chiral agent a is also present in the lower region 220A, and the chiral agent a is also sensitized and the helical twisting force is changed. However, since the alignment state of the liquid crystal compound is fixed in the lower region 220A, even if the step 4B of performing the heat treatment on the composition layer irradiated with light, which will be described later, is performed, no change in the alignment state of the liquid crystal compound occurs.
Further, since the oxygen concentration is high in the upper region 220B, even when light irradiation is performed, polymerization of the liquid crystal compound is hindered by oxygen, and polymerization is difficult. Further, since the chiral reagent a is also present in the upper region 220B, the chiral reagent a is sensitized and the helical twisting force is changed. Therefore, when step 4B described later is performed, the alignment state of the liquid crystal compound changes along the changed helical twisting force.
That is, by performing step 3B, immobilization of the alignment state of the liquid crystal compound is easily performed in the substrate-side region (lower region) of the composition layer. In addition, the alignment state of the liquid crystal compound is difficult to be fixed in a region (upper region) of the composition layer on the side opposite to the substrate side, and the helical twisting power is changed according to the photosensitive chiral agent a.
The various conditions (oxygen concentration, irradiation time, irradiation amount, etc.) of the light irradiation in the step 3B are the same as those of the light irradiation in the step 3A.
< procedure 4B >
The step 4B is as follows: after step 3B, the composition layer is subjected to a heat treatment at a higher temperature than that at the time of light irradiation. By performing this step, the alignment state of the liquid crystal compound changes in the region where the helical twisting power of the chiral agent a changes in the composition layer subjected to light irradiation. More specifically, the present process is the following process: the composition layer after step 3B is subjected to a heat treatment at a temperature higher than that at the time of irradiation to orient the liquid crystal compound in the composition layer that is not fixed in step 3B.
The mechanism of this step will be described below with reference to the drawings.
As described above, when step 3B is performed on the composition layer 220 shown in fig. 8, the alignment state of the liquid crystal compound is fixed in the lower region 220A, and the polymerization of the liquid crystal compound is difficult in the upper region 220B, and the alignment state of the liquid crystal compound is not fixed. In the upper region 220B, the helical twisting force of the chiral agent a changes. When the helical twisting power of the chiral agent a changes, the force for twisting the liquid crystal compound in the upper region 220B changes compared with the state before the light irradiation. This will be described in more detail.
In the following description, the case where the composition layer 220 contains the chiral agent a twisted in the spiral direction and the spiral twisting force is reduced by light irradiation will be described in detail.
When light irradiation is performed in the upper region 220B in this state, as shown in fig. 10, the helical twisting power of the chiral reagent a decreases according to the light irradiation amount, and the helical twisting power of the chiral reagent in the upper region 220B decreases.
Therefore, when the composition layer 220 after the step 3B in which the helical twisting power is changed is subjected to a heat treatment to promote the reorientation of the liquid crystal compound, the helical pitch of the cholesteric liquid crystal layer increases in the upper region 220B as shown in fig. 9.
On the other hand, as described above, in the lower region 220A of the composition layer 220, polymerization of the liquid crystal compound is performed at the time of step 3B, and the alignment state of the liquid crystal compound is fixed, so that the reorientation of the liquid crystal compound is not performed.
As described above, by performing step 4B, a plurality of cholesteric liquid crystal phases having different helical pitches are formed in the thickness direction of the composition layer.
In addition, although the embodiment of fig. 8 and 9 described above uses a chiral reagent having a reduced helical twisting power due to light irradiation as the chiral reagent a, the embodiment is not limited to this embodiment. For example, a chiral agent whose helical twisting power is increased by light irradiation can be used as the chiral agent a.
In fig. 8 and 9, the method using the chiral reagent twisted in the spiral direction as the chiral reagent a is described, but the method is not limited thereto. For example, a chiral reagent that turns right in the twisted helical direction may be used as the chiral reagent a.
In fig. 8 and 9, the mode in which only 1 chiral reagent a is used is described, but the mode is not limited thereto. For example, 2 kinds of chiral reagents a may be used, or chiral reagents a and B may be used simultaneously.
The heat treatment is performed at a higher temperature than when light is irradiated.
The difference between the temperature of the heat treatment and the temperature at the time of light irradiation is preferably 5 ℃ or higher, more preferably 10 to 110 ℃, and still more preferably 20 to 110 ℃.
The temperature of the heat treatment is preferably higher than the temperature at the time of light irradiation and the temperature at which the liquid crystal compound not fixed in the composition layer is aligned, more specifically, 40 to 250 ℃ is more often, 50 to 150 ℃ is more often, more than 50 ℃ and 150 ℃ or less is more often, and 60 to 130 ℃ is particularly often.
As the heating time, there are many cases of 0.01 to 60 minutes, and many cases of 0.03 to 5 minutes.
The absolute value of the helical twisting power of the chiral agent in the composition layer after light irradiation is not particularly limited, but the absolute value of the difference between the helical twisting power of the chiral agent in the composition layer after light irradiation and the helical twisting power before light irradiation is preferably 0.05. Mu.m -1 The above is more preferably 0.05 to 10.0. Mu.m -1 More preferably 0.1 to 10.0. Mu.m -1 。
In the case where the composition contains 2 or more chiral agents, the absolute value of the difference between the weighted average helical twisting power of the chiral agents in the composition layer after light irradiation and the weighted average helical twisting power before light irradiation is preferably 0.05. Mu.m -1 The above is more preferably 0.05 to 10.0. Mu.m -1 More preferably 0.1 to 10.0. Mu.m -1 。
< procedure 5B >
The step 5B is as follows: after step 4B, the composition layer is subjected to a curing treatment to form an optically anisotropic layer having a plurality of regions in which the alignment state of the liquid crystal compound is different in the thickness direction. By performing this step, the alignment state of the liquid crystal compound in the composition layer is fixed, and as a result, a predetermined optically anisotropic layer can be formed. Further, by performing this step, an optically anisotropic layer having a plurality of regions in which cholesteric liquid crystal phases are fixed and in which the helical pitches of the cholesteric liquid crystal phases are different in the thickness direction can be formed. The length of the spiral pitch in each region formed is constant in many cases. That is, by performing this step, an optically anisotropic layer can be formed in which the cholesteric liquid crystal phase is fixed and a plurality of regions having different helical pitches of the cholesteric liquid crystal phase are provided in the thickness direction, and the helical pitch in each region is constant.
As a method of the curing treatment in step 5B, a method of the curing treatment in step 5A is exemplified.
The thickness of the optically anisotropic layer is not particularly limited, but is preferably 0.05 to 10. Mu.m, more preferably 0.1 to 8.0. Mu.m, and still more preferably 0.2 to 6.0. Mu.m.
In the optically anisotropic layer formed by the above method, in which the cholesteric liquid crystal phase is fixed and a plurality of regions having different helical pitches of the cholesteric liquid crystal phase are provided in the thickness direction, the selective reflection center wavelength of the cholesteric liquid crystal phase originating from each region is different. For example, the optically anisotropic layer may be an optically anisotropic layer having a region in which a cholesteric liquid crystal phase that reflects blue light is fixed and a region in which a cholesteric liquid crystal phase that reflects green light is fixed in the thickness direction, or an optically anisotropic layer having a region in which a cholesteric liquid crystal phase that reflects green light is fixed and a region in which a cholesteric liquid crystal phase that reflects red light is fixed in the thickness direction.
In the present specification, the selective reflection center wavelength means that the minimum value of the transmittance in the target substance (member) is set to T min In the case of (%), the expression represented by the following formulaHalf value transmittance: t (T) 1/2 (%) 2 wavelengths.
The formula for determining the half value transmittance: t (T) 1/2 ＝100-(100-T min )÷2
The light in the wavelength region of 420nm or more and less than 500nm in the visible light is blue light (B light), the light in the wavelength region of 500nm or more and less than 600nm is green light (G light), and the light in the wavelength region of 600nm or more and less than 700nm is red light (R light).
In the embodiment shown in fig. 9, the optically anisotropic layer has 2 regions in which the alignment states of the liquid crystal compounds are different, but the present invention is not limited to the embodiment described above, and the optically anisotropic layer may have 3 or more regions in which the alignment states of the liquid crystal compounds are different. As described above, the optically anisotropic layer having 3 or more regions in which the alignment states of the liquid crystal compounds are different can be formed by, for example, changing the conditions of step 3B a plurality of times.
Examples of the optically anisotropic layer include an optically anisotropic layer having a region in which a cholesteric liquid crystal phase reflecting blue light is fixed, a region in which a cholesteric liquid crystal phase reflecting green light is fixed, and a region in which a cholesteric liquid crystal phase reflecting red light is fixed in the thickness direction.
Embodiment 3
Embodiment 3 of the method for producing an optically anisotropic layer of the present invention includes the following steps 1C to 5C. As described later, in embodiment 3, an optically anisotropic layer having a region in which the alignment state of a liquid crystal compound is fixed while the alignment direction of the liquid crystal compound is inclined or vertical to the layer surface is formed.
Step 1C: a step of forming a composition layer containing a photosensitive compound having polarity changed by light irradiation and a liquid crystal compound having a polymerizable group
Step 2C: a step of subjecting the composition layer to a heat treatment to orient the liquid crystal compound in the composition layer
Step 3C: after the step 2C, the oxygen concentration isAt a concentration of 1% by volume or more, 300mJ/cm of the composition layer 2 The following procedure of light irradiation for 50 seconds or less
Step 4C: a step of subjecting the composition layer to a heat treatment at a higher temperature than that at the time of light irradiation after step 3C
Step 5C: after step 4C, a step of forming an optically anisotropic layer having a plurality of regions having different alignment states of the liquid crystal compound in the thickness direction by subjecting the composition layer to a curing treatment
In embodiment 3, as described below, a photosensitive compound whose polarity is changed by light irradiation is used.
The steps of the above steps will be described in detail below.
< procedure 1C >
Step 1C is a step of forming a composition layer containing a photosensitive compound whose polarity is changed by light irradiation and a liquid crystal compound having a polymerizable group. By performing this step, a composition layer subjected to a light irradiation treatment described later can be formed.
The liquid crystal compound contained in the composition layer is as described in step 1A.
As described in step 1A, the composition layer may contain other components.
(photosensitive Compound whose polarity is changed by light irradiation)
The composition layer in step 1C contains a photosensitive compound whose polarity is changed by light irradiation (hereinafter, also referred to as "specific photosensitive compound").
The photosensitive compound whose polarity is changed by light irradiation is a compound whose polarity is changed before and after light irradiation. As will be described later, when the composition layer containing such a specific photosensitive compound is irradiated with light in step 1C, the polarity of the specific compound changes in the air-side region of the composition layer, and the alignment direction of the liquid crystal compound is inclined or perpendicular to the layer surface according to the change in polarity when step 4C is performed.
The change in polarity of the specific photosensitive compound may be a change in hydrophilization or a change in hydrophobicity. Among them, from the viewpoint that the alignment state of the liquid crystal compound in which the alignment direction of the liquid crystal compound is inclined or vertical to the layer surface can be easily formed, a change in hydrophilization is preferable.
As the specific photosensitive compound hydrophilized by light irradiation, a compound having a group generating a hydrophilic group by light irradiation is preferable. The kind of the hydrophilic group is not particularly limited, and may be any of a cationic group, an anionic group and a nonionic group, and more specifically, a carboxylic acid group, a sulfonic acid group, a phosphonic acid group, an amino group, an ammonium group, an amide group, a thiol group and a hydroxyl group may be mentioned.
The specific photosensitive compound preferably has a fluorine atom or a silicon atom. When the specific photosensitive compound has the above atoms, the specific photosensitive compound is likely to be unevenly distributed near the surface of the composition layer, and thus a desired optically anisotropic layer is likely to be formed.
The specific photosensitive compound is preferably a compound represented by the formula (X).
[ chemical formula 3]
In the above-mentioned formula (X),
t represents an aromatic hydrocarbon group having a valence of n+m,
sp represents a single bond or a 2-valent linking group,
hb represents a fluorine-substituted alkyl group having 4 to 30 carbon atoms,
m represents an integer of 1 to 4,
n represents an integer of 1 to 4,
a represents a group represented by the following formula (Y),
[ chemical formula 4]
In the above-mentioned formula (Y),
R 1 ～R 5 each independently represents a hydrogen atom or a substituent having a valence of 1,
* Indicating the bonding site.
In the above formula (X), when a plurality of Sp, hb, or a exists, the Sp, hb, or a may be the same or different from each other.
In the above formula (X), T represents an aromatic hydrocarbon group having a valence of n+m.
The aromatic hydrocarbon group is not particularly limited as long as it is a group obtained by removing n+m hydrogen atoms from an aromatic hydrocarbon ring, but is preferably a group having 6 to 22 carbon atoms, more preferably 6 to 14 carbon atoms, and still more preferably 6 to 10 carbon atoms. The aromatic hydrocarbon group is particularly preferably a benzene ring.
The aromatic hydrocarbon group may have A substituent other than the group represented by-Sp-Hb and the group represented by-C (=O) O-A. Examples of the substituent include an alkyl group (e.g., an alkyl group having 1 to 8 carbon atoms), an alkoxy group (e.g., an alkoxy group having 1 to 8 carbon atoms), a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom), a cyano group, and an acyloxy group (e.g., an acetoxy group).
In the above formula (X), sp represents a single bond or a 2-valent linking group, preferably a 2-valent linking group.
The 2-valent linking group is not particularly limited, but is preferably selected from the group consisting of a linear or branched alkylene group (preferably having 1 to 20 carbon atoms, more preferably having 1 to 10 carbon atoms, still more preferably having 1 to 6 carbon atoms), a linear or branched alkenylene group (preferably having 2 to 20 carbon atoms, more preferably having 2 to 10 carbon atoms, still more preferably having 2 to 6 carbon atoms), a linear or branched alkynylene group (preferably having 2 to 20 carbon atoms, more preferably having 2 to 10 carbon atoms, still more preferably having 2 to 6 carbon atoms) or-CH of 1 or 2 or more of these 2 -a linking group in the group consisting of groups substituted with "organic groups of valence 2" shown below.
As the aboveA 2-valent linking group, of which 1 or 2 or more-CH are preferable from the viewpoint of further improving solubility 2 Alkylene having 1 to 10 carbon atoms substituted with "a 2-valent organic group" shown below.
(organic group of valence 2)
As the above-mentioned organic group having a valence of 2, examples include-O-, -S-, -C (=o) O-, -OC (=o) -, -C (=o) S-, -SC (=o) -, -NR 6 C (=o) -or-C (=o) NR 6 -. Among the above, from the viewpoint of further performing hydrophilization, more preferable are-O-, -S-, -C (=o) O-, -OC (=o) -, -C (=o) S-or SC (=o) -, further preferable are-O-, -C (=o) O-or OC (=o) -, and particularly preferable are-O-, -C (=o) O-or OC (=o) -.
And R is as described above 6 Represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
In the case where the 2-valent linking group includes the 2-valent organic group, the 2-valent organic groups are preferably not adjacent to each other.
In the above formula (X), hb represents a fluorine-substituted alkyl group having 4 to 30 carbon atoms.
Hb is preferably a carbon number of 4 to 20, more preferably a carbon number of 4 to 10. The fluorine-substituted alkyl group may be a perfluoroalkyl group in which all of the hydrogen atoms are substituted with fluorine atoms, or may be a fluoroalkyl group in which a part of the hydrogen atoms are substituted with fluorine atoms. The fluorine-substituted alkyl group may be any of a chain, a branched chain, and a cyclic group, but is preferably a chain or a branched chain, and more preferably a chain.
Among them, a perfluoroalkyl structure is preferable as the fluoro-substituted alkyl group.
In the above formula (X), preferred embodiments of the group represented by-Sp-Hb are exemplified below.
In the following examples, the connection position with T is shown.
(C p F 2p+1 )-(CH 2 ) q -O-(CH 2 ) r -O-*
(C p F 2p+1 )-(CH 2 ) q -C(＝O)O-(CH 2 ) r -C(＝O)O-*
(C p F 2p+1 )-(CH 2 ) q -OC(＝O)-(CH 2 ) r -C(＝O)O-*
(C p F 2p+1 )-(CH 2 ) q -OC(＝O)-(CH 2 ) r -OC(＝O)-*
Among the groups represented by the above-mentioned-Sp-Hb, p is preferably 4 to 30, more preferably 4 to 20, still more preferably 4 to 10.q is preferably 0 to 6, more preferably 0 to 4, and still more preferably 0 to 3.r is preferably 1 to 6, more preferably 1 to 4, and still more preferably 1 to 3.
The total number of carbon atoms in the portion other than the perfluoro group is preferably 10 or less.
In the above formula (X), n and m each independently represent an integer of 1 to 4.
From the viewpoint of further hydrophilization, n is preferably 2 or more. m is preferably 1 to 3, more preferably 2.
In the formula (X), A represents a group represented by the formula (Y).
The following describes the formula (Y).
In the above formula (Y), R 1 ～R 5 Each independently represents a hydrogen atom or a 1-valent substituent. R is R 1 ～R 5 The substituent having 1 valence is not particularly limited.
As R 1 ～R 4 Examples of the substituent having a valence of 1 include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom), a hydroxyl group, a cyano group, a substituted or unsubstituted amino group (represented by-N (R) A ) 2 Representing 2R A Each independently represents a hydrogen atom or a 1-valent organic group (as a 1-valent organic group, for example, an alkyl group having 1 to 5 carbon atoms). ) An alkoxy group having 1 to 8 carbon atoms (e.g., methoxy group and ethoxy group), an amido group having 2 to 8 carbon atoms (e.g., -N (R) B )C(＝O)R C (R B Represents a hydrogen atom or a 1-valent organic group (as a 1-valent organic group, for example, an alkyl group having 1 to 5 carbon atoms), R C An organic group representing a valence of 1(as the 1-valent organic group, for example, an alkyl group having 1 to 5 carbon atoms). ) or-C (=O) N (R) D ) 2 (2R) D Each independently represents a hydrogen atom or a 1-valent organic group (e.g., an alkyl group having 1 to 5 carbon atoms). ) An alkoxycarbonyl group having 2 to 8 carbon atoms (for example, -C (=O) OCH) 3 ) Acyloxy groups having 2 to 8 carbon atoms (for example, -OC (=O) CH 3 ) -Sp A -Hb A 。
Sp above A Hb as described above A The meanings of Sp and Hb in the formula (X) are the same as those of Sp and Hb, respectively, and preferred embodiments thereof are the same as those of Hb. In the formula (Y), R is 1 ～R 4 Multiple representations of-Sp A -Hb A In the case of (1) there are a plurality of Sp A Hb having plural Hbs A May be the same as each other or different from each other.
Wherein R is as the above R 1 ～R 4 Preferably independently of one another, a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, an alkoxy group, -NH 2 、-NH(CH 3 )、-N(CH 3 ) 2 、-C(＝O)OCH 3 、-OC(＝O)CH 3 、-NHC(＝O)CH 3 、-N(CH 3 )C(＝O)CH 3 or-Sp A -Hb A 。
In particular, from the viewpoint of further accelerating the decomposition rate of the compound represented by the formula (X) by exposure to light to further hydrophilize and/or the viewpoint of further improving the orientation, R is more preferable 1 ～R 4 Are each independently-OCH 3 Or Sp A -Hb A . At the position of-OCH 3 In the case of (2), there is a tendency that: since the structure contains ether oxygen (in particular, the position bonded to the benzene ring in the formula (Y) is ether oxygen), the decomposition rate of the compound represented by the formula (X) by exposure is further increased, and hydrophilization is further performed. On the other hand, at-Sp A -Hb A In the case of (2), there is a tendency that: through Hb A Further improving the orientation by the presence of (3). In addition, at Sp A In the case where the structure contains ether oxygen (in particular, in Sp A And Hb of (B) A The end of the side opposite to the bonded side (exchangeThat is, the end on the side linked to the benzene ring of formula (Y)) contains ether oxygen), with the above-mentioned-OCH 3 Similarly, an effect of accelerating the decomposition speed can be obtained.
Further, R is preferably from the viewpoint of further accelerating the decomposition rate of the compound represented by the formula (X) by exposure to light and further hydrophilizing the compound 1 ～R 4 At least 2 of which are each independently-OCH 3 Or Sp B -Hb B More preferably R 2 R is R 3 Are each independently-OCH 3 Or Sp B -Hb B 。
Wherein Sp is B represents-CH 2 -O-substituted alkylene having 1 to 10 carbon atoms. Wherein, as described above, at Sp B And Hb of (B) B When the terminal on the opposite side of the bond (in other words, the terminal on the side linked to the benzene ring of formula (Y)) contains ether oxygen, the effect of accelerating the decomposition rate is more significantly obtained, and hydrophilization proceeds. In addition, the-CH in the above alkylene group 2 In the case of substitution by a plurality of-O-it is preferred that the-O-are not adjacent to one another. The alkylene group is more preferably a carbon number of 1 to 7, still more preferably a carbon number of 1 to 6, and particularly preferably a carbon number of 1 to 4. The alkylene group may be either a straight chain or a branched chain, but is preferably a straight chain.
Hb described above B Represents a fluorine-substituted alkyl group having 4 to 30 carbon atoms. Regarding Hb described above B In the preferred embodiment (b), hb of the formula (X) is the same as Hb.
In the formula (Y), R is 1 ～R 4 Multiple representations of-Sp B -Hb B In the case of (1) there are a plurality of Sp B Hb having plural Hbs B May be the same as each other or different from each other.
Among them, the above R is preferable from the viewpoint of further accelerating the decomposition rate of the compound represented by the formula (X) by exposure to further hydrophilize and further improving the orientation 1 ～R 4 At least 2 of them are-Sp B -Hb B More preferably R 2 R is R 3 Are all-Sp B -Hb B . In particular, as the above-mentioned-Sp B -Hb B The structure represented by the following formula (Z) is preferable.
(Z) (C) p F 2p+1 )-(CH 2 ) q -O-(CH 2 ) r -O-*
In the formula (Z), p is preferably 4 to 30, more preferably 4 to 20, and still more preferably 4 to 10.q is preferably 0 to 5, more preferably 0 to 4, and still more preferably 0 to 3.r is preferably 1 to 5, more preferably 1 to 4, and still more preferably 1 to 3.
In the above formula (Y), R 5 Preferably a hydrogen atom, methyl, ethyl or aromatic group.
The aromatic group is not particularly limited, but is preferably a phenyl group having 6 to 14 carbon atoms, more preferably 6 to 10 carbon atoms, and still more preferably.
Wherein R is further hydrophilized from the viewpoint of further accelerating the decomposition rate of the compound represented by the formula (X) by exposure 5 Preferably a methyl group, an ethyl group or an aromatic group, more preferably an ethyl group or an aromatic group, and still more preferably an aromatic group.
In the formula (Y), the bond site with C (=o) O-in the formula (X) is represented.
The compound represented by the formula (X) may be a compound having symmetry in molecular structure or a compound having no symmetry. The symmetry described herein means that the symmetry corresponds to any one of point symmetry, line symmetry, and rotational symmetry, and the asymmetry means that the symmetry does not correspond to any one of point symmetry, line symmetry, and rotational symmetry.
In the case where a plurality of Sp, hb, or a are present in the compound represented by the formula (X), the Sp, hb, or a may be the same or different.
The content of the specific photosensitive compound in the composition layer can be appropriately set according to the characteristics (e.g., retardation or wavelength dispersion) of the optically anisotropic layer to be formed.
Among them, the content of the specific photosensitive compound is preferably 0.01 to 10 mass%, more preferably 0.05 to 5 mass% with respect to the total mass of the liquid crystal compound, from the viewpoint of easier formation of the optically anisotropic layer of a predetermined structure.
In step 1A, a composition layer containing the above components is formed, but the procedure is not particularly limited. For example, a method in which a composition containing the above-described specific photosensitive compound and a liquid crystal compound having a polymerizable group is applied to a substrate and, if necessary, a drying treatment is performed (hereinafter, also simply referred to as "application method") and a method in which a composition layer is formed separately and transferred to the substrate are exemplified. Among them, the coating method is preferable from the viewpoint of productivity.
Hereinafter, the coating method will be described in detail.
The composition used in the coating method contains the above-described specific photosensitive compound, a liquid crystal compound having a polymerizable group, and other components (for example, a polymerization initiator, a polymerizable monomer, a surfactant, a polymer, and the like) that are used as necessary in addition to the above-described specific photosensitive compound.
The content of each component in the composition is preferably adjusted to the content of each component in the composition layer.
The coating method is not particularly limited, and examples thereof include a bar coating method, an extrusion coating method, a direct gravure coating method, a reverse gravure coating method, and a die coating method.
Further, if necessary, after the composition is applied, a treatment of drying the coating film applied on the substrate may be performed. The solvent can be removed from the coating film by performing the drying treatment.
The film thickness of the coating film is not particularly limited, but is preferably 0.1 to 20. Mu.m, more preferably 0.2 to 15. Mu.m, and still more preferably 0.5 to 10. Mu.m.
< procedure 2C >
The step 2C is as follows: the composition layer is subjected to a heat treatment to orient the liquid crystal compound in the composition layer. By performing this step, the liquid crystal compound in the composition layer is brought into a predetermined alignment state. As shown in fig. 11 described later, for example, by performing step 2C, the liquid crystal compound is uniformly aligned in the composition.
As the conditions of the heat treatment, the optimum conditions are selected according to the liquid crystal compound used.
Among them, the heating temperature is usually 25 to 250℃and 40 to 150℃and 50 to 130 ℃.
As the heating time, there are many cases of 0.1 to 60 minutes, and many cases of 0.2 to 5 minutes.
< procedure 3C >
The step 3C is as follows: after the step 2C, the composition layer was subjected to a treatment at 300mJ/cm under conditions such that the oxygen concentration was 1% by volume or more 2 The light irradiation was performed for 50 seconds or less. The mechanism of this step will be described below with reference to the drawings. Hereinafter, a case where the composition layer contains a compound hydrophilized by light irradiation will be described as an example. In fig. 11, the liquid crystal compound LC is uniformly aligned in the composition layer.
As shown in fig. 11, in step 3C, light irradiation is performed from the opposite side of the substrate 10 to the composition layer 320 side (the direction of the open arrow in fig. 11) under the condition that the oxygen concentration is 1% by volume or more. In fig. 11, the light irradiation is performed from the substrate 10 side, but may be performed from the composition layer 320 side.
At this time, when the lower region 320A of the composition layer 320 on the substrate 10 side is compared with the upper region 320B on the opposite side to the substrate 10 side, the surface of the upper region 320B is on the air side, and thus the oxygen concentration in the upper region 320B is high and the oxygen concentration in the lower region 320A is low. Therefore, when the composition layer 320 is irradiated with light, polymerization of the liquid crystal compound is easily performed in the lower region 320A, and the alignment state of the liquid crystal compound is fixed. In addition, a specific photosensitive compound is also present in the lower region 320A, and the specific photosensitive compound is also sensitized and hydrophilized. However, since the alignment state of the liquid crystal compound is fixed in the lower region 320A, even if the step 4C of performing the heat treatment on the composition layer irradiated with light, which will be described later, is performed, no change in the alignment state of the liquid crystal compound occurs.
Further, since the oxygen concentration is high in the upper region 320B, even when light irradiation is performed, polymerization of the liquid crystal compound is hindered by oxygen, and polymerization is difficult. In addition, since a specific photosensitive compound is also present in the upper region 320B, the specific photosensitive compound is sensitized and hydrophilized. Therefore, when step 4C described later is performed, the alignment state of the liquid crystal compound changes due to the influence of the changed polarity.
That is, by performing step 3C, immobilization of the alignment state of the liquid crystal compound is easily performed in the substrate-side region (lower region) of the composition layer. In addition, it is difficult to fix the alignment state of the liquid crystal compound in the region (upper region) of the composition layer on the side opposite to the substrate side, and the polarity changes depending on the specific photosensitive compound to be sensitized.
The various conditions (oxygen concentration, irradiation time, irradiation amount, etc.) of the light irradiation in the step 3C are the same as those of the light irradiation in the step 3A.
< procedure 4C >
The step 4C is as follows: after step 3C, the composition layer is subjected to a heat treatment at a higher temperature than that at the time of light irradiation. By performing this step, the alignment state of the liquid crystal compound changes in the region where the polarity changes due to the specific photosensitive compound in the composition layer subjected to light irradiation. More specifically, the present process is the following process: the composition layer after the step 3C is subjected to a heat treatment at a higher temperature than that at the time of irradiation to orient the liquid crystal compound in the composition layer which is not fixed in the step 3C.
The mechanism of this step will be described below with reference to the drawings.
As described above, when step 3C is performed on the composition layer 320 shown in fig. 11, the alignment state of the liquid crystal compound is fixed in the lower region 320A, and the polymerization of the liquid crystal compound is difficult in the upper region 320B, and the alignment state of the liquid crystal compound is not fixed. In the upper region 320B, the specific photosensitive compound is sensitized and hydrophilized. When such polarity changes, the alignment direction of the liquid crystal compound in the upper region 320B is affected compared with the state before light irradiation. This will be described in more detail. In the following, a case where the composition layer contains a specific photosensitive compound hydrophilized by light irradiation will be described as an example.
When the composition layer contains a specific photosensitive compound hydrophilized by light irradiation, as shown in fig. 12, the liquid crystal compound is vertically aligned in the upper region 320B when step 4C is performed (homeot ropic alignment). In particular, in the case where a specific photosensitive compound is present near the surface of the composition layer, the liquid crystal compound is easily oriented vertically.
On the other hand, as described above, in the lower region 320A of the composition layer 320, polymerization of the liquid crystal compound is performed at the time of step 3C, and the alignment state of the liquid crystal compound is fixed, so that the reorientation of the liquid crystal compound is not performed.
As described above, by performing step 4C, a region containing a liquid crystal compound whose alignment direction is inclined or vertical with respect to the layer surface can be formed.
In fig. 11, the mode of vertically aligning the liquid crystal compound is described, but the mode is not limited thereto. For example, the liquid crystal compound may be oriented obliquely.
The heat treatment is performed at a higher temperature than when light is irradiated.
The difference between the temperature of the heat treatment and the temperature at the time of light irradiation is preferably 5 ℃ or higher, more preferably 10 to 110 ℃, and still more preferably 20 to 110 ℃.
The temperature of the heat treatment is preferably higher than the temperature at the time of light irradiation and the temperature at which the liquid crystal compound not fixed in the composition layer is aligned, more specifically, 40 to 250 ℃ is more often, 50 to 150 ℃ is more often, more than 50 ℃ and 150 ℃ or less is more often, and 60 to 130 ℃ is particularly often.
As the heating time, there are many cases of 0.01 to 60 minutes, and many cases of 0.03 to 5 minutes.
< procedure 5C >
The step 5C is as follows: after step 4C, the composition layer is subjected to a curing treatment to form an optically anisotropic layer having a plurality of regions in which the alignment state of the liquid crystal compound is different in the thickness direction. By performing this step, the alignment state of the liquid crystal compound in the composition layer is fixed, and as a result, a predetermined optically anisotropic layer can be formed. Further, by performing this step, an optically anisotropic layer having regions in which the tilt angles of the alignment directions of the liquid crystal compounds with respect to the layer surface are different in the thickness direction can be formed. In particular, by performing this step, an optically anisotropic layer having a region in which the alignment state of the vertically aligned (homeotrop ic alignment) or obliquely aligned liquid crystal compound is fixed and a region in which the alignment state of the horizontally aligned (uniformly aligned) liquid crystal compound is fixed in the thickness direction can be formed.
As a method of the curing treatment in step 5C, a method of the curing treatment in step 5A is exemplified.
The thickness of the optically anisotropic layer is not particularly limited, but is preferably 0.05 to 10. Mu.m, more preferably 0.1 to 8.0. Mu.m, and still more preferably 0.2 to 6.0. Mu.m.
The optical characteristics of the optically anisotropic layer in embodiment 3 are not particularly limited, and the optimum value is selected according to the application. Hereinafter, as an example, a case of the optically anisotropic layer produced by the above-described steps, which has a 1 st region where the alignment state of the vertically aligned liquid crystal compound is fixed and a 2 nd region where the alignment state of the uniformly aligned liquid crystal compound is fixed in the thickness direction, will be described in detail.
When the thickness of the 1 st region of the optically anisotropic layer is d1 and the refractive index anisotropy in the plane of the 1 st region measured at a wavelength of 550nm is Δn1, the 1 st region preferably satisfies the following formula (1C-1) from the viewpoint that the optically anisotropic layer can be preferably applied to a circular polarizer and from the viewpoint that light leakage in an oblique direction can be reduced when the optically anisotropic layer is used as an optical compensation plate of a liquid crystal display device.
The formula (1C-1) is 0 nm-deltan 1d 1-30 nm
Among them, the formula (1C-2) is more preferably satisfied.
The formula (1C-2) is 0 nm-deltan 1d 1-20 nm
The retardation in the thickness direction at a wavelength of 550nm in the 1 st region of the optically anisotropic layer is preferably-150 to-20 nm, more preferably-120 to-20 nm.
When the thickness of the 2 nd region of the optically anisotropic layer is d2 and the refractive index anisotropy in the plane of the 2 nd region measured at a wavelength of 550nm is Δn2, the 2 nd region preferably satisfies the following formula (2C-1) from the viewpoint that the optically anisotropic layer can be preferably applied to a circularly polarizing plate or from the viewpoint that the optically anisotropic layer can be preferably applied to an optical compensation plate of a liquid crystal display device. That is, the in-plane retardation in the region 2 at a wavelength of 550nm is preferably 100 to 180nm.
The formula (2C-1) is 100nm less than or equal to delta n2d2 less than or equal to 180nm
Among them, the formula (2C-2) is more preferably satisfied.
Formula (2C-2) 110nm is less than or equal to delta n2d2 is less than or equal to 170nm
The refractive index anisotropy Δn2 represents the refractive index anisotropy of the 1 st region.
The optically anisotropic layer in embodiment 3 preferably exhibits inverse wavelength dispersion.
That is, it is preferable that Re (450) is an in-plane retardation measured at a wavelength of 450nm of the optically anisotropic layer, re (550) is an in-plane retardation measured at a wavelength of 550nm of the optically anisotropic layer, and Re (650) is an in-plane retardation measured at a wavelength of 650nm of the optically anisotropic layer, and Re (450). Ltoreq.Re (550). Ltoreq.Re (650) is a relationship.
The optical characteristics of the optically anisotropic layer in embodiment 3 are not particularly limited, but preferably function as a λ/4 plate or function as an optical compensation plate of a liquid crystal display device.
The λ/4 plate is a plate having a function of converting linearly polarized light of a certain specific wavelength into circularly polarized light (or converting circularly polarized light into linearly polarized light), and refers to a plate (optically anisotropic layer) whose in-plane retardation Re (λ) at a specific wavelength λnm satisfies Re (λ) =λ/4.
The expression may be realized at any wavelength (e.g., 550 nm) in the visible light region, but it is preferable that the in-plane retardation Re (550) at a wavelength of 550nm satisfies a relationship of 100 nm.ltoreq.Re (550). Ltoreq.180 nm.
Embodiment 4
Embodiment 4 of the method for producing an optically anisotropic layer of the present invention includes the following steps 1D to 5D. As described later, in embodiment 4, an optically anisotropic layer is formed which has a region in which an alignment state (for example, a horizontally aligned state) in which a liquid crystal compound is aligned is fixed and a region in which a non-alignment state (an isotropic phase of a liquid crystal compound) is fixed in the thickness direction.
Step 1D: a step of forming a composition layer containing a liquid crystal compound having a polymerizable group
Step 2D: a step of subjecting the composition layer to a heat treatment to orient the liquid crystal compound in the composition layer
Step 3D: after step 2D, the composition layer was subjected to a treatment at an oxygen concentration of not less than 1% by volume at 300mJ/cm 2 The following procedure of light irradiation for 50 seconds or less
Step 4D: after the step 3D, a step of performing a heat treatment on the composition layer at a temperature higher than the temperature at which the liquid crystal compound becomes an isotropic phase and higher than the light irradiation
Step 5D: after step 4D, a step of forming an optically anisotropic layer having a plurality of regions having different alignment states of the liquid crystal compound in the thickness direction by subjecting the composition layer to a curing treatment
The steps of the above steps will be described in detail below.
< procedure 1D >
Step 1D is a step of forming a composition layer containing a liquid crystal compound having a polymerizable group. By performing this step, a composition layer subjected to a light irradiation treatment described later can be formed.
The liquid crystal compound contained in the composition layer is as described in step 1A.
As described in step 1A, the composition layer may contain components other than the liquid crystal compound.
In step 1A, a composition layer containing the above components is formed, but the procedure is not particularly limited. For example, a method in which a composition containing the liquid crystal compound having a polymerizable group is applied to a substrate and if necessary, a drying treatment is performed (hereinafter, also simply referred to as a "coating method") and a method in which a composition layer is formed separately and transferred to the substrate are exemplified. Among them, the coating method is preferable from the viewpoint of productivity.
Hereinafter, the coating method will be described in detail.
The composition used in the coating method contains the liquid crystal compound having a polymerizable group and other components (for example, a polymerization initiator, a polymerizable monomer, a surfactant, a polymer, and the like) used as necessary in addition to the above.
The content of each component in the composition is preferably adjusted to the content of each component in the composition layer.
The coating method is not particularly limited, and examples thereof include a bar coating method, an extrusion coating method, a direct gravure coating method, a reverse gravure coating method, and a die coating method.
Further, if necessary, after the composition is applied, a treatment of drying the coating film applied on the substrate may be performed. The solvent can be removed from the coating film by performing the drying treatment.
The film thickness of the coating film is not particularly limited, but is preferably 0.1 to 20. Mu.m, more preferably 0.2 to 15. Mu.m, and still more preferably 0.5 to 10. Mu.m.
< procedure 2D >)
The process 2D is as follows: the composition layer is subjected to a heat treatment to orient the liquid crystal compound in the composition layer. By performing this step, the liquid crystal compound in the composition layer is brought into a predetermined alignment state. As shown in fig. 13 described later, for example, by performing step 2D, the liquid crystal compound is uniformly aligned in the composition.
As the conditions of the heat treatment, the optimum conditions are selected according to the liquid crystal compound used.
Among them, the heating temperature is usually 25 to 250℃and 40 to 150℃and 50 to 130 ℃.
As the heating time, there are many cases of 0.1 to 60 minutes, and many cases of 0.2 to 5 minutes.
< procedure 3D >
The process 3D is as follows: after step 2D, the composition layer was subjected to a treatment at an oxygen concentration of not less than 1% by volume at 300mJ/cm 2 The light irradiation was performed for 50 seconds or less. The mechanism of this step will be described below with reference to the drawings. In fig. 13, the liquid crystal compound LC is uniformly aligned in the composition layer.
As shown in fig. 13, in step 3D, light irradiation is performed from the opposite side of the substrate 10 from the composition layer 420 side (the direction of the open arrow in fig. 13) under the condition that the oxygen concentration is 1% by volume or more. In fig. 13, the light irradiation is performed from the substrate 10 side, but may be performed from the composition layer 420 side.
At this time, when the lower region 420A of the composition layer 420 on the substrate 10 side is compared with the upper region 420B on the opposite side to the substrate 10 side, the surface of the upper region 420B is on the air side, and thus the oxygen concentration in the upper region 420B is high and the oxygen concentration in the lower region 420A is low. Therefore, when the composition layer 420 is irradiated with light, polymerization of the liquid crystal compound is easily performed in the lower region 420A, and the alignment state of the liquid crystal compound is fixed. Therefore, even when step 4D of heat-treating the composition layer irradiated with light, which will be described later, is performed, no change in the alignment state of the liquid crystal compound occurs.
Further, since the oxygen concentration is high in the upper region 420B, even when light irradiation is performed, polymerization of the liquid crystal compound is hindered by oxygen, and polymerization is difficult. Therefore, when step 4D described later is performed, the alignment state of the liquid crystal compound changes.
That is, by performing step 3D, immobilization of the alignment state of the liquid crystal compound is easily performed in the region (lower region) of the composition layer on the substrate side. In addition, it is difficult to fix the alignment state of the liquid crystal compound in the region (upper region) of the composition layer on the side opposite to the substrate side, and the alignment state of the liquid crystal compound is changed in step 4D described later.
The various conditions (oxygen concentration, irradiation time, irradiation amount, etc.) of the light irradiation in the step 3D are the same as those of the light irradiation in the step 3A.
< procedure 4D >)
The step 4D is as follows: after step 3D, the composition layer is subjected to a heat treatment at a temperature higher than that at which the liquid crystal compound becomes an isotropic phase or higher than that at the time of light irradiation. By carrying out this step, the liquid crystal compound exhibits an isotropic phase in the upper region where the alignment state of the liquid crystal compound in the composition layer is not fixed.
The mechanism of this step will be described below with reference to the drawings.
As described above, when the composition layer 420 shown in fig. 13 is subjected to step 3D, the alignment state of the liquid crystal compound is fixed in the lower region 420A, and the polymerization of the liquid crystal compound is difficult in the upper region 420B, and the alignment state of the liquid crystal compound is not fixed.
Therefore, when step 4D is performed, as shown in fig. 14, the polymerization of the liquid crystal compound is not performed in the upper region 420B, and thus the alignment state of the liquid crystal compound is broken to become an isotropic phase.
On the other hand, as described above, in the lower region 420A of the composition layer 420, polymerization of the liquid crystal compound is performed at the time of step 3D, and the alignment state of the liquid crystal compound is fixed, so that the reorientation of the liquid crystal compound is not performed.
As described above, by performing step 4D, an optically anisotropic layer having a region in which the alignment state (for example, the horizontal alignment state) of the liquid crystal compound is fixed and a region in which the non-alignment state (the isotropic phase) of the liquid crystal compound is fixed in the thickness direction can be formed.
The heat treatment is performed at a temperature higher than the temperature at which the liquid crystal compound becomes isotropic phase or higher.
The difference between the temperature of the heat treatment and the temperature at the time of light irradiation is preferably 5 ℃ or higher, more preferably 10 to 110 ℃, and still more preferably 20 to 110 ℃.
The temperature of the heat treatment is preferably higher than the temperature at the time of light irradiation and the liquid crystal compound not fixed in the composition layer is set to an isotropic phase, more specifically, 40 to 250 ℃ is more often, 50 to 150 ℃ is more often, more than 50 ℃ and 150 ℃ is more often, and 60 to 130 ℃ is particularly often.
As the heating time, there are many cases of 0.01 to 60 minutes, and many cases of 0.03 to 5 minutes.
< procedure 5D >
The step 5D is as follows: after step 4D, the composition layer is subjected to a curing treatment to form an optically anisotropic layer having a plurality of regions in which the alignment state of the liquid crystal compound is different in the thickness direction. By performing this step, the alignment state of the liquid crystal compound in the composition layer is fixed, and as a result, a predetermined optically anisotropic layer can be formed.
As a method of the curing treatment in step 5D, a method of the curing treatment in step 5A is exemplified.
The thickness of the optically anisotropic layer is not particularly limited, but is preferably 0.05 to 10. Mu.m, more preferably 0.1 to 8.0. Mu.m, and still more preferably 0.2 to 6.0. Mu.m.
In addition, although the description has been made of the optical anisotropic layer having the region in which the alignment state of the liquid crystal compound in the horizontal alignment is fixed and the region in which the state of the liquid crystal compound in the isotropic phase is fixed in the thickness direction in fig. 13 and 14, the optical anisotropic layer is not limited to this type, as long as the region in which the state of the liquid crystal compound in the isotropic phase is fixed is included.
For example, in the case where the liquid crystal compound is a rod-like liquid crystal compound, examples of the alignment state include nematic alignment (state in which a nematic phase is formed), smectic alignment (state in which a smectic phase is formed), cholesteric alignment (state in which a cholesteric phase is formed), and hybrid alignment. In the case where the liquid crystal compound is a discotic liquid crystal compound, examples of the alignment state include nematic alignment, columnar alignment (state in which columnar phase is formed), and cholesteric alignment.
More specifically, an optically anisotropic layer having a region in which the alignment state of a vertically aligned liquid crystal compound is fixed and a region in which the state of a liquid crystal compound showing an isotropic phase is fixed in the thickness direction can be formed. Further, an optically anisotropic layer formed using a liquid crystal compound and having a region in which a cholesteric liquid crystal phase is fixed and a region in which a liquid crystal compound exhibits an isotropic phase is fixed in the thickness direction may be formed.
The optical properties of the optically anisotropic layer in embodiment 4 are not particularly limited, but preferably function as a λ/4 plate.
The λ/4 plate is a plate having a function of converting linearly polarized light of a certain specific wavelength into circularly polarized light (or converting circularly polarized light into linearly polarized light), and refers to a plate (optically anisotropic layer) whose in-plane retardation Re (λ) at a specific wavelength λnm satisfies Re (λ) =λ/4.
The expression may be realized at any wavelength (e.g., 550 nm) in the visible light region, but it is preferable that the in-plane retardation Re (550) at a wavelength of 550nm satisfies a relationship of 110 nm.ltoreq.Re (550). Ltoreq.180 nm.
Use of
The optically anisotropic layer can be combined with various components.
For example, the optically anisotropic layer described above may be combined with other optically anisotropic layers. That is, as shown in fig. 15, a laminate 24 including the substrate 10, the optically anisotropic layer 20 manufactured by the above manufacturing method, and the other optically anisotropic layer 22 can be manufactured. The laminate 24 shown in fig. 15 includes the substrate 10, but the laminate may not include the substrate.
The other optically anisotropic layer is not particularly limited, and examples thereof include an a plate (positive a plate and negative a plate) and a C plate (positive C plate and negative C plate). Among them, the C plate is preferable from the viewpoint of being easily applicable to various applications (for example, circular polarizing plates) described later.
The range of the absolute value of the retardation in the thickness direction at a wavelength of 550nm of the C plate is not particularly limited, but is preferably 5 to 300nm, more preferably 10 to 200nm.
In this specification, the a plate and the C plate are defined as follows.
The a plate has 2 types, namely, a positive a plate (positive a plate) and a negative a plate (negative a plate), and when the refractive index in the slow axis direction in the film plane (the direction in which the refractive index in the plane is the largest) is nx, the refractive index in the direction orthogonal to the slow axis in the plane is ny, and the refractive index in the thickness direction is nz, the positive a plate satisfies the relationship of the formula (A1), and the negative a plate satisfies the relationship of the formula (A2). In addition, rth of the positive a plate represents a positive value, and Rth of the negative a plate represents a negative value.
Formula (A1) nx > ny.apprxeq.nz
Formula (A2) ny < nx approximately nz
In addition, the above "≡" includes not only the case where both are identical but also the case where both are actually identical. The term "substantially the same" means that, for example, the case where (ny-nz). Times.d (where d is the thickness of the film) is-10 to 10nm, preferably-5 to 5nm is also included in "ny. Apprxeq. Nz", and the case where (nx-nz). Times.d is-10 to 10nm, preferably-5 to 5nm is also included in "nx. Apprxeq. Nz".
The C plates include 2 types of positive C plates (positive C plates) and negative C plates (negative C plates), the positive C plates satisfying the relationship of formula (C1), and the negative C plates satisfying the relationship of formula (C2). In addition, rth of the positive C plate represents a negative value, and Rth of the negative C plate represents a positive value.
Formula (C1) nz > nx≡ny
Formula (C2) nz < nx≡ny
In addition, the above "≡" includes not only the case where both are identical but also the case where both are actually identical. The term "substantially the same" means that, for example, (nx-ny). Times.d (where d is the thickness of the film) is 0 to 10nm, preferably 0 to 5nm, and is also included in "nx.apprxeq.ny".
The method for producing the laminate is not particularly limited, and a known method can be used. For example, a method of laminating an optically anisotropic layer obtained by the production method of the present invention with another optically anisotropic layer (for example, a C plate) to obtain a laminate is given. As a method of stacking the above, another optically anisotropic layer produced separately may be bonded to the optically anisotropic layer obtained by the production method of the present invention, or another optically anisotropic layer may be formed by coating the optically anisotropic layer obtained by the production method of the present invention with a composition for forming another optically anisotropic layer.
Also, the optically anisotropic layer obtained by the manufacturing method of the present invention may be combined with a polarizer. That is, as shown in fig. 16, the polarizer-attached optically anisotropic layer 28 including the substrate 10, the optically anisotropic layer 20 manufactured by the above manufacturing method, and the polarizer 26 can be manufactured. In fig. 16, the polarizer 26 is disposed on the substrate 10, but the embodiment is not limited to this, and the polarizer 26 may be disposed on the optically anisotropic layer 20.
The polarizer-attached optically anisotropic layer 28 shown in fig. 16 includes the substrate 10, but the polarizer-attached optically anisotropic layer may not include the substrate.
The positional relationship when the optically anisotropic layer and the polarizer are laminated is not particularly limited, but in the case where the optically anisotropic layer has, in the thickness direction, a 1 st region in which the alignment state of the liquid crystal compound twist-aligned along the helical axis extending in the thickness direction is fixed and a 2 nd region in which the alignment state of the uniformly aligned liquid crystal compound is fixed, the absolute value of the angle formed by the in-plane slow axis of the 2 nd region and the absorption axis of the polarizer is preferably 5 to 25 °, more preferably 10 to 20 °, from the viewpoint that the optically anisotropic layer can be preferably applied to a circularly polarizing plate or the like.
When the angle formed by the slow axis in the plane of the 2 nd region and the absorption axis of the polarizer is negative, the twist angle of the liquid crystal compound in the 1 st region is preferably negative, and the angle formed by the slow axis in the plane of the 2 nd region and the absorption axis of the polarizer is positive, and the twist angle of the liquid crystal compound in the 1 st region is preferably positive.
The case where the angle between the in-plane slow axis and the polarizer is negative when viewed from the polarizer side means that the rotation angle of the in-plane slow axis is clockwise with respect to the absorption axis of the polarizer, and the case where the angle between the in-plane slow axis and the polarizer is positive when viewed from the polarizer side means that the rotation angle of the in-plane slow axis is counterclockwise with respect to the absorption axis of the polarizer.
The twist angle of the liquid crystal compound is expressed as negative when the alignment direction of the liquid crystal compound on the back side is clockwise (right turn) and positive when the alignment direction of the liquid crystal compound on the front side is counterclockwise (left turn) with respect to the alignment direction of the liquid crystal compound on the front side (right-front side).
The polarizer may be a member having a function of converting natural light into specific linearly polarized light, and examples thereof include an absorption type polarizer.
The type of polarizer is not particularly limited, and commonly used polarizers can be used, and examples thereof include iodine polarizers, dye polarizers using dichroic dyes, and multi-polarizing polarizers. Iodine polarizers and dye polarizers are generally produced by adsorbing iodine or a dichroic dye to polyvinyl alcohol and stretching the same.
In addition, a protective film may be disposed on one or both sides of the polarizer.
The method for producing the optically anisotropic layer with a polarizer is not particularly limited, and a known method can be used. For example, a method of laminating an optically anisotropic layer obtained by the production method of the present invention and a polarizer to obtain an optically anisotropic layer with a polarizer is given.
Further, although the above description has been made of a method of laminating an optically anisotropic layer and a polarizer, in the present invention, a laminate with a polarizer may be produced by laminating the laminate and a polarizer.
The optically anisotropic layer can be suitably used for various applications. For example, the optically anisotropic layer can be preferably applied to a circularly polarizing plate, and the above-described optically anisotropic layer with a polarizer can be used as a circularly polarizing plate.
The circular polarizer having the above-described structure is preferably used for antireflection applications of image display devices such as liquid crystal display devices (LCDs), plasma Display Panels (PDPs), electroluminescent displays (ELDs), and cathode ray tube display devices (CRTs), and can improve the contrast ratio of display light.
For example, a mode in which the circularly polarizing plate of the present invention is used on the light extraction surface side of an organic EL display device is exemplified. At this time, the external light passes through the polarizing film to become linearly polarized light, and then passes through the optically anisotropic layer to become circularly polarized light. When the circularly polarized light is reflected by the metal electrode, the circularly polarized light is reversed in state, and when the circularly polarized light passes through the optically anisotropic layer again, the circularly polarized light reaches the polarizing film from the linearly polarized light inclined by 90 ° at the time of incidence, and is absorbed. As a result, the influence of external light can be suppressed.
Among them, the above-mentioned polarizer-attached optically anisotropic layer or polarizer-attached laminate is preferably used for an organic EL display device. That is, the polarizing optically anisotropic layer or the polarizing laminate is preferably disposed on an organic EL panel of an organic EL display device and is suitable for antireflection use.
The organic EL panel is a member in which a light-emitting layer or a plurality of organic compound thin films including a light-emitting layer are formed between a pair of electrodes, that is, an anode and a cathode, and may have a hole injection layer, a hole transport layer, an electron injection layer, an electron transport layer, a protective layer, and the like in addition to the light-emitting layer, and each of these layers may have other functions. As for the formation of each layer, various materials can be used.
The optically anisotropic layer can be preferably applied to an optical compensation plate of a liquid crystal display device, and the optically anisotropic layer with a polarizer can be used as an optical compensation plate of a liquid crystal display device.
The liquid crystal cell used In the liquid crystal display device is preferably a VA (Vertical Alignment: vertical alignment) mode, an OCB (Optically Compensated Bend: optically compensated bend) mode, an IPS (In-Plane-Switching) mode, an FFS (Fringe-Field-Switching) mode, or a TN (Twisted Nematic) mode, but is not limited thereto.
In the case where the above-described polarizer-attached optically anisotropic layer is used as an optical compensation plate for a liquid crystal display device of IPS mode or FFS mode, it is preferable that the optically anisotropic layer has a region in which the alignment state of a uniformly aligned (horizontally aligned) liquid crystal compound is fixed and a region in which the alignment state of a vertically aligned (homeotropic alignment) liquid crystal compound is fixed as shown in fig. 12. In this case, the in-plane slow axis of the region where the alignment state of the uniformly aligned (horizontally aligned) liquid crystal compound is fixed is preferably orthogonal or parallel to the angle formed by the absorption axis of the polarizer, and more specifically, the angle formed by the in-plane slow axis of the region where the alignment state of the uniformly aligned (horizontally aligned) liquid crystal compound is fixed and the absorption axis of the polarizer is preferably 0 to 5 ° or 85 to 95 °.
Here, the "slow axis in plane" of the region where the alignment state of the uniformly aligned (horizontally aligned) liquid crystal compound is fixed indicates the direction in which the in-plane refractive index of the region where the alignment state of the uniformly aligned (horizontally aligned) liquid crystal compound is fixed is the largest, and the "absorption axis" of the polarizer indicates the direction in which the absorbance is the highest.
In the case where the above-described optically anisotropic layer with a polarizer is used as an optical compensation plate for an IPS mode or FFS mode liquid crystal display device, it is preferable that the polarizer, a region in which the alignment state of a homeotropic alignment (homeotropic alignment) liquid crystal compound is fixed, a region in which the alignment state of a homogeneous alignment (horizontal alignment) liquid crystal compound is fixed, and a liquid crystal cell be arranged in this order, or the polarizer, a region in which the alignment state of a homogeneous alignment (horizontal alignment) liquid crystal compound is fixed, and a region in which the alignment state of a homeotropic alignment (homeotropic alignment) liquid crystal compound is fixed, and a liquid crystal cell be arranged in this order.
Examples
The features of the present invention will be described in more detail below with reference to examples and comparative examples. The materials, amounts used, ratios, treatment contents, treatment steps and the like shown in the following examples can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention should not be construed in a limiting manner by the following examples.
Example 1 >
(production of cellulose acylate film (substrate))
The following composition was put into a mixing tank and stirred, and heated at 90℃for 10 minutes. Thereafter, the obtained composition was filtered using a filter paper having an average pore size of 34 μm and a sintered metal filter having an average pore size of 10 μm, thereby preparing a dope. The solid content concentration of the dope was 23.5 mass%, the addition amount of the plasticizer was a ratio to the cellulose acylate, and the solvent of the dope was methylene chloride/methanol/butanol=81/18/1 (mass ratio).
[ chemical formula 5]
[ chemical formula 6]
The dope prepared in the above-described manner was cast using a roll laminator. After casting the dope from the die so as to be in contact with the metal support cooled to 0 ℃, the obtained web (film) was peeled off. In addition, the drum is made of SUS.
When the web (film) obtained by casting is peeled from the drum and then conveyed, the web is dried in the tenter device at 30 to 40 ℃ for 20 minutes using the tenter device which carries the web while sandwiching both ends thereof with clips. Subsequently, the sheet was post-dried by zone heating while being roll-fed. After the obtained web was subjected to knurling treatment, winding was performed.
The film thickness of the obtained cellulose acylate film was 40. Mu.m, the in-plane retardation Re (550) at a wavelength of 550nm was 1nm, and the retardation Rth (550) in the thickness direction at a wavelength of 550nm was 26nm.
(formation of optically Anisotropic layer)
The cellulose acylate film produced in the above manner is continuously subjected to a rubbing treatment. At this time, the longitudinal direction of the long film was parallel to the transport direction, and the angle formed by the longitudinal direction of the film (transport direction) and the rotation axis of the rubbing roller was set to 80 °. Assuming that the longitudinal direction (conveying direction) of the film is 90 °, when a positive value is expressed in the clockwise direction with reference to the film width direction (0 °) as viewed from the film side, the rotation axis of the rubbing roller is 10 °. In other words, the position of the rotation shaft of the rubbing roller is a position rotated counterclockwise by 80 ° with respect to the longitudinal direction of the film.
The composition layer (corresponding to step 1A) was formed by applying the composition (1) for forming an optically anisotropic layer containing a rod-like liquid crystal compound having the following composition to the substrate of the long cellulose acylate film subjected to the rubbing treatment using a die coater. In addition, the absolute value of the weighted average helical twisting power of the chiral agent in the composition layer in step 1A was 0.0. Mu.m -1 。
Subsequently, the obtained composition layer was heated at 80℃for 60 seconds (corresponding to step 2A). The rod-like liquid crystal compound of the composition layer is aligned in a predetermined direction by this heating.
Thereafter, ultraviolet rays were irradiated to the composition layer for 5 seconds (irradiation amount: 13 mJ/cm) at 40℃under an atmosphere containing oxygen (oxygen concentration: about 20 vol.) (manufactured by Acroedge Co., ltd.) using a 365nm LED lamp 2 ) (corresponding to step 3A).
Subsequently, the obtained composition layer was heated at 80℃for 10 seconds (corresponding to step 4A).
Thereafter, nitrogen purging was performed so that the oxygen concentration became 100 ppm by volume, and ultraviolet light was irradiated (irradiation amount: 500 mJ/cm) at 80℃using a metal halide lamp (EYE GRAPHICS Co., ltd.) 2 ) On the composition layer, thereby forming a liquid crystal compound fixedAn optically anisotropic layer in an aligned state (corresponding to step 5A). An optical film (F-1) was produced in the above-described manner.
In addition, the molar absorptivity at 365nm of the left-twisted chiral agent (L1) in the composition (1) for forming an optically anisotropic layer was 40L/(mol cm), and the HTP of the chiral agent was not affected by irradiation (13 mJ/cm 2 ) 365nm light was unchanged from that before irradiation.
The molar absorptivity at 365nm of the right-twisted chiral reagent (R1) was 38,450L/(mol cm), and when the HTP of the chiral reagent was irradiated (13 mJ/cm) 2 ) 365nm light, is reduced by 35 μm compared with that before irradiation -1 。
The molar absorption coefficient at 365nm of the photopolymerization initiator (Irgacure 819) was 860L/(mol. Cm).
A rod-like liquid crystal compound (A) (hereinafter, a mixture of compounds) [ chemical formula 7]
Rod-like liquid Crystal Compound (B)
[ chemical formula 8]
Polymerizable compound (C)
[ chemical formula 9]
Left twist chiral agent (L1)
[ chemical formula 10]
Right distortion chiral agent (R1)
[ chemical formula 11]
The polymer (A) (wherein the numerical values described in the respective repeating units represent the content (mass%) of each repeating unit relative to all the repeating units.)
[ chemical formula 12]
The polymer (B) (wherein the numerical values described in the respective repeating units represent the content (mass%) of each repeating unit relative to all the repeating units.)
[ chemical formula 13]
The optical film (F-1) produced in the above manner was cut parallel to the rubbing direction, and the optically anisotropic layer was observed from the cross-sectional direction by a polarized light microscope. The thickness of the optically anisotropic layer was 2.7 μm, there was no uniform alignment of twist angle in the region (region 2) of the optically anisotropic layer having a thickness (d 2) of 1.3 μm on the substrate side, and the liquid crystal compound was twist-aligned in the region (region 1) of the optically anisotropic layer having a thickness (d 1) of 1.4 μm on the air side (side opposite to the substrate).
The optical characteristics of the optical film (F-1) were determined by using Axoscan from Axometrics and Analysis software (Multi-Layer Analysis) from Axometrics. The product of Δn2 and thickness d2 at a wavelength of 550nm in region 2 (Δn2d2) was 173nm, the twist angle of the liquid crystal compound was 0 °, the alignment axis angle of the liquid crystal compound with respect to the longitudinal direction of the film was-10 ° on the side in contact with the substrate, and was-10 ° on the side in contact with region 1.
The product of Δn1 and thickness d1 at a wavelength of 550nm in region 1 (Δn1d1) was 184nm, the twist angle of the liquid crystal compound was 75 °, the alignment axis angle of the liquid crystal compound with respect to the longitudinal direction of the film was-10 ° on the side contacting region 2, and was-85 ° on the air side.
The angle of the alignment axis of the liquid crystal compound contained in the optically anisotropic layer was set to 0 ° with respect to the longitudinal direction of the film, and the film was observed from the front side of the optically anisotropic layer, and was represented as negative in the clockwise direction (right turn) and positive in the counterclockwise direction (left turn).
Further, regarding the twisted structure of the liquid crystal compound, the substrate is observed from the front surface side of the optically anisotropic layer, and the alignment direction of the liquid crystal compound on the front surface side (right-turn) is represented as negative when the alignment direction of the liquid crystal compound on the substrate side (back side) is clockwise (right-turn) and as positive when counterclockwise (left-turn) is taken as a reference.
(production of polarizer)
A polyvinyl alcohol (PVA) film having a thickness of 80 μm was immersed in an aqueous iodine solution having an iodine concentration of 0.05 mass% at 30℃for 60 seconds to be dyed. Next, the obtained film was immersed in an aqueous boric acid solution having a boric acid concentration of 4 mass% for 60 seconds and then longitudinally extended to 5 times the original length, and then dried at 50 ℃ for 4 minutes, whereby a polarizer having a thickness of 20 μm was obtained.
(production of polarizer protective film)
A commercially available cellulose acylate-based film was prepared, FUJITAC TG40UL (manufactured by Fujifilm Corporation) was immersed in an aqueous sodium hydroxide solution at 55℃at 1.5 mol/L, and then, the aqueous sodium hydroxide was sufficiently washed with water. After that, the obtained film was immersed in a dilute sulfuric acid aqueous solution at 35℃for 1 minute at 0.005 mol/liter, and then immersed in water to sufficiently rinse the dilute sulfuric acid aqueous solution. Finally, the obtained film was sufficiently dried at 120 ℃, thereby producing a polarizer protective film having a saponification-treated surface.
(production of circular polarizing plate)
The optical film (F-1) produced in the above manner is saponified in the same manner as the production of the polarizer protective film, and the polarizer protective film are continuously bonded to the substrate surface included in the optical film (F-1) using a polyvinyl alcohol-based adhesive, whereby an elongated circular polarizing plate (P-1) is produced. That is, the circularly polarizing plate (P-1) has a polarizer protective film, a polarizer, a substrate, and an optically anisotropic layer in this order.
The absorption axis of the polarizer was aligned with the longitudinal direction of the circularly polarizing plate, and the rotation angle of the in-plane slow axis of the 2 nd region with respect to the absorption axis of the polarizer was 10 °, and the rotation angle of the in-plane slow axis of the surface of the 1 st region opposite to the 2 nd region side with respect to the absorption axis of the polarizer was 85 °.
The rotation angle of the in-plane slow axis is 0 ° with respect to the longitudinal direction of the circularly polarizing plate, the counterclockwise direction is represented by a positive angle value, and the clockwise direction is represented by a negative angle value, when the optically anisotropic layer is viewed from the polarizer side.
Example 2 >
(alkali saponification treatment)
After passing the cellulose acylate film through a dielectric heating roller having a temperature of 60℃to raise the film surface temperature to 40℃an alkali solution having the composition shown below was applied in a coating amount of 14ml/m using a bar coater 2 The film was applied to the belt surface of the film, and was fed under a vapor-type far infrared heater made of LIMITED for 10 seconds to the NORITAKE co. Next, pure water was similarly applied to 3ml/m using a bar coater 2 . Next, after washing with water and dehydration with an air knife with a spray coater were repeated 3 times, the cellulose acylate film was transported to a drying zone at 70 ℃ for 10 seconds to be dried, thereby producing an alkali-saponified cellulose acylate film.
(formation of alignment film)
An alignment film coating liquid of the following composition was continuously coated on the alkali-saponification-treated face of the cellulose acylate film using a bar of # 14. The drying was performed for 60 seconds by warm air at 60℃and for 120 seconds by warm air at 100 ℃.
(modified polyvinyl alcohol)
[ chemical formula 14]
(formation of optically Anisotropic layer)
The alignment film produced in the above manner was subjected to a rubbing treatment continuously. At this time, the longitudinal direction of the long film was parallel to the transport direction, and the angle formed by the longitudinal direction of the film (transport direction) and the rotation axis of the rubbing roller was set to 45 °. Assuming that the longitudinal direction (conveying direction) of the film is 90 °, when a positive value is expressed in the clockwise direction with reference to the film width direction (0 °) as viewed from the film side, the rotation axis of the rubbing roller is 135 °. In other words, the position of the rotation shaft of the rubbing roller is a position rotated 45 ° counterclockwise with respect to the longitudinal direction of the film.
The composition layer (corresponding to step 1C) was formed by coating the composition (2) for forming an optically anisotropic layer containing a rod-like liquid crystal compound having the following composition using the above-mentioned cellulose acylate film with an alignment film as a substrate with a die coater.
Subsequently, the obtained composition layer was heated at 120℃for 80 seconds (corresponding to step 2C). The rod-like liquid crystal compound of the composition layer is aligned in a predetermined direction by this heating.
Thereafter, ultraviolet rays were irradiated to the composition layer for 5 seconds (irradiation amount: 30 mJ/cm) at 40℃under an atmosphere containing oxygen (oxygen concentration: about 20 vol.) (manufactured by Acroedge Co., ltd.) using a 365nm LED lamp 2 ) (corresponding to step 3C).
Subsequently, the obtained composition layer was heated at 90℃for 10 seconds (corresponding to step 4C).
Thereafter, nitrogen purging was performed so that the oxygen concentration became 100 ppm by volume, and ultraviolet light was irradiated (irradiation amount: 500 mJ/cm) at 55℃using a metal halide lamp (EYE GRAPHICS Co., ltd.) 2 ) An optically anisotropic layer having an alignment state of the liquid crystal compound fixed thereon is formed on the composition layer (corresponding to step 5C). An optical film (F-2) was produced in the above-described manner.
Rod-like liquid crystal compound (D)
[ chemical formula 15]
Rod-like liquid crystal compound (E)
[ chemical formula 16]
Photosensitive compound (A)
[ chemical formula 17]
Ionic compound (A)
[ chemical formula 18]
In addition, the photosensitive compound (A) in the composition (2) for forming an optically anisotropic layer was irradiated with (30 mJ/cm) 2 ) 365nm light, a decomposition product (A) having a hydrophilic carboxyl group.
Decomposition products (A)
[ chemical formula 19]
The optical film (F-2) produced in the above manner was cut parallel to the rubbing direction, and the optically anisotropic layer was observed from the cross-sectional direction by a polarized light microscope. The optically anisotropic layer had a thickness of 4.3 μm and was uniformly oriented in the region (region 2) of 3.0 μm on the substrate side of the optically anisotropic layer, and the liquid crystal compound was vertically oriented in the region (region 1) of 1.3 μm on the air side (opposite side to the substrate) of the optically anisotropic layer.
The optical characteristics of the optical film (F-2) were determined using Axoscan from Axometrics and Analysis software (Multi-Layer Analysis) from Axometrics. The in-plane retardation (Δn2d2) at the wavelength of 550nm in the 2 nd region was 140nm, and the angle of the in-plane slow axis with respect to the longitudinal direction of the film was-45 °. The in-plane retardation (Δn1d1) at the wavelength of 550nm in the 1 st region was 0nm, and the retardation in the thickness direction at the wavelength of 550nm in the 1 st region was-60 nm.
The angle of the in-plane slow axis was set to 0 ° with respect to the longitudinal direction of the film, and the substrate was observed from the front surface side of the optically anisotropic layer, and was represented as negative in the clockwise direction (right turn) and positive in the counterclockwise direction (left turn).
(production of circular polarizing plate)
In the same manner as in example 1, the optical film (F-2) produced in the above manner was subjected to saponification treatment, and the polarizer protective film were continuously bonded to the substrate surface included in the optical film (F-2) using a polyvinyl alcohol-based adhesive, thereby producing an elongated circular polarizing plate (P-2). That is, the circularly polarizing plate (P-2) has a polarizer protective film, a polarizer, a substrate, and an optically anisotropic layer in this order.
The absorption axis of the polarizer was aligned with the longitudinal direction of the circularly polarizing plate, and the rotation angle of the slow axis in the 2 nd region with respect to the absorption axis of the polarizer was 45 °.
The rotation angle of the in-plane slow axis is 0 ° with respect to the longitudinal direction of the circularly polarizing plate, the counterclockwise direction is represented by a positive angle value, and the clockwise direction is represented by a negative angle value, when the optically anisotropic layer is viewed from the polarizer side.
Example 3 >
(formation of optically Anisotropic layer)
The cellulose acylate film produced in example 1 was subjected to a rubbing treatment successively. At this time, the longitudinal direction of the long film was parallel to the transport direction, and the angle formed by the longitudinal direction of the film (transport direction) and the rotation axis of the rubbing roller was 45 °. Further, assuming that the longitudinal direction (conveying direction) of the film is 90 °, when a positive value is expressed in a counterclockwise direction with respect to the width direction (0 °) of the cellulose acylate film as viewed from the cellulose acylate film side, the rotation axis of the rubbing roller is 135 °. In other words, the position of the rotation axis of the rubbing roller is a position rotated 45 ° clockwise with reference to the longitudinal direction of the cellulose acylate film.
The composition layer (corresponding to step 1D) was formed by coating the composition (3) for forming an optically anisotropic layer containing a rod-like liquid crystal compound having the following composition using the cellulose acylate film subjected to the rubbing treatment as a substrate using a die coater.
Subsequently, the obtained composition layer was heated at 80℃for 60 seconds (corresponding to step 2D). The rod-like liquid crystal compound of the composition layer is aligned in a predetermined direction by this heating.
Thereafter, ultraviolet rays were irradiated to the composition layer for 5 seconds (irradiation amount: 50 mJ/cm) at 40℃under an atmosphere containing oxygen (oxygen concentration: about 20 vol.) (manufactured by Acroedge Co., ltd.) using a 365nm LED lamp 2 ) (corresponding to procedure 3D).
Subsequently, the obtained composition layer was heated at 120℃for 10 seconds (corresponding to step 4D). The phase transition temperature of the rod-like liquid crystal compound in the optically anisotropic layer-forming composition (3) to the isotropic phase was 110 ℃.
Thereafter, nitrogen purging was performed so that the oxygen concentration became 100 ppm by volume, and ultraviolet light was irradiated (irradiation amount: 500 mJ/cm) at 120℃using a metal halide lamp (EYE GRAPHICS Co., ltd.) 2 ) An optically anisotropic layer having an alignment state of the liquid crystal compound fixed thereon is formed on the composition layer (corresponding to step 5D). An optical film (F-3) was produced in the above-described manner.
In addition, the molar absorption coefficient at 365nm of the photopolymerization initiator (Irgacure 907) was 140L/(mol. Cm).
The optical film (F-3) produced in the above manner was cut parallel to the rubbing direction, and the optically anisotropic layer was observed from the cross-sectional direction by a polarized light microscope. The thickness of the optically anisotropic layer was 2.7. Mu.m, the liquid crystal compound was uniformly aligned in the region (region 2) of the optically anisotropic layer having a thickness of 1.1. Mu.m on the substrate side, and the liquid crystal compound was in an isotropic state (isotropic phase) in the region (region 1) of the optically anisotropic layer having a thickness of 1.6. Mu.m on the air side (opposite side to the substrate).
The optical characteristics of the optical film (F-3) were determined by using Axoscan from Axometrics and Analysis software (Multi-Layer Analysis) from Axometrics. The in-plane retardation (Δn2d2) at a wavelength of 550nm in region 2 is 140nm and the slow axis in-plane is-45 °. The in-plane retardation (Δn1d1) at the wavelength of 550nm in the 1 st region was 0nm, and the retardation in the thickness direction was 0nm.
The angle of the in-plane slow axis was set to 0 ° with respect to the longitudinal direction of the film, and the substrate was observed from the front surface side of the optically anisotropic layer, and was represented as negative in the clockwise direction (right turn) and positive in the counterclockwise direction (left turn).
(production of circular polarizing plate)
In the same manner as in example 1, the optical film (F-3) produced in the above manner was subjected to saponification treatment, and the polarizer protective film were continuously bonded to the substrate surface included in the optical film (F-3) using a polyvinyl alcohol-based adhesive, thereby producing an elongated circular polarizing plate (P-3). Namely, the circularly polarizing plate (P-3) has a polarizer protective film, a polarizer, a substrate, and an optically anisotropic layer in this order.
The absorption axis of the polarizer was aligned with the longitudinal direction of the circularly polarizing plate, and the rotation angle of the slow axis in the 2 nd region with respect to the absorption axis of the polarizer was 45 °.
The rotation angle of the in-plane slow axis is 0 ° with respect to the longitudinal direction of the circularly polarizing plate, the counterclockwise direction is represented by a positive angle value, and the clockwise direction is represented by a negative angle value, when the optically anisotropic layer is viewed from the polarizer side.
Example 4 >
(formation of optically Anisotropic layer)
The cellulose acylate film produced in example 1 was subjected to a rubbing treatment successively. At this time, the longitudinal direction of the long film is parallel to the transport direction, and the angle formed by the longitudinal direction of the film (transport direction) and the rotation axis of the rubbing roller is 90 °.
The composition layer (corresponding to step 1B) was formed by coating the composition (4) for forming an optically anisotropic layer containing a rod-like liquid crystal compound having the following composition using the cellulose acylate film subjected to the rubbing treatment as a substrate using a die coater. In addition, the absolute value of the weighted average helical twisting power of the chiral agent in the composition layer in step 1B was 31. Mu.m -1 。
Subsequently, the obtained composition layer was heated at 100℃for 80 seconds (corresponding to step 2B). The rod-like liquid crystal compound of the composition layer is aligned in a predetermined direction by this heating.
Thereafter, ultraviolet rays were irradiated to the composition layer for 10 seconds (irradiation amount: 100 mJ/cm) at 40℃under an atmosphere containing oxygen (oxygen concentration: about 20 vol.) (manufactured by Acroedge Co., ltd.) using a 365nm LED lamp 2 ) (corresponding to step 3B).
Subsequently, the obtained composition layer was heated at 90℃for 10 seconds (corresponding to step 4B).
Thereafter, nitrogen purging was performed so that the oxygen concentration became 100 ppm by volume, and ultraviolet light was irradiated (irradiation amount: 500 mJ/cm) at 55℃using a metal halide lamp (EYE GRAPHICS Co., ltd.) 2 ) An optically anisotropic layer having an alignment state of the liquid crystal compound fixed thereon is formed on the composition layer (corresponding to step 5B). An optical film (F-4) was produced in the above-described manner.
Further, the molar absorptivity of the sensitizer (KAYACURE DETX) at 365nm was 4200L/(mol.cm).
The optical film (F-4) produced in the above manner was cut parallel to the rubbing direction, and the optically anisotropic layer was observed from the cross-sectional direction by SEM. The optically anisotropic layer had a thickness of 3.6 μm and had a region (region 2) of 1.8 μm on the substrate side of the optically anisotropic layer and a region (region 1) of 1.8 μm on the air side (side opposite to the substrate) of the optically anisotropic layer, and the region 2 and the region 1 were respectively cholesterol orientations of different helical pitches.
Further, the spectral reflectance characteristics of the optical film (F-4) were obtained using an integrated reflectance meter. It was confirmed that the cholesteric liquid crystal film had a reflection band centered at 450nm from the 2 nd region and a reflection band centered at 650nm from the 1 st region.
Comparative example 1 >
In the same manner as in example 1 except that irradiation was performed under nitrogen purging (oxygen concentration 100 vol ppm) using a 365nm LED lamp instead of performing irradiation based on a 365nm LED lamp under air containing oxygen (oxygen concentration: about 20 vol%), an optical film (C-1) was produced in the same manner as in the production method of the optical film (F-1). That is, in comparative example 1, step 3A was not performed.
In addition, as a result of observing the cross section of the optically anisotropic layer in the same manner as in example 1, uniform orientation was formed throughout the entire region in the thickness direction of the obtained optically anisotropic layer, and the desired effect of the present invention was not obtained.
Comparative example 2 >
In the foregoing example 1, an optical film (C-2) was produced in the same manner as the production method of the optical film (F-1), except that irradiation was performed at 40℃using a 365nm LED lamp and then irradiation was performed at 40℃using a metal halide lamp without heating to 80 ℃. That is, in comparative example 2, step 4A was not performed.
In addition, as a result of observing the cross section of the optically anisotropic layer in the same manner as in example 1, uniform orientation was formed throughout the entire region in the thickness direction of the obtained optically anisotropic layer, and the desired effect of the present invention was not obtained.
Comparative example 3 >
In example 1, the irradiation conditions in step 3A were changed to those of 365nm LED lamp irradiation for 100 seconds (irradiation amount: 13 mJ/cm) 2 ) Except for this, an optical film (C-3) was produced in the same manner as the production method of the optical film (F-1). That is, in comparative example 3, the irradiation amount was the same as that of example 1, but the irradiation time was prolonged.
Further, as a result of observing the cross section of the optically anisotropic layer in the same manner as in example 1, a twisted orientation was formed over the entire region in the thickness direction of the obtained optically anisotropic layer, and the desired effect of the present invention was not obtained.
The in-plane retardation Re (λ) at the wavelength λ of the optical anisotropic layer produced was measured using Axoscan manufactured by Axometrics corporation. The results are shown in table 1.
Production of organic EL display device and evaluation of display Performance
(mounting on a display device)
Samsung Electronics Co., ltd. GALAXY S4, which is a laminate of an organic EL panel, is decomposed, and the circularly polarizing plates (P-1) to (P-3) produced in the above examples are peeled off, and then the circularly polarizing plates are bonded to a display device so that a polarizer protective film is disposed outside.
(evaluation of display Performance)
(front direction)
Black was displayed on the produced organic EL display device, and the color was evaluated based on the following criteria when viewed from the front under bright light. The results are shown in table 1.
4: the coloration is completely invisible. (allow)
3: although slightly visibly colored, it was slightly colored. (allow)
2: the color was visible, but the reflected light was small and there was no problem in use. (allow)
1: the visible coloration, the reflected light is also large and not permissible.
(oblique direction)
Black was displayed on the organic EL display device thus fabricated, and a fluorescent lamp was projected under bright light from a polar angle of 45 °, and reflected light was observed from all directions. The azimuth dependence of the hue change was evaluated on the following criteria. The results are shown in table 1.
4: the color difference is completely invisible. (allow)
3: although chromatic aberration is visible, it is very slight. (allow)
2: the color difference is visible, but the reflected light is small, and no problem exists in use. (allow)
1: the visible color difference, the reflected light is also large and cannot be allowed.
In table 1, "in-plane retardation" means in-plane retardation at each wavelength of the optically anisotropic layer.
TABLE 1
As shown in table 1, it was confirmed that the retardation of the optically anisotropic layer in each example exhibited inverse wavelength dispersion, and when the optically anisotropic layer was used in an organic EL display device, coloring and reflection were suppressed.
< evaluation of display Performance of liquid Crystal display device >)
(production of circular polarizing plate)
The optical film (F-1) produced in the above manner is subjected to saponification treatment, and the polarizer protective film are bonded to a substrate surface included in the optical film (F-1) using a polyvinyl alcohol-based adhesive, thereby producing a circularly polarizing plate (P-4). At this time, the polarizer was bonded so that the angle formed between the absorption axis of the polarizer and the longitudinal direction of the optical film (F-1) became 90 degrees. That is, the rotation angle of the in-plane slow axis of the 2 nd region with respect to the absorption axis of the polarizer was 100 °, and the rotation angle of the in-plane slow axis of the surface of the 1 st region on the opposite side from the 2 nd region side with respect to the absorption axis of the polarizer was 175 °.
The rotation angle of the slow axis in the plane is 0 ° with respect to the absorption axis direction of the polarizer, the counterclockwise direction is represented by a positive angle value, and the clockwise direction is represented by a negative angle value, when the optically anisotropic layer is viewed from the polarizer side.
(production of liquid Crystal display device 1)
The VA mode transflective liquid crystal display device 1 was fabricated as follows. Polyimide was used for the alignment film of the liquid crystal cell, the cell gap of the transmissive portion was set to 4.0 μm, and the cell gap of the reflective portion was set to 2.0 μm. A nematic liquid crystal having negative dielectric anisotropy is injected into the spacers. When no voltage is applied to the upper and lower substrates of the liquid crystal cell, the nematic liquid crystal is vertically aligned. When a voltage is applied, protrusions are formed on the cell substrate so that the nematic liquid crystal is tilted in 2 directions having directions 180 ° different from each other. The transmission portion having an in-plane retardation at a wavelength of 550nm when a voltage is applied to the liquid crystal cell and white is displayed is 280nm and the reflection portion is 140nm, and the transmission portion having an in-plane retardation at a wavelength of 550nm when black is displayed in a state where no voltage is applied is 0nm and the reflection portion is 0nm.
The circularly polarizing plate (P-1) and the circularly polarizing plate (P-4) thus produced were bonded to a liquid crystal cell comprising the upper and lower substrates and a liquid crystal layer sandwiched between the substrates, thereby producing a semi-transmissive liquid crystal display device 1. In this case, a circularly polarizing plate (P-1), a liquid crystal cell, a circularly polarizing plate (P-4), and a backlight are arranged in this order from the observer side. And, configured as follows: the circular polarizer (P-1) is a polarizer and an optical film (F-1) in order from the observer side, the circular polarizer (P-4) is an optical film (F-1) and a polarizer in order from the observer side, and the angle formed by the absorption axes of the polarizers included in the circular polarizer (P-1) and the circular polarizer (P-4) is 90 degrees. When the nematic liquid crystal sandwiched between the upper and lower substrates is tilted, the rotation angle of the direction (in-plane slow axis) in which the long axis of the nematic liquid crystal is projected onto the unit substrate is 45 °.
The rotation angle of the liquid crystal cell in the direction of projection (in-plane slow axis) was 0 ° with respect to the absorption axis direction of the polarizer, and the counterclockwise direction was represented by a positive angle value and the clockwise direction was represented by a negative angle value, when the liquid crystal cell was observed from the circular polarizer (P-1) side.
(production of circular polarizing plate)
An alignment film was formed on a cellulose acylate film in the same manner as described in example 1 or example 25 of japanese patent 6770649, and an optically anisotropic layer H composed of a discotic liquid crystal compound or an optically anisotropic layer Q composed of a rod-like liquid crystal compound was further produced thereon. At this time, the thickness and the rubbing angle of the coating layer were adjusted to become the following retardation and slow axis angle. The in-plane retardation of the optically anisotropic layer H at 550nm was 280nm, and the in-plane retardation of the optically anisotropic layer Q at 550nm was 120nm.
Next, a circularly polarizing plate (P-5) was produced by bonding the optically anisotropic layer Q, the optically anisotropic layer H, the polarizer and the polarizer protective film in this order with an adhesive. At this time, the cellulose acylate film and the alignment film are peeled off from the optically anisotropic layer H and the optically anisotropic layer Q, and are not included in the circularly polarizing plate. The bonding was performed so that the rotation angle of the in-plane slow axis of the optically anisotropic layer H with respect to the absorption axis of the polarizer became-75 ° and the rotation angle of the in-plane slow axis of the optically anisotropic layer Q with respect to the absorption axis of the polarizer became-15 °.
The rotation angle of the slow axis in the plane is 0 ° with respect to the absorption axis direction of the polarizer, the counterclockwise direction is represented by a positive angle value, and the clockwise direction is represented by a negative angle value, when the optically anisotropic layer is viewed from the polarizer side.
(production of liquid Crystal display device 2)
The semi-transmissive liquid crystal display device 2 of the ECB mode was fabricated as follows. Polyimide was used for the alignment film of the liquid crystal cell, and the rubbing direction was made to be parallel up and down. The cell gap of the transmissive portion was 4.0 μm, the cell gap of the reflective portion was 2.0 μm, and a nematic liquid crystal having positive dielectric anisotropy was injected into the spacer portion. The transmission portion for displaying white was 280nm, the reflection portion for displaying white was 140nm, the transmission portion for displaying black was 40nm, and the reflection portion for displaying black was 20nm, which were delayed in-plane at a wavelength of 550nm when a voltage was applied to the liquid crystal cell. When the nematic liquid crystal sandwiched between the upper and lower substrates is tilted by applying a voltage, the direction in which the long axis of the nematic liquid crystal is projected onto the unit substrate (in-plane slow axis) coincides with the rubbing direction.
The circularly polarizing plate (P-1) and the circularly polarizing plate (P-5) thus produced were bonded to a liquid crystal cell comprising the upper and lower substrates and a liquid crystal layer sandwiched between the substrates, thereby producing a semi-transmissive liquid crystal display device 2. In this case, a circularly polarizing plate (P-5), a liquid crystal cell, a circularly polarizing plate (P-1), and a backlight are arranged in this order from the observer side. And, configured as follows: the circular polarizer (P-5) is a polarizer, an optically anisotropic layer H and an optically anisotropic layer Q in this order from the observer side, and the circular polarizer (P-1) is an optical film (F-1) and a polarizer in this order from the observer side. And, configured as follows: the angle formed by the absorption axes of the polarizers included in the circular polarizer (P-5) and the circular polarizer (P-1) is 90 DEG, and the angle formed by the rubbing direction applied to the alignment film of the liquid crystal cell and the in-plane slow axis direction of the optically anisotropic layer Q included in the circular polarizer (P-5) is 0 deg.
(evaluation of display Performance)
The applied voltage was adjusted for the transmissive portion and the reflective portion of the VA-mode transflective liquid crystal display device 1 and the ECB-mode liquid crystal display device 2 manufactured as described above, and the visibility of the display of black and white was visually evaluated. It was confirmed that the optically anisotropic layer of the present embodiment can be preferably used for a liquid crystal display device, since it exhibits a good white/black contrast in any display device.
Example 5 >
(formation of optically Anisotropic layer)
The rubbing treatment was continuously performed on the alignment film produced in example 2. At this time, the longitudinal direction of the long film is parallel to the transport direction, and the angle formed by the longitudinal direction of the film (transport direction) and the rotation axis of the rubbing roller is set to 90 °.
The composition layer (corresponding to step 1C) was formed by applying the composition (5) for forming an optically anisotropic layer containing a rod-like liquid crystal compound having the following composition to the cellulose acylate film with an alignment film subjected to the rubbing treatment as a substrate using a die coater.
Subsequently, the obtained composition layer was heated at 120℃for 80 seconds (corresponding to step 2C). The rod-like liquid crystal compound of the composition layer is aligned in a predetermined direction by this heating.
Thereafter, ultraviolet rays were irradiated to the composition layer for 5 seconds (irradiation amount: 30 mJ/cm) at 40℃under an atmosphere containing oxygen (oxygen concentration: about 20 vol.) (manufactured by Acroedge Co., ltd.) using a 365nm LED lamp 2 ) (corresponding to step 3C).
Subsequently, the obtained composition layer was heated at 90℃for 10 seconds (corresponding to step 4C).
Thereafter, nitrogen purging was performed so that the oxygen concentration became 100 ppm by volume, and ultraviolet light was irradiated (irradiation amount: 500 mJ/cm) at 55℃using a metal halide lamp (EYE GRAPHICS Co., ltd.) 2 ) An optically anisotropic layer having an alignment state of the liquid crystal compound fixed thereon is formed on the composition layer (corresponding to step 5C). An optical film (F-5) was produced in the above-described manner.
Rod-like liquid Crystal Compound (F) [ chemical formula 20]
Rod-like liquid Crystal Compound (G) [ chemical formula 21]
Rod-like liquid Crystal Compound (H) [ chemical formula 22]
Rod-like liquid Crystal Compound (I) [ chemical formula 23]
The optical film (F-5) produced in the above manner was cut parallel to the rubbing direction, and the optically anisotropic layer was observed from the cross-sectional direction by a polarized light microscope. The optically anisotropic layer had a thickness of 4.3 μm and was uniformly oriented in the region (region 2) of the optically anisotropic layer having a thickness of 2.4 μm on the substrate side, and the liquid crystal compound was vertically oriented in the region (region 1) of 1.9 μm on the air side (opposite side to the substrate) of the optically anisotropic layer.
The optical characteristics of the optical film (F-5) were determined using Axoscan from Axometrics and Analysis software (Multi-Layer Analysis) from Axometrics. The in-plane retardation (Δn2d2) at the wavelength of 550nm in the 2 nd region was 130nm, and the angle of the in-plane slow axis with respect to the longitudinal direction of the film was 0 °. The in-plane retardation (Δn1d1) at the wavelength of 550nm in the 1 st region was 0nm, and the retardation in the thickness direction at the wavelength of 550nm in the 1 st region was-100 nm.
The angle of the in-plane slow axis was set to 0 ° with respect to the longitudinal direction of the film.
(production of optical Compensation plate for liquid Crystal display device)
The optical film (F-5) produced in the above manner is subjected to saponification treatment, and the polarizer protective film are continuously bonded to an optically anisotropic layer included in the optical film (F-5) using a polyvinyl alcohol-based adhesive, thereby producing a long polarizing plate (P-6). That is, the polarizing plate (P-6) has a polarizer protective film, a polarizer, an optically anisotropic layer, and a substrate in this order.
The absorption axis of the polarizer was aligned with the longitudinal direction of the polarizing plate, and the rotation angle of the slow axis in the 2 nd region with respect to the absorption axis of the polarizer was 0 °.
The rotation angle of the in-plane slow axis is 0 ° with respect to the longitudinal direction of the polarizer when the optically anisotropic layer is viewed from the polarizer side.
(production of liquid Crystal display device 3)
The front-side polarizing plate was peeled off from a commercially available liquid crystal display device (registered trademark), manufactured by Apple inc. (liquid crystal display device including FFS mode liquid crystal cell), and the polarizing plate (P-6) manufactured as described above was bonded with a 20 μm acrylic adhesive such that the optical film side was disposed on the liquid crystal cell side and such that the absorption axis of the polarizer was orthogonal to the absorption axis of the polarizer in the polarizing plate on the backlight side, thereby manufacturing a liquid crystal display device 3.
(evaluation of display Performance)
The liquid crystal display device 3 manufactured as described above was adjusted in applied voltage, and the visibility in the oblique direction of black display and white display was visually evaluated. It was confirmed that the liquid crystal display device 3 exhibited good white/black contrast, and the optically anisotropic layer of the present embodiment can be preferably used for an optical compensation plate of a liquid crystal display device.
Symbol description
10-substrate, 12, 120, 220, 320, 420-composition layer, 12A, 120A, 220A, 320A, 420A-lower region, 12B, 120B, 220B, 320B, 420B-upper region, 20-optically anisotropic layer, 22-other optically anisotropic layer, 24-stack, 26-polarizer, 28-polarizer-bearing optically anisotropic layer.
Claims (8)
1. A method of manufacturing an optically anisotropic layer, comprising:
a step 1 of forming a composition layer containing a liquid crystal compound having a polymerizable group;
a step 2 of subjecting the composition layer to a heat treatment to orient the liquid crystal compound in the composition layer;
step 3 of forming a composition layer of 300mJ/cm on the substrate under the condition that the oxygen concentration is 1% by volume or more after the step 2 2 The irradiation with light is performed for 50 seconds or less;
a step 4 of performing a heat treatment on the composition layer at a temperature higher than that at the time of the light irradiation after the step 3; a kind of electronic device with high-pressure air-conditioning system
And a step 5 of forming an optically anisotropic layer having a plurality of regions in which the alignment states of the liquid crystal compounds are different in the thickness direction by subjecting the composition layer to a curing treatment after the step 4.
2. The method for producing an optically anisotropic layer according to claim 1, wherein,
the composition layer includes a photosensitive material selected from the group consisting of photopolymerization initiators and photosensitizers,
the molar absorptivity of the photosensitive material at the wavelength of light irradiation in the step 3 is 5000L/(mol cm) or less.
3. The method for producing an optically anisotropic layer according to claim 1 or 2, wherein,
the composition layer comprises a chiral agent,
the chiral agent includes a photosensitive chiral agent whose helical twisting power is changed by light irradiation.
4. The method for producing an optically anisotropic layer according to claim 3, wherein,
the total content of the chiral agents is 5.0 mass% or less relative to the total mass of the liquid crystal compound.
5. The method for producing an optically anisotropic layer according to claim 3, wherein,
the total content of the chiral agents exceeds 5.0 mass% relative to the total mass of the liquid crystal compound.
6. The method for producing an optically anisotropic layer according to claim 1 or 2, wherein,
the composition layer contains a photosensitive compound whose polarity is changed by light irradiation.
7. The method for producing an optically anisotropic layer according to claim 6, wherein,
the photosensitive compound is a photosensitive compound hydrophilized by light irradiation.
8. The method for producing an optically anisotropic layer according to claim 1 or 2, wherein,
the temperature of the heat treatment in the step 4 is a temperature equal to or higher than a temperature at which the liquid crystal compound becomes an isotropic phase.
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| JP2020-132348 | 2020-08-04 | ||
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| JP2021040068 | 2021-03-12 | ||
| JP2021-112885 | 2021-07-07 | ||
| JP2021112885 | 2021-07-07 | ||
| PCT/JP2021/027346 WO2022030266A1 (en) | 2020-08-04 | 2021-07-21 | Method for manufacturing optically anisotropic layer |
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| JP2004145071A (en) * | 2002-10-25 | 2004-05-20 | Fuji Photo Film Co Ltd | Optical retardation plate and its manufacturing method |
| JP2010112986A (en) * | 2008-11-04 | 2010-05-20 | Konica Minolta Opto Inc | Method for producing optical film, optical film production device, optical film and liquid crystal display |
| US9128322B2 (en) | 2013-03-25 | 2015-09-08 | Fujifilm Corporation | Phase difference plate for circularly polarizing plate, circularly polarizing plate, and organic electroluminescence display apparatus |
| JP2014199359A (en) * | 2013-03-29 | 2014-10-23 | 富士フイルム株式会社 | Optical film for three-dimensional (3d) image display device and method for producing the same, polarizing plate, and 3d image display device |
| WO2015005122A1 (en) * | 2013-07-08 | 2015-01-15 | 富士フイルム株式会社 | Optical film, polarizer, image display device, and optical-film manufacturing device |
| JP2015087472A (en) | 2013-10-29 | 2015-05-07 | 日本ゼオン株式会社 | Production method of article, and counterfeit preventive medium |
| JP6954288B2 (en) * | 2016-08-09 | 2021-10-27 | Jnc株式会社 | Polymerizable liquid crystal compositions and liquid crystal polymers |
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