JP2017102259A - Optical rotatory film - Google Patents
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Abstract
Description
本発明は、旋光フィルムに関する。 The present invention relates to an optical rotatory film.
旋光フィルムは、ある方向の直線偏光を別の方向に変換(旋光)することができる機能を有しており、種々の用途に適用されている。
例えば、特許文献1においては、所定の捩れ角で配向した液晶化合物からなる旋光フィルムが開示されている。
The optical rotatory film has a function of converting (polarizing) linearly polarized light in one direction into another direction, and is applied to various uses.
For example, Patent Document 1 discloses an optical rotatory film made of a liquid crystal compound aligned at a predetermined twist angle.
一方、近年、旋光フィルムが用いられる用途においては、旋光性が優れるのみならず、斜め方向から視認した際の色づきのより一層の抑制が求められている。なお、後段で詳述するが、上記旋光性は、バックライト上に配置された2枚の偏光子間に旋光フィルムを配置して、正面輝度(旋光フィルムを正面方向から視認した際の輝度)を測定することにより評価することができる。また、上記色づきとは、正面方向と斜め方向とで色差があることを意図する。
本発明者らは、従来公知の旋光フィルムの性能評価を行ったところ、特に、斜め方向から視認した際の色づきの点で、昨今の要求レベルを満たしておらず、更なる改良が必要であることを知見している。
On the other hand, in recent years, in applications in which an optical rotation film is used, not only is optical rotation excellent, but further suppression of coloring when viewed from an oblique direction is required. In addition, although it explains in full detail behind, the said optical rotation property arrange | positions an optical rotatory film between the two polarizers arrange | positioned on a backlight, front luminance (luminance when viewing the optical rotatory film from the front direction) It can be evaluated by measuring. Further, the coloring is intended to have a color difference between the front direction and the diagonal direction.
When the present inventors performed performance evaluation of a conventionally known optical rotatory film, in particular, in view of coloring when viewed from an oblique direction, the present requirement level is not satisfied, and further improvement is necessary. I know that.
本発明は、上記実情に鑑みて、旋光性に優れると共に、斜め方向から視認した際にも色づきが抑制された旋光フィルムを提供することを目的とする。 In view of the above circumstances, an object of the present invention is to provide an optical rotatory film that is excellent in optical rotatory power and is suppressed in coloring even when viewed from an oblique direction.
本発明者らは、従来技術の問題点について鋭意検討した結果、捩れ配向した液晶化合物を含む位相差層を用いることにより、上記課題を解決できることを見出した。
すなわち、以下の構成により上記目的を達成することができることを見出した。
As a result of intensive studies on the problems of the prior art, the present inventors have found that the above problem can be solved by using a retardation layer containing a twisted liquid crystal compound.
That is, it has been found that the above object can be achieved by the following configuration.
(1) 第1位相差層と、第2位相差層とを有する旋光フィルムであって、
第1位相差層および第2位相差層の少なくとも一方は、その厚み方向に沿って延びる螺旋軸に沿って捩れ配向した液晶化合物を含み、
第1位相差層の第2位相差層側の表面での面内遅相軸と、第2位相差層の第1位相差層側の表面での面内遅相軸とのなす角が0〜15°であり、
第1位相差層の波長550nmにおける厚み方向のレタデーション値、および、第2位相差層の波長550nmにおける厚み方向のレタデーション値の一方が負の値であり、かつ、他方が正の値であり、
波長550nmで測定した第1位相差層の屈折率異方性Δn1と第1位相差層の厚みd1との積Δn1d1、および、波長550nmで測定した第2位相差層の屈折率異方性Δn2と第2位相差層の厚みd2との積Δn2d2のうち値が大きい方をΔnd・maxとし、値の小さい方をΔnd・minとした場合、Δnd・min/Δnd・maxの範囲が0.06〜0.8である、旋光フィルム。
(2) 第1位相差層および第2位相差層のうち捩れ配向した液晶化合物を含む層Xにおいて、
波長550nmで測定した層Xの屈折率異方性Δnと層Xの厚みdとの積Δndと、液晶化合物の捩れ角θとの比であるΔnd/θが、4.1〜6.1である、(1)に記載の旋光フィルム。
(3) 第1位相差層および第2位相差層の両方が、その厚み方向に沿って延びる螺旋軸に沿って捩れ配向した液晶化合物を含む、(1)または(2)に記載の旋光フィルム。
(4) 第1位相差層および第2位相差層の一方の層に含まれる液晶化合物の捩れ角が67.5±10°の範囲であり、
第1位相差層および第2位相差層の他方の層に含まれる液晶化合物の捩れ角が22.5±10°の範囲である、(3)に記載の旋光フィルム。
(5) Δn1d1とΔn2d2との合計が、400〜520nmである、(1)〜(4)のいずれかに記載の旋光フィルム。
(6) Δnd・min/Δnd・maxの範囲が0.08〜0.50である、(1)〜(5)のいずれかに記載の旋光フィルム。
(7) Δnd・min/Δnd・maxの範囲が0.10〜0.35である、(1)〜(6)のいずれかに記載の旋光フィルム。
(1) An optical rotation film having a first retardation layer and a second retardation layer,
At least one of the first retardation layer and the second retardation layer includes a liquid crystal compound that is twist-aligned along a helical axis extending along the thickness direction thereof.
The angle formed by the in-plane slow axis on the surface of the first retardation layer on the second retardation layer side and the in-plane slow axis on the surface of the second retardation layer on the first retardation layer side is 0. ~ 15 °,
One of the retardation value in the thickness direction at a wavelength of 550 nm of the first retardation layer and the retardation value in the thickness direction at a wavelength of 550 nm of the second retardation layer is a negative value, and the other is a positive value,
The product Δn1d1 of the refractive index anisotropy Δn1 of the first retardation layer measured at a wavelength of 550 nm and the thickness d1 of the first retardation layer, and the refractive index anisotropy Δn2 of the second retardation layer measured at a wavelength of 550 nm Of the product Δn2d2 of the second retardation layer and the thickness d2 of the second retardation layer is Δnd · max, and the smaller value is Δnd · min, the range of Δnd · min / Δnd · max is 0.06. An optical rotatory film that is -0.8.
(2) In the layer X containing the twisted liquid crystal compound in the first retardation layer and the second retardation layer,
Δnd / θ, which is the ratio between the product Δnd of the refractive index anisotropy Δn of the layer X measured at a wavelength of 550 nm and the thickness d of the layer X, and the twist angle θ of the liquid crystal compound is 4.1 to 6.1. The optical rotation film according to (1).
(3) The optical rotatory film according to (1) or (2), wherein both the first retardation layer and the second retardation layer include a liquid crystal compound that is twisted and aligned along a helical axis extending along a thickness direction thereof. .
(4) The twist angle of the liquid crystal compound contained in one of the first retardation layer and the second retardation layer is in the range of 67.5 ± 10 °,
The optical rotation film according to (3), wherein the twist angle of the liquid crystal compound contained in the other of the first retardation layer and the second retardation layer is in the range of 22.5 ± 10 °.
(5) The optical rotation film according to any one of (1) to (4), wherein the sum of Δn1d1 and Δn2d2 is 400 to 520 nm.
(6) The optical rotation film according to any one of (1) to (5), wherein the range of Δnd · min / Δnd · max is 0.08 to 0.50.
(7) The optical rotation film according to any one of (1) to (6), wherein the range of Δnd · min / Δnd · max is 0.10 to 0.35.
本発明によれば、旋光性に優れると共に、斜め方向から視認した際にも色づきが抑制された旋光フィルムを提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, while being excellent in optical rotation property, when it visually recognizes from the diagonal direction, the optical rotation film by which coloring was suppressed can be provided.
以下、本発明について説明する。なお、本明細書において「〜」を用いて表される数値範囲は、「〜」の前後に記載される数値を下限値および上限値として含む範囲を意味する。まず、本明細書で用いられる用語について説明する。 The present invention will be described below. In the present specification, a numerical range represented by using “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 this specification will be described.
Re(λ)、Rth(λ)は、各々、波長λにおける面内のレタデーション値、および、厚さ方向のレタデーション値を表す。Re(λ)、Rth(λ)、Δndは、AXOSCAN(AXOMETRICS社製)で測定する。 Re (λ) and Rth (λ) represent the in-plane retardation value at the wavelength λ and the retardation value in the thickness direction, respectively. Re (λ), Rth (λ), and Δnd are measured by AXOSCAN (manufactured by AXOMETRICS).
なお、本明細書では、測定波長について特に付記がない場合は、測定波長は550nmである。
また、本明細書において、角度の関係(「直交」、「平行」)については、本発明が属する技術分野において許容される誤差の範囲を含むものとする。具体的には、厳密な角度±10°未満の範囲内であることを意味し、厳密な角度との誤差は、5°以下が好ましく、3°以下がより好ましい。
In addition, in this specification, when there is no special mention about a measurement wavelength, a measurement wavelength is 550 nm.
In the present specification, the relationship between angles (“orthogonal”, “parallel”) includes a range of errors allowed in the technical field to which the present invention belongs. Specifically, it means that the angle is within a range of strict angle ± 10 °, and the error from the strict angle is preferably 5 ° or less, and more preferably 3 ° or less.
以下において、本発明の旋光フィルムの好適態様について詳述する。
本発明の旋光フィルムは、捩れ配向した液晶化合物を含む位相差層を少なくとも1層含む2層型の旋光フィルムである。その特徴点の一つとしては、旋光フィルムに含まれる、第1位相差層のΔndと第2位相差層のΔndとの比を所定の範囲に調整した点が挙げられる。
より具体的には、斜め方向での視野角特性を改良する方法として位相差層のRthに着目する考え方もあるが、本発明者らは旋光フィルムにおいてはこの考え方が適用できないことを見出し、第1位相差層のΔndと第2位相差層のΔndとの比を所定の範囲に調整することにより、所望の効果が得られることを見出している。
Below, the suitable aspect of the optical rotation film of this invention is explained in full detail.
The optical rotatory film of the present invention is a two-layer optical rotatory film including at least one retardation layer including a twisted liquid crystal compound. One of the characteristic points is that the ratio of Δnd of the first retardation layer and Δnd of the second retardation layer included in the optical rotation film is adjusted to a predetermined range.
More specifically, there is an idea that pays attention to Rth of the retardation layer as a method for improving the viewing angle characteristics in the oblique direction, but the present inventors have found that this idea cannot be applied to an optical rotation film. It has been found that a desired effect can be obtained by adjusting the ratio of Δnd of the first retardation layer and Δnd of the second retardation layer to a predetermined range.
<第1の実施態様>
以下に、本発明の旋光フィルムの第1の実施態様について図面を参照して説明する。図1に、本発明の旋光フィルムの第1の実施態様の概略断面図を示す。
旋光フィルム10aは、第1位相差層12aと、第2位相差層14aとを有する。第1位相差層12aおよび第2位相差層14aは、それぞれ、その厚み方向に沿って延びる螺旋軸に沿って捩れ配向した液晶化合物(厚み方向を螺旋軸とする捩れ配向した液晶化合物)を含む。
なお、液晶化合物が捩れ配向するとは、第1位相差層12a(または、第2位相差層14a)の厚み方向を軸(螺旋軸)として、第1位相差層12a(または、第2位相差層14a)の一方の主表面から他方の主表面までの液晶化合物が捩れることを意図する。それに伴い、液晶化合物の配向方向(面内遅相軸方向)が、第1位相差層12a(または、第2位相差層14a)の厚さ方向の位置によって異なる。
第1位相差層12aおよび第2位相差層14aは、いわゆる螺旋構造を持ったキラルネマチック相、コレステリック相などを示すことが好ましい。液晶化合物については後段で詳述するが、第1位相差層12aおよび第2位相差層14aで使用される液晶化合物としては、ネマチック液晶相を示す液晶化合物が好ましく用いられる。なお、上記相を形成する際には、ネマチック液晶相を示す液晶化合物と後述するキラル剤とを混合したものが使用されることが好ましい。
<First Embodiment>
Below, the 1st embodiment of the optical rotation film of this invention is demonstrated with reference to drawings. In FIG. 1, the schematic sectional drawing of the 1st embodiment of the optical rotation film of this invention is shown.
The optical rotatory film 10a includes a first retardation layer 12a and a second retardation layer 14a. The first retardation layer 12a and the second retardation layer 14a each include a liquid crystal compound that is twisted and aligned along a helical axis that extends along the thickness direction (a liquid crystal compound that is twisted and aligned with the thickness direction being a helical axis). .
Note that the twisted orientation of the liquid crystal compound means that the thickness direction of the first retardation layer 12a (or the second retardation layer 14a) is the axis (spiral axis) and the first retardation layer 12a (or the second retardation layer). It is intended that the liquid crystal compound from one main surface of the layer 14a) to the other main surface is twisted. Accordingly, the alignment direction (in-plane slow axis direction) of the liquid crystal compound varies depending on the position in the thickness direction of the first retardation layer 12a (or the second retardation layer 14a).
The first retardation layer 12a and the second retardation layer 14a preferably exhibit a chiral nematic phase having a so-called helical structure, a cholesteric phase, or the like. The liquid crystal compound will be described in detail later, but as the liquid crystal compound used in the first retardation layer 12a and the second retardation layer 14a, a liquid crystal compound exhibiting a nematic liquid crystal phase is preferably used. In addition, when forming the said phase, it is preferable to use what mixed the liquid crystal compound which shows a nematic liquid crystal phase, and the chiral agent mentioned later.
次に、図2を用いて、第1位相差層12aおよび第2位相差層14a中の面内遅相軸の関係について詳述する。図2に示す各層中の黒矢印は、面内遅相軸を意図する。
第1位相差層12a中の液晶化合物の捩れ方向と、第2位相差層14a中の液晶化合物の捩れ方向とは、同一である。例えば、第1位相差層12a中の液晶化合物が捩れ方向が右捩れであれば、第2位相差層14a中の液晶化合物の捩れ方向も右捩れとなる。図2において、第1位相差層12aおよび第2位相差層14aのいずれも右捩れを示すが、両者が左捩れであってもよい。
なお、第1位相差層12a中の液晶化合物の捩れ方向は、図2中の白抜き矢印で示すように、第1位相差層12a側から旋光フィルム10aを観察し、第1位相差層12a中の手前側(第2位相差層14a側とは反対側)の表面112aでの面内遅相軸を基準に右捩れ(時計回り)か、左捩れ(反時計回り)を判断する。また、第2位相差層14a中の液晶化合物の捩れ方向も、上記と同様に、第1位相差層12a側から旋光フィルム10aを観察し、第2位相差層14a中の手前側(第1位相差層12a側)の表面114aでの面内遅相軸を基準に右捩れ(時計回り)か、左捩れ(反時計回り)を判断する。
Next, the relationship between the in-plane slow axes in the first retardation layer 12a and the second retardation layer 14a will be described in detail with reference to FIG. The black arrow in each layer shown in FIG. 2 intends the in-plane slow axis.
The twist direction of the liquid crystal compound in the first retardation layer 12a and the twist direction of the liquid crystal compound in the second retardation layer 14a are the same. For example, if the twist direction of the liquid crystal compound in the first retardation layer 12a is right twist, the twist direction of the liquid crystal compound in the second retardation layer 14a is also right twist. In FIG. 2, both the first retardation layer 12a and the second retardation layer 14a show a right twist, but both may be a left twist.
Note that the twist direction of the liquid crystal compound in the first retardation layer 12a is observed from the optical retardation film 10a from the first retardation layer 12a side, as indicated by the white arrow in FIG. 2, and the first retardation layer 12a. A right twist (clockwise) or a left twist (counterclockwise) is determined on the basis of the in-plane slow axis on the surface 112a on the front side (the opposite side to the second retardation layer 14a side). Similarly to the above, the twist direction of the liquid crystal compound in the second retardation layer 14a is also observed on the optical rotation film 10a from the first retardation layer 12a side, and the front side in the second retardation layer 14a (first side) A right twist (clockwise) or a left twist (counterclockwise) is determined based on the in-plane slow axis on the surface 114a of the phase difference layer 12a side.
第1位相差層12aの第2位相差層14a側の表面212aでの面内遅相軸と、第2位相差層14aの第1位相差層12a側の表面114aでの面内遅相軸とのなす角θは0〜15°である。なお、図2においては、第1位相差層12aの第2位相差層14a側の表面212aでの面内遅相軸と、第2位相差層14aの第1位相差層12a側の表面114aでの面内遅相軸とが平行である(つまり、なす角が0°である)態様を示す。
上記なす角θの好適範囲は、本発明の効果がより優れる点で、0〜10°が好ましく、0〜5°がより好ましい。
An in-plane slow axis on the surface 212a of the first retardation layer 12a on the second retardation layer 14a side, and an in-plane slow axis on the surface 114a of the second retardation layer 14a on the first retardation layer 12a side. The angle θ formed by In FIG. 2, the in-plane slow axis on the surface 212a of the first retardation layer 12a on the second retardation layer 14a side, and the surface 114a of the second retardation layer 14a on the first retardation layer 12a side. 2 shows a mode in which the in-plane slow axis at is parallel (that is, the angle formed is 0 °).
The preferred range of the angle θ is preferably 0 to 10 °, more preferably 0 to 5 °, in that the effect of the present invention is more excellent.
第1位相差層12a中の液晶化合物の捩れ角θ1および第2位相差層14a中の液晶化合物の捩れ角θ2の範囲は特に制限されず、直線偏光を旋光させたい程度によって異なるが、旋光フィルムによって直線偏光を90°旋光させる場合、捩れ角θ1および捩れ角θ2の合計値は、60〜120°が好ましく、80〜100°がより好ましい。
また、直線偏光を90°旋光させる場合、捩れ角θ1および捩れ角θ2の一方の範囲は20〜115°が好ましく、他方の範囲は5〜40°が好ましい。なかでも、捩れ角θ1および捩れ角θ2の一方の範囲は67.5±10°がより好ましく、他方の範囲は22.5±10°がより好ましい。
なお、捩れ角θ1は、第1位相差層12aの第2位相差層14a側とは反対側の表面112aでの面内遅相軸と、第1位相差層12aの第2位相差層14a側の表面212aでの面内遅相軸とのなす角に相当し、捩れ角θ2は、第2位相差層14aの第1位相差層12a側の表面114aでの面内遅相軸と、第2位相差層14aの第1位相差層12a側とは反対側の表面214aでの面内遅相軸とのなす角に相当する。
また、捩れ角(液晶化合物の配向方向の捩れ角)の測定方法は、Axometrics社のAxoscan(ポラリメーター)装置を用い、付属の装置解析ソフトウエアを用いて測定する。
The ranges of the twist angle θ1 of the liquid crystal compound in the first retardation layer 12a and the twist angle θ2 of the liquid crystal compound in the second retardation layer 14a are not particularly limited, and vary depending on the degree of rotation of linearly polarized light. When the linearly polarized light is rotated by 90 °, the total value of the twist angle θ1 and the twist angle θ2 is preferably 60 to 120 °, and more preferably 80 to 100 °.
When linearly polarized light is rotated by 90 °, one range of the twist angle θ1 and the twist angle θ2 is preferably 20 to 115 °, and the other range is preferably 5 to 40 °. In particular, one range of the twist angle θ1 and the twist angle θ2 is more preferably 67.5 ± 10 °, and the other range is more preferably 22.5 ± 10 °.
The twist angle θ1 is determined by the in-plane slow axis on the surface 112a of the first retardation layer 12a opposite to the second retardation layer 14a, and the second retardation layer 14a of the first retardation layer 12a. The twist angle θ2 corresponds to an angle formed with the in-plane slow axis on the surface 212a on the side, and the in-plane slow axis on the surface 114a on the first retardation layer 12a side of the second retardation layer 14a, This corresponds to the angle formed by the in-plane slow axis on the surface 214a on the opposite side of the second retardation layer 14a from the first retardation layer 12a side.
The twist angle (twist angle in the alignment direction of the liquid crystal compound) is measured using an Axoscan (polarimeter) apparatus manufactured by Axometrics, using the attached apparatus analysis software.
第1位相差層12aの波長550nmにおける厚み方向のレタデーション値(Rth(550))、および、第2位相差層14aの波長550nmにおける厚み方向のレタデーション値(Rth(550))の一方は負の値であり、かつ、第1位相差層12aの波長550nmにおける厚み方向のレタデーション値、および、第2位相差層14aの波長550nmにおける厚み方向のレタデーション値の他方は正の値である。
上述したように、第1位相差層12aおよび第2位相差層14aの両方には、液晶化合物が含まれており、Rth(550)が正の値を示す層では棒状液晶化合物が含まれることが好ましく、Rth(550)が負の値を示す層では円盤状液晶化合物が含まれることが好ましい。
One of the retardation value (Rth (550)) in the thickness direction at a wavelength of 550 nm of the first retardation layer 12a and the retardation value (Rth (550)) in the thickness direction at a wavelength of 550 nm of the second retardation layer 14a are negative. And the other of the retardation value in the thickness direction at the wavelength 550 nm of the first retardation layer 12a and the retardation value in the thickness direction at the wavelength 550 nm of the second retardation layer 14a is a positive value.
As described above, both the first retardation layer 12a and the second retardation layer 14a contain a liquid crystal compound, and the layer in which Rth (550) shows a positive value contains a rod-like liquid crystal compound. The layer in which Rth (550) shows a negative value preferably contains a discotic liquid crystal compound.
第1位相差層12aのRth(550)および第2位相差層14aのRth(550)の範囲は特に制限されないが、旋光性がより優れる、および/または、色づきがより抑制される点(以後、単に「本発明の効果がより優れる点」とも称する)で、第1位相差層12aのRth(550)の絶対値および第2位相差層14aのRth(550)の絶対値の合計は150〜300nmが好ましく、200〜250nmがより好ましい。
また、本発明の効果がより優れる点で、第1位相差層12aのRth(550)の絶対値および第2位相差層14aのRth(550)の絶対値の一方の範囲は、5〜100nmが好ましく、30〜70nmがより好ましい。
また、本発明の効果がより優れる点で、第1位相差層12aのRth(550)の絶対値および第2位相差層14aのRth(550)の絶対値の他方の範囲は、50〜295nmが好ましく、130〜210nmがより好ましい。
The ranges of Rth (550) of the first retardation layer 12a and Rth (550) of the second retardation layer 14a are not particularly limited. However, the optical rotation is more excellent and / or coloring is further suppressed (hereinafter referred to as “coloring”). The sum of the absolute value of Rth (550) of the first retardation layer 12a and the absolute value of Rth (550) of the second retardation layer 14a is 150. ˜300 nm is preferable, and 200 to 250 nm is more preferable.
In addition, in terms of more excellent effects of the present invention, one range of the absolute value of Rth (550) of the first retardation layer 12a and the absolute value of Rth (550) of the second retardation layer 14a is 5 to 100 nm. Is preferable, and 30-70 nm is more preferable.
The other range of the absolute value of Rth (550) of the first retardation layer 12a and the absolute value of Rth (550) of the second retardation layer 14a is 50 to 295 nm in that the effect of the present invention is more excellent. Is preferable, and 130-210 nm is more preferable.
波長550nmで測定した第1位相差層12aの屈折率異方性Δn1と第1位相差層12aの厚みd1との積Δn1d1、および、波長550nmで測定した第2位相差層14aの屈折率異方性Δn2と第2位相差層14aの厚みd2との積Δn2d2のうち値が大きい方をΔnd・maxとし、値の小さい方をΔnd・minとした場合、Δnd・min/Δnd・maxの範囲が0.06〜0.8であり、本発明の効果がより優れる点で、0.08〜0.50が好ましく、0.10〜0.35がより好ましい。
上記Δnd・min/Δnd・maxの範囲が0.06未満および0.8超の場合は、所望の効果が得られない。
なお、屈折率異方性Δnとは、位相差層の屈折率異方性を意味する。
上記Δndの測定方法は、捩れ角の測定方法と同様にAxometrics社のAxoscan(ポラリメーター)装置を用い、同社の装置解析ソフトウエアを用いて測定する。
The product Δn1d1 of the refractive index anisotropy Δn1 of the first retardation layer 12a measured at a wavelength of 550 nm and the thickness d1 of the first retardation layer 12a, and the refractive index difference of the second retardation layer 14a measured at a wavelength of 550 nm. Of the product Δn2d2 of the directivity Δn2 and the thickness d2 of the second retardation layer 14a, the larger value is Δnd · max, and the smaller value is Δnd · min, the range of Δnd · min / Δnd · max Is 0.06 to 0.8, and 0.08 to 0.50 is preferable and 0.10 to 0.35 is more preferable in that the effect of the present invention is more excellent.
When the range of Δnd · min / Δnd · max is less than 0.06 and more than 0.8, a desired effect cannot be obtained.
The refractive index anisotropy Δn means the refractive index anisotropy of the retardation layer.
The Δnd is measured using an Axoscan (polarimeter) apparatus manufactured by Axometrics and using the apparatus analysis software of the same company as the method for measuring the twist angle.
上記Δn1d1および上記Δn2d2の範囲は特に制限されず、上述したΔnd・min/Δnd・maxが所定の範囲であればよいが、旋光フィルムによって直線偏光を90°旋光させる場合、Δn1d1およびΔn2d2の合計値は、400〜520nmが好ましく、430〜490nmがより好ましい。
Δn1d1およびΔn2d2のそれぞれの範囲は特に制限されないが、本発明の効果がより優れる点で、Δn1d1およびΔn2d2の一方の範囲は20〜160nmが好ましく、80〜140nmがより好ましく、他方の範囲は240〜500nmが好ましく、290〜410nmがより好ましい。
The range of Δn1d1 and Δn2d2 is not particularly limited, and the above-described Δnd · min / Δnd · max may be within a predetermined range. Is preferably 400 to 520 nm, and more preferably 430 to 490 nm.
The respective ranges of Δn1d1 and Δn2d2 are not particularly limited, but one of Δn1d1 and Δn2d2 is preferably from 20 to 160 nm, more preferably from 80 to 140 nm, and the other range is from 240 to 240 in that the effects of the present invention are more excellent. 500 nm is preferable and 290 to 410 nm is more preferable.
第1位相差層12aおよび第2位相差層14aはいずれも捩れ配向した液晶化合物を含む層であるが、これらの層のうち少なくとも一方の層Xにおいて、本発明の効果がより優れる点で、波長550nmで測定した層Xの屈折率異方性Δnと層Xの厚みdとの積Δndと、層X中の液晶化合物の捩れ角θ(°)との比であるΔnd/θ(nm/°)は、4.1〜6.1が好ましく、旋光フィルムの旋光性がより優れる点で、4.1超6.1未満がより好ましく、4.5〜5.7がさらに好ましい。
第1位相差層12aおよび第2位相差層14aのうち両方が捩れ配向した液晶化合物を含む層である場合、両者のうちの少なくとも一方が上記Δnd/θの範囲を満たしていることが好ましく、両方がΔnd/θの範囲を満たしていることがより好ましい。
The first retardation layer 12a and the second retardation layer 14a are both layers containing a twisted liquid crystal compound, but in at least one of the layers X, the effect of the present invention is more excellent. Δnd / θ (nm /) which is the ratio of the product Δnd of the refractive index anisotropy Δn of the layer X measured at a wavelength of 550 nm and the thickness d of the layer X to the twist angle θ (°) of the liquid crystal compound in the layer X Is preferably 4.1 to 6.1, more preferably greater than 4.1 and less than 6.1, and even more preferably 4.5 to 5.7 in that the optical rotation of the optical rotation film is more excellent.
When both the first retardation layer 12a and the second retardation layer 14a are layers containing a twisted liquid crystal compound, it is preferable that at least one of the two satisfies the range of Δnd / θ. It is more preferable that both satisfy the range of Δnd / θ.
第1位相差層12aおよび第2位相差層14aの形成に用いられる液晶化合物の種類は、特に制限されない。第1位相差層12aおよび第2位相差層14aとしては、例えば、低分子液晶化合物を液晶状態においてネマチック配向に形成後、光架橋や熱架橋によって固定化して得られる位相差層や、高分子液晶化合物を液晶状態においてネマチック配向に形成後、冷却することによって配向を固定化して得られる位相差層を用いることもできる。 The kind of liquid crystal compound used for forming the first retardation layer 12a and the second retardation layer 14a is not particularly limited. As the first retardation layer 12a and the second retardation layer 14a, for example, a retardation layer obtained by forming a low-molecular liquid crystal compound in a nematic orientation in a liquid crystal state and then fixing it by photocrosslinking or thermal crosslinking, or a polymer It is also possible to use a retardation layer obtained by forming a liquid crystal compound in a nematic alignment in a liquid crystal state and then cooling it to fix the alignment.
一般的に、液晶化合物はその形状から、棒状タイプ(棒状液晶化合物)と円盤状タイプ(円盤状液晶化合物、ディスコティック液晶化合物、)に分類できる。さらにそれぞれ低分子タイプと高分子タイプとがある。高分子とは一般に重合度が100以上のものを指す(高分子物理・相転移ダイナミクス,土井 正男 著,2頁,岩波書店,1992)。本発明では、いずれの液晶化合物を用いることもできる。2種以上の棒状液晶化合物、2種以上の円盤状液晶化合物、または、棒状液晶化合物と円盤状液晶化合物との混合物を用いてもよい。
なお、棒状液晶化合物としては、例えば、特表平11−513019号公報の請求項1や特開2005−289980号公報の段落[0026]〜[0098]に記載のものを好ましく用いることができ、円盤状液晶化合物としては、例えば、特開2007−108732号公報の段落[0020]〜[0067]や特開2010−244038号公報の段落[0013]〜[0108]に記載のものを好ましく用いることができるが、これらに限定されない。
第1位相差層12aおよび第2位相差層14aは、温度変化や湿度変化を小さくできることから、重合性基を有する棒状液晶化合物、または、重合性基を有する円盤状液晶化合物を用いて形成することがより好ましい。液晶化合物は2種類以上の混合物でもよく、その場合、少なくとも1つが2以上の重合性基を有していることが好ましい。
つまり、第1位相差層12aおよび第2位相差層14aは、重合性基を有する棒状液晶化合物または重合性基を有する円盤状液晶化合物が重合によって固定されて形成された層であることが好ましく、この場合、層となった後はもはや液晶性を示す必要はない。
棒状液晶化合物および円盤状液晶化合物に含まれる重合性基の種類は特に制限されず、付加重合反応が可能な官能基が好ましく、重合性エチレン性不飽和基または環重合性基が好ましい。より具体的には、(メタ)アクリロイル基、ビニル基、スチリル基、アリル基などが好ましく、(メタ)アクリロイル基がより好ましい。
In general, liquid crystal compounds can be classified into rod-shaped types (rod-shaped liquid crystal compounds) and disk-shaped types (disk-shaped liquid crystal compounds, discotic liquid crystal compounds) based on their shapes. Furthermore, there are a low molecular type and a high molecular type, respectively. Polymer generally refers to a polymer having a degree of polymerization of 100 or more (Polymer Physics / Phase Transition Dynamics, Masao Doi, 2 pages, Iwanami Shoten, 1992). In the present invention, any liquid crystal compound can be used. Two or more rod-like liquid crystal compounds, two or more disc-like liquid crystal compounds, or a mixture of a rod-like liquid crystal compound and a disc-like liquid crystal compound may be used.
In addition, as the rod-like liquid crystal compound, for example, those described in claim 1 of JP-A No. 11-53019 and paragraphs [0026] to [0098] of JP-A-2005-289980 can be preferably used. As the discotic liquid crystal compound, for example, those described in paragraphs [0020] to [0067] of JP-A-2007-108732 and paragraphs [0013] to [0108] of JP-A-2010-244038 are preferably used. However, it is not limited to these.
The first retardation layer 12a and the second retardation layer 14a can be formed by using a rod-like liquid crystal compound having a polymerizable group or a discotic liquid crystal compound having a polymerizable group, since temperature change and humidity change can be reduced. It is more preferable. The liquid crystal compound may be a mixture of two or more, and in that case, at least one of them preferably has two or more polymerizable groups.
That is, the first retardation layer 12a and the second retardation layer 14a are preferably layers formed by fixing a rod-like liquid crystal compound having a polymerizable group or a discotic liquid crystal compound having a polymerizable group by polymerization. In this case, it is no longer necessary to exhibit liquid crystallinity after forming a layer.
The kind of the polymerizable group contained in the rod-like liquid crystal compound and the discotic liquid crystal compound is not particularly limited, and a functional group capable of addition polymerization reaction is preferable, and a polymerizable ethylenically unsaturated group or a ring polymerizable group is preferable. More specifically, a (meth) acryloyl group, a vinyl group, a styryl group, an allyl group, and the like are preferable, and a (meth) acryloyl group is more preferable.
旋光フィルム10aには、上述した第1位相差層12aおよび第2位相差層14aが少なくとも含まれるが、本発明の効果を損なわない範囲において、他の部材が含まれていてもよい。
例えば、旋光フィルム10aには、配向膜が含まれていてもよい。ただし、図1に示すように、第1位相差層12aと第2位相差層14aとが隣接し、第1位相差層12aと第2位相差層14aとの間に、実質的に配向膜を有さないことが好ましい。第1位相差層12aと第2位相差層14aとの間に実質的に配向膜がない場合、それぞれの位相差層に含まれる化合物間での共有結合を利用できるので、密着性により優れる。
なお、本明細書において「実質的に配向膜がない」とは、配向膜として機能させるためだけに形成された膜を含んでいないことを意味する。
Although the optical rotatory film 10a includes at least the first retardation layer 12a and the second retardation layer 14a described above, other members may be included as long as the effects of the present invention are not impaired.
For example, the optical rotation film 10a may include an alignment film. However, as shown in FIG. 1, the first retardation layer 12a and the second retardation layer 14a are adjacent to each other, and the alignment film is substantially interposed between the first retardation layer 12a and the second retardation layer 14a. It is preferable not to have. In the case where there is substantially no alignment film between the first retardation layer 12a and the second retardation layer 14a, a covalent bond between the compounds contained in the respective retardation layers can be used, and thus the adhesion is excellent.
In this specification, “substantially no alignment film” means that a film formed only for functioning as an alignment film is not included.
また、旋光フィルム10aには、支持体が含まれていてもよい。
支持体としては、公知の支持体(好ましくは、透明支持体)を使用することができ、例えば、支持体を形成する材料としては、トリアセチルセルロースに代表されるセルロース系樹脂(以下、セルロースアシレートという)、熱可塑性ノルボルネン系樹脂(日本ゼオン(株)製のゼオネックス、ゼオノア、JSR(株)製のアートン等)、アクリル系樹脂、ポリエステル系樹脂を使用することができる。
支持体としては、実質的に光学的異方性がない透明支持体を用いることが好ましく、波長550nmでの面内レタデーション値が0〜10nmの透明支持体を用いることがより好ましい。
Further, the optical rotation film 10a may include a support.
As the support, a known support (preferably a transparent support) can be used. For example, as a material for forming the support, a cellulose resin represented by triacetyl cellulose (hereinafter referred to as cellulose acylate) is used. Rate), thermoplastic norbornene resins (ZEONEX, ZEONOR manufactured by Nippon Zeon Co., Ltd., Arton manufactured by JSR Co., Ltd.), acrylic resins, and polyester resins can be used.
As the support, it is preferable to use a transparent support having substantially no optical anisotropy, and it is more preferable to use a transparent support having an in-plane retardation value of 0 to 10 nm at a wavelength of 550 nm.
(旋光フィルムの製造方法)
本発明の旋光フィルムは、種々の方法で作製することができる。その一例は、以下の通りである。
まず、支持体を用意し、その上に、配向膜を形成し、配向膜表面に重合性基を有する液晶化合物および所望によりキラル剤等の添加剤を含む第1位相差層形成用組成物を塗布して、塗膜を形成する。この塗膜を所望により加熱して、塗膜中の液晶化合物を捩れ配向させる。その後、配向が固化する温度まで冷却して、塗膜に硬化処理(紫外線の照射(光照射処理)もしくは加熱処理)を施して重合を進行させて、その捩れ配向を固定し、第1位相差層を得る。次に、得られた第1位相差層表面に、重合性基を有する液晶化合物および所望によりキラル剤等の添加剤を含む第2位相差層形成用組成物を塗布して、塗膜を形成し、第1位相差層と同様の手順に従って、第2位相差層を得る。
以下の、上記方法について詳述する。
(Manufacturing method of optical rotation film)
The optical rotation film of the present invention can be produced by various methods. One example is as follows.
First, a support is prepared, an alignment film is formed thereon, a liquid crystal compound having a polymerizable group on the alignment film surface, and a first retardation layer forming composition containing an additive such as a chiral agent as required. Apply to form a coating. This coating film is heated as desired to twist and align the liquid crystal compound in the coating film. Thereafter, the film is cooled to a temperature at which the orientation is solidified, and the coating film is subjected to a curing treatment (ultraviolet irradiation (light irradiation treatment) or heat treatment) to advance the polymerization to fix the twisted orientation, and the first phase difference Get a layer. Next, a second retardation layer forming composition containing a liquid crystal compound having a polymerizable group and optionally an additive such as a chiral agent is applied to the surface of the obtained first retardation layer to form a coating film. Then, the second retardation layer is obtained according to the same procedure as that for the first retardation layer.
The following method will be described in detail.
[配向膜]
本発明では、配向膜の表面に位相差層形成用組成物を塗布して、液晶化合物を配向させてもよい。配向膜は液晶化合物の配向方向を規定する機能を有するため、本発明の好ましい態様を実現する上で利用するのが好ましい。しかし、液晶化合物を配向後にその配向状態を固定してしまえば、配向膜はその役割を果たしているために、本発明の構成要素としては必ずしも必須のものではない。
配向膜は、有機化合物(好ましくはポリマー)のラビング処理、無機化合物の斜方蒸着、マイクログルーブを有する層の形成、または、ラングミュア・ブロジェット法(LB膜)による有機化合物(例、ω−トリコサン酸、ジオクタデシルメチルアンモニウムクロライド、ステアリル酸メチル)の累積のような手段で設けることができる。さらに、電場の付与、磁場の付与、または、光照射(好ましくは偏光)により、配向膜を形成する方法も知られている。
配向膜は、ポリマー膜のラビング処理により形成することが好ましい。
[Alignment film]
In the present invention, the liquid crystal compound may be aligned by applying a composition for forming a retardation layer on the surface of the alignment film. Since the alignment film has a function of defining the alignment direction of the liquid crystal compound, it is preferably used for realizing a preferred embodiment of the present invention. However, if the alignment state is fixed after the alignment of the liquid crystal compound, the alignment film plays the role and is not necessarily an essential component of the present invention.
The alignment film is an organic compound (eg, ω-tricosane) formed by rubbing treatment of an organic compound (preferably polymer), oblique deposition of an inorganic compound, formation of a layer having a microgroove, or Langmuir-Blodgett method (LB film). Acid, dioctadecylmethylammonium chloride, methyl stearylate). Furthermore, a method of forming an alignment film by applying an electric field, applying a magnetic field, or irradiating light (preferably polarized light) is also known.
The alignment film is preferably formed by rubbing a polymer film.
配向膜の形成に用いられるポリマーとしては、例えば、特開平8−338913号公報明細書中の段落番号[0022]に記載のメタクリレート系共重合体、スチレン系共重合体、ポリオレフィン、ポリビニルアルコールおよび変性ポリビニルアルコール、ポリ(N−メチロールアクリルアミド)、ポリエステル、ポリイミド、酢酸ビニル共重合体、カルボキシメチルセルロース、ポリカーボネート等が挙げられる。 Examples of the polymer used for forming the alignment film include, for example, methacrylate copolymers, styrene copolymers, polyolefins, polyvinyl alcohols and modified polymers described in paragraph [0022] of JP-A-8-338913. Examples include polyvinyl alcohol, poly (N-methylolacrylamide), polyester, polyimide, vinyl acetate copolymer, carboxymethyl cellulose, and polycarbonate.
配向膜は、例えば、配向膜形成材料である上記ポリマーおよび任意の添加剤(例えば、架橋剤)を含む溶液を支持体上に塗布した後、塗膜を加熱乾燥(架橋させ)し、さらに塗膜にラビング処理を施すことにより形成することができる。
ラビング処理は、LCD(liquid crystal display)の液晶配向処理工程として広く採用されている処理方法を適用することができる。即ち、塗膜の表面を、紙、ガーゼ、フェルト、ゴム、ナイロン、ポリエステル繊維などを用いて一定方向に擦ることにより、配向膜を得る方法を用いることができる。一般的には、ラビング処理は、長さおよび太さが均一な繊維を平均的に植毛した布などを用いて数回程度ラビングを行うことにより実施される。
For example, the alignment film is formed by applying a solution containing the polymer as an alignment film forming material and an optional additive (for example, a cross-linking agent) on a support, and then drying (crosslinking) the coating film by heating. It can be formed by rubbing the film.
For the rubbing treatment, a treatment method widely adopted as a liquid crystal alignment treatment process of an LCD (liquid crystal display) can be applied. That is, a method of obtaining an alignment film by rubbing the surface of the coating film in a certain direction using paper, gauze, felt, rubber, nylon, polyester fiber or the like can be used. In general, the rubbing treatment is performed by rubbing about several times using a cloth in which fibers having a uniform length and thickness are flocked on average.
第1位相差層形成用組成物および第2位相差層形成用組成物には、液晶化合物、および、キラル剤などの任意成分が含まれていてもよい。
液晶化合物の説明は、上述の通りである。
以下、代表的な任意成分について詳述する。
Arbitrary components, such as a liquid crystal compound and a chiral agent, may be contained in the composition for 1st phase difference layer formation and the composition for 2nd phase difference layer formation.
The description of the liquid crystal compound is as described above.
Hereinafter, typical arbitrary components will be described in detail.
[キラル剤]
第1位相差層および第2位相差層を形成する際に、必要に応じて、上記液晶化合物と共に、所望によりキラル剤を使用していてもよい。キラル剤は、液晶化合物を捩れ配向させるために添加されるが、勿論、液晶化合物が、分子内に不斉炭素を有する等、光学活性を示す化合物である場合は、キラル剤の使用は不要である。なお、製造方法または捩れ角度によっても、キラル剤の使用は不要である。
キラル剤としては、併用する液晶化合物と相溶するものであれば、特に構造についての制限はない。公知のキラル剤(例えば、日本学術振興会第142委員会編「液晶デバイスハンドブック」,第3章4−3項,TN(twisted nematic)、STN(Super Twisted Nematic)用カイラル剤,199頁,1989年に記載)のいずれも用いることができる。キラル剤は、一般に不斉炭素原子を含むが、不斉炭素原子を含まない軸性不斉化合物または面性不斉化合物もキラル剤として用いることができる。軸性不斉化合物または面性不斉化合物としては、例えば、ビナフチル、ヘリセン、パラシクロファンおよびこれらの誘導体が挙げられる。また、キラル剤は、液晶性を有していてもよい。
[Chiral agent]
When forming the first retardation layer and the second retardation layer, if necessary, a chiral agent may be used together with the liquid crystal compound. The chiral agent is added to twist and align the liquid crystal compound. Of course, when the liquid crystal compound is an optically active compound such as having an asymmetric carbon in the molecule, the use of the chiral agent is unnecessary. is there. Note that the use of a chiral agent is not required depending on the production method or the twist angle.
The chiral agent is not particularly limited as long as it is compatible with the liquid crystal compound used in combination. Known chiral agents (for example, “Liquid Crystal Device Handbook” edited by Japan Society for the Promotion of Science 142nd Committee, Chapter 3-4-3, TN (twisted nematic), chiral agent for STN (Super Twisted Nematic), page 199, 1989 Can be used. A chiral agent generally contains an asymmetric carbon atom, but an axially asymmetric compound or a planar asymmetric compound that does not contain an asymmetric carbon atom can also be used as the chiral agent. Examples of the axial asymmetric compound or the planar asymmetric compound include binaphthyl, helicene, paracyclophane, and derivatives thereof. Moreover, the chiral agent may have liquid crystallinity.
[他の添加剤]
上記の液晶化合物と共に、界面活性剤、重合性モノマー、ポリマー、可塑剤等を併用して、塗膜の均一性、位相差層の強度、液晶化合物の配向性等を向上させることができる。これらの添加剤は液晶化合物と相溶性を有し、配向を阻害しないことが好ましい。
また、液晶化合物を水平配向状態または垂直配向状態とするために、水平配向または垂直配向を促進する添加剤(配向制御剤)を使用してもよい。
[Other additives]
Along with the above liquid crystal compound, a surfactant, a polymerizable monomer, a polymer, a plasticizer, and the like can be used in combination to improve the uniformity of the coating film, the strength of the retardation layer, the orientation of the liquid crystal compound, and the like. These additives are preferably compatible with the liquid crystal compound and do not inhibit the alignment.
Moreover, in order to make a liquid crystal compound into a horizontal alignment state or a vertical alignment state, you may use the additive (alignment control agent) which accelerates | stimulates horizontal alignment or vertical alignment.
界面活性剤としては、従来公知の化合物が挙げられるが、特にフッ素系化合物が好ましい。例えば、特開2001−330725号公報明細書中の段落番号[0028]〜[0056]に記載の化合物、特願2003−295212号明細書中の段落番号[0069]〜[0126]に記載の化合物が挙げられる。 Examples of the surfactant include conventionally known compounds, and fluorine compounds are particularly preferable. For example, compounds described in paragraph numbers [0028] to [0056] in JP 2001-330725 A, compounds described in paragraph numbers [0069] to [0126] in Japanese Patent Application No. 2003-295212 Is mentioned.
重合性モノマーとしては、ラジカル重合性またはカチオン重合性の化合物が挙げられる。好ましくは、多官能性ラジカル重合性モノマーであり、上記の重合性基含有の液晶化合物と共重合性のものが好ましい。例えば、特開2002−296423号公報明細書中の段落番号[0018]〜[0020]に記載のものが挙げられる。 Examples of the polymerizable monomer include radically polymerizable or cationically polymerizable compounds. Preferably, it is a polyfunctional radically polymerizable monomer and is preferably copolymerizable with the above-described polymerizable group-containing liquid crystal compound. Examples thereof include those described in paragraph numbers [0018] to [0020] in JP-A No. 2002-296423.
液晶化合物と共に使用するポリマーは、塗布液を増粘できることが好ましい。ポリマーの例としては、セルロースエステルを挙げることができる。セルロースエステルの好ましい例としては、特開2000−155216号公報明細書中の段落番号[0178]に記載のものが挙げられる。 The polymer used with the liquid crystal compound is preferably capable of thickening the coating solution. A cellulose ester can be mentioned as an example of a polymer. Preferable examples of the cellulose ester include those described in paragraph [0178] of JP-A No. 2000-155216.
第1位相差層形成用組成物および第2位相差層形成用組成物の調製に使用する溶媒としては、有機溶媒が好ましい。有機溶媒としては、例えば、アミド(例、N,N−ジメチルホルムアミド)、スルホキシド(例、ジメチルスルホキシド)、ヘテロ環化合物(例、ピリジン)、炭化水素(例、ベンゼン、ヘキサン)、アルキルハライド(例、クロロホルム、ジクロロメタン)、エステル(例、酢酸メチル、酢酸エチル、酢酸ブチル)、ケトン(例、アセトン、メチルエチルケトン)、エーテル(例、テトラヒドロフラン、1,2−ジメトキシエタン)が挙げられる。なかでも、アルキルハライドおよびケトンが好ましい。なお、2種類以上の有機溶媒を併用してもよい。 As the solvent used for the preparation of the first retardation layer forming composition and the second retardation layer forming composition, an organic solvent is preferable. Examples of the organic solvent include amides (eg, N, N-dimethylformamide), sulfoxides (eg, dimethyl sulfoxide), heterocyclic compounds (eg, pyridine), hydrocarbons (eg, benzene, hexane), alkyl halides (eg, , Chloroform, dichloromethane), esters (eg, methyl acetate, ethyl acetate, butyl acetate), ketones (eg, acetone, methyl ethyl ketone), ethers (eg, tetrahydrofuran, 1,2-dimethoxyethane). Of these, alkyl halides and ketones are preferred. Two or more organic solvents may be used in combination.
配向(好ましくは垂直配向)させた液晶化合物は、配向状態を維持して固定することが好ましい。固定化は、重合開始剤を用いて、液晶化合物に導入した重合性基の重合反応により実施することが好ましい。重合反応には、熱重合開始剤を用いる熱重合反応と光重合開始剤を用いる光重合反応とが含まれ、光重合反応が好ましい。 The aligned (preferably vertically aligned) liquid crystal compound is preferably fixed while maintaining the alignment state. The immobilization is preferably carried out by a polymerization reaction of a polymerizable group introduced into the liquid crystal compound using a polymerization initiator. The polymerization reaction includes a thermal polymerization reaction using a thermal polymerization initiator and a photopolymerization reaction using a photopolymerization initiator, and a photopolymerization reaction is preferred.
第1位相差層形成用組成物および第2位相差層形成用組成物の塗布は、公知の方法(例えば、ワイヤーバーコーティング法、押し出しコーティング法、ダイレクトグラビアコーティング法、リバースグラビアコーティング法、ダイコーティング法)により実施できる。また、インクジェット装置を用いて、位相差層形成用組成物を吐出して、塗膜を形成してもよい。 Application of the first retardation layer forming composition and the second retardation layer forming composition may be performed by a known method (for example, wire bar coating method, extrusion coating method, direct gravure coating method, reverse gravure coating method, die coating). Law). Moreover, you may form a coating film by discharging the composition for phase difference layer formation using an inkjet apparatus.
<第2の実施態様>
以下に、本発明の旋光フィルムの第2の実施態様について図面を参照して説明する。図3に、本発明の旋光フィルムの第2の実施態様の概略断面図を示す。
旋光フィルム10bは、第1位相差層12bと、第2位相差層14bとを有する。第1位相差層12bは、ポリマーフィルム(特に、延伸処理が施されたポリマーフィルム)であり、液晶化合物は含まれない。また、第2位相差層14bは、厚み方向を螺旋軸とする捩れ配向した液晶化合物を含む。
旋光フィルム10bは、上記旋光フィルム10aと同様に2層の位相差層より構成されるが、第1位相差層12bとしてポリマーフィルムを用いる点で異なる。
以下に、各層の構成について詳述する。
<Second Embodiment>
Below, the 2nd embodiment of the optical rotation film of this invention is described with reference to drawings. In FIG. 3, the schematic sectional drawing of the 2nd embodiment of the optical rotation film of this invention is shown.
The optical rotatory film 10b includes a first retardation layer 12b and a second retardation layer 14b. The first retardation layer 12b is a polymer film (particularly, a polymer film that has been subjected to stretching treatment) and does not include a liquid crystal compound. The second retardation layer 14b includes a twisted liquid crystal compound with the thickness direction as a helical axis.
The optical rotatory film 10b is composed of two retardation layers in the same manner as the optical rotatory film 10a, except that a polymer film is used as the first retardation layer 12b.
Below, the structure of each layer is explained in full detail.
第1位相差層12bは、いわゆるポリマーフィルム(特に、延伸処理が施されたポリマーフィルム)であり、ポリマーから構成される層である。
第1位相差層12bとして用いることのできるポリマーフィルムとしては、例えば、セルロースアシレート系フィルム(例えば、セルローストリアセテートフィルム(屈折率1.48)、セルロースジアセテートフィルム、セルロースアセテートブチレートフィルム、セルロースアセテートプロピオネートフィルム)、ポリエチレン、ポリプロピレン等のポリオレフィン系フィルム、ポリエチレンテレフタレートやポリエチレンナフタレート等のポリエステル系フィルム、ポリエーテルスルホン系フィルム、ポリメチルメタクリレート等のポリ(メタ)アクリル系フィルム、ポリウレタン系フィルム、ポリカーボネート系フィルム、ポリスルホン系フィルム、ポリエーテル系フィルム、ポリメチルペンテン系フィルム、ポリエーテルケトン系フィルム、ポリスチレン系フィルム、(メタ)アクリルニトリル系フィルムなどが挙げられる。具体的な商品としては、例えば、脂環式構造を有するポリマー(ノルボルネン系樹脂(アートン:商品名、JSR社製))のフィルム、非晶質ポリオレフィン(ゼオネックス:商品名、日本ゼオン社製))のフィルムなどが挙げられる。
The first retardation layer 12b is a so-called polymer film (particularly, a polymer film that has been subjected to stretching treatment), and is a layer composed of a polymer.
Examples of the polymer film that can be used as the first retardation layer 12b include cellulose acylate films (for example, cellulose triacetate film (refractive index 1.48), cellulose diacetate film, cellulose acetate butyrate film, cellulose acetate). Propionate film), polyolefin film such as polyethylene and polypropylene, polyester film such as polyethylene terephthalate and polyethylene naphthalate, polyethersulfone film, poly (meth) acrylic film such as polymethyl methacrylate, polyurethane film, Polycarbonate film, Polysulfone film, Polyether film, Polymethylpentene film, Polyether ketone film Irumu, polystyrene films, and the like (meth) acrylonitrile based film. Specific products include, for example, a polymer having an alicyclic structure (a film of norbornene-based resin (Arton: trade name, manufactured by JSR)), amorphous polyolefin (ZEONEX: trade name, manufactured by Nippon Zeon)) The film etc. are mentioned.
第1位相差層12bの厚さは特に制限されないが、10μm〜200μmが好ましく、10μm〜100μmがより好ましく、20μm〜90μmがさらに好ましい。
第1位相差層12bは、種々の添加剤(例えば、微粒子、可塑剤、紫外線防止剤、劣化防止剤、剥離剤など)を含んでいてもよい。
The thickness of the first retardation layer 12b is not particularly limited, but is preferably 10 μm to 200 μm, more preferably 10 μm to 100 μm, and further preferably 20 μm to 90 μm.
The first retardation layer 12b may contain various additives (for example, fine particles, plasticizers, ultraviolet inhibitors, deterioration inhibitors, release agents, etc.).
第2位相差層14bは、上述した第2位相差層14aと同様に、厚み方向を螺旋軸とする捩れ配向した液晶化合物を含む層であり、態様は上述の通りである。 The second retardation layer 14b is a layer containing a liquid crystal compound that is twisted and oriented with the thickness direction as a helical axis, similarly to the second retardation layer 14a described above, and the aspect is as described above.
次に、図4を用いて、第1位相差層12bおよび第2位相差層14b中の面内遅相軸の関係について詳述する。図4に示す各層中の黒矢印は、面内遅相軸を意図する。
図4に示すように、第1位相差層12はポリマーフィルムより構成されており、第1位相差層12bの第2位相差層14b側とは反対側の表面112bでの面内遅相軸と、第2位相差層14b側の表面212bでの面内遅相軸とは、平行である。なお、第2位相差層14bは、上述した第2位相差層14aと同じく、第1位相差層12a側の表面114bでの面内遅相軸と第1位相差層12a側とは反対側の表面214bでの面内遅相軸とが所定の角度をなす。
第1位相差層12bの第2位相差層14b側の表面212bでの面内遅相軸と、第2位相差層14bの第1位相差層12b側の表面114bでの面内遅相軸とのなす角θは、第1の実施態様と同じで、0〜15°であり、その好適範囲も上述の通りである。
第2位相差層14b中の液晶化合物の捩れ方向は右捩れであっても、左捩れであってもよい。
なお、第2位相差層14b中の液晶化合物の捩れ方向は、図4中の白抜き矢印で示すように、第1位相差層12a側から旋光フィルム10bを観察し、第2位相差層14b中の手前側(第1位相差層12a側)の表面114bでの面内遅相軸を基準に右捩れ(時計回り)か、左捩れ(反時計回り)を判断する。
Next, the relationship between the in-plane slow axes in the first retardation layer 12b and the second retardation layer 14b will be described in detail with reference to FIG. The black arrow in each layer shown in FIG. 4 intends the in-plane slow axis.
As shown in FIG. 4, the first retardation layer 12 is composed of a polymer film, and an in-plane slow axis on the surface 112b of the first retardation layer 12b opposite to the second retardation layer 14b side. And the in-plane slow axis on the surface 212b on the second retardation layer 14b side are parallel to each other. The second retardation layer 14b is the same as the above-described second retardation layer 14a, and the in-plane slow axis on the surface 114b on the first retardation layer 12a side is opposite to the first retardation layer 12a side. An in-plane slow axis on the surface 214b of the surface forms a predetermined angle.
An in-plane slow axis on the surface 212b of the first retardation layer 12b on the second retardation layer 14b side, and an in-plane slow axis on the surface 114b of the second retardation layer 14b on the first retardation layer 12b side. Is the same as in the first embodiment and is 0 to 15 °, and the preferred range is also as described above.
The twist direction of the liquid crystal compound in the second retardation layer 14b may be right-handed or left-handed.
Note that the twist direction of the liquid crystal compound in the second retardation layer 14b is determined by observing the optical rotatory film 10b from the first retardation layer 12a side as shown by the white arrow in FIG. A right twist (clockwise) or a left twist (counterclockwise) is determined based on the in-plane slow axis on the front surface 114b on the front side (the first retardation layer 12a side).
第2位相差層14b中の液晶化合物の捩れ角θ3の範囲は特に制限されず、直線偏光を旋光させたい程度によって異なるが、旋光フィルムによって直線偏光を90°旋光させる場合、60〜120°が好ましい。
なお、捩れ角θ3は、第2位相差層14bの第1位相差層12b側の表面114bでの面内遅相軸と、第2位相差層14bの第1位相差層12b側とは反対側の表面214bでの面内遅相軸とのなす角に相当する。
The range of the twist angle θ3 of the liquid crystal compound in the second retardation layer 14b is not particularly limited, and varies depending on the degree of rotation of the linearly polarized light. However, when the linearly polarized light is rotated 90 ° by the optical rotation film, 60 to 120 ° is preferable.
Note that the twist angle θ3 is opposite to the in-plane slow axis on the surface 114b of the second retardation layer 14b on the first retardation layer 12b side and the first retardation layer 12b side of the second retardation layer 14b. This corresponds to the angle formed with the in-plane slow axis at the surface 214b on the side.
第1位相差層12bの波長550nmにおける厚み方向のレタデーション値(Rth(550))、および、第2位相差層14bの波長550nmにおける厚み方向のレタデーション値(Rth(550))の一方は負の値であり、かつ、第1位相差層12bの波長550nmにおける厚み方向のレタデーション値、および、第2位相差層14bの波長550nmにおける厚み方向のレタデーション値の他方は正の値である。 One of the retardation value (Rth (550)) in the thickness direction at a wavelength of 550 nm of the first retardation layer 12b and the retardation value (Rth (550)) in the thickness direction at a wavelength of 550 nm of the second retardation layer 14b are negative. And the other of the retardation value in the thickness direction at the wavelength 550 nm of the first retardation layer 12b and the retardation value in the thickness direction at the wavelength 550 nm of the second retardation layer 14b is a positive value.
第1位相差層12bのRth(550)および第2位相差層14bのRth(550)の範囲は特に制限されないが、第1位相差層12bのRth(550)の絶対値および第2位相差層14bのRth(550)の絶対値の合計が、第1の実施態様で述べた第1位相差層12aのRth(550)の絶対値および第2位相差層14aのRth(550)の絶対値の合計の範囲であることが好ましい。
また、第1位相差層12bのRth(550)の絶対値および第2位相差層14bのRth(550)の絶対値のそれぞれの好適範囲は、第1の実施態様で述べた第1位相差層12aのRth(550)の絶対値および第2位相差層14aのRth(550)の絶対値の一方の範囲および他方の範囲のそれぞれの好適範囲と同じである。
The ranges of Rth (550) of the first retardation layer 12b and Rth (550) of the second retardation layer 14b are not particularly limited, but the absolute value and the second retardation of Rth (550) of the first retardation layer 12b are not limited. The sum of absolute values of Rth (550) of the layer 14b is the absolute value of Rth (550) of the first retardation layer 12a and the absolute value of Rth (550) of the second retardation layer 14a described in the first embodiment. A range of the total value is preferred.
Further, the preferred ranges of the absolute value of Rth (550) of the first retardation layer 12b and the absolute value of Rth (550) of the second retardation layer 14b are the first phase differences described in the first embodiment. The absolute value of Rth (550) of the layer 12a and the absolute value of Rth (550) of the second retardation layer 14a are the same as the respective preferable ranges of one range and the other range.
また、第2の実施態様において、波長550nmで測定した第1位相差層12bの屈折率異方性Δn1と第1位相差層12bの厚みd1との積Δn1d1、および、波長550nmで測定した第2位相差層14bの屈折率異方性Δn2と第2位相差層14bの厚みd2との積Δn2d2のうち値が大きい方をΔnd・maxとし、値の小さい方をΔnd・minとした場合、Δnd・min/Δnd・maxの範囲が上述した第1の実施態様と同じ範囲となる。
また、Δn1d1および上記Δn2d2のそれぞれの好適範囲も、第1の実施態様と同義である。
In the second embodiment, the product Δn1d1 of the refractive index anisotropy Δn1 of the first retardation layer 12b measured at a wavelength of 550 nm and the thickness d1 of the first retardation layer 12b, and the first measured at a wavelength of 550 nm. Of the product Δn2d2 of the refractive index anisotropy Δn2 of the two retardation layer 14b and the thickness d2 of the second retardation layer 14b, the larger value is Δnd · max, and the smaller value is Δnd · min. The range of Δnd · min / Δnd · max is the same as that of the first embodiment described above.
The preferred ranges of Δn1d1 and Δn2d2 are also synonymous with those of the first embodiment.
第2位相差層14bは捩れ配向した液晶化合物を含む層であるが、本発明の効果がより優れる点で、波長550nmで測定した第2位相差層14bの屈折率異方性Δnと第2位相差層14bの厚みdとの積Δndと、第2位相差層14b中の液晶化合物の捩れ角θ(°)との比であるΔnd/θは、4.1〜6.1が好ましく、旋光フィルムの旋光性がより優れる点で、4.1超6.1未満がより好ましく、4.5〜5.7がさらに好ましい。 The second retardation layer 14b is a layer containing a liquid crystal compound that is twisted and aligned. However, the second retardation layer 14b has a refractive index anisotropy Δn measured at a wavelength of 550 nm and a second value because the effect of the present invention is more excellent. The ratio Δnd / θ, which is the ratio of the product Δnd with the thickness d of the retardation layer 14b to the twist angle θ (°) of the liquid crystal compound in the second retardation layer 14b, is preferably 4.1 to 6.1. From the point that the optical rotation of the optical rotatory film is more excellent, it is more preferably more than 4.1 and less than 6.1, and more preferably 4.5 to 5.7.
なお、旋光フィルム10bには、上述した第1位相差層12bおよび第2位相差層14bが少なくとも含まれるが、第1の実施態様と同様に、配向膜や支持体など他の部材が含まれていてもよい。 The optical rotatory film 10b includes at least the first retardation layer 12b and the second retardation layer 14b described above, but includes other members such as an alignment film and a support as in the first embodiment. It may be.
以下に実施例と比較例を挙げて本発明の特徴をさらに具体的に説明する。以下の実施例に示す材料、使用量、割合、処理内容、処理手順等は、本発明の趣旨を逸脱しない限り適宜変更することができる。従って、本発明の範囲は以下に示す具体例により限定的に解釈されるべきものではない。 The features of the present invention will be described more specifically with reference to examples and comparative examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Accordingly, the scope of the present invention should not be construed as being limited by the specific examples shown below.
<支持体の準備および配向膜の形成>
(アルカリ鹸化処理)
市販のセルロースアセテート系フィルムZ−TAC(富士フイルム(株)製)を、温度60℃の誘電式加熱ロールを通過させ、フィルム表面温度を40℃に昇温した。次いで、昇温したフィルムの片面に下記に示す組成のアルカリ溶液を、バーコーターを用いて塗布量14ml/m2で塗布し、その後、フィルムを110℃に加熱した。次いで、得られたフィルムを、(株)ノリタケカンパニーリミテド製のスチーム式遠赤外ヒーターの下に、10秒間搬送した。次いで、バーコーターを用いて、アルカリ溶液を塗布したフィルム面上に純水を3ml/m2塗布した。次いで、得られたフィルムに対して、ファウンテンコーターによる水洗とエアナイフによる水切りを3回繰り返し実施した後に、フィルムを70℃の乾燥ゾーンに10秒間搬送して乾燥し、アルカリ鹸化処理した長尺状のセルロースアシレートフィルムを作製した。
<Preparation of support and formation of alignment film>
(Alkaline saponification treatment)
A commercially available cellulose acetate film Z-TAC (manufactured by FUJIFILM Corporation) was passed through a dielectric heating roll having a temperature of 60 ° C., and the film surface temperature was raised to 40 ° C. Next, an alkali solution having the composition shown below was applied to one surface of the heated film using a bar coater at a coating amount of 14 ml / m 2 , and then the film was heated to 110 ° C. Next, the obtained film was transported for 10 seconds under a steam far infrared heater manufactured by Noritake Company Limited. Next, using a bar coater, 3 ml / m 2 of pure water was applied onto the film surface on which the alkaline solution was applied. Next, the obtained film was repeatedly washed with a fountain coater and drained with an air knife three times, and then the film was transported to a drying zone at 70 ° C. for 10 seconds to be dried and subjected to alkali saponification treatment. A cellulose acylate film was prepared.
──────────────────────────────────
アルカリ溶液の組成
──────────────────────────────────
水酸化カリウム 4.7質量部
水 15.8質量部
イソプロパノール 63.7質量部
界面活性剤SF−1:C14H29O(CH2CH2O)20H 1.0質量部
プロピレングリコール 14.8質量部
──────────────────────────────────
──────────────────────────────────
Composition of alkaline solution ──────────────────────────────────
Potassium hydroxide 4.7 parts by weight Water 15.8 parts by weight Isopropanol 63.7 parts by weight Surfactant SF-1: C 14 H 29 O (CH 2 CH 2 O) 20 H 1.0 part by weight Propylene glycol 14. 8 parts by mass ──────────────────────────────────
(配向膜の作製)
上記のようにアルカリ鹸化処理した長尺状のセルロースアセテートフィルム上に、下記の組成の配向膜塗布液を#14のワイヤーバーで連続的に塗布した。続いて、配向膜塗布液が塗布されたフィルムに対して、60℃の温風で60秒間の乾燥処理、更に100℃の温風で120秒間の乾燥処理を施した。続いて、セルロースアセテートフィルム上に得られた塗膜に対して、連続的にラビング処理を施して、配向膜を作製した。このとき、長尺状のセルロースアセテートフィルムの長手方向と搬送方向は平行であり、フィルム長手方向に対して、ラビングローラーの回転軸は平行方向とした。
──────────────────────────────────
配向膜塗布液の組成
──────────────────────────────────
変性ポリビニルアルコール1 10質量部
水 371質量部
メタノール 119質量部
グルタルアルデヒド 0.5質量部
光重合開始剤(イルガキュアー2959、BASF社製) 0.3質量部
──────────────────────────────────
(Preparation of alignment film)
On the long cellulose acetate film subjected to alkali saponification treatment as described above, an alignment film coating solution having the following composition was continuously applied with a # 14 wire bar. Subsequently, the film coated with the alignment film coating solution was subjected to a drying process for 60 seconds with hot air at 60 ° C., and further, a drying process for 120 seconds with warm air at 100 ° C. Subsequently, the coating film obtained on the cellulose acetate film was continuously rubbed to produce an alignment film. At this time, the longitudinal direction of the long cellulose acetate film was parallel to the transport direction, and the rotation axis of the rubbing roller was parallel to the longitudinal direction of the film.
──────────────────────────────────
Composition of alignment film coating solution ──────────────────────────────────
Modified polyvinyl alcohol 1 10 parts by weight Water 371 parts by weight Methanol 119 parts by weight Glutaraldehyde 0.5 parts by weight Photopolymerization initiator (Irgacure 2959, manufactured by BASF) 0.3 parts by weight ───────── ────────────────────────
<実施例1>
(円盤状液晶化合物を用いた位相差層の作製)
上記で作製したセルロースアセテートフィルム上の配向膜の表面上に、下記の組成の円盤状液晶化合物を含む塗布液B11を連続的に塗布して、塗膜を形成した。なお、塗布液B11の塗布の際には、表1の膜厚の第1の位相差層が得られるように、塗布液B11の塗布量を調製して塗布を実施した。
続いて、塗膜に対して、70℃にて1分間乾燥処理を施して、塗膜中の溶媒を気化させた後に、115℃で3分間加熱熟成処理を施して、塗膜中において円盤状液晶化合物の均一な配向状態を得た。
その後、この塗膜を30℃に保持し、窒素雰囲気下にて、高圧水銀灯を用いて塗膜に対して紫外線照射(200mJ/cm2)を施し、円盤状液晶化合物の配向を固定化し、第1の位相差層を作製した。
<Example 1>
(Production of retardation layer using discotic liquid crystal compound)
On the surface of the alignment film on the cellulose acetate film prepared above, coating liquid B11 containing a discotic liquid crystal compound having the following composition was continuously applied to form a coating film. In applying the coating liquid B11, the coating amount of the coating liquid B11 was prepared and applied so that the first retardation layer having the thickness shown in Table 1 was obtained.
Subsequently, the coating film was subjected to a drying treatment at 70 ° C. for 1 minute to evaporate the solvent in the coating film, and then subjected to a heat aging treatment at 115 ° C. for 3 minutes. A uniform alignment state of the liquid crystal compound was obtained.
Thereafter, this coating film is kept at 30 ° C., and under a nitrogen atmosphere, the coating film is irradiated with ultraviolet rays (200 mJ / cm 2 ) using a high-pressure mercury lamp to fix the orientation of the discotic liquid crystal compound. 1 retardation layer was produced.
──────────────────────────────────
円盤状液晶化合物を含む塗布液B11の組成
――――――――――――――――――――――――――――――――――
円盤状液晶化合物(化合物101) 80質量部
円盤状液晶化合物(化合物102) 20質量部
重合性モノマー1 10質量部
DIC社製メガファックF444 0.20質量部
キラル剤1 0.123質量部
重合開始剤1 3質量部
メチルエチルケトン 196質量部
シクロヘキサノン 25質量部
t−ブタノール 25質量部
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Composition of coating liquid B11 containing discotic liquid crystal compound ――――――――――――――――――――――――――――――――――
Discotic liquid crystal compound (Compound 101) 80 parts by mass Discotic liquid crystal compound (Compound 102) 20 parts by mass Polymerizable monomer 1 10 parts by mass MegaFick F444 0.20 parts by mass Chiral agent 1 0.123 parts by mass Polymerization start Agent 1 3 parts by weight methyl ethyl ketone 196 parts by weight cyclohexanone 25 parts by weight t-butanol 25 parts by weight ――――――――――――――――――――――――――――――― ―――
(棒状液晶化合物を用いた位相差層の作製)
上記で得られた第1の位相差層上に、下記の組成の棒状液晶化合物を含む塗布液B12を連続的に塗布して、塗膜を形成した。なお、塗布液B12の塗布の際には、表1の膜厚の第2の位相差層が得られるように、塗布液B12の塗布量を調製して塗布を実施した。また、フィルムの搬送速度(V)は20m/minとした。
続いて、塗布液中の溶媒の乾燥除去および棒状液晶化合物の配向熟成のために、塗膜に対して、85℃の温風での120秒間の加熱処理を施した。続いて、塗膜に対して、80℃にて紫外線照射(300mJ/cm2)を施し、棒状液晶化合物の配向を固定化し、第2の位相差層を形成し、旋光フィルムを製造した。
(Production of retardation layer using rod-like liquid crystal compound)
On the 1st phase difference layer obtained above, the coating liquid B12 containing the rod-shaped liquid crystal compound of the following composition was apply | coated continuously, and the coating film was formed. In applying the coating liquid B12, the coating amount of the coating liquid B12 was prepared and applied so that a second retardation layer having a film thickness shown in Table 1 was obtained. The film conveyance speed (V) was 20 m / min.
Subsequently, the coating film was subjected to a heat treatment with hot air at 85 ° C. for 120 seconds for drying and removing the solvent in the coating liquid and for alignment aging of the rod-like liquid crystal compound. Subsequently, the coating film was irradiated with ultraviolet rays (300 mJ / cm 2 ) at 80 ° C., the orientation of the rod-like liquid crystal compound was fixed, the second retardation layer was formed, and an optical rotation film was produced.
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棒状液晶化合物を含む塗布液B12の組成
――――――――――――――――――――――――――――――――――
棒状液晶化合物201 83質量部
棒状液晶化合物202 15質量部
棒状液晶化合物203 2質量部
多官能モノマーA−TMMT(新中村化学工業(株)社製) 1質量部
重合開始剤IRGACURE819(BASF社製) 4質量部
キラル剤1 0.136質量部
界面活性剤2 0.05質量部
界面活性剤3 0.01質量部
メチルエチルケトン 165質量部
シクロヘキサノン 10質量部
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──────────────────────────────────
Composition of coating liquid B12 containing rod-shaped liquid crystal compound ――――――――――――――――――――――――――――――
Rod-like liquid crystal compound 201 83 parts by weight Rod-like liquid crystal compound 202 15 parts by weight Rod-like liquid crystal compound 203 2 parts by weight polyfunctional monomer A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd.) 1 part by weight polymerization initiator IRGACURE819 (manufactured by BASF) 4 parts by weight chiral agent 1 0.136 parts by weight surfactant 2 0.05 parts by weight surfactant 3 0.01 parts by weight methyl ethyl ketone 165 parts by weight cyclohexanone 10 parts by weight ――――――――――――― ―――――――――――――――――――――
<実施例2>
実施例1で実施した(棒状液晶化合物を用いた位相差層の作製)の手順に従って、セルロースアセテートフィルム上の配向膜の表面上に第1の位相差層を作製し、作製された第1の位相差層上に実施例1で実施した(円盤状液晶化合物を用いた位相差層の作製)の手順に従って、第2の位相差層を作製した以外は、実施例1と同様の手順に従って、旋光フィルを製造した。
<Example 2>
According to the procedure of Example 1 (Production of retardation layer using rod-like liquid crystal compound), a first retardation layer was produced on the surface of the alignment film on the cellulose acetate film, and the produced first According to the same procedure as in Example 1, except that the second retardation layer was prepared according to the procedure of (implementation of retardation layer using discotic liquid crystal compound) performed in Example 1 on the retardation layer. An optical rotatory fill was produced.
<実施例3>
第1の位相差層の膜厚および第2の位相差層の膜厚を表1に示す値となるように変更した以外は、実施例2と同様の手順に従って、旋光フィルムを製造した。
<Example 3>
An optical rotation film was produced according to the same procedure as in Example 2, except that the thickness of the first retardation layer and the thickness of the second retardation layer were changed to the values shown in Table 1.
<実施例4>
第1の位相差層の膜厚および第2の位相差層の膜厚を表1に示す値となるように変更した以外は、実施例1と同様の手順に従って、旋光フィルムを製造した。
<Example 4>
An optical rotation film was produced according to the same procedure as in Example 1 except that the thickness of the first retardation layer and the thickness of the second retardation layer were changed to the values shown in Table 1.
<実施例5>
第1の位相差層の膜厚および第2の位相差層の膜厚を表1に示す値となるように変更した以外は、実施例1と同様の手順に従って、旋光フィルムを製造した。
<Example 5>
An optical rotation film was produced according to the same procedure as in Example 1 except that the thickness of the first retardation layer and the thickness of the second retardation layer were changed to the values shown in Table 1.
<実施例6>
第1の位相差層の膜厚および第2の位相差層の膜厚を表1に示す値となるように変更した以外は、実施例1と同様の手順に従って、旋光フィルムを製造した。
<Example 6>
An optical rotation film was produced according to the same procedure as in Example 1 except that the thickness of the first retardation layer and the thickness of the second retardation layer were changed to the values shown in Table 1.
<実施例7>
(ポリスチレンフィルムの作製)
PSジャパン株式会社製のG9504をジクロロメタンに固形分濃度35質量%となるように溶かし、溶液を調製した。得られた溶液を流延して流延膜を形成し、流延膜に対して乾燥処理を施した。続いて、得られた流延膜に対して、延伸倍率100%の延伸処理(加熱温度:110℃、延伸速度:100%/分)を施して、長尺状のポリスチレンフィルムを作製した。
<Example 7>
(Production of polystyrene film)
G9504 manufactured by PS Japan Co., Ltd. was dissolved in dichloromethane so as to have a solid concentration of 35% by mass to prepare a solution. The obtained solution was cast to form a cast film, and the cast film was dried. Subsequently, the cast film thus obtained was subjected to a stretching treatment (heating temperature: 110 ° C., stretching speed: 100% / min) at a stretching ratio of 100% to produce a long polystyrene film.
次に、得られた長尺状のポリスチレンフィルム上に、実施例1で実施した(配向膜の作製)の手順に従って配向膜を作製し、さらに、実施例1で実施した(棒状液晶化合物を用いた位相差層の作製)の手順に従って位相差層を作製し、旋光フィルムを製造した。
なお、配向膜の作製の際には、長尺状のポリスチレンフィルムの長手方向と搬送方向は平行であり、フィルム長手方向に対して、ラビングローラーの回転軸は11.5°とした。なお、上記回転軸の角度は、ポリスチレンフィルムの配向膜塗布液の塗布面側からポリスチレンフィルムを観察した際に、ポリスチレンフィルムの長手方向を0°とし、時計回り(右回り)を負の角度値で表す。
Next, on the obtained long polystyrene film, an alignment film was prepared according to the procedure of (preparation of alignment film) carried out in Example 1 and further carried out in Example 1 (using a rod-like liquid crystal compound). The phase difference layer was produced according to the procedure of the production of the phase difference layer, and an optical rotation film was produced.
When the alignment film was produced, the longitudinal direction of the long polystyrene film was parallel to the transport direction, and the rotation axis of the rubbing roller was 11.5 ° relative to the longitudinal direction of the film. In addition, when the polystyrene film is observed from the coating surface side of the alignment film coating solution of the polystyrene film, the angle of the rotation axis is a negative angle value when the longitudinal direction of the polystyrene film is 0 ° and clockwise (clockwise). Represented by
<実施例8>
円盤状液晶化合物を含む塗布液B11に添加するキラル剤1の量を0.123質量部から0.152質量部に変更し、棒状液晶化合物を含む塗布液B12に添加するキラル剤1の量を0.136質量部から0.170質量部に変更した以外は、実施例1と同様の手順に従って、旋光フィルムを製造した。
<Example 8>
The amount of chiral agent 1 added to coating liquid B11 containing a discotic liquid crystal compound is changed from 0.123 parts by mass to 0.152 parts by mass, and the amount of chiral agent 1 added to coating liquid B12 containing a rod-like liquid crystal compound is changed. An optical rotation film was produced according to the same procedure as in Example 1 except that the amount was changed from 0.136 parts by mass to 0.170 parts by mass.
<実施例9>
円盤状液晶化合物を含む塗布液B11に添加するキラル剤1の量を0.123質量部から0.103質量部に変更し、棒状液晶化合物を含む塗布液B12に添加するキラル剤1の量を0.136質量部から0.113質量部に変更した以外は、実施例1と同様の手順に従って、旋光フィルムを製造した。
<Example 9>
The amount of chiral agent 1 added to coating liquid B11 containing a discotic liquid crystal compound is changed from 0.123 parts by mass to 0.103 parts by mass, and the amount of chiral agent 1 added to coating liquid B12 containing a rod-like liquid crystal compound is changed. An optical rotation film was produced according to the same procedure as in Example 1 except that the amount was changed from 0.136 parts by mass to 0.113 parts by mass.
<比較例1>
(円盤状液晶化合物を用いた位相差層の作製)を実施せず、かつ、(棒状液晶化合物を用いた位相差層の作製)において位相差層の膜厚を表1に示す値となるように変更した以外は、実施例1と同様の手順に従って、旋光フィルムを製造した。
<Comparative Example 1>
(Preparation of retardation layer using discotic liquid crystal compound) is not carried out, and the thickness of the retardation layer becomes the value shown in Table 1 in (Preparation of retardation layer using rod-like liquid crystal compound). An optical rotation film was produced according to the same procedure as in Example 1 except that the change was made.
<比較例2>
(棒状液晶化合物を用いた位相差層の作製)を実施せず、かつ、(円盤状液晶化合物を用いた位相差層の作製)において位相差層の膜厚を表1に示す値となるように変更した以外は、実施例1と同様の手順に従って、旋光フィルムを製造した。
<Comparative example 2>
(Preparation of retardation layer using rod-like liquid crystal compound) is not carried out, and the thickness of the retardation layer becomes the value shown in Table 1 in (Preparation of retardation layer using discotic liquid crystal compound). An optical rotation film was produced according to the same procedure as in Example 1 except that the change was made.
<比較例3>
第1の位相差層の膜厚および第2の位相差層の膜厚を表1に示す値となるように変更した以外は、実施例1と同様の手順に従って、旋光フィルムを製造した。
<Comparative Example 3>
An optical rotation film was produced according to the same procedure as in Example 1 except that the thickness of the first retardation layer and the thickness of the second retardation layer were changed to the values shown in Table 1.
上記実施例および比較例にて作製された旋光フィルムを、2枚の偏光子の間に配置して評価サンプルを作製して、液晶ディスプレイ用のバックライト上で以下の評価を実施した。
なお、旋光フィルムを2枚の偏光子の間に配置する際には、図5に示すように、セルロースアセテートフィルム20、第1の位相差層12c、および、第2の位相差層14cを含む旋光フィルム10cを、第1の偏光子30aおよび第2の偏光子30bの間に配置した。バックライトは、図5中の第2の偏光子30bの下側(第1の偏光子30a側とは反対側)に配置して、評価を実施した。
図5に示すように、第1の偏光子30aの吸収軸(第1の偏光子30a中の矢印)と、第2の偏光子30bの吸収軸(第2の偏光子30b中の矢印)とは直交するように配置され、第2の偏光子30bの吸収軸の方向を0°、第1の偏光子30aの吸収軸の方向を90°とする。
また、各実施例および比較例の旋光フィルムを上記第1の偏光子30aおよび第2の偏光子30bの間に配置する際には、第1の位相差層の面内遅相軸(上面の面内遅相軸および下面の面内遅相軸)の角度および第2の位相差層の面内遅相軸(上面の面内遅相軸および下面の面内遅相軸)の角度が、第2の偏光子30bの吸収軸を基準に、表1の値となるように配置した。なお、第1の位相差層の「上面の面内遅相軸」とは、第2の位相差層側とは反対側の表面での面内遅相軸と意図し、第1の位相差層の「下面の面内遅相軸」とは、第2の位相差層側の表面での面内遅相軸を意図する。また、第2の位相差層の「上面の面内遅相軸」とは、第1の位相差層側の表面での面内遅相軸と意図し、第2の位相差層の「下面の面内遅相軸」とは、第1の位相差層側とは反対側の表面での面内遅相軸を意図する。
なお、上記角度は、評価サンプルを第1の偏光子30a側(図5中の白抜き矢印側)から観察した際に、第2の偏光子30bの吸収軸の方向を0°とし、反時計回り(左回り)を正の角度値で表す。
The optical rotation film produced in the said Example and comparative example was arrange | positioned between two polarizers, the evaluation sample was produced, and the following evaluation was implemented on the backlight for liquid crystal displays.
In addition, when arrange | positioning an optical rotation film between two polarizers, as shown in FIG. 5, the cellulose acetate film 20, the 1st phase difference layer 12c, and the 2nd phase difference layer 14c are included. The optical rotatory film 10c was disposed between the first polarizer 30a and the second polarizer 30b. The backlight was placed below the second polarizer 30b in FIG. 5 (on the side opposite to the first polarizer 30a side) for evaluation.
As shown in FIG. 5, the absorption axis of the first polarizer 30a (arrow in the first polarizer 30a), the absorption axis of the second polarizer 30b (arrow in the second polarizer 30b), and Are arranged so as to be orthogonal, the direction of the absorption axis of the second polarizer 30b is 0 °, and the direction of the absorption axis of the first polarizer 30a is 90 °.
Further, when the optical rotatory films of the respective examples and comparative examples are disposed between the first polarizer 30a and the second polarizer 30b, the in-plane slow axis (upper surface of the first retardation layer) is obtained. The angle of the in-plane slow axis and the in-plane slow axis of the lower surface and the angle of the in-plane slow axis of the second retardation layer (the in-plane slow axis of the upper surface and the in-plane slow axis of the lower surface) are The second polarizer 30b was arranged so as to have the values shown in Table 1 with reference to the absorption axis of the second polarizer 30b. The “in-plane slow axis on the upper surface” of the first retardation layer is intended to be the in-plane slow axis on the surface opposite to the second retardation layer, and the first retardation The “in-plane slow axis of the lower surface” of the layer means an in-plane slow axis on the surface on the second retardation layer side. Further, the “in-plane slow axis on the upper surface” of the second retardation layer is intended to be an in-plane slow axis on the surface on the first retardation layer side, and the “lower surface of the second retardation layer” The term “in-plane slow axis” means an in-plane slow axis on the surface opposite to the first retardation layer side.
Note that the above-mentioned angle is set such that the direction of the absorption axis of the second polarizer 30b is 0 ° when the evaluation sample is observed from the first polarizer 30a side (the white arrow side in FIG. 5). The rotation (counterclockwise) is represented by a positive angle value.
(旋光性評価(正面輝度測定))
特開2009−93166号公報の段落0180に記載と同様に、測定機(EZ−Contrast160D、ELDIM社製)を用いて、液晶ディスプレイ用のバックライト上に配置した評価サンプルの正面輝度を測定し、以下の基準で評価した。実用上、AまたはBが好ましい。
A:実施例1の正面輝度と同等(正面輝度の95%以上)。
B:実施例1の正面輝度の85%以上95%未満。
C:実施例1の正面輝度の85%未満。
(Optical rotation evaluation (front luminance measurement))
In the same manner as described in paragraph 0180 of JP-A-2009-93166, using a measuring device (EZ-Contrast 160D, manufactured by ELDIM), the front luminance of the evaluation sample placed on the backlight for the liquid crystal display is measured, Evaluation was made according to the following criteria. Practically, A or B is preferable.
A: Equivalent to the front luminance of Example 1 (95% or more of the front luminance).
B: 85% or more and less than 95% of the front luminance of Example 1.
C: Less than 85% of the front luminance of Example 1.
(斜め方向から視認した際の色づき(斜め色づき)測定)
測定機(EZ−Contrast160D、ELDIM社製)を用いて、液晶ディスプレイ用のバックライト上に配置した評価サンプルの正面方向および斜め方向の色味u’v’を測定し、斜め色差Δu’v’を計算した。
Δu’v’の算出方法としては、まず、正面方向の色味を測定する。次に、3方位からの斜め方向の色味をそれぞれ測定する。具体的には、3方位としては、方位角225度極角60度の方位1、方位角270度極角60度の方位2、方位角315度極角60度の方位3が挙げられ、これらの方位から旋光フィルムを観察した際の色味をそれぞれ測定する。次に、正面方向の色味と方位1の色味との差である色差Δu’v’1、正面方向の色味と方位2の色味との差である色差Δu’v’2、および、正面方向の色味と方位3の色味との差である色差Δu’v’3をそれぞれ求め、それらを3つの色差を算術平均して、上記斜め色差Δu’v’とした。
得られた斜め色差Δu’v’の値をもとに、以下の基準で評価した。実用上、AまたはBが好ましい。
A:Δu’v’が0.01未満:目視で色差が目立たない。
B:Δu’v’が0.01以上0.02未満:目視でほとんど色差が目立たない。
C:Δu’v’が0.02以上0.3未満:目視でやや色差が目立つ。
D:Δu’v’が0.03以上:目視で色差が目立つ。
(Measurement of color when viewed from an oblique direction (diagonal color))
Using a measuring device (EZ-Contrast 160D, manufactured by ELDIM), the color u′v ′ in the front direction and the diagonal direction of the evaluation sample arranged on the backlight for the liquid crystal display is measured, and the diagonal color difference Δu′v ′. Was calculated.
As a method of calculating Δu′v ′, first, the color in the front direction is measured. Next, the color of the diagonal direction from three directions is measured, respectively. Specifically, the three azimuths include azimuth 1 with azimuth angle 225 degrees polar angle 60 degrees, azimuth 2 with azimuth angle 270 degrees polar angle 60 degrees, and azimuth 3 with azimuth angle 315 degrees polar angle 60 degrees, The color when the optical rotatory film is observed from each of the directions is measured. Next, a color difference Δu′v′1 that is the difference between the color in the front direction and the color in the direction 1, a color difference Δu′v′2 that is the difference between the color in the front direction and the color in the direction 2, and The color difference Δu′v′3, which is the difference between the color in the front direction and the color in direction 3, was obtained, and the three color differences were arithmetically averaged to obtain the oblique color difference Δu′v ′.
Based on the value of the obtained oblique color difference Δu′v ′, the evaluation was made according to the following criteria. Practically, A or B is preferable.
A: Δu′v ′ is less than 0.01: the color difference is not noticeable.
B: Δu′v ′ is 0.01 or more and less than 0.02: The color difference is hardly noticeable visually.
C: Δu′v ′ is 0.02 or more and less than 0.3: The color difference is slightly noticeable visually.
D: Δu′v ′ is 0.03 or more: The color difference is noticeable visually.
表1中の「DLC」は円盤状液晶化合物を意図し、「RLC」は棒状液晶化合物を意図する。
また、表1中の「角度」欄は、第1位相差層の第2位相差層側の表面での面内遅相軸と、第2位相差層の第1位相差層側の表面での面内遅相軸とのなす角の角度を意図する。
In Table 1, “DLC” intends a discotic liquid crystal compound, and “RLC” intends a rod-like liquid crystal compound.
In addition, the “angle” column in Table 1 indicates the in-plane slow axis on the surface of the first retardation layer on the second retardation layer side and the surface of the second retardation layer on the first retardation layer side. The angle formed by the in-plane slow axis is intended.
表1に示すように、本発明の旋光フィルムにおいては、所望の効果が得られることが確認された。
なかでも、実施例1〜7と実施例8〜9との比較から分かるように、Δnd/θが4.1超6.1未満の場合、旋光性がより優れることが確認された。
また、実施例1〜4と実施例5〜6との比較から分かるように、Δnd・min/Δnd・maxの範囲が0.08〜0.50の場合、色づきがより抑制されることが確認された。
As shown in Table 1, it was confirmed that the desired effect was obtained in the optical rotation film of the present invention.
In particular, as can be seen from the comparison between Examples 1 to 7 and Examples 8 to 9, it was confirmed that when Δnd / θ is more than 4.1 and less than 6.1, the optical rotation is more excellent.
Further, as can be seen from the comparison between Examples 1 to 4 and Examples 5 to 6, it is confirmed that coloring is further suppressed when the range of Δnd · min / Δnd · max is 0.08 to 0.50. It was done.
10a,10b,10c 旋光フィルム
12a,12b,12c 第1位相差層
14a,14b,14c 第2位相差層
10a, 10b, 10c Optical rotatory films 12a, 12b, 12c First retardation layer 14a, 14b, 14c Second retardation layer
Claims (7)
前記第1位相差層および前記第2位相差層の少なくとも一方は、その厚み方向に沿って延びる螺旋軸に沿って捩れ配向した液晶化合物を含み、
前記第1位相差層の前記第2位相差層側の表面での面内遅相軸と、前記第2位相差層の前記第1位相差層側の表面での面内遅相軸とのなす角が0〜15°であり、
前記第1位相差層の波長550nmにおける厚み方向のレタデーション値、および、前記第2位相差層の波長550nmにおける厚み方向のレタデーション値の一方が負の値であり、かつ、他方が正の値であり、
波長550nmで測定した前記第1位相差層の屈折率異方性Δn1と前記第1位相差層の厚みd1との積Δn1d1、および、波長550nmで測定した前記第2位相差層の屈折率異方性Δn2と前記第2位相差層の厚みd2との積Δn2d2のうち値が大きい方をΔnd・maxとし、値の小さい方をΔnd・minとした場合、Δnd・min/Δnd・maxの範囲が0.06〜0.8である、旋光フィルム。 An optical rotatory film having a first retardation layer and a second retardation layer,
At least one of the first retardation layer and the second retardation layer includes a liquid crystal compound that is twisted and aligned along a helical axis extending along a thickness direction thereof.
An in-plane slow axis on the surface of the first retardation layer on the second retardation layer side, and an in-plane slow axis on the surface of the second retardation layer on the first retardation layer side The formed angle is 0-15 °,
One of the retardation value in the thickness direction at a wavelength of 550 nm of the first retardation layer and the retardation value in the thickness direction at a wavelength of 550 nm of the second retardation layer is a negative value, and the other is a positive value. Yes,
The product Δn1d1 of the refractive index anisotropy Δn1 of the first retardation layer measured at a wavelength of 550 nm and the thickness d1 of the first retardation layer, and the refractive index difference of the second retardation layer measured at a wavelength of 550 nm. Of the products Δn2d2 of the directivity Δn2 and the thickness d2 of the second retardation layer, the larger value is Δnd · max, and the smaller value is Δnd · min, the range of Δnd · min / Δnd · max Is an optical rotatory film.
波長550nmで測定した前記層Xの屈折率異方性Δnと前記層Xの厚みdとの積Δndと、前記液晶化合物の捩れ角θとの比であるΔnd/θが、4.1〜6.1である、請求項1に記載の旋光フィルム。 In the layer X containing the twisted liquid crystal compound among the first retardation layer and the second retardation layer,
Δnd / θ, which is the ratio between the product Δnd of the refractive index anisotropy Δn of the layer X measured at a wavelength of 550 nm and the thickness d of the layer X, and the twist angle θ of the liquid crystal compound is 4.1 to 6 The optical rotation film according to claim 1, which is .1.
前記第1位相差層および前記第2位相差層の他方の層に含まれる前記液晶化合物の捩れ角が22.5±10°の範囲である、請求項3に記載の旋光フィルム。 The twist angle of the liquid crystal compound contained in one of the first retardation layer and the second retardation layer is in a range of 67.5 ± 10 °;
The optical rotation film according to claim 3, wherein the twist angle of the liquid crystal compound contained in the other layer of the first retardation layer and the second retardation layer is in the range of 22.5 ± 10 °.
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