JP2010202517A - Mixture of intermediates for producing liquid crystal compound, method for producing the same, and mixture of liquid crystal compounds - Google Patents
Mixture of intermediates for producing liquid crystal compound, method for producing the same, and mixture of liquid crystal compounds Download PDFInfo
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- JP2010202517A JP2010202517A JP2009046187A JP2009046187A JP2010202517A JP 2010202517 A JP2010202517 A JP 2010202517A JP 2009046187 A JP2009046187 A JP 2009046187A JP 2009046187 A JP2009046187 A JP 2009046187A JP 2010202517 A JP2010202517 A JP 2010202517A
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- Prior art keywords
- mixture
- liquid crystal
- formula
- compound
- compound represented
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- Granted
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- 239000000543 intermediate Substances 0.000 title abstract description 9
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- 125000000217 alkyl group Chemical group 0.000 claims description 17
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- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 9
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Abstract
Description
本発明は、配向性に優れ、輝度向上率が高い液晶化合物混合物の製造中間体混合物、その製造方法及び液晶化合物混合物に関する。 The present invention relates to a production intermediate mixture of a liquid crystal compound mixture having excellent orientation and a high luminance improvement rate, a production method thereof, and a liquid crystal compound mixture.
近年、液晶ディスプレイに使用される光学補償板等の光学フィルムとして、液晶ポリマーあるいは官能基を有する液晶化合物を配向処理した液晶配向フィルムが開発されている。このフィルムは、高分子フィルムの延伸技術を利用した複屈折フィルムでは実現不可能な、より高度な配向状態、すなわち傾斜配向、ねじれ配向等の配向を実現できるものとして注目されている。 In recent years, as an optical film such as an optical compensator used in a liquid crystal display, a liquid crystal alignment film obtained by aligning a liquid crystal polymer or a liquid crystal compound having a functional group has been developed. This film is attracting attention as being capable of realizing a higher degree of orientation, that is, an orientation such as a tilt orientation or a twist orientation, which cannot be realized by a birefringent film utilizing a polymer film stretching technique.
先に、本出願人は、このような液晶配向フィルムを製造するための液晶化合物として、後述する式（ＩＶ）で表される液晶化合物を見出している（特許文献１）。この化合物は、液晶相を示す温度範囲がより広く、化学的に安定であり、安価に製造でき、しかも、選択反射波長帯域Δλが広いものである。
後述するように、式（ＩＶ）で表される液晶化合物は、式（ＶＩＩ）
Previously, the present applicant has found a liquid crystal compound represented by the formula (IV) described later as a liquid crystal compound for producing such a liquid crystal alignment film (Patent Document 1). This compound has a wider temperature range showing a liquid crystal phase, is chemically stable, can be produced at low cost, and has a wide selective reflection wavelength band Δλ.
As will be described later, the liquid crystal compound represented by the formula (IV) is represented by the formula (VII):
（式中、Ｘ１〜Ｘ８はそれぞれ独立して、水素原子、炭素数１〜１０のアルキル基等を表す。）で表されるアジン化合物に、後述する式（Ｉ）で表される化合物を反応させることにより製造することができる。 (Wherein, X 1 to X 8 each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, etc.) or a compound represented by the formula (I) described later. Can be made to react.
また、式（Ｉ）で表される化合物の製造方法として、特許文献２には、酸触媒の存在下、アクリル酸又はメタクリル酸と、後述する式（ＩＩＩ）で表されるヒドロキシアルキル基を有する安息香酸誘導体とを反応させる方法が記載されている。 Moreover, as a manufacturing method of the compound represented by Formula (I), in patent document 2, it has acrylic acid or methacrylic acid, and the hydroxyalkyl group represented by Formula (III) mentioned later in presence of an acid catalyst. A method of reacting a benzoic acid derivative is described.
特許文献３には、実施例３において、４−ヒドロキシヘキシルオキシ安息香酸（７０ｍｍｏｌ）のベンゼン溶液に、ハイドロキノン、パラトルエンスルホン酸及びアクリル酸（２１０ｍｍｏｌ）を加え、加熱撹拌して脱水し、アクリル酸エステルを製造する方法が記載されている。 In Patent Document 3, hydroquinone, paratoluenesulfonic acid and acrylic acid (210 mmol) are added to a benzene solution of 4-hydroxyhexyloxybenzoic acid (70 mmol) in Example 3, and the mixture is heated and stirred to dehydrate, and acrylic acid is added. A method for producing an ester is described.
さらに、特許文献４には、例１において、クロロホルム中、４−（６−ヒドロキシヘキシルオキシ）安息香酸、４−トルオールスルホン酸、ハイドロキノン及びアクリル酸を撹拌することによって、４−（６−アクリロイルへキシルオキシ）安息香酸を製造する方法が記載されている。 Further, in Patent Document 4, 4- (6-acryloyl) in Example 1 was stirred by stirring 4- (6-hydroxyhexyloxy) benzoic acid, 4-toluolsulfonic acid, hydroquinone and acrylic acid in chloroform. A method for producing (hexyloxy) benzoic acid is described.
本発明者らは、上記した特許文献２〜４に記載された方法のうち、特許文献２に記載の方法により、アクリル酸を２０当量用いて反応を行ったところ、式（ＶＩ） Among the methods described in Patent Documents 2 to 4 described above, the present inventors carried out the reaction using 20 equivalents of acrylic acid by the method described in Patent Document 2, and the formula (VI)
（式中、ｎは１〜１０の整数を表す。）で表される副生物が９重量％も生成してしまうことが分かった。また、前記ヒドロキシアルキル基を有する安息香酸誘導体の二量化由来の副生物（式（ＩＩ）で表される化合物）の生成は１重量％以下であった。 It was found that the by-product represented by (wherein n represents an integer of 1 to 10) produced 9% by weight. Moreover, the production | generation of the byproduct (compound represented by Formula (II)) derived from the dimerization of the benzoic acid derivative which has the said hydroxyalkyl group was 1 weight% or less.
特許文献３に記載された方法では、前記式（ＶＩ）で表される化合物が副生し、さらに４−ヒドロキシヘキシルオキシ安息香酸が７．５重量％も残存することがわかった。
また、特許文献４に記載された方法によると、前記ヒドロキシアルキル基を有する安息香酸誘導体の二量化由来の副生物（式（ＩＩ）で表される化合物）の副生は、３重量％以下だった。
In the method described in Patent Document 3, it was found that the compound represented by the formula (VI) was by-produced, and further 4-hydroxyhexyloxybenzoic acid remained as much as 7.5% by weight.
Moreover, according to the method described in Patent Document 4, the by-product of the byproduct (compound represented by formula (II)) derived from dimerization of the benzoic acid derivative having the hydroxyalkyl group is 3% by weight or less. It was.
本発明者らは、上記特許文献４に記載の方法で得られた、式（Ｉ）で表される化合物を主成分とする混合物を、前記式（ＶＩＩ）で表される化合物と反応させて、式（ＩＶ）で表される液晶化合物を主成分とする液晶化合物の混合物を合成した。
しかしながら、得られた液晶化合物の混合物は、重要な光学特性である輝度向上率や配向性において、目標値（輝度向上率：１２４％以上、配向性評価４以上）を満足するものではなかった。
The inventors of the present invention reacted with a compound represented by the formula (VII) a mixture mainly obtained from the compound represented by the formula (I) obtained by the method described in Patent Document 4 above. A mixture of liquid crystal compounds mainly composed of the liquid crystal compound represented by the formula (IV) was synthesized.
However, the obtained mixture of liquid crystal compounds did not satisfy the target values (brightness improvement rate: 124% or more, orientation evaluation 4 or more) in the luminance improvement rate and orientation, which are important optical characteristics.
本発明は、このような実情に鑑みてなされたものであり、配向性に優れ、輝度向上率の高い液晶化合物を得ることができる、製造中間体混合物、その製造方法、及び、液晶化合物の混合物を提供することを目的とする。 The present invention has been made in view of such circumstances, and is a production intermediate mixture, a production method thereof, and a mixture of liquid crystal compounds, which can obtain a liquid crystal compound having excellent orientation and a high luminance improvement rate. The purpose is to provide.
本発明者らは、上記課題を解決すべく、鋭意研究した結果、後記式（Ｉ）で表される化合物に、式（ＩＩ）で表される化合物を混合物全体に対して３．５〜１２重量％含有させた混合物を原料（製造中間体）として用いると、配向性に優れ、輝度向上率の高い、液晶化合物の混合物が得られることを見出した。そして、式（ＩＩ）で表される化合物を３．５〜１２重量％含有する混合物を得るためには、式（Ｉ）で表される化合物を製造する際に、用いるアクリル酸又はメタクリル酸の使用量を制御すればよいことを見出し、本発明を完成するに至った。 As a result of intensive research aimed at solving the above-mentioned problems, the inventors of the present invention have added a compound represented by the formula (II) to a compound represented by the formula (I) described below to 3.5 to 12 with respect to the entire mixture. It was found that when a mixture containing wt% was used as a raw material (production intermediate), a liquid crystal compound mixture having excellent orientation and a high luminance improvement rate was obtained. In order to obtain a mixture containing 3.5 to 12% by weight of the compound represented by the formula (II), the acrylic acid or methacrylic acid used in the production of the compound represented by the formula (I) The inventors have found that the amount used can be controlled, and have completed the present invention.
かくして本発明の第１によれば、下記（１）の混合物が提供される。
（１）式（Ｉ）
Thus, according to the first aspect of the present invention, the following mixture (1) is provided.
(1) Formula (I)
（式中、Ａは水素原子又はメチル基を表し、ｎは１〜１２の整数を表す。）で表される化合物と、式（ＩＩ） (Wherein A represents a hydrogen atom or a methyl group, and n represents an integer of 1 to 12), and the formula (II)
（式中、Ａ及びｎは前記と同じ意味を表す。）で表される化合物との混合物であって、前記式（ＩＩ）で表される化合物を３．５〜１２重量％含有する混合物。 (Wherein A and n represent the same meaning as described above), and a mixture containing 3.5 to 12% by weight of the compound represented by the formula (II).
本発明の第２によれば、下記（２）〜（６）の本発明の混合物の製造方法が提供される。
（２）酸触媒の存在下、アクリル酸又はメタクリル酸と、式（III）
According to 2nd of this invention, the manufacturing method of the mixture of this invention of following (2)-(6) is provided.
(2) Acrylic acid or methacrylic acid in the presence of an acid catalyst and formula (III)
（式中、ｎは１〜１２の整数を表す。）で表される化合物とを反応させて、式（Ｉ） (Wherein n represents an integer of 1 to 12) is reacted with a compound represented by formula (I)
（式中、ｎは前記と同じ意味を表し、Ａは水素原子又はメチル基を表す。）で表される化合物と、式（ＩＩ） (Wherein n represents the same meaning as described above, and A represents a hydrogen atom or a methyl group), and a compound represented by formula (II)
（式中、Ａ及びｎは前記と同じ意味を表す。）で表される化合物との混合物を製造する方法であって、アクリル酸又はメタクリル酸の使用量を制御することにより、前記式（ＩＩ）で表される化合物の生成量を３．５〜１２重量％に制御することを特徴とする（１）に記載の混合物の製造方法。 (Wherein A and n represent the same meaning as described above), wherein the mixture of the compound represented by formula (II) is controlled by controlling the amount of acrylic acid or methacrylic acid used. The production amount of the compound represented by (1) is controlled to 3.5 to 12% by weight.
（３）アクリル酸又はメタクリル酸を、前記式（III）で表される化合物に対して、２〜１０当量使用することを特徴とする、（２）に記載の製造方法。
（４）酸触媒としてスルホン酸類を用いることを特徴とする、（２）又は（３）に記載の製造方法。
（５）スルホン酸類として、メタンスルホン酸又はパラトルエンスルホン酸を用いることを特徴とする、（４）に記載の製造方法。
（６）酸触媒を、前記式（III）で表される化合物に対して、０．０１〜０．３当量使用すること特徴とする、（２）〜（５）のいずれかに記載の製造方法。
(3) The production method according to (2), wherein 2 to 10 equivalents of acrylic acid or methacrylic acid are used with respect to the compound represented by the formula (III).
(4) The production method according to (2) or (3), wherein a sulfonic acid is used as the acid catalyst.
(5) The production method according to (4), wherein methanesulfonic acid or paratoluenesulfonic acid is used as the sulfonic acid.
(6) The production according to any one of (2) to (5), wherein the acid catalyst is used in an amount of 0.01 to 0.3 equivalents relative to the compound represented by the formula (III). Method.
本発明の第３によれば、下記（７）の液晶化合物の混合物が提供される。
（７）式（ＩＶ）
According to the third aspect of the present invention, a mixture of the following liquid crystal compounds (7) is provided.
(7) Formula (IV)
〔式中、Ａは水素原子あるいはメチル基を表し、ｎは１〜１２の整数を表し、Ｘ１〜Ｘ８はそれぞれ独立して、水素原子、ハロゲン原子、置換基を有してもよい炭素数１〜１０のアルキル基、シアノ基、ニトロ基、−ＯＲ１、−Ｏ−Ｃ（＝Ｏ）−Ｒ１、−Ｃ（＝Ｏ）−ＯＲ１、−Ｏ−Ｃ（＝Ｏ）−ＯＲ１、−ＮＲ２−Ｃ（＝Ｏ）−Ｒ１、−Ｃ（＝Ｏ）−ＮＲ２Ｒ３、又はＯ−Ｃ（＝Ｏ）−ＮＲ２Ｒ３を表す。Ｒ１は、水素原子又は置換基を有してもよい炭素数１〜１０のアルキル基を表し、Ｒ１がアルキル基である場合、当該アルキル基には、−Ｏ−、−Ｓ−、−Ｏ−Ｃ（＝Ｏ）−、−Ｃ（＝Ｏ）−Ｏ−、−Ｏ−Ｃ（＝Ｏ）−Ｏ−、−ＮＲ４−Ｃ（＝Ｏ）−、−Ｃ（＝Ｏ）−ＮＲ４−、−ＮＲ４−、又はＣ（＝Ｏ）−が介在していてもよい（ただし、−Ｏ−及び−Ｓ−がそれぞれ２以上隣接して介在する場合を除く。）。Ｒ２、Ｒ３、Ｒ４はそれぞれ独立して、水素原子又は炭素数１〜６のアルキル基を表す。〕で表される液晶化合物と、式（Ｖ） [In the formula, A represents a hydrogen atom or a methyl group, n represents an integer of 1 to 12, and X 1 to X 8 each independently represent a hydrogen atom, a halogen atom, or a carbon that may have a substituent. Formula 1-10 alkyl group, cyano group, nitro group, —OR 1 , —O—C (═O) —R 1 , —C (═O) —OR 1 , —O—C (═O) —OR 1 , —NR 2 —C (═O) —R 1 , —C (═O) —NR 2 R 3 , or O—C (═O) —NR 2 R 3 . R 1 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have a substituent. When R 1 is an alkyl group, the alkyl group includes —O—, —S—, — O—C (═O) —, —C (═O) —O—, —O—C (═O) —O—, —NR 4 —C (═O) —, —C (═O) —NR 4 -, - NR 4 -, or C (= O) - is optionally interposed (unless However, the -O- and -S- is interposed adjacent 2 or more, respectively.). R 2 , R 3 and R 4 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. A liquid crystal compound represented by formula (V)
（式中、Ａ、ｎ、Ｘ１〜Ｘ８は、前記と同じ意味を表す。）で表される液晶化合物の混合物であって、前記式（Ｖ）で表される液晶化合物を３．５〜１２重量％含有する液晶化合物の混合物。 (Wherein A, n, and X 1 to X 8 represent the same meaning as described above), and the liquid crystal compound represented by the formula (V) is 3.5. A mixture of liquid crystal compounds containing ˜12% by weight.
本発明の混合物を用いると、配向性に優れ、輝度向上率の高い、液晶化合物の混合物を収率よく製造することができる。
本発明の混合物の製造方法によれば、本発明の混合物を、一段階で簡便に、かつ収率よく製造することができる。
本発明の液晶化合物の混合物は配向性に優れ、輝度向上率が高く、光学特性に優れるものである。
When the mixture of the present invention is used, a mixture of liquid crystal compounds having excellent orientation and a high luminance improvement rate can be produced with high yield.
According to the method for producing a mixture of the present invention, the mixture of the present invention can be produced easily and with a high yield in one step.
The mixture of the liquid crystal compounds of the present invention has excellent orientation, a high luminance improvement rate, and excellent optical characteristics.
以下、本発明を、１）本発明の混合物、２）混合物の製造方法、及び３）液晶化合物の混合物に項分けして詳細に説明する。 Hereinafter, the present invention will be described in detail by dividing into 1) a mixture of the present invention, 2) a method for producing the mixture, and 3) a mixture of liquid crystal compounds.
１）本発明の混合物
本発明の第１は、前記式（Ｉ）で表される化合物（以下、「化合物（Ｉ）」という。）と、式（ＩＩ）で表される化合物（以下、「化合物（ＩＩ）」という。）との混合物であって、化合物（ＩＩ）を３．５〜１２重量％含有する混合物（以下、「本発明の混合物」ということがある。）である。本発明では化合物（Ｉ）と化合物（ＩＩ）以外の化合物（例えば安息香酸誘導体の３量化由来の副生物）を、本発明の効果を損なわない範囲で微量に含有していても良い。
1) Mixture of the Present Invention The first of the present invention is a compound represented by the formula (I) (hereinafter referred to as “compound (I)”) and a compound represented by the formula (II) (hereinafter referred to as “compound”). Compound (II) "), and a mixture containing 3.5 to 12% by weight of Compound (II) (hereinafter sometimes referred to as" the mixture of the present invention "). In the present invention, a compound other than compound (I) and compound (II) (for example, a byproduct derived from trimerization of a benzoic acid derivative) may be contained in a trace amount as long as the effects of the present invention are not impaired.
前記式（Ｉ）、（ＩＩ）中、Ａは水素原子又はメチル基を表し、水素原子が好ましい。ｎは１〜１２の整数を表し、２〜８の整数が好ましく、４〜７の整数がより好ましく、６が特に好ましい。 In the formulas (I) and (II), A represents a hydrogen atom or a methyl group, and preferably a hydrogen atom. n represents an integer of 1 to 12, an integer of 2 to 8 is preferable, an integer of 4 to 7 is more preferable, and 6 is particularly preferable.
本発明の混合物は、後述する液晶化合物の混合物の好適な製造中間体となり得る。
すなわち、本発明の混合物を製造中間体として用いると、化合物（Ｉ）のみを製造中間体として用いる場合、及び、化合物（Ｉ）と化合物（ＩＩ）の混合物であって、化合物（ＩＩ）を３．５重量％未満しか含まない混合物、又は化合物（ＩＩ）を１２重量％より多く含む混合物を製造中間体として用いる場合よりも、配向性に優れた、輝度向上率の高い、液晶化合物の混合物を収率よく製造することができる。
The mixture of the present invention can be a suitable production intermediate for a mixture of liquid crystal compounds described below.
That is, when the mixture of the present invention is used as a production intermediate, when only compound (I) is used as the production intermediate, and a mixture of compound (I) and compound (II), A mixture of liquid crystal compounds having excellent orientation and a high luminance improvement rate than the case where a mixture containing less than 5% by weight or a mixture containing more than 12% by weight of compound (II) is used as a production intermediate It can be produced with good yield.
本発明の混合物の製造方法としては、特に制限されないが、本発明の混合物を一段階で簡便に、かつ収率よく製造することができることから、後述する本発明の混合物の製造方法が好ましい。 Although it does not restrict | limit especially as a manufacturing method of the mixture of this invention, Since the mixture of this invention can be manufactured simply and with a sufficient yield in one step, the manufacturing method of this invention mentioned later is preferable.
２）混合物の製造方法
本発明の混合物の製造方法は、酸触媒の存在下、アクリル酸又はメタクリル酸（以下、両者を併せて、「（メタ）アクリル酸」ということがある。）、好ましくはアクリル酸と、前記式（ＩＩＩ）で表される化合物（以下、「化合物（ＩＩＩ）」という。）を反応させて、本発明の混合物を製造する方法であって、（メタ）アクリル酸の使用量を制御することにより、化合物（ＩＩ）の生成量を３．５〜１２重量％、好ましくは３．６〜１０重量％、更に好ましくは３．７〜８重量％、特に好ましくは３．８〜６重量％に制御することを特徴とする。
2) Method for Producing Mixture The method for producing the mixture of the present invention is acrylic acid or methacrylic acid (hereinafter sometimes referred to as “(meth) acrylic acid”) in the presence of an acid catalyst, preferably. A method for producing a mixture of the present invention by reacting acrylic acid with a compound represented by the above formula (III) (hereinafter referred to as “compound (III)”), which comprises using (meth) acrylic acid By controlling the amount, the amount of compound (II) produced is 3.5 to 12% by weight, preferably 3.6 to 10% by weight, more preferably 3.7 to 8% by weight, particularly preferably 3.8. Controlled to ˜6% by weight.
（メタ）アクリル酸の使用量を制御する方法としては、結果として、化合物（ＩＩ）の生成量が３．５〜１２重量％に制御できるものであれば、特に限定されないが、（メタ）アクリル酸の使用量を、化合物（ＩＩＩ）に対して、２〜１０当量とすることが好ましく、３〜８当量とすることがより好ましく、３．５〜５．０当量とするのが更に好ましい。このような範囲の量の（メタ）アクリル酸を用いることで、得られる混合物中の化合物（ＩＩ）の含有量を、３．５〜１２重量％により確実に制御することができる。 The method for controlling the amount of (meth) acrylic acid used is not particularly limited as long as the amount of compound (II) produced can be controlled to 3.5 to 12% by weight. The amount of acid used is preferably 2 to 10 equivalents, more preferably 3 to 8 equivalents, still more preferably 3.5 to 5.0 equivalents, relative to compound (III). By using the amount of (meth) acrylic acid in such a range, the content of compound (II) in the resulting mixture can be reliably controlled by 3.5 to 12% by weight.
用いる酸触媒としては、メタンスルホン酸、ベンゼンスルホン酸、パラトルエンスルホン酸等のスルホン酸類；塩酸、硫酸、硝酸などの無機酸類；等が挙げられる。これらの中でも、本発明の混合物を簡便に得られることから、スルホン酸類が好ましく、メタンスルホン酸、パラトルエンスルホン酸が特に好ましい。 Examples of the acid catalyst to be used include sulfonic acids such as methanesulfonic acid, benzenesulfonic acid and paratoluenesulfonic acid; inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid; Among these, sulfonic acids are preferable, and methanesulfonic acid and paratoluenesulfonic acid are particularly preferable because the mixture of the present invention can be easily obtained.
酸触媒の使用量は、化合物（ＩＩＩ）に対して、０．０１〜０．３当量であるのが好ましく、０．０５〜０．２５当量であるのがより好ましい。 The amount of the acid catalyst to be used is preferably 0.01 to 0.3 equivalent, more preferably 0.05 to 0.25 equivalent, relative to compound (III).
原料の化合物（ＩＩＩ）は、例えば、４−ヒドロキシ安息香酸とハロゲン化アルキルアルコールを、アルカリ水溶液中で加熱撹拌する方法（特許文献３）等の公知の方法によって製造することができる。 The starting compound (III) can be produced, for example, by a known method such as a method in which 4-hydroxybenzoic acid and a halogenated alkyl alcohol are heated and stirred in an aqueous alkaline solution (Patent Document 3).
（メタ）アクリル酸と化合物（ＩＩＩ）との反応は、溶媒中で行うのが好ましい。
用いる溶媒としては、不活性なものであれば、特に制限されず、例えば、トルエン、キシレン、メシチレン等の芳香族炭化水素；シクロヘキサノン、シクロペンタノン、メチルエチルケトン等のケトン類；酢酸ブチル、酢酸アミル等の酢酸エステル類；クロロホルム、ジクロロメタン、ジクロロエタン等のハロゲン化炭化水素類；シクロペンチルメチルエーテル、テトラヒドロフラン、テトラヒドロピラン等のエーテル類；及びこれらの溶媒の二種以上からなる混合溶媒；等が挙げられる。これらの中でも、取り扱い性に優れる観点から、芳香族炭化水素が好ましく、特にトルエンが好ましい。
The reaction between (meth) acrylic acid and compound (III) is preferably carried out in a solvent.
The solvent to be used is not particularly limited as long as it is inert. For example, aromatic hydrocarbons such as toluene, xylene, mesitylene; ketones such as cyclohexanone, cyclopentanone, methyl ethyl ketone; butyl acetate, amyl acetate, etc. Acetates; halogenated hydrocarbons such as chloroform, dichloromethane and dichloroethane; ethers such as cyclopentylmethyl ether, tetrahydrofuran and tetrahydropyran; and a mixed solvent composed of two or more of these solvents. Among these, from the viewpoint of excellent handleability, aromatic hydrocarbons are preferable, and toluene is particularly preferable.
反応は、例えば、適当な溶媒中、化合物（ＩＩＩ）、所定量の（メタ）アクリル酸、酸触媒、及び、所望によりヒドロキノンモノメチルエーテル等の重合禁止剤を混合し、全容を加熱撹拌することにより行う。また、反応は、生成する水を用いる溶媒との共沸脱水にて系外に除去し、蒸気温度が溶媒の沸点となるまで還流して行うのが好ましい。 The reaction is carried out, for example, by mixing compound (III), a predetermined amount of (meth) acrylic acid, an acid catalyst, and, if desired, a polymerization inhibitor such as hydroquinone monomethyl ether in a suitable solvent, and heating and stirring the whole volume. Do. Further, the reaction is preferably carried out by azeotropic dehydration with a solvent using water to be produced and refluxed until the vapor temperature reaches the boiling point of the solvent.
反応終了後は、有機合成化学における通常の後処理操作を行う。例えば、反応混合物にアルカリ水溶液を加えて水層を中和し、有機層を分離して洗浄した後、有機層に貧溶媒を加えて結晶を析出させることにより、目的とする本発明の混合物を得ることができる。 After completion of the reaction, normal post-treatment operations in organic synthetic chemistry are performed. For example, an aqueous alkali solution is added to the reaction mixture to neutralize the aqueous layer, the organic layer is separated and washed, and then a poor solvent is added to the organic layer to precipitate crystals, whereby the desired mixture of the present invention is obtained. Obtainable.
得られる本発明の混合物が、化合物（ＩＩ）を３．５〜１２重量％含有することは、例えば、該混合物を高速液体クロマトグラフィー（ＨＰＬＣ）により分析し、化合物（Ｉ）と化合物（ＩＩ）の測定データ(チャート)の面積パーセントを算出することにより確認することができる。 The resulting mixture of the present invention contains 3.5 to 12% by weight of compound (II). For example, the mixture is analyzed by high performance liquid chromatography (HPLC), and compound (I) and compound (II) are analyzed. This can be confirmed by calculating the area percentage of the measurement data (chart).
３）液晶化合物の混合物
本発明の第３は、前記式（ＩＶ）で表される液晶化合物（以下、「液晶化合物（ＩＶ）」という。）と、式（Ｖ）で表される液晶化合物（以下、「液晶化合物（Ｖ）」という。）の混合物であって、液晶化合物（Ｖ）を３．５〜１２重量％、好ましくは３．６〜１０重量％、更に好ましくは３．７〜８重量％、特に好ましくは３．８〜６重量％含有する液晶化合物の混合物である。本発明では化合物（ＩＶ）と化合物（Ｖ）以外の化合物を、本発明の効果を損なわない範囲で微量に含有していても良い。
3) Mixture of liquid crystal compounds A third aspect of the present invention is a liquid crystal compound represented by the formula (IV) (hereinafter referred to as “liquid crystal compound (IV)”) and a liquid crystal compound represented by the formula (V) ( Hereinafter, the mixture is referred to as “liquid crystal compound (V)”). The liquid crystal compound (V) is 3.5 to 12% by weight, preferably 3.6 to 10% by weight, and more preferably 3.7 to 8%. It is a mixture of liquid crystal compounds containing wt%, particularly preferably 3.8 to 6 wt%. In the present invention, a compound other than the compound (IV) and the compound (V) may be contained in a trace amount as long as the effects of the present invention are not impaired.
前記式（ＩＶ）、（Ｖ）中、Ａ、ｎは前記と同じ意味を表す。
Ｘ１〜Ｘ８はそれぞれ独立して、水素原子、ハロゲン原子、置換基を有してもよい炭素数１〜１０のアルキル基、シアノ基、ニトロ基、−ＯＲ１、−Ｏ−Ｃ（＝Ｏ）−Ｒ１、−Ｃ（＝Ｏ）−ＯＲ１、−Ｏ−Ｃ（＝Ｏ）−ＯＲ１、−ＮＲ２−Ｃ（＝Ｏ）−Ｒ１、−Ｃ（＝Ｏ）−ＮＲ２Ｒ３、又はＯ−Ｃ（＝Ｏ）−ＮＲ２Ｒ３を表す。
In the formulas (IV) and (V), A and n represent the same meaning as described above.
X 1 to X 8 are each independently a hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, a cyano group, a nitro group, —OR 1 , —O—C (= O) —R 1 , —C (═O) —OR 1 , —O—C (═O) —OR 1 , —NR 2 —C (═O) —R 1 , —C (═O) —NR 2 R 3 or O—C (═O) —NR 2 R 3 is represented.
Ｘ１〜Ｘ８のハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子等が挙げられる。 Examples of the halogen atom for X 1 to X 8 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
置換基を有してもよい炭素数１〜１２のアルキル基のアルキル基としては、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｔ−ブチル基、ｎ−ペンチル基、イソペンチル基、ネオペンチル基、ｎ−へキシル基、ｎ−オクチル基、ｎ−デシル基、ｎ−ドデシル基等が挙げられる。
これらの置換基としては、フッ素原子、塩素原子等のハロゲン原子；メトキシ基、エトキシ基等のアルコキシ基等が挙げられる。
Examples of the alkyl group having 1 to 12 carbon atoms that may have a substituent include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, t -Butyl group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, n-octyl group, n-decyl group, n-dodecyl group and the like.
Examples of these substituents include halogen atoms such as fluorine atom and chlorine atom; alkoxy groups such as methoxy group and ethoxy group.
Ｒ１は、水素原子又は置換基を有してもよい炭素数１〜１０のアルキル基を表し、Ｒ１がアルキル基である場合、当該アルキル基には、−Ｏ−、−Ｓ−、−Ｏ−Ｃ（＝Ｏ）−、−Ｃ（＝Ｏ）−Ｏ−、−Ｏ−Ｃ（＝Ｏ）−Ｏ−、−ＮＲ４−Ｃ（＝Ｏ）−、−Ｃ（＝Ｏ）−ＮＲ４−、−ＮＲ４−、又はＣ（＝Ｏ）−が介在していてもよい。これらの中でも、−Ｏ−、−Ｏ−Ｃ（＝Ｏ）−、−Ｃ（＝Ｏ）−Ｏ−が好ましい。
ただし、−Ｏ−及び−Ｓ−がそれぞれ２以上隣接して介在する場合は除かれる。
Ｒ２、Ｒ３、Ｒ４はそれぞれ独立して、水素原子；メチル基、エチル基等の炭素数１〜６のアルキル基を表す。
R 1 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have a substituent. When R 1 is an alkyl group, the alkyl group includes —O—, —S—, — O—C (═O) —, —C (═O) —O—, —O—C (═O) —O—, —NR 4 —C (═O) —, —C (═O) —NR 4 -, - NR 4 -, or C (= O) - may be interposed. Among these, —O—, —O—C (═O) —, and —C (═O) —O— are preferable.
However, the case where two or more of —O— and —S— are adjacent to each other is excluded.
R 2 , R 3 and R 4 each independently represent a hydrogen atom; an alkyl group having 1 to 6 carbon atoms such as a methyl group or an ethyl group.
前記Ｒ１の、−Ｏ−、−Ｓ−、−Ｏ−Ｃ（＝Ｏ）−、−Ｃ（＝Ｏ）−Ｏ−、−Ｏ−Ｃ（＝Ｏ）−Ｏ−、−ＮＲ４−Ｃ（＝Ｏ）−、−Ｃ（＝Ｏ）−ＮＲ４−、−ＮＲ４−、又は、−Ｃ（＝Ｏ）−が介在するアルキル基の具体例としては、−ＣＨ２−ＣＨ２−Ｏ−ＣＨ２−ＣＨ３、−ＣＨ２−ＣＨ２−Ｓ−ＣＨ２−ＣＨ３、−ＣＨ２−ＣＨ２−Ｏ−Ｃ（＝Ｏ）−ＣＨ３、−ＣＨ２−ＣＨ２−Ｃ（＝Ｏ）−Ｏ−ＣＨ３、−ＣＨ２−Ｏ−Ｃ（＝Ｏ）−Ｏ−ＣＨ２−ＣＨ３、−ＣＨ２−ＣＨ２−ＮＲ２−Ｃ（＝Ｏ）−ＣＨ３、−ＣＨ２−ＣＨ２−Ｃ（＝Ｏ）−ＮＲ２−ＣＨ３、−ＣＨ２−ＮＲ２−ＣＨ２−ＣＨ３、−ＣＨ２−ＣＨ２−Ｃ（＝Ｏ）−ＣＨ３等が挙げられる。 R 1 , —O—, —S—, —O—C (═O) —, —C (═O) —O—, —O—C (═O) —O—, —NR 4 —C Specific examples of the alkyl group mediated by (═O) —, —C (═O) —NR 4 —, —NR 4 —, or —C (═O) — include —CH 2 —CH 2 —O. —CH 2 —CH 3 , —CH 2 —CH 2 —S—CH 2 —CH 3 , —CH 2 —CH 2 —O—C (═O) —CH 3 , —CH 2 —CH 2 —C (= O) —O—CH 3 , —CH 2 —O—C (═O) —O—CH 2 —CH 3 , —CH 2 —CH 2 —NR 2 —C (═O) —CH 3 , —CH 2 —CH 2 —C (═O) —NR 2 —CH 3 , —CH 2 —NR 2 —CH 2 —CH 3 , —CH 2 —CH 2 —C (═O) —CH 3 and the like can be mentioned.
これらの中でも、本発明の液晶化合物の混合物においては、Ｘ１〜Ｘ８としては、原料の入手しやすさ、及び光学特性に優れた液晶化合物の混合物が得られる観点から、
（１）Ｘ１〜Ｘ８がいずれも水素原子であるか、
（２）Ｘ１〜Ｘ５及びＸ７がいずれも水素原子であり、かつＸ６及びＸ８がそれぞれ独立して、−ＯＣＨ３、−ＯＣＨ２ＣＨ３、若しくは−ＣＨ３であるか、
（３）Ｘ１〜Ｘ５、Ｘ７及びＸ８がいずれも水素原子であり、かつ、Ｘ６が、−Ｃ（＝Ｏ）−ＯＲ３、−ＯＣＨ３、−ＯＣＨ２ＣＨ３、−ＣＨ３、−ＣＨ２ＣＨ３、−ＣＨ２ＣＨ２ＣＨ３、若しくはフッ素原子であるか、
（４）Ｘ２〜Ｘ５、Ｘ７及びＸ８がいずれも水素原子であり、かつ、Ｘ１及びＸ６がそれぞれ独立して、−Ｃ（＝Ｏ）−ＯＲ３、−ＯＣＨ３、−ＯＣＨ２ＣＨ３、−ＣＨ３、−ＣＨ２ＣＨ３、−ＣＨ２ＣＨ２ＣＨ３若しくはフッ素原子であるか、又は
（５）Ｘ１〜Ｘ４及びＸ６〜Ｘ８がいずれも水素原子であり、かつ、Ｘ５が、−Ｃ（＝Ｏ）−Ｏ−Ｒ３、−ＯＣＨ３、−ＯＣＨ２ＣＨ３、−ＣＨ３、−ＣＨ２ＣＨ３、−ＣＨ２ＣＨ２ＣＨ３、若しくはフッ素原子であることが好ましく、
Among these, in the mixture of the liquid crystal compounds of the present invention, as X 1 to X 8 , from the viewpoint of obtaining a mixture of liquid crystal compounds excellent in raw material availability and optical characteristics,
(1) Whether X 1 to X 8 are all hydrogen atoms,
(2) X 1 to X 5 and X 7 are all hydrogen atoms, and X 6 and X 8 are each independently —OCH 3 , —OCH 2 CH 3 , or —CH 3 ,
(3) X 1 to X 5 , X 7 and X 8 are all hydrogen atoms, and X 6 is —C (═O) —OR 3 , —OCH 3 , —OCH 2 CH 3 , —CH. 3 , —CH 2 CH 3 , —CH 2 CH 2 CH 3 , or a fluorine atom,
(4) X 2 to X 5 , X 7 and X 8 are all hydrogen atoms, and X 1 and X 6 are each independently —C (═O) —OR 3 , —OCH 3 , — OCH 2 CH 3 , —CH 3 , —CH 2 CH 3 , —CH 2 CH 2 CH 3 or a fluorine atom, or (5) X 1 to X 4 and X 6 to X 8 are all hydrogen atoms. And X 5 is —C (═O) —O—R 3 , —OCH 3 , —OCH 2 CH 3 , —CH 3 , —CH 2 CH 3 , —CH 2 CH 2 CH 3 , or fluorine Preferably an atom,
（２ａ）Ｘ１〜Ｘ５及びＸ７がいずれも水素原子であり、かつ、Ｘ６及びＸ８がともに−ＯＣＨ３であるか、
（３ａ）Ｘ１〜Ｘ５、Ｘ７及びＸ８がいずれも水素原子であり、かつ、Ｘ６が、−Ｃ（＝Ｏ）−ＯＣＨ３、−Ｃ（＝Ｏ）−Ｏ−ＣＨ２ＣＨ２ＣＨ３、−Ｃ（＝Ｏ）−Ｏ−ＣＨ２ＣＨ２ＯＣＨ２ＣＨ２ＣＨ３、若しくは−Ｏ−ＣＨ２ＣＨ３であるか、又は、
（４ａ）Ｘ２〜Ｘ５、Ｘ７及びＸ８がいずれも水素原子であり、かつ、Ｘ１及びＸ６がそれぞれ独立して、−Ｏ−ＣＨ２ＣＨ３、−Ｃ（＝Ｏ）−Ｏ−ＣＨ２ＣＨ２ＣＨ２ＣＨ３、若しくは−Ｃ（＝Ｏ）−ＯＣＨ３であることがより好ましい。
(2a) X 1 to X 5 and X 7 are all hydrogen atoms, and X 6 and X 8 are both —OCH 3 ,
(3a) X 1 to X 5 , X 7 and X 8 are all hydrogen atoms, and X 6 is —C (═O) —OCH 3 , —C (═O) —O—CH 2 CH 2 CH 3, -C (= O ) -O-CH 2 CH 2 OCH 2 CH 2 CH 3, or whether it is -O-CH 2 CH 3, or,
(4a) X 2 to X 5 , X 7 and X 8 are all hydrogen atoms, and X 1 and X 6 are each independently —O—CH 2 CH 3 , —C (═O) —. O—CH 2 CH 2 CH 2 CH 3 or —C (═O) —OCH 3 is more preferable.
本発明の、液晶化合物（ＩＶ）と液晶化合物（Ｖ）の混合物であって、液晶化合物（Ｖ）を３．５〜１２重量％含有する液晶化合物の混合物は、配向性に優れ、輝度向上率が高く、光学特性に優れた液晶化合物である。
配向性は、後述の方法により評価し、通常、４以上であるのが好ましい。
輝度向上率は、後述の方法により評価し、通常、１２４％以上であるのが好ましい。
The mixture of the liquid crystal compound (IV) and the liquid crystal compound (V) according to the present invention, the mixture of the liquid crystal compound containing 3.5 to 12% by weight of the liquid crystal compound (V), is excellent in orientation and has a luminance improvement rate Is a liquid crystal compound having high optical properties.
The orientation is evaluated by the method described later, and is usually preferably 4 or more.
The luminance improvement rate is evaluated by the method described later, and is usually preferably 124% or more.
本発明の液晶化合物の混合物を製造する方法としては、特に制約はないが、前記、本発明の混合物を用いる方法が好ましい。前記本発明の混合物を用いると、簡便に本発明の液晶化合物の混合物を得ることができる。 Although there is no restriction | limiting in particular as a method of manufacturing the liquid crystal compound mixture of this invention, The method using the said mixture of this invention is preferable. When the mixture of the present invention is used, the liquid crystal compound mixture of the present invention can be easily obtained.
具体的には、本発明の混合物の溶媒溶液に、所定量の、スルホニルハライド及び塩基を添加して撹拌した後、式（ＶＩＩ） Specifically, a predetermined amount of a sulfonyl halide and a base are added to a solvent solution of the mixture of the present invention and stirred, and then the formula (VII)
（Ｘ１〜Ｘ８は前記と同じ意味を表す。）で表される化合物（以下、「化合物（ＶＩＩ）」という。）を加え、全容を所定温度で撹拌する。 (X 1 to X 8 represent the same meaning as described above) is added (hereinafter referred to as “compound (VII)”), and the whole volume is stirred at a predetermined temperature.
ここで用いるスルホニルハライドとしては、メタンスルホニルクロライド、トリフルオロメタンスルホニルクロライド、フェニルスルホニルクロライド、パラトルエンスルホニルクロライドなどが挙げられる。
スルホニルハライドの使用量は、化合物（ＶＩＩ）に対して、通常２〜３倍モルである。
Examples of the sulfonyl halide used here include methanesulfonyl chloride, trifluoromethanesulfonyl chloride, phenylsulfonyl chloride, paratoluenesulfonyl chloride, and the like.
The amount of the sulfonyl halide to be used is generally 2 to 3 moles compared to Compound (VII).
用いる塩基としては、トリエチルアミン、ジイソプロピルエチルアミン、ピリジン等の有機塩基などが挙げられる。
塩基の使用量は、化合物（ＶＩＩ）に対して、通常２〜３倍モルである。
Examples of the base used include organic bases such as triethylamine, diisopropylethylamine, and pyridine.
The amount of the base to be used is generally 2-3 moles compared to Compound (VII).
また、この場合、反応を促進する目的で、反応液に４−ジメチルアミノピリジンを添加することも好ましい。
４−ジメチルアミノピリジンの添加量は、化合物（ＶＩＩ）に対して、通常０．１〜１倍モルである。
In this case, it is also preferable to add 4-dimethylaminopyridine to the reaction solution for the purpose of promoting the reaction.
The addition amount of 4-dimethylaminopyridine is usually 0.1 to 1 times mol with respect to compound (VII).
反応温度は、通常、０℃から溶媒の還流温度、好ましくは１０℃〜５０℃である。
反応時間は、反応規模等にもよるが、通常、数分から数十時間、好ましくは数十分から数時間である。
The reaction temperature is usually from 0 ° C to the reflux temperature of the solvent, preferably from 10 ° C to 50 ° C.
Although depending on the reaction scale and the like, the reaction time is usually from several minutes to several tens of hours, preferably from several tens of minutes to several hours.
反応終了後は、反応混合物に貧溶媒を加え、析出する結晶をろ別し、必要により、得られる粗結晶を洗浄あるいは再結晶することにより、目的とする本発明の液晶化合物の混合物を得ることができる。 After completion of the reaction, a poor solvent is added to the reaction mixture, the precipitated crystals are filtered off, and the obtained crude crystals are washed or recrystallized, if necessary, to obtain the target liquid crystal compound mixture of the present invention. Can do.
得られる液晶化合物の混合物が、液晶化合物（Ｖ）を３．５〜１２重量％含有することは、例えば、該混合物を高速液体クロマトグラフィー（ＨＰＬＣ）により分析し、液晶化合物（ＩＶ）と液晶化合物（Ｖ）の測定データ(チャート)の面積パーセントを算出することにより確認することができる。 The mixture of the obtained liquid crystal compound contains 3.5 to 12% by weight of the liquid crystal compound (V). For example, the mixture is analyzed by high performance liquid chromatography (HPLC), and the liquid crystal compound (IV) and the liquid crystal compound are analyzed. This can be confirmed by calculating the area percentage of the measurement data (chart) of (V).
本発明の液晶化合物の混合物は配向性に優れ、輝度向上率が高く、光学特性に優れるものである。 The mixture of the liquid crystal compounds of the present invention has excellent orientation, a high luminance improvement rate, and excellent optical characteristics.
本発明を実施例によりさらに詳細に説明するが、本発明は以下の実施例のみに限定されるものではない。なお、部及び％は特に断りのない限り重量基準である。
本実施例において行った試験方法は以下のとおりである。
なお、用いた高速液体クロマトグラフ（ＨＰＬＣ）は以下に示すものを用いた。
ＨＰＬＣ：
使用装置 ：Ａｇｉｌｅｎｔ製 ＨＰ−１１００
使用カラム ：Ａｇｉｌｅｎｔ製 ＥＣＬＩＰＳＥ−Ｃ１８ ４．６ｍｍ×２５０ｍｍ
カラム温度 ：４０℃
流量 ：１ｍｌ／ｍｉｎ
インジェクション量(サンプル濃度)：１μＬ（１ｗｔ％）
検出器 ：ＵＶ２５４ｎｍ
The present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples. Parts and% are based on weight unless otherwise specified.
The test methods performed in this example are as follows.
The following high performance liquid chromatograph (HPLC) was used.
HPLC:
Equipment used: HP-1100 manufactured by Agilent
Column used: ECLIPSE-C18 made by Agilent 4.6 mm × 250 mm
Column temperature: 40 ° C
Flow rate: 1 ml / min
Injection volume (sample concentration): 1μL (1wt%)
Detector: UV254nm
グラジェント条件は下記の通りである。 The gradient conditions are as follows.
Ａ：アセトニトリル／ＴＨＦ／Ｈ２０（０．１ｗｔ％リン酸添加）＝ ５０／１０／４０
Ｂ：アセトニトリル／ＴＨＦ／Ｈ２０（０．１ｗｔ％リン酸添加）＝ ８５／１０／５
A: Acetonitrile / THF / H 2 0 (0.1 wt% phosphoric acid added) = 50/10/40
B: Acetonitrile / THF / H 2 0 (0.1 wt% phosphoric acid added) = 85/10/5
配向性の評価、輝度向上率の測定は、以下のように行った。
（輝度向上率の測定）
工程１：反射型偏光子の作製
厚さ１００μｍ、幅５０ｍｍ、長さ２００ｍｍの脂環式オレフィンポリマーフィルム（ゼオノアフィルム、オプテス社製）の片面を、表面の濡れ指数が５６ｄｙｎｅ／ｃｍになるように、コロナ放電処理を施した。これを基材フィルムとして用いた。
The evaluation of the orientation and the measurement of the luminance improvement rate were performed as follows.
(Measurement of luminance improvement rate)
Step 1: Production of a reflective polarizer A surface of one side of an alicyclic olefin polymer film (Zeonor film, manufactured by Optes, Inc.) having a thickness of 100 μm, a width of 50 mm, and a length of 200 mm is set to 56 dyne / cm. Corona discharge treatment was performed. This was used as a substrate film.
以下の組成からなる配向膜用組成物を、前記基材フィルムのコロナ放電処理を施した面に、ワイヤーバー＃４を用いて塗布した。塗布後１２０℃にて５分間乾燥し、膜厚０．２μｍの乾膜を作製した。 The composition for alignment film which consists of the following compositions was apply | coated to the surface which gave the corona discharge process of the said base film using wire bar # 4. After coating, the film was dried at 120 ° C. for 5 minutes to produce a dry film having a thickness of 0.2 μm.
〔配向膜用組成物〕
変性ポリアミド：
・ＦＲ１０５（鉛市社製、ファインレジン、部分メトキシメチル化ポリアミド） ９０重量部
・Ａ９０（東レ社製、ＡＱ−ナイロン、部分アルキルアミノ化ポリアミド） １０重量部
溶剤：
・１−プロパノール（溶解度パラメータ１１．８） ３２３３重量部
架橋剤：
・エラストロン ＢＮ０４ １．０重量部
[Composition for alignment film]
Modified polyamide:
FR105 (Lead City, fine resin, partially methoxymethylated polyamide) 90 parts by weight A90 (Toray, AQ-nylon, partially alkylated polyamide) 10 parts by weight Solvent:
1-propanol (solubility parameter 11.8) 3233 parts by weight crosslinker:
-Elastron BN04 1.0 part by weight
該乾膜を一方向にラビング処理することで、配向膜を得た。作成した配向膜上に下記組成の重合性液晶化合物を含む組成物をワイヤーバー＃６を用いて塗布し、１００℃にて５分間乾燥及び配向熟成した。 The dry film was rubbed in one direction to obtain an alignment film. A composition containing a polymerizable liquid crystal compound having the following composition was applied onto the prepared alignment film using a wire bar # 6, dried at 100 ° C. for 5 minutes, and alignment matured.
〔コレステリック規則性を有する樹脂層を構成する重合性液晶化合物を含む組成物〕
液晶化合物１００重量部に対し、シクロペンタノン１５３重量部に溶解して溶液とした。これに、光重合開始剤（チバ・スペシャルティ・ケミカルズ社製：イルガキュア１９１９）を３．３重量部、キラル剤６．０重量部、界面活性剤（１重量％のシクロペンタノン溶液として使用）１１．６重量部を添加して溶解した溶液を調製した。
液晶化合物として、構造式（ＩＶ−１）と構造式（Ｖ−１）の混合物を、キラル剤としてＬＣ７５６（ＢＡＳＦ社製）を、界面活性剤としてＫＨ−４０（セイミケミカル社製）を、それぞれ使用した。この調製した溶液を孔径０．４５μｍのポリテトラフルオロエチレン製シリンジフィルターにて濾過したものを重合性液晶化合物を含む組成物として使用した。
[Composition containing a polymerizable liquid crystal compound constituting a resin layer having cholesteric regularity]
A solution was prepared by dissolving in 153 parts by weight of cyclopentanone with respect to 100 parts by weight of the liquid crystal compound. To this, 3.3 parts by weight of a photopolymerization initiator (manufactured by Ciba Specialty Chemicals: Irgacure 1919), 6.0 parts by weight of a chiral agent, and a surfactant (used as a 1% by weight cyclopentanone solution) 11 A solution was prepared by adding 6 parts by weight.
As a liquid crystal compound, a mixture of structural formula (IV-1) and structural formula (V-1), LC756 (manufactured by BASF) as a chiral agent, and KH-40 (manufactured by Seimi Chemical) as a surfactant, used. A solution prepared by filtering the prepared solution with a syringe filter made of polytetrafluoroethylene having a pore diameter of 0.45 μm was used as a composition containing a polymerizable liquid crystal compound.
乾燥及び配向熟成後、塗膜に対して、照度４ｍＷ／ｃｍ2の紫外線を基材フィルム側から１秒間照射し、１００℃で６０秒間加温・乾燥処理を行った。再び、照度４ｍＷ／ｃｍ2の紫外線を基材フィルム側から１秒間照射し、１００℃で６０秒間加温・乾燥処理を行った。
前記２回の紫外線照射は、ＨＯＹＡ ＳＣＨＯＴＴ社製、装置名ＥＸＥＣＵＲＥ ３０００−Ｗを用い、３６５ｎｍのバンドパスフィルターを介して行った。３６５ｎｍバンドパスフィルターの光線透過領域は３４６〜４０３ｎｍであり、帯域幅（波長範囲の幅）は５７ｎｍである。照度はオーク製作所社製の紫外線光量計付照度計（ＵＶ−Ｍ０３、センサは３６０ｎｍにピーク感度を持つＵＶ−ＳＮ３５）を使用して測定した。
次いで、前記塗工膜に塗布面側から２５℃の窒素雰囲気下で紫外線を１００ｍＷ／ｃｍ２で５秒間照射することにより硬化させ、コレステリック規則性を有する樹脂層として反射型偏光子を得た。
After drying and orientation aging, the coating film was irradiated with ultraviolet light having an illuminance of 4 mW / cm 2 from the base film side for 1 second, and heated and dried at 100 ° C. for 60 seconds. Again, ultraviolet rays with an illuminance of 4 mW / cm 2 were irradiated from the base film side for 1 second, and a heating and drying treatment was performed at 100 ° C. for 60 seconds.
The two UV irradiations were performed through a 365 nm band pass filter using a device name EXECURE 3000-W manufactured by HOYA SCHOTT. The 365 nm band pass filter has a light transmission region of 346 to 403 nm and a bandwidth (wavelength range width) of 57 nm. The illuminance was measured using an illuminometer with an ultraviolet light meter (UV-M03, sensor: UV-SN35 having a peak sensitivity at 360 nm) manufactured by Oak Seisakusho.
Next, the coating film was cured by irradiating with ultraviolet rays at 100 mW / cm 2 for 5 seconds in a nitrogen atmosphere at 25 ° C. from the coated surface side to obtain a reflective polarizer as a resin layer having cholesteric regularity.
工程２：光学異方性層の作製
メタクリル酸メチル９７．８重量％とアクリル酸メチル２．２重量％とからなるモノマー組成物を、バルク重合法により重合させ、樹脂ペレットを得た。
Step 2: Preparation of optically anisotropic layer A monomer composition consisting of 97.8% by weight of methyl methacrylate and 2.2% by weight of methyl acrylate was polymerized by a bulk polymerization method to obtain resin pellets.
特公昭５５−２７５７６号公報の実施例３に準じて、ゴム粒子を製造した。このゴム粒子は、球形３層構造を有し、芯内層が、メタクリル酸メチル及び少量のメタクリル酸アリルの架橋重合体であり、内層が、主成分としてのアクリル酸ブチルとスチレン及び少量のアクリル酸アリルとを架橋共重合させた軟質の弾性共重合体であり、外層が、メタクリル酸メチル及び少量のアクリル酸エチルの硬質重合体である。また、内層の平均粒子径は０．１９μｍであり、外層をも含めた粒径は０．２２μｍであった。
上記樹脂ペレット７０重量部と、上記ゴム粒子３０重量部とを混合し、二軸押出機で溶融混練して、メタクリル酸エステル重合体組成物Ａ（ガラス転移温度１０５℃）を得た。
Rubber particles were produced according to Example 3 of JP-B-55-27576. This rubber particle has a spherical three-layer structure, the core inner layer is a crosslinked polymer of methyl methacrylate and a small amount of allyl methacrylate, and the inner layer is composed of butyl acrylate and styrene as main components and a small amount of acrylic acid. It is a soft elastic copolymer obtained by crosslinking and copolymerizing allyl, and the outer layer is a hard polymer of methyl methacrylate and a small amount of ethyl acrylate. The average particle size of the inner layer was 0.19 μm, and the particle size including the outer layer was 0.22 μm.
70 parts by weight of the resin pellets and 30 parts by weight of the rubber particles were mixed and melt kneaded with a twin screw extruder to obtain a methacrylic acid ester polymer composition A (glass transition temperature 105 ° C.).
上記メタクリル酸エステル重合体組成物Ａ（ｂ層）、及びスチレン無水マレイン酸共重合体（ガラス転移温度１３０℃）（ａ層）を温度２８０℃で共押出成形することにより、ｂ層／ａ層／ｂ層の三層構造で、各層が４５／７０／４５（μｍ）の平均厚みを有する複層フィルムを得た。この積層フィルムを、テンター延伸機で、遅相軸がＭＤ方向に対して４５度傾いた方向になるように、延伸温度１３４℃、延伸倍率１．８倍で斜め延伸し、光学異方性層を得た。さらにこの光学異方性層の片面を、濡れ指数が５６ｄｙｎｅ／ｃｍになるようにコロナ放電処理を施し、光学異方性層を得た。
得られた光学異方性層の波長５５０ｎｍにおけるレターデーション値は、厚み方向のレターデーションＲｔｈは−１１８ｎｍ、面内方向のレターデーションＲｅは１４０ｎｍであった。
By coextruding the methacrylic ester polymer composition A (b layer) and the styrene maleic anhydride copolymer (glass transition temperature 130 ° C.) (a layer) at a temperature of 280 ° C., a b layer / a layer A multilayer film having an average thickness of 45/70/45 (μm) with a three-layer structure of / b layers was obtained. The laminated film is stretched obliquely at a stretching temperature of 134 ° C. and a stretching ratio of 1.8 times so that the slow axis is in a direction inclined by 45 degrees with respect to the MD direction by a tenter stretching machine. Got. Further, one side of the optically anisotropic layer was subjected to a corona discharge treatment so that the wetting index was 56 dyne / cm to obtain an optically anisotropic layer.
With respect to the retardation value of the obtained optically anisotropic layer at a wavelength of 550 nm, the retardation Rth in the thickness direction was −118 nm, and the retardation Re in the in-plane direction was 140 nm.
工程３：輝度向上フィルムの作製
工程１で得られた反射型偏光子のコレステリック規則性を有する樹脂層側に、工程２で得られた光学異方性層を接着剤を介して貼り合わせ、積層シートを得た。すなわち、まずエチレン−酢酸ビニル共重合体エマルジョン（不揮発分４０重量％、酢酸ビニル含有率４０重量％）４０重量部、石油樹脂エマルジョン(不揮発分４０重量％、樹脂軟化点８５℃）３５重量部、及びパラフィンワックスエマルジョン（不揮発分４０重量％、樹脂軟化点６４℃）１０重量部からなる、２３℃における剪断貯蔵弾性率が１０ＭＰａである接着剤組成物を調製した。この接着剤組成物を、前記反射型偏光子のコレステリック規則性を有する樹脂層上に積層し、前記光学異方性層のコロナ処理面とをラミネーターを用いて、８０℃、２ｋｇｆ／５０ｍｍのニップ圧にて貼り合わせを行った。
Step 3: Production of brightness enhancement film The optically anisotropic layer obtained in Step 2 is bonded to the resin layer side having the cholesteric regularity of the reflective polarizer obtained in Step 1 with an adhesive and laminated. A sheet was obtained. That is, first, ethylene-vinyl acetate copolymer emulsion (non-volatile content 40% by weight, vinyl acetate content 40% by weight) 40 parts by weight, petroleum resin emulsion (non-volatile content 40% by weight, resin softening point 85 ° C.) 35 parts by weight, And an adhesive composition having a shear storage modulus of 10 MPa at 23 ° C., comprising 10 parts by weight of paraffin wax emulsion (non-volatile content: 40% by weight, resin softening point: 64 ° C.). The adhesive composition was laminated on the resin layer having the cholesteric regularity of the reflective polarizer, and the corona-treated surface of the optically anisotropic layer was bonded to a nip at 80 ° C. and 2 kgf / 50 mm using a laminator. Bonding was performed under pressure.
工程４：輝度向上率の測定
市販の液晶表示装置（Ｓｈａｒｐ製、ＡＱＵＯＳ、ＬＣ−３７ＢＥ１Ｗ）を分解し、輝度向上フィルムとして工程３で作製した輝度向上フィルムを用いて再び組み立て直した。液晶表示装置は、光源、拡散板、拡散シート、プリズムシート、輝度向上フィルム、液晶パネルの順で構成されている。フィルムの把持には、装置の部品をそのまま利用した。組み立て直した液晶表示装置を立てた状態で白表示させ、そのときの正面方向の輝度を、視野角測定評価装置（メーカー：Ａｕｔｒｏｎｉｃ−ＭＥＬＣＨＥＲＳ社製、商品名：ＥｒｇｏＳｃｏｐｅ）で測定した。輝度向上フィルムがない場合の正面方向の輝度も同様に測定し、輝度向上フィルムがある場合とない場合の輝度の差を算出した。
Step 4: Measurement of luminance enhancement rate A commercially available liquid crystal display device (manufactured by Sharp, AQUAS, LC-37BE1W) was disassembled and reassembled again using the luminance enhancement film produced in step 3 as the luminance enhancement film. The liquid crystal display device includes a light source, a diffusion plate, a diffusion sheet, a prism sheet, a brightness enhancement film, and a liquid crystal panel in this order. The parts of the apparatus were used as they were for gripping the film. The reassembled liquid crystal display device was displayed in white in a standing state, and the luminance in the front direction at that time was measured with a viewing angle measurement evaluation device (manufacturer: Autotronic-MELCHERS, trade name: ErgoScope). Similarly, the luminance in the front direction when there was no luminance enhancement film was also measured, and the difference in luminance between when the luminance enhancement film was present and when there was no luminance enhancement film was calculated.
（配向性の評価）
工程１で作成したコレステリック規則性を有する樹脂層を偏光顕微鏡で観察し、オイリーストリークと呼ばれる配向欠陥の量を目視で確認して判定した。評価は５段階で判定し、配向欠陥が全く見られない場合を５と判定し、全面に渡って配向欠陥が存在する場合を１と判定した。よって、値が大きいほど良い結果であることを示している。
判定のイメージを図１に示す。図１中、（Ａ）が配向性「５」の場合、（Ｂ）が配向性「３」の場合、（Ｃ）が配向性「１」の場合をそれぞれ示している。また、図１中、オイリーストリークと呼ばれる配向欠陥は黒い線として観察される。
(Evaluation of orientation)
The resin layer having cholesteric regularity created in Step 1 was observed with a polarizing microscope, and the amount of alignment defects called oily streak was visually confirmed and judged. The evaluation was made in 5 stages. The case where no alignment defect was found was determined as 5, and the case where the alignment defect existed over the entire surface was determined as 1. Therefore, a larger value indicates a better result.
An image of the determination is shown in FIG. In FIG. 1, (A) indicates orientation “5”, (B) indicates orientation “3”, and (C) indicates orientation “1”. Further, in FIG. 1, alignment defects called oily streaks are observed as black lines.
（実施例１)
式（Ｉ−１）で表される化合物（以下、「化合物（Ｉ−１）」という。）と式（ＩＩ−１）で表される化合物（以下、「化合物（ＩＩ−１）」という。）の混合物の合成
(Example 1)
A compound represented by formula (I-1) (hereinafter referred to as “compound (I-1)”) and a compound represented by formula (II-1) (hereinafter referred to as “compound (II-1)”). ) Compound synthesis
（工程１）
２０％水酸化カリウム水溶液６２．２ｇに、４−ヒドロキシ安息香酸１０ｇと、クロロヘキサノール１９．８ｇを加え、強攪拌下、加熱還流した。３時間後、反応混合物に２０％水酸化カリウム水溶液を１０．３ｇ追加し、更に４時間加熱還流した。反応混合物を室温まで冷却した後、水６０ｇ、及び２−プロパノール３０ｇを加え、１．２Ｎの塩酸６０ｇを３０分かけて滴下することで、白色固体が沈殿した。これをろ別し、水で洗浄することで、ＨＰＬＣ純度９５％以上の４−（６−ヒドロキシ−ヘキサ−１−イルオキシ）安息香酸１４．７ｇ（収率８５％）を得た。
(Process 1)
To 62.2 g of 20% aqueous potassium hydroxide solution, 10 g of 4-hydroxybenzoic acid and 19.8 g of chlorohexanol were added, and the mixture was heated to reflux with vigorous stirring. After 3 hours, 10.3 g of 20% aqueous potassium hydroxide solution was added to the reaction mixture, and the mixture was further heated to reflux for 4 hours. After the reaction mixture was cooled to room temperature, 60 g of water and 30 g of 2-propanol were added, and 60 g of 1.2N hydrochloric acid was added dropwise over 30 minutes to precipitate a white solid. This was separated by filtration and washed with water to obtain 14.7 g (yield 85%) of 4- (6-hydroxy-hex-1-yloxy) benzoic acid having an HPLC purity of 95% or more.
（工程２）
トルエン５０ｇに、工程１で得られた４−（６−ヒドロキシ−ヘキサ−１−イルオキシ）安息香酸１０ｇ（４２ｍｍｏｌ）と、重合禁止剤としてヒドロキノンモノメチルエーテル０．２ｇを加えた。更にアクリル酸１２．１ｇ（１６８ｍｍｏｌ；４．０当量）、及びメタンスルホン酸０．４ｇを加え、攪拌下、ディーンスタークを使用して、生成する水をトルエンとの共沸脱水にて系外に除去しながら、蒸気温度がトルエンの沸点となるまで還流を行った。反応混合物を室温まで放冷した後、２５％炭酸カリウム水溶液により、水層のｐＨが４〜５となるまで中和を行い、分液して水層を除去した。
(Process 2)
To 50 g of toluene, 10 g (42 mmol) of 4- (6-hydroxy-hex-1-yloxy) benzoic acid obtained in Step 1 and 0.2 g of hydroquinone monomethyl ether as a polymerization inhibitor were added. Further, 12.1 g (168 mmol; 4.0 equivalent) of acrylic acid and 0.4 g of methanesulfonic acid were added, and the resulting water was removed from the system by azeotropic dehydration with toluene using Dean Stark while stirring. While removing, refluxing was performed until the vapor temperature reached the boiling point of toluene. The reaction mixture was allowed to cool to room temperature, then neutralized with a 25% aqueous potassium carbonate solution until the pH of the aqueous layer reached 4 to 5, and separated to remove the aqueous layer.
得られた有機層に水２０ｇを加え、結晶が析出しないように４０℃に加温しながら洗浄を行った。分液後の有機層に、ｎ−ヘプタン８６ｇを滴下したところ、白色粉末が沈殿した。これをろ別、乾燥することで、化合物（Ｉ−１）〔４−（６−アクリロイル−ヘキス−１−イルオキシ）安息香酸〕と化合物（ＩＩ−１）の混合物である白色固体９．８ｇを得た（収率８０％）。得られた白色固体を、ＨＰＬＣを用いて分析したところ、化合物（ＩＩ−１）の含有量は、４．６重量％（ＨＰＬＣ面積パーセント）であった。 20 g of water was added to the obtained organic layer, and washing was performed while heating to 40 ° C. so as not to precipitate crystals. When 86 g of n-heptane was added dropwise to the organic layer after separation, a white powder precipitated. By filtering this and drying, 9.8 g of a white solid which is a mixture of compound (I-1) [4- (6-acryloyl-hex-1-yloxy) benzoic acid] and compound (II-1) was obtained. Obtained (yield 80%). When the obtained white solid was analyzed using HPLC, the content of the compound (II-1) was 4.6% by weight (HPLC area percentage).
（実施例２）
式（ＩＶ−１）で表される液晶化合物（以下、「液晶化合物（ＩＶ−１）」という。）と式（Ｖ−１）で表される液晶化合物（以下、「液晶化合物（Ｖ−１）」という。）の混合物の合成
(Example 2)
Liquid crystal compound represented by formula (IV-1) (hereinafter referred to as “liquid crystal compound (IV-1)”) and liquid crystal compound represented by formula (V-1) (hereinafter referred to as “liquid crystal compound (V-1)”. ) ”)))
テトラヒドロフラン５０ｇに、実施例１で最終的に得られた白色固体１２．３ｇを溶かし、そこに、メタンスルホニルクロライド４．８ｇ、さらにトリエチルアミン４．４ｇを添加した。３０分後、４−ジメチルアミノピリジン０．５ｇを添加した後、Ｎ−（４−ヒドロキシベンジリデン−Ｎ’−（４−ヒドロキシ−２−カルボメトキシベンジリデン）ヒドラジン ５．０ｇを添加し、更にトリエチルアミン３．７ｇを添加し、全容を撹拌した。２時間後、メタノール１２５ｇを加え、析出した結晶をろ別した。 12.3 g of the white solid finally obtained in Example 1 was dissolved in 50 g of tetrahydrofuran, and 4.8 g of methanesulfonyl chloride and 4.4 g of triethylamine were added thereto. After 30 minutes, 0.5 g of 4-dimethylaminopyridine was added, 5.0 g of N- (4-hydroxybenzylidene-N ′-(4-hydroxy-2-carbomethoxybenzylidene) hydrazine was added, and triethylamine 3 After 2 hours, 125 g of methanol was added, and the precipitated crystals were separated by filtration.
得られた粗結晶を酢酸エチル６２．５ｇに溶解し、メタノール１１２．５ｇを加えて再沈殿させ、沈殿物をろ別、乾燥して、液晶化合物（ＩＶ−１）及び液晶化合物（Ｖ−１）の混合物１０．０ｇを得た。得られた液晶化合物の混合物を、ＨＰＬＣを用いて分析したところ、液晶化合物（Ｖ−１）の含有量は４．５重量％（ＨＰＬＣ面積パーセント）であった。
得られた液晶化合物の混合物の特性を調べたところ、配向性は５、輝度向上率は１２５．０％であった。
The obtained crude crystals are dissolved in 62.5 g of ethyl acetate, 112.5 g of methanol is added for reprecipitation, the precipitate is filtered and dried, and then the liquid crystal compound (IV-1) and the liquid crystal compound (V-1 ) Was obtained. When the mixture of the obtained liquid crystal compound was analyzed using HPLC, content of the liquid crystal compound (V-1) was 4.5 weight% (HPLC area percentage).
When the characteristics of the obtained mixture of liquid crystal compounds were examined, the orientation was 5 and the luminance improvement rate was 125.0%.
（実施例３）
アクリル酸を１５．１ｇ（２１０ｍｍｏｌ、５．０当量）用いた他は、実施例１と同様にして、化合物（Ｉ−１）と化合物（ＩＩ−１）の混合物を得た。ＨＰＬＣを用いて分析したところ、化合物（ＩＩ−１）の含有量は３．８重量％（ＨＰＬＣ面積パーセント）であった。
Example 3
A mixture of compound (I-1) and compound (II-1) was obtained in the same manner as in Example 1, except that 15.1 g (210 mmol, 5.0 equivalents) of acrylic acid was used. When analyzed using HPLC, the content of compound (II-1) was 3.8% by weight (HPLC area percent).
得られた混合物を用いて、実施例２と同様にして、液晶化合物（ＩＶ−１）と液晶化合物（Ｖ−１）の混合物を得た。得られた液晶化合物の混合物をＨＰＬＣを用いて分析したところ、化合物（Ｖ−１）の含有量は３．８重量％（ＨＰＬＣ面積パーセント）であった。
得られた液晶化合物の混合物の特性を調べたところ、配向性は４、輝度向上率は１２５．０％であった。
Using the obtained mixture, a mixture of the liquid crystal compound (IV-1) and the liquid crystal compound (V-1) was obtained in the same manner as in Example 2. When the obtained mixture of liquid crystal compounds was analyzed using HPLC, the content of the compound (V-1) was 3.8% by weight (HPLC area percentage).
When the characteristics of the obtained liquid crystal compound mixture were examined, the orientation was 4 and the luminance improvement rate was 125.0%.
（実施例４）
アクリル酸を１０．６ｇ（１４７ｍｍｏｌ、３．５当量）用いた他は、実施例１と同様にして、化合物（Ｉ−１）と化合物（ＩＩ−１）の混合物を得た。ＨＰＬＣを用いて分析したところ、化合物（ＩＩ−１）の含有量は６．０重量％（ＨＰＬＣ面積パーセント）であった。
Example 4
A mixture of compound (I-1) and compound (II-1) was obtained in the same manner as in Example 1 except that 10.6 g (147 mmol, 3.5 equivalents) of acrylic acid was used. When analyzed using HPLC, the content of compound (II-1) was 6.0% by weight (HPLC area percent).
得られた混合物を用いて、実施例２と同様にして、液晶化合物（ＩＶ−１）と液晶化合物（Ｖ−１）の液混合物を得た。得られた液晶化合物の混合物を、ＨＰＬＣを用いて分析したところ、化合物（Ｖ−１）の含有量は６．０重量％（ＨＰＬＣ面積パーセント）であった。
得られた液晶化合物の混合物の特性を調べたところ、配向性は５、輝度向上率は１２４．０％であった。
Using the obtained mixture, a liquid mixture of the liquid crystal compound (IV-1) and the liquid crystal compound (V-1) was obtained in the same manner as in Example 2. When the mixture of the obtained liquid crystal compound was analyzed using HPLC, content of the compound (V-1) was 6.0 weight% (HPLC area percent).
When the characteristics of the obtained liquid crystal compound mixture were examined, the orientation was 5 and the luminance improvement rate was 124.0%.
（比較例１）
実施例１の工程２において、トルエンを用いず、アクリル酸を６０．４ｇ（８４０ｍｍｏｌ、２０当量）用いた他は、実施例１と同様にして、化合物（Ｉ−１）と化合物（ＩＩ−１）の混合物を得た。ＨＰＬＣを用いて分析したところ、化合物（ＩＩ−１）の含有量は１．０重量％（ＨＰＬＣ面積パーセント）であった。
(Comparative Example 1)
In Step 2 of Example 1, compound (I-1) and compound (II-1) were used in the same manner as in Example 1, except that toluene was not used and 60.4 g (840 mmol, 20 equivalents) of acrylic acid was used. ) Was obtained. When analyzed using HPLC, the content of compound (II-1) was 1.0% by weight (HPLC area percent).
得られた混合物を用いて、実施例２と同様にして、液晶化合物（ＩＶ−１）と液晶化合物（Ｖ−１）の混合物を得た。得られた液晶化合物の混合物をＨＰＬＣを用いて分析したところ、化合物（Ｖ−１）の含有量は０．８重量％（ＨＰＬＣ面積パーセント）であった。
得られた液晶化合物の混合物の特性を調べたところ、配向性は３、輝度向上率は１２４．０％であった。
Using the obtained mixture, a mixture of the liquid crystal compound (IV-1) and the liquid crystal compound (V-1) was obtained in the same manner as in Example 2. When the mixture of the obtained liquid crystal compound was analyzed using HPLC, content of the compound (V-1) was 0.8 weight% (HPLC area percentage).
When the characteristics of the obtained liquid crystal compound mixture were examined, the alignment property was 3, and the luminance improvement rate was 124.0%.
（比較例２）
アクリル酸を１８．１ｇ（２５１ｍｍｏｌ、６．０当量）用いた他は、実施例１と同様にして、化合物（Ｉ−１）と化合物（ＩＩ−１）の混合物を得た。ＨＰＬＣを用いて分析したところ、化合物（ＩＩ−１）の含有量は３．３重量％（ＨＰＬＣ面積パーセント）であった。
(Comparative Example 2)
A mixture of compound (I-1) and compound (II-1) was obtained in the same manner as in Example 1 except that 18.1 g (251 mmol, 6.0 equivalents) of acrylic acid was used. When analyzed using HPLC, the content of compound (II-1) was 3.3% by weight (HPLC area percent).
得られた混合物を用いて、実施例２と同様にして、液晶化合物（ＩＶ−１）と液晶化合物（Ｖ−１）の混合物を得た。得られた液晶化合物の混合物をＨＰＬＣを用いて分析したところ、化合物（Ｖ−１）の含有量は２．８重量％（ＨＰＬＣ面積パーセント）であった。
得られた液晶化合物の混合物の特性を調べたところ、配向性は３、輝度向上率は１２４．５％であった。
Using the obtained mixture, a mixture of the liquid crystal compound (IV-1) and the liquid crystal compound (V-1) was obtained in the same manner as in Example 2. When the obtained mixture of liquid crystal compounds was analyzed using HPLC, the content of the compound (V-1) was 2.8% by weight (HPLC area percentage).
When the characteristics of the obtained liquid crystal compound mixture were examined, the orientation was 3 and the luminance improvement rate was 124.5%.
（比較例３）
アクリル酸を３．６ｇ（５０ｍｍｏｌ、１．２当量）用いた他は、実施例１と同様にして、化合物（Ｉ−１）と化合物（ＩＩ−１）の混合物を得た。ＨＰＬＣを用いて分析したところ、化合物（ＩＩ−１）の含有量は１６．０重量％（ＨＰＬＣ面積パーセント）であった。
(Comparative Example 3)
A mixture of compound (I-1) and compound (II-1) was obtained in the same manner as in Example 1 except that 3.6 g (50 mmol, 1.2 equivalents) of acrylic acid was used. When analyzed using HPLC, the content of compound (II-1) was 16.0 wt% (HPLC area percentage).
得られた混合物を用いて、実施例２と同様にして、液晶化合物（ＩＶ−１）と液晶化合物（Ｖ−１）の混合物を得た。得られた液晶化合物の混合物をＨＰＬＣを用いて分析したところ、化合物（Ｖ−１）の含有量は１５．８重量％（ＨＰＬＣ面積パーセント）であった。
得られた液晶化合物の混合物の特性を調べたところ、配向性は５、輝度向上率は１１８％であった。
Using the obtained mixture, a mixture of the liquid crystal compound (IV-1) and the liquid crystal compound (V-1) was obtained in the same manner as in Example 2. When the mixture of the obtained liquid crystal compound was analyzed using HPLC, content of the compound (V-1) was 15.8 weight% (HPLC area percent).
The properties of the obtained liquid crystal compound mixture were examined. As a result, the orientation was 5 and the luminance improvement rate was 118%.
下記第１表に、実施例２〜４及び比較例１〜３において、用いた混合物中の化合物（ＩＩ−１）の含有量、用いたアクリル酸の、４−（６−ヒドロキシヘキサ−1−イルオキシ）安息香酸に対する当量数、得られた液晶化合物の混合物中の化合物（Ｖ−１）の含有量、並びに、得られた液晶化合物の混合物の配向性及び輝度向上率をまとめて示す。 In Table 1 below, in Examples 2 to 4 and Comparative Examples 1 to 3, the content of compound (II-1) in the mixture used, 4- (6-hydroxyhex-1- The number of equivalents with respect to (yloxy) benzoic acid, the content of the compound (V-1) in the obtained liquid crystal compound mixture, and the orientation and luminance improvement rate of the obtained liquid crystal compound mixture are collectively shown.
以上のことから、アクリル酸の使用量を制御することで、化合物（Ｉ−１）と化合物（ＩＩ−１）の混合物であって、化合物（ＩＩ−１）を３．５〜１２重量％含む混合物を得ることができた。また、得られた混合物を使用することで、液晶化合物（Ｖ−１）を３．５〜１２重量％含む液晶化合物（ＩＶ−１）と液晶化合物（Ｖ−１）の混合物を、一段階で容易に製造することができることがわかった。 From the above, it is a mixture of the compound (I-1) and the compound (II-1) by controlling the amount of acrylic acid used, and contains 3.5 to 12% by weight of the compound (II-1). A mixture could be obtained. Moreover, by using the obtained mixture, the liquid crystal compound (IV-1) containing 3.5 to 12% by weight of the liquid crystal compound (V-1) and the liquid crystal compound (V-1) can be mixed in one step. It was found that it can be easily manufactured.
実施例２〜４の液晶化合物の混合物は、輝度向上率１２４．０％以上、配向性評価４以上の優れた光学特性を示した。
一方、液晶化合物（ＩＶ−１）の含有量が３．５〜１２重量％ではない、比較例１、２の液晶化合物の混合物は、実施例２〜４の液晶化合物の混合物に比して、配向性に劣り、比較例３の液晶化合物の混合物は輝度向上率が低いものであった。
The mixture of the liquid crystal compounds of Examples 2 to 4 exhibited excellent optical characteristics with a luminance improvement rate of 124.0% or more and an orientation evaluation of 4 or more.
On the other hand, the mixture of the liquid crystal compounds of Comparative Examples 1 and 2, in which the content of the liquid crystal compound (IV-1) is not 3.5 to 12% by weight, compared to the mixture of the liquid crystal compounds of Examples 2 to 4, The mixture was poor in alignment, and the liquid crystal compound mixture of Comparative Example 3 had a low luminance improvement rate.
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| JP2016113555A (en) * | 2014-12-16 | 2016-06-23 | 日本ゼオン株式会社 | Liquid crystalline composition, circular polarized light separation element and method for producing the same, medium for forgery prevention and method for producing the same, brightness improvement film and security medium |
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