JP5705465B2 - Polymerizable composition, polymer, and film - Google Patents
Polymerizable composition, polymer, and film Download PDFInfo
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- JP5705465B2 JP5705465B2 JP2010141467A JP2010141467A JP5705465B2 JP 5705465 B2 JP5705465 B2 JP 5705465B2 JP 2010141467 A JP2010141467 A JP 2010141467A JP 2010141467 A JP2010141467 A JP 2010141467A JP 5705465 B2 JP5705465 B2 JP 5705465B2
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- 239000000203 mixture Substances 0.000 title claims description 97
- 229920000642 polymer Polymers 0.000 title claims description 25
- 150000001875 compounds Chemical class 0.000 claims description 194
- 125000004432 carbon atom Chemical group C* 0.000 claims description 46
- 125000000217 alkyl group Chemical group 0.000 claims description 25
- 125000001424 substituent group Chemical group 0.000 claims description 23
- 230000003287 optical effect Effects 0.000 claims description 18
- 239000004986 Cholesteric liquid crystals (ChLC) Substances 0.000 claims description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 8
- 125000003545 alkoxy group Chemical group 0.000 claims description 7
- 125000006615 aromatic heterocyclic group Chemical group 0.000 claims description 7
- 229910052717 sulfur Inorganic materials 0.000 claims description 7
- 125000005843 halogen group Chemical group 0.000 claims description 6
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 claims description 5
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 5
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 5
- 125000004434 sulfur atom Chemical group 0.000 claims description 5
- 125000003368 amide group Chemical group 0.000 claims description 4
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-M methacrylate group Chemical group C(C(=C)C)(=O)[O-] CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 4
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 4
- 125000002252 acyl group Chemical group 0.000 claims description 3
- 125000004423 acyloxy group Chemical group 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
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- UWCWUCKPEYNDNV-LBPRGKRZSA-N 2,6-dimethyl-n-[[(2s)-pyrrolidin-2-yl]methyl]aniline Chemical compound CC1=CC=CC(C)=C1NC[C@H]1NCCC1 UWCWUCKPEYNDNV-LBPRGKRZSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 6
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- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
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- 238000004528 spin coating Methods 0.000 description 3
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 description 3
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 description 3
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- OXPDQFOKSZYEMJ-UHFFFAOYSA-N 2-phenylpyrimidine Chemical group C1=CC=CC=C1C1=NC=CC=N1 OXPDQFOKSZYEMJ-UHFFFAOYSA-N 0.000 description 2
- MWKAGZWJHCTVJY-UHFFFAOYSA-N 3-hydroxyoctadecan-2-one Chemical compound CCCCCCCCCCCCCCCC(O)C(C)=O MWKAGZWJHCTVJY-UHFFFAOYSA-N 0.000 description 2
- TXFPEBPIARQUIG-UHFFFAOYSA-N 4'-hydroxyacetophenone Chemical compound CC(=O)C1=CC=C(O)C=C1 TXFPEBPIARQUIG-UHFFFAOYSA-N 0.000 description 2
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- SXJQUUPSLJTKKT-UHFFFAOYSA-N 4-amino-3-methoxyphenol Chemical compound COC1=CC(O)=CC=C1N SXJQUUPSLJTKKT-UHFFFAOYSA-N 0.000 description 2
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
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- FEIWNULTQYHCDN-UHFFFAOYSA-N mbba Chemical compound C1=CC(CCCC)=CC=C1N=CC1=CC=C(OC)C=C1 FEIWNULTQYHCDN-UHFFFAOYSA-N 0.000 description 1
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Description
本発明は、光学異方性フィルム、遮熱フィルム等の種々の光学部材の材料をはじめとする、種々の用途において有用な重合性組成物、及び高分子、並びにこれらを利用したフィルムに関する。 The present invention relates to a polymerizable composition and a polymer useful in various applications including materials of various optical members such as an optically anisotropic film and a heat shielding film, and a film using these.
近年、液晶表示装置の小型化が望まれており、それに伴い光学フィルムの薄膜化が求められている。例えば、高いΔｎを示す液晶を、位相差板等の光学フィルムの作製に用いることにより膜厚を薄くすることができる。Δｎは液晶化合物の重要な基本物性のひとつであり、高いΔｎを示す液晶は、光学素子の構成要素である位相差板、偏光素子、選択反射膜、カラーフィルタ、反射防止膜、視野角補償膜、ホログラフィー、配向膜、など多くの工業分野に利用することができる（非特許文献１）。 In recent years, downsizing of liquid crystal display devices has been desired, and accordingly, thinning of optical films has been demanded. For example, the film thickness can be reduced by using a liquid crystal exhibiting a high Δn for producing an optical film such as a retardation plate. Δn is one of the important basic physical properties of a liquid crystal compound, and a liquid crystal exhibiting a high Δn is a retardation plate, a polarizing element, a selective reflection film, a color filter, an antireflection film, a viewing angle compensation film, which are constituent elements of an optical element. , Holography, alignment film, and many other industrial fields (Non-Patent Document 1).
従来、Δｎの大きい液晶化合物としてＭＢＢＡに代表されるアゾメチン構造を有するものが知られている（非特許文献２）。液晶化合物の特徴の一つは流動性があることであるが、上記用途では、液晶の流動性が不具合となる場合があり、所望の配向を維持して固体化する必要がある。一つの手段として、アゾメチン構造を有する化合物に二官能以上の重合性基を導入することでネットワーク構造を形成できる、重合性液晶が知られている（特許文献１及び２）。 Conventionally, a liquid crystal compound having a large Δn has an azomethine structure typified by MBBA (Non-patent Document 2). One of the characteristics of the liquid crystal compound is that it has fluidity. However, in the above application, the fluidity of the liquid crystal may become a problem, and it is necessary to maintain a desired orientation and solidify. As one means, polymerizable liquid crystals capable of forming a network structure by introducing a bifunctional or higher functional group into a compound having an azomethine structure are known (Patent Documents 1 and 2).
しかし、従来の上記液晶は、高Δｎを示す化合物は黄色味を帯びているため、無色での用途に不適であるといった問題がある。また、液晶相の温度範囲が狭く、重合工程において結晶化しやすいといった問題がある。
本発明は、従来における前記問題を解決し、以下の目的を達成することを課題とする。即ち、高Δｎを示し且つ無色である重合性アゾメチン化合物を利用して、透明で且つ着色のない種々の光学部材の作製に有用な、重合性組成物、高分子、及びフィルムを提供することを課題とする。特に、薄膜で高機能特性が要求される位相差膜及び選択反射膜の作製に有用な、重合性組成物、高分子、及びフィルムを提供することを課題とする。
However, the conventional liquid crystal has a problem that a compound exhibiting a high Δn is yellowish and is therefore unsuitable for colorless use. Further, there is a problem that the temperature range of the liquid crystal phase is narrow and crystallization is easy in the polymerization process.
An object of the present invention is to solve the conventional problems and achieve the following objects. That is, the present invention provides a polymerizable composition, a polymer, and a film that are useful for the production of various optical members that are transparent and have no coloring, using a polymerizable azomethine compound that exhibits high Δn and is colorless. Let it be an issue. In particular, it is an object of the present invention to provide a polymerizable composition, a polymer, and a film that are useful for producing a retardation film and a selective reflection film that are thin and require high functional properties.
上記課題を解決するための手段は、以下の通りである。
［１］ 下記式（Ｉ）：
ｍ１及びｍ２はそれぞれ、１〜１０の整数を表し、ｍ１又はｍ２個のＣＨ2のうち、１つのＣＨ2又は隣接しない２以上のＣＨ2は、酸素原子又は硫黄原子に置き換わっていてもよく；
Ａ1、Ａ2、Ａ3及びＡ4はそれぞれ、置換されていてもよい、５〜１８員環の芳香族炭化水素環、又は５〜１８員環の芳香族複素環の基を表し；
Ｒは、水素原子又は炭素原子数１〜８のアルキル基を表し；
Ｚ1及びＺ2はそれぞれ、−ＣＯＯ−、−ＯＣＯ−、−ＮＨＣＯ−、又は−ＮＲ1ＣＯを表し、Ｒ1は炭素原子数１〜１０のアルキル基を表し；
Ｌ1及びＬ2はそれぞれ、−Ｏ−、−Ｓ−、−ＣＯＯ−、−ＯＣＯ−、−ＯＣＯＯ−、−ＮＨＣＯ−、又は−ＮＲ1ＣＯを表し、Ｒ1は炭素原子数１〜１０のアルキル基を表し；
ｎ１及びｎ２はそれぞれ、１又は２である；
で表される化合物を少なくとも１種含むことを特徴とする重合性組成物。
Means for solving the above problems are as follows.
[1] The following formula (I):
Each m1 and m2, represents an integer of 1 to 10, among the m1 or m2 amino CH 2, 1 single CH 2 or non-adjacent two or more CH 2 may be replaced by oxygen atom or a sulfur atom;
Each of A 1 , A 2 , A 3 and A 4 represents an optionally substituted 5- to 18-membered aromatic hydrocarbon ring or 5- to 18-membered aromatic heterocyclic group;
R represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms;
Z 1 and Z 2 each represent —COO—, —OCO—, —NHCO—, or —NR 1 CO, and R 1 represents an alkyl group having 1 to 10 carbon atoms;
L 1 and L 2 each represent —O—, —S—, —COO—, —OCO—, —OCOO—, —NHCO—, or —NR 1 CO, and R 1 has 1 to 10 carbon atoms. Represents an alkyl group;
n1 and n2 are each 1 or 2;
A polymerizable composition comprising at least one compound represented by the formula:
［２］ 式（Ｉ）中、Ａ2及びＡ3が置換基を有していてもよい１，４−フェニレンでありかつｎ１＝ｎ２＝１である［１］の重合性組成物。
［３］ 式（Ｉ）中、Ａ1及びＡ4が１，４−フェニレンである［２］の重合性組成物。
［４］ Ａ1、Ａ2、Ａ3及びＡ4がそれぞれ無置換の５〜１８員環の芳香族炭化水素環又は５〜１８員環の芳香族複素環の基であるか、又はＡ1、Ａ2、Ａ3及びＡ4の少なくとも一つが、炭素原子数１〜４のアルキル基、炭素原子数１〜４のアルコキシ基、炭素原子数２〜５のアミド基、炭素原子数２〜５のアルコキシカルボニル基、炭素原子数２〜５のアシルオキシ基、炭素原子数２〜５のアシル基、シアノ基、又はハロゲン原子に置換されている５〜１８員環の芳香族炭化水素環又は５〜１８員環の芳香族複素環の基である［１］〜[３］のいずれかの重合性組成物。
[2] The polymerizable composition according to [1], wherein in formula (I), A 2 and A 3 are 1,4-phenylene which may have a substituent and n1 = n2 = 1.
[3] The polymerizable composition according to [2], wherein A 1 and A 4 in formula (I) are 1,4-phenylene.
[4] A 1 , A 2 , A 3 and A 4 are each an unsubstituted 5- to 18-membered aromatic hydrocarbon ring or a 5- to 18-membered aromatic heterocyclic group, or A 1. , A 2 , A 3 and A 4 are each an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an amide group having 2 to 5 carbon atoms, or 2 to 5 carbon atoms. An alkoxycarbonyl group, an acyloxy group having 2 to 5 carbon atoms, an acyl group having 2 to 5 carbon atoms, a cyano group, or a 5- to 18-membered aromatic hydrocarbon ring substituted with a halogen atom, The polymerizable composition according to any one of [1] to [3], which is an 18-membered aromatic heterocyclic group.
［５］ 式（Ｉ）中、Ｐ1及びＰ2がそれぞれ、以下の式（Ｐ−１）〜式（Ｐ−５）で表される基からなる群から選ばれる重合性基である［１］〜[４］のいずれかの重合性組成物：
［６］ 式（Ｉ）中、Ｐ1及びＰ2はそれぞれ、メタクリレート基又はアクリレート基である［１］〜[５］のいずれかの重合性組成物。
［７］ 式（Ｉ）中、ｍ１及びｍ２がそれぞれ２〜８の整数を表す［１］〜[６］のいずれかの重合性組成物。
［８］ 少なくとも１種のキラル化合物を含有する［７］の重合性組成物。
［９］ ［１］〜[８]のいずれかの重合性組成物を重合させてなる高分子。
［１０］ ［９］の高分子の少なくとも１種を含有するフィルム。
［１１］ ［１］〜[８］のいずれかの重合性組成物のコレステリック液晶相を固定してなるフィルム。
［１２］ 光学異方性を示す［１０］又は[１１］のフィルム。
［１３］ 選択反射特性を示す［１０］〜[１２］のいずれかのフィルム。
［１４］ 赤外線波長域に選択反射特性を示す［１３］のフィルム。
[6] The polymerizable composition according to any one of [1] to [5], wherein in formula (I), P 1 and P 2 are each a methacrylate group or an acrylate group.
[7] The polymerizable composition according to any one of [1] to [6], wherein m1 and m2 each represent an integer of 2 to 8 in formula (I).
[8] The polymerizable composition according to [7], containing at least one chiral compound.
[9] A polymer obtained by polymerizing the polymerizable composition according to any one of [1] to [8].
[10] A film containing at least one polymer of [9].
[11] A film formed by fixing a cholesteric liquid crystal phase of the polymerizable composition according to any one of [1] to [8].
[12] The film according to [10] or [11], which exhibits optical anisotropy.
[13] The film according to any one of [10] to [12], which exhibits selective reflection characteristics.
[14] The film according to [13], which exhibits selective reflection characteristics in an infrared wavelength region.
本発明によれば、高Δｎを示し且つ無色である重合性アゾメチン化合物を利用して、透明で且つ着色のない種々の光学部材の作製に有用な、重合性組成物、高分子、及びフィルムを提供することができる。特に、薄膜で所望の光学特性を示すことが要求される位相差膜及び選択反射膜等の光学フィルムの作製に有用な、重合性組成物、高分子、及びフィルムを提供することができる。 According to the present invention, a polymerizable composition, a polymer, and a film, which are useful for the production of various optical members that are transparent and have no coloring, using a polymerizable azomethine compound that exhibits high Δn and is colorless. Can be provided. In particular, it is possible to provide a polymerizable composition, a polymer, and a film that are useful for producing optical films such as a retardation film and a selective reflection film that are required to exhibit a desired optical characteristic with a thin film.
以下、本発明について詳細に説明する。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及び上限値とし Hereinafter, the present invention will be described in detail. In the present specification, the numerical range expressed using “to” is the numerical value described before and after “to” as the lower limit value and the upper limit value.
１．重合性組成物
本発明は、下記式（Ｉ）で表される化合物の少なくとも１種を含有する重合性組成物に関する。下記式（Ｉ）の化合物は、メソゲンとともに、アゾメチン基を分子内に一つ有することを特徴とする。アゾメチン基を分子内に有する液晶化合物は、高Δｎを示すが、一方で、従来の、アゾメチン基を分子内に２つ有するビスアゾメチン液晶化合物は黄色に着色していて、用途が制限される。下記式（Ｉ）の化合物は、十分に高いΔｎを示すとともに、白色であるので、着色の問題はない。さらに、下記式（Ｉ）の化合物は、末端の重合性基とメソゲンを繋ぐ側鎖がある程度長いので、液晶相となる温度範囲が広く、重合工程において結晶化し、白濁化するという問題も解消できる。さらに、溶剤への溶解性、及び他の液晶材料との相溶性も良好であり、重合で硬化可能であることから、光学部材等の種々の用途に有用である。特に、Δｎが高いことから、薄膜の形態で所望の光学特性を示すことが要求される位相差膜及び選択反射膜等の光学フィルムの作製に有用である。
1. Polymeric composition TECHNICAL FIELD This invention relates to the polymeric composition containing at least 1 sort (s) of the compound represented by following formula (I). The compound of the following formula (I) is characterized by having one azomethine group in the molecule together with a mesogen. A liquid crystal compound having an azomethine group in the molecule exhibits a high Δn. On the other hand, a conventional bisazomethine liquid crystal compound having two azomethine groups in the molecule is colored yellow, and its use is limited. The compound of the following formula (I) shows sufficiently high Δn and is white, so there is no problem of coloring. Furthermore, since the compound of the following formula (I) has a long side chain connecting the terminal polymerizable group and the mesogen to some extent, the temperature range for the liquid crystal phase is wide, and the problem of crystallization and white turbidity in the polymerization process can be solved. . Furthermore, since the solubility in a solvent and the compatibility with other liquid crystal materials are also good and it can be cured by polymerization, it is useful for various applications such as optical members. In particular, since Δn is high, it is useful for production of optical films such as a retardation film and a selective reflection film that are required to exhibit desired optical characteristics in the form of a thin film.
式中、Ｐ1及びＰ2はそれぞれ、重合性基を表し；
ｍ１及びｍ２はそれぞれ、１〜１０の整数を表し、ｍ１又はｍ２個のＣＨ2のうち、１つのＣＨ2又は隣接しない２以上のＣＨ2は、酸素原子又は硫黄原子に置き換わっていてもよく；
Ａ1、Ａ2、Ａ3及びＡ4はそれぞれ、置換されていてもよい、５〜１８員環の芳香族炭化水素環又は５〜１８員環の芳香族複素環の基を表し；
Ｒは水素原子又は炭素原子数１〜８のアルキル基を表し；
Ｚ1及びＺ2はそれぞれ、−ＣＯＯ−、−ＯＣＯ−、−ＮＨＣＯ−、又は−ＮＲ1ＣＯを表し、Ｒ1は炭素原子数１〜１０のアルキル基を表し；
Ｌ1及びＬ2はそれぞれ、−Ｏ−、−Ｓ−、−ＣＯＯ−、−ＯＣＯ−、−ＯＣＯＯ−、−ＮＨＣＯ−、又は−ＮＲ1ＣＯを表し、Ｒ1は炭素原子数１〜１０のアルキル基を表し；
ｎ１及びｎ２は、１又は２である。
Wherein P 1 and P 2 each represent a polymerizable group;
Each m1 and m2, represents an integer of 1 to 10, among the m1 or m2 amino CH 2, 1 single CH 2 or non-adjacent two or more CH 2 may be replaced by oxygen atom or a sulfur atom;
Each of A 1 , A 2 , A 3 and A 4 represents an optionally substituted 5- to 18-membered aromatic hydrocarbon ring or 5- to 18-membered aromatic heterocyclic group;
R represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms;
Z 1 and Z 2 each represent —COO—, —OCO—, —NHCO—, or —NR 1 CO, and R 1 represents an alkyl group having 1 to 10 carbon atoms;
L 1 and L 2 each represent —O—, —S—, —COO—, —OCO—, —OCOO—, —NHCO—, or —NR 1 CO, and R 1 has 1 to 10 carbon atoms. Represents an alkyl group;
n1 and n2 are 1 or 2.
前記式中、Ｐ1及びＰ2はそれぞれ、重合性基を表す。重合性基としては、ラジカル重合又はカチオン重合可能な重合性基が好ましい。ラジカル重合性基としては、一般に知られているラジカル重合性基を用いることができ、好適なものとして、（メタ）アクリレート基（アクリレート基及びメタクリレート基の双方を含む意味の用語として用いる）とを挙げることができる。この場合、重合速度はアクリレート基が一般的に速いことが知られており、生産性向上の観点からアクリレート基が好ましいが、メタクリレート基も高Δｎ液晶の重合性基として同様に使用することができる。カチオン重合性基としては、一般に知られているカチオン重合性を用いることができ、具体的には、脂環式エーテル基、環状アセタール基、環状ラクトン基、環状チオエーテル基、スピロオルソエステル基、ビニルオキシ基などを挙げることができる。中でも、脂環式エーテル基、ビニルオキシ基が好適であり、エポキシ基、オキセタニル基、ビニルオキシ基が特に好ましい。前記式中、Ｐ1及びＰ2は互いに異なっていてもよく、即ち、前記式（Ｉ）の化合物は、重合性基を２種以上含んでいてもよい。その場合は、ラジカル重合性基とカチオン重合性基等、重合反応機構が異なる重合性基をそれぞれ有していてもよいし、同一の反応機構の重合性基を有していてもよい。 In the above formula, P 1 and P 2 each represent a polymerizable group. As the polymerizable group, a polymerizable group capable of radical polymerization or cationic polymerization is preferable. As the radically polymerizable group, a generally known radically polymerizable group can be used, and as a preferable one, a (meth) acrylate group (used as a term including both an acrylate group and a methacrylate group) is used. Can be mentioned. In this case, it is known that the acrylate group is generally fast in the polymerization rate, and the acrylate group is preferable from the viewpoint of improving the productivity. However, the methacrylate group can also be used as the polymerizable group of the high Δn liquid crystal. . As the cationic polymerizable group, generally known cationic polymerizable groups can be used. Specifically, alicyclic ether group, cyclic acetal group, cyclic lactone group, cyclic thioether group, spiro orthoester group, vinyloxy group Examples include groups. Of these, alicyclic ether groups and vinyloxy groups are preferable, and epoxy groups, oxetanyl groups, and vinyloxy groups are particularly preferable. In the above formula, P 1 and P 2 may be different from each other, that is, the compound of the formula (I) may contain two or more polymerizable groups. In that case, each may have a polymerizable group having a different polymerization reaction mechanism such as a radical polymerizable group and a cationic polymerizable group, or may have a polymerizable group having the same reaction mechanism.
Ｐ1及びＰ2はそれぞれ、下記式（Ｐ−１）〜（Ｐ−５）のいずれかで表される重合性基であるのが好ましい。 P 1 and P 2 are each preferably a polymerizable group represented by any of the following formulas (P-1) to (P-5).
式中、Ｒ11〜Ｒ13はそれぞれ、水素原子又はメチル基を表す。＊がアルキレン鎖との結合位置である。
Ｐ1及びＰ2はそれぞれ、（メタ）アクリレート基であるのが好ましく、即ち、以下のいずれかの基であるのが好ましい。
In the formula, R 11 to R 13 each represent a hydrogen atom or a methyl group. * Is a bonding position with an alkylene chain.
P 1 and P 2 are each preferably a (meth) acrylate group, that is, any one of the following groups.
前記式中、ｍ１及びｍ２はそれぞれ、１〜１０の整数を表す。側鎖の長さが短い（例えば、ｍ１及びｍ２が１〜３である）と液晶相を示す上限温度は高いが結晶化し易く、溶解性が低くなるので、組成物に含まれる他の成分（例えば、溶媒又は他の液晶材料）への溶解性又は相溶性の観点で、該化合物の割合を小さくする必要がある場合がある。一方、側鎖が長い（例えば、ｍ１及びｍ２が４〜６である）と、溶解性は良化するが、液晶相を示す上限温度が低下したり、スメクチック相が出やすくなりネマチック相範囲が狭くなり、配向の均一性が低下する場合がある。また、側鎖が長くなると、分子の動きの自由度を増大させることになるので、剛性の高い膜質が要求される用途には、側鎖が短めの化合物を用いるのが好ましく、また膜の脆性改良の用途には、側鎖が長めの化合物を用いるのが好ましい。また、上記式（Ｉ）中のｍ１又はｍ２個のＣＨ2のうち、１つのＣＨ2又は隣接しない２以上のＣＨ2は、酸素原子又は硫黄原子に置き換わっていてもよい。−ＣＨ2−をＳやＯで置換したものは、結合基周りの回転性が増大し、即ち、自由度が増大するため、膜の脆性改良目的に効果がある。前記式（Ｉ）の化合物は、従来のアゾメチン化合物よりもネマチック相範囲が拡大されているのが好ましく、この観点からｍ１及びｍ２はそれぞれ、２〜８であるのが好ましく、３〜６であるのがより好ましい。 In said formula, m1 and m2 represent the integer of 1-10, respectively. When the length of the side chain is short (for example, m1 and m2 are 1 to 3), the upper limit temperature indicating the liquid crystal phase is high but it is easy to crystallize and the solubility is low, so other components contained in the composition ( For example, it may be necessary to reduce the ratio of the compound from the viewpoint of solubility or compatibility in a solvent or other liquid crystal material. On the other hand, when the side chain is long (for example, m1 and m2 are 4 to 6), the solubility is improved, but the upper limit temperature indicating the liquid crystal phase is lowered or the smectic phase is easily produced, and the nematic phase range is increased. In some cases, it becomes narrower and the uniformity of orientation is lowered. In addition, when the side chain becomes longer, the degree of freedom of movement of the molecule increases, so it is preferable to use a compound having a shorter side chain for applications that require high-rigidity film quality, and the brittleness of the film. For the improvement use, it is preferable to use a compound having a long side chain. Further, the above formula (I) of the m1 or m2 amino CH 2 in one CH 2 or nonadjacent two or more CH 2 may be replaced by an oxygen atom or a sulfur atom. In the case where —CH 2 — is substituted with S or O, the rotation around the bonding group is increased, that is, the degree of freedom is increased, which is effective in improving the brittleness of the film. The compound of the formula (I) preferably has an expanded nematic phase range than conventional azomethine compounds. From this point of view, m1 and m2 are preferably 2 to 8 and 3 to 6, respectively. Is more preferable.
環の種類と個数：
高いΔｎを達成するためには、配向秩序を高くすることが必要であり、このためには液晶相の上限温度を上げることが有効である。本発明の組成物に使用する上記式（Ｉ）の化合物は、少なくとも環状の芳香族基を４環（式（Ｉ）中のＡ1〜Ａ4）以上連結したものであり、その分子構造の特徴から、ＮＩ点（ネマチック液晶相→等方相の転移温度）が高く、具体的には１８０℃以上という極めて高いＮＩ点を示し、組成物のΔｎの向上に大きく寄与する。この環数を適当な連結基を介して５環及び６環と増大することによって、着色することなしに、ＮＩ点をさらに高めて、Δｎを大きくすることができる。また、芳香族環は、不飽和環や非芳香族環と比べて分子長軸方向の分極率を増大し、Δｎの向上に寄与する。但し、環数の増大は、融点や粘性の増大を招き、光学膜に使用する用途領域では塗布工程で結晶化を起こしやすく膜均一性が下がるといった欠点もある。
Ring type and number:
In order to achieve high Δn, it is necessary to increase the alignment order. For this purpose, it is effective to increase the maximum temperature of the liquid crystal phase. The compound of the above formula (I) used in the composition of the present invention has at least four cyclic aromatic groups linked (A 1 to A 4 in the formula (I)) or more and has a molecular structure. From the characteristics, the NI point (nematic liquid crystal phase → isotropic phase transition temperature) is high, specifically, it shows an extremely high NI point of 180 ° C. or more, which greatly contributes to the improvement of Δn of the composition. By increasing the number of rings to 5 and 6 via an appropriate linking group, the NI point can be further increased and Δn can be increased without coloring. In addition, the aromatic ring increases the polarizability in the molecular long axis direction as compared with the unsaturated ring and the non-aromatic ring, and contributes to the improvement of Δn. However, an increase in the number of rings leads to an increase in melting point and viscosity, and there is a drawback that in the application area used for the optical film, crystallization is likely to occur in the coating process, and the film uniformity is lowered.
式（Ｉ）中、Ａ1、Ａ2、Ａ3、及びＡ4はそれぞれ、置換されていてもよい、５〜１８員環の芳香族炭化水素環又は５〜１８員環の芳香族複素環の基を表す。Ａ1〜Ａ4は、単環の基であっても、２以上の環を含む縮合環の基であってもよい。但し、着色をより軽減するという観点では、単環の基であるのが好ましい。単環構造としては、５〜７員環状構造が好ましく、５又は６員環構造がより好ましい。前記複素環の環構成原子は、窒素原子、硫黄原子及び酸素原子から選択される１種又は２種以上であるのが好ましい。
以下に、Ａ1〜Ａ4の例を示すが、これらに限定されるものではない。
In the formula (I), A 1 , A 2 , A 3 , and A 4 are each an optionally substituted 5- to 18-membered aromatic hydrocarbon ring or 5- to 18-membered aromatic heterocycle Represents a group of A 1 to A 4 may be a monocyclic group or a condensed ring group containing two or more rings. However, it is preferably a monocyclic group from the viewpoint of further reducing coloring. As the monocyclic structure, a 5- to 7-membered cyclic structure is preferable, and a 5- or 6-membered cyclic structure is more preferable. The ring-constituting atoms of the heterocyclic ring are preferably one or more selected from a nitrogen atom, a sulfur atom and an oxygen atom.
Examples of A 1 to A 4 are shown below, but are not limited thereto.
式（Ｉ）中、Ａ1〜Ａ4はそれぞれ、置換基を有していてもよい、単環の基（例えば、上記例示された単環の基）であるのが好ましく、６員の芳香族炭化水素環を有する２価基であるのが好ましく、置換基を有していてもよい、６員の芳香族炭化水素環の基、即ち置換基を有していてもよいフェニレン基が好ましく、置換基を有していてもよい１，４−フェニレン基が特に好ましい。また、Ａ1〜Ａ4が、置換基を有していてもよい、縮合環の基である場合は、置換基を有していてもよい、ナフタレン環の基であるのが好ましい。 In the formula (I), each of A 1 to A 4 is preferably a monocyclic group (for example, the monocyclic group exemplified above) which may have a substituent, and a 6-membered aromatic A divalent group having an aromatic hydrocarbon ring is preferable, and a 6-membered aromatic hydrocarbon ring group which may have a substituent, that is, a phenylene group which may have a substituent is preferable. The 1,4-phenylene group which may have a substituent is particularly preferable. Further, when A 1 to A 4 are a condensed ring group which may have a substituent, it is preferably a naphthalene ring group which may have a substituent.
置換基の種類と個数：
高いΔｎのためには、吸収を長波化することが有効であり、それが従来のビスアゾメチン系液晶化合物の着色の原因であったが、本発明による式（Ｉ）の化合物では、アゾメチン結合によって繋がれた２つの芳香環の置換基の種類は化合物の色味にほとんど影響を与えず、任意の置換基を有する化合物を使用することができる。溶解性の観点からみると、置換基は原子の大きさがより大きいほど溶解性の向上に寄与し、小さいほど溶解性が低下し、配向性が低下する。このことから、置換基を有することが望ましい。置換基の数としては、より多いほど溶解性の上昇が期待できるが、多過ぎると液晶性が損なわれる。
Type and number of substituents:
For high Δn, it is effective to lengthen the absorption, which is the cause of coloring of the conventional bisazomethine liquid crystal compound, but the compound of the formula (I) according to the present invention has an azomethine bond. The type of the substituents of the two linked aromatic rings hardly affects the color of the compound, and a compound having an arbitrary substituent can be used. From the viewpoint of solubility, the substituent contributes to improvement in solubility as the size of the atom is larger, and the solubility is lowered and the orientation is lowered as the size is smaller. Therefore, it is desirable to have a substituent. As the number of substituents increases, the solubility can be expected to increase, but if it is too large, the liquid crystallinity is impaired.
Ａ1〜Ａ4がそれぞれ有する置換基の例には、炭素原子数１〜４のアルキル基、炭素原子数１〜４のアルコキシ基、炭素原子数２〜５のアミド基、炭素原子数２〜５のアルコキシカルボニル基、炭素原子数２〜５のアシルオキシ基、炭素原子数２〜５のアシル基、シアノ基、又はハロゲン原子（例えば、フッ素原子、塩素原子、臭素原子及びヨウ素原子）が含まれる。より好ましくは炭素原子数１〜４のアルキル基、炭素原子数１〜４のアルコキシ基、炭素原子数２〜４のアミド基、炭素原子数２〜５のアルコキシカルボニル基、ハロゲン原子であり、さらに好ましくは炭素原子数１〜４のアルキル基、炭素原子数１〜４のアルコキシ基、炭素原子数２〜５のアルコキシカルボニル基、又はハロゲン原子である。 Examples of the substituent each A 1 to A 4 have include an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an amide group having 2 to 5 carbon atoms, and 2 to 2 carbon atoms. 5 alkoxycarbonyl groups, acyloxy groups having 2 to 5 carbon atoms, acyl groups having 2 to 5 carbon atoms, cyano groups, or halogen atoms (for example, fluorine atom, chlorine atom, bromine atom and iodine atom) are included. . More preferably an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an amide group having 2 to 4 carbon atoms, an alkoxycarbonyl group having 2 to 5 carbon atoms, a halogen atom, An alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkoxycarbonyl group having 2 to 5 carbon atoms, or a halogen atom is preferable.
これらを踏まえて、式（Ｉ）の化合物の環数としては、環の数が少ないのが好ましく、ｎ１及びｎ２は１又は２であり、より好ましくは１である。 In view of these, the number of rings of the compound of the formula (I) is preferably small, and n1 and n2 are 1 or 2, and more preferably 1.
式（Ｉ）中、Ｒは水素原子又は炭素原子数１〜８のアルキル基を表す。Ｒが水素原子であっても、十分な加水分解耐性があるが、極めて高い加水分解耐性が必要な用途において、Ｒがアルキル基である化合物を用いるのが好ましい。アルキル基の長さとしては、長過ぎると液晶相を不安定化することから、Ｒは短いことが好ましい。具体的には、Ｒは炭素原子数１〜８のアルキル基であるのが好ましく、炭素原子数１〜５のアルキル基がより好ましく、炭素原子数１〜３のアルキル基がさらに好ましい。 In formula (I), R represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. Even if R is a hydrogen atom, it has sufficient hydrolysis resistance, but it is preferable to use a compound in which R is an alkyl group in applications that require extremely high hydrolysis resistance. As the length of the alkyl group, it is preferable that R is short because too long a liquid crystal phase is destabilized. Specifically, R is preferably an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, and further preferably an alkyl group having 1 to 3 carbon atoms.
連結基の種類：
環構造をつなぐ連結基（式（Ｉ）中のＺ1及びＺ2）としては、液晶相安定化（ＮＩ点の向上）のためには剛直な構造を有するものが好ましい。一方、剛直な基が多く存在すると、結晶性向上による溶解性低下、スメクチック相安定化による、ネマチック液晶相温度範囲の縮小が考えられる。このような観点から、連結基は、ネマチック液晶相が安定化されるように適宜選ばれるのが好ましい。具体的には、前記式中、Ｚ1及びＺ2はそれぞれ、−ＣＯＯ−、−ＯＣＯ−、−ＮＨ−、又はＮＲ1を表し、Ｒ1は炭素原子数１〜１０のアルキル基を表し；より好ましくは−ＣＯＯ−、−ＯＣＯ−、−ＮＨ−であり；さらに好ましくは−ＣＯＯ−、−ＯＣＯ−である。
Linking group type:
As the linking group for linking the ring structure (Z 1 and Z 2 in formula (I)), those having a rigid structure are preferable for stabilizing the liquid crystal phase (improving the NI point). On the other hand, if there are many rigid groups, it is conceivable that the nematic liquid crystal phase temperature range is reduced due to the decrease in solubility due to the improvement in crystallinity and the stabilization of the smectic phase. From such a viewpoint, the linking group is preferably selected as appropriate so that the nematic liquid crystal phase is stabilized. Specifically, in the formula, Z 1 and Z 2 each represent —COO—, —OCO—, —NH—, or NR 1 , and R 1 represents an alkyl group having 1 to 10 carbon atoms; More preferred are —COO—, —OCO—, and —NH—; and still more preferred are —COO— and —OCO—.
式（Ｉ）中、Ｌ1及びＬ2はそれぞれ、−Ｏ−、−Ｓ−、−ＣＯＯ−、−ＯＣＯ−、−ＯＣＯＯ−、−ＮＨ−、又はＮＲ1を表し、Ｒ1は炭素原子数１〜１０のアルキル基を表し；より好ましくは−Ｏ−、−Ｓ−、−ＣＯＯ−、−ＯＣＯ−、−ＯＣＯＯ−であり；さらに好ましくは−Ｏ−、−ＯＣＯＯ−である。尚、化合物全体の吸収に対する影響（すなわち化合物の色味）は、上記に挙げた連結基の種類にあまり影響しない。 In formula (I), L 1 and L 2 each represent —O—, —S—, —COO—, —OCO—, —OCOO—, —NH—, or NR 1 , and R 1 represents the number of carbon atoms. Represents an alkyl group of 1 to 10; more preferably —O—, —S—, —COO—, —OCO—, —OCOO—; and still more preferably —O—, —OCOO—. In addition, the influence with respect to the absorption of the whole compound (namely, the color of the compound) does not greatly affect the types of the linking groups mentioned above.
以下に、式（Ｉ）で表される化合物の具体例を挙げるが、以下の具体例に限定されるものではない。 Specific examples of the compound represented by the formula (I) are shown below, but are not limited to the following specific examples.
本発明に係わる一般式（Ｉ）で表される化合物は、例えば下記の反応式（１）に従う方法により製造することができる。 The compound represented by the general formula (I) according to the present invention can be produced, for example, by a method according to the following reaction formula (1).
但し、前記反応式（１）中、Ｌ3及びＬ4は、Ｏ、Ｓ、ＮＨ又はＮＲ1を表し、Ａ1〜Ａ4、Ｚ1、Ｚ2、Ｌ1、Ｌ2、Ｒ、Ｒ1、Ｐ1及びＰ2は一般式（Ｉ）中におけるそれぞれと同義であり、好ましい範囲も同様である。 However, the reaction formula (1), L 3 and L 4 represents O, S, NH or NR 1, A 1 ~A 4, Z 1, Z 2, L 1, L 2, R, R 1 , P 1 and P 2 have the same meanings as in general formula (I), and the preferred ranges are also the same.
前記反応式（１）において、化合物（Ａ）は芳香族アルデヒドであり、市販品又は公知の方法により合成したものを用いることができる。反応式（１）において、化合物（Ｂ）はアミノフェノール、アミノチオフェノール、ジアミノベンゼン誘導体であり、市販品又は公知の方法により合成したものを用いることができる。また、化合物（Ｄ）及び化合物（Ｅ）は、特開２００２−９７１７０号公報の１０頁、［００８５］〜［００８７］段落に記載の方法を参照して合成できる。
即ち、一般式（Ｉ）で表される化合物は、前記反応式（１）における、化合物（Ａ）と化合物（Ｂ）との脱水縮合反応で化合物（Ｃ）を合成し、続いて化合物（Ｃ）と化合物（Ｄ）及び化合物（Ｅ）との反応により合成することができる。
また、反応中の熱重合を抑えるためにハイドロキノン誘導体などの重合禁止剤を用いてもよい。
In the reaction formula (1), the compound (A) is an aromatic aldehyde, and a commercially available product or one synthesized by a known method can be used. In reaction formula (1), compound (B) is an aminophenol, aminothiophenol, or diaminobenzene derivative, and a commercially available product or one synthesized by a known method can be used. In addition, the compound (D) and the compound (E) can be synthesized with reference to the method described in paragraph [0085] to [0087], page 10, JP-A-2002-97170.
That is, the compound represented by the general formula (I) is obtained by synthesizing the compound (C) by the dehydration condensation reaction between the compound (A) and the compound (B) in the reaction formula (1). ), Compound (D) and compound (E).
In order to suppress thermal polymerization during the reaction, a polymerization inhibitor such as a hydroquinone derivative may be used.
本発明の重合性組成物に含まれる式（Ｉ）の化合物は、液晶性を示す。さらに、高いΔｎを示すので、その配向を固定した膜は、より低いΔｎの液晶性化合物を利用した膜と比較して、より薄膜で所望の光学特性を達成することが期待できる。
また、該化合物は、芳香環の置換基の種類や連結基によらず、可視光領域での吸収が極めて小さいことから無色透明であり、液晶相範囲が広いために溶剤に溶解しやすい、重合しやすいなどといった複数の特性をも満足する。式（Ｉ）の化合物を含有する本発明の重合性組成物を用いて作製される硬化膜は、十分な硬度を示し、無色透明であり、耐候性・耐熱性が良好である等、複数の特性を満足し得るであろう。従って、本発明の重合性組成物を利用して形成された硬化膜は、例えば、光学素子の構成要素である位相差板、偏光素子、選択反射膜、カラーフィルタ、反射防止膜、視野角補償膜、ホログラフィー、配向膜等、種々の用途に利用することができる。
The compound of the formula (I) contained in the polymerizable composition of the present invention exhibits liquid crystallinity. Furthermore, since a high Δn is exhibited, a film whose orientation is fixed can be expected to achieve a desired optical characteristic with a thinner film than a film using a liquid crystal compound having a lower Δn.
In addition, the compound is colorless and transparent because it has very little absorption in the visible light region, regardless of the type of aromatic ring substituent or the linking group, and is easily dissolved in a solvent due to its wide liquid crystal phase range. It also satisfies multiple characteristics such as easy to do. The cured film produced using the polymerizable composition of the present invention containing the compound of formula (I) exhibits sufficient hardness, is colorless and transparent, has good weather resistance and heat resistance, and the like. The property could be satisfied. Accordingly, the cured film formed using the polymerizable composition of the present invention includes, for example, a retardation plate, a polarizing element, a selective reflection film, a color filter, an antireflection film, and a viewing angle compensation that are components of the optical element. It can be used for various applications such as films, holography, and alignment films.
本発明の組成物の一態様は、前記式（Ｉ）の化合物の少なくとも１種と、少なくとも１種のキラル化合物とを含有する重合性組成物である。本態様の組成物をコレステリック液晶相とした後、それを固定して形成された膜は、その螺旋ピッチに応じて、所定の波長の光に対して、選択反射特性を示し、反射膜（例えば、赤外線反射膜）として有用である。本発明の高いΔｎを示す重合性化合物を利用することにより、より低いΔｎの液晶性化合物を利用した同一の厚みの膜と比較して、反射波長域が広帯域化されるという利点がある。 One aspect of the composition of the present invention is a polymerizable composition containing at least one compound of the formula (I) and at least one chiral compound. A film formed by fixing the composition of the present embodiment after forming a cholesteric liquid crystal phase exhibits selective reflection characteristics with respect to light of a predetermined wavelength according to the helical pitch, and a reflective film (for example, , Useful as an infrared reflective film). By using the polymerizable compound exhibiting a high Δn of the present invention, there is an advantage that the reflection wavelength band is broadened as compared with a film having the same thickness using a liquid crystal compound having a lower Δn.
本発明の組成物について、前記式（Ｉ）の化合物は、主成分であっても、添加剤として使用されていてもよい。前記式（Ｉ）の化合物を組成物の全質量に対して、５質量％以上含有していれば、式（Ｉ）の化合物による効果を得ることができ、好ましくは１０〜８５質量％、より好ましくは１０〜７５質量％、さらに好ましくは１５〜７０質量％である。但し、この範囲に限定されるものではない。 In the composition of the present invention, the compound of the formula (I) may be a main component or may be used as an additive. If the compound of the formula (I) is contained in an amount of 5% by mass or more based on the total mass of the composition, the effect of the compound of the formula (I) can be obtained, preferably 10 to 85% by mass, more Preferably it is 10-75 mass%, More preferably, it is 15-70 mass%. However, it is not limited to this range.
（１）キラル化合物
本発明の組成物をコレステリック液晶相を示す組成物として調製するためには、キラル化合物を添加するのが好ましい。キラル化合物は液晶性であっても、非液晶性であってもよい。前記キラル化合物は、公知の種々のキラル剤（例えば、液晶デバイスハンドブック、第３章４−３項、ＴＮ、ＳＴＮ用カイラル剤、１９９頁、日本学術振興会第１４２委員会編、１９８９に記載）から選択することができる。キラル化合物は、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あるいは面性不斉化合物も用いることができる。軸性不斉化合物又は面性不斉化合物の例には、ビナフチル、ヘリセン、パラシクロファン及びこれらの誘導体が含まれる。キラル化合物（キラル剤）は、重合性基を有していてもよい。キラル化合物が重合性基を有するとともに、併用する棒状液晶化合物も重合性基を有する場合は、重合性キラル化合物と重合性棒状液晶化合物との重合反応により、棒状液晶化合物から誘導される繰り返し単位と、キラル化合物から誘導される繰り返し単位とを有するポリマーを形成することができる。この態様では、重合性キラル化合物が有する重合性基は、重合性棒状液晶化合物が有する重合性基と、同種の基であることが好ましい。従って、キラル化合物の重合性基も、不飽和重合性基、エポキシ基又はアジリジニル基であることが好ましく、不飽和重合性基であることがさらに好ましく、エチレン性不飽和重合性基であることが特に好ましい。
(1) Chiral compound In order to prepare the composition of the present invention as a composition exhibiting a cholesteric liquid crystal phase, it is preferable to add a chiral compound. The chiral compound may be liquid crystalline or non-liquid crystalline. The chiral compounds are known various chiral agents (for example, described in Liquid Crystal Device Handbook, Chapter 3-4-3, TN, chiral agent for STN, 199 pages, edited by Japan Society for the Promotion of Science, 142nd Committee, 1989) You can choose from. A chiral compound generally contains an asymmetric carbon atom, but an axial asymmetric compound or a planar asymmetric compound containing no asymmetric carbon atom can also be used. Examples of the axial asymmetric compound or the planar asymmetric compound include binaphthyl, helicene, paracyclophane, and derivatives thereof. The chiral compound (chiral agent) may have a polymerizable group. When the chiral compound has a polymerizable group and the rod-shaped liquid crystal compound used in combination also has a polymerizable group, a repeating unit derived from the rod-shaped liquid crystal compound by a polymerization reaction between the polymerizable chiral compound and the polymerizable rod-shaped liquid crystal compound And polymers having repeating units derived from chiral compounds. In this embodiment, the polymerizable group possessed by the polymerizable chiral compound is preferably the same group as the polymerizable group possessed by the polymerizable rod-like liquid crystal compound. Accordingly, the polymerizable group of the chiral compound is also preferably an unsaturated polymerizable group, an epoxy group or an aziridinyl group, more preferably an unsaturated polymerizable group, and an ethylenically unsaturated polymerizable group. Particularly preferred.
本発明の組成物中のキラル化合物は、併用される式（Ｉ）の化合物に対して、１〜３０モル％であることが好ましい。キラル化合物の使用量を、より少なくした方が液晶性に影響を及ぼさないことが多いため好まれる。従って、キラル化合物は、少量でも所望の螺旋ピッチの捩れ配向を達成可能なように、強い捩り力のある化合物が好ましい。この様な、強い捩れ力を示すキラル剤としては、例えば、特開２００３−２８７６２３公報に記載のキラル剤が挙げられ、本発明に好ましく用いることができる。 It is preferable that the chiral compound in the composition of this invention is 1-30 mol% with respect to the compound of Formula (I) used together. A smaller amount of chiral compound is preferred because it often does not affect liquid crystallinity. Accordingly, the chiral compound is preferably a compound having a strong twisting force so that the twisted orientation of the desired helical pitch can be achieved even with a small amount. Examples of such a chiral agent exhibiting a strong twisting force include the chiral agents described in JP-A-2003-287623, and can be preferably used in the present invention.
（２）他の液晶化合物
本発明の組成物は、前記式（Ｉ）の化合物とともに、他の１種以上の液晶性化合物を含有していてもよい。前記式（Ｉ）の化合物は、他の液晶性化合物との相溶性も高いので、他の液晶性化合物を混合しても、不透明化等が生じず、透明性の高い膜を形成可能である。他の液晶性化合物を併用可能であることから、種々の用途に適する種々の組成の組成物を提供できる。併用可能な他の液晶化合物の例には、棒状ネマチック液晶化合物である。前記棒状ネマチック液晶化合物の例には、アゾキシ類、シアノビフェニル類、シアノフェニルエステル類、安息香酸エステル類、シクロヘキサンカルボン酸フェニルエステル類、シアノフェニルシクロヘキサン類、シアノ置換フェニルピリミジン類、アルコキシ置換フェニルピリミジン類、フェニルジオキサン類、トラン類及びアルケニルシクロヘキシルベンゾニトリル類が含まれる。低分子液晶化合物だけではなく、高分子液晶化合物も用いることができる。
(2) Other liquid crystal compounds The composition of the present invention may contain one or more other liquid crystal compounds together with the compound of the formula (I). Since the compound of the formula (I) is highly compatible with other liquid crystal compounds, mixing with other liquid crystal compounds does not cause opacification and can form a highly transparent film. . Since other liquid crystalline compounds can be used in combination, compositions having various compositions suitable for various applications can be provided. Examples of other liquid crystal compounds that can be used in combination are rod-like nematic liquid crystal compounds. Examples of the rod-like nematic liquid crystal compound include azoxy compounds, cyanobiphenyl compounds, cyanophenyl esters, benzoic acid esters, cyclohexanecarboxylic acid phenyl esters, cyanophenylcyclohexanes, cyano substituted phenylpyrimidines, alkoxy substituted phenylpyrimidines. , Phenyldioxanes, tolanes and alkenylcyclohexylbenzonitriles. Not only low-molecular liquid crystal compounds but also high-molecular liquid crystal compounds can be used.
本発明に利用可能な他の液晶化合物は、重合性であっても非重合性であってもよい。重合性基を有しない棒状液晶化合物については、様々な文献（例えば、Y. Goto et.al., Mol. Cryst. Liq. Cryst. 1995, Vol. 260, pp.23-28）に記載がある。
重合性棒状液晶化合物は、重合性基を棒状液晶化合物に導入することで得られる。重合性基の例には、不飽和重合性基、エポキシ基、及びアジリジニル基が含まれ、不飽和重合性基が好ましく、エチレン性不飽和重合性基が特に好ましい。重合性基は種々の方法で、棒状液晶化合物の分子中に導入できる。重合性棒状液晶化合物が有する重合性基の個数は、好ましくは１〜６個、より好ましくは１〜３個である。重合性棒状液晶化合物の例は、Ｍａｋｒｏｍｏｌ．Ｃｈｅｍ．，１９０巻、２２５５頁（１９８９年）、Ａｄｖａｎｃｅｄ Ｍａｔｅｒｉａｌｓ ５巻、１０７頁（１９９３年）、米国特許第４６８３３２７号明細書、同５６２２６４８号明細書、同５７７０１０７号明細書、国際公開ＷＯ９５／２２５８６号公報、同９５／２４４５５号公報、同９７／００６００号公報、同９８／２３５８０号公報、同９８／５２９０５号公報、特開平１−２７２５５１号公報、同６−１６６１６号公報、同７−１１０４６９号公報、同１１−８００８１号公報、及び特開２００１−３２８９７３号公報などに記載の化合物が含まれる。２種類以上の重合性棒状液晶化合物を併用してもよい。２種類以上の重合性棒状液晶化合物を併用すると、配向温度を低下させることができる。
Other liquid crystal compounds that can be used in the present invention may be polymerizable or non-polymerizable. The rod-like liquid crystal compound having no polymerizable group is described in various documents (for example, Y. Goto et.al., Mol. Cryst. Liq. Cryst. 1995, Vol. 260, pp. 23-28). .
The polymerizable rod-like liquid crystal compound can be obtained by introducing a polymerizable group into the rod-like liquid crystal compound. Examples of the polymerizable group include an unsaturated polymerizable group, an epoxy group, and an aziridinyl group, preferably an unsaturated polymerizable group, and particularly preferably an ethylenically unsaturated polymerizable group. The polymerizable group can be introduced into the molecule of the rod-like liquid crystal compound by various methods. The number of polymerizable groups possessed by the polymerizable rod-like liquid crystal compound is preferably 1 to 6, and more preferably 1 to 3. Examples of the polymerizable rod-like liquid crystal compound are described in Makromol. Chem. 190, 2255 (1989), Advanced Materials 5, 107 (1993), US Pat. No. 4,683,327, US Pat. No. 5,622,648, US Pat. No. 5,770,107, International Publication WO95 / 22586. No. 95/24455, No. 97/00600, No. 98/23580, No. 98/52905, JP-A-1-272551, No. 6-16616, and No. 7-110469. 11-80081 and JP-A 2001-328773, and the like. Two or more kinds of polymerizable rod-like liquid crystal compounds may be used in combination. When two or more kinds of polymerizable rod-like liquid crystal compounds are used in combination, the alignment temperature can be lowered.
他の液晶化合物の添加量については特に制限はない。前記式（Ｉ）の化合物の含有割合が高くても、他の液晶化合物の含有割合が高くても、互いに等しい含有割合であってもよく、用途に応じて好ましい範囲に調整することができる。 There is no restriction | limiting in particular about the addition amount of another liquid crystal compound. Even if the content ratio of the compound of the formula (I) is high, the content ratio of other liquid crystal compounds may be high, or the content ratios may be equal to each other, and can be adjusted to a preferable range according to the application.
（３） 重合開始剤
本発明の組成物は、重合開始剤を含有しているのが好ましい。例えば、紫外線照射により硬化反応を進行させて硬化膜を形成する態様では、使用する重合開始剤は、紫外線照射によって重合反応を開始可能な光重合開始剤であるのが好ましい。光重合開始剤の例には、α−カルボニル化合物（米国特許第２３６７６６１号、同２３６７６７０号の各明細書記載）、アシロインエーテル（米国特許第２４４８８２８号明細書記載）、α−炭化水素置換芳香族アシロイン化合物（米国特許第２７２２５１２号明細書記載）、多核キノン化合物（米国特許第３０４６１２７号、同２９５１７５８号の各明細書記載）、トリアリールイミダゾールダイマーとｐ−アミノフェニルケトンとの組み合わせ（米国特許第３５４９３６７号明細書記載）、アクリジン及びフェナジン化合物（特開昭６０−１０５６６７号公報、米国特許第４２３９８５０号明細書記載）及びオキサジアゾール化合物（米国特許第４２１２９７０号明細書記載）等が挙げられる。
(3) Polymerization initiator The composition of the present invention preferably contains a polymerization initiator. For example, in an embodiment in which a curing reaction is caused to proceed by ultraviolet irradiation to form a cured film, the polymerization initiator used is preferably a photopolymerization initiator that can initiate a polymerization reaction by ultraviolet irradiation. Examples of the photopolymerization initiator include α-carbonyl compounds (described in US Pat. Nos. 2,367,661 and 2,367,670), acyloin ether (described in US Pat. No. 2,448,828), α-hydrocarbon substituted aromatics. Group acyloin compounds (described in US Pat. No. 2,722,512), polynuclear quinone compounds (described in US Pat. Nos. 3,046,127 and 2,951,758), combinations of triarylimidazole dimers and p-aminophenyl ketone (US patents) No. 3549367), acridine and phenazine compounds (JP-A-60-105667, US Pat. No. 4,239,850), oxadiazole compounds (US Pat. No. 4,221,970), and the like. .
光重合開始剤の使用量は、組成物（塗布液の場合は固形分）の０．１〜２０質量％であることが好ましく、１〜８質量％であることがさらに好ましい。 The amount of the photopolymerization initiator used is preferably 0.1 to 20% by mass, more preferably 1 to 8% by mass, based on the composition (solid content in the case of a coating solution).
（４） 配向制御剤
本発明の組成物中に、安定的に又は迅速に液晶相（例えば、コレステリック液晶相）となるのに寄与する配向制御剤を添加してもよい。配向制御剤の例には、含フッ素(メタ)アクリレート系ポリマー、及び下記一般式（Ｘ１）〜（Ｘ３）で表される化合物が含まれる。これらから選択される２種以上を含有していてもよい。これらの化合物は、層の空気界面において、液晶化合物の分子のチルト角を低減若しくは実質的に水平配向させることができる。尚、本明細書で「水平配向」とは、液晶分子長軸と膜面が平行であることをいうが、厳密に平行であることを要求するものではなく、本明細書では、水平面とのなす傾斜角が２０度未満の配向を意味するものとする。液晶化合物が空気界面付近で水平配向する場合、配向欠陥が生じ難いため、可視光領域での透明性が高くなる。一方、液晶化合物の分子が大きなチルト角で配向すると、例えば、コレステリック液晶相とする場合は、その螺旋軸が膜面法線からずれるため、反射率が低下したり、フィンガープリントパターンが発生し、ヘイズの増大や回折性を示すため好ましくない。
配向制御剤として利用可能な前記含フッ素(メタ)アクリレート系ポリマーの例は、特開２００７−２７２１８５号公報の［００１８］〜［００４３］等に記載がある。
(4) Alignment Control Agent An alignment control agent that contributes to a liquid crystal phase (for example, cholesteric liquid crystal phase) stably or rapidly may be added to the composition of the present invention. Examples of the orientation control agent include fluorine-containing (meth) acrylate polymers and compounds represented by the following general formulas (X1) to (X3). You may contain 2 or more types selected from these. These compounds can reduce the tilt angle of the molecules of the liquid crystal compound or can be substantially horizontally aligned at the air interface of the layer. In this specification, “horizontal alignment” means that the major axis of the liquid crystal molecule is parallel to the film surface, but it is not required to be strictly parallel. An orientation with an inclination angle of less than 20 degrees is meant. When the liquid crystal compound is horizontally aligned in the vicinity of the air interface, alignment defects are less likely to occur, and thus transparency in the visible light region is increased. On the other hand, when the molecules of the liquid crystal compound are aligned at a large tilt angle, for example, in the case of a cholesteric liquid crystal phase, the spiral axis is deviated from the film surface normal, so that the reflectance decreases or a fingerprint pattern occurs, This is not preferable because it exhibits increased haze and diffraction properties.
Examples of the fluorine-containing (meth) acrylate-based polymer that can be used as an orientation control agent are described in JP-A No. 2007-272185, [0018] to [0043].
以下、配向制御剤として利用可能な、下記一般式（Ｘ１）〜（Ｘ３）について、順に説明する。 Hereinafter, the following general formulas (X1) to (X3) that can be used as the alignment control agent will be described in order.
式中、Ｒ1、Ｒ2及びＲ3は各々独立して、水素原子又は置換基を表し、Ｘ1、Ｘ2及びＸ3は単結合又は二価の連結基を表す。Ｒ1〜Ｒ3で各々表される置換基としては、好ましくは置換もしくは無置換の、アルキル基（中でも、無置換のアルキル基又はフッ素置換アルキル基がより好ましい）、アリール基（中でもフッ素置換アルキル基を有するアリール基が好ましい）、置換もしくは無置換のアミノ基、アルコキシ基、アルキルチオ基、ハロゲン原子である。Ｘ1、Ｘ2及びＸ3で各々表される二価の連結基は、アルキレン基、アルケニレン基、二価の芳香族基、二価のヘテロ環残基、−ＣＯ−、−ＮＲａ−（Ｒａは炭素原子数が１〜５のアルキル基又は水素原子）、−Ｏ−、−Ｓ−、−ＳＯ−、−ＳＯ2−及びそれらの組み合わせからなる群より選ばれる二価の連結基であることが好ましい。二価の連結基は、アルキレン基、フェニレン基、−ＣＯ−、−ＮＲａ−、−Ｏ−、−Ｓ−及び−ＳＯ2−からなる群より選ばれる二価の連結基又は該群より選ばれる基を少なくとも二つ組み合わせた二価の連結基であることがより好ましい。アルキレン基の炭素原子数は、１〜１２であることが好ましい。アルケニレン基の炭素原子数は、２〜１２であることが好ましい。二価の芳香族基の炭素原子数は、６〜１０であることが好ましい。 In the formula, R 1 , R 2 and R 3 each independently represent a hydrogen atom or a substituent, and X 1 , X 2 and X 3 each represent a single bond or a divalent linking group. The substituent represented by each of R 1 to R 3 is preferably a substituted or unsubstituted alkyl group (more preferably an unsubstituted alkyl group or a fluorine-substituted alkyl group), an aryl group (particularly a fluorine-substituted alkyl). An aryl group having a group is preferred), a substituted or unsubstituted amino group, an alkoxy group, an alkylthio group, and a halogen atom. The divalent linking groups represented by X 1 , X 2 and X 3 are each an alkylene group, an alkenylene group, a divalent aromatic group, a divalent heterocyclic residue, —CO—, —NRa— (Ra Is a divalent linking group selected from the group consisting of an alkyl group having 1 to 5 carbon atoms or a hydrogen atom), —O—, —S—, —SO—, —SO 2 — and combinations thereof. Is preferred. The divalent linking group is selected from the group consisting of an alkylene group, a phenylene group, —CO—, —NRa—, —O—, —S— and —SO 2 —, or the group. It is more preferably a divalent linking group in which at least two groups are combined. The alkylene group preferably has 1 to 12 carbon atoms. The alkenylene group preferably has 2 to 12 carbon atoms. The number of carbon atoms of the divalent aromatic group is preferably 6-10.
式中、Ｒは置換基を表し、ｍは０〜５の整数を表す。ｍが２以上の整数を表す場合、複数個のＲは同一でも異なっていてもよい。Ｒとして好ましい置換基は、Ｒ1、Ｒ2、及びＲ3で表される置換基の好ましい範囲として挙げたものと同様である。ｍは、好ましくは１〜３の整数を表し、特に好ましくは２又は３である。 In the formula, R represents a substituent, and m represents an integer of 0 to 5. When m represents an integer greater than or equal to 2, several R may be same or different. Preferred substituents for R are the same as those listed as preferred ranges for the substituents represented by R 1 , R 2 , and R 3 . m preferably represents an integer of 1 to 3, particularly preferably 2 or 3.
式中、Ｒ4、Ｒ5、Ｒ6、Ｒ7、Ｒ8及びＲ9は各々独立して、水素原子又は置換基を表す。Ｒ4、Ｒ5、Ｒ6、Ｒ7、Ｒ8及びＲ9でそれぞれ表される置換基は、好ましくは一般式（ＸＩ）におけるＲ1、Ｒ2及びＲ3で表される置換基の好ましいものとして挙げたものと同様である。 In the formula, R 4 , R 5 , R 6 , R 7 , R 8 and R 9 each independently represent a hydrogen atom or a substituent. The substituents represented by R 4 , R 5 , R 6 , R 7 , R 8 and R 9 are each preferably a substituent represented by R 1 , R 2 and R 3 in the general formula (XI). It is the same as that mentioned as a thing.
本発明において配向制御剤として使用可能な、前記式（Ｘ１）〜（Ｘ３）で表される化合物の例には、特開２００５−９９２４８号公報に記載の化合物が含まれる。
なお、本発明では、配向制御剤として、前記一般式（Ｘ１）〜（Ｘ３）で表される化合物の一種を単独で用いてもよいし、二種以上を併用してもよい。
Examples of the compounds represented by the formulas (X1) to (X3) that can be used as the alignment control agent in the present invention include compounds described in JP-A-2005-99248.
In the present invention, as the alignment control agent, one type of the compounds represented by the general formulas (X1) to (X3) may be used alone, or two or more types may be used in combination.
前記組成物中における、一般式（Ｘ１）〜（Ｘ３）のいずれかで表される化合物の添加量は、前記式（Ｉ）の化合物の質量の０．０１〜１０質量％が好ましく、０．０１〜５質量％がより好ましく、０．０２〜１質量％が特に好ましい。 The amount of the compound represented by any one of the general formulas (X1) to (X3) in the composition is preferably 0.01 to 10% by mass with respect to the mass of the compound of the formula (I). 01-5 mass% is more preferable, and 0.02-1 mass% is especially preferable.
（５）その他の添加剤
本発明の組成物は、１種又は２種類以上の、酸化防止剤、紫外線吸収剤、増感剤、安定剤、可塑剤、連鎖移動剤、重合禁止剤、消泡剤、レべリング剤、増粘剤、難燃剤、界面活性物質、分散剤、染料、顔料等の色材、等の他の添加剤を含有していてもよい。
(5) Other additives The composition of the present invention comprises one or more kinds of antioxidants, ultraviolet absorbers, sensitizers, stabilizers, plasticizers, chain transfer agents, polymerization inhibitors, and antifoaming agents. Other additives such as a colorant such as an agent, a leveling agent, a thickener, a flame retardant, a surfactant, a dispersant, a dye and a pigment may be contained.
２．フィルム
本発明の組成物は、位相差フィルム、反射フィルム等の種々の光学フィルムの材料として有用である。
本発明は、前記式（Ｉ）の化合物の少なくとも１種を含有する、本発明の重合性組成物を用いて形成されるフィルムにも関する。本発明の重合性組成物は、位相膜、反射膜等の種々の光学フィルムの材料として有用である。
（１）本発明のフィルムの製造方法
本発明のフィルムの製造方法の一例は、
(i) 基板等の表面に、本発明の組成物を塗布して、液晶相（コレステリック液晶相等）の状態にすること、
(ii) 前記組成物の硬化反応を進行させ、液晶相を固定して硬化膜を形成すること、
を少なくとも含む製造方法である。
（i）及び（ii）の工程を、複数回繰り返して、複数の上記硬化膜が積層されたフィルムを作製することもできる。
2. Film The composition of the present invention is useful as a material for various optical films such as a retardation film and a reflective film.
The present invention also relates to a film formed using the polymerizable composition of the present invention containing at least one compound of the formula (I). The polymerizable composition of the present invention is useful as a material for various optical films such as a phase film and a reflective film.
(1) Production method of the film of the present invention An example of the production method of the film of the present invention is as follows:
(i) Applying the composition of the present invention to the surface of a substrate or the like to bring it into a liquid crystal phase (cholesteric liquid crystal phase, etc.)
(ii) allowing the curing reaction of the composition to proceed and fixing the liquid crystal phase to form a cured film;
Is a production method comprising at least
It is also possible to produce a film in which a plurality of the cured films are laminated by repeating the steps (i) and (ii) a plurality of times.
前記（i）工程では、まず、基板又はその上に形成された配向膜の表面に、本発明の組成物を塗布する。前記組成物は、溶媒に材料を溶解及び／又は分散した、塗布液として調製されるのが好ましい。塗布液の調製に使用する溶媒としては、有機溶媒が好ましく用いられる。該有機溶媒としては、アミド（例えばＮ，Ｎ−ジメチルホルムアミド）；スルホキシド（例えばジメチルスルホキシド）；ヘテロ環化合物（例えばピリジン）；炭化水素（例えばベンゼン、ヘキサン）；アルキルハライド（例えばクロロホルム、ジクロロメタン）；エステル（例えば酢酸メチル、酢酸ブチル）；ケトン（例えばアセトン、メチルエチルケトン）；エーテル（例えばテトラヒドロフラン、１，２−ジメトキシエタン）；１，４−ブタンジオールジアセテートなどが含まれる。これらの中でも、アルキルハライド及びケトンが特に好ましい。二種類以上の有機溶媒を併用してもよい。 In the step (i), first, the composition of the present invention is applied to the surface of the substrate or the alignment film formed thereon. The composition is preferably prepared as a coating solution in which a material is dissolved and / or dispersed in a solvent. As a solvent used for preparing the coating solution, an organic solvent is preferably used. 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, butyl acetate); ketones (eg, acetone, methyl ethyl ketone); ethers (eg, tetrahydrofuran, 1,2-dimethoxyethane); 1,4-butanediol diacetate, and the like. Among these, alkyl halides and ketones are particularly preferable. Two or more organic solvents may be used in combination.
前記塗布液の塗布は、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等の種々の方法によって行うことができる。また、インクジェット装置を用いて、組成物をノズルから吐出して、塗膜を形成することもできる。 The coating liquid can be applied by various methods such as a wire bar coating method, an extrusion coating method, a direct gravure coating method, a reverse gravure coating method, and a die coating method. In addition, a coating film can be formed by discharging the composition from a nozzle using an ink jet apparatus.
次に、表面に塗布され、塗膜となった組成物を、コレステリック液晶相等の液晶相の状態にする。前記組成物が、溶媒を含む塗布液として調製されている態様では、塗膜を乾燥し、溶媒を除去することで、液晶相の状態にすることができる場合がある。また、液晶相への転移温度とするために、所望により、前記塗膜を加熱してもよい。例えば、一旦等方性相の温度まで加熱し、その後、液晶相転移温度まで冷却する等によって、安定的に液晶相の状態にすることができる。前記組成物の液晶相転移温度は、製造適性等の面から１０〜２５０℃の範囲内であることが好ましく、１０〜１５０℃の範囲内であることがより好ましい。１０℃未満であると液晶相を呈する温度範囲にまで温度を下げるために冷却工程等が必要となることがある。また２００℃を超えると、一旦液晶相を呈する温度範囲よりもさらに高温の等方性液体状態にするために高温を要し、熱エネルギーの浪費、基板の変形、変質等からも不利になる。 Next, the composition applied to the surface to become a coating film is brought into a liquid crystal phase state such as a cholesteric liquid crystal phase. In the aspect in which the composition is prepared as a coating liquid containing a solvent, the liquid crystal phase may be obtained by drying the coating film and removing the solvent. Moreover, in order to set it as the transition temperature to a liquid crystal phase, you may heat the said coating film if desired. For example, the liquid crystal phase can be stably formed by heating to the temperature of the isotropic phase and then cooling to the liquid crystal phase transition temperature. The liquid crystal phase transition temperature of the composition is preferably in the range of 10 to 250 ° C., more preferably in the range of 10 to 150 ° C. from the viewpoint of production suitability and the like. When the temperature is lower than 10 ° C., a cooling step or the like may be required to lower the temperature to a temperature range exhibiting a liquid crystal phase. When the temperature exceeds 200 ° C., a high temperature is required to make the isotropic liquid state higher than the temperature range once exhibiting the liquid crystal phase, which is disadvantageous from waste of thermal energy, deformation of the substrate, and alteration.
次に、（ii）の工程では、液晶相の状態となった塗膜を硬化させる。硬化は、ラジカル重合法、アニオン重合法、カチオン重合法、配位重合法等、いずれの重合法に従って進行させてもよい。式（Ｉ）の化合物に応じて、適する重合法が選択されるであろう。この重合により、式（Ｉ）の化合物から誘導される単位を構成単位中に有する重合体が得られる。
一例では、紫外線を照射して、硬化反応を進行させる。紫外線照射には、紫外線ランプ等の光源が利用される。この工程では、紫外線を照射することによって、前記組成物の硬化反応が進行し、コレステリック液晶相が固定されて、硬化膜が形成される。
紫外線の照射エネルギー量については特に制限はないが、一般的には、１００ｍＪ／ｃｍ2〜８００ｍＪ／ｃｍ2程度が好ましい。また、前記塗膜に紫外線を照射する時間については特に制限はないが、硬化膜の充分な強度及び生産性の双方の観点から決定されるであろう。
Next, in the step (ii), the coating film in a liquid crystal phase is cured. Curing may proceed according to any polymerization method such as a radical polymerization method, an anionic polymerization method, a cationic polymerization method, or a coordination polymerization method. Depending on the compound of formula (I), a suitable polymerization method will be selected. By this polymerization, a polymer having units derived from the compound of formula (I) in the constituent units is obtained.
In one example, ultraviolet light is irradiated to advance the curing reaction. For ultraviolet irradiation, a light source such as an ultraviolet lamp is used. In this step, by irradiating with ultraviolet rays, the curing reaction of the composition proceeds, the cholesteric liquid crystal phase is fixed, and a cured film is formed.
No particular limitation is imposed on the amount of irradiation energy of ultraviolet rays, in general, 100mJ / cm 2 ~800mJ / cm 2 is preferably about. Moreover, there is no restriction | limiting in particular about the time which irradiates an ultraviolet-ray to the said coating film, but it will be determined from the viewpoint of both sufficient intensity | strength and productivity of a cured film.
硬化反応を促進するため、加熱条件下で紫外線照射を実施してもよい。また、紫外線照射時の温度は、液晶相が乱れないように、液晶相を呈する温度範囲に維持するのが好ましい。また、雰囲気の酸素濃度は重合度に関与するため、空気中で所望の重合度に達せず、膜強度が不十分の場合には、窒素置換等の方法により、雰囲気中の酸素濃度を低下させることが好ましい。 In order to accelerate the curing reaction, ultraviolet irradiation may be performed under heating conditions. Moreover, it is preferable to maintain the temperature at the time of ultraviolet irradiation in the temperature range which exhibits a liquid crystal phase so that a liquid crystal phase may not be disturbed. Also, since the oxygen concentration in the atmosphere is related to the degree of polymerization, if the desired degree of polymerization is not reached in the air and the film strength is insufficient, the oxygen concentration in the atmosphere is reduced by a method such as nitrogen substitution. It is preferable.
上記工程では、液晶相が固定されて、硬化膜が形成される。ここで、液晶相を「固定化した」状態は、液晶相となっている化合物の配向が保持された状態が最も典型的、且つ好ましい態様である。それだけには限定されず、具体的には、通常０℃〜５０℃、より過酷な条件下では−３０℃〜７０℃の温度範囲において、該層に流動性が無く、また外場や外力によって配向形態に変化を生じさせることなく、固定化された配向形態を安定に保ち続けることができる状態を意味するものとする。本発明では、紫外線照射によって進行する硬化反応により、液晶相の配向状態を固定する。
なお、本発明においては、液晶相の光学的性質が層中において保持されていれば十分であり、最終的に硬化膜中の組成物がもはや液晶性を示す必要はない。例えば、組成物が、硬化反応により高分子量化して、もはや液晶性を失っていてもよい。
In the above step, the liquid crystal phase is fixed and a cured film is formed. Here, the state in which the liquid crystal phase is “fixed” is the most typical and preferred state in which the orientation of the compound that is the liquid crystal phase is maintained. However, it is not limited to this, and specifically, it is usually 0 ° C. to 50 ° C., and under severer conditions, in the temperature range of −30 ° C. to 70 ° C., the layer has no fluidity, and is oriented by an external field or an external force. It shall mean a state in which the fixed orientation form can be kept stable without causing a change in form. In the present invention, the alignment state of the liquid crystal phase is fixed by a curing reaction that proceeds by ultraviolet irradiation.
In the present invention, it is sufficient that the optical properties of the liquid crystal phase are maintained in the layer, and the composition in the cured film no longer needs to exhibit liquid crystal properties. For example, the composition may be no longer liquid crystalline due to a high molecular weight due to the curing reaction.
上記硬化膜の厚みについては特に制限はない。用途に応じて、又は所望とされる光学特性に応じて、好ましい膜厚が決定されるであろう。一般的には、厚さは０．０５〜５０μｍが好ましく、１〜３５μｍがより好ましい。 There is no restriction | limiting in particular about the thickness of the said cured film. Depending on the application or desired optical properties, the preferred film thickness will be determined. In general, the thickness is preferably 0.05 to 50 μm, more preferably 1 to 35 μm.
（２）基板
本発明のフィルムは、基板を有していてもよい。当該基板は自己支持性があり、上記硬化膜を支持するものであれば、材料及び光学的特性についてなんら限定はない。ガラス板、石英板、及びポリマーフィルム等から選択することができる。用途によっては、紫外光に対する高い透明性が要求されるであろう。可視光に対する透過性が高いポリマーフィルムとしては、液晶表示装置等の表示装置の部材として用いられる種々の光学フィルム用のポリマーフィルムが挙げられる。前記基板としては、例えばポリエチレンテレフタレート（ＰＥＴ）、ポリブチレンテレフタレート、ポリエチレンナフタレート（ＰＥＮ）等のポリエステルフィルム；ポリカーボネート（ＰＣ）フィルム、ポリメチルメタクリレートフィルム；ポリエチレン、ポリプロピレン等のポリオレフィンフィルム；ポリイミドフィルム、トリアセチルセルロース（ＴＡＣ）フィルム、などが挙げられる。ポリエチレンテレフタレート、トリアセチルセルロースが好ましい。
(2) Substrate The film of the present invention may have a substrate. The substrate is self-supporting, and there is no limitation on the material and optical characteristics as long as it supports the cured film. It can be selected from a glass plate, a quartz plate, a polymer film, and the like. Depending on the application, high transparency to ultraviolet light will be required. Examples of the polymer film having high transparency to visible light include polymer films for various optical films used as members of display devices such as liquid crystal display devices. Examples of the substrate include polyester films such as polyethylene terephthalate (PET), polybutylene terephthalate, and polyethylene naphthalate (PEN); polycarbonate (PC) films and polymethyl methacrylate films; polyolefin films such as polyethylene and polypropylene; polyimide films, An acetyl cellulose (TAC) film etc. are mentioned. Polyethylene terephthalate and triacetyl cellulose are preferred.
（３） 配向層
本発明のフィルムは、基板と前記硬化膜との間に、配向層を有していてもよい。配向層は、液晶化合物の配向方向をより精密に規定する機能を有する。配向層は、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等の手段で設けることができる。さらには、電場の付与、磁場の付与、或いは光照射により配向機能が生じる配向層も知られている。配向層は、ポリマーの膜の表面に、ラビング処理により形成するのが好ましい。
(3) Alignment layer The film of the present invention may have an alignment layer between the substrate and the cured film. The alignment layer has a function of more precisely defining the alignment direction of the liquid crystal compound. The alignment layer can be provided by means such as a rubbing treatment of an organic compound (preferably a polymer), oblique vapor deposition of an inorganic compound, or formation of a layer having a microgroove. Furthermore, an alignment layer in which an alignment function is generated by application of an electric field, application of a magnetic field, or light irradiation is also known. The alignment layer is preferably formed on the surface of the polymer film by rubbing treatment.
配向層に用いられる材料としては、有機化合物のポリマーが好ましく、それ自体が架橋可能なポリマーか、或いは架橋剤により架橋されるポリマーがよく用いられる。当然、双方の機能を有するポリマーも用いられる。ポリマーの例としては、ポリメチルメタクリレ−ト、アクリル酸／メタクリル酸共重合体、スチレン／マレインイミド共重合体、ポリビニルアルコ−ル及び変性ポリビニルアルコ−ル、ポリ（Ｎ−メチロ−ルアクリルアミド）、スチレン／ビニルトルエン共重合体、クロロスルホン化ポリエチレン、ニトロセルロース、ポリ塩化ビニル、塩素化ポリオレフィン、ポリエステル、ポリイミド、酢酸ビニル／塩化ビニル共重合体、エチレン／酢酸ビニル共重合体、カルボキシメチルセルロ−ス、ゼラチン、ポリエチレン、ポリプロピレン及びポリカーボネート等のポリマー及びシランカップリング剤等の化合物を挙げることができる。好ましいポリマーの例としては、ポリ（Ｎ−メチロ−ルアクリルアミド）、カルボキシメチルセルロ−ス、ゼラチン、ポリビルアルコール及び変性ポリビニルアルコール等の水溶性ポリマーであり、さらにゼラチン、ポリビルアルコール及び変性ポリビニルアルコールが好ましく、特にポリビルアルコール及び変性ポリビニルアルコールを挙げることができる。 As a material used for the alignment layer, a polymer of an organic compound is preferable, and a polymer that can be crosslinked by itself or a polymer that is crosslinked by a crosslinking agent is often used. Of course, polymers having both functions are also used. Examples of the polymer include polymethyl methacrylate, acrylic acid / methacrylic acid copolymer, styrene / maleimide copolymer, polyvinyl alcohol and modified polyvinyl alcohol, and poly (N-methylol acrylamide). , Styrene / vinyl toluene copolymer, chlorosulfonated polyethylene, nitrocellulose, polyvinyl chloride, chlorinated polyolefin, polyester, polyimide, vinyl acetate / vinyl chloride copolymer, ethylene / vinyl acetate copolymer, carboxymethyl cellulose And polymers such as silica, gelatin, polyethylene, polypropylene and polycarbonate, and compounds such as silane coupling agents. Examples of preferred polymers are water-soluble polymers such as poly (N-methylacrylamide), carboxymethyl cellulose, gelatin, polyville alcohol, and modified polyvinyl alcohol, and gelatin, polyville alcohol, and modified polyvinyl alcohol. Are preferable, and in particular, polyvinyl alcohol and modified polyvinyl alcohol can be mentioned.
（４）本発明のフィルムの用途
本発明のフィルムの一態様は、本発明の組成物の、液晶相の配向（例えば、水平配向、垂直配向、ハイブリッド配向等）を固定したフィルムであって、光学異方性を示すフィルムである。当該フィルムは、液晶表示装置等の光学補償フィルム等として利用される。
本発明のフィルムの一態様は、本発明の重合性組成物のコレステリック液晶相を固定したフィルムであって、所定の波長域の光に対して選択反射特性を示すフィルムである。コレステリック液晶相では、液晶分子はらせん状に配列している。赤外線波長域（波長８００〜１３００ｎｍ）に選択反射特性を示す当該フィルムは、例えば建物又は車両の窓ガラスに貼付され、もしくは合わせガラスに組み込まれて、遮熱部材として利用される。
また、本発明のフィルムは、光学素子の構成要素である、偏光素子、選択反射膜、カラーフィルタ、反射防止膜、視野角補償膜、ホログラフィー、配向膜等、種々の用途に利用することができる。
(4) Use of the film of the present invention One aspect of the film of the present invention is a film in which the orientation of the liquid crystal phase (eg, horizontal alignment, vertical alignment, hybrid alignment, etc.) of the composition of the present invention is fixed. It is a film showing optical anisotropy. The film is used as an optical compensation film for a liquid crystal display device or the like.
One aspect of the film of the present invention is a film in which the cholesteric liquid crystal phase of the polymerizable composition of the present invention is fixed, and shows selective reflection characteristics with respect to light in a predetermined wavelength range. In the cholesteric liquid crystal phase, liquid crystal molecules are arranged in a spiral. The film exhibiting selective reflection characteristics in the infrared wavelength region (wavelength 800 to 1300 nm) is used as a heat shielding member, for example, affixed to a window glass of a building or a vehicle, or incorporated in a laminated glass.
The film of the present invention can be used for various applications such as polarizing elements, selective reflection films, color filters, antireflection films, viewing angle compensation films, holography, alignment films, which are constituent elements of optical elements. .
３．高分子
本発明は、前記式（Ｉ）の重合性化合物の１種又は２種以上を重合してなる高分子、及び本発明の重合性組成物を重合してなる高分子にも関する。該高分子は、液晶性であっても、非液晶性であってもよい。前記式（Ｉ）の重合性化合物から誘導される繰り返し単位を含むことから、高いΔｎを示し、種々の光学要素の材料として有用である。
3. Polymer The present invention also relates to a polymer obtained by polymerizing one or more polymerizable compounds of the formula (I) and a polymer obtained by polymerizing the polymerizable composition of the present invention. The polymer may be liquid crystalline or non-liquid crystalline. Since it contains a repeating unit derived from the polymerizable compound of the formula (I), it exhibits a high Δn and is useful as a material for various optical elements.
以下に実施例と比較例（なお比較例は公知技術というわけではない）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。 Hereinafter, the features of the present invention will be described more specifically with reference to examples and comparative examples (note that comparative examples are not known techniques). 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.
１．式（Ｉ）の化合物の合成例と物性
例示化合物（Ｉ−２）の合成：
（１）４−ヒドロキシベンズアルデヒド ７．３２ｇ（６０ｍｍｏｌ）を、トルエン ３０ｍｌを加えた３つ口フラスコに添加した。窒素雰囲気下、内温を４０℃まで上昇させたのち、４−アミノ−ｏ−ブロモフェノール １１．３ｇ（６０ｍｍｏｌ）を添加した。その後、２時間リフラックスを行い、ディーンシュタルク装置で水・トルエンを完全に留去させ、黄色固体を得た。この固体をＴＨＦ５０ｍｌに完溶させた（溶液Ａとする）。
（２）別途、３つ口フラスコにＭｓＣｌ １０．２ｍｌ（１３２ｍｍｏｌ）とＴＨＦ ２０ｍｌを添加し、氷・メタノールバスに浸し、内温を−５℃にした。この溶液に、内温を５℃以下に保ちながら、４−アクリロイルオキシ安息香酸 ３１．７ｇ（１２０ｍｍｏｌ）／ジイソプロピルエチルアミン（以下、ＤＩＰＥＡとする）２６．１ｍｌ（１５０ｍｍｏｌ）／２，６−ジ−ｔ−ブチル−４−メチルフェノール ０．３０ｇ／ＴＨＦ ７０ｍｌの混合溶液を滴下た。この溶液を５℃以下に保って、２時間攪拌した後、ＤＩＰＥＡ ２６．１ｍｌ（１５０ｍｍｏｌ）、ＤＭＡＰ ０．１５ｇ、（１）で調製した溶液Ａをこの順で添加した（内温を５℃以下に維持）。反応温度を２５℃に上昇し、２時間攪拌後、メタノールを１０ｍｌ加えてクエンチした。酢酸エチル／純水を加えて分液し、有機層を硫酸ナトリウムで乾燥させた後、濃縮し、粗結晶を得た。この粗結晶を酢酸エチル／メタノールにより再結晶し、白色固体である化合物（Ｉ−２）を２９．７ｇ（収率６３％）で得た。
1H-NMR(CDCl3) : δ= 1.8-2.0(brs,8H), 4.1(brs,4H), 4.3(brs,4H), 5.8(d,2H), 6.1(dd,2H), 6.4(d,2H), 7.0(d×2,4H), 7.2-7.3(d×3,6H), 7.5(s,1H), 8.0(d,2H), 8.2(d×2,4H), 8.5(s,1H)
(1) 7.32 g (60 mmol) of 4-hydroxybenzaldehyde was added to a three-necked flask to which 30 ml of toluene was added. After raising the internal temperature to 40 ° C. under a nitrogen atmosphere, 11.3 g (60 mmol) of 4-amino-o-bromophenol was added. Thereafter, reflux was performed for 2 hours, and water and toluene were completely distilled off by a Dean Stark apparatus to obtain a yellow solid. This solid was completely dissolved in 50 ml of THF (referred to as solution A).
(2) Separately, 10.3 ml (132 mmol) of MsCl and 20 ml of THF were added to a three-necked flask, immersed in an ice / methanol bath, and the internal temperature was adjusted to −5 ° C. To this solution, while keeping the internal temperature at 5 ° C. or lower, 31.7 g (120 mmol) of 4-acryloyloxybenzoic acid / diisopropylethylamine (hereinafter referred to as DIPEA) 26.1 ml (150 mmol) / 2,6-di-t A mixed solution of -butyl-4-methylphenol 0.30 g / THF 70 ml was added dropwise. After this solution was kept at 5 ° C. or lower and stirred for 2 hours, DIPEA 26.1 ml (150 mmol), DMAP 0.15 g, and solution A prepared in (1) were added in this order (internal temperature was 5 ° C. or lower). Maintained). The reaction temperature was raised to 25 ° C., and after stirring for 2 hours, 10 ml of methanol was added to quench. Ethyl acetate / pure water was added for liquid separation, and the organic layer was dried over sodium sulfate and then concentrated to obtain crude crystals. The crude crystals were recrystallized from ethyl acetate / methanol to obtain 29.7 g (yield 63%) of compound (I-2) as a white solid.
1H-NMR (CDCl 3 ): δ = 1.8-2.0 (brs, 8H), 4.1 (brs, 4H), 4.3 (brs, 4H), 5.8 (d, 2H), 6.1 (dd, 2H), 6.4 (d , 2H), 7.0 (d × 2,4H), 7.2-7.3 (d × 3,6H), 7.5 (s, 1H), 8.0 (d, 2H), 8.2 (d × 2,4H), 8.5 (s , 1H)
例示化合物（Ｉ−５）の合成：
４−アミノ−ｏ−ブロモフェノールの代わりに４−アミノ−ｍ−クレゾールを用いた以外は例示化合物（Ｉ−２）と同様の方法により合成した。収量は２８．９ｇ（収率６７％）であった。
1H-NMR(CDCl3) : δ= 1.8-2.0(brs,8H), 2.4(s,3H), 4.0-4.1(m,4H), 4.2-4.3(m,4H), 5.8(d,2H), 6.2(dd,2H), 6.4(d,2H), 6.9-7.1(d,7H), 7.3-7.4(d,2H), 8.0(d,2H), 8.1(m,4H), 8.4(s,1H)
The compound was synthesized by the same method as Example Compound (I-2) except that 4-amino-m-cresol was used instead of 4-amino-o-bromophenol. The yield was 28.9 g (67% yield).
1H-NMR (CDCl 3 ): δ = 1.8-2.0 (brs, 8H), 2.4 (s, 3H), 4.0-4.1 (m, 4H), 4.2-4.3 (m, 4H), 5.8 (d, 2H) , 6.2 (dd, 2H), 6.4 (d, 2H), 6.9-7.1 (d, 7H), 7.3-7.4 (d, 2H), 8.0 (d, 2H), 8.1 (m, 4H), 8.4 (s , 1H)
例示化合物（Ｉ−６）の合成：
４−アミノ−ｏ−ブロモフェノールの代わりに、４−アミノ−３−クロロフェノールを用いた以外は例示化合物（Ｉ−２）と同様の方法により合成した。収量は２６．６ｇ（収率６０％）であった。
1H-NMR(CDCl3) : δ= 1.8-2.0(brs,8H), 4.0-4.2(brs,4H), 4.2-4.3(brs,4H), 5.8(d,2H), 6.1(dd,2H), 6.4(d,2H), 7.0(d,4H), 7.1(d,1H), 7.2(d,1H), 7.3(m,3H), 8.0(d,2H), 8.1(d×2,4H), 8.4(s,1H)
It synthesize | combined by the method similar to exemplary compound (I-2) except having used 4-amino-3-chlorophenol instead of 4-amino-o-bromophenol. The yield was 26.6 g (60% yield).
1H-NMR (CDCl 3 ): δ = 1.8-2.0 (brs, 8H), 4.0-4.2 (brs, 4H), 4.2-4.3 (brs, 4H), 5.8 (d, 2H), 6.1 (dd, 2H) , 6.4 (d, 2H), 7.0 (d, 4H), 7.1 (d, 1H), 7.2 (d, 1H), 7.3 (m, 3H), 8.0 (d, 2H), 8.1 (d × 2,4H ), 8.4 (s, 1H)
例示化合物（Ｉ−４）の合成：
４−アミノ−ｏ−ブロモフェノールの代わりに４−アミノ−３−メトキシフェノールを用いた以外は実施例１と同様の方法により合成した。収量は２５．６ｇ（収率５８％）であった。
1H-NMR(CDCl3) : δ= 1.8-2.0(brs,8H), 3.9(s,3H), 4.1(brs,4H), 4.3(brs,4H), 5.8(d,2H), 6.1(dd,2H), 6.4(d,2H), 6.8(d,2H), 7.0(d,4H), 7.1(d,1H), 7.3(d,2H), 8.0(d,2H), 8.2(d,4H), 8.5(s,1H)
The synthesis was performed in the same manner as in Example 1 except that 4-amino-3-methoxyphenol was used instead of 4-amino-o-bromophenol. The yield was 25.6 g (58% yield).
1H-NMR (CDCl 3 ): δ = 1.8-2.0 (brs, 8H), 3.9 (s, 3H), 4.1 (brs, 4H), 4.3 (brs, 4H), 5.8 (d, 2H), 6.1 (dd , 2H), 6.4 (d, 2H), 6.8 (d, 2H), 7.0 (d, 4H), 7.1 (d, 1H), 7.3 (d, 2H), 8.0 (d, 2H), 8.2 (d, 4H), 8.5 (s, 1H)
例示化合物（Ｉ−３）の合成：
４−アミノ−ｏ−ブロモフェノールの代わりに、４−アミノ−２−クロロフェノールを用いた以外は例示化合物（Ｉ−２）と同様の方法により合成した。収量は２８．０ｇ（収率６３％）であった。
1H-NMR(CDCl3) : δ= 1.8-2.0(brs,8H), 4.1(brs,4H), 4.3(brs,4H), 5.8(d,2H), 6.1(dd,2H), 6.4(d,2H), 7.0(d,4H), 7.2(d,1H), 7.3(m,4H), 8.0(d,2H), 8.2(d×2,4H), 8.5(s,1H)
It synthesize | combined by the method similar to exemplary compound (I-2) except having used 4-amino-2-chlorophenol instead of 4-amino-o-bromophenol. The yield was 28.0 g (63% yield).
1H-NMR (CDCl 3 ): δ = 1.8-2.0 (brs, 8H), 4.1 (brs, 4H), 4.3 (brs, 4H), 5.8 (d, 2H), 6.1 (dd, 2H), 6.4 (d , 2H), 7.0 (d, 4H), 7.2 (d, 1H), 7.3 (m, 4H), 8.0 (d, 2H), 8.2 (d × 2,4H), 8.5 (s, 1H)
例示化合物（Ｉ−１）の合成：
４−アミノ−ｏ−ブロモフェノールの代わりに、４−アミノ−ｏ−クレゾールを用いた以外は例示化合物（Ｉ−２）と同様の方法により合成した。収量は３０．７ｇ（収率７１％）であった。
1H-NMR(CDCl3) : δ= 1.8-2.0(brs,8H), 2.3(s,3H), 4.1(brs,4H), 4.3(brs,4H), 5.8(d,2H), 6.1(dd,2H), 6.4(d,2H), 7.0(d,4H), 7.1-7.2(m,3H), 7.3(d,2H), 8.0(d,2H), 8.2(d,4H), 8.5(s,1H)
It synthesize | combined by the method similar to exemplary compound (I-2) except having used 4-amino-o-cresol instead of 4-amino-o-bromophenol. The yield was 30.7 g (yield 71%).
1H-NMR (CDCl 3 ): δ = 1.8-2.0 (brs, 8H), 2.3 (s, 3H), 4.1 (brs, 4H), 4.3 (brs, 4H), 5.8 (d, 2H), 6.1 (dd , 2H), 6.4 (d, 2H), 7.0 (d, 4H), 7.1-7.2 (m, 3H), 7.3 (d, 2H), 8.0 (d, 2H), 8.2 (d, 4H), 8.5 ( s, 1H)
例示化合物（Ｉ−９）の合成：
４−アミノ−ｏ−ブロモフェノールの代わりに、４−アミノフェノール、４−ヒドロキシベンズアルデヒドの代わりにバニリンを用いた以外は例示化合物（Ｉ−２）と同様の方法により合成した。収量は２８．７ｇ（収率６５％）であった。
1H-NMR(DMSO) : δ= 1.7-1.9(brs,8H), 3.8(s,3H), 4.1-4.3(m,8H), 5.9(d,2H), 6.2(dd,2H), 6.3(d,2H), 7.1(d,4H), 7.3-7.4(d×2,5H), 7.6(d,1H), 7.7(s,1H), 8.1(m,4H), 8.7(s,1H)
The compound was synthesized in the same manner as the exemplary compound (I-2) except that vanillin was used instead of 4-aminophenol and 4-hydroxybenzaldehyde instead of 4-amino-o-bromophenol. The yield was 28.7 g (65% yield).
1H-NMR (DMSO): δ = 1.7-1.9 (brs, 8H), 3.8 (s, 3H), 4.1-4.3 (m, 8H), 5.9 (d, 2H), 6.2 (dd, 2H), 6.3 ( d, 2H), 7.1 (d, 4H), 7.3-7.4 (d × 2,5H), 7.6 (d, 1H), 7.7 (s, 1H), 8.1 (m, 4H), 8.7 (s, 1H)
例示化合物（Ｉ−１３）の合成：
４−アミノ−ｏ−ブロモフェノールの代わりに、４−アミノ３−ブロモフェノール、４−ヒドロキシベンズアルデヒドの代わりにバニリンを用いた以外は例示化合物（Ｉ−２）と同様の方法により合成した。収量は３０．３ｇ（収率６２％）であった。
1H-NMR(CDCl3) : δ= 1.8-2.0(brs,8H), 3.9(s,3H), 4.1(brs,4H), 4.3(brs,4H), 5.8(d,2H), 6.1(dd,2H), 6.4(d,2H), 7.0(d,4H), 7.1(d,1H), 7.2(d,1H), 7.3(d,1H), 7,4(d,1H), 7.5(s,1H), 7.8(s,1H), 8.2(d,4H), 8.5(s,1H)
The compound was synthesized in the same manner as the exemplary compound (I-2) except that 4-amino-3-bromophenol and vanillin were used in place of 4-amino-bromophenol and 4-hydroxybenzaldehyde. The yield was 30.3 g (62% yield).
1H-NMR (CDCl 3 ): δ = 1.8-2.0 (brs, 8H), 3.9 (s, 3H), 4.1 (brs, 4H), 4.3 (brs, 4H), 5.8 (d, 2H), 6.1 (dd , 2H), 6.4 (d, 2H), 7.0 (d, 4H), 7.1 (d, 1H), 7.2 (d, 1H), 7.3 (d, 1H), 7,4 (d, 1H), 7.5 ( s, 1H), 7.8 (s, 1H), 8.2 (d, 4H), 8.5 (s, 1H)
例示化合物（Ｉ−１５）の合成：
４−アミノ−ｏ−ブロモフェノールの代わりに、４−アミノ−ｍ−クレゾール、４−ヒドロキシベンズアルデヒドの代わりにバニリンを用いた以外は例示化合物（Ｉ−２）と同様の方法により合成した。収量は２６．５ｇ（収率５９％）であった。
1H-NMR(CDCl3) : δ= 1.8-2.0(brs,8H), 2.4(s,3H), 3.9(s,3H), 4.1(m,4H), 4.3(m,4H), 5.8(d,2H), 6.1(dd,2H), 6.4(d,2H), 7.0(d×2,4H), 7.1(m,3H), 7.4(d,1H), 7.7(s,1H), 8.2(d×2,4H), 8.4(s,1H)
The compound was synthesized in the same manner as Exemplified Compound (I-2) except that 4-amino-m-cresol was used instead of 4-amino-o-bromophenol and vanillin was used instead of 4-hydroxybenzaldehyde. The yield was 26.5 g (59% yield).
1H-NMR (CDCl 3 ): δ = 1.8-2.0 (brs, 8H), 2.4 (s, 3H), 3.9 (s, 3H), 4.1 (m, 4H), 4.3 (m, 4H), 5.8 (d , 2H), 6.1 (dd, 2H), 6.4 (d, 2H), 7.0 (d × 2,4H), 7.1 (m, 3H), 7.4 (d, 1H), 7.7 (s, 1H), 8.2 ( d × 2,4H), 8.4 (s, 1H)
例示化合物（II−１）の合成：
４−アミノ−ｏ−ブロモフェノールの代わりに、４−アミノ−ｍ−クレゾール、４−ヒドロキシベンズアルデヒドの代わりに４−ヒドロキシアセトフェノンを用いた以外は例示化合物（Ｉ−２）と同様の方法により合成した。収量は２５．５ｇ（収率５８％）であった。
1H-NMR(CDCl3) : δ= 1.8-2.0(brs,8H), 2.1(s,3H), 2.3(s,3H), 4.1(brs,4H), 4.3(brs,4H), 5.8(d,2H), 6.2(dd,2H), 6.4(d,2H), 6.7(d,1H), 6.9-7.1(m,6H), 7.3-7.4(d,2H),
8.0-8.3(m,6H)
The compound was synthesized by the same method as Exemplified Compound (I-2) except that 4-amino-m-cresol was used instead of 4-amino-o-bromophenol and 4-hydroxyacetophenone was used instead of 4-hydroxybenzaldehyde. . The yield was 25.5 g (58% yield).
1H-NMR (CDCl 3 ): δ = 1.8-2.0 (brs, 8H), 2.1 (s, 3H), 2.3 (s, 3H), 4.1 (brs, 4H), 4.3 (brs, 4H), 5.8 (d , 2H), 6.2 (dd, 2H), 6.4 (d, 2H), 6.7 (d, 1H), 6.9-7.1 (m, 6H), 7.3-7.4 (d, 2H),
8.0-8.3 (m, 6H)
例示化合物（Ｉ−７）の合成：
４−アミノ−ｏ−ブロモフェノールの代わりに、４−アミノ−２−メトキシカルボニルフェノールを用いた以外は例示化合物（Ｉ−２）と同様の方法により合成した。収量は２７．５ｇ（収率６０％）であった。
1H-NMR(CDCl3) : δ= 1.8-2.0(brs,8H), 3.7(s,3H), 4.1(brs,4H), 4.3(brs,4H), 5.8(d,2H), 6.1(dd,2H), 6.4(d,2H), 7.0(d,4H), 7.3(d,2H), 7.5(d,1H), 7.9(s,1H), 8.0(d,2H), 8.2(d,4H), 8.5(s,1H)
It synthesize | combined by the method similar to exemplary compound (I-2) except having used 4-amino-2-methoxycarbonyl phenol instead of 4-amino-o-bromophenol. The yield was 27.5 g (yield 60%).
1H-NMR (CDCl 3 ): δ = 1.8-2.0 (brs, 8H), 3.7 (s, 3H), 4.1 (brs, 4H), 4.3 (brs, 4H), 5.8 (d, 2H), 6.1 (dd , 2H), 6.4 (d, 2H), 7.0 (d, 4H), 7.3 (d, 2H), 7.5 (d, 1H), 7.9 (s, 1H), 8.0 (d, 2H), 8.2 (d, 4H), 8.5 (s, 1H)
例示化合物（Ｉ−１２）の合成：
４−アミノ−ｏ−ブロモフェノールの代わりに４−アミノ−２、６−ジクロロフェノールを用いた以外は例示化合物（Ｉ−２）と同様の方法により合成した。収量は２８．４ｇ（収率６１％）であった。
1H-NMR(DMSO) : δ= 1.8-2.0(brs,8H), 4.1-4.3(brs,8H), 5.9(d,2H), 6.2(dd,2H), 6.4(d,2H), 7.1(d×2,4H), 7.4(d,2H), 7.6(s×2,2H), 8.0-8.2(d×3,6H), 8.8(s,1H)
The compound was synthesized by the same method as Example Compound (I-2) except that 4-amino-2,6-dichlorophenol was used in place of 4-amino-o-bromophenol. The yield was 28.4 g (61% yield).
1H-NMR (DMSO): δ = 1.8-2.0 (brs, 8H), 4.1-4.3 (brs, 8H), 5.9 (d, 2H), 6.2 (dd, 2H), 6.4 (d, 2H), 7.1 ( d × 2,4H), 7.4 (d, 2H), 7.6 (s × 2,2H), 8.0-8.2 (d × 3,6H), 8.8 (s, 1H)
例示化合物（Ｉ−１０）の合成：
４−アミノ−ｏ−ブロモフェノールの代わりに４−アミノ−２、５−ジクロロフェノールを用いた以外は例示化合物（Ｉ−２）と同様の方法により合成した。収量は２９．７ｇ（収率６４％）であった。
1H-NMR(DMSO) : δ= 1.8-2.0(brs,8H), 4.1-4.3(brs,8H), 5.9(d,2H), 6.2(dd,2H), 6.3(d,2H), 7.1(d×2,4H), 7.5(d,2H), 7.7(s,1H), 7.8(s,1H), 8.0-8.2(m,6H), 8.7(s,1H)
The compound was synthesized by the same method as Example Compound (I-2) except that 4-amino-2,5-dichlorophenol was used instead of 4-amino-o-bromophenol. The yield was 29.7 g (64% yield).
1H-NMR (DMSO): δ = 1.8-2.0 (brs, 8H), 4.1-4.3 (brs, 8H), 5.9 (d, 2H), 6.2 (dd, 2H), 6.3 (d, 2H), 7.1 ( d × 2,4H), 7.5 (d, 2H), 7.7 (s, 1H), 7.8 (s, 1H), 8.0-8.2 (m, 6H), 8.7 (s, 1H)
例示化合物（Ｉ−１１）の合成：
４−アミノ−ｏ−ブロモフェノールの代わりに４−アミノ−２、５−ジメチルフェノールを用いた以外は例示化合物（Ｉ−２）と同様の方法により合成した。収量は２９．５ｇ（収率６２％）であった。
1H-NMR(DMSO) : δ= 1.8-2.0(brs,8H), 2.1(s,3H), 2.3(s,3H), 4.0-4.2(brs,8H), 5.9(d,2H), 6.2(dd,2H), 6.3(d,2H), 7.1(d,2H), 7.2(d×2,4H), 7.4(d,2H), 8.0-8.2(m,6H), 8.6(s,1H)
The compound was synthesized by the same method as Example Compound (I-2) except that 4-amino-2,5-dimethylphenol was used instead of 4-amino-o-bromophenol. The yield was 29.5 g (62% yield).
1H-NMR (DMSO): δ = 1.8-2.0 (brs, 8H), 2.1 (s, 3H), 2.3 (s, 3H), 4.0-4.2 (brs, 8H), 5.9 (d, 2H), 6.2 ( dd, 2H), 6.3 (d, 2H), 7.1 (d, 2H), 7.2 (d × 2,4H), 7.4 (d, 2H), 8.0-8.2 (m, 6H), 8.6 (s, 1H)
式（Ｉ）の化合物の物性：
上記で合成した各化合物のΔｎを、液晶便覧（液晶便覧編集委員会）のｐ．２０２に記載の方法に従って、直接測定した。具体的には、上記で合成した各化合物を、くさび型セルに注入し、これに波長５５０ｎｍのレーザー光を照射し、透過光の屈折角を測定することにより、Δｎを求めた。
下記表に、各化合物のΔｎ、偏光顕微鏡によるテクスチャー観察によって求めた相転移温度、結晶の色味についても併せて示す。また、比較例として、下記比較例用化合物（Ｒ−１）〜（Ｒ−３）のΔｎ、相転移温度、及び固体の色味を併せて示した。なお、下記表中の「Δｎ」の欄の温度は、測定温度を意味する。さらに、一連の化合物の吸収スペクトルを図１及び２にそれぞれ示した。図２のグラフは、図１のグラフの一部を拡大したグラフである。
なお、（Ｒ−１）は、モノアゾメチン化合物であるが、重合性基とメソゲンとを連結する側鎖が短く；（Ｒ−２）は、ビスアゾメチン化合物であり；及び（Ｒ−３）はアゾメチン基を含まない液晶化合物である。
Physical properties of compounds of formula (I):
The Δn of each compound synthesized above is calculated according to the liquid crystal manual (Liquid Crystal Handbook Editorial Committee) p. Direct measurement was performed according to the method described in 202. Specifically, each compound synthesized above was injected into a wedge-shaped cell, irradiated with laser light having a wavelength of 550 nm, and the refraction angle of transmitted light was measured to obtain Δn.
The following table also shows Δn of each compound, the phase transition temperature obtained by texture observation with a polarizing microscope, and the color of the crystal. In addition, as comparative examples, Δn, phase transition temperature, and solid color of the following comparative compounds (R-1) to (R-3) are also shown. In addition, the temperature in the column of “Δn” in the following table means the measured temperature. Further, absorption spectra of a series of compounds are shown in FIGS. 1 and 2, respectively. The graph of FIG. 2 is a graph obtained by enlarging a part of the graph of FIG.
(R-1) is a monoazomethine compound, but the side chain connecting the polymerizable group and the mesogen is short; (R-2) is a bisazomethine compound; and (R-3) is It is a liquid crystal compound containing no azomethine group.
上記表に示す結果より、式（Ｉ）の範囲外のモノアゾメチン型重合性液晶化合物（Ｒ−１）及びアゾメチン基を含まない液晶性化合物（Ｒ−３）と比較して、式（Ｉ）の化合物はいずれも、高Δｎであることが理解できる。また、図１及び２に示す吸収スペクトル曲線から、従来知られているビスアゾメチン型重合性液晶（Ｒ−２）は波長４００ｎｍ以上に吸収を持つことから黄色味を持つが、本発明に係わる式（Ｉ）のモノアゾメチン化合物は、波長４００ｎｍ以上の吸収が小さく、白色であることが理解できる。 From the results shown in the above table, compared with the monoazomethine-type polymerizable liquid crystal compound (R-1) outside the range of the formula (I) and the liquid crystal compound (R-3) containing no azomethine group, the formula (I) It can be understood that all of these compounds have high Δn. Further, from the absorption spectrum curves shown in FIGS. 1 and 2, the conventionally known bisazomethine type polymerizable liquid crystal (R-2) has a yellowish color because it has an absorption at a wavelength of 400 nm or more. It can be understood that the monoazomethine compound (I) has a small absorption at a wavelength of 400 nm or more and is white.
２．位相差膜の作製と評価（実施例１５〜２８、比較例４及び５）
実施例１５：
上記で合成した本発明に係わる式（Ｉ）の例示化合物Ｉ−２を用いて、下記の組成の液晶性組成物塗布液（１）を調製した。
例示化合物（Ｉ−２） １００質量部
空気界面配向剤（１） ０．１質量部
重合開始剤ＩＲＧＡＣＵＲＥ８１９(チバジャパン社製) ３質量部
溶媒 クロロホルム ８００質量部
2. Production and evaluation of retardation film (Examples 15 to 28, Comparative Examples 4 and 5)
Example 15:
A liquid crystal composition coating liquid (1) having the following composition was prepared using the compound I-2 of the formula (I) according to the present invention synthesized above.
Illustrative compound (I-2) 100 parts by mass Air interface aligning agent (1) 0.1 part by mass Polymerization initiator IRGACURE 819 (manufactured by Ciba Japan) 3 parts by mass Solvent chloroform 800 parts by mass
次に、洗浄したガラス基板上に日産化学社製ポリイミド配向膜ＳＥ−１３０をスピンコート法により塗布し、乾燥後に２５０℃で１時間焼成した。これをラビング処理して配向膜付き基板を作製した。この基板の配向膜のラビング処理面上に、液晶性組成物塗布液（１）をスピンコート法により室温で塗布し、１２０℃で３０秒配向熟成を行った後に、窒素ガス雰囲気下、室温でＵＶの短波長成分を除去した高圧水銀ランプを用いて１０秒間光照射して配向を固定し、実施例１５の位相差膜を作製した。塗布後に加熱するまでの間に、塗布膜に結晶の析出は見られなかった。 Next, a polyimide alignment film SE-130 manufactured by Nissan Chemical Industries, Ltd. was applied on the cleaned glass substrate by a spin coating method, and baked at 250 ° C. for 1 hour after drying. This was rubbed to produce a substrate with an alignment film. A liquid crystal composition coating solution (1) is applied on the rubbing-treated surface of the alignment film of the substrate by spin coating at room temperature, and subjected to alignment aging at 120 ° C. for 30 seconds, and then in a nitrogen gas atmosphere at room temperature. The alignment was fixed by irradiating with light for 10 seconds using a high-pressure mercury lamp from which the short wavelength component of UV was removed, and a retardation film of Example 15 was produced. During the period after application and before heating, no crystal deposition was observed in the coating film.
得られた位相膜を偏光顕微鏡で観察したところ配向欠陥が無く均一に一軸配向していることが確認できた。
さらにこの膜をＡＸＯＭＥＴＲＩＸ社製のＡｘｏＳｃａｎを用いてＴｉｐ−Ｔｉｌｔモードで測定した結果、この装置が算出した液晶の平均傾斜角度は１度であり、Ａ−ｐｌａｔｅ型の位相差膜が形成できていることを確認した。
また、この装置を用いて測定した位相差と、共焦点レーザー膜厚測定装置（キーエンス社製ＦＶ−７５１０）を用いて測定した位相差膜の膜厚から算出した波長５５０ｎｍにおけるΔｎは０．２０８であり、ヘイズは０．０８であった。
When the obtained phase film was observed with a polarizing microscope, it was confirmed that there was no alignment defect and the film was uniformly uniaxially aligned.
Furthermore, as a result of measuring this film in Tip-Tilt mode using AxoScan manufactured by AXOMETRIX, the average tilt angle of the liquid crystal calculated by this apparatus is 1 degree, and an A-plate type retardation film can be formed. It was confirmed.
Further, Δn at a wavelength of 550 nm calculated from the retardation measured using this apparatus and the thickness of the retardation film measured using a confocal laser thickness measuring apparatus (FV-7510 manufactured by Keyence Corporation) is 0.208. And the haze was 0.08.
実施例１６〜２８：
上記でそれぞれ合成した各化合物を、例示化合物（Ｉ−２）の代わりにそれぞれ用いた以外は同様にして、液晶性組成物塗布液をそれぞれ調製した。これらの塗布液をそれぞれ用いて、実施例１５と同様にして、実施例１６〜２８の位相差膜をそれぞれ作製した。
これらの位相差膜はいずれも良好な配向性を示し、０．１以下の低いヘイズであった。実施例１５と同様にして求めた位相差膜のΔｎを、下記表にまとめた。
Examples 16-28:
A liquid crystal composition coating solution was prepared in the same manner except that each compound synthesized above was used instead of the exemplified compound (I-2). Using these coating solutions, retardation films of Examples 16 to 28 were produced in the same manner as Example 15.
All of these retardation films exhibited good orientation and had a low haze of 0.1 or less. The Δn values of the retardation film obtained in the same manner as in Example 15 are summarized in the following table.
比較例４：
実施例１５と同様にして下記の組成の液晶性組成物塗布液（２）を調製した。
上記重合性液晶化合物（Ｒ−１） １００質量部
空気界面配向剤（１） ０．１質量部
重合開始剤ＩＲＧＡＣＵＲＥ８１９(チバジャパン社製) ３質量部
溶媒 クロロホルム ８００質量部
液晶性組成物塗布液（１）の代わりに液晶性組成物塗布液（２）を用いる以外は実施例１５と同様にして、比較例４の位相差膜を作製した。但し、この重合性組成物の液晶上限温度が例示化合物Ｉ−２よりも低いため、配向熟成の温度は９０℃とした。また塗布後に加熱するまでの間に、塗布膜上に結晶が一部析出した。そのため再加熱して配向熟成後も、析出部分に膜厚ムラが残った。
実施例１５と同様な方法によって測定した比較例４の位相膜の波長５５０ｎｍにおけるΔｎは０．２５６であり、ヘイズは０．１８であった。
Comparative Example 4:
In the same manner as in Example 15, a liquid crystal composition coating liquid (2) having the following composition was prepared.
100 parts by mass of the above-mentioned polymerizable liquid crystal compound (R-1) air interface alignment agent (1) 0.1 parts by mass polymerization initiator IRGACURE819 (manufactured by Ciba Japan) 3 parts by mass solvent 800 parts by mass of chloroform liquid crystal composition coating liquid ( A retardation film of Comparative Example 4 was produced in the same manner as in Example 15 except that the liquid crystalline composition coating liquid (2) was used instead of 1). However, since the upper limit temperature of the liquid crystal of this polymerizable composition was lower than that of exemplary compound I-2, the temperature for alignment aging was 90 ° C. In addition, some crystals were deposited on the coating film before heating after coating. Therefore, even after reheating and orientation ripening, film thickness unevenness remained in the deposited portion.
Δn at a wavelength of 550 nm of the phase film of Comparative Example 4 measured by the same method as in Example 15 was 0.256, and the haze was 0.18.
比較例５：
実施例１５と同様にして下記の組成の液晶性組成物塗布液（３）を調製した。
上記重合性液晶化合物（Ｒ−２） １００質量部
空気界面配向剤（１） ０．１質量部
重合開始剤ＩＲＧＡＣＵＲＥ８１９(チバジャパン社製) ３質量部
溶媒 クロロホルム ８００質量部
液晶性組成物塗布液（１）の代わりに液晶性組成物塗布液（３）を用いる以外は実施例１５と同様にして、比較例５の位相差膜を作製した。但し、この重合性組成物の液晶上限温度が例示化合物Ｉ−２よりも低いため、配向熟成の温度は９０℃とした。また塗布後に加熱するまでの間に、塗布膜上に結晶が一部析出した。そのため再加熱して配向熟成後も、析出部分に膜厚ムラが残った。
実施例１５と同様な方法によって測定した比較例５の位相膜の波長５５０ｎｍにおけるΔｎは０．３６０であり、ヘイズは０．１３であった。
Comparative Example 5:
In the same manner as in Example 15, a liquid crystal composition coating liquid (3) having the following composition was prepared.
100 parts by mass of the above-mentioned polymerizable liquid crystal compound (R-2) Air interface alignment agent (1) 0.1 parts by mass Polymerization initiator IRGACURE819 (manufactured by Ciba Japan) 3 parts by mass Solvent chloroform 800 parts by mass Liquid crystalline composition coating liquid ( A retardation film of Comparative Example 5 was produced in the same manner as in Example 15 except that the liquid crystalline composition coating liquid (3) was used instead of 1). However, since the upper limit temperature of the liquid crystal of this polymerizable composition was lower than that of exemplary compound I-2, the temperature for alignment aging was 90 ° C. In addition, some crystals were deposited on the coating film before heating after coating. Therefore, even after reheating and orientation ripening, film thickness unevenness remained in the deposited portion.
Δn at a wavelength of 550 nm of the phase film of Comparative Example 5 measured by the same method as in Example 15 was 0.360, and the haze was 0.13.
以上の結果を、下記表に示す。 The above results are shown in the following table.
上記表に示した結果から、本発明に係わる一般式（Ｉ）の化合物を利用して作製された位相差膜は、従来のモノアゾメチン型重合性液晶性化合物（Ｒ−１）を利用して作製された位相差膜と比較して、Δｎが大きく、且つヘイズが小さいことが理解できる。また、従来のビスシッフ型重合性液晶化合物（Ｒ−２）を利用して作製された膜が黄色であるのに対し、本発明の実施例の位相差膜はいずれも白色であり、ヘイズが小さいことも理解できる。 From the results shown in the above table, the retardation film produced using the compound of the general formula (I) according to the present invention uses the conventional monoazomethine type polymerizable liquid crystalline compound (R-1). It can be understood that Δn is large and haze is small as compared with the produced retardation film. Moreover, while the film produced using the conventional bisschiff type polymerizable liquid crystal compound (R-2) is yellow, the retardation films of the examples of the present invention are all white and have low haze. I can understand that.
３．選択反射膜の作製と評価（実施例２９〜４２、比較例６及び７）
実施例２９：
上記で合成した本発明に係わる式（Ｉ）の例示化合物（Ｉ−２）を用いて、下記の組成の液晶性組成物塗布液（１１）を調製した。
例示化合物（Ｉ−２） ３３質量部
重合性液晶化合物（Ｒ−３） ６７質量部
キラル剤Ｐａｌｉｏｃｏｌｏｒ ＬＣ７５６ （ＢＡＳＦ社製） ３質量部
空気界面配向剤（１） ０．０４質量部
重合開始剤ＩＲＧＡＣＵＲＥ８１９（チバジャパン社製） ３質量部
溶媒 クロロホルム ３００質量部
3. Preparation and evaluation of selective reflection film (Examples 29 to 42, Comparative Examples 6 and 7)
Example 29:
Using the compound (I-2) of the formula (I) according to the present invention synthesized above, a liquid crystalline composition coating liquid (11) having the following composition was prepared.
Illustrative compound (I-2) 33 parts by mass polymerizable liquid crystal compound (R-3) 67 parts by mass chiral agent Palicolor LC756 (manufactured by BASF) 3 parts by mass air interface alignment agent (1) 0.04 parts by mass polymerization initiator IRGACURE819 (Ciba Japan Co., Ltd.) 3 parts by weight solvent chloroform 300 parts by weight
実施例１５と同様にして製作した配向膜付き基板の配向膜表面に液晶性組成物塗布液（１１）をスピンコート法により室温で塗布し、１２０℃で３分間配向熟成を行った後に、室温で窒素雰囲気下でＵＶの短波長成分を除去した高圧水銀ランプを用いて１０秒間光照射して配向を固定し、実施例２９の選択反射膜を得た。塗布後に加熱するまでの間に、塗布膜に結晶の析出は見られなかった。
得られた選択反射膜を偏光顕微鏡で観察したところ配向欠陥が無く均一に配向していることを確認した。さらにこの膜を島津社製の分光光度計ＵＶ−３１００ＰＣで透過スペクトルを測定したところ１０００ｎｍに中心を持つ赤外領域に選択反射ピークがあり、その半値幅が１３４ｎｍであった。ピークの半値幅と重合性組成物の螺旋周期とを用いて算出した波長１０００ｎｍにおけるΔｎは０．２１１であった。また、日本電飾社製ヘイズメータＮＨＤ２０００を用いて測定したヘイズは０．０７であった。
A liquid crystal composition coating solution (11) was applied to the alignment film surface of the substrate with an alignment film manufactured in the same manner as in Example 15 at room temperature by spin coating, and alignment aging was performed at 120 ° C. for 3 minutes. Then, the orientation was fixed by irradiating with light for 10 seconds using a high-pressure mercury lamp from which a short wavelength component of UV was removed in a nitrogen atmosphere, and a selective reflection film of Example 29 was obtained. During the period after application and before heating, no crystal deposition was observed in the coating film.
When the obtained selective reflection film was observed with a polarizing microscope, it was confirmed that there was no alignment defect and the film was uniformly aligned. Furthermore, when the transmission spectrum of this film was measured with a spectrophotometer UV-3100PC manufactured by Shimadzu Corporation, there was a selective reflection peak in the infrared region centered at 1000 nm, and the half width was 134 nm. Δn at a wavelength of 1000 nm calculated using the half width of the peak and the helical period of the polymerizable composition was 0.211. Moreover, the haze measured using Nippon Denshoku Co., Ltd. haze meter NHD2000 was 0.07.
実施例３０〜４２：
上記でそれぞれ合成した例示化合物を、例示化合物（Ｉ−２）の代わりにそれぞれ用いた以外は、実施例２９と同様にして液晶性組成物塗布液をそれぞれ調製した。これらの塗布液をそれぞれ用いて、実施例２９と同様な方法によって、実施例３０〜４２の選択反射膜をそれぞれ作製した。これらの選択反射膜はいずれも良好な配向性を示した。同様に求めた選択反射膜のピーク半値幅とそれから求められるΔｎを下記表にまとめた。
Examples 30-42:
A liquid crystal composition coating solution was prepared in the same manner as in Example 29 except that each of the exemplified compounds synthesized above was used instead of the exemplified compound (I-2). Using these coating solutions, selective reflection films of Examples 30 to 42 were produced in the same manner as in Example 29, respectively. All of these selective reflection films showed good orientation. The peak half-value width of the selective reflection film obtained in the same manner and Δn obtained therefrom are summarized in the following table.
比較例６
実施例２９と同様にして下記の組成の液晶性組成物塗布液（１２）を調製した。
重合性液晶化合物（Ｒ−１） ３３質量部
重合性液晶化合物（Ｒ−３） ６７質量部
キラル剤Ｐａｌｉｏｃｏｌｏｒ ＬＣ７５６ (ＢＡＳＦ社製) ２．８質量部
空気界面配向剤（１） ０．０４質量部
重合開始剤ＩＲＧＡＣＵＲＥ８１９(チバジャパン社製) ３質量部
溶媒 クロロホルム ３００質量部
液晶性組成物塗布液（１１）の代わりに液晶性組成物塗布液（１２）を用いる以外は実施例２９と同様にして、比較例６の選択反射膜を作製した。但し、この重合性組成物の液晶上限温度が実施例２９で用いた組成物よりも低いため、配向熟成の温度は９０℃とした。塗布後に加熱するまでの間に、塗布膜上に結晶が一部析出した。そのため再加熱して配向熟成後も、析出部分に膜厚ムラと配向不均一性が残った。
得られた比較例６の選択反射膜は、１０００ｎｍ付近に中心を持つ赤外領域に選択反射ピークがあり、その半値幅が１２０ｎｍであった。ピークの半値幅と重合性組成物の螺旋周期とを用いて算出した波長１０００ｎｍにおけるΔｎは０．１９０であった。
Comparative Example 6
In the same manner as in Example 29, a liquid crystal composition coating liquid (12) having the following composition was prepared.
Polymerizable liquid crystal compound (R-1) 33 parts by mass Polymerizable liquid crystal compound (R-3) 67 parts by mass Chiral agent Palicolor LC756 (manufactured by BASF) 2.8 parts by mass Air interface alignment agent (1) 0.04 parts by mass Polymerization initiator IRGACURE819 (manufactured by Ciba Japan) 3 parts by weight solvent Chloroform 300 parts by weight In the same manner as in Example 29 except that the liquid crystalline composition coating liquid (12) is used instead of the liquid crystalline composition coating liquid (11). A selective reflection film of Comparative Example 6 was produced. However, since the upper limit temperature of the liquid crystal of this polymerizable composition was lower than that of the composition used in Example 29, the temperature for alignment aging was 90 ° C. During the period after application and before heating, some crystals were deposited on the coating film. Therefore, even after reheating and orientation ripening, film thickness unevenness and orientation non-uniformity remained in the deposited portion.
The obtained selective reflection film of Comparative Example 6 had a selective reflection peak in the infrared region having a center near 1000 nm, and its half-value width was 120 nm. Δn at a wavelength of 1000 nm calculated using the half width of the peak and the helical period of the polymerizable composition was 0.190.
比較例７：
実施例２９と同様にして下記の組成の液晶性組成物塗布液（１３）を調製した。
重合性液晶化合物（Ｒ−２） ３３質量部
重合性液晶化合物（Ｒ−３） ６７質量部
キラル剤Ｐａｌｉｏｃｏｌｏｒ ＬＣ７５６ (ＢＡＳＦ社製) ２．８質量部
空気界面配向剤（１） ０．０４質量部
重合開始剤ＩＲＧＡＣＵＲＥ８１９(チバジャパン社製) ３質量部
溶媒 クロロホルム ３００質量部
液晶性組成物塗布液（１１）の代わりに液晶性組成物塗布液（１３）を用いる以外は実施例２９と同様にして比較例７の選択反射膜を作製した。
この選択反射膜は、１０００ｎｍ付近に中心を持つ赤外領域に選択反射ピークがあり、その半値幅が１５４ｎｍであった。ピークの半値幅と重合性組成物の螺旋周期とを用いて算出した波長１０００ｎｍにおけるΔｎは０．２４３であった。膜の色は黄色であった。
Comparative Example 7:
In the same manner as in Example 29, a liquid crystal composition coating liquid (13) having the following composition was prepared.
Polymerizable liquid crystal compound (R-2) 33 parts by mass Polymerizable liquid crystal compound (R-3) 67 parts by mass Chiral agent Palicolor LC756 (manufactured by BASF) 2.8 parts by mass Air interface alignment agent (1) 0.04 parts by mass Polymerization initiator IRGACURE819 (manufactured by Ciba Japan) 3 parts by mass Solvent chloroform 300 parts by mass In the same manner as in Example 29 except that the liquid crystalline composition coating liquid (13) is used instead of the liquid crystalline composition coating liquid (11). A selective reflection film of Comparative Example 7 was produced.
This selective reflection film had a selective reflection peak in the infrared region centered around 1000 nm, and its half-value width was 154 nm. Δn at a wavelength of 1000 nm calculated using the half width of the peak and the helical period of the polymerizable composition was 0.243. The film color was yellow.
以上の結果を、下記表に示す。 The above results are shown in the following table.
上記表に示した結果から、本発明に係わる一般式（Ｉ）の化合物を利用して作製された選択反射膜は、従来のモノアゾメチン重合性液晶化合物（Ｒ−１）を利用して作製された選択反射膜と比較して、Δｎが大きく、また、選択反射波長域も広いことが理解できる。さらに、従来のビスアゾメチン重合性液晶（Ｒ−２）を利用して作製された膜が黄色であるのに対して、本発明の実施例の選択反射膜はいずれも無色であることが理解できる。 From the results shown in the above table, the selective reflection film produced using the compound of the general formula (I) according to the present invention was produced using the conventional monoazomethine polymerizable liquid crystal compound (R-1). It can be understood that Δn is large and the selective reflection wavelength region is wide as compared with the selective reflection film. Further, it can be understood that the selective reflection films of the examples of the present invention are all colorless while the film produced using the conventional bisazomethine polymerizable liquid crystal (R-2) is yellow. .
Claims (13)
ｍ１及びｍ２はそれぞれ、１〜１０の整数を表し、ｍ１又はｍ２個のＣＨ2のうち、１つのＣＨ2又は隣接しない２以上のＣＨ2は、酸素原子又は硫黄原子に置き換わっていてもよく；
Ａ1、Ａ2、Ａ3及びＡ4はそれぞれ、置換されていてもよい、５〜１８員環の芳香族炭化水素環、又は５〜１８員環の芳香族複素環の基を表し；
Ｒは、水素原子又は炭素原子数１〜８のアルキル基を表し；
Ｚ1及びＺ2はそれぞれ、−ＣＯＯ−、−ＯＣＯ−、−ＮＨＣＯ−、又は−ＮＲ1ＣＯを表し、Ｒ1は炭素原子数１〜１０のアルキル基を表し；
Ｌ1及びＬ2はそれぞれ、−Ｏ−、−Ｓ−、−ＣＯＯ−、−ＯＣＯ−、−ＯＣＯＯ−、−ＮＨＣＯ−、又は−ＮＲ1ＣＯを表し、Ｒ1は炭素原子数１〜１０のアルキル基を表し；
ｎ１及びｎ２はそれぞれ、１又は２である；
で表される化合物を少なくとも１種含むことを特徴とする重合性組成物。 The following formula (I):
Each m1 and m2, represents an integer of 1 to 10, among the m1 or m2 amino CH 2, 1 single CH 2 or non-adjacent two or more CH 2 may be replaced by oxygen atom or a sulfur atom;
Each of A 1 , A 2 , A 3 and A 4 represents an optionally substituted 5- to 18-membered aromatic hydrocarbon ring or 5- to 18-membered aromatic heterocyclic group;
R represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms;
Z 1 and Z 2 each represent —COO—, —OCO—, —NHCO—, or —NR 1 CO, and R 1 represents an alkyl group having 1 to 10 carbon atoms;
L 1 and L 2 each represent —O—, —S—, —COO—, —OCO—, —OCOO—, —NHCO—, or —NR 1 CO, and R 1 has 1 to 10 carbon atoms. Represents an alkyl group;
n1 and n2 are each 1 or 2;
A polymerizable composition comprising at least one compound represented by the formula:
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