JP2013166879A - Polymerizable liquid crystal composition, polymer material, method of producing the same, and film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymerizable liquid crystal composition including a polymerizable liquid crystal (I-1) and a polymerizable liquid crystal similar thereto and capable of suppressing crystal deposition after application.SOLUTION: A polymerizable liquid crystal composition includes a compound represented by general formula (I) and a compound represented by general formula (II): P-Sp-A-B-C-Sp-P (I), and P-Sp-D-E-F-G-Sp-P (II). In the formulas: P is a polymerizable group; Sp is a spacer or a single bond; and A-G are each a divalent bonding group selected from formulas IIIa, IIIb and IIIc provided that at least two of D-G are divalent bonding groups represented by general formula IIIa or IIIb wherein: R, Rand Rare each a substituent; na, nb, and nc are each an integer of 0-4; and a plurality of R, Rand Rmay be the same or different mutually when na, nb and nc are each an integer of ≥2.

Description

  The present invention relates to a polymerizable liquid crystal composition, a polymer material, a production method thereof, and a film using them, which are useful in various applications including materials for various optical members such as an optically anisotropic film and a heat shielding film. About.

Liquid crystal materials are used in many industrial fields such as retardation plates, polarizing elements, selective reflection films, color filters, antireflection films, viewing angle compensation films, holography, and alignment films (Non-Patent Document 1). Among these, the polymerizable liquid crystal compound (I-1) has high versatility because of its simple structure, and is used in many applications (for example, Patent Documents 1 to 6).

JP 2010-84032 A JP 2009-286976 A JP 2009-186785 A JP 2009-184974 A JP 2009-86260 A JP 2002-536529 A

D. J. et al. Broer, G.G. N. Mol, J.M. A. M.M. M.M. Van Haaren, and J.M. Lub Adv. Mater. , 11, 573 (1999)

  However, the polymerizable liquid crystal (I-1) has very high crystallinity, and the polymerizable liquid crystal (I-1) alone or the composition containing the polymerizable liquid crystal (I-1) is easily crystallized in the coating process. Has become a problem (see, for example, Patent Document 4). Therefore, development of an additive effective in suppressing the crystal precipitation of the polymerizable liquid crystal (I-1) is desired.

  In order to suppress crystal precipitation without impairing the performance of the polymerizable liquid crystal (I-1), it is generally considered desirable to provide a liquid crystal material as an additive. For example, Patent Documents 2 to 4 include a composition in which a (meth) acrylate compound having two (meth) acryloyl groups at the end of the molecule is used in combination with the polymerizable liquid crystal (I-1). A composition prepared as a random mixture having a (meth) acryloyl group and an alkyl group at both ends of the molecule when preparing the polymerizable liquid crystal (I-1) is used. However, the compositions described in these documents are not satisfactory from the viewpoint of suppressing crystal precipitation after coating.

The problem to be solved by the present invention is to provide a polymerizable liquid crystal composition containing the polymerizable liquid crystal (I-1) and a polymerizable liquid crystal similar thereto and capable of suppressing crystal precipitation after coating.

  As a result of intensive studies, the present inventors have solved the problems of the prior art by using a polymerizable liquid crystal composition containing a polymerizable liquid crystal (I-1) and a polymerizable liquid crystal similar thereto and a compound having a specific structure. I found out that I could do it. That is, the following present invention has been provided as means for solving the above problems.

〔一般式（Ｉ）および（ＩＩ）中、Ｐはそれぞれ独立に下記の一般式（Ｐ−１）〜（Ｐ−５）のいずれかで表される重合性官能基を表し、Ｓｐはそれぞれ独立に下記一般式（Ｓｐ−１）で表される二価の連結基または単結合を表し、Ａ、Ｂ、Ｃ、Ｄ、Ｅ、ＦおよびＧはそれぞれ独立に下記一般式ＩＩＩａ、ＩＩＩｂおよびＩＩＩｃから選ばれる二価の連結基を表す。但し、Ｄ、Ｅ、ＦおよびＧのうち少なくとも２つは、下記一般式ＩＩＩａまたは一般式ＩＩＩｂで表される二価の連結基を表す。

（一般式（Ｐ−１）〜（Ｐ−５）中、Ｒ¹¹〜Ｒ¹³はそれぞれ独立に水素原子またはメチル基を表す。）

（一般式（Ｓｐ−１）中、Ｒ⁴¹は、置換もしくは無置換のアルキレン基、置換もしくは無置換のアルケニレン基、または置換もしくは無置換のアルキニレン基を表す。Ｚ⁴¹は、−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯ−Ｏ−、−Ｏ−ＣＯ−、−Ｓ−ＣＯ−、−ＣＯ−Ｓ−、−Ｏ−ＣＯ−Ｏ−、−ＣＯ−ＮＲ⁵¹−、−ＮＲ⁵¹−ＣＯ−、−ＣＲ⁵¹＝Ｎ−、−Ｎ＝ＣＲ⁵¹−または単結合を表す（Ｒ⁵¹は、水素原子または炭素原子数１〜１２のアルキル基を表す）。ｍは１〜６のいずれかの整数を表し、ｍが２以上の整数であるとき、一般式（Ｓｐ−１）内に存在する複数のＲ⁴¹は互いに同一であっても異なっていてもよく、一般式（Ｓｐ−１）内に存在する複数のＺ⁴¹は互いに同一であっても異なっていてもよい。）

（一般式ＩＩＩａ、ＩＩＩｂおよびＩＩＩｃ中、Ｒ^a、Ｒ^b及びＲ^cはそれぞれ独立に置換基を表し、ｎａ、ｎｂ及びｎｃはそれぞれ独立に０〜４の整数を表す。ｎａ、ｎｂ及びｎｃがそれぞれ２以上の整数である場合、複数存在するＲ^a、Ｒ^b及びＲ^cはそれぞれ同一であっても異なっていてもよい。）〕
［２］ ［１］に記載の重合性液晶組成物は、前記一般式（Ｉ）で表される化合物に対し、前記一般式（ＩＩ）で表される化合物を０．１〜１０質量％含むことが好ましい。
［３］ ［１］に記載の重合性液晶組成物は、前記一般式（Ｉ）で表される化合物に対し、前記一般式（ＩＩ）で表される化合物を０．１〜５質量％含むことが好ましい。
［４］ ［１］〜［３］のいずれか一項に記載の重合性液晶組成物は、さらに、少なくとも１種の重合開始剤を含有することが好ましい。
［５］ ［１］〜［４］のいずれか一項に記載の重合性液晶組成物は、さらに、少なくとも１種のキラル化合物を含有することが好ましい。
［６］ ［１］〜［５］のいずれか一項に記載の重合性液晶組成物を重合させる工程を含むことを特徴とする高分子材料の製造方法。
［７］ ［６］に記載の高分子材料の製造方法は、紫外線を照射することにより前記重合を行うことが好ましい。
［８］ ［１］〜［５］のいずれか一項に記載の重合性液晶組成物を、重合してなることを特徴とする高分子材料。
［９］ ［８］に記載の高分子材料を少なくとも１種含有することを特徴とするフィルム。
［１０］ ［５］に記載の重合性液晶組成物のコレステリック液晶相を固定してなることを特徴とするフィルム。
［１１］ ［９］または［１０］に記載のフィルムは、光学異方性を示すことが好ましい。
［１２］ ［９］〜［１１］のいずれか一項に記載のフィルムは、選択反射特性を示すことが好ましい。
［１３］ ［９］〜［１２］のいずれか一項に記載のフィルムは、赤外線波長域に選択反射特性を示すことが好ましい。 [1] A polymerizable liquid crystal composition comprising a compound represented by the following general formula (I) and a compound represented by the following general formula (II).

[In General Formulas (I) and (II), P independently represents a polymerizable functional group represented by any one of the following General Formulas (P-1) to (P-5), and Sp represents each independently Represents a divalent linking group or a single bond represented by the following general formula (Sp-1), and A, B, C, D, E, F and G are independently represented by the following general formulas IIIa, IIIb and IIIc: Represents a selected divalent linking group. However, at least two of D, E, F and G represent a divalent linking group represented by the following general formula IIIa or general formula IIIb.

(In the general formulas (P-1) to (P-5), R ^{11 to} R ¹³ each independently represents a hydrogen atom or a methyl group.)

(In the general formula (Sp-1), R ⁴¹ represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, or a substituted or unsubstituted alkynylene group. Z ⁴¹ represents —O—, — S -, - CO -, - CO-O -, - O-CO -, - S-CO -, - CO-S -, - O-CO-O -, - CO-NR 51 -, - NR 51 - CO—, —CR ⁵¹ ═N—, —N═CR ⁵¹ — or a single bond (R ⁵¹ represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms), m is any one of 1-6. When m is an integer of 2 or more, the plurality of R ⁴¹ present in the general formula (Sp-1) may be the same or different from each other, and the general formula (Sp-1) And a plurality of Z ⁴¹ existing therein may be the same as or different from each other.)

(In the general formulas IIIa, IIIb and IIIc, R ^a , R ^b and R ^c each independently represent a substituent, and na, nb and nc each independently represent an integer of 0 to 4. na, nb and nc are When each is an integer of 2 or more, a plurality of R ^a , R ^b and R ^c may be the same or different.)]
[2] The polymerizable liquid crystal composition according to [1] includes 0.1 to 10% by mass of the compound represented by the general formula (II) with respect to the compound represented by the general formula (I). It is preferable.
[3] The polymerizable liquid crystal composition according to [1] includes 0.1 to 5% by mass of the compound represented by the general formula (II) with respect to the compound represented by the general formula (I). It is preferable.
[4] The polymerizable liquid crystal composition according to any one of [1] to [3] preferably further contains at least one polymerization initiator.
[5] The polymerizable liquid crystal composition according to any one of [1] to [4] preferably further contains at least one chiral compound.
[6] A method for producing a polymer material, comprising a step of polymerizing the polymerizable liquid crystal composition according to any one of [1] to [5].
[7] In the method for producing a polymer material according to [6], the polymerization is preferably performed by irradiating with ultraviolet rays.
[8] A polymer material obtained by polymerizing the polymerizable liquid crystal composition according to any one of [1] to [5].
[9] A film comprising at least one polymer material according to [8].
[10] A film formed by fixing a cholesteric liquid crystal phase of the polymerizable liquid crystal composition according to [5].
[11] The film according to [9] or [10] preferably exhibits optical anisotropy.
[12] The film according to any one of [9] to [11] preferably exhibits selective reflection characteristics.
[13] The film according to any one of [9] to [12] preferably exhibits selective reflection characteristics in an infrared wavelength region.

  The polymerizable liquid crystal composition of the present invention is effective in suppressing crystal precipitation after application of the polymerizable liquid crystal (I-1) and a polymerizable liquid crystal similar thereto. Since it is effective in suppressing crystal precipitation of the highly versatile polymerizable liquid crystal (I-1), a polymerizable composition, a polymer material and a film using the polymerizable liquid crystal (I-1) can be used in various applications. It is possible to use.

Hereinafter, the present invention will be described in detail.
The description of the constituent elements described below may be made based on typical embodiments and specific examples of the present invention, but the present invention is not limited to such embodiments and specific examples. In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.

  The polymerizable liquid crystal composition of the invention contains a compound represented by the following general formula (I) and a compound represented by the general formula (II).

〔一般式（Ｉ）および（ＩＩ）中、Ｐはそれぞれ独立に下記の一般式（Ｐ−１）〜（Ｐ−５）のいずれかで表される重合性官能基を表し、Ｓｐはそれぞれ独立に下記一般式（Ｓｐ−１）で表される二価の連結基または単結合を表し、Ａ、Ｂ、Ｃ、Ｄ、Ｅ、ＦおよびＧはそれぞれ独立に下記一般式ＩＩＩａ、ＩＩＩｂおよびＩＩＩｃから選ばれる二価の連結基を表す。但し、Ｄ、Ｅ、ＦおよびＧのうち少なくとも２つは、下記一般式ＩＩＩａまたは一般式ＩＩＩｂで表される二価の連結基を表す。

（一般式（Ｐ−１）〜（Ｐ−５）中、Ｒ¹¹〜Ｒ¹³はそれぞれ独立に水素原子またはメチル基を表す。）

（一般式（Ｓｐ−１）中、Ｒ⁴¹は、置換もしくは無置換のアルキレン基、置換もしくは無置換のアルケニレン基、または置換もしくは無置換のアルキニレン基を表す。Ｚ⁴¹は、−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯ−Ｏ−、−Ｏ−ＣＯ−、−Ｓ−ＣＯ−、−ＣＯ−Ｓ−、−Ｏ−ＣＯ−Ｏ−、−ＣＯ−ＮＲ⁵¹−、−ＮＲ⁵¹−ＣＯ−、−ＣＲ⁵¹＝Ｎ−、−Ｎ＝ＣＲ⁵¹−または単結合を表す（Ｒ⁵¹は、水素原子または炭素原子数１〜１２のアルキル基を表す）。ｍは１〜６のいずれかの整数を表し、ｍが２以上の整数であるとき、一般式（Ｓｐ−１）内に存在する複数のＲ⁴¹は互いに同一であっても異なっていてもよく、一般式（Ｓｐ−１）内に存在する複数のＺ⁴¹は互いに同一であっても異なっていてもよい。）

（一般式ＩＩＩａ、ＩＩＩｂおよびＩＩＩｃ中、Ｒ^a、Ｒ^b及びＲ^cはそれぞれ独立に置換基を表し、ｎａ、ｎｂ及びｎｃはそれぞれ独立に０〜４の整数を表す。ｎａ、ｎｂ及びｎｃがそれぞれ２以上の整数である場合、複数存在するＲ^a、Ｒ^b及びＲ^cはそれぞれ同一であっても異なっていてもよい。）〕

[In General Formulas (I) and (II), P independently represents a polymerizable functional group represented by any one of the following General Formulas (P-1) to (P-5), and Sp represents each independently Represents a divalent linking group or a single bond represented by the following general formula (Sp-1), and A, B, C, D, E, F and G are independently represented by the following general formulas IIIa, IIIb and IIIc: Represents a selected divalent linking group. However, at least two of D, E, F and G represent a divalent linking group represented by the following general formula IIIa or general formula IIIb.

(In the general formulas (P-1) to (P-5), R ^{11 to} R ¹³ each independently represents a hydrogen atom or a methyl group.)

(In the general formula (Sp-1), R ⁴¹ represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, or a substituted or unsubstituted alkynylene group. Z ⁴¹ represents —O—, — S -, - CO -, - CO-O -, - O-CO -, - S-CO -, - CO-S -, - O-CO-O -, - CO-NR 51 -, - NR 51 - CO—, —CR ⁵¹ ═N—, —N═CR ⁵¹ — or a single bond (R ⁵¹ represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms), m is any one of 1-6. When m is an integer of 2 or more, the plurality of R ⁴¹ present in the general formula (Sp-1) may be the same or different from each other, and the general formula (Sp-1) And a plurality of Z ⁴¹ existing therein may be the same as or different from each other.)

(In the general formulas IIIa, IIIb and IIIc, R ^a , R ^b and R ^c each independently represent a substituent, and na, nb and nc each independently represent an integer of 0 to 4. na, nb and nc are When each is an integer of 2 or more, a plurality of R ^a , R ^b and R ^c may be the same or different.)]

1. Polymerizable liquid crystal compound The compound represented by the general formula (I) and the compound represented by the general formula (II) will be described below.

(1-1) Compound Represented by General Formula (II) First, the structure of the compound represented by the following general formula (II) will be described.
Formula (II)
P-Sp-D-E-F-G-Sp-P

The compound represented by the general formula (II) is a polymerizable liquid crystal compound.
In the general formula (II), each P independently represents a polymerizable functional group represented by the following formula (P-1) to formula (P-5). The polymerizable functional group herein, and those consisting of only the direct participating group (e.g. CH ₂ = CH-) in the polymerization, it has been linked directly involved group (e.g. CH ₂ = CH-) in the polymerization It is a concept that includes both functional groups (for example, —CO—, —CO—O—, —O—). As the polymerizable functional group, a polymerizable functional group capable of radical polymerization or cationic polymerization is preferable.

前記式（Ｐ−１）〜（Ｐ−５）中、Ｒ¹¹〜Ｒ¹³はそれぞれ、水素原子またはメチル基を表し、水素原子であることが好ましい。

In the formulas (P-1) to (P-5), R ^{11 to} R ¹³ each represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom.

  In the compound represented by the general formula (II), P represents the general formula (P-1) among the polymerizable functional groups represented by any one of the general formulas (P-1) to (P-5). It is preferable that it is a polymerizable functional group represented by this.

  In the compound represented by the general formula (II), it is preferable that two Ps are the same.

In the general formula (II), each Sp independently represents a divalent linking group or a single bond represented by the following general formula (Sp-1). In addition, the bivalent coupling group represented by the following general formula (Sp-1) may be called a spacer.
In the general formula (II), Sp is preferably a linking group represented by the following general formula (Sp-1).

前記一般式（Ｓｐ−１）中、Ｒ⁴¹は、置換もしくは無置換のアルキレン基、置換もしくは無置換のアルケニレン基、または置換もしくは無置換のアルキニレン基を表す。Ｚ⁴¹は、−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯ−Ｏ−、−Ｏ−ＣＯ−、−Ｓ−ＣＯ−、−ＣＯ−Ｓ−、−Ｏ−ＣＯ−Ｏ−、−ＣＯ−ＮＲ⁵¹−、−ＮＲ⁵¹−ＣＯ−、−ＣＲ⁵¹＝Ｎ−、−Ｎ＝ＣＲ⁵¹−または単結合を表す（Ｒ⁵¹は、水素原子または炭素原子数１〜１２のアルキル基を表す）。ｍは１〜６のいずれかの整数を表し、ｍが２以上の整数であるとき、Ｓｐ内に存在する複数のＲ⁴¹は互いに同一であっても異なっていてもよく、Ｓｐ内に存在する複数のＺ⁴¹は互いに同一であっても異なっていてもよい。

In the general formula (Sp-1), R ⁴¹ represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, or a substituted or unsubstituted alkynylene group. Z ⁴¹ is —O—, —S—, —CO—, —CO—O—, —O—CO—, —S—CO—, —CO—S—, —O—CO—O—, —CO. ^{-NR 51 -, - NR 51 -CO} -, - CR 51 = N -, - N = CR 51 - or a single bond (R ⁵¹ represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms) . m represents an integer of 1 to 6, and when m is an integer of 2 or more, a plurality of R ⁴¹ present in Sp may be the same as or different from each other, and are present in Sp. The plurality of Z ⁴¹ may be the same as or different from each other.

In the general formula (Sp-1), R ⁴¹ represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, or a substituted or unsubstituted alkynylene group.
In the compound represented by the general formula (II), the alkylene group which R ⁴¹ can take may be linear or branched, and is preferably linear. The number of carbon atoms of the alkylene group that R ⁴¹ can take is preferably 1 to 12, more preferably 2 to 8, and still more preferably 2 to 6.
In the compound represented by the general formula (II), the alkenylene group and the alkynylene group which R ⁴¹ can take may be linear or branched, and is preferably linear. The number of carbon atoms of the alkenylene group and alkynylene group that R ⁴¹ can take is preferably 2 to 12, more preferably 2 to 8, and even more preferably 2 to 6.
In the compound represented by the general formula (II), examples of the substituent that the alkylene group, alkenylene group, and alkynylene group that R ⁴¹ may have include a fluorine atom, a chlorine atom, a cyano group, and a carbon atom. The alkoxy group of number 1-4 can be mentioned. The alkoxy group may be linear or branched, and examples thereof include a methoxy group and an ethoxy group.
In the compound represented by the general formula (II), R ⁴¹ is preferably a substituted or unsubstituted alkylene group, more preferably an unsubstituted alkylene group, and an unsubstituted alkylene group having 2 to 8 carbon atoms. More preferably, an unsubstituted alkylene group having 2 to 6 carbon atoms is even more preferable, and an alkylene group having 3 to 5 carbon atoms is even more particularly preferable.

In the general formula (Sp-1), Z ⁴¹ represents —O—, —S—, —CO—, —CO—O—, —O—CO—, —S—CO—, —CO—S—, -O-CO-O -, - CO-NR 51 -, - NR 51 -CO -, - CR 51 = N -, - N = CR 51 - or a single bond.
R ⁵¹ represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms.
In the compound represented by the general formula (II), the alkyl group that R ⁵¹ can take may be linear or branched, and preferably has 1 to 6 carbon atoms, It is more preferable that it is 1-4, and it is especially preferable to employ a methyl group or an ethyl group. The alkyl group that R ⁵¹ can take may be substituted, and examples of the substituent in the case of substitution include a fluorine atom, a chlorine atom, and a cyano group.
In the compound represented by the general formula (II), R ⁵¹ is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom or a methyl group, and even more preferably a hydrogen atom.
In the compound represented by the general formula (II), Z ⁴¹ may be —O—, —S—, —CO—, —CO—O—, —O—CO—, —S—CO—, —CO. -S- is preferable, -O- and -S- are more preferable, and -O- is particularly preferable.

In the said general formula (Sp-1), m represents the integer in any one of 1-6.
In the compound represented by the general formula (II), m is preferably an integer of 1 to 4, and more preferably an integer of 1 to 3.
When m is an integer of 2 or more, a plurality of R ⁴¹ present in Sp may be the same or different from each other, and a plurality of Z ⁴¹ present in Sp may be the same or different from each other. May be. In the compound represented by the general formula (II), when m is an integer of 2 or more, a plurality of R ⁴¹ present in Sp is preferably the same as each other, and a plurality of Z ⁴¹ are the same as each other. It is preferable.

In the compound represented by the general formula (II), a preferred Sp includes a linking group containing a substituted or unsubstituted alkyleneoxy group. For example, an alkyleneoxy group, an alkyleneoxyalkyleneoxy group, and an alkyleneoxyalkyleneoxyalkyleneoxy group can be preferably employed. Among these, in the compound represented by the general formula (II), Sp is more preferably an alkyleneoxy group. The preferred range of the alkylene group when Sp is a linking group containing a substituted or unsubstituted alkyleneoxy group is in accordance with the preferred range of the alkyl group when R ⁵¹ represents an alkyl group.

  In the compound represented by the general formula (II), two Sps are preferably the same.

  In the general formula (II), D, E, F and G each independently represent a divalent linking group selected from the following general formulas IIIa, IIIb and IIIc. However, at least two of D, E, F and G represent a divalent linking group represented by the following general formula IIIa or general formula IIIb.

前記一般式ＩＩＩａ、ＩＩＩｂおよびＩＩＩｃ中、Ｒ^a、Ｒ^b及びＲ^cはそれぞれ置換基を表す。Ｒ^a、Ｒ^b及びＲ^cがとりうる置換基としては、例えば、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、炭素原子数２〜５のアシルオキシ基、炭素原子数２〜４のアシル基、炭素原子数２〜５のアミド基、シアノ基、アミノ基、水酸基、またはハロゲン原子を挙げることができる。
ここでいうＲ^a、Ｒ^b及びＲ^cがとりうるアルキル基、ならびにアルコキシ基、アルコキシカルボニル基、アシルオキシ基、アシル基およびアミド基のアルキル部分は、直鎖状であっても分枝状であってもよい。Ｒ^a、Ｒ^b及びＲ^cがとりうるアルキル基、ならびにアルコキシ基、アルコキシカルボニル基、アシルオキシ基、アシル基およびアミド基のアルキル部分は、さらに置換基（好ましくはハロゲン原子）を有していてもよく、該置換基としては例えばメチル基、エチル基、トリフルオロメチル基を挙げることができる。
Ｒ^a、Ｒ^b及びＲ^cがとりうるハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子を挙げることができ、前記一般式（ＩＩ）で表される化合物ではフッ素原子、塩素原子、臭素原子が好ましい。
前記一般式（ＩＩ）で表される化合物では、Ｒ^a、Ｒ^bおよびＲ^cとしては、メチル基、エチル基、トリフルオロメチル基、メトキシ基、エトキシ基、メトキシカルボニル基、エトキシカルボニル基、アセチルオキシ基、プロピオニルオキシ基、メチルアミド基、エチルアミド基、シアノ基、フッ素原子、塩素原子、臭素原子を好ましい例として挙げることができる。その中でも、メチル基、メトキシ基、トリフルオロメチル基、塩素原子がより好ましく、メチル基が特に好ましい。

In the general formulas IIIa, IIIb and IIIc, R ^a , R ^b and R ^c each represent a substituent. Examples of the substituent that R ^a , R ^b and R ^c can take include, for example, 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, and carbon. Examples thereof include an acyloxy group having 2 to 5 atoms, an acyl group having 2 to 4 carbon atoms, an amide group having 2 to 5 carbon atoms, a cyano group, an amino group, a hydroxyl group, and a halogen atom.
The alkyl group that R ^a , R ^b, and R ^c can take, and the alkyl part of the alkoxy group, alkoxycarbonyl group, acyloxy group, acyl group, and amide group are branched or branched. May be. The alkyl group which R ^a , R ^b and R ^c can take, and the alkyl part of the alkoxy group, alkoxycarbonyl group, acyloxy group, acyl group and amide group may further have a substituent (preferably a halogen atom). Well, examples of the substituent include a methyl group, an ethyl group, and a trifluoromethyl group.
Examples of the halogen atom that R ^a , R ^b, and R ^c can take include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. In the compound represented by the general formula (II), a fluorine atom, a chlorine atom A bromine atom is preferred.
In the compound represented by the general formula (II), as R ^a , R ^b and R ^c , methyl group, ethyl group, trifluoromethyl group, methoxy group, ethoxy group, methoxycarbonyl group, ethoxycarbonyl group, acetyl Preferred examples include an oxy group, a propionyloxy group, a methylamide group, an ethylamide group, a cyano group, a fluorine atom, a chlorine atom, and a bromine atom. Among these, a methyl group, a methoxy group, a trifluoromethyl group, and a chlorine atom are more preferable, and a methyl group is particularly preferable.

In the general formulas IIIa, IIIb and IIIc, na, nb and nc each independently represents an integer of 0 to 4.
In the compound represented by the general formula (II), na is preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 0.
In the compound represented by the general formula (II), nb is preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 1.
In the compound represented by the general formula (II), nc is preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 0.

In General Formulas IIIa, IIIb, and IIIc, at least two of D, E, F, and G represent a divalent linking group represented by General Formula IIIa or General Formula IIIb.
In the compound represented by the general formula (II), at least three of D, E, F and G are preferably divalent linking groups represented by the general formula IIIa or the general formula IIIb.

In the compound represented by the general formula (II), it is preferable that two of D, E, F and G are divalent linking groups represented by the general formula IIIa.
When the compound represented by the general formula (II) has a divalent linking group represented by the general formula IIIa, at least one of D, E and F is a divalent group represented by the general formula IIIa. It is preferably a linking group, more preferably at least one of D and E is a divalent linking group represented by the general formula IIIa, and D and E are divalent valences represented by the general formula IIIa. The linking group is particularly preferable.

In the compound represented by the general formula (II), it is preferable that at least one of D, E, F and G is a divalent linking group represented by the general formula IIIb.
When the compound represented by the general formula (II) has a divalent linking group represented by the general formula IIIb, it is preferable that F is a divalent linking group represented by the general formula IIIb.

In the compound represented by the general formula (II), it is preferable that the number of divalent linking groups represented by the general formula IIIc among D, E, F, and G is 2 or less, and 0 or 1 More preferably.
When the compound represented by the general formula (II) has a divalent linking group represented by the general formula IIIc, at least one of F and G is a divalent linking group represented by the general formula IIIc. It is preferable that at least G is a divalent linking group represented by the general formula IIIc.

  Specific examples of the compound represented by the general formula (II) are listed below, but the range of the compound represented by the general formula (II) should not be construed as being limited by these specific examples.

The compound represented by the general formula (II) can be synthesized by combining various synthesis methods. For example, it can be synthesized according to the following scheme 1.

P in Scheme ^{1, Sp, R a, R} c, na, nc definitions, P in Formula ^{(II), Sp, R a} , R c, na, is the same as the definition of nc.
In Scheme 1, first, the phenol derivative A and a linking chain having a leaving group are reacted to synthesize a compound B in which only one hydroxyl group is bonded to the linking group. Next, the compound represented by the general formula (II) is synthesized by condensing B and carboxylic acid C. This reaction itself is a known reaction, and known conditions can be appropriately selected and employed. After completion of the reaction, the compound represented by the general formula (II) can be obtained by carrying out usual post-treatment and purification. Examples of the purification method include recrystallization and column chromatography. The above reaction conditions can be optimized as appropriate.
As the compound used in Scheme 1, commercially available compounds may be obtained and used, or those synthesized by appropriately selecting a known synthesis method may be used.

  The compound represented by the general formula (II) exhibits liquid crystallinity. Furthermore, when the compound (II) represented by the general formula (II) is used as an additive, it has an effect of suppressing crystal precipitation after application of the highly versatile polymerizable liquid crystal (I). Applications of (I) can be further expanded. Therefore, the cured film formed using the polymerizable liquid crystal composition of the present invention includes, for example, a retardation plate, a polarizing element, a selective reflection film, a color filter, an antireflection film, a viewing angle, which are constituent elements of an optical element. It can be used for various applications such as compensation films, holography, alignment films, and the like.

(1-2) Compound Represented by General Formula (I) Next, the compound represented by the following general formula (I) will be described.
Formula (I)
P-Sp-A-B-C-Sp-P

The compound represented by the general formula (I) is a polymerizable liquid crystal compound.
The preferable range of P in the general formula (I) is the same as the preferable range of P in the general formula (II).
The preferred range of Sp in the general formula (I) is the same as the preferred range of Sp in the general formula (II).

前記一般式（Ｉ）で表される化合物における前記一般式ＩＩＩａ、ＩＩＩｂおよびＩＩＩｃ中のＲ^a、Ｒ^b、Ｒ^c、ｎａ、ｎｂおよびｎｃの定義と好ましい範囲は、前記一般式（ＩＩ）で表される化合物における前記一般式ＩＩＩａ、ＩＩＩｂおよびＩＩＩｃ中のＲ^a、Ｒ^b、Ｒ^c、ｎａ、ｎｂおよびｎｃの定義と好ましい範囲と同様である。 In the general formula (I), A, B and C each independently represent a divalent linking group selected from the following general formulas IIIa, IIIb and IIIc.

The definition and preferred range of R ^a , R ^b , R ^c , na, nb and nc in the general formulas IIIa, IIIb and IIIc in the compound represented by the general formula (I) are the same as those in the general formula (II). The definitions and preferred ranges of R ^a , R ^b , R ^c , na, nb and nc in the general formulas IIIa, IIIb and IIIc in the represented compounds are the same.

  In the general formulas IIIa, IIIb and IIIc, at least one of A, B and C is preferably a divalent linking group represented by the general formula IIIa or the general formula IIIb. More preferably, at least two are divalent linking groups represented by the general formula IIIa or general formula IIIb.

In the compound represented by the general formula (I), one of A, B and C is preferably a divalent linking group represented by the general formula IIIa.
When the compound represented by the general formula (I) has a divalent linking group represented by the general formula IIIa, at least one of A and B is a divalent linking group represented by the general formula IIIa. And A is more preferably a divalent linking group represented by the general formula IIIa.

In the compound represented by the general formula (I), it is preferable that at least one of A, B, and C is a divalent linking group represented by the general formula IIIb.
When the compound represented by the general formula (I) has a divalent linking group represented by the general formula IIIb, B is preferably a divalent linking group represented by the general formula IIIb.

In the compound represented by the general formula (I), the number of divalent linking groups represented by the general formula IIIc among A, B and C is preferably 2 or less, and 0 or 1 Is more preferable.
When the compound represented by the general formula (I) has a divalent linking group represented by the general formula IIIc, at least one of B and C is a divalent linking group represented by the general formula IIIc. It is preferable that at least C is a divalent linking group represented by the general formula IIIc.

  Specific examples of the compound represented by the general formula (I) are given below, but the range of the compound represented by the general formula (I) should not be construed as being limited by these specific examples.

2. TECHNICAL FIELD The present invention relates to a composition of a compound represented by the general formula (I) and a compound represented by the general formula (II).
In a preferred embodiment of the polymerizable liquid crystal composition of the present invention, at least two compounds of the compound represented by the general formula (I) and the compound represented by the general formula (II) and at least one chiral compound are used. It is a polymerizable composition to be contained. In a more preferred embodiment of the polymerizable liquid crystal composition of the present invention, at least one polymerizable liquid crystal compound represented by the general formula (I) and the general formula (II), at least one chiral compound, and polymerization A polymerizable liquid crystal composition containing an initiator. The film formed by fixing the polymerizable liquid crystal composition of this 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 reflects It is useful as a film (for example, an infrared reflecting film).

In the polymerizable liquid crystal composition of the present invention, the compound represented by the general formula (II) may be contained in an amount of 0.1% by mass or more based on the mass of the compound represented by the general formula (I). For example, the compound represented by the general formula (I) has a sufficiently large effect on the suppression of crystal precipitation, but is preferably 0.1 to 10% by mass, more preferably 0.1 to 5% by mass, and still more preferably It is 0.1-3 mass%. However, it is not limited to this range.
In the following, materials that can be used for the polymerizable liquid crystal composition of the present invention, methods for producing polymer materials and films using the polymerizable liquid crystal composition of the present invention, materials used therefor, and uses of the produced films Will be described.

(2-1) Chiral Compound In order to prepare the polymerizable liquid crystal composition of the present invention as a composition showing 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 functional group. When the chiral compound has a polymerizable functional group and the rod-shaped liquid crystal compound used in combination also has a polymerizable functional group, it is derived from the rod-shaped liquid crystal compound by a polymerization reaction of the polymerizable chiral compound and the polymerizable rod-shaped liquid crystal compound. Polymers having repeating units and repeating units derived from chiral compounds can be formed. In this embodiment, the polymerizable functional group possessed by the polymerizable chiral compound is preferably the same type of group as the polymerizable functional group possessed by the polymerizable rod-like liquid crystal compound. Therefore, the polymerizable functional group of the chiral compound is also preferably an unsaturated polymerizable functional group, an epoxy group or an aziridinyl group, more preferably an unsaturated polymerizable functional group, and an ethylenically unsaturated polymerizable functional group. It is particularly preferred that

  The chiral compound in the polymerizable liquid crystal composition of the present invention is used in an amount of 1 to 30 mol with respect to the total of the compound represented by the general formula (I) and the compound represented by the general formula (II). % Is preferred. 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 No. 2003-287623, and can be preferably used in the present invention.

(2-2) Other liquid crystalline compounds The polymerizable liquid crystal composition of the present invention includes one or more other compounds together with the compound represented by the general formula (I) and the compound represented by the general formula (II). A liquid crystal compound may be contained. Since the compound represented by the general formula (II) is highly compatible with other liquid crystal compounds, mixing with other liquid crystal compounds does not cause opacification or the like, and a highly transparent film is formed. It can be formed. Since such a polymerizable liquid crystal composition of the present invention can be used in combination with other liquid crystal compounds, it can provide compositions having various compositions suitable for various applications. 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 compounds include azomethines, azoxys, cyanobiphenyls, cyanophenyl esters, benzoates, cyclohexanecarboxylic acid phenyl esters, cyanophenylcyclohexanes, cyano-substituted phenylpyrimidines, alkoxy-substituted Phenylpyrimidines, phenyldioxanes, tolanes and alkenylcyclohexylbenzonitriles are included. Not only low-molecular liquid crystal compounds but also high-molecular liquid crystal compounds can be used.

Other liquid crystalline compounds that can be used in the present invention may be polymerizable or non-polymerizable. The rod-like liquid crystal compound having no polymerizable functional group is described in various documents (for example, Y. Goto et.al., Mol. Cryst. Liq. Cryst. 1995, Vol. 260, pp. 23-28). is there.
The polymerizable rod-like liquid crystal compound can be obtained by introducing a polymerizable functional group into the rod-like liquid crystal compound. Examples of the polymerizable functional group include an unsaturated polymerizable functional group, an epoxy group, and an aziridinyl group, preferably an unsaturated polymerizable functional group, and particularly preferably an ethylenically unsaturated polymerizable functional group. The polymerizable functional group can be introduced into the molecule of the rod-like liquid crystal compound by various methods. The number of polymerizable functional groups contained in 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. 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.

(2-3) Polymerization initiator The polymerizable liquid crystal 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 to be 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. .

  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).

(2-4) Alignment Control Agent An alignment control agent that contributes to a liquid crystal phase (for example, a cholesteric liquid crystal phase) stably or rapidly may be added to the polymerizable liquid crystal 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 reflectivity is reduced or a fingerprint pattern is generated. This is not preferable because it increases haze and shows diffractive properties.
Examples of the fluorine-containing (meth) acrylate polymer that can be used as the orientation control agent are described in JP-A No. 2007-272185, [0018] to [0043].

  Hereinafter, the following general formulas (X1) to (X3) that can be used as the alignment control agent will be described in order.

In the formula, R ¹⁰¹ , R ¹⁰² and R ¹⁰³ 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 ^{101 to} R ¹⁰³ 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.

In the formula, R represents a substituent, and m1 represents an integer of 0 to 5. When m1 represents an integer of 2 or more, a plurality of R may be the same or different. Preferred substituents for R are the same as those listed as preferred ranges for the substituents represented by R ¹⁰¹ , R ¹⁰² , and R ¹⁰³ . m1 preferably represents an integer of 1 to 3, particularly preferably 2 or 3.

In the formula, R ¹⁰⁴ , R ¹⁰⁵ , R ¹⁰⁶ , R ¹⁰⁷ , R ¹⁰⁸ and R ¹⁰⁹ each independently represent a hydrogen atom or a substituent. The substituents represented by R ¹⁰⁴ , R ¹⁰⁵ , R ¹⁰⁶ , R ¹⁰⁷ , R ¹⁰⁸ and R ¹⁰⁹ are preferably those represented by R ¹⁰¹ , R ¹⁰² and R ¹⁰³ in the general formula (X1). It is the same as that mentioned as a thing.

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.

  The addition amount of the compound represented by any one of the general formulas (X1) to (X3) in the polymerizable liquid crystal composition of the present invention is 0.01 mass of the compound represented by the general formula (I). 10 mass% is preferable, 0.01-5 mass% is more preferable, and 0.02-1 mass% is especially preferable.

(2-5) Other Additives The polymerizable liquid crystal composition of the present invention includes one or more kinds of antioxidants, ultraviolet absorbers, sensitizers, stabilizers, plasticizers, chain transfer agents, and polymerization. Other additives such as inhibitors, antifoaming agents, leveling agents, thickeners, flame retardants, surface active substances, dispersants, dyes, pigments and other coloring materials may be contained.

(2-6) Solvent The form of the polymerizable liquid crystal composition of the present invention is not particularly limited, and the polymerizable liquid crystal composition of the present invention may or may not contain a solvent. The polymerizable liquid crystal composition of the present invention is preferably a composition in which the compound represented by the general formula (I) and the compound represented by the general formula (II) are dissolved in a solvent. Although there is no restriction | limiting in particular as a solvent used for the polymeric liquid crystal composition of this invention, It is using preferably the organic solvent quoted as an organic solvent used for preparation of a coating liquid with the manufacturing method of the polymeric material of this invention mentioned later. it can.

3. Polymer Material and Film (3-1) Polymer Material and Film The present invention also relates to a polymer material and a film produced using the polymerizable liquid crystal composition of the present invention. The polymer material is produced by polymerizing the polymerizable liquid crystal composition of the present invention, and may be liquid crystalline or non-liquid crystalline. The film produced using the polymerizable liquid crystal composition of the present invention preferably exhibits liquid crystallinity, and the liquid crystal film is useful as various optical films such as a phase film and a reflective film. The polymerizable liquid crystal composition of the present invention is useful as a material for various optical films such as a retardation film and a reflective film.

(3-2) Polymer Material and Film Production Method Using Polymerizable Liquid Crystal Composition The method for producing the polymer material of the present invention comprises the polymerizable liquid crystal compound of the present invention or the polymerizable liquid crystal composition of the present invention. It is characterized by including the process to superpose | polymerize. In the method for producing a polymer material of the present invention, the polymerization is preferably performed by irradiating with ultraviolet rays.

An example of a method for producing the polymer material of the present invention and a method for producing the film are as follows:
(I) Applying the polymerizable liquid crystal composition of the present invention to the surface of a substrate or the like to obtain a liquid crystal phase (cholesteric liquid crystal phase or the like)
(Ii) proceeding the curing reaction of the polymerizable liquid crystal composition to fix 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.

In the step (i), first, the polymerizable liquid crystal 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, ketones are more particularly preferable, and methyl ethyl ketone is even more particularly preferable. Two or more organic solvents may be used in combination.

  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.

  Next, the polymerizable liquid crystal composition of the present invention applied to the surface to form a coating film is brought into a liquid crystal phase state such as a cholesteric liquid crystal phase. In an embodiment in which the polymerizable liquid crystal composition of the present invention 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 polymerizable liquid crystal composition of the present invention 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.

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 general formula (I), a suitable polymerization method will be selected. By this polymerization, a polymer having a unit derived from the compound of the general formula (I) of the present invention in the structural unit 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 the said coating film with an ultraviolet-ray, However, It will be determined from the viewpoint of both sufficient intensity | strength and productivity of a cured film.
Since the polymerizable liquid crystal compound represented by the general formula (I) of the present invention hardly deteriorates against ultraviolet rays, excellent liquid crystallinity and durability can be maintained even after irradiation with ultraviolet rays.

  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.

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.

  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.

(3-3) 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.

(3-4) 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.

  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.

(3-5) Use of film of the present invention In one aspect of the film of the present invention, the alignment of the liquid crystal phase (for example, horizontal alignment, vertical alignment, hybrid alignment, etc.) of the polymerizable liquid crystal composition of the present invention is fixed. A film that exhibits 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 liquid crystal composition of the present invention is fixed, and shows selective reflection characteristics with respect to light in a predetermined wavelength range. The film of the present invention preferably exhibits selective reflection characteristics in the infrared wavelength range, and the film showing selective reflection characteristics in the infrared wavelength range (wavelength 800 to 1300 nm) is attached to, for example, a window glass of a building or a vehicle, or It is incorporated in laminated glass and used as a heat shielding member.
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. .

  Hereinafter, the features of the present invention will be described more specifically with reference to examples and comparative examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Accordingly, the scope of the present invention should not be construed as being limited by the specific examples shown below.

<Synthesis of polymerizable liquid crystal compound>
[Synthesis Example 1]
According to the following scheme, a mixture (1: 1) of the polymerizable liquid crystal compound (II-1) and the polymerizable liquid crystal compound (II-41) was synthesized.

ＤＭＦ（２０ｍＬ）と酢酸エチル（３４ｍＬ）の混合溶媒に、Ａ−１（７．２８ｇ、２０ｍｍｏｌ）、炭酸カリウム（１．３８ｇ、１０ｍｍｏｌ）、ＢＨＴ（２２ｍｇ）、４−ＨＢＡのＭｓ化体（４．４４ｇ、２０ｍｍｏｌ）を加えた後、９５℃で３時間反応させた。室温に戻し、水（６２ｍＬ）を加え、分液操作を行った。１規定塩酸（４１ｍＬ）を有機層に加え、分液操作を行った後、エバポレーターで溶媒を留去した。カラムクロマトグラフィー（ジクロロメタン／酢酸エチル＝２０：１）で精製し、Ｂ−１を２．５８ｇ（５．２６ｍｍｏｌ、５３％）得た。次に、ＴＨＦ溶媒（３ｍＬ）に、メタンスルホニルクロリド（０．４３ｍＬ，５．５２ｍｍｏｌ）とＢＨＴ（１５ｍｇ）を加え、−５℃に冷却した。そこへ、Ｃ−１（１．４６ｇ、５．５２ｍｍｏｌ）とジイソプロピルエチルアミン（１．０１ｍＬ、５．７９ｍＬ）のＴＨＦ溶液（３ｍＬ）を加えた。−５℃で３０分撹拌した後、Ｂ−１（２．５８ｇ、５．２６ｍｍｏｌ）、ジイソプロピルエチルアミン（１．０１ｍＬ、５．７９ｍＬ）、ＤＭＡＰ（スパチュラ一杯）のＴＨＦ溶液（３．３ｍＬ）を加えた。室温で１時間反応させた後、メタノール（５０ｍＬ）を加え反応を停止した。水（５０ｍＬ）とクロロホルム（５０ｍＬ）を加え、分液操作を行った。有機層を濾紙でろ過した後、エバポレーターで溶媒を留去した。得られた固体を、酢酸エチルとメタノールで再結晶することによって、重合性液晶化合物（ＩＩ−１）と重合性液晶化合物（ＩＩ−４１）の混合物（１：１）を２．８７ｇ（３．９０ｍｍｏｌ、７４％）得た。
¹Ｈ−ＮＭＲ（溶媒：ＤＭＳＯ−Ｄ６）δ（ｐｐｍ）：０．７−０．９（ｍ，８Ｈ）, ３．１４（ｓ、１．５Ｈ）、３．１６（ｓ、１．５Ｈ）、４．１−４．２（ｍ、８Ｈ）、５．９（ｄ，２Ｈ）, ６．２（ｄｄ，２Ｈ）, ６．３（ｄ，２Ｈ）, ７．１−８．３（ｍ，１５Ｈ）

To a mixed solvent of DMF (20 mL) and ethyl acetate (34 mL), A-1 (7.28 g, 20 mmol), potassium carbonate (1.38 g, 10 mmol), BHT (22 mg), 4-HBA Ms compound (4 .44 g, 20 mmol) was added, followed by reaction at 95 ° C. for 3 hours. It returned to room temperature, water (62 mL) was added, and liquid separation operation was performed. 1N hydrochloric acid (41 mL) was added to the organic layer, and after performing a liquid separation operation, the solvent was distilled off with an evaporator. Purification by column chromatography (dichloromethane / ethyl acetate = 20: 1) gave 2.58 g (5.26 mmol, 53%) of B-1. Next, methanesulfonyl chloride (0.43 mL, 5.52 mmol) and BHT (15 mg) were added to a THF solvent (3 mL), and the mixture was cooled to −5 ° C. Thereto was added a THF solution (3 mL) of C-1 (1.46 g, 5.52 mmol) and diisopropylethylamine (1.01 mL, 5.79 mL). After stirring at −5 ° C. for 30 minutes, a THF solution (3.3 mL) of B-1 (2.58 g, 5.26 mmol), diisopropylethylamine (1.01 mL, 5.79 mL), DMAP (full of spatula) was added. It was. After reacting at room temperature for 1 hour, methanol (50 mL) was added to stop the reaction. Water (50 mL) and chloroform (50 mL) were added, and liquid separation operation was performed. The organic layer was filtered with a filter paper, and then the solvent was distilled off with an evaporator. The obtained solid was recrystallized from ethyl acetate and methanol to obtain 2.87 g (3. 3. 1 g) of a mixture (1: 1) of the polymerizable liquid crystal compound (II-1) and the polymerizable liquid crystal compound (II-41). 90 mmol, 74%).
¹ H-NMR (solvent: DMSO-D6) δ (ppm): 0.7-0.9 (m, 8H), 3.14 (s, 1.5H), 3.16 (s, 1.5H) 4.1-4.2 (m, 8H), 5.9 (d, 2H), 6.2 (dd, 2H), 6.3 (d, 2H), 7.1-8.3 (m , 15H)

[Example 1]
<Preparation of polymerizable composition>
Using the mixture (1: 1) of the polymerizable liquid crystal compound (II-1) and the polymerizable liquid crystal compound (II-41) synthesized in Synthesis Example 1, a liquid crystal composition (1) having the following composition was prepared. .
Polymerizable liquid crystal compound (I-1) 99 mass parts Polymerizable liquid crystal compound (II-1) 0.5 mass parts Polymerizable liquid crystal compound (II-41) 0.5 mass parts (polymerizable liquid crystal compound (II-1) And 1 part by mass of a mixture (1: 1) of polymerizable liquid crystal compound (II-41))
MEK 233 parts by mass

<Manufacture of film>
Next, the film of Example 1 was manufactured using the obtained liquid crystalline composition (1).
A polyimide alignment film SE-130 manufactured by Nissan Chemical Industries, Ltd. was applied onto the cleaned glass substrate by a spin coating method, dried and then baked at 250 ° C. for 1 hour. This was rubbed to produce a substrate with an alignment film. On the rubbing-treated surface of the alignment film of this substrate, the liquid crystalline composition coating liquid (1) was applied at room temperature by a spin coating method and allowed to stand at room temperature for 30 minutes.

<Evaluation of crystal precipitation suppression>
Using a polarizing microscope, the crystal deposition rate of an arbitrary region on the surface of the liquid crystal film of the obtained film of Example 1 was measured and found to be 5%.

[Examples 2 to 5 and Comparative Examples 1 to 5]
A mixture (1: 1) of the polymerizable liquid crystal compound (II-1) and the polymerizable liquid crystal compound (II-41) used in Example 2 was converted into the compound (I-1) at the ratio described in Table 1 below. After mixing, a liquid crystal composition coating solution was prepared in the same manner as in Example 1, and films of Examples 2 to 5 were produced. The crystal precipitation rate of the obtained film was measured. The results were as shown in Table 1 below.
A liquid crystal composition coating solution was prepared by the same method as in Example 1 except that the mixture of the polymerizable liquid crystal compound (II-1) and the polymerizable liquid crystal compound (II-41) was not used, and the film of Comparative Example 1 was produced. did. The crystal precipitation rate of the obtained film was measured. The results are shown in Comparative Example 1 in Table 1 below.
Further, in place of the mixture of the polymerizable liquid crystal compound (II-1) and the polymerizable liquid crystal compound (II-41), compounds (III-1) to (III-4) were used in the same manner as in Example 1. A liquid crystal composition coating solution was prepared, and films of Comparative Examples 2 to 5 were produced. The crystal precipitation rate of the obtained film was measured. The results are shown in Comparative Examples 2 to 5 in Table 1 below.

From the results of Examples 1 to 5, it was found that crystal precipitation can be suppressed by adding the polymerizable liquid crystal compound (II) to the polymerizable liquid crystal compound (I). Moreover, it was shown that the addition amount of the polymerizable liquid crystal compound (II) is preferably 1 to 10 parts by mass with respect to the polymerizable liquid crystal compound (I).
On the other hand, it was found from the results of Comparative Example 1 that the problem of crystal precipitation occurred when the polymerizable liquid crystal compound (I) was used alone. In addition, the results of Comparative Examples 2 to 5 indicate that the conventional polymerizable liquid crystal compound cannot suppress the crystal precipitation of the polymerizable liquid crystal compound (I) like the polymerizable liquid crystal compound (II).

[Example 11]
Using the polymerizable liquid crystal compound (I-1) and the mixture (1: 1) of the polymerizable liquid crystal compound (II-1) synthesized in Synthesis Example 1 and the polymerizable liquid crystal compound (II-41), the following composition: A liquid crystal composition (2) was prepared.
Polymerizable liquid crystal compound (I-1) 99 mass parts Polymerizable liquid crystal compound (II-1) 0.5 mass parts Polymerizable liquid crystal compound (II-41) 0.5 mass parts (polymerizable liquid crystal compound (II-1) And 1 part by mass of a mixture (1: 1) of polymerizable liquid crystal compound (II-41))
Chiral agent Paliocolor LC756 (manufactured by BASF) 3 parts by mass Air interface alignment agent (X1-1) 0.04 parts by mass Polymerization initiator IRGACURE819 (manufactured by Ciba Japan) 3 parts by mass Solvent chloroform 300 parts by mass

After applying the liquid crystalline composition coating liquid (2) to the alignment film surface of the alignment film substrate manufactured in the same manner as in Example 1 at room temperature by spin coating, and performing alignment aging at 120 ° C. for 3 minutes, The orientation 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 at room temperature, and a film having selective reflection characteristics of Example 11 was obtained. During the period after application and before heating, no crystal deposition was observed in the coating film.
When the obtained film showing selective reflection characteristics was observed with a polarizing microscope, it was confirmed that there was no alignment defect and the film was uniformly aligned. Further, 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.

[Examples 12 and 13]
5% by mass of a mixture (1: 1) of the polymerizable liquid crystal compound (II-1) and the polymerizable liquid crystal compound (II-41) synthesized in Synthesis Example 1 with respect to the polymerizable liquid crystal compound (I-1), The liquid crystal composition coating solutions used in Examples 12 and 13 were prepared in the same manner as Example 11 except that 10% by mass was added. Using these coating solutions, films showing the selective reflection characteristics of Examples 12 and 13 were formed in the same manner as Example 11. Any of these films exhibiting selective reflection characteristics exhibited good orientation. Further, when the transmission spectrum was measured with a spectrophotometer UV-3100PC, there was a selective reflection peak in the infrared region.

Claims (13)

A polymerizable liquid crystal composition comprising a compound represented by the following general formula (I) and a compound represented by the following general formula (II).
Formula (I)

[In General Formulas (I) and (II), P independently represents a polymerizable functional group represented by any one of the following General Formulas (P-1) to (P-5), and Sp represents each independently Represents a divalent linking group or a single bond represented by the following general formula (Sp-1), and A, B, C, D, E, F and G are independently represented by the following general formulas IIIa, IIIb and IIIc: Represents a selected divalent linking group. However, at least two of D, E, F and G represent a divalent linking group represented by the following general formula IIIa or general formula IIIb.

(In the general formulas (P-1) to (P-5), R ^{11 to} R ¹³ each independently represents a hydrogen atom or a methyl group.)

(In the general formula (Sp-1), R ⁴¹ represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, or a substituted or unsubstituted alkynylene group. Z ⁴¹ represents —O—, — S -, - CO -, - CO-O -, - O-CO -, - S-CO -, - CO-S -, - O-CO-O -, - CO-NR 51 -, - NR 51 - CO—, —CR ⁵¹ ═N—, —N═CR ⁵¹ — or a single bond (R ⁵¹ represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms), m is any one of 1-6. When m is an integer of 2 or more, the plurality of R ⁴¹ present in the general formula (Sp-1) may be the same or different from each other, and the general formula (Sp-1) And a plurality of Z ⁴¹ existing therein may be the same as or different from each other.)

(In the general formulas IIIa, IIIb and IIIc, R ^a , R ^b and R ^c each independently represent a substituent, and na, nb and nc each independently represent an integer of 0 to 4. na, nb and nc are When each is an integer of 2 or more, a plurality of R ^a , R ^b and R ^c may be the same or different.)]   2. The polymerizable liquid crystal composition according to claim 1, comprising 0.1 to 10% by mass of the compound represented by the general formula (II) with respect to the compound represented by the general formula (I). .   The polymerizable liquid crystal composition according to claim 1, comprising 0.1 to 5% by mass of the compound represented by the general formula (II) with respect to the compound represented by the general formula (I). .   Furthermore, at least 1 sort (s) of polymerization initiator is contained, The polymeric liquid crystal composition as described in any one of Claims 1-3 characterized by the above-mentioned.   Furthermore, at least 1 sort (s) of chiral compound is contained, The polymeric liquid crystal composition as described in any one of Claims 1-4 characterized by the above-mentioned.   The manufacturing method of the polymeric material characterized by including the process of superposing | polymerizing the polymeric liquid crystal composition as described in any one of Claims 1-5.   The method for producing a polymer material according to claim 6, wherein the polymerization is performed by irradiating ultraviolet rays.   A polymer material obtained by polymerizing the polymerizable liquid crystal composition according to claim 1.   A film comprising at least one polymer material according to claim 8.   A film formed by fixing a cholesteric liquid crystal phase of the polymerizable liquid crystal composition according to claim 5.   The film according to claim 9 or 10, which exhibits optical anisotropy.   The film according to claim 9, wherein the film exhibits selective reflection characteristics.   The film according to any one of claims 9 to 12, which exhibits selective reflection characteristics in an infrared wavelength region.