JP5093443B2 - Method for reversibly controlling self-assembled polymer film and self-assembled polymer film material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for reversibly controlling a self-organizing polymer film which reversibly controls the conjugated state and/or the optical property of a polymer chain and/or a polymer assembly and/or circular dichroism. <P>SOLUTION: The method of reversibly controlling a self-organizing polymer film comprises imparting at least one stimulus selected from the group consisting of contact with a solvent, heat, pressure, stretching, light, magnetic field and electric field to a polymer film whose polymer chain has a spiral structure to allow the spiral direction to change or to reversibly change and allowing at least one property selected from the group consisting of the spiral pitch, the spiral structure, the crystal structure of the polymer, and the molecular orientation of the polymer to change or to reversibly change at least one of the above properties to reversibly control the conjugated state and/or the optical properties of the polymer chain and/or the polymer assembly and/or circular dichroism. <P>COPYRIGHT: (C)2008,JPO&amp;INPIT

Description

The present invention relates to a reversible control method and polymeric film material of the polymer the polymer chains have a helical structure.

  Conventionally, polyacetylenes are known to exhibit excellent conductivity when doped, but cis- and trans-isomers exist through the double bond of the polymer main chain, and heat, pressure, electromagnetic waves are present. It is also known that cis-trans isomerization occurs due to stimulation such as light, radiation, or magnetic field, resulting in a change in absorption spectrum or color (for example, Patent Documents 1 to 3, Non-Patent Documents 1 and 2). reference). Utilizing such properties, polyacetylenes are used in various applications such as conductive materials, variable color materials, nonlinear optical materials, magnetic materials, and pressure sensitive materials.

  In addition, studies on polyacetylene substitution products having a stable helical structure have been conducted in recent years, and optically active polyacetylene substitution products in which an asymmetric carbon is introduced into the structure of the polyacetylene substitution product to give optical rotation have a spiral in a certain direction. It is known that it is wound regularly and changes in the helical structure such as reversal of the direction of winding of the spiral and amplification of the number of turns of the spiral can be controlled by stimulation such as heat as described above (for example, Non-Patent Document 3, (See Patent Document 4).

However, although the color change and spiral inversion of optically active polyacetylenes in solution have been reported, the movement of molecules is suppressed in the solid state and film state, so the color change is not renewed by external stimulation. It was not possible to control the formation of the structure or the winding direction of the helix.
The alignment film is useful for electronic materials, optical materials, and the like, and polysilane alignment films are known (see, for example, Patent Document 5 and Non-Patent Document 4).
Thus, although polyacetylenes show an interesting characteristic, since they have a hard and brittle property, even if a film is formed, the film is broken when stretched, and an alignment film of polyacetylenes cannot be obtained.
JP 2004-161835 A JP 2004-256690 A JP 2004-300394 A JP 2004-155929 A Japanese Patent No. 2535780 “Polymer Processing”, 2001, Vol. 50, No. 5, p. 221-223 “Macromolecule”, 2001, Vol. 34, No. 11, p. 3776-3782 “J. Am. Chem. Soc.”, 2001, Vol. 123, p. 8159-8160 “Polymer”, 1999, Vol. 40, p. 5857

The present invention, by external loads such as stretching, by reversibly changing the Lula plugs structure like Yusuke helical polymer chains, reversible control method for reversibly controlling the conjugated state of the helical polymer chains And its controlled self-assembled polymer film material.

The present inventors have result of intensive studies, the external load such as stretching, by reversibly changing the characteristics of Lula Sen構forming such Yusuke helical polymer chain, conjugated state of the helical polymer chains found that can reversibly control the like.
Further, the present inventors found that by forming the polymer film of predetermined polyacetylene substituents on the supporting film such as polypropylene, this film was also found that changes color when stretched.
Furthermore, it has been found that an optically active polyacetylene derivative having a predetermined structure can simultaneously perform color change, formation of a new helical structure, and control of the spiral winding direction even in a solid state or a film state. The present invention has been made based on such findings.

（式中、ｎは１０以上の整数、Ｒは芳香族又は脂肪族基を表す。）
（２）前記一般式（１）が下記一般式（２）で表されることを特徴とする（１）に記載の自己組織化ポリマー膜の可逆的制御方法。

（式中、ｎは１０以上の整数であり、Ｘ₁、Ｘ₂およびＸ₃はそれぞれ独立に水素原子または置換基を表す。ただし、Ｘ₁、Ｘ₂およびＸ₃のうち少なくともひとつは置換基を表す。）
（３）前記一般式（１）が下記一般式（３）で表されることを特徴とする（１）又は（２）に記載の自己組織化ポリマー膜の可逆的制御方法。

（式中、ｎは１０以上の整数であり、Ｘは水素原子または置換基を表す。）
（４）前記一般式（３）のＸが、１つ以上の不斉炭素を含みかつ該不斉炭素にＯＨ基が置換した、炭素数２〜１０のアルキル基又はアルコキシ基である（３）に記載の自己組織化ポリマー膜の可逆的制御方法。
（５）延伸可能な支持膜上に前記ポリマー膜を設け、これを延伸又は収縮し或いは張力を変化させて、前記可逆的な制御を行うことを特徴とする（１）〜（４）のいずれか１項に記載の自己組織化ポリマー膜の可逆的制御方法。
（６）下記一般式（１）で表されるポリマー分子鎖がシス体に制御されたらせん構造を有するポリマーからなる自己組織化ポリマー膜材であって、
該膜材の延伸、収縮又は張力の有無により、シス型に制御されたらせん構造状態を維持しながら前記ポリマー分子鎖のらせん構造及び／又は前記ポリマー分子の結晶構造を可逆的に変化させ、前記ポリマー分子鎖ないしはポリマー集合体の共役及び／又は膜の色彩を、膜の形状を保ったまま可逆的に制御するための自己組織化ポリマー膜材。

（式中、ｎは１０以上の整数、Ｒは芳香族又は脂肪族基を表す。）
（７）前記一般式（１）が下記一般式（２）で表されることを特徴とする（６）に記載の自己組織化ポリマー膜材。

（式中、ｎは１０以上の整数であり、Ｘ₁、Ｘ₂およびＸ₃はそれぞれ独立に水素原子または置換基を表す。ただし、Ｘ₁、Ｘ₂およびＸ₃のうち少なくともひとつは置換基を表す。）
（８）前記一般式（１）が下記一般式（３）で表されることを特徴とする（６）又は（７）に記載の自己組織化ポリマー膜材。

（式中、ｎは１０以上の整数であり、Ｘは水素原子または置換基を表す。）
（９）支持膜として、ポリエチレン、ポリプロピレン、ポリビニルアルコール、及びポリメタクリル酸メチルからなる群から得らればれる材料からなるものを適用したことを特徴とする（６）〜（８）のいずれか１項に記載の自己組織化ポリマー膜材。
（１０）ポリマー膜材の厚さが０．０１μｍ〜１ｍｍであることを特徴とする（６）〜（９）のいずれか１項に記載の自己組織化ポリマー膜材。
That is, the present invention
(1) Spiral controlled to a cis type by the presence or absence of stretching, shrinkage or tension on a film made of a polymer having a helical structure in which the polymer molecular chain represented by the following general formula (1) is controlled to a cis isomer. While maintaining the structural state, the helical structure of the polymer molecular chain and / or the crystal structure of the polymer molecule are reversibly changed, and the conjugation of the polymer molecular chain or polymer aggregate and / or the color of the film are changed to the shape of the film. Reversible control method of self-assembled polymer film that reversibly controls while maintaining

(In the formula, n represents an integer of 10 or more, and R represents an aromatic or aliphatic group.)
(2) The reversible control method for a self-assembled polymer film according to (1), wherein the general formula (1) is represented by the following general formula (2).

(In the formula, n is an integer of 10 or more, and X ₁ , X ₂ and X ₃ each independently represent a hydrogen atom or a substituent. However, at least one of X ₁ , X ₂ and X ₃ is a substituent. Represents.)
(3) The method for reversibly controlling a self-assembled polymer film according to (1) or (2), wherein the general formula (1) is represented by the following general formula (3).

(In the formula, n is an integer of 10 or more, and X represents a hydrogen atom or a substituent.)
(4) X in the general formula (3) is an alkyl group or alkoxy group having 2 to 10 carbon atoms, which contains one or more asymmetric carbon atoms and is substituted with an OH group. A method for reversibly controlling a self-assembled polymer film according to claim 1.
(5) Any one of (1) to (4), wherein the polymer film is provided on a stretchable support film, and the reversible control is performed by stretching or shrinking the polymer film or changing the tension. 2. A method for reversibly controlling a self-assembled polymer film according to claim 1.
(6) A self-assembled polymer film material composed of a polymer having a helical structure in which a polymer molecular chain represented by the following general formula (1) is controlled in a cis form,
By reversibly changing the helical structure of the polymer molecular chain and / or the crystal structure of the polymer molecule while maintaining a helical structure state controlled in a cis-type by the presence or absence of stretching, shrinkage or tension of the film material, A self-assembled polymer film material for reversibly controlling the conjugation of polymer molecular chains or polymer aggregates and / or the color of the film while maintaining the shape of the film.

(In the formula, n represents an integer of 10 or more, and R represents an aromatic or aliphatic group.)
(7) The self-assembled polymer film material according to (6), wherein the general formula (1) is represented by the following general formula (2).

(In the formula, n is an integer of 10 or more, and X ₁ , X ₂ and X ₃ each independently represent a hydrogen atom or a substituent. However, at least one of X ₁ , X ₂ and X ₃ is a substituent. Represents.)
(8) The self-organized polymer film material according to (6) or (7), wherein the general formula (1) is represented by the following general formula (3).

(In the formula, n is an integer of 10 or more, and X represents a hydrogen atom or a substituent.)
( 9 ) Any one of (6) to (8), wherein the support film is made of a material obtained from the group consisting of polyethylene, polypropylene, polyvinyl alcohol, and polymethyl methacrylate. The self-assembled polymer film material described in 1.
( 10 ) The self-assembled polymer film material according to any one of (6) to ( 9 ), wherein the polymer film material has a thickness of 0.01 μm to 1 mm.

The present invention can provide a variety of electronic and optical devices based conjugated state like your reversibly system.
The substituted polyacetylene film of the present invention has a characteristic that the color and conjugated structure change when stretched and oriented, and can be used for various sensors by utilizing the change of the color and conjugated structure.
In the optically active polymer of the present invention, the conjugation, the helical pitch, the direction of the helix and the like are changed by an external stimulus even in a solid state or a film state. Thereby, control of the color etc. in a polymer can be performed simultaneously. These can be used for various applications such as optical devices, optical memories, optical resolution agents, liquid crystals, and nonlinear optical materials.

First, the “reversible control method” of the present invention will be described.
According to the reversible control method of the present invention, at least one of external loads is imparted to a polymer having a polymer molecular chain having a helical structure, and the helical direction, helical pitch, helical structure, crystal structure, and orientation of the polymer molecular chain are determined. By reversibly or irreversibly changing at least two of the properties of the polymer chain selected, the conjugated state, optical properties and / or circular dichroism of the polymer molecular chain or polymer assembly are reversible. It is a general term for irreversible control.
In the present specification , the “helical structure” means that the polymer chain has a helical diameter, a helical pitch, and a helical continuous length within the following numerical ranges.
The helical diameter of the polymer molecular chain is 50 nm or less, preferably 0.1 to 50 nm, and more preferably 0.5 to 10 nm.
The helical pitch of the polymer molecular chain is 50 nm or less, preferably 0.1 to 50 nm, and more preferably 0.5 to 10 nm.
The helical continuous length of the polymer molecular chain is 10 nm or more, preferably 50 nm or more, and more preferably 50 nm to 500 nm.

In this specification , the “spiral direction” refers to either a right-handed direction or a left-handed direction. “Changing the spiral direction” means changing the right-handed direction from the right-handed direction or the left-handed direction to the right-handed direction. The numerical value of circular dichroism varies depending on the film thickness and packing state of the molecule. For example, in the case of a one-helix spiral using a film having a maximum absorbance of about 1 in the visible region, the numerical range of circular dichroism is 1. ˜500 mdeg, preferably 5 to 100 mdeg, and in the case of a reverse spiral, −1 to −500 mdeg, preferably −5 to −100 mdeg.
In this specification , the “spiral pitch” refers to the distance between both units when the polymer helix rotates once. Specific examples of changing the helical pitch include, for example, changing from 1.8 nm to 2.5 nm, changing from 2.5 nm to 1.8 nm, and the like. Changes in the helical pitch can be measured by direct observation with an electron microscope or the like.
In the present specification , the “crystal structure” refers to a higher order structure such as a columnar structure having a certain distance between helical axes. Specific examples of changing the crystal structure include, for example, changing from an amorphous structure to a columnar structure, changing from a columnar structure to an amorphous structure, and the like. Changes in the crystal structure can be measured by wide angle X-ray scattering.
In the present specification , “molecular orientation of polymer” refers to a structure in which the helical axis of a molecule has a certain direction. Specific examples of changing the molecular orientation of the polymer include, for example, changing from non-oriented to uniaxial orientation, changing from uniaxial orientation to non-oriented, and the like. The change in the molecular orientation of the polymer is as follows. In the polarized UV spectrum, the non-oriented orientation is constant regardless of the orientation of the film and the dichroic ratio is 1. The absorption of polarized light is reduced and is measured as an increase in dichroic ratio.

Examples of the stimulation include contact with a solvent, heat, pressure, stretching, light, a magnetic field, and an electric field. Contact with the solvent, heat, and stretching are preferable, and contact with a solvent and heat are more preferable.
Specific treatment conditions for each of the stimuli are not particularly limited, and examples thereof include the following conditions.
With regard to “contact with solvent”, for example, any polymer such as chloroform, toluene, tetrahydrofuran, or the vapor thereof can be treated with a polymer having a helical structure in the polymer molecular chain under temperature and time conditions appropriately selected. .
Examples of the “heat” treatment include heat treatment of a polymer having a helical structure in the polymer molecular chain at 50 to 300 ° C., preferably 50 to 200 ° C.
As for the “pressure” treatment, for example, the polymer molecular chain is treated with a polymer having a helical structure at 1 to 100 kPa, preferably 5 to 20 kPa.
Regarding the “stretching” treatment, the conditions and methods are described in detail later.
As for the “light” treatment, for example, the polymer molecular chain is treated with a polymer having a helical structure with a light amount of 100 mJ to 100,000 mJ, preferably 500 mJ to 10,000 mJ.
As for the “magnetic field” treatment, for example, the polymer molecular chain is treated with a polymer having a helical structure at 0.1T to 10T, preferably 1T to 10T.
Regarding the “electric field” treatment, for example, the polymer molecular chain is treated with a polymer having a helical structure at 0.01 MV / cm to 10 MV / cm, preferably 0.1 MV / cm to 1 MV / cm.
In reversible control method, (1) and the helical direction, (2) the helical pitch, the helical structure, reversibly or irreversibly change at least one property selected from the molecular orientation of the crystal structure and the polymer of the polymer It is more preferable to change (1) the helical direction and (2) at least one characteristic selected from the helical pitch and the crystal structure of the polymer, and (1) the helical direction and (2) the helical pitch Is more preferable.
“Polymer aggregate” refers to an aggregate composed of two or more polymer molecules.
By applying the external load, in the conjugate state, for example, the absorption maximum can be changed from 400 nm to 500 nm, or can be changed from 500 nm to 400 nm.
For example, the optical properties can change the color of the polymer film from yellow to red, and the optical rotation can change from positive to negative. For example, changing the optical rotation of the film from positive to negative, or changing from negative to positive means that the optical rotation of the film changes and reverses.

In the present specification , the “self-assembled polymer” refers to a polymer that can change the higher-order structure of a molecule by an external stimulus.

Polymer material of the present invention is preferably a self-assembled polymer films, the polymers the polymer molecular chains having a helical structure, wherein the at least one by applying stimulation, Sen Luo structure and / or polymer crystal structure the by reversibly changing, Ru bovine reversibly control the conjugated state of the polymer chains or polymer aggregates.
Polymer material of the present invention can reversibly alter the crystal structure of Sen Luo structure and / or polymers.
Specific examples of the configuration example of the polymer material include a film including particles, fine particles, powder, and / or a substrate, and a self-supporting film.
Specific examples of the film including particles, fine particles, powder, and / or a substrate include a spin coat film.
Specific examples of the self-supporting film include a cast film.
The polymer material can be used as various electronic / optical devices.
Specific examples of the electronic / optical device include an optical memory element and a molecular memory element.
Next, the need use reversible control method of the present invention will be described "polymer where the polymer chain is represented by the following general formula having a helical structure (I)".

(In the formula, n represents an integer of 10 or more, and R represents an aromatic or aliphatic group.)
In the compounds used in the present invention, when a specific moiety is referred to as a “group”, the moiety is substituted with one or more (up to the maximum possible) substituents even if the group itself is not substituted. Means that may have been. For example, “alkyl group” means a substituted or unsubstituted alkyl group. In addition, the “substituent” that the group in the present invention may have includes any substituent.

  The substituent is not particularly limited, and examples thereof include halogen atoms, alkyl groups (including cycloalkyl groups, bicycloalkyl groups, and tricycloalkyl groups), alkenyl groups (including cycloalkenyl groups and bicycloalkenyl groups), and alkynyls. Group)], aryl group, heterocyclic group (also referred to as heterocyclic group), cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy Group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (including anilino group), ammonio group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoyla Group, alkyl or arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl or arylsulfinyl group, alkyl or arylsulfonyl group, acyl group, alkoxycarbonyl group, aryl Oxycarbonyl group, carbamoyl group, aryl or heterocyclic azo group, imide group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, phospho group, silyl group, hydrazino group, ureido group, other known Substituents are mentioned as examples.

  More specifically, the substituent represents a halogen atom (for example, fluorine, chlorine, bromine, iodine), an alkyl group [a linear, branched, or cyclic substituted or unsubstituted alkyl group. They are alkyl groups (preferably alkyl groups having 1 to 30 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, eicosyl, 2-chloroethyl, 2-cyanoethyl, 2-ethylhexyl). A cycloalkyl group (preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, such as cyclohexyl, cyclopentyl, 4-n-dodecylcyclohexyl), a bicycloalkyl group (preferably a substituted or unsubstituted group having 5 to 30 carbon atoms). Substituted bicycloalkyl groups such as bicyclo [1.2.2] heptan-2-yl, bicyclo [2.2.2] octan-3-yl), and tricyclo structures with many ring structures are also included. . An alkyl group (for example, an alkyl group of an alkylthio group) in the substituent described below includes the following alkenyl group, cycloalkenyl group, bicycloalkenyl group, alkynyl group and the like in addition to the above-described alkyl group. ], An alkenyl group [represents a linear, branched or cyclic substituted or unsubstituted alkenyl group. They are alkenyl groups (preferably substituted or unsubstituted alkenyl groups having 2 to 30 carbon atoms such as vinyl, allyl, prenyl, geranyl, oleyl), cycloalkenyl groups (preferably substituted or unsubstituted groups having 3 to 30 carbon atoms). Cycloalkenyl groups, such as 2-cyclopenten-1-yl, 2-cyclohexen-1-yl), bicycloalkenyl groups (substituted or unsubstituted bicycloalkenyl groups, preferably substituted or unsubstituted bicycloalkenyl having 5 to 30 carbon atoms) Groups such as bicyclo [2.2.1] hept-2-en-1-yl, bicyclo [2.2.2] oct-2-en-4-yl). An alkynyl group (preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, such as ethynyl, propargyl, trimethylsilylethynyl group), an aryl group (preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, For example, phenyl, p-tolyl, naphthyl, m-chlorophenyl, o-hexadecanoylaminophenyl), a heterocyclic group (preferably a 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic compound A monovalent group obtained by removing one hydrogen atom, more preferably a 5- to 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms, such as 2-furyl, 2-thienyl, 2-pyrimidinyl, 2- Benzothiazolyl, or a cationic heterocyclic group such as 1-methyl-2-pyridinio and 1-methyl-2-quinolinio),

A cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkoxy group (preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms such as methoxy, ethoxy, isopropoxy, t-butoxy, n-octyloxy, 2- Methoxyethoxy), aryloxy groups (preferably substituted or unsubstituted aryloxy groups having 6 to 30 carbon atoms, such as phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 2-tetradecanoyl Aminophenoxy), silyloxy groups (preferably silyloxy groups having 3 to 20 carbon atoms such as trimethylsilyloxy, t-butyldimethylsilyloxy), heterocyclic oxy groups (preferably substituted or unsubstituted heterocycles having 2 to 30 carbon atoms) Oxy groups such as 1-phenyltetrazo Ru-5-oxy, 2-tetrahydropyranyloxy), acyloxy group (preferably formyloxy group, substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, substituted or unsubstituted group having 6 to 30 carbon atoms) Arylcarbonyloxy groups such as formyloxy, acetyloxy, pivaloyloxy, stearoyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy), carbamoyloxy groups (preferably substituted or unsubstituted carbamoyloxy groups having 1 to 30 carbon atoms such as N, N-dimethylcarbamoyloxy, N, N-diethylcarbamoyloxy, morpholinocarbonyloxy, N, N-di-n-octylaminocarbonyloxy, Nn-octylcarbamoyloxy), alkoxycarbonyloxy (Preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms, such as methoxycarbonyloxy, ethoxycarbonyloxy, t-butoxycarbonyloxy, n-octyloxycarbonyloxy), aryloxycarbonyloxy group (preferably carbon A substituted or unsubstituted aryloxycarbonyloxy group of formula 7-30, such as phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy, pn-hexadecyloxyphenoxycarbonyloxy),

An amino group (preferably an amino group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted anilino group having 6 to 30 carbon atoms, such as amino, methylamino, dimethylamino, anilino, N- Methylanilino, diphenylamino), ammonio group (preferably ammonio group, substituted or unsubstituted alkyl having 1 to 30 carbon atoms, aryl, heterocyclic group substituted ammonio group such as trimethylammonio, triethylammonio, diphenylmethylammonio ), An acylamino group (preferably a formylamino group, a substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms, such as formylamino, acetylamino, Pivaloylamino, Lauro Ruamino, benzoylamino, 3,4,5-tri-n-octyloxyphenylcarbonylamino), aminocarbonylamino group (preferably a substituted or unsubstituted aminocarbonylamino group having 1 to 30 carbon atoms such as carbamoylamino, N , N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino), alkoxycarbonylamino group (preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms such as methoxycarbonylamino, ethoxycarbonyl Amino, t-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methylmethoxycarbonylamino), aryloxycarbonylamino group (preferably having 7 to 30 carbon atoms) Is an unsubstituted aryloxycarbonylamino group such as phenoxycarbonylamino, p-chlorophenoxycarbonylamino, m- (n-octyloxyphenoxycarbonylamino)), a sulfamoylamino group (preferably substituted with 0 to 30 carbon atoms). Or an unsubstituted sulfamoylamino group such as sulfamoylamino, N, N-dimethylaminosulfonylamino, Nn-octylaminosulfonylamino), alkyl or arylsulfonylamino group (preferably having 1 to 30 carbon atoms) Substituted or unsubstituted alkylsulfonylamino group, substituted or unsubstituted arylsulfonylamino group having 6 to 30 carbon atoms, such as methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino, 2,3,5-trichlorophenyls Sulfonylamino, p-methylphenylsulfonylamino),

A mercapto group, an alkylthio group (preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, such as methylthio, ethylthio, n-hexadecylthio), an arylthio group (preferably a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms) , For example, phenylthio, p-chlorophenylthio, m-methoxyphenylthio), a heterocyclic thio group (preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms, such as 2-benzothiazolylthio, 1-phenyl Tetrazol-5-ylthio), a sulfamoyl group (preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms, such as N-ethylsulfamoyl, N- (3-dodecyloxypropyl) sulfamoyl, N, N-dimethyl Sulfamoyl, N-acetylsulfamoy N-benzoylsulfamoyl, N- (N′-phenylcarbamoyl) sulfamoyl), a sulfo group, an alkyl or arylsulfinyl group (preferably a substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms, 6 to 30 A substituted or unsubstituted arylsulfinyl group such as methylsulfinyl, ethylsulfinyl, phenylsulfinyl, p-methylphenylsulfinyl), an alkyl or arylsulfonyl group (preferably a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms, 6 To 30 substituted or unsubstituted arylsulfonyl group such as methylsulfonyl, ethylsulfonyl, phenylsulfonyl, p-methylphenylsulfonyl), acyl group (preferably formyl group, substituted or unsubstituted acetyl group having 2 to 30 carbon atoms). A kill carbonyl group, a substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, a heterocyclic carbonyl group bonded to the carbonyl group with a substituted or unsubstituted carbon atom having 4 to 30 carbon atoms, such as acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, pn-octyloxyphenylcarbonyl, 2-pyridylcarbonyl, 2-furylcarbonyl), an aryloxycarbonyl group (preferably a substituted or unsubstituted aryloxycarbonyl having 7 to 30 carbon atoms) Groups such as phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, pt-butylphenoxycarbonyl), alkoxycarbonyl groups (preferably substituted or unsubstituted alkoxycarbonyl groups having 2 to 30 carbon atoms such as Toxicarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxycarbonyl), carbamoyl group (preferably a substituted or unsubstituted carbamoyl group having 1 to 30 carbon atoms such as carbamoyl, N-methylcarbamoyl, N, N-dimethyl) Carbamoyl, N, N-di-n-octylcarbamoyl, N- (methylsulfonyl) carbamoyl),

Aryl and heterocyclic azo groups (preferably substituted or unsubstituted arylazo groups having 6 to 30 carbon atoms, substituted or unsubstituted heterocyclic azo groups having 3 to 30 carbon atoms such as phenylazo, p-chlorophenylazo, 5-ethylthio -1,3,4-thiadiazol-2-ylazo), an imide group (preferably N-succinimide, N-phthalimide), a phosphino group (preferably a substituted or unsubstituted phosphino group having 2 to 30 carbon atoms such as dimethylphosphine Fino, diphenylphosphino, methylphenoxyphosphino), phosphinyl group (preferably a substituted or unsubstituted phosphinyl group having 2 to 30 carbon atoms such as phosphinyl, dioctyloxyphosphinyl, diethoxyphosphinyl), phosphinyl Oxy group (preferably substituted with 2 to 30 carbon atoms) Or an unsubstituted phosphinyloxy group such as diphenoxyphosphinyloxy, dioctyloxyphosphinyloxy, a phosphinylamino group (preferably a substituted or unsubstituted phosphinylamino having 2 to 30 carbon atoms). Groups such as dimethoxyphosphinylamino, dimethylaminophosphinylamino), phospho groups, silyl groups (preferably substituted or unsubstituted silyl groups having 3 to 30 carbon atoms such as trimethylsilyl, t-butyldimethylsilyl, phenyldimethyl Silyl), a hydrazino group (preferably a substituted or unsubstituted hydrazino group having 0 to 30 carbon atoms, such as trimethylhydrazino), a ureido group (preferably a substituted or unsubstituted ureido group having 0 to 30 carbon atoms such as N, N-dimethylureido).

Among the above substituents, those having a hydrogen atom may be substituted with the above substituents after removing this. Examples of such composite substituents include acylsulfamoyl groups, alkyl or arylsulfonylcarbamoyl groups. Examples thereof include methylsulfonylcarbamoyl, p-methylphenylsulfonylcarbamoyl, acetylsulfamoyl and benzoylsulfamoyl groups.

The polymerization degree n of the polymer represented by the general formula (1) represents the polymerization degree of the polymer and is an integer of 10 or more. Preferably it is 10-10000, More preferably, it is 20-500.
Moreover, 1000-1 million are preferable and, as for the number average molecular weight of the polymer represented by the said General formula (1), 10000-100,000 are more preferable.
Next, the “method for imparting color to the polymer” of the present invention will be described.
"Method for imparting color to the polymer" of the present invention, the polymer having a polymer chain helical structure, said extrinsic at least one by applying the load, reversibly changed Sen Luo structure and / or crystal structure Or a new helical structure is formed to change the color of the polymer.
In the present invention, as a specific example of “changing the color”, the polymer chain having a helical structure is yellowish, and the external load is applied to red to yellowish Examples include changing the color such as orange to red and yellow to red. The color change can also be measured by UV absorption or polarized UV absorption.

  If the polymer represented by the general formula (1) in which the polymer chain has a helical structure is used in the method for imparting color to the polymer of the present invention, various sensors can be obtained. For example, a temperature sensor that changes color due to organic solvent gas, a temperature sensor that changes color due to temperature change, a tension sensor that changes color due to tension change, a pressure sensor that changes color due to pressure change, and a color that changes due to changes in light wavelength and intensity. Examples include a light sensor that changes.

The present invention can be a method of reversibly changing the helical direction by applying at least one of the external loads to a polymer having a one-stranded helical structure in the polymer chain.
The present invention can also be a polymer material in which a polymer chain has a one-winding helical structure and can reversibly change the helical direction by applying at least one of the external loads.
Specific examples of the configuration of the polymer material include a film including a substrate, a self-supporting film, and the like.
Specific examples of the film including the substrate include a spin coat film.
Specific examples of the self-supporting film include those described above.
The self-assembled polymer film of the present invention is preferably any one of a self-supporting film, a film provided with a substrate, or a laminate.
Moreover, it is preferable that the polymer solid material of the present invention is any one of a self-supporting film, a film including a substrate, particles, fine particles, and powder.

The polyacetylene substitute used for the polymer film of the present invention is represented by the general formula (I), and the polymer chain has a regular helical structure.

  The polymer represented by the general formula (1) is preferably a polymer represented by the general formula (2).

(In the formula, n is an integer of 10 or more, and X ₁ , X ₂ and X ₃ each independently represent a hydrogen atom or a substituent. However, at least one of X ₁ , X ₂ and X ₃ is optical. Represents an active substituent.)

In the present invention, at least one of X ₁ , X ₂ and X ₃ is preferably an optically active substituent.
At least one of X ₁ , X ₂ and X ₃ is an optically active substituent, and as a combination of X ₁ , X ₂ and X ₃ , X ₁ is a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom, X ₂ is preferably an alkyl group, alkoxy group, carboxyl group or amino group, X ₃ is preferably a hydrogen atom, alkyl group, alkoxy group or halogen atom, X ₁ is a hydrogen atom, alkyl group or halogen atom, and X ₂ is optically active. The case where an alkyl group or an optically active alkoxy group, X ₃ is a hydrogen atom, an alkyl group or a halogen atom is more preferable, and the case where X ₁ and X ₃ are a hydrogen atom and X ₂ is an optically active alkoxy group is particularly preferable.

  The optically active substituent is particularly preferably an alkyl group or alkoxyl group having 2 or more carbon atoms having one or more asymmetric carbon atoms and an OH group substituted on the asymmetric carbon group.

  The optically active alkyl group is a linear or branched alkyl group having 2 to 10 carbon atoms, which includes one or more asymmetric carbons and an OH group substituted on the asymmetric carbon. Those having 4 to 8 carbon atoms are preferred. Specific examples include 1-hydroxyethyl group, 2-hydroxypropyl group, 2-hydroxybutyl group, 1-hydroxy-1-methylpropyl group, 1-hydroxy-2-methylpropyl group, 2-hydroxypentyl group, 2 -Hydroxyhexyl group, 2-hydroxyheptyl group, 2-hydroxyoctyl group, 2-hydroxynonyl group, 2-hydroxydecyl group and the like are preferable, and 2-hydroxyhexyl group, 2-hydroxyheptyl group are particularly preferable. , 2-hydroxyoctyl group.

  The optically active alkoxy group is a linear or branched alkoxy group having 2 to 10 carbon atoms, which includes one or more asymmetric carbons and an OH group substituted on the asymmetric carbon. Those having 4 to 8 carbon atoms are preferred. Specific examples include 1-hydroxyethoxy group, 2-hydroxypropoxy group, 2-hydroxybutoxy group, 1-hydroxy-1-methylpropoxy group, 1-hydroxy-2-methylpropoxy group, 2-hydroxypentyloxy group, 2-hydroxyhexyloxy group, 2-hydroxyheptyloxy group, 2-hydroxyoctyloxy group, 2-hydroxynonyloxy group, 2-hydroxydecyloxy group, and the like, and particularly preferably, 2-hydroxyhexyloxy group, 2-hydroxyheptyloxy group and 2-hydroxyoctyloxy group.

X ₁ and X ₂ or X ₂ and X ₃ are linked to form a ring (aromatic or non-aromatic hydrocarbon ring or heterocyclic ring. These may be further combined to form a polycyclic fused ring. For example, benzene ring, naphthalene ring, anthracene ring, quinoline ring, phenanthrene ring, fluorene ring, triphenylene ring, naphthacene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring , Pyrazine ring, pyrimidine ring, pyridazine ring, indolizine ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolidine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, quinoline ring, carbazole Ring, phenanthridine ring, acridine ring, Nantororin ring, thianthrene ring, chromene ring, xanthene ring, phenoxathiin ring, a phenothiazine ring and a phenazine ring.) Structure can take.

The polymer represented by the general formula (2) can be produced by polymerizing the acetylene substituted monomer represented by the general formula (7).
The method for producing the substituted acetylene monomer is not particularly limited. D'Amato, T .; Sone, M.M. Tabata, M .; V. Russo, A.M. “Macromolecules” by Fdurani et al., Vol. 31, p. 8660 (1998).

  The polymer represented by the general formula (1) is also preferably a polymer represented by the general formula (3).

n is preferably 10 to 10,000. X is preferably a group having phenoxy oxygen. The polymer represented by the general formula (3) can be synthesized, for example, by using [Rh (norbornadiene) Cl] ₂ catalyst.

  Another embodiment of the present invention is a polymer solid material composed of a polymer having a one-helix structure of the following general formula (4).

(In the formula, n represents an integer of 10 or more, and R represents a group having at least one optically active carbon.)
n is preferably 10 to 10,000. R is preferably a group having a hydrogen bonding optically active group. The polymer represented by the general formula (4) can be synthesized, for example, by using [Rh (norbornadiene) Cl] ₂ catalyst.

In this embodiment, the polymer is preferably composed of a polymer represented by the following general formula (5).

(In the formula, n represents an integer of 10 or more, and X ₁ , X ₂ , and X ₃ represent a group having at least one optically active carbon.)
n is preferably 10 to 10,000. X ₁ , X ₂ and X ₃ are preferably groups having a hydrogen bonding optically active group. The polymer represented by the general formula (5) can be synthesized by using, for example, [Rh (norbornadiene) Cl] ₂ catalyst.

The polymerization reaction for producing the polymer used in the present invention is preferably performed in the presence of a rhodium complex catalyst. By using a rhodium complex catalyst, it is possible to produce a stereoregular polymer in which all the conjugated double bonds of the polymer main chain are controlled in a cis form.
The rhodium complex catalyst is not particularly limited, but diene and monoene ligands such as [Rh (norbornadiene) Cl] ₂ , [Rh (cyclooctadiene) Cl] ₂ , and [Rh (bis-cyclooctene) Cl] ₂ can be used. And rhodium complex catalyst, and [Rh (norbornadiene) Cl] ₂ is particularly preferably used.
In the method for producing a polymer used in the present invention, it is preferable to use [Rh (norbornadiene) Cl] ₂ as a rhodium complex catalyst and triethylamine as a cocatalyst.

  In the above reaction, examples of the solvent include nonpolar organic solvents such as hexane, toluene, and chloroform, and polar organic solvents such as tetrahydrofuran, triethylamine, and alcohols (such as methanol and ethanol).

Substituted polyacetylene film material of the present invention includes a support film.
A known stretchable polymer can be used as the support film, and examples thereof include polyethylene, polypropylene, polyvinyl alcohol, polymethyl methacrylate, and the like, but the present invention is not limited thereto.
The film thickness of the substituted polyacetylene film material of the present invention is preferably 0.01 μm to 1 mm, more preferably 0.1 to 100 μm.

Next, a method for producing a substituted polyacetylene film of the present invention will be described.
The substituted polyacetylene film of the present invention can be produced by applying and drying a solution prepared by dissolving the polyacetylene substitute represented by the general formula (2) in a solvent on the support film.
Examples of the solvent include, but are not limited to, organic solvents such as chloroform, methylene chloride, and toluene. Moreover, the application | coating method of a polymer solution can be performed by general methods, such as a spin-cast method, and is not specifically limited.

Further, the alignment film of the present invention can be produced by stretching the substituted polyacetylene film of the present invention. Since polyacetylenes are hard and brittle, even if a film is formed alone, if the film is stretched, the film is broken and an alignment film cannot be obtained. The present invention has been made based on the knowledge that when a polymer film of a predetermined polyacetylene substitution product is formed on a support film, an alignment film can be obtained without breaking the film even if it is stretched.

As a stretching method, a general method such as uniaxial stretching or biaxial stretching can be used, and a method described in JP-A No. 11-348113 can be used. In stretching, the polymer film may be heated to preferably 50 to 100 ° C, more preferably 50 to 70 ° C. The stretching speed is preferably 10 to 100 mm / min, and more preferably 20 to 30 mm / min. The draw ratio is preferably 2 to 20 times, more preferably 2.5 to 10 times.

The substituted polyacetylene film of the present invention changes in color and conjugated structure when stretched and oriented.
The alignment film of the present invention changes its color, conjugate state, and helical structure when heated or brought into contact with organic solvent vapor. Further, the direction of the helix can be controlled by heating and further contacting with the organic solvent vapor. It is not yet known how the conjugation state is changed, but it is considered that a change in the three-dimensional structure or higher order structure of a single bond in the polymer main chain occurs. This change in the conjugated state induces a color change and also induces a change in electrical and electronic properties.

The heating temperature in the above treatment is preferably 60 to 200 ° C, more preferably 80 to 120 ° C. The heating time is preferably 1 to 60 minutes, more preferably 10 to 30 minutes.

Examples of the organic solvent used in the above treatment include hydrocarbon solvents such as benzene, toluene and hexane; ethers such as tetrahydrofuran and diethyl ether; alcohols such as methanol and ethanol; ketones such as acetone; chloroform dichloromethane and the like Although a chlorine containing solvent etc. are mentioned, it does not specifically limit to these.
The conditions for bringing the vapor of the organic solvent into contact with the polymer of the present invention are preferably performed in an atmosphere of 0 to 50 ° C. under normal pressure or reduced pressure. The contact time is preferably 10 to 60 minutes. The steam temperature is preferably 20 to 30 ° C.

  The optically active polymer of the present invention is represented by the following general formula (6), and the polymer chain preferably has a regular helical structure.

In the formula, R represents an alkyl group or an alkoxy group having 2 to 10 carbon atoms, which contains one or more asymmetric carbon atoms and is substituted with an OH group. The number of asymmetric carbons is preferably 1 to 3, but 1 is particularly preferred from the viewpoint of stereocontrol.
The polymer of the present invention has a stable helical structure in which all the conjugated double bonds of the polymer main chain are controlled to a cis isomer, and is substituted with either the S isomer or the R isomer group. As a result, the spiral winding direction has a regular spiral structure. And it is thought that a helical structure can be stabilized by a hydrogen bond by substituting OH group for the asymmetric carbon.

  The alkyl group represented by R is a linear or branched alkyl group having 2 to 10 carbon atoms, which includes one or more asymmetric carbons and an OH group substituted on the asymmetric carbon. . Those having 4 to 8 carbon atoms are preferred. Specific examples include 1-hydroxyethyl group, 2-hydroxypropyl group, 2-hydroxybutyl group, 1-hydroxy-1-methylpropyl group, 1-hydroxy-2-methylpropyl group, 2-hydroxypentyl group, 2 -Hydroxyhexyl group, 2-hydroxyheptyl group, 2-hydroxyoctyl group, 2-hydroxynonyl group, 2-hydroxydecyl group and the like are preferable, and 2-hydroxyhexyl group, 2-hydroxyheptyl group are particularly preferable. , 2-hydroxyoctyl group.

  The alkoxy group represented by R is a linear or branched alkoxy group having 2 to 10 carbon atoms, which includes one or more asymmetric carbons and an OH group substituted on the asymmetric carbon. . Those having 4 to 8 carbon atoms are preferred. Specific examples include 1-hydroxyethoxy group, 2-hydroxypropoxy group, 2-hydroxybutoxy group, 1-hydroxy-1-methylpropoxy group, 1-hydroxy-2-methylpropoxy group, 2-hydroxypentyloxy group, 2-hydroxyhexyloxy group, 2-hydroxyheptyloxy group, 2-hydroxyoctyloxy group, 2-hydroxynonyloxy group, 2-hydroxydecyloxy group, and the like, and particularly preferably, 2-hydroxyhexyloxy group, 2-hydroxyheptyloxy group and 2-hydroxyoctyloxy group.

  n represents the degree of polymerization of the polymer and is an integer of 10 or more. Preferably it is 10-10000, More preferably, it is 20-500.

The polymer of the present invention has optical activity and preferably exhibits optical rotation. The polymer of the present invention may be either the S isomer or the R isomer, but is not a racemic mixture.
The number average molecular weight of the polymer of the present invention is preferably from 1,000 to 1,000,000, more preferably from 4,000 to 100,000.

The polymers of the present invention preferably change color and conjugation state upon heating or contact with organic solvent vapor, and the helical structure changes and / or forms a new helical structure. Moreover, the direction of the newly formed helix can be controlled by heating and further contacting with the organic solvent vapor. It is not yet known how the conjugation state is changed, but it is considered that a change in the three-dimensional structure or higher order structure of a single bond in the polymer main chain occurs. This change in the conjugated state induces a color change and also induces a change in electrical and electronic properties.
If necessary , the polymer of the present invention can simultaneously control the color and the helical structure not only in a solution state but also in a powder state or a film state.

  The heating temperature in the above treatment is preferably 60 to 200 ° C, more preferably 100 to 150 ° C. The heating time is preferably 1 to 60 minutes, more preferably 3 to 30 minutes.

Examples of the organic solvent used in the above treatment include hydrocarbon solvents such as benzene, toluene and hexane; ethers such as tetrahydrofuran and diethyl ether; alcohols such as methanol and ethanol; ketones such as acetone; chloroform and dichloromethane and the like. Although the chlorine-containing solvent of these is mentioned, it is not specifically limited to these.
The conditions for bringing the vapor of the organic solvent into contact with the polymer of the present invention are preferably performed in an atmosphere of 0 to 50 ° C. under normal pressure or reduced pressure. The contact time is preferably 10 to 90 minutes. The steam temperature is preferably 10 to 30 ° C.

Next, a method for producing the polymer of the present invention will be described.
The polymer represented by the general formula (2) can be produced by polymerizing an acetylene derivative represented by the following general formula (7).

In the formula, X ₁ , X ₂ and X ₃ each independently represent a hydrogen atom or a substituent. However, at least one of X ₁ , X ₂ and X ₃ represents a substituent. X ₁ , X ₂ and X ₃ have the same meanings as R in X ₁ , X ₂ and X ₃ in the general formula (2), and preferred ranges are also the same.

  Moreover, the optically active polymer represented by the general formula (6) can be produced by polymerizing an acetylene derivative represented by the following general formula (8).

  In the formula, R represents an alkyl group or an alkoxy group having 2 to 10 carbon atoms, which contains one or more asymmetric carbon atoms and is substituted with an OH group. R has the same meaning as R in formula (6), and the preferred range is also the same.

  A method for producing the substituted acetylene monomer represented by the general formula (7) or (8) is not particularly limited. D'Amato, T .; Sone, M.M. Tabata, M .; V. Russo, A.M. “Macromolecules” by Fdurani et al., Vol. 31, p. 8660 (1998).

The polymerization reaction for producing the polymer of the present invention is preferably performed in the presence of a rhodium complex catalyst. By using a rhodium complex catalyst, it is possible to produce a stereoregular polymer in which all the conjugated double bonds of the polymer main chain are controlled in a cis form.
The rhodium complex catalyst is not particularly limited, but diene and monoene ligands such as [Rh (norbornadiene) Cl] ₂ , [Rh (cyclooctadiene) Cl] ₂ , and [Rh (bis-cyclooctene) Cl] ₂ can be used. And rhodium complex catalyst, and [Rh (norbornadiene) Cl] ₂ is particularly preferably used. Moreover, it is preferable to use alkylamines as a cocatalyst, for example, diethylamine, tributylamine, triethylamine, etc. are used.
In the polymer production method of the present invention, it is preferable to use [Rh (norbornadiene) Cl] ₂ as the rhodium complex catalyst and triethylamine as the cocatalyst.

  In the above production method, examples of the solvent include nonpolar organic solvents such as hexane, toluene, and chloroform, and polar organic solvents such as tetrahydrofuran, triethylamine, and alcohols (methanol, ethanol, and the like).

Next, a polymer film using the polymer of the present invention will be described.
The polymer film can be formed by dissolving the polymer of the present invention in a solvent and coating and drying on glass or the like.
Examples of the solvent include, but are not limited to, organic solvents such as diethylamine, N, N-dimethylformamide, and dimethyl sulfoxide. Moreover, the application | coating method of a polymer solution can be performed by general methods, such as a spin-cast method, and is not specifically limited.
The film thickness of the polymer film is preferably 0.01 μm to 1 mm, and more preferably 0.1 to 10 μm.

The self-assembled polymer film made of the polymer molecule of the present invention preferably has a peak top of absorption that is uniquely and arbitrarily controllable in the range of 400 to 550 nm by the above stimulation.
In the present invention, the term “uniquely and arbitrarily” means that the peak top of absorption can be controlled by the kind of stimulus such as heating temperature.

EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited to these.
Reference example 1
<Production of (S) -1- (4-ethynylphenoxy) -2-hexanol>
(Salen) Co (O—C (CF ₃ ) ₃ ) (H ₂ O) 0.85 g, 3A molecular sieves 1 g, p-iodophenol 5 g, 1,2-epoxyhexane 5 g, t-butyl methyl ether 2 mL mixed And reacted at −15 ° C. for 12 hours. To this was added 0.7 g of pyridinium p-toluenesulfonate, diluted with 20 mL of t-butyl methyl ether, and filtered through silica gel. After removing the solvent with an evaporator, the column was purified with a solvent of ethyl acetate / hexane (volume ratio, 1/5).

  To the obtained compound, 40 mL of triethylamine, 24 mg of dichlorobis (triphenylphosphine) palladium, 35 mg of triphenylphosphine, 39 mg of copper iodide and 4.32 g of trimethylsilylacetylene were added and reacted at 40 ° C. for 1 hour. After removing the solvent with an evaporator, ethyl ether was added to extract the produced compound. This ethyl ether layer was washed with 300 mL of distilled water three times, dried over anhydrous magnesium sulfate for 24 hours, and then filtered, and the solvent of the filtrate was distilled off. Ethanol 10mL and potassium hydroxide 0.1g were added to the obtained compound, and it stirred at room temperature for 1 hour. Ethyl ether was added and the resulting compound was extracted. This ethyl ether layer was washed twice with 5% aqueous hydrochloric acid, washed with 300 mL of distilled water until the ether layer became neutral, dried over anhydrous magnesium sulfate for 24 hours, filtered, and then the solvent was distilled off. The solvent was distilled off, and column purification was performed with ethyl acetate / hexane (volume ratio, 1/5) solvent to obtain 1.7 g of (S) -1- (4-ethynylphenoxy) -2-hexanol (yield) 35%). When the optical rotation of the product was measured using P-1020 (trade name, manufactured by JASCO Corporation), the specific rotation at 589 nm measured at a concentration of 1.01 g / dL in dimethylformamide was −10.2.

<Production of poly [(S) -1- (4-ethynylphenoxy) -2-hexanol]>

In a flask purged with nitrogen gas, 34.5 mg of [Rh (norbornadiene) Cl] _2, 30.6 mg of triethylamine, and 1.5 mL of tetrahydrofuran were placed, and (S) -1- (4- Ethylylphenoxy) -2-hexanol 1.5 mL of a tetrahydrofuran solution of 327 mg was quickly added to initiate polymerization. After stirring at 25 ° C. for 30 minutes, the reaction mixture was added dropwise to 200 mL of cyclohexane to stop the reaction. The precipitated polymer was filtered off and dried under vacuum to obtain 230 mg of yellow powder (yield 70%). When the optical rotation of the product was measured using P-1020 (trade name, manufactured by JASCO Corporation), the specific rotation at 589 nm measured at a concentration of 0.10 g / dL in dimethylformamide was +170.3.
A ¹ H-NMR chart of the polymer produced is shown in FIG.

<Production of polymer film>
A diethylamine solution (2% by mass) of the polymer prepared above was spin-coated on an 18 × 18 mm cover glass at 1500 rpm, and dried to prepare a yellow polymer film (film thickness 0.3 μm). The CD spectrum and ultraviolet-visible (UV) spectrum of the produced film were measured using V-570 (trade name, manufactured by JASCO Corporation). The results are shown in FIG. In FIG. 2, the horizontal axis indicates the wavelength (nm), the vertical axis (left side) indicates the CD spectrum (mdeg), and the vertical axis (right side) indicates the absorbance. Curve 1 in FIG. 2 is the CD spectrum of the polymer film, and curve 4 is the UV-visible spectrum of the polymer film.
As is clear from FIG. 2, a large spectrum having a positive peak at 380 nm was observed, and it was found that circular dichroism was exhibited.
In addition, the measurement of the CD spectrum and the ultraviolet visible (UV) spectrum in the following reference examples and examples was also performed in the same manner.

<Chloroform vapor treatment of polymer film>
When the polymer film prepared above was brought into contact with chloroform vapor at 25 ° C. for 30 minutes at room temperature and normal pressure, the color of the film changed from yellow to red.
CD spectrum and UV-visible spectrum were measured in the same manner as above. The results are shown in FIG. Curve 2 in FIG. 2 is the CD spectrum of the polymer film treated with chloroform vapor, and curve 5 is the UV-visible spectrum of the polymer film treated with chloroform vapor.
As is clear from FIG. 2, the UV-visible spectrum shifted in the long wavelength direction as compared with the polymer film not subjected to the steam treatment. Further, regarding the CD spectrum, the peak at 380 nm observed in the polymer film not subjected to the steam treatment was greatly reduced, and instead a spectrum having a positive peak near 520 nm appeared. From this, it can be seen that a new helical structure of the polymer is formed by the chloroform vapor treatment.
Furthermore, in wide-angle X-ray scattering, a sharp peak appeared around 26 km, and it was confirmed that crystallization was promoted. When this film was brought into contact with diethylamine vapor at normal temperature and pressure for 30 minutes, the color of the film returned to yellow, and the peak at 520 nm disappeared and the peak at 380 nm increased for the CD spectrum. In addition, it was confirmed that the peak of 26 に お け る in wide angle X-ray scattering almost disappeared and returned to an amorphous state.

<Toluene vapor treatment of polymer film>
When the polymer film prepared above was brought into contact with toluene vapor at 25 ° C. for 30 minutes at room temperature and normal pressure, the color of the film changed to red.
CD spectrum and UV-visible spectrum were measured in the same manner as above. The results are shown in FIG. The broken line 3 in FIG. 2 is a CD spectrum of a polymer film treated with toluene, and the broken line 6 is an ultraviolet-visible spectrum of the polymer film treated with toluene.
As is clear from FIG. 2, the UV-visible spectrum shifted in the long wavelength direction as compared with the polymer film not subjected to the steam treatment. Further, regarding the CD spectrum, the peak at 380 nm observed in the polymer film not subjected to the steam treatment was greatly reduced, but the peak near 520 nm that appeared during the chloroform steam treatment was not observed. From this, it can be seen that the helical structure of the polymer was changed by the toluene vapor treatment, and the new helical structure formed when the chloroform vapor treatment was performed was not formed.

<Heat treatment of polymer film>
When the polymer film prepared above was heated at 100 ° C. for 3 minutes, the color of the film changed to orange.
CD spectrum and UV-visible spectrum were measured in the same manner as above. The results are shown in FIG. In FIG. 3, the horizontal axis indicates the wavelength (nm), the vertical axis (left side) indicates the CD spectrum (mdeg), and the vertical axis (right side) indicates the absorbance. The broken line 7 in FIG. 3 is the CD spectrum of the heat-treated polymer film, and the broken line 9 is the ultraviolet-visible spectrum of the heat-treated polymer film. Further, curve 1 in FIG. 3 is a CD spectrum of a polymer film that has not been heat-treated, and curve 4 is an ultraviolet-visible spectrum of a polymer film that has not been heat-treated.
As is clear from FIG. 3, the UV-visible spectrum shifted in the longer wavelength direction as compared with the polymer film that was not heat-treated. Further, regarding the CD spectrum, the peak at 380 nm observed in the polymer film that was not heat-treated was greatly reduced. From this, it can be seen that the helical structure of the polymer is changed by the heat treatment.

<Chloroform vapor treatment after heat treatment of polymer film>
When the polymer film prepared above was heated at 100 ° C. for 3 minutes and then contacted with chloroform vapor at 25 ° C. for 30 minutes, the color of the film changed from yellow to red.
CD spectrum and UV-visible spectrum were measured in the same manner as above. The results are shown in FIG. Curve 8 in FIG. 3 is a CD spectrum of a polymer film treated with chloroform vapor after heat treatment, and curve 10 is an ultraviolet-visible spectrum of a polymer film treated with chloroform vapor after heat treatment.
As is apparent from FIG. 3, the UV-visible spectrum shifted further in the longer wavelength direction than that of the heat-treated polymer film. Further, regarding the CD spectrum, the peak at 380 nm observed in the polymer film not subjected to heat treatment was greatly reduced, and instead, a spectrum having a negative peak near 530 nm appeared. Since the polarity of this peak is reversed, a new spiral structure of the polymer is formed by performing chloroform vapor treatment after heat treatment, and the spiral direction of the spiral is reversed compared with the case where heat treatment is not performed. I understand that.
Furthermore, in wide-angle X-ray scattering, a sharp peak appeared around 26 km, and it was confirmed that crystallization was promoted. When this film was brought into contact with diethylamine vapor at normal temperature and pressure for 30 minutes, the color of the film returned to yellow, and the peak at 520 nm disappeared and the peak at 380 nm increased for the CD spectrum. In addition, it was confirmed that the peak of 26 に お け る in wide angle X-ray scattering almost disappeared and returned to an amorphous state.

Reference example 2
<Production of polymer film using poly [(S) -1- (4-ethynylphenyl) -1-pentanol]>
Reference Example 1 except that poly [(S) -1- (4-ethynylphenyl) -1-pentanol] was used instead of poly [(S) -1- (4-ethynylphenoxy) -2-hexanol] When a spin coat film of poly [(S) -1- (4-ethynylphenyl) -1-pentanol] was produced from a diethylamine solution by the same method as described above, a yellow film was obtained. In the CD spectrum, a positive peak was observed near 370 nm, and a negative peak was observed near 440 nm. When this was brought into contact with acetone vapor at room temperature and normal pressure for 1 minute, the positive and negative of the two peaks were reversed, the peak near 370 nm became negative, and the peak near 440 nm became positive. From this, it was confirmed that the spiral inversion occurred by the solvent vapor. Furthermore, when this film was brought into contact with diethylamine vapor for 1 minute at room temperature and normal pressure, a positive peak was observed near 370 nm, and a negative peak was observed near 440 nm, confirming that the direction of the spiral returned to the original direction. FIG. 4 shows the CD spectrum of the polymer film immediately after this film formation and after contact with acetone vapor for 1 minute. In FIG. 4, the vertical axis represents ellipticity (Ellipticity / unit: mdeg), and the horizontal axis represents wavelength (Wavelength / unit: nm). The solid line 41 is the CD spectrum immediately after the film formation, and the broken line 42 is the CD spectrum of the film in contact with acetone vapor for 1 minute.

<Chloroform vapor treatment after heat treatment of polymer film>
When a spin coat film of poly [(S) -1- (4-ethynylphenyl) -1-pentanol] was produced from a diethylamine solution, a yellow film was obtained. In the CD spectrum, a negative peak was observed near 370 nm, and a positive peak was observed near 440 nm. When this was brought into contact with chloroform vapor at room temperature and normal pressure for 1 minute, the positive and negative of the two peaks were reversed, the peak near 370 nm was positive, and the peak near 440 nm was negative. From this, it was confirmed that the spiral inversion occurred by the solvent vapor. Furthermore, when this film was brought into contact with methanol vapor at room temperature and normal pressure for 1 minute, a negative peak was observed at around 370 nm and a positive peak was observed at around 440 nm, confirming that the direction of the spiral was reversed again and returned to the original direction. It was. These helix orientations were retained after removal of the solvent vapor. FIG. 5 shows CD spectra of the polymer film immediately after this film formation, after contact with chloroform vapor for 1 minute, and after contact with chloroform vapor for 1 minute and further after contact with methanol vapor for 1 minute. In FIG. 5, the vertical axis represents ellipticity (Ellipticity / unit: mdeg), and the horizontal axis represents wavelength (Wavelength / unit: nm). The solid line 51 is the CD spectrum immediately after film formation, the broken line 52 is the CD spectrum of the film that has been in contact with chloroform vapor for 1 minute, and the broken line 53 is the CD spectrum of the film that has been in contact with chloroform vapor for 1 minute and then is in contact with methanol vapor for 1 minute. .

<Tetrahydrofuran vapor treatment after heat treatment of polymer film>
When a spin coat film of poly [(S) -1- (4-ethynylphenyl) -1-pentanol] was produced from a diethylamine solution, a yellow film was obtained. In the CD spectrum, a positive peak was observed near 370 nm, and a negative peak was observed near 440 nm. When this was brought into contact with tetrahydrofuran vapor at room temperature and normal pressure for 1 minute, the positive and negative of the peak near 370 nm of the two peaks was reversed. On the other hand, the peak around 440 nm disappeared. From this, it was confirmed that the spiral reversal was caused by the solvent vapor and part of the helical structure was changed. Further, when this film was brought into contact with diethylamine vapor for 1 minute at room temperature and normal pressure, a positive peak was observed at around 370 nm and a negative peak was observed at around 440 nm, confirming that the direction and structure of the helix was restored. FIG. 6 shows CD spectra of the polymer film immediately after this film formation, after contact with tetrahydrofuran vapor for 1 minute, and after contact with tetrahydrofuran vapor for 1 minute and further after contact with diethylamine vapor for 1 minute. In FIG. 6, the vertical axis represents ellipticity (Ellipticity / unit: mdeg), and the horizontal axis represents wavelength (Wavelength / unit: nm). The solid line 61 is the CD spectrum immediately after film formation, the broken line 62 is the CD spectrum of the film that has been in contact with tetrahydrofuran vapor for 1 minute, and the broken line 63 is the CD spectrum of the film that has been in contact with tetrahydrofuran vapor for 1 minute and then is in contact with diethylamine vapor for 1 minute. .

Example 1
<Production of N-butyl-2- (p-ethynylphenoxy) acetamide>
To 150 mL of triethylamine, 10 g of N-butyl-2- (p-bromophenoxy) acetamide, 0.74 g of dichlorobis (triphenylphosphine) palladium, 1.10 g of triphenylphosphine, 1.20 g of copper iodide and 4.12 g of trimethylsilylacetylene are added. And reacted at 90 ° C. for 30 hours. After removing the solvent with an evaporator, ethyl ether was added to extract the produced compound. This ethyl ether layer was washed with 300 mL of distilled water three times, dried over anhydrous magnesium sulfate for 24 hours, and then filtered, and the solvent of the filtrate was distilled off. To the obtained compound were added 100 mL of toluene, 100 mL of methanol, and 2.4 g of potassium carbonate, and the mixture was stirred at room temperature for 1 hour. Ethyl ether was added and the resulting compound was extracted. This ethyl ether layer was washed twice with 5% aqueous hydrochloric acid, washed with 300 mL of distilled water until the ether layer became neutral, dried over anhydrous magnesium sulfate for 24 hours, filtered, and then the solvent was distilled off. After column purification, the solvent was distilled off, and column purification was performed using chloroform as a developing solvent to obtain 6.3 g of N-butyl-2- (p-ethynylphenoxy) acetamide (yield 78%).

<Production of poly [N-butyl-2- (p-ethynylphenoxy) acetamide]>
In a flask purged with nitrogen gas, 11.5 mg of [Rh (norbornadiene) Cl] _2, 50.6 mg of triethylamine, and 2.5 mL of chloroform were placed. N-butyl-2- (p -Ethynylphenoxy) acetamide 580 mg of a chloroform solution 2.5 mL was quickly added to initiate polymerization. After stirring at 25 ° C. for 30 minutes, the reaction mixture was added dropwise to 200 mL of cyclohexane to stop the reaction. The precipitated polymer was filtered off and dried under vacuum to obtain 430 mg of a yellow polymer (yield 74%).
¹ H NMR (270 MHz, CDCl ₃ ) δ 7.12 (s, 1H), 6.63 (d, 2H), 6.47 (d, 2H), 5.70 (s, 1H), 4.17 (s , 2H), 3.31 (s, 2H), 1.53 (tt, 2H), 1.32 (tq, 2H), 0.91 (t, 3H)

<Production of polymer film and alignment film>
The above-prepared polymer chloroform solution (2% by mass) was spin-coated at 1500 rpm on a polypropylene support film having a width of 20 mm, a length of 30 mm and a thickness of 0.2 mm, and dried to prepare a polymer film (film) Thickness 1 μm). The obtained polymer film was uniaxially stretched 5 times with the support film at a rate of 25 mm / min at 50 ° C. to obtain an alignment film. The color of the polymer film was yellow before stretching, but changed to orange by stretching 5 times. The UV spectrum of the polymer film before and after stretching was measured using a Cary 500 spectrophotometer (trade name, manufactured by Varian). The results are shown in FIG. In FIG. 7, the horizontal axis indicates the wavelength (nm), and the vertical axis indicates the absorbance. The dotted line 71 in FIG. 7 is the UV spectrum of the polymer film before stretching, and the solid line 72 is the UV spectrum of the alignment film after stretching. FIG. 7 shows that the color is changed by stretching the spectrum in the long wavelength direction due to stretching.

Moreover, about the produced alignment film, the polarization | polarized-light UV spectrum of the extending | stretching direction and the polarized UV spectrum of the orthogonal | vertical direction with respect to the extending | stretching direction were measured using the Cary500 spectrophotometer (brand name, product made by Varian). The results are shown in FIG. In FIG. 8, the horizontal axis represents wavelength (nm) and the vertical axis represents absorbance. A curve 81 in FIG. 8 is a polarized UV spectrum in the stretching direction of the alignment film, and a curve 82 is a polarized UV spectrum in a direction perpendicular to the stretching direction of the alignment film. The result of FIG. 8 shows that the light absorption in the stretching direction is larger than that in the vertical direction, and the alignment film of the present invention is highly aligned.

Example 2
<Production of p-hexyloxyphenylacetylene>
To 20 mL of N, N-dimethylformamide, 4.40 g of p-iodophenol, 5.29 g of potassium carbonate, and 3.96 g of hexane bromide were added and reacted at 70 ° C. for 8 hours. Ethyl ether was added and the resulting compound was extracted. The ether layer was washed with 100 mL of distilled water three times, dried over anhydrous magnesium sulfate for 24 hours, filtered, and the solvent of the filtrate was distilled off. The resulting compound was purified by distillation under reduced pressure to obtain 5.50 g of p-hexyloxyiodophenol (yield 91%). To 100 mL of triethylamine, 5.7 g of p-hexyloxyiodophenol, 0.014 g of dichlorobis (triphenylphosphine) palladium, 0.054 g of triphenylphosphine, 0.058 g of copper iodide and 11.8 g of trimethylsilylacetylene were added at 80 ° C. The reaction was performed for 4 hours. The reaction solution was filtered and the filtrate solvent was distilled off, followed by addition of ethyl ether. The ether layer was washed with 100 mL of distilled water three times, dried over anhydrous magnesium sulfate for 24 hours, and then filtered, and the solvent of the filtrate was distilled off. Ethanol 30mL and potassium hydroxide 2g were added to the obtained compound, and it stirred at room temperature for 2 hours. Ethyl ether was added and the resulting compound was extracted. The ether layer was washed with distilled water until neutral, then dried over anhydrous magnesium sulfate for 24 hours, filtered, and then the solvent of the filtrate was distilled off. Further, 1.57 g of p-hexyloxyphenylacetylene was obtained by distillation under reduced pressure (yield 53%).

<Production of poly (p-hexyloxyphenylacetylene)>
In a flask purged with nitrogen gas, 57.6 mg of [Rh (norbornadiene) Cl] ₂ , 57.9 mg of NaOCH ₃ , 65.6 mg of triphenylphosphine, 30.5 mg of N, N-dimethylaminopyridine, and 12 mL of tetrahydrofuran were placed. To this, 12 mL of a toluene solution of 506 mg of p-hexyloxyphenylacetylene prepared in another flask was quickly added to initiate polymerization. After stirring at room temperature for 2 hours at 25 ° C., the reaction mixture was added dropwise to 450 mL of methanol to stop the reaction. The precipitated polymer was separated by filtration and vacuum dried to obtain 360 mg of a yellow polymer (yield 71%).
According to gel permeation chromatography (GPC) measurement in chloroform, the number average molecular weight was estimated to be 33000 in terms of polystyrene.
¹ H NMR (270 MHz, CDCl ₃ ) δ 6.59 (d, 2H), 6.41 (d, 2H), 5.75 (s, 1H), 3.68 (s, 2H), 1.65 (br , 2H), 1.31 (br, 8H), 0.89 (t, 3H)

<Production of polymer film and alignment film>
A polymer film (film thickness: 1 μm) was prepared by coating and drying on a polypropylene support film in the same manner as in Reference Example 3 except that the polymer produced above was used. Further, this polymer film was uniaxially stretched to obtain an alignment film. The color of the polymer film was yellow before stretching, but changed to a slightly reddish color by stretching 5 times.
The polarized UV spectrum of the prepared alignment film was measured in the same manner as in Reference Example 3. The results are shown in FIG. In FIG. 9, the horizontal axis indicates the wavelength (nm), and the vertical axis indicates the absorbance. A curve 91 in FIG. 9 is a polarized UV spectrum in the stretching direction of the alignment film, and a curve 92 is a polarized UV spectrum in a direction perpendicular to the stretching direction of the alignment film. The result of FIG. 9 shows that the light absorption in the stretching direction is larger than that in the vertical direction, and the alignment film of the present invention is highly aligned.
Furthermore, when the alignment film was brought into contact with hexane vapor at 25 ° C. under normal temperature and pressure for 60 minutes, the color of the film changed to red. The polarization UV spectrum was measured in the same manner for the alignment film subjected to the solvent vapor treatment. The results are shown in FIG. In FIG. 10, the horizontal axis indicates the wavelength (nm), and the vertical axis indicates the absorbance. A curve 101 in FIG. 10 is a polarized UV spectrum in the stretching direction of the alignment film, and a curve 102 is a polarized UV spectrum in the direction perpendicular to the stretching direction of the alignment film. From the results of FIGS. 9 and 10, it was found that when the alignment film of the present invention is brought into contact with the solvent vapor, the light absorption moves to the long wavelength side while maintaining the alignment.

Example 3
<Production of p-ethoxyphenylacetylene>
To 100 mL of N, N-dimethylformamide, 63.4 g of iodophenol, 79.6 g of calcium carbonate, and 49.9 g of ethyl iodide were added and reacted at 70 ° C. for 4 hours. Ethyl ether was added to the reaction mixture, and the resulting compound was extracted. The ether layer was washed with 300 mL of distilled water three times, dried over anhydrous magnesium sulfate for 24 hours and filtered, and the solvent of the filtrate was distilled off. The resulting compound was produced by distillation under reduced pressure to obtain 52.6 g of p-ethoxyiodophenol (yield 74%).
To 100 mL of triethylamine are added 24.8 g of p-ethoxyiodophenol, 0.35 g of dichlorobis (triphenylphosphine) palladium, 0.53 g of triphenylphosphine, 0.57 g of copper iodide, and 11.8 g of trimethylsilylacetylene, and 2 hours at room temperature. Reacted. The reaction solution was filtered, and the solvent of the filtrate was distilled off. Then, ethyl ether was added to extract the produced compound. This ether layer was washed 3 times with 300 mL of distilled water and then dried over anhydrous magnesium sulfate for 24 hours. Thereafter, the mixture was filtered, and the solvent of the filtrate was distilled off. Ethanol 30mL and potassium hydroxide 2g were added to the obtained compound, and it stirred at room temperature for 2 hours. Ethyl ether was added and the resulting compound was extracted. The ether layer was washed with distilled water until neutral, then dried over anhydrous magnesium sulfate for 24 hours, filtered, and then the solvent of the filtrate was distilled off. Further, 6.93 g of p-ethoxyphenylacetylene was obtained by distillation under reduced pressure (yield 47%).

<Production of poly (p-ethoxyphenylacetylene)>
In a flask purged with nitrogen gas, 23.1 mg of [Rh (norbornadiene) Cl] _2, 65.2 mg of triethylamine, and 5 mL of ethanol were added, and 5 mL of an ethanol solution of 731 mg of p-ethoxyphenylacetylene prepared in another flask was added thereto. Polymerization was started quickly. After stirring at 25 ° C. for 30 minutes, the reaction mixture was added to 200 mL of methanol to stop the reaction. The precipitated polymer was separated by filtration and vacuum dried to obtain 690 mg of a yellow polymer (yield 94%). According to the gel permeation chromatography (GPC) measurement in chloroform, the number average molecular weight was estimated to be 41000 in terms of polystyrene.
¹ H NMR (270 MHz, CDCl ₃ ) δ 6.62 (d, 2H), 6.44 (d, 2H), 5.75 (s, 1H), 3.76 (q, 2H), 1.28 (t , 3H)

<Preparation of alignment film>
A polymer membrane (membrane) was prepared by applying and drying the polymer produced above on a polypropylene support membrane in the same manner as in Reference Example 3 except that the polymer produced above was used and the draw ratio was 2.5 times. A thickness of 1 μm) was produced. Further, this polymer film was uniaxially stretched to obtain an alignment film. The color of the polymer film was yellow before stretching, but changed to a slightly reddish color by stretching 2.5 times.
When the polarized UV spectrum of the prepared alignment film was measured in the same manner as in Reference Example 3, it was found that the absorption in the stretching direction was larger than that in the vertical direction, and the polymer was highly oriented.
Furthermore, when the alignment film was brought into contact with hexane vapor at 25 ° C. under normal temperature and normal pressure for 60 minutes, the color of the film returned to yellow.

Reference example 3
When a spin coat film of poly [(S) -1- (4-ethynylphenyl) -1-pentanol] was produced from a diethylamine solution, a yellow film was obtained. In the CD spectrum, a negative peak was observed near 370 nm, and a positive peak was observed near 440 nm. The optical rotation at 410 nm was -14.5 mdeg. When this film was heated at 110 ° C. for 1 minute and the CD spectrum was measured, the positive and negative of the two peaks were reversed, the peak near 370 nm was positive, and the peak near 440 nm was negative. The optical rotation at 410 nm changed to +12.3 mdeg, and the sign was reversed. Thereafter, even when the temperature was returned to room temperature, the positive / negative, size, and optical rotation of this peak did not change at all, and the inversion of the helix was maintained. FIG. 11 shows the CD spectrum of the polymer film at room temperature immediately after the film formation, at 110 ° C., and at room temperature after heating at 110 ° C. for 1 minute. In FIG. 11, the vertical axis represents ellipticity (Ellipticity / unit: mdeg), and the horizontal axis represents wavelength (Wavelength / unit: nm). A broken line 111 indicates a CD spectrum immediately after film formation, a solid line 112 indicates a CD spectrum of the film heated to 110 ° C., and a broken line 113 indicates a CD spectrum of the film returned to room temperature after heating at 110 ° C. for 1 minute.

Reference example 4
When a spin coat film of poly [(S) -1- (4-ethynylphenyl) -1-dodecanol] was prepared from a diethylamine solution, a yellow film was obtained. In the CD spectrum, a negative peak was observed near 370 nm, and a positive peak was observed near 440 nm. The optical rotation at 416 nm was −22.7 mdeg. When this film was heated at 100 ° C. for 3 seconds and the CD spectrum was measured, the positive and negative of the two peaks were reversed, the peak near 370 nm was positive, and the peak near 440 nm was negative. The optical rotation at 416 nm changed to +76.0 mdeg, and the sign was reversed. Thereafter, even when the temperature was returned to room temperature, the positive / negative, size, and optical rotation of this peak did not change at all, and the inversion of the helix was maintained. Further, when this film was brought into contact with diethylamine vapor at room temperature and normal pressure for 1 minute, a negative peak was observed near 370 nm, a positive peak was observed near 440 nm, the optical rotation at 416 nm was changed to −20.8 mdeg, and the positive and negative were reversed again. . This confirmed that the direction of the helix was reversed again and returned to the original direction. These helix orientations were retained after removal of the solvent vapor. FIG. 12 shows the CD spectrum of the polymer film at room temperature immediately after film formation, at room temperature after heating at 100 ° C. for 3 seconds, and after heating at 100 ° C. for 3 seconds and then in contact with diethylamine vapor for 1 minute. In FIG. 12, the vertical axis represents ellipticity (Ellipticity / unit: mdeg), and the horizontal axis represents wavelength (Wavelength / unit: nm). The solid line 121 shows the CD spectrum immediately after film formation, the broken line 122 shows the CD spectrum of the film heated at 100 ° C. for 3 seconds, and the broken line 123 shows the CD spectrum of the film heated at 100 ° C. for 3 seconds and then contacted with diethylamine vapor for 1 minute. .

Reference Example 5
When a spin coat film of poly [(S) -1- (4-ethynylphenyl) -1-dodecanol] was prepared from a diethylamine solution, a yellow film was obtained. In the CD spectrum, a negative peak was observed near 370 nm, and a positive peak was observed near 440 nm. The optical rotation at 416 nm was −22.7 mdeg. When the CD spectrum was measured after heating this film at 65 ° C. for 8 minutes, the positive and negative of the two peaks were reversed, the peak near 370 nm was positive, and the peak near 440 nm was negative. The optical rotation at 416 nm changed to +53.3 mdeg, and the sign was reversed. Thereafter, even when the temperature was returned to room temperature, the positive / negative, size, and optical rotation of this peak did not change at all, and the inversion of the helix was maintained. FIG. 13 shows the CD spectrum of the polymer film at room temperature immediately after this film formation and at room temperature after heating at 65 ° C. for 8 minutes. In FIG. 13, the vertical axis represents ellipticity (Ellipticity / unit: mdeg), and the horizontal axis represents wavelength (Wavelength / unit: nm). The solid line 131 shows the CD spectrum immediately after film formation, and the broken line 132 shows the CD spectrum of the film returned to room temperature after heating at 65 ° C. for 8 minutes.

Reference Example 6
When a spin coat film of poly [4-ethynylbenzoyl-L-valine methyl ester] was produced from a chloroform solution, a yellow film was obtained. In the CD spectrum, a negative peak was observed near 370 nm, and a positive peak was observed near 440 nm. The optical rotation at 403 nm was −26.3 mdeg. When this was brought into contact with methanol vapor at room temperature and normal pressure for 1 minute, the positive and negative of the two peaks were reversed, the peak near 370 nm was positive, and the peak near 440 nm was negative. The optical rotation at 403 nm changed to +15.9 mdeg, and the positive and negative signs were reversed again. From this, it was confirmed that the spiral inversion occurred by the solvent vapor. Further, when this film was brought into contact with chloroform vapor for 1 minute at room temperature and normal pressure, a negative peak was observed near 370 nm and a positive peak was observed near 440 nm, and the optical rotation at 403 nm was changed to -30.5 mdeg. This confirmed that the direction of the helix was reversed again and returned to the original direction. These helix orientations were retained after removal of the solvent vapor. FIG. 14 shows CD spectra of the polymer film immediately after this film formation, after contact with methanol vapor for 1 minute, and after contact with methanol vapor for 1 minute and further after contact with chloroform vapor for 1 minute. In FIG. 14, the vertical axis represents ellipticity (Ellipticity / unit: mdeg), and the horizontal axis represents wavelength (Wavelength / unit: nm). A solid line 141 indicates a CD spectrum immediately after film formation, a broken line 142 indicates a CD spectrum of a film contacted with methanol vapor for 1 minute, and a broken line 143 indicates a CD spectrum of a film contacted with methanol vapor for 1 minute and further contacted with chloroform vapor for 1 minute.

Example 4
When a spin coat film of poly [N-butyl-2- (4-ethynylphenoxyacetamide)] was formed on an elastic polyethylene film, a yellow film was obtained, and the dichroic ratio at this time was 1. . When this film was stretched 5.0 times at 1 cm / min at room temperature using a stretching machine, the color of the film changed to red. At this time, the absorption peak top was 461 nm. According to the polarization spectrum, the dichroic ratio was 6.28, and it was found that a highly oriented film was obtained. When the film was removed from the stretching machine, the film contracted, the stretching ratio increased to 4.5 times, the film color returned to yellow, and the absorption peak top was 436 nm, but the film orientation was maintained. . When this membrane was further stretched 5 times using a stretching machine, the color of the membrane again became red, indicating that this color change was reversible.

Example 5
When a spin coat film of poly [N-butyl-2- (4-ethynylphenoxyacetamide)] was formed on an elastic polyethylene film, a yellow film was obtained. When this film was stretched 2.2 times at 1 cm / min at room temperature using a stretching machine, the color of the film changed to red. At this time, the absorption peak top was 420 nm. The film was further stretched to 3.0 times with a stretching machine and then removed from the stretching machine. As a result, the film contracted, the stretching ratio increased to 2.2 times, and the color of the film returned to yellow. At this time, the peak top of absorption in the ultraviolet-visible spectrum was 408 nm. In this way, when compared at the same draw ratio, it was found that this color change was due to tension because it was red when tension was applied and yellow when there was no tension. FIG. 15 shows UV-visible absorption spectra of the film stretched 2.2 times, the film stretched 3.0 times, and the film stretched 3.0 times and removed from the stretching machine and contracted 2.2 times. Show. In FIG. 15, the horizontal axis indicates the wavelength (nm) and the vertical axis indicates the absorbance. The solid line 151 is the ultraviolet-visible spectrum of the film stretched 2.2 times, the broken line 152 is the ultraviolet-visible spectrum of the film stretched 3.0 times, and the broken line 153 is removed from the stretcher after stretching 3.0 times. The UV-visible spectrum of the film contracted up to 2 times is shown.

Reference Example 7
When a spin coat film of poly [N-butyl-2- (4-ethynylphenoxyacetamide)] was produced on a glass substrate from a chloroform solution, a yellow film was obtained. When this film was heated at 100 ° C. for 10 minutes, an orange film was obtained, and the peak top of the ultraviolet-visible absorption spectrum was 415 nm. Furthermore, the peak top did not change even when heated at 100 ° C. for 30 minutes. When this membrane was dissolved again in chloroform and the spectrum was measured, it was in agreement with the spectrum before heating.

Reference Example 8
When a spin coat film of poly [N-butyl-2- (4-ethynylphenoxyacetamide)] was produced on a glass substrate from a chloroform solution, a yellow film was obtained. When this film was heated at 120 ° C. for 5 minutes, an orange film was obtained, and the peak top of the ultraviolet-visible absorption spectrum was 440 nm. Further, the peak top did not change even when the heating time was extended. When this membrane was dissolved again in chloroform and the spectrum was measured, it was in agreement with the spectrum before heating.

Reference Example 9
When a spin coat film of poly [N-butyl-2- (4-ethynylphenoxyacetamide)] was produced on a glass substrate from a chloroform solution, a yellow film was obtained. When this film was heated at 160 ° C. for 1 minute, a reddish orange film was obtained, and the peak top of the ultraviolet-visible absorption spectrum was 468 nm. Further, the peak top did not change even when the heating time was extended. When this membrane was dissolved again in chloroform and the spectrum was measured, it was in agreement with the spectrum before heating.

Reference Example 10
When a spin coat film of poly [N-butyl-2- (4-ethynylphenoxyacetamide)] was produced on a glass substrate from a chloroform solution, a yellow film was obtained. When this film was heated at 200 ° C. for 10 seconds, a red film was obtained, and the peak top of the ultraviolet-visible absorption spectrum was 494 nm. When this membrane was dissolved again in chloroform and the spectrum was measured, it was in agreement with the spectrum before heating.
FIG. 16 shows ultraviolet-visible absorption spectra of the polymer films prepared in Reference Examples 7 to 10 . In FIG. 16, the horizontal axis indicates the wavelength (nm), and the vertical axis indicates the absorbance. The solid line 161 is the ultraviolet-visible spectrum of the film obtained in Reference Example 7 , the broken line 162 is the ultraviolet-visible spectrum of the film obtained in Reference Example 8 , the broken line 163 is the ultraviolet-visible spectrum of the film obtained in Reference Example 9 , A broken line 164 shows an ultraviolet-visible spectrum of the film obtained in Reference Example 10 .
From the results of Reference Examples 7 to 10 , it was found that the absorption of the film varies uniquely depending on the heating temperature.

Reference Example 11
When a spin coat film of poly [N-butyl-2- (4-ethynylphenoxyacetamide)] was produced on a glass substrate from a chloroform solution, a yellow film was obtained. A portion of this film was masked with cardboard and irradiated with 3000 mJ of 365 nm light using a mercury lamp. When this film was brought into contact with methanol vapor at room temperature and normal pressure for 30 minutes, no change in color was observed in the light-irradiated portion, but the portion that was not irradiated with light by masking turned red. FIG. 17 shows an ultraviolet-visible spectrum after the vapor contact of the irradiated part and the non-irradiated part. In FIG. 17, the horizontal axis indicates the wavelength (nm) and the vertical axis indicates the absorbance. A solid line 171 indicates an ultraviolet-visible spectrum of a film that has been exposed to methanol vapor after light irradiation, and a broken line 172 indicates an ultraviolet-visible spectrum of a film that has not been irradiated with light and is in contact with methanol vapor. It can be seen that there is a large difference in the color of the film with and without light irradiation.

Reference Example 12
When a spin coat film of poly [(S) -1- (4-ethynylphenoxy) -2-hexanol] was produced on a glass substrate from a diethylamine solution, a yellow film was obtained. A portion of this film was masked with cardboard, and irradiated with light of 365 nm at 1200 mJ using a mercury lamp. When this film was brought into contact with chloroform vapor at room temperature and normal pressure for 15 minutes, no change in color was observed in the light-irradiated portion, but the portion that was not irradiated with light by masking turned red. FIG. 18 shows an ultraviolet-visible spectrum after the vapor contact of the irradiated part and the non-irradiated part. In FIG. 18, the horizontal axis indicates the wavelength (nm) and the vertical axis indicates the absorbance. In addition, a solid line 181 indicates an ultraviolet-visible spectrum of a film that is in contact with chloroform vapor after light irradiation, and a broken line 182 indicates an ultraviolet-visible spectrum of a film that is not irradiated with light and is in contact with chloroform vapor. It can be seen that there is a large difference in the color of the film with and without light irradiation.

Reference Example 13
When a spin coat film of poly [(S) -2-heptanyl-2-propynylcarbamate] was formed on an elastic polyethylene film, a yellow film was obtained. When this film was stretched 1.9 times within 1 second, the color of the film changed to orange simultaneously with stretching. At this time, the peak peak of absorption was 420 nm, and an increase in absorption near 500 nm was observed. When this film was further stretched to 2.5 times within 1 second, the film became red simultaneously with the stretching, and an increase in absorption near 500 nm was observed. FIG. 19 shows a spectrum at each draw ratio. In FIG. 19, the horizontal axis indicates the wavelength (nm) and the vertical axis indicates the absorbance. A broken line 191 indicates an ultraviolet-visible spectrum immediately after film formation, a broken line 192 indicates an ultraviolet-visible spectrum of a film stretched at a stretch ratio of 1.5 times, a broken line 193 indicates an ultraviolet-visible spectrum of a film stretched at a stretch ratio of 1.9 times, a solid line Reference numeral 194 denotes an ultraviolet-visible spectrum of a film stretched at a stretch ratio of 2.5.

Reference Example 14
When the tension of the film obtained in Reference Example 13 was released, the film contracted within 1 second and the draw ratio returned to 1.9 times. At this time, the color of the film returned to yellow simultaneously with the shrinkage. FIG. 20 shows a spectrum at each draw ratio. In FIG. 20, the horizontal axis indicates the wavelength (nm), and the vertical axis indicates the absorbance. A solid line 201 indicates an ultraviolet-visible spectrum of a film stretched at a stretch ratio of 2.5 times, and a broken line 202 indicates an ultraviolet-visible spectrum of a film stretched at a stretch ratio of 2.5 times and then contracted by 1.9 times.

Reference Example 15
When the instant stretching and contraction of the film shown in Reference Examples 13 and 14 were repeated, the film color was red when stretched and yellow when contracted. Reproducibility was maintained even after stretching and shrinking were repeated 100 times or more.

Reference Example 16
When a spin coat film of poly [(R) -1- (4-ethynylphenyl) -1-dodecanol] was prepared from a diethylamine solution, a yellow film was obtained. In the CD spectrum, a positive peak was observed near 370 nm, and a negative peak was observed near 440 nm. The optical rotation at 405 nm was +26.6 mdeg. When the CD spectrum was measured after immersing this film in acetone for 5 seconds, the positive and negative of the above two peaks were reversed, and a negative peak appeared around 390 nm, and a positive peak appeared around 440 nm. The optical rotation at 405 nm changed to -74.0 mdeg. FIG. 21 shows the CD spectrum of the polymer film immediately after this film formation and after immersion in acetone for 5 seconds. In FIG. 21, the vertical axis represents ellipticity (Ellipticity / unit: mdeg), and the horizontal axis represents wavelength (Wavelength / unit: nm). A solid line 211 indicates a CD spectrum immediately after film formation, and a broken line 212 indicates a CD spectrum of a film immersed in acetone for 5 seconds.

Reference Example 17
When a spin coat film of poly [(S) -1-methylhexyl-N-propargylcarbamate] was produced from a tetrahydrofuran solution, a colorless film was obtained. In the CD spectrum, a positive peak was observed around 280 nm. The optical rotation at 270 nm was −256.1 mdeg. When this film was heated at 110 ° C. for 1 minute and then the CD spectrum was measured, a positive peak appeared at around 300 nm. The optical rotation at 270 nm changed to +242.0 mdeg. After that, even when the temperature was returned to room temperature, the positive / negative, size, and optical rotation dispersion of this peak did not change at all, and the inversion of the helix was maintained. Further, when this film was brought into contact with diethylamine vapor for 5 minutes at room temperature and normal pressure, a positive peak was observed near 280 nm, and the optical rotation at 270 nm was changed to -230.2 mdeg. This confirmed that the direction of the helix was reversed again and returned to the original direction. These helix orientations were retained after removal of the solvent vapor. FIG. 22 shows CD spectra of the polymer film at room temperature immediately after film formation, at room temperature after heating at 110 ° C. for 1 minute, and after heating at 110 ° C. for 1 minute and then contacted with diethylamine vapor for 5 minutes. In FIG. 22, the vertical axis represents ellipticity (Ellipticity / unit: mdeg), and the horizontal axis represents wavelength (Wavelength / unit: nm). The solid line 221 shows the CD spectrum immediately after film formation, the broken line 222 shows the CD spectrum of the film heated at 110 ° C. for 1 minute, and the broken line 223 shows the CD spectrum of the film heated at 110 ° C. for 1 minute and then contacted with diethylamine vapor for 5 minutes. .

Reference Example 18
When a spin coat film of poly [(S) -1- (4-ethynylphenyl) -1-pentanol] was produced from a diethylamine solution, a yellow film was obtained. When this film was brought into contact with tetrahydrofuran vapor at room temperature and normal pressure for 1 minute, the optical rotation at 415 nm was -2.2 mdeg, which was a value close to 0. When this film was heated at 110 ° C. for 1 minute, an optical rotation at 415 nm appeared, and its value was +25.4 mdeg.

Reference Example 19
When a spin coat film of poly [(S) -1- (4-ethynylphenoxy) -2-hexanol] was prepared from a diethylamine solution, a yellow film was obtained. The optical rotation at 502 nm of this film was −1.95 mdeg, which is a value close to 0. When this film was brought into contact with chloroform vapor at room temperature and normal pressure for 30 minutes, a new optical rotation appeared in the wavelength region longer than 500 nm, and the optical rotation value at 502 nm was −10.1 mdeg.

Reference Example 20
A spin coat film of poly [(S) -1- (4-ethynylphenyl) -1-pentanol] was prepared on a glass substrate from a diethylamine solution and contacted with chloroform vapor for 5 minutes to obtain a yellow film. It was. In the CD spectrum, a positive peak was observed near 370 nm, and a negative peak was observed near 440 nm. A portion of this film was masked with cardboard and irradiated with 3000 mJ of 365 nm light using a mercury lamp. There was no change in the CD spectrum. When this film was brought into contact with methanol vapor at room temperature and normal pressure for 15 seconds and the CD spectrum was measured, positive and negative reversal was observed in the non-light-irradiated part, but the positive / negative of the light-irradiated part was different from that before contact with methanol vapor. There wasn't. FIG. 23 shows CD spectra before and after the vapor contact of the irradiated part and the non-irradiated part. In FIG. 23, the horizontal axis indicates the wavelength (nm), and the vertical axis indicates the absorbance. The broken line 231 shows the CD spectrum of the film in contact with the methanol vapor in the light non-irradiated portion for 15 seconds, and the solid line 232 shows the CD spectrum of the film in contact with the methanol vapor after light irradiation for 15 seconds. It can be seen that the presence or absence of light irradiation can reverse the CD spectrum and the optical rotation.

Reference Example 21
When a spin coat film of poly [(S) -1- (4-ethynylphenoxy) -2-butanol] was produced on a glass substrate from a chloroform solution, a yellow film was obtained. When this film was immersed in acetone for 1 hour, a red film was obtained, and a bulge appeared in the vicinity of 500 nm in the ultraviolet-visible absorption spectrum. FIG. 24 shows ultraviolet and visible spectra before and after immersion. In FIG. 24, a solid line 241 indicates an ultraviolet-visible spectrum immediately after film formation, and a broken line 242 indicates an ultraviolet-visible spectrum of a film immersed in acetone for 1 hour.

2 is a ¹ H-NMR chart of the polymer produced in Reference Example 1. FIG. 2 is a graph showing a CD spectrum and an ultraviolet-visible spectrum of the polymer film produced in Reference Example 1. 2 is a graph showing a CD spectrum and an ultraviolet-visible spectrum of the polymer film produced in Reference Example 1. 6 is a graph showing a CD spectrum of the polymer film produced in Reference Example 2. 6 is another graph showing the CD spectrum of the polymer film produced in Reference Example 2. 10 is still another graph showing the CD spectrum of the polymer film produced in Reference Example 2. FIG. 2 is a graph showing UV spectra before and after stretching of the polymer film produced in Example 1. FIG. 2 is a graph showing a polarized UV spectrum of an alignment film produced in Example 1. FIG. 6 is a graph showing a polarized UV spectrum of an alignment film produced in Example 2 . It is a graph which shows the polarization | polarized-light UV spectrum at the time of performing a solvent vapor process about the alignment film produced in Example 2. FIG. 10 is a graph showing a CD spectrum of the polymer film produced in Reference Example 3 . 10 is a graph showing a CD spectrum of the polymer film produced in Reference Example 4 . 10 is a graph showing a CD spectrum of the polymer film produced in Reference Example 5 . 10 is a graph showing a CD spectrum of the polymer film produced in Reference Example 6 . 6 is a graph showing an ultraviolet-visible absorption spectrum after stretching of the polymer film produced in Example 5. FIG. Is a graph showing the ultraviolet-visible absorption spectrum of the polymer film prepared in Reference Example 7-10. 10 is a graph showing an ultraviolet-visible absorption spectrum of the polymer film produced in Reference Example 11 . It is a graph which shows the ultraviolet visible absorption spectrum of the polymer film produced in Reference Example 12 . It is a graph which shows the UV spectrum before and behind extending | stretching of the polymer film produced in Reference Example 13 . It is a graph which shows the UV spectrum before and behind contraction of the polymer film produced in Reference Example 14 . 19 is a graph showing a CD spectrum of the polymer film produced in Reference Example 16 . 18 is a graph showing a CD spectrum of the polymer film produced in Reference Example 17 . 14 is a graph showing a CD spectrum of the polymer film produced in Reference Example 20 . 10 is a graph showing the UV spectrum of the polymer film produced in Reference Example 21 .

1 CD spectrum of untreated polymer film 2 CD spectrum of polymer film treated with chloroform 3 CD spectrum of polymer film treated with toluene 4 UV-visible spectrum of untreated polymer film 5 UV-visible spectrum of polymer film treated with chloroform 6 Toluene UV-visible spectrum of polymer film after steam treatment 7 CD spectrum of polymer film after heat treatment 8 CD spectrum of polymer film after heat treatment with chloroform 9 UV-visible spectrum of polymer film after heat treatment 10 UV-visible of polymer film treated with chloroform vapor after heat treatment Spectrum 41 CD spectrum immediately after film formation 42 CD spectrum of film contacted with acetone vapor for 1 minute 51 CD spectrum 52 immediately after film formation 52 CD spectrum of film contacted with chloroform vapor for 1 minute 53 CD spectrum of the film contacted with Roform vapor for 1 minute, then contacted with methanol vapor for 1 minute 61 CD spectrum immediately after film formation 62 CD spectrum of the film contacted with tetrahydrofuran vapor for 1 minute 63 Contacted with tetrahydrofuran vapor for 1 minute, then contacted with diethylamine vapor for 1 minute CD spectrum 71 of the contact film 71 UV spectrum of the polymer film before stretching 72 UV spectrum of the alignment film after stretching 81 Polarized UV spectrum 82 in the stretching direction of the alignment film Polarized UV spectrum 91 perpendicular to the stretching direction of the alignment film Polarized UV spectrum in the stretching direction of the alignment film 92 Polarized UV spectrum in the direction perpendicular to the stretching direction of the alignment film 101 Polarized UV spectrum in the stretching direction of the alignment film Polarized UV spectrum in the direction perpendicular to the stretching direction of the alignment film CD spectrum immediately after film formation 112 1 CD spectrum 113 of film heated to 0 ° C. CD spectrum of film returned to room temperature after heating at 110 ° C. for 1 minute 121 CD spectrum 122 immediately after film formation 122 CD spectrum of film heated at 100 ° C. for 3 seconds 3 at 100 ° C. 3 CD spectrum 131 of film contacted with diethylamine vapor for 1 minute after heating for 1 second CD spectrum 132 immediately after film formation CD spectrum of film returned to room temperature after heating at 65 ° C. for 8 minutes 141 CD spectrum immediately after film formation 142 contact with methanol vapor for 1 minute CD spectrum 143 of the film after contact with methanol vapor for 1 minute and then CD spectrum of the film after contact with chloroform vapor for 1 minute 151 UV-visible spectrum of the film stretched 2.2 times 152 UV-visible spectrum of the film stretched 3.0 times 153 After stretching to 3.0 times, it was removed from the stretching machine and shrunk to 2.2 times Obtained in ultraviolet-visible spectrum 164 Reference Example 10 of the film obtained by ultraviolet-visible spectrum 161 Reference Example 7 of the film obtained in the ultraviolet-visible spectrum 162 of the film obtained in Reference Example 8 UV-visible spectrum 163 Reference Example 9 UV-visible spectrum 171 of the film contacted with methanol vapor after irradiation with light 172 UV-visible spectrum of a film contacted with methanol vapor without irradiation with light 181 UV-visible spectrum of a film contacted with chloroform vapor after irradiation with light 182 UV-Visible spectrum 191 of film contacted with chloroform vapor without irradiating light UV-Visible spectrum 192 immediately after film formation UV-Visible spectrum 193 of film stretched at a stretch ratio of 1.5 times Film stretched at a stretch ratio of 1.9 times UV-visible spectrum 194 UV-visible spectrum 20 of a film stretched at a draw ratio of 2.5 times 1 UV-visible spectrum 202 of a film stretched at a draw ratio of 2.5 times 202 UV-visible spectrum of a film stretched at a draw ratio of 2.5 times and then contracted to 1.9 times 211 CD spectrum immediately after film formation 212 Acetone for 5 seconds CD spectrum of the immersed film 221 CD spectrum immediately after deposition 222 CD spectrum of the film heated for 1 minute at 110 ° C. 223 CD spectrum of the film heated for 1 minute at 110 ° C. and then contacted with diethylamine vapor for 5 minutes 231 CD spectrum 232 of film contacted with methanol vapor for 15 seconds CD spectrum of film exposed to methanol vapor for 15 seconds after light irradiation 241 UV-visible spectrum immediately after film formation 242 UV-visible spectrum of film immersed in acetone for 1 hour

Claims (10)

A film composed of a polymer having a helical structure in which the polymer molecular chain represented by the following general formula (1) is controlled in a cis-form has a helical structure state controlled in a cis-type by the presence or absence of stretching, shrinkage or tension. The helical structure of the polymer molecular chain and / or the crystal structure of the polymer molecule are reversibly changed while maintaining the conjugation of the polymer molecular chain or polymer assembly and / or the color of the film while maintaining the shape of the film. A reversible control method for a self-assembled polymer film that is reversibly controlled.

(In the formula, n represents an integer of 10 or more, and R represents an aromatic or aliphatic group.) The method for reversibly controlling a self-assembled polymer film according to claim 1, wherein the general formula (1) is represented by the following general formula (2).

(In the formula, n is an integer of 10 or more, and X ₁ , X ₂ and X ₃ each independently represent a hydrogen atom or a substituent. However, at least one of X ₁ , X ₂ and X ₃ is a substituent. Represents.) The method for reversibly controlling a self-assembled polymer film according to claim 1 or 2, wherein the general formula (1) is represented by the following general formula (3).

(In the formula, n is an integer of 10 or more, and X represents a hydrogen atom or a substituent.) X in the general formula (3) is one or more contain asymmetric carbon and OH groups on the asymmetric carbon is substituted, according to claim 3 is an alkyl group or an alkoxy group having 2 to 10 carbon atoms A method for reversible control of a self-assembled polymer film.   The reversible control is performed by providing the polymer film on a stretchable support film, and stretching or shrinking the polymer film or changing a tension. Method for reversible control of self-assembled polymer film. A self-assembled polymer film material comprising a polymer having a helical structure in which a polymer molecular chain represented by the following general formula (1) is controlled in a cis form,
By reversibly changing the helical structure of the polymer molecular chain and / or the crystal structure of the polymer molecule while maintaining a helical structure state controlled in a cis-type by the presence or absence of stretching, shrinkage or tension of the film material, A self-assembled polymer film material for reversibly controlling the conjugation of polymer molecular chains or polymer aggregates and / or the color of the film while maintaining the shape of the film.

(In the formula, n represents an integer of 10 or more, and R represents an aromatic or aliphatic group.) The self-organized polymer film material according to claim 6, wherein the general formula (1) is represented by the following general formula (2).

(In the formula, n is an integer of 10 or more, and X ₁ , X ₂ and X ₃ each independently represent a hydrogen atom or a substituent. However, at least one of X ₁ , X ₂ and X ₃ is a substituent. Represents.) The self-assembled polymer film material according to claim 6 or 7, wherein the general formula (1) is represented by the following general formula (3).

(In the formula, n is an integer of 10 or more, and X represents a hydrogen atom or a substituent.) The self-organization according to any one of claims 6 to 8 , wherein the support film is made of a material obtained from the group consisting of polyethylene, polypropylene, polyvinyl alcohol, and polymethyl methacrylate. Polymer film material. The self-assembled polymer film material according to any one of claims 6 to 9 , wherein a thickness of the polymer film material is 0.01 µm to 1 mm.

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