JP2013064101A - Method for modifying polymer compound and method for producing film including modified polymer compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for obtaining a polymer compound simply imparted of optical activity, which can be applied to wide range of polymer compounds.SOLUTION: This modification method of polymer compounds comprises irradiating circularly polarized light to a polymer compound having a repeating unit represented by formula (1), in formula, Ris a bivalent aromatic group which may have a substituent, or a bivalent group of formula (2).

Description

  The present invention relates to a method for modifying a polymer compound and a method for producing a film containing the modified polymer compound.

  It is known that an optically active polymer compound can be synthesized by introducing an optically active site into a unit structure or by forming an optically active helical structure in the main chain. Recently, there has been reported a method for obtaining an optically active substance by irradiating a circularly polarized light to a polymer compound into which an azobenzene unit that is a photosensitive site is introduced (Non-patent Document 1).

Phys. Chem. Chem. Phys. 9,3671-3681 (2007)

  However, regarding the technology for obtaining an optically active substance by irradiating circularly polarized light, there are only examples applied to a polymer compound into which a light-sensitive structure such as an azobenzene unit is introduced, and the range of applicable polymer compounds has been limited. .

  Therefore, the present invention provides a method for easily obtaining a polymer compound having a wide range of applicable polymer compounds and imparting optical activity.

  In order to solve the above-mentioned problems, the present inventors have intensively studied, and as a result, found that a polymer compound having a specific structure is modified into a polymer compound imparted with optical activity by irradiating circularly polarized light. The present invention has been completed.

（式（１）中、
Ｒ^１は置換基を有していてもよい２価の芳香族基又は下記式（２）で表される２価の基である。
Ｘ^１は−Ｏ−で表される基、−Ｓ−で表される基、−Ｃ（＝Ｏ）−で表される基、−Ｃ（＝Ｏ）Ｏ−で表される基、−Ｃ（＝Ｏ）Ｎ（Ｒ^１０）−で表される基、−ＯＣ（＝Ｏ）Ｏ−で表される基、−ＯＣ（＝Ｏ）Ｎ（Ｒ^１１）−で表される基、−Ｎ（Ｒ^１２）Ｃ（＝Ｏ）Ｎ（Ｒ^１３）−で表される基、−Ｃ（Ｒ^１４）_２−で表される基、−Ｓｉ（Ｒ^１５）_２−で表される基、−Ｃ（Ｒ^１６）＝Ｃ（Ｒ^１６）−で表される基、又は、２価のアミン残基である。Ｒ^１０、Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４、Ｒ^１５及びＲ^１６は、それぞれ独立に、水素原子又は置換基を有していてもよいヒドロカルビル基であり、Ｒ^１０、Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４、Ｒ^１５及びＲ^１６が複数個存在する場合、それぞれ同じでも異なっていてもよい。
ｍ_１は１以上の整数であり、ｍ_２は０以上の整数である。ｍ_１及び／又はｍ_２が２以上であるとき、ｍ_１個存在するＲ^１及び／又はｍ_２個存在するＸ^１は、それぞれ同じでも異なっていてもよい。）

（式（２）中、
Ｒ^５、Ｒ^６及びＲ^７は、それぞれ独立に、水素原子又は置換基を有していてもよいヒドロカルビル基である。
Ｒ^８は−Ｏ−で表される基、−Ｓ−で表される基、−Ｃ（＝Ｏ）Ｏ−で表される基、−Ｃ（＝Ｏ）Ｎ（Ｒ^９）−で表される基、及び置換基を有していてもよいヒドロカルビレン基からなる群から選ばれる１個又は２個を組み合わせた２価の基、又は直接結合である。Ｒ^９は水素原子又は置換基を有していてもよいヒドロカルビル基である。
Ａｒ^２は置換基を有していてもよい１価の芳香族炭化水素基（即ち、芳香族ヒドロカルビル基）であり、該１価の芳香族炭化水素基はｓｐ^２炭素原子を７個以上含む。）
〔２〕前記式（１）において、ｍ_１が１であり、ｍ_２が０である、上記〔１〕に記載の変性方法。
〔３〕前記式（１）において、Ｒ^１が置換基を有していてもよい２価の芳香族基であるとき、該置換基を有していてもよい２価の芳香族基が、置換基を有していてもよい単環式芳香環、置換基を有していてもよい縮合多環式芳香環若しくは置換基を有していてもよい有橋多環式芳香環から環を構成する原子に直接結合する水素原子が２個除かれている２価の基であるか、又は、Ｒ^１が式（２）で表される２価の基であるとき、Ａｒ^２が置換基を有していてもよい芳香環集合から環を構成する原子に直接結合する水素原子が１個除かれている１価の基である、上記〔１〕又は〔２〕に記載の変性方法。
〔４〕前記式（１）において、Ｒ^１が式（２）で表される２価の基であるとき、Ｒ^５、Ｒ^６及びＲ^７が水素原子であり、Ｒ^８が−Ｏ−で表される基、−Ｃ（＝Ｏ）Ｏ−で表される基、−Ｃ（＝Ｏ）Ｎ（Ｒ^９）−で表される基、又は、直接結合である、上記〔１〕〜〔３〕のいずれかに記載の変性方法。
〔５〕前記高分子化合物が膜の形状である、上記〔１〕〜〔４〕のいずれかに記載の変性方法。
〔６〕下記工程（ａ）及び（ｂ）を含む、変性された高分子化合物を含む膜の製造方法。
（ａ）基材上に、下記式（１）で表される繰り返し単位を有する高分子化合物を含む膜を形成する工程。
（ｂ）前記膜に円偏光を照射する工程。

（式（１）中、
Ｒ^１は置換基を有していてもよい２価の芳香族基又は下記式（２）で表される２価の基である。
Ｘ^１は−Ｏ−で表される基、−Ｓ−で表される基、−Ｃ（＝Ｏ）−で表される基、−Ｃ（＝Ｏ）Ｏ−で表される基、−Ｃ（＝Ｏ）Ｎ（Ｒ^１０）−で表される基、−ＯＣ（＝Ｏ）Ｏ−で表される基、−ＯＣ（＝Ｏ）Ｎ（Ｒ^１１）−で表される基、−Ｎ（Ｒ^１２）Ｃ（＝Ｏ）Ｎ（Ｒ^１３）−で表される基、−Ｃ（Ｒ^１４）_２−で表される基、−Ｓｉ（Ｒ^１５）_２−で表される基、−Ｃ（Ｒ^１６）＝Ｃ（Ｒ^１６）−で表される基、又は、２価のアミン残基である。Ｒ^１０、Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４、Ｒ^１５及びＲ^１６は、それぞれ独立に、水素原子又は置換基を有していてもよいヒドロカルビル基であり、Ｒ^１０、Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４、Ｒ^１５及びＲ^１６が複数個存在する場合、それぞれ同じでも異なっていてもよい。
ｍ_１は１以上の整数であり、ｍ_２は０以上の整数である。ｍ_１及び／又はｍ_２が２以上であるとき、ｍ_１個存在するＲ^１及び／又はｍ_２個存在するＸ^１は、それぞれ同じでも異なっていてもよい。）

（式（２）中、
Ｒ^５、Ｒ^６及びＲ^７は、それぞれ独立に、水素原子又は置換基を有していてもよいヒドロカルビル基である。
Ｒ^８は−Ｏ−で表される基、−Ｓ−で表される基、−Ｃ（＝Ｏ）Ｏ−で表される基、−Ｃ（＝Ｏ）Ｎ（Ｒ^９）−で表される基、及び置換基を有していてもよいヒドロカルビレン基からなる群から選ばれる１個又は２個を組み合わせた２価の基、又は、直接結合である。Ｒ^９は水素原子又は置換基を有していてもよいヒドロカルビル基である。
Ａｒ^２は置換基を有していてもよい１価の芳香族炭化水素基であり、該１価の芳香族炭化水素基はｓｐ^２炭素原子を７個以上含む。）
〔７〕前記工程（ａ）において、前記高分子化合物を含む懸濁液又は溶液を基材に塗布する、上記〔６〕に記載の製造方法。 The present invention provides the following [1] to [7].
[1] A method for modifying a polymer compound, comprising irradiating a polymer compound having a repeating unit represented by the following formula (1) with circularly polarized light.

(In the formula (1),
R ¹ is a divalent aromatic group which may have a substituent or a divalent group represented by the following formula (2).
X ¹ is a group represented by —O—, a group represented by —S—, a group represented by —C (═O) —, a group represented by —C (═O) O—, —C A group represented by (═O) N (R ¹⁰ ) —, a group represented by —OC (═O) O—, a group represented by —OC (═O) N (R ¹¹ ) —, —N A group represented by (R ¹² ) C (═O) N (R ¹³ ) —, a group represented by —C (R ¹⁴ ) ₂ —, a group represented by —Si (R ¹⁵ ) ₂ —, ^{C (R 16) = C (} R 16) - , a group represented by or a divalent amine residue. R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently a hydrocarbyl group optionally having a hydrogen atom or a substituent, and R ¹⁰ , R ¹¹ , R ^{16 When a} plurality of ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are present, they may be the same or different.
m ₁ is an integer of 1 or more, and m ₂ is an integer of 0 or more. When m ₁ and / or _{m 2} is 2 or more, ^{R 1} and / or ^{X 1} present _{two m} existing _{one m} may be the same or different. )

(In the formula (2),
R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom or a hydrocarbyl group optionally having a substituent.
R ⁸ is a group represented by —O—, a group represented by —S—, a group represented by —C (═O) O—, and a group represented by —C (═O) N (R ⁹ ) —. And a divalent group obtained by combining one or two selected from the group consisting of an optionally substituted hydrocarbylene group, or a direct bond. R ⁹ is a hydrogen atom or a hydrocarbyl group optionally having a substituent.
Ar ² is a monovalent aromatic hydrocarbon group (that is, an aromatic hydrocarbyl group) which may have a substituent, and the monovalent aromatic hydrocarbon group contains 7 or more sp ² carbon atoms. . )
[2] The modification method according to [1], wherein m ₁ is 1 and m ₂ is 0 in the formula (1).
[3] In the formula (1), when R ¹ is a divalent aromatic group which may have a substituent, the divalent aromatic group which may have the substituent is A ring is formed from a monocyclic aromatic ring optionally having a substituent, a condensed polycyclic aromatic ring optionally having a substituent, or a bridged polycyclic aromatic ring optionally having a substituent. Ar ² is a substituent when R 2 is a divalent group represented by the formula (2) in which two hydrogen atoms directly bonded to the constituent atoms are removed or R ¹ is a divalent group represented by the formula (2) The modification method according to the above [1] or [2], which is a monovalent group in which one hydrogen atom directly bonded to an atom constituting a ring is removed from an aromatic ring assembly which may have a ring.
[4] In the formula (1), when R ¹ is a divalent group represented by the formula (2), R ⁵ , R ⁶ and R ⁷ are hydrogen atoms, and R ⁸ is —O—. a group represented by, -C (= O) O-, a group represented by, -C (= O) N ( R 9) - , a group represented by or a direct bond, [1] to [ 3] The modification | denaturation method in any one of.
[5] The modification method according to any one of [1] to [4], wherein the polymer compound is in the form of a film.
[6] A method for producing a film containing a modified polymer compound, comprising the following steps (a) and (b):
(A) The process of forming the film | membrane containing the high molecular compound which has a repeating unit represented by following formula (1) on a base material.
(B) A step of irradiating the film with circularly polarized light.

(In the formula (1),
R ¹ is a divalent aromatic group which may have a substituent or a divalent group represented by the following formula (2).
X ¹ is a group represented by —O—, a group represented by —S—, a group represented by —C (═O) —, a group represented by —C (═O) O—, —C A group represented by (═O) N (R ¹⁰ ) —, a group represented by —OC (═O) O—, a group represented by —OC (═O) N (R ¹¹ ) —, —N A group represented by (R ¹² ) C (═O) N (R ¹³ ) —, a group represented by —C (R ¹⁴ ) ₂ —, a group represented by —Si (R ¹⁵ ) ₂ —, ^{C (R 16) = C (} R 16) - , a group represented by or a divalent amine residue. R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently a hydrocarbyl group optionally having a hydrogen atom or a substituent, and R ¹⁰ , R ¹¹ , R ^{16 When a} plurality of ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are present, they may be the same or different.
m ₁ is an integer of 1 or more, and m ₂ is an integer of 0 or more. When m ₁ and / or _{m 2} is 2 or more, ^{R 1} and / or ^{X 1} present _{two m} existing _{one m} may be the same or different. )

(In the formula (2),
R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom or a hydrocarbyl group optionally having a substituent.
R ⁸ is a group represented by —O—, a group represented by —S—, a group represented by —C (═O) O—, and a group represented by —C (═O) N (R ⁹ ) —. And a divalent group obtained by combining one or two selected from the group consisting of an optionally substituted hydrocarbylene group, or a direct bond. R ⁹ is a hydrogen atom or a hydrocarbyl group optionally having a substituent.
Ar ² is a monovalent aromatic hydrocarbon group which may have a substituent, and the monovalent aromatic hydrocarbon group contains 7 or more sp ² carbon atoms. )
[7] The production method according to [6], wherein in the step (a), a suspension or solution containing the polymer compound is applied to a substrate.

  According to the modification method of the present invention, a wide range of applicable polymer compounds and a polymer compound imparted with optical activity can be easily obtained.

  Hereinafter, embodiments of the present invention will be described.

  In the present specification, “may have a substituent” means that part or all of the hydrogen atoms constituting the compound or group described immediately after that may be substituted with a substituent. means. Unless otherwise specified, examples of the substituent include a halogen atom, a hydrocarbyl group having 1 to 30 carbon atoms, a hydrocarbyloxy group having 1 to 30 carbon atoms, and a hydrocarbyl having 1 to 30 carbon atoms. Mercapto groups are mentioned, and among these, a halogen atom, a hydrocarbyl group having 1 to 18 carbon atoms, a hydrocarbyloxy group having 1 to 18 carbon atoms, or a hydrocarbyl mercapto group having 1 to 18 carbon atoms is preferable, An atom, a hydrocarbyl group having 1 to 12 carbon atoms, or a hydrocarbyloxy group having 1 to 12 carbon atoms is more preferable, and a halogen atom or a hydrocarbyl group having 1 to 12 carbon atoms is particularly preferable. The number of substituents is one or more, and when there are a plurality of substituents, each substituent may be the same or different.

  In the present specification, the “repeating unit” means a structural unit contained in a compound at least two.

  In this specification, the term “modify” as used for a polymer compound means that the polymer compound changes to a state exhibiting optical activity. Here, in this specification, “optical activity” as referred to for a polymer compound means that the polymer compound has a bias in the right and left absorbances in the circular dichroism spectrum. Whether or not the right and left absorbances in the circular dichroism spectrum are biased can be confirmed by measuring the circular dichroism ratio of the specimen under the measurement conditions of the examples described later.

<Modification method of polymer compound>
In the method for modifying a polymer compound of the present invention, the polymer compound having the repeating unit represented by the formula (1) is irradiated with circularly polarized light.

In the formula (1), R ¹ is a divalent aromatic group which may have a substituent or a divalent group represented by the formula (2).
Examples of the divalent aromatic group represented by R ¹ include a divalent aromatic hydrocarbon group (that is, an aromatic hydrocarbylene group) and a divalent aromatic heterocyclic group. Examples of the divalent aromatic group represented by R ¹ include a benzene ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a 1,3,5-triazine ring, a 1,2,4-triazine ring, 1,2,4,5-tetrazine ring, furan ring, pyrrole ring, thiophene ring, pyrazole ring, imidazole ring, oxazole ring, isoxazole ring, 1,2,5-oxadiazole ring, 1,3,4- Oxadiazole ring, 2,3-diazafuran ring, thiazole ring, isothiazole ring, 2,4-diazafuran ring, 1,3,4-thiadiazole ring, 1,2,3-thiadiazole ring, 1,2,4- A divalent group in which two hydrogen atoms directly bonded to the atoms constituting the ring are removed from a monocyclic aromatic ring such as a thiadiazole ring and a 2H-1,2,3-triazole ring; Aromatic ring A divalent group in which two hydrogen atoms directly bonded to the atoms constituting the ring are removed from a condensed polycyclic aromatic ring in which two or more are condensed; the monocyclic aromatic ring and the condensed polycyclic aromatic ring A divalent group in which two hydrogen atoms directly bonded to the atoms constituting the ring are removed from an aromatic ring assembly in which two or more aromatic rings selected from the group consisting of the above are connected by a single bond, an ethenylene group or an ethynylene group A bridged polycyclic aromatic ring having a single bond bridge by a divalent organic group such as a methylene group, an ethylene group or a carbonyl group between two adjacent aromatic rings of the group of aromatic rings And a divalent group in which two hydrogen atoms directly bonded to atoms constituting the ring are removed.
Among these, the divalent aromatic group represented by R ¹ is a divalent group in which two hydrogen atoms directly bonded to atoms constituting the ring are removed from a monocyclic aromatic ring, a condensed polycyclic ring A divalent group in which two hydrogen atoms directly bonded to the atoms constituting the ring are removed from the aromatic ring, or 2 hydrogen atoms directly bonded to the atoms constituting the ring from the bridged polycyclic aromatic ring. A divalent group that is removed is preferable, and from the viewpoint of the rigidity of the polymer compound, a divalent group in which two hydrogen atoms directly bonded to the atoms constituting the ring are removed from the condensed polycyclic aromatic ring. Or a divalent group in which two hydrogen atoms directly bonded to the atoms constituting the ring are removed from the bridged polycyclic aromatic ring, and the ring is formed from the bridged polycyclic aromatic ring. More preferred is a divalent group in which two hydrogen atoms directly bonded to the atom are removed.

  In the condensed polycyclic aromatic ring, the number of monocyclic aromatic rings to be condensed is usually 2 to 6, preferably 2 to 5, more preferably 2 to 4, and further 2 to 3 Two are particularly preferred. In the aromatic ring assembly, the number of aromatic rings to be connected is usually 2 to 6, preferably 2 to 5, more preferably 2 to 4, further preferably 2 to 3, and 2 Particularly preferred. In the bridged polycyclic aromatic ring, the number of aromatic rings to be bridged is usually 2 to 6, preferably 2 to 5, more preferably 2 to 4, and further 2 to 3 Two are particularly preferred.

  Examples of the monocyclic aromatic ring include the following rings (Formula 500 to Formula 526).

  Examples of the condensed polycyclic aromatic ring include the following rings (Formula 527 to Formula 575).

  Examples of the aromatic ring assembly include the following rings (Formula 576 to Formula 602).

  Examples of the bridged polycyclic aromatic ring include the following rings (Formula 603 to Formula 614).

The divalent aromatic group represented by R ¹ is represented by Formula 500 to Formula 505, Formula 508 to Formula 514, Formula 527 to Formula 534, Formula 543, Formula 561 to Formula 564, Formula 568, Formula 576 to Formula 584, It is a divalent group in which two hydrogen atoms directly bonded to the atoms constituting the ring are removed from the ring represented by any one of formulas 587 to 602, 603 to 608 and 611 Are preferably represented by any one of Formula 500 to Formula 505, Formula 508 to Formula 514, Formula 527 to Formula 534, Formula 543, Formula 561 to Formula 564, Formula 568, Formula 603 to Formula 608, and Formula 611. It is more preferably a divalent group in which two hydrogen atoms directly bonded to the atoms constituting the ring are removed from the ring. Formula 500, Formula 527 to Formula 534, Formula 543, Formula 561 to Formula 564, Formula 568 and Expression 603 to Expression 607 It is more preferable that the divalent group in which two hydrogen atoms directly bonded to the atoms constituting the ring are removed from the ring represented by any one of formulas 527 to 530 and 603 to 607 A divalent group in which two hydrogen atoms directly bonded to the atoms constituting the ring are removed from the ring represented by any of them is particularly preferable.

In the divalent aromatic group represented by R ¹ , the two positions from which hydrogen atoms are removed are atoms bonded to H ^x when the two hydrogen atoms to be removed are H ^x and H ^y . and it is preferable to choose between atoms bonded with H ^y as the number of atoms increases which connects shortest. Further, the number of atoms connecting the atoms bonded to H ^x and the atoms bonded to H ^y at the shortest is preferably an even number because the conjugate length is further expanded. For example, in the case of the benzene ring represented by Formula 500, when a hydrogen atom is removed at the para position, the minimum number of atoms between the carbon atoms bonded to the removed hydrogen atom is 4 atoms, and at the meta position, 3 atoms, 2 atoms in ortho position. For this reason, in the case of the benzene ring represented by Formula 500, it is preferable that a hydrogen atom be removed at the para position. Further, for example, in the case of the fluorene ring represented by the above formula 603, when the hydrogen atom is removed at the 2,7-position, the number of atoms connected in the shortest is the largest (eight), so the 2,7-position It is preferred that the hydrogen atom be removed.

Furthermore, the following positions are also preferable as the two positions (that is, the positions of H ^x and H ^y ) from which hydrogen atoms are removed.
In the case of the naphthalene ring represented by the above formula 527, there are two positions of 1-position and 4-position.
In the case of the anthracene ring represented by the formula 528, two positions of 9-position and 10-position.
In the case of the tetracene ring represented by the formula 529, there are two positions, the 2-position and the 3-position.
In the case of the pyrene ring represented by the formula 530, there are two positions of 1-position and 6-position.

The divalent aromatic group represented by R ¹ may have a substituent. The number of substituents possessed by the divalent aromatic group represented by R ¹ is preferably 0 to 4, more preferably 0 to 2, further preferably 1 to 2, and particularly preferably 2.

Examples of the substituent that the divalent aromatic group represented by R ¹ may have include a halogen atom, a hydroxy group, a hydrocarbyl group, a hydrocarbyloxy group, a dihydrocarbylamino group, a hydrocarbyl mercapto group, and a hydrocarbylcarbonyl group. Groups, hydrocarbyloxycarbonyl groups, hydrocarbylcarbonyloxy groups, and (dihydrocarbyl) aminocarbonyl groups. When the hydrocarbyl group is a group represented by "R- (specific examples will be described later)", the hydrocarbyloxy group is a group represented by "RO-", and the hydrocarbyl mercapto group is represented by "RS-". The hydrocarbylcarbonyl group is a group represented by “RC (═O) —”, and the hydrocarbyloxycarbonyl group is a group represented by “ROC (═O) —”, The carbonyloxy group is a group represented by “RC (═O) O—”, the dihydrocarbylamino group is a group represented by “R ₂ N—”, and the (dihydrocarbyl) aminocarbonyl group is “ R ₂ N—C (═O) — ”. When two R are present, they may be the same or different from each other, preferably the same as each other. Moreover, when two R exists, they may be bonded to each other to form a ring structure.

The substituent which the divalent aromatic group represented by R ¹ may have is preferably a halogen atom, a hydroxy group, a hydrocarbyl group, a hydrocarbyloxy group, a dihydrocarbylamino group, a hydrocarbylcarbonyl group, a hydrocarbyloxy group. A carbonyl group or a hydrocarbylcarbonyloxy group, more preferably a hydroxy group, a hydrocarbyl group, a hydrocarbyloxy group, or a hydrocarbylcarbonyloxy group, still more preferably a hydrocarbyl group, a hydrocarbyloxy group, or a hydrocarbylcarbonyloxy group.

  Examples of the hydrocarbyl group represented by R include a methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n A linear alkyl group having 1 to 50 carbon atoms such as nonyl group and n-decyl group; isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 2,2-dimethylpropyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, 1-ethylpropyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methyl Pentyl group, 4-methylpentyl group, 1,1-dimethylbutyl group, 2,2-dimethylbutyl group, 3,3-dimethylbutyl group, 1,2-dimethylbutyl group, 1, -Dimethylbutyl group, 2,3-dimethylbutyl group, 2,3,3-trimethylpropyl group, 2,2,3-trimethylpropyl group, 1-ethylbutyl group, 2-ethylbutyl group, 1-ethyl-2-methyl Propyl group, 1-methylhexyl group, 2-methylhexyl group, 3-methylhexyl group, 4-methylhexyl group, 5-methylhexyl group, 1,2-dimethylpentyl group, 1,3-dimethylpentyl group, 1 , 4-dimethylpentyl group, 2,3-dimethylpentyl group, 2,4-dimethylpentyl group, 3,4-dimethylpentyl group, 1-ethylpentyl group, 2-ethylpentyl group, 3-ethylpentyl group, 1 -Propylbutyl group, 1-isopropyl-2-methylpropyl group, 1-ethyl-2-methylbutyl group, 1-propyl-2-methylpropyl group, 1 Methylheptyl group, 2-methylheptyl group, 3-methylheptyl group, 4-methylheptyl group, 5-methylheptyl group, 6-methylheptyl group, 1,2-dimethylhexyl group, 1,3-dimethylhexyl group, 1,4-dimethylhexyl group, 1,5-dimethylhexyl group, 2,3-dimethylhexyl group, 2,4-dimethylhexyl group, 2,5-dimethylhexyl group, 3,4-dimethylhexyl group, 3, 5-dimethylhexyl group, 4,5-dimethylhexyl group, 1-ethylhexyl group, 2-ethylhexyl group, 3-ethylhexyl group, 4-ethylhexyl group, 1-propylpentyl group, 1-isopropylpentyl group, 1,1, 3,3-tetramethylbutyl group, 2,5-dimethylheptyl group, 1-ethylheptyl group, 1-isopropyl-2-methylbutyl group 3 to 50 carbon atoms, such as a til group, 1-isopropyl-3-methylbutyl group, 1-methyloctyl group, 1-propylhexyl group, 1-isobutyl-3-methylbutyl group and 3,7-dimethyloctyl group Branched alkyl group: Cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclononyl group, cyclododecyl group and other cycloalkyl groups, norbornyl group and adamantyl group, etc., cyclic saturated hydrocarbyl having 3 to 50 carbon atoms An alkenyl group having 2 to 50 carbon atoms, such as ethenyl group, propenyl group, 3-butenyl group, 2-butenyl group, 2-pentenyl group, 2-hexenyl group, 2-nonenyl group and 2-dodecenyl group; An alkynyl group having 2 to 50 carbon atoms such as an ethynyl group, a propynyl group and a 2-butynyl group; a phenyl group; -Naphtyl group, 2-naphthyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 4-ethylphenyl group, 4-propylphenyl group, 4-isopropylphenyl group, 4-butylphenyl group Aryl groups having 6 to 50 carbon atoms, such as 4-tert-butylphenyl group, 4-hexylphenyl group, 4-cyclohexylphenyl group, 4-adamantylphenyl group and 4-phenylphenyl group; -Phenyleneethyl group, 2-phenylethyl group, 1-phenyl-1-propyl group, 1-phenyl-2-propyl group, 2-phenyl-2-propyl group, 3-phenyl-1-propyl group, 4-phenyl 7 to 50 carbon atoms such as -1-butyl group, 5-phenyl-1-pentyl group and 6-phenyl-1-hexyl group Aralkyl group. Among them, the hydrocarbyl group represented by R includes a linear alkyl group having 1 to 50 carbon atoms, a branched alkyl group having 3 to 50 carbon atoms, an aryl group having 6 to 50 carbon atoms, or carbon. Aralkyl groups having 7 to 50 atoms are preferred, linear alkyl groups having 1 to 30 carbon atoms, branched alkyl groups having 3 to 30 carbon atoms, or aryl groups having 6 to 30 carbon atoms, A linear alkyl having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, or an aryl group having 6 to 18 carbon atoms is more preferable, and a linear alkyl having 1 to 12 carbon atoms. A group or a phenyl group is particularly preferred.

In the formula (1), X ¹ is a group represented by —O—, a group represented by —S—, a group represented by —C (═O) —, and —C (═O) O—. A group represented by —C (═O) N (R ¹⁰ ) —, a group represented by —OC (═O) O—, and —OC (═O) N (R ¹¹ ) —. a group represented ^{by, -N (R 12) C (} = O) N (R 13) - , a group represented by, ^{-C (R} _{14) 2} -, a group represented by, -Si ^(R _{15) 2} - Or a group represented by -C (R ¹⁶ ) = C (R ¹⁶ )-or a divalent amine residue. Among these, a group represented by —O—, a group represented by —C (═O) —, a group represented by —C (═O) O—, —C (═O) N (R ¹⁰ ). A group represented by —, a group represented by —OC (═O) O—, a group represented by —OC (═O) N (R ¹¹ ) —, and a group represented by —C (R ¹⁴ ) ₂ —. A group represented by -C (R ¹⁶ ) = C (R ¹⁶ )-or a divalent amine residue, a group represented by -O-, -C (= O) N ( A group represented by R ¹⁰ ) —, a group represented by —C (R ¹⁴ ) ₂ —, a group represented by —C (R ¹⁶ ) ═C (R ¹⁶ ) —, or a divalent amine residue More preferably a group represented by -C (R ¹⁴ ) _2- , a group represented by -C (R ¹⁶ ) = C (R ¹⁶ )-, or a divalent amine residue, A divalent amine residue is particularly preferred.

Examples of the divalent amine residue represented by X ¹ include a divalent aromatic amine residue represented by the following formula (3).

式（３）中、Ａｒ^３、Ａｒ^４、Ａｒ^５及びＡｒ^６は、それぞれ独立に、置換基を有していてもよい２価の芳香族基であり、Ａｒ^７、Ａｒ^８及びＡｒ^９は、それぞれ独立に、置換基を有していてもよい１価の芳香族基である。ｍ_３及びｍ_４は、それぞれ独立に、０又は１である。

In formula (3), Ar ³ , Ar ⁴ , Ar ⁵ and Ar ⁶ are each independently a divalent aromatic group which may have a substituent, and Ar ⁷ , Ar ⁸ and Ar ⁹ are These are each independently a monovalent aromatic group optionally having a substituent. m ₃ and m ₄ are each independently 0 or 1.

Examples of the divalent aromatic group which may have a substituent represented by Ar ³ , Ar ⁴ , Ar ⁵ and Ar ⁶ may have a substituent represented by R ^1. It is the same as a divalent aromatic group, and is preferably a phenylene group which may have a substituent. Examples of the monovalent aromatic group which may have a substituent represented by Ar ⁷ , Ar ⁸ and Ar ⁹ are divalent which may have a substituent represented by R ¹ . In the aromatic group, it is a monovalent group formed by bonding one hydrogen atom out of two removed hydrogen atoms, and is preferably a phenyl group which may have a substituent.

When m ₃ is 0, the carbon atom in Ar ³ and the carbon atom in Ar ⁵ may be directly bonded, and a divalent group such as a group represented by —O— or a group represented by —S—. It may be bonded via the group.
When m ₄ is 0, the carbon atom in Ar ³ and the carbon atom in Ar ⁹ may be directly bonded, and a divalent group such as a group represented by —O— or a group represented by —S—. It may be bonded via the group.
When m ₃ and m ₄ are both 0, a carbon atom in Ar ⁵ and a carbon atom in Ar ⁹ may be directly bonded to each other, a group represented by —O—, a group represented by —S— And may be bonded via a divalent group such as

  Examples of the divalent aromatic amine residue represented by the formula (3) include 2 hydrogen atoms directly bonded to the carbon atom constituting the ring from the aromatic amine represented by any of the following formulas 615 to 627. Exemplified groups are exemplified.

  The divalent amine residue represented by the formula (3) is preferably an aromatic amine represented by any one of the formulas 615 to 621 and 627 among the aromatic amines represented by the formulas 615 to 627. A group in which two hydrogen atoms directly bonded to a carbon atom constituting a ring are removed from an amine, more preferably an aromatic represented by any one of formulas 615, 617, 618, 620, and 627 A group in which two hydrogen atoms directly bonded to a carbon atom constituting a ring are removed from an aromatic amine, and more preferably a carbon constituting a ring from an aromatic amine represented by any one of formulas 615 and 617 A group in which two hydrogen atoms directly bonded to the atom are removed.

The positions of the two hydrogen atoms removed from the aromatic amine represented by the above formulas 615 to 627 are such that both of the two hydrogen atoms removed are each the amine nitrogen atom with respect to the amine nitrogen atom. Choose to be in the para position of the 6-membered aryl group attached to the atom, or both of the two hydrogen atoms removed are each attached to the nitrogen atom of the amine, relative to the nitrogen atom of the amine. Preferably selected to be in the meta position of the 6-membered ring aryl group, wherein both of the two hydrogen atoms to be removed are each bonded to the amine nitrogen atom to the amine nitrogen atom. More preferably, it is selected so as to be in the para position of the ring aryl group.
With respect to amines having three or more positions corresponding to the para-position or the meta-position, the positions at which two hydrogen atoms are removed are H 2 and H 2 when the two hydrogen atoms to be removed are H ^x and H ^y. it is preferable to choose between atoms bonded with the atoms to H ^y which joins the ^x as the number of atoms connecting the shortest increases. The 6-membered aryl group from which a hydrogen atom is removed is preferably a phenyl group.

In the formula (1), R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently a hydrogen atom or a hydrocarbyl group which may have a substituent. When there are a plurality of R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ , they may be the same or different.

Examples of the hydrocarbyl group in R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ include a linear alkyl group, a branched alkyl group, a cyclic saturated hydrocarbyl group, an alkenyl group, and an alkynyl group. An aryl group and an aralkyl group, a linear alkyl group, a branched alkyl group, an aryl group or an aralkyl group is preferable, and a linear alkyl group, a branched alkyl group or an aryl group is more preferable.
The hydrocarbyl group usually has 1 to 50 carbon atoms, preferably 1 to 30, more preferably 1 to 18, still more preferably 1 to 8, and particularly preferably 4 to 8. is there. Examples of the linear alkyl group, branched alkyl group, cyclic saturated hydrocarbyl group, alkenyl group, alkynyl group, aryl group and aralkyl group are the same as those for R.

In the formula (1), R ¹⁰ , R ¹¹ , R ¹² and R ¹³ are preferably hydrogen atoms.

In the formula (1), R ¹⁴ , R ¹⁵ and R ¹⁶ are preferably hydrocarbyl groups which may have a substituent.

In the formula (1), m ₁ is an integer of 1 or more, and m ₂ is an integer of 0 or more. m ₁ is preferably an integer of 1 to 10, more preferably an integer of 1 to 5, still more preferably 1 or 2, and particularly preferably 1. m ₂ is preferably an integer of 0 to 10, more preferably an integer of 0 to 5, still more preferably 0 or 1, and particularly preferably 0. The combination of m ₁ and m ₂ is preferably such that m ₁ is 1 and m ₂ is 0.

Determined in the above formula (1), ^{when R 1} _{R x} type, ^{X 1} is present _{X y type,} so that the m 1 / _{R x,} the ratio of m 2 / _{X y} is minimized integer ratio Is done. However, when m ₂ is 0, m ₁ / R _x = 1. For example, when the ratio of m ₁ and m ₂ is 4: 7, R _x = 3, and X _y = 5, m ₁ / R _x : m ₂ / X _y is determined to be the smallest integer ratio. Therefore, it is 20:21, and m ₁ = 60 and m ₂ = 105.
R _x is a number of 1 or more, preferably 1 or 2, and more preferably 1.
X _y is a number of 1 or more, preferably 1 or 2, and more preferably 1.

In the formula (2), R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom or a hydrocarbyl group which may have a substituent. The hydrocarbyl group represented by R ⁵ , R ⁶ and R ⁷ is the same as the hydrocarbyl group described above for R ¹⁰ .

The number of carbon atoms of the hydrocarbyl group represented by R ⁵ , R ⁶ and R ⁷ is preferably 1-18, more preferably 1-8, still more preferably 1-4, and particularly preferably 1. It is.

The hydrocarbyl group represented by R ⁵ , R ⁶ and R ⁷ is preferably a linear alkyl group, a branched alkyl group, an aryl group or an aralkyl group, more preferably a linear alkyl group or a branched group. It is an alkyl group or an aryl group, and more preferably a linear alkyl group.

In the formula (2), R ⁵ , R ⁶ and R ⁷ are preferably hydrogen atoms.

In the formula (2), R ⁸ is a group represented by —O—, a group represented by —S—, a group represented by —C (═O) O—, —C (═O) N ( R ⁹ ) — is a divalent group in which one or two selected from the group consisting of a group represented by R ⁹ ) — and an optionally substituted hydrocarbylene group, or a direct bond. . R ⁸ is preferably a group represented by —O—, a group represented by —S—, a group represented by —C (═O) O—, —C (═O) N (R ⁹ ). A group represented by-, a hydrocarbylene group which may have a substituent, or a direct bond, more preferably a group represented by -O-, -C (= O) O-. A group represented by —C (═O) N (R ⁹ ) — or a direct bond, and more preferably represented by —C (═O) N (R ⁹ ) —. A group or a direct bond.

An example of the hydrocarbylene group represented by R ⁸ is a divalent group in which one hydrogen atom is removed from the hydrocarbyl group described above for R ¹⁰ .

The number of carbon atoms of the hydrocarbylene group represented by R ⁸ is preferably 1 to 18, more preferably 1 to 10, and still more preferably 1 to 4.

The hydrocarbylene group represented by R ⁸ is preferably a linear alkylene group, a branched alkylene group, an arylene group or an aralkylene group, more preferably a linear alkylene group or an arylene group, A linear alkylene group is preferred.

R ⁹ is a hydrogen atom or a hydrocarbyl group which may have a substituent, and is preferably a hydrocarbyl group. Examples of the hydrocarbyl group represented by R ⁹ are the same as the hydrocarbyl group described above for R ¹⁰ .

The number of carbon atoms of the hydrocarbyl group represented by R ⁹ is preferably 1 to 18, more preferably 1 to 12, still more preferably 4 to 12, and particularly preferably 6 to 8.

The hydrocarbyl group represented by R ⁹ is preferably a linear alkyl group, a branched alkyl group, an aryl group or an aralkyl group, more preferably a linear alkyl group or an aryl group, still more preferably. An aryl group.

In the formula (2), Ar ² is a monovalent aromatic hydrocarbon group which may have a substituent, and the monovalent aromatic hydrocarbon group contains 7 or more sp ² carbon atoms. An example of a monovalent aromatic hydrocarbon group in Ar ² is obtained by bonding one hydrogen atom out of two hydrogen atoms removed in the divalent aromatic group represented by R ^1. Among the monovalent groups, a monovalent aromatic hydrocarbon group containing 7 or more sp ² carbon atoms.

The monovalent aromatic hydrocarbon group represented by Ar ² is preferably a ring represented by any one of Formula 527 to Formula 530, Formula 576 to Formula 579, Formula 585 to Formula 587, and Formula 603 to Formula 607. Is a group in which one hydrogen atom directly bonded to an atom constituting the ring is removed, and more preferably, the ring is constituted from the ring represented by any one of formulas 576 to 579 and 585 to 587. It is a group in which one hydrogen atom directly bonded to an atom is removed, and more preferably, one hydrogen atom directly bonded to an atom constituting the ring is removed from the ring represented by any of formulas 576 to 579. And particularly preferably a group in which one hydrogen atom directly bonded to the atom constituting the ring is removed from the ring represented by formula 576 or 577.

The monovalent aromatic hydrocarbon group represented by Ar ² may have a substituent. The number of substituents that the monovalent aromatic hydrocarbon group represented by Ar ² has is preferably 0 to 5, more preferably 0 to 4, and still more preferably 0 to 3. Particularly preferably 0 to 2.

Examples of the substituent that the monovalent aromatic hydrocarbon group represented by Ar ² may have include a halogen atom, a hydrocarbyl group having 1 to 30 carbon atoms, and a hydrocarbyloxy group having 1 to 30 carbon atoms. And a hydrocarbyl mercapto group having 1 to 30 carbon atoms, preferably a halogen atom, a hydrocarbyl group having 1 to 18 carbon atoms, or a hydrocarbyloxy group having 1 to 18 carbon atoms, and more Preferred is a hydrocarbyl group having 1 to 12 carbon atoms or a hydrocarbyloxy group having 1 to 12 carbon atoms, more preferred is a hydrocarbyl group having 1 to 12 carbon atoms, and particularly preferred is 1 carbon atom. A linear alkyl group having ˜8 or a branched alkyl group having 1 to 8 carbon atoms, and particularly preferably a branched alkyl group having 1 to 6 carbon atoms. Alkyl group.

The monovalent aromatic hydrocarbon group represented by Ar ² contains 7 or more sp ² carbon atoms. The sp ² sp ² carbon atoms of the substituents on the number of carbon atoms is not included. Since it is easy to maintain the molecular orientation, the monovalent aromatic hydrocarbon group in Ar ² preferably contains 8 or more sp ² carbon atoms, more preferably 10 or more, and particularly preferably 12 or more.
The sp ² carbon atom contained in the entire Ar ² is preferably 20% by weight or more, more preferably 40% by weight or more of the entire Ar ² because the molecular arrangement of the polymer compound is fixed by stacking of the sp ² carbon atoms. Is more preferable, 50% by weight or more is further preferable, and 60% by weight or more is particularly preferable.

R ¹ is a divalent aromatic group which may have a substituent or a divalent group represented by the above formula (2). When R ¹ is a divalent aromatic group that may have a substituent, the divalent aromatic group that may have a substituent may be a single group that may have a substituent. A hydrogen atom directly bonded to a ring-constituting aromatic ring, a condensed polycyclic aromatic ring optionally having a substituent, or a bridged polycyclic aromatic ring optionally having a substituent; A divalent group from which two are removed is preferable. When R ¹ is a divalent group represented by the formula (2), Ar ² has one hydrogen atom directly bonded to an atom constituting the ring from an aromatic ring assembly which may have a substituent. It is preferably a monovalent group that has been removed, and among them, a ring is formed from the ring represented by any one of the above formulas 576 to 579 and 585 to 587, which may have a substituent. It is preferably a group in which one hydrogen atom directly bonded to the atom to be removed is removed.

When R ¹ is a divalent group represented by the formula (2), R ⁵ , R ⁶ and R ⁷ are hydrogen atoms, R ⁸ is a group represented by —O—, —C (= O) a group represented by O—, a group represented by —C (═O) N (R ⁹ ) —, or a direct bond is preferable, and R ⁵ , R ^6, and R ⁷ are each a hydrogen atom. More preferably, R ⁸ is a group represented by —C (═O) N (R ⁹ ) — or a direct bond.

  Examples of the repeating unit represented by the formula (1) include the following repeating units (formula 100 to formula 128). In the following repeating units, t-Bu represents a tert-butyl group, n-Hex represents an n-hexyl group, and n-Oct represents an n-octyl group.

  The repeating unit represented by Formula (1) is preferably a repeating unit selected from Formula 100 to Formula 113, Formula 118 to Formula 121, and Formula 125 to Formula 128 among Formula 100 to Formula 128, and more preferably. Is a repeating unit selected from Formula 100, Formula 103 to Formula 105, Formula 107, Formula 111, Formula 112, Formula 118 to Formula 121, and Formula 125 to Formula 128, and more preferably Formula 103, Formula 104, Formula 111, It is a repeating unit selected from Formula 112, Formula 118, Formula 119, Formula 121, and Formula 126 to Formula 128.

  The high molecular compound used for this invention should just contain the repeating unit of 1 or 2 or more chemical structure chosen from the repeating unit represented by the said Formula (1) at least partially. Since it is easy to control the degree of introduction of optical activity and a high optical activity polymer compound is obtained, the polymer compound used in the present invention is a repeating unit represented by the formula (1) with respect to the weight of the whole molecule. Is preferably 1% by weight or more, more preferably 5% by weight or more, further preferably 25% by weight or more, particularly preferably 80% by weight or more, and particularly preferably 100% by weight.

  The polymer compound used in the present invention may be a homopolymer or a copolymer, but is preferably a homopolymer. Here, the polymer compound used in the present invention is a homopolymer means that the polymer compound contains only a repeating unit having a specific chemical structure selected from repeating units represented by the formula (1) in the molecule. It means to do. When the polymer compound used in the present invention is a copolymer, the polymer compound contains a repeating unit having two or more chemical structures selected from repeating units represented by the formula (1) in the molecule. In addition, the polymer compound has a repeating unit having one or more chemical structures selected from the repeating unit represented by the formula (1) in the molecule, and a repeating unit other than the repeating unit represented by the formula (1). It means containing 1 or 2 or more repeating units.

  When the polymer compound used in the present invention is a copolymer, for example, a divalent group having a triarylamine skeleton, a divalent group having a triazine skeleton, or a divalent group having a cyclic hydrocarbyl group having an asymmetric carbon atom. It may further contain a group as a repeating unit, and preferably further contains a divalent group having a triarylamine skeleton or a divalent group having a triazine skeleton as a repeating unit.

The number average molecular weight (Mn) in terms of polystyrene of the polymer compound used in the present invention is usually 5 × 10 ² to 1 × 10 ⁸ . Since the film forming property and the solubility in a solvent can be improved to ensure good molding processability, the Mn of the polymer compound of the present invention is preferably 1 × 10 ³ to 1 × 10 ⁷ and more. It is preferably 2 × 10 ³ to 1 × 10 ⁶ , more preferably 3 × 10 ^{3 to} 5 × 10 ⁵ , particularly preferably 4 × 10 ³ to 1 × 10 ⁵ , and particularly preferably 1 × 10 6. ⁴ to 1 × 10 ⁵ . The weight average molecular weight (Mw) in terms of polystyrene of the polymer compound used in the present invention is usually 1 × 10 ³ to 1 × 10 ⁹ , preferably 2 × 10 ³ to 1 × 10 ⁸ , and more. Preferably it is 5 * 10 < ³ > -1 * 10 < ⁷ >, More preferably, it is 1 * 10 < ⁴ > -5 * 10 < ⁶ >, Most preferably, it is 5 * 10 < ⁴ > -5 * 10 < ⁵ >.

  The polymer compound used in the present invention may be a polymer compound that exhibits optical activity before irradiation with circularly polarized light. When using a polymer compound exhibiting optical activity before irradiation with circularly polarized light, a polymer compound exhibiting stronger optical activity can be obtained by the modification method of the present invention.

  The polymer compound used in the present invention can be synthesized by a conventionally known polymer compound synthesis method.

  The high molecular compound used for this invention is manufactured by the method of the following Example, for example. In addition to the embodiment, it is also manufactured by the following method. For example, a THF solution of 2,7-dibromo-9,9-di-n-octylfluorene is added to a suspension obtained by adding tetrahydrofuran and 1,2-dibromoethane to metallic magnesium in a nitrogen atmosphere, and while heating. Stir. Thereafter, [1,3-bis (diphenylphosphino) propane] dichloronickel (II) is added to the obtained reaction liquid, and further stirred while heating. Next, the resulting reaction solution is extracted by adding dilute hydrochloric acid and chloroform, and washed with water. The obtained organic layer can be synthesized by drying over anhydrous magnesium sulfate, filtering and concentrating, dissolving in THF, dropping the resulting solution into methanol and reprecipitating.

  The polymer compound having a repeating unit represented by the above formula (1) is also produced by the following method. For example, a styrene derivative and a chloroform solution of 2,2'-azobis (isobutyronitrile) are mixed and stirred while heating. It can synthesize | combine by distilling a solvent off from the obtained reaction liquid, making it melt | dissolve in chloroform, dripping the obtained solution in methanol and reprecipitating.

  In the method for modifying a polymer compound of the present invention, when the polymer compound is irradiated with circularly polarized light, the polymer compound may be in any shape / state such as a powder, a film, a molded body, a solution, and a dispersion. The shape / state of the powder, film, molded product or dispersion is preferable, and the shape / state of the film or dispersion is more preferable. Since the process load is light and the control of molecular orientation is easy, the polymer compound is more preferably in the form of a film.

  The thickness of the film is usually 1 nm to 500 μm, preferably 2 nm to 100 μm, more preferably 3 nm to 20 μm, still more preferably 5 nm to 1 μm, and particularly preferably 10 nm to 200 nm. The thin film may include pinholes or irregular shapes.

  As a method for producing the membrane, for example, a suspension obtained by suspending or dissolving a polymer compound having a repeating unit represented by the above formula (1) and other components in a solvent at an arbitrary ratio. Alternatively, a method including a step of applying a solution to a substrate, and a method including a step of depositing the polymer compound having the repeating unit represented by the above formula (1) and other components on the substrate in an arbitrary ratio. Preferably, the former method is used.

  Examples of the solvent used in the coating step include benzene, toluene, xylene, chloroform, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, dichloromethane, tetrahydrofuran, 2-methyltetrahydrofuran, 1,4. -Dioxane, N, N-dimethylformamide, dimethyl sulfoxide, acetone, methyl ethyl ketone, acetonitrile, ethyl acetate, methanol, ethanol, isopropyl alcohol, hexane, cyclohexane, trifluoroacetic acid and mixtures thereof, preferably toluene, xylene , Chloroform, tetrahydrofuran, trifluoroacetic acid or mixtures thereof.

  In the coating step, examples of the coating method include spin coating, casting, dip coating, gravure printing, bar coating, roll coating, spray coating, screen printing, flexographic printing, and inkjet printing. And an offset printing method, and a spin coating method, a casting method, a roll coating method, a spray coating method, a screen printing method, a flexographic printing method, an inkjet printing method or an offset printing method is preferable.

  In the modification method of the present invention, the above-described polymer compound may be used alone, or within the range where the effects of the present invention are not impaired, the polymer compound and other components are used in combination as a composition. Also good. When used as a composition, a better and better modification effect can be obtained. Therefore, the content of the polymer compound is preferably 1% by weight or more with respect to 100% by weight of the entire composition. % Or more, more preferably 50% by weight or more, and particularly preferably 90% by weight or more. Moreover, the upper limit is 99 weight% normally.

Examples of components other than the above-described polymer compound (hereinafter also simply referred to as “other components”) that may be used to form the composition include, for example, a low-molecular organic material, a polymer organic material, and an organic inorganic material. A composite material, an inorganic material, and a mixture thereof are mentioned, and can be arbitrarily selected depending on the application.
For example, when the modified polymer compound obtained by the modification method of the present invention is used as a material for a light-emitting element, examples of the other components include the following.

(Anode material)
Examples of the anode material include conductive metal oxides such as tin oxide, zinc oxide, indium oxide, and indium tin oxide (ITO); metals such as gold, silver, chromium, and nickel; the conductive metal oxides and the above Mixtures with metals; inorganic conductive materials such as copper iodide and copper sulfide; organic conductivity such as polyaniline and its derivatives, polythiophene and its derivatives [poly (3,4) ethylenedioxythiophene, etc.], polypyrrole and its derivatives And a combination thereof, preferably polyaniline and derivatives thereof, polythiophene and derivatives thereof, or polypyrrole and derivatives thereof. These are useful when the modified polymer compound obtained by the modification method of the present invention is used for an anode of a light emitting device.

(Cathode material)
Examples of cathode materials include alkali metals (Li, Na, K, Cs, etc.) and their fluorides and oxides; alkaline earth metals (Mg, Ca, Ba, etc.) and their fluorides and oxides; gold, silver Metals such as lead, aluminum, etc .; sodium-potassium alloys, sodium-potassium mixed metals, lithium-aluminum alloys, lithium-aluminum mixed metals, magnesium-silver alloys, magnesium-silver mixed metals, and mixed metals; indium, ytterbium Rare earth metals; and combinations thereof. These are useful when the modified polymer compound obtained by the modification method of the present invention is used for the cathode of a light emitting device.

(Hole injection and hole transport materials)
Examples of hole injection and hole transport materials include carbazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, styrylanthracene derivatives, hydrazone derivatives, stilbene derivatives. , Silazane derivatives, porphyrin derivatives, polysilane derivatives, poly (N-vinylcarbazole) derivatives, and polymers containing residues of these derivatives; conductive polymer oligomers such as aniline copolymers, thiophene oligomers, and polythiophenes Preferably, it is a carbazole derivative, an arylamine derivative, or a poly (N-vinylcarbazole) derivative. These are useful when the modified polymer compound obtained by the modification method of the present invention is used for a light emitting layer, a hole injection and a hole transport layer of a light emitting device.

(Electron injection and electron transport materials)
Examples of electron injection and electron transport materials include triazole derivatives, oxazole derivatives, oxadiazole derivatives, pyridine derivatives, pyrazine derivatives, triazine derivatives, imidazole derivatives, fluorene derivatives, fluorenone derivatives, anthraquinodimethane derivatives, anthrone derivatives, Diphenylquinone derivatives, thiopyran dioxide derivatives, carbodiimide derivatives, fluorenylidenemethane derivatives, distyrylpyrazine derivatives, tetracyclic anhydrides of aromatic rings such as naphthalene and perylene, phthalocyanine derivatives, metal complexes (for example, 8-quinolinol derivatives) Metal complexes having metal phthalocyanine as a ligand, metal complexes having benzoxazole as a ligand, and metal complexes having benzothiazole as a ligand. It is a triazole derivative, an oxadiazole derivative, a triazine derivative, a metal complex of 8-quinolinol derivatives. These are useful when the modified polymer compound obtained by the modification method of the present invention is used for a light emitting layer, an electron injection and an electron transport layer of a light emitting device.

(Electrolyte material)
Examples of the electrolyte material include a supporting salt (such as lithium trifluoromethanesulfonate, lithium perchlorate, tetrabutylammonium perchlorate, potassium hexafluorophosphate, tetra-n-butylammonium tetrafluoroborate) and a supporting salt. Solvent that may be contained (propylene carbonate, acetonitrile, 2-methyltetrahydrofuran, 1,3-dioxofuran, nitrobenzene, N, N-dimethylformamide, dimethyl sulfoxide, glycerin, propyl alcohol, water, etc.) or swollen with the solvent Examples thereof include gel-like polymers (polyethylene oxide, polyacrylonitrile, a copolymer of vinylidene fluoride and propylene hexafluoride, and the like). These are useful when the modified polymer compound obtained by the modification method of the present invention is used in a light emitting layer of a light emitting device (for example, an electrochemiluminescent device) that forms an electric double layer.

(Luminescent material)
Examples of the light-emitting material include metal complexes using platinum group elements (such as iridium complexes coordinated with phenylpyridine derivatives), metal complexes using rare earth elements (such as europium complexes coordinated with phenanthroline derivatives), 8- Examples include aluminum complexes coordinated with quinolinol derivatives, naphthacene derivatives, dicyanoethylene derivatives, coumarin derivatives, quinacridone derivatives, anthracene derivatives, perylene derivatives, phenylene vinylene derivatives, fluorene derivatives, naphthalene derivatives, preferably iridium complexes or fluorene derivatives. is there. These may be used in combination when the optically active polymer compound obtained by the modification method of the present invention is used as the light emitting material of the light emitting device.

  In addition, a resin that improves the film formability can be used as the other component. Examples of the resin for improving the film forming property include polyvinyl chloride, polycarbonate, polystyrene, polymethyl methacrylate, polybutyl methacrylate, polyester, polysulfone, polyphenylene oxide, polybutadiene, hydrocarbon resin, ketone resin, phenoxy resin, polyamide, and ethyl cellulose. , Vinyl acetate, ABS resin, polyurethane, melamine resin, unsaturated polyester resin, alkyd resin, epoxy resin, and silicone resin, preferably polymethyl methacrylate, polyester, and polyurethane.

  In addition to these, proteins, antioxidants, refractive index adjusters, viscosity adjusters, heat insulating agents, light absorbers, and the like can be used.

In the method for modifying a polymer compound of the present invention, irradiation with circularly polarized light can be performed using a general light source exhibiting circular polarization. Examples of such a light source include an apparatus using an Ar ⁺ laser, a YAG laser, or the like.

The intensity of the circularly polarized light, preferably 1~1000mW / cm ^2, more preferably 2~500mW / cm ^2, more preferably ^{3~250mW / cm 2, 5~100mW / cm} 2 is particularly preferred.

The irradiation time of the circularly polarized light is preferably 0.1 second to 72 hours, more preferably 1 second to 24 hours, further preferably 10 seconds to 12 hours, particularly preferably 1 minute to 6 hours, and 5 minutes to 2 hours. Especially preferred.
The irradiation environment of circularly polarized light may be in air or in an inert gas atmosphere such as nitrogen gas or argon gas, but is preferably in air because it is simple.
Although circularly polarized light is preferably irradiated at room temperature, the specimen may be heated by irradiation with circularly polarized light.
As the circularly polarized light irradiated in the present invention, elliptically polarized light can be used.

  The optically active polymer compound obtained by the modification method of the present invention is an electronic device (for example, a light emitting device (for example, an organic electroluminescent device, preferably an organic electroluminescent device emitting circularly polarized light), a solar cell, an organic It can be used for (transistor) materials, optical resolution, asymmetric field for asymmetric reactions, polarizing materials, refractive materials, pharmaceuticals, and the like.

<Method for Producing Film Containing Modified Polymer Compound>
The method for producing a film containing a modified polymer compound according to the present invention includes the following steps (a) and (b).
(A) The process of forming the film | membrane containing the high molecular compound which has a repeating unit represented by the said Formula (1) on a base material.
(B) A step of irradiating the film with circularly polarized light.

[Step (a)]
Step (a) is a step of forming a film containing a polymer compound having a repeating unit represented by the above formula (1) on a substrate. In addition, the high molecular compound which has a repeating unit represented by the said Formula (1) used for the manufacturing method of this invention is the same as what was demonstrated by the said <modification method of a high molecular compound>.

As the substrate, for example, quartz, glass, transparent or translucent resin, or the like may be used.
When the manufactured film is used as a hole injection and hole transport layer of a light emitting element, a film containing a polymer compound may be formed on an anode manufactured by a conventional method. In this case, the anode functions as a “base material”. Similarly, when the manufactured film is used as a light emitting layer of a light emitting element, a film containing a polymer compound may be formed on the hole injection and hole transport layer manufactured by a conventional method. In this case, the hole injection and hole transport layer functions as a “substrate”. That is, the substrate may be arbitrarily selected according to the use of the membrane as long as the polymer compound can be received on the surface and the polymer compound can be physically supported.

  In the step (a), as a method for forming a film containing a polymer compound on a substrate, for example, a polymer compound having a repeating unit represented by the above formula (1) and other components may be arbitrarily selected. A method of applying a suspension or solution obtained by suspending or dissolving in a solvent in a ratio to a substrate (hereinafter also simply referred to as an application method), and a repeating unit represented by the above formula (1) A method of vapor-depositing a polymer compound and other components on a base material at an arbitrary ratio (hereinafter also simply referred to as vapor deposition method) can be mentioned. Among these, since the process can be simplified, it is preferable to form a coating by the former coating method.

  Examples and preferred examples of the solvent used in the coating method, and specific embodiments of the coating method are the same as those described in the above <Method for modifying polymer compound>.

  In the coating method, usually, after applying a suspension or solution, the solvent contained in the suspension or solution is dried. Examples of the method for drying the solvent include air drying, heat drying, reduced pressure drying, heat reduced pressure drying, and drying performed by blowing nitrogen gas. Air drying or heat drying is preferable, and heat drying is more preferable. The atmosphere for drying the solvent is not particularly limited, but is preferably an inert gas atmosphere such as nitrogen gas or argon gas.

  In the step (a), examples and preferred examples of the other components used in combination with the polymer compound having the repeating unit represented by the formula (1) are those described in the above <Modification method of polymer compound>. And can be selected according to the intended use of the resulting membrane. For example, when the film obtained by the production method of the present invention is used for the anode of a light emitting device, the anode material described in the above <Method for modifying polymer compound> may be used as the other component. When the film obtained by the production method of the present invention is used for the hole injection and hole transport layer of the light emitting device, the hole injection and hole described in the above <Method for modifying polymer compound> are used as the other components. A transport material may be used. Similarly, when the film obtained by the production method of the present invention is used for the light emitting layer of the light emitting device, the other components are the hole injection and hole transporting materials described in the above <Method for modifying polymer compound>. Electron injection and electron transport materials, electrolyte materials, and luminescent materials may be used.

  The content of the polymer compound having the repeating unit represented by the above formula (1) in the film formed in the step (a) can be determined according to the use of the film, but a more excellent modification effect is obtained. Therefore, it is preferably 1% by weight or more, more preferably 10% by weight or more, still more preferably 50% by weight or more, and 90% by weight or more, based on the total weight of the film. Is particularly preferred, with 100% by weight (excluding inevitable impurities) being particularly preferred.

  The thickness of the film formed in the step (a) can be determined according to the use of the film, but is usually 1 nm to 500 μm, preferably 2 nm to 100 μm, more preferably 3 nm to 20 μm, More preferably, it is 5 nm-1 micrometer, Most preferably, it is 10 nm-200 nm.

[Step (b)]
Step (b) is a step of irradiating circularly polarized light on the film formed in step (a) and containing the polymer compound having the repeating unit represented by the above formula (1).

  In the step (b), the polymer compound in the film is modified to exhibit optical activity by irradiating the film containing the polymer compound having the repeating unit represented by the formula (1) with circularly polarized light. be able to.

  The circularly polarized light source, the intensity of the circularly polarized light, and the irradiation time are as described above in <Method for modifying polymer compound>. Here, the intensity of the circularly polarized light and the irradiation time of the circularly polarized light to be irradiated in the step (b) can be adjusted so that the obtained film exhibits the desired optical activity.

  The film containing the modified polymer compound obtained by the production method of the present invention can be used for the same application as the optically active polymer compound described above.

  Next, the present invention will be described with reference to examples. However, the present invention is not limited to these examples.

<Synthesis Example 1> (Synthesis of polymer compound having a repeating unit represented by Formula 119)
(1) Synthesis of 2,5-bis (4-tert-butylphenyl) toluene

The reaction vessel was filled with a nitrogen gas atmosphere, and then at room temperature, dibromoethane (1.37 g) was added to a mixture of magnesium metal (3.72 g, 153 mmol) and tetrahydrofuran (hereinafter referred to as “THF”) (20 mL). , 7.30 mmol) was added slowly. After bubbling stopped, a solution of 1-bromo-4-tert-butylbenzene (31.1 g, 146 mmol) in THF (100 mL) was added to the resulting reaction solution and refluxed at 60 ° C. for 1 hour. The obtained reaction solution was added to a solution of zinc (II) chloride (19.9 g, 146 mmol) in THF (60 mL), and further, N, N, N ′, N′-tetramethylethylenediamine (16.9 g, 146 mmol) was added. And stirred at room temperature for 30 minutes.
Thereafter, tetrakis (triphenylphosphine) palladium (0) (2.32 g, 2.01 mmol) was added thereto, and further, a solution of 2,5-dibromotoluene (9.12 g, 36.5 mmol) in THF (60 mL). Was slowly added over 20 minutes and stirred at 60 ° C. for 13 hours. The obtained reaction liquid was returned to room temperature, added to ice-cooled 10% by weight hydrochloric acid (350 mL) and filtered, and the residue was extracted with chloroform. The obtained organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, filtered, the solvent was distilled off, the filtrate was washed with methanol, and 2,5-bis (4-tert-butyl Phenyl) toluene was obtained (9.31 g, yield 73.0%).

(2) Synthesis of 2,5-bis (4-tert-butylphenyl) benzyl bromide

  After making the inside of the reaction vessel a nitrogen gas atmosphere, a mixture of N-bromosuccinimide (10.8 g, 60.6 mmol) and 2,2′-azobis (isobutyronitrile) (1.99 g, 12.1 mmol) was added. A solution of 2,5-bis (4-tert-butylphenyl) toluene (20.0 g, 56.1 mmol) obtained in (1) above in carbon tetrachloride (120 mL) was added and refluxed at 80 ° C. for 4 hours. . The obtained reaction liquid was returned to room temperature, filtered, the solvent was distilled off, and the residue was washed with methanol to obtain 2,5-bis (4-tert-butylphenyl) benzyl bromide (20.6 g, Yield 84.4%).

(3) Synthesis of [2,5-bis (4-tert-butylphenyl) benzyl] triphenylphosphonium bromide

  After making the inside of the reaction vessel a nitrogen gas atmosphere, 2,5-bis (4-tert-butylphenyl) benzyl bromide (2.50 g, 5.75 mmol) obtained in the above (2) and triphenylphosphine (1. Benzene (16 mL) was added to a mixture with 82 g, 6.94 mmol) and stirred at 70 ° C. for 12 hours. The obtained reaction liquid was returned to room temperature, filtered, the solvent was distilled off, and the residue was washed with hexane to obtain [2,5-bis (4-tert-butylphenyl) benzyl] triphenylphosphonium bromide. (3.13 g, yield 78.1%).

(4) Synthesis of [2,5-bis (4-tert-butylphenyl) styrene

  After making the inside of the reaction vessel a nitrogen gas atmosphere, [2,5-bis (4-tert-butylphenyl) benzyl] triphenylphosphonium bromide (3.13 g, 4.49 mmol) obtained in (3) above and water (6 mL) was mixed, and 30 wt% formalin solution (20 mL) was added and stirred. Next, a solution of sodium hydroxide (1.44 g, 35.9 mmol) in water (6 mL) was added dropwise thereto over 20 minutes, and the mixture was stirred at room temperature for 3 hours. The obtained reaction solution was extracted with dichloromethane, and the obtained organic layer was purified by silica gel column chromatography (developing solvent: dichloromethane) after evaporating the solvent, and [2,5-bis (4-tert-butylphenyl). ) Styrene (1.56 g, yield 94.4%) was obtained.

(5) Synthesis of poly [2,5-bis (4-tert-butylphenyl) styrene]

  After making the inside of the reaction vessel a nitrogen gas atmosphere, [2,5-bis (4-tert-butylphenyl) styrene (500 mg, 1.36 mmol) obtained in the above (4) and 2,2′-azobis ( A solution of isobutyronitrile) (3.6 mg, 0.022 mmol) in chloroform (1.5 mL) was mixed and stirred at 70 ° C. for 36 hours. The obtained reaction liquid was returned to room temperature, the solvent was distilled off, and then dissolved in chloroform (20 mL). The obtained solution was added dropwise to methanol (500 mL) for reprecipitation, and the solvent was removed by decantation. Reprecipitation was performed 5 times, and the desired poly [2,5-bis (4-tert-butylphenyl) styrene] (polymer compound having a repeating unit represented by the formula 119; hereinafter, “polymer compound 1 Was obtained (25.7 mg, yield 5.14%).

  The number average molecular weight (Mn) and weight average molecular weight (Mw) in terms of polystyrene of the polymer compound 1 were measured by size exclusion chromatography (SEC). A case where the mobile phase is an organic solvent in SEC is referred to as “GPC”.

  A measurement sample (polymer compound 1) was dissolved in tetrahydrofuran at a concentration of about 0.1% by weight, and 10 μL was injected into GPC (Hitachi L7100). The mobile phase of GPC was flowed at a flow rate of 1.0 mL / min using THF. The column used was TOSOH TSK gel G3000HHR and TOSOH TSK gel G6000HHR. A UV-VIS detector (Hitachi L-7420 UV) and an RI detector (Hitachi L-7490 RI) were used as detectors.

As a result, the polymer compound 1 had Mn = 6.73 × 10 ⁴ and Mw = 1.47 × 10 ⁶ .

<Synthesis Example 2> (Synthesis of polymer compound having a repeating unit represented by Formula 118)
(1) Synthesis of N-4-biphenylaniline

  After making the inside of the reaction vessel a nitrogen gas atmosphere, a mixture of 4-bromobiphenyl (10.0 g, 42.9 mmol) and sodium tert-butoxide (5.15 g, 53.6 mmol) was dissolved in THF (340 mL). [1,1-bis (diphenylphosphino) ferrocene] dichloropalladium (II) (630 mg, 0.860 mmol), 1,1′-bis (diphenylphosphino) ferrocene (0.450 g, 0.810 mmol). ), Aniline (3.90 mL, 42.9 mmol) was added and stirred at 100 ° C. for 40 hours. 0.1 M hydrochloric acid (100 mL) was added to the resulting reaction solution, followed by extraction with chloroform, and the resulting organic layer was washed with saturated brine. The obtained organic layer was dried over anhydrous magnesium sulfate, filtered, concentrated, and purified by silica gel column chromatography (developing solvent: chloroform) to give N-4-biphenylaniline (10.1 g, yield 96. 0%) was obtained.

(2) Synthesis of N-4-biphenyl N-phenylacrylamide

  After making the inside of the reaction vessel a nitrogen gas atmosphere, N, N-dimethylaniline (2) was added to a solution of N-4-biphenylaniline (3.00 g, 12.2 mmol) obtained in (2) above in benzene (180 mL). .16 mL) and acryloyl chloride (1.20 mL, 14.7 mmol) were added, and the mixture was stirred at 23 ° C. for 20 hours. Distilled water and 0.1 M hydrochloric acid (100 mL) were added to the obtained reaction solution, and then toluene was added for extraction, and the resulting organic layer was washed with saturated brine. The obtained organic layer was dried over anhydrous sodium sulfate, filtered, concentrated, recrystallized with a methylene chloride-diethyl ether solution and filtered. The obtained filtrate was washed with hexane to obtain N-4-biphenyl N-phenylacrylamide (2.06 g, yield 56.4%).

(3) Synthesis of poly (N-4-biphenyl N-phenylacrylamide)

Toluene (19 mL) was added to a solution of tert-butyllithium in n-pentane (1.77 M, 1.0 mL) to prepare a 8.9 × 10 ⁻² M solution. This prepared solution (470 μL) was placed in a reaction vessel at −78 ° C. with toluene (6.25 mL) of N-4-biphenyl N-phenylacrylamide (250 mg, 0.835 mmol) obtained in (2) above. The solution was added dropwise to the solution, mixed and stirred for 14 hours while maintaining at -78 ° C. A small amount of ethanol was added to the obtained reaction solution, this was dropped into ethanol (150 mL), reprecipitation was performed, and the precipitate was collected by centrifugation to obtain the desired poly (N-4-biphenyl N- Phenylacrylamide) (polymer compound having a repeating unit represented by Formula 118; hereinafter referred to as “polymer compound 2”) was obtained in a yield of 76%.

When the GPC measurement of the high molecular compound 2 was performed, they were Mn = 1.09 * 10 < ⁴ > and Mw = 6.7 * 10 < ⁴ >.

<Synthesis Example 3> (Synthesis of polymer compound having a repeating unit represented by Formula 127)
Synthesis of poly (2,3-diacetoxynaphthalene-1,4-diyl)

  In a reaction vessel, pyridine (9.63 mg, 0.125 mmol) was added to a mixture of 2,3-dihydroxynaphthalene (0.200 g, 1.25 mmol) and cuprous chloride (6.19 mg, 0.0625 mmol) in an air atmosphere. ) And THF (0.4 mL) were added, and the mixture was stirred at 60 ° C. for 48 hours. Dichloromethane (2 mL), pyridine (9.63 mg, 0.125 mmol) and acetyl chloride (0.491 g, 6.25 mmol) were added to the obtained reaction solution, and the mixture was allowed to return to room temperature and stirred for 12 hours. Methanol is added to the resulting reaction solution, and the precipitate is collected by centrifugation, and the target poly (2,3-diacetoxynaphthalene-1,4-diyl) (having the repeating unit represented by the above formula 127). Polymer compound; hereinafter referred to as “polymer compound 3”) was obtained in a yield of 62%.

<Membrane Production Example 1>
A 1.0 × 10 ⁻⁴ M (monomer equivalent) chloroform solution of the polymer compound 1 obtained in Synthesis Example 1 was applied onto a quartz substrate by a casting method, and then naturally dried to produce a membrane (the membrane Thickness 40 nm).

<Membrane Production Example 2>
A solution obtained by dissolving the polymer compound 2 (5 mg) obtained in Synthesis Example 2 above in a mixed solvent (2 mL) of chloroform / trifluoroacetic acid = 10/1 (v / v) was placed on a quartz substrate by a casting method. It was applied and naturally dried to produce a film (film thickness 30 nm).

<Membrane Production Example 3>
Poly (9,9-di-n-octylfluorene-2,7-diyl) (polymer compound having a repeating unit represented by the formula 111; Aldrich, Mn = 5.7 × 10 ⁴ , Mw = A solution in which 3.0 mg of 2.11 × 10 ⁵ ) was dissolved in THF (1 mL) was applied onto a quartz substrate by a casting method and dried naturally to form a film (film thickness 25 nm).

<Membrane Production Example 4>
A solution in which the polymer compound 3 (5 mg) obtained in Synthesis Example 3 was dissolved in THF (1 mL) was applied onto a quartz substrate and allowed to dry naturally to produce a film (film thickness 350 nm).

<Membrane Production Example 5>
Poly (2,5-di-n-octyloxy-1,4-phenylene) (polymer compound having a repeating unit represented by the formula 100; manufactured by American Dye Source, Mn = 1.9 × 10 ⁴ , A solution in which 3.0 mg of Mw = 3.99 × 10 ⁴ ) was dissolved in THF (1 mL) was applied onto a quartz substrate by a casting method, and air-dried to prepare a film.

<Membrane Production Example 6>
A solution in which 3.0 mg of the above poly (2,5-di-n-octyloxy-1,4-phenylene) is dissolved in 1 mL of chloroform is applied onto a quartz substrate by a casting method, and is naturally dried to form a film. Produced.

<Membrane Production Example 7>
A solution in which 3.0 mg of the above poly (2,5-di-n-octyloxy-1,4-phenylene) is dissolved in 1 mL of toluene is applied onto a quartz substrate by a casting method, and is naturally dried to form a film. Produced.

-Irradiation of circularly polarized light-
As a circularly polarized light source, in Examples 1 and 2 to be described later, a New Wave Research, Model No. Tempest 20 Hz, YAG laser (wavelength 266 nm, output 8 mW / cm ² ) is used, and a circularly polarizing film including a 1 / 4λ element. The specimen was irradiated through. In Examples 3 to 10 described later, a specimen was irradiated through a Gran tailor polarizing prism and a Fresnel ROM wave plate using a light source of Modulex Deep UV SX-UID500MAMQQ manufactured by USHIO. All specimens were irradiated with circularly polarized light in a direction perpendicular to the specimen surface.

-Measurement of circular dichroism ratio-
The circular dichroism ratio was measured using JASCO J-820 manufactured by JASCO Corporation.

<Example 1>
The film obtained in Film Production Example 1 was irradiated with right circularly polarized light for 120 minutes (film specimen 1-1). Separately, the film obtained in Film Production Example 1 was irradiated with left circularly polarized light for 120 minutes (film specimen 1-2).
When the circular dichroism ratio of the membrane specimen 1-1 was measured, it showed a negative signal of 5.0 mdeg at a wavelength of 268 nm.
When the circular dichroism ratio of the membrane specimen 1-2 was measured, it showed a positive signal of 5.0 mdeg at a wavelength of 268 nm.
The absorbance at 268 nm in the film obtained in Production Example 1 of the film was approximately 0.5. Further, the molar extinction coefficient per unit of the polymer compound 1 obtained in Synthesis Example 1 at 268 nm in THF was 4.2 × 10 ⁴ L · cm ⁻¹ · mol ⁻¹ .

<Example 2>
The film obtained in Film Production Example 2 was irradiated with right circularly polarized light for 10 minutes (film specimen 2-1). Separately, the film obtained in Film Production Example 2 was irradiated with left circularly polarized light for 10 minutes (film specimen 2-2).
When the circular dichroism ratio was measured at a wavelength of 280 nm, the membrane specimen 2-1 showed a negative circular dichroism signal, the membrane specimen 2-2 showed a positive circular dichroism signal, and each signal intensity The difference was 1.9 mdeg.
Further, when the circular dichroism ratio was measured at a wavelength of 310 nm, the membrane specimen 2-1 showed a positive circular dichroism signal, the membrane specimen 2-2 showed a negative circular dichroism signal, The difference in signal intensity was 1.7 mdeg.
The absorbance at 280 nm and 310 nm in the film obtained in Production Example 2 of the film was approximately 0.3 and 0.2, respectively. Moreover, the molar extinction coefficients per unit of the polymer compound 2 obtained in Synthesis Example 2 in THF were approximately 1.9 × 10 ⁴ L · cm ⁻¹ · mol ⁻¹ and 1.2 at 280 nm and 310 nm, respectively. It was ^{× 10 4 L · cm -1 ·} mol -1.

<Example 3>
The film obtained in Film Production Example 3 was irradiated with right circularly polarized light for 1.5 hours (film specimen 3-1). Separately, the film obtained in Film Production Example 3 was irradiated with left circularly polarized light for 1.5 hours (film specimen 3-2).
When the circular dichroism ratio was measured at a wavelength of 390 nm, the membrane specimen 3-1 showed a negative circular dichroism signal, and the membrane specimen 3-2 showed a positive circular dichroism signal. The difference in strength was 20 mdeg.
The absorbance at 390 nm in the film obtained in Production Example 3 of the film was 0.35. The molar extinction coefficient per unit of poly (9,9-di-n-octylfluorene-2,7-diyl) at 390 nm in THF is 4.0 × 10 ⁴ L · cm ⁻¹ · mol ⁻¹ . there were.

<Example 4>
The film obtained in Film Production Example 3 was irradiated with left circularly polarized light for 6 minutes (film specimen 4-1). Membrane specimen 4-1 showed a strong positive circular dichroism signal around 400 nm.
Next, the film specimen 4-1 was irradiated with right circularly polarized light for 9.5 minutes (film specimen 4-2). Regarding membrane specimen 4-2, the circular dichroic signal almost disappeared.
Further, the film specimen 4-2 was irradiated with right circularly polarized light for 25 minutes (film specimen 4-3). With respect to the membrane specimen 4-3, negative absorption having a shape almost symmetrical to the circular dichroism spectrum of the membrane specimen 4-1 was observed.

<Example 5>
1.00 mg of poly (9,9-di-n-octylfluorene-2,7-diyl), which is a polymer compound having a repeating unit represented by the formula 111, is suspended in methylcyclohexane (8 mL), and the right When the circularly polarized light was irradiated for 10 minutes, a change was observed in the circular dichroism spectrum as compared to before irradiation with the right circularly polarized light.

<Example 6>
The film obtained in Film Production Example 4 was irradiated with left circularly polarized light for 45 minutes (film specimen 6-1). When the circular dichroism ratio was measured at a wavelength of 290 nm before and after irradiation with left circularly polarized light, the intensity of the positive circular dichroic signal before irradiation was 0.5 mdeg. Increased the intensity of the positive circular dichroism signal to 2.5 mdeg.
The absorbance at 290 nm of the film obtained in Film Production Example 4 was approximately 0.9. In addition, the molar extinction coefficient per unit of the polymer compound 3 obtained in Synthesis Example 3 in THF was approximately 4.0 × 10 ³ L · cm ⁻¹ · mol ⁻¹ at 290 nm.

<Example 7>
The film obtained in Film Production Example 5 was irradiated with right circularly polarized light for 1.5 hours (film specimen 7-1). Separately, the film obtained in Film Production Example 5 was irradiated with left circularly polarized light for 1.5 hours (film specimen 7-2).
When the circular dichroism ratio was measured at a wavelength of 360 nm, the membrane sample 7-1 showed a negative signal of 0.7 mdeg and the membrane sample 7-2 showed a positive signal of 0.6 mdeg.
The absorbance at 360 nm in the film obtained in Membrane Preparation Example 5 was 0.35. In addition, the molar extinction coefficient per unit of poly (2,5-di-n-octyloxy-1,4-phenylene) at 360 nm in chloroform is 3.0 × 10 ³ L · cm ⁻¹ · mol ⁻¹ . there were.

<Example 8>
The film obtained in Film Production Example 6 was irradiated with right circularly polarized light for 100 minutes (film specimen 8-1). Separately, the film obtained in Film Production Example 6 was irradiated with left circularly polarized light for 100 minutes (film specimen 8-2).
When the circular dichroism ratio was measured at a wavelength of 360 nm, the membrane specimen 8-1 showed a negative signal of 1.0 mdeg and the membrane specimen 8-2 showed a positive signal of 1.0 mdeg.
The absorbance at 360 nm in the film obtained in Production Example 6 of the film was 0.65.

<Example 9>
The film obtained in Film Production Example 7 was irradiated with right circularly polarized light for 100 minutes (film specimen 9-1). Separately, the film obtained in Film Production Example 7 was irradiated with left circularly polarized light for 210 minutes (film specimen 9-2).
When the circular dichroism ratio was measured at a wavelength of 360 nm, the membrane specimen 9-1 showed a negative signal of 1.8 mdeg and the membrane specimen 9-2 showed a positive signal of 2.3 mdeg.
The absorbance at 360 nm in the film obtained in Production Example 6 of the film was 0.55.

<Example 10>
The film obtained in Film Production Example 7 was irradiated with left circularly polarized light for 10 minutes (film specimen 10-1). The membrane specimen 10-1 showed a positive signal of 0.85 mdeg at a wavelength of 360 nm.
Next, the film specimen 10-1 was irradiated with right circularly polarized light for 30 minutes (film specimen 10-2). Regarding the membrane specimen 10-2, the circular dichroic signal at 360 nm almost disappeared.
Further, the film specimen 10-2 was irradiated with right circularly polarized light for 40 minutes (film specimen 10-3). The membrane specimen 10-3 showed a negative signal of 0.85 mdeg at a wavelength of 360 nm.

  As can be seen from the above results, according to the modification method of the present invention, an optically active polymer compound can be obtained by irradiating circularly polarized light without introducing a photosensitive site such as azobenzene.

Claims (7)

A method for modifying a polymer compound, comprising irradiating a polymer compound having a repeating unit represented by the following formula (1) with circularly polarized light.

(In the formula (1),
R ¹ is a divalent aromatic group which may have a substituent or a divalent group represented by the following formula (2).
X ¹ is a group represented by —O—, a group represented by —S—, a group represented by —C (═O) —, a group represented by —C (═O) O—, —C A group represented by (═O) N (R ¹⁰ ) —, a group represented by —OC (═O) O—, a group represented by —OC (═O) N (R ¹¹ ) —, —N A group represented by (R ¹² ) C (═O) N (R ¹³ ) —, a group represented by —C (R ¹⁴ ) ₂ —, a group represented by —Si (R ¹⁵ ) ₂ —, ^{C (R 16) = C (} R 16) - , a group represented by or a divalent amine residue. R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently a hydrocarbyl group optionally having a hydrogen atom or a substituent, and R ¹⁰ , R ¹¹ , R ^12. , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ may be the same or different.
m ₁ is an integer of 1 or more, and m ₂ is an integer of 0 or more. When m ₁ and / or _{m 2} is 2 or more, ^{R 1} and / or ^{X 1} present _{two m} existing _{one m} may be the same or different. )

(In the formula (2),
R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom or a hydrocarbyl group optionally having a substituent.
R ⁸ is a group represented by —O—, a group represented by —S—, a group represented by —C (═O) O—, and a group represented by —C (═O) N (R ⁹ ) —. And a divalent group obtained by combining one or two selected from the group consisting of an optionally substituted hydrocarbylene group, or a direct bond. R ⁹ is a hydrogen atom or a hydrocarbyl group optionally having a substituent.
Ar ² is a monovalent aromatic hydrocarbon group which may have a substituent, and the monovalent aromatic hydrocarbon group contains 7 or more sp ² carbon atoms. ) In the formula (1), a _{m 1} is 1, _{m 2} is 0, modified method of claim 1. In the formula (1), when R ¹ is a divalent aromatic group which may have a substituent, the divalent aromatic group which may have the substituent has a substituent. Atoms constituting a ring from a monocyclic aromatic ring optionally having, a condensed polycyclic aromatic ring optionally having a substituent, or a bridged polycyclic aromatic ring optionally having a substituent Is a divalent group in which two hydrogen atoms directly bonded to R 2 are removed, or when R ¹ is a divalent group represented by the formula (2), Ar ² has a substituent. The modification method according to claim 1 or 2, which is a monovalent group in which one hydrogen atom directly bonded to an atom constituting the ring is removed from an optionally assembled aromatic ring group. In Formula (1), when R ¹ is a divalent group represented by Formula (2), R ⁵ , R ⁶ and R ⁷ are hydrogen atoms, and R ⁸ is represented by —O—. groups, -C (= O) O-, a group represented by, -C (= O) N ( R 9) - , a group represented by or a direct bond, one of the claims 1 to 3 one The denaturing method according to item.   The modification | denaturation method as described in any one of Claims 1-4 whose said high molecular compound is a shape of a film | membrane. The manufacturing method of the film | membrane containing the modified | denatured high molecular compound including the following process (a) and (b).
(A) The process of forming the film | membrane containing the high molecular compound which has a repeating unit represented by following formula (1) on a base material.
(B) A step of irradiating the film with circularly polarized light.

(In the formula (1),
R ¹ is a divalent aromatic group which may have a substituent or a divalent group represented by the following formula (2).
X ¹ is a group represented by —O—, a group represented by —S—, a group represented by —C (═O) —, a group represented by —C (═O) O—, —C A group represented by (═O) N (R ¹⁰ ) —, a group represented by —OC (═O) O—, a group represented by —OC (═O) N (R ¹¹ ) —, —N A group represented by (R ¹² ) C (═O) N (R ¹³ ) —, a group represented by —C (R ¹⁴ ) ₂ —, a group represented by —Si (R ¹⁵ ) ₂ —, ^{C (R 16) = C (} R 16) - , a group represented by or a divalent amine residue. R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently a hydrocarbyl group optionally having a hydrogen atom or a substituent, and R ¹⁰ , R ¹¹ , R ^{16 When a} plurality of ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are present, they may be the same or different.
m ₁ is an integer of 1 or more, and m ₂ is an integer of 0 or more. When m ₁ and / or _{m 2} is 2 or more, ^{R 1} and / or ^{X 1} present _{two m} existing _{one m} may be the same or different. )

(In the formula (2),
R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom or a hydrocarbyl group optionally having a substituent.
R ⁸ is a group represented by —O—, a group represented by —S—, a group represented by —C (═O) O—, and a group represented by —C (═O) N (R ⁹ ) —. And a divalent group obtained by combining one or two selected from the group consisting of an optionally substituted hydrocarbylene group, or a direct bond. R ⁹ is a hydrogen atom or a hydrocarbyl group optionally having a substituent.
Ar ² is a monovalent aromatic hydrocarbon group which may have a substituent, and the monovalent aromatic hydrocarbon group contains 7 or more sp ² carbon atoms. )   The manufacturing method according to claim 6, wherein in the step (a), a suspension or a solution containing the polymer compound is applied to a substrate.