JP5408581B2 - Method for controlling optical anisotropy of self-assembled polymer film and method for forming self-assembled polymer film - Google Patents

Description

The present invention relates to a film forming method for controlling how contact and self-assembled polymer layer of the optical anisotropy of the self-assembled polymer films polymer chain composed of a polymer having a helical structure and optical activity.

  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).
However, in recent years, an optical device, an optical memory, an optical resolving agent, has become more optical rotation and circular polarization dichroism material larger GaMotomu Me are as.
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 relates to a method for controlling the optical anisotropy of a self-assembled polymer film in which the polymer molecular chain changes or increases the optical anisotropy of the polymer chain having a helical structure and optical activity, and the optical anisotropy An object of the present invention is to provide a method for forming a self-assembled polymer film having a large thickness.

  As a result of intensive studies, the inventors have selected the film forming method or applied external loads such as contact with solvent vapor, heat, light, magnetic field, electric field, etc. It has been found that optical anisotropy such as chromaticity can be increased.

That is, the present invention
(1) A method for controlling the optical anisotropy of a polymer film having a polymer molecular chain represented by the following general formula ( 2 ) or ( 4 ) and having a helical structure and optical activity, Control is a reversible control method, in which a solvent vapor of an organic solvent is brought into contact with a polymer film to induce a secondary or higher order ordered structure in the film and to change the optical anisotropy of the film. Method for controlling optical anisotropy of structured polymer film,

(In the formula, n represents an integer of 10 or more, and X _{1 to} X ₅ each independently represents a hydrogen atom or a substituent. However, in the general formula (2), among X ₁ , X ₂ and X ₃ At least one of X ₁ and X _{2 in} the general formula (4) represents a group having an optically active carbon in which an asymmetric carbon is substituted with OH or an alkoxy group.
(2) The self-assembled polymer film according to (1), wherein the organic solvent is selected from hydrocarbon solvents, ethers, alcohols, ketones, chlorine-containing solvents, and amine solvents. control how the optical anisotropy,

(3 ) Control of optical anisotropy of self-assembled polymer film according to (1) or (2) , wherein the optical anisotropy is optical rotation or circular dichroism of the film Method and
( 4 ) A method for producing a polymer film having a polymer molecular chain represented by the following general formula (1) or (3) and having a helical structure and optical activity, wherein the polymer concentration is 0.5 to A film forming method of a self-assembled polymer film, characterized by forming a film having a film thickness of 0.4 μm to 1 mm from a 10% by mass solution and inducing a secondary or higher order ordered structure in the film;

(In the formula, n represents an integer of 10 or more, R represents one or more optically active carbons, an optionally substituted aliphatic hydrocarbon group, or an asymmetric carbon substituted with OH or an alkoxy group. Represents an aromatic hydrocarbon group having optically active carbon, and R ′ represents an aromatic or aliphatic hydrocarbon group. )
Is to provide.

According to the present invention, an optical rotation of a film advantageous for uses such as an optical device, an optical memory, an optical resolving agent, a method for forming a polymer film having a large optical anisotropy such as circular dichroism, and an optical rotation of the film, It was possible to provide a control method or a reversible control method for changing and / or increasing optical anisotropy such as circular dichroism.

The method for controlling an optical anisotropy or a reversible control method of the present invention is based on a film formation condition or an external stimulus load on a self-assembled polymer film in which a polymer molecular chain has a helical structure and optical activity. A high-order ordered structure is induced therein, and the optical anisotropy of the film is reversibly changed and / or increased.

In the present invention, the “self-assembled polymer” refers to a polymer capable of changing the higher order structure of the molecule by an external stimulus.
In the present invention, “optical anisotropy of the film” means that the absorbance with respect to circularly polarized light is different on the left and right, and examples include the optical rotation of the film and circular dichroism. Here, the optical rotation means the angle at which the optically active substance rotates the direction of linearly polarized light to the right or left, and the circular dichroism is the counterclockwise direction when circularly polarized light passes through the optical rotatory material. A phenomenon in which clockwise absorption is different.
In the present invention, “higher order regular structure” means a structure in which molecular chains are regularly arranged. Moreover, it is confirmed by measuring X-ray scattering that the higher order ordered structure was induced in the film. The higher order regular structure means a secondary or higher order regular structure.
In the present invention, “optically active carbon” refers to carbon having chirality, and preferably an asymmetric carbon atom.

In the present invention, 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 the present invention, the “spiral direction” means 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 the present invention, when the circular dichroism is increased, the numerical value is preferably increased to 1.5 to 100 times, more preferably 1.5 to 10 times.
In the present invention, 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 invention, 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 invention, “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 external load include contact with solvent vapor, stimulation of heat, light, magnetic field, electric field and the like, and contact with solvent is preferable.
Specific treatment conditions for each of the stimuli are not particularly limited, and examples thereof include the following conditions.
Regarding the “contact with solvent vapor”, for example, the polymer film having a helical structure in which the polymer molecular chain has a helical structure may be treated at a temperature and time conditions appropriately selected from vapors of any solvent such as chloroform, toluene, and tetrahydrofuran. it can.
For the “heat” treatment, the heating temperature is preferably 60 to 200 ° C., more preferably 100 to 150 ° C., and the heating time is preferably 1 to 60 minutes, more preferably 3 to 30 minutes. Can be mentioned.
For the “light” treatment, for example, a polymer film in which the polymer molecular chain has a helical structure with a light amount of 100 mJ / 1 square cm to 100,000 mJ / 1 square cm, preferably 500 mJ / 1 square cm to 10,000 mJ / 1 square cm is used. Processing.
As for the “magnetic field” treatment, for example, the polymer film having a helical structure of the polymer molecular chain is treated with 0.1T to 10T, preferably 1T to 10T.
As for the “electric field” treatment, for example, treatment of a polymer film in which the polymer molecular chain has a helical structure at 0.01 MV / cm to 10 MV / cm, preferably 0.1 MV / cm to 1 MV / cm can be mentioned. .

By applying the external load, the conjugated state of the polymer can change, for example, the absorption maximum from 400 nm to 500 nm or from 500 nm to 400 nm.
As the optical anisotropy, for example, the color of the polymer film can be changed from yellow to red, and the optical rotation can be changed 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. Further, in the present invention, increasing the optical rotation of the film means increasing the optical rotation and / or circular dichroism. “The optical rotation is increased” means that the optical rotation and / or circular dichroism is increased by 5 times or more.

In the self-assembled polymer film of the present invention, the polymer molecular chain imparts at least one of the stimuli to a polymer having a helical structure and optical activity, and the optical rotation and / or circular dichroism of the film of the polymer chain It is preferable that the property can be reversibly controlled.
The self-assembled polymer film formed or controlled by the method of the present invention can be appropriately prepared and used as a film including particles, fine particles, powder and / or a substrate.
The self-assembled polymer film controlled by the method of the present invention 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.

Then used this onset bright, described "polymer where the polymer chain is represented by the following general formula having a helical structure (1) or (3)".

(Wherein n represents an integer of 10 or more , R represents one or more optically active carbons, an aliphatic hydrocarbon group which may have a substituent, or an asymmetric carbon substituted with OH or an alkoxy group. And represents an aromatic hydrocarbon group having optically active carbon, and R ′ represents an aromatic or aliphatic hydrocarbon 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, examples of the “substituent” that the group in the present invention may have include a phenyl group, an alkyl group, an ester group, and an amide group, and a phenyl group and an ester group are preferable.

The group substituted on the group having one or more optically active carbons is not particularly limited, and examples thereof include an alkyl group, a phenyl group, an amide group, a carbonyl group, and a hydroxyl group. Of these, an alkyl group, a phenyl group, and an amide group are preferable.

  Those having a hydrogen atom among the above groups may be removed and further substituted with a substituent. Examples of such a composite substituent include an ether group and an ester group.

The polymerization degree n of the polymer represented by the general formula (1) or (3) 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) or (3) , 10000-100,000 are more preferable .

Examples of the aromatic group represented by R ′ are preferably those having 4 to 20 carbon atoms, more preferably 6 to 14 carbon atoms, and specifically include a phenyl group, a naphthyl group, and a phenanthryl group. Examples of aliphatic hydrocarbons are preferably those having 1 to 18 carbon atoms, more preferably 1 to 10 carbon atoms, specifically methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, A decyl group and 2-ethylhexyl group are mentioned.
This aromatic group or aliphatic hydrocarbon group may have the optical activity as described above.
Further, it is preferred that the polymer represented by the general formula (1) is a polymer 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, provided that at least one of X ₁ , X ₂ and X ₃ is This represents a group having an optically active carbon in which an asymmetric carbon is substituted with OH or an alkoxy group .)

In the present invention, at least one of the group having an optically active carbon of X _1, X ₂ and X _3, i.e., OH or alkoxy groups asymmetric carbon Ru groups der having an optically active carbon substituted.
At least one of X ₁ , X ₂ and X ₃ is a group having the above-mentioned optically active carbon, 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, X More preferably, ₂ is an optically active alkyl group or an optically active alkoxy group, X ₃ is a hydrogen atom, an alkyl group or a halogen atom, X ₁ and X ₃ are hydrogen atoms, and X ₂ is an optically active alkoxy group Is particularly preferred.

The optically active group having carbon, have one or more asymmetric carbon, and it is particularly preferred OH groups to the asymmetric carbon is an alkyl group or an alkoxy group having 2 or more carbon atoms substituted.

  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 may be 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 A phenanthroline ring, a thianthrene ring, a chromene ring, a xanthene ring, a phenoxathiin ring, a phenothiazine ring and a phenazine ring).
The polymer represented by general formula (3) may be a polymer represented by the following general formula (4).

(In the formula, n represents an integer of 10 or more, and X ₁ , X ₂ , X ₄ and X ₅ each independently represents a hydrogen atom or a substituent. However, at least one of X ₁ and X ₂ is an This represents a group having an optically active carbon in which OH or an alkoxy group is substituted on the simultaneous carbon.)
Incidentally, _{X 1} and _{X 2} are the same meanings as those in formula (2), Ru likewise der preferable.
The polymer represented by the general formula (2) can be produced by polymerizing an acetylene-substituted monomer represented by the general formula (7) described later.
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 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 polymers of the general formulas (3) and (4) are preferably carried out in the presence of a group 5 transition metal catalyst such as niobium or tantalum.
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. 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.
Niobium is not particularly restricted but includes tantalum complex _{catalyst, NbCl 5, NbBr 5, TaCl} 5, TaBr 5 , etc. halide catalysts include the, particularly preferably used TaCl _5.
In the method for producing a polymer used in the present invention, it is preferable to use TaCl ₅ as a tantalum complex catalyst and triethylsilane 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).

  The polymer used in the present invention is represented by the following general formula (5), 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 carbon atoms is 1 to 1. Three is preferable, but one is particularly preferable from the viewpoint of stereocontrol.

It is also preferable that n is 10 to 10,000 and R ″ is a group having phenoxy oxygen. This compound can be synthesized by using, for example, a [Rh (norbornadiene) Cl] ₂ catalyst.
The polymer used in the present invention is considered to be able to stabilize the helical structure by hydrogen bonding by substituting the 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. Preferred are those having 4 to 8 carbon atoms, and specific examples include 1-hydroxyethyl group, 2-hydroxypropyl group, 2-hydroxybutyl group, 1-hydroxy-1-methylpropyl group, 1-hydroxy- Examples include 2-methylpropyl group, 2-hydroxypentyl group, 2-hydroxyhexyl group, 2-hydroxyheptyl group, 2-hydroxyoctyl group, 2-hydroxynonyl group, 2-hydroxydecyl group, and the like. , 2-hydroxyhexyl group, 2-hydroxyheptyl group, 2-hydroxyoctyl group.
Alternatively, it may be a group containing phenoxy oxygen.

  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. Preferred are those having 4 to 8 carbon atoms, such as 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, etc. Particularly preferred are 2-hydroxyhexyloxy group, 2-hydroxyheptyloxy group, 2-hydroxyoctylo group. Is death 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 used in the present invention has optical activity and 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 used in the present invention is preferably from 1,000 to 1,000,000, more preferably from 4,000 to 100,000.

Next, a method for producing the polymer used in the present invention will be described.
The polymer represented by the general formula (2) can be produced by polymerizing an acetylene compound represented by the following general formula (6).

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 group having one or more optically active carbons. X _1, X ₂ and X ₃ have the same meanings as 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 (5) can be produced by polymerizing an acetylene compound represented by the following general formula (7).

  In the formula, R ″ has the same meaning as R ″ in the general formula (5), and the preferred range is also the same.

  A method for producing the substituted acetylene monomer represented by the general formula (6) or (7) 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 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. Moreover, it is preferable to use alkylamines as a cocatalyst, for example, diethylamine, tributylamine, triethylamine, etc. are 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 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).

  In the present invention, a higher order ordered structure in the film may be induced by selecting a film forming method of the polymer film. Moreover, you may use combining the selection of the film-forming method of a polymer film | membrane, and at least 1 provision of the stimulus selected from the group which consists of contact with a solvent vapor | steam, a heat | fever, light, a magnetic field, and an electric field. A combination of selection of the polymer film formation method and contact with solvent vapor is preferred.

A method for producing a polymer film in the present invention will be described.
The polymer film is formed by inducing a high-order ordered structure in a film by spin-coating a concentrated solution obtained by dissolving the above polymer in a solvent onto, for example, glass. can do.
The solvent is preferably one or two selected from a chlorine solvent such as chloroform, an ether solvent such as tetrahydrofuran, an amine solvent such as diethylamine, an alcohol solvent such as methanol, and an aromatic solvent such as toluene. The above solvents are used, more preferably chloroform, tetrahydrofuran, and diethylamine, and still more preferably chloroform.
In the present invention, the polymer-rich solution differs depending on the substituent, but the polymer concentration is preferably 0.5 to 10% by mass, more preferably 0.5 to 5% by mass, and about 4% by mass. Is more preferable, and 1-3 mass% is especially preferable.

For example, when the polymer is poly [(S) -1- (4-ethynylphenyl) -1-dodecanol] and the solvent is chloroform, the concentration of the polymer is preferably 1 to 5% by mass, and 3 to 5 More preferred is mass%.
When the polymer is poly [N-propargyl- (S) -1-methylhexyl carbamate] and the solvent is chloroform, the concentration of the polymer is preferably 0.5 to 5% by mass, and 1 to 3% by mass. % Is more preferable.

The spin coating conditions are not particularly limited as long as the target higher order ordered structure can be induced in the film, but the rotational speed is preferably 500 to 10,000 rpm, More preferably, it is 2000 rpm.
Also, the drying conditions after spin coating are not particularly limited as long as the target higher order ordered structure can be induced in the film, but the temperature is 30 to 60 ° C. and 1 to 24. Preferably, the time is 40 to 50 ° C., and more preferably 1 to 3 hours.
The film forming method is not limited to spin coating as long as it induces a high-order ordered structure in the film, and may be a normal casting method, for example.
The film thickness of the polymer film is preferably 0.01 μm to 1 mm, and more preferably 0.1 to 10 μm.

  The polymer film in the present invention changes in color and conjugate state, and changes in the helical structure by contact with solvent vapor, heating, light irradiation, magnetic field application, or electric field application, preferably contact with solvent vapor. It is preferable to form a new helical structure. Moreover, the direction of the newly formed helix can be controlled by contacting with 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.

Examples of the 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 organic solvents, such as a chlorine-containing solvent, are 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.

  Further, examples of preferable treatment conditions in each treatment of heating, light irradiation, magnetic field application, and electric field application include the conditions mentioned in the treatment conditions for the polymer film in which the polymer molecular chain has a helical structure.

The self-assembled polymer film made of the polymer molecule of the present invention preferably has a peak top of absorption that can be uniquely and arbitrarily controlled 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.

Example 1
A chloroform solution (4% by mass) of poly [(S) -1- (4-ethynylphenyl) -1-dodecanol] (number average molecular weight 30000) was spin-coated on a glass substrate at 1000 rpm. It was dried for a time to produce a yellow polymer film (film thickness 0.6 μm). The absorbance at this time was 1.08. The absorption spectrum of the obtained film showed an absorption maximum in the vicinity of 350 nm, and showed the same spectrum shape as in the solution. In the CD spectrum, a negative peak was observed near 320 nm, a positive peak near 360 nm, a positive peak near 430 nm, and a negative peak near 470 nm. The peak at 320 nm was -390 mdeg. In the ORD spectrum, a negative peak was observed near 340 nm, a negative peak around 410 nm, and a positive peak around 450 nm. The peak at 340 nm was -430 mdeg. In wide-angle X-ray scattering, a sharp peak appeared in the vicinity of 28 mm, and an ordered structure between molecules was confirmed.

Example 2
A chloroform solution (4% by mass) of poly [(S) -1- (4-ethynylphenyl) -1-dodecanol] (number average molecular weight 20000) was spin-coated on a glass substrate at 1000 rpm. It was dried for a time to produce a yellow polymer film (film thickness 0.6 μm). When the obtained film was subjected to gold vapor deposition and observed 10,000 times with a scanning electron microscope, a streak pattern was observed on the surface of the film, suggesting the existence of a higher order (tertiary) ordered structure.

Example 3
A 1 μg / mL chloroform solution of poly [(S) -1- (4-ethynylphenyl) -1-dodecanol] (number average molecular weight 20000) was spin-coated on a glass substrate at 1000 rpm, and this was applied at 40 ° C. for 1 hour. Dried. When gold was vapor-deposited and observed with a scanning electron microscope at a magnification of 100,000, a large number of rod-like polymers having a length of about 600 nm and a width of about 80 nm were observed, suggesting the existence of a higher order (tertiary) ordered structure.

Example 4
A chloroform solution (1% by mass) of poly [N-propargyl- (S) -1-methylhexyl carbamate] (number average molecular weight 10,000) was spin-coated on a quartz substrate at 1000 rpm, and this was dried at 40 ° C. for 1 hour. Thus, a colorless polymer film was produced (film thickness 0.4 μm). The absorption spectrum of the obtained film showed an absorption maximum in the vicinity of 230 nm, and showed the same spectrum shape as in the solution. The absorbance at this time was 0.5. In the CD spectrum of the obtained film, positive peaks were observed near 220 nm, negative near 240 nm, positive near 280 nm, and negative peaks near 320 nm. The 240 nm peak was -190 mdeg. In the ORD spectrum, a negative peak was observed near 250 nm, and a positive peak was observed near 300 nm. The peak at 250 nm was -230 mdeg. In wide-angle X-ray scattering, a sharp peak appeared in the vicinity of 15 mm, and an ordered structure between molecules was confirmed.

Example 5
A chloroform solution (4% by mass) of poly [N-propargyl- (S) -1-methylhexyl carbamate] (number average molecular weight 10,000) was spin-coated on a quartz substrate at 1000 rpm, and this was dried at 40 ° C. for 1 hour. Thus, a colorless polymer film was produced (film thickness 0.4 μm). When the obtained film was subjected to gold vapor deposition and observed 10,000 times with a scanning electron microscope, a streak pattern was observed on the surface of the film, suggesting the existence of a higher order (tertiary) ordered structure.

Reference example 1
A 1 μg / mL tetrahydrofuran solution of poly [N-propargyl- (S) -1-methylhexylcarbamate] (number average molecular weight 10,000) was spin-coated on a quartz substrate at 1000 rpm, and this was dried at 40 ° C. for 1 hour. . When this was subjected to gold vapor deposition and observed with a scanning electron microscope at a magnification of 100,000, a rod-like polymer having a length of about 500 nm and a width of about 40 nm was observed, suggesting the existence of a higher order (tertiary) ordered structure.

Example 6
A tetrahydrofuran solution (3 mass%) of poly [N-propargyl- (S) -1-methylhexyl carbamate] (number average molecular weight 10,000) was spin-coated on a quartz substrate at 1000 rpm, and this was dried at 40 ° C. for 1 hour. Thus, a colorless polymer film was produced (film thickness 0.4 μm). In the CD spectrum of the obtained film, a negative peak was observed around 240 nm and a positive peak around 290 nm. The 240 nm peak was -250 mdeg. When this was brought into contact with diethylamine vapor at 25 ° C. and atmospheric pressure for 10 minutes, the absorbance did not change and the 240 nm peak increased to −1000 mdeg.

Example 7
A chloroform solution (4 mass%) of poly [(S) -1- (4-ethynylphenyl) -1-dodecanol] (number average molecular weight 50000) was spin-coated on a glass substrate at 1000 rpm. It was dried for a time to produce a yellow polymer film (film thickness 0.9 μm). The absorbance at this time was 1.8. The absorption spectrum of the obtained film showed an absorption maximum in the vicinity of 350 nm, and showed the same spectrum shape as in the solution. In the ORD spectrum, a negative peak was observed near 340 nm, a negative peak around 410 nm, and a positive peak around 450 nm. The peak at 340 nm was -1200 mdeg. When this was brought into contact with diethylamine vapor at 25 ° C. and atmospheric pressure for 10 minutes, the absorbance did not change, a positive peak was observed near 330 nm, and a negative peak was observed near 400 nm, and the spectrum changed greatly. The 330 nm peak was 140 mdeg, and its absolute value was greatly reduced. From Examples 1 and 7 , a reversible change in optical anisotropy was confirmed.

Example 8
A chloroform solution (2% by mass) of poly [1- (4-((S) -2-methoxyoctyloxy) phenyl) -2-phenylacetylene] (number average molecular weight 50000) was spin-coated on a glass substrate at 1000 rpm. This was dried at 40 ° C. for 1 hour to produce a yellow polymer film (film thickness 0.4 μm). The absorbance at the absorption maximum at this time was 0.5. The absorption spectrum of the obtained film showed an absorption maximum in the vicinity of 420 nm, and showed the same spectrum shape as in the solution. In the CD spectrum, a positive peak was observed around 410 nm. The peak at 410 nm was 450 mdeg. When this was brought into contact with chloroform vapor at 25 ° C. and atmospheric pressure for 15 minutes, the absorbance was hardly changed, and the peak at 410 nm was 1900 mdeg, and its absolute value increased greatly.

Example 9
A chloroform solution (4% by mass) of poly [1- (4-((S) -2-hydroxyoctyloxy) phenyl) -2-phenylacetylene] (number average molecular weight 30000) was spin-coated on a glass substrate at 1000 rpm. This was dried at 40 ° C. for 1 hour to produce a yellow polymer film (film thickness 0.6 μm). The absorbance at the absorption maximum at this time was 0.8. The absorption spectrum of the obtained film showed an absorption maximum in the vicinity of 440 nm, and showed the same spectrum shape as in the solution. In the CD spectrum, a negative peak was observed around 390 nm. The peak at 390 nm was −50 mdeg. When this was brought into contact with diethylamine vapor at 25 ° C. and normal pressure for 1 minute, the absorbance did not change, a negative peak was observed near 400 nm, a positive peak was observed near 440 nm, and the spectrum changed greatly. The peak at 400 nm was −330 mdeg, and its absolute value increased greatly.

Reference example 2
A chloroform solution (20% by mass) of poly [(S) -1- (4-ethynylphenyl) -1-dodecanol] (number average molecular weight 20000) was allowed to stand at room temperature and observed with a polarizing microscope. Was observed, confirming the formation of a cholesteric liquid crystal structure.

Reference example 3
A toluene solution (12% by mass) of poly [1- (4-((S) -2-hydroxyoctyloxy) phenyl) -2-phenylacetylene] (number average molecular weight 30000) was allowed to stand at room temperature, and this was polarized. When observed with a microscope, stripes were observed, confirming the formation of a cholesteric liquid crystal structure.

Reference example 4
A toluene solution (12% by mass) of poly [N-propargyl- (S) -1-methylhexyl carbamate] (number average molecular weight 10,000) was allowed to stand at room temperature, and when observed with a polarizing microscope, a pattern was observed and liquid crystal was observed. The formation of the structure was confirmed.

Below, the reference example of the comparison with respect to the control method of the optical anisotropy of the self-assembled polymer film of this invention is shown.
Reference example 1
A chloroform solution (1% by mass) of poly [(S) -1- (4-ethynylphenyl) -1-dodecanol] (number average molecular weight 20000) was spin-coated on a glass substrate at 1000 rpm. It was dried for a time to produce a yellow polymer film (film thickness 0.15 μm). The absorption spectrum of the obtained film showed an absorption maximum in the vicinity of 350 nm, and showed the same spectrum shape as in the solution. The absorbance at this time was 0.25. In the CD spectrum, a negative peak was observed near 310 nm, a positive peak near 360 nm, and a negative peak near 460 nm. The peak at 310 nm was -27 mdeg. In the ORD spectrum, a negative peak was observed near 340 nm and a positive peak was observed near 410 nm. The peak at 340 nm was −22 mdeg. No peaks were observed in wide angle X-ray scattering.

Reference example 2
A methanol solution (1% by mass) of poly [(S) -1- (4-ethynylphenyl) -1-dodecanol] (number average molecular weight 20000) was spin-coated on a glass substrate at 1000 rpm. It was dried for a period of time to produce a yellow polymer film (film thickness 0.2 μm). When the obtained film was subjected to gold vapor deposition and observed with a scanning electron microscope at a magnification of 10,000, the surface of the film was smooth.

Reference example 3
A 1 μg / mL methanol solution of poly [(S) -1- (4-ethynylphenyl) -1-dodecanol] (number average molecular weight 20000) was spin-coated on a glass substrate at 1000 rpm, and this was applied at 40 ° C. for 1 hour. Dried. When this was subjected to gold vapor deposition and observed with a scanning electron microscope at a magnification of 100,000, polymer particles having a diameter of 10 nm were observed.

Reference example 4
A chloroform solution (0.5% by mass) of poly [N-propargyl- (S) -1-methylhexyl carbamate] (number average molecular weight 10,000) was spin-coated on a glass substrate at 1000 rpm, and this was applied at 40 ° C. for 1 hour. It was dried to produce a yellow polymer film (film thickness 0.08 μm). The absorption spectrum of the obtained film showed an absorption maximum in the vicinity of 230 nm, and showed the same spectrum shape as in the solution. The absorbance at this time was 0.1. In the CD spectrum, a negative peak was observed near 240 nm, and a positive peak was observed near 290 nm. The 240 nm peak was -14 mdeg. In the ORD spectrum, a negative peak was observed around 240 nm. The 240 nm peak was -37 mdeg. No peaks were observed in wide angle X-ray scattering.

Reference Example 5
A chloroform solution (0.5% by mass) of poly [N-propargyl- (S) -1-methylhexyl carbamate] (number average molecular weight 10,000) was spin-coated on a glass substrate at 1000 rpm, and this was applied at 40 ° C. for 1 hour. It was dried to produce a yellow polymer film (film thickness 0.08 μm). When the obtained film was subjected to gold vapor deposition and observed with a scanning electron microscope at a magnification of 10,000, the surface of the film was smooth.

Reference Example 6
A 1 μg / mL chloroform solution of poly [N-propargyl- (S) -1-methylhexylcarbamate] (number average molecular weight 10,000) was spin-coated on a glass substrate at 1000 rpm, and this was dried at 40 ° C. for 1 hour. . When the obtained film was subjected to gold vapor deposition and observed with a scanning electron microscope at a magnification of 10,000, polymer particles having a diameter of 10 nm were observed.

Claims (4)

A polymer molecular chain represented by the following general formula ( 2 ) or ( 4 ), a method for controlling the optical anisotropy of a polymer film having a helical structure and optical activity, wherein the control of the optical anisotropy is reversible Self-assembled polymer that changes the optical anisotropy of the film by inducing a secondary or higher order structure in the film by bringing the solvent vapor of an organic solvent into contact with the polymer film. A method for controlling the optical anisotropy of a film.

(In the formula, n represents an integer of 10 or more, and X _{1 to} X ₅ each independently represents a hydrogen atom or a substituent. However, in the general formula (2), among X ₁ , X ₂ and X ₃ At least one of X ₁ and X _{2 in} the general formula (4) represents a group having an optically active carbon in which an asymmetric carbon is substituted with OH or an alkoxy group.   2. The self-assembled polymer film according to claim 1, wherein the organic solvent is selected from hydrocarbon solvents, ethers, alcohols, ketones, chlorine-containing solvents, and amine solvents. Control method. The method for controlling optical anisotropy of a self-assembled polymer film according to claim 1 or 2 , wherein the optical anisotropy is optical rotation or circular dichroism of the film. A method for producing a polymer film having a polymer molecular chain represented by the following general formula (1) or (3) and having a helical structure and optical activity, wherein the polymer concentration is 0.5 to 10% by mass using a solvent. A method for forming a self-assembled polymer film, wherein a film having a film thickness of 0.4 μm to 1 mm is formed from the solution of 1 and a secondary or higher order structure is induced in the film.

(In the formula, n represents an integer of 10 or more, R represents one or more optically active carbons, an optionally substituted aliphatic hydrocarbon group, or an asymmetric carbon substituted with OH or an alkoxy group. And represents an aromatic hydrocarbon group having optically active carbon, and R ′ represents an aromatic or aliphatic hydrocarbon group.)