WO2014109258A1

WO2014109258A1 - Method for producing living polymer on base, block copolymer, and film having microphase-separated structure produced using same and method for production thereof

Info

Publication number: WO2014109258A1
Application number: PCT/JP2013/085051
Authority: WO
Inventors: 慶太高橋; 佳明 ▲高▼田
Original assignee: 富士フイルム株式会社
Priority date: 2013-01-08
Filing date: 2013-12-27
Publication date: 2014-07-17
Also published as: JP6196635B2; JPWO2014109258A1

Abstract

A method for producing a living polymer on a base, characterized by comprising a step of carrying out the living polymerization of a monomer-containing composition on the base. The method has excellent economic performance.

Description

Method for producing living polymer on support, block copolymer, microphase separation structure membrane using the same, and method for producing the same

The present invention relates to a method for producing a living polymer on a support, a block copolymer, a microphase-separated structure membrane using the same, and a method for producing the same. More specifically, a method for producing a living polymer on a support (particularly, a production of a living polymer on a support capable of producing a block copolymer for forming a microphase-separated structure film on the support) Method), a block copolymer produced by a method for producing a living polymer on a support, a production method for producing a microphase separation structure film on a support, and a microphase separation structure film obtained by the production method About.

As a method for producing a microphase-separated structure, a method of immobilizing the obtained phase-separated structure using a block copolymer produced by living polymerization is known.

Conventionally, high temperature and long time (200 ° C., about 5 hours) have been required to produce a microphase separation structure. On the other hand, there is known an example in which the orientation of the nanoscale hexagonal cylinder structure formed by phase separation of the block copolymer is controlled by introducing “amphiphilicity” and “liquid crystal” (non-patent literature). 1, Patent Documents 1 and 2). Specifically, in Patent Document 1, a block copolymer in which a hydrophilic polymer component (A) and a hydrophobic polymer component (B) are linked by a covalent bond, and the molecular weight distribution of A and B is ≦ 1.3. Certain block copolymers have been described. In Patent Document 2, a self-supporting polymer thin film made of a block copolymer formed by covalently bonding a hydrophilic polymer component and a hydrophobic polymer component having a crosslinkable structure, wherein the self-supporting polymer thin film is A self-supporting polymer thin film having a cylinder made of the hydrophilic polymer component oriented in a certain direction in the film and having the hydrophobic polymer component crosslinked is described. The methods described in these documents were epoch-making in that a microphase-separated structure can be produced in about several minutes. For example, in Patent Document 1, a hydrophilic compound is synthesized by atom transfer radical polymerization (hereinafter abbreviated as ATRP) with a liquid crystalline monomer after synthesizing a hydrophilic macroinitiator in Patent Document 1, for example. A block copolymer in which hydrophobic portions are linked is obtained. Moreover, in patent document 2, after obtaining the living polymerization part only by a hydrophobic part by ATRP, the terminal is modified and finally the hydrophilic part is produced by polymer reaction.

On the other hand, Non-Patent Document 2 describes a method and material for synthesizing a block copolymer by living radical polymerization by reversible addition-fragmentation chain transfer (hereinafter referred to as RAFT) polymerization. Yes. In RAFT polymerization, in the presence of an appropriate chain transfer agent (also called RAFT agent), a reaction related to RAFT equilibrium is added to general free radical polymerization of substituted monomers, and the polymerization reaction is controlled by a reversible chain transfer reaction. Yes.

Also, regarding the immobilization of the obtained phase separation structure, Patent Document 2 describes a method of introducing a group capable of photodimerization into the hydrophobic polymer chain of the block copolymer and irradiating with ionizing radiation.

Patent Documents

3 and 4 describe a method of introducing an oxetanyl group for immobilization of the obtained phase separation structure, and further related compounds are described in Patent Document 5.

JP 2004-124088 A JP 2010-275349 A JP 2010-116463 A JP 2010-116466 A JP 2004-123597 A

In the methods described in these documents, it is essential to obtain a block copolymer after conducting living polymerization in a reaction vessel in advance.
Here, in general, living polymerization in a reaction vessel requires a long reaction time, and is expensive because a catalyst removal step and a monomer removal step are necessary, which is a limitation in practical use.

The problem to be solved by the present invention is to provide a method for producing a living polymer having excellent economic rationality.

As a result of intensive studies to solve the above problems, the present inventors have found that a living polymer can be provided on the support by providing a living polymer having a high economic rationality. .

[1] A method for producing a living polymer on a support, comprising a step of subjecting the monomer-containing composition to living polymerization on the support.
[2] In the method for producing a living polymer on a support according to [1], the living polymerization is preferably living radical polymerization.
[3] In the method for producing a living polymer on a support according to [1] or [2], the step of living polymerizing the monomer-containing composition on the support may be 1000 seconds or less. preferable.
[4] The method for producing a living polymer on a support according to any one of [1] to [3], wherein the monomer consumption rate in the step of living polymerizing the monomer-containing composition on the support Is preferably controlled to 10 to 100%.
[5] The method for producing a living polymer on a support according to any one of [1] to [4], wherein the step of living polymerizing the monomer-containing composition on the support comprises 50 to 50 Heating at 200 ° C. is preferable.
[6] In the method for producing a living polymer on a support according to any one of [1] to [5], the living polymer preferably has a number average molecular weight Mn of 1,000 to 100,000.
[7] The method for producing a living polymer on a support according to any one of [1] to [6], wherein the living polymerization is atom transfer radical polymerization, and
The support is preferably a metal support.
[8] In the method for producing a living polymer on a support according to [7], a surface of the monomer-containing composition that is not in contact with the metal support is covered with another support, and the monomer-containing composition is provided. It is preferable to heat while pressing the composition.
[9] In the method for producing a living polymer on a support according to [7] or [8], the metal is preferably copper.
[10] The method for producing a living polymer on a support according to any one of [7] to [9], wherein the copper ion concentration in the living polymer is 5 ppm relative to the living polymer. The following is preferable.
[11] In the method for producing a living polymer on a support according to any one of [1] to [6], the living polymerization is preferably reversible addition-fragmentation chain transfer polymerization.
[12] In the method for producing a living polymer on a support according to any one of [1] to [11], the monomer-containing composition contains a polymerizable rod-like liquid crystal compound as a monomer component. preferable.
[13] In the method for producing a living polymer on a support according to any one of [1] to [12], the living polymer is preferably a block copolymer.
[14] In the method for producing a living polymer on a support according to [13], the following steps (1) and (2) are preferably performed on the support.
(1) As the monomer-containing composition, a monomer-containing composition containing a polymer component containing an alkylene oxide chain and a monomer component containing an alkylene chain having 2 to 20 carbon atoms, and a monomer component containing an alkylene oxide chain and a carbon number of 2 (2) applying the monomer-containing composition onto the support using at least one of the monomer-containing compositions containing a polymer component containing 20 to 20 alkylene chains (2) the monomer-containing composition on the support [15] A process for obtaining a block copolymer in which a polymer component containing an alkylene oxide chain and a polymer component containing an alkylene chain having 2 to 20 carbon atoms are covalently linked to each other by living polymerizing [15] [13] The manufacturing method of the living polymer on the support of the following steps (1 ′) and (2) In is preferably performed.
(1 ′) A monomer-containing composition containing a polymer component containing an alkylene oxide chain and a monomer component containing an alkylene chain having 2 to 20 carbon atoms is used as the monomer-containing composition. (2) The monomer-containing composition is living-polymerized on the support so that the polymer component containing an alkylene oxide chain and the polymer component containing an alkylene chain having 2 to 20 carbon atoms are covalently bonded. Step [16] for obtaining a linked block copolymer [16] The method for producing a living polymer on a support according to [14], wherein the monomer component containing an alkylene chain having 2 to 20 carbon atoms is used. A polymerizable rod-like liquid crystal compound is preferable.
[17] The method for producing a living polymer on a support according to any one of [14] to [16], wherein the block copolymer is a block copolymer for forming a microphase-separated structure film. It is preferably a coalescence.
[18] A block copolymer obtained by the method for producing a living polymer on a support according to any one of [14] to [17].
[19] (3) A step comprising accelerating phase separation of the block copolymer according to [18] by heat, light, solvent vapor or electric field on the support to form a microphase separation structure. A method for producing a microphase separation structure membrane.
[20] In the method for producing a microphase separation structure film according to [19], the step of forming the microphase separation structure is preferably heating at 40 to 250 ° C.
[21] The method for producing a microphase-separated structure film according to [19] or [20] is further characterized in that (4) a block copolymer having the microphase-separated structure is crosslinked or polymerized on the support to form a micro It is preferable to include a step of immobilizing the phase separation structure.
[22] The method for producing a microphase separation structure film according to any one of [19] to [21] preferably includes a step of peeling the microphase separation structure film from the support.
[23] In the method for producing a microphase separation structure film according to any one of [19] to [22], the thickness of the microphase separation structure film is preferably 1 to 2000 nm.
[24] A microphase-separated structure film produced by the method for producing a microphase-separated structure film according to any one of [19] to [23].

According to the present invention, it is possible to provide a method for producing a living polymer that is excellent in economic efficiency.

FIG. 1 is a schematic view showing a GPC measurement area of a block copolymer in a GPC chart when a residual monomer and a residual initiator (when the initiator is a polymer) are mixed into the block copolymer. FIG. 2 is an AFM photograph of the microphase-separated structure film produced in Example 46. FIG. 3 is an AFM photograph of the microphase-separated structure film produced in Example 47. FIG. 4 is an AFM photograph of the microphase-separated structure film produced in Example 48. FIG. 5 is a schematic view of an example of an apparatus for forming a microphase-separated structure film by an example of a method for producing a living polymer on a support of the present invention.

Hereinafter, the present invention will be described in detail. The description of the constituent elements described below may be made based on representative embodiments and specific examples, but the present invention is not limited to such embodiments. In the present specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
Moreover, (meth) acrylate is used in the meaning containing both acrylate and methacrylate.

[Method for producing living polymer on support]
The method for producing a living polymer on the support of the present invention (hereinafter also referred to as the production method of the present invention) includes a step of living polymerizing the monomer-containing composition on the support.
With such a configuration, a method for producing a living polymer having excellent economic rationality can be provided. Generally, living polymerization in solution requires several hours (depending on the substrate), and the polymerization on the support in the production method of the present invention is economically reasonable from the viewpoint of time. It is not known in the art to perform living polymerization on a support on a monomer-containing composition, and it is not bound by any theory, but by performing living polymerization with the monomer-containing composition in a thin film state, Compared with living polymerization, the economic rationality is superior.

<Support>
The support used in the method for producing a living polymer on the support of the present invention is not particularly limited, and may be a glass substrate, a metallic support, or a resin film. . When the living polymerization method is ATRP, it is preferable to use a metallic support as the support, but details will be described later. When the living polymerization method is RAFT polymerization, it is preferable to use a glass substrate and a resin film.

<Monomer component>
In the method for producing a living polymer on the support of the present invention, the monomer-containing composition contains a monomer component used for living polymerization. In addition, the said monomer containing composition may also contain another component as needed.
As the monomer component, a monomer component including an alkylene oxide chain may be used, or a monomer component including an alkylene chain having 2 to 20 carbon atoms may be used. It is preferable to use a monomer component containing an alkylene chain having 2 to 20 carbon atoms.
The monomer component containing an alkylene oxide chain is a hydrophilic monomer, and the monomer component containing an alkylene chain having 2 to 20 carbon atoms is a hydrophobic monomer.

(Monomer component containing an alkylene oxide chain)
There is no restriction | limiting in particular as a monomer component containing the said alkylene oxide chain, The monomer component containing a well-known alkylene oxide chain can be used.
Examples of the monomer component containing an alkylene oxide chain include a compound in which methacrylic acid and acrylic acid and a compound obtained by alkyl etherifying one end of a polyol compound are linked by an ester bond.
“A compound obtained by alkyl etherifying one end of a polyol compound” is obtained by etherifying a polyol compound described below with an alkyl compound having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, more preferably methyl. Etherified (carbon number 1).
(I) Polyol compound Examples of the polyol compound include polyether polyol, polyester polyol, polycarbonate polyol, polycaprolactone polyol, aliphatic hydrocarbon having two or more hydroxyl groups in the molecule, and fat having two or more hydroxyl groups in the molecule. Cyclic hydrocarbons, unsaturated hydrocarbons having two or more hydroxyl groups in the molecule, and the like are used. These polyols can be used alone or in combination of two or more.

Examples of the polyether polyol include aliphatic polyether polyols, alicyclic polyether polyols, and aromatic polyether polyols.

Here, as the aliphatic polyether polyol, for example, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyhexamethylene glycol, polyheptamethylene glycol, polydecamethylene glycol, pentaerythritol, dipentaerythritol, trimethylolpropane, and Ethylene oxide addition triol of trimethylolpropane, propylene oxide addition triol of trimethylolpropane, ethylene oxide and propylene oxide addition triol of trimethylolpropane, ethylene oxide addition tetraol of pentaerythritol, ethylene oxide addition hexaol of dipentaerythritol, etc. Polyhydric alcohol such as alkylene oxide addition polyol , Or two or more types of ionic-polymerizable cyclic compounds by ring-opening polymerization polyether polyols obtained can be mentioned.

Examples of the ion-polymerizable cyclic compound include ethylene oxide, propylene oxide, butene-1-oxide, isobutene oxide, 3,3-bis (chloromethyl) oxetane, tetrahydrofuran, 2-methyltetrahydrofuran, dioxane, trioxane, tetraoxane, and cyclohexene. Such as oxide, styrene oxide, epichlorohydrin, glycidyl ether, allyl glycidyl ether, allyl glycidyl carbonate, butadiene monooxide, isoprene monooxide, vinyl oxetane, vinyl tetrahydrofuran, vinyl cyclohexene oxide, phenyl glycidyl ether, butyl glycidyl ether, benzoic acid glycidyl ester, etc. Examples include cyclic ethers. Specific combinations of the two or more types of ion-polymerizable cyclic compounds include tetrahydrofuran and ethylene oxide, tetrahydrofuran and propylene oxide, tetrahydrofuran and 2-methyltetrahydrofuran, tetrahydrofuran and 3-methyltetrahydrofuran, ethylene oxide and propylene oxide, butene-1- Examples thereof include oxide and ethylene oxide, tetrahydrofuran, butene-1-oxide, and ethylene oxide.

Further, a polyether polyol obtained by ring-opening copolymerization of the above ion-polymerizable cyclic compound with a cyclic imine such as ethyleneimine, a cyclic lactone acid such as β-propiolactone or glycolic acid lactide, or dimethylcyclopolysiloxane. Can also be used.

Examples of the alicyclic polyether polyol include hydrogenated bisphenol A alkylene oxide addition diol, hydrogenated bisphenol F alkylene oxide addition diol, 1,4-cyclohexanediol alkylene oxide addition diol, and the like.

Examples of the aromatic polyether polyol include alkylene oxide addition diol of bisphenol A, alkylene oxide addition diol of bisphenol F, alkylene oxide addition diol of hydroquinone, alkylene oxide addition diol of naphthohydroquinone, alkylene oxide addition diol of anthrahydroquinone, etc. It is done.

As a commercially available product of the above polyether polyol, for example, as an aliphatic polyether polyol, PTMG650, PTMG1000, PTMG2000 (manufactured by Mitsubishi Chemical Corporation), PPG1000, EXCENOL1020, EXCENOL2020, EXCENOL3020, EXCENOL4020 (above, Asahi Glass Co., Ltd.) )), PEG1000, Unisafe DC1100, Unisafe DC1800, Unisafe DCB1100, Unisafe DCB1800 (above, manufactured by NOF Corporation), PPTG1000, PPTG2000, PPTG4000, PTG400, PTG650, PTG2000, PTG3000, PTGL1000, PTGL2000 (above, Hodogaya Chemical Industry Co., Ltd.), PPG400, PBG400, Z-300 -4, Z-3001-5, PBG2000, PBG2000B (Daiichi Kogyo Seiyaku Co., Ltd.), TMP30, PNT4 glycol, EDA P4, EDA P8 (Nippon Emulsifier Co., Ltd.), Quadrol (Asahi Denka) Product). Examples of the aromatic polyether polyol include Uniol DA400, DA700, DA1000, DB400 (manufactured by NOF Corporation) and the like.

The polyester polyol is obtained by reacting a polyhydric alcohol and a polybasic acid. Here, as the polyhydric alcohol, ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, tetramethylene glycol, polytetramethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol 1,7-heptanediol, 1,8-octanediol, neopentyl glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,2-bis (hydroxyethyl) cyclohexane, 2,2-diethyl 1,3-propanediol, 3-methyl-1,5-pentanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, glycerin, trimethylolpropane, ethyleneoxy of trimethylolpropane Adducts, propylene oxide adducts of trimethylol propane, the adduct of ethylene oxide and propylene oxide trimethylolpropane, sorbitol, pentaerythritol, dipentaerythritol, alkylene oxide addition polyol, and the like. Examples of the polybasic acid include phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, adipic acid, sebacic acid and the like. Examples of commercially available products of these polyester polyols include Kurapol P1010, Kurapol P2010, PMIPA, PKA-A, PKA-A2, PNA-2000 (manufactured by Kuraray Co., Ltd.) and the like.

Further, examples of the polycarbonate polyol include polycarbonate diols represented by the following general formula (i).

In general formula (i), R ¹ represents an alkylene group having 2 to 20 carbon atoms, a (poly) ethylene glycol residue, a (poly) propylene glycol residue or a (poly) tetramethylene glycol residue, and m is 1 An integer in the range of ~ 30.

Specific examples of R ¹ include residues obtained by removing both terminal hydroxyl groups from the following compounds, that is, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,4 -Cyclohexanedimethanol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, Examples thereof include a residue obtained by removing a hydroxyl group from tetrapropylene glycol or the like. Commercial products of these polycarbonate polyols include DN-980, DN-981, DN-982, DN-983 (manufactured by Nippon Polyurethane Industry Co., Ltd.), PC-8000 (manufactured by PPG), PNOC1000, PNOC2000, PMC100, PMC2000 (above, manufactured by Kuraray Co., Ltd.), Plaxel CD-205, CD-208, CD-210, CD-220, CD-205PL, CD-208PL, CD-210PL, CD-220PL, CD-205HL, CD-208HL, CD-210HL, CD-220HL, CD-210T, CD-221T (above, manufactured by Daicel Chemical Industries, Ltd.) and the like can be used.

Examples of the polycaprolactone polyol include ε-caprolactone such as ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, tetramethylene glycol, polytetramethylene glycol, 1,2-polybutylene glycol, 1,6-hexanediol, neo Examples thereof include polycaprolactone diols obtained by addition reaction with diols such as pentyl glycol, 1,4-cyclohexanedimethanol and 1,4-butanediol. As these commercial products, Plaxel 205, 205AL, 212, 212AL, 220, 220AL (above, manufactured by Daicel Chemical Industries, Ltd.) or the like can be used.

Examples of the aliphatic hydrocarbon having two or more hydroxyl groups in the molecule include ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and 1,7-heptanediol. 1,8-octanediol, 1,9-nonanediol, neopentyl glycol, 2,2-diethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,8 -Octanediol, hydroxy-terminated hydrogenated polybutadiene, glycerin, trimethylolpropane, pentaerythritol, sorbitol and the like.

Examples of the alicyclic hydrocarbon having two or more hydroxyl groups in the molecule include 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,2-bis (hydroxyethyl) cyclohexane, dimethylol such as dicyclopentadiene. Compound, tricyclodecane dimethanol and the like.

Examples of the unsaturated hydrocarbon having two or more hydroxyl groups in the molecule include hydroxy-terminated polybutadiene and hydroxy-terminated polyisoprene.

Furthermore, examples of polyols other than the above include β-methyl-δ-valerolactone diol, castor oil-modified diol, terminal diol compound of polydimethylsiloxane, polydimethylsiloxane carbitol-modified diol, and the like.

These polyol compounds preferably have a weight average molecular weight of 1,000 to 10,000, particularly preferably 1,000 to 9000. The mass average molecular weight is a value measured by gel permeation chromatography (GPC) by dissolving a part of the polymer in tetrahydrofuran (THF). The mass average molecular weight in the present invention is a value using polystyrene as a standard substance.

Most preferably, it is polyethylene glycol monomethyl ether, and its number average molecular weight is from 100 to 10,000, preferably from 200 to 5,000, most preferably from 300 to 1,000.

(Monomer component containing an alkylene chain having 2 to 20 carbon atoms)
The monomer component including an alkylene chain having 2 to 20 carbon atoms is not particularly limited, and a known monomer component including an alkylene chain having 2 to 20 carbon atoms can be used. The monomer component containing an alkylene chain having 2 to 20 carbon atoms is preferably a liquid crystalline monomer from the viewpoint of low volatility and easy production of a microphase separation structure film described later. Without being bound by any theory, when a liquid crystalline monomer is used, the residual monomer component after living polymerization can promote phase separation alignment.
Moreover, the reaction rate of living polymerization can be increased by performing polymerization in a liquid crystal field.

Among the liquid crystal monomers, it is preferable to use a polymerizable liquid crystal compound. Without being bound by any theory, when a polymerizable liquid crystal compound is used, the phase separation structure is fixed by crosslinking or polymerizing the residual monomer component after living polymerization in the step of fixing the phase separation structure described later. Can be made easier. That is, the block copolymer of the present invention preferably has a mesogenic side chain having 6 to 50 carbon atoms in the polymer component (B) containing an alkylene chain having 2 to 20 carbon atoms. More preferably, the chain has at least one polymerizable group in one of the mesogenic side chains. The preferred range of the polymerizable group is the same as the preferred range of the polymerizable group represented by Q ¹ and Q ^{2 in} the general formula (X) described later.
The mesogen side chain having 6 to 50 carbon atoms is more preferably a mesogen side chain having 6 to 40 carbon atoms, and particularly preferably a mesogen side chain having 6 to 30 carbon atoms. “Mesogenic group” includes a group capable of forming a core part of a liquid crystal compound, and examples of the compound having a mesogenic group include a liquid crystalline compound and also has a mesogenic group but does not form a liquid crystal. Sexual compounds are also included. The mesogenic group will be further described. In the present invention, the mesogenic group is a group showing a main skeleton of liquid crystal molecules that contribute to liquid crystal formation. The liquid crystal molecules exhibit liquid crystallinity that is an intermediate state (mesophase) between a crystalline state and an isotropic liquid state. The mesogenic group is not particularly limited. For example, “Flushage Kristall in Tablen II” (VEB Deutsche Verlagfur Grundoff Industrie, Leipzig, published in 1984), pages 7 to 16 You can refer to the editions of the association, Liquid Crystal Handbook (Maruzen, 2000), especially the description in Chapter 3. A residue of a thermotropic liquid crystal is preferable, and a residue of a rod-like liquid crystal and a discotic liquid crystal is more preferable. In the rod-like liquid crystal, a liquid crystal residue showing a nematic phase and a smectic A phase is more preferable, and in a discotic liquid crystal, a liquid crystal residue showing a discotic nematic phase is more preferable.
Preferred examples of the residue of the discotic liquid crystal include benzene, triphenylene, truxene, trioxatruxene, anthraquinone, phthalocyanine or porphyrin, macrocyclene, bis (1,3-diketone) copper complex, tetraarylbipyranylidene, Tetrathiafulvalene and inositol are included.
The main skeleton of the liquid crystal molecules contributing to the formation of a rigid liquid crystal called a mesogenic group or core portion of the rod-like liquid crystal, that is, the residue of the rod-like liquid crystal, is -Cy ¹ -L ^2- ( ^{^{_{^{cy 2 -L 3) n -Cy 3}}}} -L 4 - is preferably a group represented by.
Among these, the mesogenic group is preferably a group represented by -Cy ¹ -L ^2- (Cy ² -L ³ ) _n -Cy ³ -L ^4- in the general formula (X) described later. The more preferable range of the group represented by the above -Cy ¹ -L ^2- (Cy ² -L ³ ) _n -Cy ³ -L ^4- is the same as the preferable range of each group in the general formula (X) described later. is there.

Among the liquid crystalline monomers, a rod-like liquid crystal compound is more preferable. When living polymerizing on a support, it was expected that the remaining monomer component or polymer (such as an initiator-derived polymer) adversely affects the formation of a microphase separation structure. However, when a specific rod-like liquid crystal compound is used as the liquid crystal monomer, the liquid crystal monomer remains and the fluidity is increased, so that a beautiful cylindrical microphase separation structure free from defects can be formed.

-Rod-shaped liquid crystal compounds-
Examples of the rod-like liquid crystal compound include azomethines, azoxys, cyanobiphenyls, cyanophenyl esters, benzoic acid esters, cyclohexanecarboxylic acid phenyl esters, cyanophenylcyclohexanes, cyano-substituted phenylpyrimidines, alkoxy-substituted phenylpyrimidines, Phenyldioxanes, tolanes and alkenylcyclohexylbenzonitriles are preferably used. In addition to the above low-molecular liquid crystalline molecules, high-molecular liquid crystalline molecules can also be used.
Among the rod-like liquid crystal compounds, a polymerizable rod-like liquid crystal compound that can fix the orientation of the rod-like liquid crystal compound by polymerization is more preferable.

As the polymerizable rod-like liquid crystal compound, Makromol. Chem. 190, 2255 (1989), Advanced Materials, 5, 107 (1993), U.S. Pat. Nos. 4,683,327, 5,622,648 and 5,770,107, WO 95/22586, 95/24455, 97/97. No. 0600, No. 98/23580, No. 98/52905, JP-A-1-272551, JP-A-6-16616, JP-A-7-110469, JP-A-11-80081, and Japanese Patent Application No. 2001-64627 2001-328893), JP 2004-1235979 A, Transactions of Materials Research Society of Japan, 28 [3], 553-556 (2003), JP 2008-127336 A, JP Compounds described like 010-116463 JP, and the like can be used compounds represented by the general formula below compounds and later the general formula represented by (X) (V).

The polymerizable rod-like liquid crystal compound is preferably a compound represented by the following general formula (X) and a compound represented by the following general formula (V), and a compound represented by the above general formula (X) Is more preferable.

Formula (X) Q ¹ -L ¹ -Cy ¹ -L ^2- (Cy ² -L ³ ) _n -Cy ³ -L ⁴ -Q ²
In general formula (X), Q ¹ and Q ² are each independently a polymerizable group, L ¹ and L ⁴ are each independently a divalent linking group, and at least one of L ¹ and L ⁴ is Including at least an alkylene group having 2 to 20 carbon atoms, L ² and L ³ are each independently a single bond or a divalent linking group, Cy ¹ , Cy ² and Cy ³ are divalent cyclic groups, n is 0, 1, 2, or 3.
The polymerizable rod-like liquid crystal compound represented by the general formula (X) will be described below.
In the general formula (X), Q ¹ and Q ² are each independently a polymerizable group. The polymerization reaction of the polymerizable group is preferably addition polymerization (including ring-opening polymerization) or condensation polymerization. In other words, the polymerizable group is preferably a functional group capable of addition polymerization reaction or condensation polymerization reaction. Examples of polymerizable groups are shown below.

Among these polymerizable groups, at least one of Q ¹ and Q ² is

And the other of Q ¹ and Q ² is preferably a group having an oxetane ring (hereinafter also referred to as oxetanyl group).

In the general formula (X), L ¹ and L ⁴ are each independently a divalent linking group, and at least one of L ¹ and L ⁴ includes at least an alkylene group having 2 to 20 carbon atoms. L ¹ and L ⁴ each independently comprise —O—, —S—, —CO—, —NR—, —C═N—, a divalent chain group, a divalent cyclic group, and combinations thereof. A divalent linking group selected from the group is preferred. R is an alkyl group having 1 to 7 carbon atoms or a hydrogen atom.
The example of the bivalent coupling group which consists of a combination is shown below. Here, the left side is coupled to Q (Q ¹ or Q ² ), and the right side is coupled to Cy (Cy ¹ or Cy ³ ).
L-1: —CO—O—divalent chain group —O—
L-2: —CO—O—divalent chain group —O—CO—
L-3: —CO—O—divalent chain group —O—CO—O—
L-4: —CO—O—divalent chain group—O—divalent cyclic group—
L-5: —CO—O—divalent chain group —O—divalent cyclic group —CO—O—
L-6: —CO—O—divalent chain group —O—divalent cyclic group —O—CO—
L-7: —CO—O—Divalent chain group—O—Divalent cyclic group—Divalent chain group—
L-8: —CO—O—divalent chain group—O—divalent cyclic group—divalent chain group —CO—O—
L-9: —CO—O—Divalent chain group—O—Divalent cyclic group—Divalent chain group —O—CO—
L-10: —CO—O—divalent chain group—O—CO—divalent cyclic group—
L-11: —CO—O—divalent chain group —O—CO—divalent cyclic group —CO—O—
L-12: —CO—O—divalent chain group —O—CO—divalent cyclic group —O—CO—
L-13: —CO—O—Divalent chain group—O—CO—Divalent cyclic group—Divalent chain group—
L-14: —CO—O—divalent chain group—O—CO—divalent cyclic group—divalent chain group—CO—O—
L-15: —CO—O—Divalent chain group—O—CO—Divalent cyclic group—Divalent chain group—O—CO—
L-16: —CO—O—divalent chain group—O—CO—O—divalent cyclic group—
L-17: —CO—O—divalent chain group —O—CO—O—divalent cyclic group —CO—O—
L-18: —CO—O—divalent chain group —O—CO—O—divalent cyclic group —O—CO—
L-19: —CO—O—divalent chain group—O—CO—O—divalent cyclic group—divalent chain group—
L-20: —CO—O—divalent chain group—O—CO—O—divalent cyclic group—divalent chain group—CO—O—
L-21: —CO—O—divalent chain group—O—CO—O—divalent cyclic group—divalent chain group—O—CO—
L-22: -Divalent chain group -O-Divalent chain group -O-
The divalent chain group means an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, or a substituted alkynylene group. An alkylene group, a substituted alkylene group, an alkenylene group and a substituted alkenylene group are preferred, and an alkylene group and an alkenylene group are more preferred.
The alkylene group may have a branch. The alkylene group preferably has 2 to 20 carbon atoms, more preferably 3 to 18 carbon atoms, still more preferably 4 to 16 carbon atoms, and most preferably 5 to 15 carbon atoms. The total number of carbon atoms of all alkylene groups contained in the divalent linking group represented by L ¹ and L ⁴ is preferably in the above range. For example, a divalent chain group in L-1 to L-22 When a plurality of are included, the total carbon number of the divalent chain group which is an alkylene group is preferably within the above range.
The alkylene part of the substituted alkylene group is the same as the above alkylene group. Examples of the substituent include a halogen atom.
The alkenylene group may have a branch. The alkenylene group preferably has 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, and most preferably 2 to 8 carbon atoms.
The alkylene part of the substituted alkylene group is the same as the above alkylene group. Examples of the substituent include a halogen atom.
The alkynylene group may have a branch. The alkynylene group preferably has 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, and most preferably 2 to 8 carbon atoms.
The alkynylene part of the substituted alkynylene group is the same as the above alkynylene group. Examples of the substituent include a halogen atom.
Specific examples of the divalent chain group include ethylene, trimethylene, propylene, tetramethylene, 2-methyl-tetramethylene, pentamethylene, hexamethylene, octamethylene, 2-butenylene, 2-butynylene and the like.
The definition and examples of the divalent cyclic group are the same as those of Cy ¹ , Cy ² and Cy ³ described later.
One of the linking groups bonded to the oxetane group out of L ¹ and L ⁴ is preferably L-21, and the other ^one of L ¹ and L ⁴ is preferably L-1.

In the general formula (X), R ² is preferably an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, more preferably a methyl group, an ethyl group or a hydrogen atom, and a hydrogen atom. Is most preferred.

In the general formula (X), L ^{2 and} L ³ are each independently a single bond or a divalent linking group. L ² and L ³ each independently comprises —O—, —S—, —CO—, —NR—, —C═N—, a divalent chain group, a divalent cyclic group, and combinations thereof. It is preferably a divalent linking group or a single bond selected from the group. R is an alkyl group having 1 to 7 carbon atoms or a hydrogen atom, preferably an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, and more preferably a methyl group, an ethyl group or a hydrogen atom. Preferably, it is a hydrogen atom. The divalent chain group and the divalent cyclic group are synonymous with the definitions of L ¹ and L ⁴ .
Preferred divalent linking groups for L ² or L ³ include —COO—, —OCO—, —OCOO—, —OCONR—, —COS—, —SCO—, —CONR—, —NRCO—, —CH _2. CH ₂ —, —C═C—COO—, —C═N—, —C═N—N═C—, and the like.
L ² and L ³ are preferably each independently —COO— or —OCO—.

In the general formula (X), n is 0, 1, 2, or 3. When n is 2 or 3, two L ³ may be the same or different, and two Cy ² may be the same or different. n is preferably 1 or 2, and more preferably 1.

In the general formula (X), Cy ¹ , Cy ² and Cy ³ are each independently a divalent cyclic group.
The ring contained in the cyclic group is preferably a 5-membered ring, 6-membered ring, or 7-membered ring, more preferably a 5-membered ring or 6-membered ring, and most preferably a 6-membered ring.
The ring contained in the cyclic group may be a condensed ring. However, it is more preferably a monocycle than a condensed ring.
The ring contained in the cyclic group may be any of an aromatic ring, an aliphatic ring, and a heterocyclic ring. Examples of the aromatic ring include a benzene ring and a naphthalene ring. Examples of the aliphatic ring include a cyclohexane ring. Examples of the heterocyclic ring include a pyridine ring and a pyrimidine ring.
As the cyclic group having a benzene ring, 1,4-phenylene is preferable. As the cyclic group having a naphthalene ring, naphthalene-1,5-diyl and naphthalene-2,6-diyl are preferable. The cyclic group having a cyclohexane ring is preferably 1,4-cyclohexylene. The cyclic group having a pyridine ring is preferably pyridine-2,5-diyl. The cyclic group having a pyrimidine ring is preferably pyrimidine-2,5-diyl.
The cyclic group may have a substituent. Examples of the substituent include a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 5 carbon atoms, a halogen-substituted alkyl group having 1 to 5 carbon atoms, and an alkoxy group having 1 to 5 carbon atoms. An alkylthio group having 1 to 5 carbon atoms, an acyloxy group having 2 to 6 carbon atoms, an alkoxycarbonyl group having 2 to 6 carbon atoms, a carbamoyl group, and an alkyl-substituted carbamoyl group having 2 to 6 carbon atoms And an acylamino group having 2 to 6 carbon atoms.

Examples of the polymerizable liquid crystal compound represented by the general formula (X) are shown below. The present invention is not limited to these.

Moreover, as a rod-shaped liquid crystal compound, the compound represented by the following general formula (V) is also preferable.
Formula (V) M ^1- (L ¹ ) p-Cy ¹ -L ^2- (Cy ² -L ³ ) _n -Cy ^3- (L ⁴ ) q-M ²
In general formula (V), M ¹ and M ² are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a heterocyclic group, a cyano group, a halogen, —SCN, —CF ₃ , a nitro group, or Q ¹ is represented, but at least one of M ¹ and M ² represents a group other than Q ¹ .
However, Q ¹ , L ¹ , L ² , L ³ , L ⁴ , Cy ¹ , Cy ² , Cy ³ and n have the same meaning as the group represented by the general formula (X). P and q are 0 or 1.
When M ¹ and M ² do not represent Q ¹ , it is preferably a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a cyano group, more preferably a carbon number It is preferably an alkyl group of 1 to 4 or a phenyl group, and p and q are preferably 0.

In addition, you may mix and use the polymeric rod-shaped liquid crystal compound represented by the said general formula (X), and the compound represented by the said general formula (V). Moreover, as a preferable mixing ratio of the compound represented by the general formula (V) in the mixture of the polymerizable liquid crystal compound represented by the general formula (X) and the compound represented by the general formula (V), 0.1% to 40%, more preferably 1% to 30%, and still more preferably 5% to 20%.

Preferred examples of the compound represented by the general formula (V) are shown below, but the present invention is not limited to these.

Of the polymerizable liquid crystal compounds that can be used in the present invention, one of the compounds having two or more acrylic groups and methacrylic groups may potentially contain a polymerizable group. That is, since a polymerizable group can be expressed from a compound as described below by a chemical reaction described in EP2130817, after one of the compounds having two or more acrylic groups and methacrylic groups is used for living polymerization, it is potentially polymerized. A portion containing a functional group may be treated by a chemical reaction to generate a polymerizable group.

In the general formulas in the present invention, the polymerizable

liquid crystal compounds

1 and 2 are described without any distinction, and are regarded as synonymous in the present invention.

<Solvent>
In the method for producing a living polymer on the support of the present invention, any solvent that does not inhibit the reaction can be used as the solvent that can be used in the monomer-containing composition.
Specifically, aromatic hydrocarbon solvents such as benzene, toluene and xylene, aliphatic hydrocarbon solvents such as pentane, hexane, heptane, octane, nonane and decane, cyclohexane, methylcyclohexane and decahydronaphthalene. Alicyclic hydrocarbon solvents, chlorinated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, trichlorobenzene, methylene chloride, chloroform, carbon tetrachloride and tetrachloroethylene, methanol, ethanol, n-propanol, iso-propanol, n Alcohol solvents such as butanol, sec-butanol and tert-butanol, ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone, and esters such as ethyl acetate, butyl acetate and dimethyl phthalate System solvent, dimethyl ether, diethyl ether, and di -n- amyl ether, diphenyl ether, ether solvents such as tetrahydrofuran and anisole, dimethyl sulfoxide, N- dimethylformamide, dioxane or the like.

Also, suspension polymerization and emulsion polymerization can be performed using water as a solvent. These solvents may be used alone or in admixture of two or more. Moreover, it is preferable that the reaction liquid becomes a homogeneous phase by using these solvents, but a plurality of non-uniform phases may be used.

(ATRP (Atom Transfer Radical Polymerization))
One of the preferable embodiments of the method for producing a living polymer on the support of the present invention is an embodiment in which the living polymerization is atom transfer radical polymerization, and the support is a metal support.

ATRP (Atom Transfer Radical Polymerization) in the present specification is one of living radical polymerizations, and is a metal complex or transition metal having an organic halide or a sulfonyl halide compound as an initiator and a transition metal as a central metal. This is a method of radical polymerization of a radically polymerizable monomer using a simple substance as a catalyst.

As a preferable aspect of ATRP, specifically, for example, Matyjazewski et al., Chem. Rev. 101, 2921 (2001), WO 96/30421, WO 97/18247, WO 98/01480, WO 98/40415, WO 00/15695, or Sawamoto et al., Chem. Rev. 101, 3689 (2001), JP-A-8-411117, JP-A-9-208616, JP-A 2000-264914, JP-A 2001-316410, JP-A 2002-80523, JP No. 2004-307872 and the like.

-Initiator-
The initiator used for ATRP is not particularly limited, and examples thereof include organic halides and sulfonyl halide compounds. In particular, carbon-carbon double bonds or carbon atoms present at the α-position of carbon-oxygen double bonds A structure in which a halogen bond or a plurality of halogen atoms are added on one carbon atom is suitable as the initiator structure. In the present invention, a carbon-halogen bond present at the α-position of a carbon-carbon double bond, or a structure in which a plurality of halogens are added on one carbon atom can be used as an initiator structure.

The initiator used for ATRP is preferably a macroinitiator containing a hydrophilic unit, more preferably a macroinitiator containing a polyalkyleneoxy structure, from the viewpoint of facilitating production of a microphase separation structure membrane. preferable.
The polyalkyleneoxy structure is not particularly limited, but the alkyleneoxy group is preferably an alkyleneoxy group having 1 to 1000 carbon atoms, more preferably an alkyleneoxy group having 10 to 400 carbon atoms, Particularly preferred is a group.
In the polyalkyleneoxy structure, the number of repeating units of the alkyleneoxy structure is not particularly limited, but is preferably 1 to 500, more preferably 3 to 250, and particularly preferably 5 to 200.

In the present invention, a commercially available initiator for ATRP may be used. Examples of the initiator for low molecular weight ATRP include ethyl-α-bromoisobutyrate (manufactured by Aldrich).

On the other hand, the ATRP initiator that is a macroinitiator may be produced by synthesis. As the initiator for ATRP, which is a macroinitiator, for example, the following can be used, but the present invention is not limited by the following specific examples.

In the monomer composition, the amount of the ATRP initiator added is preferably 1 to 60% by mass, more preferably 5 to 55% by mass, and more preferably 10 to 45% by mass with respect to the monomer component. % Is particularly preferred.

As a ligand, Macromolecules, 2006, 39, 4953. The ligands described in (1) can be preferably used.
2,2′-bipyridine, 1,1,4,7,10,10-hexamethyltriethylenetetramine, N, N, N ′, N′-tetrakis (2-pyridylmethyl) ethylenediamine, tris [2- (dimethyl It is particularly preferred to use amino) ethyl] amine.
In the monomer composition, the amount of the ligand added is preferably 0.1 to 40% by mass, more preferably 0.5 to 20% by mass, with respect to the monomer component. 10% by mass is particularly preferable.

-Polymerization catalyst-
The method for producing a living polymer on the support of the present invention is not particularly limited as a polymerization catalyst for ATRP.

Although it does not specifically limit as a transition metal complex used as a polymerization catalyst of ATRP, Preferably it is a metal complex which uses a periodic table group 7, 8, 9, 10, or 11 element as a central metal. More preferable examples include a complex of zero-valent copper, monovalent copper, divalent ruthenium, divalent iron, or divalent nickel. Of these, a copper complex is preferable. Specific examples of monovalent copper compounds include cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, cuprous oxide, cuprous perchlorate, etc. is there. When a copper compound is used, 2,2′-bipyridyl or a derivative thereof, 1,10-phenanthroline or a derivative thereof, or tetramethylethylenediamine, pentamethyldiethylenetriamine or hexamethyltris (2-aminoethyl) amine is used to increase the catalytic activity. Polyamines such as are added as ligands. A tristriphenylphosphine complex of divalent ruthenium chloride (RuCl ₂ (PPh ₃ ) ₃ ) is also suitable as a catalyst. When a ruthenium compound is used as a catalyst, an aluminum alkoxide is added as an activator. Furthermore, a divalent iron bistriphenylphosphine complex (FeCl ₂ (PPh ₃ ) ₂ ), a divalent nickel bistriphenylphosphine complex (NiCl ₂ (PPh ₃ ) ₂ ), and a divalent nickel bistributylphosphine A complex (NiBr ₂ (PBu ₃ ) ₂ ) is also suitable as a catalyst.

The simple substance of the transition metal used as the polymerization catalyst for ATRP is not particularly limited, but is preferably a metal belonging to Group 7, 8, 9, 10, or 11 of the periodic table. Further preferred are copper, ruthenium, iron or nickel. Of these, copper is preferable.

In the production method of the present invention, it is preferable that a metal support is used as the support, and the metal support is also used as an ATRP polymerization catalyst.
Living polymerization on a metal support uses a metal support as a catalyst to save the trouble of removing the metal from the composition after ordinary ATRP in which the metal catalyst is added to the monomer-containing composition. There is economic rationality.
In the method for producing a living polymer on the support of the present invention, the metal support is preferably a metallic film. A metallic film having a thickness of 5 to 50 μm is preferably used from the viewpoint of operation and economic rationality. A metal film having a width of 100 to 500 mm is preferably used from the viewpoint of continuous production.
In the method for producing a living polymer on the support of the present invention, the metal in the metal support is preferably copper. As the support used in this case, a copper film can be preferably used.
As the metallic support, a commercially available support may be used. For example, examples of the copper film include Nippon Foil Co., Ltd., rolled copper foil TCU, and the like.

In the method for producing a living polymer on the support of the present invention, the surface of the monomer-containing composition that is not in contact with the metal support is covered with another support, and the monomer-containing composition is sandwiched. It is preferable to heat from the viewpoint of making it difficult to volatilize the materials used (the monomer component and the initiator). From the viewpoint of further providing the ATRP polymerization catalytic activity, it is preferable to use another sheet of the above-mentioned metal support.
In the method for producing a living polymer on the support of the present invention, the metal in the metal film is preferably copper. The preferable range of the metal film used in this case is the same as the preferable range of the metallic support.
The pressure applied when the monomer-containing composition is sandwiched is not particularly limited, but is preferably 0.1 to 500 KPa, for example, from the viewpoint of production.

As for the manufacturing method of the living polymer on the support body of this invention, it is preferable that the copper ion concentration in the said living polymer is 5 ppm or less with respect to the said living polymer.
In addition, in normal ATRP in which a metal catalyst is added as a polymerization catalyst to the monomer-containing composition, for example, when copper is used as the metal catalyst, the copper ion concentration in the living polymer is 100 ppm with respect to the living polymer. It was a degree exceeding.

-monomer-
Examples of the monomer (radically polymerizable monomer) used in ATRP include the same monomers as those described above.

(RAFT (Reversible Addition Fragmentation Chain Transfer) Polymerization)
One of the preferable embodiments of the method for producing a living polymer on the support of the present invention is an embodiment in which the living polymerization is a reversible addition-fragmentation chain transfer polymerization.

In the method for producing a living polymer on the support of the present invention, the monomer-containing composition preferably contains a polymerizable rod-like liquid crystal compound as a monomer component.

-RAFT agent-
There is no restriction | limiting in particular as RAFT agent used by RAFT polymerization, A well-known RAFT agent can be used. For example, Macromolecules, 2006, 39, 4953. Can be mentioned.

In the present invention, a commercially available RAFT agent may be used. For example, 4-cyano-4-[(dodecylsulfanyl-thiocarbonyl) sulfanyl] pentanoic acid or 2-cyano-2-propylbenzodithioate is used as a low molecular weight RAFT agent. (Both manufactured by Aldrich). As macro RAFT agents, poly (ethylene glycol) methyl ether (4-cyano-4-pentanoate dodecyl trithiocarbonate and poly (ethylene glycol) methyl ether (4-cyano-4- (dodecylsulfanylthiocarbonyl) sulfanyl) Examples include pentanoate (all manufactured by Aldrich).

In the monomer composition, the addition amount of the RAFT agent is preferably 1 to 60% by mass, more preferably 5 to 55% by mass, and more preferably 10 to 45% by mass with respect to the monomer component. It is particularly preferred.

-Radical polymerization initiator-
A commercially available radical polymerization initiator can be used as the radical polymerization initiator. V-70, V-60 (AIBN), V-40, V-65, V-601, V-59, V-30, V-501 and the like manufactured by Wako Pure Chemical Industries are preferred, and AIBN is particularly preferred.
In the monomer composition, the addition amount of the radical polymerization initiator is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, based on the monomer component. It is particularly preferably 2 to 1% by mass.

-monomer-
Examples of the monomer (radically polymerizable monomer) used in RAFT polymerization include the same monomers as those described above.

<Photopolymerization initiator>
In the present invention, when forming a microphase-separated structure film using the method for producing a living polymer on the support of the present invention, a polymerizable rod-like liquid crystal compound is used as the monomer component, and a photopolymerization initiator is further used. Is preferably added. When forming the micro phase separation structure film, the phase separation structure can be easily fixed by using the polymerizable rod-like liquid crystal compound and the photopolymerization initiator in combination. As the photopolymerization initiator, a compound known as a photoacid generator is preferable. For example, a photoacid generator described in JP2012-150428A can be used.
As the photoacid generator, for example, the following can be used, but the present invention is not limited by the following specific examples.

In the monomer composition, the addition amount of the photopolymerization initiator is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass with respect to the monomer component. The content is particularly preferably 0.2 to 1% by mass.

<Other additives>
Other additives may be added to the monomer-containing composition. Examples of other additives include additives that can be used in combination with a polymerizable rod-like liquid crystal compound as described in Liquid Crystal Handbook, Liquid Crystal Handbook Editorial Committee, Maruzen Co., Ltd., and the like.

<Polymerization conditions>
In the method for producing a living polymer on the support of the present invention, the polymerization conditions and the polymerization method are not particularly limited as long as the living polymerization can be performed on the support. Bulk polymerization, suspension polymerization, emulsion polymerization, block Turbid polymerization or the like can be applied.
In the method for producing a living polymer on the support of the present invention,
(I) applying the monomer-containing composition onto the support;
(Ii) It is preferable to include a step of living polymerizing the monomer-containing composition on the support.

(Method of applying)
Although there is no restriction | limiting in particular as an application method in the process of applying the said monomer containing composition on the said support body, It is especially preferable to form into a film by a solution process.
Here, film formation by a solution process refers to a method in which an organic compound is dissolved in a solvent capable of dissolving, and the solution is applied onto a substrate and dried to form a film. Specifically, casting method, blade coating method, wire bar coating method, spray coating method, dipping (dipping) coating method, bead coating method, air knife coating method, curtain coating method, inkjet method, spin coating method, Langmuir- A usual method such as a Langmuir-Blodgett (LB) method can be used. In the present invention, it is more preferable to use a casting method, a spin coating method, and an ink jet method. By such a solution process, a thin film having a smooth surface and a large area can be produced at a low cost.
The spin coating is preferably performed, for example, at 100 to 5000 revolutions / minute for 5 to 60 seconds.
The preferable range of the thickness after application of the monomer-containing composition in the step of applying the monomer-containing composition on the support is the same as the preferable range of the thickness of the microphase-separated structure film of the present invention described later.

Prior to the step of applying the monomer-containing composition on the support, surface modification or guides (such as rubbing) may or may not be performed on the support. It is preferable not to perform from a viewpoint of chemical conversion. In particular, when the monomer component and the initiator are used in combination with hydrophobic and hydrophilic substances that are incompatible with each other, a micro phase separation structure described later is formed without surface modification or guide to the support. Can do. In particular, when the amphiphilic liquid crystal block copolymer described later is formed by the production method of the present invention, it is possible to form a clean cylindrical microphase separation structure without defects even without surface modification or guide to the support. it can.

(Polymerization time)
In the method for producing a living polymer on the support of the present invention, the step of living polymerizing the monomer-containing composition on the support is preferably 1000 seconds or less, more preferably 800 seconds or less. Preferably, it is particularly preferably 600 seconds or less.
The lower limit of the time for the step of living polymerizing the monomer-containing composition on the support is not particularly limited, but is preferably 5 seconds or more.

(Reaction temperature)
The reaction temperature may be any temperature as long as the polymerization reaction proceeds, and is not uniform depending on the desired degree of polymerization of the polymer and the type and amount of the polymerization initiator and solvent used. ° C.
In the method for producing a living polymer on the support of the present invention, the step of living polymerizing the monomer-containing composition on the support is preferably heating at 50 to 200 ° C., more preferably 60 ° C to 180 ° C, more preferably 80 ° C to 160 ° C.
There is no restriction | limiting in particular as a heating method, A well-known method can be used, For example, the method of mounting the said support body on a hotplate and heating the said monomer containing composition with the said support body etc. can be mentioned.
In addition, after heating, it is preferable to cool to room temperature finally and to obtain a living polymer.

The living polymerization reaction in the step of living polymerizing the monomer-containing composition on the support can be carried out under reduced pressure, normal pressure, or increased pressure depending on the case.
The polymerization reaction is preferably carried out under a flow of an inert gas such as nitrogen or argon, more preferably under a flow of nitrogen gas, particularly when the initiator is a low molecular weight initiator. There are no particular restrictions on the flow conditions of the inert gas, but it may be, for example, 0.001 to 50 L / min.

(Monomer consumption rate)
In the method for producing a living polymer on a support according to the present invention, the monomer consumption rate in the step of living polymerizing the monomer-containing composition on the support is controlled to 10 to 100%. From the viewpoint of rapid formation, it is preferable. The monomer consumption rate is more preferably 20 to 100%, and particularly preferably 30 to 100%.
The monomer consumption rate described above can be determined by performing ¹ H-NMR (BRUKER-300 MHZ) measurement on an extract obtained by extracting the obtained living polymer with deuterated THF.

<Living polymer>
A living polymer is manufactured by the manufacturing method of the living polymer on the support body of this invention. The living polymer is preferably formed into a film on the support.

In the method for producing a living polymer on the support of the present invention, the number average molecular weight Mn of the resulting living polymer is preferably 1,000 to 100,000, more preferably 2,000 to 50,000, and more preferably 3,000 to 30,000. It is particularly preferred.

The method for producing the living polymer on the support of the present invention is such that the ratio Mw / Mn of the weight average molecular weight Mw and the number average molecular weight Mn of the resulting living polymer extract exceeds 1.3 is a residual monomer. Is preferable from the viewpoint of repairing defects in the phase separation structure, and the residual macroinitiator and the residual macro RAFT agent from controlling the size of the phase separation structure.
On the other hand, Mw / Mn is preferably 1.3 or less from the viewpoint of stably forming the phase separation structure.
In the present specification, the number average molecular weight Mn of a block copolymer, a polymer component containing an alkylene oxide chain, a polymer component containing an alkylene chain having 2 to 20 carbon atoms, and the like is a value measured by the following method.
The polymer was dissolved in THF, and a high-speed GPC (HLC-8220GPC) manufactured by Tosoh was used. The number average molecular weight Mn was calculated in terms of polystyrene.
In this specification, the weight average molecular weight Mw of the block copolymer, the polymer component containing an alkylene oxide chain, the polymer component containing an alkylene chain having 2 to 20 carbon atoms, and the like is a value measured by the following method. .
The polymer was dissolved in THF, and a high-speed GPC (HLC-8220GPC) manufactured by Tosoh was used. The weight average molecular weight Mw was calculated in terms of polystyrene.

<Formation of block copolymer>
In the method for producing a living polymer on the support of the present invention, the living polymer is preferably a block copolymer. In this case, as for the manufacturing method of the living polymer on the support body of this invention, it is more preferable to implement the following process (1) and (2) on a support body.
(1) As the monomer-containing composition, a monomer-containing composition containing a polymer component containing an alkylene oxide chain and a monomer component containing an alkylene chain having 2 to 20 carbon atoms, and a monomer component containing an alkylene oxide chain and a carbon number of 2 (2) applying the monomer-containing composition onto the support using at least one of the monomer-containing compositions containing a polymer component containing 20 to 20 alkylene chains (2) the monomer-containing composition on the support Is a step of living polymerizing to obtain a block copolymer in which a polymer component containing an alkylene oxide chain and a polymer component containing an alkylene chain having 2 to 20 carbon atoms are linked by a covalent bond

In the method for producing a living polymer on the support of the present invention, the following steps (1 ′) and (2) are particularly preferably carried out on the support.
(1 ′) A monomer-containing composition containing a polymer component containing an alkylene oxide chain and a monomer component containing an alkylene chain having 2 to 20 carbon atoms is used as the monomer-containing composition. (2) The monomer-containing composition is living-polymerized on the support so that the polymer component containing an alkylene oxide chain and the polymer component containing an alkylene chain having 2 to 20 carbon atoms are covalently bonded. Process for obtaining linked block copolymer

Preferred production conditions for the steps (1) and (1 ′) are the same as the preferred production conditions for the step (i). Preferred production conditions for the step (2) are the same as the preferred production conditions for the step (ii).

In the method for producing a living polymer on the support of the present invention, the block copolymer is preferably a block copolymer for forming a microphase-separated structure film.
In order to use the obtained block copolymer as a functional material, the block copolymer reaction mixture is once taken out and purified, and then the block copolymer is applied to a substrate (or support) to form a phase separation structure. It is common to make it. On the other hand, when a block copolymer is obtained by the method for producing a living polymer according to the present invention, the phase separation structure can be formed on the support as it is after the living polymerization is performed on the support, which is further economically rational. .

[Block copolymer]
The block copolymer of the present invention is characterized in that, in the method for producing a living polymer on the support of the present invention, the block copolymer is obtained under the condition that the living polymer becomes a block copolymer. Examples of the conditions for the living polymer to be a block copolymer include the method of performing the steps (1) and (2) described above, and the method of performing the steps (1 ′) and (2) described above. Is preferred.
The preferred molecular weight range of the obtained block copolymer is the same as the preferred molecular weight range of the living polymer obtained by the method for producing a living polymer on the support of the present invention.

The use of the block copolymer of the present invention is not particularly limited, but the block copolymer of the present invention is preferably a block copolymer for forming a microphase-separated structure film.

The block copolymer of the present invention is not particularly limited in structure, but the polymer component (A) containing an alkylene oxide chain and the polymer component (B) containing an alkylene chain having 2 to 20 carbon atoms are incompatible with each other. It is a block copolymer in which a polymer is bonded by a covalent bond, and the polymer component (B) containing an alkylene chain having 2 to 20 carbon atoms preferably has a mesogenic side chain having 6 to 50 carbon atoms. Such a block copolymer is sometimes called an amphiphilic liquid crystal block copolymer.
In the block copolymer of the present invention, the polymer component (B) containing an alkylene chain having 2 to 20 carbon atoms is preferably a poly ((meth) acrylate) having a mesogenic side chain having 6 to 50 carbon atoms, More preferably, it contains a polymer component derived from the polymerizable rod-like liquid crystal compound.
In the block copolymer of the present invention, the polymer component (A) containing an alkylene oxide chain preferably contains a polyalkyleneoxy structure, and more preferably contains a polymer component derived from the macroinitiator.

Even if the polymer component (A) containing an alkylene oxide chain and the polymer component (B) containing an alkylene chain having 2 to 20 carbon atoms are directly bonded to each other, the block copolymer of the present invention can be bonded via a linking group. It may be bonded. Because of less coloring, in the light-related application, the following divalent linking group is bonded to the linking part of the polymer component (A) containing an alkylene oxide chain and the polymer component (B) containing an alkylene chain having 2 to 20 carbon atoms. It may be a block copolymer containing any of them. The method for introducing at least one of the divalent linking groups represented by the following general formulas (11) and (12) into the linking part of the polymer component (A) and the polymer component (B) is not particularly limited. Absent. For example, a method using a polymer component (A) containing an alkylene oxide chain, that is, a hydrophilic macro RAFT agent having at least one of divalent linking groups represented by the following general formulas (11) and (12) Can be mentioned.

Examples of the block copolymer of the present invention include those represented by the following general formulas (I-1) and (I-2).

Here, X represents the structure described in the following general formula (3) and a halogen atom (iodine, bromine, chlorine atom) or a hydrogen atom.

(In the general formulas (I-1) and (I-2), n and m each independently represent an integer of 1 to 500, and L ¹¹ and L ¹² each independently represents a single bond or an alkylene group, an arylene group, an alkenylene. Group, alkynylene group, metallocenylene group, —CO—N (R ¹⁰¹ ) —, —CO—O—, —SO ₂ —N (R ¹⁰² ) —, —SO ₂ —O—, —N (R ¹⁰³ ) —CO -N (R ¹⁰⁴ )-, -SO _2- , -SO-, -S-, -O-, -CO-, -N (R ¹⁰⁵ )-, or a combination of one or more heterylene groups Represents a linking group having 0 to 100 carbon atoms, preferably 1 to 20 carbon atoms (R ¹⁰¹ , R ¹⁰² , R ¹⁰³ , R ¹⁰⁴ , and R ¹⁰⁵ each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, Substituted or unsubstituted aryl The represented. However, L ¹² comprises an alkylene group having at least carbon atoms 2 ~ 20.), R ¹ each independently represent a hydrogen atom or a methyl group, R ² is independently an oxetanyl group, an epoxy group, an acrylate group Represents a methacrylate group, an optionally substituted alkyl group or an optionally substituted alkoxy group, M represents a mesogenic group having 6 to 50 carbon atoms, and Z ³ represents substituted or unsubstituted. An aryl group and a substituted or unsubstituted alkyl group, provided that m repeating units may be the same or different.
In the general formulas (I-1) and (I-2), Z ³ is preferably a substituted or unsubstituted aryl group, a substituted or unsubstituted alkyl group, and preferably a substituted or unsubstituted alkyl group. More preferably, it is an alkyl group having 4 to 20 carbon atoms.

In general formulas (I-1) and (I-2), n is preferably 1 to 500, more preferably 3 to 250, and particularly preferably 5 to 200.
In general formulas (I-1) and (I-2), m is preferably 3 to 200, more preferably 5 to 150, and particularly preferably 10 to 100.
In general formulas (I-1) and (I-2), L ¹¹ and L ¹² are each independently a single bond, a functional group described below, or two hydrogen atoms removed from a functional group described below. The divalent linking group represented by For example, phenylene, naphthylene), alkenylene group (carbon number 2 to 20, for example, ethenylene, propenylene), alkynylene group (carbon number 2 to 20, for example, ethynylene, propynylene), metallocenylene group (for example, ferrocene), —CO—N (R ¹⁰¹ _{^{) -, - CO-O -}} , - SO 2 -N (R 102) -, - SO 2 -O -, - N (R 103) -CO-N (R 104) -, _{SO 2 -, - SO -,} - S -, - O -, - CO -, - N (R 105) -, heterylene group (carbon number 1 to 26, for example 6-chloro-1,3,5-triazyl - 2,4-diyl group, pyrimidine-2,4-diyl group) or a combination of one or more thereof represents a linking group having 0 to 100 carbon atoms, preferably 1 to 20 carbon atoms.
However, L ¹² contains at least an alkylene group having 2 to 20 carbon atoms. The alkylene group contained in L ¹² preferably has 3 to 18 carbon atoms, more preferably 4 to 16 carbon atoms, and particularly preferably 5 to 15 carbon atoms.
R ¹⁰¹ , R ¹⁰² , R ¹⁰³ , R ¹⁰⁴ , and R ¹⁰⁵ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. One or more linking groups represented by L ¹¹ and L ¹² may be present, and a plurality (preferably two) of the linking groups may be bonded to form a ring.
In general formulas (I-1) and (I-2), R ¹ is preferably independently a hydrogen atom or a methyl group from the viewpoint of versatility.
In general formulas (I-1) and (I-2), M is preferably a mesogenic group having 6 to 50 carbon atoms, more preferably a mesogenic group having 6 to 40 carbon atoms, Particular preference is given to 30 mesogenic groups. A preferable range of the mesogenic group having 6 to 50 carbon atoms represented by M is a preferable range of the above -Cy ¹ -L ^2- (Cy ² -L ³ ) _n -Cy ³ -L ^{4-in the} general formula (X). It is the same.
In general formulas (I-1) and (I-2), R ² is preferably a polymerizable group, such as an oxetanyl group, an epoxy group, an acrylate group, or a methacrylate group, and preferably an oxetanyl group or an epoxy group. More preferred.

The block copolymer of the present invention has a copolymerization ratio (number average molecular weight ratio) of the polymer component (A) containing an alkylene oxide chain and the polymer component (B) containing an alkylene chain having 2 to 20 carbon atoms is 65. : 35 to 1:99 is preferable, 55:45 to 5:95 is more preferable, and 45:55 to 10:90 is particularly preferable.

[Production method of micro phase separation structure membrane]
The method for producing a microphase-separated structure film of the present invention includes (3) forming the microphase-separated structure by promoting phase separation of the block copolymer of the present invention on the support by heat, light, solvent vapor or electric field. Including the step of: As a method of promoting phase separation by heat, light, solvent vapor or electric field to the block copolymer of the present invention for forming a microphase separation structure, a method of promoting phase separation by heating is preferable.

FIG. 5 shows a schematic diagram of an example of an apparatus for producing a microphase separation structure membrane. In FIG. 5, the step of feeding the support 21 from the feed roll 11, applying the monomer-containing composition 22 onto the support by the coating device 12, and applying the monomer-containing composition onto the support is performed.
The monomer-containing composition provided on the support is subjected to living polymerization of the monomer-containing composition on the support in the first aging zone 14 after passing through the drying zone 13.
Thereafter, in the second aging zone 15, a step of forming a microphase separation structure on the support is performed, and the monomer-containing composition is subjected to high-speed phase separation.
Thereafter, the micro phase separation structure is fixed in the UV irradiation zone 16.
Thereafter, the micro phase separation structure film is peeled off from the support 21 by the peeling roll 17.
The support 21 may be wound up by the winding roll 18.
Hereinafter, preferred embodiments of each step will be described.

<Step of forming a microphase separation structure>
(Reaction time)
The method for producing a microphase-separated structure film of the present invention is such that (3) the step of heating the block copolymer of the present invention on the support to form a microphase-separated structure is 5 to 1000 seconds. It is preferably 10 to 600 seconds, more preferably 30 to 200 seconds.

(Reaction temperature)
The method for producing a microphase-separated structure film of the present invention is such that (3) the step of heating the block copolymer of the present invention on the support to form a microphase-separated structure has a heating start temperature of 40 to 250. It is preferably 0 ° C., more preferably 50 ° C. to 200 ° C., and still more preferably 60 ° C. to 190 ° C.
There is no restriction | limiting in particular as a heating method in the said (3) process, A well-known method can be used, for example, the said support body is mounted on a hotplate and the said monomer containing composition is heated with the said support body etc. Can be mentioned.
After the start of heating, it is preferable that the temperature is finally lowered to the start temperature (irradiation temperature of active radiation) of the step (4) described later. The rate of temperature decrease from the start of heating to the UV irradiation temperature is preferably 1 to 100 ° C./min, more preferably 5 to 80 ° C./min, and particularly preferably 10 to 50 ° C./min. .

<Step of immobilizing the microphase separation structure>
The method for producing a microphase separation structure membrane of the present invention further includes (4) a step of crosslinking or polymerizing the block copolymer having the microphase separation structure on the support to fix the microphase separation structure. It is preferable.
There is no particular limitation on the method of fixing the microphase separation structure by crosslinking or polymerizing the block copolymer having the microphase separation structure on the support, but the block copolymer having the microphase separation structure is not limited. It is preferable that the polymer is irradiated with actinic radiation, and UV irradiation is more preferable.

(Irradiation with actinic radiation)
The method for producing a microphase-separated structure film of the present invention comprises (4) actinic radiation in the step of immobilizing the microphase-separated structure by crosslinking or polymerizing the block copolymer having the microphase-separated structure on the support. The irradiation temperature is preferably 40 to 200 ° C., more preferably 50 to 200 ° C., and still more preferably 60 to 200 ° C.
Method for producing a microphase-separated structure membrane of the present invention, the irradiation of the active radiation is preferably from 50 ~ 2000mJ / cm ^2, is preferably ^{100 ~ 1500mJ / cm 2, 200} ~ 1000mJ / cm 2 It is particularly preferred that
There is no restriction | limiting in particular as an irradiation apparatus of the actinic radiation in the said (4) process, A well-known apparatus can be used, for example, EXERE3000 by HOYA etc. can be mentioned.
In addition, after irradiation of actinic radiation, it is preferable to cool to room temperature finally and to obtain a micro phase-separation structure film.

<Step of peeling the micro phase separation structure membrane>
The method for producing a microphase separation structure membrane of the present invention preferably includes a step of peeling the microphase separation structure membrane from the support.
There is no restriction | limiting in particular as a method of peeling the said micro phase-separation structure film | membrane from the said support body.

[Micro phase separation structure membrane]
The microphase-separated structure film of the present invention is manufactured by the method for manufacturing a microphase-separated structure film of the present invention. Here, in this specification, when a lamellar structure or a cylinder structure can be confirmed when observed with an atomic force microscope (also referred to as AFM), it is regarded as having a “microphase separation structure”.
The microphase separation structure film obtained by the method for producing a microphase separation structure film of the present invention is formed on a substrate, but may be used after peeling from the substrate.
The thickness of the microphase separation structure film is preferably 1 to 2000 nm. Although the more preferable thickness of the microphase-separated structure membrane varies depending on the application, it is more preferably 1 to 500 nm, for example.
The microphase separation structure film is preferably a cylinder type microphase separation structure film. The cylinder type micro phase separation structure membrane means a membrane in which a large number of cylinders to which the polymer component containing the alkylene oxide chain is fixed are arranged in a plane, and each cylinder is aligned at equal intervals. preferable. The height of each cylinder is preferably 1 to 2000 nm, and more preferably 1 to 500 nm. The diameter of each cylinder is preferably 1 to 1000 nm, and more preferably 1 to 200 nm.

(Use)
The microphase-separated structure film obtained by the method for producing a microphase-separated structure film of the present invention is a high-density recording such as an optical / electronic functional material (for example, a brightness enhancement film), an energy-related material, a surface modifying material, and a patterned medium Microphase separation consisting of controlled-oriented block copolymers useful as materials, various nanofilters (permeation membranes, ultrafiltration membranes, nanoreactors), anisotropic ion conductive membranes, anisotropic conductive films, etc. It is a structural film.
Such a microphase separation structure membrane can also be used as a porous structure by removing the cylinder structure portion. Porous structures obtained from microphase separation structure membranes are anisotropic, such as polymer electrolytes for fuel cells, ion exchange resins, thin films for microreactors, protein separation membranes, organic zeolites, and templates for various pillars. It can be used as a conductive ion conductive material.
Such a microphase-separated structure film can also introduce another substance by removing the cylinder structure portion.

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

In the following examples, since the residual monomer and residual initiator (when the initiator is a polymer) are mixed into the resulting living polymer (block copolymer), a GPC chart as shown in FIG. 1 is obtained. At that time, Mw (weight average molecular weight), Mn (number average molecular weight), and molecular weight distribution (Mw / Mn) of the living polymer (block copolymer) describe the values in the GPC measurement area indicated by arrows.
The monomer consumption rate was calculated from the ratio (molar ratio) of the residual monomer amount determined from the area ratio of ¹ H-NMR with respect to the monomer addition amount.

First, the materials used in each Example and Comparative Example and their preparation methods are shown below.

<Preparation of low molecular weight RAFT agent>
(Low molecular weight RAFT agent (1))
As a commercially available low molecular weight RAFT agent (1), 4-cyano-4-[(dodecylsulfanyl-thiocarbonyl) sulfanyl] pentanoic acid (manufactured by Aldrich) is used.

(Low molecular weight RAFT agent (2))
As a commercially available low molecular weight RAFT agent (2), 2-cyano-2-propylbenzodithioate (Aldrich) is used.

(Low molecular ATRP initiator (3))
Ethyl-α-bromoisobutyrate (manufactured by Aldrich) is used as a commercially available low-molecular ATRP initiator (3).

<Preparation of hydrophilic part>
(Hydrophilic macro RAFT agent A-1)
A commercially available hydrophilic macro RAFT agent A-1 (poly (ethylene glycol) methyl ether (4-cyano-4-pentanoate dodecyl trithiocarbonate) (Mn5400, manufactured by Aldrich)) is used (molecular weight Mw 8000, Mn 7500, Mw / Mn = 1.07: GPC polystyrene conversion).

(Hydrophilic macro RAFT agent A-2)
A commercially available hydrophilic macro RAFT agent A-2 (poly (ethylene glycol) methyl ether (4-cyano-4- (dodecylsulfanylthiocarbonyl) sulfanyl) pentanoate) (Mn10000, manufactured by Aldrich)) is used.

(Hydrophilic macroinitiator A-3)
30 g of commercially available poly (ethylene glycol) methyl ether (Mn5000, manufactured by Aldrich) and 0.81 g of N, N′-dimethylaminopyridine were dissolved in 180 ml of methylene chloride, and 2-bromoisolacsan bromide (manufactured by Tokyo Chemical Industry Co., Ltd.) 1 .52 g was dissolved in 20 ml of methylene chloride and then added dropwise at room temperature, followed by heating at 40 ° C. and stirring for 48 hours.
Separation operations were carried out in the order of 1 N aqueous hydrochloric acid solution, 0.5 N aqueous sodium hydrogen carbonate solution and 1 N aqueous hydrochloric acid solution, dried over magnesium sulfate, and recrystallized from diethyl ether.
22 g (molecular weight Mw 8000, Mn 7700, Mw / Mn = 1.04: GPC polystyrene conversion) of the target ATRP hydrophilic macroinitiator A-3 were obtained.

<Preparation of hydrophobic monomer>
(Hydrophobic monomer synthesis example 1)
Liquid crystalline monomer B-1 was synthesized by the synthesis method described in Transactions of Materials Research Society of Japan, 28 [3], 553-556, (2003).

(Hydrophobic monomer synthesis example 2)
Liquid crystalline monomer B-2 was synthesized by the synthesis method described in Example 1 of JP-A-2008-127336.

(Hydrophobic monomer synthesis example 3)
In the synthesis method described in Example 4 of JP-A-2008-127336, a liquid crystalline monomer B-3 was synthesized by the same synthesis method except that the chain length of the substituent of the carboxylic acid compound 10 used was changed.

(Hydrophobic monomer synthesis example 4)
Liquid crystalline monomer B-4 was synthesized based on the synthesis method described in JP 2010-116463 A.

(Hydrophobic monomer synthesis example 5)
Liquid crystalline monomer B-5 was synthesized according to the synthesis method described below.

Hydroquinone monomethyl ether (37 mg) was added to a THF solution (17 mL) of methanesulfonyl chloride (33.0 mmol, 2.6 mL), and the internal temperature was cooled to −5 ° C. A THF solution (16 mL) of a-1 (31.5 mmol, 8.33 g) and diisopropylethylamine (33.0 mmol, 5.75 mL) was added dropwise so that the internal temperature did not rise above 0 ° C. After stirring at −5 ° C. for 30 minutes, diisopropylethylamine (33.0 mmol, 5.75 mL), b-1 in THF (20 mL), and DMAP (full of spatula) were added. Then, it stirred at room temperature for 4 hours. Methanol (5 mL) was added to stop the reaction, and water and ethyl acetate were added. The solvent was removed from the organic layer extracted with ethyl acetate with a rotary evaporator to obtain a crude product of c-1.
An aqueous solution (32 mL) of sodium chlorite (42.0 mmol, 3.80 g), sodium dihydrogen phosphate dihydrate (6.0 mmol, 0.94 g) against an acetonitrile solution (67 mL) of aldehyde c-1 Aqueous solution (8.2 mL) and hydrogen peroxide (4.0 mL) were added, and the mixture was stirred at room temperature for 12 hours. After adding 100 mL of 1N hydrochloric acid aqueous solution, it filtered. The residue was washed with methanol with a small amount of acetonitrile to quantitatively obtain carboxylic acid d-1.
Hydroquinone monomethyl ether (7 mg) was added to a THF solution (3 mL) of methanesulfonyl chloride (6.0 mmol, 0.46 mL), and the internal temperature was cooled to −5 ° C. A THF solution (6 mL) of carboxylic acid d-1 (5.5 mmol, 2.1 g) and diisopropylethylamine (6.0 mmol, 1.1 mL) was added dropwise so that the internal temperature did not rise above 0 ° C. After stirring at −5 ° C. for 30 minutes, diisopropylethylamine (6.0 mmol, 1.1 mL), 4-ethylphenol e-1 (5.0 mmol, 0.82 g) in THF (4 mL), DMAP (spatula) I added a cup). Then, it stirred at room temperature for 2 hours. Methanol (5 mL) was added to stop the reaction, and water and ethyl acetate were added. From the organic layer extracted with ethyl acetate, the solvent was removed by a rotary evaporator to obtain a crude product of liquid crystalline monomer B-5. Recrystallization was performed with ethyl acetate and methanol to obtain liquid crystal monomer B-5 at a yield of 78%.
¹ H-NMR (solvent: CDCl ₃ ) δ (ppm): 1.2 (t, 3H), 1.8-2.0 (m, 4H), 2.6 (d, 2H), 4.1 4.3 (m, 4H), 5.8 (d, 1H), 6.1 (dd, 1H), 6.4 (d, 1H), 6.9-7.0 (m, 2H), 7 1-7.2 (m, 2H), 7.2-7.3 (m, 2H), 7.3-7.4 (m, 2H), 8.1-8.2 (m, 2H) , 8.2-8.3 (m, 2H)

[Examples 1 to 48: RAFT polymerization on a support]
<Example 1: Living polymer synthesis example>
Low molecular weight RAFT agent (1) (0.0081 g), liquid crystalline monomer B-1 (0.493 g), and azobisisobutyronitrile (hereinafter abbreviated as AIBN, 0.0028 g) were dissolved in 5 ml of toluene. 50 μl of the obtained toluene solution was applied onto a glass substrate (2 cm square), and spin-coated by rotating at 1500 rpm for 30 seconds using a spin coater (SPINCATOR 1H-D7 manufactured by MIKASA). Under a nitrogen flow (0.5 L / min), heating was performed according to the table below on a hot plate (DATAPLATE manufactured by PMC). Thereafter, the mixture was allowed to cool to room temperature to obtain a living polymer 1 (Example 1). The film-like living polymer of Example 1 was extracted with deuterated THF, and monomer consumption and GPC (HLC-8220GPC manufactured by TOSOH) were analyzed by ¹ H-NMR (BRUKER-300 MHZ) measurement. Here, Mw represents the weight average molecular weight, Mn represents the number average molecular weight, and PDI represents Mw / Mn, which means the molecular weight distribution. The results obtained are listed in the table below.

<Examples 2 to 5: Living polymer synthesis examples>
Living polymers were obtained in the same manner as in Synthesis Example 1 except that equimolar amounts of the liquid crystalline monomer used in Example 1 were used and B-1 was changed to B-2 to 5 (Examples 2 to 5). The monomer consumption and GPC were analyzed by ¹ H-NMR measurement in the same manner as in Example 1, and the results obtained are listed in the following table.

<Examples 6 to 10: Living polymer synthesis examples>
Living polymers were obtained in the same manner as in Example 1 except that equimolar amounts of the low molecular weight RAFT agent (1) used in Example 1 were used to change to the low molecular weight RAFT agent (2) (Examples 6 to 10). ). The monomer consumption and GPC were analyzed by ¹ H-NMR measurement in the same manner as in Example 1, and the results obtained are listed in the following table.

<Examples 11 to 22: Examples of block copolymer synthesis>
Hydrophilic macro RAFT agent A-1 (0.216 g), liquid crystalline monomer B-2 (0.677 g) and AIBN (0.0028 g) were dissolved in 5 ml of toluene. 50 μl of the obtained toluene solution was applied onto a glass substrate (2 cm square), and spin-coated by rotating at 1500 rpm for 30 seconds using a spin coater (SPINCATOR 1H-D7 manufactured by MIKASA). Under a nitrogen flow (0.5 L / min), heating was performed according to the table below on a hot plate (DATAPLATE manufactured by PMC). Thereafter, the mixture was allowed to cool to room temperature to obtain block copolymers 11 to 22 (Examples 11 to 22). The film-like block copolymers 11 to 22 of Examples 11 to 22 were extracted with deuterated THF, and monomer consumption and GPC (HLC-8220GPC manufactured by TOSOH) were measured by ¹ H-NMR (BRUKER-300 MHZ) measurement. The analysis was conducted. The results obtained are listed in the table below.

Examples 23 to 31: Examples of block copolymer synthesis
Hydrophilic macro RAFT agent A-1 (0.216 g), liquid crystalline monomer B-2 (0.677 g) and AIBN (0.0028 g) were dissolved in 5 ml of toluene. 50 μl of the obtained toluene solution was applied on a glass substrate (2 cm square) and spin-coated by rotating at 1500 rpm for 30 seconds. In the atmosphere, the glass substrate was heated on a hot plate according to the table below. Thereafter, the mixture was allowed to cool to room temperature to obtain block copolymers 23 to 31 (Examples 23 to 31). The monomer consumption and GPC were analyzed by ¹ H-NMR measurement in the same manner as in Example 1, and the results obtained are listed in the following table.

Examples 32 to 35: Examples of block copolymer synthesis
Hydrophilic macro RAFT agent A-1 (0.216 g), liquid crystal monomer B-2 (0.677 g), 1,1′-azobis (cyclohexane-1-carbonitrile) (hereinafter abbreviated as V-40) 0043 g) was dissolved in 5 ml of toluene. 50 μl of the obtained toluene solution was applied on a glass substrate (2 cm square). As a protective cover for the glass substrate, a slide glass was placed and heated according to the following table on a hot plate under a nitrogen flow (0.5 L / min). Thereafter, the mixture was allowed to cool to room temperature to obtain block copolymers 32-35 (Examples 32-35). The monomer consumption and GPC were analyzed by ¹ H-NMR measurement in the same manner as in Example 1, and the results obtained are listed in the following table.

<Examples 36 to 42: Synthesis example of block copolymer>
Hydrophilic macro RAFT agent A-1 (0.216 g), liquid crystalline monomer B-2 (0.677 g), and V-40 (0.0043 g) were dissolved in 5 ml of toluene. 50 μl of the obtained toluene solution was applied on a glass substrate (2 cm square). It heated according to the following table | surface on the hotplate under nitrogen flow (0.5 L / min). Thereafter, the mixture was allowed to cool to room temperature to obtain block copolymers 36 to 42 (Examples 36 to 42). The monomer consumption and GPC were analyzed by ¹ H-NMR measurement in the same manner as in Example 1, and the results obtained are listed in the following table.

<Examples 43 to 45: Block copolymer synthesis examples>
Hydrophilic macro RAFT agent A-1 (0.216 g), liquid crystalline monomer B-2 (0.677 g), and V-40 (0.0043 g) were dissolved in 5 ml of toluene. 50 μl of the obtained toluene solution was applied on a glass substrate (2 cm square). Heating was performed according to the following table on a hot plate in the atmosphere. Thereafter, the mixture was allowed to cool to room temperature to obtain block copolymers 43 to 45 (Examples 43 to 45). The monomer consumption and GPC were analyzed by ¹ H-NMR measurement in the same manner as in Example 1, and the results obtained are listed in the following table.

<Examples 46 to 48: Example of block copolymer synthesis / confirmation and curing of microphase separation structure>
Hydrophilic macro RAFT agent A-1 (0.216 g), liquid crystalline monomer B-2 (0.677 g), AIBN (0.0028 g), photoacid generator E-1 (0.0040 g) having the following structure was added to toluene. Dissolved in 5 ml. 50 μl of the obtained toluene solution was applied on a glass substrate (support) (2 cm square), and spin-coated by rotating at 1500 rpm for 30 seconds using a spin coater. A glass substrate is heated on a hot plate under a nitrogen flow (0.5 L / min) (ripening 1), and the temperature is lowered from a predetermined starting temperature to a UV irradiation temperature in accordance with the following table in the atmosphere using another hot plate. (Maturation 2), and cured at 500 mJ / cm ^{2 with} a UV irradiation apparatus (EXECURE 3000 manufactured by HOYA).

(AFM measurement)
The block copolymer on the glass substrate produced by the method for producing a living polymer on the glass substrate (Examples 46 to 48) was measured with AFM (SPI3800N manufactured by SII). Representative examples of the measured surface shape are shown in FIGS. Lamella and cylindrical microphase separation structures were observed.

(Peeling of micro phase separation structure film from support)
In Examples 46 to 48, it was possible to peel the microphase separation structure film from the glass substrate.
The thicknesses of the microphase-separated structure films peeled in Examples 46 to 48 were 150 nm, 200 nm, and 210 nm, respectively.

[Comparative Examples 1 to 14: RAFT polymerization in solution]
(Block copolymer comparative synthesis example 1)
Liquid crystalline monomer B-1 (0.493 g), AIBN (0.0028 g) and xylene 5 ml were added with hydrophilic macro RAFT agent A-1 (0.108 g) and nitrogen flow was started. The mixture was stirred for 11 hours. Thereafter, the mixture was allowed to cool to room temperature, and the reaction solution was added to 200 ml of hexane and filtered. Further, the obtained polymer was suspended in 40 ml of ethanol and filtered after 1 hour. 0.33 g of block copolymer D-1 was obtained. It was Mw22200, Mn17500, Mw / Mn = 1.27 from the analysis result of GPC.

(Block copolymer comparative synthesis example 2)
Liquid crystalline monomer B-1 (0.739 g), AIBN (0.0028 g), xylene 5 ml, hydrophilic macro RAFT agent A-1 (0.108 g) was added and nitrogen flow was started. The mixture was stirred for 11 hours. Thereafter, the mixture was allowed to cool to room temperature, and the reaction solution was added to 300 ml of cooled hexane, followed by filtration. Further, the obtained polymer was suspended in hexane / ethyl acetate = 20 ml / 30 ml and filtered after 1 hour. 0.6 g of block copolymer D-2 was obtained. From the analysis results of GPC, it was Mw31100, Mn25600, Mw / Mn = 1.22.

(Block copolymer comparative synthesis example 3)
Liquid crystalline monomer B-1 (0.985 g), AIBN (0.0028 g) and xylene 5 ml were added with hydrophilic macro RAFT agent A-1 (0.108 g) and nitrogen flow was started. The mixture was stirred for 11 hours. Thereafter, the mixture was allowed to cool to room temperature, and the reaction solution was added to 300 ml of cooled hexane, followed by filtration. Further, the obtained polymer was suspended in hexane / ethyl acetate = 20 ml / 30 ml and filtered after 1 hour. 0.8 g of block copolymer D-3 was obtained. It was Mw37100, Mn29100, Mw / Mn = 1.28 from the analysis result of GPC.

(Block copolymer comparative synthesis example 4)
Liquid crystalline monomer B-1 (0.493 g), AIBN (0.0028 g) and xylene 5 ml were added with hydrophilic macro RAFT agent A-2 (0.200 g) and nitrogen flow was started. The mixture was stirred for 11 hours. Thereafter, the reaction solution was allowed to cool to room temperature, and the reaction solution was added to 200 ml of cooled hexane, followed by filtration. Further, the obtained polymer was suspended in 40 ml of ethanol and filtered after 1 hour. 0.4 g of block copolymer D-4 was obtained. It was Mw22600, Mn17200, Mw / Mn = 1.31 from the analysis result of GPC.

(Block copolymer comparative synthesis example 5)
Liquid crystalline monomer B-2 (0.677 g), AIBN (0.0028 g) and xylene 5 ml were added with hydrophilic macro RAFT agent A-1 (0.108 g), and nitrogen flow was started. The mixture was heated and stirred for 9 hours. Thereafter, the mixture was allowed to cool to room temperature, and 2 ml of THF was added and then the reaction solution was added to 300 ml of cooled hexane, followed by filtration. Further, the obtained polymer was suspended in hexane / ethyl acetate = 20 ml / 30 ml and filtered after 1 hour. 0.4 g of block copolymer D-5 was obtained. From the analysis results of GPC, it was Mw24200, Mn17800, Mw / Mn = 1.35.

(Block copolymer comparative synthesis example 6)
Liquid crystalline monomer B-2 (1.015 g), AIBN (0.0028 g) and xylene 5 ml were added with hydrophilic macro RAFT agent A-1 (0.108 g) and nitrogen flow was started. The mixture was heated and stirred for 9 hours. Thereafter, the mixture was allowed to cool to room temperature, and after adding 5 ml of THF, the reaction solution was added to 300 ml of cooled hexane and filtered. Further, the obtained polymer was suspended in hexane / ethyl acetate = 20 ml / 30 ml and filtered after 1 hour. 0.7 g of block copolymer D-6 was obtained. From the analysis results of GPC, it was Mw32700, Mn24700, Mw / Mn = 1.32.

(Block copolymer comparative synthesis example 7)
Liquid crystalline monomer B-2 (1.354 g), AIBN (0.0028 g) and xylene 5 ml were added with hydrophilic macro RAFT agent A-1 (0.108 g), and nitrogen flow was started. The mixture was heated and stirred for 9 hours. Thereafter, the mixture was allowed to cool to room temperature, and after adding 5 ml of THF, the reaction solution was added to 300 ml of cooled hexane and filtered. Further, the obtained polymer was suspended in hexane / ethyl acetate = 20 ml / 30 ml and filtered after 1 hour. 1.06 g of block copolymer D-7 was obtained. From the analysis results of GPC, it was Mw38600, Mn27200, Mw / Mn = 1.42.

(Block copolymer comparative synthesis example 8)
Liquid crystalline monomer B-2 (0.846 g), AIBN (0.0028 g) and xylene 5 ml were added with hydrophilic macro RAFT agent A-1 (0.108 g), and nitrogen flow was started. The mixture was heated and stirred for 9 hours. Thereafter, the mixture was allowed to cool to room temperature, and after adding 5 ml of THF, the reaction solution was added to 300 ml of cooled hexane and filtered. Further, the obtained polymer was suspended in hexane / ethyl acetate = 20 ml / 30 ml and filtered after 1 hour. 0.6 g of block copolymer D-8 was obtained. It was Mw29200, Mn23100, Mw / Mn = 1.27 from the analysis result of GPC.

(Block copolymer comparative synthesis example 9)
Liquid crystalline monomer B-2 (1.015 g), AIBN (0.0028 g) and xylene 5 ml were added with hydrophilic macro RAFT agent A-1 (0.108 g) and nitrogen flow was started. The mixture was heated and stirred for 7 hours. Thereafter, the mixture was allowed to cool to room temperature, and after adding 5 ml of THF, the reaction solution was added to 300 ml of cooled hexane and filtered. Further, the obtained polymer was suspended in hexane / ethyl acetate = 20 ml / 30 ml and filtered after 1 hour. 0.4 g of block copolymer D-9 was obtained. From the analysis results of GPC, it was Mw26300, Mn21800, Mw / Mn = 1.21.

(Block copolymer comparative synthesis example 10)
Liquid crystalline monomer B-2 (0.677 g), AIBN (0.0028 g) and xylene 5 ml were added with hydrophilic macro RAFT agent A-2 (0.200 g), and nitrogen flow was started. The mixture was heated and stirred for 9 hours. Thereafter, the mixture was allowed to cool to room temperature, and 2 ml of THF was added and then the reaction solution was added to 300 ml of cooled hexane, followed by filtration. Further, the obtained polymer was suspended in hexane / ethyl acetate = 20 ml / 30 ml and filtered after 1 hour. 0.6 g of block copolymer D-10 was obtained. It was Mw24500, Mn18100, Mw / Mn = 1.35 from the analysis result of GPC.

(Block copolymer comparative synthesis example 11)
Liquid crystalline monomer B-3 (0.329 g), liquid crystalline monomer B-1 (0.246 g), AIBN (0.0028 g) and xylene 5 ml were added with hydrophilic macro RAFT agent A-1 (0.108 g). Nitrogen flow was started, and the mixture was heated and stirred in an oil bath at 60 ° C. for 11 hours. Thereafter, the mixture was allowed to cool to room temperature, and the reaction solution was added to 300 ml of cooled hexane, followed by filtration. Further, the obtained polymer was suspended in hexane / ethyl acetate = 20 ml / 30 ml and filtered after 1 hour. 0.4g of block copolymer D-11 was obtained. From the analysis results of GPC, it was Mw27400, Mn21500, Mw / Mn = 1.28.

(Block copolymer comparative synthesis example 12)
Liquid crystalline monomer B-3 (0.066 g), liquid crystalline monomer B-1 (0.443 g), AIBN (0.0028 g), and 5 ml of xylene were added hydrophilic macro RAFT agent A-1 (0.108 g). Nitrogen flow was started, and the mixture was heated and stirred in an oil bath at 60 ° C. for 11 hours. Thereafter, the mixture was allowed to cool to room temperature, and the reaction solution was added to 300 ml of cooled hexane, followed by filtration. Further, the obtained polymer was suspended in hexane / ethyl acetate = 20 ml / 30 ml and filtered after 1 hour. 0.3 g of block copolymer D-12 was obtained. From the analysis results of GPC, it was Mw25300, Mn19500, Mw / Mn = 1.30.

(Block copolymer comparative synthesis example 13)
Liquid crystalline monomer B-4 (0.329 g), liquid crystalline monomer B-1 (0.246 g), AIBN (0.0028 g) and xylene 5 ml were added with hydrophilic macro RAFT agent A-1 (0.108 g). Nitrogen flow was started, and the mixture was heated and stirred in an oil bath at 60 ° C. for 11 hours. Thereafter, the mixture was allowed to cool to room temperature, and the reaction solution was added to 300 ml of cooled hexane, followed by filtration. Further, the obtained polymer was suspended in hexane / ethyl acetate = 20 ml / 30 ml and filtered after 1 hour. 0.3 g of block copolymer D-13 was obtained. It was Mw23000, Mn19000, Mw / Mn = 1.21 from the analysis result of GPC.

(Block copolymer comparative synthesis example 14)
Liquid crystalline monomer B-5 (0.329 g), liquid crystalline monomer B-3 (0.246 g), AIBN (0.0028 g) and xylene 5 ml were added with hydrophilic macro RAFT agent A-1 (0.108 g). Nitrogen flow was started, and the mixture was heated and stirred in an oil bath at 60 ° C. for 11 hours. Thereafter, the mixture was allowed to cool to room temperature, and the reaction solution was added to 300 ml of cooled hexane, followed by filtration. Further, the obtained polymer was suspended in hexane / ethyl acetate = 20 ml / 30 ml and filtered after 1 hour. 0.4 g of block copolymer D-14 was obtained. It was Mw25000, Mn19000, Mw / Mn = 1.32 from the analysis result of GPC.

From the comparison of Examples 1 to 48 and Comparative Examples 1 to 14, according to the method for producing a living polymer on a support of the present invention, a living polymer (particularly a block copolymer) is used in the case of RAFT polymerization. It was found that it can be economically and reasonably manufactured in a short time.
It was also found that a microphase separation structure membrane can be produced economically rationally by using the method for producing a living polymer on the support of the present invention.

[Examples 101 to 121: ATRP examination on support]
<Example 101: Living polymer synthesis example>
ATRP initiator A-3 (0.0039 g), liquid crystalline monomer B-1 (0.492 g), N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine (hereinafter abbreviated as PMDETA) 021 g was dissolved in 5 ml of toluene. 50 μl of the obtained toluene solution was applied onto a copper film (Nihon Foil Co., Ltd., rolled copper foil TCU, thickness: 18 μm, 2 cm square), and spin-coated by rotating at 1500 rpm for 30 seconds. As a protective cover for the monomer-containing composition on the copper film, the same copper film as that used as the support was placed on the monomer-containing composition, and N ₂ flow (0.5 L / min) was applied while pressing at 5.3 KPa. ) The copper film was heated on a hot plate according to the table below. Then, it stood to cool to room temperature, and obtained the block copolymer 101 (Example 101). The monomer consumption and GPC were analyzed by ¹ H-NMR measurement in the same manner as in Example 1, and the results obtained are listed in the following table.

<Examples 102 to 105: Living polymer synthesis examples>
Living in the same manner as the living polymer synthesis example of Example 101 except that equimolar amounts of the liquid crystalline monomer used in the living polymer synthesis example of Example 101 were used and changed from B-1 to B-2 to 5 respectively. Polymers were obtained (Examples 102 to 105). The monomer consumption and GPC were analyzed by ¹ H-NMR measurement in the same manner as in Example 1, and the results obtained are listed in the following table.

<Examples 106 to 117: Block copolymer synthesis example>
Hydrophilic macroinitiator A-3 (0.103 g), liquid crystal monomer B-2 (0.677 g), and PMDETA 0.021 g were dissolved in 5 ml of toluene. 50 μl of the obtained toluene solution was applied onto a copper film (Nihon Foil Co., Ltd., rolled copper foil TCU, thickness: 18 μm, 2 cm square), and spin-coated by rotating at 1500 rpm for 30 seconds. As a protective cover for the monomer-containing composition on the copper film, the same copper film as that used as the support was placed on the monomer-containing composition, and N ₂ flow (0.5 L / min) was applied while pressing at 5.3 KPa. ) The copper film was heated on a hot plate according to the table below. Thereafter, the mixture was allowed to cool to room temperature to obtain block copolymers 106 to 117 (Examples 106 to 117). The monomer consumption and GPC were analyzed by ¹ H-NMR measurement in the same manner as in Example 1, and the results obtained are listed in the following table.

<Example 118: Synthesis example of block copolymer>
Hydrophilic macroinitiator A-3 (0.103 g), liquid crystalline monomer B-2 (0.677 g), and 0.038 g of 2,2′-bipyridine were dissolved in 5 ml of toluene. 50 μl of the obtained toluene solution was applied on a copper film (2 cm square) and spin-coated by rotating at 1500 rpm for 30 seconds. As a protective cover for the monomer-containing composition on the copper film, the same copper film (2 cm square) that was used as a support was placed on the monomer-containing composition and N ₂ flow (0 .5 L / min), the copper film was heated on a hot plate at 120 ° C. for 30 seconds. Then, it stood to cool to room temperature, and obtained the block copolymer 118 (Example 118). It was Mw55500, Mn30000, Mw / Mn = 1.85 from the analysis result of GPC.

<Example 119: Block copolymer synthesis example>
Hydrophilic macroinitiator A-3 (0.103 g), liquid crystal monomer B-2 (0.677 g), 1,1,4,7,10,10-hexamethyltriethylenetetramine 0.028 g in 5 ml of toluene Dissolved. 50 μl of the obtained toluene solution was applied on a copper film (2 cm square) and spin-coated by rotating at 1500 rpm for 30 seconds. As a protective cover for the monomer-containing composition on the copper film, the same copper film (2 cm square) that was used as a support was placed on the monomer-containing composition and N ₂ flow (0 .5 L / min), the copper film was heated on a hot plate at 120 ° C. for 30 seconds. Then, it stood to cool to room temperature, and obtained the block copolymer 119 (Example 119). It was Mw36000, Mn23500, Mw / Mn = 1.53 from the analysis result of GPC.

<Example 120: Block copolymer synthesis example>
5 ml of toluene with hydrophilic macroinitiator A-3 (0.103 g), liquid crystalline monomer B-2 (0.677 g), 0.051 g of N, N, N ′, N′-tetrakis (2-pyridylmethyl) ethylenediamine It was dissolved in. 50 μl of the obtained toluene solution was applied on a copper film (2 cm square) and spin-coated by rotating at 1500 rpm for 30 seconds. As a protective cover for the monomer-containing composition on the copper film, the same copper film (2 cm square) that was used as a support was placed on the monomer-containing composition and N ₂ flow (0 .5 L / min), the copper film was heated on a hot plate at 120 ° C. for 30 seconds. Then, it stood to cool to room temperature, and obtained the block copolymer 120 (Example 120). It was Mw60000, Mn28000, Mw / Mn = 2.14 from the analysis result of GPC.

<Example 121: Block copolymer synthesis example>
Hydrophilic macroinitiator A-3 (0.103 g), liquid crystalline monomer B-2 (0.677 g) and 0.028 g of tris [2- (dimethylamino) ethyl] amine were dissolved in 5 ml of toluene. 50 μl of the obtained toluene solution was applied on a copper film, and spin-coated by rotating at 1500 rpm for 30 seconds. As a protective cover for the monomer-containing composition on the copper film, the same copper film (2 cm square) that was used as a support was placed on the monomer-containing composition and N ₂ flow (0 .5 L / min), the copper film was heated on a hot plate at 120 ° C. for 30 seconds. Then, it stood to cool to room temperature, and obtained the block copolymer 121 (Example 121). From the analysis results of GPC, it was Mw29500, Mn21000, Mw / Mn = 1.40.

[Comparative Examples 101 to 105: ATRP in solution]
(Block copolymer comparative synthesis example 101)
Hydrophilic macroinitiator A-3 (0.4122 g), liquid crystalline monomer B-1 (1.97 g), N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine (PMDETA) 0.0832 g Copper (I) bromide (0.069 g) was dissolved in 20 ml of anisole. Nitrogen flow was started and the oil bath was heated and stirred at 80 ° C. for 10 hours. Thereafter, the mixture was allowed to cool to room temperature, treated with alumina, washed with 200 ml of THF, filtered and concentrated. Further, the obtained polymer was suspended in 250 ml of hexane and filtered after 1 hour. 0.50 g of block copolymer D-15 was obtained. From the analysis results of GPC, it was Mw26900, Mn22000, Mw / Mn = 1.22. The residual copper ion after the alumina treatment was 130 ppm.

(Block copolymer comparative synthesis example 102)
Hydrophilic macroinitiator A-3 (0.103 g), liquid crystalline monomer B-2 (0.677 g), PMDETA 0.021 g, and copper (I) bromide (0.017 g) were dissolved in 5 ml of xylene. Nitrogen flow was started and the oil bath was heated and stirred at 80 ° C. for 18 hours. Thereafter, the mixture was allowed to cool to room temperature, and the reaction solution was added to 200 ml of hexane and filtered. Further, the obtained block copolymer D-16 was suspended in hexane / ethyl acetate = 20 ml / 30 ml, and filtered after 1 hour. 0.56 g of block copolymer D-16 was obtained. It was Mw26800, Mn20500, Mw / Mn = 1.31 from the analysis result of GPC.

After 0.1 g of the obtained block copolymer D-16 was completely dissolved in 5 ml of THF, 0.1 g of alumina, KW700SN and Amberlyst 15 DRY as adsorbents was added, and the mixture was stirred at room temperature for 1 h. After celite filtration, the solvent was distilled off after washing with 10 ml of THF. Thereafter, ¹ H-NMR of the block copolymer D-16 was measured, and it was confirmed that all of the oxetanyl sites were decomposed. This is because the adsorbent worked as a Lewis acid and promoted the ring opening of the oxetanyl group. The residual copper ion after the alumina treatment was 50 ppm with respect to the block copolymer D-16.

(Comparative Example 103)
Hydrophilic macroinitiator A-3 (0.103 g), liquid crystalline monomer B-3 (0.658 g), PMDETA 0.021 g, and copper (I) bromide (0.017 g) were dissolved in 5 ml of anisole. Nitrogen flow was started, and the oil bath was heated and stirred at 80 ° C. for 12 hours. Thereafter, the mixture was allowed to cool to room temperature, and the reaction solution was added to 200 ml of hexane and filtered. Further, the obtained polymer was suspended in hexane / ethyl acetate = 20 ml / 30 ml and filtered after 1 hour. 0.45 g of block copolymer D-17 was obtained. It was Mw26800, Mn20500, Mw / Mn = 1.31 from the analysis result of GPC.

After 0.1 g of the obtained block copolymer D-17 was completely dissolved in 5 ml of THF, 0.1 g of alumina was added as an adsorbent and stirred at room temperature for 1 h. After celite filtration, the solvent was distilled off after washing with 10 ml of THF. Thereafter, ¹ H-NMR of the block copolymer D-17 was measured, and it was confirmed that all of the oxetanyl sites were decomposed. This is because the adsorbent worked as a Lewis acid and promoted the ring opening of the oxetanyl group. The residual copper ion after the alumina treatment was 120 ppm with respect to the block copolymer D-17.

(Comparative Example 104)
Hydrophilic macroinitiator A-3 (0.103 g), liquid crystalline monomer B-4 (0.773 g), PMDETA 0.021 g, and copper (I) bromide (0.017 g) were dissolved in 5 ml of anisole. Nitrogen flow was started and the oil bath was heated and stirred at 80 ° C. for 17 hours. Thereafter, the mixture was allowed to cool to room temperature, and the reaction solution was added to 300 ml of hexane and filtered. Further, the obtained polymer was suspended in hexane / ethyl acetate = 20 ml / 30 ml and filtered after 1 hour. 0.48 g of block copolymer D-18 was obtained. It was Mw30500, Mn23800, Mw / Mn = 1.28 from the analysis result of GPC.

After 0.1 g of the obtained block copolymer D-18 and 5 ml of THF were completely dissolved, 0.1 g of alumina was added as an adsorbent and stirred at room temperature for 1 h. After celite filtration, the solvent was distilled off after washing with 10 ml of THF. Thereafter, ¹ H-NMR of the block copolymer D-18 was measured, and it was confirmed that all of the oxetanyl sites were decomposed. This is because the adsorbent worked as a Lewis acid and promoted the ring opening of the oxetanyl group. The residual copper ion after the alumina treatment was 220 ppm with respect to the block copolymer D-18.

(Comparative Example 105)
Hydrophilic macroinitiator A-3 (0.103 g), liquid crystal monomer B-5 (0.4885 g), PMDETA 0.021 g, and copper (I) bromide (0.017 g) were dissolved in 5 ml of toluene. Nitrogen flow was started, and the oil bath was heated and stirred at 80 ° C. for 24 hours. Thereafter, the mixture was allowed to cool to room temperature, and the reaction solution was added to 300 ml of hexane and filtered. Further, the obtained polymer was suspended in hexane / ethyl acetate = 20 ml / 50 ml and filtered after 1 hour. 0.06 g of block copolymer D-19 was obtained. It was Mw12300, Mn9800, Mw / Mn = 1.25 from the analysis result of GPC.

After 0.1 g of the obtained block copolymer D-19 was completely dissolved in 5 ml of THF, 0.1 g of alumina was added as an adsorbent and stirred at room temperature for 1 h. After celite filtration, the solvent was distilled off after washing with 10 ml of THF. The residual copper ion after the alumina treatment was 150 ppm with respect to the block copolymer D-19.

From the comparison of Examples 101 to 121 and Comparative Examples 101 to 105, according to the method for producing a living polymer on a support of the present invention, a living polymer (particularly a block copolymer) is used in the case of ATRP. It was found that it can be economically and reasonably manufactured in a short time.
It was also found that a microphase separation structure membrane can be produced economically rationally by using the method for producing a living polymer on the support of the present invention.
Furthermore, in the living polymers (block copolymers) obtained in Examples 101 to 121, the remaining amount of copper ions was 5 ppm or less with respect to the block copolymer. In the present specification, the remaining amount of copper ions was determined by the method described in Gunma Prefectural Industrial Technology Center Research Report 2010.

1 Peak of Living Polymer (Block Copolymer) 2 Peak of Residual Initiator 3 Peak of Residual Monomer 4 GPC Measurement Area 11 Feed Roll 12 Coating Device 13 Drying Zone 14 First Aging Zone 15 Second Aging Zone 16 UV Irradiation zone 17 Stripping roll 18 Winding roll 21 Support 22 Monomer-containing composition 23 Microphase separation structure membrane

Claims

A method for producing a living polymer on a support, comprising a step of living polymerizing a monomer-containing composition on the support.
The method for producing a living polymer on a support according to claim 1, wherein the living polymerization is living radical polymerization.
The method for producing a living polymer on a support according to claim 1 or 2, wherein the step of living polymerizing the monomer-containing composition on the support is 1000 seconds or less.
The support according to any one of claims 1 to 3, wherein the monomer consumption rate in the step of living polymerizing the monomer-containing composition on the support is controlled to 10 to 100%. A method for producing a living polymer.
The living on the support according to any one of claims 1 to 4, wherein the step of living polymerizing the monomer-containing composition on the support is heating at 50 to 200 ° C. A method for producing a polymer.
6. The method for producing a living polymer on a support according to claim 1, wherein the living polymer has a number average molecular weight Mn of 1,000 to 100,000.
The living polymerization is atom transfer radical polymerization, and
The method for producing a living polymer on a support according to any one of claims 1 to 6, wherein the support is a metal support.
The surface of the monomer-containing composition that is not in contact with the metal support is covered with another support and heated while sandwiching the monomer-containing composition. For producing living polymer in Japan.
The method for producing a living polymer on a support according to claim 7 or 8, wherein the metal is copper.
The production of the living polymer on the support according to any one of claims 7 to 9, wherein a concentration of copper ions in the living polymer is 5 ppm or less with respect to the living polymer. Method.
The method for producing a living polymer on a support according to any one of claims 1 to 6, wherein the living polymerization is a reversible addition-fragmentation chain transfer polymerization.
The method for producing a living polymer on a support according to any one of claims 1 to 11, wherein the monomer-containing composition contains a polymerizable rod-like liquid crystal compound as a monomer component.
The method for producing a living polymer on a support according to any one of claims 1 to 12, wherein the living polymer is a block copolymer.
14. The method for producing a living polymer on a support according to claim 13, wherein the following steps (1) and (2) are carried out on the support.
(1) As the monomer-containing composition, a monomer-containing composition containing a polymer component containing an alkylene oxide chain and a monomer component containing an alkylene chain having 2 to 20 carbon atoms, and a monomer component containing an alkylene oxide chain and a carbon number of 2 (2) applying the monomer-containing composition onto the support using at least one of the monomer-containing compositions containing a polymer component containing 20 to 20 alkylene chains (2) the monomer-containing composition on the support Is a step of living polymerizing to obtain a block copolymer in which a polymer component containing an alkylene oxide chain and a polymer component containing an alkylene chain having 2 to 20 carbon atoms are linked by a covalent bond
14. The method for producing a living polymer on a support according to claim 13, wherein the following steps (1 ′) and (2) are carried out on the support.
(1 ′) A monomer-containing composition containing a polymer component containing an alkylene oxide chain and a monomer component containing an alkylene chain having 2 to 20 carbon atoms is used as the monomer-containing composition. (2) The monomer-containing composition is living-polymerized on the support so that the polymer component containing an alkylene oxide chain and the polymer component containing an alkylene chain having 2 to 20 carbon atoms are covalently bonded. Process for obtaining linked block copolymer
16. The method for producing a living polymer on a support according to claim 14, wherein the monomer component containing an alkylene chain having 2 to 20 carbon atoms is a polymerizable rod-like liquid crystal compound.
The production of a living polymer on a support according to any one of claims 14 to 16, wherein the block copolymer is a block copolymer for forming a microphase-separated structure film. Method.
A block copolymer obtained by the method for producing a living polymer on a support according to any one of claims 14 to 17.
(3) A step comprising accelerating phase separation of the block copolymer according to claim 18 on the support by heat, light, solvent vapor or electric field to form a microphase separation structure. A method for producing a phase separation structure membrane.
The method for producing a microphase-separated structure film according to claim 19, wherein the step of forming the microphase-separated structure is heating at 40 to 250 ° C.
21. The method according to claim 19 or 20, further comprising the step of (4) immobilizing the microphase separation structure by crosslinking or polymerizing the block copolymer having the microphase separation structure on the support. Manufacturing method of micro phase separation structure membrane.
The method for producing a microphase-separated structure film according to any one of claims 19 to 21, further comprising a step of peeling the microphase-separated structure film from the support.
The method for producing a microphase-separated structure film according to any one of claims 19 to 22, wherein the thickness of the microphase-separated structure film is 1 to 2000 nm.
A microphase separation structure membrane produced by the method for producing a microphase separation structure membrane according to any one of claims 19 to 23.