JP2015000895A - Block copolymer, micro phase separation structure membrane using the same and method for producing the micro phase separation structure membrane - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a block copolymer which has a low metal content and excellent photostability, and can be formed by living polymerization even in the case of a batch or in a microreactor, and from which a good micro phase separation structure membrane can be produced economically and rationally.SOLUTION: In the block copolymer, a polymer component (A) containing an alkylene chain having carbon atoms of 2-20 and a polymer component (B) having an alkylene oxide chain are bonded by covalent bond directly or through a linking group. The polymer component (A) has a mesogenic side chain having carbon atoms of 6-50, and at least one terminal of the main chain of the block copolymer has a group represented by below mentioned formula. In the formula, Rto Reach independently represent an aryl group, an alkyl group or a heteroaryl group.

Description

  The present invention relates to a block copolymer, a microphase-separated structure film using the same, and a method for producing the same. More specifically, block copolymers with a novel structure, optical / electronic functional materials (such as brightness enhancement films), energy-related materials, surface modification materials, high-density recording materials such as patterned media, various nanofilters ( Controlled block co-polymerization useful as permeable membrane, ultrafiltration membrane, nanoreactor, separation membrane such as gas permeable membrane and ion exchange membrane), anisotropic ion conductive membrane, anisotropic conductive film, etc. The present invention relates to a microphase-separated structure membrane manufactured using a coalescence and a manufacturing method thereof.

  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. The optical storage stability of such a micro separation structure (for example, a cylinder structure) is an important evaluation item because it is evaluated on the assumption that it is used in external light in the use of a separation membrane such as a gas permeable membrane or an ion exchange membrane. .

  Conventionally, a high temperature and a long time (about 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, the synthesis of a necessary compound is carried out by synthesizing a hydrophilic macroinitiator, followed by atom transfer radical polymerization (hereinafter abbreviated as ATRP) with a liquid crystalline monomer. A block copolymer in which hydrophobic portions are linked is obtained. In Patent Document 3, only the hydrophobic part is obtained by ATRP to obtain a living polymerized part, then the terminal is modified, and finally the hydrophilic part is produced by a polymer reaction.

  On the other hand, in classical living anionic polymerization, polar monomers such as (meth) acrylates are nucleophilic attack on C = N bond and carbonyl group by initiator and anion at the growth end, and active α hydrogen is extracted. It was difficult to obtain a living polymer because of the side reactions. However, at present, by using a sterically bulky 1,1-diphenylalkyl anion as an initiator, adding a ligand such as lithium chloride or crown ether, or a weak Lewis acid typified by dialkylzinc, the above-mentioned secondary Non-Patent Document 2 describes that the reaction can be completely suppressed. In Patent Documents 1 and 2, materials that can be used for living anion polymerization are described, but in Examples of Patent Documents 1 and 2, only examples in which a block copolymer is synthesized by ATRP are described.

  Patent Document 4 describes a polymer having a diphenylethylene unit at at least one terminal.

  Recently, Patent Document 5 describes a report of reducing the molecular weight distribution by carrying out living anionic polymerization in a microreactor.

JP 2004-124088 A JP 2010-275349 A JP 2010-116463 A JP-A-8-92377 JP 2009-67999 A

Liquid Crystal, 2009, Vol. 13 (No. 4), p. 250, Takeshi Yamada, Hirohisa Yoshida, Tomokazu Tomita Journal of Japan Rubber Association, 2006, Vol. 79 (No. 12), 567-572, Kenji Sugiyama, Akira Hirao

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. Moreover, the optical storage stability of the microphase-separated structure film using the obtained block copolymer has not been studied.
Here, in general, living polymerization in a reaction vessel requires a long reaction time, and is also expensive because a catalyst removal process and a monomer removal process are necessary in a field where contamination such as semiconductor use must be strictly controlled. There were restrictions on actual use. For example, since the block copolymers described in Patent Documents 1 and 2 were synthesized by ATRP using a metal catalyst during living polymerization, the metal remained. The block copolymer described in Patent Document 3 has a very complicated synthesis method, and in the examples, the metal catalyst remains because it was synthesized by ATRP using a metal during living polymerization. Furthermore, when this inventor formed the micro phase-separation structure by the method as described in these literatures using the block copolymer as described in patent document 3, the block copolymer of the structure as described in patent document 3 is hydrophilic. Since the polymer segment and the hydrophobic polymer segment are bonded by a covalent bond that can be cleaved by an acid, base, or reducing agent, the storage stability remains unsatisfactory. It was not possible to predict the structure of the block copolymer that could improve the properties. In Patent Documents 4 and 5, there is no description relating to the liquid crystalline block polymer, and the method of introducing “amphiphilicity” and “liquid crystal” has not been recalled.

  The problem to be solved by the present invention is that the metal content is low, the light storage stability is excellent, it can be formed by living polymerization in a batch or a microreactor, and a good microphase separation structure membrane can be economically rationally formed. It is to provide a block copolymer that can be produced.

  As a result of intensive studies to solve the above problems, the present inventors have found that the structural unit of a hydrophilic polymer component having a specific structure and the structural unit of a hydrophobic polymer component having a specific structure having a mesogenic side chain And having a specific structure group at the end of the molecular main chain, the metal content is low, the light storage stability is excellent, and it can be formed by living polymerization in a batch or a microreactor. It has been found that a block copolymer capable of forming a microphase separation structure can be provided.

The present invention which is means for solving the above problems is as follows.
[1] A block copolymer in which a polymer component (A) containing an alkylene chain having 2 to 20 carbon atoms and a polymer component (B) containing an alkylene oxide chain are bonded by a covalent bond directly or via a linking group,
The polymer component (A) has a mesogenic side chain having 6 to 50 carbon atoms,
A block copolymer characterized in that at least one terminal of the main chain of the block copolymer has a group represented by the following general formula (1).
General formula (1)
(In General Formula (1), * represents the bonding position to the main chain of the block copolymer, and R ^{1 to} R ³ are each independently a substituted or unsubstituted aryl group, a substituted or unsubstituted alkyl group, or Represents a substituted or unsubstituted heteroaryl group.)
[2] In the block copolymer according to [1], * in the general formula (1) is preferably bonded to the main chain of the structure derived from the polymer component (A).
[3] The block copolymer according to [1] or [2] is preferably a poly ((meth) acrylate) in which the polymer component (A) has a mesogenic side chain having 6 to 50 carbon atoms.
[4] The block copolymer according to any one of [1] to [3] is preferably represented by the following general formula (2).
General formula (2)
(In the general formula (2), R ¹ , R ² and R ^3A each independently represents a substituted or unsubstituted aryl group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted heteroaryl group; -B represents a polymer component B containing an alkylene oxide chain, m represents an integer of 1 to 500, L ¹¹ and L ¹² each independently represent a single bond, an alkylene group, an arylene group, an alkenylene group, an alkynylene group, a 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 ) —, a combination of one or more heterylene groups and having 0 to 100 carbon atoms. Represents a linking group (R ¹⁰¹ , R ¹⁰² , R ^{10 3} , R ¹⁰⁴ and R ¹⁰⁵ each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, provided that L ¹² contains at least an alkylene group having 2 to 20 carbon atoms. .), R ⁴ represents a hydrogen atom or a methyl group, and R ⁵ may have an oxetanyl group, an epoxy group, an acrylate group, a methacrylate group, an alkyl group which may have a substituent, or a substituent. Represents an alkoxy group, and M represents a mesogenic group having 6 to 50 carbon atoms, provided that m repeating units may be the same as or different from each other.
[5] In the block copolymer according to [4], L ¹¹ in the general formula (2) is preferably a single bond.
[6] In the block copolymer according to any one of [1] to [5], the polymer component (B) preferably includes a polyalkyleneoxy structure.
[7] The block copolymer according to any one of [1] to [6] is preferably represented by the following general formula (3).
General formula (3)
(In the general formula (3), R ¹ , R ² and R ^3A each independently represents a substituted or unsubstituted aryl group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted heteroaryl group; And m each independently represents an integer of 1 to 500, and L ¹² each independently represents a single bond, an alkylene group, an arylene group, an alkenylene group, an alkynylene group, a 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 linking group having 0 to 100 carbon atoms constituted by combining one or more heterylene groups (R ¹⁰¹ , R ¹⁰² , R ¹⁰³ , R ^104, R ¹⁰⁵ are each independently a hydrogen atom, a substituted or Substituted alkyl group, a substituted or unsubstituted aryl group. However, L ¹² includes at least an alkylene group having a carbon number of 2 to 20.), R ⁴ represents a hydrogen atom or a methyl group, R ⁵ is oxetanyl group Represents an epoxy group, an acrylate group, a methacrylate group, an optionally substituted alkyl group or an optionally substituted alkoxy group, and M represents a mesogenic group having 6 to 50 carbon atoms. , M repeating units may be the same or different from each other.)
[8] In the block copolymer according to any one of [1] to [7], the mesogenic side chain is selected from the following group (4) having at least one mesogenic side chain. It is preferable to have a reactive group.
Group (4)
[9] The block copolymer according to any one of [1] to [8] preferably has a number average molecular weight Mn of 1000 to 100,000 of the block copolymer.
[10] The block copolymer according to any one of [1] to [9] is preferably used for forming a microphase-separated structure film.
[11] The block copolymer according to any one of [1] to [10] is preferably formed by living polymerization in a microreactor.
[12] The block copolymer according to any one of [1] to [11] is preferably formed by living anion polymerization.
[13] A step of preparing a block copolymer solution dissolved in a solvent capable of dissolving the block copolymer according to any one of [1] to [12];
Applying a block copolymer solution to the support surface;
A method for producing a microphase-separated structure film comprising the step of evaporating a solvent to form a microphase-separated structure film of a block copolymer.
[14] The block copolymer according to any one of [1] to [12] or a cross-linked polymer thereof is contained, or the microphase-separated structure membrane manufacturing method according to [13] is used. A microphase-separated structure film characterized by being made.

  According to the present invention, a block copolymer that has a low metal content, excellent light storage stability, can be formed by living polymerization in a batch or a microreactor, and can produce a good microphase-separated structure membrane economically rationally. A polymer can be provided.

FIG. 1 is an AFM photograph of a microphase-separated structure film produced in Example 13 as an example of the microphase-separated structure film of the present invention, where (A) is before light irradiation and (B) is an AFM after light irradiation. It is a photograph. 2A and 2B are AFM photographs of the microphase-separated structure film produced in Comparative Example 10, wherein FIG. 2A is an AFM photograph before light irradiation and FIG. 2B is an AFM photograph after light irradiation.

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.

[Block copolymer]
The block copolymer of the present invention comprises a block copolymer in which a polymer component (A) containing an alkylene chain having 2 to 20 carbon atoms and a polymer component (B) containing an alkylene oxide chain are bonded together directly or through a linking group. A polymer, wherein the polymer component (A) has a mesogenic side chain having 6 to 50 carbon atoms, and at least one terminal of the main chain of the block copolymer is a group represented by the following general formula (1) It is characterized by having.
General formula (1)
(In General Formula (1), * represents the bonding position to the main chain of the block copolymer, and R ^{1 to} R ³ are each independently a substituted or unsubstituted aryl group, a substituted or unsubstituted alkyl group, or Represents a substituted or unsubstituted heteroaryl group.)
These block copolymers have low metal content, excellent light storage stability, can be formed by living polymerization in batch or microreactor, and can produce a good microphase separation structure membrane economically It can be manufactured reasonably. The block copolymer of the present invention preferably has a metal content (for example, copper ions) of 5 ppm or less with respect to the block copolymer.
Such block copolymers are sometimes called amphiphilic liquid crystal block copolymers.
The block copolymer of the present invention may be used in various applications. The polymer component (B) is a hydrophilic polymer component, and the polymer component (A) is a hydrophobic polymer component.
Further, such a block copolymer of the present invention is preferably formed by living anion polymerization.
Hereinafter, the block copolymer of the present invention will be described in order.

(Group represented by general formula (1))
In the block copolymer of the present invention, at least one terminal of the main chain of the block copolymer has a group represented by the following general formula (1).
General formula (1)

  In the general formula (1), * represents a bonding position to the main chain of the block copolymer. * In the main chain of the block copolymer, the main chain (terminal) of the structure derived from the polymer component (B) is bonded to the main chain (terminal of the polymer component (A)). May be bonded to. In the block copolymer of the present invention, * is preferably bonded to the main chain (terminal) of the structure derived from the polymer component (A).

In the general formula (1), R ¹ and R ² each independently represent a substituted or unsubstituted aryl group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted heteroaryl group, preferably substituted or unsubstituted It represents an unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, more preferably a substituted or unsubstituted aryl group, and particularly preferably an unsubstituted phenyl group. The aryl group, aryl group or heteroaryl group represented by R ¹ and R ² may have any substituent, and examples thereof include a substituted or unsubstituted aryl group, a substituted or unsubstituted alkyl group. Or a substituted or unsubstituted heteroaryl group.
R ¹ and R ² are more preferably an unsubstituted phenyl group.

In the general formula (1), R ³ represents a substituted or unsubstituted aryl group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted heteroaryl group, preferably a substituted or unsubstituted alkyl group. Represent.
—R ³ is —CH ₂ —R ^3A (R ^3A is a substituted or unsubstituted aryl group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted alkenyl group; It is preferably represented by a substituted or unsubstituted alkynyl group.
The aryl group represented by R ^3A is preferably a phenyl group or a naphthyl group.
As the alkyl group represented by R ^3A , a methyl group, an ethyl group, a propyl group, a butyl group (n-butyl group, sec-butyl group, iso-butyl group, tert-butyl group), pentyl group, and hexyl group are preferable. A methyl group, an ethyl group and a butyl group are more preferable, and a sec-butyl group is particularly preferable. The substituent that the alkyl group represented by R ^3A may have is preferably an alkoxy group or an aryl group, and more preferably a methoxy group, an ethoxy group, a 2-methylbutyl group, a phenyl group, or a styryl group.
The heteroaryl group represented by R ^3A is preferably a 2-thienyl group, a 4-pyridyl group, or a 2-quinolyllithium group.
As the alkenyl group represented by R ^3A , a vinyl group, an allyl group, a propenyl group, and a butenyl group are preferable.
The alkynyl group represented by R ^3A is preferably an ethynyl group, a butynyl group, a pentynyl group, or a hexynyl group.
R ^3A is more preferably represented by a substituted or unsubstituted aryl group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted heteroaryl group. It is particularly preferably represented by an unsubstituted alkyl group, more preferably an unsubstituted alkyl group, still more preferably an n-butyl, s-butyl, or t-butyl group. Either.

In the block copolymer of the present invention, the group represented by the general formula (1) is an initiator or a group derived from another material for forming an anion in combination with the initiator and the initiator. It may be a group derived from another material for forming an anion together with the initiator and the initiator. For example, —R ³ is a group derived from an initiator, and —CH ₂ —C (R ¹ ) (R ² ) — * is a group derived from another material for forming an anion in combination with the initiator. Embodiments can be mentioned.
Examples of the initiator include an organolithium reagent described later.
Examples of the material for forming an anion in combination with the initiator include 1,1-diphenylethene and derivatives thereof described later.

(Polymer component (A) containing an alkylene chain having 2 to 20 carbon atoms)
In the block copolymer of the present invention, the polymer component (A) includes an alkylene chain having 2 to 20 carbon atoms and has a mesogenic side chain having 6 to 50 carbon atoms.
In the block copolymer of the present invention, as the polymer component (A), for example, poly (methacrylate), poly (acrylate), poly (styrene), vinyl polymer having 6 to 50 carbon mesogen side chains, respectively, etc. However, it is preferably a poly ((meth) acrylate) having a mesogenic side chain having 6 to 50 carbon atoms, and more preferably a polymer component derived from a polymerizable rod-like liquid crystal compound described later.
The polymer component (A) may further include poly (methacrylate), poly (acrylate), poly (styrene), vinyl polymer, etc. each having a long alkyl side chain or a hydrophobic side chain. The long-chain alkyl side chain means an alkyl side chain having preferably 6 to 22 carbon atoms. Examples of the hydrophobic side chain include an aliphatic side chain.
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 that can form the core of a liquid crystal compound, and examples of the compound having a mesogenic group include a liquid crystalline compound and a mesogenic group, but does not form a liquid crystal. Liquid crystalline 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 Verlag fur 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 that contribute 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 -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.

The polymer component (A) is preferably formed by polymerizing a hydrophobic monomer component. There is no restriction | limiting in particular as said hydrophobic monomer component, A well-known hydrophobic monomer component can be used. The hydrophobic monomer component is preferably a liquid crystalline monomer from the viewpoint of low volatility and easy production of a microphase-separated 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, in the block copolymer of the present invention, in the polymer component (A), the mesogen side chain preferably has at least one reactive group in one mesogen side chain. The preferred range of the reactive group is the same as the preferred range of the reactive group represented by Q ¹ and Q ^{2 in} the general formula (X) described later.

  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 compound-
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.

  Examples of the polymerizable rod-like liquid crystal compound include Makromol. Chem. 190, 2255 (1989), Advanced Materials 5, 107 (1993), US Pat. Nos. 4,683,327, 5,622,648, 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-A No. 2004-1235979, Transactions of Materials Research Society of Japan, 28 [3], 553-556 (2003), JP-A 2008-127336, JP-A 2010. -116463 etc., the compound represented by the below-mentioned general formula (X), the compound represented by the below-mentioned general formula (V), etc. can be used.

  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 reactive group, L ¹ and L ⁴ are each independently a divalent linking group, and at least one of L ¹ and L ⁴ is: 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 a divalent cyclic group, and 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 reactive group. The reactive group is preferably a polymerizable group, and the polymerization reaction of the polymerizable group is preferably addition polymerization (including ring-opening polymerization) or condensation polymerization. In other words, the reactive group is preferably a functional group capable of addition polymerization reaction or condensation polymerization reaction. Examples of reactive groups are shown below.
Among these reactive groups, an oxetanyl group, an epoxy group, an acrylate group, and a methacrylate group are preferable. Further, at least one of Q ¹ and Q ² is
More preferably, ^one of Q ¹ and Q ² is more preferably a group having an oxetane ring (hereinafter also referred to as an oxetane group or an oxetanyl group) or an epoxy group, and Q ¹ and It is particularly preferred that the other one of Q ² is an 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 an alkylene group having at least 2 to 20 carbon atoms. L ¹ and L ⁴ each independently include —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, preferably 3 to 18 carbon atoms, 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 among 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), L ^{2 and} L ³ are each independently a single bond or a divalent linking group. L ² and L ³ each independently include —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, 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 have the same definitions as L ¹ and L ⁴ .
Preferred divalent linking groups as 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, a 6-membered ring, or a 7-membered ring, more preferably a 5-membered ring or a 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. As the cyclic group having a pyridine ring, pyridine-2,5-diyl is preferable. 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.
General 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 meanings 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 , they are a hydrogen atom, a substituted or unsubstituted alkyl group, an optionally substituted alkoxy group, a substituted or unsubstituted aryl group, or a cyano group. It is preferably an alkyl group or an alkoxy group which may have a substituent, particularly preferably an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, More preferably, it is an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and even more preferably an alkyl group having 1 to 4 carbon atoms.
p and q are preferably 0.

  The polymerizable rod-like liquid crystal compound represented by the general formula (X) and the compound represented by the general formula (V) may be mixed and used. 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%.

  Although the preferable example of a compound represented by the said general formula (V) is shown below, this invention is not limited to these.

  In addition, among the polymerizable liquid crystal compounds that can be used in the present invention, a compound having two or more acrylic groups and methacrylic groups, even if one of them potentially contains a reactive group (for example, a polymerizable group). I do not care. 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.

  As for the degree of polymerization of the hydrophobic polymer component (A), the number average molecular weight is 300 to 300,000, preferably 3000 to 150,000, and most preferably 6000 to 30000 from the viewpoint of controlling the size of the microphase-separated structure. is there.

(Polymer component (B) containing alkylene oxide chain)
In the block copolymer of the present invention, the polymer component (B) includes an alkylene oxide chain. Examples of the alkylene oxide chain include polyalkyleneoxy structures such as poly (ethylene oxide) and poly (propylene oxide), poly (vinyl alcohol), poly (acrylic acid), poly (methacrylic acid), poly (acrylamide), and oligo (ethylene oxide). ), Crown ether, cryptand or poly (methacrylate) or poly (acrylate) having a sugar chain in the side chain, more preferably a polyalkyleneoxy structure, and particularly preferably poly (ethylene oxide). .
In addition, the polymer component (B) may be bonded to the polymer component (A) via a linking group or directly bonded to the polymer component (A) without a linking group. It is preferable that it is directly bonded to the polymer component (A) without intervention.

  The degree of polymerization of the polymer component (B) is from 100 to 100,000, preferably from 1,000 to 50,000, and most preferably from 2,000 to 10,000, from the viewpoint of controlling the size of the microphase-separated structure.

The polymer component (B) may be formed by polymerizing a hydrophilic monomer component. There is no restriction | limiting in particular as said hydrophilic monomer component, A well-known hydrophilic monomer component can be used.
Examples of the hydrophilic monomer component include compounds 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 Alternatively polyether polyols such as two or more ion-polymerizable cyclic compounds obtained by ring-opening polymerization.

  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. 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.

  Examples of the commercially available polyether polyol include, for example, aliphatic polyether polyols such as 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-3001 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 ( Co., Ltd.). 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. As a commercially available product of these polyester polyols, Kurapol P1010, Kurapol P2010, PMIPA, PKA-A, PKA-A2, PNA-2000 (above, manufactured by Kuraray Co., Ltd.) and the like can be used.

  Moreover, as said polycarbonate polyol, the polycarbonate diol shown, for example by the following general formula (i) is mentioned.

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 hydroxyl groups at both ends from the following compounds, that is, 1,4-butanediol, 1,5-pentanediol, neopentylglycol, 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. Commercially available products of these polycarbonate polyols include DN-980, DN-981, DN-982, DN-983 (above, 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 include polycaprolactone diols obtained by addition reaction with diols such as pentyl glycol, 1,4-cyclohexanedimethanol, and 1,4-butanediol. As these commercially available products, Plaxel 205, 205AL, 212, 212AL, 220, 220AL (manufactured by Daicel Chemical Industries, Ltd.) and 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.

  The preferred mass average molecular weight of these polyol compounds is 1000 to 10,000, particularly preferably 1000 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 the number average molecular weight is 100-10000, Preferably it is 200-5000, Most preferably, it is 300-1000.

(Linking group and overall structure)
In the block copolymer of the present invention, the polymer component (A) and the polymer component (B) may be directly bonded or may be bonded via a linking group (preferably a divalent linking group). Are preferably bonded directly.

The connecting portion of the polymer component (A) and the polymer component (B) may have a divalent linking group. The divalent linking group represents a divalent linking group described below and is not particularly limited, but is preferably an alkylene group (having 1 to 20 carbon atoms, for example, methylene, ethylene, propylene, butylene, pentylene), Arylene groups (6 to 26 carbon atoms such as phenylene and naphthylene), alkenylene groups (2 to 20 carbon atoms such as ethenylene and propenylene), alkynylene groups (2 to 20 carbon atoms such as ethynylene and propynylene), metallosenylene groups (such as 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 group having 0 to 100 carbon atoms, preferably 1 to 20 carbon atoms. As the divalent linking group, an oxycarbonyl group, a carbonyloxy group, a carbonyl group, an alkylene group and a combination of these groups are preferable, and an oxycarbonyl group, a combination of an oxycarbonyl group and an alkylene group is more preferable. The alkylene group used as the divalent linking group preferably has 1 to 30 carbon atoms, more preferably 1 to 15 carbon atoms, and particularly preferably an ethylene group (—CH ₂ CH ₂ —). preferable.

The block copolymer of the present invention is preferably represented by the following general formula (2), and more preferably represented by the following general formula (3).
General formula (2)
General formula (3)

In general formulas (2) and (3), R ¹ , R ² and R ^3A each independently represents a substituted or unsubstituted aryl group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted heteroaryl group. Represent,

  In general formula (2), Poly-B represents polymer component B containing an alkylene oxide chain.

  In general formula (3), n represents an integer of 1 to 500, more preferably 3 to 250, and particularly preferably 5 to 200.

  In general formulas (2) and (3), m represents an integer of 1 to 500, m is preferably 3 to 200, more preferably 5 to 150, and particularly preferably 10 to 100. preferable.

In the general formulas (2) and (3), L ¹¹ and L ¹² are each independently a single bond, an alkylene group, an arylene group, an alkenylene group, an alkynylene group, a 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 ) —, and a linking group having 0 to 100 carbon atoms constituted by combining one or more heterylene groups (R ¹⁰¹ , R ¹⁰² , R ¹⁰³ , R ¹⁰⁴ and R ¹⁰⁵ each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, provided that L ¹² contains at least an alkylene group having 2 to 20 carbon atoms. .) A preferred embodiment of each of the linking groups listed above represented by L ¹¹ and L ¹² is preferably a divalent linking group that the linking part of the polymer component (A) and the polymer component (B) may have. This is the same as the embodiment.
In the block copolymer of the present invention, L ¹¹ in the general formula (2) is preferably a single bond.
L ¹² in the general formula (2) represents an alkylene group, an arylene group, an alkenylene group, an alkynylene group, a 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 ) — is preferably a linking group having 0 to 100 carbon atoms constituted by combining one or more heterylene groups, such as an oxycarbonyl group, a carbonyloxy group, a carbonyl group, an alkylene group, and these groups. Is more preferable, and an alkylene group or a combination of an oxycarbonyl group and an alkylene group is particularly preferable. However, L ¹² includes at least an alkylene group having 2 to 20 carbon atoms. The alkylene group contained in L ¹² has preferably 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 represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group.

In general formulas (2) and (3), R ⁴ is preferably independently a hydrogen atom or a methyl group from the viewpoint of versatility.

In general formulas (2) and (3), M is a mesogenic group having 6 to 50 carbon atoms, more preferably a mesogenic group having 6 to 40 carbon atoms, and a mesogenic group having 6 to 30 carbon atoms. Is particularly preferred. The preferred range of the mesogenic group represented by M is the same as the preferred range of -Cy ¹ -L ^2- (Cy ² -L ³ ) _n -Cy ³ -L ^{4-in the} general formula (X). However, the m repeating units in the general formulas (2) and (3) may be the same as or different from each other.

In general formulas (2) and (3), R ⁵ is an oxetanyl group, an epoxy group, an acrylate group, a methacrylate group, an alkyl group which may have a substituent, or an alkoxy group which may have a substituent. is there. As the alkyl group which may have a substituent represented by R ⁵ or the alkoxy group which may have a substituent, M ¹ and M ² in the general formula (V) do not represent Q ¹ . This is the same as the preferred range of the alkyl group which may have a substituent or the alkoxy group which may have a substituent.

Here, in the block copolymer of the present invention, the mesogen side chain preferably has at least one reactive group selected from the following group (4) in one mesogen side chain.
Group (4)
Among the reactive groups selected from the above group (4), oxetanyl group, epoxy group, acrylate group, and methacrylate group are preferable, that is, R ⁵ is oxetanyl group, epoxy group, acrylate group, and methacrylate group. It is an aspect.
Among them, R ⁵ is more preferably an oxetanyl group or an epoxy group, and particularly preferably an oxetanyl group.

<Copolymerization ratio>
The block copolymer of the present invention preferably has a copolymerization ratio (number average molecular weight ratio) of the polymer component (B) and the hydrophobic polymer component (A) of 65:35 to 1:99, 55 : 45 to 5:95 is more preferable, and 45:55 to 10:90 is particularly preferable.

<Molecular weight>
The number average molecular weight Mn of the block copolymer is preferably 1000 to 100,000, more preferably 2000 to 50000, and particularly preferably 3000 to 30000.

The method for producing the block copolymer is such that the ratio Mw / Mn of the weight average molecular weight Mw and the number average molecular weight Mn of the resulting block copolymer extract exceeds 1.3, and the residual monomer has a phase separation structure. From the point of repairing defects, the remaining macro RAFT agent is preferable from the viewpoint of 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 the block copolymer, the polymer component (A), the polymer component (B) and the like employs 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. The measurement temperature is 25 ° C. and the flow rate is 0.35 ml / min.
Moreover, the value measured with the following method is employ | adopted for weight average molecular weight Mw, such as a block copolymer, a polymer component (A), and a polymer component (B) in this specification.
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. The measurement temperature is 25 ° C. and the flow rate is 0.35 ml / min.

<Application>
Although there is no restriction | limiting in particular as a use of the block copolymer of this invention, It is preferable that the block copolymer of this invention is a block copolymer for formation of a micro phase-separation structure film.

[Method for producing block copolymer]
The block copolymer of the present invention may be either living polymerized in a solution or living polymerized on a support. When the block copolymer of the present invention is produced by living polymerization in a solution, the block copolymer of the present invention may be produced by living polymerization in a batch or in a microreactor (not batch but continuously). Although living polymerization may be performed, living polymerization is preferably performed in a microreactor. In the method of living polymerization in a microreactor, it is preferable to perform living polymerization in the presence of an initiator using a microreactor having a flow channel capable of mixing a plurality of liquids. By using a microreactor to react a monomer and an initiator, a polymer having a narrow molecular weight distribution can be efficiently produced even at a reaction temperature of −28 ° C. or higher. Furthermore, polymer growth using a microreactor By performing the reaction between the terminal carbanion and the electrophile, the block copolymer of the present invention can be produced efficiently.

As a method for living polymerizing the block copolymer, it is more preferable to carry out the following steps (1) and (2).
(1) As the monomer-containing composition, at least one of a monomer-containing composition containing a hydrophilic polymer component and a hydrophobic monomer component and a monomer-containing composition containing a hydrophilic monomer component and a hydrophobic polymer component are prepared. Step (2) Living-polymerizing the monomer-containing composition to obtain a block copolymer in which a hydrophilic polymer component and a hydrophobic polymer component are linked by a covalent bond. A method for producing a block copolymer is as follows. It is particularly preferable to carry out the steps (1 ′) and (2).
(1 ′) Step of preparing a monomer-containing composition comprising a hydrophilic polymer component and a hydrophobic monomer component as the monomer-containing composition (2) Living polymerization of the monomer-containing composition to form a hydrophilic polymer component and a hydrophobic polymer For obtaining a block copolymer in which a functional polymer component is covalently linked

  The living polymerization initiation reaction and growth reaction are usually carried out by mixing a monomer as a raw material and an initiator selected according to the desired polymerization method. The monomer and the initiator are preferably applied on a support in a liquid state solubilized in a solvent or introduced into a microreactor.

<Polymerization conditions>
In the method for producing a block copolymer, the polymerization conditions and the polymerization method are not particularly limited as long as living polymerization is possible, and bulk polymerization, suspension polymerization, emulsion polymerization, bulk / suspension polymerization, and the like can be applied.

-Living polymerization using microreactor-
The microreactor includes a minute flow path capable of mixing a plurality of liquids, and if necessary, includes an introduction path that communicates with the flow path and introduces the liquid into the flow path. Includes configurations other than the flow path and the introduction path.

  The microreactor used in the present invention is not particularly limited as long as it has a minute flow path capable of mixing a plurality of liquids, and can be appropriately selected according to the purpose. For example, a micromixer (substrate type A micromixer, a pipe joint type micromixer, etc.) and a branched tube.

The substrate-type micromixer includes a substrate having a flow path formed inside or on the surface, and is sometimes referred to as a microchannel.
The substrate type micromixer is not particularly limited as long as the effects of the present invention are not impaired, and can be appropriately selected according to the purpose. And a mixer described in the document “" Microreactors ", Chapter 3, W. Ehrfeld, V. Hessel, H. Lowe, published by Wiley-VCH, etc.).

In addition to the flow path, the substrate-type micromixer is preferably provided with an introduction path that communicates with the flow path and introduces a plurality of liquids into the flow path. That is, a configuration in which the upstream side of the flow path branches according to the number of the introduction paths is preferable.
The number of the introduction paths is not particularly limited and may be appropriately selected depending on the purpose. However, a plurality of liquids desired to be mixed are introduced from different introduction paths, and are mixed and mixed in the flow paths. Is preferred. In addition, it is good also as a structure which prepares one liquid previously in a flow path, and introduces other liquids by an introduction path.

  The pipe joint type micromixer includes a flow path formed inside, and a connection unit that connects the flow path formed inside and the tube as necessary. The connection method in the connection means is not particularly limited, and can be appropriately selected from known tube connection methods according to the purpose. For example, a screw type, a union type, a butt welding type, a plug welding type, Examples include a socket welding type, a flange type, a biting type, a flare type, and a mechanical type.

  In addition to the flow path, it is preferable that an introduction path that communicates with the flow path and introduces a plurality of liquids into the flow path is formed inside the pipe joint type micromixer. That is, a configuration in which the upstream side of the flow path is branched according to the number of the introduction paths is preferable. When the number of the introduction paths is two, for example, a T-shaped or Y-shaped can be used as the pipe joint type micromixer, and when the number of the introduction paths is three, For example, a cross shape can be used. In addition, it is good also as a structure which prepares one liquid previously in a flow path, and introduces other liquids by an introduction path.

  The material of the micromixer is not particularly limited and can be appropriately selected according to requirements such as heat resistance, pressure resistance, solvent resistance, and processability. For example, stainless steel, titanium, copper, Examples thereof include nickel, aluminum, silicon, fluorine resin such as Teflon (registered trademark) and PFA (perfluoroalkoxy resin), TFAA (trifluoroacetamide), and the like.

Since the micromixer accurately controls the flow of the reaction solution by its fine structure, it is preferable that the micromixer is manufactured by a fine processing technique.
The microfabrication technology is not particularly limited and can be appropriately selected according to the purpose. For example, (a) LIGA technology combining X-ray lithography and electroplating, (b) high aspect ratio using EPON SU8 Specific photolithography, (c) mechanical micro-cutting (such as micro-drilling that rotates a drill with a micro-order drill diameter at high speed), (d) high-aspect-ratio silicon processing by Deep RIE, (e) Hot Emboss Examples of the processing method include (f) stereolithography, (g) laser processing, and (h) ion beam method.

  Commercially available products can be used as the micromixer, for example, a microreactor having an interdigital channel structure, a single mixer and a caterpillar mixer manufactured by Institute Hugh Microtechnique Mainz (IMM); manufactured by Microglass Micrograss Reactor; CPC Systems Cytos; Yamatake YM-1 mixer, YM-2 mixer; Shimadzu GLC mixing tee and tee (T-connector); Micro Chemical Giken IMT chip reactor; Toray Engineering-developed micro-high mixer; Swagelok union tee.

  As the microreactor, the micromixer may be used alone, or a tube reactor may be connected downstream thereof to extend the flow path. The length of the flow path can be adjusted by connecting the tube reactor downstream of the micromixer. The residence time (reaction time) of the mixed liquid is proportional to the length of the flow path.

The tube reactor is a reactor for precisely controlling (retention time control) a time required for a solution rapidly mixed by a micromixer to perform a subsequent reaction.
There is no restriction | limiting in particular as said tube reactor, For example, structures, such as an inner diameter of a tube, an outer diameter, length, and a material, can be suitably selected according to desired reaction.
As the tube reactor, commercially available products can be used. For example, a stainless steel tube manufactured by GL Sciences Inc. (outer diameter 1/16 inch (1.58 mm), inner diameter 250 μm, 500 μm, and 1,000 μm can be selected. Tube length can be adjusted by the user).
There is no restriction | limiting in particular as a material of the said tube reactor, What was illustrated as a material of the said micro mixer can be utilized suitably.

--- Flow path--
The flow path has a function of mixing a plurality of liquids by diffusion and a function of removing reaction heat.
There is no restriction | limiting in particular as a mixing method of the liquid in the said flow path, According to the objective, it can select suitably, For example, mixing by a laminar flow and mixing by a turbulent flow are mentioned. Among these, laminar mixing (static mixing) is preferable because reaction control and heat removal can be performed more efficiently. In addition, since the flow path of the microreactor is very small, a plurality of liquids introduced from the introduction path tend to become a laminar flow dominant flow and are diffused and mixed in a direction perpendicular to the flow. In the mixing by the laminar flow, the laminar flow cross section of the flowing liquid may be divided by providing a branch point and a confluence in the flow path, and the mixing speed may be increased.
When mixing by turbulent flow (dynamic mixing) in the microreactor flow path, the flow velocity, the shape of the flow path (the three-dimensional shape of the wetted part, the shape of the flow path, etc., the rough surface of the wall) And so on) can be changed from laminar flow to turbulent flow. The mixing by the turbulent flow has an advantage that the mixing efficiency is high and the mixing speed is high as compared with the mixing by the laminar flow.

  Here, the inner diameter, the cross-sectional area, the length, and the cross-sectional shape of the flow path are not particularly limited, and can be appropriately selected according to the purpose. For example, the aspect described in Japanese Patent Application Laid-Open No. 2009-067999 Is mentioned as a preferred embodiment.

--Introduction path--
The introduction path communicates with the flow path and has a function of introducing the plurality of liquids into the flow path. In the introduction path, one end different from the side communicating with the flow path is usually connected to a container containing a liquid desired to be mixed.

The inner diameter of the introduction path is not particularly limited as long as the effects of the present invention are not impaired, and can be appropriately selected according to the purpose. For example, the aspect described in JP-A-2009-0679999 is preferable. It is mentioned as an aspect.
When the microreactor has a plurality of introduction paths, the inner diameters of the introduction paths may be different from each other or the same.

-Configuration other than flow path and introduction path-
The configuration other than the flow path and the introduction path is not particularly limited and can be appropriately selected depending on the purpose. For example, a pump used for liquid feeding, a temperature adjusting means, a reaction promoting means, a sensor, And a tank for storing the polymer.

  The pump is not particularly limited and can be appropriately selected from those that can be used industrially. However, pumps that do not cause pulsation during liquid feeding are preferable. For example, a plunger pump, a gear pump, a rotary pump, and a diaphragm pump Etc.

There is no restriction | limiting in particular as said temperature adjustment means, According to reaction temperature, it can select suitably, For example, a thermostat, a circulation circulator, a heat exchanger etc. are mentioned.
For example, when the reaction temperature is −28 ° C., it is preferable to use a constant temperature layer of −28 ° C. obtained by adding dry ice to methanol, and when it is 0 ° C., a constant temperature layer of ice water is preferable, For example, when it is 24 ° C., a water bath is preferable. For example, when it is −78 ° C., a constant temperature layer in which dry ice is added to acetone is preferable.

The reaction promoting means can be appropriately selected according to the liquid to be mixed and the desired reaction. Examples thereof include vibration energy applying means, heating means, light irradiation means, and voltage applying means. Examples of the microreactor provided with the voltage applying means include a microflow electrochemical reactor disclosed in JP-A-2006-104538.
There is no restriction | limiting in particular as said sensor, For example, a temperature sensor, a flow sensor, a pressure sensor for measuring the pressure in a flow path, etc. are mentioned.

  There is no restriction | limiting in particular as the density | concentration of the said monomer, Although it can select suitably according to the objective, The aspect etc. which are described in Unexamined-Japanese-Patent No. 2009-067999 are mentioned as a preferable aspect. When the concentration is within the particularly preferable range, it is advantageous in that the heat of polymerization reaction can be removed more efficiently.

  The flow rate at which the monomer is introduced from the first introduction path of the microreactor is not particularly limited and can be appropriately selected according to the purpose. The embodiment described in JP-A-2009-0679999 is preferable. As mentioned. When the flow rate is within the particularly preferable range, it is advantageous in that mixing can be performed more rapidly in a range where pressure loss does not become a problem.

  The flow rate at which the initiator is introduced from the second introduction path of the microreactor is not particularly limited and may be appropriately selected according to the purpose. The embodiment described in JP-A-2009-0679999 is preferable. It is mentioned as an aspect. When the flow rate is within the particularly preferable range, it is advantageous in that mixing can be performed more rapidly in a range where pressure loss does not become a problem.

In living polymerization using a microreactor, it is preferable that the equivalent ratio of the monomer and the initiator is equal to the product ratio of the respective concentration and flow rate.
There is no restriction | limiting in particular as an equivalent ratio of the said monomer and an initiator, According to the objective, it can select suitably, The aspect as described in Unexamined-Japanese-Patent No. 2009-067999 etc. are mentioned as a preferable aspect. It is advantageous in that a polymer having a molecular weight equal to the theoretical value can be obtained when the equivalent ratio is in the particularly preferable range.

--Reaction temperature--
There is no restriction | limiting in particular as reaction temperature in the said living polymerization, According to the objective, it can select suitably, It can apply suitably also at -78 degrees C or less applied with the conventional batch system, However, -28 degreeC or more is preferable. 0 ° C. or higher is more preferable, and 24 ° C. or higher is particularly preferable. When the temperature is −28 ° C. or higher, a polymer having M _w / M _n of 1.25 or lower can be manufactured using a cooling device having a simple configuration, which is preferable in that the manufacturing cost can be reduced. When the temperature is 24 ° C. or higher, a polymer having a M _w / M _n of 1.25 or lower can be manufactured using a cooling device having a simpler configuration, which is preferable in that the manufacturing cost can be greatly reduced. .

<Solvent>
In the method for producing a block copolymer, any solvent that can be used in the monomer-containing composition can be used as long as it does not inhibit the reaction.
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, esters such as ethyl acetate, butyl acetate and dimethyl phthalate Solvents, 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.

  Further, 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.

<Initiator (living polymerization initiator) and living polymerization method>
The initiator used in the method for producing the block copolymer (in the present specification, the term “initiator” refers to a living polymerization initiator) is not particularly limited, but is appropriately selected depending on the method of living polymerization. be able to.
By using an appropriate initiator, it is possible to synthesize a polymer having a narrow molecular weight distribution (PDI) and a high chain end functional group ratio.

Since the initiator used for living anionic polymerization does not use a heavy metal compound having cytotoxicity, the resulting block copolymer of the present invention has a low metal content.
Initiators are compatible with most functional groups and solvents (including water). Living anionic polymerization is also relatively resistant to oxygen. Living anionic polymerization does not require special equipment or a vacuum environment. Therefore, according to the present invention, it is possible to provide a block copolymer which can be formed by living polymerization in a batch or a microreactor and which can economically produce a good microphase separation structure membrane.
The block copolymer of the present invention is preferably produced using an initiator used for living anionic polymerization. The polymerization initiation reaction is performed by a typical thermal, photochemical or oxidation-reduction method, and an initiator suitable for the monomer used and reaction conditions can be selected.

  In living anionic polymerization, a low molecular initiator or a high molecular initiator may be used as an initiator, but it is preferable to use a high molecular initiator. Here, the initiator in the present specification is a polymer having the ability of initiating living anion polymerization, and represents a polymer having a site that can be the starting point of living anion polymerization in the molecular chain.

  In the method for producing the block copolymer, the living polymerization is preferably living anion polymerization, and an organic lithium reagent can be used as an initiator when the living polymerization is living anion polymerization.

  The organolithium reagent is not particularly limited and can be appropriately selected from conventionally known organolithium reagents. For example, methyllithium, ethyllithium, propyllithium, butyllithium (n-butyllithium, sec-butyllithium, iso-butyllithium, tert-butyllithium, etc.), alkyllithium such as pentyllithium, hexyllithium, methoxymethyllithium, ethoxymethyllithium; benzyl such as α-methylstyryllithium, 3-methyl-1,1-diphenylpentyllithium Lithium; alkenyl lithium such as vinyl lithium, allyl lithium, propenyl lithium, butenyl lithium; alkynyl lithium such as ethynyl lithium, butynyl lithium, pentynyl lithium, hexynyl lithium; Aralkyl lithium such as phenyl lithium and phenylethyl lithium; Aryl lithium such as phenyl lithium and naphthyl lithium; Heterocyclic lithium such as 2-thienyl lithium, 4-pyridyl lithium and 2-quinolyl lithium; Tri (n-butyl) magnesium lithium And alkyl lithium magnesium complexes such as trimethyl magnesium lithium. Of these, alkyllithium is preferred and sec-butyllithium is more preferred because it has high reactivity and can perform a fast initiation reaction. The said organic lithium reagent may be used individually by 1 type, and may use 2 or more types together.

Here, when the organic lithium is used as an initiator, the living anion polymerization reaction is started by dividing into lithium ions and organic anions.
The organic anion may be an anion derived only from the organic lithium, or may be formed by using another initiator in combination with another material. For example, the organic anion can be formed by treating 1,1-diphenylethene and its derivatives with the organolithium reagent.
When the monomer is a (meth) acrylic acid ester derivative, as the initiator, either a molecule bulky than sec-butyllithium or a molecule having a large steric hindrance is used, or the same level as sec-butyllithium. It is preferable to use in combination with other materials for forming anions in combination with the above-mentioned initiators together with initiators of bulkiness and steric hindrance, together with initiators of bulkiness and steric hindrance similar to sec-butyllithium. It is more preferable to use a combination of other materials for forming anions in combination with the above-described initiator. Examples of the bulky molecule and the molecule having a large steric hindrance include α-methylstyryl lithium, 1,1-diphenylhexyl lithium, 3-methyl-1,1-diphenylpentyl lithium, and the like. Examples of the material for forming an anion in combination with the initiator include 1,1-diphenylethene and derivatives thereof, and 1,1-diphenylethene is preferable. As a derivative of 1,1-diphenylethene, a substituent may be linked to the phenyl group portion, and examples of the substituent include a substituted or unsubstituted aryl group, an alkyl group, and a heteroaryl group.

  There is no restriction | limiting in particular as a density | concentration of the said initiator, Although it selects suitably according to the kind and density | concentration of the said monomer, 0.001-1.0M is preferable, 0.002-0.75M is more preferable, 0 0.01 to 0.5M is more preferable, and 0.02 to 0.2M is particularly preferable. When the concentration is less than 0.001M, the initiator may be decomposed by a small amount of water contained in the solvent. When the concentration exceeds 1.0 M, insoluble substances may precipitate during polymerization, and the microreactor flow path may be blocked. On the other hand, when the concentration is within the particularly preferable range, it is advantageous in that the reaction can be performed more practically without causing the microreactor flow path to be blocked.

<Photopolymerization initiator>
When forming a microphase-separated structure film using the block copolymer obtained by the block copolymer production method, a photopolymerization initiator is further added using a polymerizable rod-like liquid crystal compound as the monomer component. It is preferable. 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. It is especially preferable that it is 0.2-1 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, for example, Liquid Crystal Handbook, Liquid Crystal Handbook Editorial Committee, Maruzen Co., Ltd.

[Production method of micro phase separation structure membrane]
A block copolymer is produced by the method for producing a block copolymer. The block copolymer is preferably formed in a film form on the support.
It is preferable that the block copolymer is a block copolymer for forming a microphase-separated structure film.

<Film formation by solution process>
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) by film formation by a solution process. In general, a phase separation structure is formed. When the block copolymer is obtained by living polymerization on the support, the phase separation structure can be formed on the support as it is after the living polymerization on the support, which is further economically rational.

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, ink jet method, spin coating method, Langmuir- An ordinary 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 of the present invention is formed by a method for producing a block copolymer on a support, a clean cylinder-type microscopic structure having no defects even without surface modification or guide on the support. A phase separation structure can be formed.

<Step of forming a microphase separation structure>
The method for producing a microphase-separated structure membrane according to the first aspect of the present invention is an aspect including (3) a step of forming a microphase-separated structure by external stimulation of the block copolymer of the present invention on a support. . Examples of the external stimulation method for the block copolymer of the present invention for forming a microphase separation structure include a method of promoting phase separation by heat, light, solvent vapor, and electric field (voltage). And a method of promoting phase separation by heating is preferred.
The method for producing a microphase-separated structure membrane according to the second aspect of the present invention comprises (3′-1) a step of preparing a block copolymer solution dissolved in a solvent capable of dissolving the block copolymer of the present invention. , (3′-2) a step of applying the block copolymer solution to the surface of the support, and (3′-3) a step of evaporating the solvent to form a microphase separation structure film of the block copolymer. It is the aspect containing.
Hereinafter, the manufacturing method of the micro phase separation structure membrane of the first embodiment and the manufacturing method of the micro phase separation structure membrane of the second embodiment will be described in order.

-First embodiment-
(Reaction time)
The method for producing a microphase-separated structure membrane according to the first aspect of the present invention comprises the step of (3) heating the block copolymer of the present invention on the support to form a microphase-separated structure. 5 to 1000 seconds, preferably 10 to 600 seconds, more preferably 30 to 200 seconds.

(Reaction temperature)
The method for producing a microphase-separated structure membrane according to the first aspect of the present invention is the heating start of the step (3) of heating the block copolymer of the present invention on the support to form a microphase-separated structure. It is preferable that temperature is 40-250 degreeC, More preferably, it is 50-200 degreeC, More preferably, it is 60-190 degreeC.
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 to lower the temperature to the start temperature (irradiation temperature of active radiation) of the step (4) described later. The temperature lowering rate 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. .

-Second embodiment-
The method for producing a microphase-separated structure membrane according to the second aspect of the present invention comprises (3′-1) a step of preparing a block copolymer solution dissolved in a solvent capable of dissolving the block copolymer of the present invention. , (3′-2) a step of applying the block copolymer solution to the surface of the support, and (3′-3) a step of evaporating the solvent to form a microphase separation structure film of the block copolymer. Have

There is no restriction | limiting in particular as a process of preparing the block copolymer solution melt | dissolved in the solvent which can melt | dissolve the block copolymer of the said (3'-1) this invention, It was obtained by living-polymerizing on a support body. A block copolymer may be dissolved in a solvent, or a block copolymer obtained by living polymerization in a solution may be used. Although there is no restriction | limiting in particular as a solvent which can melt | dissolve the block copolymer of this invention, Among the solvents used in the manufacturing method of the block copolymer on a support body, the block copolymer of this invention can be dissolved. A solvent can be used. Among these, aromatic hydrocarbon solvents are preferable, and xylene is more preferable.
For living polymerization in a solution, methods described in JP-A No. 2004-1224088, JP-A 2010-275349, JP-A 2010-116463, JP-A 2010-116466, and the like can be used. . When the block copolymer of the present invention is produced by living polymerization in a solution, the reaction temperature is set to 40 to 300 ° C. using an oil bath or the like, and the living polymerization time in the solution is set to 5 to 20 hours, for example. It is preferably carried out under an inert gas flow.

There is no restriction | limiting in particular as a process of apply | coating said (3'-2) said block copolymer solution to a support surface, The method similar to the coating method in the process of carrying out the living polymerization of the said monomer containing composition on the said support body Alternatively, the methods described in JP 2004-124088 A, JP 2010-275349 A, JP 2010-116463 A, JP 2010-116466 A, and the like can be used.
Alternatively, the block copolymer reaction mixture obtained by living polymerization in solution may be once taken out from the solution and purified, and then the block copolymer solution may be prepared again as a coating solution.

  There is no restriction | limiting in particular as a process of evaporating the said (3'-3) said solvent, and forming the micro phase-separation structure membrane of the said block copolymer, Unexamined-Japanese-Patent No. 2004-124088, Unexamined-Japanese-Patent No. 2010-275349 The methods described in JP 2010-116463 A, JP 2010-116466 A, and the like can be used.

<Step of immobilizing the microphase separation structure>
The method for producing a microphase-separated structure membrane of the present invention further includes (4) a step of cross-linking or polymerizing the block copolymer having the microphase-separated structure on the support to fix the microphase-separated structure. It is preferable.
There is no particular limitation on the method of the step of immobilizing 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 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 active radiation in the said (4) process, A well-known apparatus can be used, for example, HOEA Corporation EXECURE3000 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 micro phase separation structure membrane of the present invention is characterized by containing the block copolymer of the present invention or a cross-linked polymer thereof, or manufactured by the method for producing a micro phase separation structure membrane 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”. Such a microphase-separated structure membrane of the present invention has a low metal content and good storage stability. The microphase separation structure membrane of the present invention preferably has a metal content of 5 ppm or less.
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 being peeled 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 refers to a membrane in which a large number of cylinders to which the hydrophilic polymer component is fixed are arranged in a plane, and the cylinders are preferably arranged at equal intervals. 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 1-1000 nm, more preferably 1-200 nm.
The residual ratio of retardation Rth in the film thickness direction before and after light irradiation when measured at a wavelength of 550 nm of the microphase separation structure film is preferably 70% or more, more preferably 80% or more, and 95%. The above is particularly preferable. Thus, the good optical storage stability of the micro separation structure (for example, the cylinder structure) is preferable in applications that are assumed to be used in external light, for example, separation membranes such as gas permeable membranes and ion exchange membranes. .
The retardation Rth in the film thickness direction before light irradiation when measured at a wavelength of 550 nm of the microphase-separated structure film is preferably 9 nm or more from the viewpoint of the thickness and the degree of order of the liquid crystal layer. It is preferably 11 nm or more, more preferably 12 nm or more.
The retardation Rth in the film thickness direction after light irradiation when measured at a wavelength of 550 nm of the microphase separation structure film is preferably 9 nm or more, preferably 10 nm or more, and particularly preferably 11 nm or more. .
In this specification, Rth is a value measured with an Axometrics AxoScan Mueller matrix polarimeter.

(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. Useful orientation as materials, various nanofilters (separation membranes such as permeable membranes, ultrafiltration membranes, nanoreactors, gas permeable membranes and ion exchange membranes), anisotropic ion conducting membranes, anisotropic conducting membranes, etc. It is a microphase-separated structure film made of a controlled block copolymer.

Such a microphase separation structure film 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 separation membrane such as a conductive ion conductive material, a gas permeable membrane or an ion exchange membrane.
Such a microphase-separated structure film can also remove another cylinder structure part and introduce another substance.

  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.

  First, the materials used in the examples and comparative examples and the preparation methods thereof are shown below.

<Method for Synthesizing Liquid Crystalline Monomer A1>
Liquid crystalline monomer A1 was synthesized by the synthesis method described in Transactions of Materials Research Society of Japan, 28 [3], 553-556 (2003).
Liquid crystalline monomer A1

<Method for Synthesizing Liquid Crystalline Monomer A2>
Liquid crystalline monomer A2 was synthesized by the synthesis method described below.
Liquid crystalline monomer A2
To a solution of dimethylacetamide (DMAc) (20 ml) in 11-bromoundecanol (58 mmol, 15 g) was added ethyl 4-hydroxybenzoate (58 mmol, 10 g) and potassium carbonate (126 mmol, 17.4 g) at 100 ° C. Stir for 2.5 hours. Then, it cooled to room temperature, water (100 ml) was added, and solid was suction-filtered. It was washed with water to obtain a crude product c-1.
An aqueous solution (100 ml) of potassium hydroxide (200 mmol, 11 g) was added to the crude product c-1, and the mixture was stirred at 110 ° C. for 3.5 hours. Then, after cooling to room temperature, hydrochloric acid was added until pH = 1, and the solid was suction filtered and washed with water. Acetonitrile (150 ml) was added, and the mixture was stirred for 15 minutes while heating at 100 ° C., and then cooled to room temperature. The solid was subjected to suction filtration to obtain 15 g of white solid c-2 (2-step yield: 82%).
To a DMAc solution (100 ml) of c-2 (48 mmol, 15 g), methacrylic acid chloride (71.6 mmol, 7.5 g) was added dropwise and stirred at room temperature for 5 hours. Thereafter, water (200 ml) was added at 0 ° C., the solid was suction filtered, acetonitrile (100 ml) was added, stirred and washed, and then suction filtered to give 11 g of white solid c-3 (yield 64%). Obtained.
A few drops of nitrobenzene were added to an acetone solution (100 ml) of c-3 (30 mmol, 11 g) at 0 ° C., and then methanesulfone sanchloride (33 mmol, 3.8 g) and diisopropylethylamine (DIPEA) (35 mmol, 4. 5 g) was added dropwise and stirred for 1 hour. Thereafter, 4-butylphenol (33 mmol, 5 g) was added dropwise, a very small amount of dibutylhydroxytoluene (BHT) and N, N-dimethyl-4-aminopyridine (DMAP) was added, and DIPEA (35 mmol, 4.5 g) was added dropwise. And stirred at room temperature for 4 hours. Water (50 ml) was added, the mixture was stirred for 30 minutes while cooling at 0 ° C., and the solid was filtered off with suction. Purification by column chromatography with hexane / ethyl acetate = 20/1, concentration under reduced pressure, methanol was added, and the solid was suction filtered to obtain 9 g of liquid crystalline monomer A2 (yield 59%).

<Synthesis Method of Liquid Crystalline Monomer A3>
The following liquid crystalline monomer A3 was synthesized in the same manner as liquid crystalline monomer A2.
Liquid crystalline monomer A3

<Method for Synthesizing Liquid Crystalline Monomer A4>
The following liquid crystal monomer A4 was synthesized in the same manner as liquid crystal monomer A2.
Liquid crystalline monomer A4

<Synthesis Method of Liquid Crystalline Monomer A5>
The following liquid crystalline monomer A5 was synthesized by the synthesis method described in Macromolecule, 2002, 35, 3739-3747.
Liquid crystalline monomer A5

<Method for Synthesizing Liquid Crystalline Monomer A6>
Liquid crystalline monomer A6 was synthesized by the synthesis method described in JP-A-2008-127336.
Liquid crystalline monomer A6

<Synthesis Method of Liquid Crystalline Monomer A7>
In the synthesis method described in Example 4 of JP-A-2008-127336, liquid crystal monomer A7 was synthesized by the same synthesis method except that the chain length of the substituent of carboxylic acid compound 10 used was changed.
Liquid crystalline monomer A7

<Method for Synthesizing Liquid Crystalline Monomer A8>
Liquid crystalline monomer A8 was synthesized based on the synthesis method described in JP 2010-116463 A.
Liquid crystalline monomer A8

<Method for synthesizing liquid crystalline monomer A9>
Liquid crystalline monomer A9 was synthesized according to the synthesis method described below.
Liquid crystalline monomer A9

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. The solvent was removed from the organic layer extracted with ethyl acetate with a rotary evaporator to obtain a crude product of liquid crystalline monomer A9. Recrystallization was performed with ethyl acetate and methanol to obtain liquid crystal monomer A9 in 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)

<Method of hydrophilic polymer B1>
A commercially available poly (ethylene glycol) methyl ether tosylate (product number 729124, manufactured by Aldrich) was used as the hydrophilic polymer B1. In the following structural formula, n = 40 can be calculated from GPC.
Hydrophilic polymer B1

<Method for synthesizing hydrophilic monomer C1>
The following hydrophilic monomer C1 was synthesized by the method described in the literature (J. Mater. Chem., 2012, 22, 22265-22271).
Hydrophilic monomer C1

<Method for synthesizing hydrophilic monomer C2>
The following hydrophilic monomer C2 was synthesized by the method described in the literature (Macromolecules 2003, 36, 8312-8319).

[Example 1]
<Living anionic polymerization>
Add 0.0541 g (0.3 mmol) of 1,1-diphenylethene and 0.06 ml (0.1 mmol) of n-butyllithium 1.58N hexane solution in 5 ml of THF at −78 ° C. and stir for 10 minutes. Then, an initiator 3-methyl-1,1-diphenylpentyl lithium solution was prepared to obtain an initiator solution.
After adding 0.246 g (0.5 mmol) of the liquid crystalline monomer A1 solution in the presence of the initiator solution, the reaction temperature was raised to 0 ° C. and stirred for 10 minutes to carry out living anion polymerization. . To this mixed solution, 0.3 g (0.5 mmol) of the hydrophilic polymer B1 solution was added at 0 ° C., stirred for 30 minutes, and treated with methanol after the reaction to synthesize a block copolymer (block polymer). did. The block copolymer thus obtained was used as the block copolymer of Example 1. The molecular weight distribution of the block copolymer of Example 1 was measured by GPC.
The synthesis scheme of the block copolymer of Example 1 is shown below. In the following synthesis scheme, Ph represents a phenyl group, Ts represents a tosyl group (tosyl group, i.e., p-toluenesulfonyl group), and R corresponds to the side chain of the liquid crystalline monomer component A1. Represents a group, n is the same as n in the hydrophilic polymer B1, and m is a value in a range known from Mn and Mw described in Table 1 below.

[Example 2]
In the synthesis of the block copolymer of Example 1, the reaction was carried out in the same manner as in Example 1 except that n-butyllithium used as an initiator was replaced with sec-butyllithium to obtain a block copolymer. It was.
The block copolymer thus obtained was used as the block copolymer of Example 2.

[Example 3]
In the synthesis of the block copolymer of Example 2, the reaction was carried out in the same manner as in Example 1 except that the liquid crystalline monomer A1 was replaced with the liquid crystalline monomer A2, thereby obtaining a block copolymer.
The block copolymer thus obtained was used as the block copolymer of Example 3.

[Example 4]
In the synthesis of the block copolymer of Example 2, the reaction was carried out in the same manner as in Example 1 except that the liquid crystalline monomer A1 was replaced with the liquid crystalline monomer A3 to obtain a block copolymer.
The block copolymer thus obtained was used as the block copolymer of Example 4.

[Example 5]
In the synthesis of the block copolymer of Example 2, the reaction was carried out in the same manner as in Example 1 except that the liquid crystalline monomer A1 was replaced with the liquid crystalline monomer A4 to obtain a block copolymer.
The block copolymer thus obtained was used as the block copolymer of Example 5.

[Example 6]
In the synthesis of the block copolymer of Example 2, the reaction was carried out in the same manner as in Example 1 except that the liquid crystalline monomer A1 was replaced with the liquid crystalline monomer A5 to obtain a block copolymer.
The block copolymer thus obtained was used as the block copolymer of Example 6.

[Example 7]
In the synthesis of the block copolymer of Example 2, the reaction was carried out in the same manner as in Example 1 except that the liquid crystalline monomer A1 was replaced with the liquid crystalline monomer A6 to obtain a block copolymer.
The block copolymer thus obtained was used as the block copolymer of Example 7.

[Example 8]
In the synthesis of the block copolymer of Example 2, the reaction was carried out in the same manner as in Example 1 except that the liquid crystalline monomer A1 was replaced with the liquid crystalline monomer A7 to obtain a block copolymer.
The block copolymer thus obtained was used as the block copolymer of Example 8.

[Example 9]
In the synthesis of the block copolymer of Example 2, the reaction was carried out in the same manner as in Example 1 except that the liquid crystalline monomer A1 was replaced with the liquid crystalline monomer A8 to obtain a block copolymer.
The block copolymer thus obtained was used as the block copolymer of Example 9.

[Example 10]
In the synthesis of the block copolymer of Example 2, the reaction was carried out in the same manner as in Example 1 except that the liquid crystalline monomer A1 was replaced with the liquid crystalline monomer A9 to obtain a block copolymer.
The block copolymer thus obtained was used as the block copolymer of Example 10.

[Example 11]
In the synthesis of the block copolymer of Example 2, the reaction was carried out in the same manner as in Example 1 except that the hydrophilic polymer B1 was replaced with the hydrophilic monomer C1 to obtain a block copolymer.
The block copolymer thus obtained was used as the block copolymer of Example 11.

[Example 12]
In the synthesis of the block copolymer of Example 11, the reaction was carried out in the same manner as in Example 1 except that the hydrophilic monomer C1 was replaced with the hydrophilic monomer C2, thereby obtaining a block copolymer.
The block copolymer thus obtained was used as the block copolymer of Example 12.

[Comparative Examples 1-5]
A synthesis example by atom transfer radical polymerization (ATRP) will be described as a comparative example below. Compared to the case of living anionic polymerization, atom transfer radical polymerization (ATRP) has a problem that the polymerization time is generally slow and the metal catalyst remains.

<Preparation of hydrophilic macroinitiator F-1 for ATRP>
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 Mw8000, Mn7700, Mw / Mn = 1.04: GPC polystyrene conversion) of the target hydrophilic macroinitiator F-1 for ATRP was obtained.
(It can be calculated from GPC as n = 171)

[Comparative Example 1]
ATRP hydrophilic macroinitiator F-1 (0.4122 g), liquid crystalline monomer A1 (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. As a residue, 0.50 g of block copolymer G-1 was obtained.
The block copolymer thus obtained was used as the block copolymer of Comparative Example 1.
The block copolymer of Comparative Example 1 was Mw26900, Mn22000, Mw / Mn = 1.22 from the GPC analysis results. In the block copolymer of Comparative Example 1, the copper ion remaining after the alumina treatment was 130 ppm.

Block copolymer of comparative example 1 (block copolymer G-1)

[Comparative Example 2]
In the synthesis of the block copolymer of Comparative Example 1, the reaction was carried out in the same manner as in Comparative Example 1 except that the liquid crystalline monomer A1 was replaced with the liquid crystalline monomer A2, thereby obtaining a block copolymer.
The block copolymer thus obtained was used as the block copolymer of Comparative Example 2.

[Comparative Example 3]
In the synthesis of the block copolymer of Comparative Example 1, the reaction was carried out in the same manner as in Comparative Example 1 except that the liquid crystalline monomer A1 was replaced with the liquid crystalline monomer A6 to obtain a block copolymer.
The block copolymer thus obtained was used as the block copolymer of Comparative Example 3.

<Comparative example 4>
A reaction was carried out in the same manner as in Comparative Example 1 except that the monomer A1 in Comparative Example 1 was replaced with the monomer A7 to obtain a block copolymer.
The block copolymer thus obtained was used as the block copolymer of Comparative Example 4.

<Comparative Example 5>
A reaction was carried out in the same manner as in Comparative Example 1 except that the monomer A1 in Comparative Example 1 was replaced with the monomer A8 to obtain a block copolymer.
The block copolymer thus obtained was used as the block copolymer of Comparative Example 5.

<Comparative Example 6>
A reaction was carried out in the same manner as in Comparative Example 1 except that the monomer A1 in Comparative Example 1 was replaced with the monomer A9 to obtain a block copolymer.
The block copolymer thus obtained was used as the block copolymer of Comparative Example 6.

[Evaluation]
The synthesis yield of the block copolymers of Examples 1 to 12 and Comparative Examples 1 to 6, the molecular weight of each block copolymer, and the results of evaluating the residual metal amount are shown in Table 1 below.
In addition, in the block copolymer obtained in Examples 1-12, the residual amount of copper ion was 5 ppm or less with respect to the block copolymer. The amount of copper remaining (copper ions) was determined by the method described in Gunma Prefectural Industrial Technology Center Research Report 2010.

[Example 13, Comparative Example 10]
<Manufacture of block copolymer on glass substrate and light storage stability (light resistance) test>
50 mg each of the block copolymers obtained in Example 2 (present invention) and Comparative Example 2 (ATRP) were dissolved in 950 μl of toluene to prepare a coating solution, and 35 μl was spin-coated on a glass substrate (rotating condition: 2000 rpm). , 30 seconds), and was applied to a thickness of about 150 nm. This film was annealed on a hot plate at 140 ° C. for 1 minute, then cooled down to 10 ° C./min and cooled to 80 ° C.
The obtained coating film was used as the microphase separation structure film of Example 13 and Comparative Example 10.

(Light storage stability test)
Cut filter obtained by cutting the microphase-separated structure membrane of Example 13 and Comparative Example 10 with a super xenon weather meter “SX-75” (manufactured by Suga Test Instruments Co., Ltd., 60 ° C., 50% relative humidity) at a wavelength of 340 nm or less (Asahi Spectroscopic Co., Ltd.) was used to irradiate with xenon light at 250,000 Lx for 200 hours. The retardation Rth in the film thickness direction of the microphase-separated structure film of Example 13 and Comparative Example 10 before and after that was measured at a wavelength of 550 nm with an Axometrics AxoScan Mueller matrix polarimeter. Then, the optical change of Rth before and after the light irradiation was observed from the residual rate.
The obtained results are shown in Table 2 below.

(AFM measurement)
The microphase-separated structure film of the block copolymer on the glass substrate, which was produced by the method for producing a block copolymer on the glass substrate, was measured with AFM (SPI3800N manufactured by SII). An AFM photograph of the microphase separation structure film of Example 13 before and after light irradiation is shown in FIG. 1, and an AFM photograph of the microphase separation structure film of Comparative Example 10 before and after light irradiation is shown in FIG. Indicated.
In the microphase-separated structure film of Example 13, a cylinder structure was observed before and after light irradiation, but in the microphase-separated structure film of Comparative Example 10, the structure disappeared after light irradiation.

As can be seen from the above, it was found that the microphase separation structure film of Comparative Example 10 showed significantly inferior results in the light storage stability (light resistance) test as compared with the microphase separation structure film of Example 13. In the microphase-separated structure film of Comparative Example 10, it is considered that the remaining copper catalyst caused an optical change.
As described above, the block copolymer of the present invention has a low metal content, excellent light storage stability, can be formed by living polymerization in a batch or a microreactor, and a good microphase separation structure membrane is economically rational. It can be seen that it can be manufactured.

Claims (14)

A block copolymer in which a polymer component (A) containing an alkylene chain having 2 to 20 carbon atoms and a polymer component (B) containing an alkylene oxide chain are bonded together directly or via a linking group,
The polymer component (A) has a mesogenic side chain having 6 to 50 carbon atoms,
A block copolymer, wherein at least one terminal of the main chain of the block copolymer has a group represented by the following general formula (1).
General formula (1)
(In General Formula (1), * represents the bonding position to the main chain of the block copolymer, and R ^{1 to} R ³ are each independently a substituted or unsubstituted aryl group, a substituted or unsubstituted alkyl group, or Represents a substituted or unsubstituted heteroaryl group.)   2. The block copolymer according to claim 1, wherein * in the general formula (1) is bonded to a main chain having a structure derived from the polymer component (A).   The block copolymer according to claim 1 or 2, wherein the polymer component (A) is poly ((meth) acrylate) having a mesogenic side chain having 6 to 50 carbon atoms. It represents with the following general formula (2), The block copolymer as described in any one of Claims 1-3 characterized by the above-mentioned.
General formula (2)
(In the general formula (2), R ¹ , R ² and R ^3A each independently represents a substituted or unsubstituted aryl group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted heteroaryl group; -B represents a polymer component B containing an alkylene oxide chain, m represents an integer of 1 to 500, L ¹¹ and L ¹² each independently represent a single bond, an alkylene group, an arylene group, an alkenylene group, an alkynylene group, a 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 ) —, a combination of one or more heterylene groups and having 0 to 100 carbon atoms. Represents a linking group (R ¹⁰¹ , R ¹⁰² , R ^{10 3} , R ¹⁰⁴ and R ¹⁰⁵ each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, provided that L ¹² contains at least an alkylene group having 2 to 20 carbon atoms. .), R ⁴ represents a hydrogen atom or a methyl group, and R ⁵ may have an oxetanyl group, an epoxy group, an acrylate group, a methacrylate group, an alkyl group which may have a substituent, or a substituent. Represents an alkoxy group, and M represents a mesogenic group having 6 to 50 carbon atoms, provided that m repeating units may be the same as or different from each other. The block copolymer according to claim 4, wherein L ¹¹ in the general formula (2) is a single bond.   The block copolymer according to any one of claims 1 to 5, wherein the polymer component (B) includes a polyalkyleneoxy structure. It represents with following General formula (3), The block copolymer as described in any one of Claims 1-6 characterized by the above-mentioned.
General formula (3)
(In the general formula (3), R ¹ , R ² and R ^3A each independently represents a substituted or unsubstituted aryl group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted heteroaryl group; And m each independently represents an integer of 1 to 500, and L ¹² each independently represents a single bond, an alkylene group, an arylene group, an alkenylene group, an alkynylene group, a 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 linking group having 0 to 100 carbon atoms constituted by combining one or more heterylene groups (R ¹⁰¹ , R ¹⁰² , R ¹⁰³ , R ^104, R ¹⁰⁵ are each independently a hydrogen atom, a substituted or Substituted alkyl group, a substituted or unsubstituted aryl group. However, L ¹² includes at least an alkylene group having a carbon number of 2 to 20.), R ⁴ represents a hydrogen atom or a methyl group, R ⁵ is oxetanyl group Represents an epoxy group, an acrylate group, a methacrylate group, an optionally substituted alkyl group or an optionally substituted alkoxy group, and M represents a mesogenic group having 6 to 50 carbon atoms. , M repeating units may be the same or different from each other.) The mesogen side chain has at least one reactive group selected from the following group (4) in one mesogen side chain, according to any one of claims 1 to 7, The block copolymer as described.
Group (4)
  The block copolymer according to any one of claims 1 to 8, wherein the block copolymer has a number average molecular weight Mn of 1000 to 100,000.   The block copolymer according to any one of claims 1 to 9, wherein the block copolymer is used for forming a microphase-separated structure film.   The block copolymer according to any one of claims 1 to 10, wherein the block copolymer is living polymerized in a microreactor.   The block copolymer according to any one of claims 1 to 11, wherein the block copolymer is subjected to living anion polymerization. Preparing a block copolymer solution dissolved in a solvent capable of dissolving the block copolymer according to any one of claims 1 to 12, and
Applying the block copolymer solution to a support surface;
A method for producing a microphase separation structure film comprising the step of evaporating the solvent to form a microphase separation structure film of the block copolymer.   It contains the block copolymer as described in any one of Claims 1-12, or its crosslinked polymer, or was manufactured with the manufacturing method of the micro phase-separation structure film of Claim 13. Microphase separation structure membrane.