Block copolymer and use thereof

Abstract

To provide a block copolymer in which nanoparticles or the like can be disposed in any block, and metal ions, compounds or the like can be disposed as well.SOLUTION: Provided are a block copolymer having a block A expressed by general formula (I) below and a block B expressed by general formula (II) below, a composition containing the block copolymer and use thereof, a laminate in which the block copolymer is layered on a support, the laminate having a phase-separated structure formed by a phase composed of the block A and a phase composed of the block B, and a method for producing the laminate.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a block copolymer capable of forming a phase-separated structure, a composition containing the block copolymer and its use, a laminate in which the block copolymer is laminated on a support, and a method for producing the laminate, wherein a phase composed of block A and a phase composed of block B form a phase-separated structure.

Background Art

[0002] A block copolymer in which two incompatible polymers are chemically bonded causes phase separation due to segregation between the blocks. At this time, since the respective blocks are chemically bonded and cannot separate from the interface by more than the size of each other's molecules, a periodic interface of the order of the molecular chain size is formed, and a periodic structure of several tens of nm such as a lamella or a cylinder is formed.

[0003] For example, Non-Patent Document 1 discloses a material in which nanoparticles (hereinafter referred to as nanoparticles) are arranged in a periodic structure formed by a block copolymer thin film using hydrophobic interaction and / or electrostatic interaction between a nanomaterial and the block copolymer thin film. Further, Non-Patent Document 2 discloses a material in which nanoparticles are arranged in a block copolymer having a dopamine polymer having a catechol group as one block due to the high adhesiveness and reducibility of the catechol group. A thin film made of such a material is used, for example, as a resist material or a template for arranging nanomaterials.

Prior Art Documents

Non-Patent Documents

[0004]

Non-Patent Document 1

Non-Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0005] In the block copolymer in the material disclosed in the above-mentioned literature, nanoparticles are only arranged in one block, and the other block only forms a periodic structure and no nanoparticles are arranged. That is, these materials do not have nanoparticles arranged in both periodic structures, and in fact, it is impossible to arrange nanoparticles or the like in both periodic structures of the block copolymer, nor is it possible to arrange metal ions, compounds, etc.

[0006] Therefore, an object of the present invention is to provide a block copolymer capable of arranging nanoparticles or the like in any block and also capable of arranging metal ions, compounds, etc.

Means for Solving the Problems

[0007] The present invention relates to the general formula (I): [1] General formula (I):

Chemical formula

[10] A first agent containing the composition according to [9] above, A second agent containing a metal salt and / or first particles, A third agent containing a reagent for deprotecting the protecting group in formula (II) of block B, A fourth agent containing a metal salt having a metal ion different from that of the second agent as a structural unit, and / or a second particle, and a decorative kit containing, and

[11] A step of applying a composition containing the block copolymer described in [9] above onto a support to form a layer containing the block copolymer, and a step of heat-treating the obtained layer containing the block copolymer or treating it under a solvent vapor to cause phase separation, A method for producing a laminate in which a phase composed of block A and a phase composed of block B form a phase-separated structure, containing relates to.

Advantages of the Invention

[0008] According to the present invention, nanoparticles or the like can be arranged in any block, and a block copolymer capable of arranging metal ions, compounds, or the like can be provided.

Brief Description of the Drawings

[0009]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

Modes for Carrying Out the Invention

[0010] In this specification, terms such as “(meth)acryl” and “(meth)acrylate” are general terms for “methacryl” and “acryl”, “methacrylate” and “acrylate”, respectively.

[0011] In this specification, when indicating a numerical range using “~”, the numerical values at both ends are included.

[0012] In this specification, when expressing the number of carbon atoms in the definition of “substituent” or “protecting group”, for example, it may be expressed as “C 1-20 ” etc. Specifically, the notation “C 1-20 alkyl” is synonymous with an alkyl group having 1 to 20 carbon atoms.

[0013] In this specification, the “block copolymer” means a polymer having at least two blocks derived from different monomers, and is also referred to as a “block copolymer”.

[0014] In this specification, the “weight average molecular weight (Mw)” is measured by gel permeation chromatography (GPC) and shown as a value in terms of polystyrene, as described in the examples below.

[0015] In this specification, the “number average molecular weight (Mn)” is measured by gel permeation chromatography (GPC) and shown as a value in terms of polystyrene, as described in the examples below.

[0016] In this specification, the “molecular weight distribution” is represented by weight average molecular weight (Mw) / number average molecular weight (Mn), and the weight average molecular weight (Mw) and number average molecular weight (Mn) can be derived and determined by GPC measurement, as described in the examples below.

[0017] In this specification, the “degree of polymerization” in a block copolymer is synonymous with the number of repeating units of the monomers constituting each block (for example, m and n), 1It can be determined by measuring 1H-NMR and obtaining the integration ratio of the peaks derived from the monomer and the peaks derived from the polymer in the obtained spectrum.

[0018] In the present specification, the "phase separation structure" means any periodic structural pattern formed by each block constituting the block copolymer. Generally, in a block copolymer in which two incompatible polymers are linearly bonded, microphase separation with a period of several tens of nm occurs, forming a self-organized structure. The size of the microphase separation structure in this block copolymer is generally much smaller than the phase separation structure that occurs when two different polymers are mixed.

[0019] [Block copolymer] In one embodiment, the present invention provides a block copolymer having a block A represented by the general formula (I) and a block B represented by the general formula (II).

[0020] The weight average molecular weight (Mw) of the block copolymer according to the present invention can be appropriately selected according to the use, and is not particularly limited. However, from the viewpoint of the uniformity of the thin film, 2,000 to 100,000 is preferable, 10,000 to 100,000 is more preferable, 20,000 to 100,000 is further preferable, 30,000 to 100,000 is particularly preferable, and 40,000 to 100,000 is even more particularly preferable. At this time, the molecular weight distribution is preferably 2.0 or less, more preferably 1.9 or less, further preferably 1.8 or less, even more preferably 1.7 or less, still more preferably 1.6 or less, and particularly preferably 1.5 or less from the viewpoint of the uniformity of the reaction.

[0021] <Block A> Block A is represented by the general formula (I): [Chemical formula] (In the formula, R 1 is hydrogen or methyl, X is -O-, -NH-, -O-(CH2 ) 1-6 -, -O-(CH 2 ) 1-6 -O-, -O-CH 2 -CH(OH)-CH 2 -O-C(O)-, -O-CH 2 -CH(OH)-CH 2 -O-C(O)-CH 2 -CH 2 -, -O-CH 2 -CH(OH)-CH 2 -O-C(O)-CH=CH-, or -NR 5 -(CH 2 ) 1-6 - and R 5 is hydrogen or methyl, and m is 4 to 250) is represented by

[0022] X is -O-, -NH-, -O-(CH 2 ) 1-6 -, -O-(CH 2 ) 1-6 -O-, -O-CH 2 -CH(OH)-CH 2 -O-C(O)-, -O-CH 2 -CH(OH)-CH 2 -O-C(O)-CH 2 -CH 2 -, -O-CH 2 -CH(OH)-CH 2 -O-C(O)-CH=CH-, or -NR 5 -(CH 2 ) 1-6 - but from the viewpoint of productivity, -NR 5 -(CH 2 ) 1-6 - is preferably, and -NR 5 -(CH 2 ) 2-4 - is more preferably. R 5 is hydrogen or methyl, but is preferably hydrogen from the viewpoint of the stability of the raw material monomer.

[0023] m represents the number of repeating units of the monomer constituting block A, and is from 4 to 250. m is preferably from 10 to 100, more preferably from 20 to 90, from the viewpoint of forming a periodic structure.

[0024] Also, in formula (I), the two hydroxyl groups of the dihydroxyphenyl group moiety are preferably in the ortho position from the viewpoint of being available as reaction sites in complex formation with metal ions and redox reactions, and particularly preferably a 3,4-dihydroxyphenyl group.

[0025] <Block B> Block B is represented by the general formula (II):

Chemical formula

[0026] R 2is hydrogen or methyl, with hydrogen being more preferred from the perspective of monomer stability.

[0027] R 3 and R 4 are protecting groups for the hydroxyl group. R 3 and R 4 are each independently C 1-6 alkyl, methoxymethyl (-CH 2 -O-CH 3 ), ethoxyethyl (-CH-CH 3 -O-CH 2 -CH 3 ), acetyl (-CO-CH 3 ), pivaloyl (-CO-C(CH 3 )) 3 C 1-4 alkylsilyl, benzyl (-CH 2 -Ph), p-methoxyphenyl (-Ph-O-CH 3 ), benzoyl (-O-CO-Ph), tert-butyldimethylsilyl (-Si(CH 3 )) 2 (C(CH 3 )) 3 ), tert-butyldiphenylsilyl (-Si(Ph) 2 (C(CH 3 )) 3 ), tert-butoxydiphenylsilyl (-Si(Ph) 2 (O-C(CH 3 )) 3 ), triisopropylsilyl (-Si((CH-(CH 3 )) 2 )) 3 ), or trityl (-C(Ph) 3 )); or R 3 and R 4 preferably together form an acetonide TIFF2025087359000005.tif845. Also, R 3 and R 4 are each independently C 1-6 alkyl, C 1-4is alkylsilyl, methoxymethyl, ethoxyethyl, tert-butyldimethylsilyl, or triisopropylsilyl; or R 3 and R 4 more preferably form an acetonide together.

[0028] Y is -O-, -NH-, -O-(CH 2 ) 1-6 -, -O-(CH 2 ) 1-6 -O-, -O-CH 2 -CH(OH)-CH 2 -O-C(O)-, -O-CH 2 -CH(OH)-CH 2 -O-C(O)-CH 2 -CH 2 -, -O-CH 2 -CH(OH)-CH 2 -O-C(O)-CH=CH-, or -NR 6 -(CH 2 ) 1-6 -. From the viewpoint of productivity, -NR 6 -(CH 2 ) 1-6 - is preferred, and -NR 6 -(CH 2 ) 2-4 - is more preferred. R 6 is hydrogen or methyl, and hydrogen is preferred from the viewpoint of stability.

[0029] n represents the number of repeating units of the monomers constituting block B, and is 4 to 250. From the viewpoint that the phase separation force with block A increases and the uniformity of the periodic structure of the thin film to be produced improves, n is preferably 10 to 100, and more preferably 20 to 90.

[0030] Also, in formula (II), -OR 3 and -OR 4 are preferably in the ortho position from the viewpoint of being available as a reaction point in complex formation with metal ions and redox reactions, and it is particularly preferred that each is bonded to the 3-position and 4-position of the phenyl group.

[0031] <Terminal structure> In a preferred embodiment of the block copolymer according to the present invention, Z is bonded to the terminal of the main chain on the block A side 1 group, and Z is bonded to the terminal of the main chain on the block B side 2 group has a structure.

[0032] Z 1 group and Z 2 group are not the same group, and one of them is CN-C(CH 3 ) 2 -, Ph-C(CH 3 ) 2 -, Ph-C(CH 3 )(CN)-, CH 3 -CH 2 -O-C(O)-C(CH 3 ) 2 -, CH 3 -C(CH 3 ) 2 -CH 2 -C(CH 3 ) 2 -, CN-C(CH 3 )(H)-, Ph-C(CH 3 )(H)-, CH 3 -C(CH 3 ) 2 -, CN-CH 2 -, Ph-CH 2 -, HO-C(O)-C(CH 3 ) 2 -, and HO-C(O)-(CH 2 ) 2 -C(CN)(CH 3 )- is preferably selected. From the viewpoint of the controllability of the polymerization reaction, CN-C(CH 3 ) 2 -, Ph-C(CH 3 ) 2 -, Ph-C(CH 3 )(CN)-, HO-C(O)-C(CH 3 ) 2 -, and HO-C(O)-(CH 2 ) 2 -C(CN)(CH 3It is more preferably selected from -). Further, the other is -SC(S)R 7 , -SC(S)SR 7 , -SC(S)NR 7 R 8 , and -SC(S)OR 7 It is preferably selected from, and from the viewpoint of polymerization controllability, -SC(S)R 7 or -SC(S)SR 7 is more preferably. R 7 is, for example, C 1-20 alkyl, C 2-20 alkenyl, phenyl, pyrrole, pyrrolidone, pyridine, and diethylamino, and C 1-20 alkyl is preferred from the viewpoint of controllability of the polymerization reaction, C 6-16 alkyl is more preferred, and C 10~14 alkyl is even more preferred. R 8 is, for example, selected from hydrogen, C 1-20 alkyl, and phenyl, and C 1-20 alkyl is preferred from the viewpoint of reactivity with the raw material monomer, and when R 7 is C 10-20 alkyl, R 8 is preferably hydrogen.

[0033] <Production of Block Copolymer> The block copolymer of the present invention can be obtained by RAFT polymerization (Reversible Addition-Fragmentation Chain Transfer Polymerization), which is known in the art. RAFT polymerization is a method of polymerizing vinyl monomers by adding a chain transfer agent having a high chain transfer constant called a RAFT agent to a system of ordinary radical polymerization. Specifically, polymerization is carried out by coexisting a vinyl monomer, a RAFT agent, and a polymerization initiator. The generated radical adds to a thioester compound or the C=S bond at the end of the generated polymer, and the original radical species is converted into a similar thioester type, and polymerization proceeds through exchange chain transfer in which radical addition to and cleavage of the thioester are reversibly repeated. Therefore, for example, first, a RAFT polymerization reaction is carried out with monomer A that constitutes block A to form block A with a chain transfer agent added to the end, and this is used as a chain transfer agent to carry out a RAFT polymerization reaction with monomer B that constitutes block B to extend it, and an A-b-B block copolymer can be produced. Also, after first polymerizing monomer B to obtain block B, block A can be extended with monomer A to form a B-b-A block copolymer. Incidentally, Z 1 and Z 2 have structures derived from the RAFT agent used in the production, and either one of them may have a structure derived from the initiator used in the production in some cases.

[0034] Also, in RAFT polymerization, the degree of polymerization (or molecular weight), molecular weight distribution, etc. can be freely controlled according to the ratio of the monomer and the RAFT agent at the time of charging.

[0035] (Monomer A) As monomer A, any (meth)acrylic monomer or (meth)acrylamide monomer that constitutes block A can be used without particular limitation. Specifically, examples include dopamine acrylamide, dopamine methacrylamide, etc. Dopamine acrylamide is preferred from the viewpoint of ease of synthesis, etc.

[0036] (Monomer B) As the monomer B, any (meth)acrylic monomer or (meth)acrylamide monomer that constitutes the above block B can be used without particular limitation. Specifically, compounds in which the hydroxyl groups of the catechol moiety such as dopamine acrylamide and dopamine methacrylamide are protected by R 3 and R 4 respectively can be mentioned. From the viewpoint of ease of synthesis, etc., compounds in which the hydroxyl groups of the catechol moiety of dopamine acrylamide are protected by R 3 and R 4 respectively are preferred. Further, the monomer B can also be selected so that it has the same structure as the monomer A when R 3 and R 4 are deprotected. When the block copolymer is applied to a support or the like to form a thin film, the phase composed of block A is decorated, and then the block B is deprotected and the phase composed of the deprotected block B (also referred to as block B') is decorated, if the block A before decoration and the block B' have the same structure, the block A and the block B' can be decorated by a common method, which is preferable in terms of excellent productivity.

[0037] (RAFT agent) Examples of the RAFT agent include RAFT agents containing a sulfur atom such as dithioester, trithiocarbonate, dithiocarbamate, and xanthate, which are known to those skilled in the art in this technical field. Among them, those suitable for the polymerization of (meth)acrylic monomers and (meth)acrylamide monomers can be used. Specifically, S-(2-cyano-2-propyl)-S-dodecyl trithiocarbonate, S-(cyanomethyl)-S-dodecyl trithiocarbonate, S-(4-cyano-4-[(dodecylsulfanylthiocarbonyl)sulfanyl]pentanoic acid, S-(2-dodecylthiocarbonothioylthio)-2-methylpropanoic acid, etc. are preferred.

[0038] The amount of the RAFT agent is determined by the molecular weight of the target polymer. Since the RAFT agent binds to the ends of each monomer, when a polymer with a degree of polymerization of 100 is the target product, around 1 mol% (0.5 - 3 mol%) is used relative to 100 mol% of the monomer. Therefore, in order to obtain the desired number m of repeating units of the monomer constituting block A of the block copolymer, the ratio of monomer A to the RAFT agent may be adjusted.

[0039] (Polymerization initiator) As the polymerization initiator, those known to those skilled in the art in this technical field can be used without particular limitation. Specifically, any type of polymerization initiator selected from azo compounds, peroxide compounds, redox compounds, etc. can be used.

[0040] Examples of azo compounds include 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis-2,4-dimethylvaleronitrile, 2,2'-azobis(2-methylpropionamidine) dihydrochloride, 4,4'-azobis(4-cyanovaleric acid), etc. Examples of peroxide compounds include tert-butyl peroxyacetate, tert-butyl peroxybenzoate (TBPO), dicumyl peroxide, or dibenzoyl peroxide. Examples of redox compounds include peroxosulfates such as potassium persulfate, sodium persulfate, and ammonium persulfate, which can be used together with metabisulfites such as sodium metabisulfite if necessary.

[0041] Generally, 30 - 100 mol%, preferably 40 - 100 mol% of the polymerization initiator is used relative to the RAFT agent.

[0042] The reaction temperature of RAFT polymerization is determined by the polymerization initiator used, but generally 40 to 150 °C is preferred, 50 to 100 °C is more preferred, and 60 to 70 °C is even more preferred. By setting the reaction temperature to 40 °C or higher, it becomes the polymerization initiation temperature of a general polymerization initiator, and there is a tendency for the active state and the dormant state to be in an equilibrium state at the polymerization terminus by the RAFT agent. Also, by setting the reaction temperature to 150 °C or lower, side reactions are easily suppressed, and the restrictions on the initiators and solvents that can be used tend to be relaxed. Further, the RAFT polymerization reaction can be carried out under atmospheric pressure, but it can also be carried out under reduced pressure or increased pressure. Furthermore, considering the suppression of side reactions and the reactivity of monomers, the RAFT polymerization reaction is preferably carried out under a nitrogen atmosphere.

[0043] RAFT polymerization can be carried out even in the absence of a solvent, but it is preferably carried out in the presence of a solvent. As the solvent, dimethylformamide, dimethyl sulfoxide, toluene, ethanol, etc. can be used, and dimethylformamide, dimethyl sulfoxide, and toluene are preferably used from the viewpoint of the solubility of the block copolymer.

[0044] The production of block copolymers can be carried out by ordinary methods in the art, other than RAFT polymerization, such as radical polymerization, nitroxide-mediated polymerization, ATRP method, etc., in which block B can be extended following the synthesis of block A, or block B can be extended following the synthesis of block B. The polymerization initiators and ATRP reagents used in living polymerization methods and ATRP methods are not particularly limited, and those generally used in the art can be used. Specifically, as the polymerization initiator, those known to those skilled in the art in this technical field can be used without particular limitation. Specifically, in the case of radical polymerization, azo compounds such as 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis-2,4-dimethylvaleronitrile, 2,2'-azobis(2-methylpropionamidine) dihydrochloride, 4,4'-azobis(4-cyanovaleric acid), peroxide compounds such as tert-butylperoxyacetate, tert-butylperoxybenzoate (TBPO), dicumyl peroxide or dibenzoyl peroxide, or peroxodisulfates, for example, redox compounds such as potassium persulfate, sodium persulfate and ammonium persulfate (optionally used in combination with metabisulfite, for example, sodium metabisulfite) can be used, and AIBN is preferred from the viewpoints of safety during the polymerization reaction and stability to monomers. In the case of nitroxide-mediated polymerization, 2,2,6,6-tetramethylpiperidine-1-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, etc. can be used, and 2,2,6,6-tetramethylpiperidine-1-oxyl is preferred from the viewpoint of polymerization controllability.Examples of ATRP reagents include halogenated hydrocarbon compounds such as carbon tetrachloride, chloroform, dichloromethane, monochloroethane, trichlorophenylmethane, dichlorodiphenylmethane, monobromomethane, iodomethane, iodoethane, iodopropane, iodobutane, diiodomethane, 1,2-diiodoethane, iodoform, chloroiodomethane, 1,6-diiodohexane; α-halogenocarbonyl compounds such as 2,2,2-trichloroacetone, 2,2-dichloroacetophenone; α-halogenocarboxylic acid esters such as methyl 2,2,2-trichloroacetate, methyl 2,2-dichloroacetate, methyl 2-chloropropionate, ethyl 2-bromo-2-methylpropionate, ethyl 2-iodo-2-methylpropionate, ethyl 2-bromopropionate, ethyl 2-iodopropionate, dimethyl 2-chloro-2,4,4-trimethylglutarate, dimethyl 2-bromo-2,4,4-trimethylglutarate, dimethyl 2-iodo-2,4,4-trimethylglutarate, 1,2-bis(2'-bromo-2'-methylpropionyloxy)ethane, 1,2-bis(2'-iodo-2'-methylpropionyloxy)ethane, 1,2-bis(2'-bromopropionyloxy)ethane, 1,2-bis(2'-iodopropionyloxy)ethane, 2-(2'-bromo-2'-methylpropionyloxy)ethyl alcohol, 2-(2'-iodo-2'-methylpropionyloxy)ethyl alcohol; and iodoacetonitrile, iodoacetic acid, iodoacetamide, etc. These can be used alone or in combination of two or more. Among these organic halides, organic bromides and organic chlorides are preferably used, and methyl 2-chloropropionate etc. are preferred from the viewpoint of polymerization controllability.

[0045] <Composition containing block copolymer> The above block copolymer can be used as a composition containing various solvents. Such solvents are not particularly limited, and examples include dimethylformamide, dimethyl sulfoxide, etc. Among them, dimethylformamide is preferred from the viewpoint of the solubility of the block copolymer.

[0046] Depending on its use, the composition containing the block copolymer can have various forms. For example, the concentration of the block copolymer in the composition is not particularly limited, but is preferably 0.1 to 50% by mass, more preferably 1 to 10% by mass.

[0047] In addition to the block copolymer and the solvent, such a composition can also contain a plasticizer, a salt, etc.

[0048] <Decoration kit> In one embodiment of the present invention, there is provided a decoration kit including a first agent containing the composition containing the above-mentioned block copolymer, a second agent containing a metal salt and / or first particles, a third agent containing a reagent for deprotecting the protecting group in formula (II) of block B, and a fourth agent containing a metal salt having a metal ion different from that of the second agent as a structural unit and / or second particles.

[0049] (First agent) As the first agent, the composition containing the block copolymer can be used as it is. As the solvent to be used, among the above-mentioned solvents, dimethylformamide, dimethyl sulfoxide, etc. are preferable from the viewpoints of the solubility and stability of the block copolymer, and dimethylformamide is particularly preferable.

[0050] The concentration of the block copolymer in the first agent is not particularly limited, but is preferably 0.1 to 50% by mass, more preferably 1 to 10% by mass, and particularly preferably 5% by mass from the viewpoints of easily achieving an appropriate film thickness, etc.

[0051] (Second agent) The second agent contains a metal salt and / or first particles, and preferably contains a solvent. As the solvent, water, dimethylformamide, acetonitrile, propylene carbonate, etc. can be used, and when a metal salt is contained, water is preferable from the viewpoint of its solubility.

[0052] [Metal salt] The metal salt is not particularly limited. Examples of the metal ions (cations) constituting the metal salt include Fe 2+ 、Fe 3+ 、Cu + 、Pd 2+ 、Pt 2+ 、Ag + 、Au + 、and salts of Au 3+ etc. From the viewpoints of easy availability and low susceptibility to oxidation in the atmosphere, metal ions such as iron ions such as Fe 3+ , silver ions such as Ag + , and gold ions such as Au 3+ are particularly preferably used. Specific examples of the metal salt include nitrates, sulfates, halogen compounds, and cyanide compounds of the above metal ions. When the metal ions contained in these metal salts bind to the catechol groups of block A of the block copolymer described above, a first composite phase in which a metal component is arranged in block A of the block copolymer described above is formed. Representative examples of the first composite phase derived from the metal salt in the present invention include a complex formation type first composite phase and a reduction type first composite phase. The complex formation type first composite phase is formed by the binding (coordination) of the catechol groups of block A to the metal ions. The reduction type first composite phase is a first composite phase that may be formed particularly when the redox potential of the metal salt is +0.22 V (vs. Ag / AgCl). More specifically, there may be a case where the metal salt is reduced by the catechol group to form metal nanoparticles. In this case, the formed nanoparticles and the catechol groups of block A bind to each other to form a reduction type first composite phase.

[0053] The concentration of the metal salt in the second agent is not particularly limited, but from the viewpoints of reactivity with the first agent and influence on the size of the formed particles, 50 to 500 mM is preferable, and 75 to 250 mM is more preferable.

[0054] [First particle] The first particle is at least one particle selected from metal particles, oxide particles, organic particles, polymer particles, etc. When this particle binds to the catechol group of block A through hydrogen bonding, electrostatic interaction, coordination bonding, or π-π interaction, a first composite phase (adsorbed-type first composite phase) derived from the first particle is formed.

[0055] The particle is formed from at least one particle selected from metal particles, oxide particles, organic particles, and polymer particles. Here, "particle" refers to those with a diameter of 1 mm or less. From the perspective of ease of forming the adsorbed-type first composite phase, the diameter of the first particle is preferably 10 μm or less. Further, from the same perspective, the particle diameter is more preferably submicron particles with a diameter of 0.1 - 1 μm, and even more preferably nanoparticles with a diameter of 50 nm or less. Also, the particle may be a colloidal particle composed of about 10 3 ~10 9 atoms.

[0056] The metal constituting the metal particle is not particularly limited, and examples include platinum, copper, palladium, silver, and gold, with silver and gold being more preferred.

[0057] The oxide constituting the oxide particle is not particularly limited, and examples include iron oxide, titanium oxide, zinc oxide, ceria, silica, zirconium oxide, manganese oxide, and nickel oxide. From the perspective of its stability, iron oxide, titanium oxide, silica, and zinc oxide are more preferred.

[0058] The organic substance constituting the organic particle is not particularly limited, and examples include aromatic molecules such as pyrene, perylene, anthracene, and tetracyanoquinodimethane. From the perspective of light stability, pyrene, perylene, and anthracene are more preferred.

[0059] The polymer constituting the polymer particles is not particularly limited, and examples thereof include polystyrene, polymethyl methacrylate, polythiophene, polydiacetylene, etc. From the viewpoint of stability, polystyrene, polymethyl methacrylate, and polydiacetylene are more preferable.

[0060] (Third agent) The third agent is a reagent for deprotecting the protecting group in formula (II) of block B, and depending on the type of the protecting group, reagents well-known in the art can be used. For example, when a triethylsilyl group or a tri-tert-butylsilyl group is used as the protecting group, an acid can be used as the reagent for deprotection.

[0061] (Fourth agent) The fourth agent is the same as the second agent described above, but contains at least one of a metal salt having a metal ion different from that of the second agent as a structural unit and a second particle different from the first particle. Such a fourth agent, in the same manner as the second agent, binds to the catechol group of block B' deprotected by the third agent of the block copolymer described above, thereby forming a complex-forming type second composite phase and / or a reduced type second composite phase and / or an adsorption type second composite phase as the second composite phase. Thereby, the first composite phase and the second composite phase have different structures, and a block copolymer having different colors, patterns, etc. periodically can be easily formed. The metal salt contained in the fourth agent is a metal salt having a metal ion different from that of the metal salt contained in the second agent as a structural unit, and the description of the metal salt described above in the second agent applies. Also, the second particle contained in the fourth agent is a particle different from the first particle contained in the second agent, and the description of the first particle described above in the second agent applies. It is sufficient that any of the metal, particle material, and particle diameter contained in the first composite phase and the second composite phase is different.

[0062] <Photocatalyst coating kit> In one embodiment of the present invention, there is provided a photocatalyst coating kit including a first agent containing a composition including the above-described block copolymer, a second agent containing a metal salt and / or first particles, a third agent containing a reagent for deprotecting the protecting group in formula (II) of block B, and a fourth agent containing a photocatalyst.

[0063] (The first agent, the second agent, and the third agent) The first agent, the second agent, and the third agent are as described in the above-described decoration kit.

[0064] (The fourth agent) The fourth agent contains a photocatalyst and is not particularly limited. For example, titanium oxide or the like can be used.

[0065] <Laminate> In one embodiment, the present invention provides a laminate in which the above-described block copolymer is laminated on a support, and a laminate in which a phase composed of block A and a phase composed of block B form a phase-separated structure.

[0066] (Support) The support is not particularly limited, and any material can be used as long as the composition containing the above-described block copolymer can be applied and dried to form a laminate. After manufacturing the laminate, a material that can be peeled off from the support to form a thin film and used as a thin film may be selected. Specific examples of the support include plastic substrates (e.g., polyethylene terephthalate, polypropylene, etc.), glass substrates, silicon (Si) substrates, calcium fluoride (CaF 2 ) substrates, and further ITO substrates in which an ITO (indium tin oxide) film is laminated on these plastic substrates or glass substrates.

[0067] (Composite phase) The laminate may have a phase composed of block A as a first composite phase containing metal ions bonded to block A and / or particles adsorbed on block A. Further, the laminate may have a phase composed of deprotected block B’ as a phase composed of block B, and a second composite phase containing metal ions bonded to deprotected block B’ and / or particles adsorbed on deprotected block B’. Thereby, the phase composed of block A and the phase composed of block B or the phase composed of deprotected block B’ can have different structures, and a block copolymer having different colors, patterns, etc. periodically can be easily formed. As long as there is some difference in the first composite phase and the second composite phase, such as the material, color tone, reflectance, thickness, etc. of the contained metal or particles, it can be judged by visual observation, analysis, etc. In addition, for the formation of the composite phase, the second agent or the fourth agent described in the above-described decoration kit can be used, and the metal ions and particles described in the composite phase can apply the description in the above-described decoration kit.

[0068] (Method for manufacturing a laminate) The laminate of the present invention can be obtained by various methods. Appropriate suitable conditions can be selected and manufactured according to the support to be used, the block copolymer, and the types of metal salts and particles when used.

[0069] (Step 1) Prepare a solution of the above block copolymer and apply it to the above support by spin coating to form a film. Specifically, as the solution of the block copolymer, for example, a solution in which the block copolymer is dissolved in an organic solvent at a concentration of preferably 0.1 to 10% by mass is used. The concentration in the solution of the block copolymer is more preferably 3 to 7% by mass, and even more preferably 4 to 6% by mass from the viewpoint of reactivity with the second agent. As the organic solvent, dimethylformamide, dimethyl sulfoxide, etc. can be used, and dimethylformamide is preferable from the viewpoint of the solubility and stability of the block copolymer. Of course, a composition containing the above-described novel block copolymer can also be used as the solution of the block copolymer.

[0070] The conditions for spin coating are not particularly limited. For example, the first time: 800 - 1,200 rpm for 5 - 15 seconds, the second time: 1,200 - 1,700 rpm for 90 - 150 seconds, the third time: 2,000 - 3,000 rpm for 20 - 40 seconds. Preferably, the first time: 900 - 1,100 rpm for 8 - 12 seconds, the second time: 1,400 - 1,600 rpm for 110 - 130 seconds, the third time: 2,300 - 2,700 rpm for 25 - 35 seconds are used.

[0071] The concentration of the block copolymer in the solution and the conditions for spin coating are appropriately set according to the desired film thickness.

[0072] (Step 2) The support having the thin film obtained in Step 1 is vacuum annealed. Specifically, it is annealed at 50 - 130 °C, preferably 60 - 120 °C, more preferably 70 - 110 °C for 1 - 5 hours, preferably 1.5 - 3 hours under vacuum (for example, 1.0×10 -3 Pa or less).

[0073] (Step 3a) The support having the thin film obtained in Step 2 is heat treated to form a phase separation structure in the thin film. Specifically, it is heat treated at 50 - 200 °C for 1 - 48 hours, preferably 60 - 180 °C for 6 - 24 hours, more preferably 70 - 170 °C for 10 - 20 hours.

[0074] (Step 3b) Instead of Step 3a, the thin film obtained in Step 2 is placed in a sealed container and left standing under the vapor of the solvent to form a phase separation structure in the thin film.

[0075] Thus, the laminate of the present invention can create a surface having a periodic pattern without using a multi-step process. And since the deprotection of block B can be carried out at a desired timing, different modifications can be easily made to the phase by block A and the phase by the deprotected block B'. Such a laminate with different modifications on both blocks can be used for various applications. For example, since it is expected that interactions occur between the modified substances, it is expected to be used as a photocatalyst and an electrochemical catalyst, etc. Also, due to the different modifications on both blocks, it is expected to be used for applications such as decoration. For example, when trying to form different types of metal films, etc. on a substrate in a periodic pattern, a complicated process is required and the cost tends to be high. However, according to the laminate of the present invention, this can be easily formed.

Example

[0076] Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the examples. Note that the compounds shown in the following examples and test examples do not necessarily follow the IUPAC nomenclature.

[0077] Example 1: Synthesis of Block Copolymer [Step 1] Synthesis of Block A

Chemical formula

[0078] 1.5 g of dopamine acrylamide (manufactured by Osaka Organic Chemical Industry Co., Ltd.), 25.0 mg of S-(2-cyano-2-propyl)-S-dodecyl trithiocarbonate (manufactured by Sigma-Aldrich), and 5.94 mg of 2,2'-azobisisobutyronitrile (ABIN) (manufactured by Fujifilm Wako Pure Chemical Corporation) were placed in a 15 ml pressure-resistant test tube, and 7.24 ml of dimethylformamide (DMF) was further added in a glove box under a nitrogen atmosphere, and the reaction was carried out at 60 °C for 64 hours using a water bath. Then, the reaction mixture rapidly cooled by placing it in an ice bath was dropped into a mixed solvent (100 ml) with a volume ratio of DMF:diethyl ether of 1:10 to obtain a slightly brown and viscous solid product. 1 The degree of polymerization was determined from the integration ratio of the protons of the aromatic ring and the methyl group by 1H-NMR (frequency: 500 MHz, solvent: deuterated DMSO, internal standard: TMS), and it was confirmed that m = 52.

[0079] The weight-average molecular weight (Mw) of the block A-CTA (pDOPAm-CTA) obtained in Step 1 was measured using gel permeation chromatography (GPC) (product number: 0019320, manufactured by Tosoh Corporation, column: TSKgel SuperAWM-H × 4 columns connected in series, detector: RI, mobile phase: 0.1 wt% lithium chloride / dimethylformamide solution). The number-average molecular weight and molecular weight distribution obtained by polystyrene conversion were Mn = 30300 and Mw / Mn = 1.44.

[0080] [Step 2] Extension of Block B [Chemical formula]

[0081] 0.72 g of dopamine acrylamide protected with triethylsilyl (TES-protected DOPAm), 0.12 g of block A-CTA (pDOPAm-CTA) obtained in Step 1, and 0.92 mg of 2,2'-azobisisobutyronitrile (ABIN) (manufactured by Fujifilm Wako Pure Chemical Corporation) were placed in a 15-ml pressure test tube. Under a nitrogen atmosphere in a glove box, 5.65 ml of dimethylformamide (DMF) was further added, and the mixture was reacted at 60 °C for 12 hours in a water bath. Then, the reaction mixture, which was rapidly cooled by placing it in an ice bath, was dropped into a mixed solvent (100 ml) of DMF:methanol with a volume ratio of 1:10, and a slightly brown and viscous solid product was obtained by centrifugation (10100 g, 10 minutes). 1 From the integration ratio of the protons of the aromatic ring and the methyl group determined by 1H-NMR (frequency: 500 MHz, solvent: deuterated DMSO, internal standard: TMS), the degree of polymerization was found to be n = 70.

[0082] Regarding the obtained block copolymer, 1 1H-NMR measurement was performed to identify the structure. The results are shown in Figure 1.

[0083] 1 In the 1H-NMR measurement, CH of the RAFT agent 3 (0.4 - 0.5 ppm), TES group (0.76 - 0.99 ppm), CH of the RAFT agent 2 (1.0 - 1.3 ppm), benzene ring (6.5 - 6.8 ppm), NH group (7.1 - 7.6 ppm), and OH group (8.5 - 9.0 ppm) are shown.

[0084] The number average molecular weight (Mn) of the block copolymer was measured using gel permeation chromatography (GPC) (product number: 0019320, manufactured by Tosoh Corporation, column: TSKgel SuperAWM-H × 4 columns connected in series, detector: RI, mobile phase: 0.1 wt% lithium chloride / dimethylformamide solution). The number average molecular weight and molecular weight distribution obtained in terms of polyethylene were Mn = 29100 and Mw / Mn = 1.32.

[0085] Furthermore, the obtained block copolymer was measured for its UV-vis spectrum at room temperature in a DMF solution. The results are shown in Figure 2.

[0086] As shown in Figure 2, the absorption derived from catechol was observed around 280 nm. On the other hand, the absorption derived from the bimolecular cross-linking of catechol and the quinone structure was not observed. Therefore, it was shown that the catechol groups of the product were not oxidized.

[0087] Example 2: Production of laminate A 5 mass% dimethylformamide (DMF) solution of the block copolymer obtained in Example 1 was spin-coated on the surface of a Si substrate (Silicon Wafer FZ N-type (100) 5000 - 10000Ω Single Side Polished, manufactured by FULEDA TECHNOLOGY, 1 cm × 2 cm (2 cm 2 )) at 1,000 rpm for 10 seconds for the first time, 1,500 rpm for 120 seconds for the second time, and 2,500 rpm for 30 seconds for the third time to form a thin film (film thickness: about 100 nm). This was vacuum annealed at 90 °C for 2 hours (at 1.0 × 10 -3 Pa or less) to remove the residual solvent. Then, heat treatment was performed at 80 °C for 12 hours.

[0088] (Observation of phase separation behavior) Atomic force microscopy (AFM) measurement (for AFM measurement, Hitachi AFM100plus was used, and a cantilever with a spring constant k = 1.7 N / m (OMCL-AC240TS-R3, manufactured by Olympus Corporation) was used, and the measurement was performed in dynamic mode) was used to observe the surface shape of the thin film before and after heat treatment. On the surface of the thin film after spin coating, fine patterns were observed ((a) - (d) in Figure 3). Furthermore, when heat treatment was performed, a clearer line-like phase separation pattern was observed ((e) - (h) in Figure 4). From these results, the structure of the obtained thin film is considered to be a lamellar structure or a cylinder structure.

[0089] Example 3: Production of a laminate having a nanoparticle coating To a 5 wt% DMF solvent of the block copolymer (pDOPAm-b-protected DOPAm) obtained in Example 1, 100 μL of a THF solution containing 0.23 wt% of commercially available Fe 3 O 4 nanoparticles (particle size 10 nm) was added dropwise and stirred for 30 minutes to prepare a solution according to Example 3. A laminate was obtained in the same manner as in Example 2 except that this solution was used.

[0090] (Observation of phase separation behavior) Oblique-incidence small-angle X-ray scattering (GISAXS) measurement was performed on the obtained laminate. NANO-Viewer (manufactured by Rigaku Corp.) was used for the measurement. As the X-ray source, CuKα rays (λ = 0.1542 nm) from a high-intensity X-ray generator (MicroMax-007HF, manufactured by Rigaku Corp.) were used. Also, the X-ray mirror was performed by the parallel beam (PB) method, and pillatus (manufactured by Rigaku Corp.) was used as the two-dimensional detector. The results are shown in Fig. 5.

[0091] From the 2D image and 1D profile (45°-60°) of Fig. 5, it was revealed that domains of about 8 nm were formed.

[0092] Reference Example 1: Deprotection behavior of TES-protected DOPAm Using a 5 mass% DMF solution of TES-protected DOPAm, and replacing the Si substrate with a CaF 2 substrate (C30-10-1, manufactured by Peer Optics Co., Ltd., 3 cm × 1 cm (3 cm 2 ))), a thin film was formed by spin coating in the same manner as in Example 2. The obtained TES-protected DOPAm film was exposed to HCl vapor in a sealed container at room temperature. The reaction was followed by FT-IR measurement at exposure times of 0, 5, 10, 15, 20, 25, 30, 40, 50, and 60 minutes. The results are shown in Fig. 6.

[0093] It can be seen that the IR peak related to the Si-O-C bond decreased with the passage of time (B in Fig. 6), and the IR peak derived from the OH group increased (C in Fig. 6). From this, it can be seen that deprotection proceeds by exposure to HCl vapor.

[0094] In addition, when plotting the peak intensity derived from the Si-O-C bond and the exposure time, it became clear that the decrease in intensity saturated in about 20 minutes (D in Fig. 6).

Claims

1. General formula (I): 【Chemical 1】 (In the formula, R 1 is hydrogen or methyl, X is -O-, -NH-, -O-(CH 2 ) 1-6 -, -O-(CH 2 ) 1-6 -O-, -O-CH 2 -CH(OH)-CH 2 -O-C(O)-, -O-CH 2 -CH(OH)-CH 2 -O-C(O)-CH 2 -CH 2 -, -O-CH 2 -CH(OH)-CH 2 -O-C(O)-CH=CH-, or -NR 5 -(CH 2 ) 1-6 -, and R 5 is hydrogen or methyl, and m is 4 to 250) Block A represented by, and General formula (II): 【Chemical 2】 (In the formula, R 2 is hydrogen or methyl, and R 3 and R 4 is a protecting group for a hydroxyl group, Y is -O-, -NH-, -O-(CH 2 ) 1-6 -, -O-(CH 2 ) 1-6 -O-, -O-CH 2 -CH(OH)-CH 2 -O-C(O)-, -O-CH 2 -CH(OH)-CH 2 -O-C(O)-CH 2 -CH 2 -, -O-CH 2 -CH(OH)-CH 2 -O-C(O)-CH=CH-, or -NR 6 -(CH 2 ) 1-6 -, and R 6 is hydrogen or methyl, and n is 4 to 250) Block B represented by and A block copolymer having.

2. The block copolymer according to claim 1, wherein m is 10 to 100 in formula (I) and n is 10 to 100 in formula (II).

3. The block copolymer according to claim 1, having a weight-average molecular weight of 2,000 to 100,000 and a molecular weight distribution of 2.0 or less.

4. R 3 and R 4 are each independently C 1-6 alkyl, methoxymethyl, ethoxyethyl, acetyl, pivaloyl, C 1-4 alkylsilyl, benzyl, p-methoxyphenyl, benzoyl, tert-butyldimethylsilyl, tert-butyldiphenylsilyl, tert-butoxydiphenylsilyl, triisopropylsilyl, or trityl; or R 3 and R 4 together form an acetonide The block copolymer according to claim 1.

5. R 3 and R 4 are each independently C 1-6 alkyl, C 1-4 alkylsilyl, methoxymethyl, ethoxyethyl, tert-butyldimethylsilyl, or triisopropylsilyl, or R 3 and R 4 The block copolymer according to claim 4, wherein together they form an acetonide.

6. A laminate obtained by laminating the block copolymer according to any one of claims 1 to 5 on a support, wherein a phase composed of block A and a phase composed of block B form a phase-separated structure.

7. The laminate according to claim 6, wherein the phase composed of block A is a first composite phase containing metal ions bonded to block A and / or particles adsorbed on block A.

8. The laminate according to claim 7, wherein the phase composed of block B is a phase composed of deprotected block B', and the phase composed of the deprotected block B' is a second composite phase containing metal ions bonded to block B' and / or particles adsorbed on block B'.

9. A composition containing the block copolymer according to any one of claims 1 to 5 and a solvent.

10. A first agent containing the composition according to claim 9, A second agent containing a metal salt and / or first particles, A third agent containing a reagent for deprotecting the protecting group in formula (II) of block B, A fourth agent containing a metal salt having a metal ion different from the metal salt of the second agent as a structural unit and / or second particles A decoration kit containing.

11. A step of applying a composition containing the block copolymer according to claim 9 on a support to form a layer containing the block copolymer, and A step of heat-treating the obtained layer containing the block copolymer or treating it under solvent vapor to cause phase separation, A method for producing a laminate in which a phase composed of block A and a phase composed of block B form a phase-separated structure, including.

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