JP2010221615A - Laminated structure and manufacturing method therefor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a laminated structure wherein a non-adhesive block is exposed at a higher ratio. <P>SOLUTION: A laminated structure is equipped with a substrate material and a polymer film having a molecular weight distribution of 1.0 to 1.5 which is obtained by using one kind of an adhesive block comprising an adhesive block structure unit containing an adhesive group capable of adhering to a surface of the substrate material and one or two or more kinds of non-adhesive blocks comprising a non-adhesive block structure unit. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a laminated structure and a manufacturing method thereof.

  Up to now, it is a polymer composed of a copolymer containing a plurality of types of blocks, and has an adhesive block composed of an adhesive block constitutional unit having a property capable of adhering to the substrate surface, and a property that is difficult to adhere to the substrate surface. A laminated structure having a polymer including a non-adhesive block composed of a non-adhesive block constituent unit and having an adhesive block attached to the surface of the substrate and the non-adhesive block exposed on the outermost surface is manufactured. (See Patent Document 1).

  However, in the above-described conventional laminated structure, not only the non-adhesive block but also a part of the adhesive block is exposed on the outermost surface of the laminated structure.

JP 2008-109108 A

  As a result, in the above conventional laminated structure, the exposure rate of the non-adhesive block is reduced, so that the physical and chemical properties required for the film formed on the substrate cannot be obtained sufficiently or obtained. There has been a problem that the uniformity of physical and chemical properties is impaired.

  This invention is made | formed in view of the said problem, Comprising: The objective of this invention can expose a nonadhesive block to the outermost surface in a higher ratio in the polymer film formed in the base material. The object is to provide a laminated structure.

（式中、Ａｒ¹¹、Ａｒ¹²、Ａｒ¹³、・・・、Ａｒⁿ（ｎは１４以上の整数である）は、同一又は異なり、前記付着性ブロック構成単位又は前記非付着性ブロック構成単位であって、置換基を有していてもよい共役系の２価の基である。前記非付着性ブロック同士、又は前記付着性ブロック及び前記非付着性ブロックは結合基を介して結合されていてもよく、前記非付着性ブロック同士、又は前記付着性ブロック及び前記非付着性ブロックが直接的に結合している場合には、互いに隣接する２個のブロックは異なっている。ｍ¹¹、ｍ¹²、ｍ¹³、・・・、ｍⁿは、同一又は異なり、３以上の整数である）
で表される構造を有する、〔１〕に記載の積層構造体。
〔３〕前記付着性ブロックが芳香族ポリアミン残基である、〔２〕に記載の積層構造体。
〔４〕前記式（１）で表される構造を有する高分子が、下記式（６）：

（式中、Ａｒ¹、Ａｒ²及びＡｒ³は、置換基を有していてもよい共役系の２価の基であり、Ａｒ¹とＡｒ²とは異なり、Ａｒ²とＡｒ³とは異なる。Ｒ^X及びＲ^Yは、同一又は異なり、末端基である。ｍ¹、ｍ²及びｍ³は、同一又は異なり、０以上の整数であって、ｍ¹、ｍ²及びｍ³のうち、少なくとも２個は３以上の整数である。Ａｒ²が付着基を有する場合には、Ａｒ^１及びＡｒ^３は同一であり、Ａｒ¹及びＡｒ³は付着基を有しない。Ａｒ²が付着基を有しない場合には、Ａｒ¹又はＡｒ³が付着基を有する。）
で表される高分子である、〔２〕又は〔３〕に記載の積層構造体。
〔５〕前記式（６）で表される高分子が、下記式（７）：

（式中、Ａｒ⁴及びＡｒ⁵は、相異なり、置換基を有していてもよい共役系の２価の基である。Ｒ^X及びＲ^Yは、前記と同義である。ｍ⁴及びｍ⁵は、同一又は異なり、３以上の整数である。Ａｒ⁴又はＡｒ⁵は付着基を有する。）
で表される高分子である、〔４〕に記載の積層構造体。
〔６〕前記高分子が、下記式：
Ｚ_A−Ｚ＜３．５°
（式中、Ｚは前記高分子の接触角の値であり、Ｚ_Aは前記高分子が含む付着性ブロック構成単位のみからなる化合物の接触角の値及び前記高分子が含む非付着性ブロック構成単位のみからなる化合物の接触角の値のうちの最大値である。）
又は、下記式：
Ｚ−Ｚ_B＜３．５°
（式中、Ｚは前記高分子の接触角の値であり、Ｚ_Bは前記高分子が含む付着性ブロック構成単位のみからなる化合物の接触角の値及び前記高分子が含む非付着性ブロック構成単位のみからなる化合物の接触角の値のうちの最小値である。）
を満たす、〔５〕に記載の積層構造体。
〔７〕前記Ａｒ^４が置換基を有していてもよいアリーレン残基であり、前記Ａｒ^５が置換基を有していてもよい芳香族アミン残基である〔５〕又は〔６〕に記載の積層構造体。
〔８〕前記基材を前記高分子を含む溶液に浸漬する工程を含む〔１〕〜〔７〕のいずれかに記載の積層構造体の製造方法。
〔９〕前記高分子を含む溶液を前記基材に塗布する工程を含む〔１〕〜〔７〕のいずれかに記載の積層構造体の製造方法。 The inventors of the present invention have made extensive studies to obtain a laminated structure in which non-adhesive blocks composed of non-adhesive block structural units are exposed on the outermost surface at a higher rate, and have completed the present invention described below. The present invention provides the following [1] to [9].
[1] One adhesive block composed of a base material and an adhesive block constituent unit having a molecular weight distribution of 1.0 or more and 1.5 or less and having an adhesive group capable of attaching to the surface of the base material; A laminated structure comprising a polymer film using a polymer having one or more non-adhesive blocks composed of an adhesive block constituent unit.
[2] The polymer is represented by the following formula (1):

(Wherein Ar ¹¹ , Ar ¹² , Ar ¹³ ,..., Ar ⁿ (n is an integer of 14 or more) are the same or different, and are the same as the adhesive block structural unit or the non-adhesive block structural unit. A non-adherent block, or the adhering block and the non-adhering block are bonded to each other through a linking group. may, when said non-adherent block each other or the adhesion block and the non-adherent block is directly bind, .m ^11, m ¹² are different in two blocks adjacent to each other , M ¹³ ,..., M ⁿ are the same or different and are integers of 3 or more)
The laminated structure according to [1], having a structure represented by:
[3] The laminated structure according to [2], wherein the adhesive block is an aromatic polyamine residue.
[4] The polymer having the structure represented by the formula (1) is represented by the following formula (6):

(In the formula, Ar ¹ , Ar ² and Ar ³ are conjugated divalent groups which may have a substituent, and are different from Ar ¹ and Ar ^2, and different from Ar ² and Ar ^3. R ^X and R ^Y are the same or different and are end groups, m ¹ , m ² and m ³ are the same or different and are integers of 0 or more, and m ¹ , m ² and m ³ are At least two are integers greater than or equal to ^{3. When} Ar ² has an attachment group, Ar ¹ and Ar ³ are the same, Ar ¹ and Ar ³ have no attachment group, Ar ² has an attachment group. If not, Ar ¹ or Ar ³ has an attachment group.)
The laminated structure according to [2] or [3], which is a polymer represented by:
[5] The polymer represented by the formula (6) is represented by the following formula (7):

(In the formula, Ar ⁴ and Ar ⁵ are different and are conjugated divalent groups which may have a substituent. R ^X and R ^Y are as defined above. M ⁴ and m ⁵ is the same or different and is an integer greater than or equal to 3. Ar ⁴ or Ar ⁵ has an attachment group.
The laminated structure according to [4], which is a polymer represented by:
[6] The polymer has the following formula:
Z _A -Z <3.5 °
(Wherein, Z is the value of the contact angle of the polymer, Z _A is the value of the contact angle of the compound consisting only of the adhesive block constituent unit included in the polymer and the non-adhesive block configuration included in the polymer) (It is the maximum value among the contact angle values of a compound consisting only of units.)
Or the following formula:
Z-Z _B <3.5 °
(Wherein, Z is the value of the contact angle of the polymer, Z _B is the value of the contact angle of the compound consisting only of the adhesive block constituent unit included in the polymer and the non-adhesive block configuration included in the polymer) (It is the minimum value among the contact angle values of a compound consisting only of units.)
The laminated structure according to [5], wherein
[7] In [5] or [6], Ar ⁴ is an arylene residue which may have a substituent, and Ar ⁵ is an aromatic amine residue which may have a substituent. The laminated structure described.
[8] The method for producing a laminated structure according to any one of [1] to [7], including a step of immersing the base material in a solution containing the polymer.
[9] The method for producing a laminated structure according to any one of [1] to [7], including a step of applying a solution containing the polymer to the substrate.

  According to the laminated structure of the present invention, a non-adhesive block composed of non-adhesive block constituent units can be exposed at a higher rate. As a result, the uniformity of physical and chemical properties required for the polymer film can be enhanced over the entire area, and as a result, a higher-performance film (that is, a laminated structure including this film) can be obtained.

3 is a graph showing fluorescence spectra of the polymer film of the laminated structure produced in Example 1 and the reference polymer spin coat film produced in Reference Example 2. FIG.

  Hereinafter, the laminated structure of the present invention will be described in detail. The laminated structure has a base and a molecular weight distribution in terms of polystyrene (weight average molecular weight: Mw / number average molecular weight: Mn) of 1.0 or more and 1.5 or less, and an adhesion group that can adhere to the surface of the base. Using a polymer having one type of adhesive block composed of an adhesive block constituent unit (monomer) having one type and two or more types of non-adhesive blocks consisting of a non-adhesive block constituent unit (monomer) And a polymer film.

(Laminated structure)
The polymer film of the laminated structure of the present invention is composed of one type of adhesive block composed of an adhesive block constitutional unit having an adhesion site capable of adhering to the surface of the substrate, and one type or two composed of a non-adhesive block structural unit. A polymer containing a non-adhesive block of more than one species is used.

  Here, “adhering to the surface of the base material” means that a block composed of a specific block constituent unit is preferentially contacting and adhering to the base material compared to other blocks, for example, It means that the space occupied by the blocks in the space near the surface of the substrate (usually within 1 nm from the surface of the substrate) is larger than the space occupied by other blocks.

  “Preferred” as used herein means that a certain component occupies more space, face, quantity, etc. than other components, for example, an adhesive block occupies the surface of the substrate. It means that the ratio exceeds 50%.

  In this specification, “non-adhesive block (non-adhesive block constituent unit) is exposed” means that the laminated structure is near the outermost surface (usually, the outermost surface when viewed from the side on which the polymer film is formed). The space property within 1 nm from the base material and / or the property of the non-adhesive block (non-adhesive block constituent unit) is close to the predetermined property of the non-adhesive block (non-adhesive block constituent unit). It means to become. The predetermined property of the non-adhesive block is an arbitrary property that can obtain the desired property required for the laminated structure, for example, contact angle, ionization energy (ionization potential), color tone, hardness, heat resistance. , Water resistance, adsorptivity, solvent resistance, electrical conductivity, luminescence, absorbance and the like.

  In the laminated structure of the present invention, the non-adhesive block is preferentially exposed on the outermost surface. That is, the value of the contact angle with respect to the liquid on the outermost surface of the laminated structure of the present invention decreases as the value of the contact angle with respect to the liquid of the film of the compound composed only of the non-adhesive block (non-adhesive block constituent unit) increases. It can be said that the exposure rate of the adhesive block is high. Here, the “contact angle” is an angle formed between the liquid surface and the solid surface when the solid surface comes into contact with the liquid droplet, and an angle on the side containing the liquid. Specifically, it refers to the angle on the ultrapure water side when the solid surface such as a polymer film or a comparative spin coat film described later comes into contact with ultrapure water.

Here, Z is the contact angle value of the polymer, Z _A is the contact angle value of the compound consisting of the adhesive block constituent unit containing the polymer, and the contact of the compound consisting of the non-adhesive block constituent unit containing the polymer The maximum value of the angle values, Z _B is the value of the contact angle of the compound consisting of the adhesive block constituent unit containing the polymer and the value of the contact angle of the compound consisting of the non-adhesive block constituent unit containing the polymer When the minimum value is used, the laminated structure has the following formula:
Z _A -Z <3.5 °
Or the following formula:
Z-Z _B <3.5 °
Preferably satisfying the following formula:
Z _A -Z <3 °
Or the following formula:
ZZ _B <3 °
More preferably, the following formula:
Z _A -Z <2.5 °
Or the following formula:
Z−Z _B <2.5 °
It is further preferable to satisfy

(Base material)
The base material is not limited as long as a polymer adheres to it and a polymer film can be formed on the surface thereof. Materials constituting the base material are: glass; sapphire; semiconductor such as silicon; resin; base metal; noble metal such as platinum, gold, palladium; silicon oxide, indium tin oxide (ITO), tin oxide, titanium oxide, molybdenum oxide And oxides such as tungsten oxide, tantalum oxide, and aluminum oxide; nitrides such as silicon nitride and gallium nitride; and carbides such as silicon carbide.

  These base materials may be used alone or in combination of two or more. For example, the material of the outermost layer of the substrate may be different from the internal material. As a base material, the base material etc. which provided the layer of the indium tin oxide on the surface of the glass substrate are mentioned.

  In addition, when a base material consists of 2 or more types of materials, the polymer which comprises a polymer film adheres to the material which appears on the surface of a base material. For the material appearing on the surface of the substrate, it is preferable to use a material that is physically and chemically stable.

  Although the shape of the base material depends on the use, a smooth one is preferable, and the thickness is preferably 1 μm to 1 m, more preferably 0.01 mm to 100 mm, and 0.1 mm to 10 mm. Is particularly preferred. The base material does not need to have a flat surface, and the surface may be a curved surface. The whole base material may be, for example, a particle having a size of 1 nm to 100 μm, and a spherical particle is particularly preferable. When the substrate is a spherical particle, the diameter is preferably 3 nm to 5 μm, more preferably 5 nm to 1 μm, and particularly preferably 5 nm to 500 nm.

(Polymer film)
The polymer film is a layer (thin film) formed on the surface of the base material using a polymer described later. The average thickness of the polymer film is usually from 0.1 nm to 10 μm, preferably from 0.2 nm to 1 μm, more preferably from 0.5 nm to 500 nm, still more preferably from 0.5 nm to 200 nm. It is. On the surface of the base material, the base material and the adhesive group included in the adhesive block constituent unit that preferentially adheres to the base material interact with each other (bonding forces such as van der Waals force, ionic bond and hydrogen bond). It is preferably in contact (bonding).

(High molecular)
The polymer used for the polymer film of this embodiment will be described. This polymer is a so-called block copolymer containing two or more types of blocks. Here, the block usually means a partial region in the polymer composed of three or more single types of block structural units (monomers). The block can have various structures, preferably a structure in which a single type of block structural unit is connected, more preferably a structure in which three or more are connected, and further preferably a structure in which four or more are connected. Particularly preferred is a structure in which 5 or more are connected.

When the molecular weight of the polymer is too small, it is often impossible to form a polymer layer with good reproducibility, and when the molecular weight is too large, the solubility in a solvent is often low. the number average molecular weight conversion, it preferably 1 × 10 ³ or more, 1 × 10 ³ or more, more preferably 1 × 10 ⁸ or less, 5 × 10 ³ or more and 1 × 10 ⁷ or less Is particularly preferred.

  In the polymer of this embodiment, the molecular weight distribution defined by (weight average molecular weight in terms of polystyrene: Mw) / (number average molecular weight in terms of polystyrene: Mn) is 1.00 or more and 1.50 or less. When this molecular weight distribution exceeds 1.50, not only non-adhesive blocks but also adhesive blocks tend to be exposed on the surface in a considerable proportion in the resulting laminated structure. The molecular weight distribution is preferably 1.00 or more and 1.45 or less, and particularly preferably 1.00 or more and 1.40 or less.

  By aligning the entire length of the polymer with the molecular weight distribution within this range, non-adhesive blocks (non-adhesive block constituent units) are exposed at a higher rate, and adhesive blocks (adhesive block constituent units) are exposed. Exposure can be suppressed. Therefore, it is possible to obtain a layer structure in which the adhesive block and the non-adhesive block are accurately phase-separated in the thickness direction of the laminated structure. Here, “phase separation” means that in a polymer film formed on the surface of a substrate by a polymer having a plurality of blocks having different properties, specific blocks having the same property extend from the surface of the substrate. It means an aspect as if a plurality of layers are formed in a pseudo manner by aligning in the direction. Therefore, the function of the non-adhesive block can be exhibited almost uniformly without any unevenness in the entire region where the polymer film is formed.

Examples of the “conjugated divalent group optionally having a substituent” (a divalent group represented by Ar ⁿ or the like) that can be a structural unit constituting the adhesive block and the non-adhesive block include aromatic Examples thereof include a divalent group having a ring.

  As the divalent group having an aromatic ring, the groups exemplified below can be used. Among these, from the viewpoint of stability and ease of synthesis, the formulas (C-1) to (C-20), (D-1) to (D-20), (E-1) to (E-2) , (E-7) to (E-13), (E-15) to (E-20), (E-22) to (E-26), (G-1) to (G-8) and ( Divalent groups represented by J-1) to (J-3), (J-5) to (J-14), and (J-18) to (J-22) are preferred, and are represented by the formula (C-1 ) To (C-6), (C-10), (C-11), (C-15), (D-16) to (D-20), (E-17) to (E-20), Divalent groups represented by (G-1) to (G-8) and (J-1) to (J-3) are more preferable, and the formulas (C-1) to (C-3) and (C -10), (C-11), (C-15), (D-16) to (D-19), (E-17) to (E-20), (G-1) to (G-6) ) Divalent groups are more preferred, and are represented by the formulas (C-1), (C-11), (C-15), (D-16), (E-20), (G-1), (G-2) The bivalent group represented by these is especially preferable.

In the formula, R ^a is a hydrogen atom or a substituent, and is preferably a hydrogen atom, an alkyl group, an aryl group, an arylalkyl group, or a monovalent heterocyclic group from the viewpoints of stability and ease of synthesis. More preferred are an alkyl group, an aryl group, an arylalkyl group, and a monovalent heterocyclic group, and further preferred are an alkyl group and an aryl group.

The alkyl group represented by ^Ra may be linear, branched or cyclic, and the carbon number is usually 1-20, preferably 1-15, more preferably 1-10. . Examples of the alkyl group include methyl group, ethyl group, propyl group, i-propyl group, butyl group, i-butyl group, t-butyl group, pentyl group, isoamyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, 3,7-dimethyloctyl group, lauryl group, 1-adamantyl group, 2-adamantyl group, trifluoromethyl group, pentafluoroethyl group, perfluorobutyl group, perfluorohexyl Group, perfluorooctyl group. From the balance of easiness of synthesis and heat resistance, methyl group, ethyl group, propyl group, i-propyl group, butyl group, i-butyl group, t-butyl group, pentyl Group, isoamyl group, hexyl group, octyl group, 2-ethylhexyl group, decyl group, 3,7-dimethyloctyl Group is preferred. When ^a plurality of R ^a are present, two R ^a of them may be bonded to each other to form a ring.

The aryl group represented by R ^a is an atomic group obtained by removing one hydrogen atom from an aromatic hydrocarbon, and a group having a condensed ring, an independent benzene ring or two or more condensed rings are directly Alternatively, a group indirectly bonded through a group such as vinylene is also included. Carbon number of an aryl group is 6-60 normally, Preferably it is 7-48. Examples of the aryl group include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthracenyl group, a 2-anthracenyl group, a 9-anthracenyl group, and a pentafluorophenyl group, which further include an alkyl group, an alkoxy group, It may have a substituent such as an alkyloxycarbonyl group or a substituted amino group. From the viewpoint of solubility in an organic solvent and ease of synthesis, at least one substitution selected from the group consisting of an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and an alkyloxycarbonyl group. A phenyl group having a group is preferred.

The number of carbon atoms of the arylalkyl group represented by R ^a is usually 7 to 60, preferably from 7 to 48. As the arylalkyl group, a phenyl-C ₁ -C ₁₂ alkyl group (“C ₁ -C ₁₂ alkyl” means that the alkyl moiety has 1 to 12 carbon atoms. The same shall apply hereinafter). A C ₁ -C ₁₂ alkoxyphenyl-C ₁ -C ₁₂ alkyl group (“C ₁ -C ₁₂ alkoxy” means that the alkoxy moiety has 1 to 12 carbon atoms; the same shall apply hereinafter); C ₁ -C ₁₂ alkylphenyl-C ₁ -C ₁₂ alkyl group, 1-naphthyl-C ₁ -C ₁₂ alkyl group, 2-naphthyl-C ₁ -C ₁₂ alkyl group, and solubility in organic solvents, from the viewpoint of easiness of synthesis, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkyl group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkyl group.

The monovalent heterocyclic group represented by ^Ra refers to the remaining atomic group obtained by removing one hydrogen atom from a heterocyclic compound, and the carbon number thereof is usually 4 to 60, preferably 4 to 20 It is. The carbon number of the monovalent heterocyclic group does not include the carbon number of the substituent. A heterocyclic compound refers to a group in which an organic compound having a cyclic structure contains not only carbon atoms but also hetero atoms such as oxygen, sulfur, nitrogen, phosphorus and boron in the ring. . Specifically, a thienyl group, C ₁ -C ₁₂ alkyl thienyl group, a pyrrolyl group, a furyl group, a pyridyl group, C ₁ -C ₁₂ alkyl pyridyl group, piperidyl group, quinolyl group, isoquinolyl group and the like, a thienyl group, C ₁ -C ₁₂ alkyl thienyl group, a pyridyl group, a C ₁ -C ₁₂ alkyl pyridyl group are preferable.

In formula, ^Rc is the same or different and is a hydrogen atom or a substituent. As the substituent, preferably, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an arylalkenyl group, an arylalkynyl group, an amino group, Substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, amide group, imide residue, monovalent heterocyclic group, carboxyl group, substituted carboxyl group, cyano group, more preferably alkyl Group, alkoxy group, aryl group, aryloxy group, arylalkyl group, arylalkoxy group, substituted amino group, substituted silyl group, acyl group, substituted carboxyl group, cyano group, more preferably alkyl group, alkoxy group, Aryl group, aryloxy group, a Ruarukiru group, arylalkoxy group, a substituted carboxyl group, particularly preferably an alkyl group, an alkoxy group, an aryl group, especially preferably an alkyl group.

The alkyl group represented by R ^c may be linear, branched or cyclic, and the carbon number is usually 1-20, preferably 1-15, more preferably 1-10. . Examples of the alkyl group include methyl group, ethyl group, propyl group, i-propyl group, butyl group, i-butyl group, t-butyl group, pentyl group, isoamyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, 3,7-dimethyloctyl group, lauryl group, 1-adamantyl group, 2-adamantyl group, trifluoromethyl group, pentafluoroethyl group, perfluorobutyl group, perfluorohexyl Group, perfluorooctyl group. From the balance of easiness of synthesis and heat resistance, methyl group, ethyl group, propyl group, i-propyl group, butyl group, i-butyl group, t-butyl group, pentyl Group, isoamyl group, hexyl group, octyl group, 2-ethylhexyl group, decyl group, 3,7-dimethyloctyl Group is preferred. When there are a plurality of alkyl groups, two of them may be bonded to form a ring.

The alkoxy group represented by R ^c may be linear, branched or cyclic, and the carbon number is usually 1-20, preferably 1-15. Examples of the alkoxy group include methoxy group, ethoxy group, propyloxy group, i-propyloxy group, butoxy group, i-butoxy group, t-butoxy group, pentyloxy group, hexyloxy group, cyclohexyloxy group, heptyloxy group, Octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, 3,7-dimethyloctyloxy group, lauryloxy group, trifluoromethoxy group, pentafluoroethoxy group, perfluorobutoxy group, perfluorohexyl group, perfluorohexyl group Fluorooctyl group, methoxymethyloxy group, 2-methoxyethyloxy group, 2-ethoxyethyloxy group can be mentioned. From the balance of solubility in organic solvent, ease of synthesis, and heat resistance, pentyloxy group, Hexyloxy group, octyloxy group, - ethylhexyloxy group, decyloxy group, 3,7-dimethyl octyloxy group are preferable. When there are a plurality of alkoxy groups, two of them may be bonded to each other to form a ring.

The alkylthio group represented by R ^c may be linear, branched or cyclic, and the carbon number is usually 1-20, preferably 3-20.

The aryl group represented by R ^c is an atomic group obtained by removing one hydrogen atom from an aromatic hydrocarbon, and a group having a condensed ring, an independent benzene ring, or two or more condensed rings are directly or Also included are groups bonded indirectly through groups such as vinylene. Carbon number of an aryl group is 6-60 normally, Preferably it is 7-48. Examples of the aryl group include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthracenyl group, a 2-anthracenyl group, a 9-anthracenyl group, and a pentafluorophenyl group, which further include an alkyl group, an alkoxy group, It may have a substituent such as an alkyloxycarbonyl group.

The number of carbon atoms of the aryl group represented by R ^c is usually 6 to 60, preferably from 7 to 48. The aryloxy group is a phenoxy group, C ₁ -C ₁₂ alkoxy phenoxy group, C ₁ -C ₁₂ alkylphenoxy group, 1-naphthyloxy group, 2-naphthyloxy group, pentafluorophenyloxy group and the like, organic solvents solubility, from the standpoint of easiness of synthesis, C ₁ -C ₁₂ alkoxy phenoxy group, a C ₁ -C ₁₂ alkylphenoxy group are preferable.

The carbon number of the arylthio group represented by R ^c is usually 3 to 60. Examples of the arylthio group include a phenylthio group, a C _{1 to} C ₁₂ alkoxyphenylthio group, a C _{1 to} C ₁₂ alkylphenylthio group, 1- Examples include a naphthylthio group, a 2-naphthylthio group, and a pentafluorophenylthio group.

The number of carbon atoms of the arylalkyl group represented by R ^c is usually 7 to 60, preferably from 7 to 48. The aryl alkyl group, a phenyl -C ₁ -C ₁₂ alkyl group, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkyl group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkyl group, 1- naphthyl -C ₁ -C ₁₂ alkyl group, 2-naphthyl -C ₁ -C ₁₂ alkyl groups.

The number of carbon atoms of the arylalkoxy group represented by R ^c is usually 7 to 60, preferably from 7 to 48. The arylalkoxy group, phenylmethoxy group, phenylethoxy group, phenylbutoxy group, phenylpentyl b alkoxy group, a phenyl hexyloxy group, a phenyl heptene Ciro alkoxy group, a phenyl -C ₁ -C ₁₂ alkoxy group such as a phenyl Ok Ciro alkoxy group, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkoxy group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkoxy groups, 1-naphthyl -C ₁ -C ₁₂ alkoxy groups, 2-naphthyl -C ₁ -C ₁₂ alkoxy groups.

The number of carbon atoms of the arylalkylthio group represented by R ^c is usually 7 to 60, preferably from 7 to 48.

Carbon number of the aryl alkenyl group represented by R ^c is usually 8 to 60, and includes phenyl-C ₂ -C ₁₂ alkenyl group, C ₁ -C ₁₂ alkoxyphenyl-C ₂ -C ₁₂ alkenyl group, C _1- C ₁₂ alkylphenyl -C ₂ -C ₁₂ alkenyl group, 1-naphthyl -C ₂ -C ₁₂ alkenyl group, 2-naphthyl -C ₂ -C ₁₂ alkenyl groups.

The carbon number of the arylalkynyl group represented by R ^c is usually 8 to 60, and includes phenyl-C ₂ -C ₁₂ alkynyl group, C ₁ -C ₁₂ alkoxyphenyl-C ₂ -C ₁₂ alkynyl group, C _1- C ₁₂ alkylphenyl -C ₂ -C ₁₂ alkynyl group, 1-naphthyl -C ₂ -C ₁₂ alkynyl group, 2-naphthyl -C ₂ -C ₁₂ alkynyl groups.

^Examples of the substituted amino group represented by R ^c include an amino group substituted with one or two groups selected from the group consisting of an alkyl group, an aryl group, an arylalkyl group, and a monovalent heterocyclic group. The alkyl group, aryl group, arylalkyl group or monovalent heterocyclic group may have a substituent. Carbon number of a substituted amino group is 1-60 normally without including carbon number of a substituent, Preferably it is 2-48. Examples of the substituted amino group include methylamino group, dimethylamino group, ethylamino group, diethylamino group, propylamino group, dipropylamino group, i-propylamino group, diisopropylamino group, butylamino group, i-butylamino group, t-butylamino group, pentylamino group, hexylamino group, cyclohexylamino group, heptylamino group, octylamino group, 2-ethylhexylamino group, nonylamino group, decylamino group, 3,7-dimethyloctylamino group, laurylamino group , cyclopentylamino group, dicyclopentylamino group, cyclohexylamino group, dicyclohexylamino group, pyrrolidyl group, piperidyl group, ditrifluoromethylamino group, phenylamino group, diphenylamino group, C ₁ -C ₁₂ alkoxyphenyl Ami Group, di (C ₁ -C ₁₂ alkoxyphenyl) amino group, di (C ₁ -C ₁₂ alkylphenyl) amino groups, 1-naphthylamino group, 2-naphthylamino group, pentafluorophenylamino group, pyridylamino group, Dajiniruamino group, pyrimidylamino group, Pirajiruamino group, triazyl amino group, phenyl -C ₁ -C ₁₂ alkylamino group, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkylamino group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkylamino group, di (C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkyl) amino group, di (C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkyl) amino Group, 1-naphthyl-C ₁ -C ₁₂ alkylamino group, 2-naphthyl-C ₁ -C ₁₂ alkylamino group are exemplified.

^Examples of the substituted silyl group represented by R ^c include a silyl group substituted with 1 to 3 groups selected from the group consisting of an alkyl group, an aryl group, an arylalkyl group, and a monovalent heterocyclic group. Carbon number of a substituted silyl group is 1-60 normally, Preferably it is 3-48. The alkyl group, aryl group, arylalkyl group or monovalent heterocyclic group may have a substituent.

Examples of the halogen atom represented by R ^c include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

The carbon number of the acyl group represented by R ^c is usually 2 to 20, preferably 2 to 18. Examples of the acyl group include an acetyl group, a propionyl group, and a butyryl group.

The carbon number of the acyloxy group represented by R ^c is usually 2 to 20, preferably 2 to 18. Examples of the acyloxy group include an acetoxy group, a propionyloxy group, and a butyryloxy group.

The number of carbon atoms of the amide group represented by R ^c is usually 2 to 20, preferably from 2 to 18. Examples of the amide group include a formamide group, an acetamide group, a propioamide group, a butyroamide group, a benzamide group, and a trifluoroacetamide group.

The monovalent heterocyclic group represented by R ^c means the remaining atomic group obtained by removing one hydrogen atom from a heterocyclic compound, and the carbon number of the monovalent heterocyclic group is usually 4 to 60. , Preferably 4-20. The carbon number of the monovalent heterocyclic group does not include the carbon number of the substituent. Here, the heterocyclic compound is an organic compound having a cyclic structure, and the elements constituting the ring include not only carbon atoms but also heteroatoms such as oxygen, sulfur, nitrogen, phosphorus and boron in the ring. Refers to the group. Specifically, a thienyl group, C ₁ -C ₁₂ alkyl thienyl group, a pyrrolyl group, a furyl group, a pyridyl group, C ₁ -C ₁₂ alkyl pyridyl group, piperidyl group, quinolyl group, isoquinolyl group and the like, a thienyl group, C ₁ -C ₁₂ alkyl thienyl group, a pyridyl group, a C ₁ -C ₁₂ alkyl pyridyl group are preferable.

^Examples of the substituted carboxyl group represented by R ^c include a carboxyl group substituted with an alkyl group, an aryl group, an arylalkyl group or a monovalent heterocyclic group, and the carbon number thereof is usually 2 to 60, preferably Is 2 to 48. Examples of the substituted carboxyl group include methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, i-propoxycarbonyl group, butoxycarbonyl group, i-butoxycarbonyl group, t-butoxycarbonyl group, pentyloxycarbonyl group, hexyloxycarbonyl group, Cyclohexyloxycarbonyl group, heptyloxycarbonyl group, octyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, nonyloxycarbonyl group, decyloxycarbonyl group, 3,7-dimethyloctyloxycarbonyl group, dodecyloxycarbonyl group, trifluoro Methoxycarbonyl group, pentafluoroethoxycarbonyl group, perfluorobutoxycarbonyl group, perfluorohexyloxycarbonyl group, perfluorooctyloxy Carbonyl group, a phenoxycarbonyl group, naphthoxycarbonyl group, and pyridyloxycarbonyl group. The alkyl group, aryl group, arylalkyl group or monovalent heterocyclic group may further have a substituent. The carbon number of the substituted carboxyl group does not include the carbon number of the substituent.

  In the polymer, both ends of each block are linked to other blocks or bonded to end groups. As for the part which connects adjacent blocks, the blocks may couple | bond together directly and may couple | bond together indirectly through a spacer (group) as a coupling group (bonding group). As the linking group, for example, a divalent group having 100 atoms or less and easy synthesis can be used, and a divalent group having 30 atoms or less and easy synthesis is preferable. Examples of such a divalent group that can be easily synthesized include an alkenyl group and an alkoxyalkenyl group.

  As the structure (terminal group) of the terminal portion of the polymer, a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, Arylalkenyl group, arylalkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, amide group, imide residue, monovalent heterocyclic group, carboxyl group, substituted carboxyl Group, sulfonic acid group, cyano group, hydroxyl group, phosphoric acid group and thiol group. A plurality of terminal groups present in the polymer may be the same or different, and may have an attachment group that can be attached to the substrate surface.

  In the polymer film of this embodiment, the adhesive block is preferably an aromatic polyamine residue. In the polymer film of this embodiment, the non-adherent block is preferably a polyarylene residue.

  The types of blocks constituting one polymer are preferably 2 to 10 types, more preferably 2 to 5 types, and more preferably 2 to 3 types, from the viewpoint of ease of polymer synthesis and precision of phase separation. Two are particularly preferred.

  The aromatic polyamine residue is a divalent group formed by linking three or more conjugated divalent groups containing a heterocyclic group and / or a substituted amino group. As an aromatic polyamine residue, the above (D-1), (D-4) to (D-10), (D-16) to (D-19), (D-22), (E-19) ~ (E-21), (E-24), (G-1) ~ (G-8), (J-7), (J-10), (J-20), (J-21) And a divalent group formed by connecting three or more divalent groups.

The polyarylene residue is a divalent group formed by connecting three or more divalent aromatic hydrocarbon groups. Examples of the divalent aromatic hydrocarbon group include a divalent group represented by the above (E-1) to (E-18), a fluorenediyl group which may have a substituent, and a substituent. A benzofluorenediyl group which may have a substituent, a phenylene group which may have a substituent, a thienylene group which may have a substituent, and the like. An orangeyl group and an optionally substituted benzofluorangeyl group are preferred. The substituent is the same as described and exemplified as the substituent R ^c .

  In the polymer, one of the block structural units is an adhesive block structural unit having a property of preferentially adhering to the substrate. Therefore, it is preferable that one type of block structural unit has a group that can be attached to the surface of the substrate (that is, an “attaching group”). The attachment group can be selected according to the material of the surface of the substrate to be used.

  When the material constituting the surface of the substrate is a metal or metal oxide, the attached group includes a hydroxyl group, a phosphate group, a sulfonate group, a thiol group, a carboxyl group, an ester group, an amino group, a substituted amino group, an amide group. , Alkylthio group, aryloxy group, arylthio group, arylalkoxy group, arylalkylthio group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imidyl group, monovalent heterocyclic group, cyano group, aromatic An amine residue etc. are mentioned. These groups are the same as described and exemplified above.

  Among these, when the material which comprises the surface of a base material is gold or silver, as an adhesion group, a thiol group is preferable.

  In addition, when the material constituting the surface of the base material is a metal oxide such as aluminum oxide, indium tin oxide, or glass, the adhering group includes a hydroxyl group, a phosphoric acid group, a sulfonic acid group, a thiol group, and a carboxyl group. An amino group, a substituted amino group, an amide group and an aromatic amine residue are preferred.

  From the viewpoint of preferential adhesion of the polymer, the polymer can be stably dissolved in an organic solvent, and the proportion of nitrogen atoms contained in the adhesion block constituent unit is the total adhesion block in the polymer. Preferably it is 0.05 weight% or more with respect to a structural unit, More preferably, it is 0.1 weight% or more, More preferably, it is 0.2 weight% or more.

  In the polymer film of the present embodiment, from the viewpoint of the uniformity, reproducibility, and ease of synthesis of the polymer film, the polymer is composed of one adhesive block constituent unit and one to three non-adhesive block constituent units. Are preferably composed of one type of adhesive block structural unit and one or two types of non-adhesive block structural units, and one type of adhesive block structural unit and 1 It is particularly preferred that it is composed of a seed non-adherent block constituent unit.

  In addition, in the polymer film of the present embodiment, from the viewpoint of the uniformity, reproducibility, and ease of synthesis of the polymer film, at the molecular chain terminal, at one molecular chain terminal, the end of the adhesive block The adhesive block constituent unit is bonded to the terminal group, and at the other molecular chain end, the non-adhesive block constituent unit at the end of the non-adhesive block is preferably bonded to the terminal group. Consists of two types of blocks, an adhesive block consisting of one type of adhesive block constituent unit and a non-adhesive block consisting of one type of non-adhesive block constituent unit. It is particularly preferred that the block structural unit is bonded to the terminal group at the terminal end, and that the non-adhesive block structural unit of the non-adhesive block is bonded to the terminal group at the other molecular chain terminal.

（式中、Ａｒ¹¹、Ａｒ¹²、Ａｒ¹³、・・・、Ａｒⁿ（ｎは１４以上の整数である）は、同一又は異なり、前記付着性ブロック構成単位又は前記非付着性ブロック構成単位であって、置換基を有していてもよい共役系の２価の基である。前記非付着性ブロック同士、又は前記付着性ブロック及び前記非付着性ブロックは結合基を介して結合されていてもよく、前記付着性ブロック同士、前記非付着性ブロック同士、又は前記付着性ブロック及び前記非付着性ブロックが直接的に結合している場合には、互いに隣接する２個のブロックは異なっている。ｍ¹¹、ｍ¹²、ｍ¹³、・・・、ｍⁿは、同一又は異なり、３以上の整数である。）
で表される構造を有する。 In a preferred embodiment of the present invention, the polymer is represented by the following formula (1):

(Wherein Ar ¹¹ , Ar ¹² , Ar ¹³ ,..., Ar ⁿ (n is an integer of 14 or more) are the same or different, and are the same as the adhesive block structural unit or the non-adhesive block structural unit. A non-adherent block, or the adhering block and the non-adhering block are bonded to each other through a linking group. If the adhering blocks, the non-adhering blocks, or the adhering block and the non-adhering block are directly bonded, the two adjacent blocks are different. M ¹¹ , m ¹² , m ¹³ ,..., M ⁿ are the same or different and are integers of 3 or more.)
It has the structure represented by these.

In the formula (1), the conjugated divalent group which may have a substituent represented by Ar ¹¹ , Ar ¹² , Ar ¹³ ,..., Ar ⁿ is explained and exemplified above. Is the same.

In the formula (1), at least two m ¹¹ , m ¹² , m ¹³ ,..., ^Mn are preferably an integer of 3 to 1 × 10 ⁶ , and at least two are 4 to 1 ×. It is more preferably an integer of 10 ⁴ , and at least two are particularly preferably 5 to 1 × 10 ³ .

（式中、Ａｒ¹、Ａｒ²及びＡｒ³は、同一又は異なり、置換基を有していてもよい共役系の２価の基であり、Ａｒ¹とＡｒ²とは異なり、Ａｒ²とＡｒ³とは異なる。Ｒ^X及びＲ^Yは、同一又は異なり、末端基である。ｍ¹、ｍ²及びｍ³は、同一又は異なり、０以上の整数であって、ｍ¹、ｍ²及びｍ³のうち、少なくとも２個は３以上の整数である。Ａｒ²が付着基を有する場合には、Ａｒ¹及びＡｒ³は同一であり、Ａｒ¹及びＡｒ³は付着基を有しない。Ａｒ²が付着基を有しない場合には、Ａｒ¹又はＡｒ³が付着基を有する。）
で表される高分子である。 In a more preferred embodiment of the present invention, the polymer having the structure represented by the formula (1) is represented by the following formula (6):

(In the formula, Ar ¹ , Ar ² and Ar ³ are the same or different, and are conjugated divalent groups which may have a substituent. Unlike Ar ¹ and Ar ² , Ar ² and Ar 3 ³ different .R ^X and R ^Y are the same or different from the, .m ^1, m ² and m ³ is an end group are the same or different, is 0 or an integer, m ^1, m ² and m of the ^three, the case where a .Ar ² is attached group of at least two is an integer of 3 or more is, Ar ¹ and Ar ³ are identical, Ar ¹ and Ar ³ have no adhesion groups .Ar ² In the case where does not have an attachment group, Ar ¹ or Ar ³ has an attachment group.)
It is a polymer represented by

In the formula (6), the conjugated divalent group which may have a substituent represented by Ar ¹ , Ar ² and Ar ³ is the same as described and exemplified above.

In the formula ^{(6), m 1, m} 2 and m ³ are preferably at least two are an integer of 3 to 1 × 10 ^6, an integer of at least two is 4 to 1 × 10 ⁴ It is more preferable that at least two are integers of 5 to 1 × 10 ³ .

（式中、Ａｒ⁴及びＡｒ⁵は、同一又は異なり、置換基を有していてもよい共役系の２価の基であり、Ａｒ⁴とＡｒ⁵とは異なる。Ｒ^X及びＲ^Yは、前記と同義である。ｍ⁴及びｍ⁵は、同一又は異なり、３以上の整数である。Ａｒ⁴又はＡｒ⁵は付着基を有する。）
で表される高分子である。 In a further preferred embodiment of the present invention, the polymer represented by the formula (6) is represented by the following formula (7):

(In the formula, Ar ⁴ and Ar ⁵ are the same or different and are a conjugated divalent group which may have a substituent, and are different from Ar ⁴ and Ar ^5. R ^X and R ^Y are (M ⁴ and m ⁵ are the same or different and are an integer of 3 or more. Ar ⁴ or Ar ⁵ has an attachment group.)
It is a polymer represented by

In the formula (7), the conjugated divalent group which may have a substituent represented by Ar ⁴ and Ar ⁵ is the same as described and exemplified above. Among them, Ar ⁴ is an arylene residue which may have a substituent group, it is preferably Ar ⁵ is optionally substituted aromatic amine residue.

In the formula (7), m ⁴ and m ⁵ is preferably an integer of 3 to 1 × 10 ^6, more preferably an integer of 4 to 1 × 10 ^4, the 5 to 1 × 10 ³ Particularly preferred is an integer.

As the polymer represented by the formula (7), polymers represented by the following formulas (L-1) to (L-6) are preferable, and in the formulas (K-1) to (K-6): The polymer represented is more preferred. In these polymers, m and n are synonymous with m ⁴ and m ⁵ . R ^D is a hydrogen atom, an alkyl group, an aryl group, or an arylalkyl group. Here, the alkyl group, aryl group, and arylalkyl group are the same as those described and exemplified above. R ^F and R ^G are the same or different and represent a terminal group. These end groups are synonymous with R ^X and R ^Y.

The number average molecular weight Mn in terms of polystyrene of the polymer is usually 1 × 10 ³ to 1 × 10 ⁸ , preferably 2 × 10 ³ to 1 × 10 ⁷ , more preferably 3 × 10 ³ to 1. × 10 ⁶ , more preferably 5 × 10 ^{3 to} 5 × 10 ⁵ . These number average molecular weights can be measured by polymer size exclusion chromatography (hereinafter referred to as “SEC”).

（式中、Ａｒは、置換基を有していてもよい共役系の２価の基である。Ｘ¹は、ハロゲン原子、下記式（ｃ）で表されるスルホネート基、又はメトキシ基である。Ｍ¹は、ホウ酸エステル残基、ホウ酸残基、下記式（ｄ）で表される基、下記式（ｅ）で表される基、又は下記式（ｆ）で表される基である。）

（式中、Ｒ^Pは、置換基を有していてもよいアルキル基又は置換基を有していてもよいアリール基である。）

（式中、Ｘ_Ａは、塩素原子、臭素原子又はヨウ素原子である。）

（式中、Ｘ_Ａは、塩素原子、臭素原子又はヨウ素原子である。）

（式中、Ｒ^Q、Ｒ^R及びＲ^Sは、同一又は異なり、置換基を有していてもよいアルキル基又は置換基を有していてもよいアリール基である。） The polymer may be a polymer obtained by any production process. For example, two or more compounds represented by the below formula ^{(b), P (t Bu} ) suitable for such ₃ Pd (Ph) Br It can be produced by condensation polymerization in the presence of a catalyst.

(In the formula, Ar is a conjugated divalent group which may have a substituent. X ¹ is a halogen atom, a sulfonate group represented by the following formula (c), or a methoxy group. M ¹ is a boric acid ester residue, a boric acid residue, a group represented by the following formula (d), a group represented by the following formula (e), or a group represented by the following formula (f). is there.)

(In the formula, R ^P represents an alkyl group which may have a substituent or an aryl group which may have a substituent.)

(In the formula, X _A is a chlorine atom, a bromine atom or an iodine atom.)

(In the formula, X _A is a chlorine atom, a bromine atom or an iodine atom.)

(In the formula, R ^Q , R ^R and R ^S are the same or different and are an alkyl group which may have a substituent or an aryl group which may have a substituent.)

In the formula (b), examples of the halogen atom represented by X ¹ include a chlorine atom, a bromine atom, and an iodine atom.

In the formula (c), the alkyl group which may have a substituent represented by R ^P , the alkyl group constituting the aryl group which may have a substituent, and the aryl group are as described above. It is the same as illustrated.

  Examples of the sulfonate group represented by the formula (c) include a methanesulfonate group, a trifluoromethanesulfonate group, a phenylsulfonate group, and a 4-methylphenylsulfonate group.

In the formula (b), examples of the boric acid ester residue represented by M ¹ include groups represented by the following formula.

  As methods for producing the polymer, methods described in JP-A-2008-2223015 and JP-A-2008-109108 can be referred to.

<Manufacturing method>
Next, the manufacturing method of the laminated structure of this invention is demonstrated. A laminated structure can be produced by attaching a polymer to an appropriate substrate under appropriate conditions.

  The method of attaching the polymer to the substrate depends on the type and molecular weight of the polymer, but can be performed in the gas phase, liquid phase, or solid phase, and in the liquid phase from the viewpoint of ease of handling. Is preferred. When performed in the gas phase, the polymer can be formed by being deposited on a clean substrate in a vacuum by a method such as vapor deposition. When performed in a solid phase, a method of rubbing the polymer on a clean substrate can be used. In the case of performing in a liquid phase, a method of preparing an appropriate base material and immersing it in a solution containing a polymer and applying a solution containing a polymer can be used.

  As a method for attaching the polymer to the substrate, a method in which the substrate is immersed in a solution containing the polymer to attach the polymer to the surface of the substrate, or a method in which the solution containing the polymer is applied to the substrate is suitable. It is.

  That is, the preferable manufacturing method of the laminated structure of the present invention includes (1) a step of immersing the substrate in a solution containing a polymer, or (2) a step of applying a solution containing a polymer to the substrate.

  Preferably, the method further includes a step of bringing the polymer layer formed by the step (1) or (2) into contact with a good solvent for the polymer, and a removal step described later.

  Whichever method is used, it is preferable to clean the surface of the substrate in advance. Here, if the surface of the base material is contaminated or dusty, the polymer film may be defective. Therefore, it is preferable to finish the cleaning of the substrate immediately before the attaching step and immediately enter the attaching step. A known method can be used as the cleaning method. In order to form a polymer film with few defects, it is preferable to perform surface treatment with ozone, plasma, etc. in the final cleaning step, more preferably with active oxygen species such as ozone, oxygen plasma, etc. In view of the above, it is particularly preferable to treat with ozone.

  Here, the process of immersing the substrate in a solution containing a polymer, which is a particularly preferred embodiment, will be described. The concentration of the polymer solution can be adjusted within a concentration range in which the polymer can be stably dissolved. From the viewpoint of reproducibility of the polymer membrane, the concentration of the polymer solution is preferably 0.001 to 1000 g / L, more preferably 0.01 to 100 g / L, and particularly preferably 0.01. -10 g / L. The time for immersing the substrate in the solution containing the polymer is usually within 200 hours.

  The solution containing the polymer to be used is preferably a solution from which impurities are removed as much as possible. If dust or other molecules adsorbing on the surface of the substrate are mixed in the solution, the resulting polymer film may be defective.

  Furthermore, it is preferable to perform a step of removing excess polymer from the substrate after immersion (that is, a removal step). In this removal step, washing may be performed with a solvent used for immersion.

  Hereinafter, the present invention will be described in more detail with reference to examples.

The number average molecular weight (Mn) in terms of polystyrene and the weight average molecular weight (Mw) in terms of polystyrene were determined by size exclusion chromatography (SEC) under the following conditions.
Equipment: Tosoh HLC-8220GPC
Column: The following four were connected in series.
One TSK guard column SuperH-H (manufactured by Tosoh)
Two TSKgel SuperHM-H (Tosoh products)
One TSKgel SuperH2000 (manufactured by Tosoh) Mobile phase: Tetrahydrofuran Detector: Differential refractive index detector

<Synthesis Example 1> -Synthesis of a block copolymer A having a narrow molecular weight distribution-
(i) 2-Bromo-9,9-dioctylfluorene-7-boronic acid pinacol ester was synthesized with reference to J. Am. Chem. Soc. 126, 7041 (2004).

(ii) (4-Bromophenyl)-(4-methoxyphenyl)-[4- (4,4,5,5-tetramethyl- [1,3,2] dioxaborolan-2-yl) phenyl] amine (compound (C)) was synthesized with reference to JP-A No. 2007-211237.

The ^{(iii) P (t Bu)} 3 Pd (Ph) Br, J. Am. Chem. Soc. 126, 1184 (2004) and with reference, under argon, bis (tri -t- butylphosphine) palladium ( It was synthesized by reacting 0) with bromobenzene.

(iv) Under an argon gas atmosphere, the flask was purged with argon by adding 149 mg (0.25 mmol) of 2-bromo-9,9-dioctylfluorene-7-boronic acid pinacol ester and octylbenzene (internal standard, 100 μL). . Thereto, 38 mL of dry tetrahydrofuran (THF) was added and dissolved, and then 5 mL of 2M sodium carbonate (aq) was added to prepare a monomer solution. Separately, in an argon glove _{^{box, P (t Bu) 3 Pd}} (Ph) Br5.83mg (0.0013mmol, 5.0mol%) a yellow solution was dissolved in tetrahydrofuran 2 mL, in an argon gas atmosphere, the monomer When added to the solution and stirred at room temperature for 30 minutes, disappearance of 2-bromo-9,9-dioctylfluorene-7-boronic acid pinacol ester was confirmed by high performance liquid chromatography. Here, it was confirmed that the molecular weight in terms of polystyrene at the peak top in SEC was 1.6 × 10 ⁴ .

で表される化合物（ｃ）３０ｍｇ（０．０６３ｍｍｏｌ）を加えて室温で３０分間攪拌した。ここで、ＳＥＣにおけるピークトップのポリスチレン換算の分子量は２．１×１０^４であり、共重合により分子量が増加したことを確認した。次いで、室温にて水層を分液した。また、油層中へ２規定塩酸１０ｍＬを加えて攪拌した後、得られた溶液をメタノールに注加して攪拌したところ、沈殿が析出した。この沈殿をろ過して減圧乾燥したところ、分子量分布の狭いブロック共重合体Ａ（Ｍｎ＝１４６００、Ｍｗ／Ｍｎ＝１．３４）を得た。ブロック共重合体Ａは、^１Ｈ ＮＭＲの結果から、下記式：

で表される構成単位（Ａ）と、下記式：

で表される構成単位（Ｂ）とを、８２：１８のモル比で有するものであると認められた。 Next, the following formula dissolved in dehydrated THF 2 mL:

30 mg (0.063 mmol) of the compound represented by formula (c) was added and stirred at room temperature for 30 minutes. Here, the molecular weight in terms of polystyrene at the peak top in SEC was 2.1 × 10 ⁴ , and it was confirmed that the molecular weight was increased by copolymerization. Next, the aqueous layer was separated at room temperature. In addition, 10 mL of 2N hydrochloric acid was added to the oil layer and stirred, and then the resulting solution was poured into methanol and stirred to precipitate a precipitate. When this precipitate was filtered and dried under reduced pressure, a block copolymer A (Mn = 14600, Mw / Mn = 1.34) having a narrow molecular weight distribution was obtained. From the result of ¹ H NMR, the block copolymer A has the following formula:

And a structural unit (A) represented by the following formula:

It was recognized that it has a structural unit (B) represented by a molar ratio of 82:18.

で表される化合物（ｂ）１２５ｍｇ（０．２１ｍｍｏｌ）を入れ、フラスコ内をアルゴンガスで置換した。そこに、４−ｔ−ブチルブロモベンゼン２．３ｍｇ（０．０１１ｍｍｏｌ）及びトルエン１０ｍＬを添加し、４５℃で５分間攪拌した。次いで、そこに、トリス（ジベンジリデンアセトン）ジパラジウム０．２９ｍｇ（０．０００３ｍｍｏｌ）及びトリス（２−メトキシフェニル）ホスフィン０．９ｍｇ（０．００２６ｍｍｏｌ）を加え、４５℃で１０分間攪拌し、３３重量％炭酸セシウム水溶液１．０ｍＬを加えた後、４５℃で５分間攪拌した。 <Synthesis Example 2> -Synthesis of Block Copolymer B-
In a 300 mL 3-neck flask the following formula:

125 mg (0.21 mmol) of the compound (b) represented by the formula was added, and the inside of the flask was replaced with argon gas. 4-t-butyl bromobenzene 2.3 mg (0.011 mmol) and toluene 10mL were added there, and it stirred at 45 degreeC for 5 minute (s). Next, 0.29 mg (0.0003 mmol) of tris (dibenzylideneacetone) dipalladium and 0.9 mg (0.0026 mmol) of tris (2-methoxyphenyl) phosphine were added thereto, and the mixture was stirred at 45 ° C. for 10 minutes. After adding 1.0 mL of a weight% aqueous cesium carbonate solution, the mixture was stirred at 45 ° C. for 5 minutes.

Then, it stirred at 110 degreeC for 1 hour, and the loss | disappearance of the compound (b) was confirmed by the high performance liquid chromatography. Here, it was confirmed that the molecular weight in terms of polystyrene at the peak top in SEC was 2.2 × 10 ⁴ .

Then, there were 67.4 mg (0.14 mmol) of compound (c), 0.19 mg (0.0002 mmol) of tris (dibenzylideneacetone) dipalladium, 0.59 mg (0.0016 mmol) of tris (2-methoxyphenyl) phosphine. ), 33 mL of a 33 wt% aqueous cesium carbonate solution and 1 mL of toluene were added, and the mixture was stirred at 110 ° C. for 26 hours. Thereafter, disappearance of the compound (c) was confirmed by high performance liquid chromatography. Here, the molecular weight in terms of polystyrene of the peak top in SEC is 2.8 × 10 ^4, a molecular weight was confirmed to have increased by copolymerization.

  Then, 27.9 mg (0.13 mmol) of 4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) toluene and 1 mL of toluene were added thereto at 110 ° C. Stir for 2.5 hours. After cooling to room temperature, the organic layer and aqueous layer of the obtained reaction solution were separated. And when this organic layer was dripped at methanol 45mL, precipitation precipitated. The resulting precipitate was filtered and dried to obtain a yellow solid. This yellow solid was dissolved in 25 mL of toluene, subjected to column chromatography on silica gel and activated alumina, and concentrated to dryness. When the obtained solid was dissolved in tetrahydrofuran and the solution was added dropwise to methanol, a precipitate was deposited. The operation of filtering and drying this precipitate was repeated three times to obtain a solid.

  Further, this solid was dissolved in toluene, and the resulting solution was added dropwise to methanol to precipitate a precipitate. The precipitate was filtered and dried, whereby block copolymer B (Mn = 14300, Mw / Mn = 2). .44) was obtained.

From the result of ¹ H NMR, the block copolymer B was recognized to have the structural unit (A) and the structural unit (B) at a molar ratio of 80:20.

で表される化合物（ｃ）５４０ｍｇ（１．１２ｍｍｏｌ）を仕込み、フラスコ内をアルゴンガスで置換した。そこに、４−ｔ−ブチルブロモベンゼン９．３９ｍｇ（０．０４４ｍｍｏｌ）及びトルエン７．４ｍＬを添加し、４５℃で５分間攪拌した。次いで、そこに、トリス（ジベンジリデンアセトン）ジパラジウム１．４９ｍｇ（０．００１６ｍｍｏｌ）及びトリス（２−メトキシフェニル）ホスフィン４．５９ｍｇ（０．０１３ｍｍｏｌ）を加え４５℃で１０分間攪拌し、３３重量％炭酸セシウム水溶液５ｍＬを加えた後、１１０℃で３時間攪拌し、室温まで冷却した。その後、得られた反応溶液をメタノール４７ｍＬに滴下したところ、沈殿が析出した。この沈殿を濾過することにより、固体を得た。この固体にクロロホルム６．２ｍＬを加え、得られた溶液をメタノールに滴下したところ、沈殿が析出した。この沈殿を濾過、乾燥し、構成単位（Ｂ）のみからなる重合体（以下、「重合体Ｃ」という。）を得た。重合体Ｃのポリスチレン換算の数平均分子量Ｍｎは３．４×１０^３であり、分子量分布Ｍｗ／Ｍｎは２．０６であった。 <Synthesis Example 3> -Synthesis of Polymer C-
In a 300 mL 3-neck flask the following formula:

540 mg (1.12 mmol) of the compound (c) represented by formula (1) was charged, and the inside of the flask was replaced with argon gas. 4-tert-butylbromobenzene 9.39 mg (0.044 mmol) and toluene 7.4 mL were added there, and it stirred at 45 degreeC for 5 minutes. Next, 1.49 mg (0.0016 mmol) of tris (dibenzylideneacetone) dipalladium and 4.59 mg (0.013 mmol) of tris (2-methoxyphenyl) phosphine were added thereto and stirred at 45 ° C. for 10 minutes, 5% aqueous cesium carbonate solution was added, and the mixture was stirred at 110 ° C. for 3 hours and cooled to room temperature. Then, when the obtained reaction solution was dripped at methanol 47mL, precipitation precipitated. The precipitate was filtered to obtain a solid. When 6.2 mL of chloroform was added to this solid and the resulting solution was added dropwise to methanol, a precipitate was deposited. This precipitate was filtered and dried to obtain a polymer consisting only of the structural unit (B) (hereinafter referred to as “polymer C”). The polystyrene equivalent number average molecular weight Mn of the polymer C was 3.4 × 10 ³ , and the molecular weight distribution Mw / Mn was 2.06.

<Synthesis Example 4> -Synthesis of Polymer D-
A commercially available product (manufactured by Aldrich) was used as the polymer consisting only of the structural unit (A) (hereinafter referred to as “polymer D”). The polystyrene equivalent number average molecular weight Mn of the polymer D was 1.5 × 10 ⁴ , and the molecular weight distribution Mw / Mn was 2.80.

<Reference Example 1> -Preparation of Reference Polymer Spin Coat Film-
A spin coat film was prepared on a glass substrate using a THF solution (2.5 g / L) of polymer C, and the contact angle of the obtained film was measured to be 77.7 °. The obtained results are shown in Table 1. The ionization potential of the obtained film was measured with an atmospheric photoelectron spectrometer (trade name: AC2 manufactured by Riken Keiki Co., Ltd.) and found to be 5.18 eV. The obtained results are shown in Table 1. Moreover, when the film thickness of the polymer film was measured with a stylus-type film thickness meter (trade name: Surfcorder ET3000, manufactured by Kosaka Laboratory Ltd.), it was 15 nm to 20 nm.

Reference Example 2-Preparation of Reference Polymer Spin Coat Film-
In Reference Example 1, except that the polymer D was used instead of the polymer C, a spin coat film was produced in the same manner as in Reference Example 1, and the contact angle, ionization potential, and film thickness of the obtained spin coat film were obtained. Was measured, the contact angle of the spin coat film was 88.8 °, the ionization potential was 5.78 eV, and the film thickness was 15 nm to 20 nm. The obtained results are shown in Table 1. Further, the fluorescence spectrum was measured with the excitation light wavelength set at 350 nm. The fluorescence spectrum thus obtained is shown in FIG.

<Example 1> -Production of laminated structure-
The glass substrate as a base material was washed with an organic solvent (chloroform and methanol), an aqueous solution of an alkaline detergent and distilled water, and then exposed to ozone gas for 15 minutes to remove deposits on the surface of the glass substrate. The glass substrate thus obtained was immersed in a toluene solution (2.5 g / L) of the block copolymer A, left standing for 3 days, then pulled up and washed with toluene.

  When the obtained glass substrate was irradiated with ultraviolet rays, fluorescence was confirmed with the naked eye. Furthermore, the fluorescence spectrum was measured by setting the excitation light wavelength to 350 nm. The fluorescence spectrum thus obtained is shown in FIG. From the characteristics of this fluorescence spectrum, it was confirmed that the previously confirmed fluorescence emission was fluorescence emission caused by the structural unit (A) contained in the block copolymer A. That is, it was found that the block copolymer A was adhered on the glass substrate.

  When 0.5 μL of ultrapure water was adhered to the polymer film in the obtained laminated structure and the contact angle was measured, it was 88.0 °. The obtained results are shown in Table 1. The ionization potential of the polymer film was measured with an atmospheric photoelectron spectrometer (trade name: AC2 manufactured by Riken Keiki Co., Ltd.) and found to be 5.54 eV. The obtained results are shown in Table 1. Moreover, when the film thickness of the polymer film was measured with a stylus type film thickness meter (trade name: Surfcorder ET3000, manufactured by Kosaka Laboratory Ltd.), it was 5 nm to 10 nm.

<Comparative Example 1> -Preparation of a laminated structure for comparison-
In Example 1, except that the block copolymer B was used instead of the block copolymer A, a laminated structure was produced in the same manner as in Example 1, and the polymer film in the obtained laminated structure was When the contact angle, ionization potential, and film thickness were measured, the contact angle of the polymer film was 85.0 °, the ionization potential was 5.25 eV, and the film thickness was 5 nm to 10 nm.

<Evaluation>
From Reference Example 1 and Reference Example 2, the contact angle of the outermost surface of the polymer D film consisting only of the structural unit (A) is 88.8 °, and the polymer C film consisting only of the structural unit (B) The contact angle of the outermost surface was 77.7 °. In contrast, the contact angle of the polymer film (Example 1) of the block copolymer A having a narrow molecular weight distribution is 88.0 °, and the contact angle of the polymer film of the block copolymer B (Comparative Example 1). Since the angle was 85.0 °, the contact angle of the polymer film of the block copolymer A was closer to the contact angle of the polymer D film than the contact angle of the polymer C film.
Further, from Reference Example 1 and Reference Example 2, the ionization potential of the polymer D film consisting only of the structural unit (A) is 5.78 eV, and the ionization potential of the polymer C film consisting only of the structural unit (B). Was 5.18 eV. In contrast, the ionization potential of the polymer film (Example 1) of the block copolymer A having a narrow molecular weight distribution is 5.54 eV, and the ionization potential of the polymer film of the block copolymer B (Comparative Example 1). Is 5.25 eV, the ionization potential of the polymer film of the block copolymer A was closer to the contact angle of the polymer D film than the ionization potential of the polymer C film.
From this, the polymer film of the copolymer A has a higher proportion of non-adhesive blocks composed of the structural unit (A) which is a non-adhesive block structural unit on the surface than the polymer film of the copolymer B. It is recognized that it is exposed.

  The laminated structure and the manufacturing method thereof according to the present invention can expose, for example, non-adhesive blocks having high electrical conductivity at a high rate. Therefore, when a base material or the like is provided on the manufactured laminated structure, it is possible to efficiently pass electricity between the base material and the like, and electrically excellent characteristics are exhibited. Therefore, it can be suitably applied to functional layers of advanced functional materials such as photoelectric conversion elements, light emitting materials, battery materials, electronic component materials, and the production method thereof.

Claims (9)

A substrate;
The molecular weight distribution is 1.0 or more and 1.5 or less, and it is composed of one kind of adhesive block constituent unit having an adhesive group capable of attaching to the surface of the substrate and a non-adhesive block constituent unit. A laminated structure comprising a polymer film using a polymer having one or two or more non-adhesive blocks. The polymer is represented by the following formula (1):

(In the formula, Ar ¹¹ , Ar ¹² , Ar ¹³ ,..., Ar ⁿ (n is an integer of 14 or more) are the same or different, and the adhesive block constituent unit or the non-adhesive block constituent unit. A non-adherent block, or the adhering block and the non-adhering block are bonded via a linking group. at best, when said non-adherent block each other or the adhesion block and the non-adherent block is directly bind, .m ¹¹ be different from two blocks adjacent to each other, m ¹² , m ¹³ ,..., ^Mn are the same or different and are integers of 3 or more)
The laminated structure according to claim 1, having a structure represented by:   The laminated structure according to claim 2, wherein the adhesive block is an aromatic polyamine residue. The polymer having the structure represented by the formula (1) is represented by the following formula (6):

(In the formula, Ar ¹ , Ar ² and Ar ³ are conjugated divalent groups which may have a substituent, and are different from Ar ¹ and Ar ^2, and different from Ar ² and Ar ^3. R ^X and R ^Y are the same or different and are end groups, m ¹ , m ² and m ³ are the same or different and are integers of 0 or more, and m ¹ , m ² and m ³ are At least two are integers greater than or equal to ^{3. When} Ar ² has an attachment group, Ar ¹ and Ar ³ are the same, and R ^X , R ^Y , Ar ¹ and Ar ³ do not have an attachment group. When Ar ² does not have an attachment group, Ar ¹ or Ar ³ has an attachment group.)
The laminated structure according to claim 2, which is a polymer represented by: The polymer represented by the formula (6) is represented by the following formula (7):

(In the formula, Ar ⁴ and Ar ⁵ are different and are conjugated divalent groups which may have a substituent. R ^X and R ^Y are as defined above. M ⁴ and m ⁵ is the same or different and is an integer greater than or equal to 3. Ar ⁴ or Ar ⁵ has an attachment group.
The laminated structure according to claim 4, which is a polymer represented by: The polymer has the following formula:
Z _A -Z <3.5 °
(Wherein, Z is the value of the contact angle of the polymer, Z _A is the value of the contact angle of the compound consisting only of the adhesive block constituent unit included in the polymer and the non-adhesive block configuration included in the polymer) (It is the maximum value among the contact angle values of a compound consisting only of units.)
Or the following formula:
Z-Z _B <3.5 °
(Wherein, Z is the value of the contact angle of the polymer, Z _B is the value of the contact angle of the compound consisting only of the adhesive block constituent unit included in the polymer and the non-adhesive block configuration included in the polymer) (It is the minimum value among the contact angle values of a compound consisting only of units.)
The laminated structure according to claim 5, wherein: The laminated structure according to claim 5 or 6, wherein Ar ⁴ is an arylene residue which may have a substituent, and Ar ⁵ is an aromatic amine residue which may have a substituent. body.   The manufacturing method of the laminated structure as described in any one of Claim 1 to 7 including the process of immersing the said base material in the solution containing the said polymer | macromolecule.   The manufacturing method of the laminated structure as described in any one of Claim 1 to 7 including the process of apply | coating the solution containing the said polymer to the said base material.

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