JP2010234703A - Laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a laminate which is produced with a large area and at low cost by a simpler manufacturing process such as a roll-to-roll method and which includes a polymer film having a microphase separation structure including no defect, grain structure or the like, and also to provide a method of manufacturing the laminate. <P>SOLUTION: The laminate 10a includes, on one surface, a substrate 12 having a plurality of linear recesses arrayed in parallel to each other with the surface as a reference and a polymer film 14a having a microphase separation structure including a cylinder-shaped or a lamella-shaped microdomain formed on the substrate, wherein, in the cross sectional shape of the linear recess, the recess has a projected inclined part or curved part in he depth direction, the angle (θ) formed by the inner face of the recess and the substrate surface of the reference surface is less than 90°, and the cylinder-shaped or the lamella-shaped micro domain is oriented in the thickness direction of the substrate. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a laminate, and more particularly to a laminate comprising a substrate having a recess having a predetermined structure and a polymer film having a microphase separation structure formed on the substrate.

In recent years, in the fields of optical materials and electronic materials, there have been increasing demands for improving the degree of integration, increasing the amount of information, and increasing the definition of image information. In order to meet such demands, materials and structures whose structure is controlled at the nanometer level are required.
As a fine patterning method for producing such a material / structure, a bottom-up method for producing a fine structure using so-called self-organization that spontaneously forms an ordered pattern has been proposed. Among these, it is known that a block copolymer in which two or more different polymer chains are bonded is phase-separated at a deca-nano level by self-assembly to form a so-called micro phase-separated structure. If such a micro-phase-separated cylindrical or lamellar micro-domain can be oriented perpendicular to the substrate, for example, it can be applied to retardation films, polarizing films, display members, magnetic recording media, etc. It is expected to be applied to a wide range of fields such as energy, environment and life science.

Typically, block copolymer structures (eg, membranes) have a microphase-separated structure that is regularly oriented only in narrow regions of the structure (such regions are referred to as “grains”), It has an irregularly oriented microphase separation structure in which a plurality of grains are aggregated. To date, several attempts have been made to produce block copolymer films having an ordered pattern arranged in a specific direction on a substrate.
For example, in patent document 1, it has an uneven | corrugated shape and the depth of a concave-shaped part is 0.5a or more and 1.5a or more with respect to the distance a between the nearest microdomains of the microdomain which comprises a micro phase separation structure. It is disclosed that by using a substrate, a block copolymer thin film having a uniform microphase-separated structure free from defects and grain structures can be obtained.
Moreover, in patent document 2, the neutral layer which has the surface free energy of the intermediate value of the surface free energy of the two block chains of the block copolymer used on a board | substrate is formed, and also one of the block chains A method for controlling a microphase separation structure of a block copolymer formed on a substrate by forming a guide pattern having a surface free energy close to the surface free energy of the substrate is disclosed.

JP 2007-125699 A JP 2008-36491 A

In Patent Document 1 described above, a polymer film having a phase separation structure including regularly arranged spherical microdomains is mainly disclosed. However, a cylindrical or lamellar microdomain is perpendicular to a substrate. A polymer membrane having a phase-separated structure oriented in the direction is not specifically disclosed. In addition, the cross-sectional shape of the recessed part specifically disclosed in Patent Document 1 is only a rectangle, and as a result of the inventors' study of Patent Document 1, in such a rectangular structure, from a thermodynamic viewpoint, It was found that it was difficult to obtain a phase separation structure in which microdomains were oriented in the vertical direction.
In Patent Document 2, although a polymer film having a phase separation structure in which microdomains are oriented in a direction perpendicular to the substrate is obtained, it is necessary to produce a neutral layer and a guide pattern on the substrate surface. . For this reason, the production process becomes complicated, and it is very disadvantageous in terms of productivity and cost, and is not necessarily an industrially suitable method.

  Accordingly, the present invention includes defects and grain structures that can be produced at a large area and at a low cost by a simpler manufacturing process such as a roll-to-roll method in order to solve the above problems. It is an object of the present invention to provide a laminate comprising a polymer membrane having a microphase-separated structure and a method for producing the laminate.

  As a result of intensive studies, the present inventor obtained a laminate including a polymer film having a desired microphase separation structure by using a substrate having a linear recess having a predetermined cross-sectional shape on the surface. As a result, the present invention has been completed.

That is, as a result of intensive studies, the present inventors have found that the above problems are solved by the following <1> to <10> configurations.
<1> A microphase-separated structure including a substrate having a plurality of linear recesses arranged in parallel to each other on the basis of the surface and a cylindrical or lamellar microdomain formed on the substrate A laminate comprising a polymer film having
In the cross-sectional shape of the linear recess, the recess has a sloped or curved portion that is convex in the depth direction,
An angle formed between the inner surface of the recess and the substrate surface as a reference surface is less than 90 °,
A laminate having the cylindrical or lamellar microdomains oriented in the thickness direction of the substrate.
<2> The laminate according to <1>, wherein in the cross-sectional shape of the linear recess, the width of the recess decreases from the surface of the substrate toward the deepest portion of the recess.
<3> The laminate according to <1> or <2>, wherein the concave portion is formed of a convex curved portion in the cross-sectional shape of the linear concave portion.
<4> The laminate according to any one of <1> to <3>, wherein the thickness T from the bottom of the recess to the surface of the polymer film satisfies the following relationship when the depth of the recess is h: .
T ≦ 1.2 × h Formula (1)
<5> The laminate according to any one of <1> to <4>, wherein a depth h of the linear recess is 20 nm to 1000 nm.
<6> The laminate according to any one of <1> to <5>, wherein the width W of the opening of the linear recess is 20 nm to 1000 nm.
<7> The substrate is provided with an organic layer capable of changing the shape of the heat mode on the substrate, the condensed organic layer is irradiated with the light to remove the organic layer of the irradiated portion, and the remaining organic layer The laminate according to any one of <1> to <6>, which is a substrate produced by performing an etching process on the substrate as a mask and then removing the remaining organic layer.
<8> A step of providing an organic layer capable of changing the shape of the heat mode on the substrate, irradiating the condensed light on the organic layer in a stripe shape, and removing the organic layer of the irradiated portion;
Using the remaining organic layer as a mask, etching the substrate, and then removing the remaining organic layer on the substrate, a plurality of linear recesses arranged parallel to each other with respect to the substrate surface And in the cross-sectional shape of the linear recess, the recess has a sloped portion or a curved portion that is convex in the depth direction, and an angle formed between the inner surface of the recess and the surface that is the reference surface is less than 90 ° A step of manufacturing a substrate which is
A solution containing a block copolymer in which two or more kinds of incompatible polymer chains are bonded to each other is applied to the obtained substrate and dried to form a cylindrical or lamellar microdomain on the substrate. The manufacturing method of a laminated body provided with a polymer film provided with the process of manufacturing the polymer film which has the micro phase-separation structure orientated in the thickness direction.
<9> The method for producing a polymer film according to <8>, wherein in the cross-sectional shape of the linear recess, the width of the recess decreases from the surface of the substrate toward the deepest portion of the recess.
<10> A method for producing a laminate including the polymer film according to <8> or <9>, wherein the concave portion is formed from a convex curved portion in the cross-sectional shape of the linear concave portion.

  According to the present invention, it has a microphase separation structure that can be produced at a large area and at low cost by a simpler manufacturing process such as a roll-to-roll method, and does not include defects or grain structures. A laminate comprising a polymer film and a method for producing the laminate can be provided.

FIG. 1A is a perspective sectional view showing a laminate including a polymer film having a cylindrical microphase separation structure, and FIG. 1B is a top view. FIG. 2A is a perspective sectional view showing a laminate including a polymer film having a lamellar microphase separation structure, and FIG. 2B is a top view. FIG. 3 is a schematic cross-sectional view of a preferred embodiment of a substrate used in the present invention. FIG. 4 is a schematic cross-sectional view of the concave portion of the substrate of FIG. 3, and a diagram in which the concave portion is projected on a horizontal plane. FIG. 5 is a schematic cross-sectional view of another embodiment of a substrate used in the present invention. FIG. 6 is a schematic cross-sectional view of a concave portion of the substrate of FIG. 5 and a diagram in which the concave portion is projected on a horizontal plane. FIGS. 7A and 7B are schematic cross-sectional views of other embodiments of the substrate used in the present invention. FIGS. 8A to 8C are schematic cross-sectional views of a substrate and a polymer film showing a method of manufacturing a laminate including a polymer film having a microphase separation structure in the order of steps. FIG. 9 shows an electron micrograph of the substrate on which linear concave portions are formed. 2 is an atomic force microscope (AFM) image from the upper surface of sample A. FIG.

  Below, the laminated body concerning this invention is demonstrated in detail based on suitable embodiment shown on drawing.

FIG. 1 is a perspective cross-sectional view of an embodiment of the laminate of the present invention.
A laminate 10a shown in the figure includes a substrate 12 and a polymer film 14a.
In the figure, the polymer film 14a is formed in a continuous linear recess (groove) on the substrate 12 and uses a diblock copolymer (polymer A and polymer B bonded at the end). It has a microphase separation structure obtained. The polymer film 14 a has a cylindrical microphase separation structure composed of a continuous phase 20 and cylindrical microdomains 22 distributed in the continuous phase 20. The cylindrical microdomain 22 is oriented in the thickness direction of the substrate 12 (direction perpendicular to the surface of the substrate 12). In addition, although the cross-sectional shape of the recessed part of the board | substrate 12 is formed from the curved part (arc shape) convex in the depth direction, this invention is not limited to this.

FIG. 2 is a perspective sectional view of another embodiment of the structure of the present invention.
A laminate 10b shown in the figure includes a substrate 12 and a polymer film 14b.
In the figure, the polymer film 14b is formed in a continuous linear recess (groove) on the substrate 12, and a diblock copolymer (polymer A and polymer B are bonded at the ends) is used. The resulting microphase separation structure is shown. The polymer film 14b forms a lamellar microphase separation structure composed of a lamellar phase 24 and a phase 26, and the lamellar phase 24 and the phase 26 are in the thickness direction of the substrate 12 (on the surface of the substrate 12). It is oriented in the vertical direction).
The board | substrate 12 in the laminated bodies 10a and 10b shown by FIG. 1 and FIG. 2 is the same component. 1 and 2, the layer thicknesses of the substrate 12 and the polymer films 14a and 14b are not limited depending on the drawings.
First, the substrate 12 and the polymer films 14a and 14b constituting the laminate of the present invention will be described.

<Board>
The substrate 12 of the present invention is for laminating and supporting polymer films 14a and 14b described later, and has linear recesses (grooves) arranged in parallel to each other. Specifically, a plurality of continuous linear recesses arranged in parallel with each other on the surface of the substrate are provided on one surface of the substrate. Further, in the cross-sectional shape of the linear concave portion, the concave portion has a convex inclined portion or a curved portion in the depth direction, and an angle formed between the inner surface of the concave portion and the substrate surface as the reference surface is less than 90 ° By using this, it is possible to obtain a microphase-separated structure having a predetermined arrangement structure in a polymer film described later.
Below, the board | substrate used is explained in full detail.

If the board | substrate used by this invention has the predetermined structure mentioned later, the kind in particular will not be restrict | limited. For example, a quartz substrate, a silicon wafer, a glass substrate, a metal substrate, a flexible substrate, and the like can be given. Of these, a silicon wafer, a quartz substrate, and a flexible substrate are preferable in terms of ease of etching.
Examples of flexible substrates include polyimide (PI), polyethersulfone (PES), polymethyl methacrylate (PMMA), polycarbonate (PC), cycloolefin polymer (COP), polyethylene naphthalate (PEN), and polyethylene terephthalate. (PET), polypropylene (PP), liquid crystal polymer (LCP), polymer substrates such as polydimethylsiloxane (PDMS), triacetyl cellulose (TAC), and metal films such as copper foil and aluminum foil. Among these, a polymer substrate is preferable from the viewpoint of ease of processing and handleability, and in particular, polyimide, polyethylene naphthalate, polycarbonate, polyethylene in terms of high heat resistance, excellent solvent resistance, and good mechanical strength. Terephthalate is preferred.

The board | substrate used by this invention has the convex-shaped inclination part or curved part in the depth direction in the cross-sectional shape of a linear recessed part. The concave portion may be composed of an inclined portion and a curved portion. Moreover, you may be comprised from 2 or more types of inclination parts (straight line part) from which the inclination with respect to a substrate surface differs. More specifically, examples of the cross-sectional shape of the recess include a V shape, an arc shape, and a trapezoidal shape.
The angle formed between the inner surface of the recess and the substrate surface as the reference surface is less than 90 °. More specifically, when the inner surface of the concave portion in the cross-sectional shape is an inclined portion (straight portion), the inclined line, or in the case of a curved portion, a tangent at an arbitrary point on the curved portion and the substrate surface The angle formed may be within the above range.
The present invention will be described in detail below based on preferred embodiments shown in the drawings.

FIG. 3 is a schematic cross-sectional view of a preferred embodiment of a substrate used in the present invention.
A plurality of linear recesses 32a are arranged in parallel to each other on the surface 34 of the substrate 30a shown in FIG. Further, in the cross-sectional shape of the linear recess 32a, the recess 32a is formed by a curved portion 36 having a convex shape (arc shape, elliptical arc shape) in the depth direction. It is preferable that the concave portion 32a has the curved portion 36 because a phase separation structure in which the orientation of the microdomains is more uniform is obtained.

As shown in FIG. 3, the angle θ formed between the inner surface of the recess 32 a in the cross-sectional shape (tangent at an arbitrary point on the curved portion 36 in FIG. 3) and the reference substrate surface 34 is less than 90 °, 85 ° or less is preferable, 80 ° or less is more preferable, and 60 ° or less is particularly preferable. The lower limit is 0 °, which means that the inner surface of the recess 32a (the tangent at an arbitrary point on the curved portion 36 in FIG. 3) and the substrate surface 34 are parallel. Within the above range, the microphase separation structure formed in the polymer membrane is more controlled, which is preferable. In addition, the said angle (theta) means the angle in the inner side direction of a recessed part.
The angle θ can be measured by, for example, dividing the substrate and measuring the cross section thereof with a scanning electron microscope (SEM), an atomic force microscope (AFM), or the like.

Although the distance (pitch: P) between the centers of the recessed part 32a shown by FIG. 3 is suitably changed by the use of a laminated body, 20-2000 nm is preferable, 20-1500 nm is more preferable, 20-1000 nm is especially preferable.
The pitch P can be measured by, for example, an atomic force microscope (AFM), a scanning electron microscope (SEM), or the like.

The depth h (depth from the substrate surface to the deepest part) of the recess 32a shown in FIG. 3 is appropriately selected depending on the usage of the laminate, etc., preferably 20 to 1000 nm, more preferably 20 to 750 nm, 20 to 500 nm is particularly preferable. If the depth h of the recess 32a is within the above range, it is preferable because the microphase separation structure of the polymer membrane described later is more controlled.
The depth h of the recess 32a can be measured by, for example, an atomic force microscope (AFM).

Although the width W of the opening part of the recessed part 32a shown by FIG. 3 is suitably changed by the use of a laminated body, 20-1000 nm is preferable, 20-750 nm is more preferable, 20-500 nm is especially preferable.
The width W of the recess 32a can be measured by, for example, an atomic force microscope (AFM) or a scanning electron microscope (SEM).

  As described above, in the present invention, the cross-sectional shape of the concave portion is preferably constituted by a curved portion, and the radius of curvature of the curved portion of the concave portion is preferably 50 to 1000 nm. Especially, it is more preferable that a curvature radius is 75-900 nm, and it is especially preferable that it is 100-800 nm at the point which the regularity of the micro phase-separation structure obtained improves more.

FIG. 5 is a schematic cross-sectional view of another embodiment of a substrate used in the present invention.
A plurality of continuous linear recesses 32b are arranged in parallel on the surface 34 of the substrate 30b shown in FIG. Moreover, the cross-sectional shape of the linear recessed part 32b is trapezoidal, and the recessed part 32b has the convex bottom face part 40 and the inclination part 38 in the depth direction.

In FIG. 5, the angle θ indicates an angle formed between the inner surface of the concave portion 32 b (inclined portion 38 in FIG. 5) and the substrate surface 34 serving as a reference.
Note that the angle θ, the depth h, the width W, and the pitch P shown in FIG. 5 are synonymous with the above definitions.

  In the present invention, it is preferable that the width of the recess in the cross-sectional shape gradually decreases from the surface of the substrate toward the deepest portion of the recess. If the inner surface of the recess has such a structure, the orientation of the microdomains in the direction perpendicular to the substrate surface is further promoted from the thermodynamic viewpoint. In particular, the cross-sectional shape is preferably V-shaped, semicircular, or arcuate.

  In the present invention, the projection area A obtained by vertically projecting the inclined portion and / or the curved portion of the recess in the cross-sectional shape onto the horizontal plane and the projection area B obtained by projecting the entire recess perpendicular to the horizontal plane are (A / B) × 100 ≧ It is preferable to satisfy 20%. Especially, it is preferable to satisfy (A / B) × 100 ≧ 30%, and it is more preferable to satisfy (A / B) × 100 ≧ 40%. When the (A / B) × 100 is equal to or greater than the above range, the orientation of the microdomains obtained is more controlled.

  4 is a schematic sectional view of the recess 32a, and the lower view of FIG. 4 is a diagram in which the curved portion 36 of the recess 32a is vertically projected on a horizontal plane. A projection area A (shaded portion) obtained by vertically projecting the curved portion 36 convex in the depth direction of the recess 32a onto the horizontal plane is the same as a projection area B obtained by projecting the entire recess 32a onto the horizontal plane. That is, (A / B) × 100 = 100 (%) is calculated.

The upper diagram in FIG. 6 is a schematic sectional view of the recess 32b, and the lower diagram in FIG. 4 is a diagram in which the recess 32b is vertically projected on a horizontal plane. A projection area A obtained by vertically projecting the inclined portion 38 convex in the depth direction onto the horizontal plane in a region corresponding to the opening of the recess 32b is a hatched portion in the lower diagram of FIG. A projection area B obtained by vertically projecting the entire recess 32b onto the horizontal plane is the entire area.
As described above, it is preferable to satisfy (A / B) × 100 ≧ 20%.

If the board | substrate used by this invention satisfies the said prescription | regulation, the cross-sectional shape of a linear recessed part will not be restrict | limited in particular. For example, it may be V-shaped (zigzag) as shown in FIG. 7A, or may be wavy as shown in FIG. 7B.
In the present invention, the opening may have a structure inclined to the inside of the recess as long as the effect is not impaired.

  As a board | substrate used by this invention, what is necessary is just to satisfy said predetermined requirements, and the cross-sectional shape of a linear recessed part needs to be not a rectangle (rectangular shape). When the cross-sectional shape of the recess is short, the microdomains are not easily oriented in the thickness direction of the substrate from the thermodynamic viewpoint, and a microphase separation structure having a desired orientation structure cannot be obtained.

  The thickness of the board | substrate used by this invention is not specifically limited, It selects suitably by the relationship with the depth h of the recessed part formed. In view of easy handling, the thickness is preferably 50 μm to 1.5 mm, more preferably 50 μm to 1.2 mm.

  The board | substrate which has a predetermined recessed part used by this invention can be manufactured using a well-known lithography technique. In particular, an organic layer capable of changing the shape of the heat mode is provided on the substrate, which will be described later, because the substrate is easy to manufacture and the structure of the resulting microphase separation structure is more controlled. It is a substrate manufactured by irradiating with light and removing the organic layer of the irradiated portion, further performing dry etching of the substrate using the remaining organic layer as a mask, and then removing the remaining organic layer It is preferable.

<Polymer membrane>
The polymer films 14a and 14b of the present invention are formed on the substrate 12, and a cylindrical or lamellar phase (hereinafter also referred to as microdomain) is in the thickness direction of the substrate 12 (perpendicular to the surface of the substrate 12). A microphase-separated structure oriented in the direction is formed.
Due to the structural anisotropy of the polymer films 14a and 14b, optical anisotropy, anisotropic conductivity, thermal conduction anisotropy, ionic conduction anisotropy, and the like are imparted to the laminate.
First, the block copolymer used will be described.

<Block copolymer>
Generally, a block copolymer (block copolymer) refers to a polymer in which a plurality of types of homopolymer chains are bound as a block (component). For example, a polymer in which a polymer A chain in which a repeating structural unit is composed of an A monomer and a polymer B chain in which a repeating structural unit is composed of a B monomer are bonded to each other at the ends may be mentioned.

The block copolymer used in the present invention is composed of two or more kinds of polymers that are incompatible with each other, and may be in any form of a diblock copolymer, a triblock copolymer or a multiblock copolymer. Good. Specifically, assuming that the part consisting of polymer A and the part consisting of polymer B are respectively an A block and a B block, one A block having a structure of -A-B- and one B block bonded to each other B-type block copolymer, ABA type block copolymer in which A block is bonded to both ends of a B block having a structure of -A-B-A-, and a structure of -B-A-B- And a B-A-B type block copolymer in which a B block is bonded to both ends of the A block. _{Furthermore, - (A-B) n} - may be used a block copolymer comprising a plurality of A blocks and B blocks having that structure. Among these, from the viewpoint of easy availability and ease of synthesis, an AB type block copolymer (diblock copolymer) is preferable. The chemical bond connecting the polymers is preferably a covalent bond.

  As the polymer constituting the block copolymer used in the present invention, as a vinyl polymer, polystyrenes (for example, polystyrene, polymethylstyrene, polydimethylstyrene, polytrimethylstyrene, polyethylstyrene, polyisopropylstyrene, Polychloromethylstyrene, polymethoxystyrene, polyacetoxystyrene, polychlorostyrene, polydichlorostyrene, polybromostyrene, polytrifluoromethylstyrene), poly (meth) acrylates (eg, polymethyl methacrylate, polyethyl methacrylate) , Polybutyl methacrylate, polyisobutyl methacrylate, polyhexyl methacrylate, poly-2-ethylhexyl methacrylate, polyisodecyl methacrylate, polylauryl methacrylate, polymethacrylate Phenyl phosphate, polymethoxyethyl methacrylate, polymethyl acrylate, polyethyl acrylate, polybutyl acrylate, polyhexyl acrylate, poly-2-ethylhexyl acrylate, polyphenyl acrylate, polymethoxyethyl acrylate, polyglycidyl acrylate), polyvinyl esters (Eg, polyvinyl acetate, polyvinyl propionate, polyvinyl butyrate, polyvinyl isobutyrate, polyvinyl caproate, polyvinyl chloroacetate, polyvinyl methoxyacetate, polyvinylphenyl acetate), polyalkylenes (eg, polyethylene, polypropylene, polyisobutylene) ), Polyvinyl halides (eg, polyvinyl chloride, polyvinylidene chloride, polytet) Fluoroethylene, polyvinylidene fluoride), and the like. Examples of the diene polymer include polybutadiene and polyisoprene. Examples of ether polymers include polymethylene oxide, polyethylene oxide, polythioether, polydimethylsiloxane, and polyethersulfone. Examples of the condensed ester type polymer include poly-ε-caprolactone and polylactic acid. Examples of the condensed amide polymer include nylon 6, nylon 66, poly-m-phenylene isophthalamide, poly-p-phenylene terephthalamide, and polypyromellitimide. The combination of polymer chains constituting the block copolymer is not particularly limited as long as the polymer chains to be used are incompatible with each other. For example, vinyl polymers, vinyl polymers and diene polymers, vinyl polymers A combination of a polymer and an ether polymer, a vinyl polymer and a condensation ester polymer, or a diene polymer is preferable, and one or more vinyl polymers are preferably used. Is most preferred.

More specifically, for example, polystyrene-polymethyl methacrylate, polystyrene-polyethylene oxide, polyisoprene-poly (2-vinylpyridine), polymethylacrylate-polystyrene, polybutadiene-polystyrene, polyisoprene-polystyrene, polystyrene-poly ( 2-vinylpyridine), polystyrene-poly (4-vinylpyridine), polystyrene-polydimethylsiloxane, polybutadiene-polyethylene oxide, polystyrene-polyacrylic acid and the like.
Among them, polystyrene-polymethyl methacrylate, polystyrene-polyethylene oxide, polyisoprene-polystyrene, polystyrene-poly (2-vinylpyridine), polystyrene-poly (4-vinylpyridine) are easy to obtain and versatile. Suitable examples include block copolymers such as polybutadiene-polyethylene oxide.

In the present invention, the block copolymer preferably has a large polarity difference between the incompatible polymer block chains constituting the block copolymer. The polarity difference can be expressed numerically by, for example, a solubility parameter difference (SP value difference). The SP value can be estimated from the molecular structure, and many estimation methods such as the theoretical SP values of Small, Hoy, and Fedors have been proposed. Among them, the theoretical SP value of Fedors is an effective calculation method even for a polymer having a new structure because the parameter of the density of the polymer is unnecessary (Japan Adhesion Association Journal, vol. 22, no. 10, 564-567 (1986) etc.). In the Fedors estimation method, the bond energy and molecular kinetic energy Δei possessed by an atomic group such as atoms or polar groups constituting the polymer, the bond energy and molecular kinetic energy ΣΔei of the repeating unit constituting the polymer, and the polymer The theoretical SP value (unit: (cal / cm ³ ) ^1/2 in the following equation 3 by the occupied volume Δvi of atomic groups such as atoms or polar groups and the occupied volume ΣΔvi of the repeating unit constituting the polymer. ).
Formula (3): SP = (ΣΔei / ΣΔvi) ^1/2

For example, the theoretical SP value of polystyrene ^{14.09 (cal / cm 3) 1/2} , the theoretical SP values of polymethylmethacrylate is estimated to ^{10.55 (cal / cm 3) 1/2} . Therefore, the polarity difference (SP value difference) of the block copolymer composed of polystyrene block chains and polymethylmethacrylate block chains is 3.54 (cal / cm ³ ) ^1/2 .

The weight average molecular weight (Mw) of the block copolymer according to the present invention is appropriately selected depending on the purpose of use, but is preferably 1 × 10 ⁴ or more, particularly preferably 1 × 10 ⁴ to 1 × 10 ⁷ , 5 ×. 10 ⁴ ~1 × 10 ⁶ is more preferable. The weight average molecular weight (Mw) is a weight average molecular weight measured using GPC (gel permeation chromatography) and converted to standard polystyrene.

  The block copolymer according to the present invention preferably has a narrow molecular weight distribution. Specifically, the molecular weight distribution (Mw / Mn) represented by the weight average molecular weight (Mw) and the number weight average molecular weight (Mn) is preferably 1.00 to 1.50, preferably 1.00 More preferably, it is 1.15. When the value of Mw / Mn is within the above range, a microphase separation structure having a more uniform size can be formed.

The copolymerization ratio of the block copolymer according to the present invention is appropriately selected so that a cylindrical or lamellar microphase separation structure can be obtained by the polymer films 14a and 14b.
For example, a diblock copolymer (A-B type) or a triblock copolymer (A-B-A type) having a cylindrical microphase separation structure as shown in FIG. 1 constitutes the copolymer. Ratio of polymer A to polymer B (polymer A / polymer B) = 0.9 / 0.1 to 0.65 / 0.35 (volume ratio) or 0.35 / 0.65 to 0.1 / 0 .9 (volume ratio) is preferable, and more preferably 0.8 / 0.2 to 0.7 / 0.3 (volume ratio) or 0.3 / 0.7 to 0.2 / 0.8 (volume) Ratio). Within the above range, a more ordered cylindrical microphase separation structure can be obtained.
In the case of a lamellar microphase separation structure as shown in FIG. 2, the ratio of polymer A to polymer B constituting the copolymer (polymer A / polymer B) = 0.65 / 0.35 to 0.35. /0.65 (volume ratio) is preferable, and 0.6 / 0.4 to 0.4 / 0.6 (volume ratio) is more preferable. Within the above range, a more ordered lamellar microphase separation structure can be obtained.

  The block copolymer according to the present invention can be synthesized by a known method. Moreover, you may use a commercial item.

<Micro phase separation structure>
The polymer films 14a and 14b form a microphase separation structure in which cylindrical or lamellar phases (hereinafter also referred to as microdomains) are oriented in the thickness direction of the substrate 12 (perpendicular to the substrate 12). As described above, FIG. 1 shows a perspective sectional view of a structure having a cylindrical microphase separation structure obtained by using a diblock copolymer (polymer A and polymer B are bonded at the ends). The cylindrical microphase separation structure refers to a structure in which one separated phase has a cylindrical structure.
As shown in FIG. 1, the polymer film 14 a has a microphase separation structure composed of a continuous phase 20 and cylindrical microdomains 22 distributed in the continuous phase 20, and is disposed on the surface of the substrate 12. Yes. The continuous phase 20 and the cylindrical microdomain 22 are formed from a polymer A and a polymer B constituting a block copolymer, respectively. The cylindrical microdomains 22 are distributed in the continuous phase 20 and oriented in the Z-axis direction in FIG. 1A, which is the thickness direction of the substrate 12 (the direction perpendicular to the surface of the substrate 12). That is, the longitudinal direction (center axis) of the cylindrical microdomain 22 is arranged substantially in parallel with the thickness direction of the polymer film 14a.
As shown in FIG. 1B, the cylindrical microdomains 22 preferably have a staggered arrangement on the horizontal plane of the film (XY plane in the figure), and form a regular arrangement pattern so as to have a hexagonal lattice shape in particular. It is preferable. Here, the hexagonal lattice shape means that an angle θ formed by one microdomain and two adjacent microdomains is approximately 60 degrees (approximately 60 degrees is 50 to 70 degrees, preferably 55 to 65 degrees). A structure that becomes
In addition, although the regular arrangement | sequence pattern illustrated what took the hexagonal lattice shape, it is not limited to this, For example, a square arrangement | sequence may be taken. Further, the present invention is not limited to the case of having a regular arrangement pattern, and includes the case of an irregular arrangement pattern.

The size (diameter) of the cylindrical microdomain 22 can be appropriately controlled by the molecular weight of the block copolymer to be used, and is preferably 5 to 200 nm, more preferably 10 to 100 nm. In the case of an ellipse or the like, the major axis may be in the above range.
The distance between adjacent microdomains (distance between central axes) can be appropriately controlled depending on the molecular weight of the block copolymer to be used, and is preferably 5 to 300 nm, more preferably 10 to 150 nm. The size of the microdomains and the distance between the microdomains can be measured by observation with an atomic force microscope.
The term microdomain is generally used to represent a domain in a multi-block copolymer and does not define the size of the domain.

  The cylindrical microdomain 22 is oriented in the thickness direction of the substrate 12 (perpendicular to the surface of the substrate 12), and is preferably substantially parallel. Specifically, “substantially parallel” means that the inclination angle of the central axis of the cylindrical microdomain 32 with respect to the thickness direction of the substrate 12 is within ± 45 degrees, preferably within ± 30 degrees. The tilt angle can be measured by TEM analysis of ultrathin sections, small-angle X-ray scattering analysis, or the like.

As described above, FIG. 2 shows a perspective sectional view of a structure having a lamellar microphase separation structure obtained by using a diblock copolymer (polymer A and polymer B are bonded at the ends). The lamellar microphase separation structure refers to a structure composed of lamellar (plate-like) phases. As shown in FIG. 2, in the polymer film 14b, lamellar (plate-like) phases are alternately arranged. Each of the lamellar phases 24 and 26 is formed of polymer A and polymer B constituting the block copolymer. The lamellar phase is oriented in the Z-axis direction in FIG. 2A, which is the thickness direction of the substrate 12 (the direction perpendicular to the surface of the substrate 12). That is, the interfaces between the lamellar phases 24 and 26 are arranged substantially in parallel with the thickness direction of the substrate 12.
Further, as shown in FIG. 2, the lamellar phases 24 and 26 are adjacent to each other and parallel to the direction in which the linear recesses on the substrate extend (the direction orthogonal to the direction in which the linear recesses are arranged). It is preferable that they are arranged. That is, the interface between the lamellar phases is arranged in parallel to the direction in which the linear concave portion (groove portion) extends.

  The widths of the lamellar phases 24 and 26 can be appropriately controlled depending on the molecular weight of the block copolymer to be used, and are preferably 5 to 200 nm, more preferably 10 to 100 nm. The width of the lamellar phase can be measured by observation with an atomic force microscope or the like.

  The lamellar phases 24 and 26 are oriented in the thickness direction of the substrate 12 (perpendicular to the surface of the substrate 12), and are preferably substantially parallel. Specifically, “substantially parallel” means that the inclination angle formed by the interface between the lamellar phases with respect to the thickness direction of the substrate 12 is within ± 45 degrees, preferably within ± 30 degrees. The angle can be measured by TEM analysis of ultrathin sections, small-angle X-ray scattering analysis, or the like.

  The polymer films 14a and 14b of the present invention are not limited to the case where the entire layer has a regular arrangement pattern, and may include an irregular arrangement pattern in part.

The thickness T from the bottom of the concave portions of the polymer films 14a and 14b to the surface of the polymer film can be appropriately controlled by changing the concentration of the block copolymer used, but is preferably 10 to 1200 nm, 50 -1200 nm is more preferable. If it is in the said range, the regularity of the obtained micro phase-separation structure will improve more.
The method for measuring the film thickness is a value obtained by measuring three or more arbitrary points using a known profiler device (manufactured by KLA-Teknor) and number-average.

The thickness T of the polymer films 14a and 14b preferably satisfies the relationship of the following formula (1) with the above-described depth h of the recess on the substrate.
T ≦ 1.2 × h Formula (1)
As long as the thickness T of the polymer films 14a and 14b is within the above range, a more well-structured microphase separation structure can be produced.
In addition, it is more preferable that the thickness T and the depth h of the recess satisfy the relationship of the following formula (2).
T ≦ 1.0 × h Formula (2)

<Laminated body>
The laminate of the present invention includes the substrate having the above-described predetermined structure and a polymer film having a predetermined microphase separation structure. This laminate can be expanded to a wide range of fields and applications. Examples include photomask, anisotropic conductive film, anisotropic ion conductive film, photonic crystal, retardation film, polarizing film, screen, color filter, display member, photoelectric conversion element, nanoimprint mold, magnetic recording medium , Acoustic vibration materials, sound absorbing materials, vibration damping materials, and the like. In particular, application to photomasks, anisotropic conductive films, anisotropic ion conductive films, photonic crystals, retardation films, and polarizing films is expected.

<Method for producing laminate>
The production method of the laminate of the present invention is not particularly limited, but can be produced by the following steps in that it can be produced in a short time and at a low cost, and the resulting microphase separation structure is more controlled. preferable.
(Light Irradiation Process) A process of removing an organic layer in an irradiated portion by providing an organic layer capable of changing the shape of a heat mode on a substrate, irradiating light condensed on the organic layer in a stripe shape (etching process process) ) Using the remaining organic layer as a mask, the substrate is etched, and then the organic layer remaining on the substrate is removed to thereby have a plurality of linear recesses arranged parallel to each other with respect to the substrate surface. In the cross-sectional shape of the linear recess, the recess has a convex inclined portion or a curved portion in the depth direction, and an angle formed between the inner surface of the recess and the surface that is the reference surface is less than 90 °. Step of manufacturing (film forming step) On the substrate obtained in the removing step, a solution containing a block copolymer formed by bonding two or more kinds of incompatible polymer chains is applied and dried, Cylindrical or lamellar The process described above for each step of producing a polymer film having a microphase-separated structure black domains are oriented in the thickness direction of the substrate, according to FIG. 8, will be described below.

<Light irradiation process>
The light irradiation process is a process of providing an organic layer capable of changing the shape of the heat mode on the substrate, irradiating the condensed light on the organic layer in a stripe shape, and removing the organic layer of the irradiation part. By this step, an organic layer 52 having a plurality of linear recesses 54 is formed on the surface of the substrate 50 as shown in FIG. The organic layer 52 serves as a mask in the etching process described later.
The materials and procedures used in this step are described in detail below.

<Organic layer>
The organic layer capable of changing the shape in the heat mode is not particularly limited as long as it is a layer in which light is converted into heat by irradiation of strong light and the material can change its shape by this heat to form a recess. For example, a layer containing a dye such as cyanine-based, phthalocyanine-based, quinone-based, squarylium-based, azulenium-based, thiol complex-based, or merocyanine-based can be used.
Examples of suitable dyes include, for example, methine dyes (cyanine dyes, hemicyanine dyes, styryl dyes, oxonol dyes, merocyanine dyes, etc.), macrocyclic dyes (phthalocyanine dyes, naphthalocyanine dyes, porphyrin dyes, etc.), azo dyes (azo dyes) Metal chelate dyes), arylidene dyes, complex dyes, coumarin dyes, azole derivatives, triazine derivatives, 1-aminobutadiene derivatives, cinnamic acid derivatives, quinophthalone dyes, and the like. Among these, methine dyes and azo dyes are particularly preferable. As the methine dye, a cyanine dye and an oxonol dye are particularly preferable.

In addition, the organic layer can select a pigment | dye suitably according to the wavelength of a laser light source, or can modify | change a structure.
For example, when the oscillation wavelength of the laser light source is around 780 nm, it is advantageous to select from pentamethine cyanine dye, heptamethine oxonol dye, pentamethine oxonol dye, phthalocyanine dye, naphthalocyanine dye, and the like.
When the oscillation wavelength of the laser light source is around 660 nm, it is advantageous to select from trimethine cyanine dye, pentamethine oxonol dye, azo dye, azo metal complex dye, pyromethene complex dye, and the like.
Further, when the oscillation wavelength of the laser light source is around 405 nm, monomethine cyanine dye, monomethine oxonol dye, zero methine merocyanine dye, phthalocyanine dye, azo dye, azo metal complex dye, porphyrin dye, arylidene dye, complex It is advantageous to select from dyes, coumarin dyes, azole derivatives, triazine derivatives, benzotriazole derivatives, 1-aminobutadiene derivatives, quinophthalone dyes, and the like.

In the following, examples of compounds preferable as the organic layer are given in the case where the oscillation wavelength of the laser light source is around 405 nm. The compounds represented by the following III-1 to III-14 are compounds when the oscillation wavelength of the laser light source is around 405 nm.
In addition, when the oscillation wavelength of the laser light source is around 780 nm, preferred compounds in the case of around 660 nm include the compounds described in paragraphs [0024] to [0028] of JP-A-2008-252056. It is done. In addition, this invention is not limited to the case where these compounds are used.

  JP-A-4-74690, JP-A-8-127174, JP-A-11-53758, JP-A-11-334204, JP-A-11-334205, JP-A-11-334206, The dyes described in JP-A-11-334207, JP-A-2000-43423, JP-A-2000-108513, JP-A-2000-158818, and the like are also preferably used.

Such a dye-type organic layer is prepared by dissolving a dye in a suitable solvent together with a binder or the like to prepare a coating solution, and then coating the coating solution on a substrate to form a coating film. It can be formed by drying. In that case, it is preferable that the temperature of the board | substrate surface which apply | coats a coating liquid is the range of 10-40 degreeC. The lower limit is more preferably 15 ° C. or higher, still more preferably 20 ° C. or higher, and particularly preferably 23 ° C. or higher. Moreover, as an upper limit, it is more preferable that it is 35 degrees C or less, It is still more preferable that it is 30 degrees C or less, It is especially preferable that it is 27 degrees C or less. Thus, when the coated surface temperature is within the above range, it is possible to prevent the occurrence of coating unevenness and coating failure and to make the thickness of the coating film uniform. Each of the upper limit value and the lower limit value can be arbitrarily combined.
Here, the organic layer may be a single layer or a multilayer. In the case of a multilayer structure, the organic layer is formed by performing the coating process a plurality of times.

  The concentration of the dye in the coating solution is preferably 0.3 to 30% by mass with respect to the organic solvent, more preferably 1 to 20% by mass, and 1 to 20% by mass in tetrafluoropropanol. It is particularly preferred to dissolve in

There is no restriction | limiting in particular as a solvent of a coating liquid, According to the objective, it can select suitably. For example, esters such as butyl acetate, ethyl lactate and cellosolve acetate; ketones such as methyl ethyl ketone, cyclohexanone and methyl isobutyl ketone; chlorinated hydrocarbons such as dichloromethane, 1,2-dichloroethane and chloroform; amides such as dimethylformamide; Hydrocarbons such as tetrahydrofuran, ethyl ether and dioxane; alcohols such as ethanol, n-propanol, isopropanol and n-butanol diacetone alcohol; fluorine-based solvents such as 2,2,3,3-tetrafluoropropanol; ethylene And glycol ethers such as glycol monomethyl ether, ethylene glycol monoethyl ether, and propylene glycol monomethyl ether. Among these, butyl acetate, ethyl lactate, cellosolve acetate, methyl ethyl ketone, isopropanol, and 2,2,3,3-tetrafluoropropanol are particularly preferable.
Solvents can be used alone or in combination of two or more in consideration of the solubility of the dye used. In the coating solution, various additives such as an antioxidant, a UV absorber, a plasticizer, and a lubricant may be added according to the purpose.

When the coating solution contains a binder, the binder is not particularly limited and can be appropriately selected depending on the purpose. For example, natural organic polymer materials such as gelatin, cellulose derivatives, dextran, rosin, rubber; hydrocarbon resins such as polyethylene, polypropylene, polystyrene, polyisobutylene, polyvinyl chloride, polyvinylidene chloride, polyvinyl chloride / polyvinyl acetate Of vinyl resins such as copolymers, acrylic resins such as polymethyl acrylate and polymethyl methacrylate, polyvinyl alcohol, chlorinated polyethylene, epoxy resins, butyral resins, rubber derivatives, and thermosetting resins such as phenol / formaldehyde resins And synthetic organic polymers such as initial condensates.
When a binder is used as a material for the organic layer, the amount of the binder used is generally preferably 0.01 to 50 times (mass ratio) with respect to the dye, and 0.1 to 5 times the amount. (Mass ratio) is more preferable.

The organic layer can contain various anti-fading agents in order to improve the light resistance of the organic layer.
As the antifading agent, a singlet oxygen quencher is generally used. As the singlet oxygen quencher, those described in publications such as known patent specifications can be used.
Specific examples thereof include JP-A Nos. 58-175893, 59-81194, 60-18387, 60-19586, 60-19587, and 60-35054. 60-36190, 60-36191, 60-44554, 60-44555, 60-44389, 60-44390, 60-54892, JP-A-60-47069, JP-A-63-209995, JP-A-4-25492, JP-B-1-38680, JP-A-6-26028, etc., German Patent No. 350399, Journal of the Chemical Society of Japan Examples include those described in the October 1992 issue, page 1141 and the like.
The amount of the anti-fading agent such as a singlet oxygen quencher is preferably in the range of 0.1 to 50% by mass, more preferably in the range of 0.5 to 45% by mass, based on the amount of the dye, 3 to 40 The range of mass% is more preferable, and the range of 5 to 25 mass% is particularly preferable.

Examples of the application method of the solution include a spray method, a spin coating method, a dip method, a roll coating method, a blade coating method, a doctor roll method, a doctor blade method, and a screen printing method. In addition, it is preferable to employ the spin coating method in terms of excellent productivity and easy control of the film thickness.
The dye preferably has a thermal decomposition temperature of 150 ° C. or higher and 500 ° C. or lower, and more preferably 200 ° C. or higher and 400 ° C. or lower.
During coating, the temperature of the coating solution is preferably 23 ° C to 50 ° C, more preferably 24 ° C to 40 ° C, and further preferably 25 ° C to 30 ° C.

  Although the organic layer solvent coating method has been described above, the organic layer can also be formed by a film forming method such as vapor deposition, sputtering, or CVD.

In addition, the pigment | dye has a higher light absorption rate in the wavelength of the laser beam used for the process of the recessed part 54 than other wavelengths.
The wavelength of the absorption peak of the dye is not necessarily limited to that in the visible light wavelength range, and may be in the ultraviolet range or the infrared range.

The wavelength λw for forming the recess 54 with the laser is preferably in a relationship of λa <λw. In such a relationship, the light absorption amount of the dye is appropriate, the recording efficiency is increased, and a clean uneven shape may be formed in some cases.
In addition, λa represents the peak wavelength of light absorption of the dye material, and λw represents the wavelength of the laser beam when the recess 54 is formed.

  Note that the wavelength λw of the laser light for forming the recess 54 may be a wavelength that provides a large laser power. For example, when a dye is used for the organic layer, 193 nm, 210 nm, 266 nm, 365 nm, 405 nm, 488 nm 1,000 nm or less is preferable, such as 532 nm, 633 nm, 650 nm, 680 nm, 780 nm, and 830 nm.

  The laser beam may be any laser such as a gas laser, a solid laser, or a semiconductor laser. However, in order to simplify the optical system, it is preferable to employ a solid laser or a semiconductor laser. The laser light may be continuous light or pulsed light, but it is preferable to employ laser light whose emission interval can be freely changed. For example, it is preferable to employ a semiconductor laser. When the laser cannot be directly on / off modulated, it is preferable to modulate with an external modulation element.

  Further, the laser power is preferably higher in order to increase the processing speed. However, as the laser power is increased, the scanning speed (speed at which the organic layer is scanned with laser light) must be increased. Therefore, the upper limit value of the laser power is preferably 100 W in consideration of the upper limit value of the scanning speed, more preferably 10 W, still more preferably 5 W, and particularly preferably 1 W. The lower limit of the laser power is preferably 0.1 mW, more preferably 0.5 mW, and even more preferably 1 mW.

  Further, the laser light is preferably light that has excellent transmission wavelength width and coherency, and can be narrowed down to a spot size equivalent to the wavelength. In addition, it is preferable to adopt a strategy such as that used in optical discs as the light pulse irradiation conditions for properly forming the recesses. That is, it is preferable to adopt conditions such as recording speed, the peak value of the irradiated laser beam, and the pulse width as used in an optical disc.

The irradiation region of the above-mentioned laser beam or the like on the organic layer is irradiated in a stripe shape over the entire substrate so that an organic layer 52 having linear recesses 54 arranged in parallel to each other is formed.
The width of the recess 54 produced by the above procedure is appropriately selected according to the region on the substrate to be etched in the etching process described later.

The thickness of the organic layer 52 is preferably made to correspond to the depth of a recess formed on the substrate surface described later.
This thickness can be appropriately set within a range of 1 nm to 10,000 nm, for example, and the lower limit of the thickness is preferably 10 nm or more, and more preferably 30 nm or more. If the thickness is too thin, the recesses on the substrate are formed shallow, and the regularity of the resulting microphase separation structure may be inferior. Further, the upper limit of the thickness is preferably 1,000 nm or less, and more preferably 500 nm or less. If the thickness is too thick, a large laser power is required, it may be difficult to form a deep hole on the substrate, and the processing speed may be reduced.

The principle of forming the recess 54 is as follows.
When the organic layer is irradiated with laser light having a wavelength at which the material absorbs light (wavelength absorbed by the material), the laser light is absorbed by the organic layer, and the absorbed light is converted into heat. Temperature rises. As a result, the organic layer undergoes chemical or / and physical changes such as softening, liquefaction, vaporization, sublimation, and decomposition. And the recessed part 54 is formed when the material which caused such a change moves or / and lose | disappears.

  Further, the transition temperature of chemical and / or physical changes such as softening, liquefaction, vaporization, sublimation, and decomposition has an upper limit value of preferably 2,000 ° C. or lower, more preferably 1,000 ° C. or lower. Preferably, it is 500 degrees C or less. If the transition temperature is too high, a large laser power may be required. Further, the lower limit of the transition temperature is preferably 50 ° C. or higher, more preferably 100 ° C. or higher, and further preferably 150 ° C. or higher. If the transition temperature is too low, the temperature gradient with respect to the surroundings is small, so that it may not be possible to form a clear hole edge shape.

<Etching process>
In the etching process, the substrate having the organic layer obtained in the light irradiation process is subjected to a dry etching process, the organic layer remaining on the substrate is removed, and a plurality of linear arrays arranged in parallel to each other on the substrate surface This is a process for manufacturing a substrate having a recess. As shown in FIG. 8B, a substrate 30a having a continuous linear recess 32a is formed through this step. In addition, although the board | substrate 30a in which the recessed part was formed in the curved part (arc shape) is illustrated here, this invention is not necessarily limited to this.

The etching conditions are not particularly limited as long as the substrate can be etched, and optimum processing is performed according to the type of the substrate. For example, wet etching in which corrosion is performed with a chemical solution such as sulfuric acid, nitric acid, phosphoric acid, or hydrofluoric acid, or dry etching such as reactive ion etching or reactive gas etching may be used. Among these, dry etching is preferable because the etching amount can be easily controlled. Note that the etching gas may be selected as appropriate depending on the substrate, and may be performed using a fluorine-based etching gas such as CF ₄ , NF ₃ , or SF ₆ , or a chlorine-based etching gas such as Cl ₂ or BCl ₃ .
The etching processing time can be appropriately adjusted according to the use of the substrate, but is preferably 5 to 300 seconds, more preferably 10 to 200 seconds, in terms of easier control of the etching amount.

  After the etching process, the organic layer remaining on the substrate is removed. The method of removing is not particularly limited, and examples thereof include a method of treating with a solvent in which the remaining organic film is dissolved and a method of removing by etching.

  The obtained substrate 30a having linear recesses is as defined above.

<Film formation process>
In the film formation step, a solution containing a block copolymer in which two or more incompatible polymer chains are bonded to each other is applied onto the substrate obtained in the above-described removal step, and dried to form a cylinder. Alternatively, it is a step of producing a polymer film having a microphase separation structure in which lamellar microdomains are oriented in the thickness direction of the substrate. As shown in FIG. 8 (c), a lamellar microdomain has a microphase separation structure in which the lamellar microdomain is oriented substantially parallel to the thickness direction of the substrate (perpendicular to the substrate surface) in the recess of the substrate 30a. A polymer film 14b is formed. Note that a cylindrical microdomain may be formed instead of the lamellar microdomain.

The solvent used in preparing the solution containing the block copolymer may be appropriately selected depending on the types of both polymers, as long as the block copolymer is dissolved. For example, toluene, chloroform, dichloromethane, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran, 1,4-dioxane, acetone, diethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, isopropanol, ethanol, methanol, hexane, octane, tetradecane, cyclohexane, Examples include cyclohexanenone, acetic acid, ethyl acetate, methyl acetate, pyridine, N-methyl-pyrrolidone, and water. Of these, toluene, chloroform, dichloromethane, dimethylformamide, and methyl ethyl ketone are preferable.
The concentration of the block copolymer in the solution is preferably 0.10 to 20.0% by mass, and more preferably 0.25 to 15.0% by mass. If it is in the said range, it will be easy to handle at the time of application | coating, and a uniform film | membrane will be easy to be obtained.

The method for applying the solution onto the substrate is not particularly limited, and is a spin coating method, a solvent casting method, a dip coating method, a roll coating method, a curtain coating method, a slide method, an extrusion method, a bar method, a gravure method. A general coating method such as the above can be employed, and a spin coating method is preferred from the viewpoint of productivity. The conditions for the spin coating method are appropriately selected depending on the block copolymer used. You may provide a drying process after application | coating as needed.
The drying conditions for removing the solvent are appropriately selected according to the substrate to be applied, the block copolymer to be used, etc., but the treatment is carried out at a temperature of 20 to 200 ° C. for 0.5 to 336 hours. Preferably it is done. A particularly preferable temperature is preferably 20 to 180 ° C, and more preferably 20 to 160 ° C. The drying process may be performed in several steps. This drying treatment is particularly preferably performed under a nitrogen atmosphere, under low-concentration oxygen, or at atmospheric pressure of 10 torr or less.

  After the film formation step, a process (heating step) for heating the structure (laminated body) obtained in the film formation step may be performed as necessary. The heating temperature and time are appropriately set according to the block copolymer to be used and the layer thickness. In general, heating is performed at a temperature equal to or higher than the glass transition temperature of the block copolymer. The heating temperature is usually 60 to 300 ° C., but 80 to 270 ° C. is preferable in consideration of the glass transition temperature of the monomer units constituting the block copolymer. The heating time is suitably 1 minute or longer, preferably 10 to 1440 minutes. In order to prevent oxidative deterioration of the block copolymer film due to heating, it is preferable to perform heating in an inert atmosphere or vacuum.

  After completion of the film formation process, a treatment (solvent treatment process) in which the structure (laminated body) obtained in the film formation process is exposed to a vapor atmosphere of an organic solvent may be performed as necessary. The organic solvent to be used is appropriately selected depending on the block copolymer used, but benzene, toluene, xylene, acetone, methyl ethyl ketone, chloroform, methylene chloride, tetrahydrofuran, dioxane, hexane, octane, methanol, ethanol, acetic acid. , Ethyl acetate, diethyl ether, carbon disulfide, dimethylformamide, dimethylacetamide and the like. Toluene, xylene, acetone, methyl ethyl ketone, chloroform, tetrahydrofuran, and dioxane are preferable, and toluene, methyl ethyl ketone, chloroform, and dioxane are more preferable.

In the present invention, a polymer film having a microphase separation structure in which microdomains are oriented in the thickness direction of the substrate can be easily produced by using a substrate having a predetermined linear recess. In the prior art, it is necessary to produce a predetermined surface layer or the like on the substrate. However, in the present application, it is not particularly necessary to provide such an intermediate layer. Therefore, it is excellent in cost and can be applied to a simpler manufacturing process such as a roll-to-roll method, and its industrial value is very high.
For example, when the polymer film has a lamellar phase separation structure, the lamellar phases are arranged adjacent to each other in parallel with the direction in which the linear recesses of the substrate extend. Thus, in the present invention, it is possible to control the orientation of microdomains not only in the thickness direction of the substrate but also in the horizontal direction of the substrate.

  Examples of the present invention will be described below, but the present invention is not limited to the following examples.

  In the following examples, atomic force microscope (AFM) observation was performed with SPA-400 manufactured by Seiko Instruments, and surface roughness and the like described later were measured. Scanning transmission electron microscope (STEM) observation was carried out with HD-2300 manufactured by Hitachi High-Tech.

<Example 1>
Using a silicon wafer, a solution obtained by dissolving 45 mg of an oxonol organic compound represented by the following structural formula in 1 ml of 2,2,3,3-tetrafluoro-1-propanol was rotated on the silicon wafer using a spin coater. It was applied at several 300 rpm, and then dried at 1,000 rpm to form an organic layer having a thickness of 220 nm.

Next, laser irradiation was performed on the organic layer on the substrate in a stripe shape having a width of 500 nm at 5 m / s and 5 mW using NEO1000 (manufactured by Pulstec Industrial Co., Ltd.). Thereby, the board | substrate which has an organic layer in which the linear recessed part was formed in the surface was obtained.
Next, the obtained substrate having an organic layer was etched with an RIE dry etching apparatus. The processing conditions were: etching gas: SF ₆ , output: 150 W, etching time: 32 seconds. After the treatment, the obtained sample was immersed in toluene and subjected to ultrasonic cleaning, whereby the organic layer was removed and a substrate having a recess on the surface was produced.
FIG. 9 shows an electron micrograph of the substrate having a recess formed on the surface. The cross-sectional shape of the linear recess is formed by a curved line (arc shape), the depth of the recess is 120 nm, the width of the opening is about 500 nm, and the shortest distance (pitch) between the centers of adjacent recesses is 500 nm. there were. The angle formed between the inner surface of the concave portion (tangent at an arbitrary point of the curved portion) and the substrate surface serving as the reference surface was 0 to 50 °, and the curvature radius of the concave portion was 330 nm. The relationship [(A / B) × 100] between the projection area A obtained by vertically projecting the curved portion of the concave portion on the horizontal plane and the projected area B obtained by projecting the entire concave portion perpendicularly on the horizontal plane was 100%.

  Next, PS-b-PMMA (Mw (PS) = 37,000, Mw (PMMA) = 37,000) (Polymer Source) 1.0 wt% toluene solution was spin-coated (1500 rpm, 30) on the substrate. Second). After spin coating, the polymer film (100 nm thickness from the bottom of the substrate recess to the surface of the polymer film) was produced by annealing at 200 ° C. for 5 hours in a vacuum dryer. This is designated as sample A. A surface AFM image of Sample A is shown in FIG. 10 and TEM observation of the structure in the layer thickness direction confirmed that a vertical lamellar phase separation structure in which lamellar microdomains were oriented in the thickness direction of the substrate was formed in the polymer film.

10a, 10b Laminates 12, 30a, 30b, 30c, 30d Substrates 14a, 14b having recesses Polymer film 20 Continuous phase 22 Cylindrical microdomain 24 Lamellar phase (polymer A chain)
26 Lamella phase (polymer B chain)
32a, 32b Linear concave part 34 Surface 36 Curved part 38 Inclined part 40 Bottom part 50 Substrate 52 Organic layer 54 Concave part (in organic layer)

Claims (10)

A substrate having a plurality of linear recesses arranged in parallel to each other on the basis of the surface and a microphase separation structure including a cylindrical or lamellar microdomain formed on the substrate. A laminate comprising a molecular film,
In the cross-sectional shape of the linear recess, the recess has a sloped or curved portion that is convex in the depth direction,
An angle formed between the inner surface of the recess and the substrate surface as a reference surface is less than 90 °,
A laminate having the cylindrical or lamellar microdomains oriented in the thickness direction of the substrate.   The laminate according to claim 1, wherein in the cross-sectional shape of the linear recess, the width of the recess decreases from the surface of the substrate toward the deepest portion of the recess.   The laminated body according to claim 1 or 2, wherein in the cross-sectional shape of the linear concave portion, the concave portion is formed from a convex curved portion. The laminate according to any one of claims 1 to 3, wherein the thickness T from the bottom of the recess to the surface of the polymer film satisfies the following relationship when the depth of the recess is h.
T ≦ 1.2 × h Formula (1)   The laminated body in any one of Claims 1-4 whose depth h of the said linear recessed part is 20 nm-1000 nm.   The laminated body in any one of Claims 1-5 whose width W of the opening part of the said linear recessed part is 20 nm-1000 nm.   The substrate is provided with an organic layer capable of changing the shape of the heat mode on the substrate, and the organic layer in the irradiated portion is removed by irradiating the condensed light on the organic layer, and the remaining organic layer is used as a mask. The laminate according to any one of claims 1 to 6, which is a substrate manufactured by subjecting the substrate to an etching treatment and then removing the remaining organic layer. A step of providing an organic layer capable of changing the shape of the heat mode on the substrate, irradiating the condensed light on the organic layer in a stripe shape, and removing the organic layer of the irradiation part;
Using the remaining organic layer as a mask, the substrate is etched, and then the organic layer remaining on the substrate is removed to thereby have a plurality of linear recesses arranged parallel to each other with respect to the substrate surface. In the cross-sectional shape of the linear concave portion, the concave portion has a convex inclined portion or a curved portion in the depth direction, and an angle formed between the inner surface of the concave portion and the surface that is a reference surface is less than 90 °. Manufacturing a substrate;
A solution containing a block copolymer in which two or more kinds of incompatible polymer chains are bonded to each other is applied to the obtained substrate and dried to form a cylindrical or lamellar microdomain on the substrate. The manufacturing method of a laminated body provided with a polymer film provided with the process of manufacturing the polymer film which has the micro phase-separation structure orientated in the thickness direction of this.   The method for producing a polymer film according to claim 8, wherein in the cross-sectional shape of the linear recess, the width of the recess decreases from the surface of the substrate toward the deepest portion of the recess.   The manufacturing method of a laminated body provided with the polymer film of Claim 8 or 9 with which a recessed part is formed from a convex curved part in the cross-sectional shape of the said linear recessed part.