JP2010058403A - Polymer film and laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymer film showing excellent production suitability, durability and adhesiveness to the substrate and having a fine structural pattern, a laminate having the polymer film and methods of manufacturing the polymer film and the laminate. <P>SOLUTION: The method of manufacturing the polymer film includes: a film formation process of forming a polymer film by bringing two or more polymers including one or moer polymer having radical-polymerizable groups into contact with the surface of a substrate capable of generating a radical on exposure to light to form a polymer film having a phase-separated structure on the surface of the substrate; a fixing process of exposing the polymer film formed by the film forming process to light so as to fix the polymer film to the substrate; and a cleaning process of cleaning the polymer film obtained by the fixing process with a solvent. The polymer film obtained by the manufacturing method, and bound directly to the surface of the substrate is also provided. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a polymer film and a laminate. More specifically, the present invention relates to a laminate including a polymer film formed by being directly bonded to a substrate surface capable of generating radicals upon exposure.

  In recent years, with active research and development of new materials having advanced functions and superior performance, interest in thin films having a fine pattern structure has increased along with the miniaturization and miniaturization of materials. In particular, a thin film having a fine pattern structure whose structure is controlled at the nanometer to micrometer level is expected to exhibit properties different from those of ordinary materials, and various advanced technologies such as the electronics field, environmental field, and life science field. It is positioned as one of the important materials in the field. For example, such a thin film is expected to be applied as a template that contributes to the orientation control of the material laminated on the thin film.

Currently, several pattern forming methods using a self-organized phase separation structure have been proposed as methods for forming a fine pattern structure that can be realized at a lower cost and with higher throughput.
Typical examples of a method for manufacturing a thin film having a fine pattern include an LB (Langmuir-Blodget) method (Non-Patent Documents 1 and 2) and a spin coating method (Non-Patent Documents 3 to 5). More specifically, in Non-Patent Document 1, for the purpose of producing a patterned template, a monomolecular film having a phase separation structure is produced by the LB method using two types of amphiphilic compounds. . In Non-Patent Document 3, a thin film having a microphase separation structure is produced on a substrate by spin coating using polyurethane.
On the other hand, as another method for producing a thin film, a method has been proposed in which a sensitizer is used to produce a graft polymer film directly bonded to a substrate on the substrate by exposure (Patent Document 1).

A. Takahara, et. Al. “Scanning force microscopic studies of surface structure and protein adsorption behavior of organosilane monolayers”, J. Vac. Sci. Technol. A, 1996, Vol.14, pp.1747. M. Matsumoto, et. Al. “Template-Directed Patterning Using Phase-Separated Langmuir-Blodgett Films”, Langmuir, 2004, Vol.20, pp.8728. Ken Shioshio, “Microphase separation structure of polar polymer under ultrathin film”, Polymer Journal, August 2007, Vol.64, No. 8, pp.498-503. M. Boltau, et. Al. “Surface-induced structure formation of polymer blends on patterned substrates”, Nature, 1998, Vol.39, pp.877. L. Chi, et. Al. “Tunable ordered droplets induced by convection in phase-separating P2VP / PS blend film”, Polymer, 2004, Vol.45, pp.8139. JP 2006-350307 A

However, although it is possible to produce a nanometer-level thin film using the LB method as in Non-Patent Document 1 or 2, the LB method is difficult to manufacture in a large area, and is not necessarily in terms of industriality and productivity. It was not satisfactory. Moreover, the compound which can be applied was limited and the versatility as a manufacturing method was scarce. For example, a polymer applicable to the LB method is limited to a polymer having a specific structure that is precisely designed and has a substituent such as a polar group, a hydrophilic group, and an ionic group.
Furthermore, since the thin film obtained by the spin coat method described in Non-Patent Documents 3 to 5 or the above LB method does not have sufficient adhesion to the substrate, it can be subjected to physical action such as friction or chemical treatment such as a solvent. There was a problem that it was easily peeled off from the substrate.

  On the other hand, Patent Document 1 discloses a graft polymer directly bonded on a substrate, but does not mention any thin film having a phase separation structure. In general, the phase separation structure of a polymer largely depends on the type of polymer used, and sufficient information has not been obtained yet.

  Accordingly, in view of the above circumstances, the present invention provides a polymer film having a fine structure pattern excellent in manufacturing suitability, durability, and adhesion to a substrate, a laminate having the polymer film, and a polymer film and a laminate. It aims at providing the manufacturing method of a body.

  The inventors pay attention to the structure and properties of the polymer used, and use a polymer having a predetermined structure to provide a polymer film that is directly bonded to the substrate and has a fine structure pattern. It has been found that a laminate can be obtained with good reproducibility, and 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 <14> configurations.
<1> Two or more kinds of polymers containing at least one kind of polymer having a radical polymerizable group are brought into contact with a substrate surface capable of generating radicals upon exposure to have a phase separation structure on the substrate surface. A film forming step of forming a polymer film;
An immobilization step of exposing the polymer film formed in the film formation step and immobilizing the polymer film on the substrate;
A polymer film directly bonded to the substrate surface, obtained by a method comprising a washing step of washing the polymer membrane obtained in the immobilization step with a solvent.
<2> The polymer film according to <1>, wherein the polymer film directly bonded to the substrate surface has a thickness of 0.5 to 100 nm.
<3> The polymer film according to <1> or <2>, wherein the polymer having a radical polymerizable group is a polymer having a siloxane group or a fluorine-containing group and having a radical polymerizable group.
<4> The repeating unit represented by the general formula (1) and the repeating unit represented by the general formula (2), wherein the polymer having a siloxane group or a fluorine-containing group and having a radical polymerizable group The polymer film according to <3>, which is a polymer having

(In General Formula (1), R ¹ represents a hydrogen atom or an alkyl group. L ¹ represents a divalent linking group or a simple bond. R ² represents a radical polymerizable group.
In general formula (2), R ³ represents a hydrogen atom or an alkyl group. L ² represents a divalent linking group or a simple bond. R ⁴ represents an alkyl group having a fluorine atom, an aryl group having a fluorine atom, or a group represented by the general formula (X). )

(In the general formula (X), Ra and Rb each independently represent a hydrogen atom, an alkyl group, an aryl group, or a group represented by the general formula (Y). Rc, Rd, Re, Rf and Rg are And each independently represents a hydrogen atom, an alkyl group, or an aryl group, n represents an integer of 0 to 100, and * represents a bonding position with L ^2. )

(In the general formula (Y), Rh to Rl each independently represents a hydrogen atom, an alkyl group, or an aryl group. M represents an integer of 0 to 100. ** represents the general formula (X) and Indicates the bonding position.
<5> The polymer film according to any one of <1> to <4>, wherein the exposure is performed with light having an exposure wavelength of 320 nm or more.
<6> The phase separation structure includes a continuous phase and a dispersed phase that is dispersed in the continuous phase, and the average diameter of the dispersed phase is 1 nm to 100 μm. <1> to <5> The polymer film according to any one of the above.
<7> A polymer film having a phase separation structure, which is formed on the substrate surface by directly bonding a substrate surface capable of generating radicals upon exposure to a polymer having two or more radical polymerizable groups.
<8> The polymer film according to <7>, wherein the film thickness is 0.5 to 100 nm.
<9> The <7> or <8>, wherein the phase separation structure includes a continuous phase and a dispersed phase that is dispersed in the continuous phase, and an average diameter of the dispersed phase is 1 nm to 100 μm. The polymer membrane described.
<10> Any one of <7> to <9>, wherein at least one of the polymers having a radical polymerizable group is a polymer having a siloxane group or a fluorine-containing group and having a radical polymerizable group. The polymer film described in 1.
<11> A laminate having a substrate capable of generating radicals upon exposure and the polymer film according to any one of <1> to <10> formed on the substrate capable of generating radicals upon exposure.
<12> The laminate according to <11>, wherein the substrate capable of generating radicals upon exposure is formed of a laminate structure including a substrate and a polymerization initiation layer formed on the substrate.
<13> The polymerization initiation layer is a layer formed by bonding a compound having a polymerization initiation site capable of initiating radical polymerization by exposure and a substrate binding site to the substrate via the substrate binding site <12 > The laminated body as described in>.
<14> Two or more kinds of polymers containing at least one kind of polymer having a radical polymerizable group are brought into contact with a substrate surface capable of generating radicals upon exposure to have a phase separation structure on the substrate surface. A film forming step of forming a polymer film;
An immobilization step of exposing the polymer film formed in the film formation step and immobilizing the polymer film on the substrate;
A method for producing a polymer film directly bonded to the substrate surface, comprising a washing step of washing the polymer film obtained in the immobilization step with a solvent.

  According to the present invention, there are provided a polymer film having a fine structure pattern excellent in production suitability, durability, and adhesion to a substrate, a laminate having the polymer film, and a method for producing the polymer film and the laminate. Can be provided.

Below, the polymer film and laminated body which concern on this invention, and the manufacturing method of this polymeric film and laminated body are explained in full detail.
First, materials used in the present invention will be described.

<Substrate capable of generating radicals upon exposure>
As the substrate capable of generating radicals by exposure, any substrate may be used as long as radicals can be generated by light exposure with a specific wavelength described later. In other words, the substrate itself may be a substrate having a characteristic of generating radicals upon exposure, or a polymerization initiating layer is provided on the substrate, and this polymerization initiating layer constitutes the substrate with such characteristics. But you can. Especially, a board | substrate provided with a polymerization start layer is preferable.
As a method for producing the polymerization initiating layer, for example, it is formed by dissolving necessary components in a soluble solvent, providing a coating layer on the substrate surface by a method such as coating, and hardening by heating or light irradiation. can do. The compound used for the polymerization initiating layer is not particularly limited as long as it has good adhesion to the substrate and generates active species by applying energy such as irradiation with active light.

Examples of the substrate capable of generating radicals upon exposure include (a) a substrate containing a radical generator, (b) a substrate containing a polymer compound having a radical generating site, and (c) a radical in the cross-linking agent and side chain. Examples thereof include a substrate having a polymerization initiation layer in which a coating liquid containing a polymer compound having a generation site is applied to a support surface and dried to form a crosslinked structure in the coating.
In addition, there is (d) a substrate in which a photopolymerization initiation site capable of initiating radical polymerization by photocleavage is provided on the substrate surface by a covalent bond. More specifically, a substrate having a polymerization initiation layer formed by bonding a compound having a photopolymerization initiation site capable of initiating radical polymerization by photocleavage and a substrate binding site to the substrate surface via the substrate binding site. It is. Of these, the substrate (d) is preferred because the resulting polymer thin film has excellent film thickness uniformity and flatness.

The compound capable of generating radicals upon exposure used in the substrate (a) (hereinafter, appropriately referred to as a radical generator) may be a low molecular compound or a high molecular compound, and generally known compounds are used. . Low molecular radical generators include known radical generators such as acetophenones, benzophenones, Michler's ketone, benzoylbenzoate, benzoins, α-acyloxime esters, tetramethylthiuram monosulfide, trichloromethyltriazine and thioxanthone. Agents can be used.
Examples of the polymer compound having a radical generating site (polymer radical generator) used in the substrate (b) above include paragraphs [0012] to [0030] of JP-A-9-77891, Polymer compounds having an active carbonyl group in the side chain described in paragraphs [0020] to [0073] of Kaihei 10-45927 can be used.

  In the substrate (c), a polymerization initiating layer is formed by immobilizing a polymer having a functional group having a polymerization initiating ability and a crosslinkable group on a side chain by a crosslinking reaction on an arbitrary support. The substrate is capable of generating radicals upon exposure. Specifically, a coating liquid containing a crosslinking agent and a polymer compound having a radical generating site in the side chain is applied to the surface of the support (substrate) and dried to form a crosslinked structure in the coating to form a polymerization initiating layer. Form. Such a method for forming a polymerization initiation layer is described in detail in, for example, JP-A No. 2004-123837, and such a polymerization initiation layer can be applied to the present invention.

Examples of the compound having a polymerization initiating ability applicable to the substrate of (d) above include a compound having a polymerization initiation site (Y) capable of initiating radical polymerization by photocleavage and a substrate binding site (Q) (hereinafter, (Referred to as “photocleavable compound (QY)” as appropriate).
Here, the polymerization initiation site where radical polymerization can be initiated by photocleavage (hereinafter also simply referred to as “polymerization initiation site (Y)”) is a structure containing a single bond that can be cleaved by light. As the single bond that is cleaved by this light, carbonyl α-cleavage, β-cleavage reaction, light-free rearrangement reaction, phenacyl ester cleavage reaction, sulfonimide cleavage reaction, sulfonyl ester cleavage reaction, N-hydroxysulfonyl ester cleavage reaction, benzyl Examples thereof include a single bond that can be cleaved using an imide cleavage reaction, a cleavage reaction of an active halogen compound, and the like. These reactions break a single bond that can be cleaved by light. Examples of the single bond that can be cleaved include a C—C bond, a C—N bond, a C—O bond, a C—Cl bond, a N—O bond, and a S—N bond.

  Further, the polymerization initiation site (Y) containing a single bond that can be cleaved by these lights serves as a starting point for a graft reaction of a polymer having a radical polymerizable group described later. That is, when a single bond that can be cleaved by light is cleaved, it has a function of generating a radical by the cleaving reaction. As described above, examples of the structure of the polymerization initiation site (Y) having a single bond that can be cleaved by light and capable of generating radicals include structures containing the following groups. That is, aromatic ketone group, phenacyl ester group, sulfonimide group, sulfonyl ester group, N-hydroxysulfonyl ester group, benzylimide group, trichloromethyl group, benzyl chloride group, and the like.

When such a polymerization initiation site (Y) is cleaved by exposure and a radical is generated, if there is a polymer having a radical polymerizable group around the radical, this radical functions as a starting point for the graft reaction. A graft polymer can be produced.
For this reason, when producing | generating a graft polymer using the board | substrate with which the photocleavable compound (QY) was introduce | transduced into the surface, exposure with the wavelength which can cleave a polymerization start part (Y) as an energy provision means is carried out. It is necessary to use it.

Further, the substrate binding site (Q) is composed of a reactive group capable of reacting and bonding with a functional group (hydroxyl group, carboxyl group, etc.) present on the surface of an insulating substrate typified by glass. Specifically, a substrate bonding group as shown below can be mentioned. Of these, from the viewpoint of excellent reactivity, -Si _{(OA) 3} group (A represents an alkyl group preferably a methyl group, an ethyl group.), -. SiX ₃ group (X represents a halogen atom, preferably , Chlorine atom) and the like. Examples of the bond between the substrate surface and the photoinitiating site are preferably covalent bonds such as O—C, O—Si, N—C, N—Si, S—C, S—Si, and S—O. .

  The polymerization initiation site (Y) and the substrate binding site (Q) may be directly bonded or may be bonded via a linking group. When it has a linking group (L), the photocleavable compound is represented as (QL-Y). Examples of the linking group include a linking group containing an atom selected from the group consisting of carbon, nitrogen, oxygen, and sulfur. Specific examples include a saturated hydrocarbon group (such as an alkylene group), an arylene group, an ester group, an amide group, a ureido group, an ether group, an amino group, a sulfonamide group, or a combination thereof. The linking group may further have a substituent, and examples of the substituent that can be introduced include an alkyl group, an alkoxy group, and a halogen atom.

  Hereinafter, although the example of a photocleavable compound (QY) is given, this invention is not limited to this. These compounds are immobilized on the surface by chemical reaction with the substrate surface.

  There is no restriction | limiting in particular as said board | substrate, The constituent material may be any of an organic material, an inorganic material, and a hybrid material of organic and inorganic. Specific examples include various substrates having surface hydroxyl groups such as glass, quartz, ITO, silicon, and epoxy resin, and plastic substrates such as PET, polypropylene, polyimide, and acrylic. Among them, a substrate having a surface hydroxyl group such as glass, quartz, ITO, silicon, and epoxy resin is preferable. The thickness of the substrate is selected according to the purpose of use and is not particularly limited, but is generally about 10 μm to 10 cm. The substrate may or may not be flat.

  The substrate has a functional group (Z) such as a hydroxyl group on the substrate surface due to its material. Therefore, the photocleavable compound (QY) is bonded to the substrate surface by bringing the substrate into contact with the photocleavable compound (QY) and bonding the functional group (Z) and the substrate binding site (Q). Can be introduced. When an insulating substrate such as various substrates, particularly a resin substrate is used, a hydroxyl group, a carboxyl group, or the like may be generated on the substrate surface by a surface treatment such as corona treatment, glow treatment, UV treatment, or plasma treatment.

The photocleavable compound (QY) is prepared by bonding the photocleavable compound (QY) to the substrate via the substrate binding site (Q) to produce a polymerization initiation layer (photocleavable compound binding step). A method in which a solution or dispersion is dissolved or dispersed in a suitable solvent such as toluene, hexane, or acetone, and the solution or dispersion is applied to the substrate surface by spin coating (application method), or the substrate is placed in the solution or dispersion for a certain period of time. A method of immersing and washing (immersion method) or the like can be used.
By using the dipping method, a polymerization initiating layer having a thin film thickness and excellent flatness can be obtained, and the uniformity of the film thickness of the polymer film produced on the polymerization initiating layer on the substrate surface is more excellent. It becomes. Preferably, the obtained polymerization initiating layer is a self-assembled monolayer (SAM) made of a photocleavable compound (QY).
Especially, it is preferable that the film thickness of a polymerization start layer is 1-15 nm at the point that the uniformity of the film thickness of the polymer film obtained is more excellent, and can be used suitably for the use etc. which are mentioned below. 1.0-5.0 nm is preferable, and 1.5-5.0 nm is particularly preferable. The method for measuring the film thickness of the polymerization initiating layer is a value obtained by measuring 12 or more arbitrary points on the surface of the film using ellipsometry (DHA-XA / S4 manufactured by Mizoji Optical Co., Ltd.) and averaging the number. is there.

<Polymer>
In the production of the polymer film and laminate of the present invention, two or more kinds of polymers containing at least one kind of polymer having a radical polymerizable group are used. Two or more polymers having a radical polymerizable group may be used, or a polymer having a radical polymerizable group and another polymer may be used in combination.
First, a polymer having a radical polymerizable group will be described.

<Polymer having radical polymerizable group>
The polymer having a radical polymerizable group according to the present invention refers to a polymer into which a radical polymerizable group (such as an ethylene addition polymerizable unsaturated group) such as a vinyl group, an allyl group, or a (meth) acryl group is introduced. This polymer has a radically polymerizable group at least at the terminal or side chain, and more preferably has a radically polymerizable group in the side chain. A direct bond (covalent bond) is formed between the polymer and the substrate (or the polymerization initiation layer on the substrate surface) via the radical polymerizable group, and a polymer film is formed on the substrate surface. The

  The weight average molecular weight (Mw) of the polymer having a radical polymerizable group according to the present invention is not particularly limited, but is preferably from 1,000 to 1,000,000, more preferably from 3,000 to 400,000, from the viewpoint of solubility in a solvent.

  The type of the polymer skeleton in the polymer having a radical polymerizable group is not particularly limited. For example, polyimide resin, epoxy resin, polyethylene resin, polyester resin, urethane resin, novolac resin, cresol resin, acrylic resin, styrene resin Etc. Especially, as a polymer useful by this invention, an acrylic resin and a styrene resin are preferable.

Examples of a method for synthesizing a polymer having a radical polymerizable group include, for example, (i) a method of copolymerizing a monomer having a radical polymerizable group and another monomer, and (ii) a monomer having a radical polymerizable group precursor; A method of copolymerizing with other monomers and then introducing a double bond by treatment with a base or the like; (iii) reacting a polymer having a functional group such as carboxylic acid with a monomer having a radical polymerizable group; The method of introduce | transducing a radically polymerizable group is mentioned.
A preferred synthesis method is the method (iii) from the viewpoint of synthesis suitability.

  Other monomers used together with the monomer having a radical polymerizable group in the synthesis methods (i) and (ii) are not particularly limited. For example, (meth) acrylic acid or an alkali metal salt or amine salt thereof, Itaconic acid or its alkali metal salt or amine salt, styrene sulfonic acid or its alkali metal salt or amine salt, 2-sulfoethyl (meth) acrylate or its alkali metal salt or amine salt, 2-acrylamido-2-methylpropane sulfonic acid or Its alkali metal salt or amine salt, acid phosphooxypolyoxyethylene glycol mono (meth) acrylate or its alkali metal salt or amine salt, polyoxyethylene glycol mono (meth) acrylate, 2-hydroxyethyl (meth) acrylate Rate, (meth) acrylamide, N-monomethylol (meth) acrylamide, N-dimethylol (meth) acrylamide, allylamine or its hydrohalide, N-vinylpyrrolidone, vinylimidazole, vinylpyridine, vinylthiophene, styrene, ethyl (Meth) acrylic acid ester, n-butyl (meth) acrylic acid ester, (meth) acrylic acid ester having an alkyl group having 1 to 24 carbon atoms, and the like can be exemplified.

  Examples of the monomer having a radical polymerizable group used in the method (i) are allyl group-containing monomers, and specific examples include allyl (meth) acrylate and 2-allyloxyethyl methacrylate. .

  Examples of the monomer having a polymerizable group precursor used in the synthesis method (ii) include 2- (3-chloro-1-oxopropoxy) ethyl methacrylate and compounds described in JP-A-2003-335814 ( i-1 to i-60) can be used.

  Furthermore, utilizing a reaction with a functional group such as a carboxyl group, an amino group or a salt thereof, a hydroxyl group, or an epoxy group in the polymer having an interactive group used in the synthesis method of (iii) above, Examples of the monomer having a radical polymerizable group used for introducing a polymerizable group include (meth) acrylic acid, glycidyl (meth) acrylate, allyl glycidyl ether, and 2-isocyanatoethyl (meth) acrylate.

  As an example of the polymer having a radical polymerizable group, a repeating unit represented by the general formula (3) and a polymer (copolymer) having a repeating unit represented by the general formula (4) can be given. .

(In General Formula (3), R ⁵ represents a hydrogen atom or an alkyl group. R ⁶ represents a carboxy group, an ester group, an amide group, a nitrile group, a sulfonic acid group, a sulfonic acid ester group, or a phosphonic acid group. Represents a phosphonic acid ester group, an aryl group, a pyridyl group, a pyrrolidone group, or an alkylcarbonyloxy group.
In General Formula (4), R ⁷ represents a hydrogen atom or an alkyl group. L ³ represents a divalent linking group or a simple bond. R ⁸ represents an allyl group, an acryloyl group, or a methacryloyl group. )

In general formula (3), R ⁵ represents a hydrogen atom or an alkyl group. As an alkyl group, carbon number 1 is preferable, for example, a methyl group etc. are mentioned. R ⁵ is preferably a hydrogen atom or a methyl group.

In general formula (3), R ⁶ represents a carboxyl group, an aryl group, a pyridyl group, a pyrrolidone group, an alkylcarbonyloxy group (for example, a methylcarbonyloxy group, an ethylcarbonyloxy group), an ester group, an amide group, or a nitrile group. Represents a sulfonic acid group, a sulfonic acid ester group, a phosphonic acid group, or a phosphonic acid ester group. Of these, a carboxyl group, an ester group, an amide group, or an aryl group is preferable.
Note that these groups (for example, an aryl group) may further have a substituent such as an alkyl group or an alkoxy group.

In General Formula (4), R ⁷ represents a hydrogen atom or an alkyl group. Examples of the alkyl group include a methyl group. R ⁷ is preferably a hydrogen atom or a methyl group.

In the general formula (4), L ³ represents a divalent linking group or a simple bond. Specifically, the linking group is an alkylene group (preferably having 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms. For example, methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, cyclohexyl group, -O-, arylene group (phenylene group, etc.), -CO-, -NH-, -COO-, -CONH-, or a combination thereof (for example, alkyleneoxy group, alkylene group) Oxycarbonyl group, alkylenecarbonyloxy group, etc.). These linking groups may have a substituent such as a hydroxyl group or an alkyl group.
When L ³ is a simple bond, R ^{8 in the} general formula (4) is directly bonded to C (carbon atom).

In General Formula (4), R ⁸ represents Z represents an allyl group, an acryloyl group, or a methacryloyl group, and among them, an acryloyl group and a methacryloyl group are preferable. These groups act as the above-mentioned radical polymerizable groups, and react with the substrate (or the polymerization initiation layer on the substrate surface) to form a direct bond. That is, a direct bond (covalent bond) is formed between the polymer having the repeating unit represented by the general formula (3) and the general formula (4) and the substrate via these groups.

  The polymer having the repeating units represented by the general formula (3) and the general formula (4) is not particularly limited in the manner of connection. Even if they are alternately connected one by one, they are alternately connected one by one. Or you may connect at random. Moreover, the other repeating unit may be included. In addition, as another repeating unit, the repeating unit derived from the other monomer demonstrated by the synthesis method of the above-mentioned (i) and (ii) is mentioned, for example.

  The content of the repeating unit represented by the general formula (3) in the polymer having the repeating unit represented by the general formula (3) and the repeating unit represented by the general formula (4) is particularly limited. However, it is preferably 10 to 99 mol%, more preferably 60 to 95 mol%, based on all repeating units (100 mol%) constituting the polymer. If the content is too small, the ratio of polymerizable groups increases, a cross-linking reaction between polymer molecules occurs, and the film thickness tends to increase. Moreover, when there is too much content, while the ratio of a polymeric group will decrease, a film thickness will become thin and it will become difficult to obtain the uniform thin film without a defect.

  The polymer having the repeating unit represented by the general formula (3) and the repeating unit represented by the general formula (4) can be synthesized using the methods (i) to (iii).

  Specific examples of the polymer having the radical polymerizable group described above are given below, but the present invention is not limited thereto. In addition, the numerical value described in each repeating unit represents the mol% of each repeating unit.

<Polymer having siloxane group or fluorine-containing group and having radically polymerizable group>
One preferred example of the polymer having a radical polymerizable group is a polymer having a siloxane group or a fluorine-containing group and having a radical polymerizable group.
A polymer having a siloxane group or a fluorine-containing group and having a radically polymerizable group is a radically polymerizable group such as a vinyl group, an allyl group or a (meth) acryl group (such as an ethylene addition polymerizable unsaturated group). A siloxane group-containing polymer or fluorine-containing group-containing polymer into which is introduced. These polymers have a radically polymerizable group at least at the terminal or side chain, and more preferably have a radically polymerizable group in the side chain. A direct bond (covalent bond) is formed between the polymer and the substrate (or the polymerization initiation layer on the substrate surface) via the radical polymerizable group, and a polymer film is formed on the substrate surface. The

  The weight average molecular weight (Mw) of the polymer having a siloxane group or a fluorine-containing group and having a radical polymerizable group is not particularly limited, but is preferably 1,000 to 1,000,000 from the viewpoint of solubility in a solvent, 5,000 to 500,000 is more preferable.

Further, as a method for synthesizing a polymer having a siloxane group or a fluorine-containing group and having a radical polymerizable group, i) a monomer having a siloxane group or a functional group containing a fluorine atom and a monomer having a polymerizable group; Ii) a method of copolymerizing a monomer having a functional group containing a siloxane group or a fluorine atom and a monomer having a polymerizable group precursor, and then introducing a double bond by treatment with a base or the like, iii) A method of introducing a polymerizable group by reacting a polymer having a functional group containing a siloxane group or a fluorine atom with a monomer having a polymerizable group.
A preferred synthesis method is preferably the above method ii) or iii) from the viewpoint of synthesis suitability.

  The polymer having a siloxane group or a fluorine-containing group of the present invention and having a radical polymerizable group has a siloxane group composed of oxygen and silicon, or a functional group having a fluorine atom (fluorine-containing group) as a main chain. Alternatively, it may be contained in the side chain and further contain a radical polymerizable group, and the type of the polymer skeleton is not particularly limited. Specifically, polyimide resin, epoxy resin, polyethylene resin, polyester resin, urethane resin, novolac resin, cresol resin, acrylic resin, styrene resin, and the like can be given. Especially, as a polymer useful by this invention, an acrylic resin and a styrene resin are preferable.

  As a preferred embodiment of the polymer having a siloxane group or a fluorine-containing group and having a radical polymerizable group, a repeating unit represented by the following general formula (1), and a general formula (2) And a polymer having a repeating unit represented by the formula (copolymer). The polymer only needs to have at least the repeating unit represented by the general formula (1) and the repeating unit represented by the general formula (2), and may include other repeating units. .

(In General Formula (1), R ¹ represents a hydrogen atom or an alkyl group. L ¹ represents a divalent linking group or a simple bond. R ² represents a radical polymerizable group.
In general formula (2), R ³ represents a hydrogen atom or an alkyl group. L ² represents a divalent linking group or a simple bond. R ⁴ represents an alkyl group having a fluorine atom, an aryl group having a fluorine atom, or a group represented by the general formula (X). )

(In the general formula (X), Ra and Rb each independently represent a hydrogen atom, an alkyl group, an aryl group, or a group represented by the general formula (Y). Rc, Rd, Re, Rf and Rg are And each independently represents a hydrogen atom, an alkyl group, or an aryl group, n represents an integer of 0 to 100, and * represents a bonding position with L ^2. )

(In the general formula (Y), Rh to Rl each independently represents a hydrogen atom, an alkyl group, or an aryl group. M represents an integer of 0 to 100. ** represents the general formula (X) and Indicates the bonding position.

In general formula (1), R ¹ represents a hydrogen atom or an alkyl group. The alkyl group may be branched, may be substituted with a hetero atom, and may further have an unsaturated bond. Specific examples include a methyl group, an ethyl group, a propyl group, and an isopropyl group.
Among these, R ¹ is more preferably a methyl group or an ethyl group.

In general formula (1), L ¹ represents a divalent linking group or a simple bond. The linking group is not particularly limited, and an optimal group is appropriately selected from the viewpoint of the material properties of the polymer and the viewpoint of synthesis.
Specifically, an alkylene group (C1-C20 is preferable and C1-C10 is more preferable. For example, a methylene group, ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group etc. are mentioned), -O -, - S-, (such as a phenylene group) an arylene _{group, - CO -, - NH -} , - SO 2 -, - COO -, - CONH -, - C≡C -, - N = N -, - CONR- (R represents an alkyl group) or a combination thereof (for example, an alkyleneoxy group, an alkyleneoxycarbonyl group, an alkylenecarbonyloxy group, etc.) can be mentioned.
Among these, —O—, an alkylene group, —CONH—, —COO—, an arylene group, an alkyleneoxy group, an alkyleneoxycarbonyl group, an alkylenecarbonyloxy group, or a group obtained by combining these is preferable. When L ¹ is a mere bond, it means that C (carbon atom) and R ^{2 in} the general formula (1) are directly bonded.

In general formula (1), R ² represents a radical polymerizable group. R ² is not particularly limited as long as it has radical polymerizability, and preferred examples include acryloyl group, methacryloyl group, and vinyl group.

  Although the specific example of the repeating unit represented by General formula (1) is shown, this invention is not limited to this.

In general formula (2), R ³ represents a hydrogen atom or an alkyl group. The alkyl group represented by R ³ has the same meaning as the alkyl group represented by R ¹ in the general formula (1). R ³ is preferably a hydrogen atom or a methyl group.

In the general formula (2), L ² represents a divalent linking group or a simple bond. The linking group represented by L ² has the same meaning as the linking group represented by L ¹ in the general formula (1) described above. Among them, preferable examples of the linking group include —O—, an alkylene group, —CONH—, —COO—, an arylene group, an alkyleneoxy group, an alkyleneoxycarbonyl group, an alkylenecarbonyloxy group, or a group obtained by combining these. When L ² is a simple bond, it means that R ^{4 in the} general formula (2) and C (carbon atom) are directly bonded.

In General Formula (2), R ⁴ represents an alkyl group having a fluorine atom, an aryl group having a fluorine atom, or a group represented by General Formula (X).
The alkyl group having a fluorine atom is a linear, branched or cyclic alkyl group having at least one fluorine atom, and may further have another substituent (for example, a hydroxyl group or a halogen group). In addition, a linking group such as -O- may be included. As an alkyl group, C2-C20 is preferable and C3-C10 is more preferable. Moreover, it is preferable to have 2 or more fluorine atoms. Especially, a perfluoroalkyl group (C2-C20 is preferable and C3-C10 is more preferable) is preferable.

Specific examples of the alkyl group having a fluorine atom include CF ₃ CH ₂ group, CF ₃ CF ₂ CH ₂ group, CF ₃ CF ₂ (CH ₂ ) ₆ group, CF ₃ CF ₂ CF ₂ CH ₂ group, and CF ₃ CHFCF. ₂ CH ₂ group, F (CF ₂ ) ₄ CH ₂ CH ₂ group, F (CF ₂ ) ₄ CH ₂ CH ₂ CH ₂ group, F (CF ₂ ) ₄ (CH ₂ ) ₆ group, F (CF ₂ ) ₃ OCF (CF ₃ ) CH ₂ group, F (CF ₂ ) ₆ CH ₂ CH ₂ group, F (CF ₂ ) ₆ (CH ₂ ) ₃ group, F (CF ₂ ) ₆ (CH ₂ ) ₆ group, F (CF _{2) 8} CH ₂ CH _{2 group, F (CF 2) 8 (} CH 2) 3 _{group, F (CF 2) 8 (} CH 2) 6 _{group, F (CF 2) 10 CH} 2 CH 2 group, C ₃ F ₇ OCF (CF ₃ ) CF ₂ OCF (CF ₃ ) CH ₂ group, (CF ₃ ) ₂ CF (CH ₂ ) ₆ group, (CF ₃ ) ₂ CF (CF ₂ ) ₂ CH ₂ CH ₂ group, (CF ₃ ) ₂ CF (CF ₂ ) ₄ CH ₂ CH ₂ group, (CF ₃ ) ₂ CF (CF ₂ ) ₆ CH ₂ CH ₂ group, CHF ₂ CF ₂ CH ₂ group, H (CF ₂ ) ₄ CH ₂ group, H (CF ₂ ) ₆ CH ₂ group, H (CF ₂ ) ₈ CH ₂ group, (CF ₃ ) ₂ CH group, CF ₃ CHFCF ₂ CH ₂ group, CF ₃ CF ₂ (CH ₂ ) ₆ OCH ₂ CH ₂ group, F (CF ₂ ) ₃ OCF (CF ₃ ) CH ₂ OCH ₂ CH ₂ group, H (CF ₂ ) ₄ CH ₂ OCH ₂ CH ₂ group, H (CF ₂ ) ₆ CH ₂ OCH ₂ CH ₂ group, H (CF ₂ ) ₈ CH ₂ OCH ₂ CH ₂ Group, CF ₃ CHFCF ₂ CH ₂ OCH ₂ CH ₂ group, C ₇ F ₁₅ CH ₂ OCH ₂ CH ₂ group and the like.

  Examples of the aryl group having a fluorine atom include those having at least one fluorine atom substituted on an aryl group such as a phenyl group or a naphthyl group, and may further have another substituent. The aryl group is preferably an aryl group having 6 to 14 carbon atoms, specifically, phenyl group, tolyl group, dimethylphenyl group, 2,4,6-trimethylphenyl group, naphthyl group, anthryl group, 9,10. -A dimethoxyanthryl group etc. can be mentioned preferably. Moreover, it is preferable to have 2 or more fluorine atoms.

In general formula (X), Ra and Rb each independently represent a hydrogen atom, an alkyl group, an aryl group, or a group represented by general formula (Y). As an alkyl group, Preferably it is C1-C6, More preferably, it is C1-C3. Here, the alkyl group may be branched, may be substituted with a hetero atom, and may further have an unsaturated bond. Specific examples include a methyl group, an ethyl group, a propyl group, and an isopropyl group, and a methyl group is preferable.
As an aryl group, C6-C14 is preferable and C6-C10 is more preferable. Specific examples of the aryl group include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group, and among them, a phenyl group is preferable.

  In General Formula (X), Rc, Rd, Re, Rf, and Rg each independently represent a hydrogen atom, an alkyl group, or an aryl group. The alkyl group and aryl group represented by Rc, Rd, Re, Rf and Rg have the same meanings as the alkyl group and aryl group represented by Ra and Rb, respectively.

  In general formula (X), n represents the integer of 0-100. Especially, 3-30 are preferable, More preferably, it is 5-20. When n is 2 or more, the groups represented by Rc and Rd may be the same or different.

  In general formula (Y), Rh to Rl each independently represent a hydrogen atom, an alkyl group, or an aryl group. The alkyl group represented by Rh to Rl has the same meaning as the alkyl group represented by Ra and Rb in the general formula (X) described above. Moreover, the aryl group represented by Rh-Rl is synonymous with the aryl group represented by Ra and Rb in general formula (X) mentioned above.

  In general formula (Y), m represents an integer of 0 to 100. Especially, 0-30 are preferable, More preferably, it is 5-20. When m is 2 or more, the groups represented by Rh and Ri may be the same or different.

Specific examples of the repeating unit represented by the general formula (2) are disclosed in the above-mentioned Japanese Patent Publication Nos. 51-42961, 54-6512, 57-57096, 58-53656, and the like. And repeating units derived from silicone compounds. In terms of product names, FM0711, FM0721, FM0725, PS583 (above, Chisso Corporation), KNS-50002, KNS-5100, KNS-5200, KNS-5300, KP-600, X-62-7052, X-62- 7100, X-62-7112, X-62-7140, X-62-7144, X-62-7153, X-62-7157, X-62-7158, X-62-7166, X-62-7168, X-62-7177, X-62-7180, X-62-7181, X-62-7192, X-62-7200, X-62-7203, X-62-7205, X-62-7931, KM- 875, X-62-7296 A / B, X-62-7305 A / B, X-62-7028 A / B, X-62-5039 A / B, X-62-5 40A / B (above, Shin-Etsu Chemical Co., Ltd.), RC149, RC300, RC450, RC802, RC710, RC715, RC720, RC730 (above, Goldschmidt), EBECRYL350, EBECRYL1360 (above, Daicel UCB) Is mentioned.
Moreover, the repeating unit derived from the following fluorine-containing monomers is also mentioned. CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ OCOCH═CH ₂ , CF ₃ CH ₂ OCOCH═CH ₂ , CF ₃ (CF ₂ ) ₄ CH ₂ CH ₂ OCOC (CH ₃ ) ═CH ₂ , C ₇ F ₁₅ CON _{(C 2 H 5) CH 2} OCOC (CH 3) = CH 2, CF 3 (CF 2) 7 SO 2 N (CH 3) CH 2 CH 2 OCOCH = CH 2, C 2 F 5 SO 2 N (C 3 _{H 7) CH 2 CH 2 OCOC} (CH 3) = CH 2, (CF 3) 2 CF (CF 2) 6 (CH 2) 3 OCOCH = CH 2, (CF 3) 2 CF (CF 2) 10 (CH ₂ ) ₃ OCOC (CH ₃ ) ═CH ₂ , CF ₃ (CF ₂ ) ₄ CH (CH ₃ ) OCOC (CH ₃ ) ═CH ₂ , CF ₃ CH ₂ OCH ₂ CH ₂ OCOCH═CH ₂ , C _{2 F 5 (CH 2 CH 2 O} ) 2 CH 2 OCOCH = CH 2, (CF 3) 2 CFO (CH 2) 5 OCOCH = CH 2, CF 3 (CF 2) 4 OCH 2 CH 2 OCOC (CH 3) = _{CH 2, C 2 F 5 CON} (C 2 H 5) CH 2 OCOCH = CH 2, CF 3 (CF 2) 2 CON (CH 3) CH (CH 3) CH 2 OCOCH = CH 2, H (CF 2) ₆ C (C ₂ H ₅ ) OCOC (CH ₃ ) ═CH ₂ , H (CF ₃ ) ₈ CH ₂ OCOCH═CH ₂ , H (CF ₂ ) ₄ CH ₂ OCOCH═CH ₂ , H (CF ₂ ) ₆ CH _{2 OCOC (CH 3) = CH} 2, CF 3 (CF 2) 7 SO 2 N (CH 3) CH 2 CH 2 OCOC (CH 3) = CH 2, CF 3 (CF 2) 7 SO 2 N (CH 3 _{(CH 2) 10 OCOCH = CH} 2, C 2 F 5 SO 2 N (C 2 H 5) CH 2 CH 2 OCOC (CH 3) = CH 2, CF 3 (CF 2) 7 SO 2 N (CH 3) _{(CH 2) 4 OCOCH = CH} 2, C 2 F 5 SO 2 N (C 2 H 5) C (C 2 H 5) etc. HCH ₂ OCOCH = CH 2 and the like. The present invention is not limited to these.

  The polymer (copolymer) having the repeating unit represented by the general formula (1) and the repeating unit represented by the general formula (2) includes the repeating unit represented by the general formula (1) and the general formula (2). Copolymers consisting only of repeating units represented by () may be included, and other types of repeating units may be included. The mode of connection is not particularly limited, and the repeating unit represented by the general formula (1) and the repeating unit represented by the general formula (2) may be alternately connected one by one or may be alternately connected by a plurality. , You may connect at random. The polymer may have a plurality of different types of repeating units represented by the general formula (1) and repeating units represented by the general formula (2).

  The other types of repeating units are not particularly limited, but olefins (ethylene, propylene, isoprene, vinyl chloride, vinylidene chloride, etc.), acrylate esters (methyl acrylate, ethyl acrylate, butyl acrylate, etc.) , Methacrylates (methyl methacrylate, ethyl methacrylate, butyl methacrylate, etc.), styrene derivatives (styrene, p-hydroxymethylstyrene, p-methoxystyrene, etc.), vinyl ethers (methyl vinyl ether, ethyl vinyl ether, isopropyl vinyl ether, t-butyl vinyl ether, cyclohexyl vinyl ether, etc.), vinyl esters (vinyl acetate, vinyl propionate, vinyl butyrate, vinyl cinnamate, etc.), unsaturated carboxylic acids (acrylic acid, methacrylic acid, croton) , Maleic acid, itaconic acid, etc.), acrylamides (N, N-dimethylacrylamide, N-tert-butylacrylamide, N-cyclohexylacrylamide, etc.), methacrylamides (N, N-dimethylmethacrylamide), repeated from acrylonitrile Units are listed.

The content of the repeating unit represented by the general formula (1) in the polymer having the repeating unit represented by the general formula (1) and the repeating unit represented by the general formula (2) is not particularly limited. However, 0.5-80 mol% is preferable with respect to all repeating units (100 mol%) constituting the polymer, and 1.0-60 mol% is more preferable. Within the above range, it is possible to bond to the substrate more firmly.
Further, the content of the repeating unit represented by the general formula (2) is not particularly limited, but is preferably 5 to 99 mol% with respect to all repeating units (100 mol%) constituting the polymer. 95 mol% is more preferable. If it is in the above-mentioned range, a more ordered phase separation structure can be obtained.

  Specific examples of the polymer having the repeating unit represented by the general formula (1) and the repeating unit represented by the general formula (2) are shown below, but the present invention is not limited thereto. In addition, the numerical value described in the repeating unit represented by General formula (1) and the repeating unit represented by General formula (2) in a figure means mol%. Further, the numerical value 11 in the siloxane bonding site represents the number of repeating units.

<Other polymers>
The polymer other than the above-described polymer having a radical polymerizable group used for producing the polymer film of the present invention is not particularly limited, and a general-purpose polymer can be used. For example, acrylic resins such as polystyrene, poly (2-vinylpyridine), polymethyl methacrylate, polybutyl acrylate, styrene resins such as polystyrene and poly (4-bromo) styrene, carbonate resins such as polycarbonate, polyacrylamide, poly (N Examples thereof include amide resins such as -methyl) acrylamide and polyvinylpyrrolidone, olefin resins such as polyethylene, polyvinylidene chloride, polyisobutene and polybutadiene, and vinyl resins containing a heterocycle such as polyvinylpyridine. Of these, polymethyl methacrylate, polystyrene, polyvinyl pyrrolidone, polyvinyl pyridine and the like are preferable.

  The molecular weight of the other polymer is appropriately selected depending on the type and molecular weight of the polymer having a radical polymerizable group to be used, and is preferably 1,000 to 3,000,000, and preferably 3,000 to 1,000,000 in terms of ease of handling. Is more preferable.

  In order to obtain the polymer film of the present invention, two or more kinds of polymers are used. In view of easy control of the phase separation structure of the resulting polymer membrane, it is preferable to use two types of polymers. A polymer having two kinds of radical polymerizable groups may be used, or a polymer having a radical polymerizable group and another polymer may be used in combination.

  A preferred combination of polymers used in the present invention includes a combination of a polymer having a siloxane group and a radical polymerizable group, and a polymer having a fluorine-containing group and a radical polymerizable group.

The content of the polymer having a radical polymerizable group in all the polymers used in the present invention is appropriately selected depending on the desired fine pattern structure.
For example, when using a polymer having a radical polymerizable group and a polymer other than that (for example, polystyrene), the mass mixing ratio (high value having a radical polymerizable group is high in that the fine pattern can be controlled more easily. 1: Molecule: other polymer) is preferably 1:50 to 50: 1, more preferably 1: 5 to 5: 1.
In addition, when using a polymer having a siloxane group and a radically polymerizable group and a polymer having a fluorine-containing group and a radically polymerizable group as the two types of polymers, it is easier to control the fine pattern. In particular, the mass mixing ratio (polymer having siloxane group and radical polymerizable group: polymer having fluorine-containing group and radical polymerizable group) is preferably from 1:50 to 50: 1, and preferably from 1: 5 to 5: 1 is more preferred.

<Manufacturing method>
The method for producing a polymer film and a laminate according to the present invention mainly comprises the following three steps.
<Step 1> Two or more kinds of polymers containing at least one kind of polymer having a radical polymerizable group are brought into contact with the substrate surface capable of generating radicals upon exposure to have a phase separation structure on the substrate surface. Film forming step for forming a polymer film <Step 2> The polymer film formed in the film forming step is exposed to light, and the fixing step for fixing the polymer film to the substrate <Step 3> obtained in the fixing step Cleaning step for cleaning polymer membrane with solvent Hereinafter, each step will be described in detail.

<Film formation process>
In the film forming step, two or more kinds of polymers including at least one kind of polymer having a radical polymerizable group are brought into contact with the substrate surface capable of generating radicals upon exposure to form a phase separation structure on the substrate surface. This is a step of forming a polymer film.
The method of bringing the above polymer into contact with the substrate surface is not particularly limited. For example, a method in which a solution in which the polymer to be used is dissolved or a dispersion in which the polymer is used is applied to the substrate by a spin coating method (application method). Or a method of immersing the substrate in the solution or dispersion (immersion method). From the viewpoint of handleability and production efficiency, a coating method is preferred. As the experimental conditions for the coating method and the dipping method, optimum conditions are appropriately selected depending on the polymer used.

  As the solvent to be used, an optimal solvent is appropriately selected depending on the type of polymer to be used. For example, tetrahydrofuran, toluene, 1-methoxy-2-propanol, acetone, methyl ethyl ketone, water and the like can be mentioned. Of these, tetrahydrofuran, toluene, and 1-methoxy-2-propanol are preferable.

  The concentration of the total polymer used in the solution or dispersion varies depending on the polymer used, but is preferably 0.1 to 30% by mass, and more preferably 0.5 to 10% by mass. If it is in the said range, control of the film thickness of the polymer film obtained will become easier, and the uniformity of film thickness will increase more.

  Moreover, you may add additives, such as surfactant, to the said solution as needed in the range which does not impair the objective of this invention. For example, as the surfactant, an anionic surfactant such as sodium n-dodecylbenzenesulfonate, a cationic surfactant such as n-dodecyltrimethylammonium chloride, polyoxyethylene nonylphenol ether (as a commercial product, for example, Emulgen 910, manufactured by Kao Corporation, etc.), polyoxyethylene sorbitan monolaurate (commercially available products such as “Tween 20”), nonionic surfactants such as polyoxyethylene lauryl ether, etc. Can be mentioned.

  After the above-mentioned film formation process, you may provide the process (drying process) of drying the film | membrane obtained as needed. As drying conditions, optimum conditions are appropriately selected depending on the polymer used.

  The polymer film obtained in the film forming step of the present invention has a phase separation structure composed of two or more (preferably two) polymers. The phase separation structure can be controlled to various structures depending on the polymer used and its composition, and examples thereof include a sea-island structure, a co-continuous structure, a cylinder structure, and a lamella structure.

  As the film thickness of the polymer film obtained in this step, an optimum film thickness is appropriately selected according to the application to be used. Especially, 0.1-500 nm is preferable and 0.5-100 nm is more preferable at the point which can form a phase-separation structure more reproducibly.

<Immobilization process>
In the immobilization step, the polymer film obtained in the above-described film formation step is exposed at a predetermined exposure wavelength, and a polymer having a radical polymerizable group is bound to the substrate surface from the radical generated on the substrate surface ( Fixing).

Exposure means exposure which can produce the superposition | polymerization initiating ability of a board | substrate. For example, it means exposure that can cause cleavage at the polymerization initiation site (Y) of the polymerization initiation layer.
The exposure light source is not particularly limited, and a high pressure mercury lamp, a low pressure mercury lamp, a halogen lamp, a xenon lamp, an excimer laser, a dye laser, or the like is used.

As the exposure conditions, optimum conditions are appropriately selected depending on the type of polymer to be used and the light source to be used, but the exposure time is usually 0.1 to 30 minutes. As the exposure energy is preferably at 1 mJ / cm ² or more, and more preferably 10 mJ / cm ² or more.
The exposure is preferably performed under an inert atmosphere such as nitrogen or under vacuum in order to reduce the influence of oxygen.

Note that a polymer thin film having a very thin film thickness and directly bonded to the substrate can be obtained by irradiating only light having a wavelength of 320 nm or more during exposure.
If the exposure wavelength contains light having a wavelength of less than 320 nm, not only the polymer having a radical polymerizable group reacts with the substrate, but also radicals are broken by breaking the polymer chain or absorbing the radical polymerizable group. Occurs, and intramolecular cross-linking between polymers proceeds. On the other hand, when the exposure wavelength is 320 nm or more, the polymer having a radical polymerizable group substantially reacts only with radicals generated on the substrate surface. Accordingly, the generated radical and the polymer having a radical polymerizable group react at the substrate interface, and a thin polymer film is obtained.

  When irradiating light with an exposure wavelength of 320 nm or more, a method using a light source that emits only light with a wavelength of 320 nm or more, or transmitting only light with a wavelength of 320 nm or more, that is, the radical polymerizable group absorbs light. A method is used in which exposure is performed using a cut filter that cuts off light of a wavelength that would cause the loss. Specifically, a method of performing exposure using a cut filter such as glass (blue glass, manufactured by Matsunami Glass Co.) that substantially cuts light having a wavelength of less than 320 nm is used.

<Washing process>
The washing step is a step of removing unreacted polymer that is not bonded to the substrate by washing the exposed and fixed polymer film with a predetermined solvent after the fixing step.
Specifically, this is a step of removing unreacted polymer remaining on the substrate by subjecting the obtained substrate to a treatment such as solvent immersion or solvent washing. As the solvent to be used, an optimal solvent is appropriately used depending on the type of polymer having a radical polymerizable group used in the film forming step. For example, tetrahydrofuran, toluene, dimethylacetamide, N-methylpyrrolidone, water, methanol, alkaline water and the like can be mentioned. In cleaning, ultrasonic means or the like may be used in combination.

As described above, when only the light having an exposure wavelength of 320 nm or more is irradiated, by performing this cleaning process, the unreacted polymer in the polymer film is removed and directly bonded to the substrate. A very thin polymer film can be obtained.
Further, by exposing the coating film at an exposure wavelength of 320 nm or more, a polymer thin film having a uniform film thickness after exposure can be obtained regardless of the thickness of the coating film of the solution containing the polymer having a radical polymerizable group. There is a feature. Even if the substrate has uneven surface and the difference in film thickness is large depending on the location of the coating film at the time of coating, the method according to the present application can produce a polymer thin film having a uniform film thickness on various substrates. . That is, the polymer thin film according to the present application exhibits excellent followability (irregularity followability) with respect to the surface shape of the substrate. Therefore, various surfaces are maintained while maintaining the surface shape of uneven surfaces such as various convex lenses (biconvex lens, concave / convex lens, plano-convex lens, plano-concave lens, biconcave lens) and surfaces having fine sword-like projections. An ultra-thin film with a uniform film thickness can be formed on the top. For example, the difference between the surface average roughness of the substrate and the surface average roughness of the polymer thin film is preferably about 10 nm or less in terms of Ra.

  In the case where two or more (preferably two) polymers used are polymers having a radical polymerizable group, the resulting polymer membrane has a phase separation structure formed in the membrane formation step. That is, the surface of the substrate capable of generating radicals upon exposure and the polymer having two or more kinds of radical polymerizable groups are directly bonded to each other to obtain a polymer film having a phase separation structure formed on the substrate surface. . Therefore, a fine pattern shape derived from the phase separation structure appears on the surface of the polymer film. Therefore, a polymer film having a desired fine pattern can be obtained by producing a predetermined phase separation structure in the film formation step.

  In addition, when one of two or more (preferably two) polymers used is a polymer that does not have a radical polymerizable group (for example, polystyrene, polymethyl methacrylate, etc.), the treatment in this washing step is performed. By applying, a polymer phase that does not react with the substrate and constitutes one of the separated phases of the phase separation structure formed in the film forming step is removed, and a patterned polymer film directly bonded to the substrate surface is obtained. be able to. More specifically, a patterned polymer film formed discretely in an island shape obtained by removing the sea-like portion of the sea-island structure, or an opening obtained by removing the island-like portion of the sea-island structure And the like (polymer films having through-holes dispersed in islands) and the like.

<Polymer film and laminate>
Next, the polymer film and laminate of the present invention obtained by the above-described production method will be described in detail based on preferred embodiments shown in the drawings.

FIG. 1 is a schematic cross-sectional view of an embodiment of the laminate of the present invention.
The laminate 10 shown in the figure is composed of a substrate 12 capable of generating radicals upon exposure and a polymer film 14 directly bonded to the substrate 12. In the figure, in the polymer film 14, a micro phase separation structure (sea-island structure) is formed from the phase 16 made of the polymer A and the phase 18 made of the polymer B. In the same figure, the thicknesses of the substrate 12 and the polymer film 14 that can generate radicals upon exposure are not limited by the figure. In addition, the laminated body 10 is a laminated body obtained when using the polymer which has 2 types of radically polymerizable groups.

The film thickness of the polymer film 14 can be appropriately controlled depending on the polymer used, exposure conditions, and the like. Especially, from a viewpoint of functional material design, 0.1-500 nm is preferable and 0.5-100 nm is more preferable.
The method for measuring the film thickness is a value obtained by measuring 10 or more arbitrary points on the surface of the film by a known method such as ellipsometry and performing number averaging.
Moreover, when only light of 320 nm or more is irradiated as described above, the film thickness of the polymer film directly bonded to the obtained substrate becomes very thin. Specifically, 0.1-100 nm is preferable and 0.5-20 nm is more preferable.

In the polymer film 14, a phase separation structure is formed. The phase separation structure can be controlled to various structures depending on the polymer used and the composition thereof, and examples thereof include a sea-island structure, a co-continuous structure, a cylinder structure, and a lamella structure.
In particular, when the phase separation structure has a continuous phase and a dispersed phase dispersed in the continuous phase (for example, sea-island structure), the average diameter of the dispersed phase is the polymer used and its composition. Thus, it is possible to control appropriately. Among these, the average diameter of the dispersed phase is preferably 1 nm to 100 μm, more preferably 10 nm to 10 μm, from the viewpoint of functional material design. The average diameter is a value obtained by observing the film surface with an atomic force microscope (AFM) or the like, measuring the size of 10 or more dispersed phases, and averaging them. When the dispersed phase is an ellipse, the major axis is the diameter.

FIG. 2 is a schematic cross-sectional view of another embodiment of the laminate of the present invention.
The laminate 20 shown in the figure has a laminated structure in which a substrate 22, a polymerization initiation layer 24, and a polymer film 14 are laminated in this order. In the figure, a substrate 12 capable of generating radicals upon exposure is composed of a laminated structure of a substrate 22 and a polymerization initiation layer 24. The polymer film 14 is directly bonded to the polymerization initiation layer 24. In addition, the polymer film 14 in the figure is synonymous with the polymer film 14 of the same sign shown in FIG.

FIG. 3 is a schematic cross-sectional view of another embodiment of the laminate of the present invention.
The laminated body 30 shown in the figure has a laminated structure in which a substrate 22, a polymerization initiation layer 24, and a polymer film 32 are laminated in this order. In the figure, the polymer film 32 is composed of an opening 34 and a phase 36 made of polymer B. The polymer film 32 corresponds to a structure in which the phase 16 made of the polymer A is removed from the polymer film 14 shown in FIG.
As described above, in the production method of the present invention, when a polymer having no radical polymerizable group is used, a patterned polymer film having an opening (through hole) and directly bonded to the substrate is obtained. .

<Application>
Since the polymer film in the laminate according to the present invention is bonded to the substrate, it has excellent resistance to physical action such as friction and chemical treatment such as a solvent, and structure control at the nanometer level is possible. . Further, it can be produced in a large area and in a short time, which is preferable from the viewpoint of productivity and industrial property. Furthermore, the obtained polymer film has a predetermined fine pattern structure. Therefore, this laminated body can be applied to various uses. For example, electronic information recording media, adsorbents, nano-reaction field membranes, separation membranes, film materials such as displays, potential adjustment materials for conductive substrates such as ITO, or electron and hole injection materials, surface hydrophilic materials, surface water repellency Materials, surface water-sliding materials, and the like.
In particular, the polymer film in the laminate according to the present invention is excellent in followability to the surface shape of the substrate as described above. Therefore, a polymer film having a uniform film thickness is formed on the substrate while maintaining an initial surface shape such as a curved surface or an uneven surface of the substrate. Normally, when a coating process or the like is performed to make the lens surface functional, a difference in the thickness of the coating film occurs between the center and the periphery of the lens, causing distortion and reducing the performance of the lens itself. End up. On the other hand, since the polymer film of the present invention exhibits excellent followability with respect to various surface shapes, the film is formed while maintaining the shape of the curved lens surface. That is, a polymer film having a uniform film thickness can be formed on a curved surface. Therefore, various surface functions can be realized without degrading the performance of the lens itself, and it can be suitably used for producing, for example, an anti-fogging lens and super water-repellent glass.

  The present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.

  The measurement of the polymerization initiating layer and the polymer thin film, which will be described later, was performed using an ellipsometry M-2000U manufactured by Woolam. AFM measurement was performed using Nanopics 1000 manufactured by Seiko Instruments Inc.

(Synthesis Example 1: Synthesis of polymer having fluorine-containing group and radical polymerizable group)
The following components were placed in a three-necked flask having an internal volume of 500 mL and reacted at 75 ° C. for 12 hours while stirring under a nitrogen atmosphere to obtain a solution of polymer 1.
・ Methyl ethyl ketone (MEK) [solvent] 166g
-2- (2-bromoisobutyryloxy) ethyl methacrylate (BBEM, molecular weight 279, Manac Co., Ltd.) 27.9 g (0.1 mol)
2- (perfluorohexyl) ethyl methacrylate (M-1620, molecular weight 432, manufactured by Daikin) 43.2 g (0.1 mol)
・ Dimethyl 2,2′-azobis (2-methylpropionate) 0.345 g
(V-601 Wako Pure Chemical Industries, Ltd.)

  Further, 100 g of MEK, 0.23 g of 4-methoxyphenol, and 50.2 g of 1,8-diazabicyclo [5.4.0] undecene-7 (DBU) were added into the system containing the polymer 1 obtained as described above. Add and stir at room temperature for 12 hours. Thereafter, the obtained solution was neutralized with trifluoromethanesulfonic acid and then purified by reprecipitation with water. Furthermore, vacuum drying was performed to obtain a polymer (61 g) having a fluorine-containing group and a radical polymerizable group represented by the following formula (hereinafter also referred to as a polymer having a fluorine-containing group). The weight average molecular weight (Mw) of the obtained polymer was 27000. In addition, each structural unit of the repeating unit having a fluorine-containing group and the repeating unit having a radical polymerizable group in the polymer was 50 mol%.

(Synthesis Example 2: Synthesis of polymer having siloxane group and radical polymerizable group)
The following components were charged into an autoclave having an internal volume of 500 L, and reacted at 75 ° C. for 12 hours while stirring under a nitrogen atmosphere to obtain a solution of polymer 2.
・ Methyl ethyl ketone (MEK) [solvent] 115g
-2- (2-Bromoisobutyryloxy) ethyl methacrylate (BBEM, Manac Co., Ltd., molecular weight 279) [polymerizable compound 1] 19.5 g
・ One-end methacrylate-modified dimethyl silicone (manufactured by Chisso Corporation, molecular weight 1000, FM-0711) [siloxane compound] 30 g
・ Dimethyl 2,2′-azobis (2-methylpropionate)
(V-601 Wako Pure Chemical Industries, Ltd.) 0.345g

  Further, 100 g of MEK and 35 g of 1,8-diazabicyclo [5.4.0] undecene-7 (DBU) were added to the system containing the polymer 2 obtained as described above, and the mixture was stirred at room temperature for 12 hours. . Thereafter, the obtained solution was neutralized with trifluoromethanesulfonic acid and then purified by reprecipitation with water. Furthermore, it was vacuum dried to obtain a polymer (41 g) having a siloxane group and a radical polymerizable group represented by the following formula (hereinafter also referred to as a polymer having a siloxane group). The weight average molecular weight (Mw) of the obtained polymer was 35000. In the polymer, the constitutional unit having a siloxane group was 30 mol%, and the constitutional unit having a radical polymerizable group was 70 mol%. The number of repeating units n was 11.

(Synthesis Example 3: Synthesis of polymer having radical polymerizable group)
In a 500 ml three-necked flask, 200 g of dimethylacetamide, 30 g of polyacrylic acid (manufactured by Wako Pure Chemicals, molecular weight: 25000), 2.4 g of tetraethylammonium, benzyl chloride, 25 mg of ditertiary pentyl hydroquinone, Cyclomer A (manufactured by Daicel Chemical Industries) 25 g was added and reacted at 100 ° C. for 5 hours under a nitrogen stream. Thereafter, reprecipitation was performed with acetonitrile, and the solid matter was collected by filtration, washed with water, and dried to obtain 23 g (Mw: 136000) of a polymerizable group-containing polymer (hereinafter also referred to as polymerizable group-containing polyacrylic acid). From the ¹ H NMR measurement of the obtained polymer, in the following formula, the repeating unit having a radical polymerizable group was 10 mol%, and the repeating unit having a carboxylic acid group was 90 mol%.

(Synthesis Example 4: Synthesis of polymer having radical polymerizable group)
Weighed 30 g of NMP (N-methylpyrrolidone) into a 300 ml three-necked flask purged with nitrogen and flowed with nitrogen at 100 ml / min (hereinafter flowed until the end of the reaction), at an internal temperature of 65 ° C. and a three-one motor rotation speed of 250 rpm / min. Stabilized. 200 ml female of 18.7 g (0.18 mol) of styrene, 15.6 g (0.12 mol) of methacrylic acid-2-hydroxyethyl (hereinafter, HEMA), 30 g of NMP, V-65 (0.745 g) (1 mol% vs. monomer) Weighed into a cylinder and stirred for 30 minutes. Using a plunger pump, the solution stirred in the graduated cylinder was dropped into the three-necked flask over 2 hours to initiate the reaction. After completion of the dropwise addition, a post reaction was performed for 4 hours, and the mixture was allowed to cool to room temperature after completion.
Next, the reaction solution was stirred at room temperature with a three-one motor at 250 rpm / min. A NMP 1 g solution of TEMPO (0.2 g), a NMP 1 g solution of tert-butylhydroquinone (0.1 g), and a 0.19 g NMP 1 g solution of Neostan U-600 (manufactured by Nitto Kasei) were added to a three-necked flask. A Karenz AOI (manufactured by Showa Denko) 17.15 g NMP 30 g solution was dropped into the reaction solution using a dropping funnel over 5 min. The internal temperature of the flask was raised to 55 ° C., and the reaction was performed for 6 hours. After completion of the reaction, the reaction solution was poured into methanol for reprecipitation purification to obtain a desired polymerizable group-containing polymer (25 g) (Mw: 15500) (hereinafter also referred to as polymerizable group-containing polystyrene). From the ¹ H NMR measurement of the obtained polymer, a was 60 mol% and b was 40 mol% in the following formula.

Synthesis Example 5 Synthesis of Photocleavable Compound P1
29.33 g (0.15 mol) of 4-cyano-4′-hydroxybiphenyl was weighed into a 200 ml three-necked flask, 100 ml of DMAc was added and stirred (300 rpm), and dissolved. Thereafter, the reaction was advanced while stirring was continued at the same rotational speed. In order not to generate heat, 22.81 g (0.165 mol) of K ₂ CO ₃ was added little by little, and the reaction solution was heated to 80 ° C. 11-Bromo-1-undecene 38.78 g (0.166 mol) was added dropwise over 30 minutes, and after the addition, the mixture was stirred for 1.5 hours and further stirred at 100 ° C. for 2.5 hours. After completion of the reaction, the reaction solution was poured into ice water to precipitate a solid, and after suction filtration, washed with a large amount of distilled water. The obtained solid was recrystallized from acetonitrile to obtain a cyanoether body (40.21 g) which was a slightly yellowish white solid.
10.42 g (0.03 mol) of the obtained cyanoether was weighed into a 200 ml three-necked flask, the three-necked flask was immersed in an ice bath (sodium chloride was added), cooled, and then added with 25.99 g (0.18 mol) of trichloroacetonitrile and stirred. (300 rpm) and dissolved. Thereafter, the reaction was advanced while stirring was continued at the same rotational speed. The reaction solution was bubbled with HCl gas for 1 hour. After completion of the bubbling, the mixture was stirred for 5 hours, and further stirred for 24 hours in an ice bath. After removing the ice bath and adding 6.5 g of trichloroacetonitrile, the reaction was continued at room temperature for 24 hours. After completion of the reaction, the reaction mixture was diluted with ethyl acetate, washed twice with distilled water and twice with saturated brine, and the ethyl acetate layer was dried over anhydrous magnesium sulfate. Ethyl acetate was distilled off under reduced pressure, and after isolation using silica gel column chromatography, recrystallization was further performed using n-hexane to obtain a slightly yellowish white solid triazine compound (3.37 g).
1.42 g of the obtained triazine compound having a double bond and 8 ml of THF were weighed into a 50 ml eggplant flask, the eggplant flask was cooled with ice water, and 0.9 g of trichlorosilane was added dropwise under a nitrogen stream. Further, a solution obtained by dissolving 60 mg of chloroplatinic acid in 0.6 g of isopropyl alcohol was added dropwise. The reaction solution was stirred for 6 hours under ice cooling, then returned to room temperature and allowed to stand overnight. The reaction solution was concentrated with an evaporator, and volatile components were removed with a vacuum pump to obtain the desired photocleavable compound P1 (2.3 g).

<Example 1>
The silicon substrate treated with the UV ozone cleaner was immersed in a 0.1 wt% toluene solution of the photocleavable compound P1 for 5 hours. After immersion, the substrate surface was washed with toluene. The film thickness of the polymerization initiation layer prepared on the surface of the silicon substrate was measured using ellipsometry (groove bottom optics) (measurement range: 5 mm ² ), 3.0 nm (12-point average value, standard deviation 0.91 mm) Met.
Next, a silicon substrate provided with a polymerization start layer in a nitrogen atmosphere in a methyl ethyl ketone (MEK) solution (total polymer concentration: 1 wt%) containing the fluorine-containing polymer synthesized above and a polymer having a siloxane group. It was applied on top by spin coating (rotation speed 1500 rpm). The film thickness of the obtained coating film was 30 nm. In addition, the mixing ratio (weight ratio) of the polymer having a fluorine-containing group and the polymer having a siloxane group was 1: 2.
Next, light emitted from a high-pressure mercury lamp (UVX-02516S1LP01, manufactured by USHIO INC., Main emission wavelength: 254 nm (light amount 22 mW / cm ² ), 365 nm (light amount 35 mW / cm ² )) is used only for light of 320 nm or more. The coating film on the silicon substrate was exposed for 60 seconds through a transparent glass plate (manufactured by Matsunami Glass, blue plate glass). In addition, the blue plate glass used has an absorbance (Abs.) At 300 nm of 1.4, an absorbance at 320 nm of 0.3, an absorbance at 360 nm of 0, and mainly light of 320 nm or more. Is transparent.
After the exposure, the obtained silicon substrate was immersed in a methyl ethyl ketone solution for 10 minutes and subjected to ultrasonic cleaning for 3 minutes to obtain a laminate including a silicon substrate and a polymer film directly bonded to the substrate.
After cleaning, the thickness of the polymer film obtained on the silicon substrate was measured and found to be 4.2 nm. Further, when the surface of the obtained polymer film was subjected to AFM measurement, a phase separation structure was confirmed (FIG. 4). The resulting polymer film had a surface roughness Ra of 1.22 nm. In the figure, the yellow part is a polymer having a fluorine-containing group.

<Example 2>
A laminate was produced in the same manner as in Example 1 except that the mixing ratio (weight ratio) of the polymer having a fluorine-containing group and the polymer having a siloxane group was 1: 1.
When the film thickness of the polymer film obtained on the silicon substrate was measured, it was 4.5 nm. Further, when the surface of the obtained polymer film was subjected to AFM measurement, a phase separation structure was confirmed (FIG. 5). The obtained polymer film had a surface roughness Ra of 1.02 nm. In the figure, the yellow part is a polymer having a fluorine-containing group.

<Example 3>
A laminate was produced in the same manner as in Example 1 except that the mixing ratio (weight ratio) of the polymer having a fluorine-containing group and the polymer having a siloxane group was 2: 1.
When the film thickness of the polymer film obtained on the silicon substrate was measured, it was 3.9 nm. Moreover, when the surface of the obtained polymer film was subjected to AFM measurement, a phase separation structure was confirmed (FIG. 6). The obtained polymer film had a surface roughness Ra of 1.31 nm. In the figure, the yellow part is a polymer having a fluorine-containing group.

<Example 4>
A laminate was produced in the same manner as in Example 1 except that the exposure was performed without using a glass plate that transmits only light of 320 nm or more.
When the film thickness of the polymer film obtained on the silicon substrate was measured, it was 26.5 nm. Moreover, when the surface of the obtained polymer film was subjected to AFM measurement, a phase separation structure was confirmed (FIG. 7). The obtained polymer film had a surface roughness Ra of 4.87 nm. In the figure, the yellow part is a polymer having a fluorine-containing group.

As shown in Examples 1 to 4, the polymer film obtained by AFM measurement was directly bonded to the substrate and had a desired phase separation structure.
In the AFM photographs of Examples 1 to 4, the area ratio between the polymer having a fluorine-containing group and the polymer having a siloxane group was consistent with the charging ratio.

<Example 5>
The silicon substrate treated with the UV ozone cleaner was immersed in a 0.1 wt% toluene solution of the photocleavable compound P1 for 5 hours. After immersion, the substrate surface was washed with toluene. The film thickness of the polymerization initiation layer prepared on the surface of the silicon substrate was measured using ellipsometry (groove bottom optics) (measurement range: 5 mm ² ), 3.0 nm (12-point average value, standard deviation 0.91 mm) Met.
Next, polymerization was initiated with a methyl ethyl ketone (MEK) solution (total polymer concentration: 1 wt%) containing the fluorine-containing group-synthesized polymer and polystyrene (Aldrich, weight average molecular weight 210000) in a nitrogen atmosphere. It apply | coated by the spin coat (rotation speed 1500rpm) on the silicon substrate provided with a layer. The film thickness of the obtained coating film was 35 nm. In addition, the mixing ratio (weight ratio) of the polymer having a fluorine-containing group and polystyrene was 2: 1. When AFM measurement of the coating film before exposure was performed, a sea-island-like phase separation structure was confirmed (FIGS. 8A, 8B, and 8C). From the AFM measurement diagrams of FIGS. 8A and 8B, it was confirmed that the height of the polystyrene portion (sea-like portion) was about 30 nm higher than the polymer (island-like portion) having a fluorine-containing group. In addition, in FIG.8 (c), typical sectional drawing of the obtained coating film is shown.
Next, light irradiated from a high-pressure mercury lamp (UVX-02516S1LP01, manufactured by USHIO INC., Main emission wavelength: 254 nm (light amount 22 mW / cm ² ), 365 nm (light amount 35 mW / cm ² )) is applied to the above-described silicon substrate. The coating film was exposed for 60 seconds. After the exposure, the obtained silicon substrate was immersed in a methyl ethyl ketone solution for 20 minutes and subjected to ultrasonic cleaning for 1 minute to obtain a laminate including a silicon substrate and a polymer film directly bonded to the substrate.
When the surface of the obtained polymer film was subjected to AFM measurement after exposure and washing, the same phase separation structure as that of the coating film was confirmed (FIGS. 9A, 9B, and 9C). ). By the washing step, the sea-like portion (polystyrene) not bonded to the substrate was removed, and an island-shaped polymer film composed of a polymer having a fluorine-containing group bonded to the substrate was confirmed. The obtained polymer film had a thickness of 11.0 nm and a surface roughness Ra of 1.4 nm. 9 (a) and 9 (b), the yellow part was a polymer having a fluorine-containing group. FIG. 9C shows a schematic cross-sectional view of the obtained coating film.

<Example 6>
A laminated body was produced in the same manner as in Example 5 except that the exposure was performed through the glass plate (manufactured by Matsunami Glass Co., Ltd., blue plate glass) that transmits only light of 320 nm or more as described above.
When the AFM measurement of the coating film before exposure was performed, the same sea-island-like phase separation structure as in Example 5 was confirmed.
Moreover, when the surface of the obtained polymer film was subjected to AFM measurement after exposure and washing, the same phase separation structure as that of the coating film was confirmed (FIGS. 10A, 10B, and 10C). )). By the washing step, the sea-like portion (polystyrene) not bonded to the substrate was removed, and an island-shaped polymer film composed of a polymer having a fluorine-containing group bonded to the substrate was confirmed. The obtained polymer film had a thickness of 2.0 nm and a surface roughness Ra of 0.6 nm. 10 (a) and 10 (b), the yellow part is a polymer having a fluorine-containing group. FIG. 10C shows a schematic cross-sectional view of the obtained coating film.

In Example 5, since light having a low exposure wavelength of less than 320 nm was also irradiated, polymerization progressed not only between the substrate and the polymer having a fluorine-containing group but also between the polymer having a fluorine-containing group in the coating film. Therefore, a thicker film was obtained as compared with Example 6.
On the other hand, in Example 6, since the light having an exposure wavelength of 320 nm or more was irradiated, the reaction mainly proceeded only between the substrate and the polymer having a fluorine-containing group. The membrane part was removed and a very thin membrane was obtained.

<Example 7>
Except for changing the polystyrene used in Example 5 to polystyrene (manufactured by Aldrich, weight average molecular weight 45000) to the polymer having the siloxane group synthesized above in the polymer having the fluorine-containing group used in Example 5. A laminate was produced in the same manner as in Example 5. As irradiation conditions, UV light including 254 nm and 365 nm was directly exposed for 60 seconds without using a glass plate, as in Example 5. Thereafter, the polymer was washed with MEK solvent for 20 minutes to remove excess polymer.
When AFM measurement of the coating film before exposure was performed, a sea-island-like phase separation structure was confirmed (FIGS. 11A and 11B). From the AFM measurement diagram of FIG. 11A, it was confirmed that the height of the polystyrene part (island-like part) was about 39 nm higher than the part of the polymer having a siloxane group (sea-like part). In addition, FIG.11 (b) shows typical sectional drawing of the obtained coating film.
Moreover, when the surface of the obtained polymer film was subjected to AFM measurement after exposure and washing, the same phase separation structure was confirmed (FIGS. 12A and 12B). By the washing process, the island-shaped portion (polystyrene) not bonded to the substrate was removed, and a sea-like polymer film composed of a polymer having siloxane bonded to the substrate was confirmed. The obtained polymer film had a thickness of 20 nm and a surface roughness Ra of 3.9 nm. In the figure, the yellow part was a polymer having a siloxane group. FIG. 12B shows a schematic cross-sectional view of the obtained coating film.

<Example 8>
A laminate was prepared in the same manner as in Example 7 except that the exposure was performed using the glass plate that transmits only light of 320 nm or more (made by Matsunami Glass Co., Ltd., blue plate glass). .
When AFM measurement was performed on the coating film before exposure, the same sea-island phase separation structure as in Example 7 was confirmed.
Moreover, when the surface of the obtained polymer film was subjected to AFM measurement after exposure and washing, the same phase separation structure was confirmed (FIGS. 13A and 13B). By the washing process, the island-shaped portion (polystyrene) not bonded to the substrate was removed, and a sea-like polymer film composed of a polymer having siloxane bonded to the substrate was confirmed. The obtained polymer film had a thickness of 2.0 nm and a surface roughness Ra of 0.1 nm. In the figure, the yellow part was a polymer having a siloxane group. FIG. 13B shows a schematic cross-sectional view of the obtained coating film.

In Example 7, since light having a low exposure wavelength of less than 320 nm was also irradiated, polymerization progressed not only between the substrate and the polymer having a siloxane group, but also between the polymers in the coating film. In comparison, a thick film was obtained.
On the other hand, in Example 8, since light having an exposure wavelength of 320 nm or more was irradiated, the reaction mainly proceeded only between the substrate and the polymer having a siloxane group, and an unreacted excess coating film was obtained by the cleaning process. The part was removed and a very thin film was obtained.

<Example 9>
A methyl ethyl ketone (MEK) solution (total polymer concentration: 1 wt%) containing the synthesized polymer having fluorine-containing groups and the synthesized polymerizable group-containing polyacrylic acid on the silicon substrate provided with the polymerization initiating layer produced in Example 1. %) Was applied by spin coating (rotation speed 1500 rpm). The film thickness of the obtained coating film was 45 nm. The mixing ratio (weight ratio) of the polymer having a fluorine-containing group and polymerizable polyacrylic acid was 1: 1.
When AFM measurement of the coating film before exposure was carried out, a sea-island-like phase separation structure consisting of an island-like portion of about 1 μm and the remaining sea-like portion was confirmed (Ra = 2.9 nm).
Next, the light emitted from the high-pressure mercury lamp (UVX-02516S1LP01, manufactured by USHIO INC., Main emission wavelength: 254 nm (light amount 22 mW / cm ² ), 365 nm (light amount 35 mW / cm ² )) is the above-described light of 320 nm or more. The coating film on the silicon substrate was exposed for 60 seconds through a glass plate (manufactured by Matsunami Glass Co., Ltd., blue plate glass).
After the exposure, the obtained silicon substrate was immersed in a methyl ethyl ketone solution for 20 minutes and then immersed in methanol for 20 minutes to obtain a laminate including a silicon substrate and a polymer film directly bonded to the substrate.
After cleaning, the thickness of the polymer film obtained on the silicon substrate was measured and found to be 2.0 nm. The obtained polymer film had a surface roughness Ra of 0.08 nm. Further, when the surface of the obtained polymer film was subjected to AFM measurement, a sea-island-like phase separation structure composed of an island-like portion of about 1 μm and the remaining sea-like portion was confirmed as in the case of the coating film.

<Example 10>
The polymer having a fluorine-containing group used in Example 1 was changed to poly (2-vinylpyridine) (manufactured by Aldrich, weight average molecular weight 41500), and the polymer having a siloxane group was changed to a polymerizable group-containing polystyrene. A laminate was prepared in the same manner as in Example 1 except that the coating solution containing the polymer was changed from methyl ethyl ketone to toluene.
When the surface of the obtained polymer film was subjected to AFM measurement after exposure and washing, a sea-island-like phase separation structure was confirmed (FIG. 14). By the washing step, the poly (2-vinylpyridine) in the island-like portion not bonded to the substrate was removed, and a sea-like polymer film composed of the polymerizable group-containing polystyrene bonded to the substrate was confirmed. The resulting polymer film had a thickness of 2.0 nm and a surface roughness Ra of 0.6 nm. In FIG. 14, the yellow part was a polystyrene containing a polymerizable group.

FIG. 1 is a schematic cross-sectional view of an embodiment of a laminate according to the present invention. FIG. 2 is a schematic cross-sectional view of another embodiment of the laminate according to the present invention. FIG. 3 is a schematic cross-sectional view of another embodiment of a laminate according to the present invention. 4 is an atomic force microscope (AFM) image from the top surface of the laminate obtained in Example 1. FIG. FIG. 5 is an AFM image from the top surface of the laminate obtained in Example 2. 6 is an AFM image from the top surface of the laminate obtained in Example 3. FIG. FIG. 7 is an AFM from the top surface of the laminate obtained in Example 4. 8A and 8B are AFM images from the top surface of the laminate having the coating film obtained in Example 5, where FIG. 8A is a plan view and FIG. 8B is a three-dimensional view. FIG. 8C is a schematic cross-sectional view of a laminate having a coating film obtained in Example 5. FIGS. 9A and 9B are AFM images from the top surface of the laminate having the polymer film obtained in Example 5, where FIG. 9A is a plan view and FIG. 9B is a three-dimensional view. . FIG. 9C is a schematic cross-sectional view of a laminate having the polymer film obtained in Example 5. FIGS. 10A and 10B are AFM images from the top surface of the laminate having the polymer film obtained in Example 6, where FIG. 10A is a plan view and FIG. 10B is a three-dimensional view. . FIG. 10C is a schematic cross-sectional view of a laminate having the polymer film obtained in Example 6. FIG. 11A is an AFM image from the top surface of the laminate having the coating film obtained in Example 7. FIG. FIG. 11B is a schematic cross-sectional view of a laminate having a coating film obtained in Example 7. FIG. 12A is an AFM image from the upper surface of the laminate having the polymer film obtained in Example 7. FIG. FIG. 12B is a schematic cross-sectional view of a laminate having the polymer film obtained in Example 7. FIG. 13A is an AFM image from the top surface of the laminate having the polymer film obtained in Example 8. FIG. FIG. 13B is a schematic cross-sectional view of a laminate having the polymer film obtained in Example 8. FIG. 14 is an AFM image from the top surface of the laminate having the polymer film obtained in Example 10.

Explanation of symbols

10, 20, 30, 50, 54, 70, 74 Laminate 12 Substrate capable of generating radicals upon exposure 14, 32 Polymer film 16 Phase 18 composed of polymer A 18, 36 Phase composed of polymer B 22 Substrate 24 Polymerization initiation layer 34 Opening 40, 60 Laminate having coating film 42, 62 Polystyrene phase 44 Polymer phase having fluorine-containing group 52, 56 Polymer film obtained by exposing polymer phase having fluorine-containing group 64 Siloxane Polymer phase having a group 72,76 Polymer obtained by exposing a polymer phase having a siloxane group

Claims (14)

A polymer film having a phase separation structure on the substrate surface by bringing at least one polymer containing at least one polymer having a radical polymerizable group into contact with the substrate surface capable of generating radicals upon exposure. Forming a film, and
An immobilization step of exposing the polymer film formed in the film formation step and immobilizing the polymer film on the substrate;
A polymer film directly bonded to the substrate surface, obtained by a method comprising a washing step of washing the polymer membrane obtained in the immobilization step with a solvent.   The polymer film according to claim 1, wherein the polymer film directly bonded to the substrate surface has a thickness of 0.5 to 100 nm.   The polymer film according to claim 1 or 2, wherein the polymer having a radical polymerizable group is a polymer having a siloxane group or a fluorine-containing group and having a radical polymerizable group. The polymer having a siloxane group or a fluorine-containing group and having a radical polymerizable group has a repeating unit represented by the general formula (1) and a repeating unit represented by the general formula (2). The polymer film according to claim 3, which is a molecule.

(In General Formula (1), R ¹ represents a hydrogen atom or an alkyl group. L ¹ represents a divalent linking group or a simple bond. R ² represents a radical polymerizable group.
In general formula (2), R ³ represents a hydrogen atom or an alkyl group. L ² represents a divalent linking group or a simple bond. R ⁴ represents an alkyl group having a fluorine atom, an aryl group having a fluorine atom, or a group represented by the general formula (X). )

(In the general formula (X), Ra and Rb each independently represent a hydrogen atom, an alkyl group, an aryl group, or a group represented by the general formula (Y). Rc, Rd, Re, Rf and Rg are And each independently represents a hydrogen atom, an alkyl group, or an aryl group, n represents an integer of 0 to 100, and * represents a bonding position with L ^2. )

(In the general formula (Y), Rh to Rl each independently represents a hydrogen atom, an alkyl group, or an aryl group. M represents an integer of 0 to 100. ** represents the general formula (X) and Indicates the bonding position.   The polymer film according to claim 1, wherein the exposure is performed with light having an exposure wavelength of 320 nm or more.   The said phase-separated structure has a continuous phase and the dispersed phase which is disperse | distributed and exists in the said continuous phase, The average diameter of the said dispersed phase is 1 nm-100 micrometers, The Claim 1-5 Polymer membrane.   A polymer film having a phase separation structure, wherein a substrate surface capable of generating radicals upon exposure and a polymer having two or more radical polymerizable groups are directly bonded to each other and formed on the substrate surface.   The polymer film according to claim 7, wherein the film thickness is 0.5 to 100 nm.   The polymer film according to claim 7 or 8, wherein the phase separation structure includes a continuous phase and a dispersed phase that is dispersed in the continuous phase, and an average diameter of the dispersed phase is 1 nm to 100 µm. .   The polymer according to claim 7, wherein at least one of the polymers having a radical polymerizable group is a polymer having a siloxane group or a fluorine-containing group and having a radical polymerizable group. film.   The laminated body which has a board | substrate which can generate | occur | produce a radical by exposure, and the polymer film in any one of Claims 1-10 formed on the board | substrate which can generate a radical by the said exposure.   The laminate according to claim 11, wherein the substrate capable of generating radicals upon exposure is formed of a laminate structure including a substrate and a polymerization initiation layer formed on the substrate.   13. The layer according to claim 12, wherein the polymerization initiating layer is a layer formed by bonding a compound having a polymerization initiating site capable of initiating radical polymerization by exposure and a substrate binding site to the substrate through the substrate binding site. Laminated body. A polymer film having a phase separation structure on the substrate surface by bringing at least one polymer containing at least one polymer having a radical polymerizable group into contact with the substrate surface capable of generating radicals upon exposure. Forming a film, and
An immobilization step of exposing the polymer film formed in the film formation step and immobilizing the polymer film on the substrate;
A method for producing a polymer film directly bonded to the substrate surface, comprising a washing step of washing the polymer film obtained in the immobilization step with a solvent.