JP2009270060A - Method for producing material for fixing polymerization initiator on surface, and method for producing grafted polymer pattern - Google Patents

Abstract

Disclosed is a method for producing a surface-immobilized material for a polymerization initiator, which can easily produce a domain structure in the nano-size order by a self-assembled film of a polymerization initiator without using means such as lithography. In addition, the present invention provides a method for producing a graft polymer pattern, which can easily produce a graft polymer pattern having a nano-size order domain structure.
A polymerization initiator having a site capable of binding to the support is brought into contact with the surface of the support using a dipping method or a vapor deposition method, and then the self-organization of the polymerization initiator in contact with the support. A method for producing a polymerization initiator surface immobilization material that forms a nanodomain structure by a self-assembled film of a polymerization initiator bonded to the support on the support, and production of the polymerization initiator surface immobilization material A method for producing a graft polymer pattern, comprising a step of generating a graft polymer on a nanodomain structure of a surface-immobilized material for a polymerization initiator obtained by the method.
[Selection figure] None

Description

  The present invention relates to imparting functionality to a solid surface, in particular, to a method of forming an ultra-thin film with organic molecules in a pattern on a solid surface, and more specifically, a method for producing a polymerization initiator surface immobilization material, and a graft The present invention relates to a method for producing a polymer pattern.

Attempts to immobilize molecular layers having various functions on a solid surface and control surface properties have been made for a long time.
Among them, the amphiphilic molecule is developed and compressed on the water surface, a monomolecular layer is formed, and then transferred to the solid support. A self-assembled film (SAM) in which an organic thin film is formed by reacting a long-chain alkyl compound with a solid having a surface hydroxyl group is well known.
In the SAM, an operation of compressing molecules like the LB film is not performed, but a highly oriented film having a high orientation similar to the LB film can be obtained by the interaction between the alkyl groups (for example, Non-Patent Document 1). 2).

Furthermore, in order to functionalize the molecular layer on the solid surface thus obtained, a method of patterning this molecular layer with a nano size is also well known.
For example, in order to create a SAM fine pattern, it is known that means such as microcontact printing and lithography are used, and various fine patterns are formed by this means (for example, Non-Patent Documents 3 and 4). reference.). These methods require expensive lithography, but recent research has shown that the reaction conditions such as solvent, temperature, time, etc. during SAM formation have been adequately determined without using equipment such as equipment expensive sographies. It has been reported that a domain structure pattern having a size of about 0.1 μm to 1 μm can be obtained by selecting (see, for example, Non-Patent Documents 5 and 6). In this case, it is necessary to select control of reaction conditions, but there is an advantage that a pattern with a nano-sized domain structure can be obtained at low cost. Also, application of SAM patterns obtained by these methods to high-density recording materials has been studied (for example, see Patent Documents 1 and 2).

So far, the nano-sized domain pattern obtained by using the SAM method has only been reported to use a small molecule such as a long-chain alkylsilane coupling agent. There are few reports.
However, considering application applications, the nanodomain structure made of a polymer compound is expected to be used in various applications such as optical films and surface polarity changing materials (see, for example, Non-Patent Document 7) in addition to recording materials. Therefore, it is considered that a method for easily producing a nanodomain structure on the surface of the support and a method for easily producing a nanodomain structure (pattern) using a polymer compound by applying it will be required in the future.
A. Ulman, "An Introduction to ultrathin organic films from Langmuir-Blodgett to Self-Assembly", Academic Press. Inc., San Diego (1991) "Self-organized nanomaterials" Frontier Publishing (2007) GMWhitesides, Science, 263, 60 (1994) H.-W.Le at al., 19. 1963 (2003) A. Couzis, Langmuir, 17, 2001, 7789 T.Kato, Thin Solid Films vol 379, 230 (2000) I.Luzinov, Polymer Preprints, 46 (2) 80 (2005) Japanese Patent Laid-Open No. 2003-76036 JP 2002-334414 A

Therefore, the present invention has been made in view of these circumstances, and an object thereof is to achieve the following object.
That is, the object of the present invention is to provide a method for preparing a surface-immobilized material for a polymerization initiator that can easily produce a nano-sized domain structure by a self-assembled film of a polymerization initiator, without using lithography or the like. There is to do.
Another object of the present invention is to provide a method for producing a graft polymer pattern, which can easily produce a graft polymer pattern having a nano-size order domain structure.

As a result of investigations, the present inventors have found that the above-mentioned problems can be solved by using a polymerization initiator having a site capable of binding to a support, and have completed the present invention.
Specifically, the present invention is specifically shown below.

  In the method for producing the surface-immobilized material for polymerization initiator according to the present invention, after the polymerization initiator having a portion capable of binding to the support is brought into contact with the surface of the support using an immersion method or a vapor deposition method, the support It is characterized in that a nanodomain structure is formed on the support by a self-assembled film of the polymerization initiator bonded to the support by self-assembly of the polymerization initiator in contact with the support.

In the method for producing the surface-immobilized material for polymerization initiator of the present invention, it is a preferable aspect that the diameter of the nanodomain structure is 1 nm to 10 μm.
Moreover, it is preferable that the polymerization initiator which has a site | part which can be couple | bonded with a support body has a structure represented by following General formula (1).

  In the above general formula (1), Q is a silane coupling group, thiol group, thioisocyanato group, nitrile group, carboxyl group, hydroxyl group, amino group, monoalkylsilane group, phosphonic acid group, phosphate ester group, and unsaturated carbonization. A support binding group selected from the group consisting of a hydrogen group is represented, X represents a linking group containing an alkylene group having 5 to 40 carbon atoms, and Y represents a functional group capable of generating a radical.

  In this invention, it is more preferable that the polymerization initiator which has a site | part which can be couple | bonded with a support body has a structure represented by following General formula (2).

  In the general formula (2), X represents a linking group containing an alkylene group having 5 to 40 carbon atoms, Y represents a functional group capable of generating a radical, Z represents a hydrolyzable group, and R represents a hydrogen atom or An alkyl group having 1 to 6 carbon atoms is represented. m represents an integer of 0 to 2, n represents an integer of 1 to 3, and satisfies the relationship of n + m = 3.

  In the general formulas (1) and (2), the functional group capable of generating a radical represented by Y is a functional group derived from a compound having a carbon halogen bond or a functional group derived from a pyridinium compound. Is a preferred embodiment.

  Moreover, the method for producing a graft polymer pattern of the present invention comprises a step of generating a graft polymer on the nanodomain structure of the polymerization initiator surface-immobilized material obtained by the method for producing a polymerization initiator surface-immobilized material of the present invention. It is characterized by having.

According to the present invention, there is provided a method for producing a polymerization initiator surface immobilization material capable of easily producing a nanosize order domain structure by a self-assembled film of a polymerization initiator without using means such as lithography. Can do.
In addition, according to the present invention, it is possible to provide a method for producing a graft polymer pattern, which can easily produce a graft polymer pattern having a nano-size order domain structure.

  Hereinafter, the preparation method of the polymerization initiator surface immobilization material of the present invention and the preparation method of the graft polymer pattern will be described in detail.

<Method for producing polymerization initiator surface immobilization material>
In the method for producing the surface-immobilized material for polymerization initiator according to the present invention, after the polymerization initiator having a portion capable of binding to the support is brought into contact with the surface of the support using an immersion method or a vapor deposition method, the support It is characterized in that a nanodomain structure is formed on the support by a self-assembled film of the polymerization initiator bonded to the support by self-assembly of the polymerization initiator in contact with the support.
Hereinafter, a method of bringing a polymerization initiator having a site capable of binding to the support into contact with the support surface by using an immersion method or a vapor deposition method will be described (hereinafter sometimes referred to as “step (a)”. is there).

[(A) Process]
In the step (a) in the method for producing the surface-immobilized material for polymerization initiator of the present invention, a polymerization initiator having a binding site with the support is applied to the entire support surface using an immersion method or a vapor deposition method. Make contact.
As the polymerization initiator used in this step, any compound can be used as long as it is a polymerization initiator having a site capable of binding to a support and can form a self-assembled film. The compound represented by Formula (1) is preferable. Hereinafter, the “polymerization initiator having a site capable of binding to the support” will be referred to as “support support-binding initiator” as appropriate.

  In general formula (1), Q represents a site that can be bonded to the support (support-binding group), X represents a linking group, and Y represents a polymerization initiation site (a functional group capable of generating radicals).

  The support-binding group represented by Q in the general formula (1) is preferably a reactive group capable of reacting with and binding to a functional group present on the surface of the support. Silane coupling groups such as methoxysilane and triethoxysilane, sulfur-containing functional groups such as thiol groups and thioisocyanato groups, nitrile groups, carboxyl groups, hydroxyl groups, amino groups, monoalkylsilane groups, phosphonic acid groups, phosphate ester groups, Unsaturated hydrocarbon groups such as alkenes and alkynes are preferably used.

The support-binding group represented by Q is preferably selected according to the material of the support.
For example, if the support is a metal such as gold, silver, copper, platinum, palladium, or iron, or a semiconductor compound such as GaAs or InP, the support binding group represented by Q may be a thiol group or thioisocyanato. A sulfur-containing functional group such as a group and a monoalkylsilane group are preferred. In particular, when the support is gold, a thiol group is most preferable as the support-binding group represented by Q.
If the support is a metal such as platinum, palladium, gold or silver, the support binding group represented by Q is also a preferred embodiment.

If the support is a metal oxide such as Al ₂ O ₃ , AgO, CuO, Zr / Al ₂ O _3, or an oxide such as oxide-NH ₂ , the support binding group represented by Q is carboxyl. Groups are preferred.
If the support is a metal oxide such as ZrO ₂ , TiO ₂ , Al ₂ O ₃ , Ta ₂ O ₅ , Zr / Al ₂ O ₃ , the support-binding group represented by Q is a phosphonic acid group. The phosphate group is also one of the preferred embodiments.
If the support is TiO ₂ , Al ₂ O ₃ , glass, quartz, ITO, silicon substrate, or the like, the support-binding group represented by Q is preferably an amino group.

Further, when the support is glass, mica, SiO ₂ , SnO ₂ , GeO ₂ , ZrO ₂ , TiO ₂ , Al ₂ O ₃ , ITO, SUS, PTZ, etc., the support binding group represented by Q Is preferably a silane coupling group.
If the support is hydrogen-terminated silicon (Si—H), silicon halide (Si—X, X═Cl, Br, I) or the like, the support-binding group represented by Q is a hydroxyl group or An unsaturated hydrocarbon group is preferred.
Further, if the support is hydrogen-terminated diamond (C—H), the support-binding group represented by Q is preferably an unsaturated hydrocarbon group.

Among these combinations, as the support, gold, glass, quartz, mica, ITO, TiO ₂ are easy to obtain, easy to apply as industrial materials, and easy to form a domain structure. In addition, silicon is preferable, and the support-binding group represented by Q includes a silane coupling group, a thiol group, a carboxyl group, and a phosphonic acid because of its reactivity with the support and the ease of forming a domain structure. Groups are preferred.

  X in the general formula (1) is a group capable of linking the support-binding group represented by Q and the radical generating group represented by Y and promoting self-assembly. As long as it is not particularly limited, it is preferably an organic linking group from the viewpoint of ease of synthesis and self-assembly, and particularly includes an alkylene group having 5 to 40 carbon atoms. Preferably, it further contains an alkylene group having 8 to 25 carbon atoms.

Y in the general formula (1) is not particularly limited as long as it is a functional group capable of generating a radical, but a functional group capable of generating a radical by light, a functional group capable of generating a radical by heat, ATRP polymerization, etc. A functional group capable of generating a radical applied to is used.
Specifically, a carbonyl group that generates a radical by a hydrogen abstraction reaction, a functional group having a C—C bond adjacent to a carbonyl group that generates a radical by a Norrish type 1 reaction, bromo, chloro, iodo, etc. A functional group containing a carbon atom having a halogen group, a functional group containing a heteroatom bond such as nitrogen-oxygen, nitrogen-nitrogen, oxygen-oxygen, sulfur-sulfur bond, carbon-phosphorus, phosphorus-phosphorus, azo group, And so on.

  Among them, Y is a carbonyl group that generates a radical by a hydrogen abstraction reaction or a C—C bond adjacent to a carbonyl group that generates a radical by a Norrish type 1 reaction in terms of stability over time and sensitivity. And a functional group containing a carbon atom having a halogen group such as bromo and chloro, and a functional group containing a heteroatom bond such as nitrogen-oxygen.

As Y, more specifically, (a) aromatic ketones, (b) onium salt compounds, (c) organic peroxides, (d) thio compounds, (e) hexaarylbiimidazole compounds, (f) Preferred are functional groups derived from ketoxime ester compounds, (g) borate compounds, (h) azinium compounds, (i) active ester compounds, (j) compounds having a carbon halogen bond, (k) pyridinium compounds, etc. And functional groups having structures described in JP-A No. 2004-123837, [0015] to [0146] can be used.
Among these, Y is preferably a functional group derived from a compound having a carbon halogen bond or a functional group derived from a pyridinium compound.

  In the present invention, it is more preferable that the support-bound initiator has a structure represented by the following general formula (2).

  In the general formula (2), X represents a linking group containing an alkylene group having 5 to 40 carbon atoms, Y represents a functional group capable of generating a radical, Z represents a hydrolyzable group, and R represents a hydrogen atom or An alkyl group having 1 to 6 carbon atoms is represented. m represents an integer of 0 to 2, n represents an integer of 1 to 3, and satisfies the relationship of n + m = 3.

  X and Y in the general formula (2) have the same meanings as X and Y in the general formula (1), and preferred examples are also the same.

Z in the general formula (2) represents a hydrolyzable group. Specific examples of hydrolyzable groups include alkoxy groups (methoxy groups, ethoxy groups, etc.), halogen atoms (fluorine atoms, chlorine atoms, bromine atoms, iodine atoms), acyloxy groups (acetoxy groups, propanoyloxy groups, etc.) Among them, a methoxy group, an ethoxy group, and a chlorine atom are preferable in terms of good reactivity.
In the general formula (2), when there are a plurality of Z, they may be the same or different.

R in the general formula (2) represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Of these, a methyl group and an ethyl group are preferable.
In the general formula (2), when there are a plurality of Rs, they may be the same or different.

  In general formula (2), m represents an integer of 0 to 2, n represents an integer of 1 to 3, and satisfies the relationship of n + m = 3. Among these, m is preferably 0 to 1, and n is preferably 2 to 3.

  In the present invention, in order to facilitate the formation of the nanodomain structure, in the compound represented by the general formula (1) (support-bound initiator), in addition to having a long-chain alkylene group as X, As the functional group capable of generating the represented radical, the self-aggregation property of the functional group itself needs to be somewhat low. For that purpose, in the structure represented by XY, in the case of an ester group or an amide group, a total of two or less, and in the case of an aromatic ring such as a phenyl group or a naphthyl group, 2 in total. In addition, it is preferable to include a heteroaromatic ring having no more than three rings in which no more than three rings are condensed. If a group other than an alkylene group is introduced into the structure represented by X—Y, the formability of the nanodomain structure is lowered.

  Hereinafter, although the specific example [exemplary compound T1-T8] of a compound represented by General formula (1) is shown, this invention is not restrict | limited to these.

In this step, the support-binding initiator as described above is brought into contact with the support surface using an immersion method or a vapor deposition method.
In the present invention, the dipping method is a preferred embodiment because it is easy to operate.

Here, the dipping method in this step is performed by dissolving the support-bound initiator in a solvent and immersing the support in the solution.
As the solvent used here, any solvent can be used as long as the support-bound initiator does not react, but a solvent having low polarity is preferable from the viewpoint of promoting the adsorptivity to the support.
Specifically, hydrocarbon compounds such as hexane, cyclohexane, bicyclohexyl, decane, dodecane, benzene, toluene, and xylene, and halogen-based hydrocarbon compounds such as chloroform, carbon tetrachloride, and dichloromethane are preferable. Moreover, these may be used independently and these mixed solvents are also effective.

The concentration of the support-bound initiator in the solution is preferably between 0.01% by mass and 10% by mass, more preferably between 0.1% by mass and 1% by mass. Within this range, the adsorption rate of the support-bound initiator to the support can be increased, and a good self-assembled film can be easily obtained.
The time for immersing the support in this solution may be appropriately determined according to the support-binding initiator used, and is preferably between 10 seconds and 60 minutes, particularly from 20 seconds to 30 minutes. Is more preferable.
Moreover, the immersion temperature (solution temperature) is preferably 40 ° C. or lower, and the lower limit is −20 ° C.

On the other hand, the vapor deposition method in this step is a method in which the support-bound initiator is vaporized by heating or vacuum in the atmosphere and adsorbed on the support surface. As a method for vaporizing the support-bound initiator, any method can be adopted, but in order to keep the temperature of the support as low as possible and to easily form a nanodomain structure, adsorption is performed at a low temperature. It is preferable to use a vacuum method that can be used.
In the vacuum method, a vacuum apparatus having an exhaust pump system and a decompression chamber is used. The preferred degree of vacuum is 10 pa or less, particularly 10 ⁻² Pa or less. Further, the lower limit of the degree of vacuum is preferably 10 ⁻⁸ pa.
Further, the boat temperature for heating the support-bound initiator is preferably 300 ° C. or lower, and more preferably 200 ° C. or lower.

  As described above, the conditions for applying the vapor deposition method are preferably performed under vacuum. However, when the support binding initiator to be vapor deposited is thermally stable, it can be performed under the atmosphere. In this case, the support binding initiator and the support are put in separate places in a sealed container, respectively, and heated to a range of 50 ° C to 300 ° C, preferably 100 ° C to 250 ° C. Vapor deposition is performed.

  In the present invention, the method of contacting the support-bound initiator with the support surface by the dipping method and the vapor deposition method is described, but besides these methods, for example, A. Ulman Chem. Rev., The method for forming a self-assembled film described in 96,1533, (1996) can be applied.

Next, the support used in this step will be described.
The support in the present invention is not limited in its shape and material as long as it has a surface with which the support-bound initiator is brought into contact, but considering the adsorptivity and cohesiveness with the support-bound initiator. And may be selected as appropriate.
In the present invention, as described later, the self-organization of the support-bound initiator itself can form a nanodomain structure by the self-assembled film of the polymerization initiator bound to the support, There is no need for a special support in which a region having high adsorptivity with the support-bound initiator exists locally on the surface. That is, the present invention is based on a self-assembled film of a polymerization initiator bonded to a support made of a single material and having a surface with a uniform adsorption property to the support-bound initiator. Nanodomain structures can be easily formed.

As the material of the support, as described above as a preferable combination with Q (support binding group) in the support binding initiator, metals such as gold, silver, copper, platinum, palladium, iron, Semiconductor compounds such as GaAs and InP, metal oxides such as Al ₂ O ₃ , AgO, CuO, ZrO ₂ , TiO ₂ , Ta ₂ O ₅ and Zr / Al ₂ O ₃ , oxides such as oxide-NH ₂ , glass , _{mica, SiO 2, SnO 2, GeO} 2, ITO, SUS, PTZ, hydrogen-terminated silicon (Si-H), halogenated silicon (Si-X, X = Cl , Br, I), hydrogen-terminated diamond ( C-H), and the like.
In addition, as a shape of a support body, the flat board | substrate without an unevenness | corrugation is preferable from the point of the ease of forming a self-organization film | membrane. The flatness is preferably 1 μ or less in terms of Ra, more preferably 100 nm or less, and even more preferably 10 nm or less.

As described above, the support binding initiator is applied to the entire support surface.
Then, the nanodomain structure by the self-assembled film | membrane of the polymerization initiator couple | bonded with this support body can be formed on a support body by the self-organization of the support body binding initiator provided to the support surface.
Hereinafter, after the step (a), the step until the polymerization initiator surface fixing material is produced by using the self-assembly of the support binding initiator will be referred to as the step (b) as appropriate.

[(B) Process]
In (b) in the method for producing a polymerization initiator surface immobilization material of the present invention, the fact that the support-bound initiator is self-assembled on the support after the step (a) is used.
Here, “self-assembly of a support-bound initiator” in the present invention means that the support-bound initiator provided on the support naturally moves and aggregates to form a nanodomain structure. means.
In general, it is understood that a monolayer of an organosilane compound formed by a liquid phase method grows by adsorbing a two-dimensional association of organosilane compound molecules grown in the liquid phase onto a solid surface. . The aggregates are further integrated by moving on the ultrathin adsorbed water layer existing on the surface of the oxide substrate, and as a result, grow to a nanodomain structure.
Therefore, in this step, it is preferable to form an environment in which the support binding initiator applied to the support surface is likely to aggregate, that is, the support surface is easily moved.

  For example, in the step (a), when a support binding initiator is applied to the support surface by a dipping method, the mobility / cohesion of the support binding initiator is enhanced and grown to a nanodomain structure. Is preferably 60 ° C. or lower, more preferably 40 ° C. or lower. In particular, the lower limit of the temperature of the applied liquid phase is preferably about 30 ° C. to room temperature.

  In addition, in the step (a), when a support binding initiator is applied to the support surface by vapor deposition, the mobility / cohesion of the support binding initiator is improved, and the nano domain structure is grown. The support temperature is preferably 100 ° C. or lower, more preferably 60 ° C. or lower. The lower limit of the support temperature is preferably 20 ° C. from the viewpoint of the self-assembled film formability.

  In the state as described above, the support-bound initiator self-assembles to form a nanodomain structure in which the support-bound initiator is locally aggregated on the surface of the support. In addition, a reaction between the support and the support-binding initiator occurs, and a state where the polymerization initiator is bonded to the support can be formed.

Although the mechanism in the present invention is not clear, it is assumed as follows.
That is, after the step (a), the support-bound initiator physically adsorbed on the support surface moves and aggregates with time to form a self-assembled film. After that, the support and support-bound initiator react to form a strong chemical bond, and it is assumed that a nanodomain structure is formed by the self-assembled film of the polymerization initiator bound to the support. Is done.

As described above, through the above-described steps (a) and (b), a nanodomain structure is formed on the support by a self-assembled film of a polymerization initiator bonded to the support.
In the present invention, the “nanodomain structure by a self-assembled film of a polymerization initiator” means that after the support-bound initiator is applied to the support surface, it aggregates by its own cohesive force and is about 1 nm to 10 μm. In addition, an aggregate structure fixed to the support by a chemical reaction with the support surface is taken.
This structure changes with time, and when the support-bound initiator and the support are brought into contact with each other for a long time, the support-bound initiator eventually covers the entire support surface, and the support is supported. A thin film of a polymerization initiator bonded to the support is formed on the entire body surface. In other words, the nanodomain structure in the present invention is generated in the course of forming a thin film of a uniform polymerization initiator covering the entire support surface. Non-patent document 6 describes a typical process for generating a domain structure of a self-assembled film formed by a simple long-chain alkylsilane coupling agent that is not a polymerization initiator. In general, the ease of forming a self-assembled film depends on the cohesive strength of long-chain alkyl groups. It is difficult to form an organized film. From such points, in the present invention, among the support-bound initiators, it is preferable to use the compound represented by the general formula (1) as described above. That is, a compound represented by the general formula (1) (particularly preferably, in the compound represented by the general formula (1), an ester group or an amide group is combined in the structure represented by XY. In the range of 2 or less, and in the case of aromatic rings such as phenyl and naphthyl groups, in the range of 2 or less, and in the case of heteroaromatic rings, at most 3 rings are condensed. ), A self-assembled film can be easily formed even if there is a structural unit that functions as a polymerization initiator such as a functional group capable of generating radicals. Is obtained.

Here, in the nanodomain structure in the present invention, the film thickness of the thin film formed on the support is measured using ellipsometry, and the centerline surface roughness is measured using an AFM (atomic force microscope). And by measuring the maximum height difference.
In the present invention, the diameter of the nanodomain structure is preferably in the range of 1 nm to 10 μm, and more preferably in the range of 10 nm to 3 μm.
Here, the “diameter of the nanodomain structure” means the length of the portion having the maximum distance in the amorphous aggregate because the nanodomain structure (aggregate) is irregular.
In addition, the nanodomain structure is preferably present in the range of 1% to 90%, more preferably in the range of 10% to 70%, as the covering area ratio with respect to the support surface.

<Method for producing graft polymer pattern>
The method for producing a graft polymer pattern of the present invention comprises a step of generating a graft polymer on the nanodomain structure of the polymerization initiator surface-immobilized material obtained by the method for producing a polymerization initiator surface-immobilized material of the present invention (hereinafter referred to as “graft polymer pattern”). (Referred to as step (c)).

[(C) Step]
In this step (c), a method is used in which an unsaturated compound capable of radical polymerization (hereinafter sometimes simply referred to as a polymerizable compound) is brought into contact with the nanodomain structure of the support and then exposed. .
In this step, a solution containing a polymerizable compound such as a monomer, a macromonomer, or a polymer compound having a radical polymerizable group is applied onto a support having a nanodomain structure, or a support having a nanodomain structure. By immersing the body in the solution and then performing exposure, the polymerizable compound is bonded to the nanodomain structure, or the polymerizable compounds are polymerized to form a graft polymer.

(Unsaturated compounds capable of radical polymerization)
As the unsaturated compound (polymerizable compound) capable of radical polymerization, any of a monomer, a macromonomer, and a polymer compound having a radical polymerizable group can be used.
For example, as these polymerizable compounds, known compounds can be arbitrarily used, and polymerizable compounds having various interactive groups can be used depending on applications.

As the polymerizable compound particularly useful in the present invention, those having a functional group capable of adsorbing a functional material in addition to a radical polymerizable group are preferable, and examples of such a functional group include a polar group. Among these polar groups, hydrophilic groups are preferable, and more specifically, negatively charged functional groups such as ammonium and phosphoniu, positively charged functional groups, sulfonic acid groups, carboxyl groups, phosphoric acid groups, and phosphonic acid groups. In addition to the functional group having, for example, nonionic groups such as a hydroxyl group, an amide group, a sulfonamide group, an alkoxy group, and a cyano group may be mentioned.
Hereinafter, the polymerizable compound having a polar group will be specifically described.

  Specific examples of the monomer as a polymerizable compound having a polar group that can be used in the present invention include (meth) acrylic acid or an alkali metal salt and amine salt thereof, itaconic acid or an alkali metal salt and amine salt thereof, styrene, and the like. Sulfonic acid or its alkali metal salt and amine salt, 2-sulfoethyl (meth) acrylate or its alkali metal salt and amine salt, 2-acrylamido-2-methylpropanesulfonic acid or its alkali metal salt and amine salt, acid phosphooxypoly Oxyethylene glycol mono (meth) acrylate or its alkali metal salts and amine salts, polyoxyethylene glycol mono (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (meth) acrylamide, N-monomethylol (medium) ) Acrylamide, N-dimethylol (meth) acrylamide, allylamine or its hydrohalide, N-vinylpyrrolidone, vinylimidazole, vinylpyridine, vinylthiophene, styrene, ethyl (meth) acrylate, n-butyl (meth) Examples thereof include (meth) acrylic acid esters having an alkyl group having 1 to 24 carbon atoms such as acrylic acid esters.

The macromonomer as a polymerizable compound having a polar group that can be used in the present invention can be prepared by a known method using the monomer. The method for producing the macromonomer used in this embodiment is described in, for example, Chapter 2 of “Macromonomer Chemistry and Industry” (Editor, Yuya Yamashita) published on September 20, 1999, published by the IP Publishing Department. Various production methods have been proposed in “Synthesis”.
The useful weight average molecular weight of such a macromonomer is in the range of 500 to 500,000, with a particularly preferred range being 1000 to 50,000.

The polymer compound as the polymerizable compound having a polar group that can be used in the present invention includes a polar group, an ethylene addition polymerizable unsaturated group (polymerizable group) such as a vinyl group, an allyl group, and a (meth) acryl group. , Refers to the polymer introduced. This polymer has an ethylene addition polymerizable unsaturated group at least at the terminal or side chain, more preferably has an ethylene addition polymerizable unsaturated group at the side chain, and has no ethylene addition polymerizable unsaturated group at the terminal and side chain. Those having a saturated group are more preferred.
The useful weight average molecular weight of such a polymer compound is in the range of 500 to 500,000, and a particularly preferred range is 1000 to 50,000.

As a synthesis method of a polymer compound having a polar group and a polymerizable group, i) a method of copolymerizing a monomer having a polar group and a monomer having a polymerizable group, ii) a monomer having a polar group and a polymerizable group A method in which a monomer having a precursor is copolymerized and then a double bond is introduced by treatment with a base or the like, iii) a polymer having a polar group and a monomer having a polymerizable group are reacted to introduce a polymerizable group The method of doing is mentioned.
A preferred synthesis method is, from the viewpoint of synthesis suitability, ii) a method in which a monomer having a polar group and a monomer having a polymerizable group precursor are copolymerized, and then a polymerizable group is introduced by treatment with a base or the like, iii) This is a method of introducing a polymerizable group by reacting a polymer having a polar group with a monomer having a polymerizable group.

  Examples of the monomer having a polar group used in the synthesis methods i) and ii) include (meth) acrylic acid or alkali metal salts and amine salts thereof, itaconic acid or alkali metal salts and amine salts thereof, and more specifically. Include 2-hydroxyethyl (meth) acrylate, (meth) acrylamide, N-monomethylol (meth) acrylamide, N-dimethylol (meth) acrylamide, allylamine or its hydrohalide, 3-vinylpropionic acid or its Alkali metal salts and amine salts, vinyl sulfonic acid or its alkali metal salts and amine salts, 2-sulfoethyl (meth) acrylate, polyoxyethylene glycol mono (meth) acrylate, 2-acrylamido-2-methylpropane sulfonic acid, acid phos Examples include oxypolyoxyethylene glycol mono (meth) acrylate, N-vinyl pyrrolidone (the following structure), sodium styrene sulfonate, vinyl benzoic acid and the like. Generally, carboxyl group, sulfonic acid group, phosphoric acid group, amino A monomer having a functional group such as a group or a salt thereof, a hydroxyl group, an amide group, a phosphine group, an imidazole group, a pyridine group, or a salt thereof, and an ether group can be used.

Examples of the monomer having a polymerizable group that is copolymerized with the monomer having a polar group include allyl (meth) acrylate and 2-allyloxyethyl methacrylate.
Moreover, as a monomer which has a polymeric group precursor used for the synthetic | combination method of said ii), 2- (3-chloro- 1-oxopropoxy) ethyl methacrylate [*], and Unexamined-Japanese-Patent No. 2003-335814 are described. Compounds (i-1 to i-60) can be used, and among these, the following compound (i-1) is particularly preferable.

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

  Regarding the method of introducing a polymerizable group by treatment with a base after copolymerizing a monomer having a polar group and a monomer having a polymerizable group precursor in the synthesis method of ii) above, for example, The method described in 2003-335814 can be used.

As described above, the polymerizable compound having a polar group (hydrophilic group) has been mainly described as the polymerizable compound. However, the present invention is not particularly limited to these compounds, and a graft formed depending on the application. What is necessary is just to select suitably the kind of polymer (kind of a functional group).
For example, in the method for producing a graft polymer pattern of the present invention, when a hydrophilic / hydrophobic pattern is formed, a hydrophobic support is used, and a hydrophilic compound is used using a polymerizable compound having a hydrophilic group. A polymer may be generated. Alternatively, a hydrophilic / hydrophobic pattern can also be obtained by using a hydrophilic support and generating a hydrophobic graft polymer using a polymerizable compound having a hydrophobic group.
Moreover, when producing an oil-repellent and water-repellent pattern, a polymerizable compound containing a fluorine atom may be used.

  These polymerizable compounds may be brought into contact with a support having a nanodomain structure alone, or may be brought into contact with the support in a state of being dispersed or dissolved in a solvent. As this contact method, a support having a nanodomain structure may be immersed in a liquid composition containing a specific polymer, but from the viewpoint of handleability and production efficiency, A method of forming a coating film by contacting a polymerizable compound as it is or applying a liquid composition containing the polymerizable compound, and further drying the coating film to contain the polymerizable compound on the surface of the support It is preferable to carry out by forming the layer (graft polymer precursor layer) to perform.

The solvent constituting the liquid composition containing the polymerizable compound is not particularly limited as long as the polymerizable compound as the main component can be dissolved or dispersed. When using a polymerizable compound having a polar group (hydrophilic group) as described above, an aqueous solvent such as water or a water-soluble solvent is preferable, and a mixture or a surfactant may be further added to the solvent. Good.
Examples of the solvent that can be used include alcohol solvents such as methanol, ethanol, propanol, ethylene glycol, glycerin and propylene glycol monomethyl ether, acids such as acetic acid, ketone solvents such as acetone and cyclohexanone, amides such as formamide and dimethylacetamide. System solvents, and the like.

  Further, the surfactant that can be added to the liquid composition as necessary may be any one that dissolves in a solvent. Examples of such a surfactant include n-dodecylbenzenesulfonic acid. Anionic surfactants such as sodium, cationic surfactants such as n-dodecyltrimethylammonium chloride, polyoxyethylene nonylphenol ether (commercially available products include, for example, Emulgen 190, manufactured by Kao Corporation), polyoxy Examples include ethylene sorbitan monolaurate (commercially available products such as “Tween 20”) and nonionic surfactants such as polyoxyethylene lauryl ether.

When a method of forming a coating film by applying a liquid composition containing a polymerizable compound to the surface of the support is used, the coating amount is in terms of solid content from the viewpoint of obtaining a sufficient coating film. preferably ^{0.1g / m 2 ~10g / m 2} , especially 0.5g ^{/ m 2} ~5g ^/ m 2 is preferred.
Moreover, when forming a graft polymer precursor layer, the thickness is preferably in the range of 0.01 μm to 20 μm, more preferably in the range of 0.05 μm to 10 μm, and in the range of 0.1 μm to 5 μm. More preferably.

(exposure)
The exposure in this step is not particularly limited as long as radicals can be generated from the support-bound initiator, and irradiation with light such as ultraviolet light and visible light, high energy such as electron beam, gamma ray, and X-ray. X-ray irradiation is used. In particular, from the viewpoint of the cost of the apparatus, exposure with ultraviolet rays or visible rays is preferable.
By this exposure, a graft polymer combined with a polymerization initiator constituting the nanodomain structure is formed on the nanodomain structure.

After the graft polymer is produced as described above, the support is subjected to treatments such as solvent immersion and solvent washing to remove the remaining homopolymer and be purified. Specifically, washing with water or acetone, drying and the like can be mentioned. From the viewpoint of homopolymer removability, means such as ultrasonic waves may be taken.
After purification, the homopolymer remaining on the surface is completely removed, and only the graft polymer firmly bonded to the nanodomain structure on the support exists.

  The graft polymer pattern thus obtained is the basis for materials for changing surface properties, high-density recording materials, anisotropic optical materials, biocompatible materials, superhydrophilic materials, superhydrophobic materials, etc. Useful as a material.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto.

[Example 1]
(Applying support binding initiator using vapor deposition method)
Using the small vacuum deposition apparatus VPC-1100 (manufactured by ULVAC), the above-mentioned exemplary compound T6, which is a support binding initiator, was deposited on a silicon substrate.
Here, the degree of vacuum was 1 × 10 ⁻³ Pa. The temperature for heating the polymerization initiator was 150 ° C., and the distance from the boat to the silicon substrate was 10 cm. The deposition time was 3 minutes.
After the deposition, the silicon substrate was allowed to cool in the apparatus for 10 minutes and then removed from the apparatus, and the surface was washed with acetone to remove excess support-binding initiator that was not chemically bonded to the support.

When the surface of the surface-immobilized material for the polymerization initiator obtained as described above was observed with an AFM (SPA400 / SPI3800N type, manufactured by SII-NT, AFM apparatus), a nanodomain structure having a diameter of 10 nm was confirmed. In addition, the chain length of Exemplified Compound T6 is 25 mm, and the height of this nanodomain structure is measured by ellipsometry (manufactured by Mizoji Optical Co., Ltd., DHA-XA / S4). The maximum height difference is 23 mm. Therefore, it was found that the exemplified compound T6 (support-bound initiator) has a nanodomain structure with a self-assembled film in an upright state.
Here, measurement of AFM was performed using a 100 μm scanner and an SI-DF20 cantilever, with measurement conditions: DFM mode, measurement resolution: 256 pixels × 256 line, measurement ranges: 1 μm □, 3 μm □.

[Example 2, Comparative Examples 1-3]
(Applying support binding initiator using immersion method)
The wafer (SiO ₂ ) whose surface was cleaned in advance with UV ozone was immersed in a 0.116% toluene solution of Exemplified Compound T1 as a support-bound initiator. In Example 2, the immersion time was 3 minutes, in Example 3, the immersion time was 10 minutes, in Comparative Example 1, the immersion time was 30 minutes, and in Comparative Example 2, the immersion time was 60 minutes. The temperature of the immersion liquid at this time was 20 ° C.
It was taken out from the wafer immersion liquid after immersion, the surface was washed with toluene, and the excess support-binding initiator that was not chemically bonded to the support was removed.

The surface of the polymerization initiator surface immobilization material obtained as described above was observed with an AFM (SPA400 / SPI3800N type, AFM apparatus manufactured by SII-NT) under the same conditions as in Example 1.
An AFM image of the polymerization initiator surface immobilization material obtained in Example 2 and Comparative Examples 1 to 3 is shown in FIG. The measurement range of the image shown in FIG. 1 is 3 μm □.

According to the image of the surface-immobilized material for the polymerization initiator obtained in Example 2, it can be seen that a pattern with a clear difference in concentration is seen on the whole, and a nanodomain structure is formed.
According to the image of the surface-immobilized material for the polymerization initiator obtained in Comparative Example 1, it can be seen that there is little difference in concentration as a whole and no nanodomain structure is formed.
According to the image of the surface-immobilized material for the polymerization initiator obtained in Comparative Example 2, it can be seen that there is no difference in concentration throughout, and no nanodomain structure is formed.
According to the image of the surface-immobilized material for the polymerization initiator obtained in Comparative Example 3, it can be seen that there is no difference in concentration throughout, and no nanodomain structure is formed.

Moreover, what expanded the AFM image of the polymerization initiator surface fixing material obtained in Example 2 in FIG. 1 is an image shown in FIG. FIG. 2B is a height profile image taken along the line aa in FIG.
From these images, it was confirmed that the surface-immobilized material for polymerization initiator obtained in Example 2 has a nanodomain structure with a height of about 10 mm at 20 to 60 nm.

  Here, with respect to the polymerization initiator surface-immobilized material obtained in Example 2 and Comparative Examples 1 to 3, film thickness measurement results by ellipsometry (Mizojiri Optics, DHA-XA / S4), AFM measurement The obtained centerline average roughness and maximum height difference are shown in Table 1 below.

The film thickness in Example 2 is as shown in Table 1 above, and the exemplary compound T1 has a chain length of 25.4 mm and a maximum height difference of 23 mm. It was found to be a nanodomain structure.
In Comparative Examples 1 to 3, the film thickness is large, the centerline average roughness is small, and the maximum height difference is less than half that of Example 1, so that a uniform film is formed on the entire support surface. I understand that

Example 4
(Production of graft polymer pattern)
The polymerization initiator surface-immobilized material obtained in Example 2 was immersed in a 10% by mass aqueous solution of acrylic acid, and then exposed for 10 minutes using a UV exposure machine (USHIO, model UVX02516S1). After exposure, the surface was immersed in water for 1 hour to wash the surface.
When this surface was observed with AFM (SPA400 / SPI3800N type manufactured by SII-NT, AFM apparatus), a graft polymer pattern with acrylic acid having a diameter of 30 mm and a height of 100 nm was confirmed.

[Comparative Example 4]
On the silicon wafer processed like Example 2, the 0.1 mass% toluene solution of the said exemplary compound T1 was apply | coated using the spinner. The number of revolutions was 700 rpm, and coating was performed in 20 seconds. It was 30 nm when the film thickness of the obtained coating film was measured with the ellipsometer (Grozoji Optical Co., Ltd. DHA-XA / S4).
Further, the coated surface was observed with AFM in the same manner as in Example 2. However, a uniform film was formed on the wafer, and no nanodomain structure was observed.

It is an AFM image of the polymerization initiator surface immobilization material obtained in Example 2 and Comparative Examples 1 to 3. The size of the image is 3 μm × 3 μm. FIG. 2A is an enlarged AFM image of the polymerization initiator surface fixing material obtained in Example 2 in FIG. 1, and FIG. 2B is a line of FIG. 2A. It is a height profile image in minute aa.

Claims (6)

  After contacting a polymerization initiator having a site capable of binding to the support on the surface of the support using an immersion method or a vapor deposition method, self-organization of the polymerization initiator in contact with the support results in the above-described A method for producing a surface-immobilized material for a polymerization initiator, wherein a nanodomain structure is formed on a support by a self-assembled film of a polymerization initiator bonded to the support.   The method for producing a surface-immobilized material for polymerization initiator according to claim 1, wherein the nanodomain structure has a diameter of 1 nm to 10 µm. The polymerization initiator surface immobilization material according to claim 1 or 2, wherein the polymerization initiator having a site capable of binding to the support has a structure represented by the following general formula (1). Manufacturing method.
(In the above general formula (1), Q is a silane coupling group, a thiol group, a thioisocyanato group, a nitrile group, a carboxyl group, a hydroxyl group, an amino group, a monoalkylsilane group, a phosphonic acid group, a phosphate ester group, and an unsaturated group. A support-binding group selected from the group consisting of hydrocarbon groups is represented, X represents a linking group containing an alkylene group having 5 to 40 carbon atoms, and Y represents a functional group capable of generating a radical.) The polymerization initiator according to any one of claims 1 to 3, wherein the polymerization initiator having a site capable of binding to the support has a structure represented by the following general formula (2). Preparation method of agent surface immobilization material.
(In the general formula (2), X represents a linking group containing an alkylene group having 5 to 40 carbon atoms, Y represents a functional group capable of generating a radical, Z represents a hydrolyzable group, and R represents a hydrogen atom. Or an alkyl group having 1 to 6 carbon atoms, m represents an integer of 0 to 2, n represents an integer of 1 to 3, and satisfies the relationship of n + m = 3.)   The functional group capable of generating a radical represented by Y is a functional group derived from a compound having a carbon halogen bond or a functional group derived from a pyridinium compound. 5. A method for producing a polymerization initiator surface immobilization material according to 4.   The process of producing | generating a graft polymer on the nanodomain structure of the polymerization initiator surface fixing material obtained by the preparation method of the polymerization initiator surface fixing material of any one of Claims 1-5. A method for producing a graft polymer pattern.