JP4502855B2 - Pattern formation method - Google Patents

Pattern formation method Download PDF

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JP4502855B2
JP4502855B2 JP2005082699A JP2005082699A JP4502855B2 JP 4502855 B2 JP4502855 B2 JP 4502855B2 JP 2005082699 A JP2005082699 A JP 2005082699A JP 2005082699 A JP2005082699 A JP 2005082699A JP 4502855 B2 JP4502855 B2 JP 4502855B2
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group
substrate
pattern
bond
compound
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JP2005309405A (en
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浩一 川村
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Fujifilm Corp
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1603—Process or apparatus coating on selected surface areas
    • C23C18/1607—Process or apparatus coating on selected surface areas by direct patterning
    • C23C18/1608—Process or apparatus coating on selected surface areas by direct patterning from pretreatment step, i.e. selective pre-treatment
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1603—Process or apparatus coating on selected surface areas
    • C23C18/1607—Process or apparatus coating on selected surface areas by direct patterning
    • C23C18/1612—Process or apparatus coating on selected surface areas by direct patterning through irradiation means
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
    • C23C18/1872—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment
    • C23C18/1886—Multistep pretreatment
    • C23C18/1893—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
    • C23C18/2046—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
    • C23C18/2073—Multistep pretreatment
    • C23C18/2086—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/28—Sensitising or activating
    • C23C18/30—Activating or accelerating or sensitising with palladium or other noble metal

Abstract

<P>PROBLEM TO BE SOLVED: To provide a pattern forming method by which a high resolution graft polymer pattern can easily be formed on a solid surface. <P>SOLUTION: The pattern forming method comprises a step of bonding a compound, to a substrate, having both a polymerization initiating moiety capable of undergoing photocleavage to initiate radical polymerization and a substrate bonding moiety, and a step of contacting a radical-polymerizable unsaturated compound with the substrate and exposing light thereto patternwise, so as to form a region where a graft polymer is generated and a region where a graft polymer is not generated. <P>COPYRIGHT: (C)2006,JPO&amp;NCIPI

Description

本発明はパターン形成に関し、より詳細には、固体表面に解像度に優れたパターンを容易に形成することができるパターン形成方法に関する。   The present invention relates to pattern formation, and more particularly to a pattern formation method capable of easily forming a pattern with excellent resolution on a solid surface.

固体表面のポリマーによる表面修飾は、固体表面のぬれ性、汚れ性、接着性、表面摩擦、細胞親和性などの性質を変えることができるため、工業的な分野で幅広く研究されている。その中でも、固体表面にポリマーを共有結合により直接結合させてなる表面グラフトポリマーによる表面修飾は、ｉ）表面とグラフトポリマーとの間に強固な結合が形成されるという利点を有すること、ii）グラフトポリマーの物質に対する親和性が一般的な塗布架橋で形成されたポリマーとは大きく異なり、この親和性の相違に起因した特異的な性質を発現しうること、が知られている。
上記のような利点を有する表面グラフトポリマーは、その特異的な性質を利用した種々の応用技術が提案されており、例えば、細胞培養、抗血栓性人工血管、人工関節などの生体分野や、表面に高い親水性を必要とする親水性フィルム及び印刷版の親水性支持体などに用いられている。 Surface modification with a polymer on a solid surface is widely studied in the industrial field because it can change the properties of the solid surface such as wettability, dirtiness, adhesion, surface friction, and cell affinity. Among them, surface modification with a surface graft polymer obtained by directly bonding a polymer to a solid surface by a covalent bond has the advantage that i) a strong bond is formed between the surface and the graft polymer, ii) grafting It is known that the affinity of a polymer for a substance is greatly different from that of a polymer formed by general coating crosslinking, and a specific property resulting from this difference in affinity can be expressed.
As for the surface graft polymer having the above-mentioned advantages, various applied technologies utilizing its specific properties have been proposed. For example, cell culture, antithrombotic artificial blood vessels, artificial joints and other biological fields, and surface It is used for hydrophilic films that require high hydrophilicity and hydrophilic supports for printing plates.

また、このような表面グラフトポリマーをパターン状に形成することでで、グフトポリマーの有する特異的な性質がパターン状に反映されるため、印刷原板、区画培養、及び色素画像形成などの各分野で用いられている。   In addition, by forming such a surface graft polymer in a pattern, the specific properties of the guft polymer are reflected in the pattern, so it is used in various fields such as printing master plates, compartment culture, and dye image formation. It has been.

例えば、非特許文献１には、イニファーターと呼ばれる表面に固定化した重合開始基を用いて親水性グラフトパターンを形成し、それを細胞区画培養材料として用いることが、非特許文献２には、グラフトパターンに染料（トルイジンブルー）を吸着させることで可視画像のパターンができることが報告されている。   For example, in Non-Patent Document 1, it is possible to form a hydrophilic graft pattern using a polymerization initiating group immobilized on a surface called an iniferter and use it as a cell compartment culture material. It has been reported that a visible image pattern can be formed by adsorbing a dye (toluidine blue) to a graft pattern.

非特許文献３には、表面に固定化したイニファーター重合開始剤を用いて、親水性又は疎水性モノマーをパターン状に重合させたグラフトポリマーパターンを得る技術や、色素構造を有するモノマーをグラフトさせることにより色素ポリマーのパターンを得る技術が報告されている。
非特許文献４には、マイクロコンタクト印刷法を用いて開始剤を金基板の上に画像様に付着させ，その開始剤から原子移動重合（ＡＴＲＰ重合）を起こさせ、ＨＥＭＡ（ヒドロキシエチルメタクリレート）やＭＭＡ（メチルメタクリレート）のグラフトポリマーをパターン状に形成し、それをレジストとして応用する技術が報告されている。
さらに、非特許文献５には、基板に固定化したシラン化合物からのアニオンラジカル重合や、カチオンラジカル重合によりグラフトのパターンを作製する方法が提案されている。 In Non-Patent Document 3, using an iniferter polymerization initiator immobilized on the surface, a technique for obtaining a graft polymer pattern obtained by polymerizing a hydrophilic or hydrophobic monomer in a pattern, or a monomer having a dye structure is grafted Thus, a technique for obtaining a dye polymer pattern has been reported.
In Non-Patent Document 4, an initiator is imagewise deposited on a gold substrate using a microcontact printing method, atom transfer polymerization (ATRP polymerization) is caused from the initiator, HEMA (hydroxyethyl methacrylate), There has been reported a technique of forming a MMA (methyl methacrylate) graft polymer in a pattern and applying it as a resist.
Further, Non-Patent Document 5 proposes a method for producing a graft pattern by anion radical polymerization from a silane compound immobilized on a substrate or cation radical polymerization.

しかしながら、上述したような、従来のイニファーター法や、原子移動重合法を用いて、固体表面にグラフトパターンを作製しようとすると、反応時間が長いことから、製造適性が充分ではないという欠点があった。また、アニオンラジカル重合法やカチオンラジカル重合法を用いた場合についても、重合反応に厳密な制御を必要とすることから、製造適性が充分ではないという欠点があった。   However, using the conventional iniferter method or the atom transfer polymerization method as described above to produce a graft pattern on a solid surface has a drawback that the suitability for production is not sufficient due to the long reaction time. It was. In addition, when an anion radical polymerization method or a cation radical polymerization method is used, since the polymerization reaction requires strict control, there is a drawback that the production suitability is not sufficient.

このように、固体表面をグラフトポリマーにより修飾することで、効果的な表面改質材料や高機能材料を得るためのパターン形成方法が望まれているが、グラフトポリマーパターンを、実用的な製造時間で容易に形成しうる方法については、未だ得られていないのが現状である。
松田ら著、「Journal of biomedical materials research」、2000年、第53巻、第584頁 松田ら著、「Langumuir」、1999年、第15巻、第5560頁 Metters, A,Tら 著、「Macromolecules」、2003年、第36巻、第6739頁 C.J. Hawkerら 著、「Macromolecules」、2000年、第33巻、第597頁 Ingallら 著、「J.Am.Chem.Soc」、1999年、第121巻、第3607頁 As described above, there is a demand for a pattern forming method for obtaining an effective surface-modifying material or a highly functional material by modifying a solid surface with a graft polymer. As for the method that can be easily formed, the present situation has not yet been obtained.
Matsuda et al., "Journal of biomedical materials research", 2000, 53, 584 Matsuda et al., "Langumuir", 1999, Vol. 15, p. 5560 Metters, A, T et al., "Macromolecules", 2003, 36, 6739 CJ Hawker et al., “Macromolecules”, 2000, 33, 597 Ingall et al., “J.Am.Chem.Soc”, 1999, 121, 3607

本発明の前記従来における問題点を解決し、以下の目的を達成することを課題とする。
即ち、本発明の目的は、固体表面に高解像度のグラフトポリマーパターンを容易に形成しうるパターン形成方法を提供することにある。 An object of the present invention is to solve the conventional problems of the present invention and achieve the following objects.
That is, an object of the present invention is to provide a pattern forming method capable of easily forming a high resolution graft polymer pattern on a solid surface.

前記課題を解決するための手段は以下の通りである。
即ち、本発明のパターン形成方法は、光開裂によりラジカル重合を開始しうる重合開始部位と基材結合部位とを有する化合物を基材に結合させる工程と、
該基材上にラジカル重合可能な不飽和化合物である重合性不飽和基を有する親水性ポリマーを接触させて、パターン状に露光して、グラフトポリマー生成領域と非生成領域とを形成する工程と、
をこの順に行うことを特徴とするパターン形成方法である。
また、本発明においては、前記重合開始部位が、Ｃ−Ｃ結合、Ｃ−Ｎ結合、Ｃ−Ｏ結合、Ｃ−Ｃｌ結合、Ｎ−Ｏ結合、及びＳ−Ｎ結合からなる群より選択されるいずれかを含むことが好ましい。 Means for solving the above-mentioned problems are as follows.
That is, the pattern forming method of the present invention includes a step of bonding a compound having a polymerization initiation site capable of initiating radical polymerization by photocleavage and a substrate binding site to a substrate,
A step of bringing a hydrophilic polymer having a polymerizable unsaturated group, which is a radically polymerizable unsaturated compound, onto the substrate and exposing it in a pattern to form a graft polymer formation region and a non-generation region; ,
In this order.
In the present invention, the polymerization initiation site is selected from the group consisting of C—C bond, C—N bond, C—O bond, C—Cl bond, N—O bond, and S—N bond. It is preferable to include any of them.

本発明における詳細なメカニズムは未だ明確ではないが、本発明における重合反応は、フリーラジカル重合を用いた重合反応であるため重合速度が速く、また重合反応には厳密な制御を必要としないため、固体表面に容易にグラフトポリマーパターンを形成することが可能になったものと考えられる。   Although the detailed mechanism in the present invention is not yet clear, since the polymerization reaction in the present invention is a polymerization reaction using free radical polymerization, the polymerization rate is high, and the polymerization reaction does not require strict control. It is considered that the graft polymer pattern can be easily formed on the solid surface.

本発明のパターン形成方法によれば、固体表面に高解像度のグラフトポリマーパターンを容易に形成することができる。   According to the pattern forming method of the present invention, a high-resolution graft polymer pattern can be easily formed on a solid surface.

以下、本発明について詳細に説明する。
本発明のパターン形成方法は、光開裂によりラジカル重合を開始しうる重合開始部位と基材結合部位とを有する化合物を基材に結合させる工程（以下、適宜、「光開裂化合物結合工程」と称する。）と、前記基材上にラジカル重合可能な不飽和化合物である重合性不飽和基を有する親水性ポリマーを接触させた後、パターン露光を行い、当該光重合開始部位にグラフトポリマー生成領域と非生成領域とを形成する工程（以下、適宜、「グラフトポリマー生成工程」と称する。）と、をこの順に行うことを特徴とする。 Hereinafter, the present invention will be described in detail.
The pattern forming method of the present invention is a step of bonding a compound having a polymerization initiation site capable of initiating radical polymerization by photocleavage and a substrate binding site to a substrate (hereinafter referred to as “photocleavable compound bonding step” as appropriate). And a hydrophilic polymer having a polymerizable unsaturated group that is a radically polymerizable unsaturated compound on the substrate, and then pattern exposure is performed, and a graft polymer generation region is formed at the photopolymerization start site. A step of forming a non-generated region (hereinafter, appropriately referred to as “graft polymer generating step”) is performed in this order.

まず、本発明のパターン形成方法の概略について、図１を用いて説明する。ここで、図１は本発明のパターン形成方法の概略を示す概念図である。
図１（ａ）に示されるように、基材表面には当初より官能基（図中、Ｚで表される）が存在する。ここに、基材結合部位（Ｑ）と、光開裂によりラジカル重合を開始しうる光重合開始部位（Ｙ）と、を有する化合物（Ｑ−Ｙ）を付与し、基材表面に接触させる。これにより、図１（ｂ）に示されるように、基材表面に存在する官能基（Ｚ）と、基材結合部位（Ｑ）と、が結合して、基材表面に化合物（Ｑ−Ｙ）が導入される〔光開裂化合物結合工程〕。その後、図１（ｃ）に示されるように、グラフトポリマー原料である重合性不飽和基を有する親水性ポリマーを接触させた状態で、パターン露光を行う。これにより、図１（ｄ）に示されるように、露光領域においては、化合物（Ｑ−Ｙ）の重合開始部位（Ｙ）を起点としてグラフトポリマーが生成され（グラフトポリマー生成領域）、その一方、未露光領域においては、グラフトポリマーは生成しない（グラフトポリマー非生成領域）〔グラフトポリマー生成工程〕。 First, the outline of the pattern formation method of this invention is demonstrated using FIG. Here, FIG. 1 is a conceptual diagram showing an outline of the pattern forming method of the present invention.
As shown in FIG. 1A, a functional group (represented by Z in the figure) is present on the substrate surface from the beginning. Here, a compound (QY) having a substrate binding site (Q) and a photopolymerization initiation site (Y) capable of initiating radical polymerization by photocleavage is provided and brought into contact with the substrate surface. Thereby, as shown in FIG. 1B, the functional group (Z) present on the substrate surface and the substrate binding site (Q) are bonded to each other, and the compound (QY) is bonded to the substrate surface. ) Is introduced [photocleavable compound binding step]. Thereafter, as shown in FIG. 1C, pattern exposure is performed in a state where a hydrophilic polymer having a polymerizable unsaturated group, which is a graft polymer raw material , is brought into contact. Thereby, as shown in FIG. 1 (d), in the exposed region, a graft polymer is generated starting from the polymerization initiation site (Y) of the compound (QY) (graft polymer generating region), In the unexposed area, no graft polymer is generated (graft polymer non-generated area) [graft polymer generating step].

以下、このようなパターン形成方法について具体的に説明する。
図１においてZで表示される基は、基材表面に存在する官能基であり、具体的には、例えば、水酸基、カルボキシル基、アミノ基などが挙げられる。これらの官能基はシリコン基板、ガラス基板における基材の材質に起因して基材表面にもともと存在しているものでもよく、基材表面にコロナ処理などの表面処理を施すことにより表面に存在させたものであってもよい。 Hereinafter, such a pattern forming method will be specifically described.
The group represented by Z in FIG. 1 is a functional group present on the surface of the substrate, and specific examples include a hydroxyl group, a carboxyl group, and an amino group. These functional groups may be originally present on the surface of the base material due to the material of the base material in the silicon substrate or glass substrate, and may be present on the surface by subjecting the base material surface to a surface treatment such as corona treatment. It may be.

次に、光開裂によりラジカル重合を開始しうる光重合開始部位（以下、単に、重合開始部位と称する。）と基材結合部位とを有する化合物の構造について具体的に説明する。この化合物について、図１の概念図における、基材結合部位（Ｑ）と、重合開始部位（Ｙ）と、を有する化合物（Ｑ−Ｙ）のモデルを用いて詳細に説明すれば、一般に、重合開始部位（Ｙ）は、光により開裂しうる単結合を含む構造である。
この光により開裂する単結合としては、カルボニルのα開裂、β開裂反応、光フリー転位反応、フェナシルエステルの開裂反応、スルホンイミド開裂反応、スルホニルエステル開裂反応、Ｎ−ヒドロキシスルホニルエステル開裂反応、ベンジルイミド開裂反応、活性ハロゲン化合物の開裂反応、などを利用して開裂が可能な単結合が挙げられる。これらの反応により、光により開裂しうる単結合が切断される。この開裂しうる単結合としては、Ｃ−Ｃ結合、Ｃ−Ｎ結合、Ｃ−Ｏ結合、Ｃ−Ｃｌ結合、Ｎ−Ｏ結合、及びＳ−Ｎ結合等が挙げられる。 Next, the structure of a compound having a photopolymerization initiation site (hereinafter simply referred to as polymerization initiation site) capable of initiating radical polymerization by photocleavage and a substrate binding site will be specifically described. If this compound is described in detail using a model of a compound (QY) having a base material binding site (Q) and a polymerization initiation site (Y) in the conceptual diagram of FIG. The 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.

また、これらの光により開裂しうる単結合を含む重合開始部位（Ｙ）は、グラフトポリマー生成工程におけるグラフト重合の起点となることから、光により開裂しうる単結合が開裂すると、その開裂反応によりラジカルを発生させる機能を有する。このように、光により開裂しうる単結合を有し、かつ、ラジカルを発生可能な重合開始部位（Ｙ）の構造としては、以下に挙げる基を含む構造が挙げられる。   In addition, since the polymerization initiation site (Y) containing a single bond that can be cleaved by light is the starting point of graft polymerization in the graft polymer production step, when the single bond that can be cleaved by light is cleaved, the cleavage reaction causes Has the function of generating radicals. 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.

芳香族ケトン基、フェナシルエステル基、スルホンイミド基、スルホニルエステル基、Ｎ−ヒドロキシスルホニルエステル基、ベンジルイミド基、トリクロロメチル基、ベンジルクロライド基、などが挙げられる。   Aromatic ketone groups, phenacyl ester groups, sulfonimide groups, sulfonyl ester groups, N-hydroxysulfonyl ester groups, benzylimide groups, trichloromethyl groups, benzyl chloride groups, and the like can be mentioned.

このような重合開始部位（Ｙ）は、露光により開裂して、ラジカルが発生すると、そのラジカル周辺に重合可能な化合物が存在する場合には、このラジカルがグラフト重合反応の起点として機能し、所望のグラフトポリマーを生成することができる（グラフトポリマー生成領域）。その一方、露光が行われなかった領域においては、重合開始部位（Ｙ）の開裂が起きず、当該領域にはグラフトポリマーが生成しない（グラフトポリマー非生成領域）。   When such a polymerization initiation site (Y) is cleaved by exposure and a radical is generated, if there is a polymerizable compound in the vicinity of the radical, this radical functions as a starting point for the graft polymerization reaction. The graft polymer can be produced (graft polymer production region). On the other hand, in the region where the exposure has not been performed, the polymerization initiation site (Y) is not cleaved, and no graft polymer is generated in the region (graft polymer non-generated region).

基材結合部位（Ｑ）としては、基材表面に存在する官能基Ｚと反応して結合しうる反応性基で構成され、その反応性基としては、具体的には、以下に示すような基が挙げられる。   The substrate binding site (Q) is composed of a reactive group capable of reacting with and binding to the functional group Z present on the substrate surface. Specifically, the reactive group is as shown below. Groups.

また、重合開始部位（Ｙ）と、基材結合部位（Ｑ）と、は直接結合していてもよいし、連結基を介して結合していてもよい。この連結基としては、炭素、窒素、酸素、及びイオウからなる群より選択される原子を含む連結基が挙げられ、具体的には、例えば、飽和炭素基、芳香族基、エステル基、アミド基、ウレイド基、エーテル基、アミノ基、スルホンアミド基、等が挙げられる。
また、この連結基は更に置換基を有していてもよく、その導入可能な置換基としては、アルキル基、アルコキシ基、ハロゲン原子、等が挙げられる。 The polymerization initiation site (Y) and the substrate binding site (Q) may be directly bonded or may be bonded via a linking group. Examples of the linking group include a linking group containing an atom selected from the group consisting of carbon, nitrogen, oxygen, and sulfur. Specifically, for example, a saturated carbon group, an aromatic group, an ester group, an amide group. Ureido group, ether group, amino group, sulfonamide group, and the like.
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.

基材結合部位（Ｑ）と、重合開始部位（Ｙ）と、を有する化合物（Ｑ−Ｙ）の具体例〔例示化合物１〜例示化合物１６〕を、開裂部と共に以下に示すが、本発明はこれらに制限されるものではない。   Specific examples [Exemplary Compound 1 to Exemplified Compound 16] of Compound (QY) having a substrate binding site (Q) and a polymerization initiation site (Y) are shown below together with the cleavage portion. However, it is not limited to these.

本発明における光開裂化合物結合工程は、このような化合物（Ｑ−Ｙ）を基材に結合させる工程である。
例示された如き化合物（Ｑ−Ｙ）を基材表面に存在する官能基Ｚに結合させる方法としては、化合物（Ｑ−Ｙ）を、トルエン、ヘキサン、アセトンなどの適切な溶媒に溶解又は分散し、その溶液又は分散液を基材表面に塗布する方法、又は、溶液又は分散液中に基材を浸漬する方法などを適用すればよい。このとき、溶液中又は分散液の化合物（Ｑ−Ｙ）の濃度としては、０．０１質量％〜３０質量％が好ましく、特に０．１質量％〜１５質量％であることが好ましい。接触させる場合の液温としては、０℃〜１００℃が好ましい。接触時間としては、１秒〜５０時間が好ましく、１０秒〜１０時間がより好ましい。 The photocleavable compound bonding step in the present invention is a step of bonding such a compound (QY) to a substrate.
As a method for bonding the compound (QY) as exemplified to the functional group Z present on the substrate surface, the compound (QY) is dissolved or dispersed in a suitable solvent such as toluene, hexane, acetone or the like. A method of applying the solution or dispersion to the surface of the substrate or a method of immersing the substrate in the solution or dispersion may be applied. At this time, the concentration of the compound (QY) in the solution or in the dispersion is preferably 0.01% by mass to 30% by mass, and particularly preferably 0.1% by mass to 15% by mass. As a liquid temperature in the case of making it contact, 0 to 100 degreeC is preferable. The contact time is preferably 1 second to 50 hours, and more preferably 10 seconds to 10 hours.

本発明における基材には、特に制限はなく、基材表面に水酸基、カルボキシル基、アミノ基など、グラフトポリマー生成の起点となる官能基を有する基材、或いは、コロナ処理などの表面処理により、水酸基、カルボキシル基などを発生させた基材などを適用できる。
また、一般的には、平板状の基材が用いられるが、必ずしも平板状の基材に限定されず、円筒形などの任意の形状の基材表面にも同様にグラフトポリマーを導入することができる。 The substrate in the present invention is not particularly limited, and the substrate surface has a functional group serving as a starting point for graft polymer generation, such as a hydroxyl group, a carboxyl group, an amino group, or a surface treatment such as a corona treatment. A base material in which a hydroxyl group, a carboxyl group or the like is generated can be applied.
In general, a flat substrate is used, but the substrate is not necessarily limited to a flat substrate, and the graft polymer may be similarly introduced to the surface of a substrate having an arbitrary shape such as a cylindrical shape. it can.

本発明に適用される基材として、具体的には、ガラス、石英、ＩＴＯ、シリコン等の表面水酸基を有する各種基材、コロナ処理などの表面処理により表面に、水酸基やカルボキシル基などを発生させたＰＥＴ、ポリプロピレン、ポリイミドなどのプラスチック基材が挙げられる。
基材の厚みは、使用目的に応じて選択され、特に限定はないが、一般的には、１０μｍ〜１０ｃｍ程度である。 Specifically, as a base material applied to the present invention, various base materials having surface hydroxyl groups such as glass, quartz, ITO, silicon, etc., surface treatment such as corona treatment generates hydroxyl groups or carboxyl groups on the surface. Examples thereof include plastic base materials such as PET, polypropylene, and polyimide.
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.

そして、このように、基材表面に化合物（Ｑ−Ｙ）が結合された後、グラフトポリマー生成工程が行なわれる。
このグラフトポリマー生成工程では、前述した光開裂化合物結合工程における処理を経た基材に、所望とするグラフトポリマーの材料となるラジカル重合可能な不飽和化合物として、重合性不飽和基を有する親水性ポリマーを接触させた後、パターン露光を行い、露光領域の重合開始基を活性化させてラジカルを発生させ、そのラジカルを起点として、ラジカル重合可能な不飽和化合物との間で、グラフト化反応を生起、進行させる。その結果、露光領域にのみ、グラフトポリマーが生成する。 And after a compound (QY) is couple | bonded with the base-material surface in this way, a graft polymer production | generation process is performed.
In this graft polymer generation step, a hydrophilic polymer having a polymerizable unsaturated group as a radically polymerizable unsaturated compound that becomes a material of the desired graft polymer on the base material that has undergone the treatment in the photocleavable compound bonding step described above. Then, pattern exposure is performed to activate a polymerization initiating group in the exposed region to generate a radical, and from that radical as a starting point, a grafting reaction occurs with an unsaturated compound capable of radical polymerization. , Go ahead. As a result, a graft polymer is generated only in the exposed area.

ラジカル重合可能な不飽和化合物を基材表面に接触させる方法としては、ラジカル重合可能な不飽和化合物が溶解された溶液又は分散された分散液を塗布する方法、溶液又は分散された分散液に基材を浸漬する方法などがある。   As a method of bringing the unsaturated compound capable of radical polymerization into contact with the surface of the substrate, a method in which a solution or a dispersed dispersion in which the unsaturated compound capable of radical polymerization is dissolved is applied, or a solution or dispersed dispersion is used. There is a method of immersing the material.

グラフトポリマー生成工程において用いられるラジカル重合可能な不飽和化合物としては、重合性不飽和基を有する親水性ポリマーを用いる。
以下に、グラフトポリマー生成工程において用いられる、ラジカル重合可能な不飽和化合物について具体的に例示する。 As the radically polymerizable unsaturated compound used in the graft polymer production step, a hydrophilic polymer having a polymerizable unsaturated group is used .
Specific examples of the unsaturated compound capable of radical polymerization used in the graft polymer production step are shown below.

−重合性不飽和基を有する親水性ポリマー−
重合性不飽和基を有する親水性ポリマーとは、分子内に、ビニル基、アリル基、（メタ）アクリル基などのエチレン付加重合性不飽和基が導入されたラジカル重合性基含有親水性ポリマーを指す。このラジカル重合性基含有親水性ポリマーは、重合性基を主鎖末端及び／又は側鎖に有することを要し、その双方に重合性基を有することが好ましい。以下、重合性基を（主鎖末端及び／又は側鎖に）有する親水性ポリマーを、ラジカル重合性基含有親水性ポリマーと称する。 -Hydrophilic polymer having a polymerizable unsaturated group-
The hydrophilic polymer having a polymerizable unsaturated group is a radically polymerizable group-containing hydrophilic polymer in which an ethylene addition polymerizable unsaturated group such as a vinyl group, an allyl group or a (meth) acryl group is introduced in the molecule. Point to. This radical polymerizable group-containing hydrophilic polymer needs to have a polymerizable group at the main chain end and / or side chain, and preferably has a polymerizable group at both of them. Hereinafter, a hydrophilic polymer having a polymerizable group (at the main chain end and / or side chain) is referred to as a radical polymerizable group-containing hydrophilic polymer.

このようなラジカル重合性基含有親水性ポリマーは以下のようにして合成することができる。
合成方法としては、（ａ）親水性モノマーとエチレン付加重合性不飽和基を有するモノマーを共重合する方法、（ｂ）親水性モノマーと二重結合前駆体を有するモノマーを共重合させ、次に塩基などの処理により二重結合を導入する方法、（ｃ）親水性ポリマーの官能基とエチレン付加重合性不飽和基を有するモノマーとを反応させる方法、が挙げられる。これらの中でも、特に好ましいのは、合成適性の観点から、親水性ポリマーの官能基とエチレン付加重合性不飽和基を有するモノマーとを反応させる方法である。 Such a radically polymerizable group-containing hydrophilic polymer can be synthesized as follows.
As synthesis methods, (a) a method of copolymerizing a hydrophilic monomer and a monomer having an ethylene addition polymerizable unsaturated group, (b) copolymerizing a hydrophilic monomer and a monomer having a double bond precursor, Examples thereof include a method of introducing a double bond by treatment with a base and the like, and (c) a method of reacting a functional group of a hydrophilic polymer with a monomer having an ethylene addition polymerizable unsaturated group. Among these, a method of reacting a functional group of a hydrophilic polymer with a monomer having an ethylene addition polymerizable unsaturated group is particularly preferable from the viewpoint of synthesis suitability.

また、ラジカル重合性基含有親水性ポリマーの合成に用いられる親水性モノマーとしては、（メタ）アクリル酸若しくはそのアルカリ金属塩及びアミン塩、イタコン酸若しくはそのアルカリ金属塩及びアミン塩、２−ヒドロキシエチル（メタ）アクリレート、（メタ）アクリルアミド、Ｎ−モノメチロール（メタ）アクリルアミド、Ｎ−ジメチロール（メタ）アクリルアミド、アリルアミン若しくはそのハロゲン化水素酸塩、３−ビニルプロピオン酸若しくはそのアルカリ金属塩及びアミン塩、ビニルスルホン酸若しくはそのアルカリ金属塩及びアミン塩、２−スルホエチル（メタ）アクリレート、ポリオキシエチレングリコールモノ（メタ）アクリレート、２−アクリルアミド−２−メチルプロパンスルホン酸、アシッドホスホオキシポリオキシエチレングリコールモノ（メタ）アクリレートなどの、カルボキシル基、スルホン酸基、リン酸基、アミノ基若しくはそれらの塩、水酸基、アミド基及びエーテル基などの親水性基を有するモノマーが挙げられる。
上層を構成するラジカル重合性基含有親水性ポリマーとしては、これらの親水性モノマーから選ばれる少なくとも一種を用いて得られる親水性ホモポリマー若しくはコポリマーが挙げられる。 Further, as the hydrophilic monomer used for the synthesis of the radical polymerizable group-containing hydrophilic polymer, (meth) acrylic acid or its alkali metal salt and amine salt, itaconic acid or its alkali metal salt and amine salt, 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 salt and amine salt, Vinylsulfonic acid or its alkali metal salt and amine salt, 2-sulfoethyl (meth) acrylate, polyoxyethylene glycol mono (meth) acrylate, 2-acrylamido-2-methylpropanesulfonic acid, acid phosphooxypoly Such as carboxymethyl ethylene glycol mono (meth) acrylate, a carboxyl group, a sulfonic acid group, phosphoric acid group, an amino group or a salt thereof, hydroxyl group and a monomer having a hydrophilic group such as an amide group and an ether group.
Examples of the radically polymerizable group-containing hydrophilic polymer constituting the upper layer include a hydrophilic homopolymer or copolymer obtained by using at least one selected from these hydrophilic monomers.

（ａ）の方法でラジカル重合性基含有親水性ポリマーを合成する際、親水性モノマーと共重合するエチレン付加重合性不飽和基を有するモノマーとしては、例えば、アリル基含有モノマーがあり、具体的には、アリル（メタ）アクリレート、２−アリルオキシエチルメタクリレートが挙げられる。   When the radically polymerizable group-containing hydrophilic polymer is synthesized by the method (a), examples of the monomer having an ethylene addition polymerizable unsaturated group that is copolymerized with the hydrophilic monomer include an allyl group-containing monomer. Examples include allyl (meth) acrylate and 2-allyloxyethyl methacrylate.

また、（ｂ）の方法でラジカル重合性基含有親水性ポリマーを合成する際、親水性モノマーと共重合する二重結合前駆体を有するモノマーとしては、２−（３−クロロ−１−オキソプロポキシ）エチルメタクリレー卜が挙げられる。   Further, when the radical polymerizable group-containing hydrophilic polymer is synthesized by the method (b), a monomer having a double bond precursor that is copolymerized with a hydrophilic monomer is 2- (3-chloro-1-oxopropoxy). ) Ethyl methacrylate.

更に、（ｃ）の方法でラジカル重合性基含有親水性ポリマーを合成する際、親水性ポリマー中のカルボキシル基、アミノ基若しくはそれらの塩と、水酸基及びエポキシ基などの官能基と、の反応を利用して不飽和基を導入するために用いられる付加重合性不飽和基を有するモノマーとしては、（メタ）アクリル酸、グリシジル（メタ）アクリレート、アリルグリシジルエーテル、２−イソシアナトエチル（メタ）アクリレートなど挙げられる。   Further, when the radical polymerizable group-containing hydrophilic polymer is synthesized by the method (c), a reaction between a carboxyl group, an amino group or a salt thereof in the hydrophilic polymer and a functional group such as a hydroxyl group and an epoxy group is performed. Monomers having an addition-polymerizable unsaturated group used for introducing unsaturated groups using (meth) acrylic acid, glycidyl (meth) acrylate, allyl glycidyl ether, 2-isocyanatoethyl (meth) acrylate Etc.

本発明において用いうる親水性モノマーの具体例としては、次のモノマーを挙げることができる。
例えば、（メタ）アクリル酸若しくはそのアルカリ金属塩及びアミン塩、イタコン酸若しくはそのアルカリ金属塩及びアミン塩、アリルアミン若しくはそのハロゲン化水素酸塩、３−ビニルプロピオン酸若しくはそのアルカリ金属塩及びアミン塩、ビニルスルホン酸若しくはそのアルカリ金属塩及びアミン塩、スチレンスルホン酸若しくはそのアルカリ金属塩及びアミン塩、２−スルホエチレン（メタ）アクリレート、３−スルホプロピレン（メタ）アクリレート若しくはそのアルカリ金属塩及びアミン塩、２−アクリルアミド−２−メチルプロパンスルホン酸若しくはそのアルカリ金属塩及びアミン塩、アシッドホスホオキシポリオキシエチレングリコールモノ（メタ）アクリレート若しくはそれらの塩、２−ジメチルアミノエチル（メタ）アクリレート若しくはそのハロゲン化水素酸塩、３−トリメチルアンモニウムプロピル（メタ）アクリレート、３−トリメチルアンモニウムプロピル（メタ）アクリルアミド、Ｎ，Ｎ，Ｎ−トリメチル−Ｎ−（２−ヒドロキシ−３−メタクリロイルオキシプロピル）アンモニウムクロライド、などを使用することができる。 また、２−ヒドロキシエチル（メタ）アクリレート、（メタ）アクリルアミド、Ｎ−モノメチロール（メタ）アクリルアミド、Ｎ−ジメチロール（メタ）アクリルアミド、Ｎ−ビニルピロリドン、Ｎ−ビニルアセトアミド、ポリオキシエチレングリコールモノ（メタ）アクリレートなども有用である。 Specific examples of the hydrophilic monomer that can be used in the present invention include the following monomers.
For example, (meth) acrylic acid or its alkali metal salt and amine salt, itaconic acid or its alkali metal salt and amine salt, allylamine or its hydrohalide salt, 3-vinylpropionic acid or its alkali metal salt and amine salt, Vinyl sulfonic acid or its alkali metal salt and amine salt, styrene sulfonic acid or its alkali metal salt and amine salt, 2-sulfoethylene (meth) acrylate, 3-sulfopropylene (meth) acrylate or its alkali metal salt and amine salt, 2-acrylamido-2-methylpropanesulfonic acid or alkali metal salts and amine salts thereof, acid phosphooxypolyoxyethylene glycol mono (meth) acrylate or salts thereof, 2-dimethylaminoethyl (meta Acrylate or its hydrohalide, 3-trimethylammoniumpropyl (meth) acrylate, 3-trimethylammoniumpropyl (meth) acrylamide, N, N, N-trimethyl-N- (2-hydroxy-3-methacryloyloxypropyl) Ammonium chloride, etc. can be used. In addition, 2-hydroxyethyl (meth) acrylate, (meth) acrylamide, N-monomethylol (meth) acrylamide, N-dimethylol (meth) acrylamide, N-vinylpyrrolidone, N-vinylacetamide, polyoxyethylene glycol mono (meth) ) Acrylate is also useful.

−溶媒−
上述のラジカル重合可能な不飽和化合物を溶解、分散するための溶媒としては、該化合物や必要に応じて添加される添加剤が溶解可能ならば特に制限はない。
例えば、親水性の化合物が適用される場合であれば、水、水溶性溶剤などの水性溶剤が好ましく、これらの混合物や、溶剤に更に界面活性剤を添加したものなどが好ましい。水溶性溶剤は、水と任意の割合で混和しうる溶剤を言い、そのような水溶性溶剤としては、例えば、メタノール、エタノール、プロパノール、エチレングリコール、グリセリンの如きアルコール系溶剤、酢酸の如き酸、アセトンの如きケトン系溶剤、ホルムアミドの如きアミド系溶剤、などが挙げられる。
また、疎水性の化合物が適用される場合であれば、メタノール、エタノール、１−メトキシ−２−プロパノールの如きアルコール系の溶剤、メチルエチルケトンの如きケトン系溶剤、トルエンの如き炭化水素系の溶剤などが好ましい。 -Solvent-
The solvent for dissolving and dispersing the above-mentioned radically polymerizable unsaturated compound is not particularly limited as long as the compound and additives added as necessary can be dissolved.
For example, if the compound of the parent aqueous applies, water, preferably an aqueous solvent such as water-soluble solvent, or a mixture thereof, such as those further adding a surfactant to solvent is preferred. The water-soluble solvent refers to a solvent miscible with water in an arbitrary ratio, and examples of such a water-soluble solvent include alcohol solvents such as methanol, ethanol, propanol, ethylene glycol, and glycerin, acids such as acetic acid, Examples thereof include ketone solvents such as acetone, amide solvents such as formamide, and the like.
Further, in the case where the compound of hydrophobicity is applied, methanol, ethanol, 1-methoxy-2-propanol such alcohol solvents of methyl ethyl ketone such as ketone solvents, such as solvents such as hydrocarbon toluene preferable.

本発明のパターン形成方法に用いうる露光方法には特に制限はなく、前記重合開始部位（Ｙ）において開裂を生じさせるエネルギーを付与できる露光であれば、紫外線でも、可視光でもよい。
パターン露光に用いられる光源としては、紫外光、深紫外光、レーザー光、等が挙げられるが、好ましくは、紫外光、レーザー光である。 There are no particular limitations on the exposure method that can be used in the pattern forming method of the present invention, and ultraviolet light or visible light may be used as long as it can provide energy that causes cleavage at the polymerization initiation site (Y).
Examples of the light source used for pattern exposure include ultraviolet light, deep ultraviolet light, and laser light, and ultraviolet light and laser light are preferable.

本発明により形成されるパターンの解像度は露光条件に左右される。
本発明のパターン形成方法を用いれば、高解像度のパターン形成が可能であり、高精細画像記録用のパターン露光を施すことにより、露光に応じた高精細パターンが形成される。高精細パターン形成のための露光方法としては、光学系を用いた光ビーム走査露光、マスクを用いた露光などが挙げられ、所望のパターンの解像度に応じた露光方法をとればよい。
高精細パターン露光としては、具体的には、ｉ線ステッパー、ＫｒＦステッパー、ＡｒＦステッパーのようなステッパー露光などが挙げられる。 The resolution of the pattern formed by the present invention depends on the exposure conditions.
By using the pattern forming method of the present invention, a high-resolution pattern can be formed, and a high-definition pattern corresponding to the exposure can be formed by performing pattern exposure for recording a high-definition image. Examples of the exposure method for forming a high-definition pattern include light beam scanning exposure using an optical system, exposure using a mask, and the like, and an exposure method corresponding to the resolution of a desired pattern may be taken.
Specific examples of the high-definition pattern exposure include stepper exposure such as i-line stepper, KrF stepper, and ArF stepper.

このように、本発明のパターン形成方法により、表面にパターン状にグラフトポリマー生成領域と非生成領域とが形成された基材は、露光後、溶剤浸漬などの処理を行って、残存するホモポリマーを除去し、精製する。具体的には、水やアセトンによる洗浄、乾燥、などが挙げられる。ホモポリマーの除去性の観点からは、超音波などの手段を採ることが好ましい。
精製後の基材は、その表面に残存するホモポリマーが完全の除去され、基材と強固に結合したパターン状のグラフトポリマーのみが存在することになる。 As described above, the substrate on which the graft polymer generation region and the non-generation region are formed in a pattern on the surface by the pattern formation method of the present invention is subjected to a treatment such as solvent immersion after the exposure, and the remaining homopolymer Are removed and purified. Specifically, washing with water or acetone, drying, and the like can be given. From the viewpoint of homopolymer removability, it is preferable to adopt means such as ultrasonic waves.
The purified base material has the homopolymer remaining on the surface completely removed, and only the patterned graft polymer firmly bonded to the base material is present.

本発明のパターン形成方法によれば、露光の解像度に応じた微細なパターンが容易に形成されることから、その応用範囲は広い。   According to the pattern forming method of the present invention, a fine pattern corresponding to the resolution of exposure can be easily formed, so that its application range is wide.

以下、実施例を挙げて本発明を具体的に説明するが、本発明はこれらに限定されるものではない。
（合成例１：化合物Ａの合成）
前記例示化合物１の合成は、以下の２つのステップにより行われる。それぞれのステップのスキームを挙げて説明する。
１．ステップ１（化合物ａの合成）
ＤＭＡｃ５０ｇとＴＨＦ５０ｇの混合溶媒に１−ヒドロキシシクロヘキシルフェニルケトン ２４．５ｇ（０．１２ｍｏｌ）を溶かし、氷浴下でＮａＨ（６０％ ｉｎ ｏｉｌ） ７．２ｇ（０．１８ｍｏｌ）を徐々に加えた。そこに、１１−ブロモ−１−ウンデセン（９５％）４４．２ｇ（０．１８ｍｏｌ）を滴下し、室温で反応を行った。１時間で反応が終了した。反応溶液を氷水中に投入し、酢酸エチルで抽出し、黄色溶液状の化合物ａを含む混合物が得られた。この混合物３７ｇをアセトニトリル３７０ｍｌに溶かし、水７．４ｇを加えた。ｐ−トルエンスルホン酸一水和物１．８５ｇを加え、室温で２０分間撹拌した。酢酸エチルで有機相を抽出し、溶媒を留去した。カラムクロマトグラフィー（充填剤：ワコーゲルＣ−２００、展開溶媒：酢酸エチル／ヘキサン＝１／８０）で化合物ａを単離した。
合成スキームを以下に示す。 EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.
(Synthesis Example 1: Synthesis of Compound A)
The exemplary compound 1 is synthesized by the following two steps. A description will be given of the scheme of each step.
1. Step 1 (Synthesis of Compound a)
24.5 g (0.12 mol) of 1-hydroxycyclohexyl phenyl ketone was dissolved in a mixed solvent of DMAc 50 g and THF 50 g, and 7.2 g (0.18 mol) of NaH (60% in oil) was gradually added in an ice bath. Thereto, 44.2 g (0.18 mol) of 11-bromo-1-undecene (95%) was added dropwise and reacted at room temperature. The reaction was completed in 1 hour. The reaction solution was poured into ice water and extracted with ethyl acetate to obtain a mixture containing Compound a in the form of a yellow solution. 37 g of this mixture was dissolved in 370 ml of acetonitrile, and 7.4 g of water was added. 1.85 g of p-toluenesulfonic acid monohydrate was added and stirred at room temperature for 20 minutes. The organic phase was extracted with ethyl acetate and the solvent was distilled off. Compound a was isolated by column chromatography (filler: Wakogel C-200, developing solvent: ethyl acetate / hexane = 1/80).
A synthesis scheme is shown below.

1Ｈ ＮＭＲ（３００ＭＨｚ ＣＤＣｌ3）
δ＝１．２−１．８（ｍｂ，２４Ｈ），２．０（ｑ，２Ｈ），３．２（ｔ，Ｊ＝６．６，２Ｈ），４．９−５．０（ｍ，２Ｈ）５．８（ｄｄｔ，Ｊ＝２４．４，Ｊ＝１０．５，Ｊ＝６．６，１Ｈ.），７．４（ｔ，Ｊ＝７．４，２Ｈ），７．５（ｔ，Ｊ＝７．４，１Ｈ），８．３（ｄ，１Ｈ） 1 H NMR (300 MHz CDCl 3 )
δ = 1.2-1.8 (mb, 24H), 2.0 (q, 2H), 3.2 (t, J = 6.6, 2H), 4.9-5.0 (m, 2H) ) 5.8 (ddt, J = 24.4, J = 10.5, J = 6.6, 1H . ), 7.4 (t, J = 7.4, 2H), 7.5 (t, J = 7.4, 1H), 8.3 (d, 1H)

２．ステップ２（化合物ａのハイドロシリル化による化合物Ａの合成）
化合物ａ５．０ｇ（０．０１４ｍｏｌ）にＳｐｅｉｒ ｃａｔａｌｙｓｔ（Ｈ2ＰｔＣｌ6・６Ｈ2Ｏ／２−ＰｒＯＨ、０．１ｍｏｌ／ｌ）を２滴加え、氷浴下でトリクロロシラン２．８ｇ（０．０２１ｍｏｌ）を滴下して撹拌した。さらに１時間後にトリクロロシラン１．６ｇ（０．０１２ｍｏｌ）を滴下してから室温に戻した。３時間後に反応が終了した。反応終了後、未反応のトリクロロシランを減圧留去し、化合物Ａを得た。
合成スキームを以下に示す。 2. Step 2 (Synthesis of Compound A by Hydrosilylation of Compound a)
Two drops of Spear catalyst (H 2 PtCl 6 .6H 2 O / 2-PrOH, 0.1 mol / l) was added to 5.0 g (0.014 mol) of compound a, and 2.8 g (0.021 mol) of trichlorosilane in an ice bath. ) Was added dropwise and stirred. After 1 hour, 1.6 g (0.012 mol) of trichlorosilane was added dropwise, and the temperature was returned to room temperature. The reaction was complete after 3 hours. After completion of the reaction, unreacted trichlorosilane was distilled off under reduced pressure to obtain Compound A.
A synthesis scheme is shown below.

1Ｈ ＮＭＲ（３００ＭＨｚ ＣＤＣｌ3）
δ＝１．２−１．８（ｍ，３０Ｈ），３．２（ｔ，Ｊ＝６．３，２Ｈ），７．３−７．７（ｍ，３Ｈ），８．３（ｄ，２Ｈ） 1 H NMR (300 MHz CDCl 3 )
δ = 1.2−1.8 (m, 30H), 3.2 (t, J = 6.3, 2H), 7.3-7.7 (m, 3H), 8.3 (d, 2H) )

（合成例２：重合性基を有する親水性ポリマーＰの合成）
ポリアクリル酸（平均分子量２５，０００）１８ｇをＤＭＡｃ（ジメチルアセトアミド）３００ｇに溶解し、そこに、ハイドロキノン０．４１ｇと２−メタクリロイルオキシエチルイソシアネート１９．４ｇとジブチルチンジラウレート０．２５ｇを添加し、６５℃で４時間反応させた。得られたポリマーの酸価は７．０２ｍｅｑ／ｇであった。１ｍｏｌ／ｌの水酸化ナトリウム水溶液でカルボキシル基を中和し、酢酸エチルに加えポリマーを沈殿させ、よく洗浄し、重合性基を有する親水性ポリマーＰを得た。 (Synthesis Example 2: Synthesis of hydrophilic polymer P having a polymerizable group)
18 g of polyacrylic acid (average molecular weight 25,000) is dissolved in 300 g of DMAc (dimethylacetamide), and 0.41 g of hydroquinone, 19.4 g of 2-methacryloyloxyethyl isocyanate and 0.25 g of dibutyltin dilaurate are added thereto. The reaction was carried out at 65 ° C. for 4 hours. The acid value of the obtained polymer was 7.02 meq / g. The carboxyl group was neutralized with a 1 mol / l sodium hydroxide aqueous solution, the polymer was precipitated in addition to ethyl acetate, and washed well to obtain a hydrophilic polymer P having a polymerizable group.

〔実施例１〕
（光開裂化合物結合工程）
ガラス基板（日本板硝子）を、終夜、ピランハ液（硫酸／３０％過酸化水素＝１／１ｖｏｌ混合液）に浸漬した後、純水で洗浄した。その基板を、窒素置換したセパラブルフラスコ中に入れ１２．５ｗｔ％の化合物Ａの脱水トルエン溶液に１時間浸漬した。取り出し後、トルエン、アセトン、純水で順に洗浄した。得られた基版を基板Ａ１とする。 [Example 1]
(Photocleavable compound binding step)
A glass substrate (Japanese plate glass) was immersed in a piranha solution (sulfuric acid / 30% hydrogen peroxide = 1/1 vol mixed solution) overnight, and then washed with pure water. The substrate was placed in a separable flask purged with nitrogen and immersed in a 12.5 wt% dehydrated toluene solution of Compound A for 1 hour. After taking out, it wash | cleaned in order with toluene, acetone, and a pure water. Let the obtained base plate be the board | substrate A1.

（グラフトポリマー生成工程）
親水性ポリマーＰ（０．５ｇ）を純水４．０ｇとアセトニトリル２．０ｇの混合溶媒に溶かし、グラフト形成層用塗布液を調製した。そのグラフト形成層用塗布液を、スピンコーターで基板Ａ１に塗布した。スピンコーターは、まず３００ｒｐｍで５秒間、その後１０００ｒｐｍで２０秒間回転させた。グラフト形成層塗布後の基板Ａ１は、１００℃で２分間乾燥した。乾燥後のグラフト形成層の膜厚は２μｍであった。 (Graft polymer production process)
Hydrophilic polymer P (0.5 g) was dissolved in a mixed solvent of 4.0 g of pure water and 2.0 g of acetonitrile to prepare a coating solution for a graft forming layer. The graft forming layer coating solution was applied to the substrate A1 with a spin coater. The spin coater was first rotated at 300 rpm for 5 seconds and then at 1000 rpm for 20 seconds. The substrate A1 after application of the graft forming layer was dried at 100 ° C. for 2 minutes. The thickness of the graft-forming layer after drying was 2 μm.

−パターン露光−
グラフト形成層を塗布した基板上に、パターンマスク（ＮＣ−１、凸版印刷社製）を密着させるようにクリップで留め、露光機（ＵＶＸ−０２５１６Ｓ１ＬＰ０１、ウシオ電機社製）で１分間露光した。露光後マスクを取り外し、純水で充分洗浄した。
以上のようにして、パターンＡ１（グラフトポリマー生成領域及び非生成領域）を形成した。 -Pattern exposure-
A pattern mask (NC-1, manufactured by Toppan Printing Co., Ltd.) was clipped onto the substrate coated with the graft forming layer, and exposed for 1 minute with an exposure machine (UVX-02516S1LP01, manufactured by USHIO INC.). After exposure, the mask was removed and washed thoroughly with pure water.
As described above, the pattern A1 (graft polymer generation region and non-generation region) was formed.

〔実施例２〕
（光開裂化合物結合工程）
ＩＴＯを蒸着したガラス基板（日本板硝子（株）製、表面抵抗１０Ω／□、品番．４９Ｊ１８３）を使用し、イソプロピルアルコール、アセトン、メタノール、純水の順で、それぞれ５分以上超音波洗浄し、窒素吹き付け乾燥した。その基板を、窒素置換したセパラブルフラスコ中に入れ１２．５ｗｔ％の化合物Ａの脱水トルエン溶液に１時間〜終夜浸漬した。取り出し後、トルエン、アセトン、純水ので順に洗浄した。得られた基板を基板Ａ２とする。 [Example 2]
(Photocleavable compound binding step)
Using an ITO-deposited glass substrate (manufactured by Nippon Sheet Glass Co., Ltd., surface resistance 10Ω / □, product number. 49J183), ultrasonically wash in order of isopropyl alcohol, acetone, methanol, and pure water for 5 minutes or more respectively. Nitrogen was blown dry. The substrate was placed in a separable flask purged with nitrogen and immersed in a dehydrated toluene solution of 12.5 wt% of Compound A for 1 hour to overnight. After taking out, it wash | cleaned in order with toluene, acetone, and a pure water. Let the obtained board | substrate be the board | substrate A2.

（グラフトポリマー生成工程）
実施例１と同様にして、グラフト形成層用塗布液を基板Ａ２に塗布し、乾燥した。乾燥後のグラフト形成層の膜厚は２μｍであった。 (Graft polymer production process)
In the same manner as in Example 1, the graft forming layer coating solution was applied to the substrate A2 and dried. The thickness of the graft-forming layer after drying was 2 μm.

−パターン露光−
実施例１と同様にして、パターンマスクを用いてパターン露光を行った。露光後マスクを取り外し、純水で充分洗浄した。
以上のようにして、パターンＡ２（グラフトポリマー生成領域及び非生成領域）を形成した。 -Pattern exposure-
In the same manner as in Example 1, pattern exposure was performed using a pattern mask. After exposure, the mask was removed and washed thoroughly with pure water.
As described above, a pattern A2 (graft polymer generation region and non-generation region) was formed.

＜パターンの確認及び評価＞
実施例１〜２により得られたパターンＡ１〜Ａ２について、下記確認方法（１）及び（２）によりパターンの確認を行った。 <Confirmation and evaluation of pattern>
The pattern A1 to 2 obtained in Example 1-2 was carried out to confirm the pattern by the following confirmation method (1) and (2).

確認方法（１）：
基板Ａ１〜Ａ２に形成された各パターンを、原子間顕微鏡ＡＦＭ（ナノピクス１０００，セイコーインスツルメンツ社製、ＤＦＭカンチレバー使用）で観察した。解像できた最小のラインアンドスペースの線幅を表１示す。
確認方法（２）：
０．１ｗｔ％メチレンブルー水溶液に、基板Ａ１〜Ａ２を５分間浸漬し、純水で洗浄した。その後、光学顕微鏡で各パターンを確認した。解像できた最小のラインアンドスペースの線幅を表１示す。 Confirmation method (1):
Each pattern formed on the substrate A1 to 2, atomic force microscope AFM (Nanopics 1000, manufactured by Seiko Instruments Inc., DFM cantilever used) was observed in. Table 1 shows the minimum line-and-space line width that could be resolved.
Confirmation method (2):
To 0.1 wt% aqueous solution of methylene blue, the substrate A1 to 2 were immersed for 5 minutes and then washed with pure water. Then, each pattern was confirmed with the optical microscope. Table 1 shows the minimum line-and-space line width that could be resolved.

表１に示されるように、本発明のパターン形成方法によりパターン形成を行った実施例１〜２では、いずれにおいても微細なグラフトポリマーパターンが容易に形成されたことが確認された。 As shown in Table 1, in Examples 1 and 2 in which pattern formation was performed by the pattern formation method of the present invention, it was confirmed that a fine graft polymer pattern was easily formed in any case.

本発明のパターン形成方法の概略を示す概念である。It is a concept which shows the outline of the pattern formation method of this invention.

Claims (6)

光開裂によりラジカル重合を開始しうる重合開始部位と基材結合部位とを有する化合物を基材に結合させる工程と、
該基材上にラジカル重合可能な不飽和化合物である重合性不飽和基を有する親水性ポリマーを接触させて、パターン状に露光して、グラフトポリマー生成領域と非生成領域とを形成する工程と、
をこの順に行うことを特徴とするパターン形成方法。 Binding a compound having a polymerization initiation site capable of initiating radical polymerization by photocleavage and a substrate binding site to the substrate;
A step of bringing a hydrophilic polymer having a polymerizable unsaturated group, which is a radically polymerizable unsaturated compound, onto the substrate and exposing it in a pattern to form a graft polymer formation region and a non-generation region; ,
Are formed in this order. 前記重合開始部位が、Ｃ−Ｃ結合、Ｃ−Ｎ結合、Ｃ−Ｏ結合、Ｃ−Ｃｌ結合、Ｎ−Ｏ結合、及びＳ−Ｎ結合からなる群より選択されるいずれかを含むことを特徴とする請求項１に記載のパターン形成方法。   The polymerization initiation site includes any one selected from the group consisting of C—C bond, C—N bond, C—O bond, C—Cl bond, N—O bond, and S—N bond. The pattern forming method according to claim 1. 前記重合開始部位が、芳香族ケトン基、フェナシルエステル基、スルホンイミド基、スルホニルエステル基、Ｎ−ヒドロキシスルホニルエステル基、ベンジルイミド基、トリクロロメチル基、又はベンジルクロライド基を含む構造であることを特徴とする請求項１に記載のパターン形成方法。  The polymerization initiation site is a structure containing an aromatic ketone group, a phenacyl ester group, a sulfonimide group, a sulfonyl ester group, an N-hydroxysulfonyl ester group, a benzylimide group, a trichloromethyl group, or a benzyl chloride group. The pattern forming method according to claim 1, wherein: 前記基材結合部位が、下記に示す基材結合基から選択されることを特徴とする請求項１から請求項３のいずれか1項に記載のパターン形成方法。The pattern forming method according to claim 1, wherein the substrate binding site is selected from the following substrate binding groups.
前記重合開始部位と前記基材結合部位とが、炭素、窒素、酸素、及びイオウからなる群より選択される原子を含む連結基を介して結合していることを特徴とする請求項１から請求項４のいずれか１項に記載のパターン形成方法。  The polymerization initiation site and the substrate binding site are bonded via a linking group containing an atom selected from the group consisting of carbon, nitrogen, oxygen, and sulfur. Item 5. The pattern forming method according to any one of Items4. 前記重合性不飽和基を有する親水性ポリマーが、親水性ポリマーの官能基とエチレン付加重合性不飽和基を有するモノマーとを反応させる方法により得られたポリマーであることを特徴とする請求項１から請求項５のいずれか１項に記載のパターン形成方法。The hydrophilic polymer having a polymerizable unsaturated group is a polymer obtained by a method of reacting a functional group of a hydrophilic polymer with a monomer having an ethylene addition polymerizable unsaturated group. The pattern forming method according to claim 5.
JP2005082699A 2004-03-23 2005-03-22 Pattern formation method Expired - Fee Related JP4502855B2 (en)

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Application Number Priority Date Filing Date Title
JP2005082699A JP4502855B2 (en) 2004-03-23 2005-03-22 Pattern formation method
EP05006376A EP1589376A1 (en) 2004-03-23 2005-03-23 Conductive pattern forming method, and conductive pattern material
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JPS62168134A (en) * 1985-12-16 1987-07-24 Mitsubishi Electric Corp Formation of graft-polymerized film pattern
JPH0977891A (en) * 1995-01-11 1997-03-25 Sekisui Chem Co Ltd Article having surface layer with good adhesiveness to substrate and production of the same
JP2002145971A (en) * 2000-11-13 2002-05-22 Japan Science & Technology Corp Nano structural functional material
JP2005037881A (en) * 2003-04-21 2005-02-10 Fuji Photo Film Co Ltd Pattern forming method, image forming method, fine particle adsorption pattern forming method, conductive pattern forming method, pattern forming material, and planographic printing plate
JP2005264078A (en) * 2004-03-19 2005-09-29 Fuji Photo Film Co Ltd Surface grafting material and method for forming graft pattern using the same

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JPS62168134A (en) * 1985-12-16 1987-07-24 Mitsubishi Electric Corp Formation of graft-polymerized film pattern
JPH0977891A (en) * 1995-01-11 1997-03-25 Sekisui Chem Co Ltd Article having surface layer with good adhesiveness to substrate and production of the same
JP2002145971A (en) * 2000-11-13 2002-05-22 Japan Science & Technology Corp Nano structural functional material
JP2005037881A (en) * 2003-04-21 2005-02-10 Fuji Photo Film Co Ltd Pattern forming method, image forming method, fine particle adsorption pattern forming method, conductive pattern forming method, pattern forming material, and planographic printing plate
JP2005264078A (en) * 2004-03-19 2005-09-29 Fuji Photo Film Co Ltd Surface grafting material and method for forming graft pattern using the same

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