JP4296225B2 - New polymer - Google Patents

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JP4296225B2
JP4296225B2 JP2008179943A JP2008179943A JP4296225B2 JP 4296225 B2 JP4296225 B2 JP 4296225B2 JP 2008179943 A JP2008179943 A JP 2008179943A JP 2008179943 A JP2008179943 A JP 2008179943A JP 4296225 B2 JP4296225 B2 JP 4296225B2
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稔 山口
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Nippon Shokubai Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/36—Amides or imides
    • C08F222/40—Imides, e.g. cyclic imides
    • C08F222/402—Alkyl substituted imides
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/36—Amides or imides
    • C08F222/40—Imides, e.g. cyclic imides
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/12—Monomers containing a branched unsaturated aliphatic radical or a ring substituted by an alkyl radical

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Materials For Photolithography (AREA)

Description

本発明は、耐熱性に優れた新規な重合体に関する。 The present invention relates to a novel polymer excellent in heat resistance.

従来から、耐熱性に優れた光重合性を有する重合体として、例えば、マレイミドを含む単量体成分を重合してなる重合体（例えば、特許文献１参照。）や、２−（ヒドロキシアルキル）アクリル酸エステルのエーテルダイマーである特定構造の化合物を重合してなる重合体（例えば、特許文献２参照。）等が提案されている。 Conventionally, as a polymer having photopolymerizability excellent in heat resistance, for example, a polymer obtained by polymerizing a monomer component containing maleimide (see, for example, Patent Document 1) or 2- (hydroxyalkyl) A polymer obtained by polymerizing a compound having a specific structure which is an ether dimer of an acrylate ester (for example, see Patent Document 2) has been proposed.

しかし、これらの重合体は、膜やフィルムの形成工程における加熱時に熱分解し、分解ガスが発生することが明らかとなっている。例えば、液晶ディスプレイやプリント配線基板作成用の感光性樹脂としてこれらの重合体を用いた場合、製造工程での加熱時に発生した分解物が、加熱炉を汚染したり、分解物が液晶や基板を汚染して電気絶縁性が低下すること等があった。
また、マレイミド、スチレン、及び、酸基を有する重合体（例えば、特許文献３参照。）等が提案されている。しかしながら、このような重合体は、有機溶媒やアルカリに対する溶解速度が遅いという課題があった。したがって、耐熱性を向上するとともに、樹脂組成物の調製を容易にし、また、感光性樹脂として用いる場合の現像性を向上することができる重合体が求められるところであった。
特開２００３−２０１３１６号公報 特開２００４−３００２０３号公報 特開２００２−３０１１９号公報 However, it has been clarified that these polymers are thermally decomposed during heating in the process of forming a film or film, and decomposed gas is generated. For example, when these polymers are used as photosensitive resins for creating liquid crystal displays and printed wiring boards, decomposition products generated during heating in the manufacturing process can contaminate the heating furnace, Contamination and electrical insulation properties may be reduced.
In addition, maleimide, styrene, and a polymer having an acid group (for example, see Patent Document 3) have been proposed. However, such a polymer has a problem that its dissolution rate in an organic solvent or alkali is slow. Accordingly, there has been a demand for a polymer that can improve heat resistance, facilitate the preparation of a resin composition, and improve developability when used as a photosensitive resin.
JP 2003-201316 A JP 2004-300203 A JP 2002-30119 A

そこで、本発明は、耐熱性に優れて加熱時に発生するガスを低減でき、有機溶媒やアルカリに対する溶解速度が速く、しかもアルカリ現像性に優れた重合体を提供することを目的とする。 Therefore, an object of the present invention is to provide a polymer that has excellent heat resistance, can reduce gas generated during heating, has a high dissolution rate in an organic solvent or an alkali, and is excellent in alkali developability.

本発明者は、上記課題を解決するべく、鋭意検討を行った。その結果、Ｎ−置換マレイミド及び／又は２−（ヒドロキシアルキル）アクリル酸エステルのエーテルダイマーである特定構造の化合物、ビニルトルエン、及び、酸基を有する単量体を必須成分として共重合してなるポリマーが課題を一挙に解決しうることを見出し、本発明を完成した。 The present inventor has intensively studied to solve the above problems. As a result, N-substituted maleimide and / or 2- (hydroxyalkyl) acrylic acid ester ether dimer is copolymerized as an essential component with a compound having a specific structure, vinyl toluene, and a monomer having an acid group. The present inventors have found that a polymer can solve the problems all at once, and have completed the present invention.

すなわち、本発明は、Ｎ−置換マレイミド及び／又は下記一般式（１）で示される化合物、ビニルトルエン、及び、酸基を有する単量体を必須成分として共重合してなるポリマーである、ことを特徴とする。 That is, the present invention is a polymer obtained by copolymerizing N-substituted maleimide and / or a compound represented by the following general formula (1), vinyl toluene, and a monomer having an acid group as essential components. It is characterized by.

（式（１）中、Ｒ１及びＲ２は、それぞれ独立して、水素原子又は置換基を有していてもよい炭素数１〜２５の炭化水素基を表す。） (In formula (1), R 1 and R 2 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.)

本発明の重合体は、耐熱性が高く加熱時の分解ガスが少ないものであり、また、極めて優れた塗膜を形成することができ、有機溶媒やアルカリに対する溶解速度も速いことから、例えば、感光性樹脂組成物、各種コーティング剤、塗料等の用途において好適に用いることができる。 The polymer of the present invention has high heat resistance and little decomposition gas when heated, and can form a very excellent coating film, and has a high dissolution rate in organic solvents and alkalis. It can be suitably used in applications such as photosensitive resin compositions, various coating agents, and paints.

本発明の重合体は、Ｎ−置換マレイミド及び／又は下記一般式（１）で示される化合物（以下「エーテルダイマー」と称することもある。）、ビニルトルエン、及び、酸基を有する単量体を必須成分として共重合してなる重合体である。 The polymer of the present invention is an N-substituted maleimide and / or a compound represented by the following general formula (1) (hereinafter sometimes referred to as “ether dimer”), vinyl toluene, and a monomer having an acid group. Is a polymer obtained by copolymerizing as an essential component.

（式（１）中、Ｒ１及びＲ２は、それぞれ独立して、水素原子又は置換基を有していてもよい炭素数１〜２５の炭化水素基を表す。）
これにより、本発明の重合体を用いた感光性樹脂組成物は、耐熱性とともに透明性にも極めて優れたものとなる。これは、Ｎ−置換マレイミドや前記エーテルダイマーを重合することによる主鎖の環構造、及び、ビニルトルエン構造によって、非常に耐熱性が高まり熱分解が抑制される（耐熱分解性が向上する）ためであると推測される。 (In formula (1), R 1 and R 2 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.)
Thereby, the photosensitive resin composition using the polymer of the present invention is extremely excellent in heat resistance and transparency. This is because the main chain ring structure obtained by polymerizing N-substituted maleimide and the ether dimer and the vinyl toluene structure increase heat resistance and suppress thermal decomposition (improves heat decomposition resistance). It is estimated that.

なお、本発明者は、感光性樹脂における耐熱性に関し、重合体中にエステル結合があると熱分解しやすいということも見いだした。したがって、本発明の重合体においては、構造的にエステル結合を実質的に有さないことが好ましい。このような重合体としては、環構造を有する単量体及び酸基を有する単量体に加えて、スチレンやビニルトルエン等のエステル結合を有さない単量体を共重合したものが考えられる。この中で、特に、上記課題を解決するうえで、ビニルトルエンを用いることが本技術分野において予期せぬ効果を奏し、際立って優れたものとなることも見いだした。すなわち、ビニルトルエンを用いることで、有機溶媒やアルカリに対する溶解速度が高まり、樹脂組成物の調製が容易になり、感光性樹脂として用いる場合のアルカリ現像性に優れた硬化塗膜を形成し得るものとなる。 In addition, this inventor discovered that it was easy to thermally decompose if there existed an ester bond in a polymer regarding the heat resistance in photosensitive resin. Therefore, it is preferable that the polymer of the present invention has substantially no ester bond structurally. As such a polymer, in addition to a monomer having a ring structure and a monomer having an acid group, a copolymer obtained by copolymerizing a monomer having no ester bond such as styrene or vinyltoluene is considered. . In particular, it has been found that the use of vinyltoluene has an unexpected effect in the present technical field and is remarkably excellent in solving the above problems. That is, by using vinyltoluene, the dissolution rate with respect to an organic solvent or alkali increases, the resin composition can be easily prepared, and a cured coating film excellent in alkali developability when used as a photosensitive resin can be formed. It becomes.

以下、前記重合体について説明する。
前記Ｎ−置換マレイミドとしては、Ｎ−メチルマレイミド、Ｎ−イソプロピルマレイミド、Ｎ−シクロヘキシルマレイミド等のアルキル置換マレイミド、Ｎ−フェニルマレイミド、Ｎ−ベンジルマレイミド等の芳香族基を有するマレイミドが挙げられる。これらの中で、Ｎ−フェニルマレイミド、Ｎ−シクロヘキシルマレイミド、Ｎ−ベンジルマレイミドが、溶媒への溶解性、耐熱分解性、工業的入手のし易さの点等から好ましい。これらの中でもＮ−ベンジルマレイミドが、溶媒への溶解性や、加熱での着色の少なさの点から、最も好ましい。 Hereinafter, the polymer will be described.
Examples of the N-substituted maleimide include alkyl-substituted maleimides such as N-methylmaleimide, N-isopropylmaleimide and N-cyclohexylmaleimide, and maleimides having an aromatic group such as N-phenylmaleimide and N-benzylmaleimide. Among these, N-phenylmaleimide, N-cyclohexylmaleimide, and N-benzylmaleimide are preferable from the viewpoints of solubility in a solvent, heat decomposition resistance, industrial availability, and the like. Among these, N-benzylmaleimide is most preferable from the viewpoints of solubility in a solvent and little coloring by heating.

前記エーテルダイマーを示す前記一般式（１）中、Ｒ１及びＲ２で表される置換基を有していてもよい炭素数１〜２５の炭化水素基としては、特に制限はないが、例えば、メチル、エチル、ｎ−プロピル、イソプロピル、ｎ−ブチル、イソブチル、ｔ−ブチル、ｔ−アミル、ステアリル、ラウリル、２−エチルヘキシル等の直鎖状又は分岐状のアルキル基；フェニル等のアリール基；シクロヘキシル、ｔ−ブチルシクロヘキシル、ジシクロペンタジエニル、トリシクロデカニル、イソボルニル、アダマンチル、２−メチル−２−アダマンチル等の脂環式基；１−メトキシエチル、１−エトキシエチル等のアルコキシで置換されたアルキル基；ベンジル等のアリール基で置換されたアルキル基；等が挙げられる。これらの中で炭素数は８以下が好ましく、さらに、メチル、エチル、シクロヘキシル、ベンジル、２−エチルヘキシル等のような酸や熱で脱離しにくい１級又は２級炭素の置換基が耐熱性の点で好ましい。なお、Ｒ１及びＲ２は、同種の置換基であってもよいし、異なる置換基であってもよい。 In the general formula (1) showing the ether dimer, the hydrocarbon group having 1 to 25 carbon atoms which may have a substituent represented by R 1 and R 2 is not particularly limited. A linear or branched alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, t-amyl, stearyl, lauryl, 2-ethylhexyl; an aryl group such as phenyl; Alicyclic groups such as cyclohexyl, t-butylcyclohexyl, dicyclopentadienyl, tricyclodecanyl, isobornyl, adamantyl, 2-methyl-2-adamantyl; substituted with alkoxy such as 1-methoxyethyl, 1-ethoxyethyl An alkyl group substituted with an aryl group such as benzyl; and the like. Among these, the number of carbon atoms is preferably 8 or less, and further, primary or secondary carbon substituents which are difficult to be removed by acid or heat such as methyl, ethyl, cyclohexyl, benzyl, 2-ethylhexyl, etc. are heat resistant. Is preferable. Note that R 1 and R 2 may be the same type of substituents or different substituents.

前記エーテルダイマーの具体例としては、例えば、ジメチル−２，２’−［オキシビス（メチレン）］ビス−２−プロペノエート、ジエチル−２，２’−［オキシビス（メチレン）］ビス−２−プロペノエート、ジ（ｎ−プロピル）−２，２’−［オキシビス（メチレン）］ビス−２−プロペノエート、ジ（イソプロピル）−２，２’−［オキシビス（メチレン）］ビス−２−プロペノエート、ジ（ｎ−ブチル）−２，２’−［オキシビス（メチレン）］ビス−２−プロペノエート、ジ（イソブチル）−２，２’−［オキシビス（メチレン）］ビス−２−プロペノエート、ジ（ｔ−ブチル）−２，２’−［オキシビス（メチレン）］ビス−２−プロペノエート、ジ（ｔ−アミル）−２，２’−［オキシビス（メチレン）］ビス−２−プロペノエート、ジ（ステアリル）−２，２’−［オキシビス（メチレン）］ビス−２−プロペノエート、ジ（ラウリル）−２，２’−［オキシビス（メチレン）］ビス−２−プロペノエート、ジ（２−エチルヘキシル）−２，２’−［オキシビス（メチレン）］ビス−２−プロペノエート、ジ（１−メトキシエチル）−２，２’−［オキシビス（メチレン）］ビス−２−プロペノエート、ジ（１−エトキシエチル）−２，２’−［オキシビス（メチレン）］ビス−２−プロペノエート、ジベンジル−２，２’−［オキシビス（メチレン）］ビス−２−プロペノエート、ジフェニル−２，２’−［オキシビス（メチレン）］ビス−２−プロペノエート、ジシクロヘキシル−２，２’−［オキシビス（メチレン）］ビス−２−プロペノエート、ジ（ｔ−ブチルシクロヘキシル）−２，２’−［オキシビス（メチレン）］ビス−２−プロペノエート、ジ（ジシクロペンタジエニル）−２，２’−［オキシビス（メチレン）］ビス−２−プロペノエート、ジ（トリシクロデカニル）−２，２’−［オキシビス（メチレン）］ビス−２−プロペノエート、ジ（イソボルニル）−２，２’−［オキシビス（メチレン）］ビス−２−プロペノエート、ジアダマンチル−２，２’−［オキシビス（メチレン）］ビス−２−プロペノエート、ジ（２−メチル−２−アダマンチル）−２，２’−［オキシビス（メチレン）］ビス−２−プロペノエート等が挙げられる。これらの中でも特に、ジメチル−２，２’−［オキシビス（メチレン）］ビス−２−プロペノエート、ジエチル−２，２’−［オキシビス（メチレン）］ビス−２−プロペノエート、ジシクロヘキシル−２，２’−［オキシビス（メチレン）］ビス−２−プロペノエート、ジベンジル−２，２’−［オキシビス（メチレン）］ビス−２−プロペノエート、ジ（２―エチルヘキシル）−２，２’−［オキシビス（メチレン）］ビス−２−プロペノエートが好ましい。これらエーテルダイマーは、１種のみであってもよいし、２種以上であってもよい。 Specific examples of the ether dimer include dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, (N-propyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (isopropyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (n-butyl) ) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (isobutyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (t-butyl) -2, 2 ′-[oxybis (methylene)] bis-2-propenoate, di (t-amyl) -2,2 ′-[oxybis (methylene)] bis-2-propeno , Di (stearyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (lauryl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (2 -Ethylhexyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (1-methoxyethyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (1- Ethoxyethyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, dibenzyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diphenyl-2,2 ′-[oxybis ( Methylene)] bis-2-propenoate, dicyclohexyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (t- Tilcyclohexyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (dicyclopentadienyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (tri Cyclodecanyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (isobornyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, diadamantyl-2,2 Examples include '-[oxybis (methylene)] bis-2-propenoate and di (2-methyl-2-adamantyl) -2,2'-[oxybis (methylene)] bis-2-propenoate. Among these, dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, dicyclohexyl-2,2′- [Oxybis (methylene)] bis-2-propenoate, dibenzyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (2-ethylhexyl) -2,2 ′-[oxybis (methylene)] bis -2-propenoate is preferred. These ether dimers may be only one kind or two or more kinds.

本発明の重合体を得る際の単量体成分中におけるＮ−置換マレイミド及び／又は前記エーテルダイマーの割合は、特に制限されないが、全単量体成分中２〜６０質量％、好ましくは５〜５０質量％、さらに好ましくは５〜４０質量％であるのがよい。Ｎ−置換マレイミド及び／又はエーテルダイマーの量が多すぎると、溶媒やアルカリへの溶解性が低下したり、重合の際、析出又はゲル化し易くなったりする恐れがあり、一方、少なすぎると、耐熱性が不充分となる恐れがある。 The ratio of the N-substituted maleimide and / or the ether dimer in the monomer component in obtaining the polymer of the present invention is not particularly limited, but is 2 to 60% by mass in the total monomer component, preferably 5 to 5%. It is good that it is 50 mass%, More preferably, it is 5-40 mass%. If the amount of N-substituted maleimide and / or ether dimer is too large, the solubility in a solvent or alkali may be reduced, or during polymerization, precipitation or gelation may occur easily. On the other hand, if the amount is too small, Heat resistance may be insufficient.

前記ビニルトルエンは、ｏ−ビニルトルエン、ｐ−ビニルトルエン、ｍ−ビニルトルエンがある。これらの中でも、工業的に入手しやすい、ｍ−ビニルトルエン、ｐ−ビニルトルエン、及び、ｍ−ビニルトルエンとｐ−ビニルトルエンとの混合物が好ましく、特に工業的に入手しやすい、ｍ−ビニルトルエンとｐ−ビニルトルエンとの混合物が好適である。
前記重合体の単量体成分中におけるビニルトルエンの割合は、特に制限されないが、全単量体成分中５〜８０質量％、好ましくは１０〜７０質量％、さらに好ましくは１５〜６０質量％であるのがよい。ビニルトルエンの量が多すぎると、アルカリに対する溶解性が低下する恐れがある。また、少なすぎると、熱安定性が低下し加熱時の分解ガスの発生が多くなる恐れがある。 Examples of the vinyl toluene include o-vinyl toluene, p-vinyl toluene, and m-vinyl toluene. Among these, m-vinyltoluene, p-vinyltoluene, and a mixture of m-vinyltoluene and p-vinyltoluene, which are industrially easily available, are preferable, and m-vinyltoluene that is particularly easily industrially available. A mixture of and p-vinyltoluene is preferred.
The ratio of vinyltoluene in the monomer component of the polymer is not particularly limited, but is 5 to 80% by mass, preferably 10 to 70% by mass, and more preferably 15 to 60% by mass in the total monomer components. There should be. If the amount of vinyl toluene is too large, the alkali solubility may be reduced. Moreover, when too small, there exists a possibility that thermal stability may fall and generation | occurrence | production of the decomposition gas at the time of a heating may increase.

前記酸基を有する単量体（酸基含有単量体）の例としては、酸基と重合性二重結合を有する単量体であれば特に制限はないが、アクリル酸、メタクリル酸が好ましい。特に、本発明の重合体は、ビニルトルエン単位を必須成分として含むため疎水性が強い。その為、充分アルカリ可溶性を発揮させるには、より親水性が強いアクリル酸が最も好ましい。
前記重合体の単量体成分中における酸基含有単量体の割合は特に制限されないが、実質的に、全単量体成分中５〜４０質量％が好ましく、８〜３０質量％が更に好ましく、８〜２０質量％が最も好ましい。酸基含有単量体の量が少なすぎると、アルカリ可溶性が充分でなくなる恐れがある。また、多すぎると、耐熱分解性が低下したり、溶媒に対する溶解性が低下する恐れがある。ここで、酸基含有単量体の実質的な割合とは、後述する側鎖に反応性二重結合を導入するために、（メタ）アクリル酸グリシジル等を反応させることにより消費される量を除いた割合である。本発明においては、後述のように、側鎖に反応性二重結合を導入するために（メタ）アクリル酸グリシジル等を反応させる場合がある。このような場合には、消費される酸基含有単量体の量を予め上記の量に上乗せする必要があり、上乗せした後の酸基含有単量体の総量としては、１５〜６０質量％が好ましく、２０〜５５質量％が更に好ましく、２０〜５０質量％が最も好ましい。 Examples of the monomer having an acid group (acid group-containing monomer) are not particularly limited as long as the monomer has an acid group and a polymerizable double bond, but acrylic acid and methacrylic acid are preferable. . In particular, the polymer of the present invention is highly hydrophobic because it contains a vinyltoluene unit as an essential component. Therefore, acrylic acid having stronger hydrophilicity is most preferable for sufficiently exhibiting alkali solubility.
The ratio of the acid group-containing monomer in the monomer component of the polymer is not particularly limited, but is substantially preferably 5 to 40% by mass, more preferably 8 to 30% by mass in the total monomer component. 8 to 20% by mass is most preferable. If the amount of the acid group-containing monomer is too small, alkali solubility may not be sufficient. Moreover, when too large, there exists a possibility that heat-resistant decomposition property may fall or the solubility with respect to a solvent may fall. Here, the substantial proportion of the acid group-containing monomer means the amount consumed by reacting glycidyl (meth) acrylate or the like in order to introduce a reactive double bond into the side chain described later. Excluded ratio. In the present invention, as will be described later, glycidyl (meth) acrylate may be reacted in order to introduce a reactive double bond into the side chain. In such a case, it is necessary to add the amount of the acid group-containing monomer to be consumed in advance to the above amount, and the total amount of the acid group-containing monomer after the addition is 15 to 60% by mass. Is preferable, 20-55 mass% is still more preferable, and 20-50 mass% is the most preferable.

本発明の重合体は、上記必須の単量体単位以外の単量体単位を有していても有していなくてもよいが、重合体に占める上記必須の単量体単位の合計質量割合としては、例えば、５０質量％以上であることが好ましい。より好ましくは、７０質量％以上であり、更に好ましくは、９０質量％以上であり、実質的に全ての成分が必須の単量体単位であることが最も好ましい。
本発明の重合体における単量体単位の配列形態は、例えば、ランダム共重合体、交互共重合体、ブロック共重合体のいずれでもよい。 The polymer of the present invention may or may not have monomer units other than the essential monomer units, but the total mass ratio of the essential monomer units in the polymer. For example, it is preferably 50% by mass or more. More preferably, it is 70% by mass or more, and still more preferably 90% by mass or more, and most preferably all the components are essential monomer units.
The arrangement form of the monomer units in the polymer of the present invention may be, for example, a random copolymer, an alternating copolymer, or a block copolymer.

本発明の重合体は、更に側鎖に重合性二重結合を含むことが好ましい。側鎖に重合性二重結合を持たせることにより、熱や光で硬化させることができる。その為、より耐熱分解性が向上するほか、感光性樹脂組成物としたときの光に対する感度が向上し、より少ない光で硬化し、かつ硬化後の機械強度も高くなる。側鎖に重合性二重結合を導入する方法としては、前記重合体の酸基の一部に、二重結合及び酸基と反応する官能基を持った単量体を反応させる方法が好ましい。二重結合及び酸基と反応する官能基を持った単量体としては、（メタ）アクリル酸グリシジル、（メタ）アクリル酸−３，４−エポキシシクロヘキシル、イソプロペニルオキサゾリン等が好ましく、メタクリル酸グリシジルが工業的入手性や反応性の点から最も好ましい。なお、本明細書中、「（メタ）アクリル酸」とは、メタクリル酸とアクリル酸の両方を表現した表記である。 The polymer of the present invention preferably further contains a polymerizable double bond in the side chain. By giving a polymerizable double bond to the side chain, it can be cured by heat or light. For this reason, the thermal decomposition resistance is further improved, the sensitivity to light when a photosensitive resin composition is obtained, the resin is cured with less light, and the mechanical strength after curing is also increased. As a method for introducing a polymerizable double bond into the side chain, a method in which a monomer having a functional group capable of reacting with a double bond and an acid group is reacted with a part of the acid group of the polymer. As the monomer having a double bond and a functional group that reacts with an acid group, glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, isopropenyl oxazoline, etc. are preferable. Glycidyl methacrylate Is most preferable from the viewpoint of industrial availability and reactivity. In the present specification, “(meth) acrylic acid” is a notation expressing both methacrylic acid and acrylic acid.

側鎖に二重結合を導入する場合、二重結合の含有量としては、二重結合当量は４００〜１０万が好ましく、４００〜１万が更に好ましく、５００〜３０００が最も好ましい。二重結合当量が高すぎる場合、光に対する感度が低くなる恐れがあり、また、二重結合当量が低すぎる場合、保存安定性が悪くなったり、溶媒に対する溶解性が低下する恐れがある。
重合体中の酸基の一部に（メタ）アクリル酸グリシジル等の二重結合及び酸基と反応する官能基を持った単量体を付加する方法は、公知の方法を採用すればよく、特に制限はないが、反応温度は６０℃〜１４０℃が好ましく、また、トリエチルアミンやジメチルベンジルアミン等のアミン化合物、塩化テトラエチルアンモニウム等のアンモニウム塩、臭化テトラフェニルホスホニウム等のホスホニウム塩、ジメチルホルムアミド等のアミド化合物等の公知の触媒を使用することが好ましい。 When a double bond is introduced into a side chain, the double bond equivalent is preferably 400 to 100,000, more preferably 400 to 10,000, and most preferably 500 to 3000. If the double bond equivalent is too high, the sensitivity to light may be low, and if the double bond equivalent is too low, the storage stability may be deteriorated or the solubility in a solvent may be reduced.
A method of adding a monomer having a double bond and a functional group that reacts with an acid group such as glycidyl (meth) acrylate to a part of the acid group in the polymer may be a known method, Although there is no particular limitation, the reaction temperature is preferably 60 ° C. to 140 ° C., and amine compounds such as triethylamine and dimethylbenzylamine, ammonium salts such as tetraethylammonium chloride, phosphonium salts such as tetraphenylphosphonium bromide, dimethylformamide and the like It is preferable to use a known catalyst such as an amide compound.

前記重合体は、上記のように実質的に全ての成分が必須の単量体単位であることが好ましいが、必要に応じて、他の共重合可能なモノマーを含んでいてもよい。
前記他の共重合可能なモノマーとしては、例えば、スチレン等の芳香族ビニル化合物；（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ｎ−プロピル、（メタ）アクリル酸イソプロピル、（メタ）アクリル酸ｎ−ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸ｔ−ブチル、（メタ）アクリル酸２−エチルヘキシル、（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸ベンジル、（メタ）アクリル酸２−ヒドロキシエチル等の（メタ）アクリル酸エステル類；ブタジエン、イソプレン等のブタジエン又は置換ブタジエン化合物；エチレン、プロピレン、塩化ビニル、アクリロニトリル等のエチレン又は置換エチレン化合物；酢酸ビニル等のビニルエステル類；等が挙げられる。これらの中でも、（メタ）アクリル酸メチル、（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸ベンジルが、好ましい。これら共重合可能な他のモノマーは、１種のみ用いても２種以上を併用してもよい。なお、本明細書中、「（メタ）アクリル酸」とは、メタクリル酸とアクリル酸の両方を表現した表記である。 As described above, it is preferable that substantially all components are essential monomer units as described above, but the polymer may contain other copolymerizable monomers as necessary.
Examples of the other copolymerizable monomer include aromatic vinyl compounds such as styrene; methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and isopropyl (meth) acrylate. N-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, ( (Meth) acrylic acid esters such as 2-hydroxyethyl acrylate; butadiene or substituted butadiene compounds such as butadiene and isoprene; ethylene or substituted ethylene compounds such as ethylene, propylene, vinyl chloride and acrylonitrile; vinyl such as vinyl acetate Esters; and the like. Among these, methyl (meth) acrylate, cyclohexyl (meth) acrylate, and benzyl (meth) acrylate are preferable. These other copolymerizable monomers may be used alone or in combination of two or more. In the present specification, “(meth) acrylic acid” is a notation expressing both methacrylic acid and acrylic acid.

前記重合体を得る際の単量体成分が前記共重合可能な他のモノマーをも含む場合、その含有割合は特に制限されないが、重合体中５０質量％以下が好ましく、３０質量％以下であるのがより好ましく、１０質量％以下がさらに好ましい。特に、（メタ）アクリル酸エステル類は、耐熱安定性に劣るため、加熱時にエステル構造からのアルコール脱離が発生しやすい。その為、（メタ）アクリル酸エステルの場合は２０質量％以下が好ましく、１０質量％以下が更に好ましく、実質的に含まれないことが最も好ましい。但し、（メタ）アクリル酸単位に（メタ）アクリル酸グリシジル等を付加した単位は、加熱時に架橋するため、熱安定性の低下は少ない。本発明に限り、（メタ）アクリル酸単位に（メタ）アクリル酸グリシジルを付加した単位は、（メタ）アクリル酸エステルに含まれないこととする。 When the monomer component in obtaining the polymer also includes the other copolymerizable monomer, the content ratio is not particularly limited, but is preferably 50% by mass or less and preferably 30% by mass or less in the polymer. Is more preferable, and 10 mass% or less is still more preferable. In particular, since (meth) acrylic acid esters are inferior in heat resistance stability, alcohol elimination from the ester structure is likely to occur during heating. Therefore, in the case of (meth) acrylic acid ester, 20 mass% or less is preferable, 10 mass% or less is further more preferable, and it is most preferable that it is not contained substantially. However, since a unit obtained by adding glycidyl (meth) acrylate to a (meth) acrylic acid unit is crosslinked during heating, there is little decrease in thermal stability. Only in the present invention, a unit obtained by adding glycidyl (meth) acrylate to a (meth) acrylic acid unit is not included in the (meth) acrylic acid ester.

前記単量体成分の重合反応の方法としては、特に制限はなく、従来公知の各種重合方法を採用することができるが、特に、溶液重合法によることが好ましい。なお、重合温度や重合濃度（重合濃度（％）＝［単量体成分の全重量／（単量体成分の全重量＋溶媒重量）］×１００とする）は、使用する単量体成分の種類や比率、目標とするポリマーの分子量によって異なるが、好ましくは、重合温度４０〜１５０℃、重合濃度２０〜５０％とするのがよく、さらに好ましくは、重合温度６０〜１３０℃、重合濃度３０〜４５％とするのがよい。 The method for the polymerization reaction of the monomer component is not particularly limited, and various conventionally known polymerization methods can be employed, but the solution polymerization method is particularly preferable. The polymerization temperature and the polymerization concentration (polymerization concentration (%) = [total weight of monomer component / (total weight of monomer component + solvent weight)] × 100) are determined based on the monomer component used. Although it varies depending on the type and ratio and the molecular weight of the target polymer, the polymerization temperature is preferably 40 to 150 ° C. and the polymerization concentration is 20 to 50%, and more preferably, the polymerization temperature is 60 to 130 ° C. and the polymerization concentration is 30. It should be ˜45%.

前記単量体成分の重合において溶媒を用いる場合には、溶媒として通常のラジカル重合反応で使用される溶媒を用いるようにすればよい。具体的には、例えば、テトラヒドロフラン、ジオキサン、エチレングリコールジメチルエーテル、ジエチレングリコールジメチルエーテル等のエーテル類；アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン類；酢酸エチル、酢酸ブチル、プロピレングリコールモノメチルエーテルアセテート、３−メトキシブチルアセテート等のエステル類；メタノール、エタノール、イソプロパノール、ｎ−ブタノール、エチレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテル等のアルコール類；トルエン、キシレン、エチルベンゼン等の芳香族炭化水素類；クロロホルム；ジメチルスルホキシド；等が挙げられる。これら溶媒は、１種のみを用いても２種以上を併用してもよい。また、特に、酸基含有単量体の含有量が３０質量％を越える場合には、重量体の析出を防止するために、プロピレングリコールモノメチルエーテルアセテート等のエステル系溶媒と、プロピレングリコールモノメチルエーテルやイソプロパノール等のアルコール系溶媒との混合溶媒が好ましい。なお、ここでの酸基含有単量体の含有量とは、側鎖に反応性二重結合を導入するために消費される量を上乗せしたものである。 When a solvent is used in the polymerization of the monomer component, a solvent used in a normal radical polymerization reaction may be used as the solvent. Specifically, for example, ethers such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, 3- Esters such as methoxybutyl acetate; alcohols such as methanol, ethanol, isopropanol, n-butanol, ethylene glycol monomethyl ether, and propylene glycol monomethyl ether; aromatic hydrocarbons such as toluene, xylene, and ethylbenzene; chloroform; dimethyl sulfoxide; Etc. These solvents may be used alone or in combination of two or more. In particular, when the content of the acid group-containing monomer exceeds 30% by mass, an ester solvent such as propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, A mixed solvent with an alcohol solvent such as isopropanol is preferred. In addition, content of an acid group containing monomer here adds the amount consumed in order to introduce | transduce a reactive double bond into a side chain.

前記単量体成分を重合する際には、必要に応じて、通常用いられる重合開始剤を添加してもよい。重合開始剤としては特に限定されないが、例えば、クメンハイドロパーオキサイド、ジイソプロピルベンゼンハイドロパーオキサイド、ジ−ｔ−ブチルパーオキサイド、ラウロイルパーオキサイド、ベンゾイルパーオキサイド、ｔ−ブチルパーオキシイソプロピルカーボネート、ｔ−アミルパーオキシ−２−エチルヘキサノエート、ｔ−ブチルパーオキシ−２−エチルヘキサノエート等の有機過酸化物；２，２´−アゾビス（イソブチロニトリル）、１，１´−アゾビス（シクロヘキサンカルボニトリル）、２，２´−アゾビス（２，４−ジメチルバレロニトリル）、ジメチル２，２´−アゾビス（２−メチルプロピオネート）等のアゾ化合物；が挙げられる。これら重合開始剤は、１種のみを用いても２種以上を併用してもよい。なお、開始剤の使用量は、用いる単量体の組み合わせや、反応条件、目標とするポリマーの分子量等に応じて適宜設定すればよく、特に限定されないが、ゲル化することなく重量平均分子量が数千〜数万のポリマーを得ることができる点で、全単量体成分に対して０．１〜１５質量％、より好ましくは０．５〜１０質量％とするのがよい。 When polymerizing the monomer component, a commonly used polymerization initiator may be added as necessary. Although it does not specifically limit as a polymerization initiator, For example, cumene hydroperoxide, diisopropylbenzene hydroperoxide, di-t-butyl peroxide, lauroyl peroxide, benzoyl peroxide, t-butylperoxyisopropyl carbonate, t-amyl Organic peroxides such as peroxy-2-ethylhexanoate and t-butylperoxy-2-ethylhexanoate; 2,2′-azobis (isobutyronitrile), 1,1′-azobis (cyclohexane Carbonitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), azo compounds such as dimethyl 2,2′-azobis (2-methylpropionate), and the like. These polymerization initiators may be used alone or in combination of two or more. The amount of initiator used may be appropriately set according to the combination of monomers used, reaction conditions, target polymer molecular weight, etc., and is not particularly limited, but the weight average molecular weight without gelation. It is good to set it as 0.1-15 mass% with respect to all the monomer components, More preferably, it is 0.5-10 mass% at the point which can obtain several thousand-tens of thousands of polymers.

前記単量体成分を重合する際には、分子量調整のために、必要に応じて、通常用いられる連鎖移動剤を添加してもよい。連鎖移動剤としては、例えば、ｎ−ドデシルメルカプタン、メルカプトプロピオン酸、メルカプト酢酸、メルカプト酢酸メチル等のメルカプタン系連鎖移動剤、α−メチルスチレンダイマー等が挙げられるが、好ましくは、連鎖移動効果が高く、残存モノマーを低減でき、入手も容易な、ｎ−ドデシルメルカプタン、メルカプトプロピオン酸がよい。連鎖移動剤を使用する場合、その使用量は、用いる単量体の組み合わせや、反応条件、目標とするポリマーの分子量等に応じて適宜設定すればよく、特に限定されないが、ゲル化することなく重量平均分子量が数千〜数万のポリマーを得ることができる点で、全単量体成分に対して０．１〜１５質量％、より好ましくは０．５〜１０質量％とするのが好ましい。 When polymerizing the monomer component, a chain transfer agent that is usually used may be added, if necessary, for adjusting the molecular weight. Examples of the chain transfer agent include mercaptan chain transfer agents such as n-dodecyl mercaptan, mercaptopropionic acid, mercaptoacetic acid, and methyl mercaptoacetate, and α-methylstyrene dimer. Preferably, the chain transfer effect is high. N-dodecyl mercaptan and mercaptopropionic acid, which can reduce residual monomers and are easily available, are preferred. When using a chain transfer agent, the amount used may be appropriately set according to the combination of monomers used, reaction conditions, the molecular weight of the target polymer, etc., and is not particularly limited, but without gelation. In terms of being able to obtain a polymer having a weight average molecular weight of several thousand to several tens of thousands, it is preferably 0.1 to 15% by mass, more preferably 0.5 to 10% by mass with respect to all monomer components. .

本発明の重合体の重量平均分子量は、特に制限されないが、好ましくは２０００〜２０００００、より好ましくは５０００〜１０００００である。重量平均分子量が２０００００を超える場合、高粘度となりすぎて塗膜を形成しにくくなり、一方、２０００未満であると充分な耐熱性を発現しにくくなる傾向がある。なお、重量平均分子量の測定方法は、下記実施例において示す。 The weight average molecular weight of the polymer of the present invention is not particularly limited, but is preferably 2,000 to 200,000, more preferably 5,000 to 100,000. When the weight average molecular weight exceeds 200,000, the viscosity becomes too high to form a coating film, and when it is less than 2000, sufficient heat resistance tends to be hardly exhibited. In addition, the measuring method of a weight average molecular weight is shown in the following Example.

前記重合体は、酸価が３０〜３００ｍｇＫＯＨ／ｇであるのが好ましく、より好ましくは５０〜２００ｍｇＫＯＨ／ｇであるのがよい。酸価が３０ｍｇＫＯＨ／ｇ未満の場合、アルカリ現像に適用することが難しくなり、３００ｍｇＫＯＨ／ｇを超える場合、高粘度となりすぎて塗膜を形成しにくくなる傾向がある。また、溶媒に対する溶解性が低くなり、合成中に析出して、攪拌が不可能となる恐れがある。 The polymer preferably has an acid value of 30 to 300 mgKOH / g, more preferably 50 to 200 mgKOH / g. When the acid value is less than 30 mgKOH / g, it becomes difficult to apply to alkali development, and when it exceeds 300 mgKOH / g, the viscosity tends to be too high to form a coating film. Moreover, the solubility with respect to a solvent may become low, and it may precipitate during a synthesis | combination and stirring may become impossible.

本発明の重合体は、特に熱硬化性樹脂組成物や感光性樹脂組成物のバインダーポリマーとして好適に用いられるが、特に感光性樹脂組成物のバインダーとして用いることが好ましい。感光性樹脂組成物のバインダーとして用いる場合、前記重合体の他に、ラジカル重合性化合物、光重合開始剤、溶剤の他、必要に応じて、増感剤、顔料、顔料分散剤、界面活性剤等を配合することが好ましい。 The polymer of the present invention is particularly preferably used as a binder polymer for a thermosetting resin composition or a photosensitive resin composition, but is particularly preferably used as a binder for a photosensitive resin composition. When used as a binder for a photosensitive resin composition, in addition to the polymer, in addition to a radical polymerizable compound, a photopolymerization initiator, a solvent, a sensitizer, a pigment, a pigment dispersant, and a surfactant as necessary. Etc. are preferably blended.

光重合開始剤としては、２−クロロチオキサントン等のチオキサントン類；アセトフェノンジメチルケタール、ベンジルジメチルケタール等のケタール類；ベンゾフェノン等のベンゾフェノン類；２−メチル−１−［４−（メチルチオ）フェニル］−２−モルホリノ−プロパン−１−オンや２−ベンジル−２−ジメチルアミノ−１−（４−モルホリノフェニル）−ブタノン−１；アシルホスフィンオキサイド類及びキサントン類等が挙げられ、これらは単独で用いても２種類以上用いてもよい。
またその含有割合は、前記重合体に対して、好ましくは０．１〜５０質量％、より好ましくは０．５〜３０質量％である。 Examples of the photopolymerization initiator include thioxanthones such as 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenones such as benzophenone; 2-methyl-1- [4- (methylthio) phenyl] -2 -Morpholino-propan-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1; acylphosphine oxides and xanthones, and the like may be used alone. Two or more types may be used.
Moreover, the content rate becomes like this. Preferably it is 0.1-50 mass% with respect to the said polymer, More preferably, it is 0.5-30 mass%.

本発明の重合体は、必要に応じて、希釈剤としての溶媒を含有するものであってもよい。
前記溶媒としては、重合体を均一に溶解し、かつ反応しないものであれば、特に制限はない。具体的には、例えば、テトラヒドロフラン、ジオキサン、エチレングリコールジメチルエーテル、ジエチレングリコールジメチルエーテル等のエーテル類；アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン類；酢酸エチル、酢酸ブチル、プロピレングリコールモノメチルエーテルアセテート、３−メトキシブチルアセテート等のエステル類；メタノール、エタノール、イソプロパノール、ｎ−ブタノール、エチレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテル等のアルコール類；トルエン、キシレン、エチルベンゼン等の芳香族炭化水素類；クロロホルム、ジメチルスルホキシド；等が挙げられる。なお、溶媒の含有量は、使用する際の最適粘度に応じて適宜設定すればよい。 The polymer of this invention may contain the solvent as a diluent as needed.
The solvent is not particularly limited as long as it dissolves the polymer uniformly and does not react. Specifically, for example, ethers such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, 3- Esters such as methoxybutyl acetate; Alcohols such as methanol, ethanol, isopropanol, n-butanol, ethylene glycol monomethyl ether and propylene glycol monomethyl ether; Aromatic hydrocarbons such as toluene, xylene and ethylbenzene; Chloroform and dimethyl sulfoxide; Etc. In addition, what is necessary is just to set content of a solvent suitably according to the optimal viscosity at the time of using.

以下、実施例により本発明を詳細に説明するが、本発明の範囲はこれらの実施例によって限定されるものではない。なお、特に断りのない限り、「部」は「重量部」を意味するものとする。 EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, the scope of the present invention is not limited by these Examples. Unless otherwise specified, “parts” means “parts by weight”.

以下の実施例において、各種物性等は以下のように測定した。
＜重量平均分子量＞
ポリスチレンを標準物質とし、ＴＨＦ（テトラヒドロフラン）を溶離液としてＨＬＣ−８２２０ＧＰＣ（東ソー社製）により重量平均分子量を測定した。
＜酸価＞
樹脂溶液３ｇを精秤し、アセトン７０ｇ／水３０ｇ混合溶媒に溶解し、チモールブルーを指示薬として０．１Ｎ ＫＯＨ水溶液で滴定し、固形分の濃度から固形分１ｇ当たりの酸価を求めた。 In the following examples, various physical properties and the like were measured as follows.
<Weight average molecular weight>
The weight average molecular weight was measured by HLC-8220GPC (manufactured by Tosoh Corporation) using polystyrene as a standard substance and THF (tetrahydrofuran) as an eluent.
<Acid value>
3 g of the resin solution was precisely weighed, dissolved in a mixed solvent of 70 g of acetone / 30 g of water, titrated with 0.1N KOH aqueous solution using thymol blue as an indicator, and the acid value per 1 g of the solid content was determined from the solid content concentration.

実施例１
反応槽としての冷却管付きセパラブルフラスコに、プロピレングリコールモノメチルエーテルアセテート（ＰＧＭＥＡ）１００重量部を仕込み、窒素置換した後、９０℃に昇温した。他方、滴下槽１にジメチル−２，２‘−[オキシビス（メチレンビス）]−２−プロペノエート ２０．０部、アクリル酸 ２５．０部、ｔ−ブチルパーオキシ−２−エチルヘキサノエート ２．０部、ＰＧＭＥＡ ８０部を混合した。また、滴下槽２に、ビニルトルエン（ｍ−及びｐ− ６０対４０混合物）５５部、ｎ−ドデシルメルカプタン ２．０部を混合した。反応温度を９０℃に保ちながら、滴下槽１及び２から、反応槽に４．０時間かけて等速で滴下を行った。滴下終了後、３０分、９０℃を保った後、ｔ−ブチルパーオキシ−２−エチルヘキサノエート ０．５部を投入し、更に９０℃で３０分、反応を継続した。その後、反応温度を１１５℃に昇温し、１．５時間反応を継続した。一旦室温まで冷却した後、メタクリル酸グリシジル １９．７部、６−ｔ−ブチル−２，４−キシレノール ０．１０部、トリエチルアミン ０．３０部を投入し、酸素濃度７％に調整した窒素・空気混合ガスをバブリングしながら１１０℃に昇温し、２時間反応を行った。その後、１１５℃に昇温し５時間反応させ、反応を完結させ、室温まで冷却し、重合体溶液１を得た。 Example 1
A separable flask with a cooling tube as a reaction vessel was charged with 100 parts by weight of propylene glycol monomethyl ether acetate (PGMEA), purged with nitrogen, and then heated to 90 ° C. On the other hand, dimethyl-2,2 ′-[oxybis (methylenebis)]-2-propenoate 20.0 parts, acrylic acid 25.0 parts, t-butylperoxy-2-ethylhexanoate 2.0 Part, 80 parts of PGMEA were mixed. In addition, 55 parts of vinyltoluene (m- and p-60: 40 mixture) and 2.0 parts of n-dodecyl mercaptan were mixed in the dropping tank 2. While maintaining the reaction temperature at 90 ° C., dropwise addition was performed from the dropping tanks 1 and 2 to the reaction tank at a constant speed over 4.0 hours. After maintaining the temperature at 90 ° C. for 30 minutes after completion of the dropwise addition, 0.5 part of t-butylperoxy-2-ethylhexanoate was added, and the reaction was further continued at 90 ° C. for 30 minutes. Thereafter, the reaction temperature was raised to 115 ° C., and the reaction was continued for 1.5 hours. Once cooled to room temperature, 19.7 parts of glycidyl methacrylate, 0.10 parts of 6-t-butyl-2,4-xylenol, 0.30 parts of triethylamine were added, and nitrogen and air adjusted to an oxygen concentration of 7% The temperature was raised to 110 ° C. while bubbling the mixed gas, and the reaction was carried out for 2 hours. Thereafter, the temperature was raised to 115 ° C. and reacted for 5 hours to complete the reaction and cooled to room temperature to obtain a polymer solution 1.

得られた重合体溶液１について各種物性を測定したところ、ポリスチレンを標準物質とするＧＰＣ（ゲル浸透クロマトグラフィー）にて測定した重量平均分子量は１６０００、真空下１６０℃にて乾燥させて得られた固形分濃度は３８．１％、滴定法により求めた固形分当たりの酸価は１００ｍｇＫＯＨ／ｇであった。
重合体溶液１ １００重量部、ジペンタエリスリトールペンタアクリレート ３０重量部、光重合開始剤としてイルガキュア９０７（チバガイギ社製） ３重量部、ＰＧＭＥＡ ５００重量部を混合したのち、ガラス基板上にスピンコートし、９０℃で３分間乾燥し、膜厚３μｍの塗膜１を形成した。 When various physical properties of the obtained polymer solution 1 were measured, the weight average molecular weight measured by GPC (gel permeation chromatography) using polystyrene as a standard substance was obtained by drying at 160 ° C. under vacuum at 16000. The solid concentration was 38.1%, and the acid value per solid determined by a titration method was 100 mgKOH / g.
After mixing 100 parts by weight of polymer solution 1, 30 parts by weight of dipentaerythritol pentaacrylate, 3 parts by weight of Irgacure 907 (manufactured by Ciba-Gigi) as a photopolymerization initiator, and 500 parts by weight of PGMEA, spin-coating on a glass substrate, The coating film 1 having a thickness of 3 μm was formed by drying at 90 ° C. for 3 minutes.

塗膜１を、２０℃でＰＧＭＥＡに漬けて、膜が完全に溶解するまでの時間を目視にて観察したところ、膜が溶解するまでの時間は、１５秒であった。
塗膜１を、高圧水銀灯にて３００ｍＪ／ｃｍ２のＵＶ露光を行い、更に２００℃にて３０分間加熱し、硬化を完結させた。得られた硬化膜を削り取り、ＴＧ−ＤＴＡ法（熱重量−示差熱分析法）により２３０℃で３０分保持させた時の重量減少率は、１．１％であった。 When the coating film 1 was immersed in PGMEA at 20 ° C. and the time until the film was completely dissolved was visually observed, the time until the film was dissolved was 15 seconds.
The coating film 1 was exposed to UV at 300 mJ / cm 2 with a high-pressure mercury lamp, and further heated at 200 ° C. for 30 minutes to complete the curing. The obtained cured film was shaved off, and the weight reduction rate when held at 230 ° C. for 30 minutes by the TG-DTA method (thermogravimetric-differential thermal analysis method) was 1.1%.

得られた測定結果等を表１に示す。下記表１は、実施例１〜３、比較例１〜３について、重合体成分の組成と、重合体溶液、塗膜、及び、硬化膜の物性とを示すものである。 The obtained measurement results are shown in Table 1. Table 1 below shows the composition of the polymer components and the physical properties of the polymer solution, the coating film, and the cured film for Examples 1 to 3 and Comparative Examples 1 to 3.

実施例２
表１に示すように、ジメチル−２，２‘−[オキシビス（メチレンビス）]−２−プロペノエートの代わりに、Ｎ−ベンジルマレイミドを用いた以外は、実施例１と同様の操作を行って塗膜及び硬化膜を作成し、物性等を測定した。
塗膜のＰＧＭＥＡへの溶解時間は、１４秒であった。
また、硬化膜の２３０℃、３０分での重量減少率は、０．６％であった。 Example 2
As shown in Table 1, the same procedure as in Example 1 was carried out except that N-benzylmaleimide was used instead of dimethyl-2,2 ′-[oxybis (methylenebis)]-2-propenoate. And the cured film was created and the physical property etc. were measured.
The dissolution time of the coating film in PGMEA was 14 seconds.
Further, the weight loss rate of the cured film at 230 ° C. for 30 minutes was 0.6%.

実施例３
反応槽としての冷却管付きセパラブルフラスコに、プロピレングリコールモノメチルエーテルアセテート（ＰＧＭＥＡ）１００重量部、プロピレングリコールモノメチルエーテル（ＰＧＭＥ）５０部を仕込み、窒素置換した後、９０℃に昇温した。他方、滴下槽１にＮ−ベンジルマレイミド １５．０部、アクリル酸 ３７．２部、ｔ−ブチルパーオキシ−２−エチルヘキサノエート ２．０部、ＰＧＭＥＡ ５６部、ＰＧＭＥ ２４部を混合した。また、滴下槽２に、ビニルトルエン（ｍ−及びｐ− ６０対４０混合物）４７．８部、ｎ−ドデシルメルカプタン ３．０部を混合した。反応温度を９０℃に保ちながら、滴下槽１及び２から、反応槽に４．０時間かけて等速で滴下を行った。滴下終了後、３０分９０℃を保った後、ｔ−ブチルパーオキシ−２−エチルヘキサノエート ０．５部を投入し、更に９０℃で３０分、反応を継続した。その後、反応温度を１１５℃に昇温し、１．５時間反応を継続した。一旦室温まで冷却した後、メタクリル酸グリシジル ５０．０部、６−ｔ−ブチル−２，４−キシレノール ０．１０部、トリエチルアミン ０．３０部を投入し、酸素濃度７％に調整した窒素・空気混合ガスをバブリングしながら１１０℃に昇温し、１６時間反応を行い、実施例１と同様にして反応を完結させ、室温まで冷却して、重合体溶液を得た。 Example 3
In a separable flask with a cooling tube as a reaction vessel, 100 parts by weight of propylene glycol monomethyl ether acetate (PGMEA) and 50 parts of propylene glycol monomethyl ether (PGME) were charged, and the temperature was raised to 90 ° C. after purging with nitrogen. On the other hand, 15.0 parts of N-benzylmaleimide, 37.2 parts of acrylic acid, 2.0 parts of t-butylperoxy-2-ethylhexanoate, 56 parts of PGMEA, and 24 parts of PGMA were mixed in the dropping tank 1. Moreover, 47.8 parts of vinyl toluene (m- and p-60 to 40 mixture) and 3.0 parts of n-dodecyl mercaptan were mixed in the dropping tank 2. While maintaining the reaction temperature at 90 ° C., dropwise addition was performed from the dropping tanks 1 and 2 to the reaction tank at a constant speed over 4.0 hours. After maintaining the temperature at 90 ° C. for 30 minutes, 0.5 part of t-butylperoxy-2-ethylhexanoate was added, and the reaction was further continued at 90 ° C. for 30 minutes. Thereafter, the reaction temperature was raised to 115 ° C., and the reaction was continued for 1.5 hours. Once cooled to room temperature, 50.0 parts of glycidyl methacrylate, 0.10 part of 6-t-butyl-2,4-xylenol, 0.30 part of triethylamine were added, and nitrogen and air adjusted to an oxygen concentration of 7% The temperature was raised to 110 ° C. while bubbling the mixed gas, and the reaction was performed for 16 hours. The reaction was completed in the same manner as in Example 1 and cooled to room temperature to obtain a polymer solution.

得られた重合体溶液の重量平均分子量は１３０００、固形分濃度は３６．１％、固形分当たりの酸価は８０ｍｇＫＯＨ／ｇであった。
実施例１と同様の配合を行い、塗膜を形成したところ、ＰＧＭＥＡに膜が溶解するまでの時間は、１６秒であった。
また、硬化膜の、ＴＧ−ＤＴＡ法により２３０℃で３０分保持させた時の重量減少率は０．６％であった。 The polymer solution obtained had a weight average molecular weight of 13,000, a solid content concentration of 36.1%, and an acid value per solid content of 80 mgKOH / g.
When the same composition as in Example 1 was performed to form a coating film, the time until the film was dissolved in PGMEA was 16 seconds.
Moreover, the weight reduction | decrease rate when the cured film was hold | maintained at 230 degreeC for 30 minutes by TG-DTA method was 0.6%.

また、塗膜を、ＵＶ露光装置（Ｔｏｐｃｏｎ社製 ＴＭＥ−１５０ＲＮＳ）にて、ライン幅１５μｍのラインアンドスペースのフォトマスクを介し、５０ｍＪ／ｃｍ２のＵＶ光を露光し、９０℃で３分間乾燥した後、スピン現像機（アクテス社製 ＡＤＥ−３０００Ｓ）で、０．０１％のＫＯＨ水溶液で２０秒間現像を行った。図１は、露光後の塗膜をアルカリ現像した後のガラス基板の状態を示す。図１において、上部にある格子状部分（矩形パターン）がフォトマスクを介して露光された露光部であり、その周囲がフォトマスクによって保護された未露光部である。図１に示す通り、露光部には塗膜が硬化することにより完全なパターンが形成され、未露光部では、塗膜が溶解しており、溶け残りの残渣は認められなかった。
また、上記と同様の工程を現像時間を３０秒にして行っても、パターンの欠損はなかった。 The coating film was exposed to UV light of 50 mJ / cm 2 through a line-and-space photomask with a line width of 15 μm using a UV exposure apparatus (TME-150RNS manufactured by Topcon), and dried at 90 ° C. for 3 minutes. After that, development was carried out with a 0.01% KOH aqueous solution for 20 seconds using a spin developing machine (ADE-3000S manufactured by Actes Co., Ltd.). FIG. 1 shows the state of the glass substrate after alkali-developing the exposed coating film. In FIG. 1, an upper lattice-shaped portion (rectangular pattern) is an exposed portion exposed through a photomask, and its periphery is an unexposed portion protected by the photomask. As shown in FIG. 1, a complete pattern was formed by curing the coating film in the exposed area, and in the unexposed area, the coating film was dissolved and no undissolved residue was observed.
Further, even when the same process as described above was performed with a development time of 30 seconds, there was no pattern loss.

比較例１
表１に示すように、ビニルトルエンの代わりに、メタクリル酸ベンジルを用いた以外は、実施例１と同様の操作を行った。塗膜の溶解時間は１０秒であったが、２３０℃，３０分での重量減少率は、３．５％であった。 Comparative Example 1
As shown in Table 1, the same operation as in Example 1 was performed except that benzyl methacrylate was used instead of vinyltoluene. The dissolution time of the coating film was 10 seconds, but the weight loss rate at 230 ° C. for 30 minutes was 3.5%.

比較例２
表１に示すように、ビニルトルエンの代わりに、スチレンを用いた以外は、実施例１と同様の操作を行った。塗膜の溶解時間は、２４秒と、実施例１よりも遅くなった。また、２３０℃，３０分加熱での重量減少率は、１．４％であった。 Comparative Example 2
As shown in Table 1, the same operation as in Example 1 was performed except that styrene was used instead of vinyltoluene. The dissolution time of the coating film was 24 seconds, which was slower than Example 1. Moreover, the weight reduction rate after heating at 230 ° C. for 30 minutes was 1.4%.

比較例３
表１に示すように、ビニルトルエンの代わりにスチレンを使用した以外は実施例３と同様の操作を行った。塗膜のＰＧＭＥＡへの溶解時間は３０秒と、実施例３よりも長くなった。
硬化膜の２３０℃３０分保持での重量減少率は１．１％であった。
実施例３と同様の条件でアルカリ現像を行った。図２は、露光後の塗膜をアルカリ現像した後のガラス基板の状態を示し、図１と同様に露光部と未露光部とが形成されている。図２に示す通り、露光部にはパターンが形成されているものの、未露光部では、塗膜が溶解しきれておらず、溶け残りの現像残渣が認められた。
また、上記と同様の工程で現像時間を３０秒にすると、未露光部の残渣はなくなったが、パターンの一部に欠損が見られた。このことから、スチレンはビニルトルエンと比較して、現像時間の許容幅、すなわち現像マージンが非常に狭く、アルカリ現像性に劣ることがわかる。 Comparative Example 3
As shown in Table 1, the same operation as in Example 3 was performed except that styrene was used instead of vinyltoluene. The dissolution time of the coating film in PGMEA was 30 seconds, which was longer than that in Example 3.
The weight loss rate of the cured film after maintaining at 230 ° C. for 30 minutes was 1.1%.
Alkali development was performed under the same conditions as in Example 3. FIG. 2 shows a state of the glass substrate after alkali development of the coated film after exposure, and an exposed portion and an unexposed portion are formed as in FIG. As shown in FIG. 2, although a pattern was formed in the exposed area, the coating film was not completely dissolved in the unexposed area, and undeveloped development residues were observed.
Further, when the development time was set to 30 seconds in the same process as described above, there was no residue in the unexposed area, but a defect was observed in a part of the pattern. From this, it can be seen that styrene is inferior in alkali developability as compared with vinyltoluene, in which an allowable range of development time, that is, a development margin is very narrow.

上述した実施例及び比較例から、本発明の重合体は、重量減少率が小さく耐熱分解性に優れ、溶媒溶解性やアルカリ現像性にも優れることがわかる。
本発明の重合体においては、それを形成する単量体成分として、重合体中において環構造を有することになる単量体及び酸基を有する単量体に加えて、ビニルトルエンを用いるところに本質的な技術的特徴がある。
Ｎ置換マレイミド単量体及び／又は上記一般式（１）で表されるエーテルダイマー系単量体が環構造を形成し、そのような構造によって重合体の耐熱性が発現することが本発明の一つの特徴である。上記実施例において用いられた単量体は上記単量体群の一例であり、Ｎ置換マレイミド単量体及び／又はエーテルダイマー系単量体と呼ばれる範疇の単量体であれば本発明の効果が発現することは、上記したようにそれらの化学構造から明らかである。 From the examples and comparative examples described above, it can be seen that the polymer of the present invention has a small weight loss rate and excellent thermal decomposition resistance, and is excellent in solvent solubility and alkali developability.
In the polymer of the present invention, vinyl toluene is used as a monomer component for forming the polymer in addition to a monomer having a ring structure and a monomer having an acid group in the polymer. There are essential technical features.
According to the present invention, the N-substituted maleimide monomer and / or the ether dimer monomer represented by the general formula (1) forms a ring structure, and the heat resistance of the polymer is expressed by such a structure. It is one feature. The monomers used in the above examples are examples of the above monomer group, and the effects of the present invention can be used as long as they are in a category called N-substituted maleimide monomers and / or ether dimer monomers. It is clear from their chemical structure as described above.

また重合体を形成する単量体成分として上記３成分を用いることにより構造的にエステル結合を実質的に有さないようにすることができ、それによって耐熱性が向上することになる。本発明においては、スチレンやビニルトルエン等のエステル結合を有さない単量体の中でも、ビニルトルエンを用いるところに本質的特徴があり、このことは上記実施例・比較例によって立証されている。
なお、上記実施例においては、上記３成分の割合について、本明細書中に記載された好ましい範囲内において本発明が有利な効果を奏することも立証されている。 Further, by using the above three components as monomer components for forming the polymer, it is possible to structurally have no ester bond, thereby improving the heat resistance. In the present invention, among monomers having no ester bond such as styrene and vinyltoluene, there is an essential feature in that vinyltoluene is used, and this is proved by the above-mentioned Examples and Comparative Examples.
In addition, in the said Example, it has also proved that this invention has an advantageous effect in the preferable range described in this specification about the ratio of said 3 component.

液晶ディスプレイ、プリント配線基板等の感光性樹脂組成物のバインダーポリマー、熱硬化性樹脂、各種コーティング材料として有用である。 It is useful as a binder polymer, thermosetting resin, and various coating materials for photosensitive resin compositions such as liquid crystal displays and printed wiring boards.

図１は、実施例３におけるアルカリ現像後の基板の状態を示す図である。FIG. 1 is a diagram showing the state of the substrate after alkali development in Example 3. 図２は、比較例３におけるアルカリ現像後の基板の状態を示す図である。FIG. 2 is a diagram showing the state of the substrate after alkali development in Comparative Example 3.

Claims (4)

単量体成分として、（ａ）Ｎ置換マレイミド単量体及び／又は下記一般式（１）で表される単量体、（ｂ）ビニルトルエン、及び、（ｃ）酸基を有する単量体を必須成分として重合してなる重合体であって、
該重合体は、更に、側鎖に重合性二重結合を有することを特徴とする重合体。
（式（１）中、Ｒ１及びＲ２は、それぞれ独立して、水素原子又は置換基を有していてもよい炭素数１〜２５の炭化水素基を表す。） As a monomer component, (a) an N-substituted maleimide monomer and / or a monomer represented by the following general formula (1), (b) vinyltoluene, and (c) a monomer having an acid group the a Ru polymer name by polymerizing as essential components,
The polymer further has a polymerizable double bond in a side chain .
(In formula (1), R 1 and R 2 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.) 単量体成分として、（ａ）Ｎ置換マレイミド単量体及び／又は下記一般式（１）で表される単量体、（ｂ）ビニルトルエン、及び、（ｃ）酸基を有する単量体を必須成分として重合してなる重合体であって、As a monomer component, (a) an N-substituted maleimide monomer and / or a monomer represented by the following general formula (1), (b) vinyltoluene, and (c) a monomer having an acid group Is a polymer obtained by polymerizing as an essential component,
該（ｃ）酸基を有する単量体は、（メタ）アクリル酸であることを特徴とする重合体。The (c) monomer having an acid group is (meth) acrylic acid.
（式（１）中、Ｒ(In formula (1), R １1 及びＲAnd R ２2 は、それぞれ独立して、水素原子又は置換基を有していてもよい炭素数１〜２５の炭化水素基を表す。）Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent. ) （ｃ）酸基を有する単量体が、（メタ）アクリル酸であることを特徴とする、請求項１記載の重合体。 (C) a monomer having an acid group, (meth) wherein the acrylic acid, according to claim 1 polymer according. Ｎ置換マレイミド単量体が、Ｎ−フェニルマレイミド、Ｎ−シクロヘキシルマレイミド、及び、Ｎ−ベンジルマレイミドからなる群から選ばれる少なくとも一つであることを特徴とする請求項１〜３のいずれかに記載の重合体。 N-substituted maleimide monomer, N- phenylmaleimide, N- cyclohexyl maleimide, and, according to one of claims 1 to 3, wherein the at least one selected from the group consisting of N- benzyl maleimide Polymer.
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