JP2005350609A - Macromolecular compound having acetal structure on its side chain and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new macromolecular compound useful as a photosensitive resin or the like, and to provide a method for producing the compound. <P>SOLUTION: The new macromolecular compound having acetal structure on its side chain is composed of recurring units each represented by the formula(I)[wherein, R<SP>a</SP>is H or methyl; R<SP>1</SP>is H or a 1-3C alkyl; R<SP>2</SP>is H or methyl; W is a bivalent organic group; n is 0 or 1; ring Z is either one of cyclic groups of respective formulas(1) to (4)(wherein, A<SP>1</SP>is a methylene group or carbonyl group; A<SP>2</SP>is a methylene group or oxygen atom; X<SP>1</SP>, X<SP>2</SP>, X<SP>3</SP>and X<SP>4</SP>are each a substituent bound to atoms constituting the respective rings, being a halogen atom, alkyl or the like; (a), b, c and d are each an integer of ≥0, wherein when (a), b, c or d is ≥2, the substituents in parentheses may be the same as or different from each other; and p is an integer of 0-3)]. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a polymer compound having an acetal structure in a side chain useful as a functional resin such as a photosensitive resin or an intermediate raw material used for fine processing of a semiconductor, and a method for producing the same.

The positive photoresist used in the semiconductor manufacturing process has the property that the irradiated part changes to alkali-soluble when irradiated with light (alkali-soluble, acid detachment), adhesion to a silicon wafer (substrate adhesion), plasma etching resistance ( It must have characteristics such as etching resistance and transparency to the light used. Lithographic exposure light sources used for semiconductor manufacturing have become shorter in wavelength year by year, and are shifting from KrF excimer lasers having a wavelength of 248 nm to ArF excimer lasers having a wavelength of 193 nm. Further, F ₂ excimer lasers, electron beams (EB) ) Etc. are also being studied for semiconductor manufacturing methods.

  On the other hand, it has been proposed to use partially protected polyhydroxystyrene obtained by acetalizing (acetal-protected) partially phenolic hydroxyl groups of structural units of polyhydroxystyrene as a resin for photoresist (Patent Document 1, 2 etc.). However, the photoresist resins described in these documents do not have a sufficient balance of alkali solubility (acid detachment), substrate adhesion, and etching resistance, and are not necessarily satisfactory in terms of sensitivity and development degree. Absent.

JP 2001-316418 A JP 2003-295444 A

An object of the present invention is to provide a novel polymer compound useful as a functional resin such as a photosensitive resin and a method for producing the same.
Another object of the present invention is to provide a novel polymer compound having a good balance between acid detachability, substrate adhesion and etching resistance, and a method for producing the same.

  As a result of intensive studies to achieve the above object, the present inventors have made a reaction between a polymer having a repeating unit corresponding to hydroxystyrene and a vinyl ether compound having a specific ring. The present inventors have found that a novel polymer compound in which a phenolic hydroxyl group has a specific acetal structure can be obtained, thereby completing the present invention.

［式中、Ｒ^aは水素原子又はメチル基を示し、Ｒ¹は水素原子又は炭素数１〜３のアルキル基を示し、Ｒ²は水素原子又はメチル基を示し、Ｗは２価の有機基を示し、ｎは０又は１を示す。環Ｚは、下記式（１）〜（４）

（式中、Ａ¹はメチレン基又はカルボニル基を示し、Ａ²はメチレン基又は酸素原子を示す。Ｘ¹、Ｘ²、Ｘ³及びＸ⁴は各環を構成する原子に結合している置換基であり、ハロゲン原子、アルキル基、ハロアルキル基、アリール基、保護基で保護されていてもよいヒドロキシル基、保護基で保護されていてもよいヒドロキシメチル基、保護基で保護されていてもよいアミノ基、保護基で保護されていてもよいカルボキシル基、保護基で保護されていてもよいスルホ基、オキソ基、ニトロ基、シアノ基、又は保護基で保護されていてもよいアシル基を示す。ａ、ｂ、ｃ、ｄは０以上の整数を示す。ａ、ｂ、ｃ又はｄが２以上の場合、括弧内の置換基は同一であっても異なっていてもよい。ｐは０〜３の整数を示す）
で表される何れかの環式基を示す］
で表される繰り返し単位を含む側鎖にアセタール構造を有する高分子化合物を提供する。 That is, the present invention provides the following formula (I)

[Wherein, R ^a represents a hydrogen atom or a methyl group, R ¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ² represents a hydrogen atom or a methyl group, and W represents a divalent organic group. N represents 0 or 1. Ring Z has the following formulas (1) to (4)

(In the formula, A ¹ represents a methylene group or a carbonyl group, A ² represents a methylene group or an oxygen atom. X ¹ , X ² , X ³ and X ⁴ are substituents bonded to atoms constituting each ring. Group, a halogen atom, an alkyl group, a haloalkyl group, an aryl group, a hydroxyl group that may be protected with a protecting group, a hydroxymethyl group that may be protected with a protecting group, or a group that may be protected with a protecting group An amino group, a carboxyl group that may be protected with a protective group, a sulfo group that may be protected with a protective group, an oxo group, a nitro group, a cyano group, or an acyl group that may be protected with a protective group A, b, c and d each represents an integer of 0 or more, and when a, b, c or d is 2 or more, the substituents in parentheses may be the same or different, and p is 0 to 0. Indicates an integer of 3)
Any cyclic group represented by
The polymer compound which has an acetal structure in the side chain containing the repeating unit represented by these is provided.

で表される繰り返し単位を含んでいてもよい。 This polymer compound further has the following formula (II)

The repeating unit represented by these may be included.

（式中、Ｒ^aは水素原子又はメチル基を示す）
で表される繰り返し単位を含む高分子化合物と、下記式（５）

［式中、Ｒ¹は水素原子又は炭素数１〜３のアルキル基を示し、Ｒ²は水素原子又はメチル基を示し、Ｗは２価の有機基を示し、ｎは０又は１を示す。環Ｚは、下記式（１）〜（４）

（式中、Ａ¹はメチレン基又はカルボニル基を示し、Ａ²はメチレン基又は酸素原子を示す。Ｘ¹、Ｘ²、Ｘ³及びＸ⁴は各環を構成する原子に結合している置換基であり、ハロゲン原子、アルキル基、ハロアルキル基、アリール基、保護基で保護されていてもよいヒドロキシル基、保護基で保護されていてもよいヒドロキシメチル基、保護基で保護されていてもよいアミノ基、保護基で保護されていてもよいカルボキシル基、保護基で保護されていてもよいスルホ基、オキソ基、ニトロ基、シアノ基、又は保護基で保護されていてもよいアシル基を示す。ａ、ｂ、ｃ、ｄは０以上の整数を示す。ａ、ｂ、ｃ又はｄが２以上の場合、括弧内の置換基は同一であっても異なっていてもよい。ｐは０〜３の整数を示す）
で表される何れかの環式基を示す］
で表されるビニルエーテル化合物とを反応させて、下記式（Ｉ）

（式中、Ｒ^a、Ｒ¹、Ｒ²、Ｗ、ｎ及び環Ｚは前記に同じ）
で表される繰り返し単位を含む高分子化合物を得ることを特徴とする側鎖にアセタール構造を有する高分子化合物の製造法を提供する。 The present invention relates to the following formula (II)

(Wherein R ^a represents a hydrogen atom or a methyl group)
A polymer compound containing a repeating unit represented by formula (5):

[Wherein, R ¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ² represents a hydrogen atom or a methyl group, W represents a divalent organic group, and n represents 0 or 1. Ring Z has the following formulas (1) to (4)

(In the formula, A ¹ represents a methylene group or a carbonyl group, A ² represents a methylene group or an oxygen atom. X ¹ , X ² , X ³ and X ⁴ are substituents bonded to atoms constituting each ring. Group, a halogen atom, an alkyl group, a haloalkyl group, an aryl group, a hydroxyl group that may be protected with a protecting group, a hydroxymethyl group that may be protected with a protecting group, or a group that may be protected with a protecting group An amino group, a carboxyl group that may be protected with a protective group, a sulfo group that may be protected with a protective group, an oxo group, a nitro group, a cyano group, or an acyl group that may be protected with a protective group A, b, c and d each represents an integer of 0 or more, and when a, b, c or d is 2 or more, the substituents in parentheses may be the same or different, and p is 0 to 0. Indicates an integer of 3)
Any cyclic group represented by
Is reacted with a vinyl ether compound represented by the following formula (I):

(Wherein R ^a , R ¹ , R ² , W, n and ring Z are the same as above)
A method for producing a polymer compound having an acetal structure in a side chain is provided.

  In addition, the vinyl ether compound in this specification includes a compound in which a hydrogen atom of a vinyl group is substituted with a substituent.

  ADVANTAGE OF THE INVENTION According to this invention, the novel high molecular compound useful as functional resins, such as photosensitive resin, and its manufacturing method are provided. Since this polymer compound has a monomer unit having an acetal structure, a part of the polymer compound is eliminated by an acid to form a phenolic hydroxyl group, so that it is soluble in an alkaline developer. Moreover, since the monomer unit has an alicyclic skeleton and / or a lactone or acid anhydride skeleton, it also has an etching resistance and / or substrate adhesion function. Moreover, the function requested | required as a photoresist can be exhibited with sufficient balance by incorporating the monomer unit which has another function in a polymer as needed.

The polymer compound having an acetal structure in the side chain of the present invention includes a repeating unit represented by the formula (I). In formula (I), the alkyl group having 1 to 3 carbon atoms in R ¹ includes methyl, ethyl, propyl, and isopropyl groups. R ¹ is preferably a hydrogen atom or a methyl group, particularly a hydrogen atom. R ^a and R ² each represent a hydrogen atom or a methyl group.

  W represents a divalent organic group, and n represents 0 or 1. As the divalent organic group, a group having a carbon atom at a bonding site with an adjacent oxygen atom is usually used. Preferred divalent organic groups are (i) a divalent hydrocarbon group, (ii) a divalent hydrocarbon group, and at least one linking group selected from an oxygen atom, a sulfur atom, a carbonyl group and an amino group. And a divalent group consisting of

  The divalent hydrocarbon group includes a divalent aliphatic hydrocarbon group, a divalent alicyclic hydrocarbon group, a divalent aromatic hydrocarbon group, and a divalent hydrocarbon group in which two or more of these are bonded. Is included.

  Typical examples of the divalent hydrocarbon group include 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms) such as methylene, methylmethylene, ethylmethylene, dimethylmethylene, ethylmethylmethylene, ethylene, trimethylene, and tetramethylene groups. , More preferably about 1 to 6) linear or branched alkylene group; straight chain having about 2 to 20 carbon atoms (preferably 2 to 10, more preferably 2 to 6) such as propenylene group or Branched chain alkenylene group; 3 to 20 members (preferably 3 to 1,3-cyclopentylene, 1,2-cyclohexylene, 1,3-cyclohexylene, 1,4-cyclohexylene group, etc. 15-membered, more preferably 5-8-membered) cycloalkylene group; 3-20 membered (such as cyclopropylene, cyclopentylidene, cyclohexylidene group) Mashiku 3-15 membered, more preferably cycloalkylidene group having about 5-8 membered); and the like benzylidene group; an arylene group such as phenylene group.

  The divalent hydrocarbon group may have a substituent. Examples of the substituent include a hydroxyl group which may be protected with a protective group, a hydroxymethyl group which may be protected with a protective group, an amino group which may be protected with a protective group, and a protective group. And a carboxyl group, a sulfo group optionally protected by a protecting group, a halogen atom, an oxo group, a cyano group, a nitro group, a heterocyclic group, a hydrocarbon group, a haloalkyl group, and the like. As the protecting group, a protecting group conventionally used in the field of organic synthesis can be used.

  The heterocyclic group as the substituent is a heterocyclic group of about 3 to 15 members (in particular, 5 to 8 membered heterocycles) containing at least one heteroatom selected from a nitrogen atom, an oxygen atom and a sulfur atom. Cyclic group).

The hydrocarbon group as the substituent includes an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group in which these are bonded. As an aliphatic hydrocarbon group, it is a C1-C20 (preferably 1-10, more preferably 1-3) alkyl group; C2-C20 (preferably 2-10, more preferably 2-3). Alkenyl group having about 2 to 20 carbon atoms (preferably 2 to 10 and more preferably 2 to 3). The alicyclic hydrocarbon group is a cycloalkyl group of about 3 to 20 members (preferably 3 to 15 members, more preferably 5 to 8 members); 3 to 20 members (preferably 3 to 15 members, more preferably About 5 to 8 membered cycloalkenyl group; perhydronaphthalen-1-yl group, norbornyl, adamantyl, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] bridged cyclic hydrocarbon groups such as dodecan-3-yl groups. Examples of the aromatic hydrocarbon group include aromatic hydrocarbon groups having about 6 to 14 (preferably 6 to 10) carbon atoms. The hydrocarbon group in which an aliphatic hydrocarbon group and an alicyclic hydrocarbon group are bonded includes a cycloalkyl-alkyl group such as cyclopentylmethyl, cyclohexylmethyl, 2-cyclohexylethyl group (for example, C _3-20 cycloalkyl- C _1-4 alkyl group and the like). The hydrocarbon group in which an aliphatic hydrocarbon group and an aromatic hydrocarbon group are bonded to each other includes an aralkyl group (for example, a C _7-18 aralkyl group) and an alkyl-substituted aryl group (for example, about 1 to about 4). A phenyl group substituted with a C _1-4 alkyl group or a naphthyl group).

Examples of the haloalkyl group as the substituent include haloalkyl groups having about 1 to 10 carbon atoms such as chloromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, and pentafluoroethyl groups (particularly, C _{1- 3} haloalkyl group).

  As the divalent organic group, a linear or branched alkylene group having 1 to 6 carbon atoms or a group in which the alkylene group is bonded to an oxygen atom or a sulfur atom is particularly preferable.

In the formula (I), the ring Z represents any cyclic group of the above formulas (1) to (4). In the formulas (1) to (4), X ¹ , X ² , X ³ , X ⁴ are each ring (ring shown in the formula, for example, an adamantane ring, 3-oxatricyclo [4.3.1.1 ^{4 , 8]} undecane-2-one ring, tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodecane ring, 4-oxatricyclo [5.2.1.0 ^{2, 6]} decane - 3,5-dione ring, γ-butyrolactone ring, 4-oxatricyclo [5.2.1.0 ^2,6 ] decan-3-one ring, 3-oxatricyclo [4.2.1.0 ^{4 , 8} ] nonan-2-one ring and the like. Examples of the halogen atom in X ^{1 and the} like include a fluorine atom, a chlorine atom, and a bromine atom. Examples of the alkyl group in X ^{1 and the} like include, for example, C _1-10 alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, hexyl, octyl, decyl groups (preferably C 1 _1-5 alkyl group) and the like. Examples of the haloalkyl group in X ^{1 and the} like include C _1-10 haloalkyl groups (preferably, C _1-5 haloalkyl groups) such as chloromethyl, trifluoromethyl, trifluoroethyl, and pentafluoroethyl groups. Examples of the aryl group in X ^{1 and the} like include phenyl and naphthyl groups. The aromatic ring of the aryl group includes, for example, a halogen atom such as a fluorine atom, a C _1-4 alkyl group such as a methyl group, a C _1-5 haloalkyl group such as a trifluoromethyl group, a C _1-4 such as a hydroxyl group and a methoxy group. It may have a substituent such as an alkoxy group such as an alkoxy group, amino group, dialkylamino group, carboxyl group or methoxycarbonyl group, an acyl group such as nitro group, cyano group or acetyl group.

Examples of the protecting group for hydroxyl group and hydroxymethyl group in X ^{1 and the} like include protecting groups commonly used in the field of organic synthesis, such as alkyl groups (eg, C _1-4 alkyl groups such as methyl and t-butyl groups), An alkenyl group (such as an allyl group), a cycloalkyl group (such as a cyclohexyl group), an aryl group (such as a 2,4-dinitrophenyl group), an aralkyl group (such as a benzyl group); a substituted methyl group (such as For example, methoxymethyl, methylthiomethyl, benzyloxymethyl, t-butoxymethyl, 2-methoxyethoxymethyl group, etc.), substituted ethyl group (for example, 1-ethoxyethyl group, etc.), tetrahydropyranyl group, tetrahydrofuranyl group, 1 -Hydroxy, such as a hydroxyalkyl group (eg 1-hydroxyethyl group etc.) A group capable of forming a group with acetal or hemiacetal group; an acyl group (e.g., formyl, acetyl, propionyl, butyryl, isobutyryl, C _1-6 aliphatic acyl group such as pivaloyl group; an aromatic such as benzoyl group; acetoacetyl group Aromatic acyl groups, etc.), alkoxycarbonyl groups (eg, C _1-4 alkoxy-carbonyl groups such as methoxycarbonyl groups), aralkyloxycarbonyl groups, substituted or unsubstituted carbamoyl groups, substituted silyl groups (eg, trimethylsilyl groups, etc.) And when there are two or more hydroxyl groups (including hydroxymethyl groups) in the molecule, a divalent hydrocarbon group (for example, methylene, ethylidene, isopropylidene, cyclopentyl) which may have a substituent. Ridene, cyclohexylidene, benzylidene group, etc.) Can be illustrated.

Examples of the amino-protecting group for X ^{1 and the} like include the alkyl groups, aralkyl groups, acyl groups, alkoxycarbonyl groups and the like exemplified as the hydroxyl-protecting group.

Examples of the protecting group for the carboxyl group and the sulfo group in X ¹ include, for example, an alkoxy group (for example, a C _1-6 alkoxy group such as methoxy, ethoxy, and butoxy groups), a cycloalkyloxy group, an aryloxy group, and an aralkyloxy group. Group, trialkylsilyloxy group, optionally substituted amino group, hydrazino group, alkoxycarbonylhydrazino group, aralkylcarbonylhydrazino group and the like.

Examples of the acyl group in X ¹ include C _1-6 aliphatic acyl groups such as formyl, acetyl, propionyl, butyryl, isobutyryl, and pivaloyl groups; aromatic acyl groups such as acetoacetyl groups; benzoyl groups, and the like. . As the protecting group for the acyl group, a protecting group conventionally used in the field of organic synthesis can be used. Examples of the protected form of the acyl group include acetal (including hemiacetal).

  a, b, c, and d are, for example, an integer of 0 to 5, preferably an integer of 0 to 3.

  In formula (I), the oxygen atom constituting the acetal structure may be bonded to any of the o-position, m-position and p-position of the benzene ring in the formula, but is often bonded to the p-position. The polymer compound of the present invention may contain only one type of repeating unit represented by the formula (I) or two types. For example, the polymer compound of the present invention includes (i) a polymer compound containing a repeating unit (Ia) in which ring Z is a cyclic group represented by formula (1), and (ii) ring Z is represented by formula (2). A repeating unit which is a cyclic group represented by formula (3), a repeating unit in which ring Z is a cyclic group represented by formula (3) and a repeating unit in which ring Z is a cyclic group represented by formula (4) A polymer compound containing at least one repeating unit (Ib) selected from: (iii) a repeating unit (Ia) in which ring Z is a cyclic group represented by formula (1); 2) a repeating unit which is a cyclic group represented by formula (2), a repeating unit wherein ring Z is a cyclic group represented by formula (3) and a ring Z is a cyclic group represented by formula (4). A polymer compound containing at least one repeating unit (Ib) selected from the units is included. In the polymer compound (iii), the ratio of the repeating unit (Ia) to the repeating unit (Ib) (former / latter; molar ratio) is, for example, 1/99 to 99/1, preferably 10/90 to 90. / 10, more preferably about 20/80 to 80/20.

  Since the polymer compound of the present invention has a monomer unit having an acetal structure represented by the formula (I), it is easily eliminated by an acid to generate a phenolic hydroxyl group. Therefore, it is soluble in an alkaline developer. Moreover, when the ring Z has the repeating unit (Ia) which is a cyclic group represented by the formula (1), the etching resistance is improved because it contains an alicyclic skeleton. In addition, a repeating unit in which ring Z is a cyclic group represented by formula (2), a repeating unit in which ring Z is a cyclic group represented by formula (3), and ring Z are represented by formula (4). In the case of having at least one type of repeating unit (Ib) selected from repeating units that are cyclic groups, since it contains a lactone or acid anhydride skeleton, the substrate adhesion is improved. Moreover, the function requested | required as a photoresist can be exhibited with sufficient balance by incorporating the monomer unit which has another function in a polymer as needed. Therefore, it is useful as a photoresist resin, particularly as a photoresist resin when EB (electron beam) is used as an exposure source.

  In the polymer compound of the present invention, the ratio of the repeating unit represented by the formula (I) is not particularly limited, but is usually 1 to 100 mol%, preferably 3 to 100, based on all monomer units constituting the polymer. It is mol% (for example, 3-80 mol%), More preferably, it is 5-100 mol% (for example, 5-70 mol%), About 10-100 mol% (for example, 10-50 mol%) is especially preferable.

  The polymer compound of the present invention may contain a repeating unit represented by the formula (II) in addition to the repeating unit represented by the formula (I). Since such a polymer compound has a monomer unit having a phenolic hydroxyl group, it has excellent substrate adhesion and solubility in an alkali developer.

  In the polymer compound containing the repeating unit represented by the formula (II), the ratio of the repeating unit represented by the formula (II) is, for example, 1 to 99 mol% with respect to all the monomer units constituting the polymer. Preferably it is 20-95 mol%, More preferably, it is 30-90 mol%. The ratio of the repeating unit represented by the formula (II) is represented by the formula (5) and the polymer compound containing the repeating unit represented by the formula (II) used as a raw material in the production method of the present invention described later. It can be controlled by adjusting the ratio with the vinyl ether compound or by adjusting the reaction conditions such as the reaction temperature.

  The polymer compound of the present invention may contain other monomer units other than those described above, if necessary. Examples of monomers corresponding to such monomer bodies include styrene derivatives such as styrene, pt-butyloxystyrene, 4-methoxystyrene, and 4-ethoxystyrene; N, N-dimethylacrylamide; vinylpyridine; And acrylic monomers such as methacrylic acid esters; maleic anhydride and the like.

  In the case of the polymer compound containing the repeating unit of the formula (I) and the repeating unit of the formula (II), the ratio of the other monomer units is, for example, 0 to 50 mol% with respect to all the monomer units constituting the polymer. (For example, 1-50 mol%), Preferably it is 0-30 mol% (for example, 1-30 mol%), More preferably, it is about 10-30 mol%.

  The weight average molecular weight (Mw) of the polymer compound of the present invention is, for example, about 1000 to 500000, preferably 2000 to 100000, more preferably about 4000 to 50000, and the molecular weight distribution (Mw / Mn) is, for example, 1.1. It is about -3.0. In addition, Mn shows a number average molecular weight, and both Mn and Mw are values in terms of polystyrene.

  In the production method of the present invention, a polymer compound containing a repeating unit represented by the formula (II) is reacted with a vinyl ether compound represented by the formula (5) to repeat the compound represented by the formula (I). A polymer compound containing units is obtained.

In the polymer compound containing a repeating unit represented by the formula (II) used as a raw material, Ra represents ^a hydrogen atom or a methyl group. The hydroxyl group in the formula may be bonded to any of the o-position, m-position and p-position of the benzene ring, but it is often bonded to the p-position. The high molecular compound containing the repeating unit represented by the formula (II) can be produced by subjecting p-vinylphenol (= p-hydroxystyrene) to polymerization together with other monomers as necessary. For the polymerization, conventional polymerization methods such as radical polymerization and anionic polymerization can be employed. The weight average molecular weight (Mw) of the polymer compound containing the repeating unit represented by the formula (II) is, for example, about 1000 to 500,000, preferably about 2000 to 100,000, more preferably about 4000 to 30000, and the molecular weight distribution (Mw) / Mn) is, for example, about 1.1 to 3.0.

In the vinyl ether compound represented by the formula (5), R ¹ , R ² , W, n, ring Z, A ¹ , A ² , X ¹ , X ² , X ³ , X ⁴ , a, b, c, d , P is the same as described above. The vinyl ether compound represented by Formula (5) can be manufactured by the method of Unexamined-Japanese-Patent No. 2003-73321, for example.

  Typical examples of the vinyl ether compound represented by the formula (5) include the following compounds. Examples of vinyl ether compounds in which ring Z is a cyclic group represented by formula (1) include 1-vinyloxyadamantane, 1-hydroxy-3-vinyloxyadamantane, 1,3-dihydroxy-5-vinyloxyadamantane, 1,3,5-trihydroxy-7-vinyloxyadamantane, 4-oxo-1-vinyloxyadamantane, 1,3-dimethyl-5-vinyloxyadamantane, 1-carboxy-3-vinyloxyadamantane, 1-cyano -3-vinyloxyadamantane, 1-amino-3-vinyloxyadamantane, 1-nitro-3-vinyloxyadamantane, 1-sulfo-3-vinyloxyadamantane, 1-t-butyloxycarbonyl-3-vinyloxyadamantane 1- (vinyloxymethyl) adamantane, 1 Hydroxy-3- (vinyloxymethyl) adamantane, 1,3-dihydroxy-3- (vinyloxymethyl) adamantane, 1,3,5-trihydroxy-7- (vinyloxymethyl) adamantane, 4-oxo-1- (Vinyloxymethyl) adamantane, 1- (2-vinyloxyethyl) adamantane, 1-hydroxy-3- (2-vinyloxyethyl) adamantane, 1,3-dihydroxy-5- (2-vinyloxyethyl) adamantane, 1,3,5-trihydroxy-7- (2-vinyloxyethyl) adamantane, 4-oxo-3- (2-vinyloxyethyl) adamantane, 1,3-dimethyl-5- (2-vinyloxyethyl) Adamantane, 1-carboxy-3- (2-vinyloxyethyl) adamantane, 1-cyano 3- (2-vinyloxyethyl) adamantane, 1-amino-3- (2-vinyloxyethyl) adamantane, 1-nitro-3- (2-vinyloxyethyl) adamantane, 1-sulfo-3- (2- Vinyloxyethyl) adamantane, 1-t-butyloxycarbonyl-3- (2-vinyloxyethyl) adamantane, 1- (3-vinyloxypropyl) adamantane, 1-hydroxy-3- (3-vinyloxypropyl) adamantane 1,3-dihydroxy-5- (3-vinyloxypropyl) adamantane, 1,3,5-trihydroxy-7- (3-vinyloxypropyl) adamantane, 4-oxo-3- (3-vinyloxypropyl) Adamantane, 1- (2-vinyloxypropyl) adamantane, 1- (1-methyl-1-bi) Nyloxyethyl) adamantane, 1- (4-vinyloxybutyl) adamantane, and corresponding isopropenyl ethers.

Examples of vinyl ether compounds in which ring Z is a cyclic group represented by formula (2) include 6-vinyloxy-3-oxatricyclo [4.3.1.1 ^4,8 ] undecan-2-one, 6 -Hydroxy-8-vinyloxy-3-oxatricyclo [4.3.1.1 ^4,8 ] undecan-2-one, 8-hydroxy-6-vinyloxy-3-oxatricyclo [4.3.1. 1 ^4,8 ] undecan-2-one and the corresponding isopropenyl ethers.

Examples of vinyl ether compounds in which ring Z is a cyclic group represented by formula (3) include 8-vinyloxy-4-oxatricyclo [5.2.1.0 ^2,6 ] decane-3,5-dione. 4-vinyloxy-11-oxapentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13] pentadecane-10,12-dione, alpha-vinyloxy-gamma, .gamma.-dimethyl -γ- butyrolactone, α, γ, γ- trimethyl -α- vinyloxy -γ- butyrolactone, gamma, .gamma.-dimethyl -β -Methoxycarbonyl-α-vinyloxy-γ-butyrolactone, 8-vinyloxy-4-oxatricyclo [5.2.1.0 ^2,6 ] decan-3-one, 9-vinyloxy-4-oxatricyclo [5 .2.1.0 ^2,6 ] decan-3-one, and the corresponding isopropenyl ethers.

Examples of vinyl ether compounds in which ring Z is a cyclic group represented by formula (4) include 5-vinyloxy-3-oxatricyclo [4.2.1.0 ^4,8 ] nonan-2-one, 5 -Methyl-5-vinyloxy-3-oxatricyclo [4.2.1.0 ^4,8 ] nonan-2-one, 9-methyl-5-vinyloxy-3-oxatricyclo [4.2.1. 0 ^4,8 ] nonan-2-one, and the corresponding isopropenyl ethers.

  The reaction of the polymer compound containing the repeating unit represented by the formula (II) and the vinyl ether compound represented by the formula (5) is usually performed in an organic solvent. Examples of the organic solvent include esters such as ethyl acetate, isopropyl acetate, butyl acetate and ethyl lactate; ethers such as tetrahydrofuran, dioxane and propylene glycol monomethyl ether; glycol ether acetates such as propylene glycol monomethyl ether acetate; N, N-dimethyl Amides such as formamide; nitriles such as acetonitrile, propionitrile, and benzonitrile; halogenated hydrocarbons such as dichloromethane; and mixed solvents thereof can be used.

  The amount of the vinyl ether compound represented by the formula (5) is represented by the formula (I) with the unit represented by the formula (II) in the polymer compound containing the repeating unit represented by the formula (II). It can select suitably according to the ratio replaced with a unit. For example, the vinyl ether compound represented by the formula (5) is preferably used in an amount of 1 to 1.5 times, preferably 1.1 to 1.3 times the amount of the desired number of moles of substitution.

  The presence of an acetalization catalyst such as an acid catalyst in the reaction system significantly increases the reaction rate. Examples of the catalyst include organic acids such as methanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, trifluoroacetic acid, and oxalic acid; inorganic acids such as sulfuric acid and hydrochloric acid; pyridinium p-toluenesulfonate, A salt such as ammonium p-toluenesulfonate or 4-methylpyridinium p-toluenesulfonate (for example, a salt of a strong acid and a weak base); a strongly acidic ion exchange resin, or the like can be used. The amount of the catalyst is, for example, 0.01 to 20% by weight, preferably 0.1 to 15% by weight, and more preferably 1 to 10% with respect to the polymer compound containing the repeating unit represented by the formula (II). It is about wt%.

  The reaction temperature can be appropriately selected depending on the reaction raw materials, the type of the catalyst and the like, but is generally 0 to 80 ° C., preferably about 10 to 50 ° C. The reaction can be carried out by any method such as batch, semi-batch and continuous methods.

  In the method of the present invention, the acetalization reaction of the phenolic hydroxyl group proceeds smoothly, and a part of the repeating unit represented by the formula (II) in the polymer compound containing the repeating unit represented by the formula (II) or All phenolic hydroxyl groups are acetalized (acetal protected) to produce the repeating unit represented by formula (I). After completion of the reaction, the target polymer compound can be separated and purified by using separation means such as filtration, concentration, extraction, precipitation, reprecipitation, crystallization, recrystallization, column chromatography and the like.

  The polymer compound having an acetal structure in the side chain thus obtained can be used as a functional resin such as a photosensitive resin (photoresist resin) using far ultraviolet rays or an electron beam as an exposure light source, or an intermediate material thereof.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

ポリ（４−ビニルフェノール）［＝ポリ（４−ヒドロキシスチレン）］１２．０ｇ（Ｍｗ＝８０００）と酢酸ブチル７０ｍｌの混合物に、ｐ−トルエンスルホン酸０．８６ｇを加え、次いで１−アダマンチルメチルビニルエーテル［＝１−（ビニルオキシメチル）アダマンタン］５．７７ｇを加えて、室温で１５時間撹拌し反応させた。反応混合液を水／イソプロピルアルコール混合液に入れ、ポリマーを沈殿させた。沈殿物を濾過し、水／イソプロピルアルコール混合液で洗浄し、減圧下で乾燥し、標記のポリマー１６．０ｇを得た。得られたポリマーについて、ＧＰＣ（ゲルパーミエーションクロマトグラフィー）法により測定したところ、重量平均分子量Ｍｗは１１０００であった。また、¹Ｈ−ＮＭＲ分析、¹³Ｃ−ＮＭＲ分析より、ポリ（４−ビニルフェノール）中のフェノール性水酸基の２５％がアセタール化（アセタール保護）されていることが確認された。 Example 1
Production of polymer compounds with the following structure.

To a mixture of 12.0 g of poly (4-vinylphenol) [= poly (4-hydroxystyrene)] (Mw = 8000) and 70 ml of butyl acetate was added 0.86 g of p-toluenesulfonic acid, and then 1-adamantyl methyl vinyl ether. [= 1- (vinyloxymethyl) adamantane] 5.77 g was added, and the mixture was stirred at room temperature for 15 hours to be reacted. The reaction mixture was placed in a water / isopropyl alcohol mixture to precipitate the polymer. The precipitate was filtered, washed with a water / isopropyl alcohol mixture and dried under reduced pressure to give 16.0 g of the title polymer. When the obtained polymer was measured by GPC (gel permeation chromatography) method, the weight average molecular weight Mw was 11000. From ¹ H-NMR analysis and ¹³ C-NMR analysis, it was confirmed that 25% of the phenolic hydroxyl groups in poly (4-vinylphenol) were acetalized (acetal protected).

ポリ（４−ビニルフェノール）［＝ポリ（４−ヒドロキシスチレン）］１２．０ｇ（Ｍｗ＝２００００）とテトラヒドロフラン５０ｍｌの混合物に、ｐ−トルエンスルホン酸０．８６ｇを加え、次いで６−ビニルオキシ−３−オキサトリシクロ［４．３．１．１^4,8］ウンデカン−２−オン５．２１ｇを加えて、室温で１２時間撹拌し反応させた。反応混合液を水／イソプロピルアルコール混合液に入れ、ポリマーを沈殿させた。沈殿物を濾過し、水／イソプロピルアルコール混合液で洗浄し、減圧下で乾燥し、標記のポリマー１５．４ｇを得た。得られたポリマーについて、ＧＰＣ法により測定したところ、重量平均分子量Ｍｗは２６５００であった。また、¹Ｈ−ＮＭＲ分析、¹³Ｃ−ＮＭＲ分析より、ポリ（４−ビニルフェノール）中のフェノール性水酸基の２０％がアセタール化（アセタール保護）されていることが確認された。 Example 2
Production of polymer compounds with the following structure.

To a mixture of 12.0 g of poly (4-vinylphenol) [= poly (4-hydroxystyrene)] (Mw = 20000) and 50 ml of tetrahydrofuran was added 0.86 g of p-toluenesulfonic acid, and then 6-vinyloxy-3- Oxatricyclo [4.3.1.1 ^4,8 ] undecan-2-one (5.21 g) was added, and the mixture was stirred at room temperature for 12 hours to be reacted. The reaction mixture was placed in a water / isopropyl alcohol mixture to precipitate the polymer. The precipitate was filtered, washed with a water / isopropyl alcohol mixture and dried under reduced pressure to give 15.4 g of the title polymer. When the obtained polymer was measured by GPC method, the weight average molecular weight Mw was 26500. Further, from ¹ H-NMR analysis and ¹³ C-NMR analysis, it was confirmed that 20% of the phenolic hydroxyl group in poly (4-vinylphenol) was acetalized (acetal protected).

ポリ（４−ビニルフェノール）［＝ポリ（４−ヒドロキシスチレン）］１２．０ｇ（Ｍｗ＝８０００）とプロピレングリコールモノメチルエーテルアセテート５０ｍｌの混合物に、ｐ−トルエンスルホン酸ピリジニウム塩２．５２ｇを加え、次いで２−（１−アダマンチル）エチルビニルエーテル［＝１−（２−ビニルオキシエチル）アダマンタン］６．１９ｇと、６−ビニルオキシ−３−オキサトリシクロ［４．３．１．１^4,8］ウンデカン−２−オン４．１７ｇを加えて、室温で２４時間撹拌し反応させた。反応混合液を水／イソプロピルアルコール混合液に入れ、ポリマーを沈殿させた。沈殿物を濾過し、水／イソプロピルアルコール混合液で洗浄し、減圧下で乾燥し、標記のポリマー１９．３ｇを得た。得られたポリマーについて、ＧＰＣ法により測定したところ、重量平均分子量Ｍｗは１３５００であった。また、¹Ｈ−ＮＭＲ分析、¹³Ｃ−ＮＭＲ分析より、ポリ（４−ビニルフェノール）中のフェノール性水酸基の２５％が２−（１−アダマンチル）エチルビニルエーテルとの反応によりアセタール化され、１５％が６−ビニルオキシ−３−オキサトリシクロ［４．３．１．１^4,8］ウンデカン−２−オンとの反応によりアセタール化されていることが確認された。
Example 3
Production of polymer compounds with the following structure.

To a mixture of 12.0 g of poly (4-vinylphenol) [= poly (4-hydroxystyrene)] (Mw = 8000) and 50 ml of propylene glycol monomethyl ether acetate, 2.52 g of p-toluenesulfonic acid pyridinium salt was added, 6.19 g of 2- (1-adamantyl) ethyl vinyl ether [= 1- (2-vinyloxyethyl) adamantane] and 6-vinyloxy-3-oxatricyclo [4.3.1.1 ^4,8 ] undecane- 4.17 g of 2-one was added and the reaction was allowed to stir at room temperature for 24 hours. The reaction mixture was placed in a water / isopropyl alcohol mixture to precipitate the polymer. The precipitate was filtered, washed with a water / isopropyl alcohol mixture and dried under reduced pressure to give 19.3 g of the title polymer. When the obtained polymer was measured by GPC method, the weight average molecular weight Mw was 13500. From ¹ H-NMR analysis and ¹³ C-NMR analysis, 25% of the phenolic hydroxyl group in poly (4-vinylphenol) was acetalized by reaction with 2- (1-adamantyl) ethyl vinyl ether, and 15% Was acetalized by reaction with 6-vinyloxy-3-oxatricyclo [4.3.1.1 ^4,8 ] undecan-2-one.

Claims (3)

Formula (I) below

[Wherein, R ^a represents a hydrogen atom or a methyl group, R ¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ² represents a hydrogen atom or a methyl group, and W represents a divalent organic group. N represents 0 or 1. Ring Z has the following formulas (1) to (4)

(In the formula, A ¹ represents a methylene group or a carbonyl group, A ² represents a methylene group or an oxygen atom. X ¹ , X ² , X ³ and X ⁴ are substituents bonded to atoms constituting each ring. Group, a halogen atom, an alkyl group, a haloalkyl group, an aryl group, a hydroxyl group that may be protected with a protecting group, a hydroxymethyl group that may be protected with a protecting group, or a group that may be protected with a protecting group An amino group, a carboxyl group that may be protected with a protective group, a sulfo group that may be protected with a protective group, an oxo group, a nitro group, a cyano group, or an acyl group that may be protected with a protective group A, b, c and d each represents an integer of 0 or more, and when a, b, c or d is 2 or more, the substituents in parentheses may be the same or different, and p is 0 to 0. Indicates an integer of 3)
Any cyclic group represented by
The high molecular compound which has an acetal structure in the side chain containing the repeating unit represented by these. Furthermore, the following formula (II)

The high molecular compound of Claim 1 containing the repeating unit represented by these. Following formula (II)

(Wherein R ^a represents a hydrogen atom or a methyl group)
A polymer compound containing a repeating unit represented by formula (5):

[Wherein, R ¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ² represents a hydrogen atom or a methyl group, W represents a divalent organic group, and n represents 0 or 1. Ring Z has the following formulas (1) to (4)

(In the formula, A ¹ represents a methylene group or a carbonyl group, A ² represents a methylene group or an oxygen atom. X ¹ , X ² , X ³ and X ⁴ are substituents bonded to atoms constituting each ring. Group, a halogen atom, an alkyl group, a haloalkyl group, an aryl group, a hydroxyl group that may be protected with a protecting group, a hydroxymethyl group that may be protected with a protecting group, or a group that may be protected with a protecting group An amino group, a carboxyl group that may be protected with a protective group, a sulfo group that may be protected with a protective group, an oxo group, a nitro group, a cyano group, or an acyl group that may be protected with a protective group A, b, c and d each represents an integer of 0 or more, and when a, b, c or d is 2 or more, the substituents in parentheses may be the same or different, and p is 0 to 0. Indicates an integer of 3)
Any cyclic group represented by
Is reacted with a vinyl ether compound represented by the following formula (I):

(Wherein R ^a , R ¹ , R ² , W, n and ring Z are the same as above)
A process for producing a polymer compound having an acetal structure in a side chain, wherein the polymer compound comprises a repeating unit represented by the formula: