JP2005126459A - Acid-dissociating-group-containing resin and its production method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a (meth)acrylic polymer having a specified molecular weight distribution and a production method for synthesizing the polymer. <P>SOLUTION: The (meth)acrylic polymer is produced by polymerizing (i) a compound represented by formula (1) or (ii) a mixture consisting of a compound represented by formula (1), a radical polymerization initiator, and at least one compound selected from among ditelluride compounds represented by formula (2). In formulas (1) and (2), R<SP>a</SP>is a 1-8C alkyl group, an optionally substituted aryl group, or an aromatic heterocyclic group; R<SP>b</SP>and R<SP>c</SP>are each H or a 1-8C alkyl group; and R<SP>d</SP>is an optionally substituted aryl group, an aromatic heterocyclic group, or an acyl, oxycarbonyl, or cyano group. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an acid-dissociable group-containing resin and a method for producing the same.

In the field of microfabrication represented by the manufacture of integrated circuit elements, in order to obtain a higher degree of integration, recently, an ArF excimer laser (wavelength 193 nm), an F ₂ excimer laser (wavelength 157 nm) or the like has been used. There is a need for a lithography technique capable of microfabrication at the same level.
A chemically amplified radiation-sensitive resin composition is known as a resist material used in such a lithography technique, and an acid-dissociable group-containing resin is used as the resin material.
On the other hand, synthesis of a polymer compound having a narrow molecular weight distribution by living radical polymerization using an organic tellurium compound as an initiator has been reported (see Non-Patent Documents 1 and 2).
Shigeru Yamago et al., J.AM.CHEM.SOC.13666-13667, Vol124, No46,2002 Shigeru Yamago et al., J.AM.CHEM.SOC.2874-2875, Vol124, No12, 2002

  However, in the semiconductor field, when a higher degree of integration than ever has been required, the acid-dissociable group-containing resin, which is a resin material, is also required to have a material repeatability that can contribute to manufacturing lot variations. In particular, it is considered urgently necessary to improve the solubility in a resist solvent because it is considered that minute defects generated during development are caused by a resin as a constituent component.

  The present invention has been made to cope with such a problem, and by using a specific initiator, a (meth) acrylic polymer having a specific molecular weight distribution, and a method for synthesizing the polymer. The purpose is to provide a manufacturing method.

式（１）および式（２）において、Ｒ^aは、炭素数１〜８のアルキル基、アリール基、置換アリール基または芳香族ヘテロ環基を表す。Ｒ^bおよびＲ^cは、水素原子または炭素数１〜８のアルキル基を表す。Ｒ^dは、アリール基、置換アリール基、芳香族ヘテロ環基、アシル基、オキシカルボニル基またはシアノ基を表す。 The acid-dissociable group-containing resin of the present invention comprises (i) a compound represented by the following formula (1), or (ii) a compound represented by the following formula (1), a radical polymerization initiator and the following formula ( It is characterized by being polymerized using a mixture of at least one compound selected from ditelluride compounds represented by 2).

In Formula (1) and Formula (2), R ^a represents an alkyl group having 1 to 8 carbon atoms, an aryl group, a substituted aryl group, or an aromatic heterocyclic group. R ^b and R ^c represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. R ^d represents an aryl group, a substituted aryl group, an aromatic heterocyclic group, an acyl group, an oxycarbonyl group or a cyano group.

式（３）において、Ｒは水素、メチル基、トリフロロメチル基あるいはヒドロキシメチル基を表し、Ｒ¹は相互に独立に炭素数４〜２０の１価の脂環式炭化水素基もしくはその誘導体または炭素数１〜４の直鎖状もしくは分岐状のアルキル基を表し、かつＲ¹の少なくとも１つが該脂環式炭化水素基もしくはその誘導体であるか、あるいは何れか２つのＲ¹が相互に結合して、それぞれが結合している炭素原子とともに炭素数４〜２０の２価の脂環式炭化水素基もしくはその誘導体を形成し、残りのＲ¹が炭素数１〜４の直鎖状もしくは分岐状のアルキル基または炭素数４〜２０の１価の脂環式炭化水素基もしくはその誘導体を表す。 The acid-dissociable group-containing resin of the present invention is characterized by including a repeating unit represented by the following formula (3).

In the formula (3), R represents hydrogen, a methyl group, a trifluoromethyl group or a hydroxymethyl group, and R ¹ , independently of each other, a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof, or Represents a linear or branched alkyl group having 1 to 4 carbon atoms, and at least one of R ¹ is the alicyclic hydrocarbon group or a derivative thereof, or any two R ¹ are bonded to each other Then, a divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof is formed together with the carbon atom to which each is bonded, and the remaining R ¹ is linear or branched having 1 to 4 carbon atoms. Represents an alkyl group in the form of a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof.

式（４）〜（１０）において、Ｒは式（３）におけるＲと同一である。
式（４）において、Ａは単結合もしくは炭素数１〜６の置換基を有していてもよい直鎖状もしくは分岐状のアルキレン基、モノまたはジアルキレングリコール基、アルキレンエステル基を表し、Ｂは単結合もしくは炭素数１〜３の置換基を有していてもよいアルキレン基、アルキルオキシ基、酸素原子を表す。
式（５）において、Ｅは単結合もしくは炭素数１〜３の２価のアルキル基を表し、Ｒ²は相互に独立に水酸基、シアノ基、カルボキシル基、−ＣＯＯＲ⁴、または−Ｙ−Ｒ⁵を表し、Ｒ⁴は水素原子あるいは炭素数１〜４の直鎖状もしくは分岐状のアルキル基、または炭素数３〜２０の脂環式のアルキル基、Ｙは相互に独立に単結合もしくは炭素数１〜３の２価のアルキレン基を表し、Ｒ⁵は相互に独立に水素原子、水酸基、シアノ基、または−ＣＯＯＲ⁶基を表す。ただし、少なくとも１つのＲ²が水素原子ではない。−ＣＯＯＲ⁶基におけるＲ⁶としては、水素原子あるいは炭素数１〜４の直鎖状もしくは分岐状のアルキル基、または炭素数３〜２０の脂環式のアルキル基を表す。
式（６）において、Ｇは単結合、炭素数１〜６の直鎖状もしくは分岐状のアルキレン基または炭素数４〜２０の脂環式炭化水素基、アルキレングリコール基、アルキレンエステル基を表す。
式（７）において、Ｊは単結合、炭素数１〜２０の置換基を有していてもよい直鎖状、分岐状、環状のアルキレン基、アルキレングリコール基、アルキレンエステル基を表す。
式（８）において、Ｌは単結合、炭素数１〜２０の置換基を有していてもよい直鎖状、分岐状、環状のアルキレン基、アルキレングリコール基、アルキレンエステル基を表し、Ｒ³は水素原子、炭素数１〜４の直鎖状もしくは分岐状のアルキル基、アルコキシ基、ヒドロキシアルキル基、炭素数３〜２０の２価の脂環式炭化水素基もしくはその誘導体を形成したものを表す。ｑは１または２である。
式（９）において、Ｎ、Ｍ’はそれぞれ独立して単結合、炭素数１〜２０の置換基を有していてもよい直鎖状、分岐状、環状のアルキレン基、アルキレングリコール基、アルキレンエステル基を表す。ｐは０または１である。
式（１０）においてＸは炭素数７〜２０の極性基を含まない炭素および水素のみからなる多環型脂環式炭化水素基を表す。 Moreover, the acid dissociable group-containing resin of the present invention contains at least one repeating unit selected from repeating units represented by the following formulas (4) to (10) together with the repeating unit represented by the formula (3). It is characterized by including.

In the formulas (4) to (10), R is the same as R in the formula (3).
In the formula (4), A represents a single bond or a linear or branched alkylene group, mono- or dialkylene glycol group or alkylene ester group which may have a substituent having 1 to 6 carbon atoms, and B Represents a single bond or an alkylene group, alkyloxy group or oxygen atom which may have a substituent having 1 to 3 carbon atoms.
In the formula (5), E represents a single bond or a divalent alkyl group having 1 to 3 carbon atoms, and R ² is independently a hydroxyl group, a cyano group, a carboxyl group, —COOR ⁴ , or —Y—R ^5. R ⁴ is a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or an alicyclic alkyl group having 3 to 20 carbon atoms, Y is independently a single bond or a carbon number 1 to 3 divalent alkylene groups, and R ⁵ each independently represents a hydrogen atom, a hydroxyl group, a cyano group, or a —COOR ⁶ group. However, at least one R ² is not a hydrogen atom. R ⁶ in the —COOR ⁶ group represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or an alicyclic alkyl group having 3 to 20 carbon atoms.
In Formula (6), G represents a single bond, a linear or branched alkylene group having 1 to 6 carbon atoms, an alicyclic hydrocarbon group having 4 to 20 carbon atoms, an alkylene glycol group, or an alkylene ester group.
In the formula (7), J represents a single bond, a linear, branched or cyclic alkylene group, alkylene glycol group or alkylene ester group which may have a substituent having 1 to 20 carbon atoms.
In the formula (8), L represents a single bond, a linear, branched or cyclic alkylene group, alkylene glycol group or alkylene ester group which may have a substituent having 1 to 20 carbon atoms, and R ³ Is a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, an alkoxy group, a hydroxyalkyl group, a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, or a derivative thereof. Represent. q is 1 or 2.
In the formula (9), N and M ′ are each independently a single bond, a linear, branched or cyclic alkylene group, alkylene glycol group, alkylene which may have a substituent having 1 to 20 carbon atoms. Represents an ester group. p is 0 or 1;
In the formula (10), X represents a polycyclic alicyclic hydrocarbon group composed only of carbon and hydrogen not containing a polar group having 7 to 20 carbon atoms.

The acid dissociable group-containing resin of the present invention has a ratio (Mw / Mn) of a weight average molecular weight (hereinafter abbreviated as Mw) to a number average molecular weight (hereinafter abbreviated as Mn) of less than 1.5. It is characterized by.
In the present invention, Mw and Mn refer to polystyrene-reduced average molecular weights measured by gel permeation chromatography (GPC), which are measured by the methods described later.
Moreover, it is used for the radiation sensitive resin composition used for the lithography using the radiation of wavelength 193nm or less.

  The method for producing an acid-dissociable group-containing resin of the present invention is a method for polymerizing an acid-dissociable group-containing monomer using an initiator, wherein the initiator is the above-described (i) or (ii). It is characterized by being.

  Since the acid-dissociable group-containing resin of the present invention uses (i) or (ii) described above as an initiator, Mw / Mn can be reduced, there is little variation between production lots, and solubility in a resist solvent. Excellent.

  In the present invention, the value of Mw / Mn can be made smaller than 1.5 by living radical polymerization using one or more compounds represented by formula (1) and formula (2) as initiators. As a result, the variation in the molecular weight distribution of the acid-dissociable group-containing resin can be reduced. Moreover, the solubility with respect to a solvent improves because acid dissociable group containing resin is a random polymer.

  Initiators that can be used in the present invention include (i) a compound represented by the following formula (1), (ii-1) a mixture of a compound represented by the following formula (1) and a radical polymerization initiator, (ii- 2) A mixture of a compound represented by the following formula (1) and a ditelluride compound represented by the following formula (2), (ii-3) a compound represented by the following formula (1), a radical polymerization initiator, and the following: There are four types of mixtures with ditelluride compounds represented by formula (2). Hereinafter, the compounds constituting each initiator will be described.

式（１）および式（２）において、Ｒ^aで表される基は、具体的には次の通りである。
炭素数１〜８のアルキル基としては、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、シクロプロピル基、ｎ−ブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、シクロブチル基、ｎ−ペンチル基、ｎ−ヘキシル基、ｎ−ヘプチル基、ｎ−オクチル基等の炭素数１〜８の直鎖状、分岐鎖状または環状のアルキル基を挙げることができる。好ましいアルキル基としては、炭素数１〜４の直鎖状または分岐鎖状のアルキル基、より好ましくはメチル基、エチル基またはｎ−ブチル基である。
アリール基としては、フェニル基、ナフチル基等、置換アリール基としては置換基を有しているフェニル基、置換基を有しているナフチル基等、芳香族へテロ環基としてはピリジル基、ピロール基、フリル基、チエニル基等を挙げることができる。上記置換基を有しているアリール基の置換基としては、例えば、ハロゲン原子、水酸基、アルコキシ基、アミノ基、ニトロ基、シアノ基、−ＣＯＲ^eで示されるカルボニル含有基（ここでＲ^eは炭素数１〜８のアルキル基、アリール基、炭素数１〜８のアルコキシ基、アリーロキシ基）、スルホニル基、トリフルオロメチル基等を挙げることができる。好ましいアリール基としては、フェニル基、トリフルオロメチル置換フェニル基である。また、これら置換基は、１個または２個置換しているのがよく、パラ位もしくはオルト位が好ましい。 The organic tellurium compounds that can be used in the present invention are represented by the following formulas (1) and (2).

In Formula (1) and Formula (2), the group represented by ^Ra is specifically as follows.
Examples of the alkyl group having 1 to 8 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, sec-butyl group, tert-butyl group, cyclobutyl group, and n-pentyl. And a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms such as a group, n-hexyl group, n-heptyl group and n-octyl group. A preferable alkyl group is a linear or branched alkyl group having 1 to 4 carbon atoms, more preferably a methyl group, an ethyl group or an n-butyl group.
As an aryl group, a phenyl group, a naphthyl group, etc., as a substituted aryl group, a phenyl group having a substituent, a naphthyl group having a substituent, etc., as an aromatic heterocyclic group, a pyridyl group, a pyrrole Group, furyl group, thienyl group and the like. Examples of the substituent of the aryl group having the substituent include a halogen atom, a hydroxyl group, an alkoxy group, an amino group, a nitro group, a cyano group, and a carbonyl-containing group represented by —COR ^e (where R ^e is And an alkyl group having 1 to 8 carbon atoms, an aryl group, an alkoxy group having 1 to 8 carbon atoms, and an aryloxy group), a sulfonyl group, and a trifluoromethyl group. Preferred aryl groups are a phenyl group and a trifluoromethyl-substituted phenyl group. These substituents may be substituted one or two, and the para-position or ortho-position is preferable.

Specific examples of the groups represented by R ^b and R ^c are as follows. Examples of the alkyl group having 1 to 8 carbon atoms include those similar to the alkyl group represented by ^Ra above.
Specific examples of each group represented by R ^d are as follows.
The aryl group, a substituted aryl group, an aromatic heterocyclic group can be exemplified the same groups as those indicated above R ^a. Examples of the acyl group include a formyl group, an acetyl group, and a benzoyl group. As the oxycarbonyl group, a group represented by —COOR ^f (wherein R ^f is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group) is preferable. For example, a carboxyl group, a methoxycarbonyl group, an ethoxycarbonyl group, A propoxycarbonyl group, n-butoxycarbonyl group, sec-butoxycarbonyl group, ter-butoxycarbonyl group, n-pentoxycarbonyl group, phenoxycarbonyl group and the like can be mentioned. Preferred oxycarbonyl groups are a methoxycarbonyl group and an ethoxycarbonyl group.
Each group represented by R ^d is preferably an aryl group, a substituted aryl group, an oxycarbonyl group, or a cyano group. Preferred aryl groups include a phenyl group, and preferred substituted aryl groups include a halogen atom-substituted phenyl group and a trifluoromethyl-substituted phenyl group. In addition, in the case of a halogen atom, these substituents are preferably substituted by 1-5. In the case of an alkoxy group or a trifluoromethyl group, one or two substituents are preferably substituted, and in the case of one substitution, the para position or the ortho position is preferable, and in the case of two substitutions, the meta position is preferable. A preferred oxycarbonyl group is a methoxycarbonyl group or an ethoxycarbonyl group.

As preferred organic tellurium compounds represented by the formula (1), R ^a represents an alkyl group having 1 to 4 carbon atoms, R ^b and R ^c represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ^d Is preferably an aryl group, a substituted aryl group or an oxycarbonyl group. Particularly preferably, R ^a represents an alkyl group having 1 to 4 carbon atoms, R ^b and R ^c represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ^d represents a phenyl group, a substituted phenyl group, a methoxycarbonyl group. , An ethoxycarbonyl group.
The organic tellurium compound represented by the formula (1) is specifically as follows.
Examples of the organic tellurium compound include (methylterranyl-methyl) benzene, (1-methylterranyl-ethyl) benzene, (2-methylterranyl-propyl) benzene, 1-chloro-4- (methylterranyl-methyl) benzene, 1-hydroxy-4- (Methylterranyl-methyl) benzene, 1-methoxy-4- (methylterranyl-methyl) benzene, 1-amino-4- (methylterranyl-methyl) benzene, 1-nitro-4- (methylterranyl-methyl) benzene, 1-cyano- 4- (methylterranyl-methyl) benzene, 1-methylcarbonyl-4- (methylterranyl-methyl) benzene, 1-phenylcarbonyl-4- (methylterranyl-methyl) benzene, 1-methoxycarbonyl-4- (methylterranyl-methyl) benzene 1-phenoxyca Bonyl-4- (methylterranyl-methyl) benzene, 1-sulfonyl-4- (methylterranyl-methyl) benzene, 1-trifluoromethyl-4- (methylterranyl-methyl) benzene, 1-chloro-4- (1-methylterranyl- Ethyl) benzene, 1-hydroxy-4- (1-methylterranyl-ethyl) benzene, 1-methoxy-4- (1-methylterranyl-ethyl) benzene, 1-amino-4- (1-methylterranyl-ethyl) benzene, 1 -Nitro-4- (1-methylterranyl-ethyl) benzene, 1-cyano-4- (1-methylterranyl-ethyl) benzene, 1-methylcarbonyl-4- (1-methylterranyl-ethyl) benzene, 1-phenylcarbonyl- 4- (1-methylteranyl-ethyl) benzene, 1-methoxycarbonyl- -(1-methylterranyl-ethyl) benzene, 1-phenoxycarbonyl-4- (1-methylterranyl-ethyl) benzene, 1-sulfonyl-4- (1-methylterranyl-ethyl) benzene, 1-trifluoromethyl-4- ( 1-methylterranyl-ethyl) benzene, 1- (1-methylterranyl-ethyl) -3,5-bis-trifluoromethylbenzene, 1,2,3,4,5-pentafluoro-6- (1-methylterranyl-ethyl) ) Benzene, 1-chloro-4- (2-methylterranyl-propyl) benzene, 1-hydroxy-4- (2-methylterranyl-propyl) benzene, 1-methoxy-4- (2-methylterranyl-propyl) benzene, 1- Amino-4- (2-methylterranyl-propyl) benzene, 1-nitro-4- (2-methylterra) Nyl-propyl) benzene, 1-cyano-4- (2-methylterranyl-propyl) benzene, 1-methylcarbonyl-4- (2-methylterranyl-propyl) benzene, 1-phenylcarbonyl-4- (2-methylterranyl-propyl) ) Benzene, 1-methoxycarbonyl-4- (2-methylterranyl-propyl) benzene, 1-phenoxycarbonyl-4- (2-methylterranyl-propyl) benzene, 1-sulfonyl-4- (2-methylterranyl-propyl) benzene, 1-trifluoromethyl-4- (2-methylterranyl-propyl) benzene, 2- (methylterranyl-methyl) pyridine, 2- (1-methylterranyl-ethyl) pyridine, 2- (2-methylterranyl-propyl) pyridine, 2- Methyl-2-methylterranyl-propana 3-methyl-3-methylteranyl-2-butanone, 2-methylterranyl-methyl ethanoate, methyl 2-methylterranyl-propionate, methyl 2-methylterranyl-2-methylpropionate, 2-methylterranyl-ethyl ethanoate, 2 -Ethyl methylteranyl-propionate, ethyl 2-methylterranyl-2-methylpropionate, ethyl 2- (n-butylterranyl) -2-methylpropionate, 2-methylterranylacetonitrile, 2-methylterranylpropiononitrile, 2 -Methyl-2-methylterranylpropionitrile, (phenylterranyl-methyl) benzene, (1-phenylterranyl-ethyl) benzene, (2-phenylterranyl-propyl) benzene and the like can be mentioned. Further, in the above, all compounds in which methyl teranyl, 1-methyl terranyl and 2-methyl terranyl are changed to ethyl teranyl, 1-ethyl teranyl, 2-ethyl terranyl, butyl terranyl, 1-butyl terranyl and 2-butyl terranyl, respectively, are included.

  Preferably, (methylterranyl-methyl) benzene, (1-methylterranyl-ethyl) benzene, (2-methylterranyl-propyl) benzene, 1-chloro-4- (1-methylterranyl-ethyl) benzene, 1-trifluoromethyl-4 -(1-methylterranyl-ethyl) benzene, methyl 2-methylterranyl-2-methylpropionate, ethyl 2-methylterranyl-2-methylpropionate, ethyl 2- (n-butylterranyl) -2-methylpropionate, 1- ( 1-methylterranyl-ethyl) -3,5-bis-trifluoromethylbenzene, 1,2,3,4,5-pentafluoro-6- (1-methylterranyl-ethyl) benzene, 2-methylterranylpropionitrile 2-methyl-2-methylterranylpropionitrile, (ethyltera (Ru-methyl) benzene, (1-ethylteranyl-ethyl) benzene, (2-ethylteranyl-propyl) benzene, methyl 2-ethylteranyl-2-methylpropionate, ethyl 2-ethylteranyl-2-methylpropionate, 2-ethyltera Nylpropionitrile, 2-methyl-2-ethylterranylpropionitrile, (n-butylterranyl-methyl) benzene, (1-n-butylterranyl-ethyl) benzene, (2-n-butylterranyl-propyl) benzene, 2 -Methyl n-butyl teranyl-2-methylpropionate, ethyl 2-n-butyl teranyl-2-methyl propionate, 2-n-butyl terranyl propionitrile, 2-methyl-2-n-butyl terranyl propiononitrile Is mentioned.

式（１ａ）および（１ｂ）において、Ｒ^a、Ｒ^b、Ｒ^cおよびＲ^dは、式（１）のそれと同じであり、Ｚはハロゲン原子を表し、Ｍは、アルカリ金属、アルカリ土類金属または銅原子を表す。Ｍがアルカリ金属のとき、ｍは１、Ｍがアルカリ土類金属の時、ｍは２、Ｍが銅原子の時、ｍは１または２を表す。 The living radical polymerization initiator represented by the formula (1) can be produced by reacting the compound of the formula (1a), the compound of the formula (1b) and metal tellurium.

In the formulas (1a) and (1b), R ^a , R ^b , R ^c and R ^d are the same as those in the formula (1), Z represents a halogen atom, M represents an alkali metal or alkaline earth metal Or represents a copper atom. When M is an alkali metal, m is 1, when M is an alkaline earth metal, m is 2, and when M is a copper atom, m is 1 or 2.

In the above formula (1a), examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Preferably, it is a chlorine atom or a bromine atom.
Specific examples of the compound of formula (1a) are given below.
Benzyl chloride, benzyl bromide, 1-chloro-1-phenylethane, 1-bromo-1-phenylethane, 2-chloro-2-phenylpropane, 2-bromo-2-phenylpropane, p-chlorobenzyl chloride, p- Hydroxybenzyl chloride, p-methoxybenzyl chloride, p-aminobenzyl chloride, p-nitrobenzyl chloride, p-cyanobenzyl chloride, p-methylcarbonylbenzyl chloride, phenylcarbonylbenzyl chloride, p-methoxycarbonylbenzyl chloride, p-phenoxy Carbonyl benzyl chloride, p-sulfonyl benzyl chloride, p-trifluoromethyl benzyl chloride, 1-chloro-1- (p-chlorophenyl) ethane, 1-bromo-1- (p-chloro Phenyl) ethane, 1-chloro-1- (p-hydroxyphenyl) ethane, 1-bromo-1- (p-hydroxyphenyl) ethane, 1-chloro-1- (p-methoxyphenyl) ethane, 1-bromo- 1- (p-methoxyphenyl) ethane, 1-chloro-1- (p-aminophenyl) ethane, 1-bromo-1- (p-aminophenyl) ethane, 1-chloro-1- (p-nitrophenyl) Ethane, 1-bromo-1- (p-nitrophenyl) ethane, 1-chloro-1- (p-cyanophenyl) ethane, 1-bromo-1- (p-cyanophenyl) ethane, 1-chloro-1- (P-methylcarbonylphenyl) ethane, 1-bromo-1- (p-methylcarbonylphenyl) ethane, 1-chloro-1- (p-phenylcarbonylphenyl) ethane, 1-bromo-1- (p -Phenylcarbonylphenyl) ethane, 1-chloro-1- (p-methoxycarbonylphenyl) ethane, 1-bromo-1- (p-methoxycarbonylphenyl) ethane, 1-chloro-1- (p-phenoxycarbonylphenyl) Ethane, 1-bromo-1- (p-phenoxycarbonylphenyl) ethane, 1-chloro-1- (p-sulfonylphenyl) ethane, 1-bromo-1- (p-sulfonylphenyl) ethane, 1-chloro-1 -(P-trifluoromethylphenyl) ethane, 1-bromo-1- (p-trifluoromethylphenyl) ethane, 2-chloro-2- (p-chlorophenyl) propane, 2-bromo-2- (p-chlorophenyl) ) Propane, 2-chloro-2- (p-hydroxyphenyl) propane, 2-bromo-2- (p-hydroxyphenyl) Nyl) propane, 2-chloro-2- (p-methoxyphenyl) propane, 2-bromo-2- (p-methoxyphenyl) propane, 2-chloro-2- (p-aminophenyl) propane, 2-bromo- 2- (p-aminophenyl) propane, 2-chloro-2- (p-nitrophenyl) propane, 2-bromo-2- (p-nitrophenyl) propane, 2-chloro-2- (p-cyanophenyl) Propane, 2-bromo-2- (p-cyanophenyl) propane, 2-chloro-2- (p-methylcarbonylphenyl) propane, 2-bromo-2- (p-methylcarbonylphenyl) propane, 2-chloro- 2- (p-phenylcarbonylphenyl) propane, 2-bromo-2- (p-phenylcarbonylphenyl) propane, 2-chloro-2- (p-methoxycarbonyl) Ruphenyl) propane, 2-bromo-2- (p-methoxycarbonylphenyl) propane, 2-chloro-2- (p-phenoxycarbonylphenyl) propane, 2-bromo-2- (p-phenoxycarbonylphenyl) propane, 2 -Chloro-2- (p-sulfonylphenyl) propane, 2-bromo-2- (p-sulfonylphenyl) propane, 2-chloro-2- (p-trifluoromethylphenyl) propane, 2-bromo-2- ( p-trifluoromethylphenyl) propane, 2- (chloromethyl) pyridine, 2- (bromomethyl) pyridine, 2- (1-chloroethyl) pyridine, 2- (1-bromoethyl) pyridine, 2- (2-chloropropyl) Pyridine, 2- (2-bromopropyl) pyridine, methyl 2-chloroethanoate, 2-bromoethanoic acid Chill, methyl 2-chloropropionate, methyl 2-bromoethanoate, methyl 2-chloro-2-methylpropionate, methyl 2-bromo-2-methylpropionate, ethyl 2-chloroethanoate, ethyl 2-bromoethanoate, 2 -Ethyl chloropropionate, ethyl 2-bromoethanoate, ethyl 2-chloro-2-ethylpropionate, ethyl 2-bromo-2-ethylpropionate, 2-chloroacetonitrile, 2-bromoacetonitrile, 2-chloropropionitrile 2-bromopropionitrile, 2-chloro-2-methylpropionitrile, 2-bromo-2-methylpropionitrile, (1-bromoethyl) benzene, ethyl-2-bromo-isobutyrate, 1- (1- Bromoethyl) -4-chlorobenzene, 1- (1-bromoethyl) -4-to Fluoromethylbenzene, 1- (1-bromoethyl) -3,5-bis-trifluoromethylbenzene, 1,2,3,4,5-pentafluoro-6- (1-bromoethyl) benzene, 1- (1- Bromoethyl) -4-methoxybenzene, ethyl-2-bromo-isobutyrate and the like.

In the above formula (1b), the preferred metal represented by M is lithium. When M is magnesium, the compound (1b) may be Mg (R ^a ) ₂ or ^a compound represented by R ^a MgZ (Z is a halogen atom) (Grignard reagent). Z is preferably a chlorine atom or a bromine atom.
Specific examples of the compound represented by the formula (1b) are as follows.
Examples include methyl lithium, ethyl lithium, n-butyl lithium, phenyl lithium, and p-methoxyphenyl lithium. Preferably, methyl lithium, ethyl lithium, n-butyl lithium, and phenyl lithium are preferable.

The production method of the above formula (1) is specifically as follows.
Metal tellurium is suspended in a solvent. Examples of the solvent that can be used include polar solvents such as dimethylformamide (DMF) and tetrahydrofuran (THF), aromatic solvents such as toluene and xylene, aliphatic hydrocarbons such as hexane, ethers such as dialkyl ether, and the like. Preferably, THF is good. The amount of the solvent used may be adjusted as appropriate, but is usually 1 to 100 ml, preferably 5 to 20 ml with respect to 1 g of metal tellurium.
The compound (1b) is slowly added dropwise to the suspension, and then stirred. While the reaction time varies depending on the reaction temperature and pressure, it is generally 5 minutes to 24 hours, preferably 10 minutes to 2 hours. The reaction temperature is −20 ° C. to 80 ° C., preferably 0 ° C. to 40 ° C., more preferably room temperature. The pressure is usually normal pressure, but it may be increased or decreased.
Next, the compound (1a) is added to the reaction solution and stirred. While the reaction time varies depending on the reaction temperature and pressure, it is generally 5 minutes to 24 hours, preferably 10 minutes to 2 hours. The reaction temperature is −20 ° C. to 80 ° C., preferably 0 ° C. to 40 ° C., more preferably room temperature. The pressure is usually normal pressure, but it may be increased or decreased.
As a use ratio of the metal tellurium, the compound (1a) and the compound (1b), the compound (1a) is 0.5 to 1.5 mol and the compound (1b) is 0.5 to 1.5 mol with respect to 1 mol of the metal tellurium. Preferably, the compound (1a) is 0.8 to 1.2 mol and the compound (1b) is 0.8 to 1.2 mol.
After completion of the reaction, the solvent is concentrated and the target compound is isolated and purified. The purification method can be appropriately selected depending on the compound, but usually vacuum distillation, recrystallization purification and the like are preferable.

  Specifically, the organic tellurium compound represented by the formula (2) includes dimethylditelluride, diethylditelluride, di-n-propylditelluride, diisopropylditelluride, dicyclopropylditelluride, di- n-butylditelluride, di-sec-butylditelluride, di-tert-butylditelluride, dicyclobutylditelluride, diphenylditelluride, bis- (p-methoxyphenyl) ditelluride, bis- (p-aminophenyl) ditelluride, bis- (P-nitrophenyl) ditelluride, bis- (p-cyanophenyl) ditelluride, bis- (p-sulfonylphenyl) ditelluride, dinaphthylditelluride, dipyridylditelluride and the like can be mentioned.

Specific examples of the production method include a method of reacting metal tellurium with a compound represented by the formula (1b).
Metal tellurium is suspended in a solvent. Solvents that can be used include polar solvents such as dimethylformamide (DMF) and tetrahydrofuran (THF), aromatic solvents such as toluene and xylene, aliphatic hydrocarbons such as hexane, and ethers such as dialkyl ether. Can be mentioned. Preferably, THF is good. The amount of the organic solvent used may be adjusted as appropriate, but is usually 5 to 10 ml, preferably 7 to 8 ml with respect to 1 g of metal tellurium.
The compound represented by the formula (1b) is slowly added dropwise to the suspension solution, and then stirred. While the reaction time varies depending on the reaction temperature and pressure, it is generally 5 minutes to 24 hours, preferably 10 minutes to 2 hours. The reaction temperature is −20 ° C. to 80 ° C., preferably 0 ° C. to 40 ° C., more preferably room temperature. The pressure is usually normal pressure, but it may be increased or decreased.
Next, water (neutral water such as saline, alkaline water such as aqueous ammonium chloride, or acidic water such as hydrochloric acid) may be added to the reaction solution and stirred. While the reaction time varies depending on the reaction temperature and pressure, it is generally 5 minutes to 24 hours, preferably 10 minutes to 2 hours. The reaction temperature is −20 ° C. to 80 ° C., preferably 0 ° C. to 40 ° C., more preferably room temperature. The pressure is usually normal pressure, but it may be increased or decreased.
As the use ratio of the metal tellurium and the compound of the formula (1b), the compound of the formula (1b) is 0.5 to 1.5 mol, preferably 0.8 to 1.2 mol, with respect to 1 mol of the metal tellurium. Is good.
After completion of the reaction, the solvent is concentrated and the target compound is isolated and purified. The purification method can be appropriately selected depending on the compound, but usually vacuum distillation, reprecipitation purification and the like are preferable.

式（１１）において、Ｒ^fおよびＲ^gは同一または異なってもよい炭素数１〜１０のアルキル基、カルボキシ置換された炭素数１〜４のアルキル基、置換基を有していてもよいフェニル基を表し、同じ炭素原子に結合しているＲ^fとＲ^gとで脂肪族環を形成していてもよく、Ｒ^hはシアノ基、アセトキシ基、カルバモイル基、（炭素数１〜４のアルコキシ）カルボニル基を表す。 Although the radical polymerization initiator used by this invention will not be restrict | limited especially if it is a radical polymerization initiator used by normal radical polymerization, For example, the compound shown by Formula (11) can be illustrated.

In the formula (11), R ^f and R ^g may be the same or different, and the alkyl group having 1 to 10 carbon atoms, the carboxy-substituted alkyl group having 1 to 4 carbon atoms, and the optionally substituted phenyl represents a group, may form an aliphatic ring with R ^f and R ^g are attached to the same carbon atom, R ^h represents a cyano group, an acetoxy group, a carbamoyl group, (alkoxy of 1 to 4 carbon atoms ) Represents a carbonyl group.

In the azo compound of the formula (11) used in the present invention, examples of the alkyl group having 1 to 10 carbon atoms of R ^f and R ^g include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, A hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, etc. can be illustrated. Examples of the carboxy-substituted alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group. Examples of the aliphatic ring formed by R ^f and R ^g bonded to the same carbon atom include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. The phenyl group may be substituted with a substituent such as a hydroxyl group, a methyl group, an ethyl group, a methoxy group, an ethoxy group, a nitro group, an amino group, an acetyl group, or an acetylamino group. Examples of the R ^h (C 1-4 alkoxy) carbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an isopropoxycarbonyl group, and a butoxycarbonyl group.

  Specifically, the azo compound of the formula (11) includes 2,2′-azobis (isobutyronitrile) (AIBN), 2,2′-azobis (2-methylbutyronitrile) (AMBN), 2, 2′-azobis (2,4-dimethylvaleronitrile) (ADVN), 1,1′-azobis (1-cyclohexanecarbonitrile) (ACHN), dimethyl-2,2′-azobisisobutyrate (MAIB), 4,4′-azobis (4-cyanovaleric acid) (ACVA), 1,1′-azobis (1-acetoxy-1-phenylethane), 2,2′-azobis (2-methylbutyramide), 1, And 1'-azobis (methyl 1-cyclohexanecarboxylate).

上記式（３−１）中、ＲおよびＲ¹は、それぞれ式（３）におけるＲおよびＲ¹と同一である。 As a monomer which produces the repeating unit represented by Formula (3), (meth) acrylic acid ester represented by Formula (3-1) is mentioned.

In the formula (3-1), R and R ¹ are the same as R and R ¹ in the formula (3), respectively.

R ¹ is a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof, or at least one is an alicyclic hydrocarbon group or a derivative thereof, or any two R ¹ are mutually Examples of the divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof bonded to the carbon atom to which each is bonded include bicyclo [2.2.1] heptane, tricyclo [5.2. .1.0 ^2,6] decane, tetracyclo [6.2.1 ^3,6. 0 ^2,7 ] a group consisting of an alicyclic ring derived from cycloalkanes such as dodecane, adamantane, cyclopentane, cyclohexane, etc .; a group consisting of these alicyclic rings is, for example, methyl group, ethyl group, n-propyl A linear, branched or cyclic alkyl group having 1 to 4 carbon atoms such as a group, i-propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group, etc. The above or a group substituted with one or more may be mentioned.

Examples of the derivative of the monovalent or divalent alicyclic hydrocarbon group of R ¹ include, for example, a hydroxyl group; a carboxyl group; an oxo group (that is, ═O group); a hydroxymethyl group, a 1-hydroxyethyl group, C1-C4 hydroxy such as 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group, etc. Alkyl group; alkoxy group having 1 to 4 carbon atoms such as methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, 2-methylpropoxy group, 1-methylpropoxy group, t-butoxy group Cyano group; C 2-5 cyano such as cyanomethyl group, 2-cyanomethyl group, 3-cyanopropyl group, 4-cyanobutyl group, etc. A group having a substituent such as alkyl group one or more or one or more.
Of these substituents, a hydroxyl group, a carboxyl group, a hydroxymethyl group, a cyano group, a cyanomethyl group, and the like are preferable.

Examples of the linear or branched alkyl group having 1 to 4 carbon atoms of R ¹ include, for example, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, and 2-methylpropyl. Group, 1-methylpropyl group, t-butyl group and the like.
Of these alkyl groups, a methyl group, an ethyl group, an n-propyl group, and an i-propyl group are preferable.
Preferred examples of the functional group side chain forming -C (R ¹ ) ₃ in formula (3) and formula (3-1) include:
1-methyl-1-cyclopentyl group, 1-ethyl-1-cyclopentyl group, 1-methyl-1-cyclohexyl group, 1-ethyl-1-cyclohexyl group, 2-methyladamantan-2-yl group, 2-methyl- 3-hydroxyadamantan-2-yl group, 2-ethyltyladamantan-2-yl group, 2-ethyl-3-hydroxyadamantan-2-yl group, 2-n-propyladamantan-2-yl group, 2-n -Propyl-3-hydroxyadamantan-2-yl group, 2-isopropyladamantan-2-yl group, 2-isopropyl-3-hydroxyadamantan-2-yl group, 2-methylbicyclo [2.2.1] hept- 2-yl group, 2-ethylbicyclo [2.2.1] hept-2-yl group, 8-methyltricyclo [5.2.1.0 ^{2, 6]} deca 8-yl group, 8-ethyl-tricyclo [5.2.1.0 ^{2, 6]} dec-8-yl group, 4-methyl - tetracyclo [6.2.1.1 ^{3, 6.} 0 ^2,7 ] dodec-4-yl group, 4-ethyl-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-yl group, 1- (bicyclo [2.2.1] hept-2-yl) -1-methylethyl group, 1- (tricyclo [5.2.1.0 ^{2, 6} ] dec-8-yl) -1-methylethyl group, 1- (tetracyclo [6.2.1.1 ^3,6 .0 ^2,7 ] dec-4-yl) -1-methylethyl group, 1 -(Adamantan-1-yl) -1-methylethyl group, 1- (3-hydroxyadamantan-1-yl) -1-methylethyl group, 1,1-dicyclohexylethyl group, 1,1-di (bicyclo [ 2.2.1] Hept-2-yl) ethyl group, 1,1-di (tricyclo [5.2.1.0 ^2,6 ] dec-8-yl) ethyl group, 1,1-di (tetracyclo) [6.2.1.1 ^3,6 .0 ^2,7] dodeca-4-yl) ethyl group, 1,1-di (adamantan-1-yl) ethyl group, And the like.

Moreover, a suitable example is given to the monomer which gives the repeating unit represented by Formula (3-1) below.
(Meth) acrylic acid 1-methyl-1-cyclopentyl ester, (meth) acrylic acid 1-ethyl-1-cyclopentyl ester, (meth) acrylic acid 1-methyl-1-cyclohexyl ester, (meth) acrylic acid 1-ethyl -1-cyclohexyl ester, (meth) acrylic acid 2-methyladamantan-2-yl ester, (meth) acrylic acid 2-methyl 3-hydroxyadamantan-2-yl ester, (meth) acrylic acid 2-ethyladamantane-2 -Yl ester, (meth) acrylic acid 2-ethyl 3-hydroxyadamantan-2-yl ester, (meth) acrylic acid 2-n-propyl-adamantan-2-yl ester, (meth) acrylic acid 2-n-propyl 3-hydroxyadamantan-2-yl ester, (meth) acrylic acid -Isopropyladamantan-2-yl ester, (meth) acrylic acid 2-isopropyl 3-hydroxyadamantan-2-yl ester, (meth) acrylic acid 2-methyladamantan-2-yl ester, (meth) acrylic acid 2-methyl Bicyclo [2.2.1] hept-2-yl ester, (meth) acrylic acid 2-ethylbicyclo [2.2.1] hept-2-yl ester, (meth) acrylic acid 8-methyltricyclo [5] .2.1.0 ^2,6 ] dec-8-yl ester, (meth) acrylic acid 8-ethyltricyclo [5.2.1.0 ^2,6 ] dec-8-yl ester, (meth) acrylic Acid 4-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-yl ester, (meth) acrylic acid 4-ethyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-yl ester, (meth) acrylic acid 1- (bicyclo [2.2.1] hept-2-yl) -1-methyl ester, (meth) acrylic acid 1- (tricyclo [ 5.2.1.0 ^2,6 ] dec-8-yl) -1-methyl ester, (meth) acrylic acid 1- (tetracyclo [6.2.1.1 ^3,6 .0 ^2,7 ] dodeca -4-yl) -1-methylethyl ester, (meth) acrylic acid 1- (adamantan-1-yl) -1-methylethyl ester, (meth) acrylic acid 1- (3-hydroxyadamantan-1-yl) -1-methyl ethyl ester, (meth) acrylic acid 1,1-dicyclohexyl ethyl ester, (meth) acrylic acid 1,1-di (bicyclo [2.2.1] hept-2-yl) ethyl ester, (meth Acrylic acid 1,1-di (t Cyclo [5.2.1.0 ^{2, 6]} dec-8-yl) ethyl ester, (meth) acrylic acid 1,1-di (tetracyclo [6.2.1.1 ^3,6 .0 ^2,7 Dodec-4-yl) ethyl ester, (meth) acrylic acid 1,1-di (adamantan-1-yl) ethyl ester.

  Among the monomers giving the repeating unit represented by the above formula (3-1), particularly preferable monomers include (meth) acrylic acid 1-methyl-1-cyclopentyl ester, (meth) acrylic acid. 1-ethyl-1-cyclopentyl ester, (meth) acrylic acid 1-methyl-1-cyclohexyl ester, (meth) acrylic acid 1-ethyl-1-cyclohexyl ester, (meth) acrylic acid 2-methyladamantan-2-yl Ester, (Meth) acrylic acid 2-ethyladamantan-2-yl ester, (Meth) acrylic acid 2-n-Proviradamantan-2-yl ester, (Meth) acrylic acid 2-Isoprovir adamantane-2-yl ester (Meth) acrylic acid 1- (adamantan-1-yl) -1-methylethyl ester. These can be used alone or in combination.

上記式（４）〜（１０）において、Ｒは式（３）におけるＲと同一である。
式（４）において、Ａは単結合もしくは炭素数１〜６の置換基を有していてもよい直鎖状もしくは分岐状のアルキレン基、モノまたはジアルキレングリコール基、アルキレンエステル基を表し、Ｂは単結合もしくは炭素数１〜３の置換基を有していてもよいアルキレン基、アルキルオキシ基、酸素原子を表す。
式（５）において、Ｅは単結合もしくは炭素数１〜３の２価のアルキル基を表し、Ｒ²は相互に独立に水酸基、シアノ基、カルボキシル基、−ＣＯＯＲ⁴、または−Ｙ−Ｒ⁵を表し、Ｒ⁴は水素原子あるいは炭素数１〜４の直鎖状もしくは分岐状のアルキル基、または炭素数３〜２０の脂環式のアルキル基、Ｙは相互に独立に単結合もしくは炭素数１〜３の２価のアルキレン基を表し、Ｒ⁵は相互に独立に水素原子、水酸基、シアノ基、または−ＣＯＯＲ⁶基を表す。ただし、少なくとも１つのＲ²が水素原子ではない。ＥおよびＹとしては、単結合、メチレン基、エチレン基、プロピレン基が挙げられる。
また、−ＣＯＯＲ⁶基におけるＲ⁶としては、水素原子あるいは炭素数１〜４の直鎖状もしくは分岐状のアルキル基、または炭素数３〜２０の脂環式のアルキル基を表す。炭素数１〜４の直鎖状もしくは分岐状のアルキル基としては、メチル基、エチル基、ｎ−プロピル基、ｉ−プロピル基、ｎ−ブチル基、２−メチルプロピル基、１−メチルプロピル基、ｔ−ブチル基を例示できる。炭素数３〜２０の脂環式のアルキル基としては、−Ｃ_nＨ_2n-1（ｎは３〜２０の整数）で表されるシクロアルキル基、例えば、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロオクチル基等が、また、多環型脂環式アルキル基、例えばビシクロ［２．２．１］ヘプチル基、トリシクロ［５．２．１．０^2,6］デシル基、テトラシクロ［６．２．１^3,6．０^2,7］ドデカニル基、アダマンチル基等、または、直鎖状、分岐状または環状のアルキル基の１種以上あるいは１個以上でシクロアルキル基または多環型脂環式アルキル基の一部を置換した基等が挙げられる。
式（６）において、Ｇは単結合、炭素数１〜６の直鎖状もしくは分岐状のアルキレン基または炭素数４〜２０の脂環式炭化水素基、アルキレングリコール基、アルキレンエステル基を表す。炭素数１〜６の直鎖状もしくは分岐状のアルキレン基としては、メチレン基、エチレン基、プロピレン基、ブチレン基、ペンチレン基、ヘキシレン基、シクロヘキシレン基等が挙げられる。
式（７）において、Ｊは単結合、炭素数１〜２０の置換基を有していてもよい直鎖状、分岐状、環状のアルキレン基、アルキレングリコール基、アルキレンエステル基を表す。
式（８）において、Ｌは単結合、炭素数１〜２０の置換基を有していてもよい直鎖状、分岐状、環状のアルキレン基、アルキレングリコール基、アルキレンエステル基を表し、Ｒ³は水素原子、炭素数１〜４の直鎖状もしくは分岐状のアルキル基、アルコキシ基、ヒドロキシアルキル基、炭素数３〜２０の２価の脂環式炭化水素基もしくはその誘導体を形成したものを表す。ｑは１または２である。
式（９）において、Ｎ、Ｍ’はそれぞれ独立して単結合、炭素数１〜２０の置換基を有していてもよい直鎖状、分岐状、環状のアルキレン基、アルキレングリコール基、アルキレンエステル基を表す。直鎖状もしくは分岐状のアルキレン基としては、メチレン基、エチレン基、プロピレン基、ブチレン基、ペンチレン基、ヘキシレン基、シクロヘキシレン基等が挙げられる。ｐは０または１である。
式（１０）において、Ｘは炭素数７〜２０の極性基を含まない炭素および水素のみからなる多環型脂環式炭化水素基を表す。このような多環型脂環式炭化水素基としては、例えば、ビシクロ［２．２．１］ヘプタン、ビシクロ［２．２．２］オクタン、トリシクロ［５．２．１．０^2,6］デカン、テトラシクロ［４．４．０．１^2,6．１^7,10］ドデカン、テトラシクロ［６．２．１．１^3,6．０^2,7］デカン等のシクロアルカン類に由来する脂環族環からなる炭化水素基が挙げられる。また、これらの脂環族環は、置換基を有していてもよく、例えば、メチル基、エチル基、ｎ−プロピル基、ｉ−プロピル基、ｎ−ブチル基、２−メチルプロピル基、１−メチルプロピル基、ｔ−ブチル基等の炭素数１〜４の直鎖状、分岐状または環状のアルキル基の１種以上あるいは１個以上で置換した骨格等が挙げられる。 The acid-dissociable group-containing resin according to the present invention is a repeating unit selected from at least one of repeating units represented by the following formulas (4) to (10) together with the repeating unit represented by the formula (3). Units can be included.

In the above formulas (4) to (10), R is the same as R in formula (3).
In the formula (4), A represents a single bond or a linear or branched alkylene group, mono- or dialkylene glycol group or alkylene ester group which may have a substituent having 1 to 6 carbon atoms, and B Represents a single bond or an alkylene group, alkyloxy group or oxygen atom which may have a substituent having 1 to 3 carbon atoms.
In the formula (5), E represents a single bond or a divalent alkyl group having 1 to 3 carbon atoms, and R ² is independently a hydroxyl group, a cyano group, a carboxyl group, —COOR ⁴ , or —Y—R ^5. R ⁴ is a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or an alicyclic alkyl group having 3 to 20 carbon atoms, Y is independently a single bond or a carbon number 1 to 3 divalent alkylene groups, and R ⁵ each independently represents a hydrogen atom, a hydroxyl group, a cyano group, or a —COOR ⁶ group. However, at least one R ² is not a hydrogen atom. Examples of E and Y include a single bond, a methylene group, an ethylene group, and a propylene group.
R ⁶ in the —COOR ⁶ group represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or an alicyclic alkyl group having 3 to 20 carbon atoms. Examples of the linear or branched alkyl group having 1 to 4 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, 2-methylpropyl group, and 1-methylpropyl group. , T-butyl group can be exemplified. As an alicyclic alkyl group having 3 to 20 carbon atoms, a cycloalkyl group represented by —C _n H _2n-1 (n is an integer of 3 to 20), for example, a cyclopropyl group, a cyclobutyl group, and a cyclopentyl group. , A cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and the like, and a polycyclic alicyclic alkyl group such as a bicyclo [2.2.1] heptyl group, a tricyclo [5.2.1.0 ^2,6 ]. Decyl group, tetracyclo [6.2.1 ^3,6 . 0 ^2,7 ] a dodecanyl group, an adamantyl group or the like, or one or more linear, branched or cyclic alkyl groups and a part of a cycloalkyl group or a polycyclic alicyclic alkyl group. Examples include substituted groups.
In Formula (6), G represents a single bond, a linear or branched alkylene group having 1 to 6 carbon atoms, an alicyclic hydrocarbon group having 4 to 20 carbon atoms, an alkylene glycol group, or an alkylene ester group. Examples of the linear or branched alkylene group having 1 to 6 carbon atoms include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, and a cyclohexylene group.
In the formula (7), J represents a single bond, a linear, branched or cyclic alkylene group, alkylene glycol group or alkylene ester group which may have a substituent having 1 to 20 carbon atoms.
In the formula (8), L represents a single bond, a linear, branched or cyclic alkylene group, alkylene glycol group or alkylene ester group which may have a substituent having 1 to 20 carbon atoms, and R ³ Is a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, an alkoxy group, a hydroxyalkyl group, a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, or a derivative thereof. Represent. q is 1 or 2.
In the formula (9), N and M ′ are each independently a single bond, a linear, branched or cyclic alkylene group, alkylene glycol group, alkylene which may have a substituent having 1 to 20 carbon atoms. Represents an ester group. Examples of the linear or branched alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, and a cyclohexylene group. p is 0 or 1;
In the formula (10), X represents a polycyclic alicyclic hydrocarbon group consisting only of carbon and hydrogen not containing a polar group having 7 to 20 carbon atoms. Examples of such polycyclic alicyclic hydrocarbon groups include bicyclo [2.2.1] heptane, bicyclo [2.2.2] octane, and tricyclo [5.2.1.0 ^2,6 ]. Decane, tetracyclo [4.4.0.1 ^2,6 . 1 ^7,10 ] dodecane, tetracyclo [6.2.1.1 ^3,6 . Hydrocarbon groups consisting of alicyclic rings derived from cycloalkanes such as 0 ^2,7 ] decane. Moreover, these alicyclic rings may have a substituent, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, 2-methylpropyl group, 1 -A skeleton substituted with one or more of linear, branched or cyclic alkyl groups having 1 to 4 carbon atoms such as methylpropyl group and t-butyl group.

式（４−１）におけるＲは水素原子あるいはメチル基を表し、ＡおよびＢは、式（４）におけるＡおよびＢと同一である。なお、Ａにおける炭素数１〜６の直鎖状もしくは分岐状のアルキレン基としては、メチレン基、エチレン基、プロピレン基、ブチレン基、ペンチレン基、へキシレン基、シクロヘキシレン基を例示できる。 As a monomer which produces the repeating unit represented by Formula (4), the compound represented by Formula (4-1) is mentioned.

R in the formula (4-1) represents a hydrogen atom or a methyl group, and A and B are the same as A and B in the formula (4). Examples of the linear or branched alkylene group having 1 to 6 carbon atoms in A include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, and a cyclohexylene group.

ここでＲは水素原子、メチル基、トリフルオロメチル基、ヒドロキシメチル基のいずれかであり、またノルボルナンの橋頭にあたる７位が、上記メチレン基に代わり酸素原子になったものも好ましい単量体として挙げられる。 Preferred monomers among the monomers represented by formula (4-1) include monomers represented by the following formulas (4-1-1) to (4-1-7). .

Here, R is any one of a hydrogen atom, a methyl group, a trifluoromethyl group, and a hydroxymethyl group, and a monomer in which the 7-position corresponding to the bridgehead of norbornane is an oxygen atom instead of the methylene group is also preferred. Can be mentioned.

式（５−１）において、Ｒは水素原子あるいはメチル基を表し、ＥおよびＲ²は式（５）におけるＥおよびＲ²と同一である。 As a monomer which produces the repeating unit represented by Formula (5), the compound represented by Formula (5-1) is mentioned.

In the formula (5-1), R represents a hydrogen atom or a methyl group, E and R ² is identical to E and R ² in Formula (5).

Preferred monomers among the monomers represented by formula (5-1) are listed below.
(Meth) acrylic acid 3-hydroxyadamantane ester, (meth) acrylic acid 3-hydroxyadamantan-1-ylmethyl ester, (meth) acrylic acid 3,5-dihydroxyadamantan-1-ylmethyl ester, (meth) acrylic acid 3-hydroxy-5-cyanoadamantan-1-ylmethyl ester, (meth) acrylic acid 3-hydroxy-5-carboxyladamantan-1-ylmethyl ester, (meth) acrylic acid 3-hydroxy-5-methoxycarbonyladamantane- 1-ylmethyl ester, (meth) acrylic acid 3-hydroxymethyladamantan-1-ylmethyl ester, (meth) acrylic acid 3, 5-dihydroxymethyladamantan-1-ylmethyl ester, (meth) acrylic acid 3-hydroxy -5-hydro Cymethyladamantan-1-ylmethyl ester, (meth) acrylic acid 3-cyano-5-hydroxymethyladamantan-1-ylmethyl ester, (meth) acrylic acid 3-hydroxymethyl-5-carboxyladamantan-1-ylmethyl Ester, (meth) acrylic acid 3-hydroxymethyl-5-methoxycarbonyladamantan-1-ylmethyl ester, (meth) acrylic acid 3-cyanoadamantan-1-ylmethyl ester, (meth) acrylic acid 3,5-dicyano Adamantane-1-ylmethyl ester, (meth) acrylic acid 3-cyano-5-carboxyladamantan-1-ylmethyl ester, (meth) acrylic acid 3-cyano-5-methoxycarbonyladamantan-1-ylmethyl ester, ( (Meth) acrylic acid 3-ca Boxyladamantan-1-ylmethyl ester, (meth) acrylic acid 3,5-dicarboxyladamantan-1-ylmethyl ester, (meth) acrylic acid 3-carboxyl-5-methoxycarbonyladamantan-1-ylmethyl ester, ( (Meth) acrylic acid 3-methoxycarbonyladamantan-1-ylmethyl ester, (meth) acrylic acid 3,5-dimethoxycarbonyladamantan-1-ylmethyl ester,

  (Meth) acrylic acid 3-hydroxy-5-methyladamantan-1-yl ester, (meth) acrylic acid 3,5-dihydroxy-7-methyladamantan-1-yl ester, (meth) acrylic acid 3-hydroxy-5 -Cyano-7-methyladamantan-1-yl ester, (meth) acrylic acid 3-hydroxy-5-carboxyl-7-methyladamantan-1-yl ester, (meth) acrylic acid 3-hydroxy-5-methoxycarbonyl- 7-methyladamantan-1-yl ester, (meth) acrylic acid 3-hydroxymethyl-5-methyladamantan-1-yl ester, (meth) acrylic acid 3,5-dihydroxymethyl-7-methyladamantan-1-yl Ester, (meth) acrylic acid 3-hydroxy-5-hydroxymethyl- -Methyladamantan-1-yl ester, (meth) acrylic acid 3-cyano-5-hydroxymethyl-7-methyladamantan-1-yl ester, (meth) acrylic acid 3-hydroxymethyl-5-carboxyl-7-methyl Adamantan-1-yl ester, (meth) acrylic acid 3-hydroxymethyl-5-methoxycarbonyl-7-methyladamantan-1-yl ester, (meth) acrylic acid 3-cyano-5-methyladamantan-1-yl ester (Meth) acrylic acid 3,5-dicyano-7-methyladamantan-1-yl ester, (meth) acrylic acid 3-cyano-5-carboxyl-7-methyladamantan-1-yl ester, (meth) acrylic acid 3-cyano-5-methoxycarbonyl-7-methyladamantan-1-y Ester, (meth) acrylic acid 3-carboxyl-5-methyladamantan-1-yl ester, (meth) acrylic acid 3,5-dicarboxyl-7-methyladamantan-1-yl ester, (meth) acrylic acid 3- Carboxyl-5-methoxycarbonyl-7-methyladamantan-1-yl ester, (meth) acrylic acid 3-methoxycarbonyl-5-methyladamantan-1-yl ester, (meth) acrylic acid 3, 5-dimethoxycarbonyl-7 -Methyladamantan-1-yl ester,

  (Meth) acrylic acid 3-hydroxy-5-methyladamantan-1-ylmethyl ester, (meth) acrylic acid 3,5-dihydroxy-7-methyladamantan-1-ylmethyl ester, (meth) acrylic acid 3-hydroxy -5-cyano-7-methyladamantan-1-ylmethyl ester, (meth) acrylic acid 3-hydroxy-5-carboxyl-7-methyladamantan-1-ylmethyl ester, (meth) acrylic acid 3-hydroxy-5 -Methoxycarbonyl-7-methyladamantan-1-ylmethyl ester, (meth) acrylic acid 3-hydroxymethyl-5-methyladamantan-1-ylmethyl ester, (meth) acrylic acid 3,5-dihydroxymethyl-7- Methyl adamantane-1-ylmethyl ester, (meth) acrylic Acid 3-hydroxy-5-hydroxymethyl-7-methyladamantan-1-ylmethyl ester, (meth) acrylic acid 3-cyano-5-hydroxymethyl-7-methyladamantan-1-ylmethyl ester, (meth) acrylic Acid 3-hydroxymethyl-5-carboxyl-7-methyladamantan-1-ylmethyl ester, (meth) acrylic acid 3-hydroxymethyl-5-methoxycarbonyl-7-methyladamantan-1-ylmethyl ester, (meth) Acrylic acid 3-cyano-5-methyladamantan-1-ylmethyl ester, (meth) acrylic acid 3, 5-dicyano-7-methyladamantan-1-ylmethyl ester, (meth) acrylic acid 3-cyano-5- Carboxyl-7-methyladamantan-1-ylmethyl ester, (Meth) acrylic acid 3-cyano-5-methoxycarbonyl-7-methyladamantan-1-ylmethyl ester, (meth) acrylic acid 3-carboxyl-5-methyladamantan-1-ylmethyl ester, (meth) acrylic acid 3 5-dicarboxyl-7-methyladamantan-1-ylmethyl ester, (meth) acrylic acid 3-carboxyl-5-methoxycarbonyl-7-methyladamantan-1-ylmethyl ester, (meth) acrylic acid 3-methoxy Carbonyl-5-methyladamantan-1-ylmethyl ester, (meth) acrylic acid 3, 5-dimethoxycarbonyl-7-methyladamantan-1-ylmethyl ester,

(Meth) acrylic acid 3-hydroxy-5,7-dimethyladamantan-1-yl ester, (meth) acrylic acid 3-hydroxymethyl-5,7-dimethyladamantan-1-yl ester, (meth) acrylic acid 3- Cyano-5,7-dimethyladamantan-1-yl ester, (meth) acrylic acid 3-carboxyl-5,7-dimethyladamantan-1-yl ester, (meth) acrylic acid 3-methoxycarbonyl-5,7-dimethyl Adamantane-1-yl ester,
(Meth) acrylic acid 3-hydroxy-5,7-dimethyladamantan-1-ylmethyl ester, (meth) acrylic acid 3-hydroxymethyl-5,7-dimethyladamantan-1-ylmethyl ester, (meth) acrylic acid 3-cyano-5,7-dimethyladamantan-1-ylmethyl ester, (meth) acrylic acid 3-carboxyl-5, 7-dimethyladamantan-1-ylmethyl ester, (meth) acrylic acid 3-methoxycarbonyl-5 7-dimethyladamantan-1-ylmethyl ester, and the like.

  Among the monomers represented by the formula (5-1), particularly preferable monomers are (meth) acrylic acid 3-hydroxyadamantan-1-yl ester, (meth) acrylic acid 3-hydroxyadamantane. -1-ylmethyl ester, (meth) acrylic acid 3,5-dihydroxyadamantan-1-ylmethyl ester, (meth) acrylic acid 3-cyanoadamantan-1-ylmethyl ester, (meth) acrylic acid 3-carboxyladamantane -1-ylmethyl ester, (meth) acrylic acid 3-hydroxy-5-methyladamantan-1-yl ester, (meth) acrylic acid 3, 5-dihydroxy-7-methyladamantan-1-yl ester, (meth) Acrylic acid 3-hydroxy-5,7-dimethyladamantan-1-yl ester, (meth) acrylic 3-carboxyl-5,7-dimethyl-adamantan-1-yl ester, (meth) acrylic acid 3-hydroxy-5,7-dimethyl-adamantan-1-yl methyl ester, and the like.

式（６−１）において、Ｒは水素原子、メチル基、トリフルオロメチル基またはヒドロキシメチル基を表し、Ｇは式（６）におけるＧと同一である。
式（６−１）で表される単量体の中で、特に好適な単量体としては、下記式（６−１−１）〜式（６−１−８）で表される単量体が挙げられる。

上式において、Ｒは水素原子、メチル基、トリフルオロメチル基またはヒドロキシメチル基のいずれかであり、またノルボルナンの橋頭にあたる７位が、上記メチレン基に代わり酸素原子になったものも好ましい単量体として挙げられる。 As a monomer which produces the repeating unit represented by Formula (6), the compound represented by Formula (6-1) is mentioned.

In Formula (6-1), R represents a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group, and G is the same as G in Formula (6).
Among the monomers represented by the formula (6-1), particularly preferable monomers are single monomers represented by the following formulas (6-1-1) to (6-1-8). The body is mentioned.

In the above formula, R is any one of a hydrogen atom, a methyl group, a trifluoromethyl group, and a hydroxymethyl group, and a preferred monomer in which the 7-position corresponding to the bridgehead of norbornane is an oxygen atom instead of the methylene group is preferred. Named as body.

式（７−１）において、Ｒは水素原子あるいはメチル基を表し、Ｊは式（７）におけるＪと同一である。
式（７−１）で表される単量体の中で、特に好適な単量体としては、下記式（７−１−１）〜式（７−１−４）で表される単量体が挙げられる。

上式において、Ｒは水素原子、メチル基、トリフルオロメチル基またはヒドロキシメチル基のいずれかである。 As a monomer which produces the repeating unit represented by Formula (7), the compound represented by Formula (7-1) is mentioned.

In Formula (7-1), R represents a hydrogen atom or a methyl group, and J is the same as J in Formula (7).
Among the monomers represented by the formula (7-1), particularly preferred monomers are single monomers represented by the following formulas (7-1-1) to (7-1-4). The body is mentioned.

In the above formula, R is any one of a hydrogen atom, a methyl group, a trifluoromethyl group, and a hydroxymethyl group.

式（８−１）において、Ｒは水素原子、メチル基、トリフルオロメチル基またはヒドロキシメチル基を表し、ｑ、ＬおよびＲ³は式（８）におけるｑ、ＬおよびＲ³と同一である。
式（８−１）で表される単量体の中で、特に好適な単量体としては、下記式（８−１−１）〜式（８−１−１５）で表される単量体が挙げられる。

上式において、Ｒ³の好ましい具体例としては、水素原子、メチル基、エチル基、プロピル基、ブチル基、シクロヘキシル基、ノルボルニル基、アダマンチル基、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基、ヒドロキシメチル基、ヒドロキシエチル基等が挙げられる。 As a monomer which produces the repeating unit represented by Formula (8), the compound represented by Formula (8-1) is mentioned.

In the formula (8-1), R represents a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group, q, L and R ³ are the same as q, L and R ³ in formula (8).
Among the monomers represented by the formula (8-1), particularly preferable monomers are single monomers represented by the following formulas (8-1-1) to (8-1-15). The body is mentioned.

In the above formula, preferred specific examples of R ³ include hydrogen atom, methyl group, ethyl group, propyl group, butyl group, cyclohexyl group, norbornyl group, adamantyl group, methoxy group, ethoxy group, propoxy group, butoxy group, hydroxy A methyl group, a hydroxyethyl group, etc. are mentioned.

式（９−１）において、Ｒは水素原子、メチル基、トリフルオロメチル基またはヒドロキシメチル基を表し、Ｎ、Ｍ’およびｐは式（９）におけるＮ、Ｍ’およびｐと同一である。
式（９−１）で表される単量体の中で、特に好適な単量体としては、下記式（９−１−１）〜式（９−１−１２）で表される単量体が挙げられる。

As a monomer which produces the repeating unit represented by Formula (9), the compound represented by Formula (9-1) is mentioned.

In Formula (9-1), R represents a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group, and N, M ′, and p are the same as N, M ′, and p in Formula (9).
Among the monomers represented by the formula (9-1), particularly preferable monomers are single monomers represented by the following formulas (9-1-1) to (9-1-12). The body is mentioned.

式（１０−１）において、Ｒは水素原子、メチル基、トリフルオロメチル基またはヒドロキシメチル基を表し、Ｘは式（１０）におけるＸと同一である。
式（１０−１）で表される単量体の中で、特に好適な単量体としては、下記式（１０−１−１）〜式（１０−１−１２）で表される単量体が挙げられる。またこれらは単独でも、２種以上を混合して用いることができる。

As a monomer which produces the repeating unit represented by Formula (10), the compound represented by Formula (10-1) is mentioned.

In formula (10-1), R represents a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group, and X is the same as X in formula (10).
Among the monomers represented by the formula (10-1), particularly preferred monomers are single monomers represented by the following formulas (10-1-1) to (10-1-12). The body is mentioned. These may be used alone or in combination of two or more.

The acid-dissociable group-containing resin having Mw / Mn of less than 1.5 according to the present invention includes other repeating units in addition to the repeating units represented by the formulas (3) and (4) to (10). Can be included.
Examples of the monomer that gives other repeating units include (meth) acrylic acid hydroxymethyl ester, 1- (meth) acrylic acid-2-hydroxymethyl ester, (meth) acrylic acid, (meth) acrylic acid-5 ( 6) -Hydroxybicyclo [2.2.1] hept-2-yl ester, (meth) acrylic acid-9 (10) -hydroxytetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-yl, (meth) acrylic acid carboxyl methyl ester, (meth) acrylic acid-2-carboxyl ethyl ester, (meth) acrylic acid-3-carboxyadamantan-1-yl ester, (meth ) Acrylic acid-5 (6) -carboxybicyclo [2.2.1] hept-2-yl ester, (meth) acrylic acid-9 (10) -carboxytetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-yl ester, (meth) acrylic acid cyanomethyl ester, 1- (meth) acrylic acid-2-cyanoethyl ester, (meth) acrylic acid-3-cyanoadamantan-1-yl, ( meth) acrylic acid-5 (6) - Shianobishikuro [2.2.1] hept-2-yl ester, (meth) acrylic acid-9 (10) - cyano tetracyclo [6.2.1.1 ^{3, 6} ． 0 ^2,7 ] dodec-4-yl ester, (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid adamantan-1-yl ester, (meth) acrylic acid bicyclo [2.2 .1] Hept-2-yl ester, (meth) acrylic acid-7,7-dimethylbicyclo [2.2.1] hept-1-yl ester, (meth) acrylic acid tricyclo [5.2.1.0] ^2,6 ] dec-8-yl ester;

  (Meth) acrylic acid-7-oxo-6-oxabicyclo [3.2.1] oct-4-yl ester, (meth) acrylic acid-2-methoxycarbonyl-7-oxo-6-oxabicyclo [3 2.1] Oct-4-yl ester, (meth) acrylic acid-2-oxotetrahydropyran-4-yl ester, (meth) acrylic acid-4-methyl-2-oxotetrahydropyran-4-yl ester, ( (Meth) acrylic acid-5-oxotetrahydrofuran-3-yl ester, (meth) acrylic acid-2,2-dimethyl-5-oxotetrahydrofuran-3-yl ester, (meth) acrylic acid-4,4-dimethyl-5 -Oxotetrahydrofuran-3-yl ester, (meth) acrylic acid-2-oxotetrahydrofuran-3-yl ester, ) Acrylic acid-4,4-dimethyl-2-oxotetrahydrofuran-3-yl ester, (meth) acrylic acid-5,5-dimethyl-2-oxotetrahydrofuran-3-yl ester, (meth) acrylic acid-5- Oxotetrahydrofuran-2-ylmethyl ester, (meth) acrylic acid-3,3-dimethyl-5-oxotetrahydrofuran-2-ylmethyl ester,

  N, N-dimethyl (meth) acrylamide, crotonamide, maleinamide, fumaramide, mesaconamide, citraconamide, itaconamide, etc .; methylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, 2,5-dimethyl-2 , 5-hexanediol di (meth) acrylate, 1,2-adamantanediol di (meth) acrylate, 1,3-adamantanediol di (meth) acrylate, 1,4-adamantanediol di (meth) acrylate, tricyclodeca Examples thereof include nildimethylol di (meth) acrylate.

The acid-dissociable group-containing resin having Mw / Mn smaller than 1.5 according to the present invention includes the repeating unit represented by the formula (3) and the repeating unit represented by the formula (4) to the formula (10). It is preferably composed of at least one repeating unit.
The ratio of the repeating unit (3) in the copolymer is 5 to 85 mol%, preferably 10 to 70 mol%, based on all repeating units. If it is less than 5 mol%, the resolution as a resist tends to deteriorate, and if it exceeds 85 mol%, the developability as a resist tends to decrease.
When the repeating unit (4) is contained in the copolymer, the ratio of the repeating unit (4) is 2 to 80 mol%, preferably 5 to 60 mol%, based on the total repeating units; The ratio of the repeating unit (5) in the case where it is contained in the polymer is 2 to 70 mol%, preferably 5 to 50 mol%, based on the total repeating units; in the case where the repeating unit (6) is contained in the copolymer The ratio of the repeating unit (6) is 2 to 85 mol%, preferably 5 to 70 mol%, based on all repeating units; the repeating unit (7) in the case where the repeating unit (7) is contained in the copolymer. The ratio is 2 to 70 mol%, preferably 5 to 50 mol%, based on all repeating units; the repeating unit (when the repeating unit (8) is contained in the copolymer) ( ) Is 2 to 80 mol%, preferably 5 to 70 mol%, based on all repeating units; the proportion of repeating unit (9) in the case where repeating unit (9) is contained in the copolymer is 2 to 80 mol%, preferably 5 to 70 mol% with respect to the unit; the ratio of the repeating unit (10) in the case where the repeating unit (10) is contained in the copolymer is 1 to 70 mol%, preferably 3 to 50 mol%.

  When the content of the repeating unit (4) exceeds 80 mol%, resolution tends to deteriorate and solubility in the resist solvent tends to decrease. When the content of the repeating unit (5) exceeds 70 mol%, the developability tends to be lowered. When the content of the repeating unit (6) exceeds 85 mol%, the dry etching resistance tends to be lowered. When the content of the repeating unit (7) exceeds 70 mol%, the resolution tends to decrease. When the content of the repeating unit (8) exceeds 80 mol%, the developability tends to be lowered. When the content of the repeating unit (9) exceeds 80 mol%, the developability tends to be lowered. When the content of the repeating unit (10) exceeds 70 mol%, the developability tends to be lowered.

The acid-dissociable group-containing resin can easily make the value of Mw / Mn smaller than 1.5 by living radical polymerization using a living radical polymerization initiator.
The living radical polymerization used in the present invention means radical polymerization that is maintained without losing the activity of the polymerization terminal. In the narrow sense, living polymerization refers to polymerization in which the terminal always has activity, but generally includes pseudo-living polymerization in which the terminal is inactivated and the terminal is in equilibrium. . The definition in the present invention is also the latter.
The living radical polymerization system suitable for the present invention is living radical polymerization mediated by the organic tellurium compound containing the above (i).
When the organic tellurium compound and the radical polymerization initiator are used in combination, the ratio of the combined use is not particularly limited, but a radical polymerization initiator of 0.1 to 10 mol is appropriate for 1 mol of the organic tellurium compound.
Moreover, when using together an organic tellurium compound, a radical polymerization initiator, and a ditelluride compound, the ratio of each combination is not particularly limited, but relative to 1 mol of the organic tellurium compound, 0.1-10 mol of a radical polymerization initiator, A ditelluride compound of 0.1 to 10 mol is suitable.

Examples of the solvent used in the living radical polymerization include cycloalkanes such as cyclohexane and cycloheptane; saturated carboxylic acids such as ethyl acetate, n-butyl acetate, i-butyl acetate, methyl propionate, and propylene glycol monomethyl ether acetate. Esters; alkyl lactones such as γ-butyrolactone; airs such as tetrahydrofuran, dimethoxyethanes and diethoxyethanes; alkyl ketones such as 2-butanone, 2-heptanone and methyl isobutyl ketone; cycloalkyl ketones such as cyclohexanone Alcohols such as 2-propanol and propylene glycol monomethyl ether; aromatics such as toluene, xylene and chlorobenzene; dimethylformamide, dimethyl sulfoxide, dimethylacetamide , It may be mentioned aprotic polar solvent or without a solvent, such as N- methyl-2-pyrrolidone.
These solvents can be used alone or in admixture of two or more.
Moreover, the reaction temperature in the said superposition | polymerization is 40-150 degreeC normally, Preferably it is 50-130 degreeC, and reaction time is 0.5-96 hours normally, Preferably it is 1-48 hours.

The acid-dissociable group-containing resin according to the present invention is preferably a polymer polymerized randomly without repeating each repeating unit constituting the resin.
As a means for randomly polymerizing the monomers constituting each repeating unit, the monomers for generating the repeating units represented by the above formulas (3) and (4) to (10) may be collectively or mixed. It is obtained by dropping and polymerizing.

When the organic tellurium represented by formula (1) is used as an initiator, ^a tellurium atom may remain at the molecular end in the form of -TeR ^a (wherein R ^a is the same as above). In order to improve resist properties such as sensitivity, resolution, and process stability as a resist, the residual tellurium atoms are preferably 25 ppm or less based on the entire resin.
The tellurium atom remaining at the molecular end is a radical reduction method using tributylstannane or a thiol compound after polymer formation, or a method of adsorbing with activated carbon, silica gel, activated alumina, activated clay, molecular sieves and polymer adsorbent. , Methods of adsorbing metals with ion exchange resins, etc., liquid-liquid extraction methods that remove residual tellurium compounds by combining water washing and an appropriate solvent, ultrafiltration that extracts and removes only those with a specific molecular weight or less, etc. These purification methods in a solution state can also be combined.

  The obtained acid-dissociable group-containing resin is naturally low in impurities such as halogen and metal, and the residual monomer and oligomer components are not more than predetermined values, for example, 0.1% by weight or the like by HPLC. Thus, not only the sensitivity, resolution, process stability, pattern shape and the like as a resist can be further improved, but also a resist having no temporal change such as foreign matter in liquid or sensitivity can be obtained.

Examples of the method for purifying the acid-dissociable group-containing resin according to the present invention include the following methods. As a method of removing impurities such as metals, the metal is chelated and removed by adsorbing the metal in the resin solution using a zeta potential filter or by washing the resin solution with an acidic aqueous solution such as oxalic acid or sulfonic acid. And the like. In addition, as a method of removing residual monomer and oligomer components below the specified value, a liquid-liquid extraction method that removes residual monomers and oligomer components by combining water washing and an appropriate solvent, those having a specific molecular weight or less A purification method in the form of a solution such as ultrafiltration that only extracts and removes, or a reprecipitation method that removes residual monomers by coagulating the resin in the poor solvent by dropping the resin solution into the poor solvent. There is a purification method in a solid state such as washing the separated resin slurry with a poor solvent. Moreover, these methods can also be combined.
The poor solvent used in the reprecipitation method depends on the physical properties of the resin to be purified and cannot be generally exemplified. As appropriate, the poor solvent is selected.

Mw of the acid-dissociable group-containing resin is a polystyrene-reduced weight average molecular weight by gel permeation chromatography (GPC), and the value thereof is usually 1,000 to 300,000, preferably 2,000 to 200,000, More preferably, it is 3,000-100,000. In this case, if the Mw of the resin is less than 1,000, the heat resistance as a resist tends to decrease, while if it exceeds 300,000, the developability as a resist tends to decrease.
Moreover, the ratio (Mw / Mn) of Mw and Mn of the resin is usually 1 to 1.5, preferably 1 to 1.3.
In this invention, acid dissociable group containing resin can be used individually or in mixture of 2 or more types.
A chemically amplified resist can be obtained by combining the acid-dissociable group-containing resin with a radiation-sensitive acid generator that is a component that generates an acid upon irradiation with radiation.

Hereinafter, the present invention will be specifically described with reference to examples. Here, the part is based on weight unless otherwise specified.
Each measurement and evaluation in Examples and Comparative Examples was performed by the following methods.
(1) Identification of organic tellurium compounds and ditelluride compounds
^It identified from the measurement result of < ¹ > H-NMR, < ¹³ > C-NMR, IR, and MS (HRMS). ¹ H-NMR: Varian Gemini 2000 (300 MHz for ¹ H), JEOL JNM-A400 (400 MHz for ¹ H), ¹³ C-NMR: Varian Gemini 2000, JEOL JNM-A400 IR: Shimadzu FTIR-8200 (cm ⁻¹ ) MS (HRMS): JEOL JMS-300
(2) Mw and Mn:
Using a GPC column (2 G2000HXL, 1 G3000HXL, 1 G4000HXL) manufactured by Tosoh Corporation, monodisperse polystyrene was used as the standard under the analysis conditions of a flow rate of 1.0 ml / min, elution solvent tetrahydrofuran, and column temperature of 40 ° C. Measured by gel permeation chromatography (GPC).
(3) Difference between molecular weight lots:
In each Example, the acid-dissociable group-containing resin was synthesized 5 times under the same conditions, and Mw of each obtained resin was measured. The standard deviation of the number of measurement 5 was calculated | required and it was set as the molecular weight lot difference.

Synthesis example 1
Ethyl-2-methyl-2-methylterranyl-propionate was synthesized by the following method.
6.38 g (50 mmol) of metal tellurium (manufactured by Aldrich, trade name: Tellurium (−40 mesh)) is suspended in 50 ml of THF, and 52.9 ml (1.04 M diethyl ether solution) of methyl lithium (manufactured by Kanto Chemical Co., Ltd.) is suspended therein. , 55 mmol) was slowly added dropwise at room temperature (10 minutes). The reaction solution was stirred until the metal tellurium disappeared completely (20 minutes). To this reaction solution, 10.7 g (55 mmol) of ethyl-2-bromo-isobutyrate was added at room temperature and stirred for 2 hours. After completion of the reaction, the solvent was concentrated under reduced pressure, followed by distillation under reduced pressure to obtain 6.53 g (yield 51%) of a yellow oil.
It was confirmed to be ethyl-2-methyl-2-methylterranyl-propinate by IR, HRMS, ¹ H-NMR, and ¹³ C-NMR.
IR (neat, cm ⁻¹ ): 1700, 1466, 1385, 1296, 1146, 1111 and 1028
HRMS (EI) m / z: Calcd for C ₇ H ₁₄ O ₂ Te (M) ⁺ +, 260.0056; Found 260.0053
¹ H-NMR (300 MHz, CDCl ₃ ) 1.27 (t, J = 6.9 Hz, 3H), 1.74 (s, 6H), 2.15 (s, 3H, TeCH ₃ ), 4.16 ( q, J = 7.2 Hz, 2H)
¹³ C-NMR (75 MHz, CDCl ₃ ) -17.38, 13.89, 23.42, 27.93, 60.80, 176.75

Synthesis example 2
Ethyl-2-methyl-2-n-butylteranyl-propionate was synthesized by the following method.
6.38 g (50 mmol) of metal tellurium (same as synthesis example 1) was suspended in 50 ml of THF, and 34.4 ml (55 mmol) of n-butyllithium (manufactured by Aldrich, 1.6M hexane solution) was slowly added thereto at room temperature. Added dropwise (10 minutes). The reaction solution was stirred until the metal tellurium disappeared completely (20 minutes). To this reaction solution, 10.7 g (55 mmol) of ethyl-2-bromo-isobutyrate was added at room temperature and stirred for 2 hours. After completion of the reaction, the solvent was concentrated under reduced pressure, followed by distillation under reduced pressure to obtain 8.98 g (yield 59.5%) of a yellow oil.
¹ H-NMR confirmed that it was ethyl-2-methyl-2-n-butylteranyl-propinate.
¹ H-NMR (300 MHz, CDCl ₃ ) 0.93 (t, J = 7.5 Hz, 3H), 1.25 (t, J = 7.2 Hz, 3H), 1.37 (m, 2H), 1 .74 (s, 6H), 1.76 (m, 2H), 2.90 (t, J = 7.5 Hz, 2H, CH ₂ Te), 4.14 (q, J = 7.2 Hz, 2H)

Synthesis example 3
Dimethylditelluride was synthesized by the following method.
Metallic tellurium (manufactured by Aldrich, trade name: Tellurium (−40 mesh)) 3.19 g (25 mmol) was suspended in 25 ml of THF, and 25 ml (28.5 mmol) of methyl lithium (manufactured by Kanto Chemical Co., Ltd., diethyl ether solution) was 0 ° C. Slowly added (10 minutes). The reaction solution was stirred until the metal tellurium disappeared completely (10 minutes). To this reaction solution, 20 ml of ammonium chloride solution was added at room temperature and stirred for 1 hour. The organic layer was separated and the aqueous layer was extracted 3 times with diethyl ether. The collected organic layer was dried over sodium sulfate and concentrated under reduced pressure to obtain 2.69 g (9.4 mmol: yield 75%) of a black purple oily substance.
It was confirmed to be dimethylditelluride by MS (HRMS) and ¹ H-NMR.
HRMS (EI) m / z: Calcd for C ₂ H ₆ Te ₂ (M) ⁺ , 289.8594; Found 289.8593
¹ H-NMR (300 MHz, CDCl ₃ ) 2.67 (s, 6H)

Synthesis example 4
Di-n-butyl ditelluride was synthesized by the following method.
3.19 g (25 mmol) of metal tellurium (same as synthesis example 3) was suspended in 25 ml of THF, and 17.2 ml (27.5 mmol) of n-butyllithium (manufactured by Aldrich, 1.6M hexane solution) was slowly added at 0 ° C. (10 minutes). The reaction solution was stirred until the metal tellurium disappeared completely (10 minutes). To this reaction solution, 20 ml of ammonium chloride solution was added at room temperature and stirred for 1 hour. The organic layer was separated and the aqueous layer was extracted 3 times with diethyl ether. The collected organic layer was dried over sodium sulfate and then concentrated under reduced pressure to obtain 4.41 g (11.93 mmol: 95% yield) of a black purple oily substance.
It was confirmed to be di-n-ditelluride by ¹ H-NMR.
¹ H-NMR (300 MHz, CDCl ₃ ) 0.93 (t, J = 7.3 Hz, 3H), 1.39 (m, 2H), 1.71 (m, 2H), 3.11 (t, J = 7.6, 2H, CH ₂ Te)

Example 1
In a glove box substituted with nitrogen, 0.870 g (3.5 mmol) of compound (S1-1), 1.102 g (5 mmol) of compound (S2-1), 0.224 g (1.5 mmol) of compound (S3-1) And 51.6 mg (0.2 mmol) of ethyl-2-methyl-2-methylterranyl-propinate, 16.4 mg (0.10 mmol) of AIBN (manufactured by Otsuka Chemical Co., Ltd., trade name: AIBN) and 2 ml of 2-butanone at 60 ° C. For 6 hours. After completion of the reaction, a solution prepared by dissolving 116.4 mg (0.4 mmol) of tributyltin hydroxide and 6.6 mg (0.04 mmol) of AIBN in 2 ml of 2-butanone is added and stirred at 60 ° C. for 2 hours. After completion of the reaction, the reaction mixture was diluted with 3 ml of 2-butanone and poured into 200 ml of stirring 2-propanol. The precipitated polymer was suction filtered at room temperature, and the resulting polymer was redissolved in 10 ml of 2-butanone and passed through a column made of activated alumina (manufactured by Wako Pure Chemical Industries, Ltd.). Thereafter, it was poured into 100 ml of 2-propanol. The precipitated polymer was suction filtered and dried at room temperature to obtain a polymer (2.02 g, yield 92%).
As a result of GPC analysis (based on the molecular weight of a polystyrene standard sample), this resin was Mw 7,200 and Mw / Mn was 1.21. Moreover, it melt | dissolved with respect to propylene glycol monomethyl ether acetate. The difference between the molecular weight lots was 158.

Example 2
In a glove box substituted with nitrogen, 0.870 g (3.5 mmol) of compound (S1-1), 1.102 g (5 mmol) of compound (S2-1), 0.224 g (1.5 mmol) of compound (S3-1) And 51.6 mg (0.2 mmol) of ethyl-2-methyl-2-methylterranyl-propinate, 16.4 mg (0.10 mmol) of AIBN (manufactured by Otsuka Chemical Co., Ltd., trade name: AIBN) and 2 ml of 2-butanone at 60 ° C. For 6 hours. After completion of the reaction, a solution prepared by dissolving 99.47 mg (0.4 mmol) of tris (trimethylsilyl) silane and 6.6 mg (0.04 mmol) of AIBN in 2 ml of 2-butanone is added and stirred at 75 ° C. for 16 hours. After completion of the reaction, the reaction mixture was diluted with 3 ml of 2-butanone and poured into 200 ml of stirring 2-propanol. The precipitated polymer is suction filtered at room temperature, and the resulting polymer is rinsed with 100 ml of 2-propanol / water = 9/1 solution. The precipitated polymer was suction filtered at room temperature to obtain a polymer. (1.98 g 90% yield).
As a result of GPC analysis (based on the molecular weight of a polystyrene standard sample), this resin was Mw 7,300 and Mw / Mn was 1.24. Moreover, it melt | dissolved with respect to propylene glycol monomethyl ether acetate. The difference between the molecular weight lots was 114.

窒素置換したグローブボックス内で、化合物（Ｓ１−４）１．１１ｇ（５ｍｍｏｌ）と化合物（Ｓ２−４）０．８２０ｇ（３．５ｍｍｏｌ）と化合物（Ｓ３−４）０．３５４ｇ（１．５ｍｍｏｌ）とエチル−２−メチル−２−ｎ−ブチルテラニル−プロピネート６０．４ｍｇ（０．２ｍｍｏｌ）とジ−ｎ−ブチルジテルリド３７．０ｍｇ（０．１０ｍｍｏｌ）とＭＡＩＢ（大塚化学株式会社製、商品名：ＭＡＩＢ）２３．０ｍｇ（０.１０ｍｍｏｌ）と２−ブタノン２ｍｌを６０℃で６時間撹拌した。反応終了後、チオフェノール１３２ｍｇ（１．２ｍｍｏｌ）とＭＡＩＢ２７．６ｍｇ（０.１２ｍｍｏｌ）を２−ブタノン２ｍｌに溶解した溶液を添加し、７５℃で１６時間撹拌する。反応終了後２−ブタノン３ｍｌで希釈後、撹拌している２−プロパノール２００ｍｌ中に注いだ。沈殿したポリマーを室温で吸引ろ過、得られたポリマーを１００ｍｌの２−プロパノール／水＝９／１溶液でリンス洗浄を行う。その後室温で吸引濾過し、得られたポリマーを２−ブタノン１０ｍｌに溶解し、特製白鷺（武田薬品工業株式会社製）０．２ｇを添加し室温で３０分撹拌する。室温で吸引ろ過後、撹拌している２−プロパノール１００ｍｌ中に注いだ。沈殿したポリマーを室温で吸引ろ過乾燥することによりポリマーを得た。（収量１．９４ｇ 収率８５％）。
この樹脂は、ＧＰＣ分析（ポリスチレン標準サンプルの分子量を基準）の結果、Ｍｗ１０，０００であり、Ｍｗ／Ｍｎは１．２４であった。また、プロピレングリコールモノメチルエーテルアセテートに対して溶解した。分子量ロット間差は１６７であった。 Example 3

In a glove box substituted with nitrogen, 1.11 g (5 mmol) of compound (S1-4), 0.820 g (3.5 mmol) of compound (S2-4) and 0.354 g (1.5 mmol) of compound (S3-4) And ethyl-2-methyl-2-n-butylteranyl-propinate 60.4 mg (0.2 mmol), di-n-butyl ditelluride 37.0 mg (0.10 mmol) and MAIB (made by Otsuka Chemical Co., Ltd., trade name: MAIB) 23.0 mg (0.10 mmol) and 2-butanone 2 ml were stirred at 60 ° C. for 6 hours. After completion of the reaction, a solution of 132 mg (1.2 mmol) of thiophenol and 27.6 mg (0.12 mmol) of MAIB dissolved in 2 ml of 2-butanone is added and stirred at 75 ° C. for 16 hours. After completion of the reaction, the reaction mixture was diluted with 3 ml of 2-butanone and poured into 200 ml of stirring 2-propanol. The precipitated polymer is suction filtered at room temperature, and the resulting polymer is rinsed with 100 ml of 2-propanol / water = 9/1 solution. Then, suction filtration is performed at room temperature, and the obtained polymer is dissolved in 10 ml of 2-butanone, and 0.2 g of special white birch (manufactured by Takeda Pharmaceutical Co., Ltd.) is added and stirred at room temperature for 30 minutes. After suction filtration at room temperature, it was poured into 100 ml of stirring 2-propanol. The precipitated polymer was suction filtered and dried at room temperature to obtain a polymer. (Yield 1.94 g Yield 85%).
As a result of GPC analysis (based on the molecular weight of a polystyrene standard sample), this resin was Mw 10,000 and Mw / Mn was 1.24. Moreover, it melt | dissolved with respect to propylene glycol monomethyl ether acetate. The difference between the molecular weight lots was 167.

  The acid-dissociable group-containing resin of the present invention can reduce Mw / Mn, has little variation between production lots, and has excellent solubility in a resist solvent. It can be used for resists used in the above.

Claims (6)

(I) a compound represented by the following formula (1), or (ii) a compound represented by the following formula (1), a radical polymerization initiator and a ditelluride compound represented by the following formula (2). An acid-dissociable group-containing resin which is polymerized using a mixture of at least one compound.

(In Formula (1) and Formula (2), R ^a represents an alkyl group having 1 to 8 carbon atoms, an aryl group, a substituted aryl group, or an aromatic heterocyclic group. R ^b and R ^c are a hydrogen atom or Represents an alkyl group having 1 to 8 carbon atoms, and R ^d represents an aryl group, a substituted aryl group, an aromatic heterocyclic group, an acyl group, an oxycarbonyl group or a cyano group. The acid dissociable group-containing resin according to claim 1, comprising a repeating unit represented by the following formula (3).

(In the formula (3), R represents hydrogen, a methyl group, a trifluoromethyl group or a hydroxymethyl group, and R ¹ is independently a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof. Or a linear or branched alkyl group having 1 to 4 carbon atoms and at least one of R ¹ is the alicyclic hydrocarbon group or a derivative thereof, or any two R ¹ are mutually To form a divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof together with the carbon atoms to which each is bonded, and the remaining R ¹ is a straight chain having 1 to 4 carbon atoms or Represents a branched alkyl group, a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms, or a derivative thereof.) The acid-dissociable group-containing resin according to claim 2, comprising at least one repeating unit selected from repeating units represented by the following formulas (4) to (10).

(In the formulas (4) to (10), R is the same as R in the formula (3).
In the formula (4), A represents a single bond or a linear or branched alkylene group, mono- or dialkylene glycol group or alkylene ester group which may have a substituent having 1 to 6 carbon atoms, and B Represents a single bond or an alkylene group, alkyloxy group or oxygen atom which may have a substituent having 1 to 3 carbon atoms.
In the formula (5), E represents a single bond or a divalent alkyl group having 1 to 3 carbon atoms, and R ² is independently a hydroxyl group, a cyano group, a carboxyl group, —COOR ⁴ , or —Y—R ^5. R ⁴ is a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or an alicyclic alkyl group having 3 to 20 carbon atoms, Y is independently a single bond or a carbon number 1 to 3 divalent alkylene groups, and R ⁵ each independently represents a hydrogen atom, a hydroxyl group, a cyano group, or a —COOR ⁶ group. However, at least one R ² is not a hydrogen atom. R ⁶ in the —COOR ⁶ group represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or an alicyclic alkyl group having 3 to 20 carbon atoms.
In Formula (6), G represents a single bond, a linear or branched alkylene group having 1 to 6 carbon atoms, an alicyclic hydrocarbon group having 4 to 20 carbon atoms, an alkylene glycol group, or an alkylene ester group.
In the formula (7), J represents a single bond, a linear, branched or cyclic alkylene group, alkylene glycol group or alkylene ester group which may have a substituent having 1 to 20 carbon atoms.
In the formula (8), L represents a single bond, a linear, branched or cyclic alkylene group, alkylene glycol group or alkylene ester group which may have a substituent having 1 to 20 carbon atoms, and R ³ Is a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, an alkoxy group, a hydroxyalkyl group, a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, or a derivative thereof. Represent. q is 1 or 2.
In the formula (9), N and M ′ are each independently a single bond, a linear, branched or cyclic alkylene group, alkylene glycol group, alkylene which may have a substituent having 1 to 20 carbon atoms. Represents an ester group. p is 0 or 1;
In the formula (10), X represents a polycyclic alicyclic hydrocarbon group composed only of carbon and hydrogen not containing a polar group having 7 to 20 carbon atoms.   4. The acid-dissociable group-containing resin according to claim 1, wherein the ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight / number average molecular weight) is less than 1.5. .   The acid-dissociable group-containing resin according to any one of claims 1 to 4, which is used for a radiation-sensitive resin composition used for lithography using radiation having a wavelength of 193 nm or less. In the method for producing an acid dissociable group-containing resin in which an acid dissociable group-containing monomer is polymerized using an initiator,
The initiator is (i) a compound represented by the following formula (1), or (ii) a compound represented by the following formula (1), a radical polymerization initiator, and a ditelluride represented by the following formula (2). A method for producing an acid-dissociable group-containing resin, which is a mixture with at least one compound selected from compounds.

(In Formula (1) and Formula (2), R ^a represents an alkyl group having 1 to 8 carbon atoms, an aryl group, a substituted aryl group, or an aromatic heterocyclic group. R ^b and R ^c are a hydrogen atom or Represents an alkyl group having 1 to 8 carbon atoms, and R ^d represents an aryl group, a substituted aryl group, an aromatic heterocyclic group, an acyl group, an oxycarbonyl group or a cyano group.