JP2016037594A - Copolymer and method of producing copolymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a copolymer and a method of producing the copolymer.SOLUTION: The copolymer is a copolymer of alkoxysilane being at least bifunctional, and has partial structures represented by general formulas (p-1) and (p-3).SELECTED DRAWING: None

Description

  The present invention relates to a copolymer and a method for producing the copolymer.

Conventionally, materials such as activated carbon, zeolite, and silica gel have been widely used as fillers and collection agents used for filtration and purification.
In recent years, in the manufacture of ultrafine patterns, it has been desired to remove even very low concentrations of impurities.
For example, it has been confirmed that the presence of metal ions of less than 100 ppb (parts per billion) in a resist composition used for forming a resist pattern adversely affects the lithography characteristics of the resist pattern.

In order to solve such problems, attempts have been made to remove impurities such as metal ions by filtering and purifying the material.
For example, Patent Documents 1 and 2 describe a method of filtering a resist composition with a filter sheet using functionalized silica gel.
Patent Document 3 describes an impurity removal method using an impurity filtering device using a polyolefin-based nonwoven fabric having a specific fiber diameter and a specific density as a filter member. Patent Documents 4 to 6 describe a metal removal method using a predetermined filter medium. Patent Document 7 describes a method for removing an impure metal component using an adsorbent.

JP 2006-136883 A JP 2003-238958 A JP 2013-61426 A JP 2000-281739 A JP 2004-330056 A JP 2005-243728 A JP-A-7-74073

  However, while it is desired to remove even a very small amount of impurities at a low concentration, there is a demand for a filtering material with high removal efficiency of impurities such as metal components at a ppt (trillion trillion) level.

  The present invention has been made in view of the above circumstances, and is a copolymer useful for filtering a resist composition or an organic solvent, and a copolymer having a high metal component removal efficiency, and the copolymer. It is an object to provide a manufacturing method.

  A first aspect of the present invention is a copolymer of alkoxysilanes having two or more functional groups, and having a partial structure represented by the following general formulas (p-1) and (p-3). is there.

［式中、Ｒ^４及びＲ^５はそれぞれ独立に、置換基を有していてもよい炭化水素基、又は水酸基を表し、Ｒ^４及びＲ^５の一方は、アルコキシシラン共重合体中の他のケイ素原子と結合して、架橋構造を形成していてもよい。Ｙａ^０１及びＹｂ^０１はそれぞれ独立に、２価の連結基を表し、Ｒａ^０１は置換基を有していてもよい炭化水素基を表し、Ｒａ^０２は水酸基又は置換基を有していてもよい炭素数１〜６の炭化水素基を表す。ｎ^０１は０〜５の整数である。＊は結合手を示す。］

[Wherein, R ⁴ and R ⁵ each independently represents a hydrocarbon group which may have a substituent, or a hydroxyl group, and one of R ⁴ and R ⁵ represents the other in the alkoxysilane copolymer. It may combine with a silicon atom to form a crosslinked structure. Ya ⁰¹ and Yb ⁰¹ each independently represent a divalent linking group, Ra ⁰¹ represents a hydrocarbon group which may have a substituent, and Ra ⁰² may have a hydroxyl group or a substituent. Represents a hydrocarbon group having 1 to 6 carbon atoms. n ⁰¹ is an integer of 0 to 5. * Indicates a bond. ]

  A second aspect of the present invention is a copolymer of alkoxysilanes having two or more functional groups, and having a partial structure represented by the following general formulas (p-1) and (p-5). is there.

［式中、Ｒ^４及びＲ^５はそれぞれ独立に、置換基を有していてもよい炭化水素基、又は水酸基を表し、Ｒ^４及びＲ^５の一方は、アルコキシシラン共重合体中の他のケイ素原子と結合して、架橋構造を形成していてもよい。Ｙａ^０１及びＹｂ^０１はそれぞれ独立に、２価の連結基を表し、Ｒａ^０１は置換基を有していてもよい炭化水素基を表し、Ｒａ^０２は水酸基又は置換基を有していてもよい炭素数１〜６の炭化水素基を表す。ｎ^０１は０〜５の整数である。＊は結合手を示す。］

[Wherein, R ⁴ and R ⁵ each independently represents a hydrocarbon group which may have a substituent, or a hydroxyl group, and one of R ⁴ and R ⁵ represents the other in the alkoxysilane copolymer. It may combine with a silicon atom to form a crosslinked structure. Ya ⁰¹ and Yb ⁰¹ each independently represent a divalent linking group, Ra ⁰¹ represents a hydrocarbon group which may have a substituent, and Ra ⁰² may have a hydroxyl group or a substituent. Represents a hydrocarbon group having 1 to 6 carbon atoms. n ⁰¹ is an integer of 0 to 5. * Indicates a bond. ]

  In the third aspect of the present invention, a compound represented by the following general formula (1) and a compound represented by the following general formula (2) are reacted to produce the following general formulas (p-1) and (p -2) to obtain a copolymer (A) having a partial structure represented by the formula (A), and to modify the copolymer (A) obtained in the above-mentioned step A, the following general formula (p-B-1) Step B to obtain a copolymer (B) having a partial structure represented by formula (1) and the copolymer (B) obtained in the step B are modified to give the following general formulas (p-3) and (p-1): And a step C for obtaining a copolymer (C) having a partial structure.

［式中、Ｒ^１〜Ｒ^３、及びＲ^６〜Ｒ^７はそれぞれ独立に、炭素数１〜５のアルキル基を表し、Ｒ^４及びＲ^５はそれぞれ独立に、置換基を有していてもよい炭化水素基、又は水酸基を表し、Ｒ^４及びＲ^５の一方は、アルコキシシラン共重合体中の他のケイ素原子と結合して、架橋構造を形成していてもよい。Ｙａ^０１及びＹｂ^０１はそれぞれ独立に、２価の連結基を表し、Ｒａ^０１は置換基を有していてもよい炭化水素基を表し、Ｒａ^０２は水酸基又は置換基を有していてもよい炭素数１〜６の炭化水素基を表す。ｎ^０１は０〜５の整数である。＊は結合手を示す。］

[Wherein, R ^{1 to} R ³ and R ^{6 to} R ⁷ each independently represent an alkyl group having 1 to 5 carbon atoms, and R ⁴ and R ⁵ may each independently have a substituent. It represents a good hydrocarbon group or a hydroxyl group, and one of R ⁴ and R ⁵ may be bonded to another silicon atom in the alkoxysilane copolymer to form a crosslinked structure. Ya ⁰¹ and Yb ⁰¹ each independently represent a divalent linking group, Ra ⁰¹ represents a hydrocarbon group which may have a substituent, and Ra ⁰² may have a hydroxyl group or a substituent. Represents a hydrocarbon group having 1 to 6 carbon atoms. n ⁰¹ is an integer of 0 to 5. * Indicates a bond. ]

  In the fourth aspect of the present invention, a compound represented by the following general formula (3) is reacted with a compound represented by the following general formula (2) to produce the following general formulas (p-1) and (p -4) The process X to obtain the copolymer (X) having the partial structure represented by the formula, and the copolymer (X) obtained in the process X are modified to give the following general formula (pY-1) Step Y for obtaining a copolymer (Y) having a partial structure represented by formula (1) and the copolymer (Y) obtained in the step Y are modified to give the following general formulas (p-5) and (p-1): And a process Z for obtaining a copolymer (Z) having a partial structure represented by formula (1).

［式中、Ｒ^１〜Ｒ^３、及びＲ^６〜Ｒ^７はそれぞれ独立に、炭素数１〜５のアルキル基を表し、Ｒ^４及びＲ^５はそれぞれ独立に、置換基を有していてもよい炭化水素基、又は水酸基を表し、Ｒ^４及びＲ^５の一方は、アルコキシシラン共重合体中の他のケイ素原子と結合して、架橋構造を形成していてもよい。Ｙａ^０１及びＹｂ^０１はそれぞれ独立に、２価の連結基を表し、Ｒａ^０１は置換基を有していてもよい炭化水素基を表し、Ｒａ^０２は水酸基又は置換基を有していてもよい炭素数１〜６の炭化水素基を表す。ｎ^０１は０〜５の整数である。＊は結合手を示す。］

[Wherein, R ^{1 to} R ³ and R ^{6 to} R ⁷ each independently represent an alkyl group having 1 to 5 carbon atoms, and R ⁴ and R ⁵ may each independently have a substituent. It represents a good hydrocarbon group or a hydroxyl group, and one of R ⁴ and R ⁵ may be bonded to another silicon atom in the alkoxysilane copolymer to form a crosslinked structure. Ya ⁰¹ and Yb ⁰¹ each independently represent a divalent linking group, Ra ⁰¹ represents a hydrocarbon group which may have a substituent, and Ra ⁰² may have a hydroxyl group or a substituent. Represents a hydrocarbon group having 1 to 6 carbon atoms. n ⁰¹ is an integer of 0 to 5. * Indicates a bond. ]

  A fifth aspect of the present invention is a copolymer of alkoxysilanes having two or more functional groups, and having a partial structure represented by the following general formulas (p-1) and (p-4). is there.

［式中、Ｒ^４及びＲ^５はそれぞれ独立に、置換基を有していてもよい炭化水素基、又は水酸基を表し、Ｒ^４及びＲ^５の一方は、アルコキシシラン共重合体中の他のケイ素原子と結合して、架橋構造を形成していてもよい。Ｙｂ^０１は、２価の連結基を表す。＊は結合手を示す。］

[Wherein, R ⁴ and R ⁵ each independently represents a hydrocarbon group which may have a substituent, or a hydroxyl group, and one of R ⁴ and R ⁵ represents the other in the alkoxysilane copolymer. It may combine with a silicon atom to form a crosslinked structure. Yb ⁰¹ represents a divalent linking group. * Indicates a bond. ]

  ADVANTAGE OF THE INVENTION According to this invention, the removal efficiency of a metal component is high and can provide the copolymer useful for especially filtering a resist composition or an organic solvent, and the manufacturing method of this copolymer.

In the present specification and claims, “aliphatic” is a relative concept with respect to aromatics, and is defined to mean groups, compounds, etc. that do not have aromaticity.
Unless otherwise specified, the “alkyl group” includes linear, branched and cyclic monovalent saturated hydrocarbon groups.
The “alkylene group” includes linear, branched, and cyclic divalent saturated hydrocarbon groups unless otherwise specified. The same applies to the alkyl group in the alkoxy group.
The “halogenated alkyl group” is a group in which part or all of the hydrogen atoms of the alkyl group are substituted with a halogen atom, and examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
“Fluorinated alkyl group” or “fluorinated alkylene group” refers to a group in which part or all of the hydrogen atoms of an alkyl group or alkylene group are substituted with fluorine atoms.
“Structural unit” means a monomer unit (monomer unit) constituting a polymer compound (resin, polymer, copolymer).
“A structural unit derived from an acrylate ester” means a structural unit formed by cleavage of an ethylenic double bond of an acrylate ester.
“Acrylic acid ester” is a compound in which the hydrogen atom at the carboxy group terminal of acrylic acid (CH ₂ ═CH—COOH) is substituted with an organic group.
In the acrylate ester, the hydrogen atom bonded to the carbon atom at the α-position may be substituted with a substituent. The substituent (R ^α ) for substituting the hydrogen atom bonded to the α-position carbon atom is an atom or group other than a hydrogen atom, such as an alkyl group having 1 to 5 carbon atoms or a halogenated group having 1 to 5 carbon atoms. Examples thereof include an alkyl group and a hydroxyalkyl group. The α-position carbon atom of the acrylate ester is a carbon atom to which a carbonyl group is bonded unless otherwise specified.
Hereinafter, an acrylate ester in which a hydrogen atom bonded to a carbon atom at the α-position is substituted with a substituent may be referred to as an α-substituted acrylate ester. Further, the acrylate ester and the α-substituted acrylate ester may be collectively referred to as “(α-substituted) acrylate ester”.
“A structural unit derived from hydroxystyrene or a hydroxystyrene derivative” means a structural unit formed by cleavage of an ethylenic double bond of hydroxystyrene or a hydroxystyrene derivative.
“Hydroxystyrene derivative” is a concept including those in which the hydrogen atom at the α-position of hydroxystyrene is substituted with another substituent such as an alkyl group or an alkyl halide group, and derivatives thereof. These derivatives include those in which the hydrogen atom at the α-position may be substituted with a substituent, the hydrogen atom of the hydroxyl group of hydroxystyrene substituted with an organic group, and the hydrogen atom at the α-position substituted with a substituent Examples include those in which a substituent other than a hydroxyl group is bonded to a good benzene ring of hydroxystyrene. The α-position (α-position carbon atom) means a carbon atom to which a benzene ring is bonded unless otherwise specified.
Examples of the substituent for substituting the hydrogen atom at the α-position of hydroxystyrene include the same substituents as those mentioned as the substituent at the α-position in the α-substituted acrylic ester.
The “structural unit derived from vinyl benzoic acid or a vinyl benzoic acid derivative” means a structural unit configured by cleavage of an ethylenic double bond of vinyl benzoic acid or a vinyl benzoic acid derivative.
The “vinyl benzoic acid derivative” is a concept including a compound in which the hydrogen atom at the α-position of vinyl benzoic acid is substituted with another substituent such as an alkyl group or an alkyl halide group, and derivatives thereof. These derivatives include those obtained by substituting the hydrogen atom of the carboxy group of vinyl benzoic acid with an organic group, which may be substituted with a hydrogen atom at the α-position, and the hydrogen atom at the α-position with a substituent. Examples thereof include those in which a substituent other than a hydroxyl group and a carboxy group is bonded to the benzene ring of vinyl benzoic acid. The α-position (α-position carbon atom) means a carbon atom to which a benzene ring is bonded unless otherwise specified.
The “styrene derivative” is a concept that includes those in which the hydrogen atom at the α-position of styrene is substituted with another substituent such as an alkyl group or a halogenated alkyl group.
“Structural unit derived from styrene” and “structural unit derived from styrene derivative” mean a structural unit formed by cleavage of an ethylenic double bond of styrene or a styrene derivative.
The alkyl group as a substituent at the α-position is preferably a linear or branched alkyl group, specifically, an alkyl group having 1 to 5 carbon atoms (methyl group, ethyl group, propyl group, isopropyl group). , N-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group) and the like.
Specific examples of the halogenated alkyl group as the substituent at the α-position include groups in which part or all of the hydrogen atoms of the above-mentioned “alkyl group as the substituent at the α-position” are substituted with a halogen atom. It is done. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is particularly preferable.
Specific examples of the hydroxyalkyl group as a substituent at the α-position include a group in which part or all of the hydrogen atoms of the “alkyl group as the substituent at the α-position” are substituted with a hydroxyl group. 1-5 are preferable and, as for the number of the hydroxyl groups in this hydroxyalkyl group, 1 is the most preferable.
When it is described as “may have a substituent”, when a hydrogen atom (—H) is substituted with a monovalent group, and when a methylene group (—CH ₂ —) is substituted with a divalent group Including both.
“Exposure” is a concept including general irradiation of radiation.
An “organic group” is a group containing a carbon atom and has an atom other than a carbon atom (for example, a hydrogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a halogen atom (fluorine atom, chlorine atom, etc.)). May be.

≪Copolymer≫
A first aspect of the present invention is a copolymer of alkoxysilanes having two or more functional groups, and having a partial structure represented by the following general formulas (p-1) and (p-3). is there.

［式中、Ｒ^４及びＲ^５はそれぞれ独立に、置換基を有していてもよい炭化水素基、又は水酸基を表し、Ｒ^４及びＲ^５の一方は、アルコキシシラン共重合体中の他のケイ素原子と結合して、架橋構造を形成していてもよい。Ｙａ^０１及びＹｂ^０１はそれぞれ独立に、２価の連結基を表し、Ｒａ^０１は置換基を有していてもよい炭化水素基を表し、Ｒａ^０２は水酸基又は置換基を有していてもよい炭素数１〜６の炭化水素基を表す。ｎ^０１は０〜５の整数である。＊は結合手を示す。］

[Wherein, R ⁴ and R ⁵ each independently represents a hydrocarbon group which may have a substituent, or a hydroxyl group, and one of R ⁴ and R ⁵ represents the other in the alkoxysilane copolymer. It may combine with a silicon atom to form a crosslinked structure. Ya ⁰¹ and Yb ⁰¹ each independently represent a divalent linking group, Ra ⁰¹ represents a hydrocarbon group which may have a substituent, and Ra ⁰² may have a hydroxyl group or a substituent. Represents a hydrocarbon group having 1 to 6 carbon atoms. n ⁰¹ is an integer of 0 to 5. * Indicates a bond. ]

In the present specification and claims, an alkoxysilane having two or more functional groups is an alkoxysilane represented by SiR ^x _n [OR ^Y ] _4-n , wherein n is 2 or less (R ^x is Represents a hydrocarbon group, and R ^Y represents an alkyl group.
In general formula (p-1), R ⁴ and R ⁵ are hydrocarbon groups which may have a substituent.
The hydrocarbon group for R ⁴ and R ⁵ may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. An aliphatic hydrocarbon group means a hydrocarbon group having no aromaticity.
The aliphatic hydrocarbon group as the hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated.

[Aliphatic hydrocarbon group]
More specifically, examples of the aliphatic hydrocarbon group include a linear or branched aliphatic hydrocarbon group or an aliphatic hydrocarbon group containing a ring in the structure.
The linear or branched aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6, more preferably 1 to 4, and most preferably 1 to 3.
As the linear aliphatic hydrocarbon group, a linear alkyl group is preferable, and an alkyl group having 1 to 5 carbon atoms is preferable, and specifically, a methyl group, an ethyl group, a propyl group, and an n-butyl group. , And a tert-butyl group. Of these, R ⁴ and R ⁵ are preferably methyl groups.

  Specific examples of the branched aliphatic hydrocarbon group include isopropyl group, isobutyl group, tert-butyl group, isopentyl group, neopentyl group, 1,1-dimethylethyl group, 1,1-diethylpropyl group, 2,2-dimethylpropyl group, 2,2, -dimethylbutyl group and the like can be mentioned.

  The alicyclic hydrocarbon group may be polycyclic or monocyclic. The monocyclic alicyclic hydrocarbon group is preferably a group obtained by removing one hydrogen atom from a monocycloalkane. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane. The polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing two hydrogen atoms from a polycycloalkane, and the polycycloalkane preferably has 7 to 12 carbon atoms, specifically adamantane. , Norbornane, isobornane, tricyclodecane, tetracyclododecane and the like.

[Aromatic hydrocarbon group]
The aromatic hydrocarbon group is a hydrocarbon group having an aromatic ring.
The aromatic hydrocarbon group preferably has 3 to 30 carbon atoms, more preferably 5 to 30, more preferably 5 to 20, particularly preferably 6 to 15, and most preferably 6 to 10. However, the carbon number does not include the carbon number in the substituent.
Specific examples of the aromatic ring of the aromatic hydrocarbon group include an aromatic hydrocarbon ring such as phenyl, biphenyl, fluorene, naphthalene, anthracene, and phenanthrene; a part of carbon atoms constituting the aromatic hydrocarbon ring is hetero Aromatic heterocycles substituted with atoms; and the like. Examples of the hetero atom in the aromatic heterocyclic ring include an oxygen atom, a sulfur atom, and a nitrogen atom.

[Substituent]
Examples of the substituent that the hydrocarbon group of R ⁴ and R ⁵ may have include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, and a nitro group.
The alkyl group as a substituent is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group.
The alkoxy group as a substituent is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, or a tert-butoxy group. Most preferred is an ethoxy group.
Examples of the halogen atom as a substituent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferable.
As the halogenated alkyl group as a substituent, a part or all of hydrogen atoms such as an alkyl group having 1 to 5 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, an n-butyl group, a tert-butyl group, and the like And a group substituted with a halogen atom.

R ⁴ and R ⁵ may be a hydroxyl group, and one of R ⁴ and R ⁵ is preferably a hydroxyl group.
One of R ⁴ and R ⁵ may be bonded to another silicon atom in the alkoxysilane copolymer to form a crosslinked structure.

In formula (p-3), Ya ⁰¹ and Yb ⁰¹ are each independently a divalent linking group, Ra ⁰¹ is a hydrocarbon group that may have a substituent, and Ra ⁰² is a hydroxyl group or a substituted group. a hydrocarbon group having 1 to 6 carbon atoms which may have a group, n ⁰¹ is an integer of 0 to 5.
No particular limitation is imposed on the divalent linking group for Ya ⁰¹ and Yb ^01, divalent hydrocarbon group which may have a substituent group, mentioned as the divalent linking group is preferred containing a hetero atom It is done.

(Divalent hydrocarbon group which may have a substituent)
The hydrocarbon group as the divalent linking group of Ya ⁰¹ and Yb ⁰¹ may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.
[Aliphatic hydrocarbon group]
An aliphatic hydrocarbon group means a hydrocarbon group having no aromaticity.
Examples of the aliphatic hydrocarbon group as the divalent hydrocarbon group in Ya ⁰¹ and Yb ⁰¹ include a linear or branched chain, or a group containing a ring in the structure.
The aliphatic hydrocarbon group may be saturated, unsaturated, or saturated.
Examples of Ya ⁰¹ and Yb ⁰¹ include those in which the divalent hydrocarbon group is bonded through an ether bond, a urethane bond, a sulfide bond, or an amide bond.

The linear or branched aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6, more preferably 1 to 4, and most preferably 1 to 3.
As the linear aliphatic hydrocarbon group, a linear alkylene group is preferable. Specifically, a methylene group [—CH ₂ —], an ethylene group [— (CH ₂ ) ₂ —], a trimethylene group [ _{- (CH 2) 3 -]} , a tetramethylene group _{[- (CH 2) 4 -} ], a pentamethylene group _{[- (CH 2) 5 -} ] and the like, a methylene group _[-CH 2 -], an ethylene group It is preferably [— (CH ₂ ) ₂ —] or a trimethylene group [— (CH ₂ ) ₃ —].
As the branched aliphatic hydrocarbon group, a branched alkylene group is preferred, and specifically, —CH (CH ₃ ) —, —CH (CH ₂ CH ₃ ) —, —C (CH ₃ ). _{2 -, - C (CH 3} ) (CH 2 CH 3) -, - C (CH 3) (CH 2 CH 2 CH 3) -, - C (CH 2 CH 3) 2 - ; alkylethylene groups such as - _{CH (CH 3) CH 2 -} , - CH (CH 3) CH (CH 3) -, - C (CH 3) 2 CH 2 -, - CH (CH 2 CH 3) CH 2 -, - C (CH 2 CH _{3) 2} -CH ₂ - alkyl groups such _{as; -CH (CH 3) CH 2} CH 2 -, - CH 2 CH (CH 3) CH 2 - alkyl trimethylene groups such as; -CH _(CH 3) _{CH 2 CH 2 CH 2 -,} - CH 2 CH (CH 3) CH 2 CH 2 - And the like alkyl alkylene group such as an alkyl tetramethylene group of. The alkyl group in the alkyl alkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.

Examples of the aliphatic hydrocarbon group containing a ring in the structure include an alicyclic hydrocarbon group (a group obtained by removing two hydrogen atoms from an aliphatic hydrocarbon ring), and an alicyclic hydrocarbon group that is linear or branched. Examples thereof include a group bonded to the end of a chain aliphatic hydrocarbon group and a group in which an alicyclic hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group. Examples of the linear or branched aliphatic hydrocarbon group include those described above.
The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms.
The alicyclic hydrocarbon group may be polycyclic or monocyclic. The monocyclic alicyclic hydrocarbon group is preferably a group obtained by removing two hydrogen atoms from a monocycloalkane. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane. The polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing two hydrogen atoms from a polycycloalkane, and the polycycloalkane preferably has 7 to 12 carbon atoms, specifically adamantane. , Norbornane, isobornane, tricyclodecane, tetracyclododecane and the like.

The linear or branched aliphatic hydrocarbon group may or may not have a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, and a carbonyl group.
Examples of the alkyl group as the substituent include a methyl group, an ethyl group, a propyl group, an n-butyl group, and a tert-butyl group, including an alkyl group having 1 to 5 carbon atoms.
Examples of the alkoxy group as the substituent include an alkoxy group having 1 to 5 carbon atoms, and a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, and a tert-butoxy group are preferable. A methoxy group and an ethoxy group are mentioned.
Examples of the halogen atom as the substituent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Examples of the halogenated alkyl group as the substituent include groups in which part or all of the hydrogen atoms of the alkyl group have been substituted with the halogen atoms.
In the cyclic aliphatic hydrocarbon group, a part of carbon atoms constituting the ring structure may be substituted with a substituent containing a hetero atom. Examples of the substituent containing a hetero atom include —O—, —C (═O) —O—, —S—, —S (═O) ₂ —, and —S (═O) ₂ —O—. .

As the aliphatic hydrocarbon group containing a ring in the structure, a cyclic aliphatic hydrocarbon group which may contain a substituent containing a hetero atom in the ring structure (excluding two hydrogen atoms from the aliphatic hydrocarbon ring) Group), a group in which the cyclic aliphatic hydrocarbon group is bonded to the end of a linear or branched aliphatic hydrocarbon group, and the cyclic aliphatic hydrocarbon group is a linear or branched chain fatty acid. Group intervening in the middle of the group hydrocarbon group. Examples of the linear or branched aliphatic hydrocarbon group include those described above.
The cyclic aliphatic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms.
Specific examples of the cyclic aliphatic hydrocarbon group include the groups exemplified above.
The cyclic aliphatic hydrocarbon group may or may not have a substituent. Examples of the substituent include the groups exemplified above.

[Aromatic hydrocarbon group]
The aromatic hydrocarbon group is a hydrocarbon group having an aromatic ring.
The aromatic hydrocarbon group as the divalent hydrocarbon group in Ya ⁰¹ and Yb ⁰¹ preferably has 3 to 30 carbon atoms, more preferably 5 to 30 carbon atoms, and still more preferably 5 to 20 carbon atoms. 6 to 15 are particularly preferable, and 6 to 10 are most preferable. However, the carbon number does not include the carbon number in the substituent.
Specific examples of the aromatic ring of the aromatic hydrocarbon group include aromatic hydrocarbon rings such as benzene, biphenyl, fluorene, naphthalene, anthracene, and phenanthrene; some of the carbon atoms constituting the aromatic hydrocarbon ring are heterogeneous Aromatic heterocycles substituted with atoms; and the like. Examples of the hetero atom in the aromatic heterocyclic ring include an oxygen atom, a sulfur atom, and a nitrogen atom.
Specifically, the aromatic hydrocarbon group is a group obtained by removing two hydrogen atoms from the aromatic hydrocarbon ring (arylene group); a group obtained by removing one hydrogen atom from the aromatic hydrocarbon ring (aryl group) ) In which one of the hydrogen atoms is substituted with an alkylene group (for example, arylalkyl such as benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, 2-naphthylethyl, etc.) Group in which one hydrogen atom is further removed from the aryl group in the group); and the like. The alkylene group (alkyl chain in the arylalkyl group) preferably has 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms, and particularly preferably 1 carbon atom.

Specific examples of the aromatic hydrocarbon group as the divalent hydrocarbon group include the groups exemplified above.
In the aromatic hydrocarbon group, a hydrogen atom of the aromatic hydrocarbon group may be substituted with a substituent. For example, a hydrogen atom bonded to an aromatic ring in the aromatic hydrocarbon group may be substituted with a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, and a hydroxyl group.
The alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group.
Examples of the alkoxy group, the halogen atom and the halogenated alkyl group as the substituent include those exemplified as the substituent for substituting the hydrogen atom of the cyclic aliphatic hydrocarbon group.

(Divalent linking group containing a hetero atom)
The hetero atom in the divalent linking group containing a hetero atom is an atom other than a carbon atom and a hydrogen atom, and examples thereof include an oxygen atom, a nitrogen atom, a sulfur atom, and a halogen atom.

When Ya ⁰¹ and Yb ⁰¹ are a divalent linking group containing a hetero atom, preferred examples of the linking group include —O—, —C (═O) —O—, —C (═O) —, — O—C (═O) —O—, —C (═O) —NH—, —NH—, —NH—C (═NH) — (H is substituted with a substituent such as an alkyl group or an acyl group. and may _{be), -. S -, -} S (= O) 2 -, - S (= O) 2 -O-, the formula ^{-Y 21 -O-Y 22 -,} - Y 21 -O -, - Y ²¹ —C (═O) —O—, —C (═O) —O—Y ²¹ , [Y ²¹ —C (═O) —O] _{m ′} —Y ²² — or —Y ²¹ —O—. A group represented by C (═O) —Y ²² —, wherein Y ²¹ and Y ²² are each independently a divalent hydrocarbon group which may have a substituent, and O is an oxygen atom And m ′ is 0-3. Is a number. ] Etc. are mentioned.
When the divalent linking group containing a hetero atom is —C (═O) —NH—, —NH—, —NH—C (═NH) —, H is a substituent such as an alkyl group or acyl. May be substituted. The substituent (alkyl group, acyl group, etc.) preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and particularly preferably 1 to 5 carbon atoms.
Formula ^{-Y 21 -O-Y 22 -,} - Y 21 -O -, - Y 21 -C (= O) -O -, - C (= O) -O-Y 21, - [Y 21 -C ( ═O) —O] _{m ′} —Y ²² — or —Y ²¹ —O—C (═O) —Y ²² —, wherein Y ²¹ and Y ²² each independently have a substituent. It is a good divalent hydrocarbon group. Examples of the divalent hydrocarbon group include those similar to the “divalent hydrocarbon group optionally having substituent (s)” mentioned in the description of the divalent linking group.
Y ²¹ is preferably a linear aliphatic hydrocarbon group, more preferably a linear alkylene group, still more preferably a linear alkylene group having 1 to 5 carbon atoms, and particularly preferably a methylene group or an ethylene group. preferable.
Y ²² is preferably a linear or branched aliphatic hydrocarbon group, and more preferably a methylene group, an ethylene group or an alkylmethylene group. The alkyl group in the alkylmethylene group is preferably a linear alkyl group having 1 to 5 carbon atoms, more preferably a linear alkyl group having 1 to 3 carbon atoms, and most preferably a methyl group.
In the group represented by the formula — [Y ²¹ —C (═O) —O] _{m ′} —Y ²² —, m ′ is an integer of 0 to 3, preferably an integer of 0 to 2, Or 1 is more preferable, and 1 is particularly preferable. That is, the group represented by the formula — [Y ²¹ —C (═O) —O] _{m ′} —Y ²² — is represented by the formula —Y ²¹ —C (═O) —O—Y ²² —. The group is particularly preferred. Among these, a group represented by the formula — (CH ₂ ) _{a ′} —C (═O) —O— (CH ₂ ) _{b ′} — is preferable. In the formula, a ′ is an integer of 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 5, further preferably 1 or 2, and most preferably 1. b ′ is an integer of 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 5, more preferably 1 or 2, and most preferably 1.

In the present invention, Ya ⁰¹ and Yb ⁰¹ are preferably a linear or branched alkylene group, and include a methylene group [—CH ₂ —], an ethylene group [— (CH ₂ ) ₂ —], or trimethylene. More preferably, it is a group [— (CH ₂ ) ₃ —].

In general formula (p-3), Ra ⁰¹ is a hydrocarbon group which may have a substituent.
Examples of the hydrocarbon group in Ra ⁰¹ include a linear or branched aliphatic hydrocarbon group. The linear or branched aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6, and still more preferably 1 to 4.
As the linear aliphatic hydrocarbon group, a linear alkyl group is preferable, and specifically, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, Nonyl group, decyl group and the like can be mentioned, and a methyl group, an ethyl group, a propyl group or a butyl group is preferable.
Examples of the branched aliphatic hydrocarbon group include a branched alkyl group.
The aliphatic hydrocarbon group preferably has 3 to 20 carbon atoms, more preferably 3 to 15 carbon atoms, and most preferably 3 to 10 carbon atoms. Specific examples of the branched aliphatic hydrocarbon group include 1-methylethyl group, 1-methylpropyl group, 2-methylpropyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1 -Ethylbutyl group, 2-ethylbutyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group and the like can be mentioned.

Examples of the substituent that Ra ⁰¹ may have include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, and a carbonyl group.
The alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, more preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group.
The alkoxy group as the substituent is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, or a tert-butoxy group. Most preferred are a methoxy group and an ethoxy group.
Examples of the halogen atom as the substituent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferable.
Examples of the halogenated alkyl group as the substituent include groups in which part or all of the hydrogen atoms of the alkyl group have been substituted with the halogen atoms.
In the cyclic aliphatic hydrocarbon group, a part of carbon atoms constituting the ring structure may be substituted with a substituent containing a hetero atom. As the substituent containing the hetero atom, —O—, —C (═O) —O—, —S—, —S (═O) ₂ —, and —S (═O) ₂ —O— are preferable.
Among the above, the substituent that Ra ⁰¹ may have is preferably a hydroxyl group.

In General Formula (p-3), Ra ⁰² is a hydroxyl group or a hydrocarbon group having 1 to 6 carbon atoms which may have a substituent. Examples of the hydrocarbon group having 1 to 6 carbon atoms include linear or branched alkyl groups, such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, 1-methylethyl group, Examples include 1-methylpropyl group, 2-methylpropyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group and the like.
The hydrocarbon group having 1 to 6 carbon atoms of Ra ⁰² preferably has a substituent, and examples of the substituent include the same groups as those described as the substituent that Ra ⁰¹ may have. Can be mentioned.

The partial structures represented by the general formulas (p-1) and (p-3) are bonded at arbitrary positions with a bond portion represented by “*”, and further have an optional substituent between the bonds. You may do it.
The partial structures represented by the general formulas (p-1) and (p-3) may be bonded at random or may be bonded in a block shape.

In the general formula ^{(p-3), n 01} represents an integer of 0 to 5. In the general formula (p-3), when n ⁰¹ is 0, Ra ⁰¹ is preferably a hydrocarbon group having a hydroxyl group.

  The group represented by the general formula (p-3) is preferably a group represented by the general formula (p-3-1) or (p-3-2).

［式（ｐ−３−１）又は（ｐ−３−２）中、Ｙａ^０１、Ｙｂ^０１はそれぞれ独立に２価の連結基、Ｒａ^００１は置換基を有していてもよい直鎖状の炭化水素基、Ｒａ^００２は置換基を有していてもよい分岐鎖状の炭化水素基、Ｒａ^０２は水酸基又は置換基を有していてもよい炭素数１〜６の炭化水素基、ｎ^０１は０〜５の整数である。＊は結合手を示す。］

[In formula (p-3-1) or (p-3-2), Ya ⁰¹ and Yb ⁰¹ are each independently a divalent linking group, and Ra ⁰⁰¹ is a linear group which may have a substituent. A hydrocarbon group, Ra ⁰⁰² is a branched hydrocarbon group which may have a substituent, Ra ⁰² is a hydrocarbon group having 1 to 6 carbon atoms which may have a hydroxyl group or a substituent, n ⁰¹ Is an integer from 0 to 5. * Indicates a bond. ]

In the general formulas (p-3-1) and (p-3-2), the description of Yb ⁰¹ , Ya ⁰¹ , Ra ⁰² , n ⁰¹ is the same as described above.
Ra ⁰⁰¹ is a linear hydrocarbon group which may have a substituent, preferably a linear aliphatic hydrocarbon group, and the aliphatic hydrocarbon group has 1 to 10 carbon atoms. Are preferable, 1-6 are more preferable, and 1-4 are more preferable.
As the linear aliphatic hydrocarbon group, a linear alkyl group is preferable, and specifically, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, Nonyl group, decyl group and the like can be mentioned, and a methyl group, an ethyl group, a propyl group or a butyl group is preferable.
Ra ⁰⁰² is a branched hydrocarbon group which may have a substituent, and is preferably a branched aliphatic hydrocarbon group, and the branched aliphatic hydrocarbon group includes A chain alkyl group is preferred, and specifically, it is preferably 3 to 20 carbon atoms, more preferably 3 to 15 carbon atoms, and most preferably 3 to 10 carbon atoms. Specifically, for example, 1-methylethyl group, 1-methylpropyl group, 2-methylpropyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, Examples include 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group and the like.
Examples of the substituent that Ra ⁰⁰¹ or Ra ⁰⁰² may have include the same groups as those described as the substituent that Ra ⁰¹ may have.

Specific examples of the group represented by the general formula (p-3-1) are given below. In the following formulae, the description of Yb ⁰¹ and Ya ⁰¹ is the same as described above, and * is a bond.

Specific examples of the group represented by the general formula (p-3-2) are given below. In the following formulae, the description of Yb ⁰¹ and Ya ⁰¹ is the same as described above, and * is a bond.

The copolymer according to the first aspect of the present invention is a copolymer of an alkoxysilane having two or more functional groups, and has a partial structure represented by the general formulas (p-1) and (p-3). If so, it may have a trifunctional partial structure represented by the following general formula (p-6) and a tetrafunctional partial structure represented by the following general formula (p-7). In the following formulae, R ⁴ is the same as described above, and * is a bond.

  Moreover, you may use pentafunctional or more alkoxysilane. Examples of such alkoxysilanes include bistrimethoxysilylmethane, bistrimethoxysilylethane, and bistrimethoxysilylhexane.

The copolymer of the first aspect of the present invention comprises a partial structure of a bifunctional alkoxysilane represented by the general formula (p-1) and a trifunctional group represented by the general formula (p-3). It has a partial structure of alkoxysilane and has a non-hydrolyzable group in the molecule. Therefore, it can be set as a highly flexible copolymer.
For this reason, for example, when the copolymer of the present invention is used as a filtration material, a column or the like can be easily packed. Moreover, since it has a high porosity, it can have a high specific surface area and excellent solvent absorbability.
The copolymer of the first aspect of the present invention comprises a bifunctional alkoxysilane represented by the general formula (p-1) and a trifunctional alkoxysilane represented by the general formula (p-3). From the starting composition containing both, it can be conveniently obtained through a metal-free process. For this reason, it can use suitably for the filtration material for removing metal impurities, such as a metal particle and a metal ion.

  As described above, the copolymer of the first aspect of the present invention includes a bifunctional alkoxysilane represented by the general formula (p-1) and a trifunctional represented by the general formula (p-3). The starting composition containing both of the alkoxysilanes can be obtained by forming a network of Si—O bonds by a copolymerization reaction. At this time, the ratio of the bifunctional alkoxysilane and the trifunctional alkoxysilane can be appropriately adjusted by adjusting the amount of the trifunctional alkoxysilane added. By adjusting the ratio of the bifunctional alkoxysilane and the trifunctional alkoxysilane, the pore diameter and flexibility of the copolymer can be adjusted.

In the copolymer according to the first aspect of the present invention, the compounding ratio of the partial structures represented by the general formulas (p-1) and (p-3) is not particularly limited. The abundance is preferably 10 to 90%.
In the present invention, the blending ratio of the partial structure represented by the general formula (p-1) in the copolymer is preferably 10 to 90%, more preferably 20 to 80%, It is particularly preferred that it is ˜50%.
In the present invention, the blending ratio of the partial structure represented by the general formula (p-3) in the copolymer is preferably 10 to 90%, more preferably 20 to 80%, It is particularly preferred that it is ˜70%.
The upper limit value and lower limit value of the compounding ratio of the partial structures represented by the general formulas (p-1) and (p-3) in the copolymer can be arbitrarily combined.
In the copolymer of the present invention, the blending ratio of the partial structures represented by the general formulas (p-1) and (p-3) may be appropriately adjusted depending on desired characteristics. For example, by adjusting the blending ratio of the partial structure represented by the general formula (p-1), the flexibility of the copolymer can be controlled, and the blending ratio of the partial structure represented by the general formula (p-3). By adjusting the ratio, the porosity of the copolymer can be controlled.
Further, from the viewpoint of making the pore diameter of the copolymer finer, it is preferable that the amount of the trifunctional alkoxysilane is larger than the amount of the bifunctional alkoxysilane.

  A second aspect of the present invention is a copolymer of alkoxysilanes having two or more functional groups, and having a partial structure represented by the following general formulas (p-1) and (p-5). is there.

［式中、Ｒ^４及びＲ^５はそれぞれ独立に、置換基を有していてもよい炭化水素基、又は水酸基を表し、Ｒ^４及びＲ^５の一方は、アルコキシシラン共重合体中の他のケイ素原子と結合して、架橋構造を形成していてもよい。Ｙａ^０１及びＹｂ^０１はそれぞれ独立に、２価の連結基を表し、Ｒａ^０１は置換基を有していてもよい炭化水素基を表し、Ｒａ^０２は水酸基又は置換基を有していてもよい炭素数１〜６の炭化水素基を表す。ｎ^０１は０〜５の整数である。＊は結合手を示す。］

[Wherein, R ⁴ and R ⁵ each independently represents a hydrocarbon group which may have a substituent, or a hydroxyl group, and one of R ⁴ and R ⁵ represents the other in the alkoxysilane copolymer. It may combine with a silicon atom to form a crosslinked structure. Ya ⁰¹ and Yb ⁰¹ each independently represent a divalent linking group, Ra ⁰¹ represents a hydrocarbon group which may have a substituent, and Ra ⁰² may have a hydroxyl group or a substituent. Represents a hydrocarbon group having 1 to 6 carbon atoms. n ⁰¹ is an integer of 0 to 5. * Indicates a bond. ]

In the above formula, the description of R ⁴ , R ⁵ , Ya ⁰¹ , Yb ⁰¹ , Ra ⁰¹ , Ra ⁰² , n ⁰¹ is the same as described above.

  The group represented by the general formula (p-5) is preferably a group represented by the general formula (p-5-1) or (p-5-2).

［式（ｐ−５−１）及び（ｐ−５−２）中、Ｙａ^０１及びＹｂ^０１は、それぞれ独立に２価の連結基、Ｒａ^００１は置換基を有していてもよい直鎖状の炭化水素基、Ｒａ^００２は置換基を有していてもよい分岐鎖状の炭化水素基、Ｒａ^０２は水酸基又は置換基を有していてもよい炭素数１〜６の炭化水素基、ｎ^０１は０〜５の整数である。＊は結合手を示す。］

[In the formulas (p-5-1) and (p-5-2), Ya ⁰¹ and Yb ⁰¹ are each independently a divalent linking group, and Ra ⁰⁰¹ is a linear group which may have a substituent. Ra ⁰⁰² is a branched hydrocarbon group which may have a substituent, Ra ⁰² is a hydrocarbon group having 1 to 6 carbon atoms which may have a hydroxyl group or a substituent, n ⁰¹ is an integer of 0-5. * Indicates a bond. ]

In the general formulas (p-5-1) and (p-5-2), description of Ya ⁰¹ , Yb ⁰¹ , Ra ⁰² , n ⁰¹ , Ra ⁰⁰¹ , and Ra ⁰⁰² is the same as described above.

Specific examples of the group represented by the general formula (p-5-1) are given below. In the following formulae, the explanation for Ya ⁰¹ and Yb ⁰¹ is the same as described above, and * is a bond.

Specific examples of the group represented by the general formula (p-5-2) are given below. In the following formulae, the explanation for Ya ⁰¹ and Yb ⁰¹ is the same as described above, and * is a bond.

The copolymer according to the second aspect of the present invention is a copolymer of alkoxysilane having two or more functional groups, and has a partial structure represented by the general formulas (p-1) and (p-5). If so, it may have a trifunctional partial structure represented by the following general formula (p-6) and a tetrafunctional partial structure represented by the following general formula (p-7). In the following formulae, R ⁴ is the same as described above, and * is a bond.

  Moreover, you may use pentafunctional or more alkoxysilane. Examples of such alkoxysilanes include bistrimethoxysilylmethane, bistrimethoxysilylethane, and bistrimethoxysilylhexane.

The copolymer of the second aspect of the present invention comprises a partial structure of a bifunctional alkoxysilane represented by the general formula (p-1) and a trifunctional functional group represented by the general formula (p-5). It has a partial structure of alkoxysilane and has non-hydrolyzability in the molecule. Therefore, a copolymer having both high flexibility and high porosity can be obtained.
For this reason, for example, when the copolymer of the present invention is used as a filtration material, a column or the like can be easily packed. Moreover, since it has a high porosity, it can have a high specific surface area and excellent solvent absorbability.
The copolymer of the second aspect of the present invention comprises a bifunctional alkoxysilane represented by the general formula (p-1) and a trifunctional alkoxysilane represented by the general formula (p-5). From the starting composition containing both, it can be conveniently obtained through a metal-free process. For this reason, it can use suitably for the filtration material for removing metal impurities, such as a metal particle and a metal ion.

  As described above, the copolymer of the second aspect of the present invention includes a bifunctional alkoxysilane represented by the general formula (p-1) and a trifunctional represented by the general formula (p-5). The starting composition containing both of the alkoxysilanes can be obtained by forming a network of Si—O bonds by a copolymerization reaction. At this time, the ratio of the bifunctional alkoxysilane and the trifunctional alkoxysilane can be appropriately adjusted by adjusting the amount of the trifunctional alkoxysilane added. By adjusting the ratio of the bifunctional alkoxysilane and the trifunctional alkoxysilane, the pore diameter and flexibility of the copolymer can be adjusted.

In the copolymer according to the second aspect of the present invention, the compounding ratio of the partial structures represented by the general formulas (p-1) and (p-5) is not particularly limited. The abundance is preferably 10 to 90%.
In the present invention, the blending ratio of the partial structure represented by the general formula (p-1) in the copolymer is preferably 10 to 90%, more preferably 20 to 80%, and more preferably 30 to Particularly preferred is 50%.
In the present invention, the blending ratio of the partial structure represented by the general formula (p-5) in the copolymer is preferably 10 to 90%, more preferably 20 to 80%, and more preferably 50 to 70% is particularly preferable.
The upper limit value and lower limit value of the compounding ratio of the partial structures represented by the general formulas (p-1) and (p-5) in the copolymer can be arbitrarily combined.
In the copolymer of the present invention, the blending ratio of the partial structures represented by the general formulas (p-1) and (p-5) may be appropriately adjusted depending on desired characteristics. For example, the flexibility of the copolymer can be controlled by adjusting the blending ratio of the partial structure represented by the general formula (p-1), and the blending ratio of the partial structure represented by the general formula (p-5). By adjusting the ratio, the porosity of the copolymer can be controlled.
Further, from the viewpoint of making the pore diameter of the copolymer finer, it is preferable that the amount of the trifunctional alkoxysilane is larger than the amount of the bifunctional alkoxysilane.

<< Method 1 for producing copolymer >>
In the third aspect of the present invention, a compound represented by the following general formula (1) and a compound represented by the following general formula (2) are reacted to produce the following general formulas (p-1) and (p -2) to obtain a copolymer (A) having a partial structure represented by the formula (A), and to modify the copolymer (A) obtained in the above-mentioned step A, the following general formula (p-B-1) Step B to obtain a copolymer (B) having a partial structure represented by formula (1) and the copolymer (B) obtained in the step B are modified to give the following general formulas (p-3) and (p-1): And a step C for obtaining a copolymer (C) having a partial structure, which is a method for producing a copolymer of the present invention.

［式中、Ｒ^１〜Ｒ^３、及びＲ^６〜Ｒ^７はそれぞれ独立に、炭素数１〜５のアルキル基を表し、Ｒ^４及びＲ^５はそれぞれ独立に、置換基を有していてもよい炭化水素基、又は水酸基を表し、Ｒ^４及びＲ^５の一方は、アルコキシシラン共重合体中の他のケイ素原子と結合して、架橋構造を形成していてもよい。Ｙａ^０１及びＹｂ^０１はそれぞれ独立に、２価の連結基を表し、Ｒａ^０１は置換基を有していてもよい炭化水素基を表し、Ｒａ^０２は水酸基又は置換基を有していてもよい炭素数１〜６の炭化水素基を表す。ｎ^０１は０〜５の整数である。＊は結合手を示す。］

[Wherein, R ^{1 to} R ³ and R ^{6 to} R ⁷ each independently represent an alkyl group having 1 to 5 carbon atoms, and R ⁴ and R ⁵ may each independently have a substituent. It represents a good hydrocarbon group or a hydroxyl group, and one of R ⁴ and R ⁵ may be bonded to another silicon atom in the alkoxysilane copolymer to form a crosslinked structure. Ya ⁰¹ and Yb ⁰¹ each independently represent a divalent linking group, Ra ⁰¹ represents a hydrocarbon group which may have a substituent, and Ra ⁰² may have a hydroxyl group or a substituent. Represents a hydrocarbon group having 1 to 6 carbon atoms. n ⁰¹ is an integer of 0 to 5. * Indicates a bond. ]

In the general formulas (1), (2), (p-1), (p-2), (p-B-1) and (p-3), R ⁴ , R ⁵ , Ya ⁰¹ , Yb ⁰¹ , The description of Ra ⁰¹ , Ra ⁰² and n ⁰¹ is the same as described above.
R ^{1 to} R ³ and R ^{6 to} R ⁷ are each independently an alkyl group having 1 to 5 carbon atoms. Examples of the alkyl group having 1 to 5 carbon atoms include 1 to C carbon atoms in R ⁴ and R ⁵ . This is the same as the description of the alkyl group of 5.

[Step A]
Step A is a reaction represented by the above general formulas (p-1) and (p-2) by reacting the compound represented by the general formula (1) with the compound represented by the general formula (2). This is a step of obtaining a copolymer (A) having a partial structure.
In Step A, a bifunctional alkoxysilane represented by the general formula (2) and a trifunctional alkoxysilane represented by the general formula (1) are added to an acidic solution containing a surfactant and a hydrolyzable compound. It is preferable to obtain the copolymer (A) by a sol-gel reaction.
Hereinafter, the preferable form of the process A is demonstrated.
First, using an acidic solution, the compound represented by the general formula (1) and the compound represented by the general formula (2) are hydrolyzed to sol the silicon compound. Examples of the acid in the acidic solution include carboxylic acids, and acetic acid, formic acid, propionic acid, oxalic acid, and malonic acid are preferable, and acetic acid is more preferable. The concentration of the acidic solution is preferably 0.0001 to 0.2M, and more preferably 0.002 to 0.1M.
Examples of the surfactant contained in the acidic solution include a nonionic surfactant and an ionic surfactant. An ionic surfactant is preferable, and a cationic surfactant is more preferable.
Examples of the cationic surfactant include hexadecyltrimethylammonium chloride and hexadecyltrimethylammonium bromide, and hexadecyltrimethylammonium chloride is preferable.
In the surfactant, the compound represented by the general formula (1) and the compound represented by the general formula (2) are hydrolyzed and polycondensed to cause R ⁴ or R in the general formula (2). ^When a siloxane network is formed while maintaining a non-hydrolyzable functional group such as ⁵ , the difference in chemical affinity between the solvent in the reaction system and the copolymer (A) is reduced. By reducing this difference, the pores in the copolymer become finer.
The hydrolyzable compound contained in the acidic solution is for promoting gelation of the produced sol. Examples of the hydrolyzable compound include urea, formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, hexamethylenetetramine, and urea is preferable.
The heating temperature for hydrolyzing the compound represented by the general formula (1) and the compound represented by the general formula (2) is preferably 50 to 200 ° C, more preferably 60 to 100 ° C. preferable.
Next, in order to remove moisture, acidic solution, surfactant, hydrolyzable compound, unreacted silicon compound material, etc. remaining in the gel obtained by the sol-gel reaction, a solvent using an organic polar solvent is used. It is preferable to perform the exchange.
In step A, a flexible gel network can be constructed by networking Si—O bonds.
In Step A, in addition to the compound represented by the general formula (1) and the compound represented by the general formula (2), a trifunctional compound, a tetrafunctional compound, a tetrafunctional compound or more may be added. Good.

[Step B]
Step B is a step of modifying the copolymer (A) obtained in Step A to obtain a copolymer (B) having a partial structure represented by the general formula (p-B-1). .
In step B, the copolymer (A) obtained in step A is modified with an amino group. Although the method of modifying with an amino group is not particularly limited, for example, a thiol-ene reaction using a compound represented by the following general formula (b1) can be employed.

［式中、Ｙａ^０１は前記同様である。］

[Wherein Ya ⁰¹ is the same as defined above. ]

[Step C]
Step C modifies the copolymer (B) obtained in Step B to obtain a copolymer (C) represented by the general formulas (p-3) and (p-1) and having a partial structure. It is a process.
Step C is carried out, for example, on a copolymer (B) modified with an amino group according to the method described in non-patent literature (A. Goswami et al, Anal. Chimi. Acta 2002 454, 229-240). It can be obtained by reacting the compound represented by (a0).

［上記式中、Ｒａ^０１は置換基を有していてもよい炭化水素基、Ｒａ^０２は水酸基又は置換基を有していてもよい炭素数１〜６の炭化水素基、ｎ^０１は０〜５の整数である。］

[In the above formula, Ra ⁰¹ is an optionally substituted hydrocarbon group, Ra ⁰² is a hydroxyl group or an optionally substituted hydrocarbon group having 1 to 6 carbon atoms, and n ⁰¹ is 0 to 0. It is an integer of 5. ]

The description of Ra ⁰¹ , Ra ⁰² and n ⁰¹ is the same as described above.

<< Method 2 for producing copolymer >>
In the fourth aspect of the present invention, a compound represented by the following general formula (3) is reacted with a compound represented by the following general formula (2) to produce the following general formulas (p-1) and (p -4) The process X to obtain the copolymer (X) having the partial structure represented by the formula, and the copolymer (X) obtained in the process X are modified to give the following general formula (pY-1) Step Y for obtaining a copolymer (Y) having a partial structure represented by formula (1) and the copolymer (Y) obtained in the step Y are modified to give the following general formulas (p-5) and (p-1): And a step Z for obtaining a copolymer (Z) having a partial structure represented by the formula (1): a method for producing a copolymer according to the second aspect of the present invention.

［式中、Ｒ^１〜Ｒ^３、及びＲ^６〜Ｒ^７はそれぞれ独立に、炭素数１〜５のアルキル基を表し、Ｒ^４及びＲ^５はそれぞれ独立に、置換基を有していてもよい炭化水素基、又は水酸基を表し、Ｒ^４及びＲ^５の一方は、アルコキシシラン共重合体中の他のケイ素原子と結合して、架橋構造を形成していてもよい。Ｙａ^０１及びＹｂ^０１はそれぞれ独立に、２価の連結基を表し、Ｒａ^０１は置換基を有していてもよい炭化水素基を表し、Ｒａ^０２は水酸基又は置換基を有していてもよい炭素数１〜６の炭化水素基を表す。ｎ^０１は０〜５の整数である。＊は結合手を示す。］

[Wherein, R ^{1 to} R ³ and R ^{6 to} R ⁷ each independently represent an alkyl group having 1 to 5 carbon atoms, and R ⁴ and R ⁵ may each independently have a substituent. It represents a good hydrocarbon group or a hydroxyl group, and one of R ⁴ and R ⁵ may be bonded to another silicon atom in the alkoxysilane copolymer to form a crosslinked structure. Ya ⁰¹ and Yb ⁰¹ each independently represent a divalent linking group, Ra ⁰¹ represents a hydrocarbon group which may have a substituent, and Ra ⁰² may have a hydroxyl group or a substituent. Represents a hydrocarbon group having 1 to 6 carbon atoms. n ⁰¹ is an integer of 0 to 5. * Indicates a bond. ]

In the general formulas (3), (2), (p-1), (p-4), (p-Y-1) and (p-5), R ⁴ , R ⁵ , Ya ⁰¹ , Yb ⁰¹ , The description of Ra ⁰¹ , Ra ⁰² and n ⁰¹ is the same as described above.
R ^{1 to} R ³ and R ^{6 to} R ⁷ are each independently an alkyl group having 1 to 5 carbon atoms. Examples of the alkyl group having 1 to 5 carbon atoms include 1 to C carbon atoms in R ⁴ and R ⁵ . This is the same as the description of the alkyl group of 5.

[Step X]
Step X is a reaction represented by the above general formulas (p-1) and (p-4) by reacting the compound represented by the general formula (3) with the compound represented by the general formula (2). In this step, a copolymer (X) having a partial structure is obtained.
In Step X, a bifunctional alkoxysilane represented by the general formula (2) and a trifunctional alkoxysilane represented by the general formula (3) are added to an acidic solution containing a surfactant and a hydrolyzable compound. In addition, it is preferable to obtain the copolymer (X) by a sol-gel reaction.
Hereinafter, the preferable form of the process X is demonstrated.
First, using an acidic solution, the compound represented by the general formula (3) and the compound represented by the general formula (2) are hydrolyzed to sol the silicon compound. Examples of the acid in the acidic solution include carboxylic acids, and acetic acid, formic acid, propionic acid, oxalic acid, and malonic acid are preferable, and acetic acid is more preferable. The concentration of the acidic solution is preferably 0.0001 to 0.2M, and more preferably 0.002 to 0.1M.
Examples of the surfactant contained in the acidic solution include a nonionic surfactant and an ionic surfactant. An ionic surfactant is preferable, and a cationic surfactant is more preferable.
Examples of the cationic surfactant include hexadecyltrimethylammonium chloride and hexadecyltrimethylammonium bromide, and hexadecyltrimethylammonium chloride is preferable.
In the surfactant, the compound represented by the general formula (3) and the compound represented by the general formula (2) are subjected to hydrolysis / condensation polymerization reaction, whereby R ⁴ and R in the general formula (2) ^When a siloxane network is formed while maintaining a non-hydrolyzable functional group such as ⁵ , the difference in chemical affinity between the solvent in the reaction system and the copolymer (X) is reduced. By reducing this difference, the pores in the copolymer become finer.
The hydrolyzable compound contained in the acidic solution is for promoting gelation of the produced sol. Examples of the hydrolyzable compound include urea, formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, hexamethylenetetramine, and urea is preferable.
The heating temperature for hydrolyzing the compound represented by the general formula (3) and the compound represented by the general formula (2) is preferably 50 to 200 ° C, more preferably 60 to 100 ° C. preferable.
Next, in order to remove moisture, acidic solution, surfactant, hydrolyzable compound, unreacted silicon compound material, etc. remaining in the gel obtained by the sol-gel reaction, a solvent using an organic polar solvent is used. It is preferable to perform the exchange.
In step X, a flexible gel network can be constructed by networking Si—O bonds.
In Step X, in addition to the compound represented by the general formula (3) and the compound represented by the general formula (2), a trifunctional compound, a tetrafunctional compound, a tetrafunctional compound or more may be added. Good.

[Step Y]
Step Y is a step of modifying the copolymer (X) obtained in the step X to obtain a copolymer (Y) having a partial structure represented by the general formula (p-Y-1). .
Step Y modifies the copolymer (X) obtained in Step X with an amino group. Although the method of modifying with an amino group is not particularly limited, for example, a Williamson ether reaction using an amine alcohol represented by the following general formula (b2) can be employed.

［式中、Ｙａ^０１は前記同様である。］

[Wherein Ya ⁰¹ is the same as defined above. ]

[Step Z]
Step Z modifies the copolymer (Y) obtained in Step Y to obtain a copolymer (Z) represented by the above general formulas (p-5) and (p-1) and having a partial structure. It is a process.
Step Z is carried out, for example, on a copolymer (Y) modified with an amino group according to the method described in non-patent literature (A. Goswami et al, Anal. Chimi. Acta 2002 454, 229-240), It can be obtained by reacting the compound represented by (a0).

［上記式中、Ｒａ^０１は置換基を有していてもよい炭化水素基、Ｒａ^０２は水酸基又は置換基を有していてもよい炭素数１〜６の炭化水素基、ｎ^０１は０〜５の整数である。］

[In the above formula, Ra ⁰¹ is an optionally substituted hydrocarbon group, Ra ⁰² is a hydroxyl group or an optionally substituted hydrocarbon group having 1 to 6 carbon atoms, and n ⁰¹ is 0 to 0. It is an integer of 5. ]

The description of Ra ⁰¹ , Ra ⁰² and n ⁰¹ is the same as described above.

≪Copolymer≫
A fifth aspect of the present invention is a copolymer of alkoxysilanes having two or more functional groups, and having a partial structure represented by the following general formulas (p-1) and (p-4). is there.

［式中、Ｒ^４及びＲ^５はそれぞれ独立に、炭素数１〜５のアルキル基、Ｒ^４及びＲ^５の一方は水酸基であってもよく、アルコキシシラン共重合体中の他のケイ素原子と結合して、架橋構造を形成していてもよい。
Ｙｂ^０２は、２価の連結基、＊は結合手を示す。］

[Wherein, R ⁴ and R ⁵ are each independently an alkyl group having 1 to 5 carbon atoms, one of R ⁴ and R ⁵ may be a hydroxyl group, and other silicon atoms in the alkoxysilane copolymer; It may combine to form a crosslinked structure.
Yb ⁰² represents a divalent linking group, and * represents a bond. ]

In the above formula, R ⁴ , R ⁵ and Yb ⁰² are the same as described above.

<Organic solvent>
An organic solvent capable of removing impurities with high removal efficiency by using the copolymer of the present invention will be described.
Examples of the organic solvent (hereinafter sometimes referred to as (S) component) include those known as resist solvents used in resist compositions.
For example, lactones such as γ-butyrolactone; ketones such as acetone, methyl ethyl ketone (MEK), cyclohexanone, methyl-n-pentyl ketone (2-heptanone), methyl isopentyl ketone; ethylene glycol, diethylene glycol, propylene glycol, di- Polyhydric alcohols such as propylene glycol; compounds having an ester bond such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, dipropylene glycol monoacetate, the polyhydric alcohols or compounds having the ester bond Monoalkyl ethers such as monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether or monophenyl ether Polyhydric alcohol derivatives [Among these, such a compound having an ether bond etc., propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME) are preferable examples thereof include. ]; Esters such as cyclic ethers such as dioxane, methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate An aromatic organic solvent such as anisole, ethyl benzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenetol, butyl phenyl ether, ethylbenzene, diethylbenzene, pentylbenzene, isopropylbenzene, toluene, xylene, cymene, mesitylene, Examples thereof include nitrile organic solvents such as dimethyl sulfoxide (DMSO) and acetonitrile.
These organic solvents may be used as a liquid to be filtered in a single state, or may be used as a liquid to be filtered as a mixed solvent of two or more kinds.
Of these, cyclohexanone or a mixed solvent with cyclohexanone is preferable.
Moreover, the mixed solvent which mixed PGMEA and the polar solvent is also mentioned as a preferable thing.

<Resist composition>
A resist composition capable of removing impurities with high removal efficiency by using the copolymer of the present invention will be described.
The resist composition includes a base material component (A) whose solubility in a developer is changed by the action of an acid (hereinafter referred to as “component (A)”), and an acid generator component (B) that generates an acid upon exposure. (Hereinafter referred to as “component (B)”), a quencher (acid diffusion controller) that traps acid generated by exposure from the component (B) or the like (hereinafter referred to as “component (D)”), organic At least one compound (E) selected from the group consisting of carboxylic acids and phosphorus oxo acids and derivatives thereof (hereinafter referred to as “component (E)”), a fluorine additive (hereinafter referred to as “component (F)”). ) And the like are dissolved in the organic solvent (hereinafter sometimes referred to as component (S)).

  When a resist film is formed using such a resist composition and the resist film is selectively exposed, an acid is generated from the component (B) in the exposed portion, and the component (A) is generated by the action of the acid. The solubility of the component (A) in the developing solution does not change in the unexposed area, so that there is a difference in solubility in the developing solution between the exposed area and the unexposed area. Arise. For this reason, when the resist film is developed, when the resist composition is positive, the exposed portion is dissolved and removed to form a positive resist pattern. When the resist composition is negative, the unexposed portion is formed. A negative resist pattern is formed by dissolution and removal.

<(A) component>
In the present invention, the “base component” is an organic compound having a film forming ability, and preferably an organic compound having a molecular weight of 500 or more is used. When the molecular weight of the organic compound is 500 or more, the film forming ability is improved, and in addition, a nano-level resist pattern is easily formed.
Organic compounds used as the base material component are roughly classified into non-polymers and polymers.
As the non-polymer, those having a molecular weight of 500 or more and less than 4000 are usually used. Hereinafter, the “low molecular compound” refers to a non-polymer having a molecular weight of 500 or more and less than 4000.
As the polymer, those having a molecular weight of 1000 or more are usually used. Hereinafter, the term “resin” refers to a polymer having a molecular weight of 1000 or more.
As a molecular weight of the polymer, a weight average molecular weight in terms of polystyrene by GPC (gel permeation chromatography) is used.
As the component (A), a resin may be used, a low molecular compound may be used, or these may be used in combination.
Component (A) may have increased solubility in a developer due to the action of an acid, or may decrease solubility in a developer due to the action of an acid.
In the present invention, the component (A) may generate an acid upon exposure.

As the component (A), the structural unit (a1) containing an acid-decomposable group whose polarity is increased by the action of an acid.
Structural unit (a2) containing a lactone-containing cyclic group (excluding those corresponding to the structural unit (a1) described above), Structural unit (a3) containing a polar group-containing aliphatic hydrocarbon group (provided above) Constitutional unit (a1), excluding those corresponding to (a2)), constitutional unit (a4) containing a non-acid-dissociable cyclic group, constitution containing a carbonate-containing cyclic group, or —SO ₂ -containing cyclic group It preferably has units (a5) and the like.

(Structural unit (a1))
The structural unit (a1) is a structural unit containing an acid-decomposable group whose polarity is increased by the action of an acid.
The “acid-decomposable group” is an acid-decomposable group that can cleave at least part of bonds in the structure of the acid-decomposable group by the action of an acid.
Examples of the acid-decomposable group whose polarity increases by the action of an acid include a group that decomposes by the action of an acid to generate a polar group.
Examples of the polar group include a carboxy group, a hydroxyl group, an amino group, a sulfo group (—SO ₃ H), and the like. Among these, a polar group containing —OH in the structure (hereinafter sometimes referred to as “OH-containing polar group”) is preferable, a carboxy group or a hydroxyl group is preferable, and a carboxy group is particularly preferable.
More specifically, examples of the acid-decomposable group include groups in which the polar group is protected with an acid-dissociable group (for example, a group in which a hydrogen atom of an OH-containing polar group is protected with an acid-dissociable group).
Here, “acid-dissociable group” means
(I) an acid-dissociable group capable of cleaving a bond between the acid-dissociable group and an atom adjacent to the acid-dissociable group by the action of an acid, or
(Ii) a group capable of cleaving a bond between the acid-dissociable group and an atom adjacent to the acid-dissociable group by further decarboxylation reaction after partial bond cleavage by the action of an acid ,
Both.
The acid-dissociable group constituting the acid-decomposable group needs to be a group having a lower polarity than the polar group generated by dissociation of the acid-dissociable group. Is dissociated, a polar group having a polarity higher than that of the acid dissociable group is generated to increase the polarity. As a result, the polarity of the entire component (A1) increases. As the polarity increases, the solubility in the developer changes relatively, and when the developer is an organic developer, the solubility decreases.

  The acid-dissociable group is not particularly limited, and those that have been proposed as acid-dissociable groups for base resins for chemically amplified resists can be used.

  The proportion of the structural unit (a1) in the component (A) is preferably from 20 to 80 mol%, more preferably from 20 to 75 mol%, more preferably from 25 to 70 mol%, based on all structural units constituting the component (A). Is more preferable.

(Structural unit (a2))
The structural unit (a2) is a lactone-containing cyclic group.
The lactone-containing cyclic group of the structural unit (a2) is effective in enhancing the adhesion of the resist film to the substrate when the component (A1) is used for forming the resist film.

  The “lactone-containing cyclic group” refers to a cyclic group containing a ring (lactone ring) containing —O—C (═O) — in the ring skeleton. The lactone ring is counted as the first ring. When only the lactone ring is present, it is called a monocyclic group, and when it has another ring structure, it is called a polycyclic group regardless of the structure. The lactone-containing cyclic group may be a monocyclic group or a polycyclic group.

The structural unit (a2) contained in the component (A) may be one type or two or more types.
When the component (A) has the structural unit (a2), the proportion of the structural unit (a2) is preferably 1 to 80 mol% with respect to the total of all the structural units constituting the component (A). It is more preferably 5 to 70 mol%, further preferably 10 to 65 mol%, and particularly preferably 10 to 60 mol%.

(Structural unit (a3))
The structural unit (a3) is a structural unit containing a polar group-containing aliphatic hydrocarbon group (except for those corresponding to the structural units (a1) and (a2) described above).
It is considered that when the component (A) has the structural unit (a3), the hydrophilicity of the component (A) is increased and the resolution is improved.
Examples of the polar group include a hydroxyl group, a cyano group, a carboxy group, and a hydroxyalkyl group in which a part of hydrogen atoms of an alkyl group is substituted with a fluorine atom. A hydroxyl group is particularly preferable.
Examples of the aliphatic hydrocarbon group include a linear or branched hydrocarbon group having 1 to 10 carbon atoms (preferably an alkylene group) and a cyclic aliphatic hydrocarbon group (cyclic group). The cyclic group may be a monocyclic group or a polycyclic group. For example, a resin for a resist composition for an ArF excimer laser can be appropriately selected from those proposed. The cyclic group is preferably a polycyclic group, and more preferably 7 to 30 carbon atoms.

The structural unit (a3) contained in the component (A) may be one type or two or more types.
In the component (A), the proportion of the structural unit (a3) is preferably 5 to 50 mol%, more preferably 5 to 40 mol%, based on the total of all structural units constituting the component (A). 5 to 25 mol% is more preferable.

(Structural unit (a4))
The structural unit (a4) is a structural unit containing an acid non-dissociable cyclic group. When the component (A) has the structural unit (a4), the dry etching resistance of the formed resist pattern is improved.
The “acid non-dissociable cyclic group” in the structural unit (a4) is a ring that remains in the structural unit without being dissociated even when the acid acts when an acid is generated from the component (B) by exposure. Formula group.
When the structural unit (a4) is contained in the component (A), the proportion of the structural unit (a4) is preferably 1 to 30 mol% with respect to the total of all the structural units constituting the component (A). More preferably, it is 10-20 mol%.

The structural unit (a5) is a structural unit containing a —SO ₂ — containing cyclic group or a carbonate containing cyclic group.

The “—SO ₂ -containing cyclic group” refers to a cyclic group containing a ring containing —SO ₂ — in the ring skeleton, specifically, the sulfur atom (S) in —SO ₂ — is It is a cyclic group that forms part of the ring skeleton of the cyclic group. The ring containing —SO ₂ — in the ring skeleton is counted as the first ring, and when it is only the ring, it is a monocyclic group, and when it has another ring structure, it is a polycyclic group regardless of the structure. Called. The —SO ₂ — containing cyclic group may be monocyclic or polycyclic.
The —SO ₂ — containing cyclic group as the cyclic hydrocarbon group in R ¹ is particularly a cyclic group containing —O—SO ₂ — in its ring skeleton, that is, —O— in —O—SO ₂ —. -S- is preferably a cyclic group containing a sultone ring that forms part of the ring skeleton.

  The “carbonate-containing cyclic group” refers to a cyclic group containing a ring (carbonate ring) containing —O—C (═O) —O— in the ring skeleton. When the carbonate ring is counted as the first ring, the carbonate ring alone is called a monocyclic group, and when it has another ring structure, it is called a polycyclic group regardless of the structure. The carbonate-containing cyclic group may be a monocyclic group or a polycyclic group.

The structural unit (a5) contained in the component (A) may be one type or two or more types.
When the component (A) has the structural unit (a5), the proportion of the structural unit (a5) is preferably 1 to 80 mol% with respect to the total of all the structural units constituting the component (A). It is more preferably 5 to 70 mol%, further preferably 10 to 65 mol%, and particularly preferably 10 to 60 mol%.

  In the present invention, the weight average molecular weight (Mw) of the component (A) (polystyrene conversion standard by gel permeation chromatography) is not particularly limited, preferably 1000 to 50000, more preferably 1500 to 30000, 2000 ˜20,000 is most preferred.

In the resist composition of the present invention, as the component (A), one type may be used alone, or two or more types may be used in combination.
In the resist composition of the present invention, the content of the component (A) may be adjusted according to the resist film thickness to be formed.

<Acid generator component; (B) component>
The component (B) is an acid generator component that generates an acid upon exposure.
The component (B) is not particularly limited, and those that have been proposed as acid generators for chemically amplified resists can be used.
Examples of such acid generators include onium salt acid generators such as iodonium salts and sulfonium salts, oxime sulfonate acid generators, bisalkyl or bisarylsulfonyldiazomethanes, and diazomethanes such as poly (bissulfonyl) diazomethanes. Examples include an acid generator, a nitrobenzyl sulfonate acid generator, an imino sulfonate acid generator, and a disulfone acid generator. Of these, it is preferable to use an onium salt acid generator.

  When a resist composition contains (B) component, 0.5-60 mass parts is preferable with respect to 100 mass parts of (A) component, and, as for content of (B) component, 1-50 mass parts is more preferable. 1 to 40 parts by mass is more preferable. By forming the content of the component (B2) within the above range, pattern formation is sufficiently performed. Moreover, when each component of a resist composition is melt | dissolved in the organic solvent, since a uniform solution is obtained and storage stability becomes favorable, it is preferable.

<Acid diffusion controller component; component (D)>
Component (D) is an acid diffusion controller component.
The component (D) acts as a quencher (acid diffusion controller) that traps acid generated by exposure from the component (B) and the like.
The component (D) in the present invention may be a photodegradable base (D1) (hereinafter referred to as “(D1) component”) that is decomposed by exposure and loses acid diffusion controllability. A non-corresponding nitrogen-containing organic compound (D2) (hereinafter referred to as “component (D2)”) may be used.

  The content of the component (D1) is preferably 0.5 to 10.0 parts by mass and more preferably 0.5 to 8.0 parts by mass with respect to 100 parts by mass of the component (A). 1.0 to 8.0 parts by mass is even more preferable. When it is at least the lower limit of the above range, particularly good lithography properties and resist pattern shape can be obtained. When the amount is not more than the upper limit of the above range, the sensitivity can be maintained satisfactorily and the throughput is excellent.

[(D2) component]
(D) component may contain the nitrogen-containing organic compound component (henceforth (D2) component) which does not correspond to the said (D1) component.
The component (D2) is not particularly limited as long as it functions as an acid diffusion control agent and does not correspond to the component (D1), and any known component may be used. Of these, aliphatic amines, particularly secondary aliphatic amines and tertiary aliphatic amines are preferred.
An aliphatic amine is an amine having one or more aliphatic groups, and the aliphatic groups preferably have 1 to 12 carbon atoms.
Examples of the aliphatic amine include an amine (alkyl amine or alkyl alcohol amine) or a cyclic amine in which at least one hydrogen atom of ammonia NH ₃ is substituted with an alkyl group or hydroxyalkyl group having 12 or less carbon atoms.

(D2) A component may be used independently and may be used in combination of 2 or more type.
(D2) A component is normally used in 0.01-5.0 mass parts with respect to 100 mass parts of (A) component. By setting the content in the above range, the resist pattern shape, the stability over time and the like are improved.

(D) A component may be used individually by 1 type and may be used in combination of 2 or more type.
When the resist composition of this invention contains (D) component, it is preferable that (D) component is 0.1-15 mass parts with respect to 100 mass parts of (A) component, 0.3- More preferably, it is 12 mass parts, and it is still more preferable that it is 0.5-12 mass parts. When it is at least the lower limit of the above range, lithography properties such as LWR are further improved when a resist composition is used. Further, a better resist pattern shape can be obtained. When it is not more than the upper limit of the above range, the sensitivity can be maintained satisfactorily and the throughput is excellent.

<Optional component>
[(E) component]
At least one selected from the group consisting of organic carboxylic acids and phosphorus oxoacids and derivatives thereof as an optional component for the purpose of preventing sensitivity deterioration and improving the resist pattern shape, retention time stability, etc. Compound (E) (hereinafter referred to as component (E)) can be contained.
(E) A component may be used individually by 1 type and may use 2 or more types together.
(E) A component is normally used in 0.01-5.0 mass parts with respect to 100 mass parts of (A) component.

[(F) component]
In order to impart water repellency to the resist film, it may contain a fluorine additive (hereinafter referred to as “component (F)”).
Examples of the component (F) include JP 2010-002870 A, JP 2010-032994 A, JP 2010-277043 A, JP 2011-13569 A, and JP 2011-128226 A. The described fluorine-containing polymer compound can be used.

  The resist composition further contains miscible additives as desired, for example, additional resins for improving the performance of the resist film, dissolution inhibitors, plasticizers, stabilizers, colorants, antihalation agents, dyes, and the like. It can be added and contained as appropriate.

By using the copolymer of the present invention, impurities, particularly metal components, can be removed with high removal efficiency. A chemical solution such as a solvent used in the resist composition and various organic solvents contain metal components such as trace metal fine particles, trace metal, and trace metal ion impurities.
These metal components may be originally contained in the chemical solution, but may be mixed due to contamination from a chemical solution transfer path such as a pipe or a joint.
By using the copolymer of the present invention, lithium, sodium, magnesium, potassium, chromium, manganese, iron, cobalt, nickel, copper, zinc, strontium, molybdenum, silver, cadmium, tin, antimony, barium, lead, etc. The metal component can be removed.
By using the copolymer of the present invention, even if two or more kinds of the above-mentioned metal components are mixed, it can be removed.
Among the above, it is possible to effectively remove metal components having a high ionization tendency and zinc that is easily mixed due to contamination in the manufacturing process.

The copolymer of the present invention forms a predetermined chelate structure with a metal ion. The partial structures represented by the general formulas (p-1) and (p-5) specific to the present invention are as described above. Among them, a chelate structure is efficiently formed with lithium, sodium and potassium which are alkali metals. Therefore, the copolymer of the present invention can suitably remove these metals from the liquid to be filtered.
By using the copolymer of the present invention, the above trace metals can be removed regardless of the existence form of metal ions, metal fine particles and the like.

  By passing a resist composition or an organic solvent through the copolymer of the present invention (that is, a copolymer having a partial structure represented by general formulas (p-1) and (p-5)), the resist composition or The metal component concentration in the organic solvent can be less than 500 ppt (1 trillion fraction), further less than 100 ppt, and even less than 10 ppt.

(Filter filters for resist compositions or organic solvents)
The copolymer of the present invention can be suitably used as a material for a filter filter for a resist composition or an organic solvent. Examples of the filter include a filter in which the copolymer is filled in a cylindrical container having a liquid inlet and a liquid outlet.
The filter shape and the amount of the copolymer to be filled can be appropriately adjusted, and may be appropriately selected depending on the resist composition to be filtered or the organic solvent.
The filter may be a cartridge type.

(Filtration method)
The filtration method using the copolymer of the present invention is (1) a method in which a filtration material using the copolymer is packed in a column, and a resist composition or an organic solvent is passed through the column for purification (column method). ), (2) The filtration material is placed in a resist composition or an organic solvent, and is removed by mixing and stirring for a predetermined time (badge method). In the case of the batch method, it is necessary to separate the resist composition or the organic solvent and the filter material after stirring for a predetermined time. As a separation method, techniques such as filtration with a filter and centrifugation are generally performed.
The resist composition used in the column method or batch method is preferably a solution having a concentration range of about 1 to 50% by weight.
The liquid passing rate of the resist composition or the organic solvent when passing through the filter medium has almost no influence on the metal separation efficiency, and may usually be in the range of 0.0001 to 1000 kg / (m ² · min). If the temperature when passing through a filter or the like filled with a filter material is too high, elution, deterioration of the filter medium, decomposition of the solvent, etc. may occur. On the other hand, if the temperature is too low, the viscosity of the resin in the solution becomes high and it becomes very difficult to pass the liquid. Therefore, a temperature range of 0 to 50 ° C. is appropriate.

According to the filtration material using the copolymer of the present invention, a metal component can be suitably removed as an impurity.
According to the filtering material using the copolymer of the present invention, lithium, sodium, magnesium, potassium, chromium, manganese, iron, cobalt, nickel, copper, zinc, strontium, molybdenum, silver, cadmium, tin, antimony, barium Various metal components such as lead can be removed.
According to the filtration material using the copolymer of the present invention, it can be removed even if two or more kinds of the above-mentioned metal components are mixed.
Among the above, it is possible to effectively remove metal components having a high ionization tendency and zinc that is easily mixed due to contamination in the manufacturing process.
According to the filtration material using the copolymer of the present invention, the above trace metals can be removed regardless of the existence form of metal ions, metal fine particles and the like.

  The filtration material using the copolymer of the present invention is replaced with a filter cartridge for removing particulate impurities, which has been installed so far in various chemical solution supply lines or POU (point of use) in the semiconductor manufacturing process. Alternatively, when used in combination with this, it is possible to efficiently remove particulate impurities and trace metal impurities simultaneously with the same apparatus and operation as before. That is, the present invention achieves the removal of trace metal impurities in a single filtration step, so that it can be very easily applied to an actual apparatus currently used in semiconductor element manufacturing. Has a great effect on the semiconductor industry.

  The filter cartridge using the filtering material using the copolymer of the present invention increases the metal impurities in the chemical liquid by installing it in the path of circulating the chemical liquid tank in various chemical liquid supply lines of the semiconductor element manufacturing process. Can be reduced. In addition, by installing the filter according to the present invention in a point of use (POU) in the chemical solution supply line, metal impurities and particulate impurities in various chemical solutions can be efficiently removed. Furthermore, in this case, in addition to being able to remove the metal impurities originally contained in the chemical solution, it is also possible to cope with contamination from the chemical solution transfer path such as pipes and joints.

  EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited to a following example.

Example 1:
Synthesis of Aminosilica Xerogel Metal Component Removal Material Using Silica Xerogel >>
<Synthesis of silica xerogel>
Literature (G. Hayase, et.al, Angew. Chem. Int. Ed., 2013, 52, 10788-1091., G. Hayase, et.al, Angew. Chem. Int. Ed., 2013, 52, 1986) -1989. And G. Hayase, et.al, J. Mater.Chem., 2011, 21, 17077-17079.).
Urea (10 g) and n-hexadecyltrimethylammonium chloride (CTAC) (0.8 g) are dissolved in 0.05 mol / L acetic acid aqueous solution (15 ml), and a bifunctional silane coupling agent: dimethyldimethoxysilane (DMDMS) ( 5 ml) and a trifunctional silane coupling agent: vinyltrimethoxysilane (VTMS) (5 ml) were added and stirred for 1 hour to carry out a sol reaction. After the completion of the reaction, the solution was allowed to stand in an oven at 80 ° C. and subjected to a gel reaction for one day and night. The obtained gel was washed with water three times, and then replaced with a water-isopropanol (IPA) (1: 1) solution to wash the gel. The washed gel was immersed in IPA twice for 8 hours. Thereafter, it was washed with n-hexane three times and dried at 40 ° C. for one day to obtain xerogel.
It was confirmed that the obtained gel had an appearance similar to marshmallow, was flexible, and absorbed instantaneously when immersed in a solvent. From the above, we succeeded in synthesizing silica xerogel. The synthesis scheme of silica xerogel is shown below. In the following, a wavy line shows a bond.

<Synthesis of aminosilica xerogel>
The thiol-ene reaction was adopted in the amino group modification of silica xerogel. A 2-aminoethanethiol 10 wt% isopropanol (IPA) solution (10 ml) was prepared, and a radical initiator: V-601 (0.2 g) was dissolved therein. Silica xerogel (2 g) was immersed in the solution, and the vinyl group at the end of silica xerogel was converted to sulfide in 6 hours (65 ° C.). After the reaction, the silica xerogel was sufficiently washed with IPA, further washed with diethyl ether and dried.
Since S2p was detected after the reaction by X-ray photoelectron spectroscopy (XPS), the silica xerogel was successfully modified with aminoethane sulfide to obtain an aminosilica xerogel. A modification scheme of aminoethane sulfide to silica xerogel is shown below. In the following, a wavy line shows a bond.

<Synthesis of chelate silica xerogel>
Selection and modification of the chelate moiety on aminosilica xerogel was performed by immersing aminosilica xerogel (2 g) in resacetophenone 10 wt% ethanol solution (20 ml) for 1 day. And dried at 60 ° C. for one day. The obtained xerogel was dehydrated and condensed with an amino moiety to form a phenylacetimino group and colored yellow as in the case of the bead-type silica gel synthesized so far. In the case of 2,4-dihydroxymevaloacetophenone, a chelate silica xerogel colored in the same brown color as that of the bead type silica gel was obtained in the same manner. From the above, we have succeeded in synthesizing an unprecedented chelate silica xerogel. A synthesis scheme of chelated silica xerogel is shown below. In the following, a wavy line shows a bond.

<< Example 2: Evaluation of metal ion removal by chelate silica xerogel metal component removal material >>
The metal component collection qualitative evaluation of the chelated silica xerogel was performed. A 50 ppm (1: 1) solution of FeCl ₃ cyclohexanone acetonitrile was prepared, and chelate silica xerogel was added thereto and immersed for about 2 minutes, and then the xerogel changed from yellow to blood red due to chelate formation between iron ions and chelate sites. In order to remove the xerogel, it was filtered through a 0.20 μm PTFE filter. The resulting filtrate went from yellow to colorless. Therefore, the metal component was successfully collected also in the chelate silica xerogel.

Example 3: Synthesis of aminosilica xerogel metal component removal material using chloride silica xerogel
<Synthesis of chloride silica xerogel>
A novel silica xerogel was synthesized by the above-described method so that the polymerization ratio was 1: 1 using a bifunctional silane coupling agent: dimethyldimethoxysilane and a trifunctional silane coupling agent: chloride propyltrimethoxysilane. did. Chloride appears to have a slightly reduced gel yield compared to vinylmethylsilica xerogel. This is suggested to be the influence of reaction inhibition by the terminal functional group. However, each of the obtained silica xerogels was successfully synthesized from the fact that a Cl2p peak was confirmed in the chloride silica xerogel by XPS measurement. In the following, a wavy line shows a bond.

<Synthesis of chelate silica xerogel using chloride silica xerogel>
Amino group modification using chloride silica xerogel was examined by a reaction by Williamson ether synthesis using amine alcohol. Chloride silica xerogel (1 g) was added to the container, and monoethanolamine (5 g) and triethylamine (5 g) as a nucleophilic reagent were added to the silica xerogel and heated at 65 ° C. for 6 hours. After heating, ultrapure was added and hydrolysis was performed at the same time as washing, followed by thorough washing with ethanol. After washing, it was passed through diethyl ether and dried at 60 ° C. The resulting silica gel was immersed in a 2 wt% ethanol solution of resacetophenone and 2,4-dihydroxymevaloacetophenone, respectively, and the xerogel was colored after washing, so that it was etherified from chloride and the amino group was successfully modified. Indicates. At the same time, this amine group-modified silica xerogel is chelated. From the above, we have succeeded in developing a new synthetic route for chelated silica xerogels.

  A synthesis scheme of amide silica using chloride silica xerogel is shown below. In the following, a wavy line shows a bond.

  The synthesis scheme of chelate silica xerogel from amide silica xerogel is shown below. In the following, a wavy line shows a bond.

  As shown in the above results, chelating silica xerogel was successfully used as a filtration material to remove metal ions in an organic solvent. We have also succeeded in developing a new synthetic route for chelate silica xerogels starting from chloride silica xerogels.

Claims (5)

A copolymer of alkoxysilane having two or more functional groups, wherein the copolymer has a partial structure represented by the following general formulas (p-1) and (p-3).

[Wherein, R ⁴ and R ⁵ each independently represents a hydrocarbon group which may have a substituent, or a hydroxyl group, and one of R ⁴ and R ⁵ represents the other in the alkoxysilane copolymer. It may combine with a silicon atom to form a crosslinked structure. Ya ⁰¹ and Yb ⁰¹ each independently represent a divalent linking group, Ra ⁰¹ represents a hydrocarbon group which may have a substituent, and Ra ⁰² may have a hydroxyl group or a substituent. Represents a hydrocarbon group having 1 to 6 carbon atoms. n ⁰¹ is an integer of 0 to 5. * Indicates a bond. ] A copolymer of alkoxysilane having two or more functional groups, wherein the copolymer has a partial structure represented by the following general formulas (p-1) and (p-5).

[Wherein, R ⁴ and R ⁵ each independently represents a hydrocarbon group which may have a substituent, or a hydroxyl group, and one of R ⁴ and R ⁵ represents the other in the alkoxysilane copolymer. It may combine with a silicon atom to form a crosslinked structure. Ya ⁰¹ and Yb ⁰¹ each independently represent a divalent linking group, Ra ⁰¹ represents a hydrocarbon group which may have a substituent, and Ra ⁰² may have a hydroxyl group or a substituent. Represents a hydrocarbon group having 1 to 6 carbon atoms. n ⁰¹ is an integer of 0 to 5. * Indicates a bond. ] A partial structure represented by the following general formulas (p-1) and (p-2) by reacting a compound represented by the following general formula (1) with a compound represented by the following general formula (2). Step A to obtain a copolymer (A) having
Step B for modifying the copolymer (A) obtained in Step A to obtain a copolymer (B) having a partial structure represented by the following general formula (p-B-1);
Step C for modifying the copolymer (B) obtained in Step B to obtain a copolymer (C) represented by the following general formulas (p-3) and (p-1) and having a partial structure;
The method for producing a copolymer according to claim 1, comprising:

[Wherein, R ^{1 to} R ³ and R ^{6 to} R ⁷ each independently represent an alkyl group having 1 to 5 carbon atoms, and R ⁴ and R ⁵ may each independently have a substituent. It represents a good hydrocarbon group or a hydroxyl group, and one of R ⁴ and R ⁵ may be bonded to another silicon atom in the alkoxysilane copolymer to form a crosslinked structure. Ya ⁰¹ and Yb ⁰¹ each independently represent a divalent linking group, Ra ⁰¹ represents a hydrocarbon group which may have a substituent, and Ra ⁰² may have a hydroxyl group or a substituent. Represents a hydrocarbon group having 1 to 6 carbon atoms. n ⁰¹ is an integer of 0 to 5. * Indicates a bond. ] A partial structure represented by the following general formulas (p-1) and (p-4) by reacting a compound represented by the following general formula (3) with a compound represented by the following general formula (2). Step X to obtain a copolymer (X) having
A step Y of modifying the copolymer (X) obtained in the step X to obtain a copolymer (Y) having a partial structure represented by the following general formula (p-Y-1);
Step Z for modifying the copolymer (Y) obtained in Step Y to obtain a copolymer (Z) having a partial structure represented by the following general formulas (p-5) and (p-1): ,
It has these, The manufacturing method of the copolymer of Claim 2 characterized by the above-mentioned.

[Wherein, R ^{1 to} R ³ and R ^{6 to} R ⁷ each independently represent an alkyl group having 1 to 5 carbon atoms, and R ⁴ and R ⁵ may each independently have a substituent. It represents a good hydrocarbon group or a hydroxyl group, and one of R ⁴ and R ⁵ may be bonded to another silicon atom in the alkoxysilane copolymer to form a crosslinked structure. Ya ⁰¹ and Yb ⁰¹ each independently represent a divalent linking group, Ra ⁰¹ represents a hydrocarbon group which may have a substituent, and Ra ⁰² may have a hydroxyl group or a substituent. Represents a hydrocarbon group having 1 to 6 carbon atoms. n ⁰¹ is an integer of 0 to 5. * Indicates a bond. ] A copolymer of alkoxysilane having two or more functional groups, wherein the copolymer has a partial structure represented by the following general formulas (p-1) and (p-4).

[Wherein, R ⁴ and R ⁵ each independently represents a hydrocarbon group which may have a substituent, or a hydroxyl group, and one of R ⁴ and R ⁵ represents the other in the alkoxysilane copolymer. It may combine with a silicon atom to form a crosslinked structure. Yb ⁰¹ represents a divalent linking group. * Indicates a bond. ]