JP7388022B2 - Resist underlayer film forming composition using polymeric crosslinking agent - Google Patents

Description

The present invention relates to a resist underlayer film forming composition suitable for lithography in semiconductor substrate processing, a resist underlayer film obtained from the resist underlayer film forming composition, and a patterned substrate using the resist underlayer film forming composition. The present invention relates to a manufacturing method and a method of manufacturing a semiconductor device.

2. Description of the Related Art Conventionally, in the manufacture of semiconductor devices, microfabrication has been performed by lithography using a photoresist composition. The above-mentioned microfabrication involves forming a thin film of a photoresist composition on a substrate to be processed such as a silicon wafer, irradiating the film with actinic light such as ultraviolet rays through a mask pattern on which a semiconductor device pattern is drawn, and developing the film. This is a processing method in which a substrate to be processed, such as a silicon wafer, is etched using the obtained photoresist pattern as a protective film. In recent years, semiconductor devices have become highly integrated, and the wavelength of active light used has been shortened from KrF excimer laser (248 nm) to ArF excimer laser (193 nm). Furthermore, for the purpose of further microfabrication, lithography techniques using extreme ultraviolet (EUV, 13.5 nm) or electron beam (EB) as actinic light are being developed.

In the lithography process, when a resist layer on a substrate is exposed to an ultraviolet laser such as a KrF excimer laser or an ArF excimer laser, a desired shape is formed due to the influence of standing waves generated due to the reflection of the ultraviolet laser on the substrate surface. There is a known problem in which a resist pattern having a resist pattern is not formed. To solve this problem, it has been adopted to provide a resist underlayer film (antireflection film) between the substrate and the resist layer.

The resist underlayer film formed between such a photoresist and the substrate to be processed is generally coated on the substrate to be processed in order to suppress mixing with the resist layered on the upper layer. , it is formed as a thermosetting crosslinked film that does not mix with the resist through a baking process.

It is known that various resins are used as compositions for forming resist underlayer films. For example, Patent Document 1 and Patent Document 2 disclose a photoresist underlayer film forming material containing a resin having a repeating unit obtained by converting a compound having a bisphenol group into a novolak. Further, Patent Document 3 discloses a spin-coatable antireflection coating composition that includes a polymer having three or more condensed aromatic rings in the main chain of the polymer.

By the way, when the underlying substrate to be processed has a step difference, or when a pattern-dense area and a pattern-free area exist on the same wafer, it is necessary to flatten the film surface with an underlying film. A resin suitable for such purposes has been proposed (Patent Document 4).

On the other hand, in order to form such a thermoset film, the resist underlayer film forming composition contains, in addition to the main component polymer resin, a crosslinking compound (crosslinking agent) and a catalyst for promoting the crosslinking reaction (crosslinking catalyst). ) is included. With regard to the issue of flattening the film surface with the underlying film, these components have not yet been sufficiently investigated.

Japanese Patent Application Publication No. 2006-259249 Japanese Patent Application Publication No. 2007-316282 Special Publication No. 2010-528334 WO 2014/024836 A1

An object of the present invention is to provide a composition for forming a resist underlayer film that is insoluble in resist solvents, has good optical constants, and has a high etching rate, and that has excellent embedding properties and planarization properties for stepped substrates. The goal is to provide the following.

［式中、ｍは１～３０の整数であり、
ｍ＝１のとき、
Ｔは単結合、芳香族環によって中断されていてもよい２乃至６価の飽和炭化水素基、又は酸素原子、カルボニル基若しくはアルキレン基によって中断されていてもよく、アルキル基若しくはアルケニル基で置換されていてもよい２乃至６価の芳香族基若しくは不飽和環状炭化水素基であり、
Ｇ^１、Ｇ^２、及びＴの価数が３以上に増加するに従って存在するＧ^３、Ｇ^４、Ｇ^５、Ｇ^６はそれぞれ独立に

又は

であり、
ｎはそれぞれ独立に１～８の整数であり、
ｎ個のＲはそれぞれ独立に水素原子、又は酸素原子、窒素原子若しくはカルボニル基で中断されていてもよいアルキル基であり、
Ａはそれぞれ独立にアルキレン基によって中断されていてもよいＣ_６－Ｃ_１８アリール基であり、
Ｚ^１、Ｚ^２、及びＴの価数が３以上に増加するに従って存在するＺ^３、Ｚ^４、Ｚ^５、Ｚ^６はそれぞれ独立に、酸素原子、窒素原子若しくはカルボニル基によって中断されていてもよいアルキル基、又は酸素原子、窒素原子若しくはカルボニル基によって中断されていてもよく、ヒドロキシ基、ハロゲン原子、カルボキシル基、ニトロ基、シアノ基、メチレンジオキシ基、アセトキシ基、メチルチオ基、アミノ基、Ｃ_１－Ｃ_９アルコキシ基、アルキル基、アルケニル基若しくはアルキニル基で置換されていてもよいアリール基を表す。
ｍ＞１のとき、
ｍ個のＴは単結合、芳香族環によって中断されていてもよい２価の飽和炭化水素基、又は酸素原子、カルボニル基若しくはアルキレン基によって中断されていてもよく、アルキル基若しくはアルケニル基で置換されていてもよい２価の芳香族基若しくは不飽和環状炭化水素基であり、
Ｇ^３Ｚ^３、Ｇ^４Ｚ^４、Ｇ^５Ｚ^５、Ｇ^６Ｚ^６は存在せず、
ｍ個のＧ^１、及びＧ^２はそれぞれ独立に

又は

であり、
ｎ、Ｒ、及びＡは上に定義したとおりであり、
Ｚ^１、及びＺ^２はそれぞれ独立にヒドロキシ基、エポキシ基又は水素原子を表す。]
［２］ 上記Ａはそれぞれ独立にアルキレン基によって中断されていてもよいＣ_６アリール基である、［１］に記載のレジスト下層膜形成組成物。
［３］ （Ｂ）架橋性化合物（Ａ）と架橋反応可能な膜材料を更に含む、［１］又は［２］に記載のレジスト下層膜形成組成物。
［４］ 上記架橋反応可能な膜材料（Ｂ）が、脂肪族環を含有する樹脂、ノボラック樹脂、ポリエーテル樹脂、ポリエステル樹脂、アクリル樹脂、メタクリル樹脂及び架橋性化合物（Ａ）と異なる化合物からなる群より選択される少なくとも一種を含む、［３］に記載のレジスト下層膜形成組成物。
［５］ 上記ノボラック樹脂が、下記式（１ａ）、式（１ｂ）及び式（１ｃ）：

［式中、２つのＲ^１はそれぞれ独立に炭素原子数１乃至１０のアルキル基、炭素原子数２乃至６のアルケニル基、芳香族炭化水素基、ハロゲン原子、ニトロ基又はアミノ基を表し、２つのＲ^２はそれぞれ独立に水素原子、炭素原子数１乃至１０のアルキル基、炭素原子数２乃至６のアルケニル基、アセタール基、アシル基又はグリシジル基を表し、Ｒ^３は置換基を有してもよい芳香族炭化水素基を表し、Ｒ^４は水素原子、フェニル基又はナフチル基を表し、同一の炭素原子と結合するＲ^３とＲ^４がそれぞれフェニル基を表すとき互いに結合してフルオレン環を形成してもよく、式（１ｂ）において２つのＲ^３が表す基及び２つのＲ^４が表す原子又は基は互いに異なっていてもよく、２つのｋはそれぞれ独立に０又は１を表し、ｍ_０は３乃至５００の整数を表し、ｎ_０、ｎ_１及びｎ_２は２乃至５００の整数を表し、ｐは３乃至５００の整数を表し、Ｘは単結合又はヘテロ原子を表し、２つのＱはそれぞれ独立に下記式（２）：

（式中、２つのＲ^１、２つのＲ^２、２つのＲ^３、２つのＲ^４、２つのｋ、ｎ_１、ｎ_２及びＸは式（１ｂ）と同義であり、２つのＱ^１はそれぞれ独立に前記式（２）で表される構造単位を表す。）で表される構造単位を表す。］
で表される繰り返し構造単位のうちいずれか１つ又は２つ以上で表される、［４］に記載のレジスト下層膜形成組成物。
［６］ 上記架橋性化合物（Ａ）と異なる化合物が、

（式（２）中、２つのＡｒはそれぞれアリール基を表し、該アリール基は置換基として少なくとも１つのヒドロキシ基を有し、Ｑはベンゼン環又はナフタレン環を少なくとも１つ有する二価の連結基、メチレン基又は単結合を表す。）で表される、［４］に記載のレジスト下層膜形成組成物。
［７］ （Ｃ）酸触媒を更に含む、［１］又は［２］に記載のレジスト下層膜形成組成物。
［８］ （Ｃ）酸触媒を更に含む、［３］～［６］のいずれか一項に記載のレジスト下層膜形成組成物。
［９］ 上記架橋性化合物（Ａ）が下記式（１）で表される、［８］に記載のレジスト下層膜形成組成物。

［式中、
Ｖは

又は

を表し、
ｉは２～６の整数であり、
ｉ個のＲはそれぞれ独立に水素原子、又は酸素原子、窒素原子若しくはカルボニル基で中断されていてもよいアルキル基であり、
ｉ個のｎはそれぞれ独立に１～８の整数であり、
ｉ個のＡはそれぞれ独立にアルキレン基によって中断されていてもよいＣ_６－Ｃ_１８アリール基であり、
ｉ個のＺはそれぞれ独立に酸素原子、窒素原子若しくはカルボニル基によって中断されていてもよいアルキル基、又は酸素原子、窒素原子若しくはカルボニル基によって中断されていてもよく、ヒドロキシ基、ハロゲン原子、カルボキシル基、ニトロ基、シアノ基、メチレンジオキシ基、アセトキシ基、メチルチオ基、アミノ基、Ｃ_１－Ｃ_９アルコキシ基、アルキル基、アルケニル基若しくはアルキニル基で置換されていてもよいアリール基であり、
Ｔは単結合、芳香族環によって中断されていてもよいｉ価の飽和炭化水素基、又は酸素原子若しくはアルキレン基によって中断されていてもよく、アルキル基若しくはアルケニル基で置換されていてもよいｉ価の芳香族基である。］
［１０］ 上記Ｚはそれぞれ独立にアルキル基、酸素原子、窒素原子又はカルボニル基によって中断されていてもよく、ヒドロキシ基、ハロゲン原子、カルボキシル基、ニトロ基、シアノ基、メチレンジオキシ基、アセトキシ基、メチルチオ基、アミノ基、Ｃ_１－Ｃ_９アルコキシ基、アルキル基、アルケニル基又はアルキニル基で置換されていてもよいアリール基である、［９］に記載のレジスト下層膜形成組成物。
［１１］ ［１］～［１０］のいずれか１項に記載のレジスト下層膜形成組成物からなる塗布膜の硬化物であることを特徴とするレジスト下層膜。
［１２］ 半導体基板上に［１］～［１０］のいずれか１項に記載のレジスト下層膜形成組成物を塗布し硬化してレジスト下層膜を形成する工程、前記レジスト下層膜上にレジストを塗布しベークしてレジスト膜を形成する工程、前記レジスト下層膜と前記レジストで被覆された半導体基板を露光する工程、露光後の前記レジスト膜を現像し、パターニングする工程を含む、パターニングされた基板の製造方法。
［１３］ ベークして上記硬化を行う、［１２］に記載のパターニングされた基板の製造方法。
［１４］ ベークした後、紫外線を照射することにより上記硬化を行う、［１２］に記載のパターニングされた基板の製造方法。
［１５］ 半導体基板上に［１］～［１０］のいずれか１項に記載のレジスト下層膜形成組成物によりレジスト下層膜を形成する工程、その上にレジスト膜を形成する工程、光又は電子線の照射と現像によりレジストパターンを形成する工程、レジストパターンにより該下層膜をエッチングする工程、及びパターン化された下層膜により半導体基板を加工する工程を含む半導体装置の製造方法。
［１６］ 下記式（ＩＩ）で表される化合物。

式中、ｍは１～３０の整数であり、
ｍ個のＴは単結合、芳香族環によって中断されていてもよい２価の飽和炭化水素基、又は酸素原子、カルボニル基若しくはアルキレン基によって中断されていてもよく、アルキル基若しくはアルケニル基で置換されていてもよい２価の芳香族基若しくは不飽和環状炭化水素基であり、
ｍ個のＧ^１、及びＧ^２はそれぞれ独立に

又は

であり、
ｎはそれぞれ独立に１～８の整数であり、
ｎ個のＲはそれぞれ独立に水素原子、又は酸素原子、窒素原子若しくはカルボニル基で中断されていてもよいアルキル基であり、
Ａはそれぞれ独立にアルキレン基によって中断されていてもよいＣ_６－Ｃ_１８アリール基であり、
Ｚ^１、及びＺ^２はそれぞれ独立にヒドロキシ基、エポキシ基又は水素原子を表す。]
［１７］ 下記式（１－２１）～（１－２５）で表される化合物。

（式中、ｍはそれぞれ独立に１～２０の整数であり、
ｒはそれぞれ独立に０～５の整数である） The present invention includes the following.
[1] A resist underlayer film forming composition containing (A) a crosslinkable compound represented by the following formula (I), and (D) a solvent.

[In the formula, m is an integer from 1 to 30,
When m=1,
T is a single bond, a divalent to hexavalent saturated hydrocarbon group which may be interrupted by an aromatic ring, or an oxygen atom, a carbonyl group or an alkylene group, and is substituted with an alkyl group or an alkenyl group. a divalent to hexavalent aromatic group or an unsaturated cyclic hydrocarbon group, which may be
As the valence of G ¹ , G ² , and T increases to 3 or more, G ³ , G ⁴ , G ⁵ , and G ⁶ that exist each independently

or

and
n is each independently an integer from 1 to 8,
Each of the n R's is independently a hydrogen atom, or an alkyl group optionally interrupted by an oxygen atom, a nitrogen atom, or a carbonyl group,
each A is independently a C ₆ -C ₁₈ aryl group optionally interrupted by an alkylene group;
As the valence of Z ¹ , Z ² , and T increases to 3 or more, Z ³ , Z ⁴ , Z ⁵ , and Z ⁶ present may be independently interrupted by an oxygen atom, a nitrogen atom, or a carbonyl group. alkyl groups, or optionally interrupted by oxygen atoms, nitrogen atoms or carbonyl groups, hydroxy groups, halogen atoms, carboxyl groups, nitro groups, cyano groups, methylenedioxy groups, acetoxy groups, methylthio groups, amino groups, Represents an aryl group optionally substituted with a C ₁ -C ₉ alkoxy group, alkyl group, alkenyl group or alkynyl group.
When m>1,
m T's are a single bond, a divalent saturated hydrocarbon group which may be interrupted by an aromatic ring, or an oxygen atom, a carbonyl group or an alkylene group, and substituted with an alkyl group or an alkenyl group. A divalent aromatic group or an unsaturated cyclic hydrocarbon group that may be
G ³ Z ³ , G ⁴ Z ⁴ , G ⁵ Z ⁵ , G ⁶ Z ⁶ does not exist,
m G ¹ and G ² are each independently

or

and
n, R, and A are as defined above;
Z ¹ and Z ² each independently represent a hydroxy group, an epoxy group, or a hydrogen atom. ]
[2] The resist underlayer film forming composition according to [1], wherein each of the A's is a C ₆ aryl group which may be independently interrupted by an alkylene group.
[3] (B) The resist underlayer film forming composition according to [1] or [2], further comprising a film material capable of crosslinking with the crosslinkable compound (A).
[4] The crosslinkable membrane material (B) is made of a resin containing an aliphatic ring, a novolac resin, a polyether resin, a polyester resin, an acrylic resin, a methacrylic resin, and a compound different from the crosslinkable compound (A). The resist underlayer film forming composition according to [3], which contains at least one selected from the group.
[5] The novolac resin has the following formula (1a), formula (1b) and formula (1c):

[In the formula, each of the two R ¹ independently represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aromatic hydrocarbon group, a halogen atom, a nitro group, or an amino group, and 2 Each of R ² independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an acetal group, an acyl group, or a glycidyl group, and R ³ has a substituent. ^R4 represents a hydrogen atom, a phenyl group or a naphthyl group, and when ^R3 and ^R4 bonded to the same carbon atom each represent a phenyl group, they bond to each other to form a fluorene ring. In formula (1b), the two groups represented by R ³ and the two atoms or groups represented by R ⁴ may be different from each other, the two k each independently represent 0 or 1, and m ₀ represents an integer from 3 to 500, n ₀ , n ₁ and n ₂ represent an integer from 2 to 500, p represents an integer from 3 to 500, X represents a single bond or a heteroatom, and two Q are each independently expressed by the following formula (2):

(In the formula, two R ¹ , two R ² , two R ³ , two R ⁴ , two k, n ₁ , n ₂ and X are synonymous with formula (1b), and two Q ¹ are Each independently represents a structural unit represented by the above formula (2).) represents a structural unit represented by the formula (2). ]
The resist underlayer film forming composition according to [4], which is represented by any one or two or more of the repeating structural units represented by.
[6] A compound different from the crosslinkable compound (A) is

(In formula (2), each of the two Ar represents an aryl group, the aryl group has at least one hydroxy group as a substituent, and Q is a divalent linking group having at least one benzene ring or naphthalene ring. , a methylene group or a single bond), the resist underlayer film forming composition according to [4].
[7] (C) The resist underlayer film forming composition according to [1] or [2], further comprising an acid catalyst.
[8] The resist underlayer film forming composition according to any one of [3] to [6], further comprising (C) an acid catalyst.
[9] The resist underlayer film forming composition according to [8], wherein the crosslinkable compound (A) is represented by the following formula (1).

[In the formula,
V is

or

represents,
i is an integer from 2 to 6,
i R's are each independently a hydrogen atom, or an alkyl group optionally interrupted by an oxygen atom, a nitrogen atom, or a carbonyl group,
i pieces of n are each independently an integer from 1 to 8,
each of the i A's is independently a C ₆ -C ₁₈ aryl group optionally interrupted by an alkylene group;
i Z's are each independently an alkyl group which may be interrupted by an oxygen atom, a nitrogen atom or a carbonyl group, or an alkyl group which may be interrupted by an oxygen atom, a nitrogen atom or a carbonyl group, a hydroxy group, a halogen atom, a carboxyl group; an aryl group optionally substituted with a group, a nitro group, a cyano group, a methylenedioxy group, an acetoxy group, a methylthio group, an amino group, a C ₁ -C ₉ alkoxy group, an alkyl group, an alkenyl group or an alkynyl group,
T is a single bond, an i-valent saturated hydrocarbon group which may be interrupted by an aromatic ring, or an i-valent saturated hydrocarbon group which may be interrupted by an oxygen atom or an alkylene group, and which may be substituted with an alkyl group or an alkenyl group. is a valent aromatic group. ]
[10] Each of the above Z may be independently interrupted by an alkyl group, an oxygen atom, a nitrogen atom, or a carbonyl group, and a hydroxy group, a halogen atom, a carboxyl group, a nitro group, a cyano group, a methylenedioxy group, an acetoxy group. , a methylthio group, an amino group, a C ₁ -C ₉ alkoxy group, an alkyl group, an alkenyl group, or an aryl group optionally substituted with an alkynyl group, the resist underlayer film forming composition according to [9].
[11] A resist underlayer film, which is a cured product of a coating film comprising the resist underlayer film forming composition according to any one of [1] to [10].
[12] A step of applying and curing the resist underlayer film forming composition according to any one of [1] to [10] on a semiconductor substrate to form a resist underlayer film, and applying a resist on the resist underlayer film. A patterned substrate, comprising the steps of forming a resist film by coating and baking, exposing the resist underlayer film and the semiconductor substrate covered with the resist, and developing and patterning the exposed resist film. manufacturing method.
[13] The method for manufacturing a patterned substrate according to [12], wherein the curing is performed by baking.
[14] The method for manufacturing a patterned substrate according to [12], wherein the curing is performed by irradiating ultraviolet rays after baking.
[15] Forming a resist underlayer film on a semiconductor substrate using the resist underlayer film forming composition according to any one of [1] to [10], forming a resist film thereon, photo or electronic A method for manufacturing a semiconductor device, comprising: forming a resist pattern by irradiation with a line and developing; etching the lower layer film using the resist pattern; and processing a semiconductor substrate using the patterned lower layer film.
[16] A compound represented by the following formula (II).

In the formula, m is an integer from 1 to 30,
m T's are a single bond, a divalent saturated hydrocarbon group which may be interrupted by an aromatic ring, or an oxygen atom, a carbonyl group or an alkylene group, and substituted with an alkyl group or an alkenyl group. A divalent aromatic group or an unsaturated cyclic hydrocarbon group that may be
m G ¹ and G ² are each independently

or

and
n is each independently an integer from 1 to 8,
Each of the n R's is independently a hydrogen atom, or an alkyl group optionally interrupted by an oxygen atom, a nitrogen atom, or a carbonyl group,
each A is independently a C ₆ -C ₁₈ aryl group optionally interrupted by an alkylene group;
Z ¹ and Z ² each independently represent a hydroxy group, an epoxy group, or a hydrogen atom. ]
[17] Compounds represented by the following formulas (1-21) to (1-25).

(In the formula, m is each independently an integer from 1 to 20,
(r is each independently an integer from 0 to 5)

In the crosslinking compound having a specific chemical structure according to the present invention, the crosslinking reaction with the membrane material proceeds slowly. Therefore, when a resist underlayer film forming composition containing a crosslinkable compound according to the present invention is applied to a fine pattern on a substrate, the fluidity of the composition is maintained for a certain period of time until three-dimensionalization due to crosslinking progresses. Ru. As a result, the resist underlayer film forming composition according to the present invention can be filled into the fine pattern of the stepped substrate without any gaps. Then, the resist underlayer film formed by applying and baking the resist underlayer film forming composition according to the present invention on the stepped substrate is further applied to the areas where the pattern is present (dense areas) of the coating formed thereon. The difference in film thickness (Iso-dense bias) between the (patterned area) and the area where no pattern exists (open area (patterned area)) can be suppressed to a small value.

[Resist underlayer film forming composition]
The resist underlayer film forming composition according to the present invention includes:
(A) A crosslinkable compound represented by the following formula (I) and (D) a solvent.

Optionally, the resist underlayer film forming composition according to the present invention comprises:
(B) A membrane material capable of crosslinking with the crosslinkable compound (A) and/or (C) an acid catalyst.

Furthermore, the resist underlayer film forming composition according to the present invention can contain additives such as an acid generator and a surfactant, if necessary.

［式中、ｍは１～３０の整数であり、
ｍ＝１のとき、
Ｔは単結合、芳香族環によって中断されていてもよい２乃至６価の飽和炭化水素基、又は酸素原子、カルボニル基若しくはアルキレン基によって中断されていてもよく、アルキル基若しくはアルケニル基で置換されていてもよい２乃至６価の芳香族基若しくは不飽和環状炭化水素基であり、
Ｇ^１、Ｇ^２、及びＴの価数が３以上に増加するに従って存在するＧ^３、Ｇ^４、Ｇ^５、Ｇ^６はそれぞれ独立に

又は

であり、
ｎはそれぞれ独立に１～８の整数であり、
ｎ個のＲはそれぞれ独立に水素原子、又は酸素原子、窒素原子若しくはカルボニル基で中断されていてもよいアルキル基であり、
Ａはそれぞれ独立にアルキレン基によって中断されていてもよいＣ_６－Ｃ_１８アリール基であり、
Ｚ^１、Ｚ^２、及びＴの価数が３以上に増加するに従って存在するＺ^３、Ｚ^４、Ｚ^５、Ｚ^６はそれぞれ独立に、酸素原子、窒素原子若しくはカルボニル基によって中断されていてもよいアルキル基、又は酸素原子、窒素原子若しくはカルボニル基によって中断されていてもよく、ヒドロキシ基、ハロゲン原子、カルボキシル基、ニトロ基、シアノ基、メチレンジオキシ基、アセトキシ基、メチルチオ基、アミノ基、Ｃ_１－Ｃ_９アルコキシ基、アルキル基、アルケニル基若しくはアルキニル基で置換されていてもよいアリール基を表す。
ｍ＞１のとき、
ｍ個のＴは単結合、芳香族環によって中断されていてもよい２価の飽和炭化水素基、又は酸素原子、カルボニル基若しくはアルキレン基によって中断されていてもよく、アルキル基若しくはアルケニル基で置換されていてもよい２価の芳香族基若しくは不飽和環状炭化水素基であり、
Ｇ^３Ｚ^３、Ｇ^４Ｚ^４、Ｇ^５Ｚ^５、Ｇ^６Ｚ^６は存在せず、
ｍ個のＧ^１、及びＧ^２はそれぞれ独立に

又は

であり、
ｎ、Ｒ、及びＡは上に定義したとおりであり、
Ｚ^１、及びＺ^２はそれぞれ独立にヒドロキシ基、エポキシ基又は水素原子を表す。] [(A) Crosslinkable compound]
The crosslinkable compound (A) used in the present invention is represented by the following formula (I).

[In the formula, m is an integer from 1 to 30,
When m=1,
T is a single bond, a divalent to hexavalent saturated hydrocarbon group which may be interrupted by an aromatic ring, or an oxygen atom, a carbonyl group or an alkylene group, and is substituted with an alkyl group or an alkenyl group. a divalent to hexavalent aromatic group or an unsaturated cyclic hydrocarbon group, which may be
As the valence of G ¹ , G ² , and T increases to 3 or more, G ³ , G ⁴ , G ⁵ , and G ⁶ that exist are independently

or

and
n is each independently an integer from 1 to 8,
n R's are each independently a hydrogen atom, or an alkyl group optionally interrupted by an oxygen atom, a nitrogen atom, or a carbonyl group,
each A is independently a C ₆ -C ₁₈ aryl group optionally interrupted by an alkylene group;
As the valence of Z ¹ , Z ² , and T increases to 3 or more, Z ³ , Z ⁴ , Z ⁵ , and Z ⁶ present may be independently interrupted by an oxygen atom, a nitrogen atom, or a carbonyl group. hydroxy, halogen, carboxyl, nitro, cyano, methylenedioxy, acetoxy, methylthio, amino, which may be interrupted by alkyl groups, or oxygen, nitrogen or carbonyl groups; Represents an aryl group optionally substituted with a C ₁ -C ₉ alkoxy group, alkyl group, alkenyl group or alkynyl group.
When m>1,
m T's are a single bond, a divalent saturated hydrocarbon group which may be interrupted by an aromatic ring, or an oxygen atom, a carbonyl group or an alkylene group, and substituted with an alkyl group or an alkenyl group. A divalent aromatic group or an unsaturated cyclic hydrocarbon group that may be
G ³ Z ³ , G ⁴ Z ⁴ , G ⁵ Z ⁵ , G ⁶ Z ⁶ does not exist,
m G ¹ and G ² are each independently

or

and
n, R, and A are as defined above;
Z ¹ and Z ² each independently represent a hydroxy group, an epoxy group, or a hydrogen atom. ]

式中、ｍは１～３０の整数であり、
ｍ個のＴは単結合、芳香族環によって中断されていてもよい２価の飽和炭化水素基、又は酸素原子、カルボニル基若しくはアルキレン基によって中断されていてもよく、アルキル基若しくはアルケニル基で置換されていてもよい２価の芳香族基若しくは不飽和環状炭化水素基であり、
ｍ個のＧ^１、及びＧ^２はそれぞれ独立に

又は

であり、
ｎはそれぞれ独立に１～８の整数であり、
ｎ個のＲはそれぞれ独立に水素原子、又は酸素原子、窒素原子若しくはカルボニル基で中断されていてもよいアルキル基であり、
Ａはそれぞれ独立にアルキレン基によって中断されていてもよいＣ_６－Ｃ_１８アリール基であり、
Ｚ^１、及びＺ^２はそれぞれ独立にヒドロキシ基、エポキシ基又は水素原子を表す。] Preferably, the crosslinkable compound (A) used in the present invention is represented by the following formula (II).

In the formula, m is an integer from 1 to 30,
m T's are a single bond, a divalent saturated hydrocarbon group which may be interrupted by an aromatic ring, or an oxygen atom, a carbonyl group or an alkylene group, and substituted with an alkyl group or an alkenyl group. A divalent aromatic group or an unsaturated cyclic hydrocarbon group that may be
m G ¹ and G ² are each independently

or

and
n is each independently an integer from 1 to 8,
n R's are each independently a hydrogen atom, or an alkyl group optionally interrupted by an oxygen atom, a nitrogen atom, or a carbonyl group,
each A is independently a C ₆ -C ₁₈ aryl group optionally interrupted by an alkylene group;
Z ¹ and Z ² each independently represent a hydroxy group, an epoxy group, or a hydrogen atom. ]

［式中、
Ｖは

又は

を表し、
ｉは２～６の整数であり、
ｉ個のＲはそれぞれ独立に水素原子、酸素原子、窒素原子又はカルボニル基で中断されていてもよいアルキル基であり、
ｉ個のｎはそれぞれ独立に１～８の整数であり、
ｉ個のＡはそれぞれ独立にアルキレン基によって中断されていてもよいＣ_６－Ｃ_１８アリール基であり、
ｉ個のＺはそれぞれ独立に酸素原子、窒素原子若しくはカルボニル基によって中断されていてもよいアルキル基、酸素原子、窒素原子又はカルボニル基によって中断されていてもよく、ヒドロキシ基、ハロゲン原子、カルボキシル基、ニトロ基、シアノ基、メチレンジオキシ基、アセトキシ基、メチルチオ基、アミノ基、Ｃ_１－Ｃ_９アルコキシ基、アルキル基、アルケニル基又はアルキニル基で置換されていてもよいアリール基であり、
Ｔは単結合、芳香族環によって中断されていてもよいｉ価の飽和炭化水素基、又は酸素原子若しくはアルキレン基によって中断されていてもよく、アルキル基若しくはアルケニル基で置換されていてもよいｉ価の芳香族基である。］ Preferably, the crosslinkable compound (A) used in the present invention is represented by the following formula (1).

[In the formula,
V is

or

represents,
i is an integer from 2 to 6,
i R's are each independently an alkyl group optionally interrupted by a hydrogen atom, an oxygen atom, a nitrogen atom, or a carbonyl group,
i pieces of n are each independently an integer from 1 to 8,
each of the i A's is independently a C ₆ -C ₁₈ aryl group which may be interrupted by an alkylene group;
i Z's are each independently an alkyl group which may be interrupted by an oxygen atom, a nitrogen atom or a carbonyl group, an alkyl group which may be interrupted by an oxygen atom, a nitrogen atom or a carbonyl group, a hydroxy group, a halogen atom, a carboxyl group , an aryl group optionally substituted with a nitro group, a cyano group, a methylenedioxy group, an acetoxy group, a methylthio group, an amino group, a C ₁ -C ₉ alkoxy group, an alkyl group, an alkenyl group or an alkynyl group,
T is a single bond, an i-valent saturated hydrocarbon group which may be interrupted by an aromatic ring, or an i-valent saturated hydrocarbon group which may be interrupted by an oxygen atom or an alkylene group, and which may be substituted with an alkyl group or an alkenyl group. is a valent aromatic group. ]

The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms. For example, methyl group, ethyl group, n-propyl group, i-propyl group, cyclopropyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, cyclobutyl group, 1-methyl-cyclo Propyl group, 2-methyl-cyclopropyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n -propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, 1-ethyl-n-propyl group, cyclopentyl group, 1-methyl-cyclobutyl group, 2-methyl-cyclobutyl group group, 3-methyl-cyclobutyl group, 1,2-dimethyl-cyclopropyl group, 2,3-dimethyl-cyclopropyl group, 1-ethyl-cyclopropyl group, 2-ethyl-cyclopropyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl-n-pentyl group, 4-methyl-n-pentyl group, 1,1-dimethyl-n-butyl group, 1,2 -dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, 2,2-dimethyl-n-butyl group, 2,3-dimethyl-n-butyl group, 3,3-dimethyl-n-butyl group group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1,2-trimethyl-n-propyl group, 1,2,2-trimethyl-n-propyl group, 1-ethyl- 1-methyl-n-propyl group, 1-ethyl-2-methyl-n-propyl group, cyclohexyl group, 1-methyl-cyclopentyl group, 2-methyl-cyclopentyl group, 3-methyl-cyclopentyl group, 1-ethyl- Cyclobutyl group, 2-ethyl-cyclobutyl group, 3-ethyl-cyclobutyl group, 1,2-dimethyl-cyclobutyl group, 1,3-dimethyl-cyclobutyl group, 2,2-dimethyl-cyclobutyl group, 2,3-dimethyl- Cyclobutyl group, 2,4-dimethyl-cyclobutyl group, 3,3-dimethyl-cyclobutyl group, 1-n-propyl-cyclopropyl group, 2-n-propyl-cyclopropyl group, 1-i-propyl-cyclopropyl group , 2-i-propyl-cyclopropyl group, 1,2,2-trimethyl-cyclopropyl group, 1,2,3-trimethyl-cyclopropyl group, 2,2,3-trimethyl-cyclopropyl group, 1-ethyl -2-methyl-cyclopropyl group, 2-ethyl-1-methyl-cyclopropyl group, 2-ethyl-2-methyl-cyclopropyl group, and 2-ethyl-3-methyl-cyclopropyl group.

Examples of the aryl group include a phenyl group, a naphthyl group, an anthryl group, a pyrenyl group, and the like. Preferably it is a C ₆ -C ₁₈ aryl group, more preferably a C ₆ -C ₁₄ aryl group, even more preferably a C ₆ -C ₁₀ aryl group, most preferably a C ₆ aryl group.
The above aryl group which may be interrupted by an alkylene group or the like and which may be substituted by a hydroxy group etc. is preferably an aryl group which may be interrupted by an alkylene group, an oxygen atom, a nitrogen atom or a carbonyl group. , more preferably an aryl group interrupted by a carbonyl group and substituted with an alkyl group. For example, a C ₁ -C ₁₀ alkylphenylcarbonyl group and the like can be mentioned.

The above alkoxy groups include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, s-butoxy group, t-butoxy group, n-pentoxy group, 1-methyl -n-butoxy group, 2-methyl-n-butoxy group, 3-methyl-n-butoxy group, 1,1-dimethyl-n-propoxy group, 1,2-dimethyl-n-propoxy group, 2,2- Dimethyl-n-propoxy group, 1-ethyl-n-propoxy group, n-hexyloxy group, 1-methyl-n-pentyloxy group, 2-methyl-n-pentyloxy group, 3-methyl-n-pentyloxy group group, 4-methyl-n-pentyloxy group, 1,1-dimethyl-n-butoxy group, 1,2-dimethyl-n-butoxy group, 1,3-dimethyl-n-butoxy group, 2,2-dimethyl -n-butoxy group, 2,3-dimethyl-n-butoxy group, 3,3-dimethyl-n-butoxy group, 1-ethyl-n-butoxy group, 2-ethyl-n-butoxy group, 1,1, 2-trimethyl-n-propoxy group, 1,2,2-trimethyl-n-propoxy group, 1-ethyl-1-methyl-n-propoxy group, and 1-ethyl-2-methyl-n-propoxy group are mentioned. It will be done. Preferably it is a C ₁ -C ₉ alkoxy group, more preferably a C ₁ -C ₆ alkoxy group, even more preferably a C ₁ -C ₃ alkoxy group.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

The above alkenyl groups include ethenyl group (vinyl group), 1-propenyl group, 2-propenyl group (allyl group), butenyl group, butadienyl group, pentenyl group, pentadienyl group, cyclopentenyl group, hexenyl group, hexadienyl group, hexa Examples include trienyl group and cyclohexenyl group. Preferably it is a C ₂ -C ₁₀ alkenyl group, more preferably a C ₂ -C ₈ alkenyl group, even more preferably a C ₂ -C ₆ alkenyl group.

The above alkynyl groups include ethynyl group (acetinyl group), 1-propynyl group, 2-propynyl group (propargyl group), butynyl group, pentynyl group, pent-3-en-1-ynyl group, hexynyl group, hex-2 -en-4-ynyl group and the like. Preferably it is a C ₂ -C ₁₀ alkynyl group, more preferably a C ₂ -C ₈ alkynyl group, even more preferably a C ₂ -C ₆ alkynyl group.

The above-mentioned saturated hydrocarbon group refers to a group obtained by removing an arbitrary number of hydrogen atoms from a saturated hydrocarbon compound.

The aromatic group generally refers to a group derived from an organic compound having a 4n+2 π electron system. Examples of such organic compounds include substituted or unsubstituted benzene, naphthalene, biphenyl, furan, thiophene, pyrrole, pyridine, indole, quinoline, carbazole, and the like.

The saturated hydrocarbon group optionally interrupted by an aromatic ring includes, for example, an alkylene group interrupted by phenylene and alkoxyphenylene.

The above-mentioned alkylene group refers to a group obtained by removing any one hydrogen from the above-mentioned alkyl group. Examples include methylene group, ethylene group, propylene group, cyclopropylene group, butylene group, cyclobutylene group, pentylene group, cyclopentylene group, hexylene group, and cyclohexylene group.

The above aromatic group which may be interrupted by an oxygen atom etc. and may be substituted by an alkyl group etc. is preferably an arylene group interrupted by an alkylene group and substituted by an alkenyl group, or an arylene group substituted by an alkyl group. an arylene group interrupted by an oxygen atom, and an arylene group interrupted by an alkylene group and substituted with an alkyl group. Examples include an allylphenylene group interrupted with a propylene group, a methyl group-substituted biphenylene group, a naphthylene group interrupted with an oxygen atom, a tolylene group and a naphthylene group interrupted with a methylene group.

The unsaturated cyclic hydrocarbon group which may be interrupted by an oxygen atom or the like and which may be substituted with an alkyl group is preferably a non-aromatic unsaturated cyclic hydrocarbon group, more preferably a divalent unsaturated cyclic hydrocarbon group. It is a non-aromatic unsaturated cyclic hydrocarbon group. Examples include a cyclopentenediyl group and a cyclohexenediyl group which may be substituted with an alkyl group or an alkenyl group (for example, a vinyl group). These are preferably interrupted by oxygen atoms, carbonyl groups or alkylene groups, more preferably by carbonyl groups.

（式（１－１０）中、ｍは０～３の整数を表す）

（式中、ｍはそれぞれ独立に１～２０の整数であり、
ｒはそれぞれ独立に０～５の整数である） Specific examples of the crosslinkable compound represented by formula (I) used in the present invention are as follows.

(In formula (1-10), m represents an integer from 0 to 3)

(In the formula, m is each independently an integer from 1 to 20,
(r is each independently an integer from 0 to 5)

The above formulas (1-1) to (1-11) are also specific examples of the crosslinkable compound represented by formula (1) used in the present invention. Further, the above formulas (1-21) to (1-25) are also specific examples of the crosslinkable compound represented by formula (II) used in the present invention.

The content of the crosslinkable compound (A) in the resist underlayer film forming composition according to the present invention is usually 0.01 to 50% by mass, preferably 0.01 to 40% by mass, more preferably The content is 0.1 to 30% by mass.

［式中、Ｖ、ｉ、Ｒ、ｎ、Ａ、Ｚ、Ｔは上に定義したとおりである。］ When m is 1, the compound (A) represented by the above formula (I), that is, the crosslinkable compound (A) represented by the above formula (1), is i compound represented by the following formula (101). It can be obtained by reacting a compound having a hydroxy group with a glycidyl ether compound represented by the following formula (102).

[wherein V, i, R, n, A, Z, and T are as defined above. ]

［式中、Ｖ、ｉ、Ｒ、ｎ、Ａ、Ｚ、Ｔは上に定義したとおりである。］ The crosslinkable compound (A) represented by the above formula (1) comprises a compound having i glycidyl ether groups represented by the following formula (103) and a hydroxy compound represented by the following formula (104). It can be obtained by reaction.

[wherein V, i, R, n, A, Z, and T are as defined above. ]

［式中、Ｒ、ｎ、Ａ、Ｔは上に定義したとおりである。］ When m is larger than 1, the compound (A) represented by the above formula (I), that is, the crosslinkable compound (A) represented by the above formula (II), is diglycidyl represented by the following formula (105). It can be obtained by reacting an ether compound with a dihydroxy compound represented by the following formula (106).

[wherein R, n, A, and T are as defined above. ]

［式中、Ｒ、ｎ、Ａ、Ｔは上に定義したとおりである。］ The crosslinkable compound (A) represented by the above formula (II) is obtained by reacting a dihydroxy compound represented by the following formula (107) with a diglycidyl ether compound represented by the following formula (108). be able to.

[wherein R, n, A, and T are as defined above. ]

Either reaction can be carried out in a suitable solvent in the presence of a suitable catalyst.
Such a solvent contains a compound having i hydroxy groups represented by the above formula (101), a glycidyl ether compound represented by formula (102), and a glycidyl ether compound having i glycidyl ether groups represented by formula (103). a compound represented by formula (104) and a hydroxy compound represented by formula (104), a compound represented by formula (105) and a compound represented by formula (106), or a compound represented by formula (107) and formula (108) The solvent is not particularly limited as long as it can uniformly dissolve the represented compound and does not inhibit the reaction or induce side reactions.

For example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, Propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, cycloheptanone, 4-methyl-2-pentanol, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, ethoxy Ethyl acetate, 2-hydroxyethyl acetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate , ethyl lactate, butyl lactate, 2-heptanone, methoxycyclopentane, anisole, γ-butyrolactone, N-methylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide. These solvents can be used alone or in combination of two or more. Among these solvents, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, and cyclohexanone are preferred.

Examples of the catalyst include quaternary ammonium salts such as tetrabutylammonium bromide, quaternary phosphonium salts such as ethyltriphenylphosphonium bromide, and phosphine compounds such as triphenylphosphine. Ethyltriphenylphosphonium bromide is preferred.

Further, in order to prevent unreacted acid, catalyst, inactivated catalyst, etc. from remaining in the reaction system, a cation exchange resin or an anion exchange resin for catalysts can be used.

[(B) Membrane material capable of crosslinking reaction with crosslinkable compound (A)]
The membrane material optionally used in the present invention can be used without particular limitation as long as it is a material capable of crosslinking with the crosslinkable compound (A). The membrane material may be a polymer, an oligomer, or a low molecular weight compound with a molecular weight of 1,000 or less. Crosslinking groups present in the membrane material include, but are not limited to, hydroxy groups, carboxyl groups, amino groups, and alkoxy groups.

（Ｔはポリマーの主鎖に脂肪族環を有する繰り返し単位構造を表し、Ｅはエポキシ基又はエポキシ基を有する有機基を表す。） (a) Examples of membrane materials capable of crosslinking include alicyclic epoxy polymers having a repeating structural unit represented by the following formula (1), as disclosed in WO 2011/021555 A1.

(T represents a repeating unit structure having an aliphatic ring in the main chain of the polymer, and E represents an epoxy group or an organic group having an epoxy group.)

E is a substituent to the aliphatic ring, and the epoxy group may be directly bonded to the aliphatic group, or the organic group having an epoxy group (for example, a glycidyl group) may be bonded to the aliphatic group.
The aliphatic ring is, for example, one in which 4 to 10 carbon atoms are connected in a ring, particularly 6 carbon atoms are connected in a ring. The aliphatic ring can have other substituents in addition to substituent E (an epoxy group or an organic group having an epoxy group). Examples of such substituents include alkyl groups having 1 to 10 carbon atoms, aryl groups having 6 to 20 carbon atoms, halogen atoms, nitro groups, and amino groups.
The alicyclic epoxy polymer represented by the above formula (1) has a weight average molecular weight of 600 to 1,000,000, preferably 1,000 to 200,000. The number of repeating units of the alicyclic epoxy polymer (A) represented by the above formula (1) is 2 to 3,000, or 3 to 600.

For example, the following polymers are exemplified.

［式中、２つのＲ^１はそれぞれ独立に炭素原子数１乃至１０のアルキル基、炭素原子数２乃至６のアルケニル基、芳香族炭化水素基、ハロゲン原子、ニトロ基又はアミノ基を表し、２つのＲ^２はそれぞれ独立に水素原子、炭素原子数１乃至１０のアルキル基、炭素原子数２乃至６のアルケニル基、アセタール基、アシル基又はグリシジル基を表し、Ｒ^３は置換基を有してもよい芳香族炭化水素基を表し、Ｒ^４は水素原子、フェニル基又はナフチル基を表し、同一の炭素原子と結合するＲ^３とＲ^４がそれぞれフェニル基を表すとき互いに結合してフルオレン環を形成してもよく、式（１ｂ）において２つのＲ^３が表す基及び２つのＲ^４が表す原子又は基は互いに異なっていてもよく、２つのｋはそれぞれ独立に０又は１を表し、ｍは３乃至５００の整数を表し、ｎ、ｎ_１及びｎ_２は２乃至５００の整数を表し、ｐは３乃至５００の整数を表し、Ｘは単結合又はヘテロ原子を表し、２つのＱはそれぞれ独立に下記式（２）：

（式中、２つのＲ^１、２つのＲ^２、２つのＲ^３、２つのＲ^４、２つのｋ、ｎ_１、ｎ_２及びＸは式（１ｂ）と同義であり、２つのＱ^１はそれぞれ独立に前記式（２）で表される構造単位を表す。）で表される構造単位を表す。］
で表される繰り返し構造単位のうちいずれか１つ又は２つ以上を有するポリマーが挙げられる。 (b) Membrane materials capable of crosslinking reaction include the following formulas (1a), (1b), and (1c) as disclosed in WO 2014/024836 A1:

[In the formula, each of the two R ¹ independently represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aromatic hydrocarbon group, a halogen atom, a nitro group, or an amino group, and 2 Each of R ² independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an acetal group, an acyl group, or a glycidyl group, and R ³ has a substituent. ^R4 represents a hydrogen atom, a phenyl group or a naphthyl group, and when ^R3 and ^R4 bonded to the same carbon atom each represent a phenyl group, they bond to each other to form a fluorene ring. In formula (1b), the two groups represented by R ³ and the two atoms or groups represented by R ⁴ may be different from each other, the two k each independently represent 0 or 1, and m represents an integer from 3 to 500, n, n ₁ and n ₂ represent an integer from 2 to 500, p represents an integer from 3 to 500, X represents a single bond or a heteroatom, and the two Qs each Independently the following formula (2):

(In the formula, two R ¹ , two R ² , two R ³ , two R ⁴ , two k, n ₁ , n ₂ and X are synonymous with formula (1b), and two Q ¹ are Each independently represents a structural unit represented by the above formula (2).) represents a structural unit represented by the formula (2). ]
Examples include polymers having one or more of the repeating structural units represented by the following.

Preferably, the aromatic hydrocarbon group represented by R ³ is a phenyl group, a naphthyl group, an anthryl group, or a pyrenyl group.

（式（１）中、
Ｒ_１及びＲ_２はそれぞれ水素原子、ハロゲン基、ニトロ基、アミノ基、ヒドロキシ基、炭
素原子数１乃至１０のアルキル基、炭素原子数２乃至１０のアルケニル基、炭素原子数６
乃至４０のアリール基、及びそれらの組み合わせからなる群より選択され、かつ、該アル
キル基、該アルケニル基又は該アリール基は、エーテル結合、ケトン結合若しくはエステ
ル結合を含んでいても良い基を表し、
Ｒ_３は水素原子、炭素原子数１乃至１０のアルキル基、炭素原子数２乃至１０のアルケ
ニル基、炭素原子数６乃至４０のアリール基、及びそれらの組み合わせからなる群より選
択され、かつ、該アルキル基、該アルケニル基又は該アリール基は、エーテル結合、ケト
ン結合若しくはエステル結合を含んでいても良い基を表し、
Ｒ_４はハロゲン基、ニトロ基、アミノ基若しくはヒドロキシ基で置換されていても良い
炭素原子数６乃至４０のアリール基又は複素環基を表し、
Ｒ_５は水素原子、又はハロゲン基、ニトロ基、アミノ基若しくはヒドロキシ基で置換さ
れていても良い、炭素原子数１乃至１０のアルキル基、炭素原子数６乃至４０のアリール
基又は複素環基を表し、そして
Ｒ_４とＲ_５はそれらが結合する炭素原子と一緒になって環を形成してもよく、
ｎ１及びｎ２はそれぞれ１乃至３の整数である。）で表される単位構造を含むポリマーが挙げられる。 (c) As a membrane material capable of crosslinking reaction, the following formula (1) as disclosed in WO 2010/147155 A1:

(In formula (1),
R ₁ and R ₂ are each a hydrogen atom, a halogen group, a nitro group, an amino group, a hydroxy group, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and 6 carbon atoms.
to 40 aryl groups, and combinations thereof, and the alkyl group, the alkenyl group, or the aryl group represents a group that may contain an ether bond, a ketone bond, or an ester bond;
R ₃ is selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, and a combination thereof; The alkyl group, the alkenyl group, or the aryl group represents a group that may contain an ether bond, a ketone bond, or an ester bond,
R ₄ represents an aryl group or heterocyclic group having 6 to 40 carbon atoms which may be substituted with a halogen group, nitro group, amino group or hydroxy group,
R ₅ is a hydrogen atom, or an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, or a heterocyclic group, which may be substituted with a halogen group, nitro group, amino group, or hydroxy group. and R ₄ and R ₅ together with the carbon atoms to which they are attached may form a ring,
n1 and n2 are each integers from 1 to 3. ) Polymers containing a unit structure represented by:

Preferably, in the formula (1), R ₁ , R ₂ , R ₃ , and R ₅ each represent a hydrogen atom, and R ₄ is a polymer containing a unit structure representing a phenyl group or a naphthyl group.
Preferably, in the formula (1), R ₁ , R ₂ and R ₃ each represent a hydrogen atom, and R ₄ and R ₅ together with the carbon atoms to which they are bonded form a fluorene ring, The polymer according to claim 1, wherein the carbon atom includes a unit structure in which the carbon atom is the carbon atom at the 9-position of the formed fluorene ring.

（式（２）及び式（３）中、
Ｒ_１、Ｒ_２、Ｒ_６、Ｒ_７、及びＲ_８はそれぞれ水素原子、ハロゲン基、ニトロ基、アミノ基、ヒドロキシ基、炭素原子数１乃至１０のアルキル基、炭素原子数２乃至１０のアルケニル基、炭素原子数６乃至４０のアリール基、及びそれらの組み合わせからなる群から選択され、かつ、該アルキル基、該アルケニル基又は該アリール基は、エーテル結合、ケトン結合若しくはエステル結合を含んでいても良い基を表し、
Ｒ_３は水素原子、炭素原子数１乃至１０のアルキル基、炭素原子数２乃至１０のアルケニル基、炭素原子数６乃至４０のアリール基、及びそれらの組み合わせからなる群から選択され、かつ、該アルキル基、該アルケニル基又は該アリール基は、エーテル結合、ケトン結合若しくはエステル結合を含んでいても良い基を表し、
Ｒ_４はハロゲン基、ニトロ基、アミノ基若しくはヒドロキシ基で置換されていても良い炭素原子数６乃至４０のアリール基又は複素環基を表し、
Ｒ_５は水素原子、又はハロゲン基、ニトロ基、アミノ基若しくはヒドロキシ基で置換されていても良い、炭素原子数１乃至１０のアルキル基、炭素原子数６乃至４０のアリール基又は複素環基を表し、そして
Ｒ_４とＲ_５はそれらが結合する炭素原子と一緒になって環を形成してもよく、
ｎ１及びｎ２はそれぞれ１乃至３の整数であり、
ｎ３乃至ｎ５はそれぞれ１乃至４の整数である。）で表される単位構造を含むポリマーである。 Preferably, the following formula (2) and/or formula (3):

(In formula (2) and formula (3),
R ₁ , R ₂ , R ₆ , R ₇ , and R ₈ are each a hydrogen atom, a halogen group, a nitro group, an amino group, a hydroxy group, an alkyl group having 1 to 10 carbon atoms, and an alkenyl group having 2 to 10 carbon atoms. group, an aryl group having 6 to 40 carbon atoms, and a combination thereof, and the alkyl group, the alkenyl group, or the aryl group contains an ether bond, a ketone bond, or an ester bond. also represents a good group,
R ₃ is selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, and a combination thereof; The alkyl group, the alkenyl group, or the aryl group represents a group that may contain an ether bond, a ketone bond, or an ester bond,
R ₄ represents an aryl group or heterocyclic group having 6 to 40 carbon atoms which may be substituted with a halogen group, nitro group, amino group or hydroxy group,
R ₅ is a hydrogen atom, or an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, or a heterocyclic group, which may be substituted with a halogen group, nitro group, amino group, or hydroxy group. and R ₄ and R ₅ together with the carbon atoms to which they are attached may form a ring,
n1 and n2 are each integers from 1 to 3,
n3 to n5 are integers from 1 to 4, respectively. ) is a polymer containing a unit structure represented by

Preferably, in the formula (2) and/or formula (3), R ₁ , R ₂ , R ₃ , R ₅ , R ₆ , R ₇ and R ₈ each represent a hydrogen atom, and R ₄ represents a phenyl group. Or it is a polymer containing a unit structure representing a naphthyl group.

(d) Examples of membrane materials capable of crosslinking include polymers containing a unit structure consisting of a reactant of a fused heterocyclic compound and a bicyclocyclic compound, as disclosed in WO 2013/005797 A1.

Preferably, the fused heterocyclic compound is a carbazole compound or a substituted carbazole compound.
Preferably, the bicyclo ring compound is dicyclopentadiene, substituted dicyclopentadiene, tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ] dodeca-3,8-diene, or substituted tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ] dodeca-3,8-diene.

（式中、Ｒ^１乃至Ｒ^１４は水素原子の置換基であり、それぞれ独立にハロゲン基、ニトロ基、アミノ基若しくはヒドロキシ基、又はそれらの基で置換されていても良い炭素原子数１乃至１０のアルキル基若しくは炭素原子数６乃至４０のアリール基であり、Ａｒは炭素原子数６乃至４０の芳香環基であり、ｎ_１、ｎ_２、ｎ_５、ｎ_６、ｎ_９、ｎ_１０、ｎ_１３、ｎ_１４及びｎ_１５はそれぞれ０乃至３の整数であり、ｎ_３、ｎ_４、ｎ_７、ｎ_８、ｎ_１１及びｎ_１２はそれぞれ０乃至４の整数である。）
好ましくは、上記式（３）中、Ａｒがフェニル基又はナフチル基である。 Preferably, the polymer is a polymer containing a unit structure represented by the following formula (1), a unit structure represented by formula (2), a unit structure represented by formula (3), or a combination thereof.

(In the formula, R ¹ to R ¹⁴ are substituents for a hydrogen atom, and each has a carbon atom number of 1 to 10 and may be independently substituted with a halogen group, nitro group, amino group, or hydroxy group, or a group thereof. is an alkyl group or an aryl group having 6 to 40 carbon atoms, Ar is an aromatic ring group having 6 to 40 carbon atoms, and n ₁ , n ₂ , n ₅ , n ₆ , n ₉ , n ₁₀ , n ₁₃ , n ₁₄ and n ₁₅ are each an integer from 0 to 3, and n ₃ , n ₄ , n ₇ , n ₈ , n ₁₁ and n ₁₂ are each an integer from 0 to 4.)
Preferably, in the above formula (3), Ar is a phenyl group or a naphthyl group.

（式（１）中、Ａはポリヒドロキシベンゼンに由来するヒドロキシ基置換フェニレン基であり、Ｂは２～４個のベンゼン環が縮合した１価の縮合芳香族炭化水素環基である。）の単位構造を含むポリマーが挙げられる。 (e) As a membrane material capable of crosslinking reaction, formula (1) as disclosed in WO 2012/176767 A1:

(In formula (1), A is a hydroxy group-substituted phenylene group derived from polyhydroxybenzene, and B is a monovalent fused aromatic hydrocarbon ring group in which 2 to 4 benzene rings are fused.) Examples include polymers containing unit structures.

Preferably, A is a hydroxy-substituted phenylene group derived from benzenediol or benzenetriol.
Preferably, A is a hydroxy-substituted phenylene group derived from catechol, resorcinol, hydroquinone, pyrogallol, hydroxyquinol, or phloroglucinol.
Preferably, the fused aromatic hydrocarbon ring group of B is a naphthalene ring group, an anthracene ring group, or a pyrene ring group.
Preferably, the condensed aromatic hydrocarbon ring group B has a halogen group, hydroxyl group, nitro group, amino group, carboxyl group, carboxylic acid ester group, nitrile group, or a combination thereof as a substituent.

（式（１）中、Ａｒ^１、及びＡｒ^２はそれぞれベンゼン環、又はナフタレン環を表し、Ｒ^１及びＲ^２はそれぞれこれら環上の水素原子の置換基でありハロゲン基、ニトロ基、アミノ基、ヒドロキシ基、炭素原子数１乃至１０のアルキル基、炭素原子数２乃至１０のアルケニル基、炭素原子数６乃至４０のアリール基、及びそれらの組み合わせからなる群より選択され、かつ、該アルキル基、該アルケニル基及び該アリール基は、エーテル結合、ケトン結合、若しくはエステル結合を含んでいてもよい有機基を表し、
Ｒ^３は水素原子、炭素原子数１乃至１０のアルキル基、炭素原子数２乃至１０のアルケニル基、炭素原子数６乃至４０のアリール基、及びそれらの組み合わせからなる群より選択され、かつ、該アルキル基、該アルケニル基及びアリール基は、エーテル結合、ケトン結合、若しくはエステル結合を含んでいてもよい有機基を表し、
Ｒ^４は炭素原子数６乃至４０のアリール基及び複素環基からなる群より選択され、かつ、該アリール基及び該複素環基は、ハロゲン基、ニトロ基、アミノ基、炭素原子数１乃至１０のアルキル基、炭素原子数１乃至１０のアルコキシ基、炭素原子数６乃至４０のアリール基、ホルミル基、カルボキシル基、又は水酸基で置換されていてもよい有機基を表し、
Ｒ^５は水素原子、炭素原子数１乃至１０のアルキル基、炭素原子数６乃至４０のアリール基、及び複素環基からなる群より選択され、かつ、該アルキル基、該アリール基及び該複素環基は、ハロゲン基、ニトロ基、アミノ基、若しくは水酸基で置換されていてもよい有機基を表し、そしてＲ^４とＲ^５はそれらが結合する炭素原子と一緒になって環を形成していてもよい。ｎ１及びｎ２はそれぞれ０乃至３の整数である。）で表される単位構造（Ａ）を含むポリマーが挙げられる。 (f) As a membrane material capable of crosslinking reaction, the following formula (1) as disclosed in WO 2013/047516 A1:

(In formula (1), Ar ¹ and Ar ² each represent a benzene ring or a naphthalene ring, and R ¹ and R ² each represent a substituent for the hydrogen atom on these rings, such as a halogen group, a nitro group, or an amino group. , a hydroxy group, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, and a combination thereof; , the alkenyl group and the aryl group represent an organic group that may contain an ether bond, a ketone bond, or an ester bond,
R ³ is selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, and a combination thereof; The alkyl group, the alkenyl group, and the aryl group represent an organic group that may contain an ether bond, a ketone bond, or an ester bond,
^R4 is selected from the group consisting of an aryl group and a heterocyclic group having 6 to 40 carbon atoms, and the aryl group and the heterocyclic group are halogen groups, nitro groups, amino groups, and 1 to 10 carbon atoms. represents an organic group optionally substituted with an alkyl group, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, a formyl group, a carboxyl group, or a hydroxyl group,
R ⁵ is selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, and a heterocyclic group, and The group represents an organic group which may be substituted with a halogen group, a nitro group, an amino group, or a hydroxyl group, and R ⁴ and R ⁵ together with the carbon atoms to which they are bonded form a ring. Good too. n1 and n2 are each integers from 0 to 3. ) Polymers containing the unit structure (A) represented by:

Preferably, R ⁵ in the above formula (1) is a hydrogen atom, and R ⁴ is an optionally substituted phenyl group, naphthyl group, anthryl group, or pyrenyl group.
Preferably, R ³ in the above formula (1) is a hydrogen atom or a phenyl group.
Preferably, in the unit structure (A), Ar ¹ and Ar ² include a unit structure (a1) in which one of Ar 1 and Ar 2 is a benzene ring and the other is a naphthalene ring.
Preferably, in the unit structure (A), Ar ¹ and Ar ² both include a unit structure (a2) that is a benzene ring.
Preferably, it is a copolymer containing unit structure (a1) and unit structure (a2).

（式（２）中、Ｒ^６は炭素原子数６乃至４０のアリール基及び複素環基からなる群より選択され、かつ、該アリール基及び該複素環基は、ハロゲン基、ニトロ基、アミノ基、炭素原子数１乃至１０のアルキル基、炭素原子数１乃至１０のアルコキシ基、炭素原子数６乃至４０のアリール基、ホルミル基、カルボキシル基、又は水酸基で置換されていてもよい有機基を表し、Ｒ^７は水素原子、炭素原子数１乃至１０のアルキル基、炭素原子数６乃至４０のアリール基、及び複素環基からなる群より選択され、かつ、該アルキル基、該アリール基及び該複素環基は、ハロゲン基、ニトロ基、アミノ基、若しくは水酸基で置換されていてもよい有機基を表し、そしてＲ^６とＲ^７はそれらが結合する炭素原子と一緒になって環を形成していてもよい。）を含む共重合体である。
好ましくは、単位構造（ａ１）と単位構造（Ｂ）を含む共重合体である。 Preferably, the unit structure (A) of formula (1) and the unit structure (B) of the following formula (2):

(In formula (2), R ⁶ is selected from the group consisting of an aryl group and a heterocyclic group having 6 to 40 carbon atoms, and the aryl group and the heterocyclic group are a halogen group, a nitro group, an amino group. , represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, a formyl group, a carboxyl group, or an organic group which may be substituted with a hydroxyl group. , R ⁷ is selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, and a heterocyclic group, and The cyclic group represents an organic group which may be substituted with a halogen group, a nitro group, an amino group, or a hydroxyl group, and R ⁶ and R ⁷ together with the carbon atoms to which they are bonded form a ring. ) is a copolymer containing
Preferably, it is a copolymer containing the unit structure (a1) and the unit structure (B).

（式（１）中、Ｒ^１、Ｒ^２、及びＲ^３は環の水素原子の置換基であって、それぞれ独立に、ハロゲン基、ニトロ基、アミノ基、水酸基、炭素数１乃至１０のアルキル基、炭素数２乃至１０のアルケニル基、炭素数６乃至４０のアリール基、又はエーテル結合、ケトン結合、若しくはエステル結合を含んでいても良いそれらの組み合わせである。Ｒ^４は水素原子、炭素数１乃至１０のアルキル基、炭素数２乃至１０のアルケニル基、炭素数６乃至４０のアリール基、又はエーテル結合、ケトン結合、若しくはエステル結合を含んでいても良いそれらの組み合わせである。Ｒ^５は水素原子、又はハロゲン基、ニトロ基、アミノ基、ホルミル基、カルボキシル基、カルボン酸アルキルエステル基、フェニル基、炭素数１乃至１０のアルコキシ基、若しくは水酸基で置換されていても良い炭素数６乃至４０のアリール基、又は複素環基であり、Ｒ^６は水素原子、又はハロゲン基、ニトロ基、アミノ基、ホルミル基、カルボキシル基、カルボン酸アルキルエステル基、若しくは水酸基で置換されていても良い炭素数１乃至１０のアルキル基、炭素数６乃至４０のアリール基、又は複素環基であり、あるいはＲ^５とＲ^６はそれらが結合する炭素原子と一緒になって環を形成していても良い。環Ａ及び環Ｂはそれぞれベンゼン環、ナフタレン環、又はアントラセン環を示す。ｎ１、ｎ２、及びｎ３はそれぞれ０以上で、且つ環に置換できる最大の数までの整数である。）で表される単位構造を有するポリマーが挙げられる。 (g) As a membrane material capable of crosslinking reaction, the following formula (1) as disclosed in WO 2013/146670 A1:

(In formula (1), R ¹ , R ² , and R ³ are substituents for the hydrogen atom of the ring, and each independently represents a halogen group, a nitro group, an amino group, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms) group, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, or a combination thereof which may contain an ether bond, a ketone bond, or an ester bond.R ⁴ is a hydrogen atom, a carbon number R ⁵ is an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, or a combination thereof which may contain an ether bond, a ketone bond, or an ester bond. 6 to 6 carbon atoms, which may be substituted with a hydrogen atom, or a halogen group, a nitro group, an amino group, a formyl group, a carboxyl group, a carboxylic acid alkyl ester group, a phenyl group, an alkoxy group having 1 to 10 carbon atoms, or a hydroxyl group 40 aryl group or heterocyclic group, and R ⁶ is a hydrogen atom, or a carbon group optionally substituted with a halogen group, nitro group, amino group, formyl group, carboxyl group, carboxylic acid alkyl ester group, or hydroxyl group. It is an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, or a heterocyclic group, or R ⁵ and R ⁶ may form a ring together with the carbon atoms to which they are bonded. Ring A and Ring B each represent a benzene ring, a naphthalene ring, or an anthracene ring. n1, n2, and n3 are each an integer of 0 or more and up to the maximum number that can be substituted on the ring. Examples include polymers having a unit structure.

Preferably, ring A and ring B are both benzene rings, n1, n2, and n3 are 0, and ^R4 is a hydrogen atom.
Preferably, R ⁵ is substituted with a hydrogen atom, a halogen group, a nitro group, an amino group, a formyl group, a carboxyl group, a carboxylic acid alkyl ester group, a phenyl group, an alkoxy group having 1 to 10 carbon atoms, or a hydroxyl group. is also a phenyl group, naphthyl group, anthryl group, or pyrenyl group, and R ⁶ is a hydrogen atom.

［式中、２つのＲ^１はそれぞれ独立に炭素原子数１乃至１０のアルキル基、炭素原子数２乃至６のアルケニル基、芳香族炭化水素基、ハロゲン原子、ニトロ基又はアミノ基を表し、２つのＲ^２はそれぞれ独立に水素原子、炭素原子数１乃至１０のアルキル基、炭素原子数２乃至６のアルケニル基、アセタール基、アシル基又はグリシジル基を表し、Ｒ^３は置換基を有してもよい芳香族炭化水素基を表し、Ｒ^４は水素原子、フェニル基又はナフチル基を表し、同一の炭素原子と結合するＲ^３とＲ^４がそれぞれフェニル基を表すとき互いに結合してフルオレン環を形成してもよく、式（１ｂ）において２つのＲ^３が表す基及び２つのＲ^４が表す原子又は基は互いに異なっていてもよく、２つのｋはそれぞれ独立に０又は１を表し、ｍは３乃至５００の整数を表し、ｎ、ｎ_１及びｎ_２は２乃至５００の整数を表し、ｐは３乃至５００の整数を表し、Ｘは単結合又はヘテロ原子を表し、２つのＱはそれぞれ独立に下記式（２）：

（式中、２つのＲ^１、２つのＲ^２、２つのＲ^３、２つのＲ^４、２つのｋ、ｎ_１、ｎ_２及びＸは式（１ｂ）と同義であり、２つのＱ^１はそれぞれ独立に前記式（２）で表される構造単位を表す。）
で表される構造単位を表す。］
で表される繰り返し構造単位のうちいずれか１つ又は２つ以上を有するポリマーが挙げられる。 (h) Membrane materials capable of crosslinking reaction include the following formulas (1a), (1b), and (1c) as disclosed in WO 2014/129582 A1:

[In the formula, each of the two R ¹ independently represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aromatic hydrocarbon group, a halogen atom, a nitro group, or an amino group, and 2 Each R ² independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an acetal group, an acyl group, or a glycidyl group, and R ³ has a substituent. ^R4 represents a hydrogen atom, a phenyl group or a naphthyl group, and when ^R3 and ^R4 bonded to the same carbon atom each represent a phenyl group, they bond to each other to form a fluorene ring. In formula (1b), the two groups represented by R ³ and the two atoms or groups represented by R ⁴ may be different from each other, the two k each independently represent 0 or 1, and m represents an integer from 3 to 500, n, n ₁ and n ₂ represent an integer from 2 to 500, p represents an integer from 3 to 500, X represents a single bond or a heteroatom, and the two Qs each Independently the following formula (2):

(In the formula, two R ¹ , two R ² , two R ³ , two R ⁴ , two k, n ₁ , n ₂ and X are synonymous with formula (1b), and two Q ¹ are Each independently represents a structural unit represented by the above formula (2).)
represents the structural unit represented by ]
Examples include polymers having one or more of the repeating structural units represented by the following.

Preferably, the aromatic hydrocarbon group represented by R ³ is a phenyl group, a naphthyl group, an anthryl group, or a pyrenyl group.

（式（１）中、Ｒ^１乃至Ｒ^４はそれぞれ独立に水素原子又はメチル基を示す。Ｘ^１はアルキル基、アミノ基、又はヒドロキシル基で置換されていても良い少なくとも一つのアリーレン基を含む二価の有機基を示す。）で表される単位構造を含むポリマーが挙げられる。 (i) As a membrane material capable of crosslinking reaction, the following formula (1) as disclosed in WO 2016/072316 A1:

(In formula (1), R ¹ to R ⁴ each independently represent a hydrogen atom or a methyl group. X ¹ contains at least one arylene group that may be substituted with an alkyl group, an amino group, or a hydroxyl group. (represents a divalent organic group.) Polymers containing a unit structure represented by:

Preferably, in formula (1), the arylene group in the definition of X ¹ is a phenylene group, biphenylene group, terphenylene group, fluorenylene group, naphthylene group, anthrylene group, pyrenylene group, or carbazorylene group.

〔式（２）中、Ａ^１はフェニレン基又はナフチレン基を表す。Ａ^２はフェニレン基、ナフチレン基、又は式（３）：

（式（３）中、Ａ^３及びＡ^４はそれぞれ独立にフェニレン基又はナフチレン基を表す。点線は結合を表す。）で示される有機基を表す。点線は結合を表す。〕で表される有機基である。 Preferably, in formula (1), X ¹ is formula (2):

[In formula (2), A ¹ represents a phenylene group or a naphthylene group. ^A2 is a phenylene group, a naphthylene group, or formula (3):

(In formula (3), A ³ and A ⁴ each independently represent a phenylene group or a naphthylene group. A dotted line represents a bond.) represents an organic group. Dotted lines represent bonds. ] is an organic group represented by

(j) Film materials capable of crosslinking reaction include aromatic compounds (A) and secondary or tertiary carbon atoms of alkyl groups having 2 to 26 carbon atoms, as disclosed in WO 2017/069063 A1. Examples include novolak resins obtained by reaction with an aldehyde (B) having a formyl group bonded to a carbon atom.

（式（１）中、Ａは炭素原子数６乃至４０の芳香族化合物から誘導される二価基を示し、ｂ^１は炭素原子数１乃至１６のアルキル基を示し、ｂ^２は水素原子又は炭素原子数１乃至９のアルキル基を示す。）で表される単位構造を含むものである。 Preferably, the novolac resin has the following formula (1):

(In formula (1), A represents a divalent group derived from an aromatic compound having 6 to 40 carbon atoms, b ¹ represents an alkyl group having 1 to 16 carbon atoms, and b ² represents a hydrogen atom or (representing an alkyl group having 1 to 9 carbon atoms).

Preferably, A is a divalent group derived from an aromatic compound containing an amino group, a hydroxyl group, or both.
Preferably, A is a divalent group derived from an aromatic compound including an arylamine compound, a phenolic compound, or both.
Preferably, A is a dihydric phenol derived from aniline, diphenylamine, phenylnaphthylamine, hydroxydiphenylamine, carbazole, phenol, N,N'-diphenylethylenediamine, N,N'-diphenyl-1,4-phenylenediamine, or polynuclear phenol. It is the basis.
Preferably, the polynuclear phenol is dihydroxybenzene, trihydroxybenzene, hydroxynaphthalene, dihydroxynaphthalene, trihydroxynaphthalene, tris(4-hydroxyphenyl)methane, tris(4-hydroxyphenyl)ethane, 2,2'-biphenol, or , 1,2,2-tetrakis(4-hydroxyphenyl)ethane.

（式（２）中、ａ^１及びａ^２はそれぞれ置換されていても良いベンゼン環又はナフタレン環を示し、Ｒ^１は第２級アミノ基もしくは第３級アミノ基、置換されていても良い炭素原子数１乃至１０の二価炭化水素基、アリーレン基、又はこれらの基が任意に結合した二価の基を示す。ｂ^３は炭素原子数１乃至１６のアルキル基を示し、ｂ^４は水素原子又は炭素原子数１乃至９のアルキル基を示す。）で表される単位構造を含むものである。 Preferably, the novolak resin has the following formula (2):

(In formula (2), a ¹ and a ² each represent an optionally substituted benzene ring or naphthalene ring, and R ¹ is a secondary amino group or tertiary amino group, an optionally substituted carbon Represents a divalent hydrocarbon group having 1 to 10 atoms, an arylene group, or a divalent group in which these groups are optionally bonded. b ³ represents an alkyl group having 1 to 16 carbon atoms, and b ⁴ represents hydrogen. atom or an alkyl group having 1 to 9 carbon atoms).

［式（１ａ）及び（１ｂ）中、２つのＲ^１はそれぞれ独立に炭素原子数１乃至１０のアルキル基、炭素原子数２乃至６のアルケニル基、芳香族炭化水素基、ハロゲン原子、ニトロ基又はアミノ基を表し、２つのＲ^２はそれぞれ独立に水素原子、炭素原子数１乃至１０のアルキル基、炭素原子数２乃至６のアルケニル基、アセタール基、アシル基又はグリシジル基を表し、Ｒ^３は置換基を有してもよい芳香族炭化水素基又は複素環基を表し、Ｒ^４は水素原子、フェニル基又はナフチル基を表し、同一の炭素原子と結合するＲ^３とＲ^４がそれぞれフェニル基を表すとき互いに結合してフルオレン環を形成してもよく、２つのｋはそれぞれ独立に０又は１を表し、ｍは３乃至５００の整数を表し、ｐは３乃至５００の整数を表し、Ｘはベンゼン環を表し、該ベンゼン環と結合する２つの－Ｃ（ＣＨ_３）_２－基はメタ位又はパラ位の関係にある。］
で表される繰り返し構造単位を有するポリマーが挙げられる。 (k) As a membrane material capable of crosslinking reaction, the following formula (1a) and/or formula (1b) as disclosed in WO 2017/199768 A1:

[In formulas (1a) and (1b), each of the two R ¹ 's independently represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aromatic hydrocarbon group, a halogen atom, a nitro group or represents an amino group, each of the two R ² independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an acetal group, an acyl group, or a glycidyl group, and R ³ represents an aromatic hydrocarbon group or a heterocyclic group which may have a substituent, R ⁴ represents a hydrogen atom, a phenyl group or a naphthyl group, and R ³ and R ⁴ bonded to the same carbon atom each represent phenyl When representing a group, they may be combined with each other to form a fluorene ring, the two k's each independently represent 0 or 1, m represents an integer of 3 to 500, p represents an integer of 3 to 500, X represents a benzene ring, and the two -C(CH ₃ ) ₂ - groups bonded to the benzene ring are in a meta- or para-position relationship. ]
Examples include polymers having repeating structural units represented by:

Preferably, the polymer is a polymerization reaction product of at least one bisphenol compound and at least one aromatic aldehyde or aromatic ketone.
Preferably, the aromatic hydrocarbon group represented by R ³ is a phenyl group, a naphthyl group, an anthryl group, or a pyrenyl group.

(l) Membrane materials capable of crosslinking include poly(epoxide) resins having an epoxy functionality greater than 2.0 and less than 10, as disclosed in JP-A-11-511194.

Preferably, the poly(epoxide) resin is selected from the group consisting of bisphenol A-epichlorohydrin resin products, epoxy novolacs, o-cresol epoxy novolacs, polyglycidyl ethers, polyglycidyl amines, cycloaliphatic epoxides, and polyglycidyl esters. be done.
Preferably the poly(epoxide) resin has an epoxy functionality greater than 3.5.

［式（１）中、

は単結合又は二重結合を表し、
Ｘ^１は、－Ｎ（Ｒ^１）－又は－ＣＨ（Ｒ^１）－を表し、
Ｘ^２は、－Ｎ（Ｒ^２）－又は－ＣＨ（Ｒ^２）－を表し、
Ｘ^３は、－Ｎ＝、－ＣＨ＝、－Ｎ（Ｒ^３）－又は－ＣＨ（Ｒ^３）－を表し、
Ｘ^４は、－Ｎ＝、－ＣＨ＝、－Ｎ（Ｒ^４）－又は－ＣＨ（Ｒ^４）－を表し、
Ｒ^１、Ｒ^２、Ｒ^３及びＲ^４は同一又は異なり、それぞれ水素原子、Ｃ１～２０の直鎖状、分岐状もしくは環状のアルキル基、Ｃ６～２０のアリール基、Ｃ２～１０のアルケニル基、Ｃ２～１０のアルキニル基、カルボキシル基又はシアノ基を表し、上記アルキル基及びアリール基はＣ１～６のアシル基、Ｃ１～６のアルコキシ基、Ｃ１～６のアルコキシカルボニル基、アミノ基、グリシジル基又はヒドロキシ基で置換されていてもよく、且つ、酸素原子又は硫黄原子で中断されていてもよく、
Ｒ^５、Ｒ^６、Ｒ^９及びＲ^１０は同一又は異なり、それぞれ水素原子、ヒドロキシ基、Ｃ１～６のアシル基、Ｃ１～６のアルコキシ基、Ｃ１～６のアルコキシカルボニル基、Ｃ１～１０の直鎖状、分岐状もしくは環状のアルキル基、Ｃ６～２０のアリール基、Ｃ２～２０のアルケニル基又はＣ２～１０のアルキニル基を表し、上記アシル基、アルコキシ基、アルコキシカルボニル基、アルキル基、アリール基、アルケニル基及びアルキニル基は、アミノ基、ニトロ基、シアノ基、ヒドロキシ基、グリシジル基及びカルボキシル基からなる群より選択される基を１つ又は複数有していても良く、
Ｒ^７及びＲ^８は同一又は異なり、それぞれベンゼン環又はナフタレン環を表し、
ｎ及びｏは０又は１である。］ (m) Examples of the membrane material or novolak membrane material capable of crosslinking include a compound represented by the following formula (1) and a novolak membrane material as disclosed in WO 2018/198960 A1.

[In formula (1),

represents a single bond or a double bond,
X ¹ represents -N(R ¹ )- or -CH(R ¹ )-,
X ² represents -N(R ² )- or -CH(R ² )-,
X ³ represents -N=, -CH=, -N(R ³ )- or -CH(R ³ )-,
X ⁴ represents -N=, -CH=, -N(R ⁴ )- or -CH(R ⁴ )-,
R ¹ , R ² , R ³ and R ⁴ are the same or different, and each is a hydrogen atom, a C1-20 linear, branched or cyclic alkyl group, a C6-20 aryl group, a C2-10 alkenyl group, Represents a C2-10 alkynyl group, carboxyl group or cyano group, and the alkyl group and aryl group mentioned above are a C1-6 acyl group, a C1-6 alkoxy group, a C1-6 alkoxycarbonyl group, an amino group, a glycidyl group, or may be substituted with a hydroxy group and may be interrupted with an oxygen atom or a sulfur atom,
R ⁵ , R ⁶ , R ⁹ and R ¹⁰ are the same or different and each represents a hydrogen atom, a hydroxy group, a C1-6 acyl group, a C1-6 alkoxy group, a C1-6 alkoxycarbonyl group, a C1-10 straight Represents a chain, branched or cyclic alkyl group, C6-20 aryl group, C2-20 alkenyl group or C2-10 alkynyl group, and the above acyl group, alkoxy group, alkoxycarbonyl group, alkyl group, aryl group , the alkenyl group and the alkynyl group may have one or more groups selected from the group consisting of an amino group, a nitro group, a cyano group, a hydroxy group, a glycidyl group, and a carboxyl group,
R ⁷ and R ⁸ are the same or different and each represents a benzene ring or a naphthalene ring,
n and o are 0 or 1. ]

Preferably, R ¹ , R ² , R ³ or R ⁴ in formula (1) is a hydroxy group or C1-- which may be substituted with a hydroxy group and may be interrupted with an oxygen atom or a sulfur atom. 20 linear, branched or cyclic alkyl groups.

式（２）
［式（２）中、

は単結合又は二重結合を表し、
Ｘ^１は、－Ｎ（Ｒ^１）－、－ＣＨ（Ｒ^１）－、－Ｎ＜又は－ＣＨ＜を表し、
Ｘ^２は、－Ｎ（Ｒ^２）－、－ＣＨ（Ｒ^２）－、－Ｎ＜又は－ＣＨ＜を表し、
Ｘ^３は、－Ｎ＝、－ＣＨ＝、－Ｎ（Ｒ^３）－、－ＣＨ（Ｒ^３）－、－Ｎ＜又は－ＣＨ＜を表し、
Ｘ^４は、－Ｎ＝、－ＣＨ＝、－Ｎ（Ｒ^４）－、－ＣＨ（Ｒ^４）－、－Ｎ＜又は－ＣＨ＜を表し、
Ｒ^１、Ｒ^２、Ｒ^３及びＲ^４は同一又は異なり、それぞれ水素原子、Ｃ１～２０の直鎖状、分岐状もしくは環状のアルキル基、Ｃ６～２０のアリール基、Ｃ２～１０のアルケニル基、Ｃ２～１０のアルキニル基、カルボキシル基又はシアノ基を表し、上記アルキル基及びアリール基はＣ１～６のアシル基、Ｃ１～６のアルコキシ基、Ｃ１～６のアルコキシカルボニル基、アミノ基、グリシジル基又はヒドロキシ基で置換されていてもよく、且つ、酸素原子又は硫黄原子で中断されていてもよく、
Ｒ^５、Ｒ^６、Ｒ^９及びＲ^１０は同一又は異なり、それぞれ水素原子、ヒドロキシ基、Ｃ１～６のアシル基、Ｃ１～６のアルコキシ基、Ｃ１～６のアルコキシカルボニル基、Ｃ１～１０の直鎖状、分岐状もしくは環状のアルキル基、Ｃ６～２０のアリール基、Ｃ２～２０のアルケニル基又はＣ２～１０のアルキニル基を表し、上記アシル基、アルコキシ基、アルコキシカルボニル基、アルキル基、アリール基、アルケニル基及びアルキニル基は、アミノ基、ニトロ基、シアノ基、ヒドロキシ基、グリシジル基及びカルボキシル基からなる群より選択される基を１つ又は複数有していても良く、
Ｒ^７及びＲ^８は同一又は異なり、それぞれベンゼン環又はナフタレン環を表し、
ｎ及びｏは０又は１であり、
Ｂ^１とＢ^２は同一又は異なり、それぞれ水素原子、酸素原子もしくは硫黄原子で中断されていてもよいＣ１～２０の直鎖状、分岐状もしくは環状のアルキル基又はＣ６～４０のアリール基及びＣ６～４０の複素環基からなる群より選択される芳香族化合物由来の基を表し、Ｂ^１とＢ^２はこれらが結合する炭素原子と一緒になって環を形成してもよく、前記芳香族化合物由来の基の水素原子は、Ｃ１～２０のアルキル基、フェニル基、縮合環基、複素環基、ヒドロキシ基、アミノ基、エーテル基、アルコキシ基、シアノ基、ニトロ基又はカルボキシル基で置換されていてもよい。］ Preferably, it is a compound containing one or more repeating units a, b, c, d, e, f, g, h, and i represented by the following formula (2).

Formula (2)
[In formula (2),

represents a single bond or a double bond,
X ¹ represents -N(R ¹ )-, -CH(R ¹ )-, -N< or -CH<,
X ² represents -N(R ² )-, -CH(R ² )-, -N< or -CH<,
X ³ represents -N=, -CH=, -N(R ³ )-, -CH(R ³ )-, -N< or -CH<,
X ⁴ represents -N=, -CH=, -N(R ⁴ )-, -CH(R ⁴ )-, -N< or -CH<,
R ¹ , R ² , R ³ and R ⁴ are the same or different, and each is a hydrogen atom, a C1-20 linear, branched or cyclic alkyl group, a C6-20 aryl group, a C2-10 alkenyl group, Represents a C2-10 alkynyl group, carboxyl group or cyano group, and the alkyl group and aryl group mentioned above are a C1-6 acyl group, a C1-6 alkoxy group, a C1-6 alkoxycarbonyl group, an amino group, a glycidyl group, or may be substituted with a hydroxy group and may be interrupted with an oxygen atom or a sulfur atom,
R ⁵ , R ⁶ , R ⁹ and R ¹⁰ are the same or different and each represents a hydrogen atom, a hydroxy group, a C1-6 acyl group, a C1-6 alkoxy group, a C1-6 alkoxycarbonyl group, a C1-10 straight Represents a chain, branched or cyclic alkyl group, C6-20 aryl group, C2-20 alkenyl group or C2-10 alkynyl group, and the above acyl group, alkoxy group, alkoxycarbonyl group, alkyl group, aryl group , the alkenyl group and the alkynyl group may have one or more groups selected from the group consisting of an amino group, a nitro group, a cyano group, a hydroxy group, a glycidyl group, and a carboxyl group,
R ⁷ and R ⁸ are the same or different and each represents a benzene ring or a naphthalene ring,
n and o are 0 or 1,
B ¹ and B ² are the same or different, each a C1-20 linear, branched or cyclic alkyl group which may be interrupted by a hydrogen atom, oxygen atom or sulfur atom, or a C6-40 aryl group, and a C6-40 aryl group; represents a group derived from an aromatic compound selected from the group consisting of ~40 heterocyclic groups, B ¹ and B ² may form a ring together with the carbon atoms to which they are bonded, and the aromatic The hydrogen atom of the group derived from the compound is substituted with a C1-20 alkyl group, phenyl group, fused ring group, heterocyclic group, hydroxy group, amino group, ether group, alkoxy group, cyano group, nitro group or carboxyl group. You can leave it there. ]

式（３）
［式（３）中、

は単結合又は二重結合を表し、
Ｘ^１は、－Ｎ＜又は－ＣＨ＜を表し、
Ｘ^２は、－Ｎ＜又は－ＣＨ＜を表し、
Ｘ^３は、－Ｎ＝、－ＣＨ＝、－Ｎ（Ｒ^３）－又は－ＣＨ（Ｒ^３）－を表し、
Ｘ^４は、－Ｎ＝、－ＣＨ＝、－Ｎ（Ｒ^４）－又は－ＣＨ（Ｒ^４）－を表し、
Ｒ^３及びＲ^４は同一又は異なり、それぞれ水素原子、Ｃ１～２０の直鎖状、分岐状もしくは環状のアルキル基、Ｃ６～２０のアリール基、Ｃ２～１０のアルケニル基、Ｃ２～１０のアルキニル基、カルボキシル基又はシアノ基を表し、上記アルキル基及びアリール基はＣ１～６のアシル基、Ｃ１～６のアルコキシ基、Ｃ１～６のアルコキシカルボニル基、アミノ基、グリシジル基又はヒドロキシ基で置換されていてもよく、且つ、酸素原子又は硫黄原子で中断されていてもよく、
Ｒ^５、Ｒ^６、Ｒ^９及びＲ^１０は同一又は異なり、それぞれ水素原子、ヒドロキシ基、Ｃ１～６のアシル基、Ｃ１～６のアルコキシ基、Ｃ１～６のアルコキシカルボニル基、Ｃ１～１０の直鎖状、分岐状もしくは環状のアルキル基、Ｃ６～２０のアリール基、Ｃ２～２０のアルケニル基又はＣ２～１０のアルキニル基を表し、上記アシル基、アルコキシ基、アルコキシカルボニル基、アルキル基、アリール基、アルケニル基及びアルキニル基は、アミノ基、ニトロ基、シアノ基、ヒドロキシ基、グリシジル基及びカルボキシル基からなる群より選択される基を１つ又は複数有していても良く、
Ｒ^７及びＲ^８は同一又は異なり、それぞれベンゼン環又はナフタレン環を表し、
ｎ及びｏは０又は１であり、
ｐ及びｑは０～２０の整数であり、
ｐ個のメチレン基及びｑ個のメチレン基は２個以上の場合には酸素原子又は硫黄原子で中断されていてもよく、
Ｂ^３は直接結合、又はＣ１～２０のアルキル基、フェニル基、縮合環基、複素環基、ヒドロキシ基、アミノ基、エーテル基、アルコキシ基、シアノ基、ニトロ基もしくはカルボキシル基で置換されていてもよいＣ６～４０の芳香族化合物由来の基を表す。］ Preferably, it is a compound containing one or more of one or more of repeating units j, k, l, m, r, s, t, u, v, and w represented by the following formula (3).

Formula (3)
[In formula (3),

represents a single bond or a double bond,
X ¹ represents -N< or -CH<,
X ² represents -N< or -CH<,
X ³ represents -N=, -CH=, -N(R ³ )- or -CH(R ³ )-,
X ⁴ represents -N=, -CH=, -N(R ⁴ )- or -CH(R ⁴ )-,
R ³ and R ⁴ are the same or different, and each is a hydrogen atom, a C1-20 linear, branched or cyclic alkyl group, a C6-20 aryl group, a C2-10 alkenyl group, a C2-10 alkynyl group , represents a carboxyl group or a cyano group, and the above alkyl group and aryl group are substituted with a C1-6 acyl group, a C1-6 alkoxy group, a C1-6 alkoxycarbonyl group, an amino group, a glycidyl group, or a hydroxy group. and may be interrupted by an oxygen atom or a sulfur atom,
R ⁵ , R ⁶ , R ⁹ and R ¹⁰ are the same or different and each represents a hydrogen atom, a hydroxy group, a C1-6 acyl group, a C1-6 alkoxy group, a C1-6 alkoxycarbonyl group, a C1-10 straight Represents a chain, branched or cyclic alkyl group, C6-20 aryl group, C2-20 alkenyl group or C2-10 alkynyl group, and the above acyl group, alkoxy group, alkoxycarbonyl group, alkyl group, aryl group , the alkenyl group and the alkynyl group may have one or more groups selected from the group consisting of an amino group, a nitro group, a cyano group, a hydroxy group, a glycidyl group, and a carboxyl group,
R ⁷ and R ⁸ are the same or different and each represents a benzene ring or a naphthalene ring,
n and o are 0 or 1,
p and q are integers from 0 to 20,
When there are two or more p methylene groups and q methylene groups, they may be interrupted by an oxygen atom or a sulfur atom,
^B3 is a direct bond or substituted with a C1-20 alkyl group, phenyl group, fused ring group, heterocyclic group, hydroxy group, amino group, ether group, alkoxy group, cyano group, nitro group or carboxyl group. Represents a group derived from a C6-40 aromatic compound. ]

Preferably, R ¹ , R ² , R ³ or R ⁴ in formula (1) is a hydroxy group or C1-- which may be substituted with a hydroxy group and may be interrupted with an oxygen atom or a sulfur atom. 20 linear, branched or cyclic alkyl groups.

(n) Membrane materials capable of crosslinking include epoxy group-containing compounds having at least two epoxy groups and epoxy groups having one epoxy addition-reactive group, as disclosed in WO 2017/002653 A1. Included are epoxy adducts formed by reaction with adduct-forming compounds.
Such epoxy adducts can be exemplified below.

(In the formula, a, b, c, and d are each 0 or 1, and a+b+c+d=1.)

(o) As a membrane material capable of crosslinking reaction, formula (1) as disclosed in WO 2005/098542 A1:

（式中、Ａ_１、Ａ_２、Ａ_３、Ａ_４、Ａ_５、及びＡ_６は、それぞれ、水素原子、メチル基またはエチル基を表し、Ｘ_１は式（２）、式（３）、式（４）または式（５）：

(In the formula, A ₁ , A ₂ , A ₃ , A ₄ , A ₅ , and A ₆ each represent a hydrogen atom, a methyl group, or an ethyl group, and X ₁ is a formula (2), a formula (3), Formula (4) or formula (5):

（式中Ｒ_１及びＲ_２はそれぞれ、水素原子、炭素原子数１～６のアルキル基、炭素原子数３～６のアルケニル基、ベンジル基またはフェニル基を表し、そして、前記フェニル基は、炭素原子数１～６のアルキル基、ハロゲン原子、炭素原子数１～６のアルコキシ基、ニトロ基、シアノ基、水酸基、及び炭素原子数１～６のアルキルチオ基からなる群から選ばれる基で置換されていてもよく、また、Ｒ_１とＲ_２は互いに結合して炭素原子数３～６の環を形成していてもよく、Ｒ_３は炭素原子数１～６のアルキル基、炭素原子数３～６のアルケニル基、ベンジル基またはフェニル基を表し、そして、前記フェニル基は、炭素原子数１～６のアルキル基、ハロゲン原子、炭素原子数１～６のアルコキシ基、ニトロ基、シアノ基、水酸基、及び炭素原子数１～６のアルキルチオ基からなる群から選ばれる基で置換されていてもよい）を表し、Ｑは式（６）または式（７）：

（式中Ｑ_１は炭素原子数１～１０のアルキレン基、フェニレン基、ナフチレン基、またはアントリレン基を表し、そして、前記フェニレン基、ナフチレン基、及びアントリレン基は、それぞれ、炭素原子数１～６のアルキル基、ハロゲン原子、炭素原子数１～６のアルコキシ基、ニトロ基、シアノ基、水酸基、及び炭素原子数１～６のアルキルチオ基からなる群から選ばれる基で置換されていてもよく、ｎ_１及びｎ_２はそれぞれ０または１の数を表し、Ｘ_２は式（２）、式（３）または式（５）を表す）を表す）で表される構造を有するポリマーが挙げられる。

(In the formula, R ₁ and R ₂ each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, a benzyl group, or a phenyl group, and the phenyl group is a carbon Substituted with a group selected from the group consisting of an alkyl group having 1 to 6 atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, a hydroxyl group, and an alkylthio group having 1 to 6 carbon atoms. Furthermore, R ₁ and R ₂ may be bonded to each other to form a ring having 3 to 6 carbon atoms, and R ₃ is an alkyl group having 1 to 6 carbon atoms, or an alkyl group having 3 to 6 carbon atoms. -6 alkenyl group, benzyl group or phenyl group, and the phenyl group is an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, (optionally substituted with a group selected from the group consisting of a hydroxyl group and an alkylthio group having 1 to 6 carbon atoms), and Q represents formula (6) or formula (7):

(In the formula, Q ₁ represents an alkylene group having 1 to 10 carbon atoms, a phenylene group, a naphthylene group, or an anthrylene group, and each of the phenylene group, naphthylene group, and anthrylene group has 1 to 6 carbon atoms. may be substituted with a group selected from the group consisting of an alkyl group, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, a hydroxyl group, and an alkylthio group having 1 to 6 carbon atoms, n ₁ and n ₂ each represent the number 0 or 1, and X ₂ represents formula (2), formula (3), or formula (5)).

（式中、Ｒ_１、Ｒ_２、Ｑは、上で定義されたと同じ意味を表す）
又は、式（１３）：

（式中、Ｘ_１は上で定義されたと同じ意味を表し、Ｙは炭素原子数１～６のアルキル基、ハロゲン原子、炭素原子数１～６のアルコキシ基、ニトロ基、シアノ基、水酸基または炭素原子数１～６のアルキルチオ基を表し、ｍは０乃至４の整数を表し、そしてｍが２乃至４の場合前記Ｙは同一であっても異なっていてもよい）
で表される構造である。 Preferably, the structure represented by formula (1) is represented by formula (12):

(wherein R ₁ , R ₂ , Q represent the same meanings as defined above)
Or formula (13):

(In the _formula , represents an alkylthio group having 1 to 6 carbon atoms, m represents an integer of 0 to 4, and when m is 2 to 4, the above Y may be the same or different)
This is the structure represented by .

｛式中、Ｒ_１及びＲ_２はそれぞれ、水素原子、メチル基、エチル基又はハロゲン原子を表し、Ａ_１、Ａ_２、Ａ_３、Ａ_４、Ａ_５、及びＡ_６は、それぞれ、水素原子、メチル基またはエチル基を表し、Ｑは式（３）または式（４）：

［式中、Ｑ_１は炭素原子数１～１５のアルキレン基、フェニレン基、ナフチレン基、またはアントリレン基を表し、そして、前記フェニレン基、ナフチレン基、及びアントリレン基は、それぞれ、炭素原子数１～６のアルキル基、ハロゲン原子、炭素原子数１～６のアルコキシ基、ニトロ基、シアノ基、ヒドロキシル基、及び炭素原子数１～６のアルキルチオ基からなる群から選ばれる基で置換されていてもよく、ｎ_１及びｎ_２はそれぞれ０または１の数を表し、Ｘ_１は式（５）、（６）または式（７）：

（式中、Ｒ_３及びＲ_４はそれぞれ、水素原子、炭素原子数１～６のアルキル基、炭素原子数３～６のアルケニル基、ベンジル基またはフェニル基を表し、そして、前記フェニル基は、炭素原子数１～６のアルキル基、ハロゲン原子、炭素原子数１～６のアルコキシ基、ニトロ基、シアノ基、ヒドロキシル基、及び炭素原子数１～６のアルキルチオ基からなる群から選ばれる基で置換されていてもよく、また、Ｒ_３とＲ_４は互いに結合して炭素原子数３～６の環を形成していてもよく、Ｒ_５は炭素原子数１～６のアルキル基、炭素原子数３～６のアルケニル基、ベンジル基またはフェニル基を表し、そして、前記フェニル基は、炭素原子数１～６のアルキル基、ハロゲン原子、炭素原子数１～６のアルコキシ基、ニトロ基、シアノ基、ヒドロキシル基、及び炭素原子数１～６のアルキルチオ基からなる群から選ばれる基で置換されていてもよい。）を表す。］を表す。｝で表される繰り返しの単位構造を有するポリマーが挙げられる。 (p) As a membrane material capable of crosslinking reaction, formula (1) or formula (2) as disclosed in WO 2006/115074 A1:

{In the formula, R ₁ and R ₂ each represent a hydrogen atom, a methyl group, an ethyl group, or a halogen atom, and A ₁ , A ₂ , A ₃ , A ₄ , A ₅ , and A ₆ each represent a hydrogen atom , represents a methyl group or an ethyl group, and Q is formula (3) or formula (4):

[In the formula, Q ₁ represents an alkylene group, phenylene group, naphthylene group, or anthrylene group having 1 to 15 carbon atoms, and each of the phenylene group, naphthylene group, and anthrylene group has 1 to 15 carbon atoms. 6 alkyl group, halogen atom, alkoxy group having 1 to 6 carbon atoms, nitro group, cyano group, hydroxyl group, and alkylthio group having 1 to 6 carbon atoms. Often, n ₁ and n ₂ each represent the number 0 or 1, and X ₁ is represented by formula (5), (6) or formula (7):

(In the formula, R ₃ and R ₄ each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, a benzyl group, or a phenyl group, and the phenyl group is A group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, a hydroxyl group, and an alkylthio group having 1 to 6 carbon atoms. R ₃ and R ₄ may be substituted, and R 3 and R 4 may be bonded to each other to form a ring having 3 to 6 carbon atoms, and R ₅ is an alkyl group having 1 to 6 carbon atoms, or a carbon atom. It represents an alkenyl group, a benzyl group, or a phenyl group having 3 to 6 carbon atoms, and the phenyl group is an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, or a cyano group. may be substituted with a group selected from the group consisting of a group, a hydroxyl group, and an alkylthio group having 1 to 6 carbon atoms. ] represents. } Examples include polymers having a repeating unit structure represented by .

（式中、Ｑは前記と同義である。）で表される繰り返しの単位構造を有するポリマーである。 Preferably, the polymer has formula (12):

It is a polymer having a repeating unit structure represented by (wherein Q has the same meaning as above).

［式中、Ｑ_２は式（１５）、式（１６）または式（１７）：

（式中、Ｙ、ｍ、Ｒ_３、Ｒ_４及びＲ_５は前記と同義である。）を表し、Ｑ_３は式（１８）：

（式中、Ｑ_４は炭素原子数１～１５のアルキレン基を表し、ｎ_３及びｎ_４はそれぞれ０または１の数を表す。）を表す。］で表される繰り返しの単位構造を有するポリマーである。 Preferably, the polymer has formula (13) and formula (14):

[wherein _Q2 is formula (15), formula (16) or formula (17):

(In the formula, Y, m, R ₃ , R ₄ and R ₅ have the same meanings as above.), and Q ₃ is the formula (18):

(In the formula, Q ₄ represents an alkylene group having 1 to 15 carbon atoms, and n ₃ and n ₄ each represent a number of 0 or 1.) ] It is a polymer having a repeating unit structure represented by the following.

（上記式中、
Ｘは水素原子又は芳香族縮合環を表わし、
Ｙは芳香族縮合環を表わし、ＸとＹは互いに結合して縮合環を形成していても良く、
Ｒ_１、Ｒ_２、Ｒ_３、Ｒ_４、Ｒ_５、Ｒ_１０、Ｒ_１１及びＲ_１２は、それぞれ、水素原子、ハロゲン原子又は炭素原子数１ないし３のアルキル基を表わし、
Ｒ_６、Ｒ_７及びＲ_８は、それぞれ、水素原子又は炭素原子数１ないし１０の鎖状又は環状のアルキル基を表わし、
Ｒ_９は炭素原子数１ないし１０の鎖状又は環状のアルキル基又は炭素原子数６ないし２０の芳香族基を表わし、また、
Ｒ_７とＲ_８は互いに結合して環を形成していても良く、
Ｍ及びＱはそれぞれ直接結合又は連結基を表わし、
ｎは０又は１の整数を表わす。）で表わされる単位構造からなる群から選ばれた少なくとも１種の単位構造を含むポリマー又はそれらポリマーの組み合わせからなり、該ポリマーを構成する全ての単位構造の総数を１．０とした場合、式（１）で表わされる単位構造の数（ａ）の割合、式（２）で表わされる単位構造の数（ｂ）の割合及び式（３）で表わされる単位構造の数（ｃ）の割合が、０．３≦ａ≦０．９５、０．００５≦ｂ≦０．７、０≦ｃ≦０．４５となるポリマーが挙げられる。 (q) Membrane materials capable of crosslinking reaction include the following formulas (1), (2), and (3) as disclosed in WO 2008/069047 A1:

(In the above formula,
X represents a hydrogen atom or an aromatic condensed ring,
Y represents an aromatic condensed ring, and X and Y may be bonded to each other to form a condensed ring,
R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₁₀ , R ₁₁ and R ₁₂ each represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 3 carbon atoms,
R ₆ , R ₇ and R ₈ each represent a hydrogen atom or a chain or cyclic alkyl group having 1 to 10 carbon atoms,
R ₉ represents a chain or cyclic alkyl group having 1 to 10 carbon atoms or an aromatic group having 6 to 20 carbon atoms;
R ₇ and R ₈ may be bonded to each other to form a ring,
M and Q each represent a direct bond or a connecting group,
n represents an integer of 0 or 1. ) consisting of a polymer containing at least one unit structure selected from the group consisting of unit structures represented by the formula The ratio of the number (a) of unit structures represented by (1), the ratio of the number (b) of unit structures represented by formula (2), and the ratio of the number (c) of unit structures represented by formula (3) are , 0.3≦a≦0.95, 0.005≦b≦0.7, and 0≦c≦0.45.

Preferably, a polymer containing unit structures represented by formulas (1) and (2), where the total number of all unit structures constituting the polymer is 1.0, The ratio of the number of unit structures (a) and the ratio of the number of unit structures (b) represented by formula (2) are 0.305≦a+b≦1, 0.3≦a≦0.95, 0.005≦ It is a polymer in which b≦0.7.
Preferably, a polymer containing unit structures represented by formulas (1) and (3), where the total number of all unit structures constituting the polymer is 1.0, The ratio of the number of unit structures (a) and the ratio of the number of unit structures (c) represented by formula (3) are 0.35≦a+c≦1, 0.3≦a≦0.95, 0.05≦ It is a polymer in which c≦0.7.
Preferably, the polymer includes unit structures represented by formula (1), formula (2), and formula (3), and when the total number of all unit structures constituting the polymer is 1.0, the formula ( The ratio of the number (a) of unit structures represented by 1), the ratio of the number (b) of unit structures represented by formula (2), and the ratio of the number (c) of unit structures represented by formula (3) are: The polymer satisfies 0.355≦a+b+c≦1, 0.3≦a≦0.9, 0.005≦b≦0.65, and 0.05≦c≦0.65.
Preferably, the unit structure represented by formula (1) is a unit structure composed of vinylnaphthalene, acenaphthylene, vinylanthracene, vinylcarbazole, or a derivative thereof.

（式（２）中、２つのＡｒはそれぞれアリール基を表し、該アリール基は置換基として少なくとも１つのヒドロキシ基を有し、Ｑはベンゼン環又はナフタレン環を少なくとも１つ有する二価の連結基、メチレン基又は単結合を表す。）で表される化合物が挙げられる。その分子量は、例えば１５０乃至６００である。 (r) As a membrane material capable of crosslinking reaction, the following formula (2) as disclosed in WO 2018/203464 A1:

(In formula (2), each of the two Ar represents an aryl group, the aryl group has at least one hydroxy group as a substituent, and Q is a divalent linking group having at least one benzene ring or naphthalene ring. , represents a methylene group or a single bond). Its molecular weight is, for example, 150 to 600.

（式（２－６）中、ｍは０～３の整数を表す） In formula (2), examples of the aryl group represented by Ar include a phenyl group, a biphenylyl group, a naphthyl group, an anthryl group, and a phenanthryl group. In addition, when Q represents a divalent linking group having at least one benzene ring or naphthalene ring, the divalent linking group includes, for example, a methylene group in which at least one of the two hydrogen atoms is a phenyl group or a biphenylyl group. or a divalent group substituted with a naphthyl group, a divalent aromatic group selected from the group consisting of a phenylene group, a biphenylylene group, and a naphthylene group, and the divalent aromatic group and a methylene group, an ether group (- Examples include divalent groups having a sulfide group (-O- group) or a sulfide group (-S- group). Examples of such monomers include compounds represented by the following formulas (2-1) to (2-6).

(In formula (2-6), m represents an integer from 0 to 3)

（式中、Ｒはそれぞれ独立に炭素原子数１乃至１０のアルキル基を表す。）
で表されるマロン酸ジエステルが１乃至６分子付加したフラーレン誘導体が挙げられる。 (s) As a membrane material capable of crosslinking reaction, the following formula (1) is used for one molecule of fullerene as disclosed in WO 2011/108365 A1 and WO 2016/143436 A1:

(In the formula, each R independently represents an alkyl group having 1 to 10 carbon atoms.)
Examples include fullerene derivatives to which one to six molecules of malonic acid diester represented by the following formula are added.

(t) As membrane materials capable of crosslinking reaction, polyfunctional (meth)acrylate compounds with a molecular weight of 300 to 10,000, which are in a liquid state at room temperature and atmospheric pressure, as disclosed in WO 2011/132640 A1, are used. Can be mentioned.

Preferably, the compound has 2 to 20 (meth)acrylate groups in the molecule.
Preferably, the molecular weight of the compound is 300 to 2,300.

Such compounds can be exemplified below.

（式中、Ｒ^１、Ｒ^１ａ、Ｒ^３、Ｒ^５、Ｒ^５ａ、及びＲ^６ａはそれぞれ炭素原子数１乃至１０の飽和炭化水素基、炭素原子数６乃至４０の芳香族炭化水素基、酸素原子、カルボニル基、イオウ原子、窒素原子、アミド基、アミノ基、又はそれらの組み合わせからなる基を示し、Ｒ^２、Ｒ^２ａ、Ｒ^４、及びＲ^６は、それぞれ水素原子、炭素原子数１乃至１０の飽和炭化水素基、炭素原子数２乃至１０の不飽和炭化水素基、酸素原子、カルボニル基、アミド基、アミノ基、又はそれらの組み合わせからなる基を示し、Ｒ^２、Ｒ^２ａ、Ｒ^４、Ｒ^６は１価の基を、Ｒ^１、Ｒ^１ａ、Ｒ^３、Ｒ^５ａ、及びＲ^６ａは２価の基を、Ｒ^５は３価の基を示し、Ｒ^７、Ｒ^８、Ｒ^９、Ｒ^１０及びＲ^１１はそれぞれ水素原子、又は炭素原子数１乃至１０の飽和炭化水素基を示し、ｎは１乃至１０の繰り返し単位数を示し、点線は隣接原子との化学結合を示す。） (u) A membrane material capable of crosslinking reaction is a compound (E) containing a partial structure (I) and a partial structure (II) as disclosed in WO 2017/154921 A1, wherein the partial structure (II) contains a hydroxy group generated by the reaction between an epoxy group and a proton-generating compound, and the partial structure (I) consists of a partial structure represented by the following formulas (1-1) to (1-5). At least one partial structure selected from the group, or a combination of a partial structure represented by formula (1-6) and a partial structure represented by formula (1-7) or formula (1-8) The partial structure (II) is a partial structure represented by the following formula (2-1) or formula (2-2).

(In the formula, R ¹ , R ^1a , R ³ , R ⁵ , R ^5a , and R ^6a are each a saturated hydrocarbon group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 40 carbon atoms, and oxygen Represents a group consisting of an atom, a carbonyl group, a sulfur atom, a nitrogen atom, an amide group, an amino group, or a combination thereof, and R ² , R ^2a , R ⁴ , and R ⁶ are each a hydrogen atom and a carbon atom number of 1 to 1. 10 saturated hydrocarbon groups, unsaturated hydrocarbon groups having 2 to 10 carbon atoms, oxygen atoms, carbonyl groups, amide groups, amino groups, or a combination thereof, R ² , R ^2a , R ⁴ , R ⁶ represents a monovalent group, R ¹ , R ^1a , R ³ , R ^5a and R ^6a represent a divalent group, R ⁵ represents a trivalent group, R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ each represent a hydrogen atom or a saturated hydrocarbon group having 1 to 10 carbon atoms, n represents the number of repeating units from 1 to 10, and the dotted line represents a chemical bond with an adjacent atom.)

Preferably, compound (E) contains an epoxy group and a hydroxy group in a molar ratio of 0≦(epoxy group)/(hydroxy group)≦0.5, and contains partial structure (II) of 0.01 It is included in a molar ratio such that ≦(partial structure (II))/(partial structure (I)+partial structure (II))≦0.8.
Preferably, compound (E) is a compound containing at least one partial structure (I) and at least one partial structure (II).
Preferably, R ^5a and R ^6a are each a divalent group consisting of an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 40 carbon atoms, an oxygen atom, a carbonyl group, a sulfur atom, or a combination thereof. It is the basis.
Preferably, compound (E) contains 1 to 1000 partial structures (I) and 1 to 1000 partial structures (II).

(v) The membrane material capable of crosslinking reaction includes at least one photodegradable nitrogen-containing structure and/or photodegradable sulfur-containing structure and a hydrocarbon structure, as disclosed in WO 2018/030198 A1. Examples include compounds containing.

Preferably, the above compound is a compound having one or more photodegradable nitrogen-containing structures and/or photodegradable sulfur-containing structures in the molecule.
Preferably, the above compound is a compound in which a photodegradable nitrogen-containing structure and/or a photodegradable sulfur-containing structure and a hydrocarbon structure exist in the same molecule, or the structures exist in different molecules. It is a combination of compounds that
Preferably, the hydrocarbon structure is a saturated or unsaturated group having 1 to 40 carbon atoms, and is a linear, branched or cyclic hydrocarbon group.
Preferably, the photodegradable nitrogen-containing structure is a structure that generates a reactive nitrogen-containing functional group or a reactive carbon functional group upon irradiation with ultraviolet rays, or a structure that generates a reactive nitrogen-containing functional group or a reactive carbon functional group upon irradiation with ultraviolet rays. It is a structure containing a carbon functional group.
Preferably, the photodegradable nitrogen-containing structure is a photodegradable nitrogen-containing structure that may contain a sulfur atom, and the structure is an azide structure, a tetraazole structure, a triazole structure, an imidazole structure, a pyrazole structure, an azole structure, etc. structure, diazo structure, or a combination thereof.
Preferably, the photodegradable sulfur-containing structure is a structure that generates organic sulfur radicals or carbon radicals upon irradiation with ultraviolet rays, or a structure that contains organic sulfur radicals or carbon radicals generated upon irradiation with ultraviolet rays.
Preferably, the photodegradable sulfur-containing structure is a photodegradable sulfur-containing structure that may contain a nitrogen atom, and the structure is a trisulfide structure, a disulfide structure, a sulfide structure, a thioketone structure, a thiophene structure, or a thiol structure. structure, or a structure including a combination thereof.

Preferably, the following compounds are preferred.

（式（１）中、Ｒ^１は、各々独立して炭素数１～３０の２価の基であり、Ｒ^２～Ｒ^７は、各々独立して炭素数１～１０の直鎖状、分岐状若しくは環状のアルキル基、炭素数６～１０のアリール基、炭素数２～１０のアルケニル基、チオール基又は水酸基であり、Ｒ^５の少なくとも１つは水酸基又はチオール基であり、ｍ^２、ｍ^３及びｍ^６は、各々独立して０～９の整数であり、ｍ^４及びｍ^７は、各々独立して０～８の整数であり、ｍ^５は、１～９の整数であり、ｎは、０～４の整数であり、ｐ^２～ｐ^７は、各々独立して０～２の整数である。） (w) Examples of membrane materials capable of crosslinking include compounds represented by the following formula (1) as disclosed in WO 2019/013293 A1.

(In formula (1), R ¹ is each independently a divalent group having 1 to 30 carbon atoms, and R ² to R ⁷ are each independently a linear or branched group having 1 to 10 carbon atoms. a cyclic or cyclic alkyl group, an aryl group having 6 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a thiol group, or a hydroxyl group, at least one of R ⁵ is a hydroxyl group or a thiol group, m ² , m ³ and m ⁶ are each independently an integer of 0 to 9, m ⁴ and m ⁷ are each independently an integer of 0 to 8, m ⁵ is an integer of 1 to 9, and n is an integer from 0 to 4, and p ² to p ⁷ are each independently an integer from 0 to 2.)

Preferably, the following compounds are preferred.

（式中、ｎ１及びｎ２はそれぞれ独立して０又は１を表し、Ｗは単結合又は下記式（２）で示される構造のいずれかである。Ｒ_１は下記一般式（３）で示される構造のいずれかであり、ｍ１及びｍ２はそれぞれ独立に０～７の整数を表す。ただし、ｍ１＋ｍ２は１以上１４以下である。）

（式中、ｌは０～３の整数を表し、Ｒ_ａ～Ｒ_ｆはそれぞれ独立して水素原子又はフッ素置換されてもよい炭素数１～１０のアルキル基、フェニル基、又はフェニルエチル基を表し、Ｒ_ａとＲ_ｂが結合して環状化合物を形成してもよい。）

（式中、＊は芳香環への結合部位を表し、Ｑ_１は炭素数１～３０の直鎖状、分岐状の飽和又は不飽和の炭化水素基、炭素数４～２０の脂環基、あるいは置換又は非置換のフェニル基、ナフチル基、アントラセニル基、又はピレニル基を表す。Ｑ_１が炭素数１～３０の直鎖状、分岐状の飽和又は不飽和の炭化水素基を表す場合、Ｑ_１を構成するメチレン基が酸素原子又はカルボニル基に置換されていてもよい。） (x) Examples of membrane materials capable of crosslinking include compounds represented by the following general formula (1) as disclosed in JP-A No. 2016-216367.

(In the formula, n1 and n2 each independently represent 0 or 1, and W is either a single bond or a structure represented by the following formula (2). R ₁ is represented by the following general formula (3) structure, where m1 and m2 each independently represent an integer from 0 to 7.However, m1+m2 is 1 or more and 14 or less.)

(In the formula, l represents an integer of 0 to 3, and R _a to R _f each independently represent a hydrogen atom, a fluorine-substituted alkyl group having 1 to 10 carbon atoms, a phenyl group, or a phenylethyl group. (R _a and R _b may be combined to form a cyclic compound.)

(In the formula, * represents a bonding site to an aromatic ring, Q ₁ is a linear, branched, saturated or unsaturated hydrocarbon group having 1 to 30 carbon atoms, an alicyclic group having 4 to 20 carbon atoms, Or it represents a substituted or unsubstituted phenyl group, naphthyl group, anthracenyl group, or pyrenyl group. When Q ₁ represents a linear, branched, saturated or unsaturated hydrocarbon group having 1 to 30 carbon atoms, Q The methylene group constituting ₁ may be substituted with an oxygen atom or a carbonyl group.)

（式中、ｍ３及びｍ４は１又は２を表し、Ｗ及びＲ_１は前記と同様である。） Preferably, the compound represented by the general formula (1) is a compound represented by the following general formula (4).

(In the formula, m3 and m4 represent 1 or 2, and W and R ₁ are the same as above.)

（式中、ｌは上記と同様である。） Preferably, W is either a single bond or a structure represented by the following formula (5).

(In the formula, l is the same as above.)

（式中、＊＊はカルボニル基への結合部位を表し、Ｒ_ｈは炭素数１～３０の直鎖状、分岐状の飽和又は不飽和の炭化水素基を表し、Ｒ_ｈを構成するメチレン基が酸素原子又はカルボニル基に置換されていてもよい。）

（式中、＊＊はカルボニル基への結合部位を表し、Ｒ_ｉは水素原子又は炭素数１～１０の直鎖状、分岐状の炭化水素基を表し、Ｒ_ｊは炭素数１～１０の直鎖状、分岐状の炭化水素基、ハロゲン原子、ニトロ基、アミノ基、ニトリル基、炭素数１～１０のアルコキシカルボニル基、あるいは炭素数１～１０のアルカノイルオキシ基を表す。ｎ３及びｎ４は芳香環上の置換基の数を表し、それぞれ０～７の整数を表す。ただし、ｎ３＋ｎ４は０以上７以下である。ｎ５は０～２を表す。） Preferably, the compound represented by the general formula (1) has two or more Q ₁ in the molecule, and the Q ₁ has a structure represented by the following general formula (6) and the following general formula (7). Each of these structures includes one or more of the following structures.

(In the formula, ** represents a bonding site to a carbonyl group, R _h represents a linear, branched, saturated or unsaturated hydrocarbon group having 1 to 30 carbon atoms, and a methylene group constituting R _h may be substituted with an oxygen atom or a carbonyl group.)

(In the formula, ** represents a bonding site to a carbonyl group, R _i represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 10 carbon atoms, and R _j represents a bonding site to a carbonyl group. Represents a linear or branched hydrocarbon group, a halogen atom, a nitro group, an amino group, a nitrile group, an alkoxycarbonyl group having 1 to 10 carbon atoms, or an alkanoyloxy group having 1 to 10 carbon atoms. n3 and n4 are Represents the number of substituents on the aromatic ring, each representing an integer from 0 to 7. However, n3+n4 is 0 to 7. n5 represents 0 to 2.)

（式中、Ｒは単結合、炭素数１～５０の有機基、エーテル結合、－ＳＯ－基、又は－ＳＯ_２－基であり、Ｒ_１は下記一般式（１Ｂ）で示される基であり、ｍ１及びｍ２は１≦ｍ１≦５、１≦ｍ２≦５、かつ２≦ｍ１＋ｍ２≦８を満たす整数である。）

（式中、Ｘ^１は下記一般式（１Ｃ）で示される基であり、Ｘは下記一般式（１Ｄ）で示される基である。）

（式中、（Ｘ）は前記Ｘとの結合箇所を示す。）

（式中、Ｘ^２は炭素数１～１０の二価有機基であり、ｎ１は０又は１であり、ｎ２は１又は２であり、Ｘ^３は下記一般式（１Ｅ）で示される基であり、ｎ５は０、１、又は２である。）

（式中、Ｒ^１０は水素原子又は炭素数１～１０の飽和もしくは不飽和の炭化水素基であり、式中のベンゼン環上の水素原子は、メチル基又はメトキシ基で置換されていてもよい。） (y) Examples of membrane materials capable of crosslinking include compounds represented by the following general formula (1A) as disclosed in JP-A No. 2017-119670.

(In the formula, R is a single bond, an organic group having 1 to 50 carbon atoms, an ether bond, a -SO- group, or a -SO ₂ - group, and R ₁ is a group represented by the following general formula (1B). , m1 and m2 are integers satisfying 1≦m1≦5, 1≦m2≦5, and 2≦m1+m2≦8.)

(In the formula, X ¹ is a group represented by the following general formula (1C), and X is a group represented by the following general formula (1D).)

(In the formula, (X) indicates the bonding point with the above-mentioned X.)

(In the formula, X ² is a divalent organic group having 1 to 10 carbon atoms, n1 is 0 or 1, n2 is 1 or 2, and X ³ is a group represented by the following general formula (1E). Yes, n5 is 0, 1, or 2.)

(In the formula, R ¹⁰ is a hydrogen atom or a saturated or unsaturated hydrocarbon group having 1 to 10 carbon atoms, and the hydrogen atom on the benzene ring in the formula may be substituted with a methyl group or a methoxy group. .)

Preferably, the molecular weight of the compound is 2,500 or less.

（式中、Ｒは単結合、炭素数１～５０の有機基、エーテル結合、－ＳＯ－基、又は－ＳＯ_２－基であり、Ｒ_２は下記一般式（２Ｂ）で示される基であり、ｍ３及びｍ４は１≦ｍ３≦５、１≦ｍ４≦５、かつ２≦ｍ３＋ｍ４≦８を満たす整数である。）

（式中、Ｘ^１１は下記一般式（２Ｃ）で示される基であり、Ｘ’は下記一般式（２Ｄ）で示される基である。）

（式中、（Ｘ’）は前記Ｘ’との結合箇所を示す。）

（式中、ｎ３は０又は１であり、ｎ４は１又は２であり、Ｘ^４は下記一般式（２Ｅ）で示される基であり、ｎ６は０、１、又は２である。）

（式中、Ｒ^１１は水素原子又は炭素数１～１０の飽和もしくは不飽和の炭化水素基であり、式中のベンゼン環上の水素原子は、メチル基又はメトキシ基で置換されていてもよい。）

（式中、Ｒ^１０１、Ｒ^１０２、Ｒ^１０３、Ｒ^１０４はそれぞれ独立に水酸基であり、ｍ１００は１、２、又は３であり、Ｒ^１００は、ｍ１００が１のときは水素原子又は水酸基であり、ｍ１００が２のときは単結合又は下記一般式（３Ｂ）で示される基であり、ｍ１００が３のときは下記一般式（３Ｃ）で示される基であり、式中の芳香環上の水素原子はメチル基又はメトキシ基で置換されてもよい。ｍ１０１は０又は１であり、ｍ１０２は１又は２であり、ｍ１０３は０又は１であり、ｍ１０４は１又は２であり、ｍ１０５は０又は１である。ｍ１０１が０の場合、ｎ１０１及びｎ１０２は０≦ｎ１０１≦３、０≦ｎ１０２≦３、かつ１≦ｎ１０１＋ｎ１０２≦４を満たす整数であり、ｍ１０１が１の場合、ｎ１０１、ｎ１０２、ｎ１０３、及びｎ１０４は０≦ｎ１０１≦２、０≦ｎ１０２≦２、０≦ｎ１０３≦２、０≦ｎ１０４≦２、かつ２≦ｎ１０１＋ｎ１０２＋ｎ１０３＋ｎ１０４≦８を満たす整数である。）

（式中、＊は結合位置を示し、Ｒ^１０６、Ｒ^１０７は水素原子又は炭素数１～２４のエステル結合を含まない有機基であり、Ｒ^１０６とＲ^１０７は結合して環状構造を形成してもよい。）

（式中、＊は結合位置を示し、Ｒ^１０８は水素原子又は炭素数１～１５の有機基である。） Preferred are compounds represented by the following general formula (2A) and compounds represented by the following general formula (3A).

(In the formula, R is a single bond, an organic group having 1 to 50 carbon atoms, an ether bond, a -SO- group, or a -SO ₂ - group, and R ₂ is a group represented by the following general formula (2B). , m3 and m4 are integers satisfying 1≦m3≦5, 1≦m4≦5, and 2≦m3+m4≦8.)

(In the formula, X ¹¹ is a group represented by the following general formula (2C), and X' is a group represented by the following general formula (2D).)

(In the formula, (X') indicates the bonding point with the above-mentioned X'.)

(In the formula, n3 is 0 or 1, n4 is 1 or 2, ^X4 is a group represented by the following general formula (2E), and n6 is 0, 1, or 2.)

(In the formula, R ¹¹ is a hydrogen atom or a saturated or unsaturated hydrocarbon group having 1 to 10 carbon atoms, and the hydrogen atom on the benzene ring in the formula may be substituted with a methyl group or a methoxy group. .)

(In the formula, R ¹⁰¹ , R ¹⁰² , R ¹⁰³ , and R ¹⁰⁴ are each independently a hydroxyl group, m100 is 1, 2, or 3, and R ¹⁰⁰ is a hydrogen atom or a hydroxyl group when m100 is 1. , when m100 is 2, it is a single bond or a group represented by the following general formula (3B), and when m100 is 3, it is a group represented by the following general formula (3C), and hydrogen on the aromatic ring in the formula Atoms may be substituted with methyl or methoxy groups. m101 is 0 or 1, m102 is 1 or 2, m103 is 0 or 1, m104 is 1 or 2, m105 is 0 or 1. When m101 is 0, n101 and n102 are integers that satisfy 0≦n101≦3, 0≦n102≦3, and 1≦n101+n102≦4, and when m101 is 1, n101, n102, n103, and n104 is an integer that satisfies 0≦n101≦2, 0≦n102≦2, 0≦n103≦2, 0≦n104≦2, and 2≦n101+n102+n103+n104≦8.)

(In the formula, * indicates a bonding position, R ¹⁰⁶ and R ¹⁰⁷ are a hydrogen atom or an organic group having 1 to 24 carbon atoms and not containing an ester bond, and R ¹⁰⁶ and R ¹⁰⁷ are bonded to form a cyclic structure. )

(In the formula, * indicates the bonding position, and R ¹⁰⁸ is a hydrogen atom or an organic group having 1 to 15 carbon atoms.)

（式（１）中、Ａｒ_１は炭素数６乃至５０のアリーレン基又は複素環基を含む有機基を表す。）で表される単位構造、下記式（２）：

（ただし、式（２）中、Ａｒ_２、Ａｒ_３、及びＡｒ_４はそれぞれ炭素数６乃至５０のアリーレン基又は複素環基を含む有機基を表し、Ｔはカルボニル基またはスルホニル基を表す。）で表される単位構造、又は式（１）で表される単位構造及び式（２）で表される単位構造の組み合わせを含むポリマー。 (z) Examples of the polyether film material include polymers represented by the following general formula (1) as disclosed in WO2012/050064.
The following formula (1):

(In formula (1), Ar ₁ represents an organic group containing an arylene group or a heterocyclic group having 6 to 50 carbon atoms.) A unit structure represented by the following formula (2):

(However, in formula (2), Ar ₂ , Ar ₃ , and Ar ₄ each represent an organic group containing an arylene group or a heterocyclic group having 6 to 50 carbon atoms, and T represents a carbonyl group or a sulfonyl group.) A polymer containing a unit structure represented by formula (1) or a combination of a unit structure represented by formula (1) and a unit structure represented by formula (2).

The membrane material (B) capable of crosslinking reaction preferably has the following properties:
(B1) Membrane material containing an aliphatic ring (for example, (a) and (m) above),
(B2) novolac membrane material (for example, (b) (c) (d) (e) (f) (g) (h) (i) (j) (k) (l) above),
(B3) polyether membrane material (e.g. (z) above),
(B4) polyester film material (e.g. (o) and (p) above),
(B5) A compound different from the crosslinkable compound (A) (for example, the above (m) (n) (r) (s) (t) (u) (v) (w) (x) (y)),
(B6) A membrane material containing an aromatic condensed ring (e.g. (q) above),
It contains at least one selected from the group consisting of (B7) acrylic resin and (B8) methacrylic resin.

When the resist underlayer film forming composition according to the present invention contains a film material (B) (film material or polymer) capable of a crosslinking reaction, the content ratio of the film material (B) capable of a crosslinking reaction is determined based on the total solid content. The amount is usually 1 to 99.9% by weight, preferably 50 to 99.9% by weight, more preferably 50 to 95% by weight, even more preferably 50 to 90% by weight.

[(C) Acid catalyst]
The acid catalyst optionally included in the resist underlayer film forming composition according to the present invention is particularly a catalyst that can promote the reaction between the above-mentioned crosslinking compound (A) and the film material (B) capable of crosslinking reaction. It is not limited.

Examples of acid catalysts include pyridinium p-toluenesulfonate, pyridinium p-hydroxybenzenesulfonate, pyridinium trifluoromethanesulfonate, p-toluenesulfonic acid, p-hydroxybenzenesulfonic acid, trifluoromethanesulfonic acid, salicylic acid, and camphorsulfonic acid. , 5-sulfosalicylic acid, chlorobenzenesulfonic acid, methyl 4-phenolsulfonate, benzenesulfonic acid, naphthalenesulfonic acid, citric acid, benzoic acid, etc., sulfonic acid compounds and carboxylic acid compounds, and quaternary ammonium trifluoromethanesulfonic acid. Salt K-PURE [registered trademark] TAG2689, TAG2690, TAG2678, CXC-1614 (manufactured by King Industries), 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2 - Examples include thermal acid generators such as nitrobenzyl tosylate and other organic sulfonic acid alkyl esters. These acid catalysts may be contained alone or in combination of two or more. Among the acid catalysts, pyridinium p-hydroxybenzenesulfonate is preferred.

An ion exchange resin for catalysts can be used to prevent unreacted acids, catalysts, inactivated catalysts, etc. from remaining in the reaction system. As the ion exchange resin for the catalyst, for example, a sulfonic acid type strong acid type ion exchange resin can be used.

When the resist underlayer film forming composition according to the present invention contains an acid catalyst, the acid catalyst is, for example, 1% by mass to 30% by mass, preferably 5% by mass to 15% by mass, based on the content of the crosslinking agent. Including mass%.

(D) Solvent In the resist underlayer film forming composition according to the present invention, the above-mentioned crosslinking compound (A), the optional crosslinkable film material (B), the acid catalyst (C), and other components are added. The solvent for dissolving is not particularly limited as long as it can uniformly dissolve these components.

For example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, Propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, cycloheptanone, 4-methyl-2-pentanol, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, ethoxy Ethyl acetate, 2-hydroxyethyl acetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate , ethyl lactate, butyl lactate, 2-heptanone, methoxycyclopentane, anisole, γ-butyrolactone, N-methylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide. These solvents can be used alone or in combination of two or more.

Among these solvents, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, and cyclohexanone are preferred. It is advantageous to reuse the solvent used for the preparation of the crosslinkable compound (A) and the crosslinkable membrane material (B) as a solvent, as it contributes to the effective use of resources.

Further, high boiling point solvents such as propylene glycol monobutyl ether and propylene glycol monobutyl ether acetate can be mixed with these solvents.

The amount of the solvent is selected so that the solid content of the resist underlayer film forming composition according to the present invention is preferably 0.1 to 70% by mass, more preferably 0.1 to 60% by mass. The solid content refers to the content of all components in the resist underlayer film forming composition excluding the solvent.

[Other ingredients]
In addition to the above, surfactants, rheology modifiers, adhesion aids, light absorbers, and the like may be added to the resist underlayer film-forming composition according to the present invention, if necessary.

The resist underlayer film forming composition of the present invention may contain a surfactant as an optional component in order to improve the coating properties on a semiconductor substrate. Examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, and polyoxyethylene. Polyoxyethylene alkylaryl ethers such as nonylphenyl ether, polyoxyethylene/polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan trioleate Sorbitan fatty acid esters such as stearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, etc. Nonionic surfactants such as oxyethylene sorbitan fatty acid esters, FTOP (registered trademark) EF301, EF303, EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Megafac (registered trademark) F171, F173 , R-30, R-30N, R-40, R-40-LM (manufactured by DIC Corporation), Florado FC430, FC431 (manufactured by Sumitomo 3M Ltd.), Asahi Guard Fluorine surfactants such as [Registered Trademark] AG710, Surflon [Registered Trademark] S-382, Surflon SC101, Surflon SC102, Surflon SC103, Surflon SC104, Surflon SC105, and Surflon SC106 (all manufactured by Asahi Glass Co., Ltd.), Organo Siloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can be mentioned. These surfactants can be used alone or in combination of two or more. The blending amount of these surfactants is usually 2.0% by mass or less, preferably 1.0% by mass or less, based on the total solid content of the resist underlayer film forming composition of the present invention. These surfactants may be added alone or in combination of two or more.

The rheology modifier mainly improves the fluidity of the resist underlayer film forming composition, and improves the uniformity of the resist underlayer film thickness and the filling ability of the resist underlayer film forming composition into the holes, especially in the baking process. It is added for the purpose of enhancing. Specific examples include phthalic acid derivatives such as dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, dihexyl phthalate, and butylisodecyl phthalate; adipic acid derivatives such as di-n-butyl adipate, diisobutyl adipate, diisooctyl adipate, and octyldecyl adipate; Examples include maleic acid derivatives such as normal butyl maleate, diethyl maleate, and dinonyl maleate; oleic acid derivatives such as methyl oleate, butyl oleate, and tetrahydrofurfuryl oleate; and stearic acid derivatives such as normal butyl stearate and glyceryl stearate. can. These rheology modifiers are usually blended in a proportion of less than 30% by mass based on the total solid content of the resist underlayer film forming composition.

The adhesion auxiliary agent is added mainly for the purpose of improving the adhesion between the substrate or the resist and the resist underlayer film forming composition, and particularly for preventing the resist from peeling off during development. Specific examples include chlorosilanes such as trimethylchlorosilane, dimethylvinylchlorosilane, methyldiphenylchlorosilane, and chloromethyldimethylchlorosilane, trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, dimethylvinylethoxysilane, diphenyldimethoxysilane, and phenyltriethoxy. Alkoxysilanes such as silane, silazane such as hexamethyldisilazane, N,N'-bis(trimethylsilyl)urea, dimethyltrimethylsilylamine, trimethylsilylimidazole, vinyltrichlorosilane, γ-chloropropyltrimethoxysilane, γ-aminopropyltrisilane, etc. Silanes such as ethoxysilane, γ-glycidoxypropyltrimethoxysilane, benzotriazole, benzimidazole, indazole, imidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, urazol, thiouracil, mercapto Examples include heterocyclic compounds such as imidazole and mercaptopyrimidine, urea such as 1,1-dimethylurea and 1,3-dimethylurea, and thiourea compounds. These adhesion aids are generally blended in an amount of less than 5% by mass, preferably less than 2% by mass, based on the total solid content of the composition for forming a resist underlayer film for lithography.

Examples of the light absorbing agent include commercially available light absorbing agents described in "Technology and Market of Industrial Colorants" (CMC Publishing) and "Dye Handbook" (edited by the Organic Synthetic Chemistry Association), such as C.I. I. DisperseYellow1, 3, 4, 5, 7, 8, 13, 23, 31, 49, 50, 51, 54, 60, 64, 66, 68, 79, 82, 88, 90, 93, 102, 114 and 124; C. I. DisperseOrange 1, 5, 13, 25, 29, 30, 31, 44, 57, 72 and 73; C. I. DisperseRed1, 5, 7, 13, 17, 19, 43, 50, 54, 58, 65, 72, 73, 88, 117, 137, 143, 199 and 210; C. I. DisperseViolet43;C. I. DisperseBlue96;C. I. Fluorescent Brightening Agents 112, 135 and 163; C. I. SolventOrange2 and 45;C. I. SolventRed 1, 3, 8, 23, 24, 25, 27 and 49; C. I. PigmentGreen10;C. I. Pigment Brown 2 etc. can be suitably used. The above-mentioned light absorbing agent is usually blended in a proportion of 10% by mass or less, preferably 5% by mass or less, based on the total solid content of the resist underlayer film forming composition.

Moreover, the resist underlayer film forming composition according to the present invention can contain a crosslinking agent other than the crosslinkable compound represented by formula (I). Examples of such crosslinking agents include melamine type, substituted urea type, and polymer type thereof. Preferably, the crosslinking agent has at least two crosslinking substituents, such as methoxymethylated glycoluril, butoxymethylated glycoluril, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzogwanamine, butoxymethylated benzogwanamine, These are compounds such as methoxymethylated urea, butoxymethylated urea, methoxymethylated thiourea, or methoxymethylated thiourea. Moreover, condensates of these compounds can also be used.

The resist underlayer film forming composition according to the present invention can be prepared by uniformly mixing the above components by a conventional method. The prepared resist underlayer film forming composition is preferably used after being filtered using a filter with a pore size of, for example, 0.2 μm or 0.1 μm and/or 0.01 μm.

[Method for manufacturing patterned substrate]
A method for manufacturing a patterned substrate using a resist underlayer film forming composition according to the present invention includes a step of applying a resist underlayer film forming composition onto a semiconductor substrate and curing it to form a resist underlayer film, The method includes a step of forming a resist film by applying and baking a resist thereon, a step of exposing the resist underlayer film and the semiconductor substrate covered with the resist, and a step of developing and patterning the resist film after exposure. These will be explained in order below.

Examples of semiconductor substrates to which the resist underlayer film forming composition of the present invention is applied include silicon substrates, germanium substrates, and compound semiconductor wafers such as gallium arsenide, indium phosphide, gallium nitride, indium nitride, and aluminum nitride. Can be mentioned. When using a semiconductor substrate with an inorganic film formed on the surface, the inorganic film can be formed by, for example, an ALD (atomic layer deposition) method, a CVD (chemical vapor deposition) method, a reactive sputtering method, an ion plating method, or a vacuum evaporation method. method, spin coating method (spin-on-glass: SOG). Examples of the inorganic film include a polysilicon film, a silicon oxide film, a silicon nitride film, a BPSG (Boro-Phospho Silicate Glass) film, a titanium nitride film, a titanium nitride oxide film, a tungsten film, a gallium nitride film, and a gallium arsenide film. can be mentioned.

The resist underlayer film forming composition according to the present invention is applied onto such a semiconductor substrate using a suitable coating method such as a spinner or a coater. Thereafter, the coating film is cured to form a resist underlayer film according to the present invention, which is a cured product of the coating film.
Means for curing the coating film include baking the coating film using a heating means such as a hot plate, and photocuring the coating film by irradiating it with light (for example, ultraviolet light).
The baking conditions are appropriately selected from baking temperatures of 100° C. to 400° C. and baking times of 0.3 minutes to 60 minutes. Preferably, the baking temperature is 120° C. to 350° C., the baking time is 0.5 minutes to 30 minutes, more preferably the baking temperature is 150° C. to 300° C., the baking time is 0.8 minutes to 10 minutes, most preferably the baking temperature is 200° C. C. to 260.degree. C., baking time 0.8 to 3 minutes. The thickness of the resist underlayer film to be formed is, for example, 0.001 μm to 10 μm, preferably 0.002 μm to 1 μm, more preferably 0.005 μm to 0.5 μm, and most preferably 0.02 to 0.3 μm. . If the temperature during baking is lower than the above range, crosslinking may be insufficient, and the resulting resist underlayer film may be difficult to obtain resistance to a resist solvent or an aqueous hydrogen peroxide solution. On the other hand, if the baking temperature is higher than the above range, the resist underlayer film may be decomposed by heat.
When the coating film is cured only by baking, the resist underlayer film according to the present invention is a baked product of the coating film.

Instead of curing the coating film only by baking, it is also possible to complete the curing by performing a heat treatment at a relatively low temperature (for example, at a temperature 10 to 80°C lower than the above-mentioned baking temperature) and then performing a photocuring treatment. . Alternatively, after heat treatment for a shorter time at the above baking temperature, curing can be completed by photocuring treatment.
It is preferable to use ultraviolet light for photocuring treatment. The irradiation energy is usually 100 to 1,000 mJ/cm ² .
By appropriately combining thermal curing and photocuring, the flattening properties of the resist underlayer film can be further improved.

Next, a resist pattern is formed on the resist underlayer film. The resist pattern is formed using a general method, namely, applying a photoresist solution onto the resist underlayer film (after forming one to several layers of coating material as necessary), and pre-baking (if necessary). ), irradiation (exposure) with light or electron beam through a predetermined mask, post-exposure bake abbreviated as PEB (Post Exposure Bake) (can be performed by development, rinsing, and drying if necessary. The resist used is a photoresist or an electron beam resist.The photoresist solution used for forming the resist pattern is not particularly limited as long as it is sensitive to the light used for exposure, and a positive photoresist is used. A chemically amplified photoresist consisting of a binder having a group that decomposes with acid to increase the alkali dissolution rate and a photoacid generator, and a low-molecular compound that decomposes with acid to increase the alkali dissolution rate of the photoresist. A chemically amplified photoresist consisting of an alkali-soluble binder and a photoacid generator, a binder having a group that decomposes with acid to increase the alkali dissolution rate, and a low molecular compound that decomposes with acid to increase the alkali dissolution rate of the photoresist. and a chemically amplified photoresist consisting of a photoacid generator and a DNQ-novolak type non-chemically amplified photoresist that utilizes the difference in alkali dissolution rate between exposed and unexposed areas.For example, Sumitomo Chemical Co., Ltd. Manufactured by Tokyo Ohka Kogyo Co., Ltd., product name: PAR710; manufactured by Tokyo Ohka Kogyo Co., Ltd., product name: TDUR-P3435LP; THMR-iP1800; and Shin-Etsu Chemical Co., Ltd., product name: SEPR430. Negative photoresists can also be used.

In addition, the electron beam resist coated on the upper part of the resist underlayer film in the present invention includes, for example, a resin containing a Si--Si bond in the main chain and an aromatic ring at the end, and an acid that generates an acid when irradiated with an electron beam. Examples include compositions consisting of a generator, or compositions consisting of poly(p-hydroxystyrene) in which the hydroxyl group is substituted with an organic group containing N-carboxyamine and an acid generator that generates acid when irradiated with an electron beam. . In the latter electron beam resist composition, the acid generated from the acid generator by electron beam irradiation reacts with the N-carboxyaminoxy group of the polymer side chain, and the polymer side chain decomposes into a hydroxyl group, exhibiting alkali solubility and being removed in an alkaline developer. The resist pattern is formed by dissolving the resist. The acid generators that generate acid upon irradiation with this electron beam are 1,1-bis[p-chlorophenyl]-2,2,2-trichloroethane, 1,1-bis[p-methoxyphenyl]-2,2,2 - halogenated organic compounds such as trichloroethane, 1,1-bis[p-chlorophenyl]-2,2-dichloroethane, 2-chloro-6-(trichloromethyl)pyridine, triphenylsulfonium salts, diphenyliodonium salts, etc. Examples include sulfonic acid esters such as onium salts, nitrobenzyl tosylate, and dinitrobenzyl tosylate.

The exposure is performed through a mask (reticle) for forming a predetermined pattern, and uses, for example, i-ray, KrF excimer laser, ArF excimer laser, EUV (extreme ultraviolet), or EB (electron beam). An alkaline developer is used for the development, and the development temperature is appropriately selected from 5° C. to 50° C. and the developing time from 10 seconds to 300 seconds. Examples of the alkaline developer include aqueous solutions of alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, aqueous solutions of quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline, and ethanolamine. , alkaline aqueous solutions such as amine aqueous solutions such as propylamine and ethylenediamine. Furthermore, surfactants and the like can also be added to these developers. It is also possible to use a method in which the photoresist is developed with an organic solvent such as butyl acetate instead of the alkaline developer, and the portions of the photoresist where the alkali dissolution rate has not been improved are developed.

Next, the resist underlayer film is dry etched using the formed resist pattern as a mask. At that time, if the inorganic film is formed on the surface of the semiconductor substrate used, the surface of the inorganic film is exposed, and if the inorganic film is not formed on the surface of the semiconductor substrate used, the surface of the semiconductor substrate is exposed. expose the surface.

Furthermore, using the resist underlayer film after dry etching (and the resist pattern if it remains on the resist underlayer film) as a mask, wet etching is performed using an aqueous hydrogen peroxide solution to form the desired pattern. is formed. The wet etching chemical solution is made by mixing a basic substance such as ammonia, sodium hydroxide, potassium hydroxide, sodium cyanide, potassium cyanide, or an organic amine such as triethanolamine with hydrogen peroxide solution to adjust the pH to a base. Examples thereof include a basic aqueous hydrogen peroxide solution, and an acidic aqueous hydrogen peroxide solution prepared by mixing an inorganic acid such as hydrochloric acid or sulfuric acid with aqueous hydrogen peroxide. Other substances that can make the pH basic, such as those that mix urea and hydrogen peroxide and generate ammonia by causing thermal decomposition of the urea by heating, ultimately making the pH basic. It can also be used as a wet etching chemical. The operating temperature of the basic aqueous hydrogen peroxide solution and the acidic aqueous hydrogen peroxide solution is preferably 25°C to 90°C, more preferably 40°C to 80°C. The wet etching time is preferably 0.5 minutes to 30 minutes, and more preferably 1 minute to 20 minutes.

As described above, a step of forming a resist underlayer film on a semiconductor substrate using a resist underlayer film forming composition, a step of forming a resist film thereon, a step of forming a resist pattern by irradiation with light or electron beam and development, A semiconductor device can be manufactured through the steps of etching the lower layer film using a resist pattern and processing the semiconductor substrate using the patterned lower layer film.

Next, the content of the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto.

The chemical structures and abbreviations of the raw materials used in the synthesis examples are as follows.

（上記式中、ｍは０～３の整数を表す）

The chemical structures (examples) and abbreviations of the raw materials used in the synthesis examples are as follows.

(In the above formula, m represents an integer from 0 to 3)

The weight average molecular weight of the resin (polymer) obtained in Synthesis Example 1 below is the result of measurement by gel permeation chromatography (hereinafter abbreviated as GPC). A GPC device manufactured by Tosoh Corporation was used for the measurement, and the measurement conditions were as follows.
GPC column: Shodex KF803L, Shodex KF802, Shodex KF801 [registered trademark] (Showa Denko K.K.)
Column temperature: 40℃
Solvent: Tetrahydrofuran (THF)
Flow rate: 1.0ml/min Standard sample: Polystyrene (manufactured by Tosoh Corporation)

[Synthesis example 1]
In a 100 mL two-necked flask, add 10.90 g of TMOM-BP (manufactured by Honshu Chemical Industry Co., Ltd.), 10.00 g of 2-ethylhexyl glycidyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.), and ethyltriphenylphosphonium bromide (manufactured by Hokuko Chemical Industry Co., Ltd.). ) and 21.0 g of propylene glycol monomethyl ether were added. Thereafter, the mixture was heated to 140°C and stirred under reflux for about 24 hours. After the reaction is complete, dilute with propylene glycol monomethyl ether and add 21.0 g of anion exchange resin (product name: DOWEX [registered trademark] 550A, Muromachi Technos Co., Ltd.) and cation exchange resin (product name: Amberlite) to the solution. 21.0 g of [Registered Trademark] 15JWET, manufactured by Organo Co., Ltd., was added, and ion exchange treatment was performed at room temperature for 4 hours. After separating the ion exchange resin, a solution of a compound having the structure of formula (1-1) was obtained. The weight average molecular weight Mw measured in terms of polystyrene by GPC was 960, and there was no residual epoxy.

[Synthesis example 2]
In a 100 mL two-neck flask were 9.80 g of TMOM-BP (manufactured by Honshu Chemical Industry Co., Ltd.), 12.00 g of 2-biphenylglycidyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.), and ethyltriphenylphosphonium bromide (manufactured by Hokuko Chemical Industry Co., Ltd.). ) and 22.8 g of propylene glycol monomethyl ether were added. Thereafter, the mixture was heated to 140°C and stirred under reflux for about 24 hours. After the reaction is completed, dilute with propylene glycol monomethyl ether and add 22.8 g of anion exchange resin (product name: DOWEX [registered trademark] 550A, Muromachi Technos Co., Ltd.) and cation exchange resin (product name: Amberlite) to the solution. 22.8 g of [Registered Trademark] 15JWET (Organo Co., Ltd.) was added, and ion exchange treatment was performed at room temperature for 4 hours. After separating the ion exchange resin, a solution of a compound having the structure of formula (1-2) was obtained. The weight average molecular weight Mw measured in terms of polystyrene by GPC was 680, and there was no residual epoxy.

[Synthesis example 3]
In a 100 mL two-necked flask, 9.60 g of TMOM-BP (manufactured by Honshu Chemical Industry Co., Ltd.), 12.00 g of glycidyl 4-tertbutylbenzoate (manufactured by Tokyo Chemical Industry Co., Ltd.), and ethyltriphenylphosphonium bromide (manufactured by Hokuko Chemical Industry Co., Ltd.) Co., Ltd.) and 22.6 g of propylene glycol monomethyl ether were added. Thereafter, the mixture was heated to 140°C and stirred under reflux for about 24 hours. After the reaction is complete, dilute with propylene glycol monomethyl ether and add 22.6 g of anion exchange resin (product name: DOWEX [registered trademark] 550A, Muromachi Technos Co., Ltd.) and cation exchange resin (product name: Amberlite) to the solution. 22.6 g of [Registered Trademark] 15JWET (Organo Co., Ltd.) was added, and ion exchange treatment was performed at room temperature for 4 hours. After separating the ion exchange resin, a solution of a compound having the structure of formula (1-3) was obtained. The weight average molecular weight Mw measured in terms of polystyrene by GPC was 870, and there was no residual epoxy.

[Synthesis example 4]
In a 100 mL two-necked flask, add 3.34 g of HMOM-TPPA (manufactured by Honshu Chemical Industry Co., Ltd.), 3.00 g of 2-ethylhexyl glycidyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.), and ethyltriphenylphosphonium bromide (manufactured by Hokuko Chemical Industry Co., Ltd.). ) and 15.5 g of propylene glycol monomethyl ether were added. Thereafter, the mixture was heated to 140°C and stirred under reflux for about 24 hours. After the reaction is complete, dilute with propylene glycol monomethyl ether and add 6.6 g of anion exchange resin (product name: DOWEX [registered trademark] 550A, Muromachi Technos Co., Ltd.) and cation exchange resin (product name: Amberlite) to the solution. 6.6 g of [Registered Trademark] 15JWET (Organo Co., Ltd.) was added, and ion exchange treatment was performed at room temperature for 4 hours. After separating the ion exchange resin, a solution of a compound having the structure of formula (1-4) was obtained. The weight average molecular weight Mw measured in terms of polystyrene by GPC was 1,200, and there was no residual epoxy.

[Synthesis example 5]
In a 100 mL two-necked flask, 9.62 g of TM-BIP-A (manufactured by Asahi Yokuzai Co., Ltd.), 10.00 g of 2-ethylhexyl glycidyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.), and ethyl triphenylphosphonium bromide (manufactured by Hokuko Chemical Industry Co., Ltd.) Co., Ltd.) and 48.2 g of propylene glycol monomethyl ether were added. Thereafter, the mixture was heated to 80°C and stirred for about 24 hours. After the reaction is completed, dilute with propylene glycol monomethyl ether and add 20.6 g of anion exchange resin (product name: DOWEX [registered trademark] 550A, Muromachi Technos Co., Ltd.) and cation exchange resin (product name: Amberlite) to the solution. 20.6 g of [Registered Trademark] 15JWET (Organo Co., Ltd.) was added, and ion exchange treatment was performed at room temperature for 4 hours. After separating the ion exchange resin, a solution of a compound having the structure of formula (1-5) was obtained. The weight average molecular weight Mw measured by GPC in terms of polystyrene was 1,600, and the residual epoxy was 2.5% based on the amount charged.

[Synthesis example 6]
In a 100 mL two-necked flask, 7.87 g of TM-BIP-A (manufactured by Asahi Yokuzai Co., Ltd.), 10.00 g of 2-biphenyl glycidyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.), and ethyltriphenylphosphonium bromide (manufactured by Hokuko Chemical Industry Co., Ltd.) Co., Ltd.) and 43.7 g of propylene glycol monomethyl ether were added. Thereafter, the mixture was heated to 80°C and stirred for about 21 hours. After the reaction is completed, dilute with propylene glycol monomethyl ether and add 18.7 g of anion exchange resin (product name: DOWEX [registered trademark] 550A, Muromachi Technos Co., Ltd.) and cation exchange resin (product name: Amberlite) to the solution. 18.7 g of [Registered Trademark] 15JWET (Organo Co., Ltd.) was added, and ion exchange treatment was performed at room temperature for 4 hours. After separating the ion exchange resin, a solution of a compound having the structure of formula (1-6) was obtained. The weight average molecular weight Mw measured by GPC in terms of polystyrene was 900, and the residual epoxy was 0.2% based on the amount charged.

[Synthesis example 7]
In a 100 mL two-necked flask, 7.68 g of TM-BIP-A (manufactured by Asahi Yokuzai Co., Ltd.), 10.00 g of glycidyl 4-tertbutylbenzoate (manufactured by Tokyo Chemical Industry Co., Ltd.), and ethyltriphenylphosphonium bromide (manufactured by Hokuko Co., Ltd.) 0.82 g (manufactured by Kagaku Kogyo Co., Ltd.) and 43.2 g of propylene glycol monomethyl ether were added. Thereafter, the mixture was heated to 80°C and stirred for about 21 hours. After the reaction is completed, dilute with propylene glycol monomethyl ether and add 18.5 g of anion exchange resin (product name: DOWEX [registered trademark] 550A, Muromachi Technos Co., Ltd.) and cation exchange resin (product name: Amberlite) to the solution. 18.5 g of [Registered Trademark] 15JWET (Organo Co., Ltd.) was added, and ion exchange treatment was performed at room temperature for 4 hours. After separating the ion exchange resin, a solution of a compound having the structure of formula (1-7) was obtained. The weight average molecular weight Mw measured in terms of polystyrene by GPC was 1,700, and the residual epoxy was 1.1% based on the amount charged.

[Synthesis example 8]
In a 100 mL two-necked flask, add 7.89 g of 2,6-bis(hydroxymethyl)-p-cresol (manufactured by Tokyo Chemical Industry Co., Ltd.), 10.00 g of RE-810 NM (manufactured by Nippon Kayaku Co., Ltd.), and ethyl trichloride. 0.87 g of phenylphosphonium bromide (manufactured by Hokuko Chemical Industry Co., Ltd.) and 8.42 g of propylene glycol monomethyl ether were added. Thereafter, the mixture was heated to 100°C and stirred for about 24 hours. After the reaction is completed, dilute with propylene glycol monomethyl ether and add 18.8 g of anion exchange resin (product name: DOWEX [registered trademark] 550A, Muromachi Technos Co., Ltd.) and cation exchange resin (product name: Amberlite) to the solution. [Registered Trademark] 18.8 g of 15JWET (Organo Co., Ltd.) was added, and ion exchange treatment was performed at room temperature for 4 hours. After separating the ion exchange resin, a solution of a compound having the structure of formula (1-8) was obtained. The weight average molecular weight Mw measured in terms of polystyrene by GPC was 1,900, and there was no residual epoxy.

[Synthesis example 9]
9.09 g of 2,6-bis(hydroxymethyl)-p-cresol (manufactured by Tokyo Chemical Industry Co., Ltd.), 10.00 g of YX-4000 (manufactured by Mitsubishi Chemical Corporation), and ethyltriphenylphosphonium in a 100 mL two-necked flask. 1.00 g of bromide (manufactured by Hokuko Chemical Industry Co., Ltd.) and 8.61 g of propylene glycol monomethyl ether were added. Thereafter, the mixture was heated to 100°C and stirred for about 24 hours. After the reaction is completed, dilute with propylene glycol monomethyl ether and add 20.1 g of anion exchange resin (product name: DOWEX [registered trademark] 550A, Muromachi Technos Co., Ltd.) and cation exchange resin (product name: Amberlite) to the solution. 20.1 g of [Registered Trademark] 15JWET (Organo Co., Ltd.) was added, and ion exchange treatment was performed at room temperature for 4 hours. After separating the ion exchange resin, a solution of a compound having the structure of formula (1-9) was obtained. The weight average molecular weight Mw measured by GPC in terms of polystyrene was 1,500, and there was no residual epoxy.

（式（１－１０）中、ｓは０～３の整数を表す） [Synthesis example 10]
In a 100 mL two-necked flask, add 6.89 g of 2,6-bis(hydroxymethyl)-p-cresol (manufactured by Tokyo Chemical Industry Co., Ltd.), 10.00 g of HP-6000 (manufactured by DIC Corporation), and ethyltriphenylphosphonium bromide. (manufactured by Hokuko Chemical Industry Co., Ltd.) 0.76 g and propylene glycol monomethyl ether 7.57 g were added. Thereafter, the mixture was heated to 100°C and stirred for about 24 hours. After the reaction is completed, dilute with propylene glycol monomethyl ether and add 17.7 g of anion exchange resin (product name: DOWEX [registered trademark] 550A, Muromachi Technos Co., Ltd.) and cation exchange resin (product name: Amberlite) to the solution. 17.7 g of [Registered Trademark] 15JWET (Organo Co., Ltd.) was added, and ion exchange treatment was performed at room temperature for 4 hours. After separating the ion exchange resin, a solution of a compound having the structure (exemplary) of formula (1-10) was obtained. The weight average molecular weight Mw measured in terms of polystyrene by GPC was 1,900, and there was no residual epoxy.

(In formula (1-10), s represents an integer from 0 to 3)

[Synthesis Example 11]
In a 100 mL two-necked flask, add 7.20 g of 2,6-bis(hydroxymethyl)-p-cresol (manufactured by Tokyo Chemical Industry Co., Ltd.), 10.00 g of NC-7300L (manufactured by Nippon Kayaku Co., Ltd.), and ethyltriphenyl. 0.80 g of phosphonium bromide (manufactured by Hokuko Chemical Industry Co., Ltd.) and 7.71 g of propylene glycol monomethyl ether were added. Thereafter, the mixture was heated to 100°C and stirred for about 24 hours. After the reaction is completed, dilute with propylene glycol monomethyl ether and add 18.0 g of anion exchange resin (product name: DOWEX [registered trademark] 550A, Muromachi Technos Co., Ltd.) and cation exchange resin (product name: Amberlite) to the solution. [Registered Trademark] 15JWET (Organo Co., Ltd.) (18.0 g) was added, and ion exchange treatment was performed at room temperature for 4 hours. After separating the ion exchange resin, a solution of a compound having the structure (exemplified) of formula (1-11) was obtained. The weight average molecular weight Mw measured in terms of polystyrene by GPC was 2,200, and there was no residual epoxy.

[Synthesis example 12]
A polymer was obtained by the method described in Synthesis Example 10 of Japanese Patent No. 6191831. The weight average molecular weight Mw measured by GPC in terms of polystyrene was 2,000.

[Synthesis example 13]
In a 100 mL two-neck flask, 8.74 g of 3,7-dihydroxy-2-naphthoic acid, 10.00 g of NC-7300L (manufactured by Nippon Kayaku Co., Ltd.), 0 g of ethyltriphenylphosphonium bromide (manufactured by Hokuko Chemical Industry Co., Ltd.) .40g and 44.7g of propylene glycol monomethyl ether were added. Thereafter, the mixture was heated to 120°C and stirred for about 18 hours. After the reaction is complete, dilute with propylene glycol monomethyl ether and add 19.4 g of anion exchange resin (product name: DOWEX [registered trademark] 550A, Muromachi Technos Co., Ltd.) and cation exchange resin (product name: Amberlite) to the solution. 19.4 g of [Registered Trademark] 15JWET (Organo Co., Ltd.) was added, and ion exchange treatment was performed at room temperature for 4 hours. After separating the ion exchange resin, a solution of a compound having the structure (exemplified) of formula (1-13) was obtained. The weight average molecular weight Mw measured in terms of polystyrene by GPC was 1,100, and there was no residual epoxy.

[Example 1]
The polymer obtained in Synthesis Example 12 was dissolved in propylene glycol monomethyl ether acetate, and an anion exchange resin (product name: DOWEX [registered trademark] 550A, Muromachi Technos Co., Ltd.) and a cation exchange resin (product name: Amber) were dissolved in propylene glycol monomethyl ether acetate. Light (registered trademark) 15JWET (Organo Co., Ltd.) was added, and ion exchange treatment was performed at room temperature for 4 hours to obtain a polymer solution (solid content: 34.3% by mass). 2.6 g of this polymer solution was mixed with 0.09 g of propylene glycol monomethyl ether acetate containing 1% surfactant (Megafac R-40, manufactured by DIC Corporation), and a solution of the compound obtained in Synthesis Example 1 (solid content was 24 g). .2 mass%) 1.1 g, 2 mass% pyridinium p-hydroxybenzenesulfonate (Tokyo Kasei Kogyo Co., Ltd.) containing propylene glycol monomethyl ether 2.0 g, propylene glycol monomethyl ether acetate 8.0 g, propylene glycol monomethyl ether 1 .3 g was added and dissolved, and filtered through a polytetrafluoroethylene microfilter with a diameter of 0.1 μm to prepare a solution of the resist underlayer film forming composition.

[Example 2]
A solution of the polymer obtained in Synthesis Example 12 (solid content: 34.3% by mass) was obtained in the same manner as in Example 1. 2.6 g of this polymer solution was mixed with 0.09 g of propylene glycol monomethyl ether acetate containing 1% surfactant (Megafac R-40, manufactured by DIC Corporation), and a solution of the compound obtained in Synthesis Example 2 (solid content was 26 g). .1 mass %) 1.0 g, 2 mass % pyridinium p-hydroxybenzenesulfonate (Tokyo Kasei Kogyo Co., Ltd.) containing propylene glycol monomethyl ether 2.0 g, propylene glycol monomethyl ether acetate 8.0 g, propylene glycol monomethyl ether 1 .3 g was added and dissolved, and filtered through a polytetrafluoroethylene microfilter with a diameter of 0.1 μm to prepare a solution of the resist underlayer film forming composition.

[Example 3]
A solution of the polymer obtained in Synthesis Example 12 (solid content: 34.3% by mass) was obtained in the same manner as in Example 1. To 2.6 g of this polymer solution, 0.09 g of propylene glycol monomethyl ether acetate containing 1% surfactant (Megafac R-40, manufactured by DIC Corporation) was added to a solution of the compound obtained in Synthesis Example 3 (solid content was 26 g). .5 mass%) 1.0 g, 2 mass% pyridinium p-hydroxybenzenesulfonate (Tokyo Kasei Kogyo Co., Ltd.) containing propylene glycol monomethyl ether 2.0 g, propylene glycol monomethyl ether acetate 8.0 g, propylene glycol monomethyl ether 1 .3 g was added and dissolved, and filtered through a polytetrafluoroethylene microfilter with a diameter of 0.1 μm to prepare a solution of the resist underlayer film forming composition.

[Example 4]
A solution of the polymer obtained in Synthesis Example 13 (solid content: 29.1% by mass) was obtained in the same manner as in Example 1. 2.7 g of this polymer solution was mixed with 0.16 g of propylene glycol monomethyl ether acetate containing 1% surfactant (Megafac R-40, manufactured by DIC Corporation), and a solution of the compound obtained in Synthesis Example 1 (solid content was 24 g). .2 mass%) 1.0 g, 2 mass% pyridinium p-hydroxybenzenesulfonate (Tokyo Kasei Kogyo Co., Ltd.) containing propylene glycol monomethyl ether 1.8 g, propylene glycol monomethyl ether acetate 4.0 g, propylene glycol monomethyl ether 5 .4 g was added and dissolved, and filtered through a polytetrafluoroethylene microfilter with a diameter of 0.1 μm to prepare a solution of the resist underlayer film forming composition.

[Example 5]
A solution of the polymer obtained in Synthesis Example 12 (solid content: 34.3% by mass) was obtained in the same manner as in Example 1. 2.4 g of this polymer solution was mixed with 0.08 g of propylene glycol monomethyl ether acetate containing 1% surfactant (Megafac R-40, manufactured by DIC Corporation), and a solution of the compound obtained in Synthesis Example 8 (solid content was 24 g). .1% by mass) 1.4g, 2.5g of propylene glycol monomethyl ether containing 2% by mass of pyridinium p-hydroxybenzenesulfonate (Tokyo Kasei Kogyo Co., Ltd.), 8.1g of propylene glycol monomethyl ether acetate, 0 propylene glycol monomethyl ether .6 g was added and dissolved, and filtered through a polytetrafluoroethylene microfilter with a diameter of 0.1 μm to prepare a solution of the resist underlayer film forming composition.

[Example 6]
A solution of the polymer obtained in Synthesis Example 12 (solid content: 34.3% by mass) was obtained in the same manner as in Example 1. 2.4 g of this polymer solution was mixed with 0.08 g of propylene glycol monomethyl ether acetate containing 1% surfactant (Megafac R-40, manufactured by DIC Corporation), and a solution of the compound obtained in Synthesis Example 9 (solid content was 22 g). 0 mass%) 1.5 g, 2 mass% pyridinium p-hydroxybenzenesulfonate (Tokyo Kasei Kogyo Co., Ltd.) containing propylene glycol monomethyl ether 2.5 g, propylene glycol monomethyl ether acetate 8.1 g, propylene glycol monomethyl ether 0 .5 g was added and dissolved, and filtered through a polytetrafluoroethylene microfilter with a diameter of 0.1 μm to prepare a solution of the resist underlayer film forming composition.

[Example 7]
A solution of the polymer obtained in Synthesis Example 12 (solid content: 34.3% by mass) was obtained in the same manner as in Example 1. 2.4 g of this polymer solution was mixed with 0.08 g of propylene glycol monomethyl ether acetate containing 1% surfactant (Megafac R-40, manufactured by DIC Corporation), and a solution of the compound obtained in Synthesis Example 10 (solid content was 24 g). .5% by mass) 1.3g, 2.5g of propylene glycol monomethyl ether containing 2% by mass of pyridinium p-hydroxybenzenesulfonate (Tokyo Kasei Kogyo Co., Ltd.), 8.1g of propylene glycol monomethyl ether acetate, 0 propylene glycol monomethyl ether .7 g was added and dissolved, and filtered through a polytetrafluoroethylene microfilter with a diameter of 0.1 μm to prepare a solution of the resist underlayer film forming composition.

[Example 8]
A solution of the polymer obtained in Synthesis Example 12 (solid content: 34.3% by mass) was obtained in the same manner as in Example 1. 2.4 g of this polymer solution was mixed with 0.08 g of propylene glycol monomethyl ether acetate containing 1% surfactant (Megafac R-40, manufactured by DIC Corporation), and a solution of the compound obtained in Synthesis Example 11 (solid content was 27 g). .1% by mass) 1.2g, 2.5g of propylene glycol monomethyl ether containing 2% by mass of pyridinium p-hydroxybenzenesulfonate (Tokyo Kasei Kogyo Co., Ltd.), 8.1g of propylene glycol monomethyl ether acetate, 0 propylene glycol monomethyl ether .8 g was added and dissolved, and filtered through a polytetrafluoroethylene microfilter with a diameter of 0.1 μm to prepare a solution of the resist underlayer film forming composition.

[Example 9]
A solution of the polymer obtained in Synthesis Example 12 (solid content: 34.3% by mass) was obtained in the same manner as in Example 1. 2.6 g of this polymer solution was mixed with 0.09 g of propylene glycol monomethyl ether acetate containing 1% surfactant (Megafac R-40, manufactured by DIC Corporation), and a solution of the compound obtained in Synthesis Example 4 (solid content was 26 g). .9 mass%) 1.0 g, 2 mass% pyridinium p-hydroxybenzenesulfonate (Tokyo Kasei Kogyo Co., Ltd.) containing propylene glycol monomethyl ether 2.0 g, propylene glycol monomethyl ether acetate 8.0 g, propylene glycol monomethyl ether 1 .4 g was added and dissolved, and filtered through a polytetrafluoroethylene microfilter with a diameter of 0.1 μm to prepare a solution of the resist underlayer film forming composition.

[Example 10]
A solution of the polymer obtained in Synthesis Example 12 (solid content: 34.3% by mass) was obtained in the same manner as in Example 1. 2.8 g of this polymer solution was mixed with 0.10 g of propylene glycol monomethyl ether acetate containing 1% surfactant (Megafac R-40, manufactured by DIC Corporation), and a solution of the compound obtained in Synthesis Example 5 (solid content was 20 g). .6 mass%) 0.95 g, 2 mass% pyridinium p-hydroxybenzenesulfonate (Tokyo Kasei Kogyo Co., Ltd.) containing propylene glycol monomethyl ether 1.5 g, propylene glycol monomethyl ether acetate 7.8 g, propylene glycol monomethyl ether 1 .9 g was added and dissolved, and filtered through a polytetrafluoroethylene microfilter with a diameter of 0.1 μm to prepare a solution of the resist underlayer film forming composition.

[Example 11]
A solution of the polymer obtained in Synthesis Example 12 (solid content: 34.3% by mass) was obtained in the same manner as in Example 1. 2.8 g of this polymer solution was mixed with 0.10 g of propylene glycol monomethyl ether acetate containing 1% surfactant (Megafac R-40, manufactured by DIC Corporation), and a solution of the compound obtained in Synthesis Example 6 (solid content was 23 .9 mass%) 0.82 g, 2 mass% pyridinium p-hydroxybenzenesulfonate (Tokyo Kasei Kogyo Co., Ltd.) containing propylene glycol monomethyl ether 1.5 g, propylene glycol monomethyl ether acetate 7.8 g, propylene glycol monomethyl ether 2 0.0 g was added and dissolved, and filtered through a polytetrafluoroethylene microfilter with a diameter of 0.1 μm to prepare a solution of the resist underlayer film forming composition.

[Example 12]
A solution of the polymer obtained in Synthesis Example 12 (solid content: 34.3% by mass) was obtained in the same manner as in Example 1. 2.8 g of this polymer solution was mixed with 0.10 g of propylene glycol monomethyl ether acetate containing 1% surfactant (Megafac R-40, manufactured by DIC Corporation), and a solution of the compound obtained in Synthesis Example 7 (solid content was 23 .5 mass%) 0.83 g, 2 mass% pyridinium p-hydroxybenzenesulfonate (Tokyo Kasei Kogyo Co., Ltd.) containing propylene glycol monomethyl ether 1.5 g, propylene glycol monomethyl ether acetate 7.8 g, propylene glycol monomethyl ether 2 0.0 g was added and dissolved, and filtered through a polytetrafluoroethylene microfilter with a diameter of 0.1 μm to prepare a solution of the resist underlayer film forming composition.

[Comparative example 1]
The polymer obtained in Synthesis Example 12 was dissolved in propylene glycol monomethyl ether acetate and subjected to ion exchange to obtain a polymer solution (solid content: 34.3% by mass). 2.6 g of this polymer solution, 0.09 g of propylene glycol monomethyl ether acetate containing 1% surfactant (Megafac R-40, manufactured by DIC Corporation), and 0.27 g of TMOM-BP (manufactured by Honshu Chemical Industry Co., Ltd.) , 2.0 g of propylene glycol monomethyl ether containing 2% by mass pyridinium p-hydroxybenzenesulfonate (Tokyo Kasei Kogyo Co., Ltd.), 8.0 g of propylene glycol monomethyl ether acetate, and 2.1 g of propylene glycol monomethyl ether were added and dissolved, A solution of the resist underlayer film forming composition was prepared by filtration using a polytetrafluoroethylene microfilter with a diameter of 0.1 μm.

[Comparative example 2]
A solution of the polymer obtained in Synthesis Example 13 (solid content: 29.1% by mass) was obtained in the same manner as in Example 1. 2.7 g of this polymer solution, 0.16 g of propylene glycol monomethyl ether acetate containing 1% surfactant (Megafac R-40, manufactured by DIC Corporation), and 0.23 g of TMOM-BP (manufactured by Honshu Chemical Industry Co., Ltd.) , 1.8 g of propylene glycol monomethyl ether containing 2% by mass pyridinium p-hydroxybenzenesulfonate (Tokyo Kasei Kogyo Co., Ltd.), 4.0 g of propylene glycol monomethyl ether acetate, and 6.2 g of propylene glycol monomethyl ether were added and dissolved, A solution of the resist underlayer film forming composition was prepared by filtration using a polytetrafluoroethylene microfilter with a diameter of 0.1 μm.

[Comparative example 3]
A solution of the polymer obtained in Synthesis Example 12 (solid content: 34.3% by mass) was obtained in the same manner as in Example 1. 3.6 g of this polymer solution, 0.12 g of propylene glycol monomethyl ether acetate containing 1% surfactant (Megafac R-40, manufactured by DIC Corporation), and 0.49 g of TMOM-BP (manufactured by Honshu Chemical Industry Co., Ltd.) , 1.5 g of propylene glycol monomethyl ether containing 2% by mass pyridinium p-hydroxybenzenesulfonate (Tokyo Kasei Kogyo Co., Ltd.), 10.4 g of propylene glycol monomethyl ether acetate, and 3.9 g of propylene glycol monomethyl ether were added and dissolved, A solution of the resist underlayer film forming composition was prepared by filtration using a polytetrafluoroethylene microfilter with a diameter of 0.1 μm.

[Comparative example 4]
A solution of the polymer obtained in Synthesis Example 12 (solid content: 34.3% by mass) was obtained in the same manner as in Example 1. 2.6 g of this polymer solution, 0.09 g of propylene glycol monomethyl ether acetate containing 1% surfactant (Megafac R-40, manufactured by DIC Corporation), and 0.27 g of HMOM-TPPA (manufactured by Honshu Chemical Industry Co., Ltd.) , 2.0 g of propylene glycol monomethyl ether containing 2% by mass pyridinium p-hydroxybenzenesulfonate (Tokyo Kasei Kogyo Co., Ltd.), 8.0 g of propylene glycol monomethyl ether acetate, and 2.1 g of propylene glycol monomethyl ether were added and dissolved, A solution of the resist underlayer film forming composition was prepared by filtration using a polytetrafluoroethylene microfilter with a diameter of 0.1 μm.

[Comparative example 5]
A solution of the polymer obtained in Synthesis Example 12 (solid content: 34.3% by mass) was obtained in the same manner as in Example 1. To 2.8 g of this polymer solution, 0.10 g of propylene glycol monomethyl ether acetate containing 1% surfactant (Megafac R-40, manufactured by DIC Corporation), 0.0 g of TM-BIP-A (manufactured by Asahi Yokuzai Co., Ltd.) .20g, 2% by mass pyridinium p-hydroxybenzenesulfonate (Tokyo Kasei Kogyo Co., Ltd.) containing 1.5g of propylene glycol monomethyl ether, 7.8g of propylene glycol monomethyl ether acetate, and 2.6g of propylene glycol monomethyl ether were added and dissolved. and filtered through a polytetrafluoroethylene microfilter with a diameter of 0.1 μm to prepare a solution of the resist underlayer film forming composition.

(Elution test into resist solvent)
The solutions of the resist underlayer film forming compositions prepared in Comparative Example 1-5 and Example 1-12 were each applied onto a silicon wafer using a spin coater and baked at 240°C for 60 seconds on a hot plate to form the resist underlayer film. A film (film thickness 0.20 μm) was formed. These resist underlayer films were immersed in ethyl lactate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and cyclohexanone, which are solvents used in the resist. These resist underlayer films were insoluble in these solvents.

(Optical constant measurement)
The solutions of the resist underlayer film forming compositions prepared in Comparative Example 1-5 and Example 1-12 were each applied onto a silicon wafer using a spin coater. It was baked on a hot plate at 240° C. for 60 seconds to form a resist underlayer film (thickness: 0.05 μm). The refractive index (n value) and optical absorption coefficient (k value, also referred to as extinction coefficient) of these resist underlayer films at a wavelength of 193 nm were measured using a spectroscopic ellipsometer. The results are shown in Table 1-5.

[Measurement of dry etching speed]
The etcher and etching gas used to measure the dry etching rate were as follows.
RIE-10NR (manufactured by Samco): CF ₄
The solutions of the resist underlayer film forming compositions prepared in Comparative Example 1-5 and Example 1-12 were each applied onto a silicon wafer using a spin coater. It was baked on a hot plate at 240° C. for 60 seconds to form a resist underlayer film (thickness: 0.20 μm). The dry etching rate was measured using CF ₄ gas as the etching gas, and the dry etching rate ratio of Comparative Example 1-5 and Example 1-12 was determined. The dry etching rate ratio is the dry etching rate ratio of (resist underlayer film)/(KrF photoresist). The results are shown in Table 6-10.

(Embeddability evaluation)
The embeddability was confirmed in a dense pattern area of a SiO ₂ substrate with a film thickness of 200 nm, a trench width of 50 nm, and a pitch of 100 nm. The resist underlayer film forming compositions prepared in Comparative Example 1-5 and Example 1-12 were coated on the substrate and baked at 240° C. for 60 seconds to form a resist underlayer film with a thickness of about 200 nm. The cross-sectional shape of this substrate was observed using a scanning electron microscope (S-4800) manufactured by Hitachi High-Technologies Co., Ltd., to confirm whether or not the resist underlayer film forming composition was filled inside the pattern. The results are shown in Tables 11-15. If the resist underlayer film is formed inside the pattern without any gaps, the embedding property is judged as good ("○"), and if it is not embedded inside the pattern or there are holes or gaps inside the pattern, it is judged as poor ( "×").

The crosslinkers used in Examples 1-12 exhibit good embedding properties similar to conventional crosslinkers.

(Covering test on step board)
As a coating test on a stepped substrate, we compared the coating thickness of a dense area (DENSE) with a trench width of 50 nm and a pitch of 100 nm and an open area (OPEN) where no pattern is formed on a SiO ₂ substrate with a film thickness of 200 nm. Ta. The resist underlayer film forming compositions prepared in Comparative Example 1-5 and Example 1-11 were applied to the above substrates and then baked at 240° C. for 60 seconds to form resist underlayer films with a thickness of about 200 nm. The planarity of this substrate was observed using a scanning electron microscope (S-4800) manufactured by Hitachi High-Technologies Corporation, and the film thickness of the trench area (patterned part) and open area (patterned part) of the step substrate was Flattenability was evaluated by measuring the difference (the difference in coating level between the trench area and the open area, which is called a bias). Here, flatness refers to the area where a pattern exists (dense area (pattern area)) and the area where no pattern exists (open area (unpatterned area)). This means that the film thickness difference (Iso-dense bias) is small. The results are shown in Table 16-20. In addition, examples in which an improvement (reduction of less than 15 nm) was confirmed with respect to the evaluation of △ in the comparative example (control) were evaluated as ○, and examples in which a significant improvement (reduction of 15 nm or more) was observed were evaluated as ◎.

It was confirmed that Examples 1-12 had improved flattening properties compared to Comparative Examples.

[Synthesis example 21]
In a 100 mL two-necked flask, add 19.12 g of TMOM-BP (manufactured by Honshu Chemical Industry Co., Ltd.), 15.00 g of RE810-NM (manufactured by Nippon Kayaku Co., Ltd.), and ethyltriphenylphosphonium bromide (manufactured by Hokuko Chemical Industry Co., Ltd.). ), and 81.14 g of propylene glycol monomethyl ether were added. Thereafter, the mixture was heated to 140°C and stirred under reflux for about 14 hours. After the reaction, add 34.8 g of anion exchange resin (product name: DOWEX [registered trademark] 550A, Muromachi Technos Co., Ltd.) and cation exchange resin (product name: Amberlite [registered trademark] 15JWET, Organo (product name)) to the solution. Co., Ltd.) was added thereto, and ion exchange treatment was performed at room temperature for 4 hours. After separating the ion exchange resin, a compound solution (1-21) was obtained. The weight average molecular weight Mw measured by GPC in terms of polystyrene was 6,000.

[Synthesis example 22]
In a 100 mL two-necked flask, 26.96 g of TMOM-BP (manufactured by Honshu Kagaku Kogyo Co., Ltd.), 10.00 g of 1,4-butanediol diglycidyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.), and ethyltriphenylphosphonium bromide (manufactured by Hokuko Co., Ltd.) 0.92 g (manufactured by Kagaku Kogyo Co., Ltd.) and 56.8 g of propylene glycol monomethyl ether were added. Thereafter, the mixture was heated to 140°C and stirred under reflux for about 14.5 hours. After the reaction is complete, dilute with propylene glycol monomethyl ether and add 37.9 g of anion exchange resin (product name: DOWEX [registered trademark] 550A, Muromachi Technos Co., Ltd.) and cation exchange resin (product name: Amberlite) to the solution. [Registered Trademark] 15JWET (Organo Co., Ltd.) (37.9 g) was added, and ion exchange treatment was performed at room temperature for 4 hours. After separating the ion exchange resin, a compound solution (1-22) was obtained. The weight average molecular weight Mw measured by GPC in terms of polystyrene was 4,800.

[Synthesis example 23]
In a 100 mL two-necked flask, 17.45 g of TMOM-BP (manufactured by Honshu Chemical Industry Co., Ltd.), 15.00 g of HP-6000 (manufactured by DIC Corporation), 0 g of ethyltriphenylphosphonium bromide (manufactured by Hokuko Chemical Industry Co., Ltd.) .60 g and 77.1 g of propylene glycol monomethyl ether were added. Thereafter, the mixture was heated to 140°C and stirred under reflux for about 12 hours. After the reaction, add 33.0 g of anion exchange resin (product name: DOWEX [registered trademark] 550A, Muromachi Technos Co., Ltd.) and cation exchange resin (product name: Amberlite [registered trademark] 15JWET, Organo (product name)) to the solution. Co., Ltd.) was added thereto, and ion exchange treatment was performed at room temperature for 4 hours. After separating the ion exchange resin, a compound solution (1-23) was obtained. The weight average molecular weight Mw measured by GPC in terms of polystyrene was 10,500.

[Synthesis example 24]
In a 100 mL two-necked flask, add 22.0 g of TMOM-BP (manufactured by Honshu Chemical Industry Co., Ltd.), 15.00 g of YX-4000 (manufactured by Mitsubishi Chemical Corporation), and ethyltriphenylphosphonium bromide (manufactured by Hokuko Chemical Industry Co., Ltd.). 0.75 g and 88.1 g of propylene glycol monomethyl ether were added. Thereafter, the mixture was heated to 140°C and stirred under reflux for about 12 hours. After the reaction, add 37.8 g of anion exchange resin (product name: DOWEX [registered trademark] 550A, Muromachi Technos Co., Ltd.) and cation exchange resin (product name: Amberlite [registered trademark] 15JWET, Organo (product name)) to the solution. Co., Ltd.) was added thereto, and ion exchange treatment was performed at room temperature for 4 hours. After separating the ion exchange resin, a compound solution (1-24) was obtained. The weight average molecular weight Mw measured by GPC in terms of polystyrene was 4,200.

[Synthesis example 25]
In a 100 mL two-necked flask, add 17.5 g of TMOM-BP (manufactured by Honshu Chemical Industry Co., Ltd.), 15.00 g of 9,9-bis(4-glycidyloxyphenyl)fluorene (manufactured by Tokyo Kasei Co., Ltd.), and ethyltriphenylphosphonium. 0.60 g of bromide (manufactured by Hokuko Chemical Industry Co., Ltd.) and 77.2 g of propylene glycol monomethyl ether were added. Thereafter, the mixture was heated to 140°C and stirred under reflux for about 12 hours. After the reaction, add 33.1 g of anion exchange resin (product name: DOWEX [registered trademark] 550A, Muromachi Technos Co., Ltd.) and cation exchange resin (product name: Amberlite [registered trademark] 15JWET, Organo (product name)) to the solution. Co., Ltd.) was added thereto, and ion exchange treatment was performed at room temperature for 4 hours. After separating the ion exchange resin, a compound solution (1-25) was obtained. The weight average molecular weight Mw measured in terms of polystyrene by GPC was 5,200.

[Synthesis example 26]
In a 100 mL two-necked flask, add 25.7 g of TMOM-BP (manufactured by Honshu Kagaku Kogyo Co., Ltd.), 15.00 g of diglycidyl 4-cyclohexene-1,2-dicarboxylate (manufactured by Tokyo Kasei Co., Ltd.), and ethyltriphenylphosphonium bromide (manufactured by Tokyo Kasei Co., Ltd.). 0.89 g (manufactured by Hokuko Chemical Industry Co., Ltd.) and 97.0 g of propylene glycol monomethyl ether were added. Thereafter, the mixture was heated to 140°C and stirred under reflux for about 12 hours. After the reaction, add 41.6 g of anion exchange resin (product name: DOWEX [registered trademark] 550A, Muromachi Technos Co., Ltd.) and cation exchange resin (product name: Amberlite [registered trademark] 15JWET, Organo (product name)) to the solution. Co., Ltd.) was added thereto, and ion exchange treatment was performed at room temperature for 4 hours. After separating the ion exchange resin, a compound solution (1-26) was obtained. The weight average molecular weight Mw measured in terms of polystyrene by GPC was 2,900.

[Synthesis example 27]
A polymer was obtained by the method described in Synthesis Example 10 of Japanese Patent No. 6191831. The weight average molecular weight Mw measured by GPC in terms of polystyrene was 2,000. The obtained polymer was dissolved in propylene glycol monomethyl ether acetate, and an anion exchange resin (product name: DOWEX [registered trademark] 550A, Muromachi Technos Co., Ltd.) and a cation exchange resin (product name: Amberlite [registered trademark]) were dissolved. ] 15JWET (Organo Co., Ltd.) was added and subjected to ion exchange treatment at room temperature for 4 hours to obtain a compound solution (1-27).

[Synthesis example 28]
In a 100 mL two-necked flask, add 72.46 g of propylene glycol monomethyl ether, 26.00 g of RE810-NM (manufactured by Nippon Kayaku Co., Ltd.), 20.81 g of BPA-CA (manufactured by Konishi Chemical Co., Ltd.), and 2 ethyltriphenylphosphonium bromide. After adding 0.18 g of hydroquinone and 0.32 g of hydroquinone, the mixture was reacted at 140° C. for 24 hours to obtain a solution containing the reaction product. After diluting to a 20% by weight solution with propylene glycol monomethyl ether, 147.90 g of anion exchange resin (product name: DOWEX [registered trademark] 550A, Muromachi Technos Co., Ltd.), cation exchange resin (product name: Amberlite) 147.90 g of [Registered Trademark] 15JWET, manufactured by Organo Co., Ltd. was added, stirred at 60° C. for 4 hours, filtered, and the resin was separated to obtain a compound solution (1-28). The weight average molecular weight Mw measured by GPC in terms of polystyrene was 18,000.

[Example 21]
0.10 g of propylene glycol monomethyl ether acetate containing 1% by mass surfactant (Megafac R-40, manufactured by DIC Corporation) in 3.34 g of compound solution (1-27) (solid content: 29.9% by mass); 1.74 g of compound solution (1-22) (solid content: 28.5% by mass), 7.01 g of propylene glycol monomethyl ether acetate, and 2.80 g of propylene glycol monomethyl ether were added and dissolved, and polytetra having a diameter of 0.1 μm was added. A solution of the resist underlayer film forming composition was prepared by filtration using a fluoroethylene microfilter.

[Example 22]
0.10 g of propylene glycol monomethyl ether acetate containing 1% by mass surfactant (Megafac R-40, manufactured by DIC Corporation) in 3.34 g of compound solution (1-27) (solid content: 29.9% by mass); 1.74 g of compound solution (1-21) (solid content: 28.7% by mass), 7.01 g of propylene glycol monomethyl ether acetate, and 2.81 g of propylene glycol monomethyl ether were added and dissolved, and polytetra having a diameter of 0.1 μm was added. A solution of the resist underlayer film forming composition was prepared by filtration using a fluoroethylene microfilter.

[Example 23]
0.10 g of propylene glycol monomethyl ether acetate containing 1% by mass surfactant (Megafac R-40, manufactured by DIC Corporation) in 3.34 g of compound solution (1-27) (solid content: 29.9% by mass); Add and dissolve 1.89 g of compound solution (1-23) (solid content: 26.4% by mass), 7.01 g of propylene glycol monomethyl ether acetate, and 2.66 g of propylene glycol monomethyl ether to form a polytetra A solution of the resist underlayer film forming composition was prepared by filtration using a fluoroethylene microfilter.

[Example 24]
3.34 g of compound solution (1-27) (solid content 29.9% by mass), 0.10 g of propylene glycol monomethyl ether acetate containing 1% surfactant (Megafac R-40, manufactured by DIC Corporation), compound Add and dissolve 1.99 g of solution (1-24) (solid content: 25.1% by mass), 7.01 g of propylene glycol monomethyl ether acetate, and 2.56 g of propylene glycol monomethyl ether. A solution of the resist underlayer film forming composition was prepared by filtration using an ethylene microfilter.

[Example 25]
0.10 g of propylene glycol monomethyl ether acetate containing 1% by mass surfactant (Megafac R-40, manufactured by DIC Corporation) in 3.34 g of compound solution (1-27) (solid content: 29.9% by mass); 1.84 g of compound solution (1-25) (solid content: 27.2% by mass), 7.01 g of propylene glycol monomethyl ether acetate, and 2.71 g of propylene glycol monomethyl ether were added and dissolved, and polytetra having a diameter of 0.1 μm was added. A solution of the resist underlayer film forming composition was prepared by filtration using a fluoroethylene microfilter.

[Example 26]
0.10 g of propylene glycol monomethyl ether acetate containing 1% by mass surfactant (Megafac R-40, manufactured by DIC Corporation) in 3.34 g of compound solution (1-27) (solid content: 29.9% by mass); 1.84 g of compound solution (1-26) (solid content: 26.4% by mass), 7.01 g of propylene glycol monomethyl ether acetate, and 2.66 g of propylene glycol monomethyl ether were added and dissolved, and polytetra with a diameter of 0.1 μm was added. A solution of the resist underlayer film forming composition was prepared by filtration using a fluoroethylene microfilter.

[Example 27]
NeoFARIT 7177C (manufactured by Mitsubishi Gas Chemical Co., Ltd.) containing propylene glycol monomethyl ether acetate (solid content: 28.7% by mass) 3.49g with 1% by mass surfactant (Megafac R-40, manufactured by DIC Corporation) Add 0.10 g of propylene glycol monomethyl ether acetate, 1.75 g of compound solution (1-22) (solid content is 28.5% by mass), 6.86 g of propylene glycol monomethyl ether acetate, and 2.80 g of propylene glycol monomethyl ether. The solution was dissolved and filtered through a polytetrafluoroethylene microfilter with a diameter of 0.1 μm to prepare a solution of the resist underlayer film forming composition.

[Example 28]
NeoFARIT 7177C (manufactured by Mitsubishi Gas Chemical Co., Ltd.) containing propylene glycol monomethyl ether acetate (solid content: 28.7% by mass) 3.42g containing 1% by mass surfactant (Megafac R-40, manufactured by DIC Corporation) Contains 0.10 g of propylene glycol monomethyl ether acetate, 1.72 g of compound solution (1-22) (solid content 28.5% by mass), and 2% by mass of pyridinium p-hydroxybenzenesulfonate (Tokyo Kasei Kogyo Co., Ltd.) Add and dissolve 1.47 g of propylene glycol monomethyl ether, 6.92 g of propylene glycol monomethyl ether acetate, and 1.38 g of propylene glycol monomethyl ether, and filter through a polytetrafluoroethylene microfilter with a diameter of 0.1 μm to form a resist lower layer. A solution of the film-forming composition was prepared.

[Example 29]
4.97 g of compound solution (1-28) (solid content: 20.1% by mass) and 0.10 g of propylene glycol monomethyl ether acetate containing 1% by mass surfactant (Megafac R-40, manufactured by DIC Corporation); Add and dissolve 1.75 g of compound solution (1-22) (solid content: 28.5% by mass), 3.95 g of propylene glycol monomethyl ether acetate, and 4.23 g of propylene glycol monomethyl ether, and dissolve polytetra with a diameter of 0.1 μm. A solution of the resist underlayer film forming composition was prepared by filtration using a fluoroethylene microfilter.

[Example 30]
0.10 g of propylene glycol monomethyl ether acetate containing 1% by mass surfactant (Megafac R-40, manufactured by DIC Corporation) in 4.87 g of compound solution (1-28) (solid content: 20.1% by mass); Compound solution (1-22) (solid content 28.5% by mass) 1.72g, 2% by mass pyridinium p-hydroxybenzenesulfonate (Tokyo Kasei Kogyo Co., Ltd.) containing propylene glycol monomethyl ether 1.47g, propylene glycol 3.95 g of monomethyl ether acetate and 2.89 g of propylene glycol monomethyl ether were added and dissolved, and filtered through a polytetrafluoroethylene microfilter with a diameter of 0.1 μm to prepare a solution of a resist underlayer film forming composition.

[Example 31]
0.16 g of propylene glycol monomethyl ether acetate containing 1% by mass surfactant (Megafac R-40, manufactured by DIC Corporation) in 2.78 g of compound solution (1-21) (solid content: 28.7% by mass); Add and dissolve 2.60 g of propylene glycol monomethyl ether acetate and 4.46 g of propylene glycol monomethyl ether, and filter through a polytetrafluoroethylene microfilter with a diameter of 0.1 μm to prepare a solution of the resist underlayer film forming composition. did.

[Example 32]
2.80 g of compound solution (1-22) (solid content: 28.5% by mass) and 0.16g of propylene glycol monomethyl ether acetate containing 1% by mass surfactant (Megafac R-40, manufactured by DIC Corporation); Add and dissolve 2.60 g of propylene glycol monomethyl ether acetate and 4.44 g of propylene glycol monomethyl ether, and filter through a polytetrafluoroethylene microfilter with a diameter of 0.1 μm to prepare a solution of the resist underlayer film forming composition. did.

[Example 33]
0.16 g of propylene glycol monomethyl ether acetate containing 1% by mass surfactant (Megafac R-40, manufactured by DIC Corporation) in 3.02 g of compound solution (1-23) (solid content: 26.4% by mass); Add and dissolve 2.60 g of propylene glycol monomethyl ether acetate and 4.21 g of propylene glycol monomethyl ether, and filter through a polytetrafluoroethylene microfilter with a diameter of 0.1 μm to prepare a solution of the resist underlayer film forming composition. did.

[Example 34]
3.18 g of compound solution (1-24) (solid content: 25.1% by mass) and 0.16 g of propylene glycol monomethyl ether acetate containing 1% by mass surfactant (Megafac R-40, manufactured by DIC Corporation); Add and dissolve 2.60 g of propylene glycol monomethyl ether acetate and 4.06 g of propylene glycol monomethyl ether, and filter through a polytetrafluoroethylene microfilter with a diameter of 0.1 μm to prepare a solution of the resist underlayer film forming composition. did.

[Example 35]
0.16 g of propylene glycol monomethyl ether acetate containing 1% by mass surfactant (Megafac R-40, manufactured by DIC Corporation) in 2.94 g of compound solution (1-25) (solid content: 27.2% by mass); Add and dissolve 2.60 g of propylene glycol monomethyl ether acetate and 4.30 g of propylene glycol monomethyl ether, and filter through a polytetrafluoroethylene microfilter with a diameter of 0.1 μm to prepare a solution of the resist underlayer film forming composition. did.

[Example 36]
0.16 g of propylene glycol monomethyl ether acetate containing 1% by mass surfactant (Megafac R-40, manufactured by DIC Corporation) in 3.02 g of compound solution (1-26) (solid content: 26.4% by mass); Add and dissolve 2.60 g of propylene glycol monomethyl ether acetate and 4.21 g of propylene glycol monomethyl ether, and filter through a polytetrafluoroethylene microfilter with a diameter of 0.1 μm to prepare a solution of the resist underlayer film forming composition. did.

[Example 37]
0.16 g of propylene glycol monomethyl ether acetate containing 1% by mass surfactant (Megafac R-40, manufactured by DIC Corporation) in 2.72 g of compound solution (1-22) (solid content: 28.5% by mass); 1.16 g of propylene glycol monomethyl ether containing 2% by mass pyridinium p-hydroxybenzenesulfonate (Tokyo Kasei Kogyo Co., Ltd.), 2.61 g of propylene glycol monomethyl ether acetate, and 3.36 g of propylene glycol monomethyl ether were added and dissolved. A solution of the resist underlayer film forming composition was prepared by filtration using a 0.1 μm polytetrafluoroethylene microfilter.

[Comparative example 21]
0.08 g of propylene glycol monomethyl ether acetate containing 1% by mass surfactant (Megafac R-40, manufactured by DIC Corporation) in 2.62 g of compound solution (1-27) (solid content: 29.9% by mass); 0.39 g of TMOM-BP (Honshu Chemical Industry Co., Ltd.), 1.18 g of propylene glycol monomethyl ether containing 2% by mass pyridinium p-hydroxybenzenesulfonate (Tokyo Kasei Kogyo Co., Ltd.), propylene glycol monomethyl ether acetate 7. 74 g and 2.99 g of propylene glycol monomethyl ether were added and dissolved, and filtered through a polytetrafluoroethylene microfilter with a diameter of 0.1 μm to prepare a solution of a resist underlayer film forming composition.

[Comparative example 22]
0.08 g of propylene glycol monomethyl ether acetate containing 1% by mass surfactant (Megafac R-40, manufactured by DIC Corporation) in 2.62 g of compound solution (1-27) (solid content: 29.9% by mass); PL-LI (manufactured by Midori Kagaku Co., Ltd.) 0.39 g, 2% by mass pyridinium p-hydroxybenzenesulfonate (Tokyo Kasei Kogyo Co., Ltd.) containing propylene glycol monomethyl ether 1.18 g, propylene glycol monomethyl ether acetate 7.74 g , 2.99 g of propylene glycol monomethyl ether was added and dissolved, and filtered through a polytetrafluoroethylene microfilter with a diameter of 0.1 μm to prepare a solution of a resist underlayer film forming composition.

[Comparative example 23]
NeoFARIT 7177C (manufactured by Mitsubishi Gas Chemical Co., Ltd.) containing propylene glycol monomethyl ether acetate (solid content: 28.7% by mass) 3.42g containing 1% by mass surfactant (Megafac R-40, manufactured by DIC Corporation) Propylene glycol monomethyl ether acetate containing 0.10 g, PL-LI (Midori Kagaku Co., Ltd.) 0.49 g, 2% by mass pyridinium p-hydroxybenzenesulfonate (Tokyo Kasei Kogyo Co., Ltd.) containing propylene glycol monomethyl ether 1. 47g of propylene glycol monomethyl ether acetate, 6.92g of propylene glycol monomethyl ether acetate, and 2.61g of propylene glycol monomethyl ether were added and dissolved, and filtered through a polytetrafluoroethylene microfilter with a diameter of 0.1 μm to obtain a solution of the resist underlayer film forming composition. was prepared.

[Comparative example 24]
0.10 g of propylene glycol monomethyl ether acetate containing 1% by mass surfactant (Megafac R-40, manufactured by DIC Corporation) in 4.87 g of compound solution (1-28) (solid content: 20.1% by mass); PL-LI (manufactured by Midori Kagaku Co., Ltd.) 0.49 g, 2% by mass pyridinium p-hydroxybenzenesulfonate (Tokyo Kasei Kogyo Co., Ltd.) containing propylene glycol monomethyl ether 1.47 g, propylene glycol monomethyl ether acetate 3.95 g , 4.12 g of propylene glycol monomethyl ether was added and dissolved, and filtered through a polytetrafluoroethylene microfilter with a diameter of 0.1 μm to prepare a solution of a resist underlayer film forming composition.

(Elution test into resist solvent)
The solutions of the resist underlayer film forming compositions prepared in Comparative Examples 21-24 and Examples 21-37 were each applied onto a silicon wafer using a spin coater and heated at 250°C for 60 seconds or 260°C for 60 seconds on a hot plate. It was fired to form a resist lower layer film (thickness: 0.20 μm). These resist underlayer films were immersed in ethyl lactate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and cyclohexanone, which are solvents used in the resist. These resist underlayer films were insoluble in these solvents.

(Confirmation of curing end temperature)
The solutions of the resist underlayer film forming compositions prepared in Comparative Examples 21-22 and Examples 21-26 were each applied onto a silicon wafer using a spin coater, and baked on a hot plate at an arbitrary temperature for 60 seconds. A resist underlayer film (thickness: 0.20 μm) was formed. The temperature at which these resist underlayer films would not dissolve in a 7:3 mixed solvent of propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate (=curing completion temperature) was confirmed. The method was the same as the elution test into resist solvent (Table 21).

Compared to Comparative Examples 21-22, Examples 21-26 had a higher curing completion temperature. It can be seen that the crosslinking agents used in the examples have higher fluidity and slower curing than when conventional crosslinking agents are used.

(Optical constant measurement)
The solutions of the resist underlayer film forming compositions prepared in Comparative Examples 21-24 and Examples 21-37 were each applied onto a silicon wafer using a spin coater. It was baked on a hot plate at 250° C. for 60 seconds or 260° C. for 60 seconds to form a resist underlayer film (thickness: 0.05 μm). The refractive index (n value) and optical absorption coefficient (k value, also referred to as extinction coefficient) of these resist underlayer films at a wavelength of 193 nm were measured using a spectroscopic ellipsometer. (Table 22)

As can be seen from Examples 31 to 37, the optical constants of the crosslinking agent can be greatly changed by changing the type of epoxy compound. Comparing Examples 21-26 using these crosslinking agents and Comparative Examples 21-22 using conventional crosslinking agents, it is found that changing the type of crosslinking agent can change the optical constants of materials with the same composition ratio. I can do it. This tendency is the same in Comparative Example 23 and Examples 27-28, Comparative Example 24 and Examples 30-31, and the reflectance can be suppressed by selecting an appropriate crosslinking agent.

[Measurement of dry etching speed]
The etcher and etching gas used to measure the dry etching rate were as follows.
RIE-10NR (manufactured by Samco): CF ₄
The solutions of the resist underlayer film forming compositions prepared in Comparative Examples 21-24 and Examples 21-37 were each applied onto a silicon wafer using a spin coater. A resist underlayer film (thickness: 0.20 μm) was formed by baking on a hot plate at 250° C. for 60 seconds or at 260° C. for 60 seconds. The dry etching rate was measured using CF ₄ gas as the etching gas, and the dry etching rate ratio of Comparative Examples 21-24 and Examples 21-37 was determined. The dry etching rate ratio is the dry etching rate ratio of (resist underlayer film)/(KrF photoresist). (Table 23)

As can be seen from Examples 31 to 37, the etching rate of the crosslinking agent can be greatly changed by changing the type of epoxy compound. Comparing Examples 21-26 using these crosslinking agents and Comparative Examples 21-22 using conventional crosslinking agents, it is found that changing the type of crosslinking agent can change the etching rate of materials with the same composition ratio. I can do it. This tendency is the same in Comparative Example 23 and Examples 27-28, Comparative Example 24 and Examples 30-31, and processability can be improved by adjusting the etching rate to an appropriate value.

(Embeddability evaluation)
The embeddability was confirmed in a dense pattern area of a SiO ₂ substrate with a film thickness of 200 nm, a trench width of 50 nm, and a pitch of 100 nm. The resist underlayer film forming compositions prepared in Comparative Examples 21-24 and Examples 21-37 were applied onto the above substrates and then baked at 250°C for 60 seconds or at 260°C for 60 seconds to form resist underlayer films with a thickness of about 200 nm. . The flattenability of this substrate was observed using a scanning electron microscope (S-4800) manufactured by Hitachi High-Technologies Corporation, and the presence or absence of filling of the resist underlayer film forming composition inside the pattern was confirmed (Table 24) . If the resist underlayer film is formed inside the pattern without any gaps, the embedding property is judged as good ("○"), and if it is not embedded inside the pattern or there are holes or gaps inside the pattern, it is judged as poor ( "×").

Example 21-37 shows embeddability equivalent to Comparative Example 21-24 using a conventional crosslinking agent.

(Covering test on step board)
As a coating test on a stepped substrate, a comparison was made between the coating thickness of an 800 nm trench area (TRENCH) and an open area (OPEN) where no pattern is formed using a 200 nm thick SiO ₂ substrate. The resist underlayer film forming compositions prepared in Comparative Examples 21-24 and Examples 21-37 were applied to the above substrates and then baked at 250° C. for 60 seconds or 260° C. for 60 seconds to form resist underlayer films with a thickness of about 200 nm. The planarity of this substrate was observed using a scanning electron microscope (S-4800) manufactured by Hitachi High-Technologies Corporation, and the film thickness of the trench area (patterned part) and open area (patterned part) of the step substrate was Flattenability was evaluated by measuring the difference (the difference in coating level between the trench area and the open area, which is called a bias). Here, flatness refers to the area where a pattern exists (TRENCH (pattern area)) and the area where a pattern does not exist (open area (no pattern area)), and the applied coating that exists on top of the area (TRENCH (pattern area)). This means that the film thickness difference (Iso-TRENCH bias) is small (Table 25). In addition, examples in which an improvement of 15 nm or more was confirmed over Comparative Example 21 were evaluated as ○, examples in which an improvement in 30 nm or more was confirmed in comparison to Comparative Example 21 were evaluated as ◎, and comparative examples in which no improvement was observed were evaluated as ×. .

Comparing Comparative Example 22 and Examples 21-26, Comparative Example 23 and Examples 27-28, and Comparative Example 24 and Examples 29-30, it was confirmed that Example had a significant improvement in flattening properties. Further, in Examples 31-37, in which the resist underlayer film was formed using a crosslinking agent or a crosslinking agent and an acid catalyst, it was confirmed that the flattening property was significantly improved when compared with a general composition such as Comparative Example 22. These results are considered to be due to the fact that the curing finishing temperature of the crosslinking agent used in the examples was higher than the curing finishing temperature using a conventional crosslinking agent, so that the flow time of the resin could be maintained for a long time.

(Light curing test)
The resist underlayer film forming compositions prepared in Comparative Examples 21-24 and Examples 22, 26, 31, and 36 were each applied onto a silicon wafer using a spin coater. A resist underlayer film was formed by heating on a hot plate for 60 seconds at a temperature that did not completely cure the resist. This resist underlayer film was irradiated with UV rays at 500 mJ/cm ² using a UV irradiation device manufactured by Ushio Inc. and using a UV irradiation unit (wavelength 172 nm), and the solvent removability with light irradiation (UV irradiation) was confirmed. did. Solvent removability was determined by immersing the coated film after UV irradiation in a 7:3 mixed solvent of propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate for 1 minute, then baking it at 100°C for 1 minute after spin drying, and measuring the film thickness. (Table 26). In addition, a case where the amount of decrease in film thickness was within 1% was marked as ○, and a case where the film thickness decreased by 1% or more was marked as ×.

It was confirmed that by containing a crosslinking agent having a non-aromatic unsaturated bond in the molecule, not only thermosetting properties but also photocuring properties can be obtained.

(Covering test on step board after light irradiation)
As a coating test on a stepped substrate, a comparison was made between the coating thickness of an 800 nm trench area (TRENCH) and an open area (OPEN) where no pattern is formed using a 200 nm thick SiO ₂ substrate. The resist underlayer film forming compositions prepared in Examples 22, 26, and 31 were applied to the above substrates and then baked at the temperatures shown in the table to form resist underlayer films of about 200 nm. This resist underlayer film was irradiated with ultraviolet rays at 500 mJ/cm ² using an ultraviolet irradiation device manufactured by Ushio Inc. and using a UV irradiation unit (wavelength 172 nm), and the planarization of this substrate was evaluated by Hitachi High-Technologies Co., Ltd. Evaluation was carried out using a scanning electron microscope (S-4800) made by the same method as in the above-mentioned "coating test on stepped substrate" (Table 27). The flattening properties of Examples 22, 26, and 31 were good (〇) when only the heat curing treatment was performed, but the flattening properties were good (〇) when they were heat-treated at a relatively low temperature and then the curing was completed by the photo-curing treatment. It was confirmed that the flattening property was further improved (◎).

Even if the compositions were exactly the same, it was possible to improve the flattening properties by appropriately combining heat curing and photocuring.

According to the present invention, there is provided a resist underlayer film-forming composition that has excellent embedding properties and planarization properties on a stepped substrate; the composition is formed by coating and baking the composition, is insoluble in a resist solvent, and has good optical constants; , a resist underlayer film with a high etching rate; and a method of manufacturing a patterned substrate and a method of manufacturing a semiconductor device using these can be provided.

Claims (15)

A resist underlayer film forming composition comprising (A) a crosslinkable compound represented by the following formula (I) and (D) a solvent.

[In the formula, m is an integer from 1 to 30,
When m=1,
T is a single bond, a divalent to hexavalent saturated hydrocarbon group which may be interrupted by an aromatic ring, or an oxygen atom, a carbonyl group or an alkylene group, and is substituted with an alkyl group or an alkenyl group. a divalent to hexavalent aromatic group or an unsaturated cyclic hydrocarbon group, which may be
As the valence of G ¹ , G ² , and T increases to 3 or more, G ³ , G ⁴ , G ⁵ , and G ⁶ that exist are independently

or

and
n is each independently an integer from 1 to 8,
Each of the n R's is independently a hydrogen atom, or an alkyl group optionally interrupted by an oxygen atom, a nitrogen atom, or a carbonyl group,
each A is independently a C ₆ -C ₁₈ aryl group optionally interrupted by an alkylene group;
As the valence of Z ¹ , Z ² , and T increases to 3 or more, Z ³ , Z ⁴ , Z ⁵ , and Z ⁶ present may be independently interrupted by an oxygen atom, a nitrogen atom, or a carbonyl group. alkyl groups, or optionally interrupted by oxygen atoms, nitrogen atoms or carbonyl groups, hydroxy groups, halogen atoms, carboxyl groups, nitro groups, cyano groups, methylenedioxy groups, acetoxy groups, methylthio groups, amino groups, Represents an aryl group optionally substituted with a C ₁ -C ₉ alkoxy group, alkyl group, alkenyl group or alkynyl group.
When m>1,
m T's are a single bond, a divalent saturated hydrocarbon group which may be interrupted by an aromatic ring, or an oxygen atom, a carbonyl group or an alkylene group, and substituted with an alkyl group or an alkenyl group. A divalent aromatic group or an unsaturated cyclic hydrocarbon group that may be
G ³ Z ³ , G ⁴ Z ⁴ , G ⁵ Z ⁵ , G ⁶ Z ⁶ does not exist,
m G ¹ and G ² are each independently

or

and
n, R, and A are as defined above;
Z ¹ and Z ² each independently represent a hydroxy group, an epoxy group, or a hydrogen atom. ] 2. The resist underlayer film forming composition according to claim 1, wherein each of the A's is a _C6 aryl group which may be independently interrupted by an alkylene group. (B) The resist underlayer film forming composition according to claim 1 or 2, further comprising a film material capable of crosslinking with the crosslinkable compound (A). The crosslinkable membrane material (B) is selected from the group consisting of aliphatic ring-containing resins, novolak resins, polyether resins, polyester resins, acrylic resins, methacrylic resins, and compounds different from the crosslinkable compound (A). The resist underlayer film forming composition according to claim 3, comprising at least one of: The novolac resin has the following formula (1a), formula (1b) and formula (1c):

[In the formula, each of the two R ¹ independently represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aromatic hydrocarbon group, a halogen atom, a nitro group, or an amino group, and 2 Each of R ² independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an acetal group, an acyl group, or a glycidyl group, and R ³ has a substituent. ^R4 represents a hydrogen atom, a phenyl group or a naphthyl group, and when ^R3 and ^R4 bonded to the same carbon atom each represent a phenyl group, they bond to each other to form a fluorene ring. In formula (1b), the two groups represented by R ³ and the two atoms or groups represented by R ⁴ may be different from each other, the two k each independently represent 0 or 1, and m ₀ represents an integer from 3 to 500, n ₀ , n ₁ and n ₂ represent an integer from 2 to 500, p represents an integer from 3 to 500, X represents a single bond or a heteroatom, and two Q are each independently expressed by the following formula (2):

(In the formula, two R ¹ , two R ² , two R ³ , two R ⁴ , two k, n ₁ , n ₂ and X are synonymous with formula (1b), and two Q ¹ are Each independently represents a structural unit represented by the above formula (2).) represents a structural unit represented by the formula (2). ]
The resist underlayer film forming composition according to claim 4, which is represented by any one or two or more of the repeating structural units represented by. A compound different from the crosslinkable compound (A) is

(In formula (2), each of the two Ar represents an aryl group, the aryl group has at least one hydroxy group as a substituent, and Q is a divalent linking group having at least one benzene ring or naphthalene ring. , a methylene group or a single bond), the resist underlayer film forming composition according to claim 4. (C) The resist underlayer film forming composition according to claim 1 or 2, further comprising an acid catalyst. (C) The resist underlayer film forming composition according to any one of claims 3 to 6, further comprising an acid catalyst. The resist underlayer film forming composition according to claim 8, wherein the crosslinkable compound (A) is represented by the following formula (1).

[In the formula,
V is

or

represents,
i is an integer from 2 to 6,
i R's are each independently a hydrogen atom, or an alkyl group optionally interrupted by an oxygen atom, a nitrogen atom, or a carbonyl group,
i pieces of n are each independently an integer from 1 to 8,
each of the i A's is independently a C ₆ -C ₁₈ aryl group optionally interrupted by an alkylene group;
i Z's are each independently an alkyl group which may be interrupted by an oxygen atom, a nitrogen atom or a carbonyl group, or an alkyl group which may be interrupted by an oxygen atom, a nitrogen atom or a carbonyl group, a hydroxy group, a halogen atom, a carboxyl group; an aryl group optionally substituted with a group, a nitro group, a cyano group, a methylenedioxy group, an acetoxy group, a methylthio group, an amino group, a C ₁ -C ₉ alkoxy group, an alkyl group, an alkenyl group or an alkynyl group,
T is a single bond, an i-valent saturated hydrocarbon group which may be interrupted by an aromatic ring, or an i-valent saturated hydrocarbon group which may be interrupted by an oxygen atom or an alkylene group, and which may be substituted with an alkyl group or an alkenyl group. is a valent aromatic group. ] Each of the above Z may be independently interrupted by an alkyl group, an oxygen atom, a nitrogen atom, or a carbonyl group, and a hydroxy group, a halogen atom, a carboxyl group, a nitro group, a cyano group, a methylenedioxy group, an acetoxy group, a methylthio group. The resist underlayer film forming composition according to claim 9, which is an aryl group optionally substituted with an amino group, a C ₁ -C ₉ alkoxy group, an alkyl group, an alkenyl group, or an alkynyl group. A resist underlayer film, which is a cured product of a coating film comprising the resist underlayer film forming composition according to any one of claims 1 to 10. A step of applying the resist underlayer film forming composition according to any one of claims 1 to 10 on a semiconductor substrate and curing it to form a resist underlayer film, applying a resist on the resist underlayer film and baking it. A method for manufacturing a patterned substrate, comprising the steps of forming a resist film, exposing the resist underlayer film and the semiconductor substrate covered with the resist, and developing and patterning the exposed resist film. 13. The method of manufacturing a patterned substrate according to claim 12, wherein the curing is performed by baking. The method for manufacturing a patterned substrate according to claim 12, wherein the curing is performed by irradiating ultraviolet rays after baking. A step of forming a resist underlayer film on a semiconductor substrate using the resist underlayer film forming composition according to any one of claims 1 to 10, a step of forming a resist film thereon, irradiation with light or electron beam, and development. A method for manufacturing a semiconductor device, comprising: forming a resist pattern using a resist pattern, etching the lower layer film using the resist pattern, and processing a semiconductor substrate using the patterned lower layer film.