WO2018016640A1

WO2018016640A1 - Compound, resin, composition, resist pattern formation method, and circuit pattern formation method

Info

Publication number: WO2018016640A1
Application number: PCT/JP2017/026530
Authority: WO
Inventors: 越後　雅敏
Original assignee: 三菱瓦斯化学株式会社
Priority date: 2016-07-21
Filing date: 2017-07-21
Publication date: 2018-01-25
Also published as: JP7283515B2; TW201815738A; KR20190033537A; JP7110979B2; CN109476575A; JPWO2018016640A1; JP2022033731A

Abstract

Provided is a compound represented by formula (0). (0) (R^Y is a hydrogen atom, a C1–30 alkyl group, or a C6–30 aryl group; R^Z is a C1–60 N-valent group or a single bond; and R^T is an optionally-substituted C1–30 alkyl group, an optionally-substituted C6–30 aryl group, an optionally-substituted C2–30 alkenyl group, an optionally-substituted C1–30 alkoxy group, a halogen atom, a nitro group, an amino group, a carboxylic acid group, a thiol group, a hydroxyl group, or a group in which a hydrogen atom of the hydroxyl group has been substituted with a vinylphenyl methyl–containing group (the alkyl group, aryl group, alkenyl group, and alkoxy group may include an ether bond, ketone bond, or ester bond), wherein at least one R^T includes a group in which a hydrogen atom of the hydroxyl group has been substituted with a vinylphenyl methyl–containing group. X represents an oxygen atom or a sulfur atom, or is uncrosslinked; m is an integer from 0 to 9 (with at least one m being an integer from 1 to 9); N is an integer from 1 to 4; and r is an integer from 0 to 2.)

Description

Compound, resin, composition, resist pattern forming method, and circuit pattern forming method

The present invention relates to a compound having a specific structure, a resin, and a composition containing these. The present invention also relates to a pattern forming method (resist pattern forming method and circuit pattern forming method) using the composition.

In the manufacture of semiconductor devices, microfabrication by lithography using a photoresist material is performed. In recent years, further miniaturization by pattern rules has been demanded as LSI is highly integrated and increased in speed. The light source for lithography used for resist pattern formation has been shortened from the krf excimer laser (248 nm) to the arf excimer laser (193 nm), and extreme ultraviolet light (EUV, 13.5 nm) has been introduced. Is also expected.

However, in lithography using a conventional polymer resist material, the molecular weight is as large as about 10,000 to 100,000, and the molecular weight distribution is wide, resulting in roughness on the pattern surface, making it difficult to control the pattern size, and limiting the miniaturization. There is.
Thus, various low molecular weight resist materials have been proposed so far in order to provide resist patterns with higher resolution. Since the low molecular weight resist material has a small molecular size, it is expected to provide a resist pattern with high resolution and low roughness.

At present, various kinds of low-molecular resist materials are known. For example, an alkali development negative radiation-sensitive composition (for example, see Patent Document 1 and Patent Document 2 below) using a low molecular weight polynuclear polyphenol compound as a main component has been proposed, and a low molecular weight resist having high heat resistance. As a candidate for the material, an alkali developing negative radiation-sensitive composition (for example, see Patent Document 3 and Non-Patent Document 1 below) using a low molecular weight cyclic polyphenol compound as a main component has also been proposed. In addition, as a base compound for resist materials, polyphenol compounds are known to be able to impart high heat resistance while having a low molecular weight, and are useful for improving the resolution and roughness of resist patterns (for example, the following non-patent documents) 2).

The present inventors have excellent etching resistance, and are resist compositions containing a compound having a specific structure and an organic solvent as a material that is soluble in a solvent and applicable to a wet process (for example, see Patent Document 4 below). ).

Further, as the resist pattern becomes finer, there arises a problem of resolution or a problem that the resist pattern collapses after development. Therefore, a thinner resist is desired. However, simply thinning the resist makes it difficult to obtain a resist pattern film thickness sufficient for substrate processing. Therefore, not only a resist pattern but also a process in which a resist underlayer film is formed between the resist and a semiconductor substrate to be processed and the resist underlayer film also has a function as a mask during substrate processing has become necessary.

Currently, various types of resist underlayer films for such processes are known. For example, unlike a conventional resist underlayer film having a high etching rate, a terminal layer is removed by applying a predetermined energy as a resist underlayer film for lithography having a dry etching rate selection ratio close to that of a resist. A material for forming an underlayer film for a multilayer resist process has been proposed that contains at least a resin component having a substituent that generates a sulfonic acid residue and a solvent (see, for example, Patent Document 5 below). Also, resist underlayer film materials containing a polymer having a specific repeating unit have been proposed as a material for realizing a resist underlayer film for lithography having a lower dry etching rate selectivity than resist (for example, the following patents) Reference 6). Furthermore, in order to realize a resist underlayer film for lithography having a low dry etching rate selection ratio compared with a semiconductor substrate, a repeating unit of acenaphthylenes and a repeating unit having a substituted or unsubstituted hydroxy group are copolymerized. A resist underlayer film material containing a polymer is proposed (see, for example, Patent Document 7 below).

On the other hand, as a material having high etching resistance in this type of resist underlayer film, an amorphous carbon underlayer film formed by CVD using methane gas, ethane gas, acetylene gas or the like as a raw material is well known. However, from the viewpoint of the process, a resist underlayer film material capable of forming a resist underlayer film by a wet process such as spin coating or screen printing is required.

In addition, the present inventors have a composition for forming an underlayer film for lithography containing a compound having a specific structure and an organic solvent as a material having excellent etching resistance, high heat resistance, soluble in a solvent and applicable to a wet process. The thing (refer the following patent document 8) is proposed.

In addition, regarding the formation method of the intermediate layer used in the formation of the resist underlayer film in the three-layer process, for example, a silicon nitride film formation method (for example, see Patent Document 9 below) or a silicon nitride film CVD formation method (for example, And the following Patent Document 10) are known. As an intermediate layer material for a three-layer process, a material containing a silsesquioxane-based silicon compound is known (see, for example, Patent Documents 11 and 12 below).
Further, various optical component forming compositions have been proposed. Examples thereof include acrylic resins (see, for example, Patent Documents 13 to 14 below).

JP 2005-326838 A JP 2008-145539 A JP 2009-173623 A International Publication No. 2013/024778 JP 2004-177668 A JP 2004-271838 A JP 2005-250434 A International Publication No. 2013/024779 JP 2002-334869 A International Publication No. 2004/066377 JP 2007-226170 A JP 2007-226204 A JP 2010-138393 A Japanese Patent Laying-Open No. 2015-174877

As described above, many lithographic film-forming compositions for resist applications and lithographic film-forming compositions for underlayer films have been proposed, but wet processes such as spin coating and screen printing are highly applicable. There is nothing that has not only solvent solubility but also high heat resistance and etching resistance at a high level, and development of new materials is required. In addition, development of a new material suitable for obtaining a resist permanent film excellent in alkali developability, photosensitivity, and resolution is also demanded.
In addition, many compositions for optical members have been proposed in the past, but none of them has both high heat resistance, transparency and refractive index, and development of new materials is required.

The present invention has been made in view of the above-mentioned problems, and the object thereof is a compound and resin having high solubility in a safe solvent, good heat resistance and etching resistance, a composition using the same, and The present invention relates to a resist pattern forming method and a circuit pattern forming method using the composition.

As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by using a compound or resin having a specific structure, and have completed the present invention.
That is, the present invention is as follows.
<1> A compound represented by the following formula (0).

(0)
(In Formula (0), R ^Y is a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms,
R ^Z is an N-valent group having 1 to 60 carbon atoms or a single bond,
R ^T each independently has an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, or a substituent. An optionally substituted alkenyl group having 2 to 30 carbon atoms, an optionally substituted alkoxy group having 1 to 30 carbon atoms, a halogen atom, a nitro group, an amino group, a carboxylic acid group, a thiol group, a hydroxyl group or a hydroxyl group Wherein the hydrogen atom is substituted with a vinyl-containing phenylmethyl group, and the alkyl group, the aryl group, the alkenyl group, and the alkoxy group may include an ether bond, a ketone bond, or an ester bond. And at least one of ^RT is a group in which a hydrogen atom of a hydroxyl group is substituted with a vinylphenylmethyl group,
X represents an oxygen atom, a sulfur atom or no bridge,
M is each independently an integer of 0 to 9, wherein at least one of m is an integer of 1 to 9,
N is an integer of 1 to 4, and when N is an integer of 2 or more, the structural formulas in N [] may be the same or different,
Each R is independently an integer of 0-2. )
<2> The compound according to <1>, wherein the compound represented by the formula (0) is a compound represented by the following formula (1).

(1)
(In Formula (1), R ⁰ has the same meaning as R ^Y ,
R ¹ is an n-valent group having 1 to 60 carbon atoms or a single bond,
R ² to R ⁵ are each independently an optionally substituted alkyl group having 1 to 30 carbon atoms, an optionally substituted aryl group having 6 to 30 carbon atoms, or a substituent. An alkenyl group having 2 to 30 carbon atoms which may have a substituent, an alkoxy group having 1 to 30 carbon atoms which may have a substituent, a halogen atom, a nitro group, an amino group, a carboxylic acid group, a thiol group, A hydroxyl group or a group in which a hydrogen atom of a hydroxyl group is substituted with a vinylphenylmethyl group, and the alkyl group, the aryl group, the alkenyl group, and the alkoxy group may include an ether bond, a ketone bond, or an ester bond. Here, at least one of R ² to R ⁵ is a group in which a hydrogen atom of a hydroxyl group is substituted with a vinylphenylmethyl group,
M ² and m ³ are each independently an integer of 0 to 8,
M ⁴ and m ⁵ are each independently an integer of 0 to 9,
However, m ² , m ³ , m ⁴ and m ⁵ are not 0 simultaneously,
N is synonymous with N, and when n is an integer of 2 or more, the structural formulas in n [] may be the same or different,
P ² to p ⁵ are as defined above for r. )
<3> The compound according to <1>, wherein the compound represented by the formula (0) is a compound represented by the following formula (2).

(2)
(In Formula (2), R ^0A has the same meaning as R ^Y ,
R ^1A is ^a na-valent group having 1 to 60 carbon atoms or a single bond,
R ^2A each independently has an optionally substituted alkyl group having 1 to 30 carbon atoms, an optionally substituted aryl group having 6 to 30 carbon atoms, or a substituent. An optionally substituted alkenyl group having 2 to 30 carbon atoms, an optionally substituted alkoxy group having 1 to 30 carbon atoms, a halogen atom, a nitro group, an amino group, a carboxylic acid group, a thiol group, a hydroxyl group or a hydroxyl group Wherein the hydrogen atom is substituted with a vinyl-containing phenylmethyl group, and the alkyl group, the aryl group, the alkenyl group, and the alkoxy group may include an ether bond, a ketone bond, or an ester bond. And at least one of R ^2A is a group in which a hydrogen atom of a hydroxyl group is substituted with a vinylphenylmethyl group,
N ^a is the same as defined above N, where, if n ^a is an integer of 2 or more, n structural formulas of ^a number of brackets [] may be the same or different and
X ^A is synonymous with X,
M ^2a is each independently an integer of 0 to 7, provided that at least one m ^2a is an integer of 1 to 7;
Q ^a is independently 0 or 1. )
<4> The compound according to <2>, wherein the compound represented by the formula (1) is a compound represented by the following formula (1-1).

(1-1)
(In the formula (1-1), R ⁰ , R ¹ , R ⁴ , R ⁵ , n, p ² to p ⁵ , m ⁴ and m ⁵ are as defined above.
R ⁶ to R ⁷ are each independently an optionally substituted alkyl group having 1 to 30 carbon atoms, an optionally substituted aryl group having 6 to 30 carbon atoms, or a substituent. An alkenyl group having 2 to 30 carbon atoms, a halogen atom, a nitro group, an amino group, a carboxylic acid group, or a thiol group, which may have
R ¹⁰ to R ¹¹ are each independently a hydrogen atom or a vinylphenylmethyl group,
Here, at least one of R ¹⁰ to R ^{11 is} a vinylphenylmethyl group,
M ⁶ and m ⁷ are each independently an integer of 0 to 7,
However, m ⁴ , m ⁵ , m ⁶ and m ⁷ are not 0 at the same time. )
<5> The compound according to <4>, wherein the compound represented by the formula (1-1) is a compound represented by the following formula (1-2).

(1-2)
(In the formula (1-2), R ⁰ , R ¹ , R ⁶ , R ⁷ , R ¹⁰ , R ¹¹ , n, p ² to p ⁵ , m ⁶ and m ⁷ are as defined above.
R ⁸ to R ⁹ have the same meanings as R ⁶ to R ⁷ ,
R ¹² to R ¹³ have the same meanings as R ¹⁰ to R ¹¹ ,
M ⁸ and m ⁹ are each independently an integer of 0 to 8,
However, m ⁶ , m ⁷ , m ⁸ and m ⁹ are not 0 at the same time. )
<6> The compound according to <3>, wherein the compound represented by the formula (2) is a compound represented by the following formula (2-1).

(2-1)
(In the formula (2-1), R ^0A , R ^1A , n ^a , q ^a and X ^A have the same meanings as described in the formula (2).
R ^3A each independently has an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, or a substituent. Which may be an alkenyl group having 2 to 30 carbon atoms, a halogen atom, a nitro group, an amino group, a carboxylic acid group, or a thiol group,
R ^4A is each independently a hydrogen atom or a vinyl-containing phenylmethyl group,
Here, at least one of R ^{4A is} a vinyl-containing phenylmethyl group,
M ^6a is each independently an integer of 0 to 5. )
<7> A resin obtained by using the compound according to <1> as a monomer.
<8> The resin according to <7>, which has a structure represented by the following formula (3).

(3)
(In the formula (3), L has an optionally substituted alkylene group having 1 to 30 carbon atoms, an optionally substituted arylene group having 6 to 30 carbon atoms, and a substituent. The alkylene group, the arylene group and the alkoxylene group may contain an ether bond, a ketone bond or an ester bond,
R ⁰ has the same meaning as R ^Y ,
R ¹ is an n-valent group having 1 to 60 carbon atoms or a single bond,
R ² to R ⁵ are each independently an optionally substituted alkyl group having 1 to 30 carbon atoms, an optionally substituted aryl group having 6 to 30 carbon atoms, or a substituent. An alkenyl group having 2 to 30 carbon atoms which may have a substituent, an alkoxy group having 1 to 30 carbon atoms which may have a substituent, a halogen atom, a nitro group, an amino group, a carboxylic acid group, a thiol group, A hydroxyl group or a group in which a hydrogen atom of a hydroxyl group is substituted with a vinylphenylmethyl group, and the alkyl group, the aryl group, the alkenyl group, and the alkoxy group may include an ether bond, a ketone bond, or an ester bond. Often,
M ² and m ³ are each independently an integer of 0 to 8,
M ⁴ and m ⁵ are each independently an integer of 0 to 9,
However, m ² , m ³ , m ⁴ and m ⁵ are not simultaneously 0, and at least one of R ² to R ⁵ is a group in which a hydrogen atom of a hydroxyl group is substituted with a vinylphenylmethyl group.
N is synonymous with N, and when n is an integer of 2 or more, the structural formulas in n [] may be the same or different,
P ² to p ⁵ are as defined above for r. )
<9> The resin according to <7>, having a structure represented by the following formula (4).

(4)
(In Formula (4), L has an optionally substituted alkylene group having 1 to 30 carbon atoms, an optionally substituted arylene group having 6 to 30 carbon atoms, and a substituent. The alkylene group, the arylene group and the alkoxylene group may contain an ether bond, a ketone bond or an ester bond,
R ^0A has the same meaning as R ^Y ,
R ^1A is ^a na-valent group having 1 to 30 carbon atoms or a single bond,
R ^2A each independently has an optionally substituted alkyl group having 1 to 30 carbon atoms, an optionally substituted aryl group having 6 to 30 carbon atoms, or a substituent. An optionally substituted alkenyl group having 2 to 30 carbon atoms, an optionally substituted alkoxy group having 1 to 30 carbon atoms, a halogen atom, a nitro group, an amino group, a carboxylic acid group, a thiol group, a hydroxyl group or a hydroxyl group Wherein the hydrogen atom is substituted with a vinyl-containing phenylmethyl group, and the alkyl group, the aryl group, the alkenyl group, and the alkoxy group may include an ether bond, a ketone bond, or an ester bond. And at least one of R ^2A is a group in which a hydrogen atom of a hydroxyl group is substituted with a vinylphenylmethyl group,
N ^a is the same as defined above N, where, if n ^a is an integer of 2 or more, n structural formulas of ^a number of brackets [] may be the same or different and
X ^A is synonymous with X,
M ^2a is each independently an integer of 0 to 7, provided that at least one m ^2a is an integer of 1 to 6;
Q ^a is independently 0 or 1. )
<10> Contains one or more selected from the group consisting of the compound according to any one of <1> to <6> and the resin according to any one of <7> to <9>. ,Composition.
<11> The composition according to <10>, further including a solvent.
<12> The composition according to <10> or <11>, further including an acid generator.
<13> The composition according to any one of <10> to <12>, further including a crosslinking agent.
<14> The crosslinking agent is at least one selected from the group consisting of phenol compounds, epoxy compounds, cyanate compounds, amino compounds, benzoxazine compounds, melamine compounds, guanamine compounds, glycoluril compounds, urea compounds, isocyanate compounds, and azide compounds. The composition according to <13>, which is a seed.
<15> The composition according to <13> or <14>, wherein the crosslinking agent has at least one allyl group.
<16> The content of the cross-linking agent is selected from the group consisting of the compound according to any one of the above <1> to <6> and the resin according to any one of the above <7> to <9>. The composition according to any one of <13> to <15>, which is 0.1 to 100 parts by mass with respect to 100 parts by mass of the total mass of the composition containing one or more selected.
<17> The composition according to any one of <13> to <16>, further including a crosslinking accelerator.
<18> The composition according to <17>, wherein the crosslinking accelerator is at least one selected from the group consisting of amines, imidazoles, organic phosphines, and Lewis acids.
<19> The group consisting of the compound according to any one of <1> to <6> and the resin according to any one of <7> to <9>, wherein the content of the crosslinking accelerator is The composition according to <17> or <18>, which is 0.1 to 5 parts by mass with respect to 100 parts by mass of the total mass of the composition containing one or more selected from the above.
<20> The composition according to any one of <10> to <19>, further comprising a radical polymerization initiator.
<21> The <10> to <20, wherein the radical polymerization initiator is at least one selected from the group consisting of a ketone photopolymerization initiator, an organic peroxide polymerization initiator, and an azo polymerization initiator. > The composition as described in any one of>.
<22> The content of the radical polymerization initiator includes the compound according to any one of <1> to <6> and the resin according to any one of <7> to <9>. The composition according to any one of the above <10> to <21>, which is 0.05 to 25 parts by mass with respect to 100 parts by mass of the total mass of the composition containing one or more selected from the group.
<23> The composition according to any one of <10> to <22>, which is used for forming a film for lithography.
<24> The composition according to any one of <10> to <22>, which is used for forming a resist permanent film.
<25> The composition according to any one of <10> to <22>, which is used for forming an optical component.
<26> A resist pattern including a step of forming a photoresist layer on the substrate by using the composition according to the above <23>, irradiating a predetermined region of the photoresist layer with radiation, and performing development. Forming method.
<27> A lower layer film is formed on the substrate using the composition according to the above <23>, and at least one photoresist layer is formed on the lower layer film, and then a predetermined layer of the photoresist layer is formed. A resist pattern forming method including a step of irradiating a region with radiation and performing development.
<28> A lower layer film is formed on the substrate using the composition described in <23>, an intermediate layer film is formed on the lower layer film using a resist intermediate layer film material, and the intermediate layer film is formed. After forming at least one photoresist layer thereon, a predetermined region of the photoresist layer is irradiated with radiation, developed to form a resist pattern, and then the intermediate layer film using the resist pattern as a mask A circuit pattern including a step of forming a pattern on the substrate by etching the substrate using the obtained intermediate layer film pattern as an etching mask and etching the substrate using the obtained lower layer film pattern as an etching mask Forming method.
<29>
The compound represented by following formula (5).

(5)
(In the formula (5), R ^5A is an N-valent group having 1 to 60 carbon atoms or a single bond,
M ¹⁰ is each independently an integer of 1 to 3 ^{N B,} is an integer of 1 to 4. When the ^{N B} an integer of 2 or more, the structural formula of N in [] was identical Or different. )

According to the present invention, a compound and a resin having high solubility in a safe solvent, good heat resistance and etching resistance, a composition using the same, and a resist pattern forming method and a circuit pattern using the composition The forming method can be done.

Embodiments of the present invention will be described below. In addition, the following embodiment is an illustration for demonstrating this invention, and this invention is not limited only to the embodiment. The compound of this embodiment is a compound represented by the formula (0) described later, or a resin obtained using the compound as a monomer. The compound and resin of this embodiment can be applied to a wet process, and is useful for forming a photoresist and an underlayer film for photoresist excellent in heat resistance, solubility in a safe solvent, and etching resistance. It can be used for a composition useful for formation, a pattern formation method using the composition, and the like. In addition, the compound and resin of the present embodiment are excellent in sensitivity and resolution when used in a photosensitive material, and while maintaining high heat resistance, further, general-purpose organic solvents, other compounds, and resin components , And a resist permanent film having excellent compatibility with the additive.
The above-described composition uses a compound or resin having a specific structure that has high heat resistance and high solvent solubility, so that deterioration of the film during high-temperature baking is suppressed, and etching resistance against oxygen plasma etching and the like is also improved. An excellent resist and lower layer film can be formed. In addition, when the lower layer film is formed, the adhesion with the resist layer is also excellent, so that an excellent resist pattern can be formed.
Furthermore, since the above-described composition has a high refractive index and coloration is suppressed by a wide range of heat treatment from low temperature to high temperature, it is useful as various optical forming compositions.

<< Compound and resin >>
The compound of this embodiment is represented by the following formula (0).

(0)
(In Formula (0), R ^Y is a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms,
R ^Z is an N-valent group having 1 to 60 carbon atoms or a single bond,
R ^T each independently has an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, or a substituent. An optionally substituted alkenyl group having 2 to 30 carbon atoms, an optionally substituted alkoxy group having 1 to 30 carbon atoms, a halogen atom, a nitro group, an amino group, a carboxylic acid group, a thiol group, a hydroxyl group or a hydroxyl group Wherein the hydrogen atom is substituted with a vinyl-containing phenylmethyl group, and the alkyl group, the aryl group, the alkenyl group, and the alkoxy group may include an ether bond, a ketone bond, or an ester bond. And at least one of ^RT is a group in which a hydrogen atom of a hydroxyl group is substituted with a vinylphenylmethyl group,
X represents an oxygen atom, a sulfur atom or no bridge,
M is each independently an integer of 0 to 9, wherein at least one of m is an integer of 1 to 9,
N is an integer of 1 to 4, and when N is an integer of 2 or more, the structural formulas in N [] may be the same or different,
Each R is independently an integer of 0-2. )

R ^Y is a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms. As the alkyl group, a linear, branched or cyclic alkyl group can be used. Since ^RY is a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, heat resistance is relatively high and solvent solubility is improved. Let
In addition, when R ^Y is a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, the oxidative decomposition of the compound is further suppressed, coloring is suppressed, and heat resistance is improved. From the viewpoint of improving the solubility of the solvent and the solvent.

R ^z is an N-valent group having 1 to 60 carbon atoms or a single bond, and each aromatic ring is bonded through this R ^z . N is an integer of 1 to 4, and when N is an integer of 2 or more, the structural formulas in N [] may be the same or different. The N-valent group refers to an alkyl group having 1 to 60 carbon atoms when N = 1, an alkylene group having 1 to 30 carbon atoms when N = 2, and 2 to carbon atoms when N = 3. 60 alkanepropyl group, and when N = 4, it represents an alkanetetrayl group having 3 to 60 carbon atoms. Examples of the N-valent group include those having a linear hydrocarbon group, a branched hydrocarbon group, or an alicyclic hydrocarbon group. Here, the alicyclic hydrocarbon group includes a bridged alicyclic hydrocarbon group. The N-valent hydrocarbon group may have an alicyclic hydrocarbon group, a double bond, a hetero atom, or an aromatic group having 6 to 60 carbon atoms.

R ^T each independently has an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, or a substituent. An optionally substituted alkenyl group having 2 to 30 carbon atoms, an optionally substituted alkoxy group having 1 to 30 carbon atoms, a halogen atom, a nitro group, an amino group, a carboxylic acid group, a thiol group, a hydroxyl group or a hydroxyl group In which the alkyl group, the aryl group, the alkenyl group, and the alkoxy group may include an ether bond, a ketone bond, or an ester bond. At least one of ^RT is a group in which a hydrogen atom of a hydroxyl group is substituted with a vinyl-containing phenylmethyl group. The alkyl group, alkenyl group and alkoxy group may be a linear, branched or cyclic group.
Here, the “vinyl-phenylmethyl group” is a group having a vinylphenylmethyl group. For example, in addition to the vinylphenylmethyl group, a vinylphenylmethylmethyl group, a vinylphenylmethylphenyl group, etc., an oxygen atom, an alkylene group , A group in which a vinylphenylmethyl group is substituted on a phenylene group, an oxyalkylene group or the like.

X represents an oxygen atom, a sulfur atom or no bridge. When X is an oxygen atom or a sulfur atom, it tends to develop high heat resistance, and is preferably an oxygen atom. X is preferably non-crosslinked from the viewpoint of solubility. M is each independently an integer of 0 to 9, and at least one of m is an integer of 1 to 9.
In the formula (0), the site represented by the naphthalene structure is a monocyclic structure when r = 0, a bicyclic structure when r = 1, and a tricyclic structure when r = 2. It becomes. Each R is independently an integer of 0-2. The numerical range of m described above is determined according to the ring structure determined by r.

The compound represented by the formula (0) has a relatively low molecular weight, but has high heat resistance due to the rigidity of its structure, and therefore can be used under high temperature baking conditions. Moreover, it has tertiary carbon or quaternary carbon in the molecule, the crystallinity is suppressed, and it is suitably used as a film forming composition for lithography that can be used for manufacturing a film for lithography.

Further, the compound represented by the formula (0) has high solubility in a safe solvent, and has good heat resistance and etching resistance, and the resist forming composition for lithography according to this embodiment gives a good resist pattern shape. .

Furthermore, since the compound represented by the formula (0) has a relatively low molecular weight and a low viscosity, even if the substrate has a step (particularly, a fine space or a hole pattern), the step It is easy to improve the flatness of the film while uniformly filling every corner, and as a result, the underlayer film forming composition for lithography using the same can have relatively advantageous enhancement of embedding and planarization characteristics. . Moreover, since it is a compound having a relatively high carbon concentration, high etching resistance is also imparted.

The compound represented by the formula (0) has a high aromatic density and a high refractive index, and is also useful as a composition for forming various optical parts because coloration is suppressed by a wide range of heat treatment from low to high temperatures. It is. The compound represented by the formula (0) preferably has a quaternary carbon from the viewpoint of suppressing oxidative decomposition of the compound, suppressing coloring, high heat resistance, and improving solvent solubility. Optical parts are used in the form of films and sheets, as well as plastic lenses (prism lenses, lenticular lenses, micro lenses, Fresnel lenses, viewing angle control lenses, contrast enhancement lenses, etc.), retardation films, electromagnetic wave shielding films, prisms It is useful as an optical fiber, a solder resist for flexible printed wiring, a plating resist, an interlayer insulating film for multilayer printed wiring boards, and a photosensitive optical waveguide.

[Compound represented by Formula (1)]
It is preferable that the compound of this embodiment is represented by following formula (1). Since the compound represented by Formula (1) is comprised as follows, its heat resistance is high and its solvent solubility is also high.

(1)
(In Formula (1), R ⁰ has the same meaning as R ^Y ,
R ¹ is an n-valent group having 1 to 60 carbon atoms or a single bond,
R ² to R ⁵ are each independently an optionally substituted alkyl group having 1 to 30 carbon atoms, an optionally substituted aryl group having 6 to 30 carbon atoms, or a substituent. An alkenyl group having 2 to 30 carbon atoms which may have a substituent, an alkoxy group having 1 to 30 carbon atoms which may have a substituent, a halogen atom, a nitro group, an amino group, a carboxylic acid group, a thiol group, A hydroxyl group or a group in which a hydrogen atom of a hydroxyl group is substituted with a vinylphenylmethyl group, and the alkyl group, the aryl group, the alkenyl group, and the alkoxy group may include an ether bond, a ketone bond, or an ester bond. Here, at least one of R ² to R ⁵ is a group in which a hydrogen atom of a hydroxyl group is substituted with a vinylphenylmethyl group, and m ² and m ³ are each independently an integer of 0 to 8 And
M ⁴ and m ⁵ are each independently an integer of 0 to 9,
However, m ² , m ³ , m ⁴ and m ⁵ are not 0 simultaneously,
N is synonymous with N, and when n is an integer of 2 or more, the structural formulas in n [] may be the same or different,
P ² to p ⁵ are as defined above for r. )

R ⁰ has the same meaning as R ^Y described above.
R ¹ is an n-valent group having 1 to 60 carbon atoms or a single bond, and each aromatic ring is bonded through R ¹ . N is synonymous with N, and when n is an integer of 2 or more, the structural formulas in n [] may be the same or different. The n-valent group is an alkyl group having 1 to 60 carbon atoms when n = 1, an alkylene group having 1 to 60 carbon atoms when n = 2, and 2 to carbon atoms when n = 3. 60 alkanepropyl group, and when n = 4, an alkanetetrayl group having 3 to 60 carbon atoms. Examples of the n-valent group include those having a linear hydrocarbon group, a branched hydrocarbon group, or an alicyclic hydrocarbon group. Here, the alicyclic hydrocarbon group includes a bridged alicyclic hydrocarbon group. The n-valent hydrocarbon group may have an alicyclic hydrocarbon group, a double bond, a hetero atom, or an aromatic group having 6 to 60 carbon atoms.

R ² to R ⁵ are each independently an optionally substituted alkyl group having 1 to 30 carbon atoms, an optionally substituted aryl group having 6 to 30 carbon atoms, or a substituent. An alkenyl group having 2 to 30 carbon atoms which may have a substituent, an alkoxy group having 1 to 30 carbon atoms which may have a substituent, a halogen atom, a nitro group, an amino group, a carboxylic acid group, a thiol group, A hydroxyl group or a group in which a hydrogen atom of a hydroxyl group is substituted with a vinylphenylmethyl group, and the alkyl group, the aryl group, the alkenyl group, or the alkoxy group is an ether bond, a ketone bond, or an ester bond May be included. At least one of R ² to R ⁵ is a group in which a hydrogen atom of a hydroxyl group is substituted with a vinyl-containing phenylmethyl group. The alkyl group, alkenyl group and alkoxy group may be a linear, branched or cyclic group.

M ² and m ³ are each independently an integer of 0 to 8, and m ⁴ and m ⁵ are each independently an integer of 0 to 9. However, m ² , m ³ , m ⁴ and m ⁵ are not 0 at the same time. P ² to p ⁵ are each independently synonymous with r.

The compound represented by the formula (1) has a relatively low molecular weight, but has high heat resistance due to the rigidity of its structure, and therefore can be used under high temperature baking conditions. Moreover, it has tertiary carbon or quaternary carbon in the molecule, the crystallinity is suppressed, and it is suitably used as a film forming composition for lithography that can be used for manufacturing a film for lithography.

Also, the solubility in a safe solvent is high, the heat resistance and the etching resistance are good, and the resist forming composition for lithography according to this embodiment gives a good resist pattern shape.

Furthermore, since the film has a relatively low molecular weight and low viscosity, even a substrate having a step (particularly, a fine space or a hole pattern) can be uniformly filled to every corner of the step and the film can be flattened. As a result, the composition for forming an underlayer film for lithography using the same can be relatively advantageously enhanced in embedding and planarization characteristics. Moreover, since it is a compound having a relatively high carbon concentration, high etching resistance is also imparted.

The compound represented by the formula (1) has a high refractive index due to its high aromatic density, and is also useful as a composition for forming various optical parts because it suppresses coloring by a wide range of heat treatments from a low temperature to a high temperature. . The one having quaternary carbon is preferable from the viewpoint of suppressing oxidative decomposition of the present compound to suppress coloring, high heat resistance, and improving solvent solubility. Optical parts are used in the form of films and sheets, as well as plastic lenses (prism lenses, lenticular lenses, micro lenses, Fresnel lenses, viewing angle control lenses, contrast enhancement lenses, etc.), retardation films, electromagnetic wave shielding films, prisms It is useful as an optical fiber, a solder resist for flexible printed wiring, a plating resist, an interlayer insulating film for multilayer printed wiring boards, and a photosensitive optical waveguide.

The compound represented by the formula (1) is preferably a compound represented by the following formula (1-1) from the viewpoint of easy crosslinking and solubility in an organic solvent.

(1-1)

In formula (1-1), R ⁰ , R ¹ , R ⁴ , R ⁵ , n, p ² to p ⁵ , m ⁴ and m ⁵ are as defined above, and R ⁶ to R ⁷ are each independently A linear, branched or cyclic alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, and a substituent. an alkenyl group having 2 to 30 carbon atoms which may have a halogen atom, a nitro group, an amino group, a carboxylic acid group, a thiol group, R ^{10 ~} R ¹¹ are each independently a hydrogen atom or a free Vinyl phenylmethyl group.
Here, at least one of R ¹⁰ to R ^{11 is} a vinyl-containing phenylmethyl group, and m ⁶ and m ⁷ are each independently an integer of 0 to 7. However, m ⁴ , m ⁵ , m ⁶ and m ⁷ are not 0 at the same time.

Further, the compound represented by the formula (1-1) is preferably a compound represented by the following formula (1-2) from the viewpoint of further crosslinkability and solubility in an organic solvent.

(1-2)

In formula (1-2), R ⁰ , R ¹ , R ⁶ , R ⁷ , R ¹⁰ , R ¹¹ , n, p ² to p ⁵ , m ⁶ and m ⁷ are as defined above, and R ⁸ to R ⁹ has the same meaning as R ⁶ to R ⁷ , and R ¹² to R ¹³ have the same meaning as R ¹⁰ to R ¹¹ . M ⁸ and m ⁹ are each independently an integer of 0 to 8. However, m ⁶ , m ⁷ , m ⁸ and m ⁹ are not 0 at the same time.

Further, from the viewpoint of raw material supply, the compound represented by the formula (1-2) is preferably a compound represented by the following formula (1a).

(1a)

In the formula (1a), R ⁰ to R ⁵ , m ² to m ⁵ and n have the same meaning as described in the formula (1).

The compound represented by the formula (1a) is more preferably a compound represented by the following formula (1b) from the viewpoint of solubility in an organic solvent.

(1b)

In the formula (1b), R ⁰ , R ¹ , R ⁴ , R ⁵ , R ¹⁰ , R ¹¹ , m ⁴ , m ⁵ , and n are as defined in the formula (1), and R ⁶ , R ⁷ , R ¹⁰ , R ¹¹ , m ⁶ and m ⁷ have the same meanings as described in the formula (1-1).

The compound represented by the formula (1a) is more preferably a compound represented by the following formula (1b ′) from the viewpoint of reactivity.

(1b ')

In the formula (1b), R ⁰ , R ¹ , R ⁴ , R ⁵ , R ¹⁰ , R ¹¹ , m ⁴ , m ⁵ , and n are as defined in the formula (1), and R ⁶ , R ⁷ , R ¹⁰ , R ¹¹ m ⁶ and m ⁷ have the same meanings as described in the formula (1-1).

The compound represented by the formula (1b) is more preferably a compound represented by the following formula (1c) from the viewpoint of solubility in an organic solvent.

(1c)

In the formula (1c), R ⁰ , R ¹ , R ⁶ to R ¹³ , m ⁶ to m ⁹ , and n are as defined in the formula (1-2).

The compound represented by the formula (1b ′) is more preferably a compound represented by the following formula (1c ′) from the viewpoint of reactivity.

(1c ')

In the formula (1c ′), R ⁰ , R ¹ , R ⁶ to R ¹³ , m ⁶ to m ⁹ , and n are as defined in the formula (1-2).

Specific examples of the compound represented by the formula (0) are illustrated below, but the compound represented by the formula (0) is not limited to the specific examples listed here.

In the formula, X is the formula (0) have the same meanings as those described in, R T ^'has the same meaning as R ^T described by the formula (0), m each independently 1-6 Is an integer.

In the formula, X is the same meaning as those described for the formula (0), R T ^'has the same meaning as R ^T described by the above formula (0), m each independently 1-6 Is an integer.

Specific examples of the compound represented by the formula (0) are further exemplified below, but are not limited to those listed here.

In the formula, X is the same meaning as those described for the formula ^{(0), R Y ',} R Z' are as defined ^R Y, ^{R Z} described by the formula (0). Further, at least one of OR ^4A is a group in which a hydrogen atom of a hydroxyl group is substituted with a vinyl-containing phenylmethyl group.

In the formula, X is the formula (0) have the same meanings as those described in, R Z ^'are as defined R ^Z described by the formula (0). Further, at least one of OR ^4A is a group in which a hydrogen atom of a hydroxyl group is substituted with a vinyl-containing phenylmethyl group.

In said formula, X is synonymous with what was demonstrated by the said Formula (0). Also, R ^{Z 'are} as defined ^{R Z} described by the formula (0). Further, at least one of OR ^4A is a group in which a hydrogen atom of a hydroxyl group is substituted with a vinyl-containing phenylmethyl group.

In the formula, X is the formula (0) have the same meanings as those explained in, also, R Z ^'are as defined R ^Z described by the formula (0). Further, at least one of OR ^4A is a group in which a hydrogen atom of a hydroxyl group is substituted with a vinyl-containing phenylmethyl group.

Specific examples of the compound represented by the formula (1) are illustrated below, but are not limited to those listed here.

In the compound, R ² , R ³ , R ⁴ , and R ⁵ have the same meaning as described in the formula (1). m ² and m ³ are integers from 0 to 6, and m ⁴ and m ⁵ are integers from 0 to 7.
However, at least one selected from R ² , R ³ , R ⁴ , and R ⁵ is a group in which the hydrogen atom of the hydroxyl group is substituted with a vinyl-containing phenylmethyl group. m ² , m ³ , m ⁴ , and m ⁵ are not 0 at the same time.

In the compound, R ² , R ³ , R ⁴ , and R ⁵ have the same meaning as described in the formula (1). M ² and m ³ are integers from 0 to 6, and m ⁴ and m ⁵ are integers from 0 to 7.
However, at least one selected from R ² , R ³ , R ⁴ , and R ⁵ is a group in which a hydrogen atom of a hydroxyl group is substituted with a vinyl-containing phenylmethyl group, and m ² , m ³ , m ⁴ , and m ⁵ are It is never 0 at the same time.

In the compounds, R ¹⁰ , R ¹¹ , R ¹² , and R ¹³ have the same meanings as described in the formula (1-2), wherein at least one of R ¹⁰ to R ¹³ is a hydroxyl group hydrogen atom. It is a group substituted with a vinyl-containing phenylmethyl group.

The compound represented by the formula (1) is particularly preferably a compound represented by the following formulas (bif-1) to (bif-10) from the viewpoint of further solubility in an organic solvent (specific examples) R ¹⁰ to R ¹³ therein are as defined above).

(Bif-1)

(Bif-2)

(Bif-3)

(Bif-4)

(Bif-5)

(Bif-6)

(Bif-7)

(Bif-8)

(Bif-9)

(Bif-10)

Hereinafter, specific examples of the compound represented by the formula (0) will be further illustrated, but the compound represented by the formula (0) is not limited to the specific examples listed here.

In the above formula, R ⁰ , R ¹ and n are as defined in the formula (1-1), and R ^{10 ′} and R ^{11 ′} are R ¹⁰ and R described in the formula (1-1). ¹¹ and R ^{4 ′} and R ^{5 ′} each independently represents an alkyl group having 1 to 30 carbon atoms which may have a substituent, and 6 to 6 carbon atoms which may have a substituent. 30 aryl groups, an optionally substituted alkenyl group having 2 to 30 carbon atoms, an optionally substituted alkoxy group having 1 to 30 carbon atoms, a halogen atom, a nitro group, an amino group, A carboxylic acid group, a thiol group, a hydroxyl group or a group in which a hydrogen atom of the hydroxyl group is substituted with a vinyl-containing phenylmethyl group, and the alkyl group, the aryl group, the alkenyl group, and the alkoxy group include an ether bond, a ketone bond, or It may contain an ester bond and R ^{10 ′} And at least one of R ^{11 ′} is a group in which a hydrogen atom of a hydroxyl group is substituted with a vinyl-containing phenylmethyl group, m ^{4 ′} and m ^{5 ′} are integers of 0 to 8, and m ^{10 ′} and m ^{11 '} Is an integer of 1 to 9, and m ^4' + m ^{10 '} and m ^4' + m ^{11 '} are each independently an integer of 1 to 9.
R ⁰ is, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, triacontyl group, phenyl group, naphthyl group , Anthracene group, pyrenyl group, biphenyl group and heptacene group.
R ^{4 ′} and R ^{5 ′} are, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, triacontyl group, Cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, cycloundecyl group, cyclododecyl group, cyclotriacontyl group, norbornyl group, adamantyl group, phenyl group , Naphthyl group, anthracene group, pyrenyl group, biphenyl group, heptacene group, vinyl group, allyl group, triacontenyl group, methoxy group, ethoxy group, triacontoxy group, fluorine atom, chlorine atom, bromine atom, iodine atom, A thiol group is mentioned.
Each example of R ⁰ , R ^{4 ′} and R ^{5 ′} includes an isomer. For example, the butyl group includes an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group.

In the above formula, R ¹⁰ to R ¹³ have the same meanings as described in the formula (1-2), R ¹⁶ represents a linear, branched or cyclic alkylene group having 1 to 30 carbon atoms, carbon number A bivalent aryl group having 6 to 30 carbon atoms or a divalent alkenyl group having 2 to 30 carbon atoms.
R ¹⁶ is, for example, a methylene group, ethylene group, propene group, butene group, pentene group, hexene group, heptene group, octene group, nonene group, decene group, undecene group, dodecene group, triacontene group, cyclopropene group, Cyclobutene group, cyclopentene group, cyclohexene group, cycloheptene group, cyclooctene group, cyclononene group, cyclodecene group, cycloundecene group, cyclododecene group, cyclotriacontene group, divalent norbornyl group, divalent adamantyl group, divalent Phenyl group, divalent naphthyl group, divalent anthracene group, divalent pyrene group, divalent biphenyl group, divalent heptacene group, divalent vinyl group, divalent allyl group, divalent triaconte Nyl group is mentioned.
Each example of R ¹⁶ includes isomers. For example, the butyl group includes an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group.

In the above formula, R ¹⁰ to R ¹³ have the same meanings as described in the above formula (1-2), and R ¹⁴ each independently represents a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms. A group, an aryl group having 6 to 30 carbon atoms, or an alkenyl group having 2 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a halogen atom, and a thiol group, and m ¹⁴ is an integer of 0 to 5. M ^{14 ′} is an integer from 0 to 4, and m ¹⁴ is an integer from 0 to 5.
R ¹⁴ is, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, triacontyl group, cyclopropyl group, cyclobutyl. Group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, cycloundecyl group, cyclododecyl group, cyclotriacontyl group, norbornyl group, adamantyl group, phenyl group, naphthyl group, anthracene Group, pyrenyl group, biphenyl group, heptacene group, vinyl group, allyl group, triacontenyl group, methoxy group, ethoxy group, triacontoxy group, fluorine atom, chlorine atom, bromine atom, iodine atom, thiol group .
Each example of R ¹⁴ includes an isomer. For example, the butyl group includes an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group.

In the above formula, R ⁰ , R ^{4 ′} , R ^{5 ′} , m ^{4 ′} , m ^{5 ′} , m ^{10 ′} and m ^{11 ′} are as defined above, and R ^{1 ′} is a group having 1 to 60 carbon atoms. is there.

In the above formula, R ¹⁰ to R ¹³ have the same meanings as described in the above formula (1-2), and R ¹⁴ each independently represents a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms. A group, an aryl group having 6 to 30 carbon atoms, or an alkenyl group having 2 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a halogen atom, and a thiol group, m ¹⁴ is an integer of 0 to 5; ^{14 ′} is an integer from 0 to 4, and m ^{14 ″} is an integer from 0 to 3.
R ¹⁴ is, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, triacontyl group, cyclopropyl group, cyclobutyl. Group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, cycloundecyl group, cyclododecyl group, cyclotriacontyl group, norbornyl group, adamantyl group, phenyl group, naphthyl group, anthracene Group, pyrenyl group, biphenyl group, heptacene group, vinyl group, allyl group, triacontenyl group, methoxy group, ethoxy group, triacontoxy group, fluorine atom, chlorine atom, bromine atom, iodine atom, thiol group .
Each example of R ¹⁴ includes an isomer. For example, the butyl group includes an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group.

In the above formula, R ¹⁰ to R ¹³ have the same meanings as described in the formula (1-2), R ¹⁵ represents a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, An aryl group having 6 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a halogen atom, and a thiol group.
R ¹⁵ is, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, triacontyl group, cyclopropyl group, cyclobutyl. Group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, cycloundecyl group, cyclododecyl group, cyclotriacontyl group, norbornyl group, adamantyl group, phenyl group, naphthyl group, anthracene Group, pyrenyl group, biphenyl group, heptacene group, vinyl group, allyl group, triacontenyl group, methoxy group, ethoxy group, triacontoxy group, fluorine atom, chlorine atom, bromine atom, iodine atom, thiol group .
Each example of R ¹⁵ includes an isomer. For example, the butyl group includes an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group.

In the above formula, R ¹⁰ to R ¹³ have the same meanings as described in the formula (1-2).

The compound represented by the formula (0) is more preferably a compound represented by the following from the viewpoint of availability of raw materials.

In the above formula, R ¹⁰ to R ¹³ have the same meanings as described in the formula (1-2).
Furthermore, the compound represented by the formula (0) preferably has the following structure from the viewpoint of etching resistance.

In the formula, R ^0A has the same meaning as the formula R ^Y , R ^{1A ′} has the same meaning as R ^Z , and R ¹⁰ to R ¹³ have the same meaning as described in the formula (1-2).

In the formula, R ^0A has the same meaning as the formula R ^Y , R ^{1A ′} has the same meaning as R ^Z , and R ¹⁰ to R ¹³ have the same meaning as described in the formula (1-2). R ¹⁴ each independently represents a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an alkenyl group having 2 to 30 carbon atoms, or 1 to 30 carbon atoms. An alkoxy group, a halogen atom, and a thiol group, and m ^{14 ′} is an integer of 0 to 4.
R ¹⁴ is, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, triacontyl group, cyclopropyl group, cyclobutyl. Group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, cycloundecyl group, cyclododecyl group, cyclotriacontyl group, norbornyl group, adamantyl group, phenyl group, naphthyl group, anthracene Group, heptacene group, vinyl group, allyl group, triacontenyl group, methoxy group, ethoxy group, triacontoxy group, fluorine atom, chlorine atom, bromine atom, iodine atom, thiol group.
Each example of R ¹⁴ includes an isomer. For example, the butyl group includes an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group.

In the above formula, R ¹⁰ to R ¹³ have the same meanings as described in the formula (1-2), R ¹⁵ represents a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, An aryl group having 6 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a halogen atom, and a thiol group.
R ¹⁵ is, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, triacontyl group, cyclopropyl group, cyclobutyl. Group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, cycloundecyl group, cyclododecyl group, cyclotriacontyl group, norbornyl group, adamantyl group, phenyl group, naphthyl group, anthracene Group, heptacene group, vinyl group, allyl group, triacontenyl group, methoxy group, ethoxy group, triacontoxy group, fluorine atom, chlorine atom, bromine atom, iodine atom, thiol group.
Each example of R ¹⁵ includes an isomer. For example, the butyl group includes an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group.

In the above formula, R ¹⁰ to R ¹³ have the same meanings as described in the formula (1-2), R ¹⁶ represents a linear, branched or cyclic alkylene group having 1 to 30 carbon atoms, carbon number A bivalent aryl group having 6 to 30 carbon atoms or a divalent alkenyl group having 2 to 30 carbon atoms.
R ¹⁶ is, for example, a methylene group, ethylene group, propene group, butene group, pentene group, hexene group, heptene group, octene group, nonene group, decene group, undecene group, dodecene group, triacontene group, cyclopropene group, Cyclobutene group, cyclopentene group, cyclohexene group, cycloheptene group, cyclooctene group, cyclononene group, cyclodecene group, cycloundecene group, cyclododecene group, cyclotriacontene group, divalent norbornyl group, divalent adamantyl group, divalent Examples thereof include a phenyl group, a divalent naphthyl group, a divalent anthracene group, a divalent heptacene group, a divalent vinyl group, a divalent allyl group, and a divalent triacontenyl group.
Each example of R ¹⁶ includes isomers. For example, the butyl group includes an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group.

In the ^formula, R 10 ^{~ R 13} have the same meanings as those described by the formula ^{(1-2), R 14} are each independently C 1 -C 30 linear, alkyl branched or cyclic Group, an aryl group having 6 to 30 carbon atoms, or an alkenyl group having 2 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a halogen atom, and a thiol group, and m ^{14 ′} is an integer of 0 to 4.
R ¹⁴ is, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, triacontyl group, cyclopropyl group, cyclobutyl. Group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, cycloundecyl group, cyclododecyl group, cyclotriacontyl group, norbornyl group, adamantyl group, phenyl group, naphthyl group, anthracene Group, heptacene group, vinyl group, allyl group, triacontenyl group, methoxy group, ethoxy group, triacontoxy group, fluorine atom, chlorine atom, bromine atom, iodine atom, thiol group.
Each example of R ¹⁴ includes an isomer. For example, the butyl group includes an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group.

In the above formula, R ¹⁰ to R ¹³ have the same meanings as described in the above formula (1-2), and R ¹⁴ each independently represents a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms. A group, an aryl group having 6 to 30 carbon atoms, or an alkenyl group having 2 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a halogen atom, and a thiol group, and m ¹⁴ is an integer of 0 to 5.
R ¹⁴ is, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, triacontyl group, cyclopropyl group, cyclobutyl. Group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, cycloundecyl group, cyclododecyl group, cyclotriacontyl group, norbornyl group, adamantyl group, phenyl group, naphthyl group, anthracene Group, heptacene group, vinyl group, allyl group, triacontenyl group, methoxy group, ethoxy group, triacontoxy group, fluorine atom, chlorine atom, bromine atom, iodine atom, thiol group.
Each example of R ¹⁴ includes an isomer. For example, the butyl group includes an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group.

In the above formula, R ¹⁰ to R ¹³ have the same meanings as described in the formula (1-2).
The compound preferably has a dibenzoxanthene skeleton from the viewpoint of heat resistance.

In the above formula, R ¹⁰ to R ¹³ have the same meanings as described in the formula (1-2). The above formula is preferably a compound having a dibenzoxanthene skeleton from the viewpoint of heat resistance.

The compound described in the formula (0) preferably has the following structure from the viewpoint of raw material availability.

In the formula, R ^0A has the same meaning as the formula R ^Y , R ^{1A ′} has the same meaning as R ^Z , and R ¹⁰ to R ¹³ have the same meaning as described in the formula (1-2). The above formula is preferably a compound having a xanthene skeleton from the viewpoint of heat resistance.

In the above formulas, R ¹⁰ to R ¹³ have the same meanings as described in formula (1-2), and R ¹⁴ , R ¹⁵ , R ¹⁶ , m ¹⁴ and m ^{14 ′} have the same meanings as described above.

(Compound represented by Formula (5))
As a raw material of the compound represented by the formula (0), for example, a polyphenol raw material can be used, and for example, a compound represented by the following formula (5) can be used.

Catechol, resorcinol and pyrogallol are used as the polyphenol raw material of the compound of the above formula (5), and examples thereof include the following structures.

In the formula, R ^{1A ′} has the same meaning as R ^Z , and R ¹⁴ , R ¹⁵ , R ¹⁶ , m ¹⁴ , and m ^{14 ′} have the same meaning as described above.

[Production Method of Compound Represented by Formula (0)]
The compound represented by the formula (0) used in the present embodiment can be appropriately synthesized by applying a known technique, and the synthesis technique is not particularly limited. For example, taking the compound represented by formula (1) as an example, the compound represented by formula (0) can be synthesized as follows.
For example, the compound represented by the formula (1) can be obtained by subjecting a biphenol, binaphthol or bianthracenol and a corresponding aldehyde or ketone to a polycondensation reaction in the presence of an acid catalyst under normal pressure. A compound represented by the formula (1) can be obtained. Further, a vinyl-containing phenylmethyl group can be introduced into at least one phenolic hydroxyl group of the compound by a known method. Moreover, it can also carry out under pressure as needed.

Examples of the biphenols include, but are not limited to, biphenol, methyl biphenol, methoxy binaphthol, and the like. These can be used individually by 1 type or in combination of 2 or more types. Among these, it is more preferable to use biphenol from the viewpoint of stable supply of raw materials.

Examples of the binaphthols include, but are not limited to, binaphthol, methyl binaphthol, methoxy binaphthol, and the like. These can be used alone or in combination of two or more. Among these, it is more preferable to use binaphthol in terms of increasing the carbon atom concentration and improving heat resistance.

Examples of the bianthraceneols include, but are not particularly limited to, bianthraceneol, methylbianthracenol, methoxybianthracenol, and the like. These can be used alone or in combination of two or more. Among these, it is more preferable to use bianthraceneol in terms of increasing the carbon atom concentration and improving heat resistance.

Examples of the aldehydes include formaldehyde, trioxane, paraformaldehyde, benzaldehyde, acetaldehyde, propylaldehyde, phenylacetaldehyde, phenylpropylaldehyde, hydroxybenzaldehyde, chlorobenzaldehyde, nitrobenzaldehyde, methylbenzaldehyde, ethylbenzaldehyde, butylbenzaldehyde, biphenylaldehyde, Examples include naphthaldehyde, anthracene carbaldehyde, phenanthrene carbaldehyde, pyrene carbaldehyde, furfural, and the like, but are not limited thereto. These can be used alone or in combination of two or more. Among these, benzaldehyde, phenylacetaldehyde, phenylpropylaldehyde, hydroxybenzaldehyde, chlorobenzaldehyde, nitrobenzaldehyde, methylbenzaldehyde, ethylbenzaldehyde, butylbenzaldehyde, cyclohexylbenzaldehyde, biphenylaldehyde, naphthaldehyde, anthracenecarbaldehyde, phenanthrenecarbaldehyde, pyrene The use of carbaldehyde and furfural is preferable in terms of giving high heat resistance, and benzaldehyde, hydroxybenzaldehyde, chlorobenzaldehyde, nitrobenzaldehyde, methylbenzaldehyde, ethylbenzaldehyde, butylbenzaldehyde, cyclohexylbenzaldehyde, biphenylamide. Dehydrogenase, naphthaldehyde, anthracene carbaldehyde, phenanthrene carbaldehyde, pyrene carbaldehyde be used furfural, high etching resistance, and more preferably.

Examples of the ketones include acetone, methyl ethyl ketone, cyclobutanone, cyclopentanone, cyclohexanone, norbornanone, tricyclohexanone, tricyclodecanone, adamantanone, fluorenone, benzofluorenone, acenaphthenequinone, acenaphthenone, anthraquinone, acetophenone, diacetylbenzene. , Triacetylbenzene, acetonaphthone, diphenylcarbonylnaphthalene, phenylcarbonylbiphenyl, diphenylcarbonylbiphenyl, benzophenone, diphenylcarbonylbenzene, triphenylcarbonylbenzene, benzonaphthone, diphenylcarbonylnaphthalene, phenylcarbonylbiphenyl, diphenylcarbonylbiphenyl, etc. Is particularly limited to There. These can be used alone or in combination of two or more. Among these, cyclopentanone, cyclohexanone, norbornanone, tricyclohexanone, tricyclodecanone, adamantanone, fluorenone, benzofluorenone, acenaphthenequinone, acenaphthenone, anthraquinone, acetophenone, diacetylbenzene, triacetylbenzene, acetonaphthone, diphenylcarbonyl Naphthalene, phenylcarbonylbiphenyl, diphenylcarbonylbiphenyl, benzophenone, diphenylcarbonylbenzene, triphenylcarbonylbenzene, benzonaphthone, diphenylcarbonylnaphthalene, phenylcarbonylbiphenyl, diphenylcarbonylbiphenyl are preferably used in terms of giving high heat resistance, acetophenone, Diacetylbenzene, triacetylbenzene Zen, acetonaphthone, diphenylcarbonylnaphthalene, phenylcarbonylbiphenyl, diphenylcarbonylbiphenyl, benzophenone, diphenylcarbonylbenzene, triphenylcarbonylbenzene, benzonaphthone, diphenylcarbonylnaphthalene, phenylcarbonylbiphenyl, diphenylcarbonylbiphenyl have high etching resistance, More preferred.

As the aldehyde group or ketone, it is preferable to use an aldehyde having an aromatic group or an aromatic ketone having both high heat resistance and high etching resistance.

The acid catalyst used in the reaction can be appropriately selected from known ones and is not particularly limited. As such an acid catalyst, inorganic acids and organic acids are widely known. For example, inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, hydrofluoric acid, oxalic acid, malonic acid, and succinic acid. , Adipic acid, sebacic acid, citric acid, fumaric acid, maleic acid, formic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid Organic acids such as naphthalenedisulfonic acid, Lewis acids such as zinc chloride, aluminum chloride, iron chloride, boron trifluoride, or solid acids such as silicotungstic acid, phosphotungstic acid, silicomolybdic acid or phosphomolybdic acid Although it is mentioned, it is not specifically limited to these. Among these, an organic acid and a solid acid are preferable from the viewpoint of production, and hydrochloric acid or sulfuric acid is preferably used from the viewpoint of production such as availability and ease of handling. In addition, about an acid catalyst, 1 type can be used individually or in combination of 2 or more types. The amount of the acid catalyst used can be appropriately set according to the raw material to be used, the type of catalyst to be used, and further the reaction conditions, and is not particularly limited. It is preferable that it is a mass part.

In the reaction, a reaction solvent may be used. The reaction solvent is not particularly limited as long as the reaction between the aldehyde group or ketone to be used and the biphenols, binaphthols, or bianthracenediol proceeds, and may be appropriately selected from known ones. it can. Examples thereof include water, methanol, ethanol, propanol, butanol, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, or a mixed solvent thereof. In addition, a solvent can be used individually by 1 type or in combination of 2 or more types.

The amount of these solvents used can be appropriately set according to the raw material used, the type of catalyst used, and the reaction conditions, and is not particularly limited, but is 0 to 2000 parts by mass with respect to 100 parts by mass of the reaction raw material. It is preferable that it is the range of these. Furthermore, the reaction temperature in the reaction can be appropriately selected according to the reactivity of the reaction raw material, and is not particularly limited, but is usually in the range of 10 to 200 ° C.

In order to obtain the compound represented by the formula (1) of the present embodiment, the reaction temperature is preferably higher, and specifically in the range of 60 to 200 ° C. The reaction method can be appropriately selected from known methods, and is not particularly limited. However, biphenols, binaphthols or bianthracenediol, aldehyde groups or ketones, a method of charging a catalyst in a lump, or biphenols Further, there is a method in which binaphthols, bianthracenediol, aldehydes or ketones are dropped in the presence of a catalyst. After completion of the polycondensation reaction, the obtained compound can be isolated according to a conventional method, and is not particularly limited. For example, in order to remove unreacted raw materials, catalysts, etc. existing in the system, the temperature of the reaction kettle is increased to 130 to 230 ° C., and a general method such as removing volatile matter at about 1 to 50 mmhg is adopted. Thus, the target compound can be obtained.

As preferable reaction conditions, 1.0 mol to excess amount of biphenols, binaphthols or bianthracenediol and 0.001 to 1 mol of an acid catalyst are used at normal pressure with respect to 1 mol of an aldehyde group or ketone. The reaction proceeds at 50 to 150 ° C. for about 20 minutes to 100 hours.

After completion of the reaction, the target product can be isolated by a known method. For example, the reaction solution is concentrated, pure water is added to precipitate the reaction product, cooled to room temperature, filtered and separated, and the resulting solid is filtered and dried, followed by column chromatography. The compound represented by the above formula (1), which is the target product, can be obtained by separating and purifying from the by-product, and performing solvent distillation, filtration and drying.

A method for introducing a vinylphenylmethyl group into at least one phenolic hydroxyl group of a polyphenol compound is known. For example, a vinyl-containing phenylmethyl group can be introduced into at least one phenolic hydroxyl group of a polyphenol compound as follows. A compound for introducing a vinyl-containing phenylmethyl group can be synthesized or easily obtained by a known method, and examples thereof include vinyl benzyl chloride, vinyl benzyl bromide, and vinyl benzyl iodoide, but are not particularly limited.

For example, a polyphenol compound and a compound for introducing the above-mentioned vinylphenylmethyl group are dissolved or suspended in an aprotic solvent such as acetone, tetrahydrofuran (THF), propylene glycol monomethyl ether acetate or the like. Subsequently, the reaction is carried out at 20 to 150 ° C. for 6 to 72 hours at normal pressure in the presence of a base catalyst such as sodium hydroxide, potassium hydroxide, sodium methoxide, sodium ethoxide and the like. The reaction solution is neutralized with an acid and added to distilled water to precipitate a white solid, and then the separated solid is washed with distilled water, or the solvent is evaporated to dryness and washed with distilled water as necessary. By drying, a compound in which the hydrogen atom of the hydroxyl group is substituted with the vinyl-containing phenylmethyl group can be obtained.

In addition, about the timing which introduce | transduces a vinyl-containing phenylmethyl group, not only after the condensation reaction of binaphthol and aldehydes or ketones, but the stage before a condensation reaction may be sufficient. Moreover, you may carry out after manufacturing resin mentioned later.

A method of introducing a hydroxyalkyl group into at least one phenolic hydroxyl group of a polyphenol compound and introducing a vinylphenylmethyl group into the hydroxy group is also known. The hydroxyalkyl group may be introduced into the phenolic hydroxyl group via an oxyalkyl group. For example, a hydroxyalkyloxyalkyl group or a hydroxyalkyloxyalkyloxyalkyl group is introduced.
For example, as described below, a hydroxyalkyl group can be introduced into at least one phenolic hydroxyl group of the compound, and a vinylphenylmethyl group can be introduced into the hydroxy group.
A compound for introducing a hydroxyalkyl group can be synthesized or easily obtained by a known method. For example, chloroethanol, bromoethanol, 2-chloroethyl acetate, 2-bromoethyl acetate, 2-iodoethyl acetate, ethylene oxide , Propylene oxide, butylene oxide, ethylene carbonate, propylene carbonate, and butylene carbonate, but are not particularly limited.

For example, a polyphenol compound and a compound for introducing a hydroxyalkyl group are dissolved or suspended in an aprotic solvent such as acetone, tetrahydrofuran (THF), propylene glycol monomethyl ether acetate or the like. Subsequently, the reaction is carried out at 20 to 150 ° C. for 6 to 72 hours at normal pressure in the presence of a base catalyst such as sodium hydroxide, potassium hydroxide, sodium methoxide, sodium ethoxide and the like. The reaction solution is neutralized with an acid and added to distilled water to precipitate a white solid, and then the separated solid is washed with distilled water, or the solvent is evaporated to dryness and washed with distilled water as necessary. By drying, a compound in which a hydrogen atom of a hydroxyl group is substituted with a hydroxyalkyl group can be obtained.

For example, in the case of using 2-chloroethyl acetate, 2-bromoethyl acetate, or 2-iodoethyl acetate, a hydroxyethyl group is introduced by causing a deacylation reaction after the acetoxyethyl group is introduced.
Further, for example, when ethylene carbonate, propylene carbonate, or butylene carbonate is used, a hydroxyalkyl group is introduced by adding an alkylene carbonate to cause a decarboxylation reaction.
Thereafter, the compound and a compound for introducing a vinyl-containing phenylmethyl group are dissolved or suspended in an aprotic solvent such as acetone, tetrahydrofuran (THF), propylene glycol monomethyl ether acetate or the like. Subsequently, the reaction is carried out at 20 to 150 ° C. for 6 to 72 hours at normal pressure in the presence of a base catalyst such as sodium hydroxide, potassium hydroxide, sodium methoxide, sodium ethoxide and the like. The reaction solution is neutralized with an acid and added to distilled water to precipitate a white solid, and then the separated solid is washed with distilled water, or the solvent is evaporated to dryness and washed with distilled water as necessary. By drying, a compound in which a hydrogen atom of a hydroxy group is substituted with a vinyl-containing phenylmethyl group can be obtained.

In this embodiment, the vinyl-containing phenylmethyl group reacts in the presence of a radical or an acid / alkali, and the solubility in an acid, alkali or organic solvent used in a coating solvent or developer changes. The vinyl-containing phenylmethyl group preferably has a property of causing a chain reaction in the presence of a radical or an acid / alkali in order to enable pattern formation with higher sensitivity and higher resolution.

[Resin obtained by using compound represented by formula (0) as monomer]
The compound represented by the formula (0) can be used as it is as a film-forming composition for lithography. Moreover, it can be used also as resin obtained by using the compound represented by the said Formula (0) as a monomer. In other words, the resin of this embodiment is a resin having a unit structure derived from the general formula (0). For example, it can also be used as a resin obtained by reacting a compound represented by the formula (0) with a compound having crosslinking reactivity.
Examples of the resin obtained using the compound represented by the formula (0) as a monomer include those having a structure represented by the following formula (3). That is, the composition of the present embodiment may contain a resin having a structure represented by the following formula (3).

(3)
(In the formula (3), L has an optionally substituted alkylene group having 1 to 30 carbon atoms, an optionally substituted arylene group having 6 to 30 carbon atoms, and a substituent. The alkylene group, the arylene group and the alkoxylene group may contain an ether bond, a ketone bond or an ester bond,
R ⁰ has the same meaning as R ^Y ,
R ¹ is an n-valent group having 1 to 60 carbon atoms or a single bond,
R ² to R ⁵ are each independently an optionally substituted alkyl group having 1 to 30 carbon atoms, an optionally substituted aryl group having 6 to 30 carbon atoms, or a substituent. An alkenyl group having 2 to 30 carbon atoms which may have a substituent, an alkoxy group having 1 to 30 carbon atoms which may have a substituent, a halogen atom, a nitro group, an amino group, a carboxylic acid group, a thiol group, A hydroxyl group or a group in which a hydrogen atom of a hydroxyl group is substituted with a vinylphenylmethyl group, and the alkyl group, the aryl group, the alkenyl group, and the alkoxy group may include an ether bond, a ketone bond, or an ester bond. Often,
M ² and m ³ are each independently an integer of 0 to 8,
M ⁴ and m ⁵ are each independently an integer of 0 to 9,
However, m ² , m ³ , m ⁴ and m ⁵ are not simultaneously 0, and at least one of R ² to R ⁵ is a group in which a hydrogen atom of a hydroxyl group is substituted with a vinylphenylmethyl group.
N is synonymous with N, and when n is an integer of 2 or more, the structural formulas in n [] may be the same or different,
P ² to p ⁵ are as defined above for r. )

In formula (3), L has an optionally substituted alkylene group having 1 to 30 carbon atoms, an optionally substituted arylene group having 6 to 30 carbon atoms, and a substituent. It may be an alkoxylene group having 1 to 30 carbon atoms or a single bond. The alkylene group, the arylene group, and the alkoxylene group may include an ether bond, a ketone bond, or an ester bond. The alkylene group and alkoxylene group may be a linear, branched or cyclic group.

In the formula (3), R ⁰ , R ¹ , R ² to R ⁵ , m ² and m ³ , m ⁴ and m ⁵ , p ² to p ⁵ , and n are as defined in the formula (1). However, m ² , m ³ , m ⁴ and m ⁵ are not simultaneously 0, and at least one of R ² to R ⁵ is a group in which a hydrogen atom of a hydroxyl group is substituted with a vinylphenylmethyl group.

[Method for producing resin obtained by using compound represented by formula (0) as monomer]
The resin of the present embodiment can be obtained by reacting the compound represented by the formula (0) with a compound having crosslinking reactivity. As the compound having crosslinking reactivity, a known compound can be used without particular limitation as long as the compound represented by the formula (0) can be oligomerized or polymerized. Specific examples thereof include, but are not limited to, aldehydes, ketones, carboxylic acids, carboxylic acid halides, halogen-containing compounds, amino compounds, imino compounds, isocyanates, unsaturated hydrocarbon group-containing compounds, and the like.

Specific examples of the resin obtained using the compound represented by the formula (0) as a monomer include, for example, the compound represented by the formula (0) with an aldehyde and / or a ketone having a crosslinking reactivity. Examples thereof include resins that have been novolakized by a condensation reaction or the like.

Here, as an aldehyde used when novolak-forming the compound represented by the formula (0), for example, formaldehyde, trioxane, paraformaldehyde, benzaldehyde, acetaldehyde, propylaldehyde, phenylacetaldehyde, phenylpropylaldehyde, hydroxybenzaldehyde, Examples thereof include, but are not limited to, chlorobenzaldehyde, nitrobenzaldehyde, methylbenzaldehyde, ethylbenzaldehyde, butylbenzaldehyde, biphenylaldehyde, naphthaldehyde, anthracenecarbaldehyde, phenanthrenecarbaldehyde, pyrenecarbaldehyde, and furfural. Examples of ketones include the aforementioned ketones. Among these, formaldehyde is more preferable. In addition, these aldehydes and / or ketones can be used individually by 1 type or in combination of 2 or more types. The amount of the aldehyde and / or ketone used is not particularly limited, but is preferably 0.2 to 5 moles, more preferably 0.5 moles relative to 1 mole of the compound represented by the formula (0). ~ 2 moles.

In the condensation reaction between the compound represented by the formula (0) and the aldehyde and / or ketone, a catalyst may be used. The acid catalyst used here can be appropriately selected from known ones and is not particularly limited. As such an acid catalyst, inorganic acids and organic acids are widely known. For example, inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, hydrofluoric acid, oxalic acid, malonic acid, and succinic acid. , Adipic acid, sebacic acid, citric acid, fumaric acid, maleic acid, formic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid Organic acids such as naphthalenedisulfonic acid, Lewis acids such as zinc chloride, aluminum chloride, iron chloride, boron trifluoride, or solid acids such as silicotungstic acid, phosphotungstic acid, silicomolybdic acid or phosphomolybdic acid Although it is mentioned, it is not specifically limited to these. Among these, organic acids and solid acids are preferable from the viewpoint of production, and hydrochloric acid or sulfuric acid is preferable from the viewpoint of production such as availability and ease of handling. In addition, about an acid catalyst, 1 type can be used individually or in combination of 2 or more types.

The amount of the acid catalyst used can be appropriately set according to the raw material to be used, the type of catalyst to be used, and further the reaction conditions, and is not particularly limited. It is preferable that it is a mass part. However, indene, hydroxyindene, benzofuran, hydroxyanthracene, acenaphthylene, biphenyl, bisphenol, trisphenol, dicyclopentadiene, tetrahydroindene, 4-vinylcyclohexene, norbornadiene, 5-vinylnorborna-2-ene, α-pinene, β-pinene In the case of a copolymerization reaction with a compound having a nonconjugated double bond such as limonene, aldehydes are not necessarily required.

In the condensation reaction between the compound represented by the formula (0) and the aldehyde and / or ketone, a reaction solvent can be used. The reaction solvent in this polycondensation can be appropriately selected from known solvents and is not particularly limited. Examples thereof include water, methanol, ethanol, propanol, butanol, tetrahydrofuran, dioxane, and mixed solvents thereof. Illustrated. In addition, a solvent can be used individually by 1 type or in combination of 2 or more types.

The amount of these solvents used can be appropriately set according to the raw material used, the type of catalyst used, and the reaction conditions, and is not particularly limited, but is 0 to 2000 parts by mass with respect to 100 parts by mass of the reaction raw material. It is preferable that it is the range of these. Furthermore, the reaction temperature can be appropriately selected according to the reactivity of the reaction raw material, and is not particularly limited, but is usually in the range of 10 to 200 ° C. The reaction method can be appropriately selected from known methods, and is not particularly limited. However, the reaction method may be a method in which the compound represented by the formula (0), the aldehyde and / or ketone, and a catalyst are charged together, There is a method in which a compound represented by the formula (0), an aldehyde and / or a ketone are dropped in the presence of a catalyst.

After completion of the polycondensation reaction, the obtained compound can be isolated according to a conventional method, and is not particularly limited. For example, in order to remove unreacted raw materials, catalysts, etc. existing in the system, the temperature of the reaction kettle is increased to 130 to 230 ° C., and a general method such as removing volatile matter at about 1 to 50 mmhg is adopted. As a result, a novolak resin as the target product can be obtained.

Here, the resin having the structure represented by the formula (3) may be a homopolymer of the compound represented by the formula (0), but is a copolymer with other phenols. May be. Examples of the copolymerizable phenols include phenol, cresol, dimethylphenol, trimethylphenol, butylphenol, phenylphenol, diphenylphenol, naphthylphenol, resorcinol, methylresorcinol, catechol, butylcatechol, methoxyphenol, methoxyphenol, Although propylphenol, pyrogallol, thymol, etc. are mentioned, it is not specifically limited to these.

Further, the resin having the structure represented by the formula (3) may be copolymerized with a polymerizable monomer other than the above-described phenols. Examples of the copolymerization monomer include naphthol, methylnaphthol, methoxynaphthol, dihydroxynaphthalene, indene, hydroxyindene, benzofuran, hydroxyanthracene, acenaphthylene, biphenyl, bisphenol, trisphenol, dicyclopentadiene, tetrahydroindene, 4-vinylcyclohexene. , Norbornadiene, vinylnorbornaene, pinene, limonene and the like, but are not particularly limited thereto. The resin having the structure represented by the formula (3) is a binary or more (for example, a quaternary system) copolymer of the compound represented by the formula (1) and the above-described phenols. Even if it is a binary or more (for example, 2-4 quaternary) copolymer of the compound represented by the formula (1) and the above-mentioned copolymerization monomer, it is represented by the formula (1). It may be a ternary or more (for example, ternary to quaternary) copolymer of the above compound, the above-mentioned phenols, and the above-mentioned copolymerization monomer.

The molecular weight of the resin having the structure represented by the formula (3) is not particularly limited, but the polystyrene equivalent weight average molecular weight (Mw) is preferably 500 to 30,000, more preferably 750 to 20,000. Further, from the viewpoint of enhancing the crosslinking efficiency and suppressing the volatile components in the baking, the resin having the structure represented by the formula (3) has a dispersity (weight average molecular weight Mw / number average molecular weight Mn) of 1.2. Those within the range of ˜7 are preferred. The Mn can be obtained by the method described in Examples described later.

The resin having the structure represented by the formula (3) is preferably highly soluble in a solvent from the viewpoint of easier application of a wet process. More specifically, when these compounds and / or resins use 1-methoxy-2-propanol (PGME) and / or propylene glycol monomethyl ether acetate (PGMEA) as a solvent, the solubility in the solvent is 10% by mass or more. It is preferable that Here, the solubility in PGM and / or PGMEA is defined as “resin mass ÷ (resin mass + solvent mass) × 100 (mass%)”. For example, when 10 g of the resin is dissolved in 90 g of PGMEA, the solubility of the resin in PGMEA is “10 mass% or more”, and when it is not dissolved, it is “less than 10 mass%”.

[Compound represented by Formula (2)]
It is also preferable that the compound of this embodiment is represented by following formula (2). Since the compound represented by Formula (2) is comprised as follows, its heat resistance is high and its solvent solubility is also high.

(2)
(In Formula (2), R ^0A has the same meaning as R ^Y ,
R ^1A is ^a na-valent group having 1 to 30 carbon atoms or a single bond,
R ^2A each independently has an optionally substituted alkyl group having 1 to 30 carbon atoms, an optionally substituted aryl group having 6 to 30 carbon atoms, or a substituent. An optionally substituted alkenyl group having 2 to 30 carbon atoms, an optionally substituted alkoxy group having 1 to 30 carbon atoms, a halogen atom, a nitro group, an amino group, a carboxylic acid group, a thiol group, a hydroxyl group or a hydroxyl group Wherein the hydrogen atom is substituted with a vinyl-containing phenylmethyl group, and the alkyl group, the aryl group, the alkenyl group, and the alkoxy group may include an ether bond, a ketone bond, or an ester bond. And at least one of R ^2A is a group in which a hydrogen atom of a hydroxyl group is substituted with a vinylphenylmethyl group,
N ^a is the same as defined above N, where, if n ^a is an integer of 2 or more, n structural formulas of ^a number of brackets [] may be the same or different and
X ^A is synonymous with X,
M ^2a is each independently an integer of 0 to 7, provided that at least one m ^2a is an integer of 1 to 7;
Q ^a is independently 0 or 1. )

In Formula (2), R ^0A has the same ^{meaning as} R ^Y described above.
R ^1A is ^a na-valent group having 1 to 60 carbon atoms or a single bond. N ^a is synonymous with N and is an integer of 1 to 4. In the formula (2), when n ^a is an integer of 2 or more, the structural formula of n ^a number of in [] may be the same or different.
The ^na valent group is an alkyl group having 1 to 60 carbon atoms when n ^a = 1, an alkylene group having 1 to 30 carbon atoms when n ^a = 2, and when n ^a = 3, An alkanepropyl group having 2 to 60 carbon atoms, and when n ^a = 4, an alkanetetrayl group having 3 to 60 carbon atoms. Examples of the n-valent group include those having a linear hydrocarbon group, a branched hydrocarbon group, or an alicyclic hydrocarbon group. Here, the alicyclic hydrocarbon group includes a bridged alicyclic hydrocarbon group. The n-valent hydrocarbon group may have an alicyclic hydrocarbon group, a double bond, a hetero atom, or an aromatic group having 6 to 60 carbon atoms.

R ^2A each independently has an optionally substituted alkyl group having 1 to 30 carbon atoms, an optionally substituted aryl group having 6 to 30 carbon atoms, or a substituent. An optionally substituted alkenyl group having 2 to 30 carbon atoms, an optionally substituted alkoxy group having 1 to 30 carbon atoms, a halogen atom, a nitro group, an amino group, a carboxylic acid group, a thiol group, a hydroxyl group or a hydroxyl group In which the alkyl group, the aryl group, the alkenyl group, and the alkoxy group may include an ether bond, a ketone bond, or an ester bond. , R ^2A is a group in which a hydrogen atom of a hydroxyl group is substituted with a vinyl-containing phenylmethyl group. The alkyl group, alkenyl group and alkoxy group may be a linear, branched or cyclic group.

X ^A is synonymous with X, and each independently represents an oxygen atom, a sulfur atom, or no bridge. Here, if X ^A is an oxygen atom or a sulfur atom, preferably because of the tendency to exhibit high heat resistance, and more preferably an oxygen atom. X ^A, in terms of solubility, it is preferable that the non-crosslinked.

M ^2a is each independently an integer of 0 to 6. However, at least one m ^2a is an integer of 1 to 6. Q ^a is independently 0 or 1. In formula (2), the site represented by the naphthalene structure is a monocyclic structure when q ^a = 0, and is a bicyclic structure when q ^a = 1. The numerical range of m ^2a described above is determined according to the ring structure determined by q ^a .

The compound represented by the formula (2) has a relatively low molecular weight, but has high heat resistance due to the rigidity of its structure, and therefore can be used under high temperature baking conditions. Moreover, it has tertiary carbon or quaternary carbon in the molecule, the crystallinity is suppressed, and it is suitably used as a film forming composition for lithography that can be used for manufacturing a film for lithography.

Since the aromatic density is high, the refractive index is high, and coloring is suppressed by a wide range of heat treatments from low to high temperatures, so that it is also useful as a composition for forming various optical parts. The one having quaternary carbon is preferable from the viewpoint of suppressing oxidative decomposition of the present compound to suppress coloring, high heat resistance, and improving solvent solubility. Optical parts are used in the form of films and sheets, as well as plastic lenses (prism lenses, lenticular lenses, micro lenses, Fresnel lenses, viewing angle control lenses, contrast enhancement lenses, etc.), retardation films, electromagnetic wave shielding films, prisms It is useful as an optical fiber, a solder resist for flexible printed wiring, a plating resist, an interlayer insulating film for multilayer printed wiring boards, and a photosensitive optical waveguide.

The compound represented by the formula (2) is preferably a compound represented by the following formula (2-1) from the viewpoint of easy crosslinking and solubility in an organic solvent.

(2-1)

In the formula (2-1), R ^0A , R ^1A , n ^a, q ^a and X ^A have the same meaning as described in the formula (2). R ^3A is a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, substituted An alkenyl group having 2 to 30 carbon atoms which may have a group, a halogen atom, a nitro group, an amino group, a carboxylic acid group, or a thiol group, and may be the same or different in the same naphthalene ring or benzene ring. May be.
R ^4A is each independently a hydrogen atom or a vinyl-containing phenylmethyl group, wherein at least one of R ^4A is a vinyl-containing phenylmethyl group, and m ^6a is each independently 0 to 5 Is an integer.

When the compound represented by formula (2-1) is used as a film forming composition for lithography for an alkali development positive resist or an organic development negative resist, at least one of R ^4A is a vinyl-containing phenylmethyl group. It is. On the other hand, when the compound represented by the formula (2-1) is used as a lithographic film-forming composition for an alkali development negative resist, a lithographic film-forming composition for an underlayer film, or an optical component-forming composition, R ^4A At least one of is a hydrogen atom.

Further, from the viewpoint of raw material supply, the compound represented by the formula (2-1) is preferably a compound represented by the following formula (2a).

(2a)

In the formula ^{^{^{(2a), X A, R}}} 0A ~ R 2A, m 2a and ^{n a} have the same meanings as those described for the formula (2).

Further, from the viewpoint of solubility in an organic solvent, the compound represented by the formula (2-1) is more preferably a compound represented by the following formula (2b).

(2b)

In the formula ^{^{^{(2b), X A, R}}} 0A, R 1A, R 3A, R 4A, m 6a and ^{n a} have the same meanings as those described by the formula (2-1).

Further, from the viewpoint of solubility in an organic solvent, the compound represented by the formula (2-1) is more preferably a compound represented by the following formula (2c).

(2c)

In the formula ^{^{^{(2c), X A, R}}} 0A, R 1A, R 3A, R 4A, m 6a and ^{n a} have the same meanings as those described by the formula (2-1).

From the viewpoint of further solubility in an organic solvent, the compound represented by the formula (2) is represented by the following formulas (bisn-1) to (bisn-4), (xbisn-1) to (xbisn-3), ( Particularly preferred are compounds represented by bin-1) to (bin-4) or (xbin-1) to (xbin-3). (R ^4A in the specific examples is as defined above).

(Bisn-1)

(Bisn-2)

(Bisn-3)

(Bisn-4)

(Xbisn-1)

(Xbisn-2)

(Xbisn-3)

(Bin-1)

(Bin-2)

(Bin-3)

(Bin-4)

(Xbin-1)

(Xbin-2)

(Xbin-3)

[Production Method of Compound Represented by Formula (2)]
The compound represented by the formula (2) used in the present embodiment can be appropriately synthesized by applying a known technique, and the synthesis technique is not particularly limited.
For example, a polyphenol compound is obtained by subjecting phenols, naphthols, and corresponding ketones or aldehydes to a polycondensation reaction under an acid catalyst under normal pressure, and then at least one phenolic hydroxyl group of the polyphenol compound. It can be obtained by introducing a vinyl-containing phenylmethyl group.
Moreover, the said synthesis | combination can also be performed under pressure as needed.

The naphthols are not particularly limited, and examples thereof include naphthol, methyl naphthol, methoxy naphthol, naphthalene diol, and the like. It is more preferable to use naphthalene diol because a xanthene structure can be easily formed.

The phenols are not particularly limited, and examples thereof include phenol, methylphenol, methoxybenzene, catechol, resorcinol, hydroquinone, and trimethylhydroquinone.

Examples of the ketones include acetone, methyl ethyl ketone, cyclobutanone, cyclopentanone, cyclohexanone, norbornanone, tricyclohexanone, tricyclodecanone, adamantanone, fluorenone, benzofluorenone, acenaphthenequinone, acenaphthenone, anthraquinone, acetophenone, diacetylbenzene. , Triacetylbenzene, acetonaphthone, diphenylcarbonylnaphthalene, phenylcarbonylbiphenyl, diphenylcarbonylbiphenyl, benzophenone, diphenylcarbonylbenzene, triphenylcarbonylbenzene, benzonaphthone, diphenylcarbonylnaphthalene, phenylcarbonylbiphenyl, diphenylcarbonylbiphenyl, etc. Not particularly limited to . These can be used alone or in combination of two or more. Among these, cyclopentanone, cyclohexanone, norbornanone, tricyclohexanone, tricyclodecanone, adamantanone, fluorenone, benzofluorenone, acenaphthenequinone, acenaphthenone, anthraquinone, acetophenone, diacetylbenzene, triacetylbenzene, acetonaphthone, diphenylcarbonyl Naphthalene, phenylcarbonylbiphenyl, diphenylcarbonylbiphenyl, benzophenone, diphenylcarbonylbenzene, triphenylcarbonylbenzene, benzonaphthone, diphenylcarbonylnaphthalene, phenylcarbonylbiphenyl, diphenylcarbonylbiphenyl are preferably used in terms of giving high heat resistance, acetophenone, Diacetylbenzene, triacetylbenzene Zen, acetonaphthone, diphenylcarbonylnaphthalene, phenylcarbonylbiphenyl, diphenylcarbonylbiphenyl, benzophenone, diphenylcarbonylbenzene, triphenylcarbonylbenzene, benzonaphthone, diphenylcarbonylnaphthalene, phenylcarbonylbiphenyl, diphenylcarbonylbiphenyl have high etching resistance, More preferred.
It is preferable to use a ketone having an aromatic ring as the ketone, since it has both high heat resistance and high etching resistance.

The acid catalyst is not particularly limited, and can be appropriately selected from known inorganic acids and organic acids. For example, inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, hydrofluoric acid; oxalic acid, formic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, naphthalene Organic acids such as sulfonic acid and naphthalenedisulfonic acid; Lewis acids such as zinc chloride, aluminum chloride, iron chloride, and boron trifluoride; or solid acids such as silicotungstic acid, phosphotungstic acid, silicomolybdic acid, and phosphomolybdic acid Can be mentioned. It is preferable to use hydrochloric acid or sulfuric acid from the viewpoint of production such as availability and ease of handling. Moreover, about an acid catalyst, 1 type or 2 types or more can be used.

When producing the compound represented by the formula (2), a reaction solvent may be used. The reaction solvent is not particularly limited as long as the reaction between the aldehyde or ketone to be used and naphthol proceeds, but for example, water, methanol, ethanol, propanol, butanol, tetrahydrofuran, dioxane or a mixed solvent thereof is used. Can do. The amount of the solvent is not particularly limited, and is, for example, in the range of 0 to 2000 parts by mass with respect to 100 parts by mass of the reaction raw material.
When the polyphenol compound is produced, the reaction temperature is not particularly limited and can be appropriately selected according to the reactivity of the reaction raw material, but is preferably in the range of 10 to 200 ° C. In order to synthesize the compound represented by formula (2) of this embodiment with good selectivity, the lower the temperature, the higher the effect and the more preferable the range is 10 to 60 ° C.
The method for producing the compound represented by the formula (2) is not particularly limited. For example, naphthols and the like, aldehydes or ketones, a method in which a catalyst is charged in a lump, or naphthols and ketones are dropped in the presence of a catalyst. There is a way to do it. After the polycondensation reaction, in order to remove unreacted raw materials, catalyst, etc. existing in the system, the temperature of the reaction kettle can be raised to 130-230 ° C. and volatile matter can be removed at about 1-50 mmhg. .

The amount of the raw material for producing the compound represented by the formula (2) is not particularly limited. For example, 2 mol to an excess amount of naphthol or the like with respect to 1 mol of aldehydes or ketones, and an acid catalyst The reaction proceeds at a normal pressure at 20 to 60 ° C. for 20 minutes to 100 hours.

When the compound represented by the formula (2) is produced, the target product is isolated by a known method after the completion of the reaction. The method for isolating the target product is not particularly limited. For example, the reaction solution is concentrated, pure water is added to precipitate the reaction product, the solution is cooled to room temperature, filtered, and separated to obtain a solid product. After filtering and drying, a method of separating and purifying from by-products by column chromatography, evaporating the solvent, filtering and drying to obtain the target compound can be mentioned.

A method for introducing a group substituted with a vinylphenylmethyl group into at least one phenolic hydroxyl group of a polyphenol compound is known. For example, a group substituted with a vinylphenylmethyl group can be introduced into at least one phenolic hydroxyl group of a polyphenol compound as follows. A compound for introducing a group substituted with a vinyl-containing phenylmethyl group can be synthesized or easily obtained by a known method, and examples thereof include vinyl benzyl chloride, vinyl benzyl bromide, and vinyl benzyl iodoide. Not.

For example, a compound for introducing a polyphenol compound and a group substituted with a vinyl-containing phenylmethyl group is dissolved or suspended in an aprotic solvent such as acetone, tetrahydrofuran (THF), propylene glycol monomethyl ether acetate or the like. Subsequently, the reaction is carried out at 20 to 150 ° C. for 6 to 72 hours at normal pressure in the presence of a base catalyst such as sodium hydroxide, potassium hydroxide, sodium methoxide, sodium ethoxide and the like. The reaction solution is neutralized with an acid and added to distilled water to precipitate a white solid, and then the separated solid is washed with distilled water, or the solvent is evaporated to dryness and washed with distilled water as necessary. By drying, a compound in which a hydrogen atom of a hydroxyl group is substituted with a group substituted with a vinyl-containing phenylmethyl group can be obtained.

The timing for introducing a group substituted with a vinyl-containing phenylmethyl group may be not only after the condensation reaction of binaphthols with aldehydes or ketones, but also before the condensation reaction. Moreover, you may carry out after manufacturing resin mentioned later.

A method of introducing a hydroxyalkyl group into at least one phenolic hydroxyl group of a polyphenol compound and introducing a vinylphenylmethyl group into the hydroxy group is also known.
The hydroxyalkyl group may be introduced into the phenolic hydroxyl group via an oxyalkyl group. For example, a hydroxyalkyloxyalkyl group or a hydroxyalkyloxyalkyloxyalkyl group is introduced. For example, as described below, a hydroxyalkyl group can be introduced into at least one phenolic hydroxyl group of the compound, and a group substituted with a vinylphenylmethyl group can be introduced into the hydroxy group.
For example, as described below, a hydroxyalkyl group can be introduced into at least one phenolic hydroxyl group of the compound, and a vinylphenylmethyl group can be introduced into the hydroxy group.
A compound for introducing a hydroxyalkyl group can be synthesized or easily obtained by a known method. For example, chloroethanol, bromoethanol, 2-chloroethyl acetate, 2-bromoethyl acetate, 2-iodoethyl acetate, ethylene oxide , Propylene oxide, butylene oxide, ethylene carbonate, propylene carbonate, and butylene carbonate, but are not particularly limited.

For example, the polyphenol compound and a compound for introducing a hydroxyalkyl group are dissolved or suspended in an aprotic solvent such as acetone, tetrahydrofuran (THF) or propylene glycol monomethyl ether acetate. Subsequently, the reaction is carried out at 20 to 150 ° C. for 6 to 72 hours at normal pressure in the presence of a base catalyst such as sodium hydroxide, potassium hydroxide, sodium methoxide, sodium ethoxide and the like. The reaction solution is neutralized with an acid and added to distilled water to precipitate a white solid, and then the separated solid is washed with distilled water, or the solvent is evaporated to dryness and washed with distilled water as necessary. By drying, a compound in which a hydrogen atom of a hydroxyl group is substituted with a hydroxyalkyl group can be obtained.
For example, in the case of using 2-chloroethyl acetate, 2-bromoethyl acetate, or 2-iodoethyl acetate, a hydroxyethyl group is introduced by causing a deacylation reaction after the acetoxyethyl group is introduced.
Further, for example, when ethylene carbonate, propylene carbonate, or butylene carbonate is used, a hydroxyalkyl group is introduced by adding an alkylene carbonate to cause a decarboxylation reaction.
Thereafter, the compound and a compound for introducing a vinyl-containing phenylmethyl group are dissolved or suspended in an aprotic solvent such as acetone, tetrahydrofuran (THF), propylene glycol monomethyl ether acetate or the like. Subsequently, the reaction is carried out at 20 to 150 ° C. for 6 to 72 hours at normal pressure in the presence of a base catalyst such as sodium hydroxide, potassium hydroxide, sodium methoxide, sodium ethoxide and the like. The reaction solution is neutralized with an acid and added to distilled water to precipitate a white solid, and then the separated solid is washed with distilled water, or the solvent is evaporated to dryness and washed with distilled water as necessary. By drying, a compound in which a hydrogen atom of a hydroxy group is substituted with a vinyl-containing phenylmethyl group can be obtained.

[Method for producing resin obtained by using compound represented by formula (2) as monomer]
The compound represented by the formula (2) can be used as it is as a film-forming composition for lithography. Moreover, it can be used also as resin obtained by using the compound represented by the said Formula (2) as a monomer. For example, it can also be used as a resin obtained by reacting a compound represented by the formula (2) with a compound having crosslinking reactivity.
Examples of the resin obtained using the compound represented by the formula (2) as a monomer include those having a structure represented by the following formula (4). That is, the composition of the present embodiment may contain a resin having a structure represented by the following formula (4).

(4)

In the formula (4), L has an optionally substituted alkylene group having 1 to 30 carbon atoms, an optionally substituted arylene group having 6 to 30 carbon atoms, and a substituent. The alkylene group, the arylene group, and the alkoxylene group may include an ether bond, a ketone bond, or an ester bond,
R ^0A , R ^1A , R ^2A , m ^2a , n ^a , q ^a and X ^A are as defined in the above formula (2),
When N ^a is an integer of 2 or more, the structural formulas in n ^a [] may be the same or different.
However, at least one of R ^2A includes a group in which a hydrogen atom of a hydroxyl group is substituted with a vinylphenylmethyl group.

The resin of this embodiment can be obtained by reacting the compound represented by the formula (2) with a compound having a crosslinking reactivity.

As the compound having crosslinking reactivity, a known compound can be used without particular limitation as long as the compound represented by the formula (2) can be oligomerized or polymerized. Specific examples thereof include, but are not limited to, aldehydes, ketones, carboxylic acids, carboxylic acid halides, halogen-containing compounds, amino compounds, imino compounds, isocyanates, unsaturated hydrocarbon group-containing compounds, and the like.

Specific examples of the resin having the structure represented by the formula (2) include, for example, a condensation reaction of the compound represented by the formula (2) with an aldehyde and / or a ketone having a crosslinking reaction. And a novolak resin.

Here, as an aldehyde used when novolak-forming the compound represented by the formula (2), for example, formaldehyde, trioxane, paraformaldehyde, benzaldehyde, acetaldehyde, propylaldehyde, phenylacetaldehyde, phenylpropylaldehyde, hydroxybenzaldehyde, Examples thereof include, but are not limited to, chlorobenzaldehyde, nitrobenzaldehyde, methylbenzaldehyde, ethylbenzaldehyde, butylbenzaldehyde, biphenylaldehyde, naphthaldehyde, anthracenecarbaldehyde, phenanthrenecarbaldehyde, pyrenecarbaldehyde, and furfural. Examples of ketones include the aforementioned ketones. Among these, formaldehyde is more preferable. In addition, these aldehydes and / or ketones can be used individually by 1 type or in combination of 2 or more types. The amount of the aldehyde and / or ketone used is not particularly limited, but is preferably 0.2 to 5 mol, more preferably 0.5 mol, relative to 1 mol of the compound represented by the formula (2). ~ 2 moles.

In the condensation reaction between the compound represented by the formula (2) and the aldehyde and / or ketone, a catalyst may be used. The acid catalyst used here can be appropriately selected from known ones and is not particularly limited. As such an acid catalyst, inorganic acids and organic acids are widely known. For example, inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, hydrofluoric acid, oxalic acid, malonic acid, and succinic acid. , Adipic acid, sebacic acid, citric acid, fumaric acid, maleic acid, formic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid Organic acids such as naphthalenedisulfonic acid, Lewis acids such as zinc chloride, aluminum chloride, iron chloride, boron trifluoride, or solid acids such as silicotungstic acid, phosphotungstic acid, silicomolybdic acid or phosphomolybdic acid Although it is mentioned, it is not specifically limited to these. Among these, an organic acid or a solid acid is preferable from the viewpoint of manufacturing, and hydrochloric acid or sulfuric acid is preferable from the viewpoint of manufacturing such as availability and ease of handling. In addition, about an acid catalyst, 1 type can be used individually or in combination of 2 or more types. The amount of the acid catalyst used can be appropriately set according to the raw material to be used, the type of catalyst to be used, and further the reaction conditions, and is not particularly limited. It is preferable that it is a mass part. However, indene, hydroxyindene, benzofuran, hydroxyanthracene, acenaphthylene, biphenyl, bisphenol, trisphenol, dicyclopentadiene, tetrahydroindene, 4-vinylcyclohexene, norbornadiene, 5-vinylnorborna-2-ene, α-pinene, β-pinene In the case of a copolymerization reaction with a compound having a nonconjugated double bond such as limonene, aldehydes are not necessarily required.

In the condensation reaction between the compound represented by the formula (2) and the aldehyde and / or ketone, a reaction solvent can be used. The reaction solvent in this polycondensation can be appropriately selected from known solvents and is not particularly limited. Examples thereof include water, methanol, ethanol, propanol, butanol, tetrahydrofuran, dioxane, and mixed solvents thereof. Illustrated. In addition, a solvent can be used individually by 1 type or in combination of 2 or more types.

The amount of these solvents used can be appropriately set according to the raw material used, the type of catalyst used, and the reaction conditions, and is not particularly limited, but is 0 to 2000 parts by mass with respect to 100 parts by mass of the reaction raw material. It is preferable that it is the range of these. Furthermore, the reaction temperature can be appropriately selected according to the reactivity of the reaction raw material, and is not particularly limited, but is usually in the range of 10 to 200 ° C. The reaction method can be appropriately selected from known methods and is not particularly limited. However, the reaction method may be a method in which the compound represented by the formula (2), the aldehyde and / or ketone, and a catalyst are charged all together, There is a method in which a compound represented by the formula (2), an aldehyde and / or a ketone are added dropwise in the presence of a catalyst.

Here, the resin having the structure represented by the formula (4) may be a homopolymer of the compound represented by the formula (2), but is a copolymer with other phenols. May be. Examples of the copolymerizable phenols include phenol, cresol, dimethylphenol, trimethylphenol, butylphenol, phenylphenol, diphenylphenol, naphthylphenol, resorcinol, methylresorcinol, catechol, butylcatechol, methoxyphenol, methoxyphenol, Although propylphenol, pyrogallol, thymol, etc. are mentioned, it is not specifically limited to these.

In addition, the resin having the structure represented by the formula (4) may be copolymerized with a polymerizable monomer other than the above-described phenols. Examples of the copolymerization monomer include naphthol, methylnaphthol, methoxynaphthol, dihydroxynaphthalene, indene, hydroxyindene, benzofuran, hydroxyanthracene, acenaphthylene, biphenyl, bisphenol, trisphenol, dicyclopentadiene, tetrahydroindene, 4-vinylcyclohexene. , Norbornadiene, vinylnorbornaene, pinene, limonene and the like, but are not particularly limited thereto. The resin having the structure represented by the formula (2) is a binary or more (for example, 2-4 quaternary) copolymer of the compound represented by the formula (2) and the above-described phenols. Even in the case of a binary or more (for example, 2-4 quaternary) copolymer of the compound represented by the formula (2) and the above-described copolymerization monomer, it is represented by the formula (2). It may be a ternary or more (for example, ternary to quaternary) copolymer of the above compound, the above-mentioned phenols, and the above-mentioned copolymerization monomer.

The molecular weight of the resin having the structure represented by the formula (4) is not particularly limited, but the polystyrene-equivalent weight average molecular weight (Mw) is preferably 500 to 30,000, more preferably 750 to 20,000. Further, from the viewpoint of increasing the crosslinking efficiency and suppressing the volatile components in the baking, the resin having the structure represented by the formula (4) has a dispersity (weight average molecular weight Mw / number average molecular weight Mn) of 1.2. Those within the range of ˜7 are preferred. The Mn can be obtained by the method described in Examples described later.

The resin having the structure represented by the formula (4) is preferably highly soluble in a solvent from the viewpoint of easier application of a wet process. More specifically, when these compounds and / or resins use 1-methoxy-2-propanol (PGME) and / or propylene glycol monomethyl ether acetate (PGMEA) as a solvent, the solubility in the solvent is 10% by mass or more. It is preferable that Here, the solubility in PGM and / or PGMEA is defined as “resin mass ÷ (resin mass + solvent mass) × 100 (mass%)”. For example, when 10 g of the resin is dissolved in 90 g of PGMEA, the solubility of the resin in PGMEA is “10 mass% or more”, and when it is not dissolved, it is “less than 10 mass%”.

[Method of purifying compound and / or resin]
The compound represented by the formula (0) and the resin obtained using this as a monomer can be purified by the following purification method. That is, the compound and / or resin purification method of the present embodiment includes a compound represented by the formula (0) and a resin obtained using the compound as a monomer (for example, a compound represented by the formula (1), the formula A resin obtained using the compound represented by (1) as a monomer, one or more selected from a compound represented by the formula (2) and a resin obtained using the compound represented by the formula (2) as a monomer) A step of obtaining a solution (S) by dissolving in a solvent, and a step of contacting the obtained solution (S) with an acidic aqueous solution to extract impurities in the compound and / or the resin (first extraction) And a solvent used in the step of obtaining the solution (S) includes an organic solvent that is arbitrarily immiscible with water.
In the first extraction step, the resin is, for example, a resin obtained by a reaction between the compound represented by the formula (1) and / or the compound represented by the formula (2) and a compound having a crosslinking reaction. Preferably there is. According to the said purification method, content of the various metals which can be contained as an impurity in the compound or resin which has the specific structure mentioned above can be reduced.
More specifically, in the purification method, the compound and / or the resin is dissolved in an organic solvent that is arbitrarily immiscible with water to obtain a solution (S), and the solution (S) is further converted into an acidic aqueous solution. The extraction process can be performed by contact. Thereby, after transferring the metal content contained in the solution (S) to the aqueous phase, the organic phase and the aqueous phase can be separated to obtain a compound and / or resin having a reduced metal content.

The compound and resin used in the purification method may be used alone or in combination of two or more. Moreover, the said compound and resin may contain various surfactant, various crosslinking agents, various acid generators, various stabilizers, etc.

The solvent that is arbitrarily miscible with water used in the purification method is not particularly limited, but is preferably an organic solvent that can be safely applied to a semiconductor manufacturing process. Specifically, the solubility in water at room temperature is 30%. The organic solvent is less than 20%, more preferably less than 20%, particularly preferably less than 10%. The amount of the organic solvent used is preferably 1 to 100 times by mass with respect to the total amount of the compound to be used and the resin.

Specific examples of solvents that are not arbitrarily miscible with water include, but are not limited to, ethers such as diethyl ether and diisopropyl ether, esters such as ethyl acetate, n-butyl acetate, and isoamyl acetate, methyl ethyl ketone, and methyl isobutyl. Ketones such as ketone, ethyl isobutyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 2-pentanone; ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl Glycol ether acetates such as ether acetate; Aliphatic hydrocarbons such as n-hexane and n-heptane; Aromatic hydrocarbons such as toluene and xylene Methylene chloride, halogenated hydrocarbons such as chloroform and the like. Among these, toluene, 2-heptanone, cyclohexanone, cyclopentanone, methyl isobutyl ketone, propylene glycol monomethyl ether acetate, ethyl acetate and the like are preferable, methyl isobutyl ketone, ethyl acetate, cyclohexanone, propylene glycol monomethyl ether acetate are more preferable, More preferred are methyl isobutyl ketone and ethyl acetate. Methyl isobutyl ketone, ethyl acetate, etc. are removed when the solvent is industrially distilled off or dried because the compound and the resin containing the compound as a constituent component have a relatively high saturation solubility and a relatively low boiling point. It is possible to reduce the load in the process. These solvents can be used alone or in combination of two or more.

The acidic aqueous solution used in the purification method is appropriately selected from aqueous solutions in which generally known organic compounds or inorganic compounds are dissolved in water. Although not limited to the following, for example, a mineral acid aqueous solution in which a mineral acid such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid or the like is dissolved in water, or acetic acid, propionic acid, succinic acid, malonic acid, succinic acid, fumaric acid, maleic acid An organic acid aqueous solution in which an organic acid such as tartaric acid, citric acid, methanesulfonic acid, phenolsulfonic acid, p-toluenesulfonic acid, trifluoroacetic acid, etc. is dissolved in water. These acidic aqueous solutions can be used alone or in combination of two or more. Among these acidic aqueous solutions, one or more mineral acid aqueous solutions selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid, or acetic acid, propionic acid, succinic acid, malonic acid, succinic acid, fumaric acid, maleic acid, One or more organic acid aqueous solutions selected from the group consisting of tartaric acid, citric acid, methanesulfonic acid, phenolsulfonic acid, p-toluenesulfonic acid and trifluoroacetic acid are preferred, and sulfuric acid, nitric acid, acetic acid, oxalic acid, An aqueous solution of carboxylic acid such as tartaric acid and citric acid is more preferable, an aqueous solution of sulfuric acid, succinic acid, tartaric acid and citric acid is more preferable, and an aqueous solution of succinic acid is more preferable. Since polyvalent carboxylic acids such as succinic acid, tartaric acid, and citric acid are coordinated to metal ions to produce a chelate effect, it is considered that the metal tends to be removed more effectively. Further, as the water used here, it is preferable to use water having a low metal content, such as ion-exchanged water, in accordance with the purpose of the purification method of the present embodiment.

The pH of the acidic aqueous solution used in the purification method is not particularly limited, but it is preferable to adjust the acidity of the aqueous solution in consideration of the influence on the compound and the resin. Usually, the ph range is about 0 to 5, preferably about ph 0 to 3.

The amount of the acidic aqueous solution used in the purification method is not particularly limited, but from the viewpoint of reducing the number of extractions for metal removal and from the viewpoint of securing operability in consideration of the total amount of liquid, the amount used is It is preferable to adjust. From the above viewpoint, the amount of the acidic aqueous solution used is preferably 10 to 200% by mass, and more preferably 20 to 100% by mass with respect to 100% by mass of the solution (S).

In the purification method, a metal component can be extracted from the compound or the resin in the solution (S) by bringing the acidic aqueous solution into contact with the solution (S).

In the purification method, it is preferable that the solution (S) further contains an organic solvent arbitrarily mixed with water. When an organic solvent arbitrarily mixed with water is included, the amount of the compound and / or resin charged can be increased, the liquid separation property is improved, and purification can be performed with high pot efficiency. . The method for adding an organic solvent arbitrarily mixed with water is not particularly limited. For example, any of a method of adding to a solution containing an organic solvent in advance, a method of adding to water or an acidic aqueous solution in advance, and a method of adding after bringing a solution containing an organic solvent into contact with water or an acidic aqueous solution may be used. Among these, the method of adding to the solution containing an organic solvent in advance is preferable from the viewpoint of the workability of the operation and the ease of management of the charged amount.

The organic solvent arbitrarily mixed with water used in the purification method is not particularly limited, but an organic solvent that can be safely applied to a semiconductor manufacturing process is preferable. The amount of the organic solvent arbitrarily mixed with water is not particularly limited as long as the solution phase and the aqueous phase are separated from each other, but is 0.1 to 100 times by mass with respect to the total amount of the compound and the resin to be used. It is preferably 0.1 to 50 times by mass, more preferably 0.1 to 20 times by mass.

Specific examples of the organic solvent arbitrarily mixed with water used in the purification method include, but are not limited to, ethers such as tetrahydrofuran and 1,3-dioxolane; alcohols such as methanol, ethanol and isopropanol; acetone And ketones such as N-methylpyrrolidone; aliphatic hydrocarbons such as glycol ethers such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), and propylene glycol monoethyl ether. Among these, N-methylpyrrolidone, propylene glycol monomethyl ether and the like are preferable, and N-methylpyrrolidone and propylene glycol monomethyl ether are more preferable. These solvents can be used alone or in combination of two or more.

The temperature at the time of the extraction treatment is usually 20 to 90 ° C, preferably 30 to 80 ° C. The extraction operation is performed, for example, by mixing the mixture well by stirring or the like and then allowing it to stand. Thereby, the metal part contained in solution (S) transfers to an aqueous phase. Moreover, the acidity of a solution falls by this operation and the quality change of a compound and / or resin can be suppressed.

Since the mixed solution is allowed to stand to separate into a solution phase containing a compound and / or a resin and a solvent and an aqueous phase, the solution phase is recovered by decantation or the like. The standing time is not particularly limited, but it is preferable to adjust the standing time from the viewpoint of improving the separation between the solvent-containing solution phase and the aqueous phase. Usually, the time for standing is 1 minute or longer, preferably 10 minutes or longer, more preferably 30 minutes or longer. The extraction process may be performed only once, but it is also effective to repeat the operations of mixing, standing, and separation a plurality of times.

In the purification method, after the first extraction step, the solution phase containing the compound or the resin is further brought into contact with water to extract impurities in the compound or the resin (second extraction step). It is preferable. Specifically, for example, after performing the extraction treatment using an acidic aqueous solution, the solution phase containing the compound and / or resin and solvent extracted and recovered from the aqueous solution is further subjected to an extraction treatment with water. It is preferable. The extraction treatment with water is not particularly limited. For example, after the solution phase and water are mixed well by stirring or the like, the obtained mixed solution can be left still. Since the mixed solution after standing is separated into a solution phase containing a compound and / or a resin and a solvent and an aqueous phase, the solution phase can be recovered by decantation or the like.
Moreover, it is preferable that the water used here is water with a small metal content, for example, ion-exchanged water or the like in accordance with the purpose of the present embodiment. The extraction process may be performed only once, but it is also effective to repeat the operations of mixing, standing, and separation a plurality of times. Further, the use ratio of both in the extraction process, conditions such as temperature and time are not particularly limited, but they may be the same as those in the contact process with the acidic aqueous solution.

The water that can be mixed into the solution containing the compound and / or resin and solvent thus obtained can be easily removed by performing an operation such as vacuum distillation. Moreover, a solvent can be added to the said solution as needed, and the density | concentration of a compound and / or resin can be adjusted to arbitrary density | concentrations.

The method for isolating the compound and / or resin from the solution containing the obtained compound and / or resin and solvent is not particularly limited, and known methods such as removal under reduced pressure, separation by reprecipitation, and combinations thereof. Can be done. If necessary, known processes such as a concentration operation, a filtration operation, a centrifugal separation operation, and a drying operation can be performed.

"Composition"
The composition of this embodiment contains 1 or more types chosen from the group which consists of a compound and resin of the above-mentioned this embodiment. The composition of this embodiment can further contain a solvent, an acid generator, a crosslinking agent, a crosslinking accelerator, a radical polymerization initiator, and the like. The composition of the present embodiment can be used for a film forming application for lithography (that is, a film forming composition for lithography) and an optical component forming application.

[Film-forming composition for lithography]
The composition of the present embodiment is one or more selected from the group consisting of the compound of the present embodiment and a resin (for example, a compound represented by the formula (1), a compound represented by the formula (1) Resin as a monomer, one or more selected from the group consisting of a compound represented by the formula (2) and a resin obtained by using the compound represented by the formula (2) as a monomer) as a resist base material can do.

[Film-forming composition for lithography for chemically amplified resist applications]
The composition of this embodiment can be used as a film-forming composition for lithography for chemical amplification resist applications (hereinafter also referred to as a resist composition). The resist composition contains, for example, one or more selected from the group consisting of the compound and resin of the present embodiment.

The resist composition preferably contains a solvent. Examples of the solvent include, but are not limited to, ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, and ethylene glycol mono-n-butyl ether acetate. Ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether acetate, propylene glycol mono -Propylene glycol such as n-butyl ether acetate Cole monoalkyl ether acetates; propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether (PGME) and propylene glycol monoethyl ether; methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, n-amyl lactate, etc. Lactate esters; aliphatic carboxylic acid esters such as methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, n-amyl acetate, n-hexyl acetate, methyl propionate, ethyl propionate; Methyl propionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyrate Other esters such as acetate, butyl 3-methoxy-3-methylpropionate, butyl 3-methoxy-3-methylbutyrate, methyl acetoacetate, methyl pyruvate and ethyl pyruvate; aromatic hydrocarbons such as toluene and xylene Ketones such as 2-heptanone, 3-heptanone, 4-heptanone, cyclopentanone (CPN), cyclohexanone (CHN); N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide, N -Amides such as methylpyrrolidone; lactones such as γ-lactone can be mentioned, but there is no particular limitation. These solvents can be used alone or in combination of two or more.

The solvent used in this embodiment is preferably a safe solvent, more preferably at least one selected from PGMEA, PGME, CHN, CPN, 2-heptanone, anisole, butyl acetate, ethyl propionate and ethyl lactate. A seed, more preferably at least one selected from PGMEA, PGME and CHN.

In this embodiment, the amount of the solid component and the amount of the solvent are not particularly limited, but 1 to 80% by weight of the solid component and 20 to 99% of the solvent with respect to 100% by weight of the total amount of the solid component and the solvent. The solid component is preferably 1 to 50% by mass, more preferably 1 to 50% by mass of the solid component and 50 to 99% by mass of the solvent, further preferably 2 to 40% by mass of the solid component and 60 to 98% by mass of the solvent, and particularly preferably solid The component is 2 to 10% by mass and the solvent is 90 to 98% by mass.

The resist composition contains at least one selected from the group consisting of an acid generator (C), an acid crosslinking agent (G), an acid diffusion controller (E), and other components (F) as other solid components. May be. In addition, in this specification, a solid component means components other than a solvent.

Here, the acid generator (C), the acid crosslinking agent (G), the acid diffusion controller (E) and other components (F) may be known ones, and are not particularly limited. Those described in 2013/024778 are preferred.

[Combination ratio of each component]
In the resist composition, the content of the compound and resin of the above-described embodiment used as a resist base material is not particularly limited, but the total mass of the solid components (resist base material, acid generator (C), acid crosslinking agent) (G), acid diffusion controller (E), and other components (F) and the like. More preferably, it is 55 to 90% by mass, still more preferably 60 to 80% by mass, and particularly preferably 60 to 70% by mass. In the case of the content, the resolution is further improved and the line edge roughness (LER) is further reduced.
In addition, when containing both a compound and resin as a resist base material, the said content is the total amount of both components.

[Other components (F)]
In the resist composition, components other than the resist base material, the acid generator (C), the acid cross-linking agent (G), and the acid diffusion controller (E) may be added as necessary without departing from the object of the present invention. As dissolution accelerators, dissolution control agents, sensitizers, surfactants, organic carboxylic acids or phosphorus oxo acids or derivatives, heat and / or photocuring catalysts, polymerization inhibitors, flame retardants, fillers, couplings Additives, thermosetting resins, photocurable resins, dyes, pigments, thickeners, lubricants, antifoaming agents, leveling agents, UV absorbers, surfactants, colorants, nonionic surfactants, etc. 1 type, or 2 or more types can be added. In addition, in this specification, another component (F) may be called arbitrary component (F).

The resist composition contains a resist substrate (hereinafter also referred to as component (A)), an acid generator (C), an acid crosslinking agent (G), an acid diffusion controller (E), and an optional component (F). The amount (component (A) / acid generator (C) / acid crosslinking agent (G) / acid diffusion controller (E) / optional component (F)) is mass% based on solids,
Preferably 50 to 99.4 / 0.001 to 49 / 0.5 to 49 / 0.001 to 49/0 to 49,
More preferably 55 to 90/1 to 40 / 0.5 to 40 / 0.01 to 10/0 to 5,
More preferably 60 to 80/3 to 30/1 to 30 / 0.01 to 5/0 to 1,
Particularly preferred is 60 to 70/10 to 25/2 to 20 / 0.01 to 3/0.
The blending ratio of each component is selected from each range so that the sum is 100% by mass. When the above composition is used, the performance such as sensitivity, resolution and developability is excellent.

The resist composition is usually prepared by dissolving each component in a solvent at the time of use to obtain a uniform solution, and then filtering with a filter having a pore size of about 0.2 μm, for example, as necessary.

The resist composition may contain a resin other than the compound and resin of the present embodiment as long as the object of the present invention is not impaired. The resin is not particularly limited, and for example, a novolac resin, polyvinylphenols, polyacrylic acid, polyvinyl alcohol, styrene-maleic anhydride resin, and a polymer containing acrylic acid, vinyl alcohol, or vinylphenol as monomer units. A combination or a derivative thereof may be used. The content of the resin is not particularly limited and is appropriately adjusted according to the type of the component (A) to be used, but is preferably 30 parts by mass or less, more preferably 100 parts by mass of the component (A). It is 10 mass parts or less, More preferably, it is 5 mass parts or less, Most preferably, it is 0 mass part.

[Physical properties of resist composition]
The resist composition can form an amorphous film by spin coating. Further, it can be applied to a general semiconductor manufacturing process. Either a positive resist pattern or a negative resist pattern can be created depending on the type of compound and resin of the present embodiment and / or the type of developer used.

In the case of a positive resist pattern, the dissolution rate of the amorphous film formed by spin-coating the resist composition in a developing solution at 23 ° C. is preferably 5 Å / sec or less, more preferably 0.05 to 5 Å / sec, More preferred is .0005 to 5 liters / sec. When the dissolution rate is 5 kg / sec or less, the resist is insoluble in the developer and can be a resist. In addition, when the dissolution rate is 0.0005 kg / sec or more, the resolution may be improved. This is presumed that the contrast between the exposed portion dissolved in the developer and the unexposed portion not dissolved in the developer increases due to the change in solubility of the compound and resin of the present embodiment before and after exposure. Is done. Further, there is an effect of reducing LER and reducing defects.
In the case of a negative resist pattern, the dissolution rate of the amorphous film formed by spin-coating the resist composition in a developer at 23 ° C. is preferably 10 Å / sec or more. When the dissolution rate is 10 Å / sec or more, it is easily dissolved in a developer and more suitable for a resist. Further, when the dissolution rate is 10 Å / sec or more, the resolution may be improved. This is presumed to be because the micro surface portion of the compound and resin of the present embodiment described above dissolves and LER is reduced. There is also an effect of reducing defects.
The dissolution rate can be determined by immersing an amorphous film in a developing solution for a predetermined time at 23 ° C., and measuring the film thickness before and after the immersion by a known method such as visual observation, an ellipsometer, or a QCM method.

In the case of a positive resist pattern, the dissolution rate of the amorphous film formed by spin-coating the resist composition in a developing solution at 23 ° C. of a portion exposed by radiation such as krf excimer laser, extreme ultraviolet light, electron beam or X-ray is It is preferably 10 Å / sec or more. When the dissolution rate is 10 Å / sec or more, it is easily dissolved in a developer and more suitable for a resist. Further, when the dissolution rate is 10 Å / sec or more, the resolution may be improved. This is presumed to be because the micro surface portion of the compound and resin of the present embodiment described above dissolves and LER is reduced. There is also an effect of reducing defects.
In the case of a negative resist pattern, the dissolution rate of the amorphous film formed by spin-coating the resist composition in a developer at 23 ° C. at a portion exposed by radiation such as krf excimer laser, extreme ultraviolet light, electron beam or X-ray is 5 Å / sec or less is preferable, 0.05 to 5 Å / sec is more preferable, and 0.0005 to 5 Å / sec is more preferable. When the dissolution rate is 5 kg / sec or less, the resist is insoluble in the developer and can be a resist. In addition, when the dissolution rate is 0.0005 kg / sec or more, the resolution may be improved. This is because the interface between the unexposed portion that dissolves in the developer and the exposed portion that does not dissolve in the developer due to a change in the solubility of the resin containing the compound and resin of the present embodiment as constituents before and after the exposure. Is estimated to be larger. Further, there is an effect of reducing LER and reducing defects.

[Film-forming composition for lithography for non-chemically amplified resist applications]
The composition of this embodiment can be used as a film-forming composition for lithography for non-chemically amplified resist applications (hereinafter also referred to as a radiation-sensitive composition). The component (A) (the compound and resin of the above-described embodiment) contained in the radiation-sensitive composition is used in combination with the diazonaphthoquinone photoactive compound (B) described later, and g-line, h-line, i-line, krf It is useful as a positive resist substrate that becomes a compound that is easily soluble in a developer by irradiation with an excimer laser, an arf excimer laser, extreme ultraviolet light, electron beam, or X-ray. G-ray, h-ray, i-ray, krf excimer laser, arf excimer laser, extreme ultraviolet light, electron beam or X-ray does not change the property of component (A) greatly, but diazonaphthoquinone photoactivity is hardly soluble in the developer. By changing the compound (B) into a readily soluble compound, a resist pattern can be formed by a development process.
Since the component (A) contained in the radiation-sensitive composition is a compound having a relatively low molecular weight, the roughness of the obtained resist pattern is very small. In the formula (1), at least one selected from the group consisting of R ⁰ to R ⁵ is preferably a group containing an iodine atom. In the formula (2), R ^0A , R ^1A and R ^2A It is preferable that at least one selected from the group consisting of is a group containing an iodine atom. When the component (A) having a group containing an iodine atom, which is such a preferred embodiment, is applied to the resist composition, the resist composition increases the ability to absorb radiation such as electron beams, extreme ultraviolet rays (EUV), and X-rays. As a result, the sensitivity can be increased, which is preferable.

The glass transition temperature of the component (A) (resist base material) contained in the radiation-sensitive composition is preferably 100 ° C. or higher, more preferably 120 ° C. or higher, further preferably 140 ° C. or higher, and particularly preferably 150 ° C. or higher. It is. Although the upper limit of the glass transition temperature of a component (A) is not specifically limited, For example, it is 400 degreeC. When the glass transition temperature of the component (A) is within the above range, the semiconductor lithography process has heat resistance capable of maintaining the pattern shape, and performance such as high resolution is improved.

The crystallization calorific value obtained by differential scanning calorimetric analysis of the glass transition temperature of the component (A) contained in the radiation-sensitive composition is preferably less than 20 J / g. Further, (crystallization temperature) − (glass transition temperature) is preferably 70 ° C. or higher, more preferably 80 ° C. or higher, still more preferably 100 ° C. or higher, and particularly preferably 130 ° C. or higher. When the crystallization heat generation amount is less than 20 J / g, or (crystallization temperature) − (glass transition temperature) is in the above range, an amorphous film can be easily formed by spin-coating the radiation-sensitive composition, and The film formability required for the resist can be maintained for a long time, and the resolution can be improved.

In this embodiment, the crystallization heat generation amount, the crystallization temperature, and the glass transition temperature can be obtained by differential scanning calorimetry using DSC / TA-50WS manufactured by Shimadzu Corporation. About 10 mg of a sample is put into an aluminum non-sealed container and heated to a melting point or higher at a temperature rising rate of 20 ° C./min in a nitrogen gas stream (50 ml / min). After the rapid cooling, the temperature is again raised to the melting point or higher at a temperature rising rate of 20 ° C./min in a nitrogen gas stream (30 ml / min). After further rapid cooling, the temperature is raised again to 400 ° C. at a rate of temperature increase of 20 ° C./min in a nitrogen gas stream (30 ml / min). The temperature at the midpoint of the step difference of the baseline that has changed in a step shape (where the specific heat has changed to half) is the glass transition temperature (Tg), and the temperature of the exothermic peak that appears thereafter is the crystallization temperature. The calorific value is obtained from the area of the region surrounded by the exothermic peak and the baseline, and is defined as the crystallization calorific value.

The component (A) contained in the radiation-sensitive composition is sublimated under normal pressure at 100 or less, preferably 120 ° C. or less, more preferably 130 ° C. or less, further preferably 140 ° C. or less, particularly preferably 150 ° C. or less. It is preferable that the property is low. The low sublimation property means that in thermogravimetric analysis, the weight loss when held at a predetermined temperature for 10 minutes is 10% or less, preferably 5% or less, more preferably 3% or less, still more preferably 1% or less, particularly preferably. Indicates 0.1% or less. Since the sublimation property is low, it is possible to prevent exposure apparatus from being contaminated by outgas during exposure. In addition, a good pattern shape can be obtained with low roughness.

Component (A) contained in the radiation-sensitive composition is propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone (CHN), cyclopentanone (CPN), 2-heptanone, anisole, A solvent selected from butyl acetate, ethyl propionate and ethyl lactate and having the highest solubility in component (A) at 23 ° C., preferably 1% by mass or more, more preferably 5% by mass or more, More preferably 10% by mass or more, particularly preferably selected from PGMEA, PGME, CHN, and (A) 20% by mass or more at 23 ° C. in a solvent having the highest solubility in the resist base material, Particularly preferably, it dissolves in PGMEA at 20 ° C. or more at 23 ° C. By satisfying the above conditions, the semiconductor manufacturing process can be used in actual production.

[Diazonaphthoquinone Photoactive Compound (B)]
The diazonaphthoquinone photoactive compound (B) contained in the radiation-sensitive composition is a diazonaphthoquinone substance containing a polymeric and non-polymeric diazonaphthoquinone photoactive compound. Generally, in a positive resist composition, a photosensitive component As long as it is used as (photosensitive agent), one or two or more kinds can be arbitrarily selected and used without particular limitation.

As such a photosensitizer, it was obtained by reacting naphthoquinone diazide sulfonic acid chloride, benzoquinone diazide sulfonic acid chloride, etc. with a low molecular compound or a high molecular compound having a functional group capable of condensation reaction with these acid chlorides. Compounds are preferred. Here, the functional group capable of condensing with acid chloride is not particularly limited, and examples thereof include a hydroxyl group and an amino group, and a hydroxyl group is particularly preferable. The compound capable of condensing with an acid chloride containing a hydroxyl group is not particularly limited. For example, hydroquinone, resorcin, 2,4-dihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, 2,4,4′-trihydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2,2 ′, 3,4,6′- Hydroxybenzophenones such as pentahydroxybenzophenone, hydroxyphenylalkanes such as bis (2,4-dihydroxyphenyl) methane, bis (2,3,4-trihydroxyphenyl) methane, bis (2,4-dihydroxyphenyl) propane 4,4 ', 3 ", 4" -tetrahydroxy-3,5, Hydroxytriphenylmethanes such as', 5'-tetramethyltriphenylmethane, 4,4 ', 2 ", 3", 4 "-pentahydroxy-3,5,3', 5'-tetramethyltriphenylmethane And so on.
Examples of acid chlorides such as naphthoquinone diazide sulfonic acid chloride and benzoquinone diazide sulfonic acid chloride include 1,2-naphthoquinone diazide-5-sulfonyl chloride, 1,2-naphthoquinone diazide-4-sulfonyl chloride, and the like. Can be mentioned.

The radiation-sensitive composition is prepared by, for example, dissolving each component in a solvent at the time of use to obtain a uniform solution, and then filtering, for example, with a filter having a pore size of about 0.2 μm as necessary. Is preferred.

[Characteristics of radiation-sensitive composition]
The radiation-sensitive composition can form an amorphous film by spin coating. Further, it can be applied to a general semiconductor manufacturing process. Depending on the type of developer used, either a positive resist pattern or a negative resist pattern can be created.
In the case of a positive resist pattern, the dissolution rate of the amorphous film formed by spin-coating the radiation-sensitive composition in a developing solution at 23 ° C. is preferably 5 Å / sec or less, more preferably 0.05 to 5 Å / sec. 0.0005 to 5 cm / sec is more preferable. When the dissolution rate is 5 kg / sec or less, the resist is insoluble in the developer and can be a resist. In addition, when the dissolution rate is 0.0005 kg / sec or more, the resolution may be improved. This is due to the contrast of the interface between the exposed portion dissolved in the developer and the unexposed portion not dissolved in the developer due to a change in the solubility of the resin containing the compound and resin of the present embodiment as constituents before and after exposure. Is estimated to be larger. Further, there is an effect of reducing LER and reducing defects.
In the case of a negative resist pattern, the dissolution rate of the amorphous film formed by spin-coating the radiation-sensitive composition in a developing solution at 23 ° C. is preferably 10 Å / sec or more. When the dissolution rate is 10 Å / sec or more, it is easily dissolved in a developer and more suitable for a resist. Further, when the dissolution rate is 10 Å / sec or more, the resolution may be improved. This is presumed to be because the micro surface portion of the resin containing the compound and resin of the present embodiment described above as constituent components dissolves and LER is reduced. There is also an effect of reducing defects.
The dissolution rate can be determined by immersing an amorphous film in a developing solution for a predetermined time at 23 ° C., and measuring the film thickness before and after the immersion by a known method such as visual observation, an ellipsometer, or a QCM method.

In the case of a positive resist pattern, the amorphous film formed by spin-coating the radiation-sensitive composition is irradiated with radiation such as krf excimer laser, extreme ultraviolet light, electron beam or X-ray, or at 20 to 500 ° C. The dissolution rate of the exposed portion after heating in the developing solution at 23 ° C. is preferably 10 Å / sec or more, more preferably 10 to 10000 Å / sec, and further preferably 100 to 1000 Å / sec. When the dissolution rate is 10 Å / sec or more, it is easily dissolved in a developer and more suitable for a resist. In addition, when the dissolution rate is 10000 kg / sec or less, the resolution may be improved. This is presumed to be because the micro surface portion of the resin containing the compound and resin of the present embodiment described above as constituent components dissolves and LER is reduced. There is also an effect of reducing defects.
In the case of a negative resist pattern, the amorphous film formed by spin-coating the radiation-sensitive composition is irradiated with radiation such as krf excimer laser, extreme ultraviolet light, electron beam or X-ray, or at 20 to 500 ° C. The dissolution rate of the exposed portion after heating with respect to the developer at 23 ° C. is preferably 5 K / sec or less, more preferably 0.05 to 5 K / sec, and further preferably 0.0005 to 5 K / sec. When the dissolution rate is 5 kg / sec or less, the resist is insoluble in the developer and can be a resist. In addition, when the dissolution rate is 0.0005 kg / sec or more, the resolution may be improved. This is presumed that the contrast of the unexposed portion that dissolves in the developer and the interface between the exposed portion that does not dissolve in the developer increases due to the change in solubility of the compound and resin of the present embodiment before and after exposure. Is done. Further, there is an effect of reducing LER and reducing defects.

[Combination ratio of each component]
In the radiation-sensitive composition, the content of the component (A) is the solid component total weight (component (A), diazonaphthoquinone photoactive compound (B) and other components (D), etc.) The total of the components, the same shall apply hereinafter) is preferably 1 to 99% by mass, more preferably 5 to 95% by mass, still more preferably 10 to 90% by mass, and particularly preferably 25 to 75% by mass. . When the content of the component (A) is within the above range, the radiation-sensitive composition can obtain a pattern with high sensitivity and small roughness.

In the radiation-sensitive composition, the content of the diazonaphthoquinone photoactive compound (B) is arbitrarily selected from the total weight of the solid component (component (A), diazonaphthoquinone photoactive compound (B), and other components (D)). The total of solid components used, the same shall apply hereinafter) is preferably 1 to 99% by mass, more preferably 5 to 95% by mass, still more preferably 10 to 90% by mass, and particularly preferably 25 to 75%. % By mass. When the content of the diazonaphthoquinone photoactive compound (B) is within the above range, the radiation-sensitive composition of the present embodiment can obtain a highly sensitive and small roughness pattern.

[Other components (D)]
The radiation-sensitive composition includes an acid generator, an acid cross-linking agent, and a component other than the component (A) and the diazonaphthoquinone photoactive compound (B) as necessary, as long as the object of the present invention is not impaired. Acid diffusion control agent, dissolution accelerator, dissolution control agent, sensitizer, surfactant, organic carboxylic acid or phosphorus oxo acid or derivative thereof, heat and / or photocuring catalyst, polymerization inhibitor, flame retardant, filler , Coupling agents, thermosetting resins, photocurable resins, dyes, pigments, thickeners, lubricants, antifoaming agents, leveling agents, UV absorbers, surfactants, colorants, nonionic surfactants, etc. Various additives can be added alone or in combination of two or more. In addition, in this specification, another component (D) may be called arbitrary component (D).

In the radiation-sensitive composition, the blending ratio of each component (component (A) / diazonaphthoquinone photoactive compound (B) / arbitrary component (D)) is mass% based on the solid component,
Preferably 1 to 99/99 to 1/0 to 98,
More preferably 5 to 95/95 to 5/0 to 49,
More preferably, 10 to 90/90 to 10/0 to 10,
Particularly preferably 20 to 80/80 to 20/0 to 5,
Most preferably, it is 25 to 75/75 to 25/0.
The blending ratio of each component is selected from each range so that the sum is 100% by mass. The radiation-sensitive composition is excellent in performance such as sensitivity and resolution in addition to roughness when the blending ratio of each component is in the above range.

The radiation-sensitive composition may contain compounds and resins other than the present embodiment as long as the object of the present invention is not impaired. Examples of such resins include novolak resins, polyvinylphenols, polyacrylic acid, polyvinyl alcohol, styrene-maleic anhydride resins, and polymers containing acrylic acid, vinyl alcohol, or vinyl phenol as monomer units, or these resins. Derivatives and the like. Although the compounding quantity of these resin is suitably adjusted according to the kind of component (A) to be used, 30 mass parts or less are preferable with respect to 100 mass parts of components (A), More preferably, 10 mass parts or less More preferably, it is 5 parts by mass or less, and particularly preferably 0 part by mass.

[Method of forming resist pattern]
The method for forming a resist pattern according to the present embodiment includes forming a photoresist layer using the above-described composition of the present embodiment (the resist composition or the radiation sensitive composition), and then a predetermined region of the photoresist layer. And a step of performing development by irradiating with radiation. Specifically, the method for forming a resist pattern according to the present embodiment includes a step of forming a resist film on a substrate, a step of exposing the formed resist film, and developing the resist film to form a resist pattern. A process. The resist pattern in this embodiment can also be formed as an upper layer resist in a multilayer process.

The method for forming the resist pattern is not particularly limited, and examples thereof include the following methods. First, a resist film is formed by applying the resist composition or radiation sensitive composition on a conventionally known substrate by a coating means such as spin coating, cast coating, roll coating or the like. The conventionally known substrate is not particularly limited, and examples thereof include a substrate for electronic components and a substrate on which a predetermined wiring pattern is formed. More specifically, a silicon substrate, a metal substrate such as copper, chromium, iron, and aluminum, a glass substrate, and the like can be given. Examples of the wiring pattern material include copper, aluminum, nickel, and gold. Further, if necessary, an inorganic and / or organic film may be provided on the substrate. An inorganic antireflection film (inorganic BARC) is an example of the inorganic film. Examples of the organic film include an organic antireflection film (organic BARC). Surface treatment with hexamethylene disilazane or the like may be performed.

Next, the coated substrate is heated as necessary. The heating conditions vary depending on the composition of the resist composition, but are preferably 20 to 250 ° C., more preferably 20 to 150 ° C. Heating may improve the adhesion of the resist to the substrate, which is preferable. Next, the resist film is exposed to a desired pattern with any radiation selected from the group consisting of visible light, ultraviolet light, excimer laser, electron beam, extreme ultraviolet light (EUV), X-ray, and ion beam. The exposure conditions and the like are appropriately selected according to the composition of the resist composition or the radiation sensitive composition. In this embodiment, in order to stably form a high-precision fine pattern in exposure, heating is preferably performed after radiation irradiation. The heating conditions vary depending on the composition of the resist composition or the radiation-sensitive composition, but are preferably 20 to 250 ° C, more preferably 20 to 150 ° C.

Next, a predetermined resist pattern is formed by developing the exposed resist film with a developer. As the developer, it is preferable to select a solvent having a solubility parameter (SP value) close to that of the compound and resin of the above-described embodiment to be used, ketone solvent, ester solvent, alcohol solvent, amide solvent. A polar solvent such as a solvent, an ether solvent, a hydrocarbon solvent, or an alkaline aqueous solution can be used.

Examples of the ketone solvent include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone. Methyl isobutyl ketone, acetyl acetone, acetonyl acetone, ionone, diacetyl alcohol, acetyl carbinol, acetophenone, methyl naphthyl ketone, isophorone, propylene carbonate, and the like.

Examples of ester solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3 -Ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate and the like.

Examples of the alcohol solvent include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol (2-propanol), n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, Alcohols such as 4-methyl-2-pentanol, n-heptyl alcohol, n-octyl alcohol, n-decanol, glycol solvents such as ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl Ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene Glycol monoethyl ether, and triethylene glycol monoethyl ether and methoxymethyl butanol.

Examples of the ether solvent include dioxane, tetrahydrofuran and the like in addition to the glycol ether solvent.

Examples of amide solvents include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoric triamide, 1,3-dimethyl-2-imidazolidinone and the like. Can be used.

Examples of the hydrocarbon solvent include aromatic hydrocarbon solvents such as toluene and xylene, and aliphatic hydrocarbon solvents such as pentane, hexane, octane and decane.

A plurality of the above-mentioned solvents may be mixed, or may be used by mixing with a solvent other than the above or water within a range having performance. However, in order to fully achieve the effects of the present invention, the water content of the developer as a whole is less than 70% by mass, preferably less than 50% by mass, and more preferably less than 30% by mass. Preferably, it is more preferably less than 10% by mass, and it is particularly preferable that it contains substantially no water. That is, the content of the organic solvent with respect to the developer is 30% by mass to 100% by mass, preferably 50% by mass to 100% by mass, and preferably 70% by mass to 100% by mass with respect to the total amount of the developer. More preferably, it is 90 mass% or less, More preferably, it is 90 mass% or more and 100 mass% or less, It is especially preferable that it is 95 mass% or more and 100 mass% or less.

Examples of the alkaline aqueous solution include alkaline compounds such as mono-, di- or trialkylamines, mono-, di- or trialkanolamines, heterocyclic amines, tetramethylammonium hydroxide (TMAH), and choline. Can be mentioned.

In particular, the developer is a developer containing at least one solvent selected from ketone solvents, ester solvents, alcohol solvents, amide solvents and ether solvents, such as resist pattern resolution and roughness. It is preferable for improving the resist performance.

The vapor pressure of the developer is preferably 5 kpa or less, more preferably 3 kpa or less, and particularly preferably 2 kpa or less at 20 ° C. By setting the vapor pressure of the developing solution to 5 kpa or less, evaporation of the developing solution on the substrate or in the developing cup is suppressed, temperature uniformity in the wafer surface is improved, and as a result, dimensional uniformity in the wafer surface is improved. It improves.

Specific examples having a vapor pressure of 5 kpa or less include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 4-heptanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl Ketone solvents such as isobutyl ketone, butyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methoxy Esters such as butyl acetate, 3-methyl-3-methoxybutyl acetate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate Solvent, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, 4-methyl-2-pentanol, n-heptyl alcohol, n-octyl Alcohol solvents such as alcohol and n-decanol, glycol solvents such as ethylene glycol, diethylene glycol and triethylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl Glycol ethers such as ether, triethylene glycol monoethyl ether, methoxymethylbutanol Agent, ether solvents such as tetrahydrofuran, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, amide solvents of N, N-dimethylformamide, aromatic hydrocarbon solvents such as toluene and xylene, octane, decane Aliphatic hydrocarbon solvents such as

Specific examples having a vapor pressure of 2 kpa or less, which is a particularly preferable range, include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 4-heptanone, 2-hexanone, diisobutylketone, cyclohexanone, methylcyclohexanone. , Ketone solvents such as phenylacetone, butyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3- Methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, ester solvents such as ethyl lactate, butyl lactate and propyl lactate, n-butyl alcohol alcohol solvents such as sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, 4-methyl-2-pentanol, n-heptyl alcohol, n-octyl alcohol, n-decanol, ethylene glycol, diethylene glycol , Glycol solvents such as triethylene glycol, and glycols such as ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methoxymethyl butanol Ether solvents, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethyl Le formamide amide solvent, aromatic hydrocarbon solvents such as xylene, octane, aliphatic hydrocarbon solvents decane.

An appropriate amount of a surfactant can be added to the developer as necessary.
The surfactant is not particularly limited, and for example, ionic or nonionic fluorine-based and / or silicon-based surfactants can be used. Examples of these fluorine and / or silicon surfactants include, for example, JP-A-62-36663, JP-A-61-226746, JP-A-61-226745, JP-A-62-170950. JP-A-63-34540, JP-A-7-230165, JP-A-8-62834, JP-A-9-54432, JP-A-9-5988, US Pat. No. 5,405,720, Mention may be made of the surfactants described in US Pat. Nos. 5,360,692, 5,529,881, 5,296,330, 5,436,098, 5,576,143, 5,294,511, and 5,824,451. Preferably, it is a nonionic surfactant. Although it does not specifically limit as a nonionic surfactant, It is more preferable to use a fluorochemical surfactant or a silicon-type surfactant.

The amount of the surfactant used is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, and more preferably 0.01 to 0.5% by mass with respect to the total amount of the developer.

As a developing method, for example, a method in which a substrate is immersed in a tank filled with a developer for a certain period of time (dip method), a method in which the developer is raised on the surface of the substrate by surface tension and is left stationary for a certain time (paddle) Method), a method of spraying the developer on the substrate surface (spray method), a method of continuously applying the developer while scanning the developer application nozzle at a constant speed on a substrate rotating at a constant speed (dynamic dispensing method) ) Etc. can be applied. The time for developing the pattern is not particularly limited, but is preferably 10 seconds to 90 seconds.

In addition, after the step of developing, a step of stopping development may be performed while substituting with another solvent.

After the development, it is preferable to include a step of washing with a rinse solution containing an organic solvent.

The rinsing liquid used in the rinsing step after development is not particularly limited as long as the resist pattern cured by crosslinking is not dissolved, and a solution or water containing a general organic solvent can be used. As the rinsing liquid, it is preferable to use a rinsing liquid containing at least one organic solvent selected from hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents and ether solvents. . More preferably, after the development, a cleaning step is performed using a rinse solution containing at least one organic solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, and amide solvents. Even more preferably, after the development, a washing step is performed using a rinse solution containing an alcohol solvent or an ester solvent. Even more preferably, after the development, a step of washing with a rinsing solution containing a monohydric alcohol is performed. Particularly preferably, after the development, a washing step is performed using a rinsing liquid containing a monohydric alcohol having 5 or more carbon atoms. The time for rinsing the pattern is not particularly limited, but is preferably 10 seconds to 90 seconds.

Here, examples of the monohydric alcohol used in the rinsing step after development include linear, branched, and cyclic monohydric alcohols, and specifically, 1-butanol, 2-butanol, 3-methyl- 1-butanol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 1-hexanol, 4-methyl-2-pentanol, 1-heptanol, 1-octanol, 2-hexanol, cyclopentanol, 2- Heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol and the like can be used. Particularly preferable monohydric alcohols having 5 or more carbon atoms include 1-hexanol, 2-hexanol, 4 -Methyl-2-pentanol, 1-pentanol, 3-methyl-1-butanol, etc. It is possible to have.

A plurality of the above components may be mixed, or may be used by mixing with an organic solvent other than the above.

The water content in the rinse liquid is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 3% by mass or less. By setting the water content to 10% by mass or less, better development characteristics can be obtained.

The vapor pressure of the rinsing solution used after development is preferably 0.05 kpa or more and 5 kpa or less at 20 ° C., more preferably 0.1 kpa or more and 5 kpa or less, and most preferably 0.12 kpa or more and 3 kpa or less. By setting the vapor pressure of the rinsing liquid to 0.05 kpa or more and 5 kpa or less, the temperature uniformity in the wafer surface is further improved, and further, the swelling due to the penetration of the rinsing liquid is further suppressed, and the dimensions in the wafer surface are reduced. Uniformity is improved.

An appropriate amount of a surfactant can be added to the rinse solution.

In the rinsing step, the developed wafer is cleaned using a rinsing solution containing the organic solvent. The method of the cleaning treatment is not particularly limited. For example, a method of continuously applying the rinse liquid onto the substrate rotating at a constant speed (rotary coating method), or immersing the substrate in a tank filled with the rinse liquid for a certain period of time. A method (dip method), a method of spraying a rinsing liquid onto the substrate surface (spray method), etc. can be applied. Among these, a cleaning process is performed by a spin coating method, and after cleaning, the substrate is rotated at a speed of 2000 rpm to 4000 rpm. It is preferable to rotate and remove the rinse liquid from the substrate.

After forming the resist pattern, the pattern wiring board is obtained by etching. The etching can be performed by a known method such as dry etching using plasma gas and wet etching using an alkali solution, a cupric chloride solution, a ferric chloride solution, or the like.

Plating can be performed after forming the resist pattern. Examples of the plating method include copper plating, solder plating, nickel plating, and gold plating.

The residual resist pattern after etching can be peeled off with an organic solvent. Examples of the organic solvent include PGMEA (propylene glycol monomethyl ether acetate), PGME (propylene glycol monomethyl ether), EL (ethyl lactate), and the like. Examples of the peeling method include a dipping method and a spray method. The wiring board on which the resist pattern is formed may be a multilayer wiring board or may have a small diameter through hole.

The wiring substrate obtained in this embodiment can also be formed by a method of depositing a metal in a vacuum after forming a resist pattern and then dissolving the resist pattern with a solution, that is, a lift-off method.

[Film-forming composition for lithography for lower layer applications]
The composition of this embodiment can also be used as a film forming composition for lithography for use in lower layer films (hereinafter also referred to as a lower layer film forming material). The lower layer film-forming material contains at least one substance selected from the group consisting of the compound and resin of the above-described embodiment. In this embodiment, the substance is preferably 1 to 100% by mass, more preferably 10 to 100% by mass, and more preferably 50 to 100% by mass in the lower layer film-forming material from the viewpoints of coatability and quality stability. % Is more preferable, and 100% by mass is particularly preferable.

The lower layer film forming material can be applied to a wet process and has excellent heat resistance and etching resistance. Furthermore, since the material for forming the lower layer film uses the substance, it is possible to form a lower layer film that suppresses deterioration of the film during high-temperature baking and has excellent etching resistance against oxygen plasma etching and the like. Furthermore, since the lower layer film forming material is also excellent in adhesion to the resist layer, an excellent resist pattern can be obtained. The underlayer film forming material may contain a known underlayer film forming material for lithography and the like as long as the effects of the present invention are not impaired.

[solvent]
The lower layer film forming material may contain a solvent. As a solvent used for the lower layer film forming material, a known one can be appropriately used as long as it can dissolve at least the above-described substances.

Specific examples of the solvent include, but are not limited to, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; cellosolv solvents such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate; ethyl lactate and methyl acetate Ester solvents such as ethyl acetate, butyl acetate, isoamyl acetate, ethyl lactate, methyl methoxypropionate, methyl hydroxyisobutyrate; alcohol solvents such as methanol, ethanol, isopropanol, 1-ethoxy-2-propanol; toluene, xylene And aromatic hydrocarbons such as anisole. These solvents can be used alone or in combination of two or more.

Among these solvents, cyclohexanone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, methyl hydroxyisobutyrate and anisole are particularly preferable from the viewpoint of safety.

The content of the solvent is not particularly limited, but from the viewpoint of solubility and film formation, it is preferably 100 to 10,000 parts by mass with respect to 100 parts by mass of the lower layer film-forming material, and 200 to 5, The amount is more preferably 000 parts by mass, and even more preferably 200 to 1,000 parts by mass.

[Crosslinking agent]
The lower layer film-forming material may contain a crosslinking agent as necessary from the viewpoint of suppressing intermixing. Although the crosslinking agent which can be used in this embodiment is not specifically limited, For example, the acid crosslinking agent as described in international publication 2013/024779 can be used.

Specific examples of the crosslinking agent that can be used in this embodiment include, for example, phenol compounds, epoxy compounds, cyanate compounds, amino compounds, benzoxazine compounds, acrylate compounds, melamine compounds, guanamine compounds, glycoluril compounds, urea compounds, isocyanates. Examples thereof include, but are not limited to, compounds and azide compounds. These crosslinking agents can be used alone or in combination of two or more. Among these, a benzoxazine compound, an epoxy compound, or a cyanate compound is preferable, and a benzoxazine compound is more preferable from the viewpoint of improving etching resistance.

The active group possessed by these crosslinking agents (phenolic hydroxyl group, epoxy group, cyanate group, amino group, or phenolic hydroxyl group formed by opening the alicyclic portion of benzoxazine) is the carbon-carbon dioxygen constituting the maleimide group. In addition to crosslinking by addition reaction with a heavy bond, two carbon-carbon double bonds of the bismaleimide compound of this embodiment are polymerized and crosslinked.

As the epoxy compound, known compounds can be used and selected from those having two or more epoxy groups in one molecule. For example, bisphenol A, bisphenol F, 3,3 ′, 5,5′-tetramethyl-bisphenol F, bisphenol S, fluorene bisphenol, 2,2′-biphenol, 3,3 ′, 5,5′-tetramethyl- Epoxidized dihydric phenols such as 4,4'-dihydroxybiphenol, resorcin, naphthalenediols, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane Tris (2,3-epoxypropyl) isocyanurate, trimethylol methane triglycidyl ether, trimethylol propane triglycidyl ether, triethylol ethane triglycidyl ether, phenol novolac, o-cresol novolac, etc. Epoch Epoxides of co-condensation resins of dicyclopentadiene and phenols, epoxides of phenol aralkyl resins synthesized from phenols and paraxylylene dichloride, biphenyl aralkyls synthesized from phenols and bischloromethylbiphenyl, etc. And epoxidized products of naphthol aralkyl resins synthesized from naphthols and paraxylylene dichloride, and the like. These epoxy resins may be used alone or in combination of two or more. From the viewpoint of heat resistance and solubility, an epoxy resin that is solid at room temperature such as an epoxy resin obtained from phenol aralkyl resins or biphenyl aralkyl resins is preferable.

The cyanate compound is not particularly limited as long as it is a compound having two or more cyanate groups in one molecule, and a known one can be used. In the present embodiment, as a preferred cyanate compound, one having a structure in which a hydroxyl group of a compound having two or more hydroxyl groups in one molecule is substituted with a cyanate group can be mentioned. Further, the cyanate compound preferably has an aromatic group, and a cyanate compound having a structure in which the cyanate group is directly connected to the aromatic group can be suitably used. Examples of such cyanate compounds include bisphenol A, bisphenol F, bisphenol M, bisphenol P, bisphenol E, phenol novolac resin, cresol novolac resin, dicyclopentadiene novolac resin, tetramethylbisphenol F, bisphenol A novolac resin, bromine. Bisphenol A, brominated phenol novolak resin, trifunctional phenol, tetrafunctional phenol, naphthalene type phenol, biphenyl type phenol, phenol aralkyl resin, biphenyl aralkyl resin, naphthol aralkyl resin, dicyclopentadiene aralkyl resin, alicyclic phenol, phosphorus The thing of the structure which substituted hydroxyl groups, such as containing phenol, by the cyanate group is mentioned. These cyanate compounds may be used alone or in combination of two or more. Further, the cyanate compound described above may be in any form of a monomer, an oligomer and a resin.

Examples of the amino compound include m-phenylenediamine, p-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylpropane, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 3 , 3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl Sulfide, 3,3′-diaminodiphenyl sulfide, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene Bis [4- (4-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 4,4′-bis (4-aminophenoxy) biphenyl, 4,4′-bis (3-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] ether, bis [4- (3-amino Phenoxy) phenyl] ether, 9,9-bis (4-aminophenyl) fluorene, 9,9-bis (4-amino-3-chlorophenyl) fluorene, 9,9-bis (4-amino-3-fluorophenyl) Fluorene, O-tolidine, m-tolidine, 4,4'-diaminobenzanilide, 2,2'-bis (trifluoromethyl) -4,4'-diaminobifu Alkenyl, 4-aminophenyl-4-amino benzoate, 2- (4-aminophenyl) -6-amino-benzoxazole and the like. Among these, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylpropane, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl ether, 4,4′- Diaminodiphenyl sulfone, 3,3′-diaminodiphenyl sulfone, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) Benzene, 1,3-bis (3-aminophenoxy) benzene, bis [4- (4-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2 -Bis [4- (3-aminophenoxy) phenyl] propane, 4,4′-bis (4-aminophenoxy) Aromatic amines such as biphenyl, 4,4′-bis (3-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] ether, bis [4- (3-aminophenoxy) phenyl] ether , Diaminocyclohexane, diaminodicyclohexylmethane, dimethyl-diaminodicyclohexylmethane, tetramethyl-diaminodicyclohexylmethane, diaminodicyclohexylpropane, diaminobicyclo [2.2.1] heptane, bis (aminomethyl) -bicyclo [2.2.1] Cycloaliphatic amines such as heptane, 3 (4), 8 (9) -bis (aminomethyl) tricyclo [5.2.1.02,6] decane, 1,3-bisaminomethylcyclohexane, isophoronediamine, Ethylenediamine, hexamethylenediamine, o Data diamine, decamethylene diamine, diethylene triamine, aliphatic amines such as triethylenetetramine, and the like.

Examples of the benzoxazine compound include Pd-type benzoxazine obtained from bifunctional diamines and monofunctional phenols, and Fa-type benzoxazine obtained from monofunctional diamines and bifunctional phenols. It is done.

Specific examples of the melamine compound include hexamethylol melamine, hexamethoxymethyl melamine, a compound in which 1 to 6 methylol groups of hexamethylol melamine are methoxymethylated or a mixture thereof, hexamethoxyethyl melamine, hexaacyloxymethyl. Examples thereof include compounds in which 1 to 6 methylol groups of melamine and hexamethylolmelamine are acyloxymethylated, or a mixture thereof.

Specific examples of the guanamine compound include, for example, tetramethylolguanamine, tetramethoxymethylguanamine, a compound in which 1 to 4 methylol groups of tetramethylolguanamine are methoxymethylated, or a mixture thereof, tetramethoxyethylguanamine, tetraacyloxyguanamine And compounds in which 1 to 4 methylol groups of tetramethylolguanamine are acyloxymethylated, or a mixture thereof.

Specific examples of the glycoluril compound include, for example, tetramethylol glycoluril, tetramethoxyglycoluril, tetramethoxymethylglycoluril, a compound in which 1 to 4 methylol groups of tetramethylolglycoluril are methoxymethylated, or a mixture thereof, Examples thereof include compounds in which 1 to 4 methylol groups of tetramethylol glycoluril are acyloxymethylated, or mixtures thereof.

Specific examples of the urea compound include tetramethylol urea, tetramethoxymethyl urea, a compound in which 1 to 4 methylol groups of tetramethylol urea are methoxymethylated or a mixture thereof, tetramethoxyethyl urea, and the like.

In this embodiment, a crosslinking agent having at least one allyl group may be used from the viewpoint of improving the crosslinkability. Specific examples of the crosslinking agent having at least one allyl group include 2,2-bis (3-allyl-4-hydroxyphenyl) propane, 1,1,1,3,3,3-hexafluoro-2,2 -Bis (3-allyl-4-hydroxyphenyl) propane, bis (3-allyl-4-hydroxyphenyl) sulfone, bis (3-allyl-4-hydroxyphenyl) sulfide, bis (3-allyl-4-hydroxyphenyl) ) Allylphenols such as ether, 2,2-bis (3-allyl-4-cyanatophenyl) propane, 1,1,1,3,3,3-hexafluoro-2,2-bis (3 -Allyl-4-cyanatophenyl) propane, bis (3-allyl-4-cyanatosiphenyl) sulfone, bis (3-allyl-4-cyanatophenyl) sulfide, bis (3- Examples include allyl cyanates such as (ryl-4-cyanatophenyl) ether, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, triallyl isocyanurate, trimethylolpropane diallyl ether, pentaerythritol allyl ether, and the like. It is not limited to what was done. These may be used alone or as a mixture of two or more. Among these, 2,2-bis (3-allyl-4-hydroxyphenyl) propane, 1,1,1,3,3,3-hexafluoro-2,2-bis (3-allyl-4-hydroxyphenyl) Allylphenols such as propane, bis (3-allyl-4-hydroxyphenyl) sulfone, bis (3-allyl-4-hydroxyphenyl) sulfide, bis (3-allyl-4-hydroxyphenyl) ether are preferred. .

The content of the crosslinking agent in the composition is not particularly limited, but is preferably 0.1 to 100 parts by mass with respect to 100 parts by mass of the total composition including the above-described compound or resin. The amount is more preferably part by mass, and further preferably 10 to 40 parts by mass. By making the content of the crosslinking agent in the above range, the occurrence of the mixing phenomenon with the resist layer tends to be suppressed, the antireflection effect is enhanced, and the film forming property after crosslinking tends to be enhanced. .

[Crosslinking accelerator]
In the lower layer film forming material of the present embodiment, a crosslinking accelerator for accelerating crosslinking and curing reaction can be used as necessary.

The crosslinking accelerator is not particularly limited as long as it promotes crosslinking and curing reaction, and examples thereof include amines, imidazoles, organic phosphines, and Lewis acids. These crosslinking accelerators can be used alone or in combination of two or more. Among these, imidazoles or organic phosphines are preferable, and imidazoles are more preferable from the viewpoint of lowering the crosslinking temperature.

Examples of the crosslinking accelerator include, but are not limited to, for example, 1,8-diazabicyclo (5,4,0) undecene-7, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylamino). Tertiary amines such as methyl) phenol, 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole, 2,4,5- Imidazoles such as triphenylimidazole, organic phosphines such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, phenylphosphine, tetraphenylphosphonium tetraphenylborate, teto Tetraphenyl such as phenylphosphonium / ethyltriphenylborate, tetrabutylphosphonium / tetrabutylborate, etc., 2-ethyl-4-methylimidazole / tetraphenylborate, N-methylmorpholine / tetraphenylborate, etc. Examples thereof include boron salts.

The content of the crosslinking accelerator is usually preferably 0.1 to 10 parts by mass when the total mass of the composition is 100 parts by mass, and more preferably from the viewpoint of ease of control and economy. Of 0.1 to 5 parts by weight, more preferably 0.1 to 3 parts by weight.

[Radical polymerization initiator]
In the lower layer film forming material of the present embodiment, a radical polymerization initiator can be blended as necessary. The radical polymerization initiator may be a photopolymerization initiator that initiates radical polymerization with light or a thermal polymerization initiator that initiates radical polymerization with heat. The radical polymerization initiator can be, for example, at least one selected from the group consisting of ketone photopolymerization initiators, organic peroxide polymerization initiators, and azo polymerization initiators.

Such a radical polymerization initiator is not particularly limited, and those conventionally used can be appropriately employed. For example, 1-hydroxycyclohexyl phenyl ketone, benzyl dimethyl ketal, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2 -Methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methylpropan-1-one, 2 , 4,6-Trimethylbenzoyl-diphenyl-phosphine oxide, ketone photopolymerization initiators such as bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, methylcyclohexanone peroxide Oxide, methyl acetoacetate Oxide, acetyl acetate peroxide, 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) -cyclohexane, 1,1-bis ( t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) -2-methylcyclohexane, 1,1-bis (t-butylperoxy) -cyclohexane, 1 , 1-bis (t-butylperoxy) cyclododecane, 1,1-bis (t-butylperoxy) butane, 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane, p -Menthane hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutylhydride Peroxide, cumene hydroperoxide, t-hexyl hydroperoxide, t-butyl hydroperoxide, α, α'-bis (t-butylperoxy) diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2 , 5-bis (t-butylperoxy) hexane, t-butylcumyl peroxide, di-t-butylperoxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3, Isobutyryl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearoyl peroxide, succinic acid peroxide, m-toluoylbenzoyl peroxide, benzoyl peroxide, di-n -Propyl par Xydicarbonate, diisopropylperoxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, di-2-ethoxyethylperoxydicarbonate, di-2-ethoxyhexylperoxydicarbonate, di-3- Methoxybutyl peroxydicarbonate, di-s-butylperoxydicarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, α, α'-bis (neodecanoylperoxy) diisopropylbenzene, kumi Luperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, 1-cyclohexyl-1-methylethylperoxyneodecanoate, t-hexylperoxyneodecanoate, t-Butylperoxyneodecanoe , T-hexyl peroxypivalate, t-butyl peroxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5- Bis (2-ethylhexanoylperoxy) hexanoate, 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2 -Ethylhexanoate, t-hexylperoxyisopropyl monocarbonate, t-butylperoxyisobutyrate, t-butylperoxymalate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butyl peroxylaurate, t-butyl peroxyisopropyl monocarbonate, t-butyl Ruperoxy-2-ethylhexyl monocarbonate, t-butylperoxyacetate, t-butylperoxy-m-toluylbenzoate, t-butylperoxybenzoate, bis (t-butylperoxy) isophthalate, 2,5-dimethyl- 2,5-bis (m-toluylperoxy) hexane, t-hexylperoxybenzoate, 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane, t-butylperoxyallyl monocarbonate, t- Organic peroxide polymerization initiators such as butyltrimethylsilyl peroxide, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 2,3-dimethyl-2,3-diphenylbutane It is done.

2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile, 1-[(1-cyano-1-methylethyl) azo] formamide, 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis ( 2-methylpropionamidine) dihydrochloride, 2,2′-azobis (2-methyl-N-phenylpropionamidine) dihydrochloride, 2,2′-azobis [N- (4-chlorophenyl) -2-methylpropionamidine] Dihydride chloride, 2,2′-azobis [N- (4-hydrophenyl) -2-methylpropionamidine] dihydrochloride, 2, '-Azobis [2-methyl-N- (phenylmethyl) propionamidine] dihydrochloride, 2,2'-azobis [2-methyl-N- (2-propenyl) propionamidine] dihydrochloride, 2,2'-azobis [N- (2-hydroxyethyl) -2-methylpropionamidine] dihydrochloride, 2,2′-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] dihydrochloride, 2,2 ′ -Azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis [2- (4,5,6,7-tetrahydro-1H-1,3-diazepin-2-yl ) Propane] dihydrochloride, 2,2′-azobis [2- (3,4,5,6-tetrahydropyrimidin-2-yl) propane] dihydrochloride 2,2′-azobis [2- (5-hydroxy-3,4,5,6-tetrahydropyrimidin-2-yl) propane] dihydrochloride, 2,2′-azobis [2- [1- (2-hydroxy Ethyl) -2-imidazolin-2-yl] propane] dihydrochloride, 2,2′-azobis [2- (2-imidazolin-2-yl) propane], 2,2′-azobis [2-methyl-N— [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide], 2,2′-azobis [2-methyl-N- [1,1-bis (hydroxymethyl) ethyl] propionamide], 2 , 2'-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], 2,2'-azobis (2-methylpropionamide), 2,2'-azobis (2,4,4-tri Methylpentane), 2,2′-azobis (2-methylpropane), dimethyl-2,2-azobis (2-methylpropionate), 4,4′-azobis (4-cyanopentanoic acid), 2,2 Examples also include azo polymerization initiators such as' -azobis [2- (hydroxymethyl) propionitrile]. As the radical polymerization initiator in the present embodiment, one of these may be used alone, or two or more may be used in combination, or other known polymerization initiators may be used in further combination.

The content of the radical polymerization initiator may be any stoichiometrically required amount, but 0.05 to 25 masses when the total mass of the composition containing the compound or resin is 100 mass parts. Part is preferable, and 0.1 to 10 parts by mass is more preferable. When the content of the radical polymerization initiator is 0.05 parts by mass or more, there is a tendency that curing can be prevented from being insufficient. On the other hand, the content of the radical polymerization initiator is 25 parts by mass or less. In such a case, the long-term storage stability of the lower layer film-forming material at room temperature tends to be prevented from being impaired.

[Acid generator]
The lower layer film-forming material may contain an acid generator as required from the viewpoint of further promoting the crosslinking reaction by heat. As the acid generator, those that generate an acid by thermal decomposition and those that generate an acid by light irradiation are known, and any of them can be used. For example, those described in International Publication No. 2013/024779 can be used.

In the lower layer film forming material, the content of the acid generator is not particularly limited, but is preferably 0.1 to 50 parts by weight, more preferably 0.5 parts by weight with respect to 100 parts by weight of the lower layer film forming material. ~ 40 parts by mass. By setting the amount within the above preferable range, the acid generation amount tends to increase and the crosslinking reaction tends to be enhanced, and the occurrence of the mixing phenomenon with the resist layer tends to be suppressed.

[Basic compounds]
Furthermore, the lower layer film-forming material may contain a basic compound from the viewpoint of improving storage stability.

The basic compound serves as a quencher for the acid to prevent the acid generated in a trace amount from the acid generator from causing the crosslinking reaction to proceed. Such a basic compound is not particularly limited, and examples thereof include those described in International Publication No. 2013/024779.

In the lower layer film forming material, the content of the basic compound is not particularly limited, but is preferably 0.001 to 2 parts by mass, more preferably 0.01 to 100 parts by mass of the lower layer film forming material. ~ 1 part by mass. By setting it as the said preferable range, it exists in the tendency for storage stability to be improved, without impairing a crosslinking reaction too much.

[Other additives]
Moreover, the lower layer film forming material in the present embodiment may contain other resins and / or compounds for the purpose of imparting curability by heat or light and controlling the absorbance. Examples of such other resins and / or compounds include naphthol resins, xylene resins, naphthol-modified resins, phenol-modified resins of naphthalene resins, polyhydroxystyrene, dicyclopentadiene resins, (meth) acrylates, dimethacrylates, trimethacrylates, tetra Resins containing no heterocyclic ring or aromatic ring such as methacrylate, vinyl naphthalene, polyacenaphthylene and other naphthalene rings, phenanthrenequinone, biphenyl rings such as fluorene, hetero rings having hetero atoms such as thiophene and indene; rosin resins; Examples thereof include resins or compounds containing an alicyclic structure such as cyclodextrin, adamantane (poly) ol, tricyclodecane (poly) ol, and derivatives thereof, but are not particularly limited thereto. Furthermore, the lower layer film-forming material in the present embodiment may contain a known additive. Examples of the known additives include, but are not limited to, heat and / or photocuring catalysts, polymerization inhibitors, flame retardants, fillers, coupling agents, thermosetting resins, photocurable resins, dyes, Examples thereof include pigments, thickeners, lubricants, antifoaming agents, leveling agents, ultraviolet absorbers, surfactants, colorants, and nonionic surfactants.

[Liquid lower layer film and multilayer resist pattern forming method]
The lower layer film for lithography can be formed using the lower layer film forming material.

At this time, a step (A-1) of forming a lower layer film on the substrate using the lower layer film forming material (the composition of the present embodiment), and at least one photoresist layer is formed on the lower layer film. A resist pattern forming method comprising: a forming step (A-2); and a step (A-3) of irradiating a predetermined region of the photoresist layer with radiation after the second forming step and developing Can be used.

Furthermore, another pattern forming method (circuit pattern forming method) of the present embodiment is a step (B-1) of forming a lower layer film on a substrate using the lower layer film forming material (the composition of the present embodiment). A step of forming an intermediate layer film on the lower layer film using a resist intermediate layer film material (B-2), and a step of forming at least one photoresist layer on the intermediate layer film (B -3) and after the step (B-3), a step (B-4) of irradiating a predetermined region of the photoresist layer with radiation and developing to form a resist pattern, and the step (B- 4) After that, the intermediate layer film is etched using the resist pattern as a mask, the lower layer film is etched using the obtained intermediate layer film pattern as an etching mask, and the substrate is etched using the obtained lower layer film pattern as an etching mask. Having a step (B-5) to form a pattern on the substrate by. The resist intermediate layer film material may contain silicon atoms.

The formation method of the lower layer film for lithography in the present embodiment is not particularly limited as long as it is formed from the lower layer film forming material, and a known method can be applied. For example, after applying the lower layer film material of the present embodiment on a substrate by a known coating method such as spin coating or screen printing or a printing method, and removing the organic solvent by volatilizing the organic solvent, the lower layer film material is crosslinked by a known method. And cured to form the lower layer film for lithography of the present embodiment. Examples of the crosslinking method include methods such as thermosetting and photocuring.

During the formation of the lower layer film, it is preferable to perform baking in order to suppress the occurrence of the mixing phenomenon with the upper layer resist and to promote the crosslinking reaction. In this case, the baking temperature is not particularly limited, but is preferably in the range of 80 to 450 ° C., more preferably 200 to 400 ° C. Also, the baking time is not particularly limited, but is preferably within the range of 10 to 300 seconds. The thickness of the lower layer film can be appropriately selected according to the required performance and is not particularly limited, but is usually preferably about 30 to 20,000 nm, more preferably 50 to 15,000 nm. It is preferable.

After the formation of the lower layer film, in the case of a two-layer process, a silicon-containing resist layer is formed thereon, or a single-layer resist made of ordinary hydrocarbons. In the case of a three-layer process, a silicon-containing intermediate layer is formed thereon, and further thereon. It is preferable to produce a single-layer resist layer that does not contain silicon. In this case, a well-known thing can be used as a photoresist material for forming this resist layer.

After forming the lower layer film on the substrate, in the case of the two-layer process, a silicon-containing resist layer or a single layer resist made of ordinary hydrocarbon can be formed on the lower layer film. In the case of a three-layer process, a silicon-containing intermediate layer can be formed on the lower layer film, and a single-layer resist layer not containing silicon can be formed on the silicon-containing intermediate layer. In these cases, the photoresist material for forming the resist layer can be appropriately selected from known materials and is not particularly limited.

As a silicon-containing resist material for a two-layer process, from the viewpoint of oxygen gas etching resistance, a silicon atom-containing polymer such as a polysilsesquioxane derivative or a vinylsilane derivative is used as a base polymer, and an organic solvent, an acid generator, If necessary, a positive photoresist material containing a basic compound or the like is preferably used. Here, as the silicon atom-containing polymer, a known polymer used in this type of resist material can be used.

As the silicon-containing intermediate layer for the three-layer process, a polysilsesquioxane-based intermediate layer is preferably used. By giving the intermediate layer an effect as an antireflection film, reflection tends to be effectively suppressed. For example, in a 193 nm exposure process, if a material containing many aromatic groups and high substrate etching resistance is used as the lower layer film, the k value increases and the substrate reflection tends to increase, but the reflection is suppressed in the intermediate layer. Thus, the substrate reflection can be reduced to 0.5% or less. The intermediate layer having such an antireflection effect is not limited to the following, but for 193 nm exposure, a polysilsesquioxy crosslinked with acid or heat into which a light absorbing group having a phenyl group or a silicon-silicon bond is introduced. Sun is preferably used.

In addition, an intermediate layer formed by a chemical vapor deposition (CVD) method can also be used. The intermediate layer having a high effect as an antireflection film produced by the CVD method is not limited to the following, but for example, a sion film is known. In general, the formation of the intermediate layer by a wet process such as spin coating or screen printing has a simpler and more cost-effective advantage than the CVD method. The upper layer resist in the three-layer process may be either a positive type or a negative type, and the same one as a commonly used single layer resist can be used.

Furthermore, the lower layer film in this embodiment can also be used as an antireflection film for a normal single layer resist or a base material for suppressing pattern collapse. Since the lower layer film of this embodiment is excellent in etching resistance for the base processing, it can be expected to function as a hard mask for the base processing.

In the case of forming a resist layer from the photoresist material, a wet process such as spin coating or screen printing is preferably used as in the case of forming the lower layer film. Further, after the resist material is applied by spin coating or the like, prebaking is usually performed, but this prebaking is preferably performed at 80 to 180 ° C. for 10 to 300 seconds. Then, according to a conventional method, a resist pattern can be obtained by performing exposure, post-exposure baking (PEB), and development. The thickness of the resist film is not particularly limited, but is generally preferably 30 to 500 nm, more preferably 50 to 400 nm.

Further, the exposure light may be appropriately selected and used according to the photoresist material to be used. In general, high energy rays having a wavelength of 300 nm or less, specifically, 248 nm, 193 nm, 157 nm excimer laser, 3 to 20 nm soft X-ray, electron beam, X-ray and the like can be mentioned.

The resist pattern formed by the above method is one in which pattern collapse is suppressed by the lower layer film in the present embodiment. Therefore, by using the lower layer film in the present embodiment, a finer pattern can be obtained, and the exposure amount necessary for obtaining the resist pattern can be reduced.

Next, etching is performed using the obtained resist pattern as a mask. Gas etching is preferably used as the etching of the lower layer film in the two-layer process. As gas etching, etching using oxygen gas is suitable. In addition to oxygen gas, an inert gas such as He or Ar, or CO, CO ₂ , NH ₃ , SO ₂ , N ₂ , NO _{2 or} H ₂ gas may be added. Further, gas etching can be performed only with CO, CO ₂ , NH ₃ , N ₂ , NO _{2, and} H ₂ gas without using oxygen gas. In particular, the latter gas is preferably used for side wall protection for preventing undercut of the pattern side wall.

On the other hand, gas etching is also preferably used for etching the intermediate layer in the three-layer process. As the gas etching, the same gas etching as that described in the above two-layer process can be applied. In particular, the processing of the intermediate layer in the three-layer process is preferably performed using a fluorocarbon gas and a resist pattern as a mask. Thereafter, as described above, the lower layer film can be processed by, for example, oxygen gas etching using the intermediate layer pattern as a mask.

Here, when an inorganic hard mask intermediate layer film is formed as an intermediate layer, a silicon oxide film, a silicon nitride film, or a silicon oxynitride film (sion film) is formed by a CVD method, an ALD method, or the like. The method for forming the nitride film is not limited to the following, but for example, the method described in Japanese Patent Application Laid-Open No. 2002-334869 (the above-mentioned Patent Document 6) and WO 2004/066377 (the above-mentioned Patent Document 7) is used. it can. A photoresist film can be formed directly on such an intermediate film, but an organic antireflection film (BARC) is formed on the intermediate film by spin coating, and a photoresist film is formed thereon. May be.

As the intermediate layer, an intermediate layer based on polysilsesquioxane is also preferably used. By providing the resist intermediate layer film with an effect as an antireflection film, reflection tends to be effectively suppressed. Specific materials of the polysilsesquioxane-based intermediate layer are not limited to the following, but examples thereof include Japanese Patent Application Laid-Open No. 2007-226170 (the above-mentioned Patent Document 8) and Japanese Patent Application Laid-Open No. 2007-226204 (the above-mentioned Patent Document). Those described in 9) can be used.

Etching of the next substrate can also be performed by a conventional method. For example, if the substrate is sio ₂ or sin, etching mainly using a chlorofluorocarbon gas, if p-Si, Al, or W is chlorine or bromine, Etching mainly with gas can be performed. When the substrate is etched with a chlorofluorocarbon gas, the silicon-containing resist of the two-layer resist process and the silicon-containing intermediate layer of the three-layer process are peeled off simultaneously with the substrate processing. On the other hand, when the substrate is etched with a chlorine-based or bromine-based gas, the silicon-containing resist layer or the silicon-containing intermediate layer is separately peeled, and generally, dry etching peeling with a chlorofluorocarbon-based gas is performed after the substrate is processed. .

The lower layer film is characterized by excellent etching resistance of these substrates. A known substrate can be appropriately selected and used, and is not particularly limited. Examples thereof include Si, α-Si, p-Si, sio ₂ , sin, sion, W, tin, and Al. . The substrate may be a laminate having a film to be processed (substrate to be processed) on a base material (support). Examples of such a film to be processed include various low-k films such as Si, sio ₂ , sion, sin, p-Si, α-Si, W, W-Si, Al, Cu, Al-Si, and stopper films thereof. In general, a material different from the base material (support) is used. The thickness of the substrate to be processed or the film to be processed is not particularly limited, but is usually preferably about 50 to 10,000 nm, more preferably 75 to 5,000 nm.

[Resist permanent film]
The resist permanent film formed by applying the composition of the present embodiment can also be prepared using the composition, and the resist permanent film remains in the final product after forming a resist pattern as necessary. It is suitable as a permanent film. Specific examples of the permanent film include a solder resist, a package material, an underfill material, a package adhesive layer such as a circuit element, an adhesive layer between an integrated circuit element and a circuit board, and a thin film display protective film for a thin display. Examples include a liquid crystal color filter protective film, a black matrix, and a spacer. In particular, the permanent film made of the composition of the present embodiment has excellent advantages in that it has excellent heat resistance and moisture resistance and is less contaminated by sublimation components. In particular, a display material is a material having high sensitivity, high heat resistance, and moisture absorption reliability with little image quality deterioration due to important contamination.

When the composition of this embodiment is used for resist permanent film applications, in addition to the curing agent, if necessary, various additions such as other resins, surfactants and dyes, fillers, crosslinking agents, dissolution accelerators, etc. A composition for a resist permanent film can be obtained by adding an agent and dissolving in an organic solvent.

The film-forming composition for lithography and the composition for permanent resist film of the present embodiment can be prepared by blending the above components and mixing them using a stirrer or the like. Further, when the resist underlayer film composition or resist permanent film composition of the present embodiment contains a filler or a pigment, the resist underlayer film composition or the resist permanent film composition may be dispersed or mixed using a dispersing device such as a dissolver, a homogenizer, or a three-roll mill. Can be adjusted.

Hereinafter, the present embodiment will be described in more detail with reference to synthesis examples and examples, but the present invention is not limited to these examples.

[Molecular weight]
The molecular weight of the compound was measured by LC-MS analysis using Water's Acquity UPLC / MALDI-Synapt HDMS.
Moreover, the gel permeation chromatography (GPC) analysis was performed on the following conditions, and the polystyrene conversion weight average molecular weight (Mw), number average molecular weight (Mn), and dispersity (Mw / Mn) were calculated | required.
Apparatus: Shodex GPC-101 (manufactured by Showa Denko KK)
Column: KF-80M x 3
Eluent: THF 1ml / min
Temperature: 40 ° C

[Solubility]
At 23 ° C., the compound was stirred so as to be a 3% by mass solution with respect to propylene glycol monomethyl ether (PGME), cyclohexanone (CHN), ethyl lactate (EL), methyl amyl ketone (MAK) or tetramethyl urea (TMU). And 1 week after the dissolution. The solubility of the compounds was evaluated according to the following criteria.
Evaluation A: It was confirmed by visual observation that no precipitate was formed in any solvent.
Evaluation C: It was confirmed by visual observation that a precipitate was produced with any solvent.

[Structure of compound]
The structure of the compound was confirmed by ¹ H-NMR measurement under the following conditions using “Advanced600II spectrometer” manufactured by Bruker.
Frequency: 400mhz
Solvent: d6-DMSO
Internal standard: TMS
Measurement temperature: 23 ° C

<Synthesis Example 1> Synthesis of XBisN-1 In a 100 ml container equipped with a stirrer, a condenser tube and a burette, 3.20 g (20 mmol) of 2,6-naphthalenediol (Sigma-Aldrich reagent) and 4-biphenylcarboxy 1.82 g (10 mmol) of aldehyde (manufactured by Mitsubishi Gas Chemical Co., Inc.) was charged into 30 ml methyl isobutyl ketone, 5 ml of 95% sulfuric acid was added, and the reaction solution was stirred at 100 ° C. for 6 hours for reaction. Next, the reaction solution was concentrated, 50 g of pure water was added to precipitate the reaction product, cooled to room temperature, and then filtered to separate. The obtained solid was filtered and dried, followed by separation and purification by column chromatography to obtain 3.05 g of the target compound represented by the following formula (XBisN-1). It was confirmed by 400 mhz- ¹ H-NMR that the compound had a chemical structure of the following formula (XBisN-1).
¹ H-NMR: (d-DMSO, internal standard TMS)
Δ (ppm) 9.7 (2H, OH), 7.2 to 8.5 (19H, Ph—H), 6.6 (1H, C—H)
It was confirmed that the substitution position of 2,6-naphthalenediol was the 1st position because the proton signals at the 3rd and 4th positions were doublets.

(XBisN-1)

<Synthesis Example 1A> Synthesis of E-XBisN-1 10 g (21 mmol) of the compound represented by the above formula (XBisN-1) and 14.8 g of potassium carbonate were placed in a container having an internal volume of 100 ml equipped with a stirrer, a condenser tube and a burette. 107 mmol) in 50 ml dimethylformamide, 6.56 g (54 mmol) of 2-chloroethyl acetate was added, and the reaction was stirred at 90 ° C. for 12 hours to carry out the reaction. Next, the reaction solution was cooled in an ice bath to precipitate crystals, which were separated by filtration. Subsequently, 40 g of the crystal, 40 g of methanol, 100 g of THF, and 24% aqueous sodium hydroxide solution were charged in a 100-ml container equipped with a stirrer, a condenser, and a burette, and the reaction was stirred for 4 hours under reflux to carry out the reaction. . Thereafter, the mixture is cooled in an ice bath, the reaction mixture is concentrated, and the precipitated solid is filtered and dried, followed by separation and purification by column chromatography. The target compound represented by the following formula (E-XBisN-1) is 5 .9 g was obtained. It was confirmed by 400 mhz- ¹ H-NMR that the compound had a chemical structure of the following formula (E-XBisN-1).
¹ H-NMR: (d-DMSO, internal standard TMS)
Δ (ppm) 8.6 (2H, OH), 7.2 to 7.8 (19H, Ph—H), 6.7 (1H, C—H), 4.0 (4H, —O—) CH ₂ —), 3.8 (4H, —CH ₂ —OH)

(E-XBisN-1)

<Synthesis Example 2> Synthesis of BisF-1 A container having an internal volume of 200 ml equipped with a stirrer, a cooling tube and a burette was prepared. In this container, 30 g (161 mmol) of 4,4-biphenol (reagent manufactured by Tokyo Chemical Industry Co., Ltd.), 15 g (82 mmol) of 4-biphenylaldehyde (manufactured by Mitsubishi Gas Chemical Co., Inc.) and 100 ml of butyl acetate are charged, and p-toluenesulfone is added. 3.9 g (21 mmol) of acid (a reagent manufactured by Kanto Chemical Co., Inc.) was added to prepare a reaction solution. The reaction was stirred at 90 ° C. for 3 hours to carry out the reaction. Next, the reaction solution was concentrated and 50 g of heptane was added to precipitate the reaction product. After cooling to room temperature, the solution was filtered and separated. The solid obtained by filtration was dried and then separated and purified by column chromatography to obtain 5.8 g of the target compound (BisF-1) represented by the following formula.
The following peaks were found by 400 mhz- ¹ H-NMR and confirmed to have a chemical structure of the following formula (BisF-1).
¹ H-NMR: (d-DMSO, internal standard TMS)
Δ (ppm) 9.4 (4H, OH), 6.8 to 7.8 (22H, Ph—H), 6.2 (1H, C—H)
It was 536 as a result of measuring molecular weight by the said method about the obtained compound.

(BisF-1)

<Synthesis Example 2A> Synthesis of E-BisF-1 11.2 g (21 mmol) of the compound represented by the above formula (BisF-1) and potassium carbonate in a container with a volume of 100 ml equipped with a stirrer, a condenser tube and a burette. 8 g (107 mmol) was charged into 50 ml dimethylformamide, 6.56 g (54 mmol) of 2-chloroethyl acetate was added, and the reaction was stirred at 90 ° C. for 12 hours to carry out the reaction. Next, the reaction solution was cooled in an ice bath to precipitate crystals, which were separated by filtration. Subsequently, 40 g of the crystal, 40 g of methanol, 100 g of THF, and 24% aqueous sodium hydroxide solution were charged in a 100-ml container equipped with a stirrer, a condenser, and a burette, and the reaction was stirred for 4 hours under reflux to carry out the reaction. . Thereafter, the reaction mixture is cooled in an ice bath, the reaction mixture is concentrated, and the precipitated solid is filtered and dried, followed by separation and purification by column chromatography. The target compound represented by the following formula (E-BisF-1) is obtained. 5.9 g was obtained.

It was confirmed by 400 mhz- ¹ H-NMR that the compound had a chemical structure of the following formula (E-BisF-1).
¹ H-NMR: (d-DMSO, internal standard TMS)
Δ (ppm) 8.6 (4H, OH), 6.8 to 7.8 (22H, Ph—H), 6.2 (1H, C—H), 4.0 (8H, —O—) CH ₂ —), 3.8 (8H, —CH ₂ —OH)
As a result of measuring the molecular weight of the obtained compound by the above method, it was 712.

(E-BisF-1)

<Synthesis Example 1-1> Synthesis of SXBisN-1 10.0 g (21 mmol) of the compound represented by the above formula (XBisN-1) and vinylbenzyl chloride in a 100-ml container equipped with a stirrer, a condenser tube and a burette. 6.4 g (trade name CMS-P; manufactured by Seimi Chemical Co., Ltd.) was charged into 50 ml dimethylformamide, heated to 50 ° C. and stirred, and 8.0 g of 28% by mass sodium methoxide (methanol solution). Was added over 20 minutes from the dropping funnel, and the reaction solution was stirred at 50 ° C. for 1 hour to carry out the reaction. Next, 1.6 g of 28% by mass sodium methoxide (methanol solution) was added, the reaction solution was heated at 60 ° C. and stirred for 3 hours, and further 1.2 g of 85% by mass phosphoric acid was added and stirred for 10 minutes. The reaction solution is dropped into pure water and the precipitated solid is filtered and dried, followed by separation and purification by column chromatography. The target compound represented by the following formula (SXBisN-1) is obtained. 4.0 g was obtained.
It was confirmed by 400 mhz- ¹ H-NMR that the compound had a chemical structure of the following formula (SXBisN-1).
¹ H-NMR: (d-DMSO, internal standard TMS)
Δ (ppm) 7.2 to 8.5 (27H, Ph—H), 5.2 to 6.7 (11H, —CH2—, —CH═CH2, C—H)

(SXBisN-1)

It was 698 as a result of measuring molecular weight by the said method about the obtained compound.
The thermal decomposition temperature was 400 ° C., the glass transition point was 115 ° C., and the melting point was 225 ° C., confirming high heat resistance.

<Synthesis Example 1-2> Synthesis of SE-XBisN-1 A compound represented by the formula (E-XBisN-1) was used in place of the compound represented by the formula (XBisN-1). The reaction was conducted in the same manner as in Synthesis Example 1-1 to obtain 4.0 g of the target compound represented by the following formula (SE-XBisN-1).
It was confirmed by 400 mhz- ¹ H-NMR that the compound had a chemical structure of the following formula (SE-XBisN-1).
¹ H-NMR: (d-DMSO, internal standard TMS)
Δ (ppm) 7.2 to 7.8 (19H, Ph—H), 6.7 (19H, —CH 2 —CH 2 —, —CH 2 —, —CH═CH 2, C—H)

(SE-XBisN-1)

It was 786 as a result of measuring molecular weight by the said method about the obtained compound.
The thermal decomposition temperature was 380 ° C., the glass transition point was 100 ° C., and the melting point was 205 ° C., confirming high heat resistance.

<Synthesis Example 2-1> Synthesis of SBisF-1 Synthesis Example 1 except that the compound represented by the formula (BisF-1) was used instead of the compound represented by the formula (XBisN-1). The reaction was carried out in the same manner as for -1, and 3.2 g of the target compound represented by the following formula (SBisF-1) was obtained.
It was confirmed by 400 mhz- ¹ H-NMR that the compound had a chemical structure of the following formula (sbisf-1).
¹ H-NMR: (d-DMSO, internal standard TMS)
Δ (ppm) 6.8 to 7.8 (38H, Ph—H), 6.2 (21H, —CH2—, —CH═CH2, C—H)

(SBisF-1)

As a result of measuring the molecular weight of the obtained compound by the above method, it was 1000.
The thermal decomposition temperature was 400 ° C, the glass transition point was 90 ° C, and the melting point was 225 ° C, confirming high heat resistance.

<Synthesis Example 2-2> Synthesis of SE-BisF-1 A compound represented by the formula (E-BisF-1) was used in place of the compound represented by the formula (BisF-1). The reaction was carried out in the same manner as in Synthesis Example 2-1, and 3.3 g of the target compound represented by the following formula (SE-BisF-1) was obtained.
It was confirmed by 400 mhz- ¹ H-NMR that the compound had a chemical structure of the following formula (SE-BisF-1).
¹ H-NMR: (d-DMSO, internal standard TMS)
Δ (ppm) 6.8 to 7.8 (22H, Ph—H), 6.2 (37H, —CH 2 —CH 2 —, —CH 2 —, —CH═CH 2, C—H)
The thermal decomposition temperature was 380 ° C., the glass transition point was 70 ° C., and the melting point was 200 ° C., confirming high heat resistance.

(SE-BisF-1)

As a result of measuring the molecular weight of the obtained compound by the above method, it was 1177.
The thermal decomposition temperature was 375 ° C., the glass transition point was 65 ° C., and the melting point was 190 ° C., confirming high heat resistance.
<Synthesis Example 3> Synthesis of BiN-1 After melting 10 g (69.0 mmol) of 2-naphthol (reagent manufactured by Sigma-Aldrich) at 120 ° C. in a 300 mL internal vessel equipped with a stirrer, a condenser and a burette, 0.27 g of sulfuric acid was added, 2.7 g (13.8 mmol) of 4-acetylbiphenyl (Sigma-Aldrich reagent) was added, and the contents were stirred at 120 ° C. for 6 hours to carry out the reaction to obtain a reaction solution. It was. Next, 100 mL of N-methyl-2-pyrrolidone (manufactured by Kanto Chemical Co., Inc.) and 50 mL of pure water were added to the reaction solution, followed by extraction with ethyl acetate. Next, pure water was added to separate the solution until neutrality, followed by concentration to obtain a solution.
After separation of the resulting solution by column chromatography, 1.0 g of the target compound (BiN-1) represented by the following formula (BiN-1) was obtained.
The obtained compound (BiN-1) was measured to have a molecular weight of 466 by the method described above.
The obtained compound (BiN-1) was subjected to NMR measurement under the above-described measurement conditions. As a result, the following peaks were found and confirmed to have a chemical structure of the following formula (BiN-1).
δ (ppm) 9.69 (2H, OH), 7.01 to 7.67 (21H, Ph—H), 2.28 (3H, C—H)

<Synthesis Example 3A> Synthesis of E-BiN-1 10.5 g (21 mmol) of the compound (BiN-1) represented by the above formula and 14.8 g of potassium carbonate were placed in a container having a volume of 100 ml equipped with a stirrer, a condenser tube and a burette. (107 mmol) was charged into 50 ml dimethylformamide, 6.56 g (54 mmol) of 2-chloroethyl acetate was added, and the reaction solution was stirred at 90 ° C. for 12 hours to carry out the reaction. Next, the reaction solution was cooled in an ice bath to precipitate crystals, which were separated by filtration. Subsequently, 40 g of the crystal, 40 g of methanol, 100 g of THF and 24% aqueous sodium hydroxide solution were charged in a 100 ml internal container equipped with a stirrer, a condenser and a burette, and the reaction was stirred for 5 hours under reflux to carry out the reaction. . Thereafter, the mixture was cooled in an ice bath, the reaction solution was concentrated, and the precipitated solid was filtered and dried, followed by separation and purification by column chromatography to obtain 4.6 g of the target compound represented by the following formula. It was confirmed by 400 MHz- ¹ H-NMR that it had a chemical structure of the following formula.
¹ H-NMR: (d-DMSO, internal standard TMS)
δ (ppm) 8.6 (2H, OH), 7.2 to 7.8 (19H, Ph—H), 6.7 (1H, C—H), 4.0 (4H, —O—) CH ₂ —), 3.8 (4H, —CH ₂ —OH)

<Synthesis Example 3-1> Synthesis of SBiN-1 10.0 g (21 mmol) of the compound represented by the above formula (BiN-1) and vinylbenzyl chloride in a container having a volume of 100 ml equipped with a stirrer, a condenser tube and a burette. 6.4 g (trade name CMS-P; manufactured by Seimi Chemical Co., Ltd.) was charged into 50 ml dimethylformamide, heated to 50 ° C. and stirred, and 8.0 g of 28% by mass sodium methoxide (methanol solution). Was added over 20 minutes from the dropping funnel, and the reaction solution was stirred at 50 ° C. for 1 hour to carry out the reaction. Next, 1.6 g of 28% by mass sodium methoxide (methanol solution) was added, the reaction solution was heated at 60 ° C. and stirred for 3 hours, and further 1.2 g of 85% by mass phosphoric acid was added and stirred for 10 minutes. The reaction mixture was cooled to 0 ° C., the reaction solution was dropped into pure water, and the precipitated solid was filtered and dried, followed by separation and purification by column chromatography, and the target compound represented by the following formula (SBiN-1) 4.0 g was obtained.
It was confirmed by 400 MHz- ¹ H-NMR that the compound had a chemical structure of the following formula (SBiN-1).
¹ H-NMR: (d-DMSO, internal standard TMS)
δ (ppm) 7.2 to 7.8 (19H, Ph—H), 5.2 to 6.7 (10H, —CH 2 —, —CH═CH 2, C—H), 2.3 (3H, − CH ₃₎

It was 698 as a result of measuring molecular weight by the said method about the obtained compound.
The thermal decomposition temperature was 375 ° C., the glass transition point was 105 ° C., and the melting point was 212 ° C., confirming that it had high heat resistance.

<Synthesis Example 3-2> Synthesis of SE-BiN-1 A compound represented by the formula (E-BiN-1) was used in place of the compound represented by the formula (BiN-1). The reaction was carried out in the same manner as in Synthesis Example 3-1, and 3.6 g of the target compound represented by the following formula (SE-BiN-1) was obtained.
It was confirmed by 400 MHz- ¹ H-NMR that the compound had a chemical structure of the following formula (SE-BiN-1).
¹ H-NMR: (d-DMSO, internal standard TMS)
δ (ppm) 7.2 to 7.8 (19H, Ph—H), 6.7 (18H, —CH 2 —CH 2 —, —CH 2 —, —CH═CH 2, C—H), 2.3 (3H , -CH3)

It was 786 as a result of measuring molecular weight by the said method about the obtained compound.
The thermal decomposition temperature was 361 ° C., the glass transition point was 112 ° C., and the melting point was 212 ° C., confirming that it had high heat resistance.

<Synthesis Example 4> Synthesis of BiP-1 The reaction was conducted in the same manner as in Synthesis Example 1 except that o-phenylphenol was used instead of 2-naphthol, and the target compound represented by the following formula (BiP-1) was 1 0.0 g was obtained.
The obtained compound (BiP-1) was measured to have a molecular weight of 466 by the method described above.
The obtained compound (BiP-1) was subjected to NMR measurement under the above-described measurement conditions. As a result, the following peaks were found and confirmed to have a chemical structure of the following formula (BiP-1).
δ (ppm) 9.67 (2H, OH), 6.98-7.60 (25H, Ph-H), 2.25 (3H, C—H)

<Synthesis Example 4A>
In a 100 ml container equipped with a stirrer, a condenser and a burette, 11.2 g (21 mmol) of the compound represented by the above formula (BiP-1) and 14.8 g (107 mmol) of potassium carbonate were charged in 50 ml dimethylformamide. The reaction was carried out by adding 6.56 g (54 mmol) of 2-chloroethyl acetate and stirring the reaction solution at 90 ° C. for 12 hours. Next, the reaction solution was cooled in an ice bath to precipitate crystals, which were separated by filtration. Subsequently, 40 g of the crystal, 40 g of methanol, 100 g of THF, and 24% aqueous sodium hydroxide solution were charged in a 100-ml container equipped with a stirrer, a condenser, and a burette, and the reaction was stirred for 4 hours under reflux to carry out the reaction. . Thereafter, the reaction mixture is cooled in an ice bath, the reaction mixture is concentrated and the precipitated solid is filtered and dried, followed by separation and purification by column chromatography, and the target compound represented by the following formula (E-BisP-1) 5.9 g was obtained.
It was confirmed by 400 MHz- ¹ H-NMR that the compound had a chemical structure of the following formula (E-BiP-1).
¹ H-NMR: (d-DMSO, internal standard TMS)
δ (ppm) 8.6 (4H, OH), 6.8 to 7.6 (25H, Ph—H), 4.0 (4H, —O—CH ₂ —), 3.8 (4H, —CH ₂ —OH), 2.2 (3H, C—H)
It was 606 as a result of measuring molecular weight about the obtained compound by the said method.

<Synthesis Example 4-1> Synthesis of SBiP-1 Synthesis Example except that the compound represented by the formula (BiP-1) was used instead of the compound represented by the formula (XBisN-1). The reaction was carried out in the same manner as in 1-1 to obtain 3.0 g of the target compound represented by the following formula (SBiP-1).
It was confirmed by 400 MHz- ¹ H-NMR that the compound had a chemical structure of the following formula (SBiP-1).
¹ H-NMR: (d-DMSO, internal standard TMS)
δ (ppm) 6.8 to 7.8 (25H, Ph—H), 5.2 to 6.7 (10H, —CH 2 —, —CH═CH 2, C—H), 2.3 (3H, — CH ₃₎
The thermal decomposition temperature was 390 ° C., the glass transition point was 74 ° C., and the melting point was 202 ° C., confirming that it had high heat resistance.

As a result of measuring the molecular weight of the obtained compound by the above method, it was 750.

<Synthesis Example 4-2> Synthesis of SE-BiP-1 A compound represented by the formula (E-BiP-1) was used in place of the compound represented by the formula (BiP-1). The reaction was conducted in the same manner as in Synthesis Example 4-1, to obtain 2.9 g of the target compound represented by the following formula (SE-BiP-1).
It was confirmed by 400 MHz- ¹ H-NMR that the compound had a chemical structure of the following formula (SE-BiP-1).
¹ H-NMR: (d-DMSO, internal standard TMS)
δ (ppm) 6.8 to 7.8 (25H, Ph—H), 6.7 (18H, —CH 2 —CH 2 —, —CH 2 —, —CH═CH 2, C—H), 2.3 (3H , -CH3)

It was 838 as a result of measuring molecular weight by the said method about the obtained compound.
The thermal decomposition temperature was 365 ° C., the glass transition point was 82 ° C., and the melting point was 220 ° C., confirming that it had high heat resistance.

(Synthesis Examples 5 to 17)
2-naphthol (raw material 1) and 4-acetylbiphenyl (starting material 2), which are the raw materials of Synthesis Example 3, were changed as shown in Table 1, and the others were carried out in the same manner as in Synthesis Example 3 to obtain each target product.
Each was identified by 1H-NMR.

(Synthesis Examples 18 to 20)
4-biphenylcarboxaldehyde, which is a raw material of Synthesis Example 1, was changed as shown in Table 3, and the others were carried out in the same manner as in Synthesis Example 1 to obtain each target product.
Each was identified by 1H-NMR.

(Synthesis Examples 21 to 22)
The raw materials of Synthesis Example 3, 2-naphthol (raw material 1) and 4-acetylbiphenyl (raw material 2) were changed as shown in Table 5, 1.5 mL of water, 73 mg (0.35 mmol) of dodecyl mercaptan, 37% hydrochloric acid 2 .3 g (22 mmol) was added, the reaction temperature was changed to 55 ° C., and the others were performed in the same manner as in Synthesis Example 31 to obtain each target product.
Each was identified by 1H-NMR.

(Synthesis Examples 5A to 22A)
The compound represented by the formula (BiN-1), which is the raw material of Synthesis Example 3A, was changed as shown in Table 7, and the others were synthesized under the same conditions as in Synthesis Example 3A, and the respective target products were obtained. . The structure of each compound was identified by confirming the molecular weight with 400 MHz- ¹ H-NMR (d-DMSO, internal standard TMS) and LC-MS.

(Synthesis Examples 5-1 to 22-1)
The compound represented by the formula (BiN-1) as the raw material of Synthesis Example 3-1 was changed as shown in Table 7, and the others were synthesized under the same conditions as in Synthesis Example 3-1, The target was obtained. The structure of each compound was identified by confirming the molecular weight with 400 MHz- ¹ H-NMR (d-DMSO, internal standard TMS) and LC-MS.

(Synthesis Examples 5-2 to 22-2)
The compound represented by the formula (E-BiN-1) as the raw material of Synthesis Example 3-2 was changed as shown in Table 7, and the others were synthesized under the same conditions as in Synthesis Example 3-2. , Respectively, obtained the object. The structure of each compound was identified by confirming the molecular weight with 400 MHz- ¹ H-NMR (d-DMSO, internal standard TMS) and LC-MS.

<Synthesis Example 23> Synthesis of Resin (R1-XBisN-1) A four-necked flask having an internal volume of 1 L and equipped with a Dimroth condenser, a thermometer, and a stirring blade and capable of bottoming out was prepared. In a four-necked flask, 32.6 g (70 mmol, manufactured by Mitsubishi Gas Chemical Co., Ltd.) of the compound (XBisN-1) obtained in Synthesis Example 1 and 21.0 g of a 40 mass% formalin aqueous solution (formaldehyde) were added in a nitrogen stream. 280 mmol, manufactured by Mitsubishi Gas Chemical Co., Ltd.) and 0.97 mL of 98% by mass sulfuric acid (manufactured by Kanto Chemical Co., Ltd.) were charged and reacted for 7 hours while refluxing at 100 ° C. under normal pressure. Thereafter, 180.0 g of ortho-xylene (special grade reagent manufactured by Wako Pure Chemical Industries, Ltd.) as a diluent solvent was added to the reaction solution, and after standing, the lower aqueous phase was removed. Further, neutralization and washing with water were carried out, and orthoxylene was distilled off under reduced pressure to obtain 34.1 g of a brown solid resin (R1-XBisN-1).

The obtained resin (R1-XBisN-1) had Mn: 1975, Mw: 3650, and Mw / Mn: 1.84.

<Synthesis Example 24> Synthesis of Resin (R2-XBisN-1) A four-necked flask having an internal volume of 1 L and equipped with a Dimroth condenser, thermometer, and stirring blade and capable of bottoming out was prepared. In a four-necked flask, 32.6 g (70 mmol, manufactured by Mitsubishi Gas Chemical Co., Ltd.) of the compound (XBisN-1) obtained in Synthesis Example 1 and 50.9 g (280 mmol, 4-biphenylaldehyde) were obtained in a nitrogen stream. Mitsubishi Gas Chemical Co., Ltd.), Anisole (Kanto Chemical Co., Ltd.) 100 mL and oxalic acid dihydrate (Kanto Chemical Co., Ltd.) 10 mL were charged and reacted at normal pressure for 7 hours while refluxing at 100 ° C. I let you. Thereafter, 180.0 g of ortho-xylene (special grade reagent manufactured by Wako Pure Chemical Industries, Ltd.) as a diluent solvent was added to the reaction solution, and after standing, the lower aqueous phase was removed. Further, neutralization and washing with water were performed, and the organic phase solvent and unreacted 4-biphenylaldehyde were distilled off under reduced pressure to obtain 34.7 g of a brown solid resin (R2-XBisN-1).

The obtained resin (R2-XBisN-1) had Mn: 1610, Mw: 2567, and Mw / Mn: 1.59.

<Synthesis Example 23A> Synthesis of E-R1-XBisN-1 30 g of a resin (R1-XBisN-1) represented by the above formula and 29. potassium carbonate in a container with an internal volume of 500 ml equipped with a stirrer, a condenser tube and a burette. 6 g (214 mmol) was charged into 100 ml dimethylformamide, 13.12 g (108 mmol) of 2-chloroethyl acetate was added, and the reaction was stirred at 90 ° C. for 12 hours to carry out the reaction. Next, the reaction solution was cooled in an ice bath to precipitate crystals, which were separated by filtration. Subsequently, 40 g of the crystal, 80 g of methanol, 100 g of THF, and 24% aqueous sodium hydroxide solution were charged into a 100-ml container equipped with a stirrer, a condenser and a burette, and the reaction was stirred for 4 hours under reflux to carry out the reaction. . Thereafter, the mixture was cooled in an ice bath, the reaction solution was concentrated, and the precipitated solid was filtered and dried to obtain 26.5 g of a brown solid resin (E-R1-XBisN-1).

The obtained resin (E-R1-XBisN-1) was Mn: 2176, Mw: 3540, and Mw / Mn: 1.62.

<Synthesis Example 23-1> Synthesis of SR1-XBisN-1 20.0 g of the resin represented by the above formula (R1-XBisN-1) and vinylbenzyl were placed in a 500-ml container equipped with a stirrer, a condenser tube and a burette. 12.8 g of chloride (trade name CMS-P; manufactured by Seimi Chemical Co., Ltd.) was charged in 200 ml dimethylformamide, heated to 50 ° C. and stirred, and 28 mass% sodium methoxide (methanol solution) 16. 0 g was added over 20 minutes from the dropping funnel, and the reaction was stirred at 50 ° C. for 1 hour to carry out the reaction. Next, 3.2 g of 28% by mass sodium methoxide (methanol solution) was added, the reaction solution was heated at 60 ° C. and stirred for 5 hours, and further 2.4 g of 85% by mass phosphoric acid was added and stirred for 10 minutes. The reaction mixture is cooled to 50 ° C., the reaction solution is dropped into pure water, and the precipitated solid is filtered and dried. After cooling to 50 ° C., the reaction solution is dropped into pure water and the precipitated solid is filtered. After drying, 27.2 g of a resin represented by (SR1-XBisN-1) as a gray solid was obtained.

The obtained resin (SR1-XBisN-1) was Mn: 1989, Mw: 2840, and Mw / Mn: 1.43.

<Synthesis Example 23-2> Synthesis of SE-R1-XBisN-1 Instead of the resin represented by the formula (R1-XBisN-1) obtained in Synthesis Example 23, the above-mentioned obtained in Synthesis Example 23A The reaction was conducted in the same manner as in Synthesis Example 23-1, except that the formula (E-R1-XBisN-1) was used, to obtain 31.3 g of a resin represented by (SE-R1-XBisN-1) as a brown solid It was.

The obtained resin (SE-R1-XBisN-1) was Mn: 2378, Mw: 3930, and Mw / Mn: 1.65.

<Synthesis Example 24A> Synthesis of E-R2-XBisN-1 30 g of the above resin (R2-XBisN-1) and 29.6 g (214 mmol) of potassium carbonate were placed in a 500-ml container equipped with a stirrer, a condenser tube and a burette. Was added to 100 ml dimethylformamide, 13.12 g (108 mmol) of 2-chloroethyl acetate was added, and the reaction was stirred at 90 ° C. for 12 hours to carry out the reaction. Next, the reaction solution was cooled in an ice bath to precipitate crystals, which were separated by filtration. Subsequently, 40 g of the crystal, 80 g of methanol, 100 g of THF, and 24% aqueous sodium hydroxide solution were charged into a 100-ml container equipped with a stirrer, a condenser and a burette, and the reaction was stirred for 4 hours under reflux to carry out the reaction. . Thereafter, the mixture was cooled in an ice bath, the reaction mixture was concentrated, and the precipitated solid was filtered and dried to obtain 22.3 g of a brown solid resin (E-R2-XBisN-1).

The obtained resin (E-R2-XBisN-1) was Mn: 2516, Mw: 3960, and Mw / Mn: 1.62.

<Synthesis Example 24-1> Synthesis of SR2-XBisN-1 Instead of the above formula (R1-XBisN-1) obtained in Synthesis Example 23, the above formula (R2-XBisN-1) obtained in Synthesis Example 24 was used. The reaction was conducted in the same manner as in Synthesis Example 23-1, except that 30.5 g of the compound represented by (II) was used to obtain 35.1 g of a resin represented by (SR2-XBisN-1) as a light gray solid.

The obtained resin (SR2-XBisN-1) had Mn: 2344, Mw: 4215, and Mw / Mn: 1.80.

<Synthesis Example 24-2> Synthesis of SE-R2-XBisN-1 In place of the resin represented by the above formula (R1-XBisN-1) obtained in Synthesis Example 23, the above-mentioned obtained in Synthesis Example 24A The reaction was conducted in the same manner as in Synthesis Example 23-1, except that the formula (E-R2-XBisN-1) was used, to obtain 28.4 g of a resin represented by (SE-R2-XBisN-1) as a brown solid. It was.

The obtained resin (SE-R2-XBisN-1) was Mn: 2676, Mw: 4730, and Mw / Mn: 1.77.

<Synthesis Comparative Example 1>
A four-necked flask with an internal volume of 10 L capable of bottoming was prepared, equipped with a Dimroth condenser, thermometer, and stirring blade. To this four-necked flask, in a nitrogen stream, 1.09 kg of 1,5-dimethylnaphthalene (7 mol, manufactured by Mitsubishi Gas Chemical Co., Ltd.), 2.1 kg of 40% by weight formalin aqueous solution (28 mol of formaldehyde, Mitsubishi Gas Chemical Co., Ltd.) )) And 98 mass% sulfuric acid (manufactured by Kanto Chemical Co., Ltd.) 0.97 ml were charged and reacted for 7 hours while refluxing at 100 ° C. under normal pressure. Thereafter, 1.8 kg of ethylbenzene (special grade reagent manufactured by Wako Pure Chemical Industries, Ltd.) as a diluent solvent was added to the reaction solution, and after standing, the lower aqueous phase was removed. Further, neutralization and washing with water were performed, and ethylbenzene and unreacted 1,5-dimethylnaphthalene were distilled off under reduced pressure to obtain 1.25 kg of a light brown solid dimethylnaphthalene formaldehyde resin.
The molecular weight of the obtained dimethylnaphthalene formaldehyde was Mn: 562.

Subsequently, a four-necked flask having an internal volume of 0.5 L equipped with a Dimroth condenser, a thermometer, and a stirring blade was prepared. This four-necked flask was charged with 100 g (0.51 mol) of the dimethylnaphthalene formaldehyde resin obtained as described above and 0.05 g of paratoluenesulfonic acid in a nitrogen stream, and the temperature was raised to 190 ° C. Stir after heating for hours. Thereafter, 52.0 g (0.36 mol) of 1-naphthol was further added, and the temperature was further raised to 220 ° C. to react for 2 hours. After the solvent was diluted, neutralization and water washing were performed, and the solvent was removed under reduced pressure to obtain 126.1 g of a dark brown solid modified resin (CR-1).
The obtained resin (CR-1) was Mn: 885, Mw: 2220, and Mw / Mn: 4.17.

[Examples 1-1 to 24-2, Comparative Example 1]
A solubility test was conducted using the compounds or resins described in Synthesis Examples 1-1 to 24-2 and CR-1 described in Synthesis Comparative Example 1. The results are shown in Table 8.
In addition, materials for forming a lower layer film for lithography having the compositions shown in Table 8 below were prepared. Next, these lower-layer film forming materials for lithography were spin-coated on a silicon substrate, and then baked at 240 ° C. for 60 seconds and further at 400 ° C. for 120 seconds to prepare 200 nm-thick underlayer films. The following were used about the acid generator, the crosslinking agent, and the organic solvent.

[Examples 25 to 44]
・ Acid generator: Ditertiary butyl diphenyliodonium nonafluoromethanesulfonate (DTDDPI) manufactured by Midori Chemical Co., Ltd.
・ Crosslinking agent: Nikalac MX270 (Nikalac) manufactured by Sanwa Chemical Co., Ltd.
Organic solvent: Propylene glycol monomethyl ether acetate acetate (PGMEA)
・ Novolac: PSM4357 manufactured by Gunei Chemical Co., Ltd.

In addition, materials for forming a lower layer film for lithography having the composition shown in Table 9 below were prepared. Next, these lower layer film forming materials for lithography are spin-coated on a silicon substrate, and then baked at 110 ° C. for 60 seconds to remove the solvent of the coating film. / cm ^2, and is cured by irradiation time of 20 seconds to produce each an underlying film having a thickness of 200 nm. The following were used for the photoacid generator, crosslinking agent and organic solvent.

-Radical polymerization initiator: IRGACURE184 manufactured by BASF
・ Crosslinking agent:
Diallyl bisphenol A cyanate manufactured by Mitsubishi Gas Chemical (DABPA-CN)
Konishi Chemical Industry Diallylbisphenol A (BPA-CA)
Benzoxazine (BF-BXZ) manufactured by Konishi Chemical Industries
Nippon Kayaku Biphenyl Aralkyl Epoxy Resin (NC-3000-L)
・ Organic solvent:
Propylene glycol monomethyl ether acetate acetate (PGMEA)

The structure of the crosslinking agent is represented by the following formula.

[Evaluation of etching resistance]
An etching test was performed under the following conditions to evaluate etching resistance. The evaluation results are shown in Table 8 and Table 9.

(Etching test conditions)
Etching system: “RIE-10NR” manufactured by Samco International
Output: 50W
Pressure: 20Pa
Time: 2min
Etching gas Ar gas flow rate: CF ₄ gas flow rate: O ₂ gas flow rate = 50: 5: 5 (sccm)

Etching resistance was evaluated according to the following procedure.
First, a novolac underlayer film was produced under the same conditions as in Example 1 except that novolak (“PSM4357” manufactured by Gunei Chemical Co., Ltd.) was used instead of the compound (SXBisN-1) used in Example 1-1. did. And the above-mentioned etching test was done for the lower layer film of this novolak, and the etching rate at that time was measured.

Next, the above-mentioned etching test was similarly performed for the lower layer films of the examples and comparative examples, and the etching rate at that time was measured.
Then, the etching resistance was evaluated according to the following evaluation criteria based on the etching rate of the novolak underlayer film.

[Evaluation criteria]
A: Etching rate is less than -10% compared to the novolac lower layer film B: Etching rate is -10% to + 5% compared to the novolac lower layer film
C: Etching rate is more than + 5% compared to the novolak underlayer

As is clear from Tables 8 and 9, it was confirmed that the examples using the lower layer forming material containing the compound of the present embodiment were good in both solubility and etching resistance. On the other hand, Comparative Example 1 using CR-1 (phenol-modified dimethylnaphthalene formaldehyde resin) had poor etching resistance.
Further, as described above, the compounds of the examples were excellent in heat resistance.

[Examples 45 to 48]
Next, each solution of an underlayer film forming material for lithography containing SXBisN-1, SE-XBisN-1, SBisF-1, or SE-BisF-1 is applied onto a 300 nm thick sio ₂ substrate, By baking at 240 ° C. for 60 seconds and further at 400 ° C. for 120 seconds, a lower layer film having a thickness of 70 nm was formed. On this lower layer film, a resist solution for arf was applied and baked at 130 ° C. for 60 seconds to form a 140 nm-thick photoresist layer. In addition, as an arf resist solution, the compound of the following formula (11): 5 parts by mass, triphenylsulfonium nonafluoromethanesulfonate: 1 part by mass, tributylamine: 2 parts by mass, and PGMEA: 92 parts by mass are blended. The prepared one was used.

The compound of the following formula (11) was prepared as follows. First, 4.15 g of 2-methyl-2-methacryloyloxyadamantane, 3.00 g of methacryloyloxy-γ-butyrolactone, 2.08 g of 3-hydroxy-1-adamantyl methacrylate, 0.38 g of azobisisobutyronitrile, The reaction solution was dissolved in 80 ml. This reaction solution was polymerized for 22 hours under a nitrogen atmosphere while maintaining the reaction temperature at 63 ° C., and then the reaction solution was dropped into 400 ml of n-hexane. The product resin thus obtained was coagulated and purified, and the resulting white powder was filtered and obtained by drying overnight at 40 ° C. under reduced pressure.

(11)

In the formula (11), “40”, “40”, and “20” indicate the ratio of each structural unit, and do not indicate a block copolymer.

Subsequently, the photoresist layer was exposed using an electron beam drawing apparatus (manufactured by Elionix; ELS-7500, 50 kev), baked (PEB) at 115 ° C. for 90 seconds, and 2.38 mass% tetramethylammonium hydroxide ( A positive resist pattern was obtained by developing with an aqueous solution of TMAH for 60 seconds.

The shapes of the obtained resist patterns of 55 nml / S (1: 1) and 80 nml / S (1: 1) were observed using an electron microscope (S-4800) manufactured by Hitachi, Ltd. As for the shape of the resist pattern after development, the resist pattern was evaluated as “good” when the pattern was not collapsed and the rectangularity was good, and “bad”. As a result of the observation, the minimum line width with no pattern collapse and good rectangularity was used as an evaluation index as “resolution”. Furthermore, the minimum electron beam energy amount capable of drawing a good pattern shape was defined as “sensitivity” and used as an evaluation index. The results are shown in Table 10.

[Comparative Example 2]
A photoresist layer was directly formed on the sio ₂ substrate in the same manner as in Example 45 except that the lower layer film was not formed, and a positive resist pattern was obtained. The results are shown in Table 10.

As is apparent from Table 10, in the examples using the lower layer forming material containing the compound of the present embodiment, it was confirmed that the resist pattern shape after development was good and no defects were seen. It was confirmed that both the resolution and sensitivity were significantly superior to those of Comparative Example 2 in which the formation of the lower layer film was omitted.
From the difference in the resist pattern shape after development, it was shown that the lower layer film forming material for lithography used in Examples 45 to 48 had good adhesion to the resist material.

[Examples 49 to 52]
A solution of the material for forming a lower layer film for lithography of Examples 1-1 to 2-2 was applied on a 300 nm thick sio ₂ substrate, and baked at 240 ° C. for 60 seconds and further at 400 ° C. for 120 seconds to form a film. A lower layer film having a thickness of 80 nm was formed. On this lower layer film, a silicon-containing intermediate layer material was applied and baked at 200 ° C. for 60 seconds to form an intermediate layer film having a thickness of 35 nm. Further, the alf resist solution was applied on the intermediate layer film, and baked at 130 ° C. for 60 seconds to form a 150 nm-thick photoresist layer. As the silicon-containing intermediate layer material, a silicon atom-containing polymer described in JP-A-2007-226170 <Synthesis Example 1> was used.

Next, the photoresist layer was subjected to mask exposure using an electron beam drawing apparatus (ELIONS Corp .; ELS-7500, 50 kev), baked (PEB) at 115 ° C. for 90 seconds, and 2.38 mass% tetramethylammonium hydroxide. By developing for 60 seconds with an aqueous solution of (TMAH), a positive resist pattern of 55 nml / S (1: 1) was obtained.
Thereafter, using RIE-10NR manufactured by Samco International, the silicon-containing intermediate layer film (SOG) was dry-etched using the obtained resist pattern as a mask, and then the obtained silicon-containing intermediate layer film pattern was Dry etching processing of the lower layer film using the mask and dry etching processing of the sio ₂ film using the obtained lower layer film pattern as a mask were sequentially performed.

Each etching condition is as shown below.
(Etching conditions for resist pattern to resist interlayer film)
Output: 50W
Pressure: 20Pa
Time: 1 min
Etching gas Ar gas flow rate: CF ₄ gas flow rate: O ₂ gas flow rate = 50: 8: 2 (sccm)

(Etching condition for resist underlayer film of resist interlayer film)
Output: 50W
Pressure: 20Pa
Time: 2min
Etching gas Ar gas flow rate: CF ₄ gas flow rate: O ₂ gas flow rate = 50: 5: 5 (sccm)

(Etching condition for resist underlayer film pattern to sio ₂ film)
Output: 50W
Pressure: 20Pa
Time: 2min
Etching gas Ar gas flow rate: C ₅ F ₁₂ gas flow rate: C ₂ F ₆ gas flow rate: O ₂ gas flow rate = 50: 4: 3: 1 (sccm)

[Evaluation]
When a-obtained pattern section as described above (shape of sio ₂ film after etching), was observed with a Hitachi Ltd. manufactured electron microscope (S-4800) use the underlayer film of the present embodiment examples had the shape of sio ₂ film after etching in a multilayer resist process is rectangular, it was confirmed defects is good not observed.

[Examples 53 to 56]
Using each compound synthesized in the synthesis example, an optical component-forming composition was prepared with the formulation shown in Table 11 below. Of the components of the optical component-forming composition in Table 11, the following were used for the acid generator, the crosslinking agent, the acid diffusion inhibitor, and the solvent.
・ Acid generator: Ditertiary butyl diphenyliodonium nonafluoromethanesulfonate (DTDDPI) manufactured by Midori Chemical Co., Ltd.
・ Crosslinking agent: Nikalac MX270 (Nikalac) manufactured by Sanwa Chemical Co., Ltd.
Organic solvent: Propylene glycol monomethyl ether acetate acetate (PGMEA)
The optical component-forming composition in a uniform state was spin-coated on a clean silicon wafer, and then pre-baked (PB) in an oven at 110 ° C. to form an optical component-forming film having a thickness of 1 μm. The prepared optical component-forming composition was evaluated as “A” when the film formation was good and “C” when the formed film had defects.

A uniform optical component-forming composition was spin-coated on a clean silicon wafer, and then PB was performed in an oven at 110 ° C. to form a film having a thickness of 1 μm. The refractive index (λ = 589.3 nm) at 25 ° C. of the film was measured with a multi-angle-of-incidence spectroscopic ellipsometer VASE manufactured by JA Woollam. The prepared film was evaluated as “A” when the refractive index was 1.65 or more, “B” when it was 1.6 or more and less than 1.65, and “C” when it was less than 1.6. . Further, when the transparency (λ = 632.8 nm) was 90% or more, “A” was evaluated, and when it was less than 90%, “C” was evaluated.

[Examples 57 to 60]
Using each of the compounds synthesized in the synthesis examples and synthesis examples, a resist composition was prepared with the formulation shown in Table 12 below. Of the components of the resist composition in Table 12, the following were used for the radical generator, radical diffusion inhibitor, and solvent.
-Radical polymerization initiator: IRGACURE184 manufactured by BASF
-Radical diffusion control agent: IRGACURE1010 manufactured by BASF
Organic solvent: Propylene glycol monomethyl ether acetate acetate (PGMEA)

[Evaluation methods]
(1) Storage stability of resist composition and thin film formation The storage stability of the resist composition was determined by standing the resist composition at 23 ° C. and 50% RH for 3 days and visually checking for the presence or absence of precipitation. Evaluation was made by observation. The resist composition after standing for 3 days was evaluated as A when it was a homogeneous solution and there was no precipitation, and C when there was precipitation. Moreover, after spin-coating the resist composition of a uniform state on the clean silicon wafer, it prebaked (PB) in 110 degreeC oven, and formed the resist film with a thickness of 40 nm. The prepared resist composition was evaluated as A when the thin film formation was good and as C when the formed film had defects.

(2) Pattern evaluation of resist pattern A uniform resist composition was spin-coated on a clean silicon wafer and then pre-exposure baked (PB) in an oven at 110 ° C. to form a resist film having a thickness of 60 nm. The obtained resist film was irradiated with an electron beam with a line and space setting of 1: 1 at intervals of 50 nm, 40 nm, and 30 nm using an electron beam drawing apparatus (ELS-7500, manufactured by Elionix Co., Ltd.). . After the irradiation, each resist film was heated at a predetermined temperature for 90 seconds and immersed in PGME for 60 seconds for development. Thereafter, the resist film was washed with ultrapure water for 30 seconds and dried to form a negative resist pattern. With respect to the formed resist pattern, the line and space was observed with a scanning electron microscope (S-4800, manufactured by Hitachi High-Technology Corporation), and the reactivity of the resist composition by electron beam irradiation was evaluated.
Sensitivity was expressed as the minimum amount of energy per unit area necessary for obtaining a pattern, and was evaluated according to the following.
A: When a pattern is obtained at less than 50 μC / cm 2 C: When a pattern is obtained at 50 μC / cm 2 or more In pattern formation, the obtained pattern shape is observed with an SEM (Scanning Electron Microscope) And evaluated according to the following.
A: When a rectangular pattern is obtained B: When a substantially rectangular pattern is obtained C: When a non-rectangular pattern is obtained

As described above, the present invention is not limited to the above-described embodiments and examples, and appropriate modifications can be made without departing from the scope of the invention.

The compound and resin of this embodiment have high solubility in a safe solvent, good heat resistance and etching resistance, and the resist composition provides a good resist pattern shape.
In addition, a wet process can be applied, and a compound, a resin, and a film forming composition for lithography useful for forming a photoresist underlayer film having excellent heat resistance and etching resistance can be realized. And since this film-forming composition for lithography uses a compound or resin having a specific structure that has high heat resistance and high solvent solubility, deterioration of the film during high-temperature baking is suppressed, oxygen plasma etching, etc. It is possible to form a resist and an underlayer film that are also excellent in etching resistance to. Furthermore, when the lower layer film is formed, the adhesion with the resist layer is also excellent, so that an excellent resist pattern can be formed.
Furthermore, since the refractive index is high and coloring is suppressed by low-temperature to high-temperature treatment, it is useful as various optical component-forming compositions.

Accordingly, the present invention provides, for example, an electrical insulating material, a resist resin, a semiconductor sealing resin, an adhesive for a printed wiring board, an electrical laminate mounted on an electrical device / electronic device / industrial device, etc.・ Matrix resin for prepregs, built-up laminate materials, resin for fiber reinforced plastics, sealing resin for liquid crystal display panels, paints, various coating agents, adhesives, and coatings for semiconductors installed in electronic equipment and industrial equipment In addition to resin, resist resin for semiconductors, resin for forming lower layer film, film and sheet, plastic lens (prism lens, lenticular lens, micro lens, Fresnel lens, viewing angle control lens, contrast enhancement lens, etc.) , Retardation film, electromagnetic shielding film, prism, optical fiber, flexible Solder resist printed wiring, plating resist, multilayer printed wiring boards interlayer insulating film, the optical component such as a photosensitive optical waveguide, it is widely and effectively available.
In particular, the present invention can be used particularly effectively in the fields of lithography resists, lithography underlayer films, multilayer resist underlayer films, and optical components.

The disclosure of Japanese Patent Application No. 2016-143622 filed on July 21, 2016 is incorporated herein by reference in its entirety.
In addition, all the documents, patent applications, and technical standards described in the specification are as much as if the individual documents, patent applications, and technical standards were specifically and individually stated to be incorporated by reference. , Incorporated herein by reference.

Claims

The compound represented by following formula (0).

(0)
(In Formula (0), R Y is a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms,
R Z is an N-valent group having 1 to 60 carbon atoms or a single bond,
R T each independently has an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, or a substituent. An optionally substituted alkenyl group having 2 to 30 carbon atoms, an optionally substituted alkoxy group having 1 to 30 carbon atoms, a halogen atom, a nitro group, an amino group, a carboxylic acid group, a thiol group, a hydroxyl group or a hydroxyl group Wherein the hydrogen atom is substituted with a vinyl-containing phenylmethyl group, and the alkyl group, the aryl group, the alkenyl group, and the alkoxy group may include an ether bond, a ketone bond, or an ester bond. And at least one of RT is a group in which a hydrogen atom of a hydroxyl group is substituted with a vinylphenylmethyl group,
X represents an oxygen atom, a sulfur atom or no bridge,
M is each independently an integer of 0 to 9, wherein at least one of m is an integer of 1 to 9,
N is an integer of 1 to 4, and when N is an integer of 2 or more, the structural formulas in N [] may be the same or different,
Each R is independently an integer of 0-2. )
The compound of Claim 1 whose compound represented by said Formula (0) is a compound represented by following formula (1).

(1)
(In Formula (1), R 0 has the same meaning as R Y ,
R 1 is an n-valent group having 1 to 60 carbon atoms or a single bond,
R 2 to R 5 are each independently an optionally substituted alkyl group having 1 to 30 carbon atoms, an optionally substituted aryl group having 6 to 30 carbon atoms, or a substituent. An alkenyl group having 2 to 30 carbon atoms which may have a substituent, an alkoxy group having 1 to 30 carbon atoms which may have a substituent, a halogen atom, a nitro group, an amino group, a carboxylic acid group, a thiol group, A hydroxyl group or a group in which a hydrogen atom of a hydroxyl group is substituted with a vinylphenylmethyl group, and the alkyl group, the aryl group, the alkenyl group, and the alkoxy group may include an ether bond, a ketone bond, or an ester bond. Here, at least one of R 2 to R 5 is a group in which a hydrogen atom of a hydroxyl group is substituted with a vinylphenylmethyl group,
M 2 and m 3 are each independently an integer of 0 to 8,
M 4 and m 5 are each independently an integer of 0 to 9,
However, m 2 , m 3 , m 4 and m 5 are not 0 simultaneously,
N is synonymous with N, and when n is an integer of 2 or more, the structural formulas in n [] may be the same or different,
P 2 to p 5 are as defined above for r. )
The compound of Claim 1 whose compound represented by said Formula (0) is a compound represented by following formula (2).

(2)
(In Formula (2), R 0A has the same meaning as R Y ,
R 1A is a na-valent group having 1 to 60 carbon atoms or a single bond,
R 2A each independently has an optionally substituted alkyl group having 1 to 30 carbon atoms, an optionally substituted aryl group having 6 to 30 carbon atoms, or a substituent. An optionally substituted alkenyl group having 2 to 30 carbon atoms, an optionally substituted alkoxy group having 1 to 30 carbon atoms, a halogen atom, a nitro group, an amino group, a carboxylic acid group, a thiol group, a hydroxyl group or a hydroxyl group Wherein the hydrogen atom is substituted with a vinyl-containing phenylmethyl group, and the alkyl group, the aryl group, the alkenyl group, and the alkoxy group may include an ether bond, a ketone bond, or an ester bond. And at least one of R 2A is a group in which a hydrogen atom of a hydroxyl group is substituted with a vinylphenylmethyl group,
N a is the same as defined above N, where, if n a is an integer of 2 or more, n structural formulas of a number of brackets [] may be the same or different and
X A is synonymous with X,
M 2a is each independently an integer of 0 to 7, provided that at least one m 2a is an integer of 1 to 7;
Q a is independently 0 or 1. )
The compound according to claim 2, wherein the compound represented by the formula (1) is a compound represented by the following formula (1-1).

(1-1)
(In the formula (1-1), R 0 , R 1 , R 4 , R 5 , n, p 2 to p 5 , m 4 and m 5 are as defined above.
R 6 to R 7 are each independently an optionally substituted alkyl group having 1 to 30 carbon atoms, an optionally substituted aryl group having 6 to 30 carbon atoms, or a substituent. An alkenyl group having 2 to 30 carbon atoms, a halogen atom, a nitro group, an amino group, a carboxylic acid group, or a thiol group, which may have
R 10 to R 11 are each independently a hydrogen atom or a vinylphenylmethyl group,
Here, at least one of R 10 to R 11 is a vinylphenylmethyl group,
M 6 and m 7 are each independently an integer of 0 to 7,
However, m 4 , m 5 , m 6 and m 7 are not 0 at the same time. )
The compound according to claim 4, wherein the compound represented by the formula (1-1) is a compound represented by the following formula (1-2).

(1-2)
(In the formula (1-2), R 0 , R 1 , R 6 , R 7 , R 10 , R 11 , n, p 2 to p 5 , m 6 and m 7 are as defined above.
R 8 to R 9 have the same meanings as R 6 to R 7 ,
R 12 to R 13 have the same meanings as R 10 to R 11 ,
M 8 and m 9 are each independently an integer of 0 to 8,
However, m 6 , m 7 , m 8 and m 9 are not 0 at the same time. )
The compound according to claim 3, wherein the compound represented by the formula (2) is a compound represented by the following formula (2-1).

(2-1)
(In the formula (2-1), R 0A , R 1A , n a , q a and X A have the same meanings as described in the formula (2).
R 3A each independently has an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, or a substituent. Which may be an alkenyl group having 2 to 30 carbon atoms, a halogen atom, a nitro group, an amino group, a carboxylic acid group, or a thiol group,
R 4A is each independently a hydrogen atom or a vinyl-containing phenylmethyl group,
Here, at least one of R 4A is a vinyl-containing phenylmethyl group,
M 6a is each independently an integer of 0 to 5. )
A resin obtained by using the compound according to claim 1 as a monomer.
The resin of Claim 7 which has a structure represented by following formula (3).

(3)
(In the formula (3), L has an optionally substituted alkylene group having 1 to 30 carbon atoms, an optionally substituted arylene group having 6 to 30 carbon atoms, and a substituent. The alkylene group, the arylene group and the alkoxylene group may contain an ether bond, a ketone bond or an ester bond,
R 0 has the same meaning as R Y ,
R 1 is an n-valent group having 1 to 60 carbon atoms or a single bond,
R 2 to R 5 are each independently an optionally substituted alkyl group having 1 to 30 carbon atoms, an optionally substituted aryl group having 6 to 30 carbon atoms, or a substituent. An alkenyl group having 2 to 30 carbon atoms which may have a substituent, an alkoxy group having 1 to 30 carbon atoms which may have a substituent, a halogen atom, a nitro group, an amino group, a carboxylic acid group, a thiol group, A hydroxyl group or a group in which a hydrogen atom of a hydroxyl group is substituted with a vinylphenylmethyl group, and the alkyl group, the aryl group, the alkenyl group, and the alkoxy group may include an ether bond, a ketone bond, or an ester bond. Often,
M 2 and m 3 are each independently an integer of 0 to 8,
M 4 and m 5 are each independently an integer of 0 to 9,
However, m 2 , m 3 , m 4 and m 5 are not simultaneously 0, and at least one of R 2 to R 5 is a group in which a hydrogen atom of a hydroxyl group is substituted with a vinylphenylmethyl group.
N is synonymous with N, and when n is an integer of 2 or more, the structural formulas in n [] may be the same or different,
P 2 to p 5 are as defined above for r. )
The resin of Claim 7 which has a structure represented by following formula (4).

(4)
(In Formula (4), L has an optionally substituted alkylene group having 1 to 30 carbon atoms, an optionally substituted arylene group having 6 to 30 carbon atoms, and a substituent. The alkylene group, the arylene group and the alkoxylene group may contain an ether bond, a ketone bond or an ester bond,
R 0A has the same meaning as R Y ,
R 1A is a na-valent group having 1 to 30 carbon atoms or a single bond,
R 2A each independently has an optionally substituted alkyl group having 1 to 30 carbon atoms, an optionally substituted aryl group having 6 to 30 carbon atoms, or a substituent. An optionally substituted alkenyl group having 2 to 30 carbon atoms, an optionally substituted alkoxy group having 1 to 30 carbon atoms, a halogen atom, a nitro group, an amino group, a carboxylic acid group, a thiol group, a hydroxyl group or a hydroxyl group Wherein the hydrogen atom is substituted with a vinyl-containing phenylmethyl group, and the alkyl group, the aryl group, the alkenyl group, and the alkoxy group may include an ether bond, a ketone bond, or an ester bond. And at least one of R 2A is a group in which a hydrogen atom of a hydroxyl group is substituted with a vinylphenylmethyl group,
N a is the same as defined above N, where, if n a is an integer of 2 or more, n structural formulas of a number of brackets [] may be the same or different and
X A is synonymous with X,
M 2a is each independently an integer of 0 to 7, provided that at least one m 2a is an integer of 1 to 6;
Q a is independently 0 or 1. )
A composition comprising at least one selected from the group consisting of the compound according to any one of claims 1 to 6 and the resin according to any one of claims 7 to 9.
The composition according to claim 10, further comprising a solvent.
The composition according to claim 10 or 11, further comprising an acid generator.
The composition according to any one of claims 10 to 12, further comprising a crosslinking agent.
The crosslinking agent is at least one selected from the group consisting of phenol compounds, epoxy compounds, cyanate compounds, amino compounds, benzoxazine compounds, melamine compounds, guanamine compounds, glycoluril compounds, urea compounds, isocyanate compounds, and azide compounds. The composition according to claim 13.
The composition according to claim 13 or 14, wherein the crosslinking agent has at least one allyl group.
A composition containing at least one member selected from the group consisting of the compound according to any one of Claims 1 to 6 and the resin according to any one of Claims 7 to 9, wherein the content of the crosslinking agent is The composition according to any one of claims 13 to 15, which is 0.1 to 100 parts by mass with respect to 100 parts by mass of the total mass of the product.
The composition according to any one of claims 13 to 16, further comprising a crosslinking accelerator.
The composition according to claim 17, wherein the crosslinking accelerator is at least one selected from the group consisting of amines, imidazoles, organic phosphines, and Lewis acids.
The content of the crosslinking accelerator contains at least one selected from the group consisting of the compound according to any one of claims 1 to 6 and the resin according to any one of claims 7 to 9. The composition according to claim 17 or 18, which is 0.1 to 5 parts by mass with respect to 100 parts by mass of the total mass of the composition.
The composition according to any one of claims 10 to 19, further comprising a radical polymerization initiator.
The radical polymerization initiator is at least one selected from the group consisting of a ketone photopolymerization initiator, an organic peroxide polymerization initiator, and an azo polymerization initiator. A composition according to 1.
The content of the radical polymerization initiator contains at least one selected from the group consisting of the compound according to any one of claims 1 to 6 and the resin according to any one of claims 7 to 9. The composition according to any one of claims 10 to 21, which is 0.05 to 25 parts by mass with respect to 100 parts by mass of the total composition.
The composition according to any one of claims 10 to 22, which is used for forming a film for lithography.
The composition according to any one of claims 10 to 22, which is used for forming a resist permanent film.
The composition according to any one of claims 10 to 22, which is used for forming an optical component.
A method for forming a resist pattern, comprising: forming a photoresist layer on a substrate using the composition according to claim 23; and irradiating a predetermined region of the photoresist layer with radiation and developing the photoresist layer.
A lower layer film is formed on the substrate using the composition according to claim 23, and at least one photoresist layer is formed on the lower layer film, and then radiation is applied to a predetermined region of the photoresist layer. A resist pattern forming method including a step of irradiating and developing.
An underlayer film is formed on a substrate using the composition according to claim 23, an intermediate layer film is formed on the underlayer film using a resist intermediate layer film material, and at least on the intermediate layer film, After forming a single photoresist layer, a predetermined region of the photoresist layer is irradiated with radiation, developed to form a resist pattern, and then the intermediate layer film is etched using the resist pattern as a mask, A circuit pattern forming method, comprising: etching the lower layer film using the obtained intermediate layer film pattern as an etching mask; and etching the substrate using the obtained lower layer film pattern as an etching mask to form a pattern on the substrate.
The compound represented by following formula (5).

(5)
(In the formula (5), R 5A is an N-valent group having 1 to 60 carbon atoms or a single bond,
m 10 is each independently an integer of 1 to 3 N B, is an integer of 1 to 4. When the N B an integer of 2 or more, the structural formula of N in [] was identical Or different. )