KR20190034149A - COMPOSITIONS, RESINS AND COMPOSITIONS, AND RESIST PATTERN FORMING METHOD - Google Patents

Abstract

(0)
(식(0) 중, R^Y는, 수소원자, 탄소수 1~30의 알킬기 또는 탄소수 6~30의 아릴기이고, R^Z는, 탄소수 1~60의 N가의 기 또는 단결합이고, R^T는, 각각 독립적으로, 치환기를 갖고 있을 수도 있는 탄소수 1~30의 알킬기, 치환기를 갖고 있을 수도 있는 탄소수 6~30의 아릴기, 치환기를 갖고 있을 수도 있는 탄소수 2~30의 알케닐기, 치환기를 갖고 있을 수도 있는 탄소수 1~30의 알콕시기, 할로겐원자, 니트로기, 아미노기, 카르본산기, 티올기, 수산기 또는 수산기의 수소원자가 하기 식(0-1)로 표시되는 기로 치환된 기이고, 해당 알킬기, 해당 아릴기, 해당 알케닐기, 해당 알콕시기는, 에테르결합, 케톤결합 또는 에스테르결합을 포함하고 있을 수도 있고, 여기서, R^T의 적어도 1개는 하기 식(0-1)로 표시되는 기를 포함하고, X는, 산소원자, 황원자 또는 무가교인 것을 나타내고, m은, 각각 독립적으로 0~9의 정수이고, 여기서, m의 적어도 1개는 1~9의 정수이고, N은, 1~4의 정수이고, N이 2 이상의 정수인 경우, N개의 [ ] 내의 구조식은 동일할 수도 상이할 수도 있고, r은, 각각 독립적으로 0~2의 정수이다.)

(0-1)
(식(0-1) 중, R^X는, 수소원자 또는 메틸기이다.)(0). ≪ / RTI >

(0)
(Wherein 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 or a single bond having 1 to 60 carbon atoms, and R ^T is , Independently of each other, 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, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, An alkyl 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 with a group represented by the following formula (0-1) The aryl group, the corresponding alkenyl group and the corresponding alkoxy group may include an ether bond, a ketone bond or an ester bond, wherein at least one of R ^T includes a group represented by the following formula (0-1) X represents an oxygen atom, a sulfur atom or a non- and m are each independently an integer of 0 to 9, provided that 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, May be the same or different, and r is independently an integer of 0 to 2.)

(0-1)
(In the formula (0-1), R ^X is a hydrogen atom or a methyl group.)

Description

COMPOSITIONS, RESINS AND COMPOSITIONS, AND RESIST PATTERN FORMING METHOD

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

In the production of semiconductor devices, fine processing by lithography using a photoresist material has been performed. Recently, along with the increase in integration and the increase in the speed of LSI, further miniaturization by pattern rules has been demanded. The lithography light source used for forming a resist pattern is short-wavelengthed by an ArF excimer laser (193 nm) in a KrF excimer laser (248 nm), and extreme ultraviolet light (EUV, 13.5 nm) is also expected to be introduced.

However, in lithography using a conventional high molecular weight resist material, the molecular weight is as large as about 10,000 to 100,000 and the molecular weight distribution is wide. As a result, roughness is generated on the pattern surface and control of the pattern dimension becomes difficult.

To date, various low-molecular-weight resist materials have been proposed in order to impart a resist pattern with higher resolution. The low molecular weight resist material is expected to give a resist pattern with high resolution and low roughness because of its small molecular size.

At present, various such low-molecular-weight resist materials are known. For example, an alkali developing type negative radiation sensitive composition (see, for example, Patent Document 1 and Patent Document 2) 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 a material, an alkali developing type negative radiation sensitive composition using a low molecular weight cyclic polyphenol compound as a main component (see, for example, Patent Document 3 and Non-Patent Document 1) has also been proposed. Further, it is known that a polyphenol compound as a base compound of a resist material can impart a high heat resistance with a low molecular weight, and is useful for improving the resolution and roughness of a resist pattern (see, for example, Non-Patent Document 2 ).

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

Further, when the resist pattern becomes finer, there arises a problem of resolution or a problem that the resist pattern collapses after development. Therefore, it is desired to reduce the thickness of the resist. However, if the thinning of the resist is simply performed, it becomes difficult to obtain a film thickness of the resist pattern sufficient for processing the substrate. Thus, there has been a need for a process for manufacturing a resist underlayer film between a resist and a semiconductor substrate to be processed, as well as a resist pattern, so that the resist underlayer film has a function as a mask at the time of substrate processing.

At present, various kinds of resist undercoat films for such processes are known. For example, unlike a conventional resist underlayer film having a high etching rate, a resist underlayer film having a selectivity ratio of a dry etching rate close to that of a resist is realized. When a predetermined energy is applied, the terminal group is eliminated, (See, for example, Patent Document 5). The lower layer film forming material for a multi-layer resist process contains a resin component having at least a substituent that generates a low refractive index layer and a solvent. Furthermore, a resist underlayer film material containing a polymer having a specific repeating unit has been proposed for realizing a resist underlayer film having a selectivity of a dry etching rate lower than that of a resist (for example, refer to Patent Document 6) . Furthermore, to realize a resist underlayer film having a selectivity of a dry etching rate lower than that of a semiconductor substrate, a polymer obtained by copolymerizing a repeating unit of acenaphthylene and a repeating unit having a substituted or unsubstituted hydroxy group (For example, refer to Patent Document 7).

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

Furthermore, the present inventors have found that a composition for forming a lower layer for lithography (for example, a composition for forming a lower layer film for lithography, which contains a compound having a specific structure and an organic solvent, as a material which is excellent in etching resistance, high in heat resistance, For example, Patent Document 8).

On the other hand, as to the method of forming the intermediate layer used in the formation of the resist underlayer film in the three-layer process, for example, a method of forming a silicon nitride film (for example, see Patent Document 9) (See, for example, 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).

Furthermore, various optical component forming compositions have been proposed. For example, an acrylic resin (see, for example, Patent Documents 13 to 14).

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

T. Nakayama, M. Nomura, K. Haga, M. Ueda: Bull. Chem. Soc. Jpn., 71, 2979 (1998) Shinji Okazaki, et al. 22 "New Development of Photoresist Material Development" by MC Corporation, September 2009, p.211-259

As described above, a number of conventionally proposed film forming compositions for lithography for use in resist applications and film forming compositions for lithography for use in a lower layer film have been proposed, and a high-temperature Not only has solubility in solvents, but also high heat resistance and etching resistance are not compatible with each other 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 required.

Furthermore, although a large number of conventional compositions for optical members have been proposed, there is no compatibility with heat resistance, transparency and refractive index at a high level, and development of new materials is required.

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems of the prior art, and an object of the present invention is to provide a photoresist and a photoresist lower layer film which can apply a wet process and has excellent heat resistance and excellent solubility and etching resistance. , A compound, a resin and a composition. It is another object of the present invention to provide a resist film, a resist underlayer film, a resist permanent film, and a pattern forming method using the composition. And further to provide a composition for an optical member.

DISCLOSURE OF THE INVENTION The inventors of the present invention have made intensive investigations to solve the problems of the prior art, and as a result, they found that the aforementioned problems can be solved by using a compound or a resin having a specific structure, and completed the present invention.

That is, the present invention is as follows.

[One]

(0). ≪ / RTI >

[Chemical Formula 1]

(0)

(In the 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 or a single bond having 1 to 60 carbon atoms,

R ^T each independently represents 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, an alkenyl group having 2 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 hydroxyl group with a group represented by the formula (0-1) 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, wherein at least one of R ^T is a group represented by the following formula (0-1) Including,

X represents an oxygen atom, a sulfur atom or a non-

m is independently an integer of 0 to 9, provided that 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 within N [] may be the same or different,

r is independently an integer of 0 to 2.)

(2)

(0-1)

(In the formula (0-1), R ^X is a hydrogen atom or a methyl group.)

[2]

The compound according to [1], wherein the compound represented by the formula (0) is a compound represented by the following formula (1).

(3)

(One)

(In the formula (1), R ⁰ is synonymous with R ^Y ,

R ¹ is an n-valent group or a single bond having 1 to 60 carbon atoms,

Each of R ² to R ⁵ independently represents 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, an alkenyl group having 2 to 30 carbon atoms 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 hydroxyl group is substituted with a group represented by the formula (0-1) 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, wherein at least one of R ² to R ⁵ is a group represented by the formula (0- 1), < / RTI >

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,

Provided that m ² , m ³ , m ⁴ and m ⁵ do not become 0 at the same time,

n is a synonym with the above N, wherein when n is an integer of 2 or more, the structural formulas within n [] may be the same or different,

and p ² to p ⁵ are synonymous with r.

[3]

The compound according to [1], wherein the compound represented by the formula (0) is a compound represented by the following formula (2).

[Chemical Formula 4]

(2)

(In formula (2), R ^0A is synonymous with R ^Y ,

R ^1A is an n ^A -valent group or a single bond having 1 to 60 carbon atoms,

R ^2A each independently represents 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, an alkenyl group having 2 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 hydrogen atom of a hydroxyl group is substituted with a group represented by the formula (0-1) 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, wherein at least one of R ^2A is a group represented by the formula (0-1) Including,

n ^A is the same as the above N, wherein when n ^A is an integer of 2 or more, the structural formulas within n ^A [] may be the same or different,

X ^A represents an oxygen atom, a sulfur atom or a non-

m ^2A is independently an integer of 0 to 7, provided that at least one of m ^2A is an integer of 1 to 7,

q ^A are each 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).

[Chemical Formula 5]

(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 the same as those in the formula (1)

R ⁶ to R ⁷ each independently represent 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, an alkenyl group having 2 to 30 carbon atoms, A halogen atom, a nitro group, an amino group, a carboxylic acid group, and a thiol group,

R ¹⁰ to R ¹¹ are each independently a hydrogen atom or a group represented by the following formula (0-2)

At least one of R ¹⁰ to R ¹¹ is a group represented by the following formula (0-2)

m ⁶ and m ⁷ are each independently an integer of 0 to 7,

Provided that m ⁴ , m ⁵ , m ⁶ and m ⁷ do not become 0 at the same time.)

[Chemical Formula 6]

(0-2)

(In the formula (0-2), R ^X is the same as that in the formula (0-1), and s is an integer of 0 to 30.)

[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).

(7)

(1-2)

(Wherein R ⁰ , R ¹ , R ⁶ , R ⁷ , R ¹⁰ , R ¹¹ , n, p ² to p ⁵ , m ⁶ and m ⁷ in the formula (1-2) In agreement with what's in it,

R ⁸ to R ⁹ are as defined above for R ⁶ to R ⁷ ,

R ¹² to R ¹³ are as defined above for 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 is not at the same time work is zero.)

[6]

The compound according to [3], wherein the compound represented by the formula (2) is a compound represented by the following formula (2-1).

[Chemical Formula 8]

(2-1)

(In the formula (2-1), R ^0A , R ^{1 A} , n ^A , q ^A and X ^A are the same as those in the formula (2)

R ^3A each independently represents a linear, branched or cyclic alkyl group of 1 to 30 carbon atoms which may have a substituent, an aryl group of 6 to 30 carbon atoms which may have a substituent, a carbon number which may have a substituent A halogen atom, a nitro group, an amino group, a carboxylic acid group or a thiol group,

R ^4A each independently represents a hydrogen atom or a group represented by the following formula (0-2)

Here, at least one of R ^4A is a group represented by the following formula (0-2)

m ^6A are each independently an integer of 0 to 5.)

[Chemical Formula 9]

(0-2)

(In the formula (0-2), R ^X is the same as that in the formula (0-1), and s is an integer of 0 to 30.)

[7]

A resin obtained by using the compound described in [1] as a monomer.

[8]

The resin according to [7], having a structure represented by the following formula (3).

[Chemical formula 10]

(3)

(In the formula (3), L represents an alkylene group having 1 to 30 carbon atoms which may have a substituent, an arylene group having 6 to 30 carbon atoms which may have a substituent, an alkoxy group having 1 to 30 carbon atoms And the alkylene group, the arylene group and the alkoxylene group may contain an ether bond, a ketone bond or an ester bond,

R ⁰ is synonymous with R ^Y ,

R ¹ is an n-valent group or a single bond having 1 to 60 carbon atoms,

Each of R ² to R ⁵ independently represents 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, an alkenyl group having 2 to 30 carbon atoms 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 hydroxyl group is substituted with a group represented by the formula (0-1) 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, wherein at least one of R ² to R ⁵ is a group represented by the formula (0- 1), < / RTI >

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,

Provided that m ² , m ³ , m ⁴ and m ⁵ do not become 0 at the same time,

n is a synonym with the above N, wherein when n is an integer of 2 or more, the structural formulas within n [] may be the same or different,

and p ² to p ⁵ are synonymous with r.

[9]

The resin according to [7], having a structure represented by the following formula (4).

(11)

(4)

(In the formula (4), L represents an alkylene group having 1 to 30 carbon atoms which may have a substituent, an arylene group having 6 to 30 carbon atoms which may have a substituent, an alkoxy group having 1 to 30 carbon atoms A silylene group or a single bond, and the alkylene group, the arylene group and the alkoxylene group may contain an ether bond, a ketone bond or an ester bond,

R ^0A is synonymous with R ^Y ,

R ^1A is an n ^A -valent group having 1 to 30 carbon atoms or a single bond,

R ^2A each independently represents 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, an alkenyl group having 2 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 hydrogen atom of a hydroxyl group is substituted with a group represented by the formula (0-1) 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, wherein at least one of R ^2A is a group represented by the formula (0-1) Including,

n ^A is the same as the above N, wherein when n ^A is an integer of 2 or more, the structural formulas within n ^A [] may be the same or different,

X ^A represents an oxygen atom, a sulfur atom or a non-

m ^2A is independently an integer of 0 to 7, provided that at least one of m ^2A is an integer of 1 to 6,

q ^A are each independently 0 or 1.)

[10]

A composition comprising at least one member selected from the group consisting of the compounds described in any one of [1] to [6] and the resins described in any one of [7] to [9].

[11]

The composition according to [10], further comprising a solvent.

[12]

The composition according to [10] or [11], further comprising an acid generator.

[13]

The composition according to any one of [10] to [12], further comprising a crosslinking agent.

[14]

The crosslinking agent is at least one selected from the group consisting of a phenol compound, an epoxy compound, a cyanate compound, an amino compound, a benzoxazine compound, a melamine compound, a guanamine compound, a glycoluril compound, a urea compound, an isocyanate compound and an azide compound The composition according to [13].

[15]

The composition according to [13] or [14], wherein the crosslinking agent has at least one allyl group.

[16]

The total mass of the composition containing at least one member selected from the group consisting of the compound described in any one of [1] to [6] and the resin described in any one of [7] to [9] Is from 0.1 to 100 parts by weight based on 100 parts by weight of the total amount of the composition.

[17]

The composition according to any one of [13] to [16], further comprising 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 total amount of the composition containing at least one member selected from the group consisting of the compound described in any one of [1] to [6] and the resin described in any one of [7] to [9] The composition according to [17] or [18], wherein the amount is 0.1 to 5 parts by mass when the mass is 100 parts by mass.

[20]

The composition according to any one of [10] to [19], further comprising a radical polymerization initiator.

[21]

The composition according to any one of [10] to [20], wherein the radical polymerization initiator is at least one selected from the group consisting of a ketone-based photopolymerization initiator, an organic peroxide-based polymerization initiator and an azo-based polymerization initiator.

[22]

Wherein the content of the radical polymerization initiator is at least one kind selected from the group consisting of a compound according to any one of [1] to [6] and a resin according to any one of [7] to [9] The composition according to any one of [10] to [21], wherein the amount is 0.05 to 25 parts by mass when the total mass is 100 parts by mass.

[23]

The composition according to any one of [10] to [22], which is used for film formation for lithography.

[24]

The composition according to any one of [10] to [22], which is used for resist permanent film formation.

[25]

The composition according to any one of [10] to [22], which is used for forming an optical component.

[26]

A step of forming a photoresist layer on the substrate using the composition described in [23], and then irradiating a predetermined region of the photoresist layer with radiation to perform development.

[27]

Forming a lower layer film on the substrate using the composition described in [23], forming at least one photoresist layer on the lower layer film, irradiating a predetermined region of the photoresist layer with radiation, Thereby forming a resist pattern.

[28]

An undercoat film is formed on a substrate using the composition described in [23], an interlayer film is formed on the undercoat film using a resist interlayer film material, and at least one photoresist layer is formed on the interlayer film And then the resist pattern is used as a mask to etch the intermediate layer film, and the obtained intermediate layer film pattern is etched using 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 and the resin according to the present invention have high solubility in safety solvents, good heat resistance and etching resistance, and the composition according to the present invention gives a good resist pattern shape.

Hereinafter, a mode for carrying out the present invention (hereinafter also referred to as " present embodiment ") will be described. The following embodiments are illustrative of the present invention, and the present invention is not limited to the embodiments.

The compound of this embodiment is a resin obtained by using a compound represented by the following formula (0) or a corresponding compound as a monomer. The compounds and resins according to the present invention are useful for forming a photoresist underlayer film which can apply a wet process and is excellent in heat resistance and etching resistance. Since the film forming composition for lithography uses a compound or resin having a specific structure and high heat resistance and high solvent solubility, deterioration of the film at the time of high-temperature baking is suppressed and etching resistance against oxygen plasma etching and the like is also excellent A resist and a lower layer film can be formed. In addition, when a lower layer film is formed, adhesion with the resist layer is also excellent, so that an excellent resist pattern can be formed. The compound and the resin in the present embodiment are excellent in sensitivity and resolution when used in a photosensitive material and can be used in combination with a general-purpose organic solvent, another compound, a resin component, And is useful for forming a resist permanent film excellent in compatibility.

Further, it is also useful as various optical forming compositions because the refractive index is high and coloring is suppressed by a wide range of heat treatment from low temperature to high temperature.

[Compound represented by formula (0)

The compound of this embodiment is represented by the following formula (0).

[Chemical Formula 12]

(0)

(In the 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 or a single bond having 1 to 60 carbon atoms,

R ^T each independently represents 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, an alkenyl group having 2 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 hydroxyl group with a group represented by the formula (0-1) 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, wherein at least one of R ^T is a group represented by the following formula (0-1) Including,

X represents an oxygen atom, a sulfur atom or a non-

m is independently an integer of 0 to 9, provided that 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 within N [] may be the same or different,

r is independently an integer of 0 to 2.)

[Chemical Formula 13]

(0-1)

(In the formula (0-1), R ^X is a hydrogen atom or a methyl group.)

The group containing a group represented by formula (0-1) is a group having a group represented by formula (0-1), and examples thereof include a group represented by formula (0-1) and a group represented by formula (0-1) Ethoxy group substituted with a group represented by the formula (0-1), propoxy group substituted with a group represented by the formula (0-1), or a group represented by the formula (0-1) An ethoxyethoxy group, a propoxypropoxy group substituted with a group represented by the formula (0-1), and a phenyloxy group substituted with a group represented by the formula (0-1).

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. The alkyl group may be a linear, branched or cyclic alkyl group. R ^Y is a hydrogen atom, a straight chain, branched or cyclic alkyl group having 1 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms, whereby excellent heat resistance and solvent solubility can be imparted.

R ^z is an N-valent group or a single bond having 1 to 60 carbon atoms, and each aromatic ring is bonded via R ^z . N is an integer of 1 to 4, and when N is an integer of 2 or more, the structural formulas within 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 30 carbon atoms when N = 2, an alkane-containing group having 2 to 60 carbon atoms when N = 3, = 4 means an alkane tetrayl group having 3 to 60 carbon atoms. The N-valent groups include, for example, those having a straight-chain 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 represents 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, an alkenyl group having 2 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 hydrogen atom of a hydroxyl group is substituted with a group represented by the formula (0-1) 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, wherein at least one of R ^T is a group in which the hydrogen atom of the hydroxyl group is an allyloxyalkyl group, And a group substituted with one group selected from an acryloxyalkyl group. On the other hand, the alkyl group, alkenyl group and alkoxy group may be a straight chain, branched or cyclic group.

Here, the group in which the hydrogen atom of the hydroxyl group is substituted with a vinylphenylmethyl group is a group having a vinylphenylmethyl group, and examples thereof include a vinylphenylmethyl group, a vinylphenylmethylmethyl group, and a vinylphenylmethylphenyl group.

X is an oxygen atom, a sulfur atom, or a non-condensed, and when X is an oxygen atom or a sulfur atom, it is preferable because it tends to exhibit high heat resistance and is more preferably an oxygen atom. From the viewpoint of solubility, X is preferably a non-crosslinked one. M is 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 moiety 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. r is independently an integer of 0 to 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, and has a high heat resistance due to the rigidity of its structure, so that it can be used even under high-temperature baking conditions. Further, it has tertiary carbon or quaternary carbon in the molecule and is suppressed in crystallinity, and is suitably used as a film-forming composition for lithography that can be used in the production of a film for lithography.

In addition, since the solubility in a safe solvent is high and the heat resistance and the etching resistance are good, the resist-forming composition for lithography containing the compound represented by the formula (0) can give a good resist pattern shape.

Further, even in the case of a substrate having a step (particularly, a minute space or a hole pattern) at a point of a relatively low molecular weight and a low viscosity, it is easy to increase the flatness of the film while uniformly filling the corners of the step, (0), the underlayer film-forming composition for lithography has good burial and planarization characteristics. In addition, since the compound represented by the formula (0) is a compound having a relatively high carbon concentration, it can also impart high etching resistance.

Furthermore, the composition containing the compound represented by the formula (0) has a high refractive index because of its high aromatic density and is also useful as a composition for forming various optical parts from the viewpoint that coloration is suppressed by a wide range of heat treatment from a low temperature to a high temperature Do. Among them, a compound having quaternary carbon is preferable from the viewpoints of inhibiting oxidation decomposition to suppress coloring of a compound, having high heat resistance, and improving solvent solubility. In addition to being used in the form of a film or a sheet, the optical component can be used in various forms such as a plastic lens (a prism lens, a lenticular lens, a microlens, a Fresnel lens, a viewing angle control lens, a contrast enhancement lens and the like), a retardation film, , An optical fiber, a solder resist for flexible printed wiring, a plating resist, an interlayer insulating film for a multilayer printed wiring board, and a photosensitive optical waveguide.

[Compound represented by the formula (1)

The compound represented by the formula (0) in the present embodiment is preferably a compound represented by the following formula (1). The compound of the present embodiment is a compound represented by the following formula (1), which tends to have higher heat resistance and higher solvent solubility.

[Chemical Formula 14]

(One)

In the above formula (1), R ⁰ is a hydrogen atom, an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, which is the same as R ^Y. When R ⁰ is a hydrogen atom, an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, the heat resistance is relatively high, and the solvent solubility tends to be improved. R ⁰ is preferably an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms from the viewpoint of inhibiting oxidation decomposition to suppress coloring of the compound and improving heat resistance and solvent solubility.

R ¹ is an n-valent group or a single bond having 1 to 60 carbon atoms, and each aromatic ring is bonded via this R ¹ .

Each of R ² to R ⁵ independently represents 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, an alkenyl group having 2 to 30 carbon atoms 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 hydroxyl group is substituted with a group represented by the formula (0-1) 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, wherein at least one of R ² to R ⁵ is a group represented by the formula (0- 1). ≪ / RTI >

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. Provided that m ² , m ³ , m ⁴ and m ⁵ do not become 0 at the same time.

n is a synonym of N and is an integer of 1 to 4; Here, when n is an integer of 2 or more, the structural formulas within n [] may be the same or different.

p ² to p ⁵ each independently represent an integer of 0 to 2;

On the other hand, the alkyl group, alkenyl group and alkoxy group may be a straight chain, branched or cyclic group.

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, an alkane-containing group having 2 to 60 carbon atoms when n = 3, = 4 means an alkane tetrayl group having 3 to 60 carbon atoms. Examples of the n-valent group include those having a straight-chain hydrocarbon group, a branched hydrocarbon group, and an alicyclic hydrocarbon group. Here, the alicyclic hydrocarbon group includes a bridged alicyclic hydrocarbon group. The n-valent group may be an aromatic group having 6 to 60 carbon atoms.

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. Here, the alicyclic hydrocarbon group includes a bridged alicyclic hydrocarbon group.

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

In addition, since the solubility in a safe solvent is high and the heat resistance and the etching resistance are good, a resist pattern forming composition for lithography containing the compound represented by the formula (1) can give a good resist pattern shape.

Furthermore, even in the case of a substrate having a step (particularly, a minute space or a hole pattern or the like) at a relatively low molecular weight and low viscosity, it is easy to increase the flatness of the film while uniformly filling the corners of the step, The lower layer film forming composition for lithography used has favorable buried and planarized characteristics. In addition, since it is a compound having a relatively high carbon concentration, high etching resistance can also be imparted.

In addition, since the aromatic densities are high, the refractive index is high and the coloring is suppressed by a wide range of heat treatment from a low temperature to a high temperature. Among them, a compound having quaternary carbon is preferable from the viewpoints of inhibiting oxidation decomposition to suppress coloring of a compound, having high heat resistance, and improving solvent solubility. In addition to being used in the form of a film or a sheet, the optical component can be used in various forms such as a plastic lens (a prism lens, a lenticular lens, a microlens, a Fresnel lens, a viewing angle control lens, a contrast enhancement lens and the like), a retardation film, , An optical fiber, a solder resist for flexible printed wiring, a plating resist, an interlayer insulating film for a multilayer printed wiring board, 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 viewpoints of ease of crosslinking and solubility in an organic solvent.

[Chemical Formula 15]

(1-1)

In the formula (1-1)

R ² , R ¹ , R ⁴ , R ⁵ , n, p ² to p ⁵ , m ⁴ and m ⁵ are the same as those in the formula (1)

R ⁶ to R ⁷ each independently represent 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, an alkenyl group having 2 to 30 carbon atoms, A halogen atom, a nitro group, an amino group, a carboxylic acid group, and a thiol group,

R ¹⁰ to R ¹¹ are each independently a hydrogen atom or a group represented by the following formula (0-2)

At least one of R ¹⁰ to R ¹¹ is a group represented by the following formula (0-2)

m ⁶ and m ⁷ each independently represents an integer of 0 to 7,

Provided that m ⁴ , m ⁵ , m ⁶ and m ⁷ do not become 0 at the same time.

[Chemical Formula 16]

(0-2)

(In the formula (0-2), R ^X is the same as that in the formula (0-1), and s is an integer of 0 to 30.)

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

[Chemical Formula 17]

(1-2)

In the formula (1-2)

^{R 0, R 1, R 6} , R 7, R 10, R 11, n, p 2 ~ p 5, m 6 and m is ^7, and as agreed in the formula (1-1),

R ⁸ to R ⁹ are as defined above for R ⁶ to R ⁷ ,

R ¹² to R ¹³ are as defined above for R ¹⁰ to R ¹¹ ,

m ⁸ and m ⁹ are each independently an integer of 0 to 8; Provided that m ⁶ , m ⁷ , m ⁸ and m ⁹ do not become 0 at the same time.

Furthermore, the compound represented by the formula (1-1) is preferably a compound represented by the following formula (1a) from the viewpoint of the feedability of the starting material.

[Chemical Formula 18]

(1a)

In the formula (1a), R ⁰ to R ⁵ , m ² to m ⁵ and n are synonymous with those 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.

[Chemical Formula 19]

(1b)

And In the formula ^{(1b), R 0, R} 1, R 4, R 5, R 10, R 11, m 4, m 5, n is agreed that described in the formula ^{(1), R 6, R} 7, R ¹⁰ , R ¹¹ , m ⁶ and m ⁷ are as defined in the above formula (1-1).

From the viewpoint of reactivity, the compound represented by the formula (1a) is more preferably a compound represented by the following formula (1b ').

[Chemical Formula 20]

(1b ')

In the formula ^{(1b), R 0, R} 1, R 4, R 5, m 4, m 5, n is as accept the above-described formula ^{(1), R 6, R} 7, R 10, R 11, m ⁶ , and m ⁷ are as defined in the above 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.

[Chemical Formula 21]

(1c)

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

From the viewpoint of reactivity, the compound represented by the above formula (1b ') is more preferably a compound represented by the following formula (1c').

[Chemical Formula 22]

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

(23)

≪ EMI ID =

(25)

(26)

(27)

(28)

[Chemical Formula 29]

(30)

(31)

(32)

(33)

(34)

(35)

(36)

(37)

(38)

[Chemical Formula 39]

(40)

(41)

X is the same as that described in formula (0), R ^{T '} is the same as R ^T described in formula (0), and m is independently an integer of 1 to 6.

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.

(42)

(43)

(44)

[Chemical Formula 45]

(46)

(47)

(48)

(49)

(50)

(51)

(52)

(53)

(54)

(55)

(56)

(57)

(58)

[Chemical Formula 59]

(60)

(61)

(62)

(63)

≪ EMI ID =

Wherein X is the same as that described in the formula (0), R ^{Y '} R ^{Z '} is the same as R ^Y and R ^Z described in the formula (0). Also, at least one of OR ^4A includes a group represented by the following formula (0-1).

(65)

(0-1)

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

(66)

(67)

(68)

(69)

(70)

(71)

(72)

(73)

≪ EMI ID =

(75)

[Formula 76]

[Formula 77]

(78)

(79)

Among these compounds, R ² , R ³ , R ⁴ and R ⁵ are the same as those described in the formula (1). m ² and m ³ are integers of 0 to 6, and m ⁴ and m ⁵ are integers of 0 to 7.

Provided that at least one selected from R ² , R ³ , R ⁴ and R ⁵ contains a group represented by the following formula (0-1), and m ² , m ³ , m ⁴ and m ⁵ are simultaneously 0 There is no work.

(80)

(0-1)

(In the formula (0-1), R ^X is a hydrogen atom or a methyl group.)

[Formula 81]

(82)

(83)

(84)

(85)

≪ EMI ID =

[Chemical Formula 87]

[Formula 88]

(89)

(90)

[Formula 91]

≪ EMI ID =

≪ EMI ID =

Wherein R ¹⁰ , R ¹¹ , R ¹² and R ¹³ are the same as those described in the above formula (1-2), and at least one of R ¹⁰ to R ¹³ is a group represented by the formula (0-2) to be.

(94)

(0-2)

(In the formula (0-2), R ^X is the same as that in the formula (0-1), and s is an integer of 0 to 30.)

The compound represented by the above formula (1) is particularly preferably a compound represented by the following formulas (BiF-1) to (BiF-10) from the viewpoint of solubility in a further organic solvent.

≪ EMI ID =

(BiF-1)

≪ EMI ID =

(BiF-2)

[Formula 97]

(BiF-3)

(98)

(BiF-4)

[Formula 99]

(BiF-5)

(100)

(BiF-6)

(101)

(BiF-7)

≪ EMI ID =

(BiF-8)

≪ EMI ID =

(BiF-9)

≪ EMI ID =

(BiF-10)

Wherein R ¹⁰ , R ¹¹ , R ¹² and R ¹³ are the same as those described in the above formula (1-2), and at least one of R ¹⁰ to R ¹³ is a group represented by the formula (0-2) to be.

≪ EMI ID =

(0-2)

(In the formula (0-2), R ^X is the same as that in the formula (0-1), and s is an integer of 0 to 30.)

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

≪ EMI ID =

Wherein R ⁰ , R ¹ and n are the same as those described in the above formula (1-1), R ^{10 '} and R ^11' are the same as R ¹⁰ and R ¹¹ described in the above formula (1-1) , R ^{4 '} and R ^5' each independently represent 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, an aryl group having 2 to 30 carbon atoms An alkoxy group having 1 to 30 carbon atoms which may have a substituent, a group in which a hydrogen atom of a halogen atom, a nitro group, an amino group, a carboxylic acid group, a thiol group, a hydroxyl group or a hydroxyl group is substituted with the following formula (0-1) And at least one of R ^{10 '} and R ^11' may be an ether bond, a ketone bond or an ester bond, and the alkyl group, the aryl group, the alkenyl group and the alkoxy group may have the following formulas (0-2 ). ≪ / RTI > m ^{4 '} and m ^5' are integers of 0 to 8, m ^{10 '} and m ^11' are integers of 1 to 9, m ^{4 '} + m ^10' and m ^{4 '} + m ^11' It is an integer from 1 to 9.

≪ EMI ID =

(0-2)

(In the formula (0-2), R ^X is the same as that in the formula (0-1), and s is an integer of 0 to 30.)

Examples of R ⁰ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a triacontyl group, Anthracene group, pyrenyl group, biphenyl group, and heptacene group.

Examples of R ^{4 '} and R ^5' include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, , A cyclopropyl group, a cyclopropyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, a cyclododecyl group, a cyclododecyl group, A bromine atom, an allyl group, a triacontenyl group, a methoxy group, an ethoxy group, a triacontic group, a fluorine atom, a chlorine atom, a bromine atom, a bromine atom, An iodine atom, and a thiol group.

Each of the examples 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.

(108)

Wherein R ¹⁰ to R ¹³ are the same as those described in the above formula (1-2), R ¹⁶ is a linear, branched or cyclic alkylene group having 1 to 30 carbon atoms, a divalent An aryl group, or a divalent alkenyl group having 2 to 30 carbon atoms.

Examples of R ¹⁶ include methylene, ethylene, propene, butene, pentene, hexene, heptene, octene, nonene, decene, A cycloheptene group, a cyclopentene group, a cyclopentene group, a cyclopentene group, a cyclohexene group, a cycloheptene group, a cyclooctene group, a cyclopentene group, a cyclodecene group, a cyclododecene group, a cyclododecene group, A divalent bivalent group, a divalent bivalent group, a divalent heptacyclic group, a divalent vinyl group, a divalent allyl group, a divalent trialkadenyl group, .

Each of the examples of R < ¹⁶ > 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.

(109)

(110)

(111)

(112)

(113)

Wherein R ¹⁰ to R ¹³ are the same as those described in the above formula (1-2), R ¹⁴ each independently represents a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, a linear, branched or cyclic alkyl group having 6 to 30 carbon atoms An alkoxy group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a halogen atom, a thiol group, m ¹⁴ is an integer of 0 to 5, m ^{14 '} is an integer of 0 to 4, m ¹⁴ Is an integer of 0 to 5.

Examples of R ¹⁴ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a triacontyl group, A cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, a cyclodecyl group, a cyclododecyl group, a cyclotriacontyl group, a norbornyl group, an adamantyl group, a phenyl group, A chlorine atom, a bromine atom, an iodine atom, a thiol group, a bromine atom, a bromine atom, an iodine atom, a thiol group, a cyano group, a nitro group, an anthracene group, a pyrenyl group, a biphenyl group, .

Each of the examples 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.

(114)

In the above formulas, 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.

(115)

Wherein R ¹⁰ to R ¹³ are the same as those described in the above formula (1-2), R ¹⁴ each independently represents a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, a linear, branched or cyclic alkyl group having 6 to 30 carbon atoms An alkoxy group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a halogen atom, a thiol group, m ¹⁴ is an integer of 0 to 5, m ^{14 '} is an integer of 0 to 4, m ^{14 ''} Is an integer from 0 to 3.

Examples of R ¹⁴ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a triacontyl group, A cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, a cyclodecyl group, a cyclododecyl group, a cyclotriacontyl group, a norbornyl group, an adamantyl group, a phenyl group, A chlorine atom, a bromine atom, an iodine atom, a thiol group, a bromine atom, a bromine atom, an iodine atom, a thiol group, a cyano group, a nitro group, an anthracene group, a pyrenyl group, a biphenyl group, .

Each of the examples 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.

≪ EMI ID =

Wherein R ¹⁰ to R ¹³ are the same as those described in the above formula (1-2), R ¹⁵ is 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.

Examples of R ¹⁵ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a triacontyl group, A cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, a cyclodecyl group, a cyclododecyl group, a cyclotriacontyl group, a norbornyl group, an adamantyl group, a phenyl group, A chlorine atom, a bromine atom, an iodine atom, a thiol group, a bromine atom, a bromine atom, an iodine atom, a thiol group, a cyano group, a nitro group, an anthracene group, a pyrenyl group, a biphenyl group, .

Each of the examples 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.

(117)

(118)

(119)

(120)

(121)

(122)

(123)

(124)

(125)

In the formula, R ¹⁰ to R ¹³ are the same as those described in the formula (1-2).

The compound represented by the formula (0) is more preferably the compounds listed below from the viewpoint of the availability of the starting material.

(126)

(127)

(128)

≪ EMI ID =

(130)

[Formula 131]

(132)

(133)

(134)

(135)

≪ EMI ID =

(137)

≪ EMI ID =

[Chemical Formula 139]

≪ EMI ID =

(141)

(142)

(143)

(144)

(145)

(146)

(147)

(148)

[Chemical Formula 149]

(150)

(151)

(152)

[Formula 153]

(154)

(155)

(156)

(157)

(158)

(159)

[Formula 160]

[Formula 161]

(162)

[163]

≪ EMI ID =

(165)

≪ EMI ID =

≪ EMI ID =

≪ EMI ID =

[169]

(170)

[171]

(172)

[173]

≪ EMI ID =

(175)

[176]

[177]

[178]

[179]

(180)

[181]

[Formula 182]

[183]

[184]

[185]

[186]

[187]

[188]

[189]

(190)

[191]

(192)

[193]

[194]

[195]

[196]

[197]

[198]

[199]

In the formula, R ¹⁰ to R ¹³ are the same as those described in the formula (1-2).

Further, the compound represented by the formula (0) is preferably a compound having the following structure from the viewpoint of etching resistance.

(200)

[201]

(202)

^Wherein R ^0A is the same as R ^Y in the formula (0), R ^{1A '} is the same as R ^Z in the formula (0), and R ¹⁰ to R ¹³ are the same as those in the formula It is described and agreed.

(203)

≪ EMI ID =

In the formula, R ¹⁰ to R ¹³ are the same as those described in the formula (1-2). R ¹⁴ each independently represents a linear, branched or cyclic alkyl group of 1 to 30 carbon atoms, an aryl group of 6 to 30 carbon atoms, an alkenyl group of 2 to 30 carbon atoms, an alkoxy group of 1 to 30 carbon atoms, a halogen atom, Thiol group, and m ¹⁴ is an integer of 0 to 4.

Examples of R ¹⁴ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a triacontyl group, A cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, a cyclodecyl group, a cyclododecyl group, a cyclotriacontyl group, a norbornyl group, an adamantyl group, a phenyl group, An alkoxy group, a methoxy group, an ethoxy group, a triacontic group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and a thiol group.

Each of the examples 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.

(205)

(206)

(207)

(208)

≪ EMI ID =

Wherein R ¹⁰ to R ¹³ are the same as those described in the above formula (1-2), R ¹⁵ is 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.

Examples of R ¹⁵ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a triacontyl group, A cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, a cyclodecyl group, a cyclododecyl group, a cyclotriacontyl group, a norbornyl group, an adamantyl group, a phenyl group, An alkoxy group, a methoxy group, an ethoxy group, a triacontic group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and a thiol group.

Each of the examples 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.

(210)

(211)

(212)

Wherein R ¹⁰ to R ¹³ are the same as those described in the above formula (1-2), R ¹⁶ is a linear, branched or cyclic alkylene group having 1 to 30 carbon atoms, a divalent An aryl group, or a divalent alkenyl group having 2 to 30 carbon atoms.

Examples of R ¹⁶ include methylene, ethylene, propene, butene, pentene, hexene, heptene, octene, nonene, decene, A cycloheptene group, a cyclopentene group, a cyclopentene group, a cyclopentene group, a cyclohexene group, a cycloheptene group, a cyclooctene group, a cyclopentene group, a cyclodecene group, a cyclododecene group, a cyclododecene group, A divalent naphthyl group, a divalent anthracene group, a divalent heptasene group, a divalent vinyl group, a divalent allyl group, and a divalent triacontenyl group can be given.

Each of the examples of R < ¹⁶ > 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.

(213)

(214)

(215)

(216)

[217]

[218]

[219]

Wherein R ¹⁰ to R ¹³ are the same as those described in the above formula (1-2), R ¹⁴ each independently represents a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, a linear, branched or cyclic alkyl group having 6 to 30 carbon atoms An aryl group or an alkenyl group having 2 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a halogen atom or a thiol group, and m ^{14 '} is an integer of 0 to 4.

Examples of R ¹⁴ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a triacontyl group, A cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, a cyclodecyl group, a cyclododecyl group, a cyclotriacontyl group, a norbornyl group, an adamantyl group, a phenyl group, An alkoxy group, a methoxy group, an ethoxy group, a triacontic group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and a thiol group.

Each of the examples 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.

(220)

[Formula 221]

Wherein R ¹⁰ to R ¹³ are the same as those described in the above formula (1-2), R ¹⁴ each independently represents a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, a linear, branched or cyclic alkyl group having 6 to 30 carbon atoms An aryl group 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.

Examples of R ¹⁴ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a triacontyl group, A cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, a cyclodecyl group, a cyclododecyl group, a cyclotriacontyl group, a norbornyl group, an adamantyl group, a phenyl group, An alkoxy group, a methoxy group, an ethoxy group, a triacontic group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and a thiol group.

Each of the examples 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.

(222)

[223]

[224]

[225]

[226]

[227]

[228]

[229]

[230]

[231]

(232)

[233]

In the formula, R ¹⁰ to R ¹³ are the same as those described in the formula (1-2).

Among the above-listed compounds, compounds having a dibenzo xanthene skeleton are more preferable from the viewpoint of heat resistance.

The compound represented by the formula (0) is more preferably the compounds listed below from the viewpoint of the availability of the starting material.

[234]

[235]

[236]

[237]

[238]

[239]

(240)

[241]

[242]

[243]

[244]

[245]

[246]

[247]

[248]

[249]

(250)

[251]

≪ EMI ID =

[253]

≪ EMI ID =

[255]

[Formula 256]

[257]

[258]

[259]

[260]

[261]

[262]

[263]

[264]

[265]

[266]

In the formula, R ¹⁰ to R ¹³ are the same as those described in the formula (1-2).

Among the above-listed compounds, compounds having a dibenzo xanthene skeleton are more preferable from the viewpoint of heat resistance.

The compound represented by the formula (0) is preferably a compound having the following structure from the viewpoint of raw material availability.

[267]

[268]

^Wherein R ^0A is the same as R ^Y in the formula (0), R ^{1A '} is the same as R ^Z in the formula (0), and R ¹⁰ to R ¹³ are the same as those in the formula It is described and agreed.

From the viewpoint of heat resistance, the compounds listed above are more preferably compounds having a xanthene skeleton.

Examples of the compound represented by the formula (0) include compounds represented by the following formulas.

[269]

(270)

[271]

[272]

[273]

[274]

[275]

[276]

[277]

[278]

[279]

(280)

[281]

[282]

[283]

≪ EMI ID =

[285]

[286]

[287]

[288]

[289]

[290]

[291]

[292]

[293]

[294]

[295]

[296]

[297]

[298]

≪ EMI ID =

(300)

(301)

(302)

≪ EMI ID =

(304)

≪ EMI ID =

(306)

≪ EMI ID =

≪ EMI ID =

≪ EMI ID =

≪ EMI ID =

≪ EMI ID =

(312)

[313]

≪ EMI ID =

[315]

[316]

[317]

[318]

[319]

(320)

≪ EMI ID =

(322)

(323)

(324)

(325)

(326)

(327)

(328)

≪ EMI ID =

(330)

≪ EMI ID =

(332)

In the formula, R ¹⁰ to R ¹³ are the same as those described in the formula (1-2), and R ¹⁴ , R ¹⁵ , R ¹⁶ , m ¹⁴ and m ^{14 '} are as defined in the above formula.

[Method for producing the compound represented by the formula (1)

The compound represented by the formula (1) used in the present embodiment can be appropriately synthesized by applying a known technique, and the synthesis method thereof is not particularly limited.

For example, a polyphenol compound is obtained by subjecting a non-phenol, a non-naphthol or a nonanthracene and a corresponding aldehyde or ketone under polycondensation under an acid catalyst to at least one phenolic hydroxyl group of a polyphenol compound By introducing a group represented by the following formula (0-1A).

Further, a group represented by the following formula (0-1B) is introduced, and a group represented by the following formula (0-1A) is introduced into the hydroxyl group. Further, if necessary, it may be carried out under pressure.

[333]

(0-1A)

(In the formula (0-1A), R ^X is a hydrogen atom or a methyl group.)

[334]

(0-1B)

(In the formula (0-1B), R ^W is a linear, branched or cyclic alkylene group having 1 to 30 carbon atoms, and s is an integer of 0 to 30)

Examples of the non-phenol include biphenol, methyl biphenol, methoxybiphentol, and the like, but they are not particularly limited thereto. These may be used singly or in combination of two or more. Of these, the use of biphenol is more preferable in terms of stable supply of raw materials.

Examples of the non-naphthols include, for example, binaphthol, methyl binaphthol, methoxybiphentol and the like, but they are not particularly limited thereto. These may be used singly or in combination of two or more. Among them, it is more preferable to use binaphthol in view of increasing the carbon atom concentration and improving the heat resistance.

Examples of the aldehydes include formaldehyde, trioxane, paraformaldehyde, benzaldehyde, acetaldehyde, propylaldehyde, phenylacetaldehyde, phenylpropylaldehyde, hydroxybenzaldehyde, chlorobenzaldehyde, nitrobenzaldehyde, methylbenzaldehyde, ethyl Benzaldehyde, butylbenzaldehyde, biphenylaldehyde, naphthalaldehyde, anthracene carbaldehyde, phenanthrenecarbaldehyde, pyrenecarbaldehyde, furfural, and the like, but are not limited thereto. These may be used singly or in combination of two or more. Among them, benzaldehyde, phenylacetaldehyde, phenylpropylaldehyde, hydroxybenzaldehyde, chlorobenzaldehyde, nitrobenzaldehyde, methylbenzaldehyde, ethylbenzaldehyde, butylbenzaldehyde, cyclohexylbenzaldehyde, biphenylaldehyde, naphthalaldehyde, anthracene carbaldehyde, phenan It is preferable to use trenecarboaldehyde, pyrenecarboaldehyde and furfural in view of imparting high heat resistance, and it is preferable to use benzaldehyde, hydroxybenzaldehyde, chlorobenzaldehyde, nitrobenzaldehyde, methylbenzaldehyde, ethylbenzaldehyde, butylbenzaldehyde, cyclohexylbenzaldehyde, It is more preferable to use biphenylaldehyde, naphthalaldehyde, anthracene carbaldehyde, phenanthrenecarbaldehyde, pyrencarboaldehyde, and furfural because of their high etching resistance.

The ketones include, for example, acetone, methyl ethyl ketone, cyclobutanone, cyclopentanone, cyclohexanone, norbornanone, tricyclohexanone, tricyclodecanone, adamantanone, fluoro There is provided a process for the production of a compound represented by the general formula (1), wherein R < 1 > is selected from the group consisting of lenone, benzofluorenone, acenaphthenequinone, acenaphthenone, anthraquinone, acetophenone, diacetylbenzene, triacetylbenzene, acetonaphtone, diphenylcarbonylnaphthalene, phenylcarbonylbiphenyl, But are not limited to, benzophenone, diphenylcarbonylbenzene, triphenylcarbonylbenzene, benzonaphtone, diphenylcarbonylnaphthalene, phenylcarbonylbiphenyl, diphenylcarbonylbiphenyl, and the like. These may be used singly or in combination of two or more. Of these, preferred are cyclopentanone, cyclohexanone, norbornanone, tricyclohexanone, tricyclodecanone, adamantanone, fluorenone, benzofluorenone, acenaphthenequinone, acenaphthenone, anthraquinone, acetophenone, Benzene, triacetylbenzene, acetonaphtone, diphenylcarbonylnaphthalene, phenylcarbonylbiphenyl, diphenylcarbonylbiphenyl, benzophenone, diphenylcarbonylbenzene, triphenylcarbonylbenzene, benzonaphtone, diphenyl It is preferable to use carbonylnaphthalene, phenylcarbonylbiphenyl or diphenylcarbonylbiphenyl from the viewpoint of imparting high heat resistance, and it is preferable to use acetophenone, diacetylbenzene, triacetylbenzene, acetonaphtone, diphenylcarbonylnaphthalene , Phenylcarbonylbiphenyl, diphenylcarbonylbiphenyl, benzophenone, diphenylcarbonylbenzene, triphenylcarbonylbenzene, benzonaphthone, diphenylcarbonylnaphthalene, phenyl Carbonylbiphenyl and diphenylcarbonylbiphenyl are more preferred because of their high etching resistance.

As aldehydes or ketones, it is preferable to use an aldehyde having an aromatic ring or a ketone having an aromatic group in view of having high heat resistance and high etching resistance.

The acid catalyst to be used in the reaction can be appropriately selected from known ones and is not particularly limited. As such acid catalysts, inorganic acids and organic acids are widely known and include, for example, inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, and hydrofluoric acid; But are not limited to, oxalic, malonic, succinic, adipic, sebacic, citric, fumaric, maleic, formic, p-toluenesulfonic, methanesulfonic, trifluoroacetic, Organic acids such as sulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid, and naphthalenedisulfonic acid; Lewis acids such as zinc chloride, aluminum chloride, iron chloride and boron trifluoride; And silicic acid such as tungstic acid, tungstic acid, silicomolybdic acid or phosphomolybdic acid, and the like are not particularly limited. Of these, from the viewpoint of production, organic acids and solid acids are preferable, and hydrochloric acid or sulfuric acid is preferably used from the viewpoint of production easiness, ease of handling, and the like. On the other hand, as for the acid catalyst, one type may be used alone, or two or more types may be used in combination. The amount of the acid catalyst to be used can be suitably set according to the kind of the raw material to be used and the type of the catalyst to be used and furthermore the reaction conditions and is not particularly limited but is preferably 0.01 to 100 parts by mass with respect to 100 parts by mass of the reaction raw material .

In the reaction, 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 the non-phenol, binaphthol or nonanthracene diol proceeds, and can be appropriately selected from known ones. Examples of the reaction solvent include water, methanol, ethanol, propanol, butanol, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether or a mixed solvent thereof. On the other hand, one solvent may be used alone, or two or more solvents may be used in combination.

The amount of these reaction solvents to be used can be suitably set according to the kind of the raw materials to be used and the type of catalyst used and furthermore the reaction conditions and is not particularly limited but may be in the range of 0 to 2,000 parts by mass per 100 parts by mass of the reaction raw material . Further, the reaction temperature in the above-mentioned 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 a polyphenol compound, the reaction temperature is preferably high, and specifically preferably in the range of 60 to 200 ° C. On the other hand, the reaction method can be carried out by appropriately selecting a known method, and is not particularly limited. However, a method in which a nonphenol, a naphthol or a nonanthracene diol, an aldehyde or a ketone, And a method of dropping non-naphthols or nonanthracene diols, aldehydes or ketones 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 starting materials and catalysts present in the system, by employing a general method such as raising the temperature of the reaction pot to 130 to 230 DEG C and removing volatile matter at about 1 to 50 mmHg, The phosphorus compound can be isolated.

Preferable reaction conditions are as follows: 1.0 mol to excess amount of non-phenols, binaphthol or nonanthracene diol per mole of aldehydes or ketones, 0.001 to 1 mol of an acid catalyst and 0.001 to 1 mol of an acid catalyst at 50 to 150 DEG C For about 20 minutes to about 100 hours.

After completion of the reaction, the desired product can be isolated by a known method. For example, the reaction solution is concentrated, pure water is added to precipitate a reaction product, the reaction product is cooled to room temperature, filtered and separated, and the resulting solid is filtered and dried, , Followed by solvent evaporation, filtration and drying to obtain the target compound represented by the above formula (1).

A method of introducing a group represented by the formula (0-1A) into at least one phenolic hydroxyl group of a polyphenol compound is known. For example, a group represented by the formula (0-1A) can be introduced into at least one phenolic hydroxyl group of the compound as follows. The compound for introducing the group represented by formula (0-1A) can be synthesized or easily obtained by a known method, and examples thereof include 2-isonatoethyl methacrylate, 2-isonatoethyl acrylate But are not limited to these.

For example, the compound 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 under normal pressure in the presence of a base catalyst such as sodium hydroxide, potassium hydroxide, sodium methoxide or sodium ethoxide. The reaction solution is neutralized with an acid and added to distilled water to precipitate a white solid. The separated solid is washed with distilled water, or the solvent is evaporated to dryness, washed with distilled water if necessary, A compound in which the hydrogen atom of the hydroxyl group is substituted with the group represented by the formula (0-1A) can be obtained.

On the other hand, the timing of introduction of a group substituted with a group represented by the formula (0-1A) may be not only after the condensation reaction of the binaphthol compound with the aldehydes or the ketones, but also before the condensation reaction. It may be carried out after the production of a resin to be described later.

It is also known that a group represented by the formula (0-1B) is introduced into at least one phenolic hydroxyl group of the polyphenol compound to introduce a group represented by the formula (0-1A) into the hydroxyl group.

For example, a group represented by the formula (0-1B) may be introduced into at least one phenolic hydroxyl group of the compound to introduce a group represented by the formula (0-1A) into the hydroxyl group have.

The compound for introducing a group represented by the formula (0-1B) can be synthesized or easily obtained by a known method, for example, chloroethanol, bromoethanol, 2-chloroethyl acetate, -Bromoethyl acetate, 2-iodoethyl acetate, ethylene oxide, propylene oxide, butylene oxide, ethylene carbonate, propylene carbonate, and butylene carbonate.

For example, the compound 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 under normal pressure in the presence of a base catalyst such as sodium hydroxide, potassium hydroxide, sodium methoxide or sodium ethoxide. The reaction solution is neutralized with an acid and added to distilled water to precipitate a white solid. The separated solid is washed with distilled water, or the solvent is evaporated to dryness, washed with distilled water if necessary, and dried, A compound substituted with a group represented by formula (0-1B) can be obtained.

In the case of using 2-chloroethyl acetate, 2-bromoethyl acetate or 2-iodoethyl acetate, a hydroxyethyl group is introduced by introducing an acetoxy group and then generating a deacylation reaction.

When ethylene carbonate, propylene carbonate, or butylene carbonate is used, an alkylene carbonate is added and a decarboxylation reaction occurs to introduce a hydroxyalkyl group.

Thereafter, the compound 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 under normal pressure in the presence of a base catalyst such as sodium hydroxide, potassium hydroxide, sodium methoxide or sodium ethoxide. The reaction solution is neutralized with an acid and added to distilled water to precipitate a white solid. The separated solid is washed with distilled water, or the solvent is evaporated to dryness, washed with distilled water if necessary, and dried to obtain a A compound in which a hydrogen atom is substituted with a group substituted with a group represented by the formula (0-1A) can be obtained.

In the present embodiment, the group substituted with a group represented by the formula (0-1A) reacts in the presence of a radical or an acid / alkali to change the solubility in an acid, an alkali, or an organic solvent used in a coating solvent or a developer . The group substituted with a group represented by the formula (0-1A) preferably has a property of generating a chain reaction in the presence of a radical or an acid / alkali in order to enable pattern formation with a higher sensitivity and a high resolution.

[Resin obtained by using the compound represented by the formula (1) as a monomer]

The compound represented by the above formula (1) can be used as it is as a film-forming composition for lithography or a composition used for forming optical parts (hereinafter, simply referred to as " composition "). Further, a resin obtained by using the compound represented by the above formula (1) as a monomer may be used as the composition. The resin is obtained, for example, by reacting a compound represented by the formula (1) with a compound having a crosslinking reactivity.

Examples of the resin obtained by using the compound represented by the above formula (1) 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).

[335]

(3)

In formula (3), L represents an alkylene group having 1 to 30 carbon atoms which may have a substituent, an arylene group having 6 to 30 carbon atoms which may have a substituent, an alkoxysilane having 1 to 30 carbon atoms which may have a substituent And the alkylene group, the arylene group, and the alkoxylene group may contain an ether bond, a ketone bond or an ester bond. The alkylene group and alkoxylene group may be a straight chain, branched or cyclic group.

R ⁰ is synonymous with R ^Y ,

R ¹ is an n-valent group or a single bond having 1 to 60 carbon atoms,

Each of R ² to R ⁵ independently represents 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, an alkenyl group having 2 to 30 carbon atoms 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 hydrogen atom of a hydroxyl group is substituted with an acid-dissociable group, The alkenyl group, the alkenyl group and the alkoxy group may include an ether bond, a ketone bond or an ester bond, wherein at least one of R ² to R ⁵ includes a group represented by the formula (0-1) ,

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,

Provided that m ² , m ³ , m ⁴ and m ⁵ do not become 0 at the same time,

n is a synonym with the above N, wherein when n is an integer of 2 or more, the structural formulas within n [] may be the same or different,

p ² to p ⁵ are synonymous with r.

[Process for producing a resin obtained by using a compound represented by the formula (1) as a monomer]

The resin of the present embodiment is obtained by reacting the compound represented by the formula (1) with a compound having a crosslinking reactivity. As the compound having a crosslinking reactivity, known compounds can be used as long as they can oligomerize or polymerize the compound represented by the formula (1). Specific examples thereof include, for example, aldehydes, ketones, carboxylic acids, carboxylic acid halides, halogen-containing compounds, amino compounds, imino compounds, isocyanates and unsaturated hydrocarbon group-containing compounds, Do not.

Specific examples of the resin having the structure represented by the formula (3) include a resin obtained by condensation reaction of the compound represented by the formula (1) with an aldehyde and / or a ketone, which is a crosslinkable compound, And a resin which is made into a boric acid.

Examples of the aldehyde used in the novolak of the compound represented by the formula (1) include formaldehyde, trioxane, paraformaldehyde, benzaldehyde, acetaldehyde, propylaldehyde, phenylacetaldehyde, phenylpropylaldehyde Benzenesulfonic acid, benzenesulfonic acid, benzenesulfonic acid, benzenesulfonic acid, benzenesulfonic acid, hydroxymethylbenzaldehyde, chlorobenzaldehyde, nitrobenzaldehyde, methylbenzaldehyde, ethylbenzaldehyde, butylbenzaldehyde, biphenylaldehyde, naphthaldehyde, anthracenecarbaldehyde, phenanthrenecarbaldehyde, But are not limited to these. Examples of the ketone include the above-mentioned ketones. Of these, formaldehyde is more preferable. On the other hand, these aldehydes and / or ketones may be used singly or in combination of two or more kinds. The amount of the aldehyde and / or ketone to be used is not particularly limited, but is preferably 0.2 to 5 moles, more preferably 0.5 to 2 moles, per 1 mole of the compound represented by the formula (1).

In the condensation reaction of the compound represented by the formula (1) with an aldehyde and / or a ketone, a catalyst may be used. The acid catalyst to be used here can be appropriately selected from known ones and is not particularly limited. As such acid catalysts, inorganic acids and organic acids are widely known and include, for example, inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, and hydrofluoric acid; But are not limited to, oxalic, malonic, succinic, adipic, sebacic, citric, fumaric, maleic, formic, p-toluenesulfonic, methanesulfonic, trifluoroacetic, Organic acids such as sulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid, and naphthalenedisulfonic acid; Lewis acids such as zinc chloride, aluminum chloride, iron chloride and boron trifluoride; And silicic acid such as tungstic acid, tungstic acid, silicomolybdic acid or phosphomolybdic acid, and the like are not particularly limited. Of these, from the viewpoint of production, organic acids and solid acids are preferable, and hydrochloric acid or sulfuric acid is preferable from the viewpoint of production easiness, ease of handling, and the like. On the other hand, as for the acid catalyst, one type may be used alone, or two or more types may be used in combination.

The amount of the acid catalyst to be used can be suitably set according to the kind of the raw material to be used and the type of the catalyst to be used and furthermore the reaction conditions and is not particularly limited but is preferably 0.01 to 100 parts by mass with respect to 100 parts by mass of the reaction raw material . However, it is preferable to use a compound selected from the group consisting of indene, hydroxyindene, benzofuran, hydroxyanthracene, acenaphthylene, biphenyl, bisphenol, trisphenol, dicyclopentadiene, tetrahydroindene, 4-vinylcyclohexene, In the case of a copolymerization reaction with a compound having a non-conjugated double bond such as vinyl norborna-2-ene,? -Pinene,? -Pinene and limonene, an aldehyde is not necessarily required.

In the condensation reaction of the compound represented by the formula (1) with an aldehyde and / or a ketone, a reaction solvent may be used. The reaction solvent in the polycondensation is not particularly limited and may be appropriately selected from known ones. Examples of the solvent include water, methanol, ethanol, propanol, butanol, tetrahydrofuran, dioxane, Mixed solvents, and the like. On the other hand, one solvent may be used alone, or two or more solvents may be used in combination.

The amount of these solvents to be used can be suitably set according to the type of raw material to be used and the type of catalyst to be used and further the reaction conditions and is not particularly limited but is preferably 0 to 2000 parts by mass with respect to 100 parts by mass of the reaction raw material desirable. 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. On the other hand, as the reaction method, a known method can be appropriately selected and used. Without particular limitation, a method of collectively introducing the compound represented by the formula (1), the aldehyde and / or the ketone and the catalyst, 1) or an aldehyde and / or a ketone is added dropwise 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 starting materials and catalysts present in the system, by employing a general method such as raising the temperature of the reaction pot to 130 to 230 DEG C and removing volatile matter at about 1 to 50 mmHg, The novolak resin can be isolated.

Here, the resin having the structure represented by the formula (3) may be a homopolymer of the compound represented by the formula (1), or may be a copolymer with other phenols. Examples of the copolymerizable phenol include phenol, cresol, dimethyl phenol, trimethyl phenol, butyl phenol, phenyl phenol, diphenyl phenol, naphthyl phenol, resorcinol, methyl resorcinol, catechol, , Methoxyphenol, methoxyphenol, propylphenol, pyrogallol, thymol, and the like, but they are not particularly limited thereto.

In addition to the above-mentioned other phenols, the resin having the structure represented by the formula (3) may be a copolymer obtained by copolymerizing with a polymerizable monomer. Examples of such copolymerizable monomers include monomers such as naphthol, methylnaphthol, methoxynaphthol, dihydroxynaphthalene, indene, hydroxyindene, benzofuran, hydroxyanthracene, acenaphthylene, biphenyl, bisphenol, Dicyclopentadiene, tetrahydroindene, 4-vinylcyclohexene, norbornadiene, vinyl norbornene, pinene, limonene, and the like, but they are not particularly limited thereto. On the other hand, the resin having the structure represented by the formula (2) may be a copolymer of two or more atoms (for example, a two to four member system) of the compound represented by the formula (1) Even a copolymer of two or more atoms (for example, a two to four member system) of the compound represented by the formula (1) and the above-described copolymerizable monomer can be obtained by copolymerizing the compound represented by the formula (1) (For example, a 3 to 4 member system) copolymer with one copolymerizable monomer.

On the other hand, the molecular weight of the resin having the structure represented by the formula (3) is not particularly limited, but the weight average molecular weight (Mw) in terms of polystyrene is preferably 500 to 30,000, more preferably 750 to 20,000. 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 (3) has a dispersion degree (weight average molecular weight Mw / number average molecular weight Mn) of 1.2 to 7 . On the other hand, the Mw and Mn can be obtained by the methods described in Examples described later.

The resin having the structure represented by the above formula (3) is preferably one having a high solubility in a solvent from the viewpoint that the application of the wet process becomes easier. More specifically, when 1-methoxy-2-propanol (PGME) and / or propylene glycol monomethyl ether acetate (PGMEA) are used as a solvent, the solubility in the solvent is preferably 10 mass% or more. Here, the solubility in PGME and / or PGMEA is defined as "mass of resin ÷ (mass of resin + mass of solvent) × 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)

The compound represented by the formula (0) in the present embodiment is preferably a compound represented by the following formula (2). The compound of the present embodiment is a compound represented by the following formula (2), which has a high heat resistance and a high solvent solubility.

[336]

(2)

In formula (2), R ^0A represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms.

R ^1A is an n ^A -valent group or a single bond having 1 to 60 carbon atoms,

R ^2A each independently represents 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, an alkenyl group having 2 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 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, wherein at least one of R ^2A includes a group represented by the formula (0-1).

and ^A n is an integer from 1 to 4, wherein the formula (2) in the structural formula of, n ^A is an integer of 2 or more, n ^A of [] are may be the same or different.

X ^A represents, independently of each other, an oxygen atom, a sulfur atom or a non-substituted group. Herein, when X ^A is an oxygen atom or a sulfur atom, it is preferable because it tends to exhibit high heat resistance, and more preferably it is an oxygen atom. From the viewpoint of solubility, X ^A is preferably a non-crosslinked.

m ^2A are each independently an integer of 0 to 6; Provided that at least one m ^2A is an integer of 1 to 6;

q ^A is independently 0 or 1;

The n-valent group is an alkyl group having 1 to 60 carbon atoms when n = 1, an alkylene group having 1 to 30 carbon atoms when n = 2, an alkane-containing group having 2 to 60 carbon atoms when n = 3, = 4 means an alkane tetrayl group having 3 to 60 carbon atoms. Examples of the n-valent group include those having a straight-chain 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 group may have an aromatic group having 6 to 60 carbon atoms.

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. 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 30 carbon atoms. Here, the alicyclic hydrocarbon group includes a bridged alicyclic hydrocarbon group.

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

In addition, since the solubility in a safe solvent is high and the heat resistance and the etching resistance are good, a resist pattern forming composition for lithography containing the compound represented by the formula (2) can give a good resist pattern shape.

Furthermore, even in the case of a substrate having a step (particularly, a minute space or a hole pattern or the like) at a relatively low molecular weight and low viscosity, it is easy to increase the flatness of the film while uniformly filling the corners of the step, The lower layer film forming composition for lithography used has good filling and planarizing properties. In addition, since it is a compound having a relatively high carbon concentration, high etching resistance can also be imparted.

In addition, since the aromatic densities are high, the refractive index is high and the coloring is suppressed by a wide range of heat treatment from a low temperature to a high temperature. Among them, a compound having quaternary carbon is preferable from the viewpoints of inhibiting oxidation decomposition to suppress coloring of a compound, having high heat resistance, and improving solvent solubility. In addition to being used in the form of a film or a sheet, the optical component can be used in various forms such as a plastic lens (a prism lens, a lenticular lens, a microlens, a Fresnel lens, a viewing angle control lens, a contrast enhancement lens and the like), a retardation film, , An optical fiber, a solder resist for flexible printed wiring, a plating resist, an interlayer insulating film for a multilayer printed wiring board, 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 viewpoints of ease of crosslinking and solubility in an organic solvent.

[337]

(2-1)

In formula (2-1), R ^0A , R ^{1 A} , n ^A , q ^A and X ^A are synonymous with those in formula (2).

R ^3A each independently represents a linear, branched or cyclic alkyl group of 1 to 30 carbon atoms which may have a substituent, an aryl group of 6 to 30 carbon atoms which may have a substituent, a carbon number which may have a substituent A halogen atom, a nitro group, an amino group, a carboxylic acid group and a thiol group, and may be the same or different in the same naphthalene ring or benzene ring.

R ^4A each independently represents a hydrogen atom or a group represented by the following formula (0-2)

Here, at least one of R ^4A is a group represented by the following formula (0-2)

m ^6A are each independently an integer of 0 to 5;

[338]

(0-2)

(In the formula (0-2), R ^X is the same as that in the formula (0-1), and s is an integer of 0 to 30.)

When the compound represented by the formula (2-1) is used as a film forming composition for lithography of an alkali development positive resist or an organic development negative type resist, at least one of R ^4A is an acid dissociable group. On the other hand, when the compound represented by the formula (2-1) is used as a film forming composition for lithography for an alkali development negative resist, a film forming composition for lithography for a lower layer film or a composition for forming an optical component, at least one of R ^4A is a hydrogen atom to be.

The compound represented by the formula (2-1) is preferably a compound represented by the following formula (2a) from the viewpoint of the feedability of the starting material.

[339]

(2a)

In the formula (2a), X ^A , R ^0A to R ^2A , m ^2A and n ^A are the same as those described in the formula (2).

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

(340)

(2b)

In the formula (2b), X ^A , R ^0A , R ^1A , R ^3A , R ^4A , m ^6A and n ^A are the same as those described in the formula (2-1).

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

≪ EMI ID =

(2c)

In the formula (2c), X ^A , R ^0A , R ^1A , R ^3A , R ^4A , m ^6A and n ^A are the same as those described in the formula (2-1).

(BisN-1) to (XBisN-1) to (XBisN-3), (BiN-4), 1) to (BiN-4) or (XBiN-1) to (XBiN-3).

≪ EMI ID =

(BisN-1)

[0300]

(BisN-2)

≪ EMI ID =

(BisN-3)

≪ EMI ID =

(BisN-4)

≪ EMI ID =

(XBisN-1)

≪ EMI ID =

(XBisN-2)

≪ EMI ID =

(XBisN-3)

≪ EMI ID =

(BiN-1)

[350]

(BiN-2)

≪ EMI ID =

(BiN-3)

≪ EMI ID =

(BiN-4)

≪ EMI ID =

(XBiN-1)

≪ EMI ID =

(XBiN-2)

≪ EMI ID =

(XBiN-3)

[Process for producing the compound represented by the 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 method thereof is not particularly limited.

For example, a polyphenol compound is obtained by subjecting a phenol, naphthol and a corresponding aldehyde or ketone to polycondensation reaction under an atmospheric pressure under an acid catalyst to obtain a polyphenol compound having at least one phenolic hydroxyl group of the polyphenol compound represented by the following formula -1A). ≪ / RTI >

Alternatively, a group represented by the following formula (0-1B) is introduced, and a group represented by the formula (0-1A) is introduced into the hydroxyl group. Further, if necessary, it may be carried out under pressure.

≪ EMI ID =

(0-1A)

(In the formula (0-1A), R ^X is a hydrogen atom or a methyl group.)

≪ EMI ID =

(0-1B)

(In the formula (0-1B), R ^W is a linear, branched or cyclic alkylene group having 1 to 30 carbon atoms, and s is an integer of 0 to 30)

Examples of the naphthols include, but are not limited to, naphthol, methylnaphthol, methoxynaphthol, naphthalene diol, and the like. The use of naphthalene diol is more preferable because it can easily form a xanthene structure Do.

The phenol is not particularly limited, and examples thereof include phenol, methylphenol, methoxybenzene, catechol, resorcinol, hydroquinone, trimethylhydroquinone, and the like.

Examples of the aldehydes include formaldehyde, trioxane, paraformaldehyde, benzaldehyde, acetaldehyde, propylaldehyde, phenylacetaldehyde, phenylpropylaldehyde, hydroxybenzaldehyde, chlorobenzaldehyde, nitrobenzaldehyde, methylbenzaldehyde, ethyl Benzaldehyde, butylbenzaldehyde, biphenylaldehyde, naphthalaldehyde, anthracene carbaldehyde, phenanthrenecarbaldehyde, pyrenecarbaldehyde, furfural, and the like, but are not limited thereto. These may be used singly or in combination of two or more. Among them, benzaldehyde, phenylacetaldehyde, phenylpropylaldehyde, hydroxybenzaldehyde, chlorobenzaldehyde, nitrobenzaldehyde, methylbenzaldehyde, ethylbenzaldehyde, butylbenzaldehyde, cyclohexylbenzaldehyde, biphenylaldehyde, naphthalaldehyde, anthracene carbaldehyde, phenan It is preferable to use trenecarboaldehyde, pyrenecarboaldehyde and furfural in view of imparting high heat resistance, and it is preferable to use benzaldehyde, hydroxybenzaldehyde, chlorobenzaldehyde, nitrobenzaldehyde, methylbenzaldehyde, ethylbenzaldehyde, butylbenzaldehyde, cyclohexylbenzaldehyde, It is more preferable to use biphenylaldehyde, naphthalaldehyde, anthracene carbaldehyde, phenanthrenecarbaldehyde, pyrencarboaldehyde, and furfural because of their high etching resistance.

The ketones include, for example, acetone, methyl ethyl ketone, cyclobutanone, cyclopentanone, cyclohexanone, norbornanone, tricyclohexanone, tricyclodecanone, adamantanone, fluorenone, benzofluorenone , Acenaphthenequinone, acenaphthenone, anthraquinone, acetophenone, diacetylbenzene, triacetylbenzene, acetonaphtone, diphenylcarbonylnaphthalene, phenylcarbonylbiphenyl, diphenylcarbonylbiphenyl, benzophenone, diphenyl But are not limited to, carbonylbenzene, triphenylcarbonylbenzene, benzonaphtone, diphenylcarbonylnaphthalene, phenylcarbonylbiphenyl, diphenylcarbonylbiphenyl and the like. These may be used singly or in combination of two or more. Of these, preferred are cyclopentanone, cyclohexanone, norbornanone, tricyclohexanone, tricyclodecanone, adamantanone, fluorenone, benzofluorenone, acenaphthenequinone, acenaphthenone, anthraquinone, acetophenone, Benzene, triacetylbenzene, acetonaphtone, diphenylcarbonylnaphthalene, phenylcarbonylbiphenyl, diphenylcarbonylbiphenyl, benzophenone, diphenylcarbonylbenzene, triphenylcarbonylbenzene, benzonaphtone, diphenyl It is preferable to use carbonylnaphthalene, phenylcarbonylbiphenyl or diphenylcarbonylbiphenyl from the viewpoint of imparting high heat resistance, and it is preferable to use acetophenone, diacetylbenzene, triacetylbenzene, acetonaphtone, diphenylcarbonylnaphthalene , Phenylcarbonylbiphenyl, diphenylcarbonylbiphenyl, benzophenone, diphenylcarbonylbenzene, triphenylcarbonylbenzene, benzonaphthone, diphenylcarbonylnaphthalene, phenyl Carbonylbiphenyl and diphenylcarbonylbiphenyl are more preferred because of their high etching resistance.

As the ketone, it is preferable to use a ketone having an aromatic ring in view of having high heat resistance and high etching resistance.

The acid catalyst to be used in the reaction can be appropriately selected from known ones and is not particularly limited. The acid catalyst is not particularly limited and may be appropriately selected from well-known inorganic acids and organic acids. For example, inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid and hydrofluoric acid; Organic acids such as oxalic acid, formic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid and naphthalenedisulfonic acid; Lewis acids such as zinc chloride, aluminum chloride, iron chloride and boron trifluoride; Tungstic acid, tungstic acid, silicomolybdic acid or phosphomolybdic acid. It is preferable to use hydrochloric acid or sulfuric acid from the viewpoint of production, such as ease of access and ease of handling. As for the acid catalyst, one kind or two or more kinds can be used.

In the reaction, a reaction solvent may be used. The reaction solvent is not particularly limited as long as the reaction with the aldehyde or ketone to be used and the naphthol or the like proceeds. For example, water, methanol, ethanol, propanol, butanol, tetrahydrofuran, dioxane, Can be used. The amount of the solvent is not particularly limited, and is, for example, in the range of 0 to 2,000 parts by mass based on 100 parts by mass of the reaction raw material.

When the polyphenol compound is prepared, the reaction temperature is not particularly limited and may be appropriately selected depending on the reactivity of the reaction raw material, and is preferably in the range of 10 to 200 ° C. In order to selectively synthesize the polyphenol compound, the temperature is preferably low, and the effect is high, and the range of 10 to 60 ° C is more preferable.

The method for producing the polyphenol compound is not particularly limited. For example, a method of collectively introducing aldehydes, ketones, or catalysts such as naphthols, or a method of dropping naphthols, aldehydes or ketones in the presence of a catalyst . After completion of the polycondensation reaction, in order to remove unreacted raw materials, catalysts, and the like existing in the system, the temperature of the reaction pot may be raised to 130 to 230 ° C and volatile components may be removed at about 1 to 50 mmHg.

The amount of the raw material in the production of the polyphenol compound is not particularly limited. For example, the amount of the naphthol or the like is 2 mol to an excess amount, and the acid catalyst is used in an amount of 0.001 to 1 mol relative to 1 mol of the aldehyde or ketone , At normal pressure, at 20 to 60 ° C for 20 minutes to 100 hours.

When the polyphenol compound is produced, after completion of the reaction, the object is isolated by a known method. The isolation method of the object is not particularly limited, and for example, the reaction solution is concentrated, pure water is added to precipitate the reaction product, the reaction product is cooled to room temperature, filtered and separated, and the obtained solid is filtered, Followed by separation and purification from the by-product by column chromatography, and solvent evaporation, filtration and drying are carried out to obtain the target compound.

A method of introducing a group represented by the formula (0-1A) into at least one phenolic hydroxyl group of a polyphenol compound is known. For example, a group represented by the formula (0-1A) can be introduced into at least one phenolic hydroxyl group of the compound as follows. The compound for introducing the group represented by formula (0-1A) can be synthesized or easily obtained by a known method, and examples thereof include 2-isocyanatoethyl methacrylate, 2-isocyanatoethyl acrylate Rate, but are not limited to these.

For example, the compound 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 under normal pressure in the presence of a base catalyst such as sodium hydroxide, potassium hydroxide, sodium methoxide or sodium ethoxide. The reaction solution is neutralized with an acid and added to distilled water to precipitate a white solid. The separated solid is washed with distilled water, or the solvent is evaporated to dryness, washed with distilled water if necessary, and dried, A compound substituted with a group represented by the formula (0-1A) can be obtained.

On the other hand, the timing of introduction of a group substituted with a group represented by formula (0-1A) may be not only after the condensation reaction of binaphthol with an aldehyde or a ketone, but also before the condensation reaction. It may be carried out after the production of a resin to be described later.

It is also known to introduce a group represented by the formula (0-1B) into at least one phenolic hydroxyl group of the polyphenol compound to introduce the group represented by the formula (0-1A) into the hydroxyl group.

For example, a group represented by the formula (0-1B) may be introduced into at least one phenolic hydroxyl group of the compound to introduce a group represented by the formula (0-1A) into the hydroxyl group have.

The compound for introducing a group represented by the formula (0-1B) can be synthesized or easily obtained by a known method, for example, chloroethanol, bromoethanol, 2-chloroethyl acetate, -Bromoethyl acetate, 2-iodoethyl acetate, ethylene oxide, propylene oxide, butylene oxide, ethylene carbonate, propylene carbonate, and butylene carbonate.

For example, the compound 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 under normal pressure in the presence of a base catalyst such as sodium hydroxide, potassium hydroxide, sodium methoxide or sodium ethoxide. The reaction solution is neutralized with an acid and added to distilled water to precipitate a white solid. The separated solid is washed with distilled water, or the solvent is evaporated to dryness, washed with distilled water if necessary, and dried, A compound substituted with a group represented by formula (0-1B) can be obtained.

In the case of using 2-chloroethyl acetate, 2-bromoethyl acetate or 2-iodoethyl acetate, a hydroxyethyl group is introduced by introducing an acetoxy group and then generating a deacylation reaction.

When ethylene carbonate, propylene carbonate, or butylene carbonate is used, an alkylene carbonate is added and a decarboxylation reaction occurs to introduce a hydroxyalkyl group.

Thereafter, the compound 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 under normal pressure in the presence of a base catalyst such as sodium hydroxide, potassium hydroxide, sodium methoxide or sodium ethoxide. The reaction solution is neutralized with an acid and added to distilled water to precipitate a white solid. The separated solid is washed with distilled water, or the solvent is evaporated to dryness, washed with distilled water if necessary, and dried to obtain a A compound in which a hydrogen atom is substituted with a group substituted with a group represented by the formula (0-1A) can be obtained.

In the present embodiment, the group substituted with a group represented by the formula (0-1A) reacts in the presence of a radical or an acid / alkali, and the solubility in an acid, an alkali, or an organic solvent used in a coating solvent or a developer varies . The group substituted with a group represented by the formula (0-1A) preferably has a property of generating a chain reaction in the presence of a radical or an acid / alkali in order to enable pattern formation with a higher sensitivity and a high resolution.

[Process for producing a resin obtained by using a compound represented by the formula (2) as a monomer]

The compound represented by the above formula (2) can be used as it is as a film-forming composition for lithography or a composition used for forming optical parts. Further, a resin obtained by using the compound represented by the formula (2) as a monomer can be used as the composition. The resin can also be used, for example, as a resin obtained by reacting a compound represented by the formula (2) with a compound having a crosslinking reactivity.

Examples of the resin obtained by 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 film forming composition for lithography of the present embodiment may contain a resin having a structure represented by the following formula (4).

≪ EMI ID =

(4)

In formula (4), L represents an alkylene group having 1 to 30 carbon atoms which may have a substituent, an arylene group having 6 to 30 carbon atoms which may have a substituent, an alkoxysilane having 1 to 30 carbon atoms, And the alkylene group, the arylene group, and the alkoxylene group may contain an ether bond, a ketone bond or an ester bond. The alkylene group and alkoxylene group may be a straight chain, branched or cyclic group.

R ^0A is synonymous with R ^Y ,

R ^1A is an n ^A -valent group having 1 to 30 carbon atoms or a single bond,

R ^2A each independently represents 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, an alkenyl group having 2 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 hydrogen atom of a hydroxyl group is substituted with a group represented by the formula (0-1) 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, wherein at least one of R ^2A is a group represented by the formula (0-1) Including,

n ^A is the same as the above N, wherein when n ^A is an integer of 2 or more, the structural formulas within n ^A [] may be the same or different,

X ^A represents an oxygen atom, a sulfur atom or a non-

m ^2A is independently an integer of 0 to 7, provided that at least one of m ^2A is an integer of 1 to 6,

q ^A is independently 0 or 1;

[Process for producing a resin obtained by using a compound represented by the formula (2) as a monomer]

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

As the compound having a crosslinking reactivity, any known compound can be used as long as it can oligomerize or polymerize the compound represented by the formula (2). Specific examples thereof include, for example, aldehydes, ketones, carboxylic acids, carboxylic acid halides, halogen-containing compounds, amino compounds, imino compounds, isocyanates and unsaturated hydrocarbon group-containing compounds, Do not.

Specific examples of the resin having the structure represented by the formula (4) include, for example, a compound represented by the formula (2) by a condensation reaction with an aldehyde and / or a ketone, And a resin which is made into a boric acid.

Examples of the aldehyde used in the novolakization of the compound represented by the formula (2) include formaldehyde, trioxane, paraformaldehyde, benzaldehyde, acetaldehyde, propylaldehyde, phenylacetaldehyde, phenylpropylaldehyde Benzenesulfonic acid, benzenesulfonic acid, benzenesulfonic acid, benzenesulfonic acid, benzenesulfonic acid, hydroxymethylbenzaldehyde, chlorobenzaldehyde, nitrobenzaldehyde, methylbenzaldehyde, ethylbenzaldehyde, butylbenzaldehyde, biphenylaldehyde, naphthaldehyde, anthracenecarbaldehyde, phenanthrenecarbaldehyde, But are not limited to these. Examples of the ketone include the above-mentioned ketones. Of these, formaldehyde is more preferable. On the other hand, these aldehydes and / or ketones may be used singly or in combination of two or more kinds. The amount of the aldehyde and / or ketone to be used is not particularly limited, but is preferably 0.2 to 5 moles, more preferably 0.5 to 2 moles, per 1 mole of the compound represented by the formula (2).

In the condensation reaction of the compound represented by the formula (2) with an aldehyde and / or a ketone, an acid catalyst may be used. The acid catalyst to be used here can be appropriately selected from known ones and is not particularly limited. As such acid catalysts, inorganic acids and organic acids are widely known and include, for example, inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, and hydrofluoric acid; But are not limited to, oxalic, malonic, succinic, adipic, sebacic, citric, fumaric, maleic, formic, p-toluenesulfonic, methanesulfonic, trifluoroacetic, Organic acids such as sulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid, and naphthalenedisulfonic acid; Lewis acids such as zinc chloride, aluminum chloride, iron chloride and boron trifluoride; And silicic acid such as tungstic acid, tungstic acid, silicomolybdic acid or phosphomolybdic acid, and the like are not particularly limited. Of these, from the viewpoint of production, organic acids or solid acids are preferable, and hydrochloric acid or sulfuric acid is preferable from the viewpoint of production easiness, easy handling, and the like. On the other hand, as for the acid catalyst, one type may be used alone, or two or more types may be used in combination.

The amount of the acid catalyst to be used can be suitably set according to the kind of the raw material to be used and the type of the catalyst to be used and furthermore the reaction conditions and is not particularly limited but is preferably 0.01 to 100 parts by mass with respect to 100 parts by mass of the reaction raw material . However, it is preferable to use a compound selected from the group consisting of indene, hydroxyindene, benzofuran, hydroxyanthracene, acenaphthylene, biphenyl, bisphenol, trisphenol, dicyclopentadiene, tetrahydroindene, 4-vinylcyclohexene, In the case of a copolymerization reaction with a compound having a non-conjugated double bond such as vinyl norborna-2-ene,? -Pinene,? -Pinene and limonene, an aldehyde is not necessarily required.

In the condensation reaction of the compound represented by the formula (2) with an aldehyde and / or a ketone, a reaction solvent may be used. The reaction solvent in the polycondensation is not particularly limited and may be appropriately selected from known ones. Examples of the solvent include water, methanol, ethanol, propanol, butanol, tetrahydrofuran, dioxane, Mixed solvents, and the like. On the other hand, one solvent may be used alone, or two or more solvents may be used in combination.

The amount of these solvents to be used can be suitably set according to the type of raw material to be used and the type of catalyst to be used and further the reaction conditions and is not particularly limited but is preferably 0 to 2000 parts by mass with respect to 100 parts by mass of the reaction raw material desirable. 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. On the other hand, as the reaction method, a known method can be appropriately selected and used. Without particular limitation, a method of collectively introducing the compound represented by the formula (2), the aldehyde and / or the ketone and the catalyst, 2) or an aldehyde and / or a ketone is added dropwise 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 starting materials and catalysts present in the system, by employing a general method such as raising the temperature of the reaction pot to 130 to 230 DEG C and removing volatile matter at about 1 to 50 mmHg, The novolak resin can be isolated.

Here, the resin having the structure represented by the formula (4) may be a homopolymer of the compound represented by the formula (2), or may be a copolymer with other phenols. Examples of the copolymerizable phenol include phenol, cresol, dimethyl phenol, trimethyl phenol, butyl phenol, phenyl phenol, diphenyl phenol, naphthyl phenol, resorcinol, methyl resorcinol, catechol, , Methoxyphenol, methoxyphenol, propylphenol, pyrogallol, thymol, and the like, but they are not particularly limited thereto.

In addition to the above-mentioned other phenols, the resin having the structure represented by the formula (4) may be a copolymer obtained by copolymerizing with a polymerizable monomer. Examples of such copolymerizable monomers include monomers such as naphthol, methylnaphthol, methoxynaphthol, dihydroxynaphthalene, indene, hydroxyindene, benzofuran, hydroxyanthracene, acenaphthylene, biphenyl, bisphenol, Dicyclopentadiene, tetrahydroindene, 4-vinylcyclohexene, norbornadiene, vinyl norbornene, pinene, limonene, and the like, but they are not particularly limited thereto. On the other hand, the resin having the structure represented by the formula (4) may be a copolymer of two or more atoms (for example, a two to four member system) of the compound represented by the formula (2) Even if a copolymer having two or more atoms (for example, a two to four member system) of the compound represented by the formula (2) and the above-described copolymerizable monomer is used, the compound represented by the formula (2) (For example, a 3 to 4 member system) copolymer with one copolymerizable monomer.

On the other hand, the molecular weight of the resin having the structure represented by the formula (4) is not particularly limited, but the weight average molecular weight (Mw) in terms of polystyrene is preferably 500 to 30,000, more preferably 750 to 20,000. 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 dispersion degree (weight average molecular weight Mw / number average molecular weight Mn) of 1.2 to 7 . On the other hand, the Mw and Mn can be obtained by the methods described in Examples described later.

The resin having the structure represented by the above formula (4) is preferably one having high solubility in a solvent from the viewpoint that the application of the wet process becomes easier. More specifically, when 1-methoxy-2-propanol (PGME) and / or propylene glycol monomethyl ether acetate (PGMEA) are used as a solvent, the solubility in the solvent is preferably 10 mass% or more. Here, the solubility in PGME and / or PGMEA is defined as "mass of resin ÷ (mass of resin + mass of solvent) × 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 for purifying compound and / or resin]

The method of purifying a compound and / or a resin of the present embodiment is a method of purifying a compound represented by the formula (1), a resin obtained using the compound represented by the formula (1) as a monomer, a compound represented by the formula (2) A step of dissolving at least one member selected from the resins obtained by using the compound represented by the formula (2) as a monomer in a solvent to obtain a solution (S); and a step of bringing the obtained solution (S) And a step of extracting impurities in the resin and / or the resin (first extraction step), and the solvent used in the step of obtaining the solution (S) includes an organic solvent which is not arbitrarily miscible with water.

In the first extraction step, the resin is preferably a resin obtained by reacting the compound represented by the formula (1) and / or the compound represented by the formula (2) with a compound having a crosslinking reactivity. According to the purification method of the present embodiment, the content of various metals that may be contained as impurities in the compound or resin having the above-described specific structure can be reduced.

More specifically, in the purification method of the present embodiment, the compound (S) is obtained by dissolving the compound and / or the resin in an organic solvent which is not optionally miscible with water to obtain a solution (S) So that the extraction treatment can be performed. Thus, after the metal component contained in the solution (S) is transferred to the aqueous phase, the organic phase and the aqueous phase are separated to obtain a compound and / or a resin having a reduced metal content.

The compound and / or the resin used in the purification method of the present embodiment may be used alone or in combination of two or more. The compound or resin may contain various surfactants, various crosslinking agents, various acid generators, various stabilizers, and the like.

The solvent that is not optionally miscible with water used in the present embodiment is not particularly limited, but an organic solvent that can be safely applied to a semiconductor manufacturing process is preferable, and specifically, a solubility in water at room temperature of 30 %, More preferably less than 20%, and more preferably less than 10%. The amount of the organic solvent to be used is preferably 1 to 100 times the total amount of the compound and the resin to be used.

Specific examples of the solvent which is not optionally miscible with water include, but are not limited to, ethers such as diethyl ether and diisopropyl ether, ethyl acetate, n-butyl acetate, Esters, ketones such as methyl ethyl ketone, methyl isobutyl ketone, ethyl isobutyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, and 2-pentanone; Glycol ether acetates such as ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monoethyl ether acetate; aliphatic hydrocarbons such as n-hexane and n-heptane; Aromatic hydrocarbons such as toluene and xylene; And halogenated hydrocarbons such as methylene chloride and chloroform. Of these, toluene, 2-heptanone, cyclohexanone, cyclopentanone, methylisobutylketone, propylene glycol monomethyl ether acetate and ethyl acetate are preferable, and methyl isobutyl ketone, ethyl acetate, cyclohexanone, propylene Glycol monomethyl ether acetate is more preferable, and methyl isobutyl ketone and ethyl acetate are still more preferable. Methyl isobutyl ketone, ethyl acetate and the like are industrially removed by drying or by evaporation of the solvent industrially in view of the relatively high saturation solubility of the above compound and the resin containing the compound as a constituent component The load in the process can be reduced. These solvents may be used alone or in combination of two or more.

The acidic aqueous solution used in the purification method of the present embodiment is appropriately selected from aqueous solutions in which generally known organic compounds or inorganic compounds are dissolved in water. Examples of the acidic aqueous solution include, but are not limited to, aqueous solutions of inorganic acids in which inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid are dissolved in water, organic acids such as acetic acid, propionic acid, oxalic acid, malonic acid, succinic acid, fumaric acid, And an organic acid aqueous solution prepared by dissolving an organic acid such as acetic acid, tartaric acid, citric acid, methane sulfonic acid, phenol sulfonic acid, p-toluenesulfonic acid, trifluoroacetic acid, etc. in water. These acidic aqueous solutions may be used alone, or two or more kinds may be used in combination. Among these acidic aqueous solutions, at least one inorganic acid aqueous solution selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid, or an aqueous solution of at least one selected from the group consisting of acetic acid, propionic acid, oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, It is preferable that the aqueous solution is at least one aqueous solution of organic acid selected from the group consisting of acetic acid, p-toluenesulfonic acid, p-toluenesulfonic acid and trifluoroacetic acid, More preferably an aqueous solution of sulfuric acid, oxalic acid, tartaric acid and citric acid, and still more preferably an aqueous solution of oxalic acid. It is believed that polyvalent carboxylic acids such as oxalic acid, tartaric acid, and citric acid are coordinated with metal ions and a chelating effect is generated, so that there is a tendency that metal can be more effectively removed. It is preferable to use water having a small metal content, for example, ion-exchanged water, etc., 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 of the present embodiment is not particularly limited, but it is preferable to adjust the acidity of the aqueous solution in consideration of the influence on the compound or the resin. The pH of the acidic aqueous solution is preferably about 0 to 5, and more preferably about 0 to 3.

The amount of the acidic aqueous solution to be used in the purification method of the present embodiment is not particularly limited, but from the viewpoint of reducing the number of times of extraction for metal removal and securing operability in consideration of the total liquid amount, desirable. From the above viewpoint, the amount of the acidic aqueous solution to be used is preferably 10 to 200 mass%, and more preferably 20 to 100 mass%, based on 100 mass% of the solution (S).

In the refining method of the present embodiment, the metal component can be extracted from the compound or the resin in the solution (S) by contacting the acidic aqueous solution with the solution (S).

In the purification method of the present embodiment, it is preferable that the solution (S) further contains an organic solvent optionally mixed with water. When the solution (S) contains an organic solvent optionally miscible with water, the amount of the compound and / or the resin can be increased, and the liquidity can be improved and the purification can be performed with high pot efficiency have. The method of adding an organic solvent optionally mixed with water is not particularly limited. For example, it may be one of a method of adding it to a solution containing an organic solvent in advance, a method of adding it to water or an acidic aqueous solution in advance, a method of adding a solution containing an organic solvent and a water or acidic aqueous solution after the contact . Among them, a method of adding the solution to a solution containing an organic solvent in advance is preferable from the viewpoint of workability of the operation and ease of control of the amount of injection.

The organic solvent optionally mixed with water used in the purification method of the present embodiment is not particularly limited, but an organic solvent which can be safely applied to a semiconductor manufacturing process is preferable. The amount of the organic solvent optionally mixed with water is not particularly limited as far as the solution phase and the water phase are separated, but is preferably 0.1 to 100 mass times, more preferably 0.1 to 50 mass times More preferably 0.1 to 20 times by mass.

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

The temperature at which extraction treatment is carried out is usually 20 to 90 占 폚, preferably 30 to 80 占 폚. The extraction operation is carried out, for example, by mixing by stirring or the like, and then left to stand. As a result, the metal component contained in the solution (S) migrates to the aqueous phase. Further, by this operation, the acidity of the solution is lowered and the deterioration of the compound and / or the resin can be suppressed.

The mixed solution is separated into a solution phase containing a compound and / or a resin and a solvent and a water phase by standing, so that the solution phase is recovered by decantation or the like. The time for which the solution is allowed to stand is not particularly limited, but from the viewpoint of better separation of the solution phase containing the solvent and the aqueous phase, it is preferable to adjust the time for which the solution is allowed to stand. Normally, the standing time is at least 1 minute, preferably at least 10 minutes, and more preferably at least 30 minutes. The extraction process may be performed only once, but it is also effective to repeat the operations of mixing, setting, and separation a plurality of times.

In the purification method of the present embodiment, after the first extraction step, a step of bringing the compound or the solution phase containing the resin into contact with water to extract the compound or impurities in the resin (second extraction step ). Specifically, for example, after the extraction treatment is performed using an aqueous acidic solution, the solution phase extracted from the aqueous solution and containing the recovered compound and / or resin and solvent is subjected to extraction treatment with water again . The extraction treatment with water is not particularly limited, but can be performed, for example, by mixing the solution phase and water well by stirring or the like, and then allowing the obtained mixed solution to stand. The mixed solution after the standing is separated into the solution phase containing the compound and / or the resin and the solvent and the water phase, so that the solution phase can be recovered by decantation or the like.

It is preferable that the water used here is water having a small metal content, for example, ion-exchanged water, etc., in accordance with the object of the present embodiment. The extraction process may be performed only once, but it is also effective to repeat the operations of mixing, setting, and separation a plurality of times. The conditions such as the ratio of use in the extraction treatment, the temperature, the time, and the like are not particularly limited, but may be the same as in the case of the treatment with an acidic aqueous solution.

The water that can be incorporated into the solution thus obtained and / or the solution containing the resin and the solvent can be easily removed by an operation such as distillation under reduced pressure. If necessary, a solvent may be added to the solution to adjust the concentration of the compound and / or the resin to an arbitrary concentration.

The method of isolating a compound and / or a resin from a solution containing the obtained compound and / or resin and a solvent is not particularly limited and may be carried out by a known method such as removal under reduced pressure, separation by re-precipitation, have. If necessary, known processes such as a concentration operation, a filtration operation, a centrifugation operation, and a drying operation can be performed.

[Composition]

The composition of the present embodiment is a composition comprising a resin represented by the formula (1), a resin obtained by using the compound represented by the formula (1) as a monomer, a compound represented by the formula (2) And a resin obtained by using a compound obtained by subjecting a compound represented by the general formula (1) as a monomer. The composition of the present embodiment may be a film forming composition for lithography or an optical component forming composition.

[Film forming composition for lithography for chemically amplified resist application]

(Hereinafter also referred to as " resist composition ") for use in the chemically amplified resist in the present embodiment is a composition comprising a compound represented by the formula (1), a compound represented by the formula (1) At least one member selected from the group consisting of a resin obtained as a monomer, a resin obtained by using the compound represented by the formula (2) and a compound obtained by using the compound represented by the formula (2) as a monomer.

It is preferable that the composition (resist composition) of the present embodiment further contains a solvent. Examples of the solvent include, but are not limited to, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate and ethylene glycol mono-n- Monoalkyl ether acetates; Ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; Propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether acetate and propylene glycol mono-n-butyl ether acetate; Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether (PGME) and propylene glycol monoethyl ether; Lactic acid esters such as methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, and n-amyl lactate; Aliphatic carboxylic acid esters such as methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, n-amyl acetate, n-hexyl acetate, methyl propionate and ethyl propionate; Methoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxy- Other esters such as 3-methoxybutyl 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), and cyclohexanone (CHN); Amides such as N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide and N-methylpyrrolidone; lactones such as? -lactone, and the like, but are not limited thereto. These solvents may be used alone or in combination of two or more.

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

In the present embodiment, the amount of the solid component and the amount of the solvent are not particularly limited, but it is preferably from 1 to 80 mass% of the solid component and from 20 to 99 mass% of the solvent, based on 100 mass% of the total mass of the solid component and the solvent , More preferably from 1 to 50 mass% of a solid component and from 50 to 99 mass% of a solvent, more preferably from 2 to 40 mass% of a solid component and from 60 to 98 mass% of a solvent, and particularly preferably from 2 to 10 Mass% and the solvent is 90 to 98 mass%.

The composition (resist composition) of the present embodiment contains at least one kind selected from the group consisting of the acid generator (C), the crosslinking agent (G), the acid diffusion controlling agent (E) May be further contained. In the present specification, the solid component means a component other than the solvent.

As the acid generator (C), the cross-linking agent (G), the acid diffusion controller (E) and the other components (F), publicly known ones can be used. 024778 is preferable.

[Compounding ratio of each component]

In the resist composition of the present embodiment, the content of the compound and / or resin used as the resist base material is not particularly limited, but the total mass of the solid component (resist substrate, acid generator (C), crosslinking agent (G) More preferably from 55 to 90% by mass, more preferably from 55 to 90% by mass, more preferably from 50 to 90% by mass of the total amount of solid components including optional components such as the control agent (E) Preferably 60 to 80% by mass, and particularly preferably 60 to 70% by mass. When the content of the compound and / or resin used as the resist base material is in the above range, the resolution is further improved and the line edge roughness (LER) tends to be further reduced.

On the other hand, when both the compound and the resin are contained as the resist base material, the above content is the total amount of the positive components.

[Other components (F)]

The resist composition of the present embodiment may contain, as necessary, components other than the resist substrate, the acid generator (C), the crosslinking agent (G) and the acid diffusion control agent (E) A polymerization inhibitor, a flame retardant, a filler, a coupling agent, a thermosetting resin, a photo-curable resin, a dye, and the like. , A pigment, a thickener, a lubricant, a defoaming agent, a leveling agent, an ultraviolet absorber, a surfactant, a colorant, and a nonionic surfactant. In the present specification, the other component (F) may be referred to as an optional component (F).

The acid generator (C), the crosslinking agent (G), the acid diffusion control agent (E), the optional component (F), and the acid generator (C) (C) / crosslinking agent (G) / acid diffusion control agent (E) / optional component (F) in terms of 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,

And particularly preferably 60 to 70/10 to 25/2 to 20/0 0.01 to 3/0.

The blending ratio of each component is selected from each range so that the total sum is 100% by mass. When the mixing ratio of each component is in the above range, performance such as sensitivity, resolution, developability tends to be excellent.

The resist composition of the present embodiment is usually prepared by dissolving each component in a solvent to prepare a homogeneous solution at the time of use and then filtering it with a filter having a pore diameter of about 0.2 m if necessary.

The resist composition of the present embodiment may contain other resins than the resin of this embodiment within the range not hindering the object of the present invention. The other resin is not particularly limited and includes, for example, novolac resins, polyvinyl phenols, polyacrylic acid, polyvinyl alcohol, styrene-maleic anhydride resin, and acrylic acid, vinyl alcohol, or vinylphenol as monomer units Or a derivative thereof, and the like. The content of other resin is not particularly limited and may be appropriately controlled according to the kind of the component (A) to be used. It is preferably 30 parts by mass or less, more preferably 10 parts by mass or less, More preferably 5 parts by mass or less, and particularly preferably 0 parts by mass.

[Physical properties of resist composition]

By using the resist composition of the present embodiment, an amorphous film can be formed by spin coating. Further, the resist composition of the present embodiment can be applied to a general semiconductor manufacturing process. Depending on the kind of the resin obtained by using the compound represented by the formula (1) and / or the formula (2), and the type of the developer obtained by using these as the monomer and / or the type of the developer to be used, any one of the positive resist pattern and the negative resist pattern Can be made.

In the case of the positive resist pattern, the dissolution rate of the amorphous film formed by spin-coating the resist composition of the present embodiment in a developer at 23 캜 is preferably 5 Å / sec or less, more preferably 0.05 to 5 Å / sec , And more preferably 0.0005 to 5 占 sec. When the dissolution rate is 5 Å / sec or less, it is insoluble in a developer and can be a resist. When the dissolution rate is 0.0005 Å / sec or more, the resolution is likely to be improved. This is because, depending on the change in the solubility before and after exposure of the compound represented by the above formula (1) and / or the resin containing the compound as a constituent component, the difference between the exposed part dissolved in the developing solution and the unexposed part It is presumed that the contrast is increased. There is also an effect of reducing LER and reducing defects.

In the case of the negative resist pattern, the dissolution rate of the amorphous film formed by spin-coating the resist composition of the present embodiment with respect to the developer at 23 캜 is preferably 10 Å / sec or more. When the dissolution rate is 10 Å / sec or more, it is easily soluble in a developing solution and is more suitable for resists. If the dissolution rate is 10 Å / sec or more, the resolution may be improved. This is presumably because the surface area of the microparticles of the compound represented by the formula (1) and / or the resin containing the compound as the constituent component is dissolved and LER is reduced. It also has the effect of reducing defects.

The dissolution rate can be determined by immersing the amorphous film in a developer for a predetermined time at 23 占 폚 and measuring the film thickness before and after the immersion by a known method such as naked eye, ellipsometer or QCM method.

In the case of a positive resist pattern, the resist composition of the present embodiment is dissolved in a developing solution at 23 deg. C in a KrF excimer laser of an amorphous film formed by spin-coating the resist composition of the present embodiment, a part exposed by radiation such as extreme ultraviolet rays, The speed is preferably 10 angstroms / sec or more. When the dissolution rate is 10 Å / sec or more, it is used for a developing solution, and it is more suitable for a resist. If the dissolution rate is 10 Å / sec or more, the resolution may be improved. This is presumably because the surface portions of the microparticles of the compound represented by the above-mentioned formulas (1) and (2) and / or the resin containing the compound as the constituent component are dissolved and the LER is reduced. It also has the effect of reducing defects.

In the case of a negative resist pattern, the resist composition of the present embodiment is dissolved in a developing solution at 23 占 폚 in a KrF excimer laser of an amorphous film formed by spin-coating the resist composition of this embodiment, a part exposed by radiation such as extreme ultraviolet ray, electron beam or X- The speed is preferably 5 angstroms / sec or less, more preferably 0.05 to 5 angstroms / sec, and still more preferably 0.0005 to 5 angstroms / sec. When the dissolution rate is 5 Å / sec or less, it is insoluble in a developer and can be a resist. Further, if the dissolution rate is 0.0005 Å / sec or more, the resolution may be improved. This is because, depending on the change in the solubility before and after exposure of the compound represented by the formula (1) and / or the resin containing the compound as a component, the ratio of the unexposed portion dissolved in the developer to the exposed portion It is presumed that the contrast increases. There is also an effect of reducing LER and reducing defects.

[Film forming composition for lithography for non-chemically amplified resist application]

The component (A) to be contained in the film forming composition for lithography for a non-chemically amplified resist application (hereinafter also referred to as " radiation-sensitive composition ") of the present embodiment can be obtained by reacting a diazonaphthoquinone photoactive compound (B) And is useful as a substrate for a positive type resist which is used as a phosphorus compound in a developer by irradiation with a g line, h line, i line, KrF excimer laser, ArF excimer laser, extreme ultraviolet ray, electron beam or X-ray. The properties of the component (A) do not largely change by the g line, h line, i line, KrF excimer laser, ArF excimer laser, extreme ultraviolet ray, electron beam or X- The resist pattern can be formed by a developing process by changing the compound used for the photoactive compound (B).

Since the component (A) contained in the radiation sensitive composition of the present embodiment is a compound having a relatively low molecular weight, the obtained resist pattern has a very low roughness. In the formula (1), at least one group 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 ^{1 A} and R ² A Is at least one group selected from the group consisting of iodine atoms. When the component (A) having a group containing an iodine atom as such preferred embodiment is applied, the radiation-sensitive composition of the present embodiment is capable of increasing the absorption ability for radiation such as electron beam, extreme ultraviolet (EUV), and X- As a result, it is possible to increase the sensitivity, which is preferable.

The glass transition temperature of the component (A) contained in the radiation sensitive composition of this embodiment is preferably 100 占 폚 or higher, more preferably 120 占 폚 or higher, even more preferably 140 占 폚 or higher, particularly preferably 150 占 폚 Or more. The upper limit of the glass transition temperature of the component (A) is not particularly limited, but is, for example, 400 占 폚. When the glass transition temperature of the component (A) is within the above range, heat resistance capable of maintaining the pattern shape in the semiconductor lithography process tends to be improved, such as high resolution.

The crystallization calorific value determined by a differential scanning calorimetry of the glass transition temperature of the component (A) contained in the radiation sensitive composition of the present embodiment is preferably less than 20 J / g. The (crystallization temperature) - (glass transition temperature) is preferably 70 占 폚 or higher, more preferably 80 占 폚 or higher, even more preferably 100 占 폚 or higher, particularly preferably 130 占 폚 or higher. When the crystallization calorific value is less than 20 J / g or (crystallization temperature) - (glass transition temperature) falls within the above range, the amorphous film is easily formed by spin coating the radiation sensitive composition, And it tends to be able to improve the resolution.

In the present embodiment, the crystallization heat generation amount, crystallization temperature and glass transition temperature can be obtained by differential scanning calorimetry using DSC / TA-50WS manufactured by Shimadzu Corporation. Approximately 10 mg of the sample is placed in a container made of aluminum and heated in a nitrogen gas stream (50 mL / min) to a melting point or more at a heating rate of 20 캜 / minute. After quenching, the temperature is raised again to the melting point or higher in a nitrogen gas stream (30 mL / min) at a heating rate of 20 DEG C / min. After quenching again, the temperature is raised again to 400 DEG C in a nitrogen gas stream (30 mL / min) at a heating rate of 20 DEG C / min. The glass transition temperature (Tg) and the temperature of the exothermic peak appearing thereafter are referred to as the crystallization temperature, the temperature at the midpoint (the part where the specific heat is changed to half) of the step of the baseline changed stepwise. The calorific value is obtained from the area of the area surrounded by the exothermic peak and the baseline, and is used as the calorific calorific value.

The component (A) contained in the radiation sensitive composition of the present embodiment is preferably at most 100, preferably at most 120, more preferably at most 130, more preferably at most 140, It is preferable that the sublimation property is low at 150 占 폚 or lower. The reason why the sublimation property is low is that in the 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, further preferably 1% Or less, particularly preferably 0.1% or less. By lowering the sublimation property, it is possible to prevent the exposure apparatus from being contaminated by the outgassing during exposure. In addition, a good pattern shape can be obtained with low roughness.

The component (A) to be contained in the radiation sensitive composition of the present embodiment is at least one selected from the group consisting of propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone (CHN), cyclopentanone Preferably 1% by mass or more, at 23 占 폚, to a solvent which is selected from the group consisting of ethyl acetate, 2-heptanone, anisole, butyl acetate, ethyl propionate and ethyl lactate and which exhibits the highest solubility to component (A) Or more, more preferably 5 mass% or more, and further preferably 10 mass% or more. Particularly preferably, the solvent is selected from the group consisting of PGMEA, PGME and CHN, and (A) a solvent which exhibits the highest solubility to resist base at 20 占 폚% or more at 23 占 폚, particularly preferably PGMEA At 23 占 폚 for 20% by mass or more. By satisfying the above condition, use in the semiconductor manufacturing process in the actual production becomes easy.

[Diazonaphthoquinone photoactive compound (B)]

The diazonaphthoquinone photoactive compound (B) contained in the radiation sensitive composition of the present embodiment is a diazonaphthoquinone substance including a polymerizable and non-polymerizable diazonaphthoquinone photoactive compound, In the composition, any one or more of them may be arbitrarily selected and used without particular limitation, as long as they are used as a photosensitive component (photosensitive agent).

As the component (B), a compound obtained by reacting a naphthoquinone diazide sulfonic acid chloride, benzoquinone diazide sulfonic acid chloride or the like with a low molecular compound having a functional group capable of condensation reaction with these acid chloride or a polymer compound is preferable. Here, the functional group capable of condensation with an acid chloride is not particularly limited, and examples thereof include a hydroxyl group and an amino group. The hydroxyl group is particularly preferred. Examples of the compound capable of condensing with an acid chloride including a hydroxyl group include, but are not limited to, 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'-tetra Hydroxybenzophenones such as hydroxybenzophenone, 2,2 ', 3,4,6'-pentahydroxybenzophenone, bis (2,4-dihydroxyphenyl) methane, bis Hydroxyphenyl) methane, bis (2,4-dihydroxyphenyl) propane, and the like, 4,4 ', 3 ", 4" -tetrahydroxy- Hydroxytriphenylmethanes such as 5'-tetramethyltriphenylmethane and 4,4 ', 2 ", 3", 4 "-pentahydroxy-3,5,3', 5'-tetramethyltriphenylmethane And the like.

Examples of the acid chloride such as naphthoquinone diazide sulfonic acid chloride and benzoquinone diazide sulfonic acid chloride include 1,2-naphthoquinonediazide-5-sulfonyl chloride, 1,2-naphthoquinone diazide sulfonic acid chloride, Toquinonediazide-4-sulfonyl chloride, and the like.

The radiation sensitive composition of the present embodiment can be obtained by, for example, dissolving each component in a solvent to prepare a homogeneous solution at the time of use, and then, if necessary, filtering with a filter having a pore diameter of about 0.2 m It is preferable to prepare them.

[Characteristics of radiation-sensitive composition]

The radiation sensitive composition of the present embodiment can form an amorphous film by spin coating. Further, the radiation sensitive composition of this embodiment can be applied to a general semiconductor manufacturing process. Depending on the type of developing solution to be used, any one of the positive resist pattern and the negative resist pattern can be separately formed.

In the case of the positive resist pattern, the dissolution rate of the amorphous film formed by spin-coating the radiation sensitive composition of the present embodiment in the developer at 23 캜 is preferably 5 Å / sec or less, more preferably 0.05 to 5 Å / sec More preferably 0.0005 to 5 ANGSTROM / sec. When the dissolution rate is 5 Å / sec or less, it is insoluble in a developer and can be a resist. When the dissolution rate is 0.0005 Å / sec or more, the resolution is likely to be improved. This is because, depending on the change in the solubility before and after exposure of the compound represented by the above-mentioned formulas (1) and (2) and / or the resin containing the compound as a constituent component, the exposure part dissolving in the developing solution, It is presumed that the contrast of the interface of the unexposed portion increases. There is also 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 of the present embodiment to a developer at 23 캜 is preferably 10 Å / sec or more. When the dissolution rate is 10 Å / sec or more, it is used for a developing solution, and it is more suitable for a resist. If the dissolution rate is 10 Å / sec or more, the resolution may be improved. This is presumably because the surface portions of the microparticles of the compound represented by the above-mentioned formulas (1) and (2) and / or the resin containing the compound as the constituent component are dissolved and the LER is reduced. It also has the effect of reducing defects.

The dissolution rate can be determined by immersing the amorphous film in a developer for a predetermined time at 23 占 폚 and measuring the film thickness before and after the immersion by a known method such as naked eye, ellipsometer or QCM method.

In the case of the positive resist pattern, the radiation sensitive composition of the present embodiment is irradiated with radiation such as KrF excimer laser, extreme ultraviolet ray, electron beam or X-ray of an amorphous film formed by spin coating, The dissolution rate of the exposed portion to the developer at 23 캜 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 used for a developing solution, and it is more suitable for a resist. If the dissolution rate is less than 10,000 A / sec, the resolution may be improved. This is presumably because the surface portions of the microparticles of the compound represented by the above-mentioned formulas (1) and (2) and / or the resin containing the compound as the constituent component are dissolved and the LER is reduced. In addition, there is a tendency to have a reduction effect of defects.

In the case of a negative resist pattern, the resist composition is irradiated with radiation such as KrF excimer laser, extreme ultraviolet ray, electron beam or X-ray of an amorphous film formed by spin coating of the radiation sensitive composition of the present embodiment, The dissolution rate of the exposed portion to the developer at 23 캜 is preferably 5 Å / sec or less, more preferably 0.05 to 5 Å / sec, and still more preferably 0.0005 to 5 Å / sec. When the dissolution rate is 5 Å / sec or less, it is insoluble in a developer and can be a resist. When the dissolution rate is 0.0005 Å / sec or more, the resolution may be improved. This is because, depending on the change in the solubility before and after exposure of the compound represented by the above-mentioned formulas (1) and (2) and / or the resin containing the compound as a component, the unexposed portion dissolved in the developer, It is presumed that the contrast of the interface of the exposed portion increases. In addition, there is a tendency to reduce LER and reduce defects.

[Compounding ratio of each component]

The content of the component (A) in the radiation sensitive composition of the present embodiment is preferably such that the solid component (A), the diazonaphthoquinone photoactive compound (B) and other components (D) Is preferably from 1 to 99% by mass, more preferably from 5 to 95% by mass, still more preferably from 10 to 90% by mass, and particularly preferably from 25 to 75% by mass, based on the total amount . When the content of the component (A) is within the above range, the radiation sensitive composition of the present embodiment tends to obtain a pattern with a high sensitivity and a small roughness.

The content of the diazonaphthoquinone photoactive compound (B) in the radiation sensitive composition of the present embodiment is preferably such that the total weight of the solid component (component (A), diazonaphthoquinone photoactive compound (B) Is preferably from 1 to 99% by mass, more preferably from 5 to 95% by mass, further preferably from 10 to 90% by mass, particularly preferably from 25 to 95% by mass, based on the total amount 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 tends to obtain a pattern with high sensitivity and small roughness.

[Other components (D)]

The radiation sensitive composition of the present embodiment may contain, as necessary, components other than the component (A) and the diazonaphthoquinone photoactive compound (B), such as an acid generator, a crosslinking agent, A heat and / or light curing catalyst, a polymerization inhibitor, a flame retardant, a filler, a coupling agent, a thermosetting resin, a heat stabilizer, an acid diffusion controlling agent, a dissolution accelerator, a solubilizer, a sensitizer, a surfactant, It is possible to add one or more kinds of additives such as a photo-curing resin, a dye, a pigment, a thickener, a lubricant, a defoaming agent, a leveling agent, an ultraviolet absorber, a surfactant, a colorant and a nonionic surfactant. On the other hand, in the present specification, the other component (D) may be referred to as optional component (D).

In the radiation sensitive composition of the present embodiment, the compounding ratio (component (A) / diazonaphthoquinone photoactive compound (B) / optional component (D)) of each component is,

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,

Still more preferably 20 to 80/80 to 20/0 to 5,

Still more preferably 25 to 75/75 to 25/0.

The blending ratio of each component is selected from each range so that the total sum is 100% by mass. When the compounding ratio of each component in the radiation sensitive composition of the present embodiment is in the above range, performance such as sensitivity and resolution tends to be excellent in addition to roughness.

The radiation sensitive composition of the present embodiment may contain other resins than the present embodiment within the range not hindering the object of the present invention. Examples of other resins include novolac resins, polyvinyl phenols, polyacrylic acid, polyvinyl alcohol, styrene-maleic anhydride resins, and polymers containing acrylic acid, vinyl alcohol, or vinylphenol as monomer units or derivatives thereof . The amount of these resins to be blended is appropriately controlled depending on the kind of the component (A) to be used, and it is preferably 30 parts by mass or less, more preferably 10 parts by mass or less, further preferably 10 parts by mass or less, Is 5 parts by mass or less, particularly preferably 0 parts by mass.

[Method of forming resist pattern]

The method of forming a resist pattern according to the present embodiment is a method of forming a resist pattern on a substrate by using the resist composition or the radiation sensitive composition of the present embodiment described above and then irradiating a predetermined region of the photoresist layer with radiation And performing a developing process. Specifically, the method includes a step of forming a resist film on a substrate, a step of exposing the formed resist film, and a step of developing the resist film to form a resist pattern. The resist pattern in the present embodiment may be formed as an upper layer resist in a multilayer process.

The method for forming the resist pattern is not particularly limited, and for example, the following methods can be used. First, the resist composition or the radiation-sensitive composition of the present embodiment is applied onto a conventionally known substrate by a coating means such as spin coating, soft coating or roll coating to form a resist film. The conventionally known substrate is not particularly limited and includes, for example, a substrate for electronic parts and a substrate having a predetermined wiring pattern formed thereon. More specifically, examples thereof include substrates made of metal such as silicon wafers, copper, chromium, iron and aluminum, and glass substrates. Examples of the material of the wiring pattern include copper, aluminum, nickel, gold, and the like. In addition, if necessary, an inorganic and / or organic film may be provided on the above-described substrate. As the inorganic film, an inorganic anti-reflection film (inorganic BARC) can be mentioned. The organic film may be an organic anti-reflection film (organic BARC). On the substrate, surface treatment with hexamethylene disilazane or the like may be performed.

Next, the resist composition or the substrate coated with the radiation-sensitive composition is heated, if necessary. The heating conditions vary depending on the composition of the resist composition or radiation-sensitive composition, and are preferably from 20 to 250 캜, more preferably from 20 to 150 캜. By heating, the adhesion of the resist to the substrate tends to be improved, which is preferable. Subsequently, the resist film is exposed in a desired pattern by any one of radiation selected from the group consisting of visible light, ultraviolet light, excimer laser, electron beam, extreme ultraviolet (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 fine pattern with high precision in exposure, it is preferable to heat after irradiation with radiation. The heating conditions vary depending on the composition of the resist composition or the radiation-sensitive composition, and are preferably 20 to 250 占 폚, and more preferably 20 to 150 占 폚.

Subsequently, the exposed resist film is developed with a developing solution to form a predetermined resist pattern. As the developer, a resin obtained by using a compound represented by the formula (1) or (2) or a compound represented by the formula (1) or (2) as a monomer has a solubility parameter (SP value) It is preferable to use a solvent, and a polar solvent such as a ketone solvent, an ester solvent, an alcohol solvent, an amide solvent or an ether solvent, a hydrocarbon solvent or an aqueous alkali solution may be used.

Examples of the ketone-based solvent include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 4-heptanone, 1-hexanone, Ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methylethylketone, methylisobutylketone, acetylacetone, acetonyl acetone, ionone, diacetonyl alcohol, acetylcarbinol, acetophenone, methylnaphthyl ketone, Isophorone, propylene carbonate, and the like.

Examples of the ester-based solvent 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 Methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, lactic acid, ethyl lactate, ethyl lactate, ethyl lactate, ethyl lactate, Butyl, and propyl lactate.

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

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

Examples of the amide-based solvent include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoric triamide, - imidazolidinone, and the like.

Examples of the hydrocarbon-based 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 they may be mixed with a solvent or water other than the above in a range of performance. However, in order to exhibit the effect of the present invention for the twenty minutes, the water content of the developer as a whole is preferably less than 70 mass%, more preferably less than 50 mass%, more preferably less than 30 mass%, and more preferably less than 10 mass% It is more preferable that substantially no water is contained. That is, the content of the organic solvent in the developer is preferably 30 mass% or more and 100 mass% or less, more preferably 50 mass% or more and 100 mass% or less, more preferably 70 mass% or more and 100 mass% or less More preferably 90 mass% or more and 100 mass% or less, still more preferably 95 mass% or more and 100 mass% or less.

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

Particularly, as the developer, a developer containing at least one solvent selected from a ketone solvent, an ester solvent, an alcohol solvent, an amide solvent and an ether solvent is preferably used as a resist for resist pattern resolution and roughness, It is desirable to improve the performance.

The vapor pressure of the developer is preferably 5 kPa or less at 20 캜, more preferably 3 kPa or less, and particularly preferably 2 kPa or less. When the vapor pressure of the developing solution is 5 kPa or less, evaporation of the developer on the substrate or in the developing cup is suppressed, the temperature uniformity in the wafer surface is improved, and as a result, the dimensional uniformity within the wafer surface tends to be quantified.

Examples of a specific developer having a vapor pressure of 5 kPa or less at 20 占 폚 include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 4-heptanone, 2-hexanone, diisobutylketone , Ketone solvents such as cyclohexanone, methylcyclohexanone, phenylacetone and methylisobutylketone; 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 Ester solvents such as butyl acetate, 3-methyl-3-methoxybutyl acetate, butyl formate, propyl formate, ethyl lactate, butyl lactate and propyl lactate; propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, Alcohol solvents such as alcohol and n-decanol; Glycol solvents such as ethylene glycol, diethylene glycol and triethylene glycol; Glycol ether solvents 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 and methoxymethyl butanol; Ether solvents such as tetrahydrofuran; Amide solvents such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide and N, N-dimethylformamide; Aromatic hydrocarbon solvents such as toluene and xylene; And aliphatic hydrocarbon solvents such as octane and decane.

Examples of a specific developer having a vapor pressure of 2 kPa or less at 20 캜, which is a particularly preferable range, include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 4-heptanone, Ketone solvents such as diisobutyl ketone, cyclohexanone, methylcyclohexanone and 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-methoxy Ester solvents such as butyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl lactate, butyl lactate, and propyl lactate; alcohols such as n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, Based solvent; Glycol solvents such as ethylene glycol, diethylene glycol and triethylene glycol; Glycol ether solvents 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 and methoxymethyl butanol; Amide solvents such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide and N, N-dimethylformamide; Aromatic hydrocarbon solvents such as xylene; And aliphatic hydrocarbon solvents such as octane and decane.

To the developer, an appropriate amount of a surfactant may be added, if necessary. The surfactant is not particularly limited and, for example, ionic or nonionic fluorine-based and / or silicon-based surfactants can be used. As these fluorine- and / or silicon-based surfactants, for example, Japanese Patent Application Laid-Open Nos. S62-36663, S61-226746, S61-226745, S62-170950, Japanese Patent Application Laid-Open Nos. S63-34540, H7-230165, H8-62834, H9-54432, H9-5988, US5405720 Surfactants described in JP-B-5360692, JP-B-5529881, JP-A-5296330, JP-A-5436098, JP-A-5576143, JP-B-5294511 and JP-A-5824451, Is a nonionic surfactant. The nonionic surfactant is not particularly limited, but it is more preferable to use a fluorinated surfactant or a silicone surfactant.

The amount of the surfactant to be used is usually 0.001 to 5 mass%, preferably 0.005 to 2 mass%, more preferably 0.01 to 0.5 mass%, based on the whole amount of the developer.

Examples of the developing method include a method (dip method) of immersing the substrate in a tank filled with the developer for a predetermined time (dip method), a method of immobilizing the developer on the surface of the substrate by surface tension, (Spraying method), a method of continuously extracting the developer while scanning the developing solution drawing 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.

Further, after the step of performing development, a step of stopping development while replacing with another solvent may be performed.

After the development, it is preferable to include a step of cleaning using a rinsing liquid containing an organic solvent.

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

Examples of the monohydric alcohol used in the rinsing step after development include linear, branched, and cyclic monohydric alcohols. Specific examples thereof include 1-butanol, 2-butanol, 3-methyl- 2-pentanol, 1-heptanol, 1-octanol, 2-hexanol, cyclopentanol, 2-pentanol, 2-butanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol and the like can be used. Particularly preferred monohydric alcohols having 5 or more carbon atoms include 1-hexanol, 2-hexanol, 4-methyl-2-pentanol, 1-pentanol, 3-methyl-1-butanol and the like.

A plurality of the above components may be mixed together, or they may be mixed with other organic solvents.

The water content in the rinsing liquid is preferably 10 mass% or less, more preferably 5 mass% or less, particularly preferably 3 mass% or less. By setting the moisture content to 10 mass% or less, more excellent developing characteristics tend to be obtained.

The vapor pressure of the rinsing liquid used after development is preferably 0.05 kPa or more and 5 kPa or less at 20 캜, more preferably 0.1 kPa or more and 5 kPa or less, and further preferably 0.12 kPa or more and 3 kPa or less. By adjusting the vapor pressure of the rinsing liquid to 0.05 kPa or more and 5 kPa or less, the temperature uniformity within the wafer surface is further improved, swelling due to infiltration of the rinsing liquid is further suppressed, and the dimensional uniformity within the wafer surface is further improved .

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

In the rinsing process, the developed wafer is cleaned using a rinsing liquid containing the organic solvent. The method of the rinsing treatment is not particularly limited. For example, there is a method of continuously extracting the rinsing liquid onto the substrate rotating at a constant speed (spin coating method), a method of immersing the substrate in the rinsing liquid filled tank for a certain time A method of spraying a rinsing liquid onto the surface of a substrate (spraying method), or the like can be applied. Among them, a cleaning treatment is carried out by a rotation coating method, the substrate is rotated at a rotation speed of 2000 rpm to 4000 rpm, Is removed from the substrate.

After the resist pattern is formed, etching is performed to obtain a pattern wiring substrate. The etching can be performed by a known method such as dry etching using a plasma gas and wet etching using an alkali solution, copper chloride solution, ferric chloride solution or the like.

After the resist pattern is formed, plating may be performed. Examples of the plating method include copper plating, solder plating, nickel plating, and gold plating.

The remaining 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 an immersion method and a spraying 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 board obtained in the present embodiment may be formed by depositing a metal in a vacuum after forming a resist pattern, and thereafter dissolving the resist pattern in a solution, that is, by a lift-off method.

[Film forming composition for lithography for underlayer film application]

The film forming composition for lithography for use in a lower layer film of the present embodiment (hereinafter, also referred to as a "lower layer film forming material") is obtained by mixing a compound represented by the formula (1) and a compound represented by the formula (1) (2), and a resin obtained by using a compound represented by the formula (2) as a monomer. In the present embodiment, the material 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 , And particularly preferably 100% by mass.

The lower layer film forming material of the present embodiment is applicable to a wet process, and is excellent in heat resistance and etching resistance. Since the lower layer film forming material of the present embodiment uses the above-mentioned material, deterioration of the film at the time of high-temperature baking is suppressed, and a lower layer film excellent in etching resistance against oxygen plasma etching and the like can be formed. Furthermore, the lower layer film forming material of the present embodiment is also excellent in adhesion to the resist layer, so that an excellent resist pattern can be obtained. On the other hand, the lower film forming material of the present embodiment may contain a known material for forming a lower layer film for lithography within the range in which the effect of the present invention is not impaired.

[menstruum]

The lower layer film forming material of this embodiment may contain a solvent. As the solvent used in the lower layer film forming material of the present embodiment, known solvents can be appropriately used as long as the above-mentioned substances are dissolved at least.

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

Of 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 is preferably 100 to 10,000 parts by mass, more preferably 200 to 5000 parts by mass, and most preferably 200 to 1000 parts by mass with respect to 100 parts by mass of the lower layer film forming material from the viewpoints of solubility and film- Mass part is more preferable.

[Crosslinking agent]

The lower layer film forming material of the present embodiment may contain a crosslinking agent, if necessary, from the viewpoint of suppressing intermixing or the like. The crosslinking agent usable in the present embodiment is not particularly limited, but for example, those described in International Publication No. 2013/024779 can be used.

Specific examples of the crosslinking agent that can be used in the present embodiment include a phenol compound, an epoxy compound, a cyanate compound, an amino compound, a benzoxazine compound, an acrylate compound, a melamine compound, a guanamine compound, a glycoluril compound , A urea compound, an isocyanate compound, an azide compound, and the like, but are not limited thereto. These crosslinking agents may be used singly or in combination of two or more kinds. Among them, a benzoxazine compound, an epoxy compound or a cyanate compound is preferable, and a benzoxazine compound is more preferable from the viewpoint of improvement of etching resistance.

As the phenol compound, known ones can be used. Examples of the phenols include, in addition to phenol, alkyl phenols such as cresols and xylenols, polyhydric phenols such as hydroquinone, polycyclic phenols such as naphthols and naphthalene diols, bisphenols such as bisphenol A and bisphenol F, And polyfunctional phenol compounds such as phenol novolak and phenol aralkyl resin. Among them, an aralkyl type phenol resin is preferable in view of heat resistance and solubility.

As the epoxy compound, known epoxy compounds can be used, and those having two or more epoxy groups in one molecule are selected. For example, bisphenol A, bisphenol F, 3,3 ', 5,5'-tetramethyl-bisphenol F, bisphenol S, fluorene bisphenol, 2,2'- -Tetramethyl-4,4'-dihydroxybiphenol, resorcin, naphthalene diol, and other divalent phenols such as tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetra Tris (2,3-epoxypropyl) isocyanurate, trimethylol methane triglycidyl ether, trimethylolpropane triglycidyl ether, triethylol ethane triglycidyl ether, phenol (4-hydroxyphenyl) Epoxides of tri- or higher-valent phenols such as novolak and o-cresol novolak, epoxides of dicyclopentadiene and phenol-co-condensation resins, epoxides of phenol aralkyl resins synthesized from phenols and para-xylylene di- Biphenyl aralkyl type phenol synthesized from cargo, phenols and bischloromethylbiphenyl Epoxides of naphthol aralkyl resins synthesized from naphthols and para-xylylene dichloride, and the like. These epoxy resins may be used alone or in combination of two or more. Among them, from the viewpoints of heat resistance and solubility, solid epoxy resins are preferred at room temperature such as phenol aralkyl resins and epoxy resins obtained from biphenyl aralkyl resins.

As the cyanate compound, a compound having two or more cyanate groups in one molecule may be used without particular limitation. In the present embodiment, preferred examples of the cyanate compound include those 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. The cyanate compound preferably has an aromatic group, and a cyanate compound having a structure in which a cyanate group is directly bonded to an aromatic group can be suitably used. Examples of such cyanate compounds include bisphenol A, bisphenol F, bisphenol M, bisphenol P, bisphenol E, phenol novolak resin, cresol novolac resin, dicyclopentadiene novolac resin, tetramethyl bisphenol F, A novolac resin, brominated 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, Pentadiene aralkyl resin, alicyclic phenol, phosphorus-containing phenol and the like are substituted with a cyanate group. These cyanate compounds may be used alone or in combination of two or more. The cyanate compound may be any 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'-diaminodiphenylether , 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 3,3'- Diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfide, 3,4'-diaminodiphenylsulfide, 3,3'-diaminodiphenylsulfide, 1,4-bis (4-aminophenoxy ) Benzene, 1,3- bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) biphenyl, 4,4'-bis (4-aminophenoxy) 3-aminophenoxy) phenyl] (4-aminophenyl) fluorene, 9,9-bis (4-amino-3-chlorophenyl) fluorene, 9,9- (Trifluoromethyl) -4,4'-diaminobiphenyl, 4-aminophenyl, 4,4'-diaminobenzanilide, 2,2'-bis Aminobenzoate, 2- (4-aminophenyl) -6-aminobenzoxazole, and the like. Further, there can be mentioned 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, Diaminodiphenylsulfone, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4 (Aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,3-bis Bis [4- (3-aminophenoxy) phenyl] propane, 4,4'-bis (4-aminophenoxy) phenyl] propane, 2,2- Biphenyl, 4,4'-bis (3-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] ether, bis [4- Aromatic amines such as diaminocyclohexane, diaminodicyclohexylmethane, dimethyl-diamino dicyclohexylmethane, tetramethyl-diamino dicyclohexylmethane, diamino dicyclohexyl Bis (aminomethyl) tricyclo [2.2.1] heptane, bis (aminomethyl) -bicyclo [2.2.1] heptane, 3 (4) , 6] decane, 1,3-bisaminomethylcyclohexane, and isophoronediamine; alicyclic amines such as ethylenediamine, hexamethylenediamine, octamethylenediamine, decamethylenediamine, diethylenetriamine and triethylenetetramine; Aliphatic amines and the like.

Examples of the benzoxazine photographic compound include P-d type benzoxazine obtained from bifunctional diamines and monofunctional phenols, F-a type benzoxazine obtained from monofunctional diamines and monofunctional phenols, and the like.

Specific examples of the melamine compound include, for example, compounds obtained by methoxymethylating 1 to 6 methylol groups of hexamethylol melamine, hexamethoxymethyl melamine, hexamethylol melamine, or mixtures thereof, hexamethoxyethyl melamine , Hexaacyloxymethyl melamine, compounds obtained by acyloxymethylating 1 to 6 methylol groups of hexamethylol melamine, and mixtures thereof.

Specific examples of the above-mentioned guanamine compound include compounds obtained by methoxymethylating 1 to 4 methylol groups of tetramethylolguanamine, tetramethoxymethylguanamine, tetramethylolguanamine, or a mixture thereof, tetra A compound obtained by acyloxymethylating 1 to 4 methylol groups of methoxyethylguanamine, tetraacyloxyguanamine and tetramethylolguanamine, or a mixture thereof.

Specific examples of the glycoluril compound include, for example, methoxymethylated 1 to 4 methylol groups of tetramethylolglycoluril, tetramethoxyglycoluril, tetramethoxymethylglycoluril, tetramethylolglycoluril, A compound or a mixture thereof, a compound obtained by acyloxymethylating 1 to 4 methylol groups of tetramethylolglycoluril, or a mixture thereof.

Specific examples of the urea compound include, for example, a compound obtained by methoxymethylating 1 to 4 methylol groups of tetramethylol urea, tetramethoxymethyl urea, tetramethylol urea, or a mixture thereof, tetramethoxyethylurea And the like.

In the present embodiment, a crosslinking agent having at least one allyl group may also 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 Allyl phenols such as 2,2-bis (3-allyl-4-cyanatophenyl) propane, 1,1,1,3,3,3-hexafluoro-2,2-bis (3-allyl-4-cyanatophenyl) sulfone, bis (3-allyl-4-cyanatophenyl) Diallyl phthalate, diallyl terephthalate, triallyl isocyanurate, trimethylolpropane diallyl ether, pentaerythritol allyl ether, and the like can be given. Among these, allyl cyanates such as diallyl phthalate, diallyl isophthalate, diallyl terephthalate, The present invention is not limited thereto. These may be used singly or as a mixture of two or more kinds. Among them, 2,2-bis (3-allyl-4-hydroxyphenyl) propane, 1,1, 1, 2, (3-allyl-4-hydroxyphenyl) propane, bis (3-allyl-4-hydroxyphenyl) sulfone, bis Hydroxyphenyl) sulfide, and bis (3-allyl-4-hydroxyphenyl) ether.

The content of the crosslinking agent in the lower layer film forming material is not particularly limited, but is preferably 0.1 to 100 parts by mass, more preferably 5 to 50 parts by mass, further preferably 10 to 100 parts by mass, 40 parts by mass. When the content of the crosslinking agent is within the above range, the occurrence of the mixing phenomenon with the resist layer tends to be suppressed, the antireflection effect tends to increase, and the film formability after crosslinking tends to increase.

[Crosslinking accelerator]

As the lower layer film forming material of the present embodiment, a cross-linking accelerator for promoting cross-linking and curing reaction may be used if necessary.

Examples of the crosslinking accelerator include amines, imidazoles, organic phosphines, and Lewis acids, as long as they facilitate crosslinking and curing reactions. These crosslinking accelerators may be used singly or in combination of two or more. Of 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, 1,8-diazabicyclo (5,4,0) undecene-7, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 2-methylimidazole, Imidazoles such as heptadecylimidazole and 2,4,5-triphenylimidazole, and imidazoles such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, phenylphosphine and the like Tetra-substituted phosphonium tetra-substituted borates such as tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium ethyltriphenylborate, tetrabutylphosphonium tetrabutylborate and the like, 2-ethyl- And tetraphenylboron salts such as N-methylmorpholine, tetraphenylborate and the like, .

The blending amount of the crosslinking accelerator is usually from 0.1 to 10 parts by mass, preferably from 0.1 to 5 parts by mass, more preferably from 0.1 to 5 parts by mass from the viewpoints of control easiness and economical efficiency when the total amount of the lower layer film forming material is 100 parts by mass More preferably 0.1 to 3 parts by mass.

[Radical polymerization initiator]

The lower layer film forming material of the present embodiment may contain a radical polymerization initiator if necessary. The radical polymerization initiator may be a photopolymerization initiator that initiates radical polymerization by light, or may be a thermal polymerization initiator that initiates radical polymerization by heat.

Such a radical polymerization initiator is not particularly limited, and any conventionally used radical polymerization initiator can be suitably employed. For example, 1-hydroxycyclohexyl phenyl ketone, benzyldimethyl ketal, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) 2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2- Ketone-based photopolymerization initiators such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide; Ethylhexyl ketone peroxide, ethyl ketone peroxide, cyclohexanone peroxide, methylcyclohexanone peroxide, methyl acetoacetate peroxide, acetylacetate peroxide, 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane, (T-butylperoxy) -cyclohexane, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1- ) -2-methylcyclohexane, 1,1-bis (t-butylperoxy) -cyclohexane, 1,1- Bis (4,4-di-t-butylperoxycyclohexyl) propane, p-menthol hydroperoxide, di Butyl hydroperoxide, t-butyl hydroperoxide, t-butyl hydroperoxide, t-butyl hydroperoxide, 1,1,3,3-tetramethyl butyl hydroperoxide, cumene hydroperoxide, t- Butylperoxy) diisopropylbenzene, dicumylperoxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, Dimethyl-2,5-bis (t-butylperoxy) hexyne-3, isobutyryl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, Di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, bis (4-t-butyl) propyl peroxydicarbonate, Cyclohexyl) peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, di-2-ethoxyhexyl peroxydicarbonate, di-3-methoxybutyl peroxydicarbonate, di- (3-methyl-3-methoxybutyl) peroxydicarbonate, α, α'-bis (neodecanoylperoxy) diisopropylbenzene, cumylperoxy neodecanoate, 1,1,3,3-tetra Methyl butyl peroxyneodecanoate, 1-cyclohexyl-1-methyl ethyl peroxyneodecanoate, t-hexyl peroxyneodecanoate, t-butyl peroxyneodecanoate, t-hexyl peroxy Butyl peroxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate (hexanooate), 2,5-dimethyl-2,5-bis (2 Ethylhexanoylperoxy) hexanoate (hexanoate), 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, t- part T-butylperoxy-2-ethylhexanoate, t-hexylperoxyisopropylmonocarbonate, t-butylperoxyisobutyrate, t-butylperoxymaleate, t-butylperoxy- T-butyl peroxyacetate, t-butyl peroxy-t-butyl peroxyacetate, t-butyl peroxyacetate, t-butyl peroxyacetate, Butyl peroxybenzoate, bis (t-butylperoxy) isophthalate, 2,5-dimethyl-2,5-bis (m-toluylperoxy) hexane, t- Butyl peroxyallyl monocarbonate, t-butyltrimethylsilyl peroxide, 3,3 ', 4,4'-tetra ((2,2,2,2- t-butyl peroxycarbonyl) benzophenone, and 2,3-dimethyl-2,3-diphenylbutane.

Also, examples of the azo compounds include 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile, 1 - [(1-cyano- Azobis (2-methylbutyronitrile), 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvalero Aziridine), 2,2'-azobis (2-methylpropionamidine) dihydrochloride, 2,2'-azobis (2-methyl-N- phenylpropionamidine) dihydrochloride, 2,2'- Azobis [N- (4-chlorophenyl) -2-methylpropionamidine] dihydrochloride, 2,2'-azobis [N- Azobis [2-methyl-N- (2-propenyl) propionamidine] dihydrochloride, 2,2'- Dihydro] dihydrochloride, 2,2'-azobis [N- (2-hydroxyethyl) -2-methylpropionamidine] Azo compounds such as 2,2'-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] dihydrochloride, 2,2'- Dihydrochloride, 2,2'-azobis [2- (4,5,6,7-tetrahydro-1H-1,3-diazepin-2-yl) propane] dihydrochloride Azo [2- (3,4,5,6-tetrahydropyrimidin-2-yl) propane] dihydrochloride, 2,2'-azobis [2- Dihydrochloride, 2,2'-azobis [2- [1- (2-hydroxyethyl) -2-imide 2-yl] propane] dihydrochloride, 2,2'-azobis [2- (2-imidazolin- Bis [(hydroxymethyl) ethyl] propionamide], 2,2'-azobis [2-methyl-N- [1,1- Amide], 2,2'-azobis [2-methyl-N- ( Azobis (2-methylpropionamide), 2,2'-azobis (2,4,4-trimethylpentane), 2,2'-azobis (2-methylpropionate), 4,4'-azobis (4-cyanopentanoic acid), 2,2'-azobis [2- Hydroxymethyl) propionitrile], and the like. As the radical polymerization initiator in the present embodiment, one of these radical polymerization initiators may be used alone or in combination of two or more, and other known polymerization initiators may be further used in combination.

The radical polymerization initiator may be contained in an amount that is stoichiometrically required. When the amount of the lower layer film forming material is 100 parts by mass, the content is preferably 0.05 to 25 parts by mass, more preferably 0.1 to 10 parts by mass. When the content of the radical polymerization initiator is 0.05 parts by mass or more, insufficient curing tends to be prevented. On the other hand, when the content of the radical polymerization initiator is 25 parts by mass or less, The storage stability tends to be prevented from being impaired.

[Acid generator]

The lower layer film forming material of the present embodiment may contain an acid generator if necessary from the viewpoint of further promoting the crosslinking reaction by heat or the like. As the acid generating agent, it is known that an acid is generated by thermal decomposition and an acid is generated by light irradiation, 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 of the present embodiment, the content of the acid generating agent is not particularly limited, but is preferably 0.1 to 50 parts by mass, more preferably 0.5 to 40 parts by mass with respect to 100 parts by mass of the lower layer film forming material Wealth. By setting the above-mentioned range to the above range, the amount of acid generated is increased, the crosslinking reaction tends to be enhanced, and the occurrence of the mixing phenomenon with the resist layer tends to be suppressed.

[Basic compound]

Further, the lower layer film forming material of the present embodiment may contain a basic compound from the viewpoint of improving storage stability and the like.

The basic compound plays a role of an acid to prevent an acid generated from a small amount of an acid from proceeding a crosslinking reaction. Such a basic compound is not particularly limited, and examples thereof include those described in International Publication No. 2013/024779.

The content of the basic compound in the lower layer film forming material in the present embodiment is not particularly limited, but is preferably 0.001 to 2 parts by mass, more preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the lower layer film forming material Mass part. By setting the amount in the above-mentioned preferable range, the storage stability tends to be enhanced without excessively damaging the crosslinking reaction.

[Other additives]

The lower layer film forming material in this embodiment may contain other resins and / or compounds for the purpose of imparting curability by heat or light and controlling the absorbance. Examples of other resins and / or compounds include naphthol resins, xylene resin naphthol-modified resins, phenol-modified resins of naphthalene resins, polyhydroxystyrene, dicyclopentadiene resins, (meth) acrylates, dimethacrylates, Naphthalene rings such as methacrylate, tetramethacrylate, vinylnaphthalene and polyacenaphthylene, biphenyl rings such as phenanthrenequinone and fluorene, and heterocyclic rings having hetero atoms such as thiophene and indene. A resin not containing an aromatic ring; A resin or a compound containing an alicyclic structure such as a rosin resin, a cyclodextrin, an adamantane (poly) ol, a tricyclodecane (poly) ol or a derivative thereof, and the like. Furthermore, the lower layer film forming material in this embodiment mode may contain known additives. The known additives include, but are not limited to, for example, thermal and / or photocurable catalysts, polymerization inhibitors, flame retardants, fillers, coupling agents, thermosetting resins, photocurable resins, dyes, pigments, thickeners, , A defoaming agent, a leveling agent, an ultraviolet absorber, a surfactant, a colorant, and a nonionic surfactant.

[Lower layer film for lithography and method of forming multi-layer resist pattern]

The lower layer film for lithography in this embodiment is formed from the lower layer film forming material.

The resist pattern forming method of the present embodiment is a method for forming a resist pattern by forming a lower layer film on a substrate using the composition and forming at least one photoresist layer on the lower layer film, Irradiating the region with radiation, and performing development. (A-1) forming a lower layer film using the lower layer film forming material of the present embodiment on a substrate, a step of forming at least one photoresist layer on the lower layer film And (A-2) a step of irradiating a predetermined region of the photoresist layer with radiation after the step (A-2), and performing development.

Further, the circuit pattern forming method of the present embodiment is a method of forming a circuit pattern by forming a lower layer film on a substrate by using the above composition, forming an intermediate layer film on the lower layer film by using a resist interlayer film material, A step of forming a photoresist layer of the photoresist layer, a step of irradiating a predetermined region of the photoresist layer with radiation and developing to form a resist pattern, the intermediate layer film is etched using the resist pattern as a mask, And etching the substrate using the obtained lower layer film pattern as an etching mask to form a pattern on the substrate.

(B-1) of forming a lower layer film using the lower layer film forming material of the present embodiment on a substrate and a step (B-1) of forming a lower layer film on the lower layer film using a resist interlayer film material containing silicon atoms A step (B-3) of forming at least one photoresist layer on the intermediate layer film; and a step (B-2) of forming a photoresist layer after the step (B-3) A step (B-4) of forming a resist pattern by irradiating a predetermined region with radiation and developing the resist pattern; and (B-4) a step of etching the intermediate layer film using the resist pattern as a mask, (B-5) of forming a pattern on the substrate by etching the lower layer film using the lower layer film as an etching mask and etching the substrate using the obtained lower layer film pattern as an etching mask.

The forming 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 of the present embodiment, and a known method can be applied. For example, the lower layer film material of the present embodiment is applied on a substrate by a known coating method such as spin coating or screen printing, printing or the like, and then the organic solvent is removed by volatilization, And the lower layer film for lithography of the present embodiment can be formed. Examples of the crosslinking method include thermosetting and photo-curing.

At the time of forming 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 accelerate the crosslinking reaction. In this case, the bake temperature is not particularly limited, but is preferably in the range of 80 to 450 占 폚, more preferably 200 to 400 占 폚. The baking time is not particularly limited, but is preferably in the range of 10 to 300 seconds. On the other hand, the thickness of the lower layer film can be appropriately selected in accordance with the required performance, and is not particularly limited, but is usually about 30 to 20,000 nm, more preferably 50 to 15,000 nm.

In the case of a two-layer process, a silicon-containing resist layer or a single-layer resist made of ordinary hydrocarbon, a silicon-containing intermediate layer on the three-layer process, and a silicon- It is preferable to produce a layer. In this case, known photoresist materials for forming the resist layer can be used.

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

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

As the silicon-containing intermediate layer for the three-layer process, an intermediate layer of a polysilsesquioxane base is preferably used. Reflection layer on the intermediate layer, there is a tendency that the reflection can be effectively suppressed. For example, in a process for 193 nm exposure, when a material containing a large amount of aromatic groups as a lower layer film and having high substrate etching resistance is used, the k value tends to be high and substrate reflection tends to be high. By suppressing reflection to the intermediate layer, To 0.5% or less. The intermediate layer having such an antireflection effect is preferably, but not limited to, an acid or thermally crosslinked polysilsesquioxane having a phenyl group or a light-absorbing group having a silicon-silicon bond introduced therein for 193 nm exposure.

An intermediate layer formed by a chemical vapor deposition (CVD) method may also be used. The intermediate layer which is highly effective 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 intermediate layer is formed by a wet process such as a spin coating method or a screen printing method rather than the CVD method, which is advantageous in terms of simplicity and cost. On the other hand, the upper-layer resist in the three-layer process may be either positive or negative, and may be the same as a commonly used single-layer resist.

Furthermore, the lower layer film in the present embodiment can be used as a general antireflection film for single-layer resist or as a foundation material for suppressing pattern collapse. Since the lower layer film of the present embodiment is excellent in etching resistance for undercut processing, a function as a hard mask for undercut processing can also be expected.

In the case of forming the resist layer by 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. After the resist material is applied by spin coating or the like, prebaking is usually carried out. It is preferable that the prebaking is performed at 80 to 180 DEG C for 10 to 300 seconds. Thereafter, a resist pattern is obtained by performing exposure in accordance with a conventional method, and performing post exposure bake (PEB) and development. On the other hand, the thickness of the resist film is not particularly limited, but is generally from 30 to 500 nm, more preferably from 50 to 400 nm.

The exposure light may be suitably selected in accordance with the photoresist material to be used. Generally, a high energy ray having a wavelength of 300 nm or less, specifically, an excimer laser having a wavelength of 248 nm, 193 nm or 157 nm, a soft X-ray having a wavelength of 3 to 20 nm, an electron beam or an X-ray can be given.

The resist pattern formed by the above method has pattern collapse suppressed by the lower layer film in the present embodiment. Thus, by using the lower layer film in the present embodiment, a finer pattern can be obtained, and the amount of exposure necessary for obtaining the resist pattern can be lowered.

Next, etching is performed using the obtained resist pattern as a mask. As the etching of the lower layer film in the two-layer process, gas etching is preferably used. As gas etching, etching using oxygen gas is favorable. It is also possible to add an inert gas such as He or Ar or CO, CO ₂ , NH ₃ , SO ₂ , N ₂ , NO ₂ or H ₂ gas in addition to the oxygen gas. Further, gas etching can be performed using only CO, CO ₂ , NH ₃ , N ₂ , NO ₂ , and H ₂ gas without using oxygen gas. Particularly, the latter gas is preferably used for side wall protection for preventing undercut of the pattern side wall.

On the other hand, also in the etching of the intermediate layer in the three-layer process, gas etching is preferably used. As the gas etching, the same process as described in the two-layer process can be applied. Particularly, it is preferable that the processing of the intermediate layer in the three-layer process is carried out using a resist pattern as a mask using a fluorine-based gas. Thereafter, the lower layer film can be processed by performing, for example, oxygen gas etching using the intermediate layer pattern as a mask as described above.

Here, when an inorganic hard mask intermediate layer film is formed as an intermediate layer, a silicon oxide film, a silicon nitride film, and a silicon oxynitride film (SiON film) are formed by a CVD method, an ALD method, or the like. The method for forming the nitride film is not limited to the following method, but the method described in Japanese Patent Application Laid-Open No. 2002-334869 (Patent Document 6) and WO2004 / 066377 (Patent Document 7) can be used. Although a photoresist film can be directly formed on such an interlayer film, an organic antireflection film (BARC) may be formed on the interlayer film by spin coating and a photoresist film may be formed thereon.

As the intermediate layer, an intermediate layer of a polysilsesquioxane base is also preferably used. By making the resist interlayer film serve as an antireflection film, there is a tendency to effectively suppress reflection. Specific materials of the intermediate layer of the polysilsesquioxane base are not limited to the following examples, but examples thereof include those described in Japanese Patent Application Laid-Open No. 2007-226170 (Patent Document 8) and Japanese Patent Application Laid-Open No. 2007-226204 (Patent Document 9) May be used.

For example, when the substrate is made of SiO ₂ or SiN, it is possible to etch the next substrate mainly by using a fluorine-based gas as the etching gas, p-Si or Al as the etching gas, or chlorine or bromine gas as the source of W, Etching can be performed. When the substrate is etched with a fluorine-based 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 peeled off separately, and dry etching peeling is generally performed with a fluorine-based gas after processing the substrate.

The lower layer film in the present embodiment is characterized by excellent etching resistance of these substrates. Si, p-Si, SiO ₂ , SiN, SiON, W, TiN, Al, and the like can be given as examples of the substrate to which a known substrate can be suitably selected. Further, the substrate may be a laminate having a workpiece (substrate to be processed) on a substrate (support). Various films such as Si, SiO ₂ , SiON, SiN, p-Si, α-Si, W, W-Si, Al, Cu and Al- And usually a material different from that of the substrate (support) is used. On the other hand, the thickness of the substrate or the workpiece to be processed is not particularly limited, but is usually about 50 to 10,000 nm, more preferably about 75 to 5,000 nm.

The resist permanent film formed by applying the composition according to the present embodiment is suitable as a permanent film remaining after the resist pattern is formed, if necessary, in the final product. Specific examples of the permanent film include a thin film transistor protective film, a liquid crystal color filter protective film, and a thin film transistor protective film in connection with a package adhesive layer such as a solder resist, a package material, an underfill material, a circuit element, , A black matrix, a spacer, and the like. Particularly, the permanent film made of the composition according to the present embodiment has a very excellent advantage of being excellent in heat resistance and moisture resistance, and being less contaminated by sublimation components. In particular, it becomes a material having high sensitivity, high heat resistance, and hygroscopic reliability with less deterioration of image quality due to significant contamination in a display material.

When the composition of the present embodiment is used for a resist permanent film application, various additives such as other resins, surfactants, dyes, fillers, crosslinking agents and dissolution accelerators are added in addition to the curing agent, To prepare a composition for a resist permanent film.

The composition for forming a film for lithography and the composition for a resist permanent film in the present embodiment can be prepared by mixing the components described above and mixing using a stirrer or the like. When the composition for a resist underlayer film or the composition for a resist permanent film in the present embodiment contains a filler or a pigment, it is dispersed or mixed using a dispersing device such as a dissolver, a homogenizer or a triple roll mill .

Example

Hereinafter, the present embodiment will be described in more detail with reference to synthesis examples and examples, but the present embodiment is by no means limited to these examples.

(Carbon concentration and oxygen concentration)

The carbon concentration and oxygen concentration (mass%) were measured by organic element analysis using the following apparatus.

Apparatus: CHN coder MT-6 (manufactured by Yanako Analytical Industry Co., Ltd.)

(Molecular Weight)

The molecular weight of the compound was measured by LC-MS analysis using Acquity UPLC / MALDI-Synapt HDMS manufactured by Water.

Gel permeation chromatography (GPC) analysis was carried out under the following conditions to determine the weight average molecular weight (Mw), the number average molecular weight (Mn) and the degree of dispersion (Mw / Mn) in terms of polystyrene.

Device: Shodex GPC-101 (manufactured by Showa Denko K.K.)

Column: KF-80M x 3

Eluent: THF 1 mL / min

Temperature: 40 ° C

(Solubility)

(3) mass% solution of propylene glycol monomethyl ether (PGME), cyclohexanone (CHN), ethyl lactate (EL), methyl amyl ketone (MAK) or tetramethylurea And the results after one week were evaluated by the following criteria.

Evaluation A: It was confirmed by naked eyes that there was no precipitate in any one of the solvents.

Evaluation C: It was confirmed by naked eyes that there was a precipitate in any one of the solvents.

[Structure of Compound]

The structure of the compound was confirmed by carrying out < 1 > H-NMR measurement under the following conditions using an Advance 600II spectrometer manufactured by Bruker.

Frequency: 400MHz

Solvent: d6-DMSO

Internal standard: TMS

Measuring temperature: 23 ° C

Synthesis Example 1 Synthesis of XBisN-1

(20 mmol) of 2,6-naphthalene diol (reagent manufactured by Sigma-Aldrich) and 1.82 g (10 mmol) of 4-biphenylcarboxyaldehyde (manufactured by Mitsubishi Gas Chemical Company) were placed in an internal volume of 100 mL equipped with a stirrer, ) Was added to 30 mL of methyl isobutyl ketone, 5 mL of 95% sulfuric acid was added, and the reaction solution was stirred at 100 DEG C for 6 hours to carry out the reaction. Next, the reaction solution was concentrated, and 50 g of pure water was added to precipitate the reaction product. The reaction product was cooled to room temperature, filtered, and separated. The resulting solid was filtered, dried and then separated and purified 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 the chemical structure of the formula (XBisN-1).

≪ ¹ > H-NMR: (d-DMSO, internal standard TMS)

(ppm) 9.7 (2H, O-H), 7.2-8.5 (19H, Ph-H), 6.6

On the other hand, the substitution position of 2,6-naphthalenediol was found to be the first position because the signal of the third and fourth protons was doublet.

≪ EMI ID =

(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 (107 mmol) of potassium carbonate were added to 50 ml of dimethylformamide in an inner volume of 100 ml equipped with a stirrer, a cooling tube and a burette, -Chloroethyl (6.56 g, 54 mmol) were added, and the reaction solution was stirred at 90 占 폚 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. Then, 40 g of the above crystals, 40 g of methanol, 100 g of THF, and 24% aqueous sodium hydroxide solution were added to a container of 100 mL in an internal volume equipped with a stirrer, a cooling tube and a burette, and the reaction solution was stirred under reflux for 4 hours to carry out the reaction. Thereafter, the reaction mixture was cooled in an ice bath and the reaction mixture was concentrated. The precipitated solid was filtered, dried and purified by column chromatography to obtain 5.9 g of the target compound represented by the following formula (E-XBisN-1) . It was confirmed by 400 MHz- ¹ H-NMR that the compound had the 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 ~ 7.8 (19H, Ph-H), 6.7 (1H, CH), 4.0 (4H, -O-CH 2 -), 3.8 (4H, -CH 2 -OH )

(360)

(E-XBisN-1)

Synthesis Example 2 Synthesis of BisF-1

An internal 200 mL vessel equipped with a stirrer, a cooling tube and a burette was prepared. 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.) and 100 mL of butyl acetate were fed into the vessel, 3.9 g (21 mmol) of p-toluenesulfonic acid (reagent manufactured by Kanto Chemical Co., Ltd.) was added thereto to prepare a reaction solution. The reaction solution was stirred at 90 캜 for 3 hours to carry out the reaction. Next, the reaction solution was concentrated, and 50 g of heptane was added to precipitate a reaction product. The reaction product was cooled to room temperature, filtered, and separated. The solids obtained by filtration were dried and then separated and purified by column chromatography to obtain 5.8 g of the target compound represented by the following formula (BisF-1). The following peaks were found by 400 MHz- ¹ H-NMR, and it was confirmed that it had the chemical structure of the following formula (BisF-1).

≪ ¹ > H-NMR: (d-DMSO, internal standard TMS)

? (ppm) 9.4 (4H, O-H), 6.8-7.8 (22H, Ph-

Further, the molecular weight of the obtained compound was measured by the above-mentioned method and found to be 536. [

≪ EMI ID =

(BisF-1)

Synthesis Example 2A Synthesis of E-BisF-1

11.2 g (21 mmol) of the compound represented by the formula (BisF-1) and 14.8 g (107 mmol) of potassium carbonate were added to 50 mL of dimethylformamide in a container of 100 mL in an internal volume equipped with a stirrer, a cooling tube and a burette, 6.56 g (54 mmol) of 2-chloroethyl was added, and the reaction solution was stirred at 90 캜 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. Then, 40 g of the above crystals, 40 g of methanol, 100 g of THF, and 24% aqueous sodium hydroxide solution were added to a container of 100 mL in an internal volume equipped with a stirrer, a cooling tube and a burette, and the reaction solution was stirred under reflux for 4 hours to carry out the reaction. Thereafter, the reaction mixture was cooled in an ice bath and the reaction solution was concentrated. The precipitated solid was filtered and dried, and then separated and purified by column chromatography to obtain 5.9 g of the target compound represented by the following formula (E-BisF-1) . It was confirmed by 400 MHz - < ¹ > H-NMR to have the 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 ~ 7.8 (22H, Ph-H), 6.2 (1H, CH), 4.0 (8H, -O-CH 2 -), 3.8 (8H, -CH 2 -OH )

Further, the molecular weight of the obtained compound was measured by the above-mentioned method and found to be 712.

≪ EMI ID =

(E-BisF-1)

<Synthesis Example 1-1> Synthesis of UaXBisN-1

10.0 g (21 mmol) of the compound represented by the above formula (XBisN-1), 6.1 g of 2-isocyanatoethyl methacrylate, 0.5 g of triethylamine, 0.05 g of p-methoxyphenol was added to 50 mL of methyl isobutyl ketone, and the mixture was stirred for 24 hours while being heated to 80 DEG C and stirred. The reaction mixture was cooled to 50 DEG C and the reaction solution was added dropwise to pure water. The precipitated solid was filtered, dried and then separated and purified by column chromatography to obtain 3.0 g of the target compound represented by the following formula (UaXBisN-1) . It was confirmed by 400 MHz - &lt; ¹ &gt; H-NMR to have the chemical structure of the following formula (UaXBisN-1).

&Lt; ¹ &gt; H-NMR: (d-DMSO, internal standard TMS)

δ (ppm) 7.2 ~ 7.8 ( 19H, Ph-H), 6.8 (2H, NH), 6.7 (1H, CH), 6.5 (4H, = CH 2), 3.1 ~ 4.6 (8H, -O-CH 2 - CH ₂ -N-), 2.0 (6H, -CH ₃ )

Further, the molecular weight of the obtained compound was measured by the above-mentioned method and found to be 776.

The thermal decomposition temperature was 370 占 폚, the glass transition point was 90 占 폚, and the melting point was 200 占 폚, and high heat resistance was confirmed.

[363]

(UaXBisN-1)

<Synthesis Example 1-2> Synthesis of UaE-XBisN-1

Except that the compound represented by the above formula (E-XBisN-1) was used instead of the compound represented by the above formula (XBisN-1) to obtain a compound represented by the following formula (UaE-XBisN -1) was obtained. It was confirmed by 400 MHz - &lt; ¹ &gt; H-NMR to have the chemical structure of the following formula (UaE-XBisN-1).

&Lt; ¹ &gt; H-NMR: (d-DMSO, internal standard TMS)

CH ₂ ), 3.1 to 4.6 (16H, -O-CH ₂ -CH ₂ -O (CH ₃ ) ₂ ) _{-, -O-CH 2 -CH 2} -N-), 2.0 (6H, -CH 3)

Further, the molecular weight of the obtained compound was measured by the above-mentioned method and found to be 864.

The thermal decomposition temperature was 360 占 폚, the glass transition point was 85 占 폚, and the melting point was 195 占 폚, and high heat resistance was confirmed.

&Lt; EMI ID =

(UaE-XBisN-1)

<Synthesis Example 2-1> Synthesis of UaBisF-1

Except that the compound represented by the above formula (BisF-1) was used instead of the compound represented by the above formula (XBisN-1) to obtain a compound represented by the following formula (UaBisF-1 ) Was obtained in an amount of 2.5 g. It was confirmed by 400 MHz - &lt; ¹ &gt; H-NMR to have the chemical structure of the following formula (UaBisF-1).

&Lt; ¹ &gt; H-NMR: (d-DMSO, internal standard TMS)

δ (ppm) 6.8 ~ 7.8 ( 22H, Ph-H), 6.5 (8H, = CH 2), 6.2 (1H, CH), 4.1 ~ 4.7 (16H, -O-CH 2 -CH 2 -N-), 2.0 (12H, -CH ₃ ) Further, the molecular weight of the obtained compound was measured by the above-mentioned method and found to be 1156.

The thermal decomposition temperature was 365 DEG C, the glass transition point was 65 DEG C, and the melting point was 185 DEG C, and high heat resistance was confirmed.

[365]

(UaBisF-1)

<Synthesis Example 2-2> Synthesis of UaE-BisF-1

Except that the compound represented by the above formula (E-BisF-1) was used instead of the compound represented by the above formula (XBisN-1) to obtain a compound represented by the following formula (UaE -BisF-1) was obtained. It was confirmed by 400 MHz - &lt; ¹ &gt; H-NMR to have the chemical structure of the following formula (UaE-BisF-1).

&Lt; ¹ &gt; H-NMR: (d-DMSO, internal standard TMS)

δ (ppm) 6.8 ~ 7.8 ( 22H, Ph-H), 6.5 (8H, = CH 2), 6.2 (1H, CH), 4.1 ~ 4.7 (32H, -O-CH 2 -CH 2 -O-, - _{O-CH 2 -CH 2 -N-)} , 2.0 (12H, -CH 3)

The molecular weight of the resulting compound was measured by the above-mentioned method and found to be 1133.

The thermal decomposition temperature was 355 占 폚, the glass transition point was 60 占 폚, and the melting point was 175 占 폚, and high heat resistance was confirmed.

[366]

(UaE-BisF-1)

Synthesis Example 3 Synthesis of BiN-1

10 g (69.0 mmol) of 2-naphthol (reagent manufactured by Sigma-Aldrich) was melted at 120 DEG C in an inner volume of 300 mL equipped with a stirrer, a cooling tube and a buret. Then 0.27 g of sulfuric acid was added, 2.7 g (13.8 mmol) of phenyl (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. Next, 100 mL of N-methyl-2-pyrrolidone (manufactured by KANTO CHEMICAL Co., Ltd.) and 50 mL of pure water were added to the reaction solution, followed by extraction with ethyl acetate. Next, pure water was added to the mixture to separate it until it became neutral, and then concentrated to obtain a solution.

After separation of the obtained solution by column chromatography, 1.0 g of a target compound (BiN-1) represented by the following formula (BiN-1) was obtained.

The obtained compound (BiN-1) was found to have a molecular weight of 466 by the above-mentioned method.

The obtained compound (BiN-1) was subjected to NMR measurement under the above-described measurement conditions, and the following peaks were found and it was confirmed that the compound had the chemical structure of the following formula (BiN-1).

(ppm) 9.69 (2H, O-H), 7.01-7.67 (21H, Ph-H), 2.28

&Lt; EMI ID =

(BiN-1)

<Synthesis Example 3A> Synthesis of E-BiN-1

10.5 g (21 mmol) of the compound (BisN-1) represented by the above formula and 14.8 g (107 mmol) of potassium carbonate were added to 50 mL of dimethylformamide in an internal volume of 100 mL equipped with a stirrer, a cooling tube and a burette, 6.56 g (54 mmol) of 2-chloroethyl was added, and the reaction solution was stirred at 90 캜 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 above crystals, 40 g of methanol, 100 g of THF, and 24% aqueous sodium hydroxide solution were added to a container of 100 mL in an internal volume equipped with a stirrer, a cooling tube and a burette, and the reaction solution was stirred under reflux for 5 hours to carry out the reaction. Thereafter, the reaction mixture was cooled in an ice bath, and the reaction solution was concentrated. The precipitated solid was filtered and dried, and then separated and purified by column chromatography to obtain 4.6 g of the target compound represented by the following formula. It was confirmed by 400 MHz - &lt; ¹ &gt; H-NMR to have the chemical structure of the following formula.

&Lt; ¹ &gt; H-NMR: (d-DMSO, internal standard TMS)

δ (ppm) 8.6 (2H, OH), 7.2 ~ 7.8 (19H, Ph-H), 6.7 (1H, CH), 4.0 (4H, -O-CH 2 -), 3.8 (4H, -CH 2 -OH )

&Lt; EMI ID =

(E-BiN-1)

<Synthesis Example 3-1> Synthesis of UaBiN-1

(UaBiN-1) was obtained in the same manner as in Synthesis Example 1-1 except that the compound represented by the formula (BiN-1) was used instead of the compound represented by the formula (XBisN-1) 3.5 g of the desired compound was obtained.

It was confirmed by 400 MHz - &lt; ¹ &gt; H-NMR to have the chemical structure of the following formula (UaBiN-1).

&Lt; ¹ &gt; H-NMR: (d-DMSO, internal standard TMS)

δ (ppm) 7.2 ~ 7.8 ( 21H, Ph-H), 6.8 (2H, NH), 6.7 (1H, CH), 6.5 (4H, = CH 2), 3.1 ~ 4.6 (16H, -O-CH 2 - CH ₂ -O-, -O-CH ₂ -CH ₂ -N-), 2.3 (3H, -CH ₃ ), 2.0 (6H,

&Lt; EMI ID =

(UaBiN-1)

The molecular weight of the obtained compound was measured by the above-mentioned method and found to be 776.

It was confirmed that the thermal decomposition temperature was 390 占 폚, the glass transition point was 72 占 폚, and the melting point was 224 占 폚 and that it had high heat resistance.

<Synthesis Example 3-2> Synthesis of UaE-BiN-1

BiN-1) was used in place of the compound represented by the above formula (XBisN-1) to obtain a compound represented by the following formula (UaE-BiN -1) was obtained.

It was confirmed by 400 MHz - &lt; ¹ &gt; H-NMR to have the chemical structure of the following formula (UaE-BiN-1).

&Lt; ¹ &gt; H-NMR: (d-DMSO, internal standard TMS)

δ (ppm) 7.2 ~ 7.8 ( 21H, Ph-H), 6.8 (2H, NH), 6.7 (1H, CH), 6.5 (4H, = CH 2), 3.1 ~ 4.6 (16H, -O-CH 2 - CH ₂ -O-, -O-CH ₂ -CH ₂ -N-), 2.3 (3H, -CH ₃ ), 2.0 (6H,

[370]

(UaE-BiN-1)

The molecular weight of the obtained compound was measured by the above-mentioned method and found to be 864.

It was confirmed that the thermal decomposition temperature was 362 占 폚, the glass transition point was 70 占 폚, and the melting point was 226 占 폚 and had high heat resistance.

Synthesis Example 4 Synthesis of BiP-1

1.0 g of the aimed compound represented by the following formula (BiP-1) was obtained by carrying out the reaction in the same manner as in Synthesis Example 1 except that o-phenylphenol was used instead of 2-naphthol.

The obtained compound (BiP-1) was found to have a molecular weight of 466 by the above-mentioned method.

The obtained compound (BiP-1) was subjected to NMR measurement under the above-described measurement conditions, and the following peaks were found, and it was confirmed that the compound had the chemical structure of the following formula (BiP-1).

? (ppm) 9.67 (2H, O-H), 6.98-7.60 (25H, Ph-

&Lt; EMI ID =

(BiP-1)

Synthesis Example 4A Synthesis of E-BiP-1

11.2 g (21 mmol) of the compound represented by the formula (BiP-1) and 14.8 g (107 mmol) of potassium carbonate were added to 50 ml of dimethylformamide in a container of 100 ml in an internal volume equipped with a stirrer, a cooling tube and a burette, 6.56 g (54 mmol) of 2-chloroethyl was added, and the reaction solution was stirred at 90 캜 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. Then, 40 g of the above crystals, 40 g of methanol, 100 g of THF, and 24% aqueous sodium hydroxide solution were added to a container of 100 mL in an internal volume equipped with a stirrer, a cooling tube and a burette, and the reaction solution was stirred under reflux for 4 hours to carry out the reaction. Thereafter, the reaction mixture was cooled in an ice bath, and the reaction mixture was concentrated. The precipitated solid was filtered, dried and then separated and purified by column chromatography to obtain 5.9 g of the desired compound represented by the following formula (E-BisF-1) &Lt; / RTI &gt;

It was confirmed by 400 MHz - &lt; ¹ &gt; H-NMR to have the chemical structure of the following formula (E-BiP-1).

&Lt; ¹ &gt; H-NMR: (d-DMSO, internal standard TMS)

δ (ppm) 8.6 (4H, OH), 6.8 ~ 7.6 (25H, Ph-H), 4.0 (4H, -O-CH 2 -), 3.8 (4H, -CH 2 -OH), 2.2 (3H, CH )

The molecular weight of the compound thus obtained was measured by the above-mentioned method. As a result, it was found to be 606.

[372]

(E-BiP-1)

<Synthesis Example 4-1> Synthesis of UaBiP-1

(UaBiP-1) was obtained in the same manner as in Synthesis Example 1-2, except that the compound represented by the formula (BiP-1) was used instead of the compound represented by the formula (XBisN-1) 6.6 g of the desired compound was obtained.

It was confirmed by 400 MHz - &lt; ¹ &gt; H-NMR to have the chemical structure of the following formula (UaBiP-1).

&Lt; ¹ &gt; H-NMR: (d-DMSO, internal standard TMS)

δ (ppm) 6.8 ~ 7.8 ( 25H, Ph-H), 6.5 (4H, = CH 2), 4.1 ~ 4.7 (8H, -O-CH 2 -CH 2 -N-), 2.3 (3H, -CH3) , 2.0 (6H, -CH ₃₎

The thermal decomposition temperature was 371 占 폚, the glass transition point was 84 占 폚, and the melting point was 232 占 폚.

[373]

(UaBiP-1)

The molecular weight of the resulting compound was measured by the above-mentioned method and found to be 828.

<Synthesis Example 4-2> Synthesis of UaE-BiP-1

(Ea-BiP-1) was obtained in the same manner as in Synthesis Example 1-2 except that the compound represented by the formula (E-BiP-1) was used instead of the compound represented by the formula (XBisN- -1) was obtained.

It was confirmed by 400 MHz - &lt; ¹ &gt; H-NMR to have the chemical structure of the following formula (UaE-BiP-1).

&Lt; ¹ &gt; H-NMR: (d-DMSO, internal standard TMS)

δ (ppm) 6.8 ~ 7.8 ( 25H, Ph-H), 6.8 (2H, NH), 6.5 (4H, = CH 2), 3.1 ~ 4.6 (16H, -O-CH 2 -CH 2 -O-, - O-CH ₂ -CH ₂ -N-), 2.3 (3H, -CH ₃ ) 2.0 (6H, -CH ₃ )

&Lt; EMI ID =

(UaE-BiP-1)

The molecular weight of the obtained compound was measured by the above-mentioned method and found to be 916.

The thermal decomposition temperature was 372 占 폚, the glass transition point was 70 占 폚, and the melting point was 210 占 폚.

(Synthesis Examples 5 to 17)

2-naphthol (raw material 1) and 4-acetyl biphenyl (raw material 2), which were the raw materials of Synthesis Example 3, were changed as shown in Table 1, and otherwise, the same procedures as in Synthesis Example 3 were carried out.

Each target compound was identified by ¹ H-NMR (Table 2).

[Table 1]

[Table 2]

[375]

(BiN-2)

[376]

(BiN-3)

[377]

(BiN-4)

[378]

(XBiN-1)

[379]

(XBiN-2)

(380)

(XBiN-3)

&Lt; EMI ID =

(BiP-2)

&Lt; EMI ID =

(BiP-3)

&Lt; EMI ID =

(BiP-4)

&Lt; EMI ID =

(P-1)

&Lt; EMI ID =

(P-2)

[386]

(P-3)

&Lt; EMI ID =

(P-4)

(Synthesis Examples 18 to 20)

Biphenylaldehyde (raw material 2) as a raw material of Synthesis Example 1 was changed as shown in Table 3, and otherwise, the same procedure as in Synthesis Example 3 was carried out to obtain respective target compounds.

Each target compound was identified by 1 H-NMR (Table 4).

[Table 3]

[Table 4]

(388)

(XBisN-2)

&Lt; EMI ID =

(XBisN-3)

[390]

(XBisN-4)

(Synthesis Examples 21 to 22)

2-naphthol (raw material 1) and 4-acetyl biphenyl (raw material 2) as raw materials of Synthesis Example 3 were changed as shown in Table 5, and 1.5 mL of water, 73 mg (0.35 mmol) of dodecylmercaptan, 2.3 g (22 mmol) were added, and the reaction temperature was changed to 55 캜. Otherwise, each of the objective compounds was obtained in the same manner as in Synthesis Example 3.

The respective target compounds were identified by 1 H-NMR (Table 6).

[Table 5]

[Table 6]

[391]

(P-5)

[392]

(P-6)

(Synthesis Examples 5A to 22A)

The synthesis was carried out under the same conditions as in Synthesis Example 3A except that the compound represented by the formula (BiN-1) as the raw material of Synthesis Example 3A was changed as shown in Table 7, and the desired compound was obtained, respectively. The structure of each target compound was identified by confirming the molecular weight by 400 MHz - ¹ H-NMR (d-DMSO, internal standard TMS) and LC-MS.

(Synthesis Examples 5-1 to 22-1)

Synthesis was carried out under the same conditions as in Synthesis Example 3-1 except that the compound represented by the formula (E-BiN-1) as the raw material of Synthesis Example 3-1 was changed as shown in Table 7, &Lt; / RTI &gt; The structure of each target compound was identified by confirming the molecular weight by 400 MHz - ¹ H-NMR (d-DMSO, internal standard TMS) and LC-MS.

(Synthesis Examples 5-2 to 22-2)

Synthesis was carried out under the same conditions as in Synthesis Example 3-2 except that 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, Compound. The structure of each target compound was identified by confirming the molecular weight by 400 MHz - ¹ H-NMR (d-DMSO, internal standard TMS) and LC-MS.

[Table 7]

[393]

(E-BiN-2)

[394]

(UaBiN-2)

[395]

(UaE-BiN-2)

[396]

(E-BiN-3)

[397]

(UaBiN-3)

[398]

(UaE-BiN-3)

[399]

(E-BiN-4)

(400)

(UaBiN-4)

(401)

(UaE-BiN-4)

(402)

(E-BiP-2)

&Lt; EMI ID =

(UaBiP-2)

(404)

(UaE-BiP-2)

&Lt; EMI ID =

(E-BiP-3)

&Lt; EMI ID =

(UaBiP-3)

&Lt; EMI ID =

(UaE-BiP-3)

&Lt; EMI ID =

(E-BiP-4)

&Lt; EMI ID =

(UaBiP-4)

(410)

(UaE-BiP-4)

[411]

(E-P-1)

[412]

(UaP-1)

&Lt; EMI ID =

(UaE-P-1)

&Lt; EMI ID =

(E-P-2)

&Lt; EMI ID =

(UaP-2)

&Lt; EMI ID =

(UaE-P-2)

&Lt; EMI ID =

(E-BisN-1)

&Lt; EMI ID =

(UaBisN-1)

&Lt; EMI ID =

(UaE-BisN-1)

(420)

(E-XBiN-2)

[421]

(UaXBiN-2)

(422)

(UaE-XBiN-2)

[423]

(E-XBiN-3)

[424]

(UaXBiN-3)

[425]

(UaE-XBiN-3)

[426]

(E-P-3)

[427]

(UaP-3)

[428]

(UaE-P-3)

[429]

(E-P-4)

[430]

(UaP-4)

[431]

(UaE-P-4)

[432]

(E-XBisN-2)

[433]

(UaXBisN-2)

[434]

(UaE-XBisN-2)

[435]

(E-XBisN-3)

[436]

(UaXBisN-3)

[Chemical Formula 437]

(UaE-XBisN-3)

[438]

(E-XBisN-4)

[439]

(UaXBisN-4)

[440]

(UaE-XBisN-4)

&Lt; EMI ID =

(E-P-5)

[442]

(UaP-5)

443]

(UaE-P-5)

444]

(E-P-6)

[445]

(UaP-6)

[446]

(UaE-P-6)

(Synthesis Example 23) Synthesis of Resin (R1-XBisN-1)

A four liter flask with an internal volume of 1 L, equipped with a Dimros cooling tube, a thermometer and a stirrer, was prepared. 32.0 g (70 mmol, manufactured by Mitsubishi Gas Chemical Co., Ltd.) of the compound (XBisN-1) obtained in Synthetic Example 1 and 21.0 g of a 40 mass% formalin aqueous solution (280 mmol as formaldehyde, (Manufactured by Kagaku Kagaku Kogyo Co., Ltd.) and 98% by mass sulfuric acid (manufactured by Kanto Chemical Co., Ltd.) were charged and reacted for 7 hours while refluxing at 100 ° C under atmospheric pressure. Thereafter, 180.0 g of ortho xylene (Wako Pure Chemical Industries, Ltd.) as a diluting solvent was added to the reaction solution, and after standing, the water phase of the lower phase was removed. Again, neutralization and washing were carried out, and ortho-xylene 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 liter flask with an internal volume of 1 L, equipped with a Dimros cooling tube, a thermometer and a stirrer, was prepared. (70 mmol, manufactured by Mitsubishi Gas Chemical Co., Ltd.), 50.9 g (280 mmol, manufactured by Mitsubishi Gas Chemical Co., Ltd.) of the compound (XBisN-1) obtained in Synthesis Example 1 100 mL of anisole (manufactured by Kanto Chemical Co., Ltd.) and 10 mL of oxalic acid dihydrate (manufactured by Kanto Chemical Co., Ltd.) were charged and reacted for 7 hours while refluxing at 100 DEG C under normal pressure. Thereafter, 180.0 g of ortho xylene (Wako Pure Chemical Industries, Ltd.) as a diluting solvent was added to the reaction solution, and after standing, the water phase was removed. The organic phase solvent and the 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 the resin (R1-XBisN-1) obtained in Synthesis Example 23 and 29.6 g (214 mmol) of potassium carbonate were added to 100 ml of dimethylformamide in a container having an internal volume of 500 ml equipped with a stirrer, a cooling tube and a burette, 13.12 g (108 mmol) of chloroethyl was added, and the reaction solution was stirred at 90 캜 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 above crystals, 80 g of methanol, 100 g of THF, and 24% aqueous sodium hydroxide solution were added to a container of 100 mL in an internal volume equipped with a stirrer, a cooling tube and a burette, and the reaction solution was stirred under reflux for 4 hours for reaction. Thereafter, the solution was cooled in an ice bath, and the reaction solution was concentrated. 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) had Mn: 2176, Mw: 3540, and Mw / Mn: 1.62.

<Synthesis Example 23-1> Synthesis of UaR1-XBisN-1

20.0 g of a resin represented by the above formula (R1-XBisN-1), 12.2 g of 2-isocyanatoethyl methacrylate, 1.0 g of triethylamine, 1.0 g of p -Methoxyphenol were added to 100 mL of methyl isobutyl ketone, and the mixture was stirred for 24 hours while heating at 80 DEG C and the reaction was carried out. The reaction solution was cooled to 50 deg. C and the reaction solution was added dropwise to pure water. The precipitated solid was filtered and dried to obtain 23.6 g of a brown solid (UaR1-XBisN-1) resin.

The obtained resin (UaR1-XBisN-1) had Mn: 2130, Mw: 3590, and Mw / Mn: 1.55.

<Synthesis Example 23-2> Synthesis of UaE-R1-XBisN-1

(E-R1-XBisN-1) obtained in Synthesis Example 23A was used instead of the resin represented by the formula (R1-XBisN-1) obtained in Synthesis Example 23 in the same manner as in Synthesis Example 23-1 To obtain 25.0 g of a resin represented by (UaE-R1-XBisN-1) as a brown solid.

The obtained resin (UaE-R1-XBisN-1) had Mn: 2371, Mw: 4240, and Mw / Mn: 1.79.

Synthesis Example 24A Synthesis of E-R2-XBisN-1

30 g of the above-mentioned resin (R2-XBisN-1) and 29.6 g (214 mmol) of potassium carbonate were added to 100 ml of dimethylformamide in a container having an internal volume of 500 ml equipped with a stirrer, a cooling tube and a burette, (108 mmol) were added, and the reaction solution was stirred at 90 占 폚 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 above crystals, 80 g of methanol, 100 g of THF, and 24% aqueous sodium hydroxide solution were added to a container of 100 mL in an internal volume equipped with a stirrer, a cooling tube and a burette, and the reaction solution was stirred under reflux for 4 hours for reaction. Thereafter, the mixture was cooled in an ice bath, and the reaction solution was concentrated. 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) had Mn of 2516, Mw of 3960 and Mw / Mn of 1.62.

<Synthesis Example 24-1> Synthesis of UaR2-XBisN-1

Except that 33.2 g of the compound represented by the formula (R2-XBisN-1) obtained in Synthesis Example 24 was used in place of the compound represented by the formula (R1-XBisN-1) obtained in Synthesis Example 23 To obtain 40.1 g of a resin represented by (UaR2-XBisN-1) as a brown solid.

The obtained resin (UaR2-XBisN-1) had Mn: 2446, Mw: 4510, and Mw / Mn: 1.84.

<Synthesis Example 24-2> Synthesis of UaE-R2-XBisN-1

(E-R2-XBisN-1) obtained in Synthesis Example 24A was used instead of the resin represented by the formula (R1-XBisN-1) obtained in Synthesis Example 23, To obtain 29.0 g of a resin represented by (UaE-R2-XBisN-1) as a brown solid.

The obtained resin (UaE-R2-XBisN-1) had Mn: 2679, Mw: 4830, and Mw / Mn: 1.80.

(Synthetic Comparative Example 1)

A four-necked flask with an inner volume of 10 L was provided with a bottom-detachable flask equipped with a Dimros cooling tube, a thermometer and a stirrer. To this four-necked flask, 1.09 kg (7 mol, manufactured by Mitsubishi Gas Chemical Co., Ltd.) of 1,5-dimethylnaphthalene, 2.1 kg (40 mol% formaldehyde solution: 28 mol, manufactured by Mitsubishi Gas Chemical Co., ) And 0.97 mL of 98 mass% sulfuric acid (manufactured by Kanto Kagaku K.K.), and the mixture was reacted for 7 hours while refluxing at 100 ° C under atmospheric pressure. Thereafter, 1.8 kg of ethylbenzene (a reagent grade manufactured by Wako Pure Chemical Industries, Ltd.) as a diluting solvent was added to the reaction solution, and after standing, the water phase of the bed was removed. Again, neutralization and washing were carried out, and ethylbenzene and unreacted 1,5-dimethylnaphthalene were distilled off under reduced pressure to obtain 1.25 kg of a dimethylnaphthalene formaldehyde resin having a pale brown solid. The molecular weight of the obtained dimethylnaphthalene formaldehyde was Mn: 562.

Then, an inner 0.5 L four-necked flask equipped with a Dimros cooling tube, a thermometer and a stirring blade was prepared. 100 g (0.51 mol) of the dimethyl naphthalene formaldehyde resin obtained as described above and 0.05 g of paratoluene sulfonic acid were introduced into the four-necked flask under a nitrogen stream. The mixture was heated to 190 DEG C and heated for 2 hours and stirred. Thereafter, again 52.0 g (0.36 mol) of 1-naphthol was added, and further the temperature was raised to 220 ° C and the reaction was carried out for 2 hours. After solvent dilution, neutralization and washing were carried out, and the solvent was removed under reduced pressure to obtain 126.1 g of a modified resin (CR-1) as a dark brown solid. The obtained resin (CR-1) had Mn of 885, Mw of 2220 and Mw / Mn of 4.17.

(Examples 1-1 to 24-2, Comparative Example 1)

The solubility test was carried out using the compound or resin 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.

Further, the lower layer film forming material for lithography having the composition shown in Table 8 was prepared.

Subsequently, these lower layer film forming materials for lithography were spin-coated on the silicon substrate, and then baked at 240 캜 for 60 seconds and then at 400 캜 for 120 seconds to prepare lower layer films each having a film thickness of 200 nm. The following acid generators, crosslinking agents and organic solvents were used.

Acid generator: di-tert-butyl diphenyl iodonium nonafluoromethane sulfonate (DTDPI) manufactured by Midori Kagaku Co.,

Crosslinking agent: NIKARAK MX270 (NIKARAK) manufactured by SANWA CHEMICAL CO.

Organic solvent: Propylene glycol monomethyl ether acetate acetate (PGMEA)

(Examples 25 to 44)

Further, materials for forming a lower layer film for lithography having the compositions shown in Table 9 were prepared. Next, these coated lithographic rotate the lower layer film formation material for the silicon substrate, and thereafter, after removal of the solvent in the coating film by baking at 110 ℃ 60 seconds, with a high-pressure mercury lamp, the integrated exposure dose 600mJ / cm ^2, irradiation And the time was 20 seconds to prepare a lower layer film having a film thickness of 200 nm. For the photo-radical polymerization initiator, crosslinking agent and organic solvent, the following were used.

Radical polymerization initiator: IRGACURE 184 manufactured by BASF

Crosslinking agent:

(1) NIKARAK MX270 manufactured by SANWA CHEMICAL Co., Ltd. (NIKARAK)

(2) Mitsubishi Gas Chemical Diallyl bisphenol A cyanate (DABPA-CN)

(3) Diallyl bisphenol A (BPA-CA) manufactured by Konishi Chemical Industry Co.,

(4) benzooxane photo (BF-BXZ) manufactured by Konishi Chemical Industry Co.,

(5) Japanese Chemical Agent Biphenyl aralkyl type 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.

447 &lt;

(DABPA-CN)

[448]

(BPA-CA)

&Lt; EMI ID =

(BF-BXZ)

[Formula 450]

(NC-3000-L)

(Wherein n is an integer of 1 to 4)

[Etching Resistance]

An etching test was conducted under the conditions shown below to evaluate the etching resistance. The evaluation results are shown in Tables 1 and 8 and Table 9.

(Etching test conditions)

Etching apparatus: RIE-10NR manufactured by SAMCO INTERNATIONAL

Output: 50W

Pressure: 20 Pa

Time: 2min

Etching gas

Ar gas flow rate: CF ₄ gas flow rate: O ₂ gas flow rate = 50: 5: 5 (sccm)

The evaluation of the etching resistance was carried out in the following order.

First, a novolac underlayer film was prepared under the same conditions as in Example 1-1, except that novolac (PSM4357, manufactured by Gene Chemical Co., Ltd.) was used instead of the compound (UaXBisN-1) used in Example 1-1. Then, the novolak underlayer film was subjected to the above etching test, and the etching rate at that time was measured.

Next, the lower layer films of Example 1-1 and Comparative Example 1 were subjected to the same etching test, and the etching rate at that time was measured. Then, with respect to the etching rate of the novolac underlayer film, the etching resistance was evaluated based on the following evaluation criteria.

[Evaluation standard]

A: The etching rate was less than -10% as compared with the novolak underlayer film

B: an etching rate of -10% to + 5%, as compared with the lower layer film of novolak;

C: Etching rate exceeded + 5% as compared with the lower layer film of novolac

[Table 8]

[Table 9]

(Examples 45 to 48)

Subsequently, each solution of the lower layer film forming material for lithography including UaXBisN-1, UaE-XBisN-1, UaBisF-1, or UaE-BisF-1 was applied on a SiO ₂ substrate having a film thickness of 300 nm, For 60 seconds and again at 400 DEG C for 120 seconds to form a lower film having a film thickness of 70 nm. On this lower layer film, a resist solution for ArF was applied and baked at 130 캜 for 60 seconds to form a photoresist layer having a thickness of 140 nm. On the other hand, as the ArF resist solution, 5 parts by mass of the compound of the following formula (11), 1 part by mass of triphenylsulfonium nonafluoromethane sulfonate, 2 parts by mass of tributylamine, and 92 parts by mass of PGMEA Were used.

The compound of the formula (11) was prepared by reacting 4.15 g of 2-methyl-2-methacryloyloxyadamantane, 3.00 g of methacryloyloxy- gamma -butyrolactone, 3.00 g of 3-hydroxy- 2.08 g of the compound and 0.38 g of azobisisobutyronitrile were dissolved in 80 mL of tetrahydrofuran to prepare a reaction solution. The reaction solution was polymerized for 22 hours while maintaining the reaction temperature at 63 캜 in a nitrogen atmosphere, and then the reaction solution was added dropwise to 400 mL of n-hexane. The resulting resin thus obtained was coagulated and purified, and the resulting white powder was filtered and dried overnight at 40 캜 under reduced pressure.

[451]

(11)

In the above formula (11), "40", "40" and "20" represent the ratio of each constituent unit and do not represent a block copolymer.

Subsequently, the photoresist layer was exposed using an electron beam lithography apparatus (ELS-7500, 50 keV, manufactured by Erionix), baked at 115 캜 for 90 seconds (PEB), and immersed in 2.38 mass% tetramethylammonium hydroxide (TMAH) And then developed with an aqueous solution for 60 seconds to obtain a positive resist pattern.

The shapes and defects of the obtained resist patterns of 55 nm L / S (1: 1) and 80 nm L / S (1: 1) were observed using an electron microscope (S-4800) manufactured by Hitachi, Ltd. Regarding the shape of the resist pattern after development, evaluation was made for "no pattern collapse", "good" for good rectangularity and "poor" for other. As a result of the above observation, the minimum line width with no pattern collapse and good rectangularity was regarded as an index of evaluation as &quot; resolution. &Quot; Furthermore, the minimum amount of electron beam energy capable of drawing a good pattern shape was defined as &quot; sensitivity &quot; 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 formation of the lower layer film was not performed, and a positive resist pattern was obtained. The results are shown in Table 10.

[Table 10]

As is evident from Table 10, the examples using UaXBisN-1, UaE-XBisN-1, UaBisF-1 and UaE-BisF-1, which are compounds of the present embodiment, are all excellent in heat resistance, solubility and etching resistance . On the other hand, in Comparative Example 1 using CR-1 (phenol-modified dimethylnaphthalene formaldehyde resin), the etching resistance was poor.

In Examples 45 to 48, it was confirmed that the resist pattern shape after development was satisfactory and no defects were seen. It was confirmed that both the resolution and the sensitivity were significantly superior to those of Comparative Example 2 in which formation of the lower layer film was omitted.

Furthermore, from the difference in shape of the resist pattern after development, it was found that the lower layer film forming material for lithography used in Examples 45 to 48 had a high adhesion to a resist material.

&Lt; Examples 49 to 52 >

The solution of the lower layer film forming material for lithography obtained in Examples 1-1 and 2-2 was coated on a SiO ₂ substrate having a film thickness of 300 nm and baked at 240 캜 for 60 seconds and again at 400 캜 for 120 seconds to form a film having a thickness of 80 nm Of the lower layer was formed. A silicon-containing intermediate layer material was coated on the lower layer film and baked at 200 캜 for 60 seconds to form an intermediate layer film having a film thickness of 35 nm. The resist solution for ArF was coated on the intermediate layer film and baked at 130 캜 for 60 seconds to form a photoresist layer having a film thickness of 150 nm. On the other hand, as the silicon-containing intermediate layer material, a silicon atom-containing polymer described in Synthesis Example 1 of JP-A-2007-226170 was used.

Subsequently, the photoresist layer was exposed to a mask using an electron beam lithography apparatus (ELS-7500, 50 keV, manufactured by Erionix), baked (PEB) at 115 DEG C for 90 seconds and then immersed in 2.38 mass% tetramethylammonium hydroxide ) Aqueous solution for 60 seconds to obtain a positive resist pattern of 55 nm L / S (1: 1).

Thereafter, dry etching of the silicon-containing interlayer film (SOG) was performed using RIE-10NR manufactured by Sanko International Co., using the obtained resist pattern as a mask, and then dry etching of the lower layer film using the obtained silicon- And the dry etching process of the SiO ₂ film using the obtained lower layer film pattern as a mask were sequentially performed.

The respective etching conditions are as follows.

Etching conditions for the resist interlayer film of the resist pattern

Output: 50W

Pressure: 20 Pa

Time: 1min

Etching gas

Ar gas flow rate: CF ₄ gas flow rate: O ₂ gas flow rate = 50: 8: 2 (sccm)

Etching conditions for resist lower layer film of resist interlayer film pattern

Output: 50W

Pressure: 20 Pa

Time: 2min

Etching gas

Ar gas flow rate: CF ₄ gas flow rate: O ₂ gas flow rate = 50: 5: 5 (sccm)

The resist underlayer film pattern SiO ₂ Etching conditions for the film

Output: 50W

Pressure: 20 Pa

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]

As a result of observing the pattern end face thus obtained (the shape of the SiO ₂ film after etching) using an electron microscope (S-4800) manufactured by Hitachi, Ltd., the example using the lower layer film of this embodiment, It was confirmed that the shape of the SiO ₂ film after etching in processing was rectangular, and no defects were seen, and that it was good.

[Examples 53 to 56]

Using the respective compounds synthesized in the above Synthesis Examples, optical component forming compositions were prepared in the formulations shown in Table 11 below. On the other hand, the following components were used for the acid generator, the crosslinking agent, the acid diffusion inhibitor and the solvent in the respective components of the optical component forming composition in Table 11.

Acid generator: di-tert-butyl diphenyl iodonium nonafluoromethane sulfonate (DTDPI) manufactured by Midori Kagaku Co.,

Crosslinking agent: NIKARAK MX270 (NIKARAK) manufactured by SANWA CHEMICAL CO.

Organic solvent: Propylene glycol monomethyl ether acetate acetate (PGMEA)

[Evaluation of film formation]

The optical component-forming composition in a uniform state was spin-coated on a clean silicon wafer and then prebaked (PB) in an oven at 110 캜 to form an optical component-forming film having a thickness of 1 탆. The prepared optical component-forming composition was evaluated as "A" when the film formation was good and "C" when the film was defective.

[Evaluation of refractive index and transmittance]

A uniform optical component-forming composition was spin-coated on a clean silicon wafer, and then the film was baked in an oven at 110 캜 to form a film having a thickness of 1 탆. For the film, the refractive index (? = 589.3 nm) at 25 占 폚 was measured with a spectroscopic ellipsometer VASE of the? When the refractive index was 1.6 or more, the prepared film was evaluated as "A". When the refractive index was 1.55 or more and 1.6 or less, the film was evaluated as "B". When the refractive index was less than 1.55, the film was evaluated as "C". When the transmittance (? = 632.8 nm) was 90% or more, it was evaluated as "A" and when it was less than 90%, it was evaluated as "C".

[Table 11]

[Examples 57 to 60]

Using the respective compounds synthesized in the above Synthesis Examples, resist compositions were prepared in the formulations shown in Table 12 below. On the other hand, of the components of the resist composition in Table 12, the following were used for the radical generator, the radical diffusion inhibitor, and the solvent.

Radical generator: IRGACURE 184 from BASF

Radical Diffusion Control Agent: IRGACURE 1010 from BASF

Organic solvent: Propylene glycol monomethyl ether acetate acetate (PGMEA)

[Assessment Methods]

(1) Storage stability and thin film formation of resist composition

The storage stability of the resist composition was evaluated by observing the presence or absence of precipitation with naked eyes after the resist composition was prepared and allowed to stand at 23 캜 and 50% RH for 3 days. In the resist composition after standing for 3 days, the resist composition was evaluated as A in the case of uniform solution and no precipitation, and C in the case of precipitation. Further, the resist composition in a uniform state was spin-coated on a clean silicon wafer, and then baked (PB) in an oven at 110 캜 before exposure to form a resist film having a thickness of 40 nm. The prepared resist composition was evaluated as A when the film formation was good and C when the film formed was defective.

(2) Evaluation of pattern of resist pattern

A uniform resist composition was spin-coated on a clean silicon wafer, and then baked (PB) in an oven at 110 캜 before exposure to form a resist film having a thickness of 60 nm. The obtained resist film was irradiated with electron beams at a 1: 1 line-and-space setting of 50 nm, 40 nm, and 30 nm intervals using an electron beam drawing apparatus (ELS-7500, manufactured by Eriionix Co., Ltd.). After the irradiation, the resist film was heated at a predetermined temperature for 90 seconds and immersed in PGME for 60 seconds to carry out development. Thereafter, the resist film was rinsed with ultrapure water for 30 seconds and dried to form a negative resist pattern. The resist pattern thus formed was observed with a scanning electron microscope (S-4800, Hitachi High-Technologies Co., Ltd.) and the reactivity of the resist composition by electron beam irradiation was evaluated.

The sensitivity was expressed by the minimum amount of energy per unit area required for obtaining the pattern, and evaluated according to the following.

A: When the pattern is obtained at less than 50 μC / cm ²

C: When a pattern is obtained at 50 μC / cm ² or more

In the pattern formation, the obtained pattern shape was 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

[Table 12]

As described above, the present invention is not limited to the above-described embodiments and examples, and can be appropriately changed within a range not departing from the gist of the present invention.

The compound and resin of the present embodiment have high solubility in a safe solvent, good heat resistance and etching resistance, and the resist composition of the present embodiment gives a good resist pattern shape.

In addition, it is possible to realize a compound, a resin and a film forming composition for lithography that can apply a wet process and are useful for forming a photoresist underlayer film excellent in heat resistance and etching resistance. Since the film forming composition for lithography uses a compound or resin having a specific structure and high heat resistance and high solvent solubility, deterioration of the film at the time of high-temperature baking is suppressed and etching resistance against oxygen plasma etching and the like is also excellent A resist and a lower layer film can be formed. Furthermore, when a lower layer film is formed, adhesion with the resist layer is also excellent, so that an excellent resist pattern can be formed.

Further, it is useful as a composition for forming various optical parts in that the refractive index is high and the coloration is suppressed by the treatment at a low temperature to a high temperature.

Therefore, the present invention is applicable to, for example, electric insulating materials, resist resins, sealing resins for semiconductors, adhesives for printed wiring boards, electric laminated boards mounted on electric devices, Resin for resin for fiber reinforced plastic, resin for encapsulating liquid crystal display panel, coating material, coating agent, adhesive, coating material for semiconductor, resin for resist for semiconductor, lower layer of matrix resin, build-up laminate material, (Prism lens, lenticular lens, microlens, Fresnel lens, viewing angle control lens, contrast enhancement lens, etc.), a retardation film, a film for electromagnetic wave shielding, Prisms, optical fibers, solder resists for flexible printed wiring, plating resists, interlayer insulating films for multilayer printed wiring boards, and optical devices such as photosensitive optical waveguides In such products, it is possible to use widely available as well.

Particularly, the present invention can be effectively used particularly in the field of a resist for lithography, a lower layer film for lithography, a lower layer film for a multilayer resist and an optical component.

The present application is based on Japanese Patent Application (Japanese Patent Application No. 2016-143661) filed on July 21, 2016, filed with the Japanese Patent Office, the contents of which are incorporated herein by reference.

Industrial availability

INDUSTRIAL APPLICABILITY The present invention has industrial applicability in the fields of lithography resists, underlayers for lithography, underlayers for multilayer resists, and optical components.

Claims (28)

(0). &Lt; / RTI &gt;
[Chemical Formula 1]

(0)
(In the 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 or a single bond having 1 to 60 carbon atoms,
R ^T each independently represents 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, an alkenyl group having 2 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 hydroxyl group with a group represented by the formula (0-1) 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, wherein at least one of R ^T is a group represented by the following formula (0-1) Including,
X represents an oxygen atom, a sulfur atom or a non-
m is independently an integer of 0 to 9, provided that 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 within N [] may be the same or different,
r is independently an integer of 0 to 2.)
(2)

(0-1)
(In the formula (0-1), R ^X is a hydrogen atom or a methyl group.) The method according to claim 1,
Wherein the compound represented by the formula (0) is a compound represented by the following formula (1).
(3)

(One)
(In the formula (1), R ⁰ is synonymous with R ^Y ,
R ¹ is an n-valent group or a single bond having 1 to 60 carbon atoms,
Each of R ² to R ⁵ independently represents 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, an alkenyl group having 2 to 30 carbon atoms 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 hydroxyl group is substituted with a group represented by the formula (0-1) 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, wherein at least one of R ² to R ⁵ is a group represented by the formula (0- 1), &lt; / RTI &gt;
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,
Provided that m ² , m ³ , m ⁴ and m ⁵ do not become 0 at the same time,
n is a synonym with the above N, wherein when n is an integer of 2 or more, the structural formulas within n [] may be the same or different,
and p ² to p ⁵ are synonymous with r. The method according to claim 1,
Wherein the compound represented by the formula (0) is a compound represented by the following formula (2).
[Chemical Formula 4]

(2)
(In formula (2), R ^0A is synonymous with R ^Y ,
R ^1A is an n ^A -valent group or a single bond having 1 to 60 carbon atoms,
R ^2A each independently represents 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, an alkenyl group having 2 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 hydrogen atom of a hydroxyl group is substituted with a group represented by the formula (0-1) 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, wherein at least one of R ^2A is a group represented by the formula (0-1) Including,
n ^A is the same as the above N, wherein when n ^A is an integer of 2 or more, the structural formulas within n ^A [] may be the same or different,
X ^A represents an oxygen atom, a sulfur atom or a non-
m ^2A is independently an integer of 0 to 7, provided that at least one of m ^2A is an integer of 1 to 7,
q ^A are each independently 0 or 1.) 3. The method of claim 2,
Wherein the compound represented by the formula (1) is a compound represented by the following formula (1-1).
[Chemical Formula 5]

(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 the same as those in the formula (1)
R ⁶ to R ⁷ each independently represent 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, an alkenyl group having 2 to 30 carbon atoms, A halogen atom, a nitro group, an amino group, a carboxylic acid group, and a thiol group,
R ¹⁰ to R ¹¹ are each independently a hydrogen atom or a group represented by the following formula (0-2)
At least one of R ¹⁰ to R ¹¹ is a group represented by the following formula (0-2)
m ⁶ and m ⁷ are each independently an integer of 0 to 7,
Provided that m ⁴ , m ⁵ , m ⁶ and m ⁷ do not become 0 at the same time.)
[Chemical Formula 6]

(0-2)
(In the formula (0-2), R ^X is the same as that in the formula (0-1), and s is an integer of 0 to 30.) 5. The method of claim 4,
Wherein the compound represented by the formula (1-1) is a compound represented by the following formula (1-2).
(7)

(1-2)
(Wherein R ⁰ , R ¹ , R ⁶ , R ⁷ , R ¹⁰ , R ¹¹ , n, p ² to p ⁵ , m ⁶ and m ⁷ in the formula (1-2) In agreement with what's in it,
R ⁸ to R ⁹ are as defined above for R ⁶ to R ⁷ ,
R ¹² to R ¹³ are as defined above for 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 is not at the same time work is zero.) The method of claim 3,
Wherein the compound represented by the formula (2) is a compound represented by the following formula (2-1).
[Chemical Formula 8]

(2-1)
(In the formula (2-1), R ^0A , R ^{1 A} , n ^A , q ^A and X ^A are the same as those in the formula (2)
R ^3A each independently represents a linear, branched or cyclic alkyl group of 1 to 30 carbon atoms which may have a substituent, an aryl group of 6 to 30 carbon atoms which may have a substituent, a carbon number which may have a substituent A halogen atom, a nitro group, an amino group, a carboxylic acid group or a thiol group,
R ^4A each independently represents a hydrogen atom or a group represented by the following formula (0-2)
Here, at least one of R ^4A is a group represented by the following formula (0-2)
m ^6A are each independently an integer of 0 to 5.)
[Chemical Formula 9]

(0-2)
(In the formula (0-2), R ^X is the same as that in the formula (0-1), and s is an integer of 0 to 30.) A resin obtained by using the compound according to claim 1 as a monomer. 8. The method of claim 7,
Having a structure represented by the following formula (3).
[Chemical formula 10]

(3)
(In the formula (3), L represents an alkylene group having 1 to 30 carbon atoms which may have a substituent, an arylene group having 6 to 30 carbon atoms which may have a substituent, an alkoxy group having 1 to 30 carbon atoms A silylene group or a single bond, and the alkylene group, the arylene group and the alkoxylene group may contain an ether bond, a ketone bond or an ester bond,
R ⁰ is synonymous with R ^Y ,
R ¹ is an n-valent group or a single bond having 1 to 60 carbon atoms,
Each of R ² to R ⁵ independently represents 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, an alkenyl group having 2 to 30 carbon atoms 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 hydroxyl group is substituted with a group represented by the formula (0-1) 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, wherein at least one of R ² to R ⁵ is a group represented by the formula (0- 1), &lt; / RTI &gt;
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,
Provided that m ² , m ³ , m ⁴ and m ⁵ do not become 0 at the same time,
n is a synonym with the above N, wherein when n is an integer of 2 or more, the structural formulas within n [] may be the same or different,
and p ² to p ⁵ are synonymous with r. 8. The method of claim 7,
Having a structure represented by the following formula (4).
(11)

(4)
(In the formula (4), L represents an alkylene group having 1 to 30 carbon atoms which may have a substituent, an arylene group having 6 to 30 carbon atoms which may have a substituent, an alkoxy group having 1 to 30 carbon atoms A silylene group or a single bond, and the alkylene group, the arylene group and the alkoxylene group may contain an ether bond, a ketone bond or an ester bond,
R ^0A is synonymous with R ^Y ,
R ^1A is an n ^A -valent group having 1 to 30 carbon atoms or a single bond,
R ^2A each independently represents 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, an alkenyl group having 2 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 hydrogen atom of a hydroxyl group is substituted with a group represented by the formula (0-1) 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, wherein at least one of R ^2A is a group represented by the formula (0-1) Including,
n ^A is the same as the above N, wherein when n ^A is an integer of 2 or more, the structural formulas within n ^A [] may be the same or different,
X ^A represents an oxygen atom, a sulfur atom or a non-
m ^2A is independently an integer of 0 to 7, provided that at least one of m ^2A is an integer of 1 to 6,
q ^A are each independently 0 or 1.) A composition comprising at least one compound 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. 11. The method of claim 10,
Wherein the composition further comprises a solvent. The method according to claim 10 or 11,
&Lt; / RTI &gt; further comprising an acid generator. 13. The method according to any one of claims 10 to 12,
Wherein the composition further comprises a crosslinking agent. 14. The method of claim 13,
The crosslinking agent is at least one selected from the group consisting of a phenol compound, an epoxy compound, a cyanate compound, an amino compound, a benzoxazine compound, a melamine compound, a guanamine compound, a glycoluril compound, a urea compound, an isocyanate compound and an azide compound Lt; / RTI &gt; The method according to claim 13 or 14,
Wherein the crosslinking agent has at least one allyl group. 16. The method according to any one of claims 13 to 15,
Wherein the content of the crosslinking agent is at least one kind 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 And 0.1 to 100 parts by mass when the total mass is 100 parts by mass. 17. The method according to any one of claims 13 to 16,
Wherein the composition further comprises a crosslinking accelerator. 18. The method of claim 17,
Wherein the crosslinking accelerator is at least one selected from the group consisting of amines, imidazoles, organic phosphines, and Lewis acids. The method according to claim 17 or 18,
Wherein the content of the crosslinking accelerator is 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 Is from 0.1 to 5 parts by mass based on 100 parts by mass of the total mass of the composition. 20. The method according to any one of claims 10 to 19,
Further comprising a radical polymerization initiator. 21. The method according to any one of claims 10 to 20,
Wherein the radical polymerization initiator is at least one selected from the group consisting of a ketone-based photopolymerization initiator, an organic peroxide-based polymerization initiator, and an azo-based polymerization initiator. 22. The method according to any one of claims 10 to 21,
Wherein the content of the radical polymerization initiator is 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 Wherein the composition is 0.05 to 25 parts by mass when the total mass of the composition is 100 parts by mass. 23. The method according to any one of claims 10 to 22,
A composition for use in forming a film for lithography. 23. The method according to any one of claims 10 to 22,
A composition for use in resist permanent film formation. 14. The method according to any one of claims 10 to 13,
A composition for use in 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 to perform development. Forming a lower layer film on the substrate using the composition according to claim 23, forming at least one photoresist layer on the lower layer film, irradiating a predetermined region of the photoresist layer with radiation, Thereby forming a resist pattern. Forming a lower layer film on the substrate using the composition according to claim 23, forming an intermediate layer film on the lower layer film using a resist interlayer film material, and forming at least one photoresist layer on the intermediate layer film And then the resist pattern is used as a mask to etch the intermediate layer film, and the obtained intermediate layer film pattern is etched using 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.