JP7194355B2 - Compound, resin, composition and pattern forming method - Google Patents

Description

TECHNICAL FIELD The present invention relates to compounds having specific structures, resins, and compositions containing these. It also relates to a pattern forming method using the composition.

In the manufacture of semiconductor devices, microfabrication is performed by lithography using a photoresist material. However, in recent years, with the increase in the integration density and speed of LSIs, there is a demand for further miniaturization based on pattern rules. In addition, the light source for lithography used in resist pattern formation has been shortened from KrF excimer laser (248 nm) to ArF excimer laser (193 nm), and extreme ultraviolet light (EUV, 13.5 nm) has been introduced. is also expected.

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

Currently, various materials are known as such low-molecular-weight resist materials. For example, an alkali-developable negative radiation-sensitive composition using a low-molecular-weight polynuclear polyphenol compound as a main component (see, for example, Patent Documents 1 and 2) has been proposed, and a low-molecular-weight resist material having high heat resistance has been proposed. As a candidate for this, an alkali-developable 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. In addition, as a base compound of a resist material, a polyphenol compound is known to be capable of imparting high heat resistance while having a low molecular weight, and is useful for improving the resolution and roughness of resist patterns (for example, Non-Patent Document 2). reference).

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

In addition, as the resist pattern becomes finer and finer, there arises a problem of resolution or collapse of the resist pattern after development. However, simply thinning the resist makes it difficult to obtain a resist pattern with a film thickness sufficient for substrate processing. Therefore, in addition to the resist pattern, there is a need for a process in which a resist underlayer film is formed between the resist and the semiconductor substrate to be processed, and this resist underlayer film also functions as a mask during substrate processing.

At present, various types of resist underlayer films are known for such processes. For example, unlike conventional resist underlayer films with a high etching rate, terminal groups are removed by applying a predetermined energy to realize a resist underlayer film for lithography that has a dry etching rate selectivity close to that of resist. An underlayer film-forming material for multi-layer resist processes containing a solvent and a resin component having at least a substituent group that is separated to form a sulfonic acid residue has been proposed (see Patent Document 5). In addition, a resist underlayer film material containing a polymer having a specific repeating unit has been proposed as a material for realizing a resist underlayer film for lithography having a dry etching rate selectivity ratio lower than that of a resist (see Patent Document 6). ). Furthermore, in order to realize a resist underlayer film for lithography having a dry etching rate selectivity ratio smaller than that of a semiconductor substrate, acenaphthylene repeating units and repeating units having a substituted or unsubstituted hydroxy group are copolymerized. A resist underlayer film material containing a polymer has been proposed (see Patent Document 7).

On the other hand, an amorphous carbon underlayer film formed by CVD using methane gas, ethane gas, acetylene gas, etc. as raw materials is well known as a material having high etching resistance in this type of resist underlayer film. However, from the viewpoint of process, there is a demand for a resist underlayer film material that can form a resist underlayer film by a wet process such as spin coating or screen printing.

In addition, the present inventors have found an underlayer film-forming composition for lithography containing a compound having a specific structure and an organic solvent as a material having excellent etching resistance, high heat resistance, solubility in a solvent, and application of a wet process. proposed a product (see Patent Document 8).

Furthermore, regarding the method of forming the intermediate layer used in forming the resist underlayer film in the three-layer process, for example, a method of forming a silicon nitride film (see Patent Document 9) and a method of forming a silicon nitride film by CVD (see Patent Document 10). )It has been known. Also, materials containing silsesquioxane-based silicon compounds are known as intermediate layer materials for three-layer processes (see Patent Documents 11 and 12).

Various optical component-forming compositions have been proposed, for example, acrylic resins (see Patent Documents 13 and 14) and polyphenols having a specific structure derived from allyl groups (see Patent Document 15). Proposed.

JP-A-2005-326838 JP 2008-145539 A JP 2009-173623 A WO2013/024778 JP-A-2004-177668 JP 2004-271838 A JP-A-2005-250434 WO2013/024779 JP-A-2002-334869 WO2004/066377 Japanese Patent Application Laid-Open No. 2007-226170 JP 2007-226204 A JP 2010-138393 A JP 2015-174877 A WO2014/123005

T. Nakayama, M.; Nomura, K.; Haga, M.; Ueda: Bull. Chem. Soc. Jpn. , 71, 2979 (1998) Shinji Okazaki, 22 others, "New Development of Photoresist Material Development," CMC Publishing Co., Ltd., September 2009, p. 211-259

As described above, a large number of lithographic film-forming compositions for resist applications and lithographic film-forming compositions for underlayer film applications have been proposed, but wet processes such as spin coating and screen printing are applicable. There is no material that not only has high solvent solubility but also has high heat resistance and etching resistance, and development of a new material is desired.
There is also a demand for the development of new materials suitable for obtaining permanent resist films with excellent alkali developability, photosensitivity and resolution.
Further, many compositions for optical members have been proposed so far, but none of them achieves a high level of heat resistance, transparency and refractive index, and development of new materials is required.

The present invention has been made in view of the above problems, and an object of the present invention is to form a photoresist and a photoresist underlayer film that can be applied to a wet process and has excellent heat resistance, solubility and etching resistance. It is an object of the present invention to provide a compound, a resin, and a film-forming composition for lithography, which are useful for lithography. Another object of the present invention is to provide a resist film, a resist underlayer film, a resist permanent film, and a pattern forming method using the composition. Another object of the present invention is to provide a composition for optical members.

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

(In formula (0), R ^Y is a hydrogen atom, an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms,
R ^Z is an N-valent group or a single bond having 1 to 60 carbon atoms,
Each R ^T is independently an optionally substituted alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms which may be substituted, and a substituent. an alkenyl group having 2 to 30 carbon atoms which may be substituted, 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 a group in which the hydrogen atom of is substituted with one group selected from an allyloxyalkyl group, an acryloxyalkyl group, or a methacryloxyalkyl group, and the alkyl group, the aryl group, the alkenyl group, and the alkoxy group are ether may contain a bond, a ketone bond or an ester bond, wherein at least one of R ^T is a group selected from an allyloxyalkyl group, an acryloxyalkyl group or a methacryloxyalkyl group as a hydrogen atom of a hydroxyl group; including substituted groups;
X represents an oxygen atom, a sulfur atom or no cross-linking,
each m is independently an integer from 0 to 9, wherein at least one of m is an integer from 1 to 9;
N is an integer of 1 to 4, wherein when N is an integer of 2 or more, the structural formulas in N [ ] may be the same or different,
Each r is independently an integer of 0-2. )
[2]
The compound according to the above [1], wherein the compound represented by the formula (0) is a compound represented by the following formula (1).

(In formula (1), R ⁰ has the same meaning as R ^Y ,
R ¹ is an n-valent group having 1 to 60 carbon atoms or a single bond,
R ² to R ⁵ are each independently an optionally substituted alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms which may be substituted, or a substituent an alkenyl group having 2 to 30 carbon atoms which may have, an alkoxy group having 1 to 30 carbon atoms which may have a substituent, a halogen atom, a nitro group, an amino group, a carboxylic acid group, a thiol group, A hydroxyl group or a group in which a hydrogen atom of the hydroxyl group is substituted with one group selected from an allyloxyalkyl group, an acryloxyalkyl group, or a methacryloxyalkyl group, wherein the alkyl group, the aryl group, the alkenyl group, and the alkoxy group may contain an ether bond, a ketone bond or an ester bond, wherein at least one of R ² to R ⁵ has a hydrogen atom of a hydroxyl group from an allyloxyalkyl group, an acryloxyalkyl group or a methacryloxyalkyl group Including a group substituted with one selected group,
m ² and m ³ are each independently an integer of 0 to 8;
^m4 and ^m5 are each independently an integer of 0 to 9;
However, m ² , m ³ , m ⁴ and m ⁵ are never 0 at the same time,
n is the same as the above N, where n is an integer of 2 or more, n structural formulas in [ ] may be the same or different,
p ² to p ⁵ have the same meaning as r above. )
[3]
The compound according to [1] above, wherein the compound represented by the formula (0) is a compound represented by the following formula (2).

(In formula (2), R ^0A is synonymous with R ^Y ,
R ^1A is an n ^A -valent group having 1 to 60 carbon atoms or a single bond;
Each R ^2A is independently an optionally substituted alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms which may be substituted, and a substituent. an alkenyl group having 2 to 30 carbon atoms which may be substituted, 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 a group in which the hydrogen atom of is substituted with one group selected from an allyloxyalkyl group, an acryloxyalkyl group, or a methacryloxyalkyl group, and the alkyl group, the aryl group, the alkenyl group, and the alkoxy group are ether may contain a bond, a ketone bond or an ester bond, wherein at least one of R ^2A is a hydroxyl hydrogen atom of one group selected from an allyloxyalkyl group, an acryloxyalkyl group or a methacryloxyalkyl group; including substituted groups;
n ^A has the same definition as the above N, where n ^A is an integer of 2 or more, n ^A structural formulas in [ ] may be the same or different,
X ^A represents an oxygen atom, a sulfur atom or non-crosslinked,
each m ^2A is independently an integer from 0 to 7, with the proviso that at least one m ^2A is an integer from 1 to 7;
q ^A is each independently 0 or 1; )
[4]
The compound according to [2] above, wherein the compound represented by the formula (1) is a compound represented by the following formula (1-1).

(in formula (1-1), R ⁰ , R ¹ , R ⁴ , R ⁵ , n, p ² to p ⁵ , m ⁴ and m ⁵ are as defined above;
R ⁶ to R ⁷ are each independently an optionally substituted alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms which may be substituted, or a substituent an alkenyl group having 2 to 30 carbon atoms, a halogen atom, a nitro group, an amino group, a carboxylic acid group, a thiol group, which may have
R ¹⁰ to R ¹¹ are each independently a hydrogen atom or one group selected from an allyloxyalkyl group, an acryloxyalkyl group or a methacryloxyalkyl group,
wherein at least one of R ¹⁰ to R ¹¹ is one group selected from an allyloxyalkyl group, an acryloxyalkyl group or a methacryloxyalkyl group;
m ⁶ and m ⁷ are each independently an integer of 0 to 7;
However, m ⁴ , m ⁵ , m ⁶ and m ⁷ cannot be 0 at the same time. )
[5]
The compound according to [4] above, wherein the compound represented by the formula (1-1) is a compound represented by the following formula (1-2).

(in formula (1-2), R ⁰ , R ¹ , R ⁶ , R ⁷ , R ¹⁰ , R ¹¹ , n, p ² to p ⁵ , m ⁶ and m ⁷ are as defined above;
R ⁸ to R ⁹ have the same definitions as R ⁶ to R ⁷ ,
R ¹² to R ¹³ have the same definitions as R ¹⁰ to R ¹¹ ;
m ⁸ and m ⁹ are each independently an integer from 0 to 8;
However, m ⁶ , m ⁷ , m ⁸ and m ⁹ cannot be 0 at the same time. )
[6]
The compound according to [3] above, wherein the compound represented by the formula (2) is a compound represented by the following formula (2-1).

(In formula (2-1), R ^0A , R ^1A , n ^A , q ^A and X ^A have the same definitions as in formula (2) above;
Each R ^3A is independently an optionally substituted alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms which may be substituted, and a substituent. an alkenyl group having 2 to 30 carbon atoms, a halogen atom, a nitro group, an amino group, a carboxylic acid group, a thiol group, which may be
Each R ^4A is independently a group in which a hydrogen atom or a hydrogen atom of a hydroxyl group is substituted with one group selected from an allyloxyalkyl group, an acryloxyalkyl group or a methacryloxyalkyl group, where R ^4A is one group selected from an allyloxyalkyl group, an acryloxyalkyl group or a methacryloxyalkyl group,
Each ^m6A is independently an integer of 0-5. )
[7]
A resin obtained by using the compound described in [1] above as a monomer.
[8]
The resin according to [7] above, which has a structure represented by the following formula (3).

(In formula (3),
L is 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, and the number of carbon atoms which may have a substituent 1 to 30 alkoxylene groups or single bonds, and the alkylene group, the arylene group, and the alkoxylylene group may contain an ether bond, a ketone bond or an ester bond,
R ⁰ has the same definition as R ^Y ,
R ¹ is an n-valent group having 1 to 60 carbon atoms or a single bond,
R ² to R ⁵ are each independently an optionally substituted alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms which may be substituted, or a substituent an alkenyl group having 2 to 30 carbon atoms which may have, an alkoxy group having 1 to 30 carbon atoms which may have a substituent, a halogen atom, a nitro group, an amino group, a carboxylic acid group, a thiol group, A hydroxyl group or a group in which a hydrogen atom of the hydroxyl group is substituted with one group selected from an allyloxyalkyl group, an acryloxyalkyl group, or a methacryloxyalkyl group, wherein the alkyl group, the aryl group, the alkenyl group, and the alkoxy group may contain an ether bond, a ketone bond or an ester bond, wherein at least one of R ² to R ⁵ has a hydrogen atom of a hydroxyl group from an allyloxyalkyl group, an acryloxyalkyl group or a methacryloxyalkyl group Including a group substituted with one selected group,
m ² and m ³ are each independently an integer of 0 to 8;
^m4 and ^m5 are each independently an integer of 0 to 9;
However, m ² , m ³ , m ⁴ and m ⁵ cannot be 0 at the same time, and at least one of R ² to R ⁵ has a hydroxyl hydrogen atom of an allyloxyalkyl group, acryloxyalkyl group or methacryloxyalkyl group. It is a group substituted with one group selected from groups. )
[9]
The resin according to [7] above, which has a structure represented by the following formula (4).

(In formula (4), L is 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 alkoxylylene group having 1 to 30 carbon atoms or a single bond, wherein the alkylene group, the arylene group, and the alkoxylylene group may contain an ether bond, a ketone bond, or an ester bond,
R ^0A is synonymous with R ^Y above,
R ^1A is an n ^A -valent group having 1 to 30 carbon atoms or a single bond;
Each R ^2A is independently an optionally substituted alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms which may be substituted, and a substituent. an alkenyl group having 2 to 30 carbon atoms which may be substituted, 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 a group in which the hydrogen atom of is substituted with one group selected from an allyloxyalkyl group, an acryloxyalkyl group, or a methacryloxyalkyl group, and the alkyl group, the aryl group, the alkenyl group, and the alkoxy group are ether may contain a bond, a ketone bond or an ester bond, wherein at least one of R ^2A is a hydroxyl hydrogen atom of one group selected from an allyloxyalkyl group, an acryloxyalkyl group or a methacryloxyalkyl group; including substituted groups;
n ^A has the same definition as the above N, where n ^A is an integer of 2 or more, n ^A structural formulas in [ ] may be the same or different,
X ^A represents an oxygen atom, a sulfur atom or non-crosslinked,
each m ^2A is independently an integer from 0 to 7, with the proviso that at least one m ^2A is an integer from 1 to 7;
q ^A is each independently 0 or 1; )
[10]
A composition comprising one or more selected from the group consisting of the compound according to any one of [1] to [6] above and the resin according to any one of [7] to [9] above.
[11]
The composition according to [10] above, further comprising a solvent.
[12]
The composition according to [10] or [11] above, further comprising an acid generator.
[13]
The composition according to any one of [10] to [12] above, further comprising a cross-linking agent.
[14]
The cross-linking agent is at least one selected from the group consisting of phenol compounds, epoxy compounds, cyanate compounds, amino compounds, benzoxazine compounds, melamine compounds, guanamine compounds, glycoluril compounds, urea compounds, isocyanate compounds and azide compounds. , the composition according to the above [13].
[15]
The composition according to the above [13] or [14], wherein the cross-linking agent has at least one allyl group.
[16]
The content of the cross-linking agent is one or more selected from the group consisting of the compound according to any one of [1] to [6] and the resin according to any one of [7] to [9]. The composition according to any one of [13] to [15], which is 0.1 to 100 parts by mass when the total mass of the composition containing is 100 parts by mass.
[17]
The composition according to any one of [13] to [16], further comprising a cross-linking accelerator.
[18]
The composition according to [17] above, wherein the crosslinking accelerator is at least one selected from the group consisting of amines, imidazoles, organic phosphines, and Lewis acids.
[19]
The content ratio of the cross-linking accelerator is one or more selected from the group consisting of the compound according to any one of [1] to [6] and the resin according to any one of [7] to [9]. The composition according to [17] or [18], which is 0.1 to 5 parts by mass when the total mass of the composition contained is 100 parts by mass.
[20] The composition according to any one of [10] to [19], further comprising a radical polymerization initiator.
[21] The radical polymerization initiator is at least one selected from the group consisting of ketone-based photopolymerization initiators, organic peroxide-based polymerization initiators and azo-based polymerization initiators. ] The composition according to any one of the above.
[22] The content of the radical polymerization initiator is composed of the compound according to any one of [1] to [6] and the resin according to any one of [7] to [9]. When the total mass of the composition containing one or more selected from the group is 100 parts by mass, it is 0.05 to 25 parts by mass, according to any one of [10] to [21] Composition.
[23] The composition according to any one of [10] to [22], which is used for forming a film for lithography.
[24] The composition according to any one of [10] to [22], which is used for forming a permanent resist film.
[25] The composition according to any one of [10] to [22], which is used for forming an optical component.
[26] A resist pattern comprising the step of forming a photoresist layer on a substrate using the composition described in [23], then irradiating a predetermined region of the photoresist layer with radiation and developing the photoresist layer. Forming method.
[27] Form an underlayer film on a substrate using the composition described in [23] above, form at least one photoresist layer on the underlayer film, and then remove a predetermined amount of the photoresist layer. A method of forming a resist pattern, comprising the steps of irradiating a region with radiation and developing the region.
[28] forming an underlayer film on a substrate using the composition described in [23] above; forming an intermediate layer film on the underlayer film using a resist intermediate layer film material; After forming at least one layer of photoresist layer thereon, a predetermined region of the photoresist layer is irradiated with radiation and developed to form a resist pattern, and then the intermediate layer film is formed using the resist pattern as a mask. is etched, the underlayer film is etched using the obtained intermediate layer film pattern as an etching mask, and the substrate is etched using the obtained underlayer film pattern as an etching mask to form a pattern on the substrate. Forming method.

The compounds and resins of the present invention have high solubility in safe solvents and good heat resistance and etching resistance. Also, a resist composition containing the compound and/or resin of the present invention provides a good resist pattern shape.

EMBODIMENT OF THE INVENTION Hereinafter, the form (henceforth "this embodiment") for implementing this invention is demonstrated. The following embodiments are examples for explaining the present invention, and the present invention is not limited only to these embodiments.

The compound, resin, and composition containing the same in the present embodiment are applicable to wet processes and are useful for forming a photoresist underlayer film having excellent heat resistance and etching resistance. In addition, since the composition of the present embodiment uses a compound or resin having a specific structure that is highly heat-resistant and solvent-soluble, deterioration of the film during high-temperature baking is suppressed, and etching resistance to oxygen plasma etching etc. It is possible to form a resist and an underlayer film which are also excellent in In addition, when an underlayer film is formed, the adhesiveness to the resist layer is excellent, so an excellent resist pattern can be formed.
In addition, the compounds and resins in the present embodiment are excellent in sensitivity and resolution when used in photosensitive materials, and while maintaining high heat resistance, they can also be used as general-purpose organic solvents, other compounds, and resin components. , and is useful for forming a resist permanent film excellent in compatibility with additives.
Furthermore, since it has a high refractive index and suppresses coloration due to heat treatment over a wide range from low to high temperatures, it is also useful as various optical-forming compositions.

[Compound represented by formula (0)]
The compound in this embodiment is represented by the following formula (0).

(In formula (0), R ^Y is a hydrogen atom, an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms,
R ^Z is an N-valent group or a single bond having 1 to 60 carbon atoms,
Each R ^T is independently an optionally substituted alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms which may be substituted, and a substituent. an alkenyl group having 2 to 30 carbon atoms which may be substituted, 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 a group in which the hydrogen atom of is substituted with one group selected from an allyloxyalkyl group, an acryloxyalkyl group, or a methacryloxyalkyl group, and the alkyl group, the aryl group, the alkenyl group, and the alkoxy group are ether may contain a bond, a ketone bond or an ester bond, wherein at least one of R ^T is a group selected from an allyloxyalkyl group, an acryloxyalkyl group or a methacryloxyalkyl group as a hydrogen atom of a hydroxyl group; including substituted groups;
X represents an oxygen atom, a sulfur atom or no cross-linking,
each m is independently an integer from 0 to 9, wherein at least one of m is an integer from 1 to 9;
N is an integer of 1 to 4, wherein when N is an integer of 2 or more, the structural formulas in N [ ] may be the same or different,
Each r is independently an integer of 0-2. )

R ^Y is a hydrogen atom, an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms. A linear, branched or cyclic alkyl group can be used as the alkyl group. R ^Y is a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms, thereby imparting excellent heat resistance and solvent solubility. can be done.

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

Each R ^T is independently an optionally substituted alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms which may be substituted, and a substituent. an alkenyl group having 2 to 30 carbon atoms which may be substituted, 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 a group in which the hydrogen atom of is substituted with one group selected from an allyloxyalkyl group, an acryloxyalkyl group, or a methacryloxyalkyl group, and the alkyl group, the aryl group, the alkenyl group, and the alkoxy group are ether may contain a bond, a ketone bond or an ester bond, wherein at least one of R ^T is a group selected from an allyloxyalkyl group, an acryloxyalkyl group or a methacryloxyalkyl group as a hydrogen atom of a hydroxyl group; Including substituted groups. The alkyl group, alkenyl group and alkoxy group may be linear, branched or cyclic groups.
Here, the group in which the hydrogen atom of the hydroxyl group is substituted with one group selected from an allyloxyalkyl group, an acryloxyalkyl group, or a methacryloxyalkyl group means an allyloxyalkyl group, an acryloxyalkyl group, or a methacryloxyalkyl group. A group having one group selected from, for example, an allyloxyalkyl group, an acryloxyalkyl group or a methacryloxyalkyl group.

X represents an oxygen atom, a sulfur atom, or no cross-linking. When X is an oxygen atom or a sulfur atom, it tends to exhibit high heat resistance, and is more preferably an oxygen atom. From the viewpoint of solubility, X is preferably non-crosslinked. In addition, each m is independently an integer of 0 to 9, and at least one of m is an integer of 1 to 9.

In formula (0), the portion 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. becomes. Each r is independently an integer of 0-2. The numerical range of m described above is determined according to the ring structure determined by r.

[Compound represented by formula (1)]
Compound (0) in the present embodiment is preferably a compound represented by the following formula (1) from the viewpoint of heat resistance and solvent solubility.

In formula (1) above, 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. When R ⁰ is a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms, heat resistance is relatively high and solvent solubility is improved. tend to In addition, R ⁰ is a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms or a An aryl group of 6 to 30 is preferred.
R ¹ is an n-valent group having 1 to 60 carbon atoms or a single bond, and each aromatic ring is bonded via R ¹ .
R ² to R ⁵ are each independently an optionally substituted alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms which may be substituted, or a substituent an alkenyl group having 2 to 30 carbon atoms which may have, an alkoxy group having 1 to 30 carbon atoms which may have a substituent, a halogen atom, a nitro group, an amino group, a carboxylic acid group, a thiol group, A hydroxyl group or a group in which a hydrogen atom of the hydroxyl group is substituted with one group selected from an allyloxyalkyl group, an acryloxyalkyl group, or a methacryloxyalkyl group, wherein the alkyl group, the aryl group, the alkenyl group, and the alkoxy group may contain an ether bond, a ketone bond or an ester bond, wherein at least one of R ² to R ⁵ has a hydrogen atom of a hydroxyl group from an allyloxyalkyl group, an acryloxyalkyl group or a methacryloxyalkyl group Including groups substituted with one selected group.
m ² and m ³ are each independently an integer of 0-8, and m ⁴ and m ⁵ are each independently an integer of 0-9. However, m ² , m ³ , m ⁴ and m ⁵ cannot be 0 at the same time.
n is an integer of 1-4. Here, when n is an integer of 2 or more, n structural formulas in [ ] may be the same or different.
p ² to p ⁵ are each independently an integer of 0 to 2;
Here, the alkyl group, alkenyl group and alkoxy group may be linear, branched or cyclic groups.

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, and a carbon An alkanepropyl group with a number of 2 to 60, and an alkanetetrayl group with a carbon number of 3 to 60 when n=4. Examples of the n-valent group include those having a linear hydrocarbon group, a branched hydrocarbon group, or an alicyclic hydrocarbon group. Here, the alicyclic hydrocarbon group also includes a bridged alicyclic hydrocarbon group. Further, the n-valent group may have an aromatic group having 6 to 60 carbon atoms.

In addition, 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 also includes a bridged alicyclic hydrocarbon group.

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

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

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

Furthermore, since the aromatic density is high, the refractive index is high, and coloring is suppressed by heat treatment over a wide range from low temperature to high temperature, so it is also useful as a composition for forming various optical parts. Among them, a compound having quaternary carbon is preferable from the viewpoint of suppressing oxidative decomposition of the compound, suppressing coloration, and improving heat resistance and solvent solubility. As optical parts, in addition to film-shaped and sheet-shaped parts, plastic lenses (prism lenses, lenticular lenses, micro lenses, Fresnel lenses, viewing angle control lenses, contrast enhancement lenses, etc.), retardation films, electromagnetic shielding films, It is useful as a prism, an optical fiber, a solder resist for flexible printed wiring, a plating resist, an interlayer insulating film for multilayer printed wiring boards, and a photosensitive optical waveguide.

The compound represented by the above formula (1) is preferably a compound represented by the following formula (1-1) from the viewpoint of ease of cross-linking and solubility in organic solvents.

In formula (1-1),
R ⁰ , R ¹ , R ⁴ , R ⁵ , n, p ² to p ⁵ , m ⁴ and m ⁵ are as defined above;
R ⁶ to R ⁷ are each independently an optionally substituted alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms which may be substituted, or a substituent an alkenyl group having 2 to 30 carbon atoms, a halogen atom, a nitro group, an amino group, a carboxylic acid group, a thiol group, which may have
R ¹⁰ to R ¹¹ are each independently a hydrogen atom or one group selected from an allyloxyalkyl group, an acryloxyalkyl group or a methacryloxyalkyl group,
wherein at least one of R ¹⁰ to R ¹¹ is one group selected from an allyloxyalkyl group, an acryloxyalkyl group or a methacryloxyalkyl group;
m ⁶ and m ⁷ are each independently an integer of 0 to 7;
However, m ⁴ , m ⁵ , m ⁶ and m ⁷ cannot be 0 at the same time.

In addition, the compound represented by the above formula (1-1) is preferably a compound represented by the following formula (1-2) from the viewpoint of ease of further cross-linking and solubility in organic solvents.

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

In addition, the compound represented by the above formula (1-1) is preferably a compound represented by the following formula (1a) from the viewpoint of supply of raw materials.

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

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

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

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

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

From the viewpoint of solubility in organic solvents, the compound represented by the above formula (1b) is more preferably a compound represented by the following formula (1c).

In formula (1c) above, R ⁰ , R ¹ , R ⁶ to R ¹³ , m ⁶ to m ⁹ , and n have the same definitions as in formula (1-2) above.

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

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

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

In the above formula, X has the same meaning as defined in formula (0) above, R ^T' has the same meaning as R ^T defined in formula (0) above, and each m is independently 1 to 6. is an integer of

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

In the above formula, X has the same meaning as defined in formula (0) above, and R ^Y′ and R ^Z′ have the same meanings as R ^Y and R ^Z defined in formula (0) above. Furthermore, at least one of OR ^4A includes a group in which a hydrogen atom of a hydroxyl group is substituted with one group selected from an allyloxyalkyl group, an acryloxyalkyl group, or a methacryloxyalkyl group.

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

In the above formula, R ² , R ³ , R ⁴ and R ⁵ have the same meanings as those explained in formula (1) above. m ² and m ³ are integers of 0-6, and m ⁴ and m ⁵ are integers of 0-7. provided that at least one selected from R ² , R ³ , R ⁴ and R ⁵ is a group in which the hydrogen atom of the hydroxyl group is substituted with one group selected from an allyloxyalkyl group, an acryloxyalkyl group or a methacryloxyalkyl group , and m ² , m ³ , m ⁴ , and m ⁵ are never 0 at the same time.

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

In the above formula, R ¹⁰ , R ¹¹ , R ¹² and R ¹³ have the same definitions as those described in formula (1-2) above, and at least one of R ¹⁰ to R ¹³ is an allyloxyalkyl group, an acryloxyalkyl It is one group selected from a group and a methacryloxyalkyl group.

Compounds represented by the formula (1) are particularly preferably compounds represented by the following formulas (BiF-1) to (BiF-10) from the viewpoint of solubility in further organic solvents.

In the above formula, R ¹⁰ to R ¹³ are each independently a hydrogen atom or one group selected from an allyloxyalkyl group, an acryloxyalkyl group or a methacryloxyalkyl group, where R ¹⁰ to R ¹³ is one group selected from an allyloxyalkyl group, an acryloxyalkyl group or a methacryloxyalkyl group.

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

前記式中、Ｒ^０、Ｒ^１、ｎは上記式（１－１）で説明したものと同義であり、Ｒ^１０’及びＲ^１１’は上記式（１－１）で説明したＲ^１０及びＲ^１１と同義であり、Ｒ^４’及びＲ^５’は各々独立して、置換基を有していてもよい炭素数１～３０のアルキル基、置換基を有していてもよい炭素数６～３０のアリール基、置換基を有していてもよい炭素数２～３０のアルケニル基、置換基を有していてもよい炭素数１～３０のアルコキシ基、ハロゲン原子、ニトロ基、アミノ基、カルボン酸基、チオール基、水酸基又は水酸基の水素原子がアリルオキシアルキル基、アクリルオキシアルキル基またはメタクリルオキシアルキル基から選ばれる１つの基で置換された基であり、前記アルキル基、前記アリール基、前記アルケニル基、前記アルコキシ基は、エーテル結合、ケトン結合またはエステル結合を含んでいてもよく、Ｒ^１０’及びＲ^１１’の少なくとも１つは、アリルオキシアルキル基、アクリルオキシアルキル基またはメタクリルオキシアルキル基から選ばれる１つの基である。ｍ^４’及びｍ^５’は０～８の整数であり、ｍ^１０’及びｍ^１１’は１～９の整数であり、ｍ^４’＋ｍ^１０’及びｍ^４’＋ｍ^１１’は各々独立して１～９の整数である。

In the above formula, R ⁰ , R ¹ and n are the same as those described in formula (1-1) above, and R ^10′ and R ^11′ are R ¹⁰ and R described in formula (1-1) above. ¹¹ , and R ^4′ and R ^5′ are each independently an optionally substituted alkyl group having 1 to 30 carbon atoms, an optionally substituted carbon number of 6 to 30 aryl groups, optionally substituted alkenyl groups having 2 to 30 carbon atoms, alkoxy groups having 1 to 30 carbon atoms which may have substituents, halogen atoms, nitro groups, amino groups, A carboxylic acid group, a thiol group, a hydroxyl group, or a group in which a hydrogen atom of a hydroxyl group is substituted with one group selected from an allyloxyalkyl group, an acryloxyalkyl group, or a methacryloxyalkyl group, wherein the alkyl group, the aryl group, The alkenyl group and the alkoxy group may contain an ether bond, a ketone bond or an ester bond, and at least one of R ^10' and R ^11' is an allyloxyalkyl group, an acryloxyalkyl group or a methacryloxyalkyl group. is one group selected from groups. 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' are each independently An integer from 1 to 9.

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

Examples of R4 ^' and R5 ^' include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group and triacontyl group. , cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, cyclododecyl, cyclotriacontyl, norbornyl, adamantyl, phenyl group, naphthyl group, anthracene group, pyrenyl group, biphenyl group, heptacene group, vinyl group, allyl group, triacontenyl group, methoxy group, ethoxy group, triacontoxy group, fluorine atom, chlorine atom, bromine atom, iodine atom , and thiol groups.

Each example of R ⁰ , R ^4′ and R ^5′ includes isomers. For example, a butyl group includes n-butyl, isobutyl, sec-butyl, and tert-butyl groups.

In the above formula, R ¹⁰ to R ¹³ have the same definitions 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, It is a 6-30 divalent aryl group or a C2-30 divalent alkenyl group.

Examples of R ¹⁶ include methylene group, ethylene group, propene group, butene group, pentene group, hexene group, heptene group, octene group, nonene group, decene group, undecene group, dodecene group, triacontene group and cyclopropene group. , cyclobutene group, cyclopentene group, cyclohexene group, cycloheptene group, cyclooctene group, cyclononene group, cyclodecene group, cycloundecene group, cyclododecene group, cyclotriacontene group, divalent norbornyl group, divalent adamantyl group, divalent phenyl group, divalent naphthyl group, divalent anthracene group, divalent pyrene group, divalent biphenyl group, divalent heptacene group, divalent vinyl group, divalent allyl group, divalent tria A contenyl group is mentioned.

Each example of R ¹⁶ above includes isomers. For example, a butyl group includes n-butyl, isobutyl, sec-butyl, and tert-butyl groups.

In the above formula, R ¹⁰ to R ¹³ have the same definitions as those described in formula (1-2) above, and R ¹⁴ each independently represents a linear, branched or cyclic alkyl having 1 to 30 carbon atoms. group, 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, a thiol group, m ¹⁴ is an integer of 0 to 5, m ^14' is an integer of 0-4.

Examples of R ¹⁴ include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, triacontyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, cycloundecyl group, cyclododecyl group, cyclotriacontyl group, norbornyl group, adamantyl group, phenyl group, naphthyl group, Anthracene group, pyrenyl group, biphenyl group, heptacene group, vinyl group, allyl group, triacontenyl group, methoxy group, ethoxy group, triacontoxy group, fluorine atom, chlorine atom, bromine atom, iodine atom, thiol group. be done.

Each example of R ¹⁴ above includes isomers. For example, a butyl group includes n-butyl, isobutyl, sec-butyl, and tert-butyl groups.

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

In the above formula, R ¹⁰ to R ¹³ have the same definitions as those described in formula (1-2) above, and R ¹⁴ each independently represents a linear, branched or cyclic alkyl having 1 to 30 carbon atoms. group, 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, a thiol group, m ¹⁴ is an integer of 0 to 5, m ^14′ is an integer of 0-4 and m ^14″ is an integer of 0-3.

Examples of R ¹⁴ include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, triacontyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, cycloundecyl group, cyclododecyl group, cyclotriacontyl group, norbornyl group, adamantyl group, phenyl group, naphthyl group, Anthracene group, pyrenyl group, biphenyl group, heptacene group, vinyl group, allyl group, triacontenyl group, methoxy group, ethoxy group, triacontoxy group, fluorine atom, chlorine atom, bromine atom, iodine atom, thiol group. be done.

Each example of R ¹⁴ above includes isomers. For example, a butyl group includes n-butyl, isobutyl, sec-butyl, and tert-butyl groups.

In the above formula, R ¹⁰ to R ¹³ have the same definitions 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, or a thiol group.

Examples of R ¹⁵ include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, triacontyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, cycloundecyl group, cyclododecyl group, cyclotriacontyl group, norbornyl group, adamantyl group, phenyl group, naphthyl group, Anthracene group, pyrenyl group, biphenyl group, heptacene group, vinyl group, allyl group, triacontenyl group, methoxy group, ethoxy group, triacontoxy group, fluorine atom, chlorine atom, bromine atom, iodine atom, thiol group. be done.

Each example of R ¹⁵ above includes isomers. For example, a butyl group includes n-butyl, isobutyl, sec-butyl, and tert-butyl groups.

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

From the viewpoint of raw material availability, the compound represented by the formula (0) is more preferably the compounds listed below.

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

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

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

In the above formula, R ¹⁰ to R ¹³ have the same meanings as explained in formula (1-2) above. Each R ¹⁴ is independently 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, or 1 to 30 carbon atoms. is an alkoxy group, a halogen atom or a thiol group, and ^m14 is an integer of 0-4.

Examples of R ¹⁴ include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, triacontyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, cycloundecyl group, cyclododecyl group, cyclotriacontyl group, norbornyl group, adamantyl group, phenyl group, naphthyl group, Examples include anthracene group, heptacene group, vinyl group, allyl group, triacontenyl group, methoxy group, ethoxy group, triacontoxy group, fluorine atom, chlorine atom, bromine atom, iodine atom and thiol group.

Each example of R ¹⁴ above includes isomers. For example, a butyl group includes n-butyl, isobutyl, sec-butyl, and tert-butyl groups.

In the above formula, R ¹⁰ to R ¹³ have the same definitions 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, or a thiol group.

Examples of R ¹⁵ include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, triacontyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, cycloundecyl group, cyclododecyl group, cyclotriacontyl group, norbornyl group, adamantyl group, phenyl group, naphthyl group, Examples include anthracene group, heptacene group, vinyl group, allyl group, triacontenyl group, methoxy group, ethoxy group, triacontoxy group, fluorine atom, chlorine atom, bromine atom, iodine atom and thiol group.

Each example of R ¹⁵ above includes isomers. For example, a butyl group includes n-butyl, isobutyl, sec-butyl, and tert-butyl groups.

In the above formula, R ¹⁰ to R ¹³ have the same definitions 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, It is a 6-30 divalent aryl group or a C2-30 divalent alkenyl group.

Examples of R ¹⁶ include methylene group, ethylene group, propene group, butene group, pentene group, hexene group, heptene group, octene group, nonene group, decene group, undecene group, dodecene group, triacontene group and cyclopropene group. , cyclobutene group, cyclopentene group, cyclohexene group, cycloheptene group, cyclooctene group, cyclononene group, cyclodecene group, cycloundecene group, cyclododecene group, cyclotriacontene group, divalent norbonyl group, divalent adamantyl group, divalent phenyl group, divalent naphthyl group, divalent anthracene group, divalent heptacene group, divalent vinyl group, divalent allyl group, and divalent triacontenyl group.

Each example of R ¹⁶ above includes isomers. For example, a butyl group includes n-butyl, isobutyl, sec-butyl, and tert-butyl groups.

In the above formula, R ¹⁰ to R ¹³ have the same definitions as those described in formula (1-2) above, and R ¹⁴ each independently represents a linear, branched or cyclic alkyl 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, or a ^thiol group;

Examples of R ¹⁴ include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, triacontyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, cycloundecyl group, cyclododecyl group, cyclotriacontyl group, norbornyl group, adamantyl group, phenyl group, naphthyl group, Examples include anthracene group, heptacene group, vinyl group, allyl group, triacontenyl group, methoxy group, ethoxy group, triacontoxy group, fluorine atom, chlorine atom, bromine atom, iodine atom and thiol group.

Each example of R ¹⁴ above includes isomers. For example, a butyl group includes n-butyl, isobutyl, sec-butyl, and tert-butyl groups.

In the above formula, R ¹⁰ to R ¹³ have the same definitions as those described in formula (1-2) above, and R ¹⁴ each independently represents a linear, branched or cyclic alkyl 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, or a thiol group, and m ¹⁴ is an integer of 0 to 5.

Examples of R ¹⁴ include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, triacontyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, cycloundecyl group, cyclododecyl group, cyclotriacontyl group, norbornyl group, adamantyl group, phenyl group, naphthyl group, Examples include anthracene group, heptacene group, vinyl group, allyl group, triacontenyl group, methoxy group, ethoxy group, triacontoxy group, fluorine atom, chlorine atom, bromine atom, iodine atom and thiol group.

Each example of R ¹⁴ above includes isomers. For example, a butyl group includes n-butyl, isobutyl, sec-butyl, and tert-butyl groups.

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

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

From the viewpoint of raw material availability, the compound represented by formula (0) is more preferably the compounds listed below.

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

Among the compounds listed above, compounds having a dibenzoxanthene skeleton are preferable from the viewpoint of heat resistance.

Compounds represented by the above formula (0) further include compounds represented by the following formulas.

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

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 above formula (0) further include compounds represented by the following formula

In the above formula, R ¹⁰ to R ¹³ have the same definitions as those described in formula (1-2) above, and R ¹⁴ , R ¹⁵ , R ¹⁶ , m ¹⁴ and m ^14′ have the same definitions as those described in formula (1-2) above. is.

As an example of a method for producing a compound represented by formula (0), a method for producing a compound represented by formula (1) and a method for producing a compound represented by formula (2) will be described below.

[Method for producing compound represented by formula (1)]
The compound represented by formula (1) in the present embodiment can be appropriately synthesized by applying a known technique, and the synthesis technique is not particularly limited.
For example, under normal pressure, biphenols, binaphthols or bianthracenol and corresponding aldehydes or ketones are polycondensed under an acid catalyst to obtain a polyphenol compound, followed by at least one of the polyphenol compounds. It can be obtained by introducing a hydroxyalkyl group into one phenolic hydroxyl group and introducing one group selected from an allyl group, an acryl group or a methacryl group into the hydroxy group. Also, if necessary, it can be carried out under pressure.

The timing for introducing the hydroxyalkyl group may be before the condensation reaction, as well as after the condensation reaction between the binaphthols and the aldehydes or ketones. Alternatively, it may be introduced after the production of the resin, which will be described later.
The timing of introducing one group selected from an allyl group, an acryl group, or a methacrylic group may be after the introduction of the hydroxyalkyl group, and the pre-stage or post-stage of the condensation reaction or production of the resin described later may be performed. May be introduced later.

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

Examples of the binaphthols include, but are not limited to, binaphthol, methylbinaphthol, methoxybinaphthol, and the like. These can be used individually by 1 type or in combination of 2 or more types. Among these, it is more preferable to use binaphthol from the viewpoint 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, ethylbenzaldehyde, butylbenzaldehyde, biphenylaldehyde, Naphthaldehyde, anthracenecarbaldehyde, phenanthrenecarbaldehyde, pyrenecarbaldehyde, furfural and the like can be mentioned, but are not particularly limited to these. These can be used individually by 1 type or in combination of 2 or more types. Among these, from the viewpoint of imparting high heat resistance, benzaldehyde, phenylacetaldehyde, phenylpropylaldehyde, hydroxybenzaldehyde, chlorobenzaldehyde, nitrobenzaldehyde, methylbenzaldehyde, ethylbenzaldehyde, butylbenzaldehyde, cyclohexylbenzaldehyde, biphenylaldehyde, naphthaldehyde, anthracene It is preferable to use carbaldehyde, phenanthrenecarbaldehyde, pyrenecarbaldehyde, furfural, and from the viewpoint of improving etching resistance, benzaldehyde, hydroxybenzaldehyde, chlorobenzaldehyde, nitrobenzaldehyde, methylbenzaldehyde, ethylbenzaldehyde, butylbenzaldehyde, cyclohexylbenzaldehyde, biphenyl Aldehyde, naphthaldehyde, anthracenecarbaldehyde, phenanthrenecarbaldehyde, pyrenecarbaldehyde and furfural are more preferably used.

Examples of the ketones include acetone, methyl ethyl ketone, cyclobutanone, cyclopentanone, cyclohexanone, norbornanone, tricyclohexanone, tricyclodecanone, adamantanone, fluorenone, benzofluorenone, acenaphthenequinone, acenaphthenone, anthraquinone, acetophenone, and diacetylbenzene. , triacetylbenzene, acetonaphthone, diphenylcarbonylnaphthalene, phenylcarbonylbiphenyl, diphenylcarbonylbiphenyl, benzophenone, diphenylcarbonylbenzene, triphenylcarbonylbenzene, benzonaphthone, diphenylcarbonylnaphthalene, phenylcarbonylbiphenyl, diphenylcarbonylbiphenyl and the like. is not particularly limited to These can be used individually by 1 type or in combination of 2 or more types. Among these, from the viewpoint of imparting high heat resistance, cyclopentanone, cyclohexanone, norbornanone, tricyclohexanone, tricyclodecanone, adamantanone, fluorenone, benzofluorenone, acenaphthenequinone, acenaphthenone, anthraquinone, acetophenone, diacetylbenzene, It is preferable to use triacetylbenzene, acetonaphthone, diphenylcarbonylnaphthalene, phenylcarbonylbiphenyl, diphenylcarbonylbiphenyl, benzophenone, diphenylcarbonylbenzene, triphenylcarbonylbenzene, benzonaphthone, diphenylcarbonylnaphthalene, phenylcarbonylbiphenyl, diphenylcarbonylbiphenyl, and etching resistance. From the viewpoint of improving the More preferably, diphenylcarbonylbiphenyl is used.
As the aldehydes or ketones, it is preferable to use an aldehyde having an aromatic ring or a ketone having an aromatic group from the viewpoint of having both high heat resistance and high etching resistance.

The acid catalyst used in the above reaction is not particularly limited and can be appropriately selected from known catalysts. As such acid catalysts, inorganic acids and organic acids are widely known. For example, inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, and hydrofluoric acid; adipic acid, sebacic acid, citric acid, fumaric acid, maleic acid, formic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid, organic acids such as naphthalenedisulfonic acid; Lewis acids such as zinc chloride, aluminum chloride, iron chloride and boron trifluoride; solid acids such as silicotungstic acid, phosphotungstic acid, silicomolybdic acid and phosphomolybdic acid However, it is not particularly limited to these. Among these, organic acids and solid acids are preferred from the viewpoint of production, and hydrochloric acid or sulfuric acid is more preferred from the viewpoint of production such as availability and ease of handling. In addition, about an acid catalyst, it can be used individually by 1 type or in combination of 2 or more types. In addition, the amount of the acid catalyst used can be appropriately set according to the type of raw material and catalyst used, and the reaction conditions, etc., and is not particularly limited, but is 0.01 to 100 parts by mass with respect to 100 parts by mass of the reaction raw material. is preferably

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

In addition, the amount of these reaction solvents used can be appropriately set according to the types of raw materials and catalysts used, as well as the reaction conditions, etc., and is not particularly limited. A range is preferred. Furthermore, the reaction temperature in the above reaction can be appropriately selected according to the reactivity of the reaction raw materials, and is not particularly limited, but is usually in the range of 10 to 200°C.

In order to obtain a polyphenol compound, the higher the reaction temperature is, the more preferable it is. Specifically, the range of 60 to 200° C. is preferable. In addition, the reaction method can be appropriately selected from known methods and is not particularly limited. , binaphthols or bianthracenediol, aldehydes or ketones are added dropwise in the presence of a catalyst. After completion of the polycondensation reaction, isolation of the obtained compound can be carried out according to a conventional method, and is not particularly limited. For example, in order to remove unreacted raw materials, catalysts, etc. present in the system, a general method such as raising the temperature of the reactor to 130 to 230 ° C. and removing volatile matter at about 1 to 50 mmHg is adopted. Thus, the target compound can be isolated.

As preferable reaction conditions, 1 mol to excess of biphenols, binaphthols or bianthracenediol per 1 mol of aldehydes or ketones, and 0.001 to 1 mol of an acid catalyst are used, and at normal pressure, 50 For example, the reaction may be carried out at a temperature of up to 150° C. for about 20 minutes to 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 the reaction product, cooled to room temperature, filtered to separate, the obtained solid is filtered, dried, and then column chromatographed. By separating and purifying the by-products, the solvent is distilled off, filtered and dried to obtain the target compound represented by the above formula (1).

A method of introducing a hydroxyalkyl group into at least one phenolic hydroxyl group of a polyphenol compound and introducing an allyl, acryl or methacryl group into the hydroxy group is also known.
For example, a hydroxyalkyl group can be introduced into at least one phenolic hydroxyl group of the compound as follows.
A hydroxyalkyl group can also be introduced into a phenolic hydroxyl group via an oxyalkyl group, for example, a hydroxyalkyloxyalkyl group or a hydroxyalkyloxyalkyloxyalkyl group is introduced.
Compounds for introducing a hydroxyalkyl group can be synthesized by known methods or easily available, and examples include chloroethanol, bromoethanol, 2-chloroethyl acetate, 2-bromoethyl acetate, 2-iodoethyl acetate, ethylene oxide. , propylene oxide, butylene oxide, ethylene carbonate, propylene carbonate, and butylene carbonate, but are not particularly limited to these.

For example, the compound is dissolved or suspended in an aprotic solvent such as acetone, tetrahydrofuran (THF), propylene glycol monomethyl ether acetate and the like. Subsequently, metal alkoxide (alkoxide such as sodium methoxide, sodium ethoxide, potassium methoxide, potassium ethoxide or alkaline earth metal alkoxide, etc.), metal hydroxide (alkali metal such as sodium hydroxide, potassium hydroxide, etc.) or alkaline earth metal carbonates, etc.), alkali metal or alkaline earth hydrogen carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate, amines (e.g., tertiary amines (trialkylamines such as triethylamine, N, N - Aromatic tertiary amines such as dimethylaniline, heterocyclic tertiary amines such as 1-methylimidazole), etc., carboxylic acid metal salts (alkali metal acetates such as sodium acetate and calcium acetate, or alkaline earth metal salts, etc.) ) in the presence of a basic catalyst such as an organic base at normal pressure at 20 to 150° C. for 0.5 to 100 hours.The reaction solution is neutralized with an acid and added to distilled water to precipitate a white solid. , Wash the separated solid with distilled water, or evaporate the solvent to dryness, wash with distilled water if necessary, and dry to obtain a compound in which the hydrogen atom of the hydroxyl group is substituted with a hydroxyalkylene group. be able to.

When 2-chloroethyl acetate, 2-bromoethyl acetate, or 2-iodoethyl acetate is used, a hydroxyethyl group is introduced by deacylation after the introduction of an acetoxyethyl group.
When ethylene carbonate, propylene carbonate, or butylene carbonate is used, a hydroxyalkyl group is introduced by adding alkylene carbonate and causing a decarboxylation reaction.

An allyl, acryl or methacryl group can then be introduced to at least one hydroxy group of the compound, for example as follows. A method for introducing an allyl, acryl or methacryl group into a hydroxy group is also known.

Compounds for introducing an allyl, acrylic or methacrylic group can be synthesized by known methods or easily available. Examples include, but are not limited to, chloride.

First, the compound is dissolved or suspended in an aprotic solvent such as acetone, tetrahydrofuran (THF), propylene glycol monomethyl ether acetate and the like. Subsequently, in the presence of a base catalyst such as sodium hydroxide, potassium hydroxide, sodium methoxide, sodium ethoxide, etc., the mixture is reacted at normal pressure at 20 to 150° C. for 6 to 72 hours. After neutralizing the reaction solution with an acid and adding distilled water to precipitate a white solid, the separated solid is washed with distilled water, or the solvent is evaporated to dryness and, if necessary, washed with distilled water, By drying, a compound in which the hydrogen atom of the hydroxy group is substituted with an allyl, acryl or methacryl group can be obtained.

In this embodiment, groups substituted with allyl, acryl or methacryl groups react in the presence of radicals or acids/alkalis, and the solubility in acids, alkalis or organic solvents used in coating solvents and developers changes. do. The allyl-, acryl-, or methacryl-substituted group may have the property of undergoing a chain reaction in the presence of radicals or acids/alkalis in order to enable pattern formation with higher sensitivity and higher resolution. preferable.

[Resin obtained by using the compound represented by formula (1) as a monomer]
The compound represented by the formula (1) can be used as it is as a composition (hereinafter also simply referred to as "composition") used for forming films for lithography and optical parts. A resin obtained by using the compound represented by the formula (1) as a monomer can also be used as the composition. The resin is obtained, for example, by reacting the compound represented by the formula (1) with a compound having cross-linking reactivity.
Examples of the resin obtained by using the compound represented by the formula (1) as a monomer include those having a structure represented by the following formula (3). That is, the composition in this embodiment may contain a resin having a structure represented by the following formula (3).

In formula (3), L is an optionally substituted alkylene group having 1 to 30 carbon atoms, an arylene group having 6 to 30 carbon atoms which may be substituted, and a substituent an alkoxylylene group having 1 to 30 carbon atoms or a single bond, and the alkylene group, the arylene group, and the alkoxylylene group may contain an ether bond, a ketone bond, or an ester bond. Further, the alkylene group and alkoxylene group may be linear, branched or cyclic groups.
R ⁰ , R ¹ , R ² to R ⁵ , m ² and m ³ , m ⁴ and m ⁵ , p ² to p ⁵ and n are the same as defined in formula (1) above.
However, m ² , m ³ , m ⁴ and m ⁵ cannot be 0 at the same time, and at least one of R ² to R ⁵ has a hydroxyl hydrogen atom of an allyloxyalkyl group, acryloxyalkyl group or methacryloxyalkyl group. It is a group substituted with one group selected from groups.

[Method for producing a resin obtained by using a compound represented by formula (1) as a monomer]
The resin in this embodiment is obtained by reacting the compound represented by the above formula (1) with a compound having cross-linking reactivity. As the cross-linkable compound, known compounds can be used without particular limitation as long as they can oligomerize or polymerize the compound represented by the formula (1). Specific examples thereof include, but are not limited to, aldehydes, ketones, carboxylic acids, carboxylic acid halides, halogen-containing compounds, amino compounds, imino compounds, isocyanates, unsaturated hydrocarbon group-containing compounds, and the like.

Specific examples of the resin having the structure represented by the formula (3) include, for example, condensation reaction of the compound represented by the formula (1) with an aldehyde and/or ketone, which is a compound having cross-linking reactivity. and the like.

Examples of aldehydes used in novolac-forming the compound represented by formula (1) include formaldehyde, trioxane, paraformaldehyde, benzaldehyde, acetaldehyde, propylaldehyde, phenylacetaldehyde, phenylpropylaldehyde, hydroxybenzaldehyde, Examples include, but are not limited to, chlorobenzaldehyde, nitrobenzaldehyde, methylbenzaldehyde, ethylbenzaldehyde, butylbenzaldehyde, biphenylaldehyde, naphthaldehyde, anthracenecarbaldehyde, phenanthrenecarbaldehyde, pyrenecarbaldehyde, furfural and the like. Examples of ketones include the ketones described above. Among these, formaldehyde is more preferred. In addition, these aldehydes and/or ketones can be used individually by 1 type or in combination of 2 or more types. The amount of the aldehyde and/or ketone used is not particularly limited, but is preferably 0.2 to 5 mol, more preferably 1 mol of the compound represented by the formula (1). 0.5 to 2 mol.

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

In addition, the amount of the acid catalyst used can be appropriately set according to the type of raw material and catalyst used, and the reaction conditions, etc., and is not particularly limited, but is 0.01 to 100 parts by mass with respect to 100 parts by mass of the reaction raw material. is preferably However, indene, hydroxyindene, benzofuran, hydroxyanthracene, acenaphthylene, biphenyl, bisphenol, trisphenol, dicyclopentadiene, tetrahydroindene, 4-vinylcyclohexene, norbornadiene, 5-vinylnorborn-2-ene, α-pinene, β-pinene Aldehydes are not necessarily required in the case of a copolymerization reaction with a compound having a non-conjugated double bond such as limonene.

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

In addition, the amount of these solvents used can be appropriately set according to the types of raw materials and catalysts used, as well as the reaction conditions, etc., and is not particularly limited, but is in the range of 0 to 2000 parts by mass with respect to 100 parts by mass of the reaction raw material. is preferably Furthermore, the reaction temperature can be appropriately selected according to the reactivity of the reaction raw materials, and is not particularly limited, but is usually in the range of 10 to 200°C. In addition, the reaction method can be appropriately selected from known methods and is not particularly limited, but a method of charging the compound represented by the above formula (1), an aldehyde and/or ketones, and a catalyst all at once, A method of dropping the compound represented by the above formula (1), aldehyde and/or ketones in the presence of a catalyst can be mentioned.

After completion of the polycondensation reaction, isolation of the obtained compound can be carried out according to a conventional method, and is not particularly limited. For example, in order to remove unreacted raw materials, catalysts, etc. present in the system, a general method such as raising the temperature of the reactor to 130 to 230 ° C. and removing volatile matter at about 1 to 50 mmHg is adopted. As a result, the target 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. may Examples of copolymerizable phenols include phenol, cresol, dimethylphenol, trimethylphenol, butylphenol, phenylphenol, diphenylphenol, naphthylphenol, resorcinol, methylresorcinol, catechol, butylcatechol, methoxyphenol, methoxyphenol, Examples include, but are not limited to, propylphenol, pyrogallol, thymol, and the like.

Moreover, the resin having the structure represented by the formula (3) may be one obtained by copolymerizing with a polymerizable monomer other than the other phenols described above. Examples of such copolymerizable monomers include naphthol, methylnaphthol, methoxynaphthol, dihydroxynaphthalene, indene, hydroxyindene, benzofuran, hydroxyanthracene, acenaphthylene, biphenyl, bisphenol, trisphenol, dicyclopentadiene, tetrahydroindene, and 4-vinylcyclohexene. , norbornadiene, vinylnorbornaene, pinene, limonene and the like, but are not particularly limited thereto. The resin having the structure represented by the formula (3) is a binary or higher (for example, two to four) copolymer of the compound represented by the formula (1) and the above phenols. Even if the compound represented by the formula (1) and the copolymerization monomer described above are two or more (for example, two to quaternary) copolymers, the above formula (1) It may be a ternary or more (for example, ternary to quaternary) copolymer of the compound, the above-described phenols, and the above-described copolymerization monomer.

The molecular weight of the resin having the structure represented by the formula (3) is not particularly limited, but the polystyrene equivalent weight average molecular weight (Mw) is preferably 500 to 30,000, more preferably 750 to 20, 000. In addition, from the viewpoint of increasing the cross-linking efficiency and suppressing volatile components during baking, the resin having the structure represented by the formula (3) has a degree of dispersion (weight average molecular weight Mw/number average molecular weight Mn) of 1.2. It is preferably within the range of ~7. The above Mw and Mn can be determined by the method described in Examples below.

It is preferable that the resin having the structure represented by the formula (3) has high solubility in a solvent from the viewpoint of easier application of the wet process. More specifically, when using 1-methoxy-2-propanol (PGME) and/or propylene glycol monomethyl ether acetate (PGMEA) as a solvent, the solubility in the solvent is preferably 10% by 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 dissolves in 90 g of PGMEA, the solubility of the resin in PGMEA is "10% by mass or more", and when it does not dissolve, "less than 10% by mass".

[Compound represented by formula (2)]
Compound (0) in the present embodiment is preferably a compound represented by the following formula (2) from the viewpoint of heat resistance and solvent solubility.

In formula (2), R ^0A is 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 having 1 to 60 carbon atoms or a single bond;
Each R ^2A is independently an optionally substituted linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, or 6 to 30 carbon atoms which may be substituted. An aryl group, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, an alkoxy group having 1 to 30 carbon atoms which may have a substituent, a halogen atom, a nitro group, an amino group, carboxylic An acid group, a thiol group, a hydroxyl group, or a group in which a hydrogen atom of a hydroxyl group is substituted with one group selected from an allyloxyalkyl group, an acryloxyalkyl group, or a methacryloxyalkyl group, and the alkyl group, the aryl group, the The alkenyl group and the alkoxy group may contain an ether bond, a ketone bond or an ester bond, wherein at least one of R ^2A is an allyloxyalkyl group, an acryloxyalkyl group or a methacryloxy It includes a group substituted with one group selected from alkyl groups.
n ^A is an integer of 1 to 4, where in formula (2), when n ^A is an integer of 2 or more,
n ^A structural formulas in brackets [ ] may be the same or different.
Each X ^A independently represents an oxygen atom, a sulfur atom, or no cross-linking. Here, X ^A is preferably an oxygen atom or a sulfur atom, more preferably an oxygen atom, since it tends to exhibit excellent heat resistance. ^XA is preferably non-crosslinked from the viewpoint of solubility.
Each ^m2A is independently an integer of 0-6. provided that at least one ^m2A is an integer of 1-6.
q ^A is each 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, and a carbon An alkanepropyl group with a number of 2 to 60, and an alkanetetrayl group with a carbon number of 3 to 60 when n=4. Examples of the n-valent group include those having a linear hydrocarbon group, a branched hydrocarbon group, or an alicyclic hydrocarbon group. Here, the alicyclic hydrocarbon group also includes a bridged alicyclic hydrocarbon group. Further, the n-valent group may have an aromatic group having 6 to 60 carbon atoms.

In addition, 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 also includes a bridged alicyclic hydrocarbon group.

In addition, 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 also includes a bridged alicyclic hydrocarbon group.

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

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

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

Furthermore, since the aromatic density is high, the refractive index is high, and coloring is suppressed by heat treatment over a wide range from low temperature to high temperature, so it is also useful as a composition for forming various optical parts. Among them, a compound having quaternary carbon is preferable from the viewpoint of suppressing oxidative decomposition of the compound, suppressing coloration, and improving heat resistance and solvent solubility. As optical parts, in addition to film-shaped and sheet-shaped parts, plastic lenses (prism lenses, lenticular lenses, micro lenses, Fresnel lenses, viewing angle control lenses, contrast enhancement lenses, etc.), retardation films, electromagnetic shielding films, It is useful as a prism, an optical fiber, a solder resist for flexible printed wiring, a plating resist, an interlayer insulating film for multilayer printed wiring boards, and a photosensitive optical waveguide.

The compound represented by the above formula (2) is preferably a compound represented by the following formula (2-1) from the viewpoint of ease of cross-linking and solubility in organic solvents.

In formula (2-1), R ^0A , R ^1A , n ^A and q ^A and X ^A are the same as defined in formula (2) above.
R ^3A is an optionally substituted linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, an optionally substituted aryl group having 6 to 30 carbon atoms, a substituted an alkenyl group having 2 to 30 carbon atoms which may have a group, a halogen atom, a nitro group, an amino group, a carboxylic acid group, a thiol group, which may be the same or different in the same naphthalene ring or benzene ring; may
Each R ^4A is independently a hydrogen atom or one group selected from an allyloxyalkyl group, an acryloxyalkyl group or a methacryloxyalkyl group, wherein at least one of R ^4A is an allyloxyalkyl group, one group selected from an acryloxyalkyl group or a methacryloxyalkyl group,
Each ^m6A is independently an integer of 0-5.

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

In addition, the compound represented by the above formula (2-1) is preferably a compound represented by the following formula (2a) from the viewpoint of supply of raw materials.

In the above formula (2a), X ^A , R ^0A to R ^2A , m ^2A and n ^A have the same meanings as explained in the above formula (2).

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

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

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

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

From the viewpoint of solubility in further organic solvents, the compound represented by the above formula (2) has the following formulas (BisN-1) to (BisN-4), (XBisN-1) to (XBisN-3), ( Compounds represented by BiN-1) to (BiN-4) or (XBiN-1) to (XBiN-3) are particularly preferred.

[Method for producing compound represented by formula (2)]
The compound represented by Formula (2) in the present embodiment can be appropriately synthesized by applying a known technique, and the synthesis technique is not particularly limited.
For example, under normal pressure, phenols, naphthols and corresponding aldehydes or ketones are polycondensed under an acid catalyst to obtain a polyphenol compound, followed by at least one phenolic hydroxyl group of the polyphenol compound. can be obtained by introducing a hydroxyalkyl group into the hydroxy group and introducing one group selected from an allyl group, an acryl group or a methacryl group into the hydroxy group. Also, if necessary, it can be carried out under pressure.

The timing for introducing the hydroxyalkyl group may be not only after the condensation reaction of phenols, naphthols and aldehydes or ketones, but also before the condensation reaction. Alternatively, it may be introduced after the production of the resin, which will be described later.
The timing of introducing one group selected from an allyl group, an acryl group, or a methacrylic group may be after the introduction of the hydroxyalkyl group, and the pre-stage or post-stage of the condensation reaction or production of the resin described later may be performed. May be introduced later.

The naphthols are not particularly limited, and examples include naphthol, methylnaphthol, methoxynaphthol, naphthalenediol, etc. Among them, naphthalenediol is preferably used from the viewpoint that a xanthene structure can be easily formed. .

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

Examples of the aldehydes include formaldehyde, trioxane, paraformaldehyde, benzaldehyde, acetaldehyde, propylaldehyde, phenylacetaldehyde, phenylpropylaldehyde, hydroxybenzaldehyde, chlorobenzaldehyde, nitrobenzaldehyde, methylbenzaldehyde, ethylbenzaldehyde, butylbenzaldehyde, biphenylaldehyde, Naphthaldehyde, anthracenecarbaldehyde, phenanthrenecarbaldehyde, pyrenecarbaldehyde, furfural and the like can be mentioned, but are not particularly limited to these. These can be used individually by 1 type or in combination of 2 or more types. Among these, from the viewpoint of imparting high heat resistance, benzaldehyde, phenylacetaldehyde, phenylpropylaldehyde, hydroxybenzaldehyde, chlorobenzaldehyde, nitrobenzaldehyde, methylbenzaldehyde, ethylbenzaldehyde, butylbenzaldehyde, cyclohexylbenzaldehyde, biphenylaldehyde, naphthaldehyde, anthracene It is preferable to use carbaldehyde, phenanthrenecarbaldehyde, pyrenecarbaldehyde, furfural, and from the viewpoint of improving etching resistance, benzaldehyde, hydroxybenzaldehyde, chlorobenzaldehyde, nitrobenzaldehyde, methylbenzaldehyde, ethylbenzaldehyde, butylbenzaldehyde, cyclohexylbenzaldehyde, biphenyl Aldehyde, naphthaldehyde, anthracenecarbaldehyde, phenanthrenecarbaldehyde, pyrenecarbaldehyde and furfural are more preferably used.

Examples of the ketones include acetone, methyl ethyl ketone, cyclobutanone, cyclopentanone, cyclohexanone, norbornanone, tricyclohexanone, tricyclodecanone, adamantanone, fluorenone, benzofluorenone, acenaphthenequinone, acenaphthenone, anthraquinone, acetophenone, and diacetylbenzene. , triacetylbenzene, acetonaphthone, diphenylcarbonylnaphthalene, phenylcarbonylbiphenyl, diphenylcarbonylbiphenyl, benzophenone, diphenylcarbonylbenzene, triphenylcarbonylbenzene, benzonaphthone, diphenylcarbonylnaphthalene, phenylcarbonylbiphenyl, diphenylcarbonylbiphenyl and the like. is not particularly limited to These can be used individually by 1 type or in combination of 2 or more types. Among these, from the viewpoint of imparting high heat resistance, cyclopentanone, cyclohexanone, norbornanone, tricyclohexanone, tricyclodecanone, adamantanone, fluorenone, benzofluorenone, acenaphthenequinone, acenaphthenone, anthraquinone, acetophenone, diacetylbenzene, It is preferable to use triacetylbenzene, acetonaphthone, diphenylcarbonylnaphthalene, phenylcarbonylbiphenyl, diphenylcarbonylbiphenyl, benzophenone, diphenylcarbonylbenzene, triphenylcarbonylbenzene, benzonaphthone, diphenylcarbonylnaphthalene, phenylcarbonylbiphenyl, diphenylcarbonylbiphenyl, and etching resistance. From the viewpoint of improving the More preferably, diphenylcarbonylbiphenyl is used.
As the ketones, ketones having an aromatic ring are preferably used from the viewpoint of having both high heat resistance and high etching resistance.

The acid catalyst used in the above reaction is not particularly limited and can be appropriately selected from known catalysts. The acid catalyst can 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; acids, organic acids such as methanesulfonic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid, naphthalenedisulfonic acid; Lewis acids such as zinc chloride, aluminum chloride, iron chloride, boron trifluoride; Solid acids such as silicotungstic acid, phosphotungstic acid, silicomolybdic acid or phosphomolybdic acid can be mentioned. Among these, it is preferable to use hydrochloric acid or sulfuric acid from the viewpoint of production such as availability and ease of handling. About an acid catalyst, it can be used individually by 1 type or in combination of 2 or more types.

A reaction solvent may be used in the above reaction. The reaction solvent is not particularly limited as long as the reaction between the aldehydes or ketones used and the naphthols and the like proceeds. For example, water, methanol, ethanol, propanol, butanol, tetrahydrofuran, dioxane, or a mixed solvent thereof can be used. can be done. The amount of the reaction solvent is not particularly limited, and is, for example, in the range of 0 to 2000 parts by mass with respect to 100 parts by mass of the reaction raw material.

The reaction temperature is not particularly limited and can be appropriately selected according to the reactivity of the reaction raw materials, but is preferably in the range of 10 to 200°C. From the viewpoint of synthesizing the compound represented by formula (2) in the present embodiment with good selectivity, the temperature is preferably low, and more preferably in the range of 10 to 60°C.

The reaction method is not particularly limited, but examples thereof include a method of charging naphthols, aldehydes or ketones, and a catalyst all at once, and 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, etc. present in the system, the temperature of the reactor can be raised to 130 to 230° C., and volatile matter can be removed at about 1 to 50 mmHg. .

The amount of raw materials is not particularly limited, but for example, 2 mol to excess of naphthols or the like and 0.001 to 1 mol of an acid catalyst are used per 1 mol of aldehydes or ketones, and at normal pressure, 20 The reaction is preferably carried out at ~60°C for about 20 minutes to 100 hours.

After completion of the reaction, the desired product is isolated by a known method. The method for isolating the target product is not particularly limited. For example, the reaction solution is concentrated, pure water is added to precipitate the reaction product, cooled to room temperature, filtered and separated, and the resulting solid After filtering and drying the product, it is separated and purified from by-products by column chromatography, followed by distilling off the solvent, filtering and drying to isolate the target compound.

A method of introducing a hydroxyalkyl group into at least one phenolic hydroxyl group of a polyphenol compound and introducing an allyl, acryl or methacryl group into the hydroxy group is also known.
For example, a hydroxyalkyl group can be introduced into at least one phenolic hydroxyl group of the compound as follows.
A hydroxyalkyl group can also be introduced into a phenolic hydroxyl group via an oxyalkyl group. For example, hydroxyalkyloxyalkyl groups and hydroxyalkyloxyalkyloxyalkyl groups are introduced.
Compounds for introducing a hydroxyalkyl group can be synthesized by known methods or easily available, and examples include chloroethanol, bromoethanol, 2-chloroethyl acetate, 2-bromoethyl acetate, 2-iodoethyl acetate, ethylene oxide. , propylene oxide, butylene oxide, ethylene carbonate, propylene carbonate, and butylene carbonate, but are not particularly limited to these.

For example, the compound is dissolved or suspended in an aprotic solvent such as acetone, tetrahydrofuran (THF), propylene glycol monomethyl ether acetate and the like. Subsequently, metal alkoxide (alkoxide such as sodium methoxide, sodium ethoxide, potassium methoxide, potassium ethoxide or alkaline earth metal alkoxide, etc.), metal hydroxide (alkali metal such as sodium hydroxide, potassium hydroxide, etc.) or alkaline earth metal carbonates, etc.), alkali metal or alkaline earth hydrogen carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate, amines (e.g., tertiary amines (trialkylamines such as triethylamine, N, N - Aromatic tertiary amines such as dimethylaniline, heterocyclic tertiary amines such as 1-methylimidazole), etc., carboxylic acid metal salts (alkali metal acetates such as sodium acetate and calcium acetate, or alkaline earth metal salts, etc.) ) in the presence of a basic catalyst such as an organic base at normal pressure at 20 to 150° C. for 0.5 to 100 hours.The reaction solution is neutralized with an acid and added to distilled water to precipitate a white solid. , Wash the separated solid with distilled water, or evaporate the solvent to dryness, wash with distilled water if necessary, and dry to obtain a compound in which the hydrogen atom of the hydroxyl group is substituted with a hydroxyalkylene group. be able to.

When 2-chloroethyl acetate, 2-bromoethyl acetate, or 2-iodoethyl acetate is used, a hydroxyethyl group is introduced by deacylation after the introduction of an acetoxyethyl group.
When ethylene carbonate, propylene carbonate, or butylene carbonate is used, a hydroxyalkyl group is introduced by adding alkylene carbonate and causing a decarboxylation reaction.

An allyl, acryl or methacryl group can then be introduced to at least one hydroxy group of the compound, for example as follows. A method for introducing an allyl, acryl or methacryl group into the hydroxy group is also known.

Compounds for introducing an allyl, acrylic or methacrylic group can be synthesized by known methods or easily available. Examples include, but are not limited to, chloride.

First, the compound is dissolved or suspended in an aprotic solvent such as acetone, tetrahydrofuran (THF), propylene glycol monomethyl ether acetate and the like. Subsequently, in the presence of a base catalyst such as sodium hydroxide, potassium hydroxide, sodium methoxide, sodium ethoxide, etc., the mixture is reacted at normal pressure at 20 to 150° C. for 6 to 72 hours. After neutralizing the reaction solution with an acid and adding distilled water to precipitate a white solid, the separated solid is washed with distilled water, or the solvent is evaporated to dryness and, if necessary, washed with distilled water, By drying, a compound in which the hydrogen atom of the hydroxy group is substituted with an allyl, acryl or methacryl group can be obtained.

In this embodiment, groups substituted with allyl, acryl or methacryl groups react in the presence of radicals or acids/alkalis, and the solubility in acids, alkalis or organic solvents used in coating solvents and developers changes. do. The allyl-, acryl-, or methacryl-substituted group may have the property of undergoing a chain reaction in the presence of radicals or acids/alkalis in order to enable pattern formation with higher sensitivity and higher resolution. preferable.

[Resin obtained by using the compound represented by the formula (2) as a monomer]
The compound represented by the formula (2) can be used as it is as a film-forming composition for lithography or a composition used for forming optical parts. Also, a resin obtained by using the compound represented by the formula (2) as a monomer can be used as the composition. The resin is obtained, for example, by reacting the compound represented by the formula (2) with a compound having cross-linking 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 composition in this embodiment may contain a resin having a structure represented by the following formula (4).

In formula (4), L is an optionally substituted alkylene group having 1 to 30 carbon atoms, an arylene group having 6 to 30 carbon atoms which may be substituted, and a substituent an alkoxylylene group having 1 to 30 carbon atoms or a single bond, and the alkylene group, the arylene group, and the alkoxylylene group may contain an ether bond, a ketone bond, or an ester bond. Further, the alkylene group and alkoxylene group may be linear, branched or cyclic groups.
R ^0A , R ^1A , R ^2A , m ^2A , n ^A , q ^A and ^XA have the same definitions as in formula (2);
However, when n ^A is an integer of 2 or more, n ^A structural formulas in [ ] may be the same or different, at least one m ^2A is an integer of 1 to 6, and R ^2A contains a group in which a hydrogen atom of a hydroxyl group is substituted with one group selected from an allyloxyalkyl group, an acryloxyalkyl group or a methacryloxyalkyl group.

[Method for producing a resin obtained by using a compound represented by formula (2) as a monomer]
The resin in this embodiment is obtained by reacting the compound represented by the above formula (2) with a compound having cross-linking reactivity. As the cross-linkable compound, known compounds can be used without particular limitation as long as they can oligomerize or polymerize the compound represented by the formula (2). Specific examples thereof include, but are not limited to, aldehydes, ketones, carboxylic acids, carboxylic acid halides, halogen-containing compounds, amino compounds, imino compounds, isocyanates, unsaturated hydrocarbon group-containing compounds, and the like.

Specific examples of the resin having the structure represented by the formula (4) include, for example, condensation reaction of the compound represented by the formula (2) with an aldehyde and/or ketone, which is a compound having cross-linking reactivity. and the like.

Examples of aldehydes used in novolac-forming the compound represented by formula (2) include formaldehyde, trioxane, paraformaldehyde, benzaldehyde, acetaldehyde, propylaldehyde, phenylacetaldehyde, phenylpropylaldehyde, hydroxybenzaldehyde, Examples include, but are not limited to, chlorobenzaldehyde, nitrobenzaldehyde, methylbenzaldehyde, ethylbenzaldehyde, butylbenzaldehyde, biphenylaldehyde, naphthaldehyde, anthracenecarbaldehyde, phenanthrenecarbaldehyde, pyrenecarbaldehyde, furfural and the like. Examples of ketones include the ketones described above. Among these, formaldehyde is more preferred. In addition, these aldehydes and/or ketones can be used individually by 1 type or in combination of 2 or more types. The amount of the aldehyde and/or ketone used is not particularly limited, but it is preferably 0.2 to 5 mol, more preferably 1 mol of the compound represented by the above formula (2). 0.5 to 2 mol.

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

In addition, the amount of the acid catalyst used can be appropriately set according to the type of raw material and catalyst used, and the reaction conditions, etc., and is not particularly limited, but is 0.01 to 100 parts by mass with respect to 100 parts by mass of the reaction raw material. is preferably However, indene, hydroxyindene, benzofuran, hydroxyanthracene, acenaphthylene, biphenyl, bisphenol, trisphenol, dicyclopentadiene, tetrahydroindene, 4-vinylcyclohexene, norbornadiene, 5-vinylnorborn-2-ene, α-pinene, β-pinene Aldehydes are not necessarily required in the case of a copolymerization reaction with a compound having a non-conjugated double bond such as limonene.

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

In addition, the amount of these solvents used can be appropriately set according to the types of raw materials and catalysts used, as well as the reaction conditions, etc., and is not particularly limited, but is in the range of 0 to 2000 parts by mass with respect to 100 parts by mass of the reaction raw material. is preferably Furthermore, the reaction temperature can be appropriately selected according to the reactivity of the reaction raw materials, and is not particularly limited, but is usually in the range of 10 to 200°C. In addition, the reaction method can be appropriately selected from known methods and is not particularly limited, but a method of charging the compound represented by the above formula (2), an aldehyde and/or ketones, and a catalyst all at once, A method of dropping the compound represented by the above formula (2), aldehyde and/or ketones in the presence of a catalyst can be mentioned.

After completion of the polycondensation reaction, isolation of the obtained compound can be carried out according to a conventional method, and is not particularly limited. For example, in order to remove unreacted raw materials, catalysts, etc. present in the system, a general method such as raising the temperature of the reactor to 130 to 230 ° C. and removing volatile matter at about 1 to 50 mmHg is adopted. As a result, the target 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. may Examples of copolymerizable phenols include phenol, cresol, dimethylphenol, trimethylphenol, butylphenol, phenylphenol, diphenylphenol, naphthylphenol, resorcinol, methylresorcinol, catechol, butylcatechol, methoxyphenol, methoxyphenol, Examples include, but are not limited to, propylphenol, pyrogallol, thymol, and the like.

Moreover, the resin having the structure represented by the formula (4) may be one obtained by copolymerizing with a polymerizable monomer other than the other phenols described above. Examples of such copolymerizable monomers include naphthol, methylnaphthol, methoxynaphthol, dihydroxynaphthalene, indene, hydroxyindene, benzofuran, hydroxyanthracene, acenaphthylene, biphenyl, bisphenol, trisphenol, dicyclopentadiene, tetrahydroindene, and 4-vinylcyclohexene. , norbornadiene, vinylnorbornaene, pinene, limonene and the like, but are not particularly limited thereto. Incidentally, the resin having the structure represented by the formula (4) is a binary or higher (for example, 2 to 4) copolymer of the compound represented by the formula (2) and the phenols described above. Even if it is a two or more (for example, two to quaternary) copolymer of the compound represented by the formula (2) and the copolymerization monomer described above, the compound represented by the formula (2) It may be a ternary or more (for example, ternary to quaternary) copolymer of the compound, the above-described phenols, and the above-described copolymerization monomer.

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 750. 20,000. In addition, from the viewpoint of enhancing crosslinking efficiency and suppressing volatile components during baking, the resin having the structure represented by the formula (4) has a degree of dispersion (weight average molecular weight Mw/number average molecular weight Mn) of 1.2. It is preferably within the range of ~7. The above Mw and Mn can be determined by the method described in Examples below.

It is preferable that the resin having the structure represented by the formula (4) has high solubility in a solvent from the viewpoint of easier application of a wet process. More specifically, when using 1-methoxy-2-propanol (PGME) and/or propylene glycol monomethyl ether acetate (PGMEA) as a solvent, the solubility in the solvent is preferably 10% by 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 dissolves in 90 g of PGMEA, the solubility of the resin in PGMEA is "10% by mass or more", and when it does not dissolve, "less than 10% by mass".

[Method for Purifying Compound and/or Resin]
The method for purifying the compound and/or resin in the present embodiment includes the compound represented by the formula (1), the resin obtained by using the compound represented by the formula (1) as a monomer, and the compound represented by the formula (2). and a resin obtained by using the compound represented by the formula (2) as a monomer, a step of dissolving in a solvent to obtain a solution (S), and the obtained solution (S) a step of extracting impurities in the compound and/or the resin by contacting it with an acidic aqueous solution (first extraction step), wherein the solvent used in the step of obtaining the solution (S) is water and optionally Contains immiscible solvents.
In the first extraction step, the resin is 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 cross-linking reactivity. preferable. According to the purification method of the present embodiment, it is possible to reduce the contents of various metals that may be contained as impurities in the compound or resin having the specific structure described above.
More specifically, in the purification method of the present embodiment, the compound and/or the resin are dissolved in an organic solvent that is arbitrarily immiscible with water to obtain a solution (S), and the solution (S) is Extraction treatment can be performed by contacting with an acidic aqueous solution. As a result, after transferring the metal contained in the solution (S) to the aqueous phase, the organic phase and the aqueous phase are separated to obtain a compound and/or resin having a reduced metal content.

The compounds and/or resins used in the purification method of the present embodiment may be used alone or in combination of two or more. Further, the compounds and resins may contain various surfactants, various cross-linking agents, various acid generators, various stabilizers, and the like.

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

Specific examples of water-immiscible solvents include, but are not limited to, ethers such as diethyl ether and diisopropyl ether; esters such as ethyl acetate, n-butyl acetate and isoamyl acetate; methyl ethyl ketone and methyl isobutyl; Ketones such as ketone, ethyl isobutyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 2-pentanone; ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl glycol ether acetates such as ether acetate; aliphatic hydrocarbons such as n-hexane and n-heptane; aromatic hydrocarbons such as toluene and xylene; and halogenated hydrocarbons such as methylene chloride and chloroform. . Among these, toluene, 2-heptanone, cyclohexanone, cyclopentanone, methyl isobutyl ketone, propylene glycol monomethyl ether acetate, and ethyl acetate are preferable, methyl isobutyl ketone, ethyl acetate, cyclohexanone, propylene glycol monomethyl ether acetate are more preferable, and methyl Isobutyl ketone and ethyl acetate are more preferred. Methyl isobutyl ketone, ethyl acetate, etc. have relatively high saturation solubility in the above compounds and resins containing these compounds as constituents, and relatively low boiling points. It becomes possible to reduce the load in the process. Each of these solvents can be used alone, or two or more of them can be used in combination.

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 acidic aqueous solutions include, but are not limited to, mineral acid aqueous solutions obtained by dissolving mineral acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid in water; acetic acid, propionic acid, oxalic acid, malonic acid, succinic acid, and fumaric acid. , maleic acid, tartaric acid, citric acid, methanesulfonic acid, phenolsulfonic acid, p-toluenesulfonic acid, trifluoroacetic acid, and the like dissolved in water. These acidic aqueous solutions can be used alone or in combination of two or more. Among these acidic aqueous solutions, one or more mineral acid aqueous solutions selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid, or acetic acid, propionic acid, oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, It is preferably an aqueous solution of one or more organic acids selected from the group consisting of tartaric acid, citric acid, methanesulfonic acid, phenolsulfonic acid, p-toluenesulfonic acid and trifluoroacetic acid, sulfuric acid, nitric acid, acetic acid, oxalic acid, More preferred are aqueous solutions of carboxylic acids such as tartaric acid and citric acid, more preferred are aqueous solutions of sulfuric acid, oxalic acid, tartaric acid and citric acid, and even more preferred are aqueous solutions of oxalic acid. Polyvalent carboxylic acids such as oxalic acid, tartaric acid, and citric acid coordinate with metal ions to produce a chelating effect, and therefore tend to remove metals more effectively. Moreover, the water used here is preferably water with a low metal content, such as ion-exchanged water, in line with the purpose of the purification method of the present embodiment.

Although the pH of the acidic aqueous solution used in the purification method of the present embodiment is not particularly limited, it is preferable to adjust the acidity of the aqueous solution in consideration of the effects on the above compounds and resins. The pH of the acidic aqueous solution is usually about 0 to 5, preferably about 0 to 3.

The amount of the acidic aqueous solution 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 removing metals, and from the viewpoint of ensuring operability in consideration of the total liquid volume, use It is preferable to adjust the amount. From the above viewpoint, the amount of the acidic aqueous solution used is preferably 10 to 200% by mass, more preferably 20 to 100% by mass, relative to 100% by mass of the solution (S).

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

In the purification method of the present embodiment, the solution (S) preferably further contains an organic solvent arbitrarily miscible with water. When the solution (S) contains an organic solvent that is arbitrarily miscible with water, it is possible to increase the amount of the compound and/or resin to be charged, improve liquid separation, and perform purification with high pot efficiency. tends to be possible. The method of adding the organic solvent arbitrarily miscible with water is not particularly limited. Any method of adding after contact may be used. Among these, the method of adding to a solution containing an organic solvent in advance is preferable from the viewpoint of the workability of the operation and the ease of controlling the amount to be charged.

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

Specific examples of the organic solvent optionally miscible 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 glycol ethers such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), and propylene glycol monoethyl ether; mentioned. Among these, N-methylpyrrolidone, propylene glycol monomethyl ether and the like are preferred, and N-methylpyrrolidone and propylene glycol monomethyl ether are more preferred. Each of these solvents can be used alone, or two or more of them can be used in combination.

The temperature for the extraction treatment is usually 20 to 90°C, preferably 30 to 80°C. The extraction operation is performed, for example, by mixing well by stirring or the like, and then allowing the mixture to stand still. As a result, the metal content contained in the solution (S) migrates to the aqueous phase. In addition, this operation reduces the acidity of the solution, thereby suppressing deterioration of the compound and/or the resin.

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

In the purification method of the present embodiment, after the first extraction step, the solution phase containing the compound or the resin is further brought into contact with water to extract impurities in the compound or the resin (second extraction step). Specifically, for example, after performing the extraction treatment using an acidic aqueous solution, the solution phase containing the recovered compound and/or resin and solvent extracted from the aqueous solution is further subjected to extraction treatment with water. is preferred. This extraction treatment with water is not particularly limited, but can be carried out, for example, by mixing the solution phase and water well by stirring or the like, and then allowing the resulting mixed solution to stand still. Since the mixed solution after standing is separated into a solution phase containing a compound and/or resin and a solvent and an aqueous phase, the solution phase can be recovered by decantation or the like.

Moreover, the water used here is preferably water with a low metal content, such as ion-exchanged water, in line with the purpose of the present embodiment. The extraction process may be performed only once, but it is also effective to repeat the operations of mixing, standing, and separating multiple times. In the extraction process, conditions such as the ratio of both used, temperature, time, etc. are not particularly limited, but may be the same as in the case of the contact process with the acidic aqueous solution.

Water that may be mixed in the solution containing the compound and/or resin and solvent thus obtained can be easily removed by performing an operation such as distillation under reduced pressure. Moreover, if necessary, a solvent can be added to the solution to adjust the concentration of the compound and/or the resin to an arbitrary concentration.

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

[Film-forming composition for lithography]
The film-forming composition for lithography in this embodiment includes the compound represented by the formula (1), the resin obtained by using the compound represented by the formula (1) as a monomer, and the compound represented by the formula (2). , and one or more selected from the group consisting of resins obtained by using the compound represented by the formula (2) as a monomer.

[Film-forming composition for lithography for chemically amplified resist applications]
The film-forming composition for lithography for chemically amplified resist applications in the present embodiment (hereinafter also referred to as "resist composition") is the compound represented by the above formula (1), the compound represented by the above formula (1) One or more selected from the group consisting of a resin obtained by using a compound as a monomer, a compound represented by the above formula (2), and a resin obtained by using the compound represented by the above formula (2) as a resist base material. contains.

Moreover, the resist composition in the present embodiment preferably contains a solvent. Examples of the solvent include, but are not limited to, ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, and ethylene glycol mono-n-butyl ether acetate. ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether acetate, propylene glycol mono - propylene glycol monoalkyl ether acetates such as n-butyl ether acetate; propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether (PGME) and propylene glycol monoethyl ether; methyl lactate, ethyl lactate, n-propyl lactate, lactic acid n -Lactic acid esters such as butyl and n-amyl lactate; Carboxylic acid esters; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxy-2-methylpropionate, 3-methoxybutyl acetate, Other esters such as 3-methyl-3-methoxybutyl acetate, butyl 3-methoxy-3-methylpropionate, butyl 3-methoxy-3-methylbutyrate, methyl acetoacetate, methyl pyruvate, ethyl pyruvate; toluene , xylene and other aromatic hydrocarbons; 2-heptanone, 3-heptanone, 4-heptanone, cyclopentanone (CPN), cyclohexanone (CHN) and other ketones; N,N-dimethylformamide, N-methylacetamide, Examples include amides such as N,N-dimethylacetamide and N-methylpyrrolidone; lactones such as γ-lactone, but are not particularly 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, more preferably at least one selected from PGMEA, PGME, CHN, CPN, 2-heptanone, anisole, butyl acetate, ethyl propionate and ethyl lactate. seeds, and more preferably at least one 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. % by mass, more preferably 1 to 50% by mass solid component and 50 to 99% by mass solvent, more preferably 2 to 40% by mass solid component and 60 to 98% by mass solvent, particularly preferably solid 2-10% by weight of components and 90-98% by weight of solvent.

In the resist composition of the present embodiment, as another solid component, at least one selected from the group consisting of an acid generator (C), a cross-linking agent (G), an acid diffusion controller (E) and other components (F). may contain. In addition, in this specification, a "solid component" means components other than a solvent.

Here, known acid generators (C), cross-linking agents (G), acid diffusion controllers (E) and other components (F) can be used without particular limitation. /024778 are preferred.

[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 solid components (resist base material, acid generator (C), cross-linking agent (G ), acid diffusion control agent (E) and other components (F), and the like. It is preferably 55 to 90% by mass, more 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 within the above range, the resolution tends to be further improved and the line edge roughness (LER) tends to be further reduced.
In addition, when containing both a compound and resin as a resist base material, said content is the total amount of both components.

[Other components (F)]
In the resist composition of the present embodiment, other than the resist base material, the acid generator (C), the cross-linking agent (G), and the acid diffusion control agent (E) may optionally be added to the extent that the objects of the present invention are not hindered. As a component of, a dissolution accelerator, a dissolution control agent, a sensitizer, a surfactant, an organic carboxylic acid or a phosphorus oxo acid or a derivative thereof, a heat and/or photocuring catalyst, a polymerization inhibitor, a flame retardant, a filler, Coupling agents, thermosetting resins, photosetting resins, dyes, pigments, thickeners, lubricants, antifoaming agents, leveling agents, UV absorbers, surfactants, coloring agents, nonionic surfactants, etc. One or more additives can be added. In addition, in this specification, another component (F) may be called an arbitrary component (F).

In the resist composition of the present embodiment, a resist base material (hereinafter also referred to as "component (A)"), an acid generator (C), a cross-linking agent (G), an acid diffusion controller (E), optional components ( The content of F) (component (A)/acid generator (C)/crosslinking agent (G)/acid diffusion controller (E)/optional component (F)) is mass % based on solid matter,
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,
Especially preferred is 60-70/10-25/2-20/0.01-3/0.
The blending ratio of each component is selected from each range so that the sum total is 100% by mass. When the blending ratio of each component is within the above range, performances such as sensitivity, resolution and developability tend to be excellent.

The resist composition of the present embodiment is usually prepared by dissolving each component in a solvent to form a uniform solution at the time of use, and then, if necessary, filtering through a filter having a pore size of about 0.2 μm. be.

The resist composition of the present embodiment can contain resins other than the resin of the present embodiment within a range that does not impede the object of the present invention. Other resins are not particularly limited. Polymers containing or derivatives thereof may be mentioned. The content of other resins is not particularly limited and is appropriately adjusted according to the type of component (A) used, but is preferably 30 parts by mass or less with respect to 100 parts by mass of component (A). , more preferably 10 parts by mass or less, still more preferably 5 parts by mass or less, and particularly preferably 0 parts by mass.

[Physical properties of resist composition]
An amorphous film can be formed by spin coating using the resist composition of the present embodiment. Moreover, the resist composition of the present embodiment can be applied to general semiconductor manufacturing processes. Depending on the compound represented by the formula (1) and/or formula (2), the type of resin obtained by using these as monomers, and/or the type of developer used, either a positive resist pattern or a negative resist pattern is formed. can be made separately.

In the case of a 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° C. is preferably 5 Å/sec or less, and preferably 0.05 to 5 Å/sec. It is more preferably 0.0005 to 5 Å/sec, more preferably 0.0005 to 5 Å/sec. If the dissolution rate is 5 Å/sec or less, it tends to be insoluble in a developer and easy to form into a resist. Moreover, when the dissolution rate is 0.0005 Å/sec or more, the resolution may be improved. This is due to changes in the solubility of the compounds represented by the above formulas (1) and (2) and/or the resin containing the compound as a component before and after exposure to light. It is presumed that this is because the contrast at the interface with the undissolved unexposed portion increases. In addition, effects of reducing LER and reducing defects are also observed.

In the case of a negative resist pattern, the dissolution rate in a developer at 23° C. of an amorphous film formed by spin-coating the resist composition of this embodiment is preferably 10 Å/sec or more. When the dissolution rate is 10 Å/sec or more, it is easily soluble in a developer and is suitable for resist. Also, when the dissolution rate is 10 Å/sec or more, the resolution may be improved. This is presumed to be due to the fact that the compounds represented by formulas (1) and (2) above and/or the microscopic surface sites of the resin containing the compounds as constituents are dissolved to reduce the LER. In addition, an effect of reducing defects is also observed.

The dissolution rate can be determined by immersing an amorphous film in a developer at 23° C. for a predetermined time, and measuring the film thickness before and after the immersion visually, by an ellipsometer, QCM method, or other known method.

In the case of a positive resist pattern, the portion of the amorphous film formed by spin coating the resist composition of the present embodiment exposed to radiation such as KrF excimer laser, extreme ultraviolet ray, electron beam or X-ray is exposed to a developer at 23 ° C. The dissolution rate is preferably 10 Å/sec or more. When the dissolution rate is 10 Å/sec or more, it is easily soluble in a developer and is suitable for resist. Also, when the dissolution rate is 10 Å/sec or more, the resolution may be improved. This is presumed to be due to the fact that the compounds represented by formulas (1) and (2) above and/or the microscopic surface sites of the resin containing the compounds as constituents are dissolved to reduce the LER. In addition, an effect of reducing defects is also observed.

In the case of a negative resist pattern, the portion of the amorphous film formed by spin-coating the resist composition of the present embodiment exposed to radiation such as KrF excimer laser, extreme ultraviolet ray, electron beam or X-ray is exposed to a developer at 23 ° C. The dissolution rate is preferably 5 Å/sec or less, more preferably 0.05 to 5 Å/sec, even more preferably 0.0005 to 5 Å/sec. If the dissolution rate is 5 Å/sec or less, it tends to be insoluble in a developer and easy to form into a resist. Also, when the dissolution rate is 0.0005 Å/sec or more, the resolution may be improved. This is due to changes in the solubility of the compounds represented by the above formulas (1) and (2) and/or the resin containing the compound as a constituent before and after exposure to light, causing the unexposed portion to dissolve in the developer and the developer to It is presumed that this is because the contrast at the interface with the exposed portion that does not dissolve in the ions increases. In addition, effects of reducing LER and reducing defects are also observed.

[Film-forming composition for lithography for non-chemically amplified resist applications]
The component (A) to be contained in the film-forming composition for lithography for non-chemically amplified resist applications of the present embodiment (hereinafter also referred to as "radiation-sensitive composition") is a diazonaphthoquinone photoactive compound (B), which will be described later. and is irradiated with g-line, h-line, i-line, KrF excimer laser, ArF excimer laser, extreme ultraviolet ray, electron beam or X-ray to become a compound readily soluble in a developer. is useful as The properties of component (A) do not change significantly when exposed to g-line, h-line, i-line, KrF excimer laser, ArF excimer laser, extreme ultraviolet rays, electron beams, or X-rays, but diazonaphthoquinone, which is sparingly soluble in a developer, is photoactive. Since the compound (B) changes into a readily soluble compound, it becomes possible to form a resist pattern by the development process.

Since the component (A) contained in the radiation-sensitive composition of this embodiment is a compound with a relatively low molecular weight, the resulting resist pattern has very little roughness. In formula (1), at least one selected from the group consisting of R ⁰ to R ⁵ is preferably a group containing an iodine atom, and in formula (2), R ^0A , R ^1A and At least one selected from the group consisting of R ^2A is preferably a group containing an iodine atom. When the component (A) having a group containing an iodine atom is applied to the radiation-sensitive composition of the present embodiment, the ability to absorb radiation such as electron beams, extreme ultraviolet rays (EUV), and X-rays is increased, and as a result, , is preferable because it is possible to increase the sensitivity.

The glass transition temperature of component (A) contained in the radiation-sensitive composition of the present embodiment is preferably 100°C or higher, more preferably 120°C or higher, still more preferably 140°C or higher, and particularly preferably 150°C or higher. . Although the upper limit of the glass transition temperature of component (A) is not particularly limited, it is, for example, 400°C. When the glass transition temperature of the component (A) is within the above range, it tends to have heat resistance capable of maintaining the pattern shape in the semiconductor lithography process and improve performance such as high resolution.

The amount of heat generated by crystallization of the component (A) contained in the radiation-sensitive composition of the present embodiment, determined by differential scanning calorimetric analysis of the glass transition temperature, is preferably less than 20 J/g. In addition, (crystallization temperature) - (glass transition temperature) is preferably 70°C or higher, more preferably 80°C or higher, still more preferably 100°C or higher, and particularly preferably 130°C or higher. When the heat value of crystallization is less than 20 J/g, or (crystallization temperature) - (glass transition temperature) is within the above range, an amorphous film can be easily formed by spin-coating the radiation-sensitive composition, and the resist It tends to be possible to maintain the film formability necessary for the above for a long period of time and to improve the resolution.

In the present embodiment, the crystallization heat value, crystallization temperature and glass transition temperature can be determined by differential scanning calorimetry using DSC/TA-50WS manufactured by Shimadzu Corporation. About 10 mg of a sample is placed in an aluminum unsealed container and heated to the melting point or higher at a heating rate of 20° C./min in a nitrogen gas stream (50 mL/min). After quenching, the temperature is again raised to the melting point or higher at a heating rate of 20° C./min in a nitrogen gas stream (30 mL/min). After further rapid cooling, the temperature is again raised to 400° C. in a nitrogen gas stream (30 mL/min) at a heating rate of 20° C./min. The glass transition temperature (Tg) is defined as the temperature at the midpoint of the stepped change in the baseline (where the specific heat is halved), and the temperature of the exothermic peak that appears after that is defined as the crystallization temperature. The calorific value is obtained from the area of the region surrounded by the exothermic peak and the baseline, and is defined as the crystallization calorific value.

Component (A) to be contained in the radiation-sensitive composition of the present embodiment has a temperature of 100° C. or less, preferably 120° C. or less, more preferably 130° C. or less, even more preferably 140° C. or less, and particularly preferably 150° C. or less under normal pressure. WHEREIN: It is preferable that sublimability is low. Low sublimability means that the weight loss when held at a predetermined temperature for 10 minutes in thermogravimetric analysis is 10% or less, preferably 5% or less, more preferably 3% or less, further preferably 1% or less, and particularly preferably 1% or less. indicates that it is 0.1% or less. Due to the low sublimability, it is possible to prevent contamination of the exposure apparatus due to outgassing during exposure. Also, a good pattern shape with low roughness can be obtained.

Component (A) to be contained in the radiation-sensitive composition of the present embodiment includes propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone (CHN), cyclopentanone (CPN), and 2-heptanone. , anisole, butyl acetate, ethyl propionate and ethyl lactate, and in a solvent exhibiting the highest solubility for component (A) at 23° C., preferably 1% by mass or more, more preferably dissolves in an amount of 5% by mass or more, more preferably 10% by mass or more. Particularly preferably, it is selected from the group consisting of PGMEA, PGME, and CHN, and (A) a solvent exhibiting the highest dissolving ability for the resist substrate at 23 ° C., 20% by mass or more, particularly preferably PGMEA On the other hand, at 23° C., it dissolves in an amount of 20% by mass or more. Satisfying the above conditions facilitates use in semiconductor manufacturing processes in actual production.

[Diazonaphthoquinone photoactive compound (B)]
The diazonaphthoquinone photoactive compound (B) to be contained in the radiation-sensitive composition of the present embodiment is a diazonaphthoquinone substance including polymeric and non-polymeric diazonaphthoquinone photoactive compounds, and is generally used in positive resist compositions. As long as it is used as a photosensitive component (photosensitizer), one or more of them can be arbitrarily selected and used without any particular limitation.

Component (B) includes compounds obtained by reacting naphthoquinonediazide sulfonyl chloride, benzoquinonediazide sulfonyl chloride, etc. with a low-molecular-weight compound or high-molecular-weight compound having a functional group capable of condensation reaction with these acid chlorides. preferable. Here, the functional group capable of condensing with the acid chloride is not particularly limited, and examples thereof include a hydroxyl group and an amino group, with the hydroxyl group being particularly preferred. The compound that can be condensed with an acid chloride containing a hydroxyl group is not particularly limited, and examples thereof include hydroquinone, resorcinol, 2,4-dihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, and 2,4,6-trihydroxybenzophenone. , 2,4,4′-trihydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 2,2′,4,4′-tetrahydroxybenzophenone, 2,2′,3,4,6′ - hydroxybenzophenones such as pentahydroxybenzophenone; hydroxyphenylalkanes such as bis(2,4-dihydroxyphenyl)methane, bis(2,3,4-trihydroxyphenyl)methane and bis(2,4-dihydroxyphenyl)propane 4,4′,3″,4″-tetrahydroxy-3,5,3′,5′-tetramethyltriphenylmethane, 4,4′,2″,3″,4″-pentahydroxy-3 , 5,3′,5′-tetramethyltriphenylmethane and other hydroxytriphenylmethanes.
Further, as acid chlorides such as naphthoquinonediazide sulfonyl chloride and benzoquinonediazide sulfonyl chloride, for example, 1,2-naphthoquinonediazide-5-sulfonyl chloride, 1,2-naphthoquinonediazide-4-sulfonyl chloride and the like are preferable. mentioned.

The radiation-sensitive composition of the present embodiment is prepared, for example, by dissolving each component in a solvent at the time of use to form a uniform solution, and then, if necessary, filtering through a filter having a pore size of about 0.2 μm. preferably.

[Characteristics of Radiation-Sensitive Composition]
An amorphous film can be formed by spin coating using the radiation-sensitive composition of the present embodiment. Moreover, the radiation-sensitive composition of the present embodiment can be applied to general semiconductor manufacturing processes. Either a positive resist pattern or a negative resist pattern can be produced depending on the type of developer used.

In the case of a positive resist pattern, the dissolution rate of the amorphous film formed by spin-coating the radiation-sensitive composition of the present embodiment in a developer at 23° C. is preferably 5 Å/sec or less, and is preferably 0.05 to 0.05 Å/sec. It is more preferably 5 Å/sec, and even more preferably 0.0005 to 5 Å/sec. If the dissolution rate is 5 Å/sec or less, it tends to be insoluble in a developer and easy to form into a resist. Moreover, when the dissolution rate is 0.0005 Å/sec or more, the resolution may be improved. This is due to changes in the solubility of the compounds represented by the above formulas (1) and (2) and/or the resin containing the compound as a component before and after exposure to light. It is presumed that this is because the contrast at the interface with the undissolved unexposed portion increases. In addition, effects of reducing LER and reducing defects are also observed.

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 in a developer at 23° C. is preferably 10 Å/sec or more. When the dissolution rate is 10 Å/sec or more, it is easily soluble in a developer and is suitable for a resist. Also, when the dissolution rate is 10 Å/sec or more, the resolution may be improved. This is presumed to be due to the fact that the compounds represented by formulas (1) and (2) above and/or the microscopic surface sites of the resin containing the compounds as constituents are dissolved to reduce the LER. In addition, an effect of reducing defects is also observed.

The dissolution rate can be determined by immersing an amorphous film in a developer at 23° C. for a predetermined period of time and measuring the film thickness before and after the immersion by visual observation, an ellipsometer, a QCM method, or other known methods. .

In the case of a positive resist pattern, the amorphous film formed by spin-coating the radiation-sensitive composition of the present embodiment is irradiated with radiation such as KrF excimer laser, extreme ultraviolet rays, electron beams or X-rays, or after 20 to The dissolution rate of the exposed portion after heating at 500° C. in the developer at 23° C. is preferably 10 Å/sec or more, more preferably 10 to 10000 Å/sec, and even more preferably 100 to 1000 Å/sec. When the dissolution rate is 10 Å/sec or more, it is easily soluble in a developer and is suitable for resist. Also, when the dissolution rate is 10000 Å/sec or less, the resolution may be improved. This is presumed to be due to the fact that the compounds represented by formulas (1) and (2) above and/or the microscopic surface sites of the resin containing the compounds as constituents are dissolved to reduce the LER. In addition, an effect of reducing defects is also observed.

In the case of a negative resist pattern, the amorphous film formed by spin-coating the radiation-sensitive composition of the present embodiment is irradiated with radiation such as KrF excimer laser, extreme ultraviolet rays, electron beams or X-rays, or after 20 to The dissolution rate in the developer at 23° C. of the exposed portion after heating at 500° C. is preferably 5 Å/sec or less, more preferably 0.05 to 5 Å/sec, more preferably 0.0005 to 0.0005. More preferably, it is 5 Å/sec. If the dissolution rate is 5 Å/sec or less, it tends to be insoluble in a developer and easy to form into a resist. Also, when the dissolution rate is 0.0005 Å/sec or more, the resolution may be improved. This is due to changes in the solubility of the compounds represented by the above formulas (1) and (2) and/or the resin containing the compound as a constituent before and after exposure to light, causing the unexposed portion to dissolve in the developer and the developer to It is presumed that this is because the contrast at the interface with the exposed portion that does not dissolve in the ions increases. In addition, effects of reducing LER and reducing defects are also observed.

[Ratio of each component]
In the radiation-sensitive composition of the present embodiment, the content of component (A) is the total weight of solid components (component (A), diazonaphthoquinone photoactive compound (B) and other components (D), etc., which are optionally used). is preferably 1 to 99% by mass, more preferably 5 to 95% by mass, still more preferably 10 to 90% by mass, and particularly preferably 25 to 75% by mass, based on the total amount of solid components that are used, the same applies hereinafter). %. When the content of the component (A) is within the above range, the radiation-sensitive composition of the present embodiment tends to be able to obtain a pattern with high sensitivity and low roughness.

In the radiation-sensitive composition of the present embodiment, the content of the diazonaphthoquinone photoactive compound (B) is the total weight of solid components (component (A), diazonaphthoquinone photoactive compound (B) and other components (D), etc.). The sum of optionally used solid components, hereinafter the same), preferably 1 to 99% by mass, more preferably 5 to 95% by mass, still more preferably 10 to 90% by mass, particularly preferably 25 to 75% by mass. When the content of the diazonaphthoquinone photoactive compound (B) is within the above range, the radiation-sensitive composition of the present embodiment tends to be able to obtain a pattern with high sensitivity and low roughness.

[Other components (D)]
The radiation-sensitive composition of the present embodiment may optionally contain an acid generator and a cross-linking component as components other than the component (A) and the diazonaphthoquinone photoactive compound (B), as long as the objects of the present invention are not hindered. agent, acid diffusion controller, dissolution accelerator, dissolution controller, sensitizer, surfactant, organic carboxylic acid or phosphorus oxoacid or derivative thereof, heat and/or photocuring catalyst, polymerization inhibitor, flame retardant, Fillers, coupling agents, thermosetting resins, photosetting resins, dyes, pigments, thickeners, lubricants, antifoaming agents, leveling agents, UV absorbers, surfactants, coloring agents, nonionic surfactants 1 type or 2 types or more of various additives can be added. In addition, in this specification, another component (D) may be called an arbitrary component (D).

In the radiation-sensitive composition of the present embodiment, the blending ratio of each component (component (A)/diazonaphthoquinone photoactive compound (B)/optional component (D)) is mass % based on solid components,
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,
Even more preferably 20 to 80/80 to 20/0 to 5,
Especially preferred is 25-75/75-25/0.
The blending ratio of each component is selected from each range so that the sum total is 100% by mass. When the mixing ratio of each component of the radiation-sensitive composition of the present embodiment is within the above range, the composition tends to be excellent in performance such as sensitivity and resolution in addition to roughness.

The radiation-sensitive composition of the present embodiment may contain other resins as long as the object of the present invention is not impaired. Such other resins include novolak resins, polyvinylphenols, polyacrylic acid, polyvinyl alcohol, styrene-maleic anhydride resins, and polymers containing acrylic acid, vinyl alcohol, or vinylphenol as monomer units, or Derivatives of these and the like are included. The blending amount of these resins is appropriately adjusted according to the type of component (A) used, but it is preferably 30 parts by mass or less, more preferably 10 parts by mass per 100 parts by mass of component (A). It is not more than 5 parts by mass, more preferably not more than 5 parts by mass, and particularly preferably 0 part by mass.

[Method of forming a resist pattern]
The method for forming a resist pattern in the present embodiment comprises forming a photoresist layer on a substrate using the resist composition or the radiation-sensitive composition of the present embodiment described above, and then applying radiation to a predetermined region of the photoresist layer. and developing.
More specifically, a step of forming a resist film on a substrate using the resist composition or radiation-sensitive composition of the present embodiment described above, a step of exposing the formed resist film, and a step of developing the resist film. and forming a resist pattern. The resist pattern in this embodiment can also be formed as an upper layer resist in a multilayer process.

The method for forming the resist pattern is not particularly limited, but includes, for example, the following methods. First, a resist film is formed by coating a conventionally known substrate with a resist composition or a radiation-sensitive composition by a coating means such as spin coating, casting coating, or roll coating. Conventionally known substrates are not particularly limited, and examples thereof include substrates for electronic components and substrates having predetermined wiring patterns formed thereon. More specifically, silicon wafers, metal substrates such as copper, chromium, iron, and aluminum substrates, glass substrates, and the like can be used. Materials for the wiring pattern include, for example, copper, aluminum, nickel, and gold. In addition, if necessary, an inorganic and/or organic film may be provided on the substrate. Inorganic films include inorganic antireflection coatings (inorganic BARC). Organic films include organic antireflection coatings (organic BARC). The substrate may be surface-treated with hexamethylenedisilazane or the like.

Next, if necessary, the substrate coated with the resist composition or radiation-sensitive composition is heated. The heating conditions vary depending on the composition of the resist composition or the radiation-sensitive composition, but are preferably 20 to 250°C, more preferably 20 to 150°C. Heating is preferable because it tends to improve the adhesion of the resist to the substrate. Then, the resist film is exposed to a desired pattern with radiation selected from the group consisting of visible light, ultraviolet light, excimer laser, electron beam, extreme ultraviolet (EUV), X-ray, and ion beam. 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 radiation irradiation. The heating conditions are preferably 20 to 250.degree. C., more preferably 20 to 150.degree.

Next, a predetermined resist pattern is formed by developing the exposed resist film with a developer. As the developer, the solubility parameter (SP value ), and polar solvents such as ketone-based solvents, ester-based solvents, alcohol-based solvents, amide-based solvents, ether-based solvents, hydrocarbon-based solvents, or alkaline aqueous solutions can be used.

Examples of ketone solvents include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, and methyl ethyl ketone. , methyl isobutyl ketone, acetylacetone, acetonyl acetone, ionone, diacetonyl alcohol, acetylcarbinol, acetophenone, methylnaphthyl ketone, isophorone, propylene carbonate and the like.

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

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

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

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

Examples of hydrocarbon solvents 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 solvents may be mixed, or a solvent other than the above or water may be mixed and used within the range of performance. However, from the viewpoint of sufficiently exhibiting the effects of the present invention, the water content of the developer as a whole is preferably less than 70% by mass, more preferably less than 50% by mass, and less than 30% by mass. More preferably, it is less than 10% by mass, and particularly preferably contains substantially no water. That is, the content of the organic solvent in the developer is preferably 30% by mass or more and 100% by mass or less, more preferably 50% by mass or more and 100% by mass or less, relative to the total amount of the developer. It is more preferably 90% by mass or more and 100% by mass or less, and particularly preferably 95% by mass or more and 100% by mass or less.

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

In particular, the developer is at least selected from ketone solvents, ester solvents, alcohol solvents, amide solvents and ether solvents from the viewpoint of improving the resist performance such as the resolution and roughness of the resist pattern. Developers containing one solvent are preferred.

The vapor pressure of the developer at 20° C. is preferably 5 kPa or less, more preferably 3 kPa or less, and even more preferably 2 kPa or less. When the vapor pressure of the developer is 5 kPa or less, evaporation of the developer on the substrate or in the developing cup is suppressed, temperature uniformity in the wafer surface is improved, and as a result, dimensional uniformity in the wafer surface is improved. tend to become

Examples of specific developers having a vapor pressure of 5 kPa or less at 20° C. include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 4-heptanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methyl Ketone solvents such as cyclohexanone, phenylacetone, and methyl isobutyl ketone; butyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropyl ester solvents such as pionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate; n-propyl alcohol, isopropyl alcohol, n-butyl Alcohol solvents such as alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, 4-methyl-2-pentanol, n-heptyl alcohol, n-octyl alcohol, n-decanol; ethylene glycol , diethylene glycol, triethylene glycol, etc.; ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methoxymethylbutanol, etc. glycol ether solvents; 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; Examples include aliphatic hydrocarbon solvents such as octane and decane.

Examples of specific developers having a vapor pressure of 2 kPa or less at 20° C. include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 4-heptanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methyl Ketone solvents such as cyclohexanone 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 Ester solvents such as -methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl lactate, butyl lactate, propyl lactate; n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl Alcohol solvents such as alcohol, 4-methyl-2-pentanol, n-heptyl alcohol, n-octyl alcohol, n-decanol; glycol solvents such as ethylene glycol, diethylene glycol and triethylene glycol; ethylene glycol monomethyl ether, propylene Glycol ether solvents such as glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methoxymethylbutanol; N-methyl-2-pyrrolidone, N,N-dimethyl Amide solvents such as acetamide and N,N-dimethylformamide, aromatic hydrocarbon solvents such as xylene; and aliphatic hydrocarbon solvents such as octane and decane.

An appropriate amount of surfactant can be added to the developer if necessary. Although the surfactant is not particularly limited, for example, ionic or nonionic fluorine-based and/or silicon-based surfactants can be used. Examples of these fluorine and/or silicon surfactants include, for example, JP-A-62-36663, JP-A-61-226746, JP-A-61-226745, and JP-A-62-170950. Publications, JP-A-63-34540, JP-A-7-230165, JP-A-8-62834, JP-A-9-54432, JP-A-9-5988, US Pat. No. 5,405,720 , Nos. 5,360,692, 5,529,881, 5,296,330, 5,436,098, 5,576,143, 5,294,511, and 5,824,451. Nonionic surfactants are preferred. Nonionic surfactants are not particularly limited, but fluorine-based surfactants or silicon-based surfactants are preferred.

The amount of surfactant used is generally 0.001 to 5% by mass, preferably 0.005 to 2% by mass, more preferably 0.01 to 0.5% by mass, relative to the total amount of the developer.

Examples of the developing method include a method of immersing the substrate in a tank filled with a developer for a certain period of time (dip method), and a method of developing by standing still for a certain period of time while the developer is heaped up on the surface of the substrate by surface tension (puddle method). method), a method in which the developer is sprayed onto the surface of the substrate (spray method), and a method in which the developer dispense nozzle continues to dispense the developer onto the substrate rotating at a constant speed while scanning the nozzle at a constant speed (dynamic dispense method). ) etc. can be applied. The time for pattern development is not particularly limited, but is preferably 10 to 90 seconds.

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

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

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

Here, the monohydric alcohol used in the rinse step after development includes linear, branched and cyclic monohydric alcohols, specifically 1-butanol, 2-butanol, 3-methyl- 1-butanol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 1-hexanol, 4-methyl-2-pentanol, 1-heptanol, 1-octanol, 2-hexanol, cyclopentanol, 2- Heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol and the like can be used, and 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, or may be used by mixing with an organic solvent other than the above.

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

The vapor pressure of the rinse used after development is preferably 0.05 kPa or more and 5 kPa or less, more preferably 0.1 kPa or more and 5 kPa or less, and 0.12 kPa or more and 3 kPa or less at 20°C. is more preferred. When the vapor pressure of the rinsing liquid is 0.05 kPa or more and 5 kPa or less, the temperature uniformity in the wafer surface is further improved, swelling caused by the permeation of the rinsing liquid is further suppressed, and the dimensional uniformity in the wafer surface is improved. characteristics tend to improve.

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

In the rinsing step, the developed wafer is washed with the rinsing liquid containing the organic solvent. The method of the cleaning treatment is not particularly limited, but for example, a method of continuously applying the rinse solution onto the substrate rotating at a constant speed (rotation coating method), or immersing the substrate in a tank filled with the rinse solution for a certain period of time. A method (dip method), a method of spraying a rinse solution onto the substrate surface (spray method), etc. can be applied. It is preferable to remove the rinsing liquid from the substrate.

A patterned wiring board is obtained by etching after forming a resist pattern. Etching can be carried out by known methods such as dry etching using plasma gas and wet etching with alkaline solution, cupric chloride solution, ferric chloride solution or the like.

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

Residual resist patterns after etching can be removed with an organic solvent. Examples of organic solvents 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 spray method. Also, the wiring board on which the resist pattern is formed may be a multilayer wiring board and may have a small-diameter through hole.

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

[Film-forming composition for lithography for underlayer film applications]
The film-forming composition for lithography for use as an underlayer film in the present embodiment (hereinafter also referred to as “underlayer film-forming material”) is a compound represented by the above formula (1), a compound represented by the above formula (1) as a monomer, , a compound represented by formula (2), and a resin obtained by using the compound represented by formula (2) as a monomer. In the present embodiment, the substance is preferably 1 to 100% by mass, more preferably 10 to 100% by mass, more preferably 50 to 100% by mass, in the underlayer film-forming material from the viewpoint of coatability and quality stability. %, and particularly preferably 100% by mass.

The underlayer film-forming material of the present embodiment can be applied to a wet process and has excellent heat resistance and etching resistance. Furthermore, since the above-described substances are used for the underlayer film forming material of the present embodiment, deterioration of the film during high-temperature baking is suppressed, and an underlayer film having excellent etching resistance to oxygen plasma etching or the like can be formed. . Furthermore, since the underlayer film-forming material of the present embodiment has excellent adhesion to the resist layer, an excellent resist pattern can be obtained. The underlayer film-forming material of the present embodiment may contain a known underlayer film-forming material for lithography, etc., as long as the effects of the present invention are not impaired.

[solvent]
The underlayer film-forming material in this embodiment may contain a solvent. As the solvent used for the underlayer film-forming material, any known solvent can be appropriately used as long as it dissolves at least the above-mentioned substances.

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

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

Although the content of the solvent is not particularly limited, it is preferably 100 to 10,000 parts by mass, based on 100 parts by mass of the lower layer film-forming material, from the viewpoint of solubility and film formation. It is more preferably 000 parts by mass, and even more preferably 200 to 1,000 parts by mass.

[Crosslinking agent]
From the viewpoint of suppressing intermixing, the underlayer film-forming material in the present embodiment may contain a cross-linking agent, if necessary. Although the cross-linking agent is not particularly limited, for example, those described in International Publication No. 2013/024779 can be used.

Specific examples of cross-linking agents that can be used in the present embodiment include phenol compounds, epoxy compounds, cyanate compounds, amino compounds, benzoxazine compounds, acrylate compounds, melamine compounds, guanamine compounds, glycoluril compounds, urea compounds, and isocyanates. compounds, azide compounds and the like, but are not particularly limited thereto. These cross-linking agents can be used singly or in combination of two or more. Among these, a benzoxazine compound, an epoxy compound, or a cyanate compound is preferred, and a benzoxazine compound is more preferred from the viewpoint of improving etching resistance.

A well-known thing can be used as said phenol compound. For example, phenols include, in addition to phenol, alkylphenols such as cresols and xylenols, polyhydric phenols such as hydroquinone, polycyclic phenols such as naphthols and naphthalene diols, and bisphenols such as bisphenol A and bisphenol F. and polyfunctional phenol compounds such as phenol novolak and phenol aralkyl resins. Among them, aralkyl-type phenolic resins are preferable from the viewpoint of heat resistance and solubility.

A known epoxy compound can be used as the epoxy compound, and is selected from those having two or more epoxy groups in one molecule. For example, bisphenol A, bisphenol F, 3,3′,5,5′-tetramethyl-bisphenol F, bisphenol S, fluorene bisphenol, 2,2′-biphenol, 3,3′,5,5′-tetramethyl- 4,4'-dihydroxybiphenol, resorcinol, epoxidized dihydric phenols such as naphthalene diols, tris-(4-hydroxyphenyl)methane, 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane , tris(2,3-epoxypropyl) isocyanurate, trimethylolmethane triglycidyl ether, trimethylolpropane triglycidyl ether, triethylolethane triglycidyl ether, phenol novolak, o-cresol novolak, and other trihydric or higher phenols Epoxidized products, epoxidized products of co-condensation resins of dicyclopentadiene and phenols, epoxidized products of phenol aralkyl resins synthesized from phenols and paraxylylene dichloride, etc., biphenyls synthesized from phenols and bischloromethylbiphenyl, etc. Examples include epoxidized aralkyl phenol resins and epoxidized naphthol aralkyl resins synthesized from naphthols and paraxylylene dichloride. These epoxy resins may be used alone or in combination of two or more. Among them, epoxy resins that are solid at room temperature, such as epoxy resins obtained from phenol aralkyl resins and biphenyl aralkyl resins, are preferred from the viewpoint of heat resistance and solubility.

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

Examples of the amino compounds include m-phenylenediamine, p-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylpropane, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 3 ,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3′-diaminodiphenyl sulfide, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(3-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]sulfone, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis [4-(3-aminophenoxy)phenyl]propane, 4,4′-bis(4-aminophenoxy)biphenyl, 4,4′-bis(3-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy) ) phenyl]ether, bis[4-(3-aminophenoxy)phenyl]ether, 9,9-bis(4-aminophenyl)fluorene, 9,9-bis(4-amino-3-chlorophenyl)fluorene, 9, 9-bis(4-amino-3-fluorophenyl)fluorene, O-tolidine, m-tolidine, 4,4'-diaminobenzanilide, 2,2'-bis(trifluoromethyl)-4,4'-diamino Examples include biphenyl, 4-aminophenyl-4-aminobenzoate, 2-(4-aminophenyl)-6-aminobenzoxazole and the like. Furthermore, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 3,3′-diaminodiphenyl sulfone, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(3-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]sulfone, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis [4-(3-aminophenoxy)phenyl]propane, 4,4′-bis(4-aminophenoxy)biphenyl, 4,4′-bis(3-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy) ) phenyl]ether, bis[4-(3-aminophenoxy)phenyl]ether and other aromatic amines, diaminocyclohexane, diaminodicyclohexylmethane, dimethyl-diaminodicyclohexylmethane, tetramethyl-diaminodicyclohexylmethane, diaminodicyclohexylpropane, diamino bicyclo[2.2.1]heptane, bis(aminomethyl)-bicyclo[2.2.1]heptane, 3(4),8(9)-bis(aminomethyl)tricyclo[5.2.1.02 ,6] Alicyclic amines such as decane, 1,3-bisaminomethylcyclohexane and isophoronediamine; aliphatic amines such as ethylenediamine, hexamethylenediamine, octamethylenediamine, decamethylenediamine, diethylenetriamine and triethylenetetramine; is mentioned.

Examples of the benzoxazine compounds include Pd-type benzoxazines obtained from bifunctional diamines and monofunctional phenols, Fa-type benzoxazines obtained from monofunctional diamines and bifunctional phenols, and the like. be done.

Specific examples of the melamine compound include hexamethylolmelamine, hexamethoxymethylmelamine, compounds in which 1 to 6 methylol groups of hexamethylolmelamine are methoxymethylated, or mixtures thereof, hexamethoxyethylmelamine, and hexaacyloxymethyl. Examples include compounds in which 1 to 6 methylol groups of melamine and hexamethylolmelamine are acyloxymethylated, or mixtures thereof.

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

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

Specific examples of the urea compound include tetramethylol urea, tetramethoxymethyl urea, compounds in which 1 to 4 methylol groups of tetramethylol urea are methoxymethylated, mixtures thereof, and tetramethoxyethyl urea.

Moreover, in the present embodiment, a cross-linking agent having at least one allyl group may be used from the viewpoint of improving the cross-linkability. Specific examples of cross-linking agents having at least one allyl group include 2,2-bis(3-allyl-4-hydroxyphenyl)propane, 1,1,1,3,3,3-hexafluoro-2,2 -bis(3-allyl-4-hydroxyphenyl)propane, bis(3-allyl-4-hydroxyphenyl)sulfone, bis(3-allyl-4-hydroxyphenyl)sulfide, bis(3-allyl-4-hydroxyphenyl) ) ether and other allylphenols, 2,2-bis(3-allyl-4-cyanatophenyl)propane, 1,1,1,3,3,3-hexafluoro-2,2-bis(3 -allyl-4-cyanatophenyl)propane, bis(3-allyl-4-cyanatophenyl)sulfone, bis(3-allyl-4-cyanatophenyl)sulfide, bis(3-allyl-4-cyanatophenyl) ) Allyl cyanates such as ether, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, triallyl isocyanurate, trimethylolpropane diallyl ether, pentaerythritol allyl ether, etc., but are limited to those exemplified. not a thing These may be used alone or as a mixture of two or more. Among these, 2,2-bis(3-allyl-4-hydroxyphenyl)propane, 1,1,1,3,3,3-hexafluoro-2,2-bis(3-allyl-4-hydroxyphenyl) ) Allylphenols such as propane, bis(3-allyl-4-hydroxyphenyl)sulfone, bis(3-allyl-4-hydroxyphenyl)sulfide, bis(3-allyl-4-hydroxyphenyl)ether are preferred. .

The content of the cross-linking agent in the underlayer 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, with respect to 100 parts by mass of the underlayer film-forming material. is more preferable, more preferably 10 to 40 parts by mass. By setting the content of the cross-linking agent within the above range, the occurrence of the mixing phenomenon with the resist layer tends to be suppressed, the antireflection effect is enhanced, and the film formability after cross-linking tends to be enhanced. .

[Crosslinking accelerator]
A cross-linking accelerator for promoting cross-linking and curing reaction can be used in the underlayer film-forming material of the present embodiment, if necessary.

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

Examples of the crosslinking accelerator include, but are not limited to, 1,8-diazabicyclo(5,4,0)undecene-7, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris(dimethylamino methyl)phenol, 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole, 2,4,5- Imidazoles such as triphenylimidazole, organic phosphines such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine and phenylphosphine, tetraphenylphosphonium/tetraphenylborate, tetraphenylphosphonium/ethyltriphenylborate, tetrabutyl Examples thereof include tetra-substituted phosphonium/tetra-substituted borate such as phosphonium/tetrabutyl borate, 2-ethyl-4-methylimidazole/tetraphenyl borate, and tetraphenyl boron salts such as N-methylmorpholine/tetraphenyl borate.

The amount of the cross-linking accelerator is usually preferably 0.1 to 10 parts by mass, and more preferably for ease of control and economic efficiency, when the entire underlayer film-forming material is 100 parts by mass. From the point of view, it is 0.1 to 5 parts by mass, more preferably 0.1 to 3 parts by mass.

[Radical polymerization initiator]
A radical polymerization initiator can be blended into the underlayer film-forming material of the present embodiment, if necessary. The radical polymerization initiator may be a photopolymerization initiator that initiates radical polymerization with light, or a thermal polymerization initiator that initiates radical polymerization with heat.

Such a radical polymerization initiator is not particularly limited, and conventionally used ones can be appropriately employed. For example, 1-hydroxycyclohexylphenyl ketone, benzyl dimethyl ketal, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2 -methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methylpropan-1-one, 2 ,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide and other ketone photoinitiators, methyl ethyl ketone peroxide, cyclohexanone peroxide, methylcyclohexanone peroxide, etc. oxide, methyl acetoacetate peroxide, acetyl acetate peroxide, 1,1-bis(t-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-hexylperoxy)-cyclohexane, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)-2-methylcyclohexane, 1,1-bis(t-butylperoxy) oxy)-cyclohexane, 1,1-bis(t-butylperoxy)cyclododecane, 1,1-bis(t-butylperoxy)butane, 2,2-bis(4,4-di-t-butylperoxy) oxycyclohexyl)propane, p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-hexyl hydroperoxide, t-butyl hydroperoxide oxide, α,α'-bis(t-butylperoxy)diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane, t-butylcumyl peroxide, Di-t-butyl peroxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexyne-3, isobutyryl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide oxide, lauroyl peroxide, stearoyl peroxide, succinic acid peroxide, m-toluoyl benzoyl peroxide, benzoyl peroxide, di-n-propyl peroxide -oxydicarbonate, diisopropylperoxydicarbonate, bis(4-t-butylcyclohexyl)peroxydicarbonate, di-2-ethoxyethylperoxydicarbonate, di-2-ethoxyhexylperoxydicarbonate, di-3 - methoxybutyl peroxydicarbonate, di-s-butyl peroxydicarbonate, di(3-methyl-3-methoxybutyl)peroxydicarbonate, α,α'-bis(neodecanoylperoxy)diisopropylbenzene, Cumyl peroxyneodecanoate, 1,1,3,3-tetramethylbutyl peroxyneodecanoate, 1-cyclohexyl-1-methylethyl peroxyneodecanoate, t-hexyl peroxyneodecanoate , t-butyl peroxyneodecanoate, t-hexyl peroxypivalate, t-butyl peroxypivalate, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanooate, 2, 5-dimethyl-2,5-bis(2-ethylhexanoylperoxy)hexanoate, 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate , t-butylperoxy-2-ethylhexanoate, t-hexylperoxyisopropyl monocarbonate, t-butylperoxyisobutyrate, t-butylperoxymalate, t-butylperoxy-3,5, 5-trimethylhexanoate, t-butyl peroxylaurate, t-butyl peroxy isopropyl monocarbonate, t-butyl peroxy-2-ethylhexyl monocarbonate, t-butyl peroxy acetate, t-butyl peroxy- m-toluyl benzoate, t-butyl peroxybenzoate, bis(t-butylperoxy)isophthalate, 2,5-dimethyl-2,5-bis(m-toluylperoxy)hexane, t-hexylperoxybenzoate, 2,5-dimethyl-2,5-bis(benzoylperoxy)hexane, t-butylperoxyallylmonocarbonate, t-butyltrimethylsilylperoxide, 3,3′,4,4′-tetra(t-butylperoxy) oxycarbonyl)benzophenone, 2,3-dimethyl-2,3-diphenylbutane and other organic peroxide polymerization initiators.

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

The content of the radical polymerization initiator may be a stoichiometrically necessary amount, but is preferably 0.05 to 25 parts by mass based on 100 parts by mass of the underlayer film-forming material. , 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, it tends to be possible to prevent insufficient curing, while the content of the radical polymerization initiator is 25 parts by mass or less. In the case of , it tends to be possible to prevent the long-term storage stability of the underlayer film-forming material at room temperature from being impaired.

[Acid generator]
The underlayer film-forming material in the present embodiment may contain an acid generator, if necessary, from the viewpoint of further accelerating the cross-linking reaction by heat. As acid generators, those that generate acid by thermal decomposition, those that generate acid by light irradiation, and the like are known, and any of them can be used. As the acid generator, for example, those described in International Publication No. 2013/024779 can be used.

The content of the acid generator in the lower layer film forming material is not particularly limited, but is preferably 0.1 to 50 parts by mass, more preferably 0.5 to 50 parts by mass, based on 100 parts by mass of the lower layer film forming material. 40 parts by mass. By setting the content of the acid generator within the above range, the amount of acid generated tends to increase and the cross-linking reaction tends to be enhanced, and the occurrence of the mixing phenomenon with the resist layer tends to be suppressed.

[Basic compound]
The underlayer film-forming material in the present embodiment may contain a basic compound from the viewpoint of improving storage stability.

The basic compound plays a role of a quencher for the acid to prevent the slight amount of acid generated from the acid generator from proceeding with the cross-linking reaction. Examples of such a basic compound include, but are not particularly limited to, those described in International Publication No. 2013/024779.

The content of the basic compound in the underlayer film forming material is not particularly limited, but is preferably 0.001 to 2 parts by mass, more preferably 0.01 to 2 parts by mass, relative to 100 parts by mass of the underlayer film forming material. 1 part by mass. By setting the content of the basic compound within the above range, the storage stability tends to be enhanced without excessively impairing the cross-linking reaction.

[Other additives]
Further, the underlayer film-forming material in the present embodiment may contain other resins and/or compounds for the purpose of imparting heat or light curability and controlling absorbance. Such other resins and/or compounds include naphthol resins, xylene resins naphthol-modified resins, phenol-modified naphthalene resins; Naphthalene rings such as methacrylate, vinylnaphthalene and polyacenaphthylene; biphenyl rings such as phenanthrenequinone and fluorene; resins containing heterocycles having heteroatoms such as thiophene and indene; and resins free of aromatic rings; Resins or compounds containing an alicyclic structure such as cyclodextrin, adamantane (poly)ol, tricyclodecane (poly)ol, and derivatives thereof may be mentioned, but not limited thereto. Furthermore, the underlayer film-forming material in the present embodiment may contain known additives. Known additives include, but are not limited to, heat and/or photocuring catalysts, polymerization inhibitors, flame retardants, fillers, coupling agents, thermosetting resins, photosetting resins, dyes, pigments , thickeners, lubricants, antifoaming agents, leveling agents, UV absorbers, surfactants, coloring agents, nonionic surfactants and the like.

[Method for forming underlayer film for lithography and multilayer resist pattern]
The underlayer film for lithography in this embodiment is formed from the underlayer film-forming material described above.

Further, in the resist pattern forming method of the present embodiment, an underlayer film is formed on a substrate using the above composition, at least one photoresist layer is formed on the underlayer film, and then the photoresist layer is formed. It includes a step of irradiating a predetermined area with radiation and performing development. More specifically, the step (A-1) of forming an underlayer film on a substrate using the underlayer film forming material of the present embodiment, and the step of forming at least one photoresist layer on the underlayer film ( A-2) and, after the step (A-2), a step (A-3) of irradiating a predetermined region of the photoresist layer with radiation and developing.

Further, the circuit pattern forming method of the present embodiment comprises forming an underlayer film on a substrate using the above composition, forming an intermediate layer film on the underlayer film using a resist intermediate layer film material, forming at least one photoresist layer on the film;
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, the lower layer film is etched using the obtained intermediate layer film pattern as an etching mask, and the substrate is etched using the obtained lower layer film pattern as an etching mask. forming a pattern.
More specifically, the step (B-1) of forming an underlayer film on a substrate using the underlayer film-forming material of the present embodiment, and the use of a resist intermediate layer film material containing silicon atoms on the underlayer film. forming an intermediate layer film (B-2), forming at least one photoresist layer on the intermediate layer film (B-3), and after the step (B-3), a step (B-4) of irradiating a predetermined region of the photoresist layer with radiation and developing to form a resist pattern; and after the step (B-4), using the resist pattern as a mask, the intermediate layer film is etched, the underlayer film is etched using the obtained intermediate layer film pattern as an etching mask, and the substrate is etched using the obtained underlayer film pattern as an etching mask to form a pattern on the substrate (B-5). and have

As long as the underlayer film for lithography in this embodiment is formed from the underlayer film-forming material of this embodiment, the formation method is not particularly limited, and known techniques can be applied. For example, after the underlayer film material of the present embodiment is applied onto a substrate by a known coating method such as spin coating or screen printing or a printing method, the organic solvent is removed by volatilization or the like, and then, by a known method. By cross-linking and curing, the underlayer film for lithography of the present embodiment can be formed. Examples of cross-linking methods include techniques such as heat curing and photo-curing.

When 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 promote the cross-linking reaction. In this case, the baking temperature is not particularly limited, but is preferably in the range of 80 to 450.degree. C., more preferably 200 to 400.degree. Also, the baking time is not particularly limited, but it is preferably in the range of 10 to 300 seconds. The thickness of the underlayer film can be appropriately selected according to the required performance, and is not particularly limited, but is usually preferably about 30 to 20,000 nm, more preferably 50 to 15,000 nm. .

After forming the underlayer film, in the case of a two-layer process, a silicon-containing resist layer or a single-layer resist made of ordinary hydrocarbons is placed thereon. It is preferable to fabricate a single-layer resist layer that does not contain silicon. In this case, a known photoresist material can be used for forming this resist layer.

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

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

Polysilsesquioxane-based intermediate layers are preferably used as silicon-containing intermediate layers for three-layer processes. Reflection tends to be effectively suppressed by providing the intermediate layer with the effect of an antireflection film. For example, in a 193 nm exposure process, if a material containing many aromatic groups and having high substrate etching resistance is used as the underlayer film, the k value tends to increase and the substrate reflection tends to increase. can reduce the substrate reflection to 0.5% or less. The intermediate layer having such an antireflection effect is not limited to the following, but for 193 nm exposure, an acid- or heat-crosslinking polysilsesquivalent layer into which a light-absorbing group having a phenyl group or a silicon-silicon bond is introduced. Oxane is preferably used.

An intermediate layer formed by a chemical vapor deposition (CVD) method can also be used. Although not limited to the following, for example, a SiON film is known as an intermediate layer that is produced by a CVD method and is highly effective as an antireflection film. In general, forming an intermediate layer by a wet process such as a spin coating method or screen printing is simpler and more cost effective than a CVD method. The upper layer resist in the three-layer process may be either positive type or negative type, and may be the same as a commonly used single layer resist.

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

When the resist layer is formed from the photoresist material, a wet process such as spin coating or screen printing is preferably used as in the case of forming the underlayer film. After the resist material is applied by spin coating or the like, prebaking is usually performed, and this prebaking is preferably performed at 80 to 180° C. for 10 to 300 seconds. After that, exposure, post-exposure baking (PEB), and development are carried out according to a conventional method, whereby a resist pattern can be obtained. Although the thickness of the resist film is not particularly limited, it is generally preferably 30 to 500 nm, more preferably 50 to 400 nm.

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

In the resist pattern formed by the above-described method, pattern collapse is suppressed by the lower layer film. Therefore, by using the underlayer film of this embodiment, a finer pattern can be obtained, and the exposure dose required for obtaining the resist pattern can be reduced.

Next, etching is performed using the obtained resist pattern as a mask. Gas etching is preferably used for etching the lower layer film in the two-layer process. As the gas etching, etching using oxygen gas is suitable. _In addition to oxygen gas, it is also possible to add inert gases such as He and Ar, and CO, _CO2 , _NH3 , SO2, _N2 , _{NO2 and} H2 gases. Gas etching can also be performed using only CO, CO ₂ , NH ₃ , N ₂ , NO _{2 and} H ₂ gases without using oxygen gas. In particular, the latter gas is preferably used for sidewall protection to prevent undercutting of pattern sidewalls.

On the other hand, gas etching is also preferably used for etching the intermediate layer in the three-layer process. As the gas etching, the same one as described in the above two-layer process can be applied. In particular, it is preferable to process the intermediate layer in the three-layer process using a freon-based gas and using a resist pattern as a mask. After that, as described above, the intermediate layer pattern is used as a mask to perform, for example, oxygen gas etching, whereby the lower layer film can be processed.

Here, when an inorganic hard mask intermediate layer film is formed as the intermediate layer, a silicon oxide film, a silicon nitride film, or a silicon oxynitride film (SiON film) is formed by a CVD method, an ALD method, or the like. The method for forming the nitride film is not limited to the following, but for example, the methods 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 intermediate layer film, an organic anti-reflective coating (BARC) is formed on the intermediate layer film by spin coating, and a photoresist film is formed thereon. You may

As the intermediate layer, a polysilsesquioxane-based intermediate layer is also preferably used. Reflection tends to be effectively suppressed by imparting an antireflection film effect to the resist intermediate layer film. Specific materials for the polysilsesquioxane-based intermediate layer are not limited to the following, but are described in, for example, JP-A-2007-226170 (Patent Document 8) and JP-A-2007-226204 (Patent Document 9). can be used.

Etching of the next substrate can also be carried out by a conventional method. For example, if the substrate is SiO ₂ or SiN, etching mainly using Freon-based gas, and for p-Si, Al, or W, chlorine-based or bromine-based etching is performed. Gas-based etching can be performed. When the substrate is etched with Freon-based gas, the silicon-containing resist in the two-layer resist process and the silicon-containing intermediate layer in the three-layer process are stripped at the same time as the substrate is processed. 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 removed separately, and generally, after the substrate is processed, the dry-etching removal is performed with a flon-based gas. .

The underlayer film in this embodiment is characterized by excellent etching resistance of the substrate. As the substrate, a known substrate can be appropriately selected and used, and it is not particularly limited, but examples thereof include Si, α-Si, p-Si, SiO ₂ , SiN, SiON, W, TiN, and Al. be done. The substrate may also be a laminate having a film to be processed (substrate to be processed) on a base material (support). Such films to be processed include various Low-k films such as Si, SiO ₂ , SiON, SiN, p-Si, α-Si, W, W-Si, Al, Cu, Al-Si, and their stoppers. A film or the like is mentioned, and usually a material different from that of the substrate (support) is used. Although the thickness of the substrate to be processed or the film to be processed is not particularly limited, it is generally preferably about 50 to 10,000 nm, more preferably 75 to 5,000 nm.

The resist permanent film obtained by applying the composition of the present embodiment is suitable as a permanent film that remains in the final product after forming a resist pattern as necessary. Specific examples of permanent films include solder resists, package materials, underfill materials, package adhesive layers such as circuit elements and adhesive layers between integrated circuit elements and circuit boards in relation to semiconductor devices, and protective films for thin film transistors in relation to thin displays. Liquid crystal color filter protective film, black matrix, spacer and the like. In particular, the permanent film made of the composition of the present embodiment has excellent heat resistance and moisture resistance, and also has the very excellent advantage of being less susceptible to contamination by sublimation components. Especially in the display material, it becomes a material with high sensitivity, high heat resistance, and moisture absorption reliability, with less deterioration of image quality due to contamination, which is important.

When using the composition in this embodiment for resist permanent film applications, in addition to the curing agent, various additions such as other resins, surfactants and dyes, fillers, cross-linking agents, and dissolution accelerators as necessary By adding the agent and dissolving in an organic solvent, a resist permanent film composition can be obtained.

The film-forming composition for lithography and the composition for permanent resist film in the present embodiment can be prepared by blending the components described above and mixing them using a stirrer or the like. Further, when the resist underlayer film composition and the resist permanent film composition in the present embodiment contain fillers and pigments, they are dispersed or mixed using a dispersing device such as a dissolver, homogenizer, or three-roll mill. can be prepared.

Hereinafter, this embodiment will be described in more detail by way of Synthesis Examples and Examples, but this embodiment is not limited by these examples.
(Carbon concentration and oxygen concentration)
Carbon concentration and oxygen concentration (% by mass) were measured by organic elemental analysis.
Apparatus: CHN coder MT-6 (manufactured by Yanako Analysis Industry Co., Ltd.)

(molecular weight)
Molecular weights of compounds were determined by LC-MS analysis using a Water Acquity UPLC/MALDI-Synapt HDMS.
In addition, gel permeation chromatography (GPC) analysis was performed under the following conditions to obtain polystyrene-equivalent weight average molecular weight (Mw), number average molecular weight (Mn), and degree of dispersion (Mw/Mn).
Apparatus: Shodex GPC-101 type (manufactured by Showa Denko Co., Ltd.)
Column: KF-80M x 3
Eluent: THF 1 mL/min
Temperature: 40°C

(solubility)
At 23° C., the compound is stirred to form a 3 wt % solution in propylene glycol monomethyl ether (PGME), cyclohexanone (CHN), ethyl lactate (EL), methyl amyl ketone (MAK) or tetramethyl urea (TMU). and dissolved, and the results after one week were evaluated according to the following criteria.
Evaluation A: It was visually confirmed that there was no precipitate in any solvent. Evaluation C: It was visually confirmed that there was a precipitate in all solvents.

(Structure of compound)
The structure of the compound was confirmed by ¹ H-NMR measurement under the following conditions using an "Advance 600II spectrometer" manufactured by Bruker.
Frequency: 400MHz
Solvent: d6-DMSO
Internal standard: TMS
Measurement temperature: 23°C

<Synthesis Example 1> Synthesis of XBisN-1 3.20 g (20 mmol) of 2,6-naphthalenediol (reagent manufactured by Sigma-Aldrich) and 4-biphenylcarboxyl were placed in a container having an inner volume of 100 ml equipped with a stirrer, a cooling tube and a burette. 1.82 g (10 mmol) of aldehyde (manufactured by Mitsubishi Gas Chemical Co., Ltd.) 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° C. for 6 hours to carry out a reaction. Next, the reaction solution was concentrated, 50 g of pure water was added to precipitate a reaction product, cooled to room temperature, and separated by filtration. The resulting solid matter was filtered, dried, and separated and purified by column chromatography to obtain 3.05 g of the target compound represented by the following formula. It was confirmed by 400 MHz- ¹ H-NMR that it had the chemical structure of the following formula.
¹ H-NMR: (d-DMSO, internal standard TMS)
δ (ppm) 9.7 (2H, OH), 7.2-8.5 (19H, Ph-H), 6.6 (1H, CH)
It should be noted that the fact that the substitution position of 2,6-naphthalenediol is at the 1st position was confirmed from the fact that the signals of the protons at the 3rd and 4th positions are doublets.

<Synthesis Example 1A> Synthesis of E-XBisN-1 10 g (21 mmol) of the compound (XBisN-1) represented by the above formula and 14.8 g (107 mmol) of potassium carbonate were placed in a container having an internal volume of 100 ml equipped with a stirrer, a cooling tube and a burette. ) was added to 50 ml of dimethylformamide, 6.56 g (54 mmol) of 2-chloroethyl acetate was added, and the reaction mixture was stirred at 90° C. for 12 hours to carry out a reaction. Next, the reaction solution was cooled in an ice bath to deposit crystals, which were separated by filtration. Subsequently, 40 g of the crystals, 40 g of methanol, 100 g of THF, and 24% aqueous sodium hydroxide solution were charged into a container having an inner volume of 100 ml equipped with a stirrer, a condenser, and a burette, and the reaction mixture was stirred under reflux for 4 hours to carry out the reaction. . Thereafter, the reaction mixture was cooled in an ice bath, the reaction mixture was concentrated, and the precipitated solid matter was filtered, dried, and separated and purified by column chromatography to obtain 5.9 g of the target compound represented by the following formula. It was confirmed by 400 MHz- ¹ H-NMR that it had the chemical structure of the following formula.
¹ H-NMR: (d-DMSO, internal standard TMS)
δ (ppm) 8.6 (2H, OH), 7.2 to 7.8 (19H, Ph-H), 6.7 (1H, CH), 4.0 (4H, -O- CH ₂ —), 3.8(4H, —CH ₂ —OH)

<Synthesis Example 1-1> Synthesis of AlE-XBisN-1 10.3 g (21 mmol) of the compound represented by the above formula (E-XBisN-1) was placed in a container with an internal volume of 100 ml equipped with a stirrer, a cooling tube and a burette. and 6.2 g (45 mmol) of potassium carbonate in 100 ml of acetone were added, and 5.4 (45 mmol) g of allyl bromide and 2.0 g of 10-crown-6 were added to obtain a reaction mixture. The reaction was stirred under reflux for 9 hours. Next, the solid content was removed from the reaction liquid by filtration, cooled in an ice bath, and the reaction liquid was concentrated to deposit a solid substance. The precipitated solid matter was filtered, dried, and separated and purified by column chromatography to obtain 3.2 g of the desired compound represented by the following formula (AlE-XBisN-1).
By 400 MHz- ¹ H-NMR, it was confirmed to have a chemical structure of the following formula (AlE-XBisN-1).
¹ H-NMR: (d-DMSO, internal standard TMS)
δ (ppm) 7.2-7.8 (19H, Ph—H), 6.7 (1H, CH), 6.1 (2H, —CH—CH ₂ ), 5.4-5.5 (4H, —CH—CH ₂ ), 4.7 (4H, —O—CH ₂ —), 4.0 (4H, —O—CH ₂ —), 3.8 (4H, —CH ₂ —OH)

As a result of measuring the molecular weight of the obtained compound by the method described above, it was 634.
It has a thermal decomposition temperature of 390° C., a glass transition point of 105° C., and a melting point of 205° C., confirming high heat resistance.

<Synthesis Example 1-2> Synthesis of AcE-XBisN-1 A reaction was carried out in the same manner as in Synthesis Example 1-1 except that acrylic acid was used instead of the above allyl bromide, and the following formula (AcE-XBisN- 4.0 g of the target compound represented by 1) was obtained.
By 400 MHz- ¹ H-NMR, it was confirmed to have a chemical structure of the following formula (AcE-XBisN-1).
¹ H-NMR: (d-DMSO, internal standard TMS)
δ (ppm) 7.2-7.8 (19H, Ph—H), 6.7 (1H, CH), 5.8-6.4 (6H, —CH—CH ₂ ), 4.0 (4H, —O—CH ₂ —), 3.8(4H, —CH ₂ —OH)

<Synthesis Example 2> Synthesis of BisF-1 A vessel with an inner volume of 200 ml equipped with a stirrer, a condenser and a burette was prepared. Into this container, 30 g (161 mmol) of 4,4-biphenol (reagent manufactured by Tokyo Kasei Co., Ltd.), 15 g (82 mmol) of 4-biphenylaldehyde (manufactured by Mitsubishi Gas Chemical Co., Ltd.), and 100 ml of butyl acetate were charged. 3.9 g (21 mmol) of acid (reagent manufactured by Kanto Chemical Co., Ltd.) was added to prepare a reaction solution. This reaction solution was stirred at 90° C. for 3 hours to carry out the reaction. Next, the reaction solution was concentrated, 50 g of heptane was added to precipitate the reaction product, cooled to room temperature, and separated by filtration. The solid matter obtained by filtration was dried and then separated and purified by column chromatography to obtain 5.8 g of the target compound (BisF-1) represented by the following formula.
The following peaks were found by 400 MHz- ¹ H-NMR, confirming that the compound had the chemical structure of the following formula.
¹ H-NMR: (d-DMSO, internal standard TMS)
δ (ppm) 9.4 (4H, OH), 6.8-7.8 (22H, Ph-H), 6.2 (1H, CH)
As a result of measuring the molecular weight of the obtained compound by the above method, it was 536.

<Synthesis Example 2A>
11.2 g (21 mmol) of the compound represented by the above formula (BisF-1) and 14.8 g (107 mmol) of potassium carbonate were placed in 50 ml of dimethylformamide in a container having an internal volume of 100 ml equipped with a stirrer, a condenser tube and a burette, 6.56 g (54 mmol) of 2-chloroethyl acetate was added, and the reaction solution was stirred at 90° C. for 12 hours to carry out the reaction. Next, the reaction solution was cooled in an ice bath to deposit crystals, which were separated by filtration. Subsequently, 40 g of the crystals, 40 g of methanol, 100 g of THF, and 24% aqueous sodium hydroxide solution were charged into a container having an inner volume of 100 ml equipped with a stirrer, a condenser, and a burette, and the reaction mixture was stirred under reflux for 4 hours to carry out the reaction. . Then, after cooling in an ice bath, the reaction solution is concentrated, the precipitated solid is filtered, dried, and then separated and purified by column chromatography to obtain the target compound represented by the following formula (E-BisF-1). 5.9 g was obtained.
By 400 MHz- ¹ H-NMR, it was confirmed to have a chemical structure of the following formula (E-BisF-1).
¹ H-NMR: (d-DMSO, internal standard TMS)
δ (ppm) 8.6 (4H, OH), 6.8-7.8 (22H, Ph-H), 6.2 (1H, CH), 4.0 (8H, -O- CH ₂ —), 3.8(8H, —CH ₂ —OH)
As a result of measuring the molecular weight of the obtained compound by the above method, it was 712.

<Synthesis Example 2-1> Synthesis of AlE-BisF-1 Instead of the compound represented by the above formula (E-XBisN-1), the compound represented by the above formula (E-BisF-1) was used. Except for the above, the reaction was carried out in the same manner as in Synthesis Example 1-1 to obtain 3.0 g of the target compound represented by the following formula (AlE-BisF-1).
By 400 MHz- ¹ H-NMR, it was confirmed to have a chemical structure of the following formula (AlE-BisF-1).
¹ H-NMR: (d-DMSO, internal standard TMS)
δ (ppm) 6.8-7.8 (22H, Ph—H), 6.2 (1H, CH), 6.1 (4H, —CH—CH ₂ ), 5.4-5.5 (8H, —CH—CH ₂ ), 4.7 (8H, —O—CH ₂ —), 4.0 (8H, —O—CH ₂ —), 3.8 (8H, —CH ₂ —OH)
It has a thermal decomposition temperature of 380° C., a glass transition point of 70° C., and a melting point of 200° C., confirming high heat resistance.

As a result of measuring the molecular weight of the obtained compound by the method described above, it was 872.

<Synthesis Example 2-2> Synthesis of AcE-BisF-1 Instead of the compound represented by the above formula (E-XBisN-1), using the compound represented by the above formula (E-BisF-1), A reaction was carried out in the same manner as in Synthesis Example 1-1, except that acrylic acid was used instead of allyl bromide, to obtain 3.3 g of the target compound represented by the following formula (AcE-BisF-1).
By 400 MHz- ¹ H-NMR, it was confirmed to have a chemical structure of the following formula (AcE-BisF-1).
¹ H-NMR: (d-DMSO, internal standard TMS)
δ (ppm) 6.8-7.8 (22H, Ph—H), 6.2 (1H, CH), 5.8-6.4 (6H, —CH—CH ₂ ), 4.0 (8H, —O—CH ₂ —), 3.8(8H, —CH ₂ —OH)

As a result of measuring the molecular weight of the obtained compound by the above method, it was 928.
It has a thermal decomposition temperature of 375° C., a glass transition point of 65° C., and a melting point of 190° C., confirming that it has high heat resistance.

<Synthesis Example 3> Synthesis of BiN-1 In a container with an internal volume of 300 mL equipped with a stirrer, a cooling tube and a burette, 10 g (69.0 mmol) of 2-naphthol (reagent manufactured by Sigma-Aldrich) was melted at 120°C, 0.27 g of sulfuric acid was charged, 2.7 g (13.8 mmol) of 4-acetylbiphenyl (reagent manufactured by Sigma-Aldrich) was added, and the contents were stirred at 120° C. for 6 hours to carry out a reaction to obtain a reaction solution. rice field. Next, 100 mL of N-methyl-2-pyrrolidone (manufactured by Kanto Kagaku 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 separate the liquids until the mixture became neutral, and then the mixture was concentrated to obtain a solution.
After the resulting solution was separated by column chromatography, 1.0 g of the objective compound (BiN-1) represented by the following formula (BiN-1) was obtained.
The molecular weight of the resulting compound (BiN-1) was measured by the method described above and was 466.
When the obtained compound (BiN-1) was subjected to NMR measurement under the above measurement conditions, the following peaks were found, confirming that it has the chemical structure of the following formula (BiN-1).
δ (ppm) 9.69 (2H, OH), 7.01 to 7.67 (21H, Ph-H), 2.28 (3H, CH)

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

<Synthesis Example 3-1> Synthesis of AlE-BiN-1 12.3 g (21 mmol) of the compound represented by the above formula (E-BiN-1) was placed in a container having an internal volume of 100 ml equipped with a stirrer, a condenser tube and a burette. and 6.2 g (45 mmol) of potassium carbonate added to 100 ml of acetone, and then 5.4 g (45 mmol) of allyl bromide and 2.0 g of 10-crown-6 were added, and the resulting reaction mixture was refluxed. The reaction was carried out under stirring for 7 hours. Next, the solid content was removed from the reaction liquid by filtration, cooled in an ice bath, and the reaction liquid was concentrated to deposit a solid substance. The precipitated solid matter was filtered, dried, and separated and purified by column chromatography to obtain 4.0 g of the target compound represented by the following formula (AlE-BiN-1).
By 400 MHz- ¹ H-NMR, it was confirmed to have a chemical structure of the following formula (AlE-BiN-1).
¹ H-NMR: (d-DMSO, internal standard TMS)
δ (ppm) 7.2-7.8 (19H, Ph—H), 6.7 (1H, CH), 6.1 (2H, —CH—CH ₂ ), 5.4-5.5 (4H, —CH—CH ₂ ), 4.7 (4H, —O—CH ₂ —), 4.0 (4H, —O—CH ₂ —), 3.8 (4H, —CH ₂ —OH)

As a result of measuring the molecular weight of the obtained compound by the method described above, it was 634.
It has a thermal decomposition temperature of 380° C., a glass transition point of 115° C., and a melting point of 215° C., confirming high heat resistance.

<Synthesis Example 3-2> Synthesis of AcE-BiN-1 A reaction was carried out in the same manner as in Synthesis Example 3-1 except that acrylic acid was used instead of the above allyl bromide, and the following formula (AcE-BiN- 3.3 g of the target compound represented by 1) was obtained.
By 400 MHz- ¹ H-NMR, it was confirmed to have a chemical structure of the following formula (AcE-BiN-1).
¹ H-NMR: (d-DMSO, internal standard TMS)
δ (ppm) 7.2-7.8 (19H, Ph—H), 6.7 (1H, CH), 5.8-6.4 (6H, —CH—CH ₂ ), 4.0 (4H, —O—CH ₂ —), 3.8(4H, —CH ₂ —OH)

As a result of measuring the molecular weight of the obtained compound by the method described above, it was 662.
It has a thermal decomposition temperature of 371° C., a glass transition point of 102° C., and a melting point of 221° C., confirming that it has high heat resistance.

<Synthesis Example 4> Synthesis of BiP-1 Instead of 2-naphthol, the reaction was carried out in the same manner as in Synthesis Example 3 except that o-phenylphenol was used to obtain the target compound 1 represented by the following formula (BiP-1). .0 g was obtained.
The molecular weight of the resulting compound (BiP-1) was measured by the method described above and was 466.
When the obtained compound (BiP-1) was subjected to NMR measurement under the above measurement conditions, the following peaks were found, confirming that it has the chemical structure of the following formula (BiP-1).
δ (ppm) 9.67 (2H, OH), 6.98-7.60 (25H, Ph-H), 2.25 (3H, CH)

<Synthesis Example 4A> Synthesis of E-BiP-1 11.2 g (21 mmol) of the compound represented by the above formula (BiP-1) and 14.0 mmol of potassium carbonate were placed in a container having an internal volume of 100 ml equipped with a stirrer, a cooling tube and a burette. 8 g (107 mmol) of the product was placed in 50 ml of dimethylformamide, 6.56 g (54 mmol) of 2-chloroethyl acetate was added, and the reaction solution was stirred at 90° C. for 12 hours to carry out the reaction. Next, the reaction solution was cooled in an ice bath to deposit crystals, which were separated by filtration. Subsequently, 40 g of the crystals, 40 g of methanol, 100 g of THF, and 24% aqueous sodium hydroxide solution were charged into a container having an inner volume of 100 ml equipped with a stirrer, a condenser, and a burette, and the reaction mixture was stirred under reflux for 4 hours to carry out the reaction. . Then, after cooling in an ice bath, the reaction solution is concentrated, the precipitated solid is filtered, dried, and then separated and purified by column chromatography to obtain the target compound represented by the following formula (E-BiP-1). 5.9 g was obtained.
By 400 MHz- ¹ H-NMR, it was confirmed to have a chemical structure of the following formula (E-BiP-1).
¹ H-NMR: (d-DMSO, internal standard TMS)
δ (ppm) 8.6 (4H, O—H), 6.8-7.6 (25H, Ph—H), 4.0 (4H, —O—CH ₂ —), 3.8 (4H, —CH ₂ —OH), 2.2 (3H, CH)
As a result of measuring the molecular weight of the obtained compound by the method described above, it was 606.

<Synthesis Example 4-1> Synthesis of AlE-BiP-1 Instead of the compound represented by the above formula (E-BiN-1), the compound represented by the above formula (E-BiP-1) was used. Except for the above, the reaction was carried out in the same manner as in Synthesis Example 3-1 to obtain 3.0 g of the target compound represented by the following formula (AlE-BiP-1).
By 400 MHz- ¹ H-NMR, it was confirmed to have a chemical structure of the following formula (AlE-BiP-1).
¹ H-NMR: (d-DMSO, internal standard TMS)
δ (ppm) 6.8-7.8 (25H, Ph—H), 6.1 (4H, —CH—CH ₂ ), 5.4-5.5 (4H, —CH—CH ₂ ), 4 .7 (4H, —O—CH ₂ —), 4.0 (4H, —O—CH ₂ —), 3.8 (4H, —CH ₂ —OH), 2.2 (3H, CH)
It has a thermal decomposition temperature of 390° C., a glass transition point of 74° C., and a melting point of 202° C., confirming that it has high heat resistance.

The molecular weight of the resulting compound was measured by the method described above and found to be 686.

<Synthesis Example 4-2> Synthesis of AcE-BiP-1 Instead of the compound represented by the above formula (E-XBisN-1), using the compound represented by the above formula (E-BiP-1), A reaction was carried out in the same manner as in Synthesis Example 1-1, except that acrylic acid was used instead of allyl bromide, to obtain 3.8 g of the target compound represented by the following formula (AcE-BiP-1).
By 400 MHz- ¹ H-NMR, it was confirmed to have a chemical structure of the following formula (AcE-BiP-1).
¹ H-NMR: (d-DMSO, internal standard TMS)
δ (ppm) 6.8-7.8 (25H, Ph—H), 5.8-6.4 (3H, —CH—CH ₂ ), 4.0 (4H, —O—CH ₂ —), 3.8 (4H, —CH ₂ —OH), 2.2 (3H, CH),

As a result of measuring the molecular weight of the obtained compound by the above method, it was 700.
It has a thermal decomposition temperature of 365° C., a glass transition point of 85° C., and a melting point of 220° C., confirming high heat resistance.

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

(Synthesis Examples 18-20)
2-naphthol (raw material 1) and 4-biphenylaldehyde (raw material 2), which are the raw materials of Synthesis Example 3, were changed as shown in Table 3, and the rest was carried out in the same manner as in Synthesis Example 3 to obtain each target compound.
Each target compound was identified by 1H-NMR.

(Synthesis Examples 21-22)
2-naphthol (raw material 1) and 4-acetylbiphenyl (raw material 2), which are 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 dodecyl mercaptan, 37% hydrochloric acid 2 .3 g (22 mmol) was added, the reaction temperature was changed to 55° C., and the rest was carried out in the same manner as in Synthesis Example 3 to obtain each target compound.
Each target compound was identified by 1H-NMR.

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

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

(Synthesis 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 above formula (E-BiN-1), which is the raw material of Synthesis Example 3-2, was changed as shown in Table 7. , obtained each object. The structure of each compound was identified by confirming the molecular weight with 400 MHz- ¹ H-NMR (d-DMSO, internal standard TMS) and LC-MS.

(Synthesis Example 23) Synthesis of Resin (R1-XBisN-1) A four-necked flask with an inner volume of 1 L and capable of bottom extraction, equipped with a Dimroth condenser, a thermometer and a stirring blade was prepared. Into this four-necked flask, 32.6 g (70 mmol, manufactured by Mitsubishi Gas Chemical Co., Ltd.) of the compound (XBisN-1) obtained in Synthesis Example 1, 21.0 g of a 40% by mass formalin aqueous solution (formaldehyde 280 mmol, manufactured by Mitsubishi Gas Chemical Co., Ltd.) and 0.97 mL of 98% by mass sulfuric acid (manufactured by Kanto Chemical Co., Ltd.) were charged and reacted for 7 hours while refluxing at 100° C. under normal pressure. After that, 180.0 g of ortho-xylene (special reagent grade manufactured by Wako Pure Chemical Industries, Ltd.) was added as a diluting solvent to the reaction solution, and after standing, the lower aqueous phase was removed. Furthermore, neutralization and washing with water 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 resulting resin (R1-XBisN-1) had Mn: 1975, Mw: 3650, and Mw/Mn: 1.84.

(Synthesis Example 24) Synthesis of Resin (R2-XBisN-1) A four-necked flask with an inner volume of 1 L and capable of bottom extraction, equipped with a Dimroth condenser, a thermometer and a stirring blade was prepared. Into this four-neck flask, 32.6 g (70 mmol, manufactured by Mitsubishi Gas Chemical Co., Ltd.) of the compound (XBisN-1) obtained in Synthesis Example 1 and 50.9 g (280 mmol, Mitsubishi Gas Chemical Co., Ltd.), 100 mL of anisole (Kanto Chemical Co., Ltd.), and 10 mL of oxalic acid dihydrate (Kanto Chemical Co., Ltd.) were charged and reacted under normal pressure at 100° C. for 7 hours while refluxing. let me After that, 180.0 g of ortho-xylene (special reagent grade manufactured by Wako Pure Chemical Industries, Ltd.) was added as a diluting solvent to the reaction solution, and after standing, the lower aqueous phase was removed. Furthermore, neutralization and washing with water were carried out, and the organic phase solvent and unreacted 4-biphenylaldehyde were distilled off under reduced pressure to obtain 34.7 g of a brown solid resin (R2-XBisN-2).

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 above resin (R1-XBisN-1) and 29.6 g (214 mmol) of potassium carbonate were placed in a container having an internal volume of 500 ml equipped with a stirrer, a cooling tube and a burette. was added to 100 ml of dimethylformamide, 13.12 g (108 mmol) of 2-chloroethyl acetate was added, and the reaction solution was stirred at 90° C. for 12 hours to carry out the reaction. Next, the reaction solution was cooled in an ice bath to deposit crystals, which were separated by filtration. Subsequently, 40 g of the crystals, 80 g of methanol, 100 g of THF, and 24% sodium hydroxide aqueous solution were charged into a container having an internal volume of 100 ml equipped with a stirrer, a condenser, and a burette, and the reaction mixture was stirred under reflux for 4 hours to carry out the reaction. . After cooling in an ice bath, the reaction solution was concentrated, and the precipitated solid was filtered and dried to obtain 26.5 g of a brown solid resin (ER1-XBisN-1).

The resulting resin (ER1-XBisN-1) had Mn: 2176, Mw: 3540, and Mw/Mn: 1.62.

<Synthesis Example 23-1> Synthesis of AlE-R1-XBisN-1 Compound 30.R1-XBisN-1 represented by the above formula (E-R1-XBisN-1) was placed in a container having an inner volume of 500 ml equipped with a stirrer, a cooling tube and a burette. A solution obtained by adding 6 g of potassium carbonate and 12.4 g (90 mmol) of potassium carbonate to 200 ml of acetone was charged, and further 10.8 (90 mmol) g of allyl bromide and 4.0 g of 10-crown-6 were added to obtain a reaction solution. was stirred under reflux for 9 hours to carry out the reaction. Next, the solid content was removed from the reaction liquid by filtration, cooled in an ice bath, and the reaction liquid was concentrated to deposit a solid substance. The precipitated solid was filtered and dried to obtain 46.2 g of a resin represented by (AlE-R1-XBisN-1) as a gray solid.

The resulting resin (AlE-R1-XBisN-1) had Mn: 2021, Mw: 3040 and Mw/Mn: 1.50.

<Synthesis Example 23-2> Synthesis of AcE-R1-XBisN-1 A brown solid (AcE -R1-XBisN-1) was obtained.

The resulting resin (AcE-R1-XBisN-1) had Mn: 2476, Mw: 3930 and Mw/Mn: 1.61.

<Synthesis Example 24A> Synthesis of E-R2-XBisN-1 30 g of the above resin (R2-XBisN-1) and 29.6 g (214 mmol) of potassium carbonate were placed in a container having an internal volume of 500 ml equipped with a stirrer, a cooling tube and a burette. was added to 100 ml of dimethylformamide, 13.12 g (108 mmol) of 2-chloroethyl acetate was added, and the reaction solution was stirred at 90° C. for 12 hours to carry out the reaction. Next, the reaction solution was cooled in an ice bath to deposit crystals, which were separated by filtration. Subsequently, 40 g of the crystals, 80 g of methanol, 100 g of THF, and 24% sodium hydroxide aqueous solution were charged into a container having an internal volume of 100 ml equipped with a stirrer, a condenser, and a burette, and the reaction mixture was stirred under reflux for 4 hours to carry out the reaction. . Thereafter, the mixture was cooled in an ice bath, the reaction solution was concentrated, and the precipitated solid was filtered and dried to obtain 22.3 g of a brown solid resin (ER2-XBisN-1).

The resulting resin (ER2-XBisN-1) had Mn: 2516, Mw: 3960, and Mw/Mn: 1.62.

<Synthesis Example 24-1> Synthesis of AlE-R2-XBisN-1 Instead of the above formula (E-R1-XBisN-1), the compound represented by the above formula (E-R2-XBisN-1) 30. A reaction was carried out in the same manner as in Synthesis Example 23-1 except that 6 g of the compound was used to obtain 36.5 g of a resin represented by (AlE-R2-XBisN-1) as a gray solid.

The resulting resin (AlE-R2-XBisN-1) had Mn: 2411, Mw: 3845 and Mw/Mn: 1.59.

<Synthesis Example 24-2> Synthesis of AcE-R1-XBisN-1 Instead of the above allyl bromide, the reaction was carried out in the same manner as in Synthesis Example 24-1 except that acrylic acid was used. -R2-XBisN-1) was obtained.

The resulting resin (AcE-R2-XBisN-1) had Mn: 2676, Mw: 4630 and Mw/Mn: 1.73.

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

Subsequently, a four-necked flask with an internal volume of 0.5 L equipped with a Dimroth condenser, a thermometer and a stirring blade was prepared. In this four-necked flask, 100 g (0.51 mol) of the dimethylnaphthalene formaldehyde resin obtained as described above and 0.05 g of p-toluenesulfonic acid were charged under a nitrogen stream, and the temperature was raised to 190 ° C. After heating for 1 hour, it was stirred. After that, 52.0 g (0.36 mol) of 1-naphthol was further added, and the temperature was raised to 220° C. and reacted for 2 hours. After dilution with the solvent, neutralization and washing were carried out, and the solvent was removed under reduced pressure to obtain 126.1 g of modified resin (CR-1) as a dark brown solid.
The resulting resin (CR-1) had Mn: 885, Mw: 2220 and Mw/Mn: 4.17.

(Examples 1-1 to 24-2, Comparative Example 1)
Using the compounds or resins described in Synthesis Examples 1-1 to 24-2 and CR-1 of Synthesis Comparative Example 1, a solubility test was conducted. Table 8 shows the results.
In addition, underlayer film-forming materials for lithography having compositions shown in Table 8 were prepared. Next, these underlayer film-forming materials for lithography were spin-coated on a silicon substrate, and then baked at 240° C. for 60 seconds and further at 400° C. for 120 seconds to prepare underlayer films each having a thickness of 200 nm. The following acid generators, cross-linking agents and organic solvents were used.
Acid generator: Ditert-butyldiphenyliodonium nonafluoromethanesulfonate (DTDPI) manufactured by Midori Chemical Co., Ltd.
Cross-linking agent: Nikalac MX270 (Nikalac) manufactured by Sanwa Chemical Co., Ltd.
Organic solvent: propylene glycol monomethyl ether acetate (PGMEA)

(Examples 25-44)
In addition, underlayer film-forming materials for lithography having compositions shown in Table 9 below were prepared. Next, these materials for forming an underlayer film for lithography were spin-coated on a silicon substrate, and then baked at 110° C. for 60 seconds to remove the solvent from the coating film. /cm ² and an irradiation time of 20 seconds to prepare an underlayer film having a thickness of 200 nm. The photoradical polymerization initiator, cross-linking agent and organic solvent used were as follows.

Radical polymerization initiator: BASF IRGACURE184
Crosslinker:
(1) Nikalac MX270 (Nikalac) manufactured by Sanwa Chemical Co., Ltd.
(2) Mitsubishi Gas Chemical diallyl bisphenol A type cyanate (DABPA-CN)
(3) Diallyl bisphenol A (BPA-CA) manufactured by Konishi Chemical Industry
(4) Benzoxazine (BF-BXZ) manufactured by Konishi Chemical Industry
(5) Nippon Kayaku biphenyl aralkyl type epoxy resin (NC-3000-L)
Organic solvent: propylene glycol monomethyl ether acetate (PGMEA)

The structure of the cross-linking agent is shown by the following formula.

Then, an etching test was performed under the conditions shown below to evaluate the etching resistance. Evaluation results are shown in Tables 8 and 9.
[Etching test]
Etching device: RIE-10NR manufactured by Samco International
Output: 50W
Pressure: 20Pa
Time: 2min
Etching gas Ar gas flow rate: CF4 gas flow rate: _O2 gas flow rate = 50: ₅ :5 (sccm)
[Evaluation of etching resistance]
Etching resistance was evaluated by the following procedure.
First, a novolac underlayer film was prepared under the same conditions as in Example 1, except that novolac (PSM4357 manufactured by Gunei Chemical Co., Ltd.) was used instead of the compound (AlE-XBisN-1). Then, the above-described etching test was performed on this novolac underlayer film, and the etching rate at that time was measured.
Next, the etching test was performed in the same manner for the lower layer films of each example and comparative example 1, and the etching rate at that time was measured.
Using the etching rate of the novolac underlayer film as a reference, the etching resistance was evaluated according to the following evaluation criteria.
[Evaluation criteria]
A: The etching rate is less than −10% compared to the novolac underlayer film B: The etching rate is −10% to +5% compared to the novolac underlayer film
C: The etching rate is more than +5% compared to the novolac underlayer film

(Examples 45-48)
Next, each solution of a lithographic underlayer film forming material containing AlE-XBisN-1, AcE-XBisN-1, AlE-BisF-1 or AcE-BisF-1 was applied onto a 300 nm thick SiO ₂ substrate. Then, the substrate was baked at 240° C. for 60 seconds and further at 400° C. for 120 seconds to form an underlayer film with a film thickness of 70 nm. An ArF resist solution was applied on the underlayer film and baked at 130° C. for 60 seconds to form a photoresist layer with a film thickness of 140 nm. As the ArF resist solution, a compound of the following formula (11): 5 parts by mass, triphenylsulfonium nonafluoromethanesulfonate: 1 part by mass, tributylamine: 2 parts by mass, and PGMEA: 92 parts by mass were blended. The prepared one was used.
The compound of formula (11) contains 4.15 g of 2-methyl-2-methacryloyloxyadamantane, 3.00 g of methacryloyloxy-γ-butyrolactone, 2.08 g of 3-hydroxy-1-adamantyl methacrylate, and azobisisobutyronitrile. 0.38 g was dissolved in 80 mL of tetrahydrofuran to prepare a reaction solution. This reaction solution was polymerized for 22 hours while maintaining the reaction temperature at 63° C. under a nitrogen atmosphere, and then added dropwise to 400 ml of n-hexane. The produced resin thus obtained was coagulated and purified, and the produced white powder was filtered and dried under reduced pressure at 40° C. overnight.

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

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

The shapes and defects of the resulting 55 nm L/S (1:1) and 80 nm L/S (1:1) resist patterns were observed.
With respect to the shape of the resist pattern after development, a pattern with good rectangularity without pattern collapse was evaluated as "good", and other than that was evaluated as "bad". As a result of the observation, the minimum line width with good rectangularity without pattern collapse was defined as "resolution" and used as an index for evaluation. Furthermore, the minimum electron beam energy amount capable of drawing a good pattern shape was defined as "sensitivity" and used as an evaluation index.
Table 10 shows the evaluation results.

(Comparative example 2)
A photoresist layer was formed directly on the SiO ₂ substrate in the same manner as in Example 45, except that no underlayer film was formed, to obtain a positive resist pattern. Table 10 shows the results.

As is clear from Table 8, it was confirmed that Examples 1-1 to 24-2 using the compounds or resins of the present embodiment were excellent in terms of 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.
Further, in Examples 45 to 48, it was confirmed that the shape of the resist pattern after development was good and no defect was observed. It was confirmed that both resolution and sensitivity were significantly superior to Comparative Example 2 in which the formation of the underlayer film was omitted.
From the difference in resist pattern shape after development, it was shown that the underlayer film-forming materials for lithography used in Examples 45 to 48 had good adhesion to the resist material.

<Examples 49 to 52>
The solutions of the underlayer film-forming materials for lithography of Examples 1-1 and 2-2 were applied onto a SiO ₂ substrate having a film thickness of 300 nm, and baked at 240° C. for 60 seconds and then at 400° C. for 120 seconds to form films. An underlayer film having a thickness of 80 nm was formed. A silicon-containing intermediate layer material was applied onto the underlayer film and baked at 200° C. for 60 seconds to form an intermediate layer film having a thickness of 35 nm. Further, the ArF resist solution was applied onto the intermediate layer film and baked at 130° C. for 60 seconds to form a photoresist layer with a film thickness of 150 nm. As the silicon-containing intermediate layer material, a silicon atom-containing polymer described in <Synthesis Example 1> of JP-A-2007-226170 was used.
Next, using an electron beam lithography system (manufactured by Elionix; ELS-7500, 50 keV), the photoresist layer is mask-exposed, baked (PEB) at 115 ° C. for 90 seconds, and 2.38% by mass of tetramethylammonium hydroxide. A positive resist pattern of 55 nm L/S (1:1) was obtained by developing with a (TMAH) aqueous solution for 60 seconds.
After that, using RIE-10NR manufactured by Samco International, the silicon-containing intermediate layer film (SOG) was dry-etched using the obtained resist pattern as a mask, and then the obtained silicon-containing intermediate layer film pattern was removed. Dry etching processing of the lower layer film used as a mask and dry etching processing of the SiO ₂ film using the obtained lower layer film pattern as a mask were sequentially performed.

Each etching condition is as shown below.
Conditions for etching the resist pattern to the resist intermediate layer film
Output: 50W
Pressure: 20Pa
Time: 1 minute
Etching gas Ar gas flow rate: CF4 gas flow rate: _O2 gas flow rate = 50: ₈ :2 (sccm)
Conditions for etching the resist intermediate film pattern to the resist underlayer film
Output: 50W
Pressure: 20Pa
Time: 2min
Etching gas Ar gas flow rate: CF4 gas flow rate: _O2 gas flow rate = 50: ₅ :5 (sccm)
Etching conditions for the _SiO2 film of the resist underlayer film pattern
Output: 50W
Pressure: 20Pa
Time: 2min
_Etching gas Ar gas flow rate: _C5F12 gas flow rate: _C2F6 gas flow rate: _{O2 gas} flow rate
= 50:4:3:1 (sccm)

[evaluation]
When the cross section of the pattern obtained as described above ₍ the shape of the SiO film after etching) was observed using an electron microscope (S-4800) manufactured by Hitachi, Ltd., it was found that the underlayer film of this embodiment was used. It was confirmed that, in the example, the shape of the SiO ₂ film after etching in the multi-layer resist processing was rectangular, and no defects were observed.

[Examples 53-56]
Using the compounds synthesized in the above Synthesis Examples and Synthesis Examples, optical component-forming compositions were prepared according to the formulations shown in Table 11 below. Among the components of the optical component-forming composition shown in Table 4, the following acid generators, cross-linking agents, acid diffusion inhibitors, and solvents were used.
Acid generator: Ditert-butyldiphenyliodonium nonafluoromethanesulfonate (DTDPI) manufactured by Midori Chemical Co., Ltd.
Cross-linking agent: Nikalac MX270 (Nikalac) manufactured by Sanwa Chemical Co., Ltd.
Organic solvent: propylene glycol monomethyl ether acetate (PGMEA)

[Evaluation of film formation]
A uniform optical component-forming composition was spin-coated on a clean silicon wafer and then prebaked (PB) in an oven at 110° C. to form an optical component-forming film having a thickness of 1 μm. The prepared optical component-forming composition was evaluated as "A" when film formation was good, and as "C" when the formed film had defects.

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

[Examples 57-60]
Using the compounds synthesized in the Synthesis Examples, resist compositions were prepared according to the formulations shown in Table 12 below. Among the components of the resist composition shown in Table 12, the following radical generators, radical diffusion inhibitors, and solvents were used.
Radical generator: BASF IRGACURE184
Radical diffusion control agent: IRGACURE1010 manufactured by BASF
Organic solvent: propylene glycol monomethyl ether acetate (PGMEA)

[Evaluation method]
(1) Storage stability and thin film formation of the resist composition The storage stability of the resist composition was evaluated by standing at 23 ° C. and 50% RH for 3 days after preparing the resist composition, and visually checking for the presence or absence of precipitation. It was evaluated by observation. The resist composition after standing still for 3 days was evaluated as A when it was a uniform solution and no precipitation, and as C when there was precipitation. Also, a uniform resist composition was spin-coated on a clean silicon wafer, and then pre-exposure baked (PB) in an oven at 110° C. to form a resist film with a thickness of 40 nm. The prepared resist composition was evaluated as A when the thin film was formed well, and as C when the formed film had defects.

(2) Pattern Evaluation of Resist Pattern A uniform resist composition was spin-coated on a clean silicon wafer, and then pre-exposure baked (PB) in an oven at 110° C. to form a resist film with a thickness of 60 nm. The resulting resist film was irradiated with electron beams set at 1:1 line-and-space intervals of 50 nm, 40 nm, and 30 nm using an electron beam lithography system (ELS-7500, manufactured by Elionix Co., Ltd.). . After the irradiation, each resist film was heated at a predetermined temperature for 90 seconds and immersed in PGME for 60 seconds for development. Thereafter, the resist film was washed with ultrapure water for 30 seconds and dried to form a negative resist pattern. The lines and spaces of the formed resist pattern were observed with a scanning electron microscope (S-4800, manufactured by Hitachi High Technology Co., Ltd.) to evaluate the reactivity of the resist composition to electron beam irradiation.
The sensitivity was indicated by the minimum amount of energy required per unit area to obtain a pattern and was evaluated according to the following.
A: When a pattern is obtained at less than 50 μC/cm ² C: When a pattern is obtained at 50 μC/cm ² or more For pattern formation, the obtained pattern shape is subjected to a SEM (Scanning Electron Microscope). was observed and evaluated according to the following.
A: When a rectangular pattern is obtained B: When an almost rectangular pattern is obtained C: When a non-rectangular pattern is obtained

As described above, the present invention is not limited to the above embodiments and examples, and can be modified as appropriate without departing from the scope of the 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 are applicable to a wet process and are useful for forming a photoresist underlayer film having excellent heat resistance and etching resistance. Further, since this film-forming composition for lithography uses a compound or resin having a specific structure, which has high heat resistance and high solvent solubility, deterioration of the film during high-temperature baking is suppressed, and oxygen plasma etching or the like is performed. It is possible to form a resist and an underlayer film that are also excellent in etching resistance to. Furthermore, when an underlayer film is formed, the adhesiveness to the resist layer is also excellent, so an excellent resist pattern can be formed.
Furthermore, it is useful as a composition for forming various optical parts because it has a high refractive index and can be prevented from being colored by low-temperature to high-temperature treatment.
Therefore, the present invention provides, for example, electrical insulating materials, resist resins, semiconductor sealing resins, printed wiring board adhesives, electrical laminates mounted in electrical equipment, electronic equipment, industrial equipment, etc., electrical equipment・Prepreg matrix resin, build-up laminate material, resin for fiber-reinforced plastic, sealing resin for liquid crystal display panels, paints, various coating agents, adhesives, coatings for semiconductors, which are mounted on electronic equipment and industrial equipment, etc. In addition to being used in resins for resists for semiconductors, resins for forming underlayer films, films and sheets, and plastic lenses (prism lenses, lenticular lenses, microlenses, Fresnel lenses, viewing angle control lenses, contrast enhancement lenses, etc.) , retardation film, electromagnetic wave shielding film, prism, optical fiber, solder resist for flexible printed wiring, plating resist, interlayer insulating film for multilayer printed wiring board, optical parts such as photosensitive optical waveguide, etc. is.

This application is based on a Japanese patent application (Japanese Patent Application No. 2016-143659) filed with the Japan Patent Office on July 21, 2016, the contents of which are incorporated herein by reference.

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

Claims (28)

A compound represented by the following formula (0).

(In formula (0), R ^Y is an alkyl group having 1 to 30 carbon atoms,
R ^Z is a biphenyl group or a cyclohexylphenyl group;
Each R ^T is independently an 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, or a nitro group. , an amino group, a carboxylic acid group, a thiol group, a hydroxyl group, or a group in which a hydrogen atom of a hydroxyl group is substituted with one group selected from an allyloxyalkyl group, an acryloxyalkyl group, or a methacryloxyalkyl group, the alkyl group, The aryl group, the alkenyl group, and the alkoxy group may contain an ether bond, a ketone bond, or an ester bond, wherein at least one of R ^T is an allyloxyalkyl group, acryloxy Including a group substituted with one group selected from an alkyl group or a methacryloxyalkyl group,
X represents an oxygen atom, a sulfur atom or no cross-linking,
each m is independently an integer from 0 to 9, wherein at least one of m is an integer from 1 to 9;
N is an integer of 1 to 4, wherein when N is an integer of 2 or more, the structural formulas in N [ ] may be the same or different,
Each r is independently an integer of 0-2. ) 2. The compound according to claim 1, wherein the compound represented by the formula (0) is a compound represented by the following formula (1).

(In formula (1), R ⁰ has the same meaning as R ^Y above,
R ¹ is a biphenyl group or a cyclohexylphenyl group,
R ² to R ⁵ each independently represents an 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, or a halogen atom. , a nitro group, an amino group, a carboxylic acid group, a thiol group, a hydroxyl group, or a group in which a hydrogen atom of a hydroxyl group is substituted with one group selected from an allyloxyalkyl group, an acryloxyalkyl group, or a methacryloxyalkyl group, The alkyl group, the aryl group, the alkenyl group, and the alkoxy group may contain an ether bond, a ketone bond, or an ester bond, wherein at least one of R ² to R ⁵ has an allyl hydrogen atom of the hydroxyl group. including a group substituted with one group selected from an oxyalkyl group, an acryloxyalkyl group or a methacryloxyalkyl group,
m ² and m ³ are each independently an integer of 0 to 8;
m ⁴ and m ⁵ are each independently an integer of 0 to 9;
However, m ² , m ³ , m ⁴ and m ⁵ cannot be 0 at the same time,
n is the same as the above N, where n is an integer of 2 or more, n structural formulas in [ ] may be the same or different,
p ² to p ⁵ have the same meaning as r above. ) 2. The compound according to claim 1, wherein the compound represented by the formula (0) is a compound represented by the following formula (2).

(In formula (2), R ^0A is synonymous with R ^Y above,
R ^1A is a biphenyl group or a cyclohexylphenyl group,
Each R ^2A is independently an 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, or a nitro group. , an amino group, a carboxylic acid group, a thiol group, a hydroxyl group, or a group in which a hydrogen atom of a hydroxyl group is substituted with one group selected from an allyloxyalkyl group, an acryloxyalkyl group, or a methacryloxyalkyl group, the alkyl group, The aryl group, the alkenyl group, and the alkoxy group may contain an ether bond, a ketone bond, or an ester bond, wherein at least one of R ^2A is an allyloxyalkyl group, acryloxy Including a group substituted with one group selected from an alkyl group or a methacryloxyalkyl group,
n ^A has the same definition as the above N, where n ^A is an integer of 2 or more, n ^A structural formulas in [ ] may be the same or different,
X ^A is an oxygen atom, a sulfur atom or non-crosslinked,
each m ^2A is independently an integer from 0 to 7, with the proviso that at least one m ^2A is an integer from 1 to 7;
q ^A is each independently 0 or 1; ) The compound according to claim 2, wherein the compound represented by the formula (1) is a compound represented by the following formula (1-1).

(in formula (1-1), R ⁰ , R ¹ , R ⁴ , R ⁵ , n, p ² to p ⁵ , m ⁴ and m ⁵ are as defined above;
R ⁶ to R ⁷ each independently represents an 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, a halogen atom, a nitro group, an amino group, or a carboxylic acid; a group, a thiol group,
R ¹⁰ to R ¹¹ are each independently a hydrogen atom or one group selected from an allyloxyalkyl group, an acryloxyalkyl group or a methacryloxyalkyl group,
wherein at least one of R ¹⁰ to R ¹¹ is one group selected from an allyloxyalkyl group, an acryloxyalkyl group or a methacryloxyalkyl group;
m ⁶ and m ⁷ are each independently an integer of 0 to 7;
However, m ⁴ , m ⁵ , m ⁶ and m ⁷ cannot be 0 at the same time. ) The compound according to claim 4, wherein the compound represented by the formula (1-1) is a compound represented by the following formula (1-2).

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

(In formula (2-1), R ^0A , R ^1A , n ^A , q ^A and X ^A have the same definitions as in formula (2) above;
Each R ^3A is independently an 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, a halogen atom, a nitro group, an amino group, a carboxylic acid group, or a thiol. is the basis,
Each R ^4A is independently a group in which a hydrogen atom or a hydrogen atom of a hydroxyl group is substituted with one group selected from an allyloxyalkyl group, an acryloxyalkyl group or a methacryloxyalkyl group, wherein R ^4A is one group selected from an allyloxyalkyl group, an acryloxyalkyl group or a methacryloxyalkyl group,
Each m ^6A is independently an integer of 0-5. ) A resin obtained by using the compound according to claim 1 as a monomer. 8. The resin according to claim 7, having a structure represented by the following formula (3).

(In formula (3),
L is an alkylene group having 1 to 30 carbon atoms, an arylene group having 6 to 30 carbon atoms, an alkoxylylene group having 1 to 30 carbon atoms, or a single bond, and the alkylene group, the arylene group, and the alkoxyylene group are may contain an ether bond, a ketone bond or an ester bond,
R ⁰ has the same definition as R ^Y above,
R ¹ is a biphenyl group or a cyclohexylphenyl group,
R ² to R ⁵ each independently represents an 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, or a halogen atom. , a nitro group, an amino group, a carboxylic acid group, a thiol group, a hydroxyl group, or a group in which a hydrogen atom of a hydroxyl group is substituted with one group selected from an allyloxyalkyl group, an acryloxyalkyl group, or a methacryloxyalkyl group, The alkyl group, the aryl group, the alkenyl group, and the alkoxy group may contain an ether bond, a ketone bond, or an ester bond, wherein at least one of R ² to R ⁵ has an allyl hydrogen atom of the hydroxyl group. including a group substituted with one group selected from an oxyalkyl group, an acryloxyalkyl group or a methacryloxyalkyl group,
m ² and m ³ are each independently an integer of 0 to 8;
m ⁴ and m ⁵ are each independently an integer of 0 to 9;
However, m ² , m ³ , m ⁴ and m ⁵ cannot be 0 at the same time, and at least one of R ² to R ⁵ has a hydroxyl hydrogen atom of an allyloxyalkyl group, an acryloxyalkyl group or a methacryloxyalkyl group. A group substituted with one group selected from
n is an integer of 1 to 4, where n is an integer of 2 or more, n structural formulas in [ ] may be the same or different,
p ² to p ⁵ are each independently an integer of 0 to 2 ; ) 8. The resin according to claim 7, having a structure represented by the following formula (4).

(In formula (4), L is an alkylene group having 1 to 30 carbon atoms, an arylene group having 6 to 30 carbon atoms, an alkoxylylene group having 1 to 30 carbon atoms, or a single bond, and the alkylene group and the arylene group , the alkoxylene group may contain an ether bond, a ketone bond or an ester bond,
R ^0A has the same definition as R ^Y above,
R ^1A is a biphenyl group or a cyclohexylphenyl group,
Each R ^2A is independently an 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, or a nitro group. , an amino group, a carboxylic acid group, a thiol group, a hydroxyl group, or a group in which a hydrogen atom of a hydroxyl group is substituted with one group selected from an allyloxyalkyl group, an acryloxyalkyl group, or a methacryloxyalkyl group, the alkyl group, The aryl group, the alkenyl group, and the alkoxy group may contain an ether bond, a ketone bond, or an ester bond, wherein at least one of R ^2A is an allyloxyalkyl group, acryloxy Including a group substituted with one group selected from an alkyl group or a methacryloxyalkyl group,
n ^A has the same definition as the above N, where n ^A is an integer of 2 or more, n ^A structural formulas in [ ] may be the same or different,
X ^A is an oxygen atom, a sulfur atom or non-crosslinked,
each m ^2A is independently an integer from 0 to 7, with the proviso that at least one m ^2A is an integer from 1 to 7;
q ^A is each independently 0 or 1; ) A composition comprising one or more 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 composition of Claim 10, further comprising a solvent. 12. The composition according to claim 10 or 11, further comprising an acid generator. A composition according to any one of claims 10 to 12, further comprising a cross-linking agent. The cross-linking agent is at least one selected from the group consisting of phenol compounds, epoxy compounds, cyanate compounds, amino compounds, benzoxazine compounds, melamine compounds, guanamine compounds, glycoluril compounds, urea compounds, isocyanate compounds and azide compounds. 14. The composition of claim 13. 15. A composition according to claim 13 or 14, wherein the cross-linking agent has at least one allyl group. A composition containing one or more 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, in which the content of the cross-linking agent is The composition according to any one of claims 13 to 15, which is 0.1 to 100 parts by mass when the total mass of the substances is 100 parts by mass. The composition according to any one of claims 13-16, further comprising a cross-linking accelerator. 18. The composition according to claim 17, wherein the cross-linking accelerator is at least one selected from the group consisting of amines, imidazoles, organic phosphines, and Lewis acids. The content of the cross-linking accelerator contains one or more selected from the group consisting of the compound according to any one of claims 1 to 6 and the resin according to any one of claims 7 to 9. The composition according to claim 17 or 18, which is 0.1 to 5 parts by weight when the total weight of the composition is 100 parts by weight. The composition according to any one of claims 10 to 19, further comprising a radical polymerization initiator. The composition according to claim 20, wherein the radical polymerization initiator is at least one selected from the group consisting of ketone-based photopolymerization initiators, organic peroxide-based polymerization initiators and azo-based polymerization initiators. The content of the radical polymerization initiator contains one or more selected from the group consisting of the compound according to any one of claims 1 to 6 and the resin according to any one of claims 7 to 9. The composition according to claim 20 or 21, which is 0.05 to 25 parts by weight when the total weight of the composition is 100 parts by weight. The composition according to any one of claims 10 to 22, which is used for lithographic film formation. The composition according to any one of claims 10 to 22, which is used for forming a resist permanent film. The composition according to any one of claims 10 to 22, which is used for forming optical components. 24. A method of forming a resist pattern, comprising forming a photoresist layer on a substrate using the composition according to claim 23, and then irradiating a predetermined region of the photoresist layer with radiation and developing the photoresist layer. An underlayer film is formed on a substrate using the composition according to claim 23, and after forming at least one photoresist layer on the underlayer film, a predetermined region of the photoresist layer is irradiated with radiation. and developing a resist pattern. A lower layer film is formed on a substrate using the composition according to claim 23, an intermediate layer film is formed on the lower layer film using a resist intermediate layer film material, and at least one layer is formed on the intermediate layer film forming a photoresist layer of
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, the lower layer film is etched using the obtained intermediate layer film pattern as an etching mask, and the substrate is etched using the obtained lower layer film pattern as an etching mask. forming a pattern;
A method of forming a circuit pattern, comprising: