JPWO2018016614A1 - Compound, resin, composition and pattern forming method - Google Patents

Abstract

The compound represented by following formula (0). [Chemical formula 1]

Description

  The present invention relates to a compound having a specific structure, a resin, and a composition containing the same. The present invention also relates to a pattern formation method using the composition.

  In the manufacture of semiconductor devices, microfabrication by lithography using a photoresist material is performed, but in recent years, with the high integration and high speed of LSI, further miniaturization by pattern rules is required. In addition, the light source for lithography used at the time of resist pattern formation is shortened in wavelength from KrF excimer laser (248 nm) to ArF excimer laser (193 nm), and the introduction of extreme ultraviolet light (EUV, 13.5 nm) It is also expected.

  However, in lithography using a conventional polymer-based resist material, the molecular weight is as large as about 10,000 to 100,000, and the molecular weight distribution is also broad, so that roughness occurs on the surface of the pattern, making it difficult to control the pattern dimension and limiting to miniaturization There is. Therefore, various low molecular weight resist materials have been proposed so far to provide a resist pattern of higher resolution. The low molecular weight resist material is expected to give a resist pattern having high resolution and small roughness because the molecular size is small.

  At present, various low molecular weight resist materials are known. For example, an alkali-developable negative type radiation sensitive composition (see, for example, Patent Document 1 and Patent Document 2) using a low molecular weight polynuclear polyphenol compound as a main component is proposed, and a low molecular weight resist material having high heat resistance As a candidate for the above, an alkali-developable negative radiation-sensitive composition (see, for example, Patent Document 3 and Non-patent Document 1) using a low molecular weight cyclic polyphenol compound as a main component has also been proposed. In addition, as a base compound for resist materials, it is known that polyphenol compounds can impart high heat resistance despite their low molecular weight, and are useful for improving the resolution and roughness of resist patterns (for example, Non-Patent Document 2) reference).

  The inventors of the present invention have so far obtained a resist composition containing a compound of a specific structure and an organic solvent as a material which is excellent in etching resistance, is soluble in a solvent, and is applicable to a wet process (see Patent Document 4). .) Is proposed.

  Further, as miniaturization of the resist pattern progresses, a problem of resolution or a problem that the resist pattern collapses after development occurs, so that thinning of the resist becomes desirable. However, simply reducing the thickness of the resist makes it difficult to obtain a film thickness of a resist pattern sufficient for substrate processing. Therefore, not only a resist pattern, but a resist underlayer film is produced between the resist and the semiconductor substrate to be processed, and a process for providing this resist underlayer film with a function as a mask at the time of substrate processing is also required.

  At present, various types of resist underlayer films for such processes are known. For example, unlike a conventional resist underlayer film having a high etching rate, as a material for realizing a resist underlayer film for lithography having a dry etching rate selectivity close to that of the resist, the end groups are removed by application of a predetermined energy. An underlayer film forming material for a multilayer resist process has been proposed which contains a resin component having at least a substituent which generates a sulfonic acid residue apart and a solvent (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 selection ratio of dry etching rate smaller 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 selection ratio smaller than that of a semiconductor substrate, a repeating unit of acenaphthylene is copolymerized with a repeating unit having a substituted or non-substituted hydroxy group. Patent Document 7 proposes a resist underlayer film material containing a polymer obtained by

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

  Moreover, the present inventors are excellent in etching resistance, high heat resistance, and soluble in a solvent, and as a material applicable to a wet process, a lower layer film forming composition for lithography containing a compound of a specific structure and an organic solvent (See Patent Document 8).

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

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

JP 2005-326838 A JP 2008-145539 A JP, 2009-173623, A International Publication No. 2013/024778 Unexamined-Japanese-Patent No. 2004-177668 Unexamined-Japanese-Patent No. 2004-271838 JP 2005-250434 A International Publication No. 2013/024779 JP 2002-334869 A WO 2004/066377 JP 2007-226170 A JP 2007-226204 A Unexamined-Japanese-Patent No. 2010-138393 JP, 2015-174877, A International Publication No. 2014/123005

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, many film-forming compositions for lithography for resist applications and film-forming compositions for lithography for lower layer films have been proposed, but wet processes such as spin coating and screen printing can be applied. As well as having high solvent solubility, none have achieved both heat resistance and etching resistance at a high level, and development of new materials is required.
In addition, development of a new material suitable for obtaining a resist permanent film excellent in alkali developability, photosensitivity and resolution is also required.
Furthermore, although many compositions for optical members have been conventionally proposed, none have achieved high levels of both 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 thereof is to apply a wet process and to form a photoresist and an underlayer film for photoresist excellent in heat resistance, solubility and etching resistance. Compounds, resins, and film-forming compositions 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 is to provide a composition for optical members.

MEANS TO SOLVE THE PROBLEM As a result of repeating earnestly examining in order to solve the said subject, the present inventors discover that the said subject can be solved with the compound or resin which has a specific structure, and came to complete this invention.
That is, the present invention is as follows.
[1]
The compound represented by following formula (0).

In the formula (0), R ^Y is a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms,
R ^Z is a C 1 to C 60 N valent group or a single bond,
R ^T each independently has an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, and a substituent Alkenyl group having 2 to 30 carbon atoms which may be substituted, alkoxy group having 1 to 30 carbon atoms which may have a substituent, halogen atom, nitro group, amino group, carboxylic acid group, thiol group, hydroxyl group or hydroxyl group Is a group substituted by one group selected from an aryloxyalkyl group, an acryloxyalkyl group or a methacryloxyalkyl group, and the alkyl group, the aryl group, the alkenyl group and the alkoxy group are ethers binding, may contain ketone or ester bond, wherein at least one hydroxyl group of a hydrogen atom allyl oxyalkyl group R ^T, acryloxy a Includes one substituted group with a group selected from the kill group or methacryloxy group,
X represents an oxygen atom, a sulfur atom or no crosslinking,
m is each independently an integer of 0 to 9, wherein at least one of m is an integer of 1 to 9,
N is an integer of 1 to 4, and when N is an integer of 2 or more, structural formulas in N [] may be the same or different.
r is each independently an integer of 0 to 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 is synonymous with said R ^Y ,
R ¹ is a C ¹ to C 60 n-valent group or a single bond,
R ^{2 to} R ⁵ each independently represent an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, and a substituent 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, And the hydrogen atom of the hydroxyl group or the hydroxyl group is a group substituted by one group selected from an aryloxy alkyl group, an acryloxy alkyl group or a methacryl oxy alkyl group, and the alkyl group, the aryl group, the alkenyl group, the alkoxy group is an ether bond, may contain ketone or ester bond, wherein at least one hydrogen atom of the hydroxyl group is allyloxy alkyl group R ² to R ^5, a Includes one substituted group with a group selected from Lil oxyalkyl group or methacryloxy 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 can not simultaneously be 0,
n is synonymous with said N, Here, when n is an integer greater than or equal to 2, Structural formula in n [] may be same or different,
p ² ~p ⁵ have the same meanings as defined above r. )
[3]
The compound according to the above [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 said R ^Y ,
R ^1A is a C ¹ to C 60 n ^A valent group or a single bond,
R ^2A each independently has an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, and a substituent Alkenyl group having 2 to 30 carbon atoms which may be substituted, alkoxy group having 1 to 30 carbon atoms which may have a substituent, halogen atom, nitro group, amino group, carboxylic acid group, thiol group, hydroxyl group or hydroxyl group Is a group substituted by one group selected from an aryloxyalkyl group, an acryloxyalkyl group or a methacryloxyalkyl group, and the alkyl group, the aryl group, the alkenyl group and the alkoxy group are ethers binding, it may contain ketone or ester bond, wherein at least one hydroxyl group of a hydrogen atom allyl oxyalkyl group R ^2A, acrylic Oki Includes one substituted group with a group selected from an alkyl or methacryloxyalkyl group,
n ^A has the same meaning as N, and in the case where n ^A is an integer of 2 or more, structural formulas in n ^A [] may be the same or different.
X ^A represents an oxygen atom, a sulfur atom or no crosslinking,
m ^2A is each independently an integer of 0 to 7, provided that at least one m ^2A is an integer of 1 to 7,
Each q ^A is independently 0 or 1. )
[4]
The compound as described in said [2] whose compound represented by said Formula (1) is a compound represented by 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 represent an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, and a substituent A C 2-30 alkenyl group which may have a halogen atom, a halogen atom, a nitro group, an amino group, a carboxylic acid group, a thiol group,
R ^{10 to} R ¹¹ each independently represent a hydrogen atom or one group selected from an allyloxyalkyl group, an acryloxyalkyl group or a methacryloxyalkyl group,
Here, at least one of R ^{10 to} R ¹¹ is one group selected from an aryloxyalkyl 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 can not be 0 simultaneously. )
[5]
The compound as described in the above [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, and
R ^{8 to} R ⁹ have the same meaning as R ^{6 to} R ⁷ above,
R ^{12 to} R ¹³ have the same meaning as R ^{10 to} R ¹¹ above,
m ⁸ and m ⁹ are each independently an integer of 0 to 8,
However, m ⁶ , m ⁷ , m ⁸ and m ⁹ can not be 0 at the same time. )
[6]
The compound as described in the above [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 are as defined in the above formula (2),
R ^3A each independently has an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, 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 and a thiol group, which may be
R ^4A is independently a hydrogen atom of hydrogen or hydroxyl allyloxyalkyl group is one substituted group with a group selected from acryloxy group or methacryloxy group, wherein, R ^4A At least one of them is one group selected from an aryloxyalkyl group, an acryloxyalkyl group or a methacryloxyalkyl group,
m ^6A is each independently an integer of 0 to 5; )
[7]
Resin obtained as a monomer with the compound as described in said [1].
[8]
Resin as described in said [7] which has a structure represented by following formula (3).

(In the formula (3),
L represents an alkylene group having 1 to 30 carbon atoms which may have a substituent, an arylene group having 6 to 30 carbon atoms which may have a substituent, and a carbon number which may have a substituent 1 to 30 alkoxyl group or single bond, and the alkylene group, the arylene group and the alkoxyl group may contain an ether bond, a ketone bond or an ester bond,
R ⁰ is synonymous with the above R ^Y ,
R ¹ is a C ¹ to C 60 n-valent group or a single bond,
R ^{2 to} R ⁵ each independently represent an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, and a substituent 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, And the hydrogen atom of the hydroxyl group or the hydroxyl group is a group substituted by one group selected from an aryloxy alkyl group, an acryloxy alkyl group or a methacryl oxy alkyl group, and the alkyl group, the aryl group, the alkenyl group, the alkoxy group is an ether bond, may contain ketone or ester bond, wherein at least one hydrogen atom of the hydroxyl group is allyloxy alkyl group R ² to R ^5, a Includes one substituted group with a group selected from Lil oxyalkyl group or methacryloxy 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 do not simultaneously become 0, and at least one of R ^{2 to} R ⁵ is a hydrogen atom of a hydroxyl group being an allyloxy alkyl group, an acryloxy alkyl group or a methacryl oxy alkyl It is a group substituted by one group selected from a group. )
[9]
Resin as described in said [7] which has a structure represented by following formula (4).

(In the formula (4), L has 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 a substituent And the alkylene group, the arylene group and the alkoxylene group may contain an ether bond, a ketone bond or an ester bond,
R ^0A is synonymous with the above R ^Y ,
R ^1A is a C ¹ to C 30 n ^A valent group or a single bond,
R ^2A each independently has an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, and a substituent Alkenyl group having 2 to 30 carbon atoms which may be substituted, alkoxy group having 1 to 30 carbon atoms which may have a substituent, halogen atom, nitro group, amino group, carboxylic acid group, thiol group, hydroxyl group or hydroxyl group Is a group substituted by one group selected from an aryloxyalkyl group, an acryloxyalkyl group or a methacryloxyalkyl group, and the alkyl group, the aryl group, the alkenyl group and the alkoxy group are ethers binding, it may contain ketone or ester bond, wherein at least one hydroxyl group of a hydrogen atom allyl oxyalkyl group R ^2A, acrylic Oki Includes one substituted group with a group selected from an alkyl or methacryloxyalkyl group,
n ^A has the same meaning as N, and in the case where n ^A is an integer of 2 or more, structural formulas in n ^A [] may be the same or different.
X ^A represents an oxygen atom, a sulfur atom or no crosslinking,
m ^2A is each independently an integer of 0 to 7, provided that at least one m ^2A is an integer of 1 to 7,
Each q ^A is independently 0 or 1. )
[10]
The composition containing 1 or more types chosen from the group which consists of a compound in any one of said [1]-[6], and resin in any one of said [7]-[9].
[11]
The composition according to the above [10], further comprising a solvent.
[12]
The composition according to the above [10] or [11], further comprising an acid generator.
[13]
The composition according to any one of the above [10] to [12], further comprising a crosslinking agent.
[14]
The crosslinking agent is at least one selected from the group consisting of phenolic compounds, epoxy compounds, cyanate compounds, amino compounds, benzoxazine compounds, melamine compounds, guanamine compounds, glycoluril compounds, urea compounds, isocyanate compounds and azide compounds. , The composition as described in said [13].
[15]
The composition according to the above [13] or [14], wherein the crosslinking agent has at least one allyl group.
[16]
At least one selected from the group consisting of the compound according to any one of the above [1] to [6] and the resin according to any one of the above [7] to [9] The composition according to any one of the above [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 the above [13] to [16], further comprising a crosslinking accelerator.
[18]
The composition according to the above [17], wherein the crosslinking accelerator is at least one selected from the group consisting of amines, imidazoles, organic phosphines, and Lewis acids.
[19]
At least one selected from the group consisting of the compound according to any one of the above [1] to [6] and the resin according to any one of the above [7] to [9] The composition as described in said [17] or [18] which is 0.1-5 mass parts, when the total mass of the composition to contain is made into 100 mass parts.
[20] The composition according to any one of the above [10] to [19], further comprising a radical polymerization initiator.
[21] [10] to [20], wherein the radical polymerization initiator is at least one selected from the group consisting of ketone photopolymerization initiators, organic peroxide polymerization initiators and azo polymerization initiators. ] The composition as described in any one.
[22] The content ratio of the radical polymerization initiator comprises the compound according to any one of the above [1] to [6] and the resin according to any one of the above [7] to [9] When the total mass of the composition containing one or more types selected from the group is 100 parts by mass, it is from 0.05 to 25 parts by mass, as described in any one of the above [10] to [21] Composition.
[23] The composition according to any one of the above [10] to [22], which is used for film formation for lithography.
[24] The composition according to any one of the above [10] to [22], which is used for forming a permanent resist film.
[25] The composition according to any one of the above [10] to [22], which is used for forming an optical component.
[26] A resist pattern comprising a step of forming a photoresist layer on the substrate using the composition according to the above [23], and then irradiating a predetermined region of the photoresist layer with radiation for development Formation method.
[27] An underlayer film is formed on the substrate using the composition described in the above [23], and at least one photoresist layer is formed on the underlayer film, and then a predetermined layer of the photoresist layer is formed. A method of forming a resist pattern, comprising the steps of irradiating a region with radiation and performing development.
[28] An underlayer film is formed on the substrate using the composition described in the above [23], and an interlayer film is formed on the underlayer film using a resist interlayer film material, and the interlayer film After forming at least one photoresist layer thereon, radiation is applied to a predetermined region of the photoresist layer and developed to form a resist pattern, and then the intermediate layer film is formed using the resist pattern as a mask Forming a pattern on the substrate by etching the lower layer film using the obtained intermediate layer film pattern as an etching mask and etching the substrate using the obtained lower layer film pattern as an etching mask Formation method.

  The compound and resin in the present invention have high solubility in a safe solvent, and good heat resistance and etching resistance. Moreover, the resist composition containing the compound and / or resin in this invention gives a favorable resist pattern shape.

  Hereinafter, modes for carrying out the present invention (hereinafter, also referred to as “the present embodiment”) will be described. In addition, the following embodiment is an illustration for demonstrating this invention, and this invention is not limited only to the embodiment.

The compound, the resin, and the composition containing the compound in this embodiment are applicable to a wet process and are useful for forming a photoresist underlayer film excellent in heat resistance and etching resistance. Further, since the composition in the present embodiment uses a compound or resin having a specific structure having high heat resistance and solvent solubility, deterioration of the film at the time of high temperature baking is suppressed, and etching resistance to oxygen plasma etching and the like It is possible to form an excellent resist and an underlayer film. In addition, when the lower layer film is formed, the adhesion with the resist layer is also excellent, so that an excellent resist pattern can be formed.
Moreover, the compound and resin in the present embodiment are excellent in sensitivity and resolution when used for a photosensitive material, and while maintaining high heat resistance, general-purpose organic solvents, other compounds, resin components, and the like. And is useful for forming a resist permanent film excellent in compatibility with additives.
Furthermore, since the refractive index is high and the coloring due to a wide range of heat treatment from low temperature to high temperature is suppressed, it is also useful as various optical forming compositions.

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

In the formula (0), R ^Y is a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms,
R ^Z is a C 1 to C 60 N valent group or a single bond,
R ^T each independently has an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, and a substituent Alkenyl group having 2 to 30 carbon atoms which may be substituted, alkoxy group having 1 to 30 carbon atoms which may have a substituent, halogen atom, nitro group, amino group, carboxylic acid group, thiol group, hydroxyl group or hydroxyl group Is a group substituted by one group selected from an aryloxyalkyl group, an acryloxyalkyl group or a methacryloxyalkyl group, and the alkyl group, the aryl group, the alkenyl group and the alkoxy group are ethers binding, may contain ketone or ester bond, wherein at least one hydroxyl group of a hydrogen atom allyl oxyalkyl group R ^T, acryloxy a Includes one substituted group with a group selected from the kill group or methacryloxy group,
X represents an oxygen atom, a sulfur atom or no crosslinking,
m is each independently an integer of 0 to 9, wherein at least one of m is an integer of 1 to 9,
N is an integer of 1 to 4, and when N is an integer of 2 or more, structural formulas in N [] may be the same or different.
r is each independently an integer of 0 to 2; )

R ^Y is a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms. As the alkyl group, a linear, branched or cyclic alkyl group can be used. Providing excellent heat resistance and solvent solubility because 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 Can.

R ^z is a C 1 to C 60 N valent group 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, structural formulas in N [] may be the same or different. The N-valent group is an alkyl group having 1 to 60 carbon atoms when N = 1, an alkylene group having 1 to 30 carbon atoms when N = 2, and 2 to 2 carbon atoms when N = 3. In the case of 60 alkanepropyl groups and N = 4, it indicates an alkanetetrayl group having 3 to 60 carbon atoms. As said N-valent group, what has a linear hydrocarbon group, a branched hydrocarbon group, or an alicyclic hydrocarbon group etc. are mentioned, for example. Here, as for the alicyclic hydrocarbon group, a bridged alicyclic hydrocarbon group is also included. The N-valent hydrocarbon group may have an alicyclic hydrocarbon group, a double bond, a hetero atom or an aromatic group having 6 to 60 carbon atoms.

R ^T each independently has an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, and a substituent Alkenyl group having 2 to 30 carbon atoms which may be substituted, alkoxy group having 1 to 30 carbon atoms which may have a substituent, halogen atom, nitro group, amino group, carboxylic acid group, thiol group, hydroxyl group or hydroxyl group Is a group substituted by one group selected from an aryloxyalkyl group, an acryloxyalkyl group or a methacryloxyalkyl group, and the alkyl group, the aryl group, the alkenyl group and the alkoxy group are ethers binding, may contain ketone or ester bond, wherein at least one hydroxyl group of a hydrogen atom allyl oxyalkyl group R ^T, acryloxy a Including one substituted group with a group selected from the kill group or methacryloxy group. The alkyl group, the alkenyl group and the alkoxy group may be a linear, branched or cyclic group.
Here, a group in which a hydrogen atom of a hydroxyl group is substituted by one group selected from an aryloxyalkyl group, an acryloxyalkyl group or a methacryloxyalkyl group is an allyloxyalkyl group, an acryloxyalkyl group or a methacryloxyalkyl group. And a group having one group selected from, for example, an aryloxyalkyl group, an acryloxyalkyl group or a methacryloxyalkyl group.

  X represents an oxygen atom, a sulfur atom or non-crosslinking, and when X is an oxygen atom or a sulfur atom, it tends to develop high heat resistance, and is preferably an oxygen atom. From the viewpoint of solubility, X is preferably non-crosslinked. Moreover, m is respectively independently an integer of 0-9, and at least one of m is an integer of 1-9.

  In the formula (0), the site represented by a naphthalene structure is a single ring structure in the case of r = 0, a bicyclic structure in the case of r = 1, and a tricyclic structure in the case of r = 2 It becomes. r is each independently an integer of 0 to 2; The above-mentioned m has its numerical range determined in accordance with the ring structure determined by r.

[Compound represented by formula (1)]
The 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 said Formula (1), ^R0 is a hydrogen atom, a C1-C30 alkyl group, or a C6-C30 aryl group. 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, the heat resistance is relatively high, and the solvent solubility is improved. Tend to Further, R ⁰ is a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms or carbon number from the viewpoint of suppressing oxidative decomposition and suppressing coloring of the compound and improving heat resistance and solvent solubility. It is preferable that it is a 6-30 aryl group.
R ¹ is a C ¹ to C 60 n-valent group or a single bond, and each aromatic ring is bonded via R ¹ .
R ^{2 to} R ⁵ each independently represent an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, and a substituent 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, And the hydrogen atom of the hydroxyl group or the hydroxyl group is a group substituted by one group selected from an aryloxy alkyl group, an acryloxy alkyl group or a methacryl oxy alkyl group, and the alkyl group, the aryl group, the alkenyl group, the alkoxy group is an ether bond, may contain ketone or ester bond, wherein at least one hydrogen atom of the hydroxyl group is allyloxy alkyl group R ² to R ^5, a Including one substituted group with a group selected from Lil oxyalkyl group or methacryloxy group.
m ² and m ³ are each independently an integer of 0 to 8, and m ⁴ and m ⁵ are each independently an integer of 0 to 9. However, m ² , m ³ , m ⁴ and m ⁵ can not be 0 at the same time.
n is an integer of 1 to 4; Here, when n is an integer of 2 or more, structural formulas in n [] may be the same or different.
p ² ~p ⁵ are each independently represent an integer of 0 to 2.
Here, the alkyl group, the alkenyl group and the alkoxy group may be a linear, branched or cyclic group.

  The n-valent group is an alkyl group having 1 to 60 carbon atoms in the case of n = 1, an alkylene group having 1 to 30 carbon atoms in the case of n = 2, carbon in the case of n = 3 In the case of alkanepropiyl group of several 2-60, in the case of n = 4, a C3-C60 alkane tetrayl group is shown. As said n valent group, what has a linear hydrocarbon group, a branched hydrocarbon group, or an alicyclic hydrocarbon group etc. are mentioned, for example. Here, as for the alicyclic hydrocarbon group, a bridged alicyclic hydrocarbon group is also included. Moreover, the said n valent group may have a C6-C60 aromatic group.

  The n-valent hydrocarbon group may have an alicyclic hydrocarbon group, a double bond, a hetero atom or an aromatic group having 6 to 60 carbon atoms. Here, as for the alicyclic hydrocarbon group, a bridged alicyclic hydrocarbon group is also included.

  The compound represented by the above formula (1) has high heat resistance due to the rigidity of its structure although having a relatively low molecular weight, and therefore can be used under high temperature bake conditions. In addition, it has tertiary carbon or quaternary carbon in the molecule, and is suitably used as a film forming composition for lithography which can suppress crystallinity and can be used for manufacturing a film for lithography.

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

  Furthermore, because of the relatively low molecular weight and low viscosity, even in the case of a substrate having a step (in particular, a fine space, a hole pattern, etc.), the film is flat while being uniformly filled to every corner of the step. As a result, it is easy to enhance the properties, and 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, high etching resistance can also be imparted.

  Furthermore, since the aromatic density is high, the refractive index is high, and the coloring is suppressed also by a wide range of heat treatment from low temperature to high temperature, and therefore, they are useful as various optical component forming compositions. Among them, a compound having quaternary carbon is preferable from the viewpoint of suppressing oxidative decomposition of the compound to suppress coloring and improving heat resistance and solvent solubility. Optical parts include film-like and sheet-like parts, plastic lenses (prism lenses, lenticular lenses, microlenses, Fresnel lenses, viewing angle control lenses, contrast improvement lenses, etc.), retardation films, films for shielding electromagnetic waves, It is useful as a prism, an optical fiber, a solder resist for flexible printed wiring, a plating resist, an interlayer insulating film for a multilayer printed wiring board, and a photosensitive optical waveguide.

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

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 represent an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, and a substituent A C 2-30 alkenyl group which may have a halogen atom, a halogen atom, a nitro group, an amino group, a carboxylic acid group, a thiol group,
R ^{10 to} R ¹¹ each independently represent a hydrogen atom or one group selected from an allyloxyalkyl group, an acryloxyalkyl group or a methacryloxyalkyl group,
Here, at least one of R ^{10 to} R ¹¹ is one group selected from an aryloxyalkyl 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 can not be 0 simultaneously.

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

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 meaning as R ^{6 to} R ⁷ above,
R ^{12 to} R ¹³ have the same meaning as R ^{10 to} R ¹¹ above,
m ⁸ and m ⁹ are each independently an integer of 0 to 8.
However, m ⁶ , m ⁷ , m ⁸ and m ⁹ can not be 0 at the same time.

  Moreover, it is preferable that the compound represented by the said Formula (1-1) is a compound represented by following formula (1a) from a viewpoint of supply property of a raw material.

In the above formula ^{(1a), R 0 ~R 5} , m 2 ~m 5 and n have the same meanings as those described by the above formula (1).

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

In the above formula (1b), R ⁰ , R ¹ , R ⁴ , R ⁵ , m ⁴ , m ⁵ and n are as defined in the above formula (1), and R ⁶ , R ⁷ , R ¹⁰ , R < ¹¹ >, m < ⁶ >, m < ⁷ > is synonymous with what was demonstrated by said Formula (1-1).

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

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

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

In the above formula ^{(1c), R 0, R} 1, R 6 ~R 13, m 6 ~m 9, n has the same meaning as described in the above formula (1-2).

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

In the formula ^{(1c '), R 0,} R 1, R 6 ~R 13, m 6 ~m 9, n has the same meaning as described in the formula (1-2).

  Although the specific example of a compound represented by said Formula (0) is illustrated below, the compound represented by Formula (0) is not limited to the specific example enumerated here.

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

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

In the above formulas, X is the same as those described in the above formula ^{(0), R Y ',} R Z' are as defined ^R Y, ^{R Z} described by the above formula (0). 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.

  Although the specific example of a compound represented by the said Formula (1) is illustrated below, the compound represented by Formula (1) is not limited to the compound enumerated here.

In said formula, R < ² >, R < ³ >, R < ⁴ >, R < ⁵ > is synonymous with what was demonstrated by said Formula (1). m ² and m ³ are integers of 0 to 6, and m ⁴ and m ⁵ are integers of 0 to 7. Provided that at least one selected from R ² , R ³ , R ⁴ and R ⁵ is a group in which the hydrogen atom of the hydroxyl group is substituted by one group selected from an aryloxyalkyl group, an acryloxyalkyl group or a methacryloxyalkyl group And m ² , m ³ , m ⁴ and m ⁵ can not be 0 simultaneously.

  Although the specific example of a compound represented by the said Formula (1) is further illustrated below, the compound represented by Formula (1) is not limited to the compound enumerated here.

In the ^{formula, R 10, R 11, R} 12, R 13 have the same meanings as those described by the above formula ^(1-2), at least one allyloxy group of R 10 ^{to R 13,} acryloxyalkyl It is one group selected from a group or methacryloxyalkyl group.

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

In the above formulae, R ^{10 to} R ¹³ each independently represent a hydrogen atom or one group selected from an allyloxyalkyl group, an acryloxyalkyl group or a methacryloxyalkyl group, wherein R ^{10 to} R ¹³ Is at least one group selected from an aryloxyalkyl group, an acryloxyalkyl group or a methacryloxyalkyl group.

  Hereinafter, although the specific example of a compound represented by the said Formula (0) is further illustrated, the compound represented by Formula (0) is not limited to the specific example enumerated 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 formulae, R ⁰ , R ¹ and n are as defined in the above formula (1-1), and R ^{10 ′} and R ^{11 ′} are the same as R ¹⁰ and R described in the above formula (1-1) ¹¹ in the above formula, R 4 ^'and R ^5' are each independently an alkyl group having 1 to 30 carbon atoms which may have a substituent carbon atoms, which may have a substituent 6 30, an aryl group having 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, an alkoxy group having 1 to 30 carbon atoms which may have a substituent, a halogen atom, a nitro group, an amino group, A hydrogen atom of a carboxylic acid group, a thiol group, a hydroxyl group or a hydroxyl group is a group substituted with one group selected from an aryloxyalkyl group, an acryloxyalkyl group or a methacryloxyalkyl group, the alkyl group, the aryl group, Said alkenyl group, said alkoxy group Group may contain an ether bond, ketone bond or an ester bond, at least one of R ^{10 'and} R ^11' are, allyloxy group, of one selected from acryloxy group or methacryloxy group It is a group. m ^{4 'and} m ^5' is an integer of 0 to 8, ^{m 10 'and m 11'} is an integer of 1 to 9, ^{m 4 '+} m ^10' and ^{m 4 '+} m ^11' are each independently It is an integer of 1-9.

As R ⁰ , for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, triacontyl group, phenyl group, naphthyl Groups, anthracene groups, pyrenyl groups, biphenyl groups and heptacene groups.

As R ^{4 ′} and R ^{5 ′} , for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, triacontyl group , Cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, cycloundecyl group, cyclododecyl group, cyclotriacontyl group, norbornyl group, adamantyl group, phenyl Group, naphthyl group, anthracene group, pyrenyl group, biphenyl group, heptacene group, vinyl group, allyl group, triaclactonyl group, methoxy group, ethoxy group, triacontylic group, fluorine atom, chlorine atom, bromine atom, iodine atom And thiol groups.

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

In the ^formula, R 10 ^{to R 13} have the same meanings as those described by the formula ^{(1-2), R 16} represents a linear, branched or cyclic alkylene group having 1 to 30 carbon atoms, carbon atoms 6 to 30 divalent aryl groups or C 2 to C 30 divalent alkenyl groups.

As R ¹⁶ , for example, methylene group, ethylene group, propene group, butene group, pentene group, hexene group, heptene group, octene group, nonene group, decene group, undecene group, dodecene group, triaconten group, cyclopropene group Cyclobutene group, cyclopentene group, cyclohexene group, cycloheptene group, cyclooctene group, cyclononene group, cyclodecene group, cycloundecene group, cyclododecene group, cyclotriaconten group, divalent norbornyl group, divalent adamantyl group, divalent Of 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 illustration of R ¹⁶ includes isomers. For example, a butyl group contains n-butyl group, isobutyl group, sec-butyl group, tert-butyl group.

In the above formulae, R ^{10 to} R ¹³ are as defined in the formula (1-2), and each R ¹⁴ 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 or a thiol group, m ¹⁴ is an integer of 0 to 5 and m ^{14 '} is an integer of 0-4.

As R ¹⁴ , for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, triacontyl group, cyclopropyl group, Cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, cycloundecyl group, cyclododecyl group, cyclotriacontyl group, norbornyl group, adamantyl group, phenyl group, naphthyl group, Anthracene group, pyrenyl group, biphenyl group, heptacene group, vinyl group, allyl group, triaccontenyl group, methoxy group, ethoxy group, ethoxy group, triacontoxy group, fluorine atom, chlorine atom, bromine atom, iodine atom, thiol group Be

Each illustration of R ¹⁴ includes an isomer. For example, a butyl group contains n-butyl group, isobutyl group, sec-butyl group, tert-butyl group.

In the above formulae, 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 formulae, R ^{10 to} R ¹³ are as defined in the formula (1-2), and each R ¹⁴ 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 or a thiol group, m ¹⁴ is an integer of 0 to 5 and m ^{14 '} is an integer of 0 to 4 and m ^14'' is an integer of 0 to 3.

As R ¹⁴ , for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, triacontyl group, cyclopropyl group, Cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, cycloundecyl group, cyclododecyl group, cyclotriacontyl group, norbornyl group, adamantyl group, phenyl group, naphthyl group, Anthracene group, pyrenyl group, biphenyl group, heptacene group, vinyl group, allyl group, triaccontenyl group, methoxy group, ethoxy group, ethoxy group, triacontoxy group, fluorine atom, chlorine atom, bromine atom, iodine atom, thiol group Be

Each illustration of R ¹⁴ includes an isomer. For example, a butyl group contains n-butyl group, isobutyl group, sec-butyl group, tert-butyl group.

In the ^formula, R 10 ^{to R 13} have the same meanings as those described by the formula ^{(1-2), R 15} represents a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, carbon atoms 6 to 30 aryl groups, or alkenyl groups having 2 to 30 carbon atoms, alkoxy groups having 1 to 30 carbon atoms, halogen atoms, and thiol groups.

As R ^15, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, triacontyl group, a 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, triaccontenyl group, methoxy group, ethoxy group, ethoxy group, triacontoxy group, fluorine atom, chlorine atom, bromine atom, iodine atom, thiol group Be

Each illustration of R ¹⁵ includes an isomer. For example, a butyl group contains n-butyl group, isobutyl group, sec-butyl group, tert-butyl group.

In said formula, R < ¹⁰ > -R < ¹³ > is synonymous with what was demonstrated by said Formula (1-2).

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

In said formula, R < ¹⁰ > -R < ¹³ > is synonymous with what was demonstrated by said Formula (1-2).

  Furthermore, it is preferable that the compound represented by said Formula (0) is a compound which has the following structures from an etching tolerance viewpoint.

In the formula, R ^0A is synonymous with R ^Y in the formula (0), R ^{1A ′} is synonymous with R ^Z in the formula (0), and R ^{10 to} R ¹³ are the groups represented by the formula (1) It is synonymous with what was demonstrated by -2).

In said formula, R < ¹⁰ > -R < ¹³ > is synonymous with what was demonstrated by said Formula (1-2). R ¹⁴ each independently represents a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an alkenyl group having 2 to 30 carbon atoms, having 1 to 30 carbon atoms Are an alkoxy group, a halogen atom and a thiol group, and m ¹⁴ is an integer of 0 to 4.

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

Each illustration of R ¹⁴ includes an isomer. For example, a butyl group contains n-butyl group, isobutyl group, sec-butyl group, tert-butyl group.

In the ^formula, R 10 ^{to R 13} have the same meanings as those described by the formula ^{(1-2), R 15} represents a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, carbon atoms 6 to 30 aryl groups, or alkenyl groups having 2 to 30 carbon atoms, alkoxy groups having 1 to 30 carbon atoms, halogen atoms, and thiol groups.

As R ^15, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, triacontyl group, a 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 thereof include anthracene group, heptacene group, vinyl group, allyl group, triacetonyl group, methoxy group, ethoxy group, triacontitic group, fluorine atom, chlorine atom, bromine atom, iodine atom and thiol group.

Each illustration of R ¹⁵ includes an isomer. For example, a butyl group contains n-butyl group, isobutyl group, sec-butyl group, tert-butyl group.

In the ^formula, R 10 ^{to R 13} have the same meanings as those described by the formula ^{(1-2), R 16} represents a linear, branched or cyclic alkylene group having 1 to 30 carbon atoms, carbon atoms 6 to 30 divalent aryl groups or C 2 to C 30 divalent alkenyl groups.

As R ¹⁶ , for example, methylene group, ethylene group, propene group, butene group, pentene group, hexene group, heptene group, octene group, nonene group, decene group, undecene group, dodecene group, triaconten group, cyclopropene group , Cyclobutene group, cyclopentene group, cyclohexene group, cycloheptene group, cyclooctene group, cyclononene group, cyclodecene group, cycloundecene group, cyclododecene group, cyclotriaconten group, divalent norbornyl group, divalent adamantyl group, divalent And a divalent naphthyl group, a divalent anthracene group, a divalent heptacene group, a divalent vinyl group, a divalent allyl group, and a divalent triaccontenyl group.

Each illustration of R ¹⁶ includes isomers. For example, a butyl group contains n-butyl group, isobutyl group, sec-butyl group, tert-butyl group.

In the above formulae, R ^{10 to} R ¹³ are as defined in the formula (1-2), and each R ¹⁴ independently represents a linear, branched or cyclic alkyl having 1 to 30 carbon atoms. A 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 or a thiol group, and m ^{14 '} is an integer of 0 to 4;

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

Each illustration of R ¹⁴ includes an isomer. For example, a butyl group contains n-butyl group, isobutyl group, sec-butyl group, tert-butyl group.

In the above formulae, R ^{10 to} R ¹³ are as defined in the formula (1-2), and each R ¹⁴ 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 or a thiol group, and m ¹⁴ is an integer of 0 to 5;

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

Each illustration of R ¹⁴ includes an isomer. For example, a butyl group contains n-butyl group, isobutyl group, sec-butyl group, tert-butyl group.

In said formula, R < ¹⁰ > -R < ¹³ > is synonymous with what was demonstrated by said Formula (1-2).

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

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

In said formula, R < ¹⁰ > -R < ¹³ > is synonymous with what was demonstrated by said Formula (1-2).

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

  As a compound represented by the said Formula (0), the compound represented by the following formula is mentioned further.

In the formula, R ^0A is synonymous with R ^Y in the formula (0), R ^{1A ′} is synonymous with R ^Z in the formula (0), and R ^{10 to} R ¹³ are the groups represented by the formula (1) It is synonymous with what was demonstrated by -2).

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

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

In the ^formula, R 10 ^{to R 13} have the same meanings as those described by the formula ^{(1-2), R 14, R} 15, R 16, m 14, m 14 ' are synonymous with those described by the formula It is.

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

[Method for Producing Compound Represented by Formula (1)]
The compound represented by Formula (1) in this embodiment can be appropriately synthesized by applying a known method, and the synthesis method is not particularly limited.
For example, a polyphenol compound is obtained by subjecting a biphenol, binaphthol or bianthraceneol and a corresponding aldehyde or ketone to a polycondensation reaction under an acid pressure under normal pressure to obtain a polyphenol compound, and subsequently, at least one polyphenol compound is selected. It can obtain by introduce | transducing a hydroxyalkyl group into two phenolic hydroxyl groups, and introduce | transducing one group chosen from an allyl group, an acryl group, or a methacryl group to the hydroxy group. Moreover, it can also carry out under pressure as needed.

The timing for introducing a hydroxyalkyl group may be not only after the condensation reaction of binaphthols with aldehydes or ketones, but also before the condensation reaction. Moreover, you may introduce | transduce, after manufacturing of resin mentioned later.
The timing for introducing one group selected from an allyl group, an acryl group or a methacryl group may be after the introduction of a hydroxyalkyl group, and the resin before or after the condensation reaction was produced. You may introduce it later.

  Examples of the biphenols include, but not limited to, biphenol, methyl biphenol, methoxy binaphthol and the like. These can be used singly or in combination of two or more. Among these, biphenol is more preferably used from the viewpoint of stable supply of raw materials.

  Examples of the binaphthols include binaphthol, methyl binaphthol, methoxy binaphthol and the like, but are not particularly limited thereto. These can be used singly or in combination of two or more. Among these, binaphthol is more preferable 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, phenanthrene carbaldehyde, pyrene carbaldehyde, furfural and the like can be mentioned, but it is not particularly limited thereto. These can be used singly or in combination of two or more. Among these, from the viewpoint of imparting high heat resistance, benzaldehyde, phenylacetaldehyde, phenylpropylaldehyde, hydroxybenzaldehyde, chlorobenzaldehyde, nitrobenzaldehyde, nitrobenzaldehyde, methylbenzaldehyde, ethylbenzaldehyde, butylbenzaldehyde, cyclohexylbenzaldehyde, biphenylaldehyde, naphthaldehyde, anthracene It is preferable to use carboaldehyde, phenanthrene carbaldehyde, pyrenecarbaldehyde, furfural, and from the viewpoint of improving etching resistance, benzaldehyde, hydroxybenzaldehyde, chlorobenzaldehyde, nitrobenzaldehyde, methylbenzaldehyde, ethylbenzaldehyde, butylbenzaldehyde, cyclic benzaldehyde Hexyl benzaldehyde, biphenyl aldehyde, naphthaldehyde, anthracene carbaldehyde, phenanthrene carbaldehyde, pyrene carbaldehyde, it is preferable to use a furfural.

Examples of the ketones include acetone, methyl ethyl ketone, cyclobutanone, cyclopentanone, cyclohexanone, norbornanone, tricyclohexanone, tricyclodecanone, adamantanone, fluorenone, benzofluorenone, acenaphthenequinone, acenaphthenone, anthraquinone, acetophenone, diacetylbenzene And triacetylbenzene, acetonaphthone, diphenylcarbonylnaphthalene, phenylcarbonylbiphenyl, diphenylcarbonylbiphenyl, benzophenone, diphenylcarbonylbenzene, triphenylcarbonylbenzene, benzonaphthone, diphenylcarbonylnaphthalene, phenylcarbonylbiphenyl, diphenylcarbonylbiphenyl and the like. Not particularly limited to . These can be used singly or in combination of two or more. Among these, from the viewpoint of imparting high heat resistance, cyclopentanone, cyclohexanone, norbornanone, tricyclohexanone, tricyclodecanone, adamantanone, adamantanone, fluorenone, benzofluorenone, acenaphthenquinone, 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 perspective of improving Using diacetylbenzene, triacetylbenzene, acetonaphthone, diphenylcarbonylnaphthalene, phenylcarbonylbiphenyl, diphenylcarbonylbiphenyl, benzophenone, diphenylcarbonylbenzene, triphenylcarbonylbenzene, benzonaphthone, diphenylcarbonylnaphthalene, phenylcarbonylbiphenyl and diphenylcarbonylbiphenyl Is more preferred.
As the aldehydes or ketones, it is preferable to use an aldehyde-containing aldehyde or an aromatic-containing ketone from the viewpoint of providing both high heat resistance and high etching resistance.

  The acid catalyst used for the above reaction can be appropriately selected from known ones and used without particular limitation. As such an acid catalyst, inorganic acids and organic acids are widely known. For example, inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, hydrofluoric acid; oxalic acid, malonic acid, succinic acid, Adipic acid, sebacic acid, citric acid, fumaric acid, maleic acid, formic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, dichloroacetic acid, trichloroacetic acid, trichloromethanesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid, Organic acids such as naphthalenedisulfonic acid; Lewis acids such as zinc chloride, aluminum chloride, iron chloride, boron trifluoride or solid acids such as silicotungstic acid, phosphotungstic acid, silicomolybdic acid or phosphomolybdic acid However, it is not particularly limited to these. Among these, organic acids and solid acids are preferable from the viewpoint of production, and it is more preferable to use hydrochloric acid or sulfuric acid from the viewpoint of production such as availability and handling. In addition, about an acid catalyst, it can be used individually by 1 type or in combination of 2 or more types. The amount of the acid catalyst 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 0.01 to 100 parts by mass with respect to 100 parts by mass of reaction raw materials Is preferred.

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

  Further, 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. It is preferable that it is a range. Furthermore, the reaction temperature in the above reaction can be appropriately selected depending on the reactivity of the reaction raw material and is not particularly limited, but it is usually in the range of 10 to 200 ° C.

  In order to obtain the polyphenol compound, the reaction temperature is preferably higher, and specifically, the range of 60 to 200 ° C. is preferable. The reaction method may be appropriately selected from known methods, and is not particularly limited. However, biphenols, binaphthols or bianthracenediol, aldehydes or ketones, a method of preparing a batch of catalysts, biphenols And binaphthols, bianthracenediol, aldehydes or ketones 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 and catalysts present in the system, the temperature of the reaction kettle is raised to 130 to 230 ° C., and a general method such as removing volatile components at about 1 to 50 mmHg is taken. Thus, the compound of interest can be isolated.

  As preferable reaction conditions, 1 mole to excess amount of biphenols, binaphthols or bianthracenediol and 0.001 to 1 mole of an acid catalyst are used per 1 mole of aldehydes or ketones, under normal pressure, 50 The reaction may be carried out at about 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 a reaction product, and after cooling to room temperature, filtration is performed to separate, the obtained solid is filtered and dried, and then column chromatography is performed. The reaction product is separated and purified from by-products, the solvent is distilled off, filtration, and drying are performed to obtain the compound represented by the above-mentioned formula (1), which is the desired product.

Also known is 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.
For example, a hydroxyalkyl group can be introduced into at least one phenolic hydroxyl group of the compound as follows.
The hydroxyalkyl group can also be introduced into the phenolic hydroxyl group via an oxyalkyl group, and for example, a hydroxyalkyloxyalkyl group or a hydroxyalkyloxyalkyloxyalkyl group is introduced.
Compounds for introducing a hydroxyalkyl group can be synthesized or easily obtained by known methods, for example, chloroethanol, bromoethanol, 2-chloroethyl acetate, 2-bromoethyl acetate, 2-iodoethyl acetate, ethylene oxide And propylene oxide, butylene oxide, ethylene carbonate, propylene carbonate, and butylene carbonate, but not limited thereto.

  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 alkoxides (eg, alkali metal or alkaline earth metal alkoxides such as sodium methoxide, sodium ethoxide, potassium methoxide, potassium ethoxide etc.), metal hydroxides (eg alkali metals such as sodium hydroxide and potassium hydroxide) Or alkaline earth metal carbonates, etc., alkali metal or alkaline earth hydrogen carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate, amines (eg, tertiary amines (trialkyl amines such as triethylamine, N, N) -Aromatic tertiary amines such as dimethylaniline, heterocyclic tertiary amines such as 1-methylimidazole, etc., metal salts of carboxylic acids (sodium acetate, calcium acetate, etc. alkali metal or alkaline earth metal acetates etc.) Under normal pressure in the presence of a base catalyst such as an organic base of The reaction solution is neutralized with acid, and added to distilled water to precipitate a white solid, and then the separated solid is washed with distilled water or the solvent is evaporated to dryness. If necessary, washing with distilled water and drying can yield a compound in which a hydrogen atom of a hydroxyl group is substituted by a hydroxyalkylene group.

When 2-chloroethyl acetate, 2-bromoethyl acetate or 2-iodoethyl acetate is used, an acetoxyethyl group is introduced and then a deacylation reaction is caused to introduce a hydroxyethyl group.
When ethylene carbonate, propylene carbonate or butylene carbonate is used, a hydroxyalkyl group is introduced by adding an alkylene carbonate and causing a decarboxylation reaction.

  Subsequently, an allyl, acryl or methacryl group can be introduced into at least one hydroxy group of the compound, for example, as follows. Methods for introducing allyl, acrylic or methacrylic groups to hydroxy groups are also known.

  The compounds for introducing allyl, acryl or methacryl groups can be synthesized or easily obtained by known methods, for example, allyl chloride, allyl bromide, allyl iodide, acrylic acid, acrylic acid chloride, methacrylic acid, methacrylic acid Although a chloride is mentioned, limitation in particular is not carried out to these.

  First, the compound is dissolved or suspended in an aprotic solvent such as acetone, tetrahydrofuran (THF), propylene glycol monomethyl ether acetate or the like. Then, in the presence of a base catalyst such as sodium hydroxide, potassium hydroxide, sodium methoxide or sodium ethoxide, the reaction is carried out at 20 to 150 ° C. for 6 to 72 hours under normal pressure. The reaction solution is neutralized with acid, added to distilled water to precipitate a white solid, and the separated solid is washed with distilled water, or the solvent is evaporated to dryness, and if necessary, washed with distilled water, By drying, it is possible to obtain a compound in which the hydrogen atom of the hydroxy group is substituted with an allyl, acryl or methacryl group.

  In this embodiment, a group substituted with an allyl, acryl or methacryl group reacts in the presence of a radical or an acid / alkali, and the solubility in an acid, an alkali or an organic solvent used in a coating solvent or a developer changes. Do. The aryl, acrylic or methacrylic group-substituted group should have the property of causing chain reaction in the presence of a radical or acid / alkali in order to enable high sensitivity and high resolution pattern formation. preferable.

[A resin obtained by using a compound represented by the 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 film formation for lithography or optical component formation. Moreover, resin obtained by using the compound represented by said Formula (1) as a monomer can also be used as a composition. The resin is obtained, for example, by reacting the compound represented by the formula (1) with a compound having a crosslinking reactivity.
As resin obtained by using the compound represented by said Formula (1) as a monomer, what has a structure represented by the following Formula (3) is mentioned, for example. That is, the composition in the present embodiment may contain a resin having a structure represented by the following formula (3).

In the formula (3), L has 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 a substituent It may be an alkoxyl group having 1 to 30 carbon atoms or a single bond, and the alkylene group, the arylene group and the alkoxyl group may contain an ether bond, a ketone bond or an ester bond. In addition, the alkylene group and the alkoxylene group may be a linear, branched or cyclic group.
R ⁰ , R ¹ , R ^{2 to} R ⁵ , m ² and m ³ , m ⁴ and m ⁵ , p ^{2 to} p ⁵ and n are as defined in the formula (1).
However, m ² , m ³ , m ⁴ and m ⁵ do not simultaneously become 0, and at least one of R ^{2 to} R ⁵ is a hydrogen atom of a hydroxyl group being an allyloxy alkyl group, an acryloxy alkyl group or a methacryl oxy alkyl It is a group substituted by one group selected from a group.

[Method for Producing Resin Obtained by Using Compound Represented by Formula (1) as Monomer]
The resin in the present embodiment is obtained by reacting the compound represented by the above-mentioned formula (1) with a compound having crosslinking reactivity. As the compound having crosslinking reactivity, 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 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.

  As a specific example of resin which has a structure represented by said Formula (3), the condensation reaction of the compound represented by said Formula (1) with the aldehyde and / or ketone which is a compound with a crosslinking reactivity is carried out, for example Etc. may be mentioned.

  Here, examples of the aldehyde used when novolacizing the compound represented by the formula (1) include formaldehyde, trioxane, paraformaldehyde, benzaldehyde, acetaldehyde, propylaldehyde, phenylacetaldehyde, phenylpropylaldehyde, hydroxybenzaldehyde, Chlorobenzaldehyde, nitrobenzaldehyde, methyl benzaldehyde, ethyl benzaldehyde, butyl benzaldehyde, biphenyl aldehyde, naphthaldehyde, anthracenecarbaldehyde, phenanthrene carbaldehyde, pyrene carbaldehyde, furfural and the like, but not limited thereto. The ketones include the above-mentioned ketones. Among these, formaldehyde is more preferable. In addition, these aldehydes and / or ketones can be used individually by 1 type or in combination of 2 or more types. Further, the amount of the above-mentioned aldehyde and / or ketone used is not particularly limited, but it is preferably 0.2 to 5 moles, more preferably 2 moles to 1 mole of the compound represented by the above formula (1). 0.5 to 2 moles.

  An acid catalyst can also be used in the condensation reaction of the compound represented by the formula (1) with an aldehyde and / or a ketone. The acid catalyst used herein can be appropriately selected from known ones and used without particular limitation. As such an acid catalyst, inorganic acids and organic acids are widely known. For example, inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, hydrofluoric acid; oxalic acid, malonic acid, succinic acid, Adipic acid, sebacic acid, citric acid, fumaric acid, maleic acid, formic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, dichloroacetic acid, trichloroacetic acid, trichloromethanesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid, Organic acids such as naphthalenedisulfonic acid; Lewis acids such as zinc chloride, aluminum chloride, iron chloride, boron trifluoride or solid acids such as silicotungstic acid, phosphotungstic acid, silicomolybdic acid or phosphomolybdic acid 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.

  The amount of the acid catalyst 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 0.01 to 100 parts by mass with respect to 100 parts by mass of reaction raw materials Is preferred. However, indene, hydroxyindene, benzofuran, hydroxyanthracene, acenaphthylene, biphenyl, bisphenol, trisphenol, dicyclopentadiene, tetrahydroindene, 4-vinylcyclohexene, norbornadiene, 5-vinyl norborn-2-ene, α-pinene, β-pinene In the case of a copolymerization reaction with a compound having a non-conjugated double bond such as limonene, aldehydes are not necessarily required.

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

  The amount of these solvents used can be appropriately set according to the types of raw materials and catalysts used, as well as the reaction conditions, etc., and is not particularly limited. Is preferred. Furthermore, reaction temperature can be suitably selected according to the reactivity of the reaction raw material, and although it is not particularly limited, it is usually in the range of 10 to 200 ° C. The reaction method may be appropriately selected from known methods and used, and is not particularly limited. However, a method in which a compound represented by the above formula (1), an aldehyde and / or a ketone, and a catalyst are charged at one time, The method of dropping the compound represented by the said Formula (1), an aldehyde, and / or ketones in catalyst presence is 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 and catalysts present in the system, the temperature of the reaction kettle is raised to 130 to 230 ° C., and a general method such as removing volatile components at about 1 to 50 mmHg is taken. Thus, it is possible to isolate the desired novolakized resin.

  Here, the resin having the structure represented by the formula (3) may be a homopolymer of the compound represented by the formula (1), but is a copolymer with other phenols. May be Examples of phenols that can be copolymerized here include phenol, cresol, dimethylphenol, trimethylphenol, butylphenol, phenylphenol, diphenylphenol, naphthylphenol, resorcinol, methylresorcinol, catechol, butylcatechol, methoxyphenol, methoxyphenol, Examples include propylphenol, pyrogallol, thymol and the like, but are not particularly limited thereto.

  In addition to the above-mentioned other phenols, the resin having a structure represented by the above-mentioned formula (3) may be copolymerized with a polymerizable monomer. Such copolymerization monomers include, for example, naphthol, methyl naphthol, methoxy naphthol, dihydroxy naphthalene, indene, hydroxy indene, benzofuran, hydroxy anthracene, acenaphthylene, biphenyl, bisphenol, tris phenol, dicyclopentadiene, tetrahydro indene, 4-vinylcyclohexene And norbornadiene, vinyl norbornaene, pinene, limonene and the like, but not limited thereto. In addition, the resin which has a structure represented by said Formula (3) is a binary (for example, 2-4-component system) copolymer of the compound represented by said Formula (1), and the phenols mentioned above Even if it is a binary or more (for example, a 2 to 4 component system) copolymer of the compound represented by the formula (1) and the copolymerization monomer described above, the table by the formula (1) It may be a ternary or higher (e.g., three- to four-component) copolymer of the compound to be produced, the above-mentioned phenol and the above-mentioned copolymer monomer.

  The molecular weight of the resin having the structure represented by the above formula (3) is not particularly limited, but the weight average molecular weight (Mw) in terms of polystyrene is preferably 500 to 30,000, and more preferably 750 to 20, It is 000. In addition, from the viewpoint of enhancing the crosslinking efficiency and suppressing the volatile component during baking, the resin having the structure represented by the above formula (3) has a degree of dispersion (weight average molecular weight Mw / number average molecular weight Mn) of 1.2. It is preferable to be in the range of -7. In addition, said Mw and Mn can be calculated | required by the method as described in the Example mentioned later.

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

[Compound Represented by Formula (2)]
The 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 a C ¹ to C 60 n ^A valent group or a single bond,
Each R ^2A is independently a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms which may have a substituent, or a carbon number of 6 to 30 which may have a substituent. The aryl group of the above, an alkenyl group of 2 to 30 carbon atoms which may have a substituent, an alkoxy group of 1 to 30 carbon atoms which may have a substituent, a halogen atom, a nitro group, an amino group, a carbonic acid A hydrogen atom of an acid group, a thiol group, a hydroxyl group or a hydroxyl group is a group substituted by one group selected from an aryloxyalkyl group, an acryloxyalkyl group or a methacryloxyalkyl group, and the alkyl group, the aryl group, alkenyl group, the alkoxy group, an ether bond, may contain ketone or ester bond, wherein at least one hydrogen atom of the hydroxyl group of R ^2A Ariruo Shiarukiru containing group, a single substituted group with a group selected from acryloxy group or methacryloxy group.
n ^A is an integer of 1 to 4, and in the case where n ^A is an integer of 2 or more in the formula (2),
The structural formulas in n ^A [] may be the same or different.
X ^A shows that each independently, an oxygen atom, a sulfur atom or uncrosslinked. Here, X ^A, because there is a tendency to exhibit excellent heat resistance, it is preferable that an oxygen atom or a sulfur atom, more preferably oxygen atom. From the viewpoint of solubility, X ^A is preferably non-crosslinked.
^m2A is respectively independently an integer of 0-6. However, at least one m ^2A is an integer of 1 to 6.
Each q ^A is independently 0 or 1.

  The n-valent group is an alkyl group having 1 to 60 carbon atoms in the case of n = 1, an alkylene group having 1 to 30 carbon atoms in the case of n = 2, carbon in the case of n = 3 In the case of alkanepropiyl group of several 2-60, in the case of n = 4, a C3-C60 alkane tetrayl group is shown. As said n valent group, what has a linear hydrocarbon group, a branched hydrocarbon group, or an alicyclic hydrocarbon group etc. are mentioned, for example. Here, as for the alicyclic hydrocarbon group, a bridged alicyclic hydrocarbon group is also included. Moreover, the said n valent group may have a C6-C60 aromatic group.

  The n-valent hydrocarbon group may have an alicyclic hydrocarbon group, a double bond, a hetero atom or an aromatic group having 6 to 60 carbon atoms. Here, as for the alicyclic hydrocarbon group, a bridged alicyclic hydrocarbon group is also included.

  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, as for the alicyclic hydrocarbon group, a bridged alicyclic hydrocarbon group is also included.

  The compound represented by the above formula (2) has high heat resistance due to the rigidity of its structure although having a relatively low molecular weight, and therefore can be used under high temperature bake conditions. In addition, it has tertiary carbon or quaternary carbon in the molecule, and is suitably used as a film forming composition for lithography which can suppress crystallinity and can be used for manufacturing a film for lithography.

  Moreover, since the solubility with respect to a safe solvent is high and heat resistance and etching tolerance are favorable, the resist formation composition for lithography containing the compound represented by said Formula (2) gives a favorable resist pattern shape. it can.

  Furthermore, because of the relatively low molecular weight and low viscosity, even in the case of a substrate having a step (in particular, a fine space, a hole pattern, etc.), the film is flat while being uniformly filled to every corner of the step. As a result, it is easy to enhance the properties, and 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, high etching resistance can also be imparted.

  Furthermore, since the aromatic density is high, the refractive index is high, and the coloring is suppressed also by a wide range of heat treatment from low temperature to high temperature, and therefore, they are useful as various optical component forming compositions. Among them, compounds having quaternary carbon are preferable from the viewpoint of suppressing oxidative decomposition of the compound to suppress coloring and improving heat resistance and solvent solubility. Optical parts include film-like and sheet-like parts, plastic lenses (prism lenses, lenticular lenses, microlenses, Fresnel lenses, viewing angle control lenses, contrast improvement lenses, etc.), retardation films, films for shielding electromagnetic waves, It is useful as a prism, an optical fiber, a solder resist for flexible printed wiring, a plating resist, an interlayer insulating film for a multilayer printed wiring board, and a photosensitive optical waveguide.

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

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

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

  Moreover, it is preferable that the compound represented by the said Formula (2-1) is a compound represented by following formula (2a) from a viewpoint of supply property of a raw material.

In the above formula (2a), X ^A , R ^{0A to} R ^2A , m ^2A and n ^A are as defined in the above formula (2).

  Moreover, as for the compound represented by said Formula (2-1), it is more preferable that it is a compound represented by a following formula (2b) from a soluble viewpoint to an organic solvent.

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

  Moreover, it is more preferable that the compound represented by the said Formula (2-1) is a compound represented by a following formula (2c) from a soluble viewpoint to the organic solvent.

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

  The compound represented by the above formula (2) has the following formulas (BisN-1) to (BisN-4), (XBisN-1) to (XBisN-3), and (XBisN-3), from the viewpoint of solubility in a further organic solvent. The compounds represented by BiN-1) to (BiN-4) or (XBiN-1) to (XBiN-3) are particularly preferable.

[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 method, and the synthesis method is not particularly limited.
For example, a polyphenol compound is obtained by subjecting phenols, naphthols, and corresponding aldehydes or ketones to a polycondensation reaction under an acid catalyst under normal pressure to obtain a polyphenol compound, and subsequently, at least one phenolic hydroxyl group of the polyphenol compound It is possible to obtain a hydroxyalkyl group by introducing one group selected from an allyl group, an acryl group or a methacryl group into the hydroxy group. Moreover, it can also carry out under pressure as needed.

The timing for introducing a hydroxyalkyl group may be not only after the condensation reaction of phenols, naphthols and aldehydes or ketones, but also before the condensation reaction. Moreover, you may introduce | transduce, after manufacturing of resin mentioned later.
The timing for introducing one group selected from an allyl group, an acryl group or a methacryl group may be after the introduction of a hydroxyalkyl group, and the resin before or after the condensation reaction was produced. You may introduce it later.

  The naphthols are not particularly limited, and examples thereof include naphthol, methyl naphthol, methoxy naphthol, naphthalene diol and the like. Among them, naphthalene diol is preferably used from the viewpoint of easily forming a xanthene structure. .

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

  Examples of the aldehydes include formaldehyde, trioxane, paraformaldehyde, benzaldehyde, acetaldehyde, propylaldehyde, phenylacetaldehyde, phenylpropylaldehyde, hydroxybenzaldehyde, chlorobenzaldehyde, nitrobenzaldehyde, methylbenzaldehyde, ethylbenzaldehyde, butylbenzaldehyde, biphenylaldehyde, Naphthaldehyde, anthracenecarbaldehyde, phenanthrene carbaldehyde, pyrene carbaldehyde, furfural and the like can be mentioned, but it is not particularly limited thereto. These can be used singly or in combination of two or more. Among these, from the viewpoint of imparting high heat resistance, benzaldehyde, phenylacetaldehyde, phenylpropylaldehyde, hydroxybenzaldehyde, chlorobenzaldehyde, nitrobenzaldehyde, nitrobenzaldehyde, methylbenzaldehyde, ethylbenzaldehyde, butylbenzaldehyde, cyclohexylbenzaldehyde, biphenylaldehyde, naphthaldehyde, anthracene It is preferable to use carboaldehyde, phenanthrene carbaldehyde, pyrenecarbaldehyde, furfural, and from the viewpoint of improving etching resistance, benzaldehyde, hydroxybenzaldehyde, chlorobenzaldehyde, nitrobenzaldehyde, methylbenzaldehyde, ethylbenzaldehyde, butylbenzaldehyde, cyclic benzaldehyde Hexyl benzaldehyde, biphenyl aldehyde, naphthaldehyde, anthracene carbaldehyde, phenanthrene carbaldehyde, pyrene carbaldehyde, it is preferable to use a furfural.

Examples of the ketones include acetone, methyl ethyl ketone, cyclobutanone, cyclopentanone, cyclohexanone, norbornanone, tricyclohexanone, tricyclodecanone, adamantanone, fluorenone, benzofluorenone, acenaphthenequinone, acenaphthenone, anthraquinone, acetophenone, diacetylbenzene And triacetylbenzene, acetonaphthone, diphenylcarbonylnaphthalene, phenylcarbonylbiphenyl, diphenylcarbonylbiphenyl, benzophenone, diphenylcarbonylbenzene, triphenylcarbonylbenzene, benzonaphthone, diphenylcarbonylnaphthalene, phenylcarbonylbiphenyl, diphenylcarbonylbiphenyl and the like. Not particularly limited to . These can be used singly or in combination of two or more. Among these, from the viewpoint of imparting high heat resistance, cyclopentanone, cyclohexanone, norbornanone, tricyclohexanone, tricyclodecanone, adamantanone, adamantanone, fluorenone, benzofluorenone, acenaphthenquinone, 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 perspective of improving Using diacetylbenzene, triacetylbenzene, acetonaphthone, diphenylcarbonylnaphthalene, phenylcarbonylbiphenyl, diphenylcarbonylbiphenyl, benzophenone, diphenylcarbonylbenzene, triphenylcarbonylbenzene, benzonaphthone, diphenylcarbonylnaphthalene, phenylcarbonylbiphenyl and diphenylcarbonylbiphenyl Is more preferred.
As ketones, it is preferable to use a ketone having an aromatic ring from the viewpoint of combining high heat resistance and high etching resistance.

  The acid catalyst used for the above reaction can be appropriately selected from known ones and used without particular limitation. The acid catalyst can be appropriately selected from known inorganic acids and organic acids. For example, inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, and hydrofluoric acid; oxalic acid, formic acid, p-toluene sulfone Organic acids such as acid, methanesulfonic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid, 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 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 easy availability and handling. About an acid catalyst, it can be used individually by 1 type or in combination of 2 or more types.

  At the time of the above reaction, a reaction solvent may be used. The reaction solvent is not particularly limited as long as the reaction between the aldehyde or ketone to be used and the naphthols proceed, but, for example, water, methanol, ethanol, propanol, butanol, tetrahydrofuran, dioxane or a mixed solvent thereof is used. Can. 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 may be appropriately selected according to the reactivity of the reaction raw material, 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 high selectivity, the temperature is preferably low, and more preferably in the range of 10 to 60 ° C.

  The reaction method is not particularly limited, and examples thereof include a method in which naphthols and the like, aldehydes or ketones, a catalyst are charged at once, and a method in which naphthols, aldehydes or ketones are dropped in the presence of the catalyst. After completion of the polycondensation reaction, the temperature of the reaction kettle can be raised to 130 to 230 ° C. to remove volatile components at about 1 to 50 mmHg in order to remove unreacted raw materials, catalysts, etc. present in the system. .

  The amount of the raw material is not particularly limited. For example, 2 moles to excess of naphthols etc. and 0.001 to 1 moles of an acid catalyst are used per 1 mole of aldehydes or ketones, under normal pressure, 20 The reaction is preferably carried out at about 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 desired product is not particularly limited. For example, the reaction solution is concentrated, pure water is added to precipitate a reaction product, and after cooling to room temperature, filtration is performed to separate the obtained solid. The product is filtered and dried, and then the product is separated and purified from the by-product by column chromatography, and the solvent is distilled off, filtered, and dried to isolate the target compound.

Also known is 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.
For example, a hydroxyalkyl group can be introduced into at least one phenolic hydroxyl group of the compound as follows.
Hydroxyalkyl groups can also be introduced into phenolic hydroxyl groups via oxyalkyl groups. For example, hydroxyalkyloxyalkyl groups and hydroxyalkyloxyalkyloxyalkyl groups are introduced.
Compounds for introducing a hydroxyalkyl group can be synthesized or easily obtained by known methods, for example, chloroethanol, bromoethanol, 2-chloroethyl acetate, 2-bromoethyl acetate, 2-iodoethyl acetate, ethylene oxide And propylene oxide, butylene oxide, ethylene carbonate, propylene carbonate, and butylene carbonate, but not limited thereto.

  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 alkoxides (eg, alkali metal or alkaline earth metal alkoxides such as sodium methoxide, sodium ethoxide, potassium methoxide, potassium ethoxide etc.), metal hydroxides (eg alkali metals such as sodium hydroxide and potassium hydroxide) Or alkaline earth metal carbonates, etc., alkali metal or alkaline earth hydrogen carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate, amines (eg, tertiary amines (trialkyl amines such as triethylamine, N, N) -Aromatic tertiary amines such as dimethylaniline, heterocyclic tertiary amines such as 1-methylimidazole, etc., metal salts of carboxylic acids (sodium acetate, calcium acetate, etc. alkali metal or alkaline earth metal acetates etc.) Under normal pressure in the presence of a base catalyst such as an organic base of The reaction solution is neutralized with acid, and added to distilled water to precipitate a white solid, and then the separated solid is washed with distilled water or the solvent is evaporated to dryness. If necessary, washing with distilled water and drying can yield a compound in which a hydrogen atom of a hydroxyl group is substituted by a hydroxyalkylene group.

When 2-chloroethyl acetate, 2-bromoethyl acetate or 2-iodoethyl acetate is used, an acetoxyethyl group is introduced and then a deacylation reaction is caused to introduce a hydroxyethyl group.
When ethylene carbonate, propylene carbonate or butylene carbonate is used, a hydroxyalkyl group is introduced by adding an alkylene carbonate and causing a decarboxylation reaction.

  Subsequently, an allyl, acryl or methacryl group can be introduced into at least one hydroxy group of the compound, for example, as follows. Methods of introducing allyl, acrylic or methacrylic groups to the hydroxy groups are also known.

  The compounds for introducing allyl, acryl or methacryl groups can be synthesized or easily obtained by known methods, for example, allyl chloride, allyl bromide, allyl iodide, acrylic acid, acrylic acid chloride, methacrylic acid, methacrylic acid Although a chloride is mentioned, limitation in particular is not carried out to these.

  First, the compound is dissolved or suspended in an aprotic solvent such as acetone, tetrahydrofuran (THF), propylene glycol monomethyl ether acetate or the like. Then, in the presence of a base catalyst such as sodium hydroxide, potassium hydroxide, sodium methoxide or sodium ethoxide, the reaction is carried out at 20 to 150 ° C. for 6 to 72 hours under normal pressure. The reaction solution is neutralized with acid, added to distilled water to precipitate a white solid, and the separated solid is washed with distilled water, or the solvent is evaporated to dryness, and if necessary, washed with distilled water, By drying, it is possible to obtain a compound in which the hydrogen atom of the hydroxy group is substituted with an allyl, acryl or methacryl group.

  In this embodiment, a group substituted with an allyl, acryl or methacryl group reacts in the presence of a radical or an acid / alkali, and the solubility in an acid, an alkali or an organic solvent used in a coating solvent or a developer changes. Do. The aryl, acrylic or methacrylic group-substituted group should have the property of causing chain reaction in the presence of a radical or acid / alkali in order to enable high sensitivity and high resolution pattern formation. preferable.

[A resin obtained by using a compound represented by the formula (2) as a monomer]
The compound represented by said Formula (2) can be used as it is as a film formation composition for lithography, and a composition used for optical component formation. Moreover, resin obtained by using the compound represented by said Formula (2) as a monomer can be used as a composition. The resin is obtained, for example, by reacting the compound represented by the formula (2) with a compound having a crosslinking reactivity.
As resin obtained by using the compound represented by said Formula (2) as a monomer, what has a structure represented by the following Formula (4) is mentioned, for example. That is, the composition in the present embodiment may contain a resin having a structure represented by the following formula (4).

In the formula (4), L has 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 a substituent It may be an alkoxyl group having 1 to 30 carbon atoms or a single bond, and the alkylene group, the arylene group and the alkoxyl group may contain an ether bond, a ketone bond or an ester bond. In addition, the alkylene group and the alkoxylene group may be a linear, branched or cyclic group.
R ^0A , R ^1A , R ^2A , m ^2A , n ^A , q ^A and X ^A are as defined in the above formula (2),
However, when n ^A is an integer of 2 or more, the structural formulas in n ^A [] may be the same or different, and at least one m ^2A is an integer of 1 to 6, R ^2A And at least one of them contains a group in which the hydrogen atom of the hydroxyl group is substituted with one group selected from an aryloxyalkyl group, an acryloxyalkyl group or a methacryloxyalkyl group.

[Method for Producing Resin Obtained by Using Compound Represented by Formula (2) as Monomer]
The resin in the present embodiment is obtained by reacting the compound represented by the above formula (2) with a compound having crosslinking reactivity. As the compound having crosslinking reactivity, known compounds can be used without particular limitation as long as the compound represented by the formula (2) can be oligomerized or polymerized. Specific examples thereof include, but 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.

  As a specific example of resin which has a structure represented by said Formula (4), the condensation reaction of the compound represented by the said Formula (2) with the aldehyde and / or ketone which is a compound with a crosslinking reactivity is carried out, for example Etc. may be mentioned.

  Here, examples of the aldehyde used when novolacizing the compound represented by the formula (2) include formaldehyde, trioxane, paraformaldehyde, benzaldehyde, acetaldehyde, propylaldehyde, phenylacetaldehyde, phenylpropylaldehyde, hydroxybenzaldehyde, Chlorobenzaldehyde, nitrobenzaldehyde, methyl benzaldehyde, ethyl benzaldehyde, butyl benzaldehyde, biphenyl aldehyde, naphthaldehyde, anthracenecarbaldehyde, phenanthrene carbaldehyde, pyrene carbaldehyde, furfural and the like, but not limited thereto. The ketones include the above-mentioned ketones. Among these, formaldehyde is more preferable. In addition, these aldehydes and / or ketones can be used individually by 1 type or in combination of 2 or more types. Further, the amount of the above-mentioned aldehyde and / or ketone used is not particularly limited, but it is preferably 0.2 to 5 moles, and more preferably 0.2 mole to 1 mole of the compound represented by the above formula (2). 0.5 to 2 moles.

  An acid catalyst can also be used in the condensation reaction of the compound represented by the formula (2) with an aldehyde and / or a ketone. The acid catalyst used herein can be appropriately selected from known ones and used without particular limitation. As such an acid catalyst, inorganic acids and organic acids are widely known. For example, inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, hydrofluoric acid; oxalic acid, malonic acid, succinic acid, Adipic acid, sebacic acid, citric acid, fumaric acid, maleic acid, formic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, dichloroacetic acid, trichloroacetic acid, trichloromethanesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid, Organic acids such as naphthalenedisulfonic acid; Lewis acids such as zinc chloride, aluminum chloride, iron chloride, boron trifluoride or solid acids such as silicotungstic acid, phosphotungstic acid, silicomolybdic acid or phosphomolybdic acid However, it is not particularly limited to these. Among these, from the viewpoint of production, an organic acid or a solid acid is preferable, and from the viewpoint of production such as availability and handling, hydrochloric acid or sulfuric acid is preferable. In addition, about an acid catalyst, it can be used individually by 1 type or in combination of 2 or more types.

  The amount of the acid catalyst 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 0.01 to 100 parts by mass with respect to 100 parts by mass of reaction raw materials Is preferred. However, indene, hydroxyindene, benzofuran, hydroxyanthracene, acenaphthylene, biphenyl, bisphenol, trisphenol, dicyclopentadiene, tetrahydroindene, 4-vinylcyclohexene, norbornadiene, 5-vinyl norborn-2-ene, α-pinene, β-pinene In the case of a copolymerization reaction with a compound having a non-conjugated double bond such as limonene, aldehydes are not necessarily required.

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

  The amount of these solvents used can be appropriately set according to the types of raw materials and catalysts used, as well as the reaction conditions, etc., and is not particularly limited. Is preferred. Furthermore, the reaction temperature can be appropriately selected depending on the reactivity of the reaction raw material, and is not particularly limited, but is usually in the range of 10 to 200 ° C. The reaction method may be appropriately selected from known methods and used, and is not particularly limited. However, a method in which a compound represented by the above formula (2), an aldehyde and / or a ketone, and a catalyst are charged at one time, The method of dropping the compound represented by the said Formula (2), an aldehyde, and / or ketones in catalyst presence is 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 and catalysts present in the system, the temperature of the reaction kettle is raised to 130 to 230 ° C., and a general method such as removing volatile components at about 1 to 50 mmHg is taken. Thus, it is possible to isolate the desired novolakized resin.

  Here, the resin having the structure represented by the formula (4) may be a homopolymer of the compound represented by the formula (2), but is a copolymer with other phenols. May be Examples of phenols that can be copolymerized here include phenol, cresol, dimethylphenol, trimethylphenol, butylphenol, phenylphenol, diphenylphenol, naphthylphenol, resorcinol, methylresorcinol, catechol, butylcatechol, methoxyphenol, methoxyphenol, Examples include propylphenol, pyrogallol, thymol and the like, but are not particularly limited thereto.

  In addition to the above-mentioned other phenols, the resin having a structure represented by the above-mentioned formula (4) may be copolymerized with a polymerizable monomer. Such copolymerization monomers include, for example, naphthol, methyl naphthol, methoxy naphthol, dihydroxy naphthalene, indene, hydroxy indene, benzofuran, hydroxy anthracene, acenaphthylene, biphenyl, bisphenol, tris phenol, dicyclopentadiene, tetrahydro indene, 4-vinylcyclohexene And norbornadiene, vinyl norbornaene, pinene, limonene and the like, but not limited thereto. In addition, the resin which has a structure represented by said Formula (4) is a binary (for example, 2-4-component system) copolymer of the compound represented by said Formula (2), and the phenols mentioned above Even if the copolymer represented by the formula (2) and the copolymerizable monomer described above is a binary or more (for example, a two- to four-component system) copolymer of the compound represented by the formula (2), It may be a ternary or higher (e.g., three- to four-component) copolymer of the compound to be produced, the above-mentioned phenol and the above-mentioned copolymer monomer.

  The molecular weight of the resin having the structure represented by the above formula (4) is not particularly limited, but the weight average molecular weight (Mw) in terms of polystyrene is preferably 500 to 30,000, and more preferably 750 to 30,000. It is 20,000. Further, from the viewpoint of enhancing the crosslinking efficiency and suppressing the volatile component during baking, the resin having the structure represented by the above formula (4) has a degree of dispersion (weight average molecular weight Mw / number average molecular weight Mn) of 1.2. It is preferable to be in the range of -7. In addition, said Mw and Mn can be calculated | required by the method as described in the Example mentioned later.

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

[Method of purifying compound and / or resin]
The purification method of the compound and / or resin in the present embodiment is represented by the compound represented by the formula (1), the resin obtained by using the compound represented by the formula (1) as a monomer, and the formula (2) And the step of obtaining a solution (S) by dissolving one or more selected from a compound obtained by using the compound represented by the formula (2) and a compound represented by the formula (2) as a monomer in a solvent; Contacting the acid solution with an aqueous solution to extract impurities in the compound and / or the resin (first extraction step), and the solvent used in the step of obtaining the solution (S) is optionally combined with water Contains immiscible solvents.
In the first extraction step, the resin is a resin obtained by the reaction of the compound represented by the formula (1) and / or the compound represented by the formula (2) with a compound having crosslinking reactivity preferable. According to the purification method of this embodiment, the content of various metals that can be contained as impurities in the compound or resin having the specific structure described above can be reduced.
More specifically, in the purification method of the present embodiment, the compound and / or the resin is dissolved in an organic solvent that is not arbitrarily mixed with water to obtain a solution (S), and the solution (S) is further obtained. An extraction process can be performed by contacting with an acidic aqueous solution. As a result, after the metal component contained in the solution (S) is transferred to the aqueous phase, the organic phase and the aqueous phase can be separated to obtain a compound and / or resin with 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. The compounds and resins may contain various surfactants, various crosslinking agents, various acid generators, various stabilizers and the like.

  The solvent used in the purification method of the present embodiment is not particularly limited, but 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 preferable. Is an organic solvent having a ratio of less than 30%, more preferably less than 20%, and even more preferably less than 10%. It is preferable that the usage-amount of the said organic solvent is 1-100 mass times with respect to the total amount of the compound to be used and resin.

  Specific examples of the solvent which is not miscible with water optionally include, but are not limited to, for example, 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, ketones such as ethyl isobutyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 2-pentanone; ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl Glycol ether acetates such as ether acetate; Aliphatic hydrocarbons such as n-hexane and n-heptane; Aromatic hydrocarbons such as toluene and xylene; Methylene, halogenated hydrocarbons such as chloroform and the like. Among these, toluene, 2-heptanone, cyclohexanone, cyclopentanone, methyl isobutyl ketone, propylene glycol monomethyl ether acetate and ethyl acetate are preferable, and methyl isobutyl ketone, ethyl acetate, cyclohexanone and propylene glycol monomethyl ether acetate are more preferable, and methyl Isobutyl ketone and ethyl acetate are more preferred. Methyl isobutyl ketone, ethyl acetate, etc. are removed by distilling off the solvent industrially or by drying since the saturated solubility of the above-mentioned compound and the resin containing the compound is relatively high and the boiling point is relatively low. It is possible to reduce the process load. These solvents can be used alone or in combination of two or more.

  The acidic aqueous solution used in the purification method of the present embodiment is appropriately selected from aqueous solutions in which generally known organic compounds or inorganic compounds are dissolved in water. Examples of acidic aqueous solutions include, but are not limited to, mineral acid aqueous solutions in which mineral acids such as hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid are dissolved in water; acetic acid, propionic acid, oxalic acid, malonic acid, succinic acid, fumaric acid An organic acid aqueous solution in which an organic acid such as maleic acid, tartaric acid, citric acid, methanesulfonic acid, phenolsulfonic acid, p-toluenesulfonic acid, trifluoroacetic acid or the like is dissolved in water can be mentioned. Each of 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, such as sulfuric acid, nitric acid, acetic acid, oxalic acid, An aqueous solution of carboxylic acid such as tartaric acid and citric acid is more preferable, an aqueous solution of sulfuric acid, oxalic acid, tartaric acid and citric acid is more preferable, and an aqueous solution of oxalic acid is still more preferable. It is considered that polyvalent carboxylic acids such as boric acid, tartaric acid and citric acid tend to be able to remove metals more effectively because they coordinate to metal ions and a chelating effect occurs. Moreover, it is preferable to use water with small metal content, for example, ion-exchange water etc., in accordance with the purpose of the purification method of this embodiment.

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

  The use 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 extractions for metal removal and from the viewpoint of ensuring operability considering the entire liquid volume It is preferred 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, with respect to 100% by mass of the solution (S).

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

  In the purification method of the present embodiment, the solution (S) preferably further includes an organic solvent optionally mixed with water. When the solution (S) contains an organic solvent optionally mixed with water, the amount of the compound and / or resin can be increased, and the liquid separation property is improved, and purification is performed with high efficiency. Tend to The method of adding an organic solvent which is optionally mixed with water is not particularly limited. For example, a method of adding it to a solution containing an organic solvent beforehand, a method of adding it to water or an acidic aqueous solution in advance, a solution containing an organic solvent and water or an acidic aqueous solution It may be any of the methods added after the contact. Among these, the method of adding to a solution containing an organic solvent in advance is preferable from the viewpoint of the operability of operation and the ease of management of the preparation amount.

  The organic solvent optionally mixed 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 use amount of the organic solvent optionally mixed with water is not particularly limited as long as the solution phase and the water phase are separated, but 0.1 to 100 times by mass the total amount of the compound and the resin used Is preferably 0.1 to 50 times by mass, more preferably 0.1 to 20 times by mass.

  Specific examples of the organic solvent optionally mixed with water used in the purification method of the present embodiment include, but are not limited to, ethers such as tetrahydrofuran and 1,3-dioxolane; alcohols such as methanol, ethanol and isopropanol 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 It can be mentioned. Among these, N-methyl pyrrolidone, propylene glycol monomethyl ether and the like are preferable, and N-methyl pyrrolidone and propylene glycol monomethyl ether are more preferable. These solvents may be used alone or in combination of two or more.

  The temperature at which the extraction treatment is carried out is usually 20 to 90 ° C., preferably 30 to 80 ° C. The extraction operation is performed, for example, by mixing the mixture well by stirring or the like and then leaving it to stand. Thereby, the metal contained in the solution (S) is transferred to the aqueous phase. In addition, by this operation, the acidity of the solution is lowered, and deterioration of the compound and / or the resin can be suppressed.

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

  In the purification method of the present embodiment, after the first extraction step, a 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 It is preferable to include a process step). Specifically, for example, after the above-mentioned extraction treatment using an acidic aqueous solution, a solution phase containing a compound and / or a resin and a solvent extracted and recovered from the aqueous solution is subjected to a further extraction treatment with water Is preferred. The extraction process with water is not particularly limited, but can be performed, for example, by mixing the solution phase and water well by stirring or the like and then allowing the obtained mixed solution to stand. The mixed solution after standing is separated into a solution phase containing a compound and / or a resin and a solvent and an aqueous phase, so that the solution phase can be recovered by decantation or the like.

  Further, in accordance with the object of the present embodiment, the water used here is preferably water having a low metal content, for example, ion exchanged water or the like. Although the extraction process may be performed only once, it is also effective to repeat the operation of mixing, standing, and separating several times. In addition, conditions such as the use ratio of the both and temperature, time, and the like in the extraction process are not particularly limited, but may be the same as in the case of the previous contact process with the acidic aqueous solution.

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

  The method for isolating the compound and / or resin from the solution containing the obtained compound and / or resin and solvent is not particularly limited, and known methods such as removal under reduced pressure, separation by reprecipitation, and a combination 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 the present embodiment includes a compound represented by the formula (1), a resin obtained by using a compound represented by the formula (1) as a monomer, and a 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 use in chemically amplified resists]
The film forming composition for lithography for chemical amplification type resist applications (hereinafter also referred to as “resist composition”) in the present embodiment is a compound represented by the formula (1), represented by the 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 a compound represented by the above formula (2) as a monomer contains.

  Moreover, it is preferable that the resist composition in this embodiment contains a solvent. The solvent is not particularly limited. For example, ethylene glycol monoalkyl ether acetate such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, ethylene glycol mono-n-butyl ether acetate, etc. 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 such as n-butyl ether acetate Cole monoalkyl ether acetates; Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether (PGME) and propylene glycol monoethyl ether; methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, n-amyl lactate and the like Fatty acid esters of methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, n-amyl acetate, n-hexyl acetate, methyl propionate, ethyl propionate and the like; 3-methoxy Methyl propionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl Other esters such as acetate, butyl 3-methoxy-3-methylpropionate, butyl 3-methoxy-3-methylbutyrate, methyl acetoacetate, methyl pyruvate and ethyl pyruvate; aromatic hydrocarbons such as toluene and xylene Ketones such as 2-heptanone, 3-heptanone, 4-heptanone, cyclopentanone (CPN), cyclohexanone (CHN), etc .; N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide, N -Amides such as methyl pyrrolidone; Lactones such as γ-lactone and the like can be mentioned, but the invention is not particularly limited thereto. These solvents may be used alone or in combination of two or more.

  The solvent used in the present 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. It is a species, 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, but 1 to 80% by mass of the solid component and the solvent 20 to 99 with respect to the total mass 100% by mass of the amount of the solid component and the solvent. It is preferably mass%, more preferably 1 to 50 mass% solid component and 50 to 99 mass% solvent, still more preferably 2 to 40 mass% solid component and 60 to 98 mass% solvent, particularly preferably solid mass It is 2 to 10% by mass of the component and 90 to 98% by mass of the solvent.

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

  Here, as the acid generator (C), the crosslinking agent (G), the acid diffusion control agent (E) and the other components (F), known ones can be used and are not particularly limited. Preferred are those described in US Pat.

[Blending ratio of each component]
In the resist composition of the present embodiment, the content of the compound and / or resin used as the resist substrate is not particularly limited, but the total mass of solid components (resist substrate, acid generator (C), crosslinking agent (G A total of solid components including optionally used components such as acid diffusion control agent (E) and other components (F), and so on), preferably 50 to 99.4% by mass, and more preferably The content 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 substrate is in the above range, the resolution is further improved, and the line edge roughness (LER) tends to be further reduced.
In addition, when both a compound and resin are contained as a resist base material, the said content is the total amount of both components.

[Other ingredients (F)]
The resist composition according to the present embodiment may be other than the resist substrate, the acid generator (C), the crosslinking agent (G) and the acid diffusion control agent (E), as needed, as long as the object of the present invention is not impaired. As components of the dissolution promoter, dissolution control agent, sensitizer, surfactant, organic carboxylic acid or phosphorus oxo acid or derivative thereof, heat and / or photo-curing catalyst, polymerization inhibitor, flame retardant, filler, Coupling agents, thermosetting resins, photocurable resins, dyes, pigments, thickeners, lubricants, antifoaming agents, leveling agents, ultraviolet absorbers, surfactants, colorants, nonionic surfactants, etc. One or more additives can be added. In the present specification, the other component (F) may be referred to as an optional component (F).

In the resist composition of the present embodiment, a resist substrate (hereinafter, also referred to as “component (A)”), an acid generator (C), a crosslinking agent (G), an acid diffusion control agent (E), an optional component ( The content of F) (component (A) / acid generator (C) / crosslinking agent (G) / acid diffusion control agent (E) / optional component (F)) is in% by mass on the basis of solids
Preferably 50 to 99.4 / 0.001 to 49 / 0.5 to 49 / 0.001 to 49/50,
More preferably, 55 to 90/1 to 40 / 0.5 to 40 / 0.01 to 10/5,
More preferably, it is 60-80 / 3-30 / 1-30 / 0.01-5 / 0-1.
Particularly preferred is 60 to 70/10 to 25/2 to 20 / 0.01 to 3/0.
The compounding ratio of each component is selected from each range so that the sum total becomes 100 mass%. When the blending ratio of each component is in the above range, the performance such as sensitivity, resolution, and developability tends to be excellent.

  The resist composition of the present embodiment is usually prepared by dissolving each component in a solvent at the time of use to form a uniform solution, and then filtering it with, for example, a filter with a pore diameter of about 0.2 μm, if necessary. Ru.

  The resist composition of the present embodiment can contain other resins other than the resin of the present embodiment, as long as the object of the present invention is not hindered. The other resin is not particularly limited. For example, novolak resin, polyvinyl phenols, polyacrylic acid, polyvinyl alcohol, styrene-maleic anhydride resin, and acrylic acid, vinyl alcohol, or vinyl phenol as a monomer unit And polymers containing these or derivatives thereof. The content of the other resin is not particularly limited and may be appropriately adjusted according to the type of the component (A) to be used, but is preferably 30 parts by mass or less with respect to 100 parts by mass of the component (A) More preferably, it is 10 parts by mass or less, more preferably 5 parts by mass or less, and particularly preferably 0 parts by mass.

[Physical Properties of Resist Composition, etc.]
An amorphous film can be formed by spin coating using the resist composition of the present embodiment. Moreover, the resist composition of this embodiment can be applied to a general semiconductor manufacturing process. Depending on the type of the compound represented by the above formula (1) and / or the formula (2), the type of resin obtained using these as monomers, and / or the type of developer used, either a positive resist pattern or a negative resist pattern It 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 this embodiment in a developer at 23 ° C. is preferably 5 Å / sec or less, preferably 0.05 to 5 Å / sec is more preferable, and 0.0005 to 5 Å / sec is further preferable. When the dissolution rate is 5 Å / sec or less, it tends to be insoluble in a developer and to be easy to form a resist. When the dissolution rate is 0.0005 Å / sec or more, the resolution may be improved. This is because the exposed portion dissolves in the developer and the developer by the change in solubility before and after exposure of the compound represented by the above formulas (1) and (2) and / or the resin containing the compound as a component. It is inferred that the contrast at the interface with the unexposed undissolved portion increases. In addition, LER reduction and defect reduction effects can also be seen.

  In the case of a negative resist pattern, the dissolution rate in a developer at 23 ° C. of the amorphous film formed by spin coating the resist composition of the present 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 a resist. In addition, when the dissolution rate is 10 Å / sec or more, the resolution may be improved. It is presumed that this is because the micro surface part of the compound represented by the above formulas (1) and (2) and / or the resin containing the compound as a component dissolves to reduce LER. Moreover, the reduction effect of a defect is also seen.

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

  In the case of a positive resist pattern, the developer film of the amorphous film formed by spin coating the resist composition of this embodiment with a KrF excimer laser, a portion exposed to radiation such as extreme ultraviolet light, an electron beam or X-ray against 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 a resist. In addition, when the dissolution rate is 10 Å / sec or more, the resolution may be improved. It is presumed that this is because the micro surface part of the compound represented by the above formulas (1) and (2) and / or the resin containing the compound as a component dissolves to reduce LER. Moreover, the reduction effect of a defect is also seen.

  In the case of a negative resist pattern, the developer film of the amorphous film formed by spin coating the resist composition of the present embodiment with a KrF excimer laser, a portion exposed to radiation such as extreme ultraviolet light, electron beam or X-ray against a developer at 23 ° C. The dissolution rate is preferably 5 Å / sec or less, more preferably 0.05 to 5 Å / sec, and still more preferably 0.0005 to 5 Å / sec. When the dissolution rate is 5 Å / sec or less, it tends to be insoluble in a developer and to be easy to form a resist. When the dissolution rate is 0.0005 Å / sec or more, the resolution may be improved. This is because the unexposed area which is dissolved in the developer due to the change in solubility before and after exposure of the compound represented by the above formulas (1) and (2) and / or the resin containing the compound as a component, It is inferred that the contrast of the interface with the exposed portion which is not dissolved is increased. In addition, LER reduction and defect reduction effects can also be seen.

[Film-forming composition for lithography for non-chemical amplification resist applications]
The component (A) to be contained in the film forming composition for lithography for non-chemical amplification type resist applications of the present embodiment (hereinafter, also referred to as "radiation sensitive composition") is a diazonaphthoquinone photoactive compound (B) described later And a substrate for a positive resist, which becomes a compound easily soluble in a developer, by irradiating it with g-ray, h-ray, i-ray, KrF excimer laser, ArF excimer laser, extreme ultraviolet light, electron beam or X-ray Useful as. The properties of component (A) do not change significantly due to g-line, h-line, i-line, KrF excimer laser, ArF excimer laser, extreme ultraviolet light, electron beam or X-ray, but diazonaphthoquinone photoactivity poorly soluble in developer Since the compound (B) changes to a readily soluble compound, a resist pattern can be formed by the development step.

The component (A) to be contained in the radiation sensitive composition of the present embodiment is a compound having a relatively low molecular weight, so that the roughness of the obtained resist pattern is very small. Further, in the formula (1), at least one selected from the group consisting of R ^{0 to} R ⁵ is preferably a group containing an iodine atom, and in the formula (2), R ^0A , R ^1A and It is preferable that at least one selected from the group consisting of R ^2A be 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 absorption ability to radiation such as electron beam, extreme ultraviolet (EUV), X-ray and the like is increased. Because it is possible to increase the sensitivity, it is preferable.

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

  The crystallization calorific value obtained by differential scanning calorimetry of the glass transition temperature of the component (A) to be contained in the radiation sensitive composition of the present embodiment is preferably less than 20 J / g. The (crystallization temperature)-(glass transition temperature) is preferably 70 ° C. or more, more preferably 80 ° C. or more, still more preferably 100 ° C. or more, and particularly preferably 130 ° C. or more. It is easy to form an amorphous film by spin-coating the radiation sensitive composition when the crystallization calorific value is less than 20 J / g, or (crystallization temperature)-(glass transition temperature) is within the above range, and a resist Tends to be able to maintain the film forming properties required for the long term and to improve the resolution.

  In the embodiment, the crystallization calorific value, the crystallization temperature and the glass transition temperature can be determined by differential scanning calorimetry using DSC / TA-50 WS manufactured by Shimadzu Corporation. About 10 mg of a sample is placed in an aluminum non-sealed container, and heated to a temperature above the melting point at a heating rate of 20 ° C./minute in a nitrogen gas stream (50 mL / minute). After quenching, the temperature is raised again above the melting point at a heating rate of 20 ° C./min in a nitrogen gas stream (30 mL / min). After quenching, the temperature is raised again to 400 ° C. at a heating rate of 20 ° C./min in a nitrogen gas stream (30 mL / min). The temperature at the middle point (where the specific heat changes to half) of the step difference of the base line is defined as the glass transition temperature (Tg), and the temperature of the exothermic peak appearing thereafter is the crystallization temperature. The calorific value is determined from the area of the region surrounded by the calorific 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 is 100 or less under normal pressure, preferably 120 ° C. or less, more preferably 130 ° C. or less, still more preferably 140 ° C. or less, particularly preferably 150 ° C. or less Preferably, the sublimation property is low. The low sublimation property means that in thermogravimetric analysis, the weight loss when held at a predetermined temperature for 10 minutes is 10% or less, preferably 5% or less, more preferably 3% or less, still more preferably 1% or less, particularly preferably Indicates that it is 0.1% or less. The low sublimation property can prevent the contamination of the exposure apparatus due to the outgas at the time of exposure. Also, good pattern shape can be obtained with low roughness.

  Component (A) to be contained in the radiation sensitive composition of this embodiment is propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone (CHN), cyclopentanone (CPN), 2-heptanone Selected from the group consisting of anisole, butyl acetate, ethyl propionate and ethyl lactate and exhibiting the highest dissolving power to the component (A) at 23 ° C., preferably at least 1% by mass, more preferably Is dissolved in an amount of 5% by mass or more, more preferably 10% by mass or more. Particularly preferred is a solvent selected from the group consisting of PGMEA, PGME and CHN and having a highest solubility in the (A) resist substrate at 20% by mass or more at 23 ° C., particularly preferably PGMEA. On the other hand, 20 mass% or more melt | dissolves at 23 degreeC. By satisfying the above conditions, use in a semiconductor manufacturing process in actual production becomes easy.

[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 containing a polymeric and nonpolymeric diazonaphthoquinone photoactive compound, and in general, in a positive resist composition, There is no particular limitation as long as it is used as a color component (photosensitive agent), and one or two or more kinds can be arbitrarily selected and used.

As the component (B), compounds obtained by reacting naphthoquinone diazide sulfonic acid chloride, benzoquinone diazide sulfonic acid chloride and the like with a low molecular weight compound or polymer compound having a functional group capable of condensation reaction with these acid chlorides preferable. Here, the functional group that can be condensed with the acid chloride is not particularly limited, and examples thereof include a hydroxyl group and an amino group, and a hydroxyl group is particularly preferable. The compound that can be condensed with the acid chloride containing a hydroxyl group is not particularly limited, and examples thereof include hydroquinone, resorcinol, 2,4-dihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone 2,4,4'-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,2', 3,4,6 ' Hydroxybenzophenones such as pentahydroxybenzophenone; bis (2,4-dihydroxyphenyl) methane, bis (2,3,4-trihydroxyphenyl) methane, hydroxyphenylalkanes such as bis (2,4-dihydroxyphenyl) propane 4; 4 ′, 3 ′ ′, 4 ′ ′-tetrahydroxy-3, 5, Hydroxytriphenylmethane such as 3 ', 5'-tetramethyltriphenylmethane, 4,4', 2 ", 3", 4 "-pentahydroxy-3,5,3 ', 5'-tetramethyltriphenylmethane And the like.
Further, as acid chlorides such as naphthoquinone diazide sulfonic acid chloride and benzoquinone diazide sulfonic acid chloride, for example, 1,2-naphthoquinone diazide-5-sulfonyl chloride, 1,2-naphthoquinone diazide-4-sulfonyl chloride and the like are preferable. It can be 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 make a uniform solution, and then filtering it with, for example, a filter with a pore diameter of about 0.2 μm, if necessary. 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 this embodiment can be applied to a general semiconductor manufacturing process. Depending on the type of developer used, either a positive resist pattern or a negative resist pattern can be made separately.

  In the case of a positive resist pattern, the dissolution rate in a developer at 23 ° C. of the amorphous film formed by spin coating the radiation sensitive composition of this embodiment is preferably 5 Å / sec or less, The thickness is more preferably 5 Å / sec, further preferably 0.0005 to 5 Å / sec. When the dissolution rate is 5 Å / sec or less, it tends to be insoluble in a developer and to be easy to form a resist. When the dissolution rate is 0.0005 Å / sec or more, the resolution may be improved. This is because the exposed portion dissolves in the developer and the developer by the change in solubility before and after exposure of the compound represented by the above formulas (1) and (2) and / or the resin containing the compound as a component. It is inferred that the contrast at the interface with the unexposed undissolved portion increases. In addition, LER reduction and defect reduction effects can also be seen.

  In the case of a negative resist pattern, the dissolution rate of the amorphous film formed by spin coating the radiation sensitive composition of this 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. In addition, when the dissolution rate is 10 Å / sec or more, the resolution may be improved. It is presumed that this is because the micro surface part of the compound represented by the above formulas (1) and (2) and / or the resin containing the compound as a component dissolves to reduce LER. Moreover, the reduction effect of a defect is also seen.

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

  In the case of a positive resist pattern, the amorphous film formed by spin coating the radiation sensitive composition of this embodiment is irradiated with radiation such as KrF excimer laser, extreme ultraviolet light, electron beam or X-ray, or The dissolution rate of the exposed portion after heating at 500 ° C. in a developer at 23 ° C. is preferably 10 Å / sec or more, more preferably 10 to 10000 Å / sec, further 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 a resist. In addition, when the dissolution rate is 10000 Å / sec or less, the resolution may be improved. It is presumed that this is because the micro surface part of the compound represented by the above formulas (1) and (2) and / or the resin containing the compound as a component dissolves to reduce LER. Moreover, the reduction effect of a defect is also seen.

  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 light, electron beam or X-ray, or The dissolution rate of the exposed part after heating at 500 ° C. to the developer at 23 ° C. is preferably 5 Å / sec or less, more preferably 0.05 to 5 Å / sec, and 0.0005 to 25 Å / sec. More preferably, it is 5 Å / sec. When the dissolution rate is 5 Å / sec or less, it tends to be insoluble in a developer and to be easy to form a resist. When the dissolution rate is 0.0005 Å / sec or more, the resolution may be improved. This is because the unexposed area which is dissolved in the developer due to the change in solubility before and after exposure of the compound represented by the above formulas (1) and (2) and / or the resin containing the compound as a component, It is inferred that the contrast of the interface with the exposed portion which is not dissolved is increased. In addition, LER reduction and defect reduction effects can also be seen.

[Blending ratio of each component]
In the radiation sensitive composition of the present embodiment, the content of the component (A) may be any one of solid component total weight (component (A), diazonaphthoquinone photoactive compound (B) and other components (D), etc. 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 of the total of the solid components to be %. 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 small roughness.

  In the radiation sensitive composition of the present embodiment, the content of the diazonaphthoquinone photoactive compound (B) is the total solid component weight (component (A), diazonaphthoquinone photoactive compound (B), other components (D), etc.) Preferably 1 to 99% by mass, more preferably 5 to 95% by mass, still more preferably 10 to 90% by mass, particularly preferably 1 to 99% by mass of the solid component optionally used in It is 25-75 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 small roughness.

[Other ingredients (D)]
In the radiation sensitive composition of the present embodiment, an acid generator and a crosslinker as components other than the component (A) and the diazonaphthoquinone photoactive compound (B), if necessary, within the range that does not inhibit the object of the present invention. Agent, acid diffusion control agent, solubility promoter, solubility control agent, sensitizer, surfactant, organic carboxylic acid or phosphorus oxo acid or derivative thereof, heat and / or photo curing catalyst, polymerization inhibitor, flame retardant, Fillers, coupling agents, thermosetting resins, photocurable resins, dyes, pigments, thickeners, lubricants, antifoaming agents, leveling agents, ultraviolet absorbers, surfactants, colorants, nonionic surfactants Etc. can be added singly or in combination of two or more. In the present specification, the other component (D) may be referred to as an optional 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 by mass% on the basis of solid component,
Preferably, 1 to 99/99 to 1/0 to 98,
More preferably 5 to 95/95 to 5/0 to 49,
More preferably, it is 10-90 / 90-10 / 0-10.
Still more preferably 20-80 / 80-20 / 0-5,
Particularly preferred is 25 to 75/75 to 25/0.
The compounding ratio of each component is selected from each range so that the sum total becomes 100 mass%. When the blend ratio of each component of the radiation sensitive composition of the present embodiment is in the above range, in addition to the roughness, it tends to be excellent in performance such as sensitivity, resolution and the like.

  The radiation sensitive composition of the present embodiment may contain other resins as long as the object of the present invention is not impaired. As such other resins, novolak resin, polyvinyl phenols, polyacrylic acid, polyvinyl alcohol, styrene-maleic anhydride resin, and polymers containing acrylic acid, vinyl alcohol or vinyl phenol as a monomer unit or These derivatives etc. are mentioned. Although the compounding quantity of these resin is suitably adjusted according to the kind of component (A) to be used, it is preferable that it is 30 mass parts or less with respect to 100 mass parts of component (A), More preferably, 10 It is not more than mass part, more preferably not more than 5 mass parts, and particularly preferably 0 mass parts.

[Method of forming resist pattern]
In the method for forming a resist pattern according to the present embodiment, after a photoresist layer is formed on a substrate using the resist composition or the radiation sensitive composition according to the present embodiment described above, radiation is applied to a predetermined region of the photoresist layer. And develop.
More specifically, a step of forming a resist film on a substrate using the resist composition or the radiation sensitive composition of the present embodiment described above, a step of exposing the formed resist film, and developing the resist film And forming a resist pattern. The resist pattern in the present embodiment can also be formed as an upper layer resist in a multilayer process.

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

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

  Next, the exposed resist film is developed with a developer to form a predetermined resist pattern. As a developing solution, the solubility parameter (SP value) with respect to the resin obtained using the compound represented by Formula (1) or Formula (2) to be used or the compound represented by Formula (1) or Formula (2) as a monomer It is preferable to select a solvent close to), and polar solvents such as ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents, hydrocarbon solvents or alkaline aqueous solution 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, methyl ethyl ketone And methyl isobutyl ketone, acetylacetone, acetonylacetone, ionone, diacetonyl alcohol, acetylcarbinol, acetophenone, methylnaphthyl ketone, isophorone, propylene carbonate and the like.

  As an ester solvent, for example, 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, n-decanol, glycol solvents such as ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl Ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene Recall monoethyl ether, glycol monoethyl ether and methoxymethyl butanol.

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

  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. It can be mentioned.

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

  A plurality of the above solvents may be mixed, or may be used by mixing with solvents or water other than the above as long as they have performance. However, from the viewpoint of achieving the effects of the present invention sufficiently, the water content of the whole developer is preferably less than 70% by mass, more preferably less than 50% by mass, and less than 30% by mass It is further preferred that the water content be less than 10% by mass, and it is particularly preferable that the water content be substantially free. That is, the content of the organic solvent in the developer is preferably 30% by mass to 100% by mass, and more preferably 50% by mass to 100% by mass, with respect to the total amount of the developer. It is more preferable that the content be 100% by mass or more, still 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 alkaline compounds such as mono-, di- or trialkylamines, mono-, di- or trialkanolamines, heterocyclic amines, tetramethylammonium hydroxide (TMAH) and choline. It can be mentioned.

  In particular, the developing solution 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 resolution and roughness of the resist pattern. Preferred are developers containing one solvent.

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

  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-ethoxy pro Peonate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, butyl formate, propyl formate, ethyl lactate, butyl lactate, lactate Ester solvents such as ropir; n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, 4-methyl-2-pentanol, n-heptyl Alcohol solvents such as alcohol, n-octyl alcohol and n-decanol; glycol solvents such as ethylene glycol, diethylene glycol and triethylene glycol; ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl Such as ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methoxymethyl butanol Chole ether solvents; ether solvents such as tetrahydrofuran; amide solvents of N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide; aromatic hydrocarbon solvents such as toluene and xylene; Aliphatic hydrocarbon solvents such as octane and decane can be mentioned.

  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 and propyl lactate; n-butyl alcohol, Alcohol solvents such as ec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, 4-methyl-2-pentanol, n-heptyl alcohol, n-octyl alcohol and n-decanol; ethylene glycol, diethylene glycol Glycol solvents such as triethylene glycol; ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, glycol ether such as methoxymethyl butanol N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethyl Amide solvents formamide, aromatic hydrocarbon solvents such as xylene; octane include aliphatic hydrocarbon solvents decane.

  An appropriate amount of surfactant can be added to the developer as needed. The surfactant is not particularly limited, but for example, ionic or nonionic fluorine-based and / or silicon-based surfactants can be used. As these fluorine and / or silicon surfactants, for example, JP-A-62-36663, JP-A-61-226746, JP-A-61-226745, JP-A-62-170950. Patent documents: 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 The surfactants described in JP-A-5,360,692, JP-A-5529881, JP-A-5296330, JP-A-54,360,98, JP-A-5,576,143, and JP-A-5,294,451 are disclosed. It can mention, Preferably, it is nonionic surfactant. The nonionic surfactant is not particularly limited, but is preferably a fluorine-based surfactant or a silicon-based surfactant.

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

  As a developing method, for example, a method of immersing a substrate in a bath filled with a developer for a fixed time (dip method), a method of developing by standing up the developer on the substrate surface by surface tension and standing for a fixed time (paddle Method): Spraying the developer onto the substrate surface (spraying method), continuing the coating of the developer while scanning the developer coating nozzle at a constant speed on the substrate rotating at a constant speed (dynamic dispensing method Etc. can be applied. The time for developing the pattern is not particularly limited but is preferably 10 seconds to 90 seconds.

  Moreover, you may implement the process of stopping development, substituting with another solvent after the process of developing.

  It is preferable to include the process of washing | cleaning using the rinse solution containing an organic solvent after image development.

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

  Here, examples of the monohydric alcohol used in the rinse step after development include 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 preferable 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. That.

  Each of the components may be mixed, or mixed with an organic solvent other than the above.

  The water content in the rinse solution is preferably 10% by mass or less, more preferably 5% by mass or less, and still more preferably 3% by mass or less. By setting the water content in the rinse solution to 10% by mass or less, better developing characteristics tend to be obtained.

  The vapor pressure of the rinse solution used after development is preferably 0.05 kPa or more and 5 kPa or less at 20 ° C., more preferably 0.1 kPa or more and 5 kPa or less, and 0.12 kPa or more and 3 kPa or less Is more preferred. When the vapor pressure of the rinse solution is 0.05 kPa or more and 5 kPa or less, the temperature uniformity in the wafer surface is further improved, and further, the swelling due to the penetration of the rinse solution is further suppressed, and the dimension uniformity in the wafer surface Sex tends to improve.

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

  In the rinse step, the wafer subjected to development is washed using the above-mentioned rinse solution containing an organic solvent. Although the method of the cleaning process is not particularly limited, for example, a method of continuously applying the rinse liquid onto the substrate rotating at a constant speed (rotation coating method), and immersing the substrate in a bath filled with the rinse liquid for a predetermined time A method (dip method), a method of spraying a rinse liquid on the substrate surface (spray method), etc. can be applied, among which the cleaning treatment is performed by the spin coating method and the substrate is rotated at a rotation speed of 2000 rpm to 4000 rpm after cleaning. And the rinse solution is preferably removed from the substrate.

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

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

  The remaining resist pattern after etching can be peeled off with an organic solvent. Examples of the organic solvent include PGMEA (propylene glycol monomethyl ether acetate), PGME (propylene glycol monomethyl ether), EL (ethyl lactate) and the like. As a peeling method, an immersion method, a spray system, etc. are mentioned, for example. The wiring substrate on which the resist pattern is formed may be a multilayer wiring substrate, and may have a small diameter through hole.

  The wiring substrate in the present embodiment can also be formed by a method in which metal is deposited in vacuum after forming a resist pattern, and then the resist pattern is dissolved with a solution, that is, a lift-off method.

[Film-forming composition for lithography for lower layer film application]
The film forming composition for lithography for lower layer film use in the present embodiment (hereinafter, also referred to as “lower layer film forming material”) is a compound represented by the above formula (1), a compound represented by the above formula (1) as a monomer And at least one substance selected from the group consisting of a compound represented by the formula (2) and a resin represented by the 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, and further preferably 50 to 100% by mass in the material for forming the lower layer film, from the viewpoint of coatability and quality stability. % Is more preferable, and 100% by mass is particularly preferable.

  The lower layer film forming material of the present embodiment can be applied to a wet process, and is excellent in heat resistance and etching resistance. Furthermore, since the lower layer film forming material of the present embodiment uses the above-mentioned substance, deterioration of the film at the time of high temperature baking is suppressed, and a lower layer film excellent in etching resistance to oxygen plasma etching and the like can be formed. . Furthermore, since the underlayer film forming material of the present embodiment is also excellent in adhesion to the resist layer, an excellent resist pattern can be obtained. In addition, the lower layer film forming material of the present embodiment may include the already known lower layer film forming material for lithography and the like within the range where the effects of the present invention are not impaired.

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

  Specific examples of the solvent are not particularly limited. For example, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; Cellosolv solvents such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate; ethyl lactate, methyl acetate Ester solvents such as ethyl acetate, butyl acetate, isoamyl acetate, ethyl lactate, methyl methoxypropionate and methyl hydroxyisobutyrate; alcohol solvents such as methanol, ethanol, isopropanol and 1-ethoxy-2-propanol; toluene, xylene And aromatic hydrocarbons such as anisole. These solvents may be used alone 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 preferable from the viewpoint of safety.

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

[Crosslinking agent]
The lower layer film-forming material in the present embodiment may contain a crosslinking agent as necessary, from the viewpoint of suppressing intermixing and the like. The crosslinking agent is not particularly limited, and for example, those described in WO 2013/024779 can be used.

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

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

  A well-known thing can be used as said epoxy compound, It selects from among what has 2 or more of epoxy groups in 1 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- Epoxides of dihydric phenols such as 4,4'-dihydroxybiphenol, resorcin and naphthalenediols, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane Tris (2,3-epoxypropyl) isocyanurate, trimethylolmethane triglycidyl ether, trimethylolpropane triglycidyl ether, triethylol ethane triglycidyl ether, phenol novolac, o-cresol novolac, etc. Epo Oxidized compounds, epoxy compounds of co-condensed resin of dicyclopentadiene and phenols, epoxy compounds of phenolaralkyl resins synthesized from phenols and paraxylylene dichloride, etc., and biphenyls synthesized from phenols and bischloromethylbiphenyl, etc. Epoxides of aralkyl type phenol resins, epoxidates of naphthol aralkyl resins synthesized from naphthols and paraxylylene dichloride, etc. may be mentioned. These epoxy resins may be used alone or in combination of two or more. Among them, in view of heat resistance and solubility, solid epoxy resins at room temperature such as epoxy resins obtained from phenol aralkyl resins and biphenyl aralkyl resins are preferable.

  Any known cyanate compound can be used without particular limitation as long as it is a compound having two or more cyanate groups in one molecule. In this embodiment, as a preferable cyanate compound, the thing of the structure which substituted the hydroxyl group of the compound which has a 2 or more hydroxyl group in 1 molecule by the cyanate group is mentioned. The cyanate compound is preferably one having an aromatic group, and one having a structure in which the cyanate group is directly linked to the aromatic group can be suitably used. As such a cyanate compound, for example, bisphenol A, bisphenol F, bisphenol M, bisphenol P, bisphenol E, phenol novolac resin, cresol novolac resin, dicyclopentadiene novolac resin, tetramethyl bisphenol F, bisphenol A novolac 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 The thing of the structure which substituted hydroxyl groups, such as content phenol, to the cyanate group is mentioned. These cyanate compounds may be used alone or in combination of two or more. Moreover, the above-mentioned cyanate compound may be in any form of a monomer, an oligomer and a resin.

  Examples of the amino compound include m-phenylenediamine, p-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylpropane, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 3 3,3'-Diaminodiphenylether, 4,4'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 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- (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, '- diamino biphenyl, 4-aminophenyl-4-amino benzoate, 2- (4-aminophenyl) -6-amino-benzoxazole and the like. Furthermore, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenylether, 3,4'-diaminodiphenylether, 3,3'-diaminodiphenylether, 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-aminopheno Aromatic amines such as biphenyl, 4,4'-bis (3-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] ether, bis [4- (3-aminophenoxy) phenyl] ether Diaminocyclohexane, Diaminodicyclohexylmethane, Dimethyldiaminodicyclohexylmethane, Tetramethyldiaminodicyclohexylmethane, Diaminodicyclohexylpropane, Diaminobicyclo [2.2.1] heptane, Bis (aminomethyl) -bicyclo [2.2.1 Alicyclic amines such as heptane, 3 (4), 8 (9) -bis (aminomethyl) tricyclo [5.2.1.02,6] decane, 1,3-bisaminomethylcyclohexane, isophorone diamine and the like , Ethylenediamine, hexamethylenediamine, Kuta diamine, decamethylene diamine, diethylene triamine, aliphatic amines such as triethylenetetramine, and the like.

  Examples of the benzoxazine compounds include P-d-type benzoxazines obtained from difunctional diamines and monofunctional phenols, and Fa-type benzooxazines obtained from monofunctional diamines and difunctional phenols. Be

  Specific examples of the melamine compound include, for example, hexamethylolmelamine, hexamethoxymethylmelamine, a compound in which 1 to 6 methylol groups of hexamethylolmelamine are methoxymethylated, or a mixture thereof, hexamethoxyethylmelamine, hexaacyloxymethyl Examples thereof include melamine, a compound in which 1 to 6 methylol groups of hexamethylolmelamine are acyloxymethylated, or a mixture thereof.

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

  Specific examples of the glycoluril compound include, for example, tetramethylol glycoluril, tetramethoxy glycoluril, tetramethoxymethyl glycoluril, a compound in which 1 to 4 methylol groups of tetramethylol glycoluril are methoxymethylated, or a mixture thereof. The compound etc. which the acyloxymethylation of 1 to 4 of the methylol group of tetramethylol glycol uryl carried out, or its mixture are mentioned.

  Specific examples of the urea compound include tetramethylolurea, tetramethoxymethylurea, a compound in which 1 to 4 methylol groups of tetramethylolurea are methoxymethylated or a mixture thereof, and tetramethoxyethylurea.

  In addition, in the present embodiment, a crosslinking agent having at least one allyl group may be used from the viewpoint of improving the crosslinkability. Specific examples of the crosslinking agent having at least one allyl group include 2,2-bis (3-allyl-4-hydroxyphenyl) propane and 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) Allyl phenols such as ether, 2,2-bis (3-allyl-4-cyanatophenyl) propane, 1,1,1,3,3,3-hexafluoro-2,2-bis (3) -Allyl-4-cyanatophenyl) propane, bis (3-allyl-4-cyanatophenyl) sulfone, bis (3-allyl-4-cyanatophenyl) sulfide, bis (3- Allyl cyanates such as lyl-4-cyanatophenyl) ether, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, triallyl isocyanurate, trimethylolpropane diallyl ether, pentaerythritol allyl ether, etc. It is not limited to what was done. These may be individual or 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 and bis (3-allyl-4-hydroxyphenyl) ether are preferred .

  The content of the crosslinking agent in the lower layer film forming material is not particularly limited, but is preferably 0.1 to 100 parts by mass, and 5 to 50 parts by mass with respect to 100 parts by mass of the lower layer film forming material. Is more preferably 10 to 40 parts by mass. By setting the content of the crosslinking agent in the above range, the occurrence of the mixing phenomenon with the resist layer tends to be suppressed, and the antireflective effect tends to be enhanced and the film formation after crosslinking tends to be enhanced. .

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

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

  Examples of the crosslinking accelerator include, but are not limited to, for example, 1,8-diazabicyclo (5,4,0) undecen-7, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylamino) Tertiary amines such as methyl) phenol, 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole, 2,4,5- Imidazoles such as triphenylimidazole, tributyl phosphine, methyl diphenyl phosphine, triphenyl phosphine, organic phosphines such as diphenyl phosphine, phenyl phosphine, etc., tetraphenyl phosphonium tetraphenyl borate, tetra Tetraphenylphosphonium tetraethyl phosphonate such as tetraphenylphosphonium tetrabutyl borate, tetraphenyl phosphonium tetra-substituted borate such as tetrabutyl phosphonium tetrabutyl borate, tetraphenyl such as 2-ethyl-4-methylimidazole tetraphenylborate, N-methylmorpholine tetraphenylborate Boron salt etc. are mentioned.

  The compounding amount of the crosslinking accelerator is usually 0.1 to 10 parts by mass, preferably 100 parts by mass, based on 100 parts by mass of the whole lower layer film forming material, and more preferably, in terms of controllability and economy. It is 0.1-5 mass parts from a viewpoint, More preferably, it is 0.1-3 mass parts.

[Radical polymerization initiator]
A radical polymerization initiator can be blended with the material for forming a lower layer film of the present embodiment as required. The radical polymerization initiator may be a photopolymerization initiator that initiates radical polymerization by light, or may be a thermal polymerization initiator that initiates radical polymerization by heat.

  Such a radical polymerization initiator is not particularly limited, and those conventionally used can be appropriately adopted. For example, 1-hydroxycyclohexyl phenyl ketone, benzyl dimethyl ketal, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2 -Methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methylpropan-1-one, 2 Ketone photopolymerization initiators such as 4, 6, 4-trimethyl benzoyl diphenyl phosphine oxide, bis (2, 4, 6 trimethyl benzoyl) phenyl phosphine oxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, methyl cyclohexanone peroxide Oxide, methyl acetoacetate Oxide, acetyl acetate peroxide, 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) -cyclohexane, 1,1-bis t-Butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) -2-methylcyclohexane, 1,1-bis (t-butylperoxy) -cyclohexane, 1 1-bis (t-butylperoxy) cyclododecane, 1,1-bis (t-butylperoxy) butane, 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane, p -Mentan hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydride Peroxide, cumene hydroperoxide, t-hexyl hydroperoxide, t-butyl hydroperoxide, α, α'-bis (t-butylperoxy) diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2 5-bis (t-butylperoxy) hexane, t-butylcumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3, Isobutyryl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearoyl peroxide, succinic acid peroxide, m-toluoyl benzoyl peroxide, benzoyl peroxide, di-n -Propylpa Oxydicarbonate, diisopropylperoxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, di-2-ethoxyethylperoxydicarbonate, di-2-ethoxyhexylperoxydicarbonate, di-3- Methoxybutylperoxydicarbonate, di-s-butylperoxydicarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, α, α'-bis (neodecanoylperoxy) diisopropylbenzene, Kumi Ruperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, 1-cyclohexyl-1-methylethylperoxyneodecanoate, t-hexylperoxyneodecanoate, t-Butyl peroxy neodeca Aate, t-hexylperoxypivalate, t-butylperoxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-bis (2-ethylhexanoylperoxy) hexanoate, 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2- Ethyl hexanoate, t-hexylperoxyisopropyl monocarbonate, t-butylperoxyisobutyrate, t-butylperoxymalate, t-butylperoxy-3,5,5-trimetrohexanoate, t -Butyl peroxy laurate, t-butyl peroxy isopropyl monocarbonate, t- Butylperoxy-2-ethylhexyl monocarbonate, t-butylperoxyacetate, t-butylperoxy-m-toluylbenzoate, t-butylperoxybenzoate, bis (t-butylperoxy) isophthalate, 2,5- Dimethyl-2,5-bis (m-toluylperoxy) hexane, t-hexylperoxybenzoate, 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane, t-butylperoxyallyl monocarbonate, Organic peroxide based polymerization initiators such as t-butyltrimethylsilyl peroxide, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone and 2,3-dimethyl-2,3-diphenylbutane Can be mentioned.

  Further, 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] Dihydridochloride, 2,2′-azobis [N- (4-hydrophenyl) -2-methylpropionamidine] dihydrochlori 2,2'-azobis [2-methyl-N- (phenylmethyl) propionamidine] dihydrochloride, 2,2'-azobis [2-methyl-N- (2-propenyl) propionamidine] dihydrochloride, 2, 2'-azobis [N- (2-hydroxyethyl) -2-methylpropionamidine] dihydrochloride, 2,2'-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis [2- (4,5,6,7-tetrahydro-1H-1,3-diazepine) -2-yl) propane] dihydrochloride, 2,2'-azobis [2- (3,4,5,6-tetrahydropyrimidin-2-yl) propane Dihydrochloride, 2,2′-azobis [2- (5-hydroxy-3,4,5,6-tetrahydropyrimidin-2-yl) propane] dihydrochloride, 2,2′-azobis [2- [1- ( 2-Hydroxyethyl) -2-imidazolin-2-yl] propane] dihydrochloride, 2,2'-azobis [2- (2-imidazolin-2-yl) propane], 2,2'-azobis [2-methyl -N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide], 2,2'-azobis [2-methyl-N- [1,1-bis (hydroxymethyl) ethyl] propionamide ], 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], 2,2'-azobis (2-methylpropionamide), 2,2 ' -Azobis (2,4,4-trimethylpentane), 2,2'-azobis (2-methylpropane), dimethyl-2,2-azobis (2-methylpropionate), 4,4'-azobis (4) Also included are azo polymerization initiators such as -cyanopentanoic acid) and 2,2'-azobis [2- (hydroxymethyl) propionitrile]. As the radical polymerization initiator in the present embodiment, one of these may be used alone, or two or more may be used in combination, 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 it is preferably 0.05 to 25 parts by mass when the lower layer film forming material is 100 parts by mass. And 0.1 to 10 parts by mass are more preferable. If the content of the radical polymerization initiator is 0.05 parts by mass or more, the curing tends to be insufficient, and on the other hand, the content of the radical polymerization initiator is 25 parts by mass or less In such a case, the long-term storage stability at room temperature of the underlayer film-forming material tends to be prevented from being impaired.

[Acid generator]
The material for forming a lower layer film in the present embodiment may contain an acid generator as needed, from the viewpoint of further promoting a crosslinking reaction by heat. As an acid generator, although what generate | occur | produces an acid by thermal decomposition, the thing which generate | occur | produces an acid by light irradiation, etc. are known, all can be used. As the acid generator, for example, those described in WO 2013/024779 can be used.

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

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

  The basic compound plays the role of a quencher for the acid to prevent the acid generated in a small amount from the acid generator from proceeding with the crosslinking reaction. Such a basic compound is not particularly limited, and examples thereof include those described in WO 2013/024779.

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

[Other additives]
In addition, the lower layer film-forming material in the present embodiment may contain another resin and / or compound for the purpose of imparting the curability by heat or light and controlling the absorbance. As such other resins and / or compounds, naphthol resin, xylene resin naphthol modified resin, phenol modified resin of naphthalene resin; polyhydroxystyrene, dicyclopentadiene resin, (meth) acrylate, dimethacrylate, trimethacrylate, tetramer Resin containing naphthalene ring such as methacrylate, vinyl naphthalene and polyacenaphthylene, biphenyl ring such as phenanthrene quinone and fluorene, hetero ring having hetero atom such as thiophene and indene, resin not containing aromatic ring; rosin based resin Examples thereof include, but not particularly limited to, resins or compounds containing an alicyclic structure such as cyclodextrin, adamantane (poly) ol, tricyclodecane (poly) ol and derivatives thereof. Furthermore, the underlayer film forming material in the present embodiment may contain known additives. Examples of known additives include, but are not limited to, heat and / or light curing catalysts, polymerization inhibitors, flame retardants, fillers, coupling agents, thermosetting resins, photocurable resins, dyes, and pigments. And thickeners, lubricants, antifoaming agents, leveling agents, UV absorbers, surfactants, colorants, nonionic surfactants and the like.

[Formation method of underlayer film for lithography and multilayer resist pattern]
The underlayer film for lithography in the present embodiment is formed of the above-mentioned underlayer film forming material.

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

Furthermore, in the circuit pattern forming method of the present embodiment, an underlayer film is formed on a substrate using the above composition, and an interlayer film is formed on the underlayer film using a resist interlayer film material, and the interlayer Forming at least one photoresist layer on the film;
Irradiating a predetermined area of the photoresist layer with radiation for development 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 using the underlayer film forming material of the present embodiment on a substrate, and using a resist interlayer film material containing silicon atoms on the underlayer film Forming an interlayer film (B-2), forming at least one photoresist layer on the interlayer film (B-3), and after the step (B-3), A predetermined area of the photoresist layer is irradiated with radiation and developed to form a resist pattern (B-4), and after the step (B-4), the intermediate layer film using the resist pattern as a mask Forming the pattern on the substrate by etching the lower layer film using the obtained intermediate layer film pattern as an etching mask and etching the substrate using the obtained lower layer film pattern as an etching mask (B-5) When Having.

  The lower layer film for lithography in the present embodiment is not particularly limited as long as it is formed of the material for forming a lower layer film of the present embodiment, and known methods 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 the like, the organic solvent is removed by volatilization, and then removed by a known method. The lower layer film for lithography of this embodiment can be formed by crosslinking and curing. Examples of the crosslinking method include methods such as heat curing and light curing.

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

  After the underlayer film is formed, in the case of a two-layer process, a silicon-containing resist layer or a single layer resist composed of ordinary hydrocarbons is formed thereon, and in the case of a three-layer process, a silicon-containing intermediate layer is further formed thereon It is preferable to prepare a single layer resist layer not containing silicon. In this case, known photoresist materials can be used as the photoresist material for forming the resist layer.

  After the lower layer film is formed on the substrate, in the case of a two-layer process, a silicon-containing resist layer or a single-layer resist made of ordinary hydrocarbon can be formed on the lower layer film. In the case of the three-layer process, it is possible to form a silicon-containing intermediate layer on the lower layer film and a single-layer resist layer not containing silicon on the silicon-containing intermediate layer. 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, a silicon atom-containing polymer such as a polysilsesquioxane derivative or a vinylsilane derivative is used as a base polymer from the viewpoint of oxygen gas etching resistance, and an organic solvent, an acid generator, A positive photoresist material containing a basic compound and the like as needed is preferably used. Here, as the silicon atom-containing polymer, known polymers used in this type of resist material can be used.

  As a silicon-containing intermediate layer for the three-layer process, an intermediate layer based on polysilsesquioxane is preferably used. There is a tendency that the reflection can be effectively suppressed by giving the intermediate layer an effect as an antireflective film. For example, in the process for 193 nm exposure, if a material having a large amount of aromatic groups and high substrate etching resistance is used as the lower layer film, the k value tends to be high and the substrate reflection tends to be high. Can make the substrate reflection 0.5% or less. The intermediate layer having such an antireflective effect is not limited to the following, but for exposure at 193 nm, an acid or thermally crosslinked polysilsesqui having a light absorbing group having a phenyl group or a silicon-silicon bond is introduced. Oxane is preferably used.

  Further, an intermediate layer formed by a chemical vapor deposition (CVD) method can also be used. For example, a SiON film is known as an intermediate layer produced by a CVD method and having high effect as an antireflective film, although not limited thereto. In general, forming the intermediate layer by a wet process such as spin coating or screen printing rather than the CVD method is simpler and more cost effective. The upper layer resist in the three-layer process may be either positive or negative, and may be the same as a commonly used single layer resist.

  Furthermore, the lower layer film in the present embodiment can also be used as a general antireflective film for a single layer resist or a base material for suppressing pattern collapse. The lower layer film is excellent in etching resistance for base processing, so that it can also be expected to function as a hard mask for base processing.

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

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

  The resist pattern formed by the above-described method is such that the lower layer film suppresses the pattern collapse. Therefore, by using the lower layer film in the present embodiment, a finer pattern can be obtained, and the amount of exposure required to obtain the resist pattern can be reduced.

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

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

  Here, when forming an inorganic hard mask intermediate layer film as an intermediate layer, a silicon oxide film, a silicon nitride film, and a silicon oxynitride film (SiON film) are formed by a CVD method, an ALD method, or the like. The method for forming the nitride film is not limited to the following. For example, the methods described in JP-A-2002-334869 (Patent Document 6) and WO 2004/066377 (Patent Document 7) can be used. Although a photoresist film can be formed directly on such an interlayer film, an organic antireflective film (BARC) is formed by spin coating on the interlayer film, and a photoresist film is formed thereon. You may

  As the intermediate layer, an intermediate layer based on polysilsesquioxane is also preferably used. There is a tendency that the reflection can be effectively suppressed by giving the resist interlayer film an effect as an antireflective film. Specific materials for the polysilsesquioxane-based intermediate layer are not limited to the following, but, for example, they are described in JP-A-2007-226170 (Patent Document 8) and JP-A-2007-226204 (Patent Document 9). Can be used.

In addition, the etching of the next substrate can also be performed by a conventional method, for example, etching using a fluorocarbon gas as the main component if the substrate is SiO ₂ or SiN, chlorine or bromine if it is p-Si, Al or W Gas-based etching can be performed. When the substrate is etched with a fluorocarbon gas, the silicon-containing resist in the two-layer resist process and the silicon-containing intermediate layer in the three-layer process are peeled off simultaneously with the substrate processing. On the other hand, when the substrate is etched with a chlorine-based or bromine-based gas, the silicon-containing resist layer or the silicon-containing intermediate layer is separately peeled off, and in general, the dry etching peeling by fluorocarbon-based gas is performed after processing the substrate. .

The lower layer film in the present embodiment is characterized in that the etching resistance of the substrate is excellent. As the substrate, it can be appropriately selected and used those known, but are not limited to, include _{Si, α-Si, p-} Si, SiO 2, SiN, SiON, W, TiN, Al and the like Be The substrate may be a laminate having a film to be processed (substrate to be processed) on a base material (support). As such a film to be processed, various Low-k films and stoppers thereof such as Si, SiO ₂ , SiON, SiN, p-Si, α-Si, W, W-Si, Al, Cu, Al-Si, etc. A film etc. are mentioned, Usually, the thing of the material different from a base material (support body) is used. The thickness of the substrate to be processed or the film to be processed is not particularly limited, but in general, it is preferably about 50 to 10,000 nm, and more preferably 75 to 5,000 nm.

  The resist permanent film formed by applying the composition in the present embodiment is suitable as a permanent film remaining also in the final product after forming a resist pattern as needed. Specific examples of permanent films include solder resists, package materials, underfill materials, package adhesive layers such as circuit elements for semiconductor devices, adhesive layers for integrated circuit elements and circuit boards, thin film transistor protective films for thin displays, A liquid crystal color filter protective film, a black matrix, a spacer etc. are mentioned. In particular, the permanent film made of the composition in the present embodiment is excellent in heat resistance and moisture resistance, and also has a very excellent advantage that the contamination by the sublimation component is small. In particular, in the display material, the material has high image quality, high heat resistance, and moisture absorption reliability with little deterioration in image quality due to important contamination.

  When the composition in the present embodiment is used for a resist permanent film application, various additives such as other resins, surfactants, dyes, fillers, crosslinking agents, and dissolution accelerators may be added in addition to the curing agent, if necessary. An agent is added and it melt | dissolves in the organic solvent, It can be set as the composition for resist permanent films.

  The film forming composition for lithography and the composition for a resist permanent film in the present embodiment can be prepared by blending the above-mentioned components and mixing them using a stirrer or the like. When the composition for a resist lower layer film or the composition for a resist permanent film in the present embodiment contains a filler or a pigment, it is dispersed or mixed using a disperser such as a dissolver, a homogenizer, or a 3-roll mill. It can be prepared.

Hereinafter, the present embodiment will be described in more detail by synthetic examples and examples, but the present embodiment is not limited by these examples.
(Carbon concentration and oxygen concentration)
Carbon concentration and oxygen concentration (mass%) were measured by organic elemental analysis.
Device: CHN coder MT-6 (Yanako Analytical Industry Co., Ltd. product)

(Molecular weight)
The molecular weight of the compound was measured by LC-MS analysis using Water manufactured by Acquity UPLC / MALDI-Synapt HDMS.
In addition, gel permeation chromatography (GPC) analysis was performed under the following conditions to determine polystyrene-equivalent weight average molecular weight (Mw), number average molecular weight (Mn), and dispersion degree (Mw / Mn).
Device: Shodex GPC-101 (manufactured by Showa Denko KK)
Column: KF-80M × 3
Eluent: THF 1mL / min
Temperature: 40 ° C

(Solubility)
The compound is stirred at 23 ° C. so as to be a 3 mass% solution with respect to propylene glycol monomethyl ether (PGME), cyclohexanone (CHN), ethyl lactate (EL), methyl amyl ketone (MAK) or tetramethyl urea (TMU) And the results after one week were evaluated according to the following criteria.
Evaluation A: Visually confirmed that there was no precipitate in any of the solvents Evaluation C: Visually confirmed that there was a precipitate in all the solvents

(Structure of compound)
The structure of the compound was confirmed by ¹ H-NMR measurement under the following conditions using “Advance 600 II spectrometer” manufactured by Bruker.
Frequency: 400 MHz
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-biphenyl carboxy in a container with an internal volume of 100 ml equipped with a stirrer, a condenser and a burette An aldehyde (manufactured by Mitsubishi Gas Chemical Co., Ltd.) 1.82 g (10 mmol) 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 for reaction. Next, the reaction solution was concentrated, 50 g of pure water was added to precipitate a reaction product, and after cooling to room temperature, filtration was performed to separate. The obtained solid was filtered and dried, and then separated and purified by column chromatography to obtain 3.05 g of the objective compound represented by the following formula. It confirmed having a chemical structure of a following formula by 400 MHz ¹ H-NMR.
¹ H-NMR: (d-DMSO, internal standard TMS)
δ (ppm) 9.7 (2 H, O-H), 7.2 to 8.5 (19 H, Ph-H), 6.6 (1 H, C-H)
In addition, it was confirmed that the signals of protons at the 3- and 4-positions are doublets that the substitution position of 2,6-naphthalenediol is 1-position.

<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 in a container with an internal volume of 100 ml equipped with a stirrer, a condenser and a burette ) Was added to 50 ml of dimethylformamide, 6.56 g (54 mmol) of 2-chloroethyl acetate was added, and the reaction was stirred at 90 ° C. for 12 hours for reaction. Next, the reaction solution was cooled in an ice bath to precipitate crystals, which were separated by filtration. Subsequently, 40 g of the crystals, 40 g of methanol, 100 g of THF and a 24% aqueous solution of sodium hydroxide were charged in a container having an internal volume of 100 ml equipped with a stirrer, a condenser and a burette, and the reaction solution was stirred for 4 hours under reflux to carry out a reaction. . After cooling in an ice bath, the reaction solution is concentrated, and the precipitated solid is filtered and dried, followed by separation and purification by column chromatograph to obtain 5.9 g of the objective compound represented by the following formula. It confirmed having a chemical structure of a following formula by 400 MHz ¹ H-NMR.
¹ H-NMR: (d-DMSO, internal standard TMS)
δ (ppm) 8.6 (2 H, O-H), 7.2 to 7.8 (19 H, Ph-H), 6.7 (1 H, C-H), 4.0 (4 H, -O- _{CH 2 -), 3.8 (4H} , -CH 2 -OH)

<Synthesis Example 1-1> Synthesis of AlE-XBisN-1 10.3 g (21 mmol) of a compound represented by the above formula (E-XBisN-1) in a container with an internal volume of 100 ml equipped with a stirrer, a condenser and a burette A solution obtained by adding 0.1 g of potassium carbonate and 6.2 g (45 mmol) of potassium carbonate to 100 ml acetone is charged, and further 5.4 g of allyl bromide (45 mmol) and 2.0 g of 10-crown-6 are added. The reaction was carried out with stirring for 9 hours under reflux. Next, solid content was removed from the reaction solution by filtration, cooled in an ice bath, and the reaction solution was concentrated to precipitate a solid. The precipitated solid was filtered and dried, and then separated and purified by column chromatography to obtain 3.2 g of the objective compound represented by the following formula (AlE-XBisN-1).
The 400MHz- ¹ H-NMR, it was confirmed to have the following chemical structure formula (AlE-XBisN-1).
¹ H-NMR: (d-DMSO, internal standard TMS)
δ (ppm) 7.2 to 7.8 (19 H, Ph-H), 6.7 (1 H, C-H), 6.1 (2 H, -CH-CH ₂ ), 5.4 to 5.5 _{(4H, -CH-CH 2)} , 4.7 (4H, -O-CH 2 -), 4.0 (4H, -O-CH 2 -), 3.8 (4H, -CH 2 -OH)

It was 634 as a result of measuring molecular weight by the said method about the obtained compound.
The thermal decomposition temperature is 390 ° C., the glass transition point is 105 ° C., and the melting point is 205 ° C., and it has been confirmed that the material has high heat resistance.

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

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

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

<Synthesis Example 2-1> Synthesis of AlE-BisF-1 Instead of the compound represented by the above formula (E-XBisN-1), a compound represented by the above formula (E-BisF-1) was used The reaction was conducted in the same manner as in Synthesis Example 1-1 except for the above to obtain 3.0 g of the objective compound represented by the following formula (AlE-BisF-1).
The 400MHz- ¹ H-NMR, it was confirmed to have the following chemical structure formula (AlE-BisF-1).
¹ H-NMR: (d-DMSO, internal standard TMS)
δ (ppm) 6.8 to 7.8 (22 H, Ph-H), 6.2 (1 H, C-H), 6.1 (4 H, -CH-CH ₂ ), 5.4 to 5.5 _{(8H, -CH-CH 2)} , 4.7 (8H, -O-CH 2 -), 4.0 (8H, -O-CH 2 -), 3.8 (8H, -CH 2 -OH)
The thermal decomposition temperature was 380.degree. C., the glass transition point was 70.degree. C., and the melting point was 200.degree. C., which confirmed that they had high heat resistance.

  It was 872 as a result of measuring molecular weight by the said method about the obtained compound.

<Synthesis Example 2-2> Synthesis of AcE-BisF-1 Instead of the compound represented by the above formula (E-XBisN-1), a compound represented by the above formula (E-BisF-1) is used, The 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 objective compound represented by the following formula (AcE-BisF-1).
The 400MHz- ¹ H-NMR, it was confirmed to have the following chemical structure formula (AcE-BisF-1).
¹ H-NMR: (d-DMSO, internal standard TMS)
δ (ppm) 6.8 to 7.8 (22 H, Ph-H), 6.2 (1 H, C-H), 5.8 to 6.4 (6 H, -CH-CH ₂ ), 4.0 _{(8H, -O-CH 2 -} ), 3.8 (8H, -CH 2 -OH)

It was 928 as a result of measuring molecular weight by the said method about the obtained compound.
The thermal decomposition temperature was 375 ° C., the glass transition point was 65 ° C., and the melting point was 190 ° C., which confirmed that the material had high heat resistance.

Synthesis Example 3 Synthesis of BiN-1 After melting 10 g (69.0 mmol) of 2-naphthol (reagent manufactured by Sigma-Aldrich Co.) at 120 ° C. in a 300 mL container equipped with a stirrer, a condenser and a burette, 0.27 g of sulfuric acid is charged, 2.7 g (13.8 mmol) of 4-acetylbiphenyl (reagent manufactured by Sigma-Aldrich) is added, and the contents are stirred at 120 ° C. for 6 hours to carry out a reaction to obtain a reaction solution. The Next, 100 mL of N-methyl-2-pyrrolidone (manufactured by Kanto Chemical Co., Ltd.) and 50 mL of pure water were added to the reaction solution, and the mixture was extracted with ethyl acetate. Next, pure water was added, and liquid separation was carried out until it became neutral, followed by concentration to obtain a solution.
The obtained solution was separated by column chromatography to obtain 1.0 g of a target compound (BiN-1) represented by the following formula (BiN-1).
It was 466 as a result of measuring a molecular weight by the above-mentioned method about the obtained compound (BiN-1).
About the obtained compound (BiN-1), when NMR measurement was performed on the above-mentioned measurement conditions, the following peaks were discovered and it confirmed having a chemical structure of 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 (BiN-1) represented by the above formula in a container with an internal volume of 100 ml equipped with a stirrer, a cooling pipe and a burette and 14.8 g of potassium carbonate (107 mmol) was added to 50 ml of dimethylformamide, 6.56 g (54 mmol) of 2-chloroethyl acetate was added, and the reaction was stirred at 90 ° C. for 12 hours for reaction. Next, the reaction solution was cooled in an ice bath to precipitate crystals, which were separated by filtration. Subsequently, 40 g of the crystals, 40 g of methanol, 100 g of THF and a 24% aqueous solution of sodium hydroxide were charged in a vessel having an inner volume of 100 ml equipped with a stirrer, a condenser and a burette, and the reaction solution was stirred for 5 hours under reflux to carry out a reaction. . After cooling in an ice bath, the reaction solution is concentrated, and the precipitated solid is filtered and dried, followed by separation and purification by column chromatography to obtain 4.6 g of the objective compound represented by the following formula. It confirmed having a chemical structure of a following formula by 400 MHz ¹ H-NMR.
¹ H-NMR: (d-DMSO, internal standard TMS)
δ (ppm) 8.6 (2 H, O-H), 7.2 to 7.8 (19 H, Ph-H), 6.7 (1 H, C-H), 4.0 (4 H, -O- _{CH 2 -), 3.8 (4H} , -CH 2 -OH)

<Synthesis Example 3-1> Synthesis of AlE-BiN-1 12.3 g (21 mmol) of a compound represented by the above formula (E-BiN-1) in a container with an inner volume of 100 ml equipped with a stirrer, a condenser and a burette A solution prepared by adding 100 g of acetone and 6.2 g (45 mmol) of potassium carbonate, and further adding 2.0 g of 5.4 g (45 mmol) of allyl bromide and 10-crown-6 and refluxing the obtained reaction solution The reaction was allowed to stir for 7 hours below. Next, solid content was removed from the reaction solution by filtration, cooled in an ice bath, and the reaction solution was concentrated to precipitate a solid. The precipitated solid substance was filtered and dried, and then separated and purified by column chromatography to obtain 4.0 g of the objective compound represented by the following formula (AlE-BiN-1).
The 400MHz- ¹ H-NMR, it was confirmed to have the following chemical structure formula (AlE-BiN-1).
¹ H-NMR: (d-DMSO, internal standard TMS)
δ (ppm) 7.2 to 7.8 (19 H, Ph-H), 6.7 (1 H, C-H), 6.1 (2 H, -CH-CH ₂ ), 5.4 to 5.5 _{(4H, -CH-CH 2)} , 4.7 (4H, -O-CH 2 -), 4.0 (4H, -O-CH 2 -), 3.8 (4H, -CH 2 -OH)

It was 634 as a result of measuring molecular weight by the said method about the obtained compound.
The thermal decomposition temperature was 380.degree. C., the glass transition temperature was 115.degree. C., and the melting point was 215.degree. C., which confirmed that they had high heat resistance.

<Synthesis Example 3-2> Synthesis of AcE-BiN-1 The reaction was performed 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- was used. 3.3 g of the target compound represented by 1) was obtained.
The 400MHz- ¹ H-NMR, it was confirmed to have the following chemical structure formula (AcE-BiN-1).
¹ H-NMR: (d-DMSO, internal standard TMS)
δ (ppm) 7.2 to 7.8 (19 H, Ph-H), 6.7 (1 H, C-H), 5.8 to 6.4 (6 H, -CH-CH ₂ ), 4.0 _{(4H, -O-CH 2 -} ), 3.8 (4H, -CH 2 -OH)

It was 662 as a result of measuring molecular weight by the said method about the obtained compound.
The thermal decomposition temperature was 371 ° C., the glass transition point was 102 ° C., and the melting point was 221 ° C., which confirmed that the material had high heat resistance.

Synthesis Example 4 Synthesis of BiP-1 The target compound 1 represented by the following formula (BiP-1) was produced by the same reaction as in Synthesis Example 3 except that o-phenylphenol was used instead of 2-naphthol. I got .0g.
It was 466 as a result of measuring a molecular weight by the above-mentioned method about the obtained compound (BiP-1).
About the obtained compound (BiP-1), when NMR measurement was performed on the above-mentioned measurement conditions, the following peaks were discovered and it confirmed having a chemical structure of following formula (BiP-1).
δ (ppm) 9.67 (2H, OH), 6.98 to 7.60 (25H, Ph-H), 2.25 (3H, CH)

Synthesis Example 4A Synthesis of E-BiP-1 11.2 g (21 mmol) of a compound represented by the above formula (BiP-1) and potassium carbonate 14. in a container with an internal volume of 100 ml equipped with a stirrer, a condenser and a burette. 8 g (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 for reaction. Next, the reaction solution was cooled in an ice bath to precipitate crystals, which were separated by filtration. Subsequently, 40 g of the crystals, 40 g of methanol, 100 g of THF and a 24% aqueous solution of sodium hydroxide were charged in a container having an internal volume of 100 ml equipped with a stirrer, a condenser and a burette, and the reaction solution was stirred for 4 hours under reflux to carry out a reaction. . Then, the reaction solution is cooled in an ice bath, and the precipitated solid is filtered and dried, and then separated and purified by column chromatograph, and the target compound represented by the following formula (E-BiP-1) I got 5.9 g.
The 400MHz- ¹ H-NMR, it was confirmed to have the following chemical structure formula (E-BiP-1).
¹ H-NMR: (d-DMSO, internal standard TMS)
δ (ppm) 8.6 (4 H, O-H), 6.8-7.6 (25 H, Ph-H), 4.0 (4 H, -O-CH _2- ), 3.8 (4 H, O-CH _2- ) _{-CH 2 -OH), 2.2 (3H} , C-H)
It was 606 as a result of measuring molecular weight by the said method about the obtained compound.

Synthesis Example 4-1 Synthesis of AlE-BiP-1 A compound represented by the formula (E-BiP-1) was used instead of the compound represented by the formula (E-BiN-1). The reaction was conducted in the same manner as in Synthesis Example 3-1 except for the above to obtain 3.0 g of the objective compound represented by the following formula (AlE-BiP-1).
The 400MHz- ¹ H-NMR, it was confirmed to have the following chemical structure formula (AlE-BiP-1).
¹ H-NMR: (d-DMSO, internal standard TMS)
δ (ppm) 6.8 to 7.8 (25 H, Ph-H), 6.1 (4 H, -CH-CH ₂ ), 5.4 to 5.5 (4 H, -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)
The thermal decomposition temperature was 390 ° C., the glass transition point was 74 ° C., and the melting point was 202 ° C., which confirmed that the material had high heat resistance.

  It was 686 as a result of measuring molecular weight by the said method about the obtained compound.

<Synthesis Example 4-2> Synthesis of AcE-BiP-1 Using a compound represented by the above formula (E-BiP-1) instead of the compound represented by the above formula (E-XBisN-1), The 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 objective compound represented by the following formula (AcE-BiP-1).
The 400MHz- ¹ H-NMR, it was confirmed to have the following chemical structure formula (AcE-BiP-1).
¹ H-NMR: (d-DMSO, internal standard TMS)
δ (ppm) 6.8 to 7.8 (25 H, Ph-H), 5.8 to 6.4 (3 H, -CH-CH ₂ ), 4.0 (4 H, -O-CH _2- ), _{3.8 (4H, -CH 2 -OH)} , 2.2 (3H, C-H),

It was 700 as a result of measuring molecular weight by the said method about the obtained compound.
The thermal decomposition temperature was 365 ° C., the glass transition point was 85 ° C., and the melting point was 220 ° C., which confirmed that the material had high heat resistance.

(Composition Examples 5 to 17)
The 2-naphthol (raw material 1) and 4-acetylbiphenyl (raw material 2) which are the raw materials of the synthesis example 3 were changed as shown in Table 1, and others were performed similarly to the synthesis example 3, and each target compound was obtained.
Each target compound was identified by 1 H-NMR.

(Composition Examples 18 to 20)
The 2-naphthol (raw material 1) and the 4-biphenyl aldehyde (raw material 2) which are the raw materials of the synthesis example 3 were changed like Table 3, others were performed similarly to the synthesis example 3, and each target compound was obtained.
Each target compound was identified by 1 H-NMR.

(Synthesis example 21-22)
The 2-naphthol (raw material 1) and 4-acetylbiphenyl (raw material 2) which are the raw materials of Synthesis Example 3 are 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 other procedures were carried out in the same manner as in Synthesis Example 3 to obtain respective target compounds.
Each target compound was identified by 1 H-NMR.

(Composition examples 5A to 22A)
The compound represented by the said Formula (BiN-1) which is a raw material of the synthesis example 3A was changed like Table 7, and others synthesize | combined on the conditions similar to the synthesis example 3A, and the target compound was obtained. Structure ^{400MHz- 1 H-NMR (d-} DMSO, internal standard TMS) of the target compound by confirming the molecular weight and LC-MS, was identified.

(Synthesis Example 5-1 to 22-1)
The compound represented by the formula (E-BiN-1), which is a raw material of Synthesis Example 3-1, is changed as shown in Table 7, and the other synthesis is performed under the same conditions as in Synthesis Example 3-1. , I got each object. Structure of each compound ^{400MHz- 1 H-NMR (d-} DMSO, internal standard TMS) by confirming the molecular weight and LC-MS, was identified.

Synthesis Examples 5-2 to 22-2
The compound represented by the formula (E-BiN-1), which is a raw material of Synthesis Example 3-2, is changed as shown in Table 7, and the other synthesis is performed under the same conditions as in Synthesis Example 3-2. , I got each object. Structure of each compound ^{400MHz- 1 H-NMR (d-} DMSO, internal standard TMS) by confirming the molecular weight and LC-MS, was identified.

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

  Obtained resin (R1-XBisN-1) was Mn: 1975, Mw: 3650, Mw / Mn: 1.84.

Synthesis Example 24 Synthesis of Resin (R2-XBisN-1) A four-necked flask having an inner volume of 1 L capable of removing bottom and equipped with a Dimroth condenser, a thermometer and a stirring blade was prepared. In the nitrogen stream, 32.6 g (70 mmol, manufactured by Mitsubishi Gas Chemical Company, Inc.) of the compound (XBisN-1) obtained in Synthesis Example 1 and 50.9 g (280 mmol, 4-biphenylaldehyde) were added to this four-necked flask. Charge Mitsubishi Gas Chemical Co., Ltd. product, 100 mL of anisole (Kanto Chemical Co., Ltd. product) and 10 mL of oxalic acid dihydrate (Kanto Chemical Co., Ltd. product), and react for 7 hours while refluxing at 100 ° C under normal pressure. I did. Thereafter, 180.0 g of ortho-xylene (reagent special grade manufactured by Wako Pure Chemical Industries, Ltd.) as a dilution solvent was added to the reaction solution, and after standing, the lower aqueous phase was removed. Furthermore, neutralization and water washing were performed, and 34.7 g of resin (R2-XBisN-2) as a brown solid was obtained by distilling off the solvent of the organic phase and unreacted 4-biphenyl aldehyde under reduced pressure.

  Obtained resin (R2-XBisN-1) was Mn: 1610, Mw: 2567, Mw / Mn: 1.59.

<Synthesis Example 23A> Synthesis of E-R1-XBisN-1 30 g of the above-mentioned resin (R1-XBisN-1) and 29.6 g (214 mmol) of potassium carbonate in a 500 ml container equipped with a stirrer, a condenser and a burette The reaction mixture 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 for reaction. Next, the reaction solution was cooled in an ice bath to precipitate crystals, which were separated by filtration. Subsequently, 40 g of the crystals, 80 g of methanol, 100 g of THF and a 24% aqueous solution of sodium hydroxide were charged in a vessel having an inner volume of 100 ml equipped with a stirrer, a condenser and a burette, and the reaction solution was stirred under reflux for 4 hours for reaction. . Then, it cooled with an ice bath, the reaction liquid was concentrated and the precipitated solid was filtered and dried to obtain 26.5 g of a brown solid resin (E-R1-XBisN-1).

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

<Synthesis Example 23-1> Synthesis of AlE-R1-XBisN-1 A compound represented by the above formula (E-R1-XBisN-1) in a vessel having an internal volume of 500 ml equipped with a stirrer, a condenser and a burette. A solution obtained by adding 6 g and 12.4 g (90 mmol) of potassium carbonate to 200 ml acetone was charged, and further 10.8 g of allyl bromide (90 mmol) and 4.0 g of 10-crown-6 were added to obtain a reaction solution. The reaction was allowed to stir under reflux for 9 hours. Next, solid content was removed from the reaction solution by filtration, cooled in an ice bath, and the reaction solution was concentrated to precipitate a solid. 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.

  Obtained resin (AlE-R1-XBisN-1) was Mn: 2021, Mw: 3040, Mw / Mn: 1.50.

<Synthesis Example 23-2> Synthesis of AcE-R1-XBisN-1 The reaction was carried out in the same manner as in Synthesis Example 23-1 except that acrylic acid was used instead of the above allyl bromide, to give brown solid (AcE 5.0 g of a resin represented by -R1-XBisN-1) was obtained.

  Obtained resin (AcE-R1-XBisN-1) was Mn: 2476, Mw: 3930, Mw / Mn: 1.61.

Synthesis Example 24A Synthesis of E-R2-XBisN-1 30 g of the above-mentioned resin (R2-XBisN-1) and 29.6 g (214 mmol) of potassium carbonate in a 500 ml container equipped with a stirrer, a condenser and a burette The reaction mixture 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 for reaction. Next, the reaction solution was cooled in an ice bath to precipitate crystals, which were separated by filtration. Subsequently, 40 g of the crystals, 80 g of methanol, 100 g of THF and a 24% aqueous solution of sodium hydroxide were charged in a vessel having an inner volume of 100 ml equipped with a stirrer, a condenser and a burette, and the reaction solution was stirred for 4 hours under reflux to carry out a reaction. . Then, it cooled by an ice bath, the reaction liquid was concentrated, the precipitated solid was filtered and dried, and 22.3 g of resin (E-R2-XBisN-1) of brown solid was obtained.

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

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

  Obtained resin (AlE-R2-XBisN-1) was Mn: 2411, Mw: 3845, Mw / Mn: 1.59.

<Synthesis Example 24-2> Synthesis of AcE-R1-XBisN-1 The reaction was carried out in the same manner as in Synthesis Example 24-1 except that acrylic acid was used instead of allyl bromide, to give brown solid (AcE 5.0 g of resin represented by -R2-XBisN-1) was obtained.

  Obtained resin (AcE-R2-XBisN-1) was Mn: 2676, Mw: 4630, Mw / Mn: 1.73.

(Composition comparative example 1)
A four-necked flask with an inner volume of 10 L capable of removing bottom and equipped with a Dimroth condenser, a thermometer and a stirrer 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 a 40% by mass formalin aqueous solution (28 mol as formaldehyde, Mitsubishi Gas Chemical (stock ) And 98 mass% sulfuric acid (Kanto Kagaku Co., Ltd. product) were charged and reacted for 7 hours while refluxing at 100 ° C. under normal pressure. Thereafter, 1.8 kg of ethylbenzene (reagent special grade manufactured by Wako Pure Chemical Industries, Ltd.) as a dilution solvent was added to the reaction liquid, and after standing, the lower aqueous phase was removed. Furthermore, neutralization and washing with water were performed, and ethylbenzene and unreacted 1,5-dimethylnaphthalene were distilled off under reduced pressure to obtain 1.25 kg of a light brown solid dimethylnaphthalene formaldehyde resin.
The molecular weight of the obtained dimethyl naphthalene formaldehyde was Mn: 562.

Subsequently, a 0.5 L four-necked flask equipped with a Dimroth condenser, a thermometer and a stirring blade was prepared. In this four-necked flask, 100 g (0.51 mol) of dimethyl naphthalene formaldehyde resin obtained as described above and 0.05 g of para-toluenesulfonic acid are charged under a nitrogen stream, and the temperature is raised to 190 ° C. 2 After heating for a while, it was stirred. Thereafter, 52.0 g (0.36 mol) of 1-naphthol was further added, and the temperature was raised to 220 ° C. for reaction for 2 hours. The solvent was diluted, neutralized and washed with water, and the solvent was removed under reduced pressure to obtain 126.1 g of a black-brown solid modified resin (CR-1).
Obtained resin (CR-1) was Mn: 885, Mw: 2220, Mw / Mn: 4.17.

(Examples 1-1 to 24-2, Comparative Example 1)
The solubility test was conducted using the compound or resin described in the above-mentioned Synthesis Examples 1-1 to 24-2 and CR-1 of Synthesis Comparative Example 1. The results are shown in Table 8.
Moreover, the lower layer film forming material for lithography of the composition shown in Table 8 was prepared respectively. Next, these materials for forming a lower layer film 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 form lower layer films each having a film thickness of 200 nm. The following were used as the acid generator, the crosslinking agent and the organic solvent.
Acid generator: Midori Chemical Co., Ltd. Ditertiary butyldiphenyliodonium nonafluoromethanesulfonate (DTDPI)
Crosslinking agent: Sanwa Chemical Co., Ltd. Nicarak MX 270 (Nicarak)
Organic solvent: Propylene glycol monomethyl ether acetate (PGMEA)

(Examples 25 to 44)
Moreover, the underlayer film forming material for lithography of the composition shown in the following Table 9 was prepared, respectively. Next, the underlayer film forming material for lithography is spin-coated on a silicon substrate, and then baked at 110 ° C. for 60 seconds to remove the solvent of the coating, and then the integrated exposure amount 600 mJ with a high pressure mercury lamp. / cm ^2, and is cured by irradiation time of 20 seconds to produce each an underlying film having a thickness of 200 nm. The following were used about the radical photopolymerization initiator, the crosslinking agent, and the organic solvent.

Radical polymerization initiator: IRGACURE 184 manufactured by BASF
Crosslinking agent:
(1) Sanwa Chemical Corporation Nicarak MX 270 (Nicarak)
(2) Mitsubishi Gas Chemical's diallyl bisphenol A type cyanate (DABPA-CN)
(3) Konishi Chemical Industries diallyl bisphenol A (BPA-CA)
(4) Konishi Chemical Industries Benzooxazine (BF-BXZ)
(5) Nippon Kayaku biphenylaralkyl epoxy resin (NC-3000-L)
Organic solvent: Propylene glycol monomethyl ether acetate (PGMEA)

  The structure of the above crosslinking agent is shown by the following formula.

And the etching test was done on condition shown below, and etching tolerance was evaluated. The evaluation results are shown in Table 8 and Table 9.
[Etching test]
Etching equipment: RIE-10NR manufactured by Samco International
Output: 50W
Pressure: 20 Pa
Time: 2 min
Etching gas Ar gas flow rate: CF ₄ gas flow rate: O ₂ gas flow rate = 50: 5: 5 (sccm)
[Evaluation of etching resistance]
Evaluation of etching resistance was performed in the following procedures.
First, a lower layer film of novolac was produced 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-mentioned etching test was conducted on the lower layer film of this novolak, and the etching rate at that time was measured.
Next, the above-mentioned etching test was similarly conducted for the lower layer films of the respective examples and the comparative example 1, and the etching rate at that time was measured.
And based on the etching rate of the lower layer film of novolak, etching resistance was evaluated by the following evaluation criteria.
[Evaluation criteria]
A: The etching rate is less than -10% compared to the novolak underlayer film. B: The etching rate is -10% to + 5% compared to the novolac underlayer film.
C: + 5% or more etching rate compared to novolak underlayer film

(Examples 45 to 48)
Next, each solution of the underlayer film forming material for lithography containing AlE-XBisN-1, AcE-XBisN-1, AlE-BisF-1 or AcE-BisF-1 is applied onto a SiO ₂ substrate with a film thickness of 300 nm. The resultant was baked at 240.degree. C. for 60 seconds and further at 400.degree. C. for 120 seconds to form an underlayer film having a thickness of 70 nm. A resist solution for ArF was coated on this lower layer film, and baked at 130 ° C. for 60 seconds to form a photoresist layer with a film thickness of 140 nm. In addition, as an 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 What was prepared was used.
The compound of the formula (11) is 4.15 g of 2-methyl-2-methacryloyloxyadamantane, 3.00 g of methacryloyloxy-γ-butyrolactone, 2.08 g of 3-hydroxy-1-adamantyl methacrylate, azobisisobutyronitrile 0.38 g was dissolved in 80 mL of tetrahydrofuran to make a reaction solution. The reaction solution was polymerized under a nitrogen atmosphere at a reaction temperature of 63 ° C. for 22 hours, and then the reaction solution was dropped into 400 ml of n-hexane. The resulting resin thus obtained was coagulated and purified, and the resulting white powder was filtered and dried overnight at 40 ° C. under reduced pressure.

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

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

The shapes and defects of the obtained 55 nm L / S (1: 1) and 80 nm L / S (1: 1) resist patterns were observed.
The shape of the resist pattern after development was evaluated as “good” with no pattern collapse and good rectangularity, and evaluated as “defect” with the others. Moreover, as a result of the said observation, there is no pattern fall and the minimum line width with favorable rectangularity was made into the index of evaluation as "resolution." Furthermore, the minimum amount of electron beam energy capable of drawing a good pattern shape is used as an index of evaluation as the “sensitivity”.
The evaluation results are shown in Table 10.

(Comparative example 2)
A photoresist layer was formed directly on the SiO ₂ substrate in the same manner as in Example 45 except that the lower layer film was not formed, to obtain a positive resist pattern. The results are shown in Table 10.

As is clear from Table 8, in Examples 1-1 to 24-2 using the compound or resin in the present embodiment, it was confirmed that the heat resistance, the solubility, and the etching resistance are all good. On the other hand, in Comparative Example 1 using CR-1 (phenol-modified dimethyl naphthalene formaldehyde resin), the etching resistance was poor.
Further, in Examples 45 to 48, it was confirmed that the resist pattern shape after development was good, and no defect was observed. It was confirmed that both the resolution and the sensitivity were significantly superior to Comparative Example 2 in which the formation of the lower layer film was omitted.
From the difference in resist pattern shape after development, it was shown that the underlayer film forming material for lithography used in Examples 45 to 48 has good adhesion to the resist material.

Examples 49 to 52
The solution of the underlayer film forming material for lithography of Examples 1-1 and 2-2 is coated on a 300 nm thick SiO ₂ substrate, and the film is baked at 240 ° C. for 60 seconds and further at 400 ° C. for 120 seconds. An underlying film with a thickness of 80 nm was formed. A silicon-containing intermediate layer material was coated on this lower layer film and baked at 200 ° C. for 60 seconds to form an intermediate layer film with a film thickness of 35 nm. Further, the resist solution for ArF was coated on the intermediate layer film and baked at 130 ° C. for 60 seconds to form a photoresist layer having a film thickness of 150 nm. In addition, as a silicon containing intermediate | middle layer material, the silicon atom containing polymer as described in Unexamined-Japanese-Patent No. 2007-226170 <synthesis example 1> was used.
Next, the photoresist layer is mask-exposed using an electron beam lithography system (manufactured by Elionix; ELS-7500, 50 keV), baked at 115 ° C. for 90 seconds (PEB), 2.38% by mass tetramethyl ammonium hydroxide By developing with an aqueous solution (TMAH) for 60 seconds, a 55 nm L / S (1: 1) positive resist pattern was obtained.
Thereafter, dry etching of the silicon-containing intermediate layer film (SOG) is performed using the obtained resist pattern as a mask using RIE-10NR manufactured by Samco International, and then, the obtained silicon-containing intermediate layer film pattern is used as a mask. The dry etching process of the lower layer film used as the mask and the dry etching process of the SiO ₂ film using the obtained lower layer film pattern as the mask were sequentially performed.

The respective etching conditions are as shown below.
Etching condition output of resist pattern to resist interlayer film : 50 W
Pressure: 20 Pa
Time: 1 min
Etching gas Ar gas flow rate: CF ₄ gas flow rate: O ₂ gas flow rate = 50: 8: 2 (sccm)
Etching condition output of resist interlayer film pattern to resist underlayer film : 50 W
Pressure: 20 Pa
Time: 2 min
Etching gas Ar gas flow rate: CF ₄ gas flow rate: O ₂ gas flow rate = 50: 5: 5 (sccm)
Etching condition output of resist lower layer film pattern to SiO ₂ film : 50 W
Pressure: 20 Pa
Time: 2 min
Etching gas Ar gas flow rate: C ₅ F ₁₂ gas flow rate: C ₂ F ₆ gas flow rate: O ₂ gas flow rate
= 50: 4: 3: 1 (sccm)

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

[Examples 53 to 56]
An optical component forming composition was prepared using the compounds shown in Table 11 below, using the compounds synthesized in the above-mentioned Synthesis Examples and Synthesis Examples. Among the components of the optical component forming composition in Table 4, the following were used as the acid generator, the crosslinking agent, the acid diffusion inhibitor, and the solvent.
Acid generator: Midori Chemical Co., Ltd. Ditertiary butyldiphenyliodonium nonafluoromethanesulfonate (DTDPI)
Crosslinking agent: Sanwa Chemical Co., Ltd. Nicarak MX 270 (Nicarak)
Organic solvent: Propylene glycol monomethyl ether acetate (PGMEA)

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

[Evaluation of refractive index and transmittance]
The uniform optical component forming composition was spin coated on a clean silicon wafer and then PB in an oven at 110 ° C. to form a 1 μm thick film. The refractive index (λ = 589.3 nm) at 25 ° C. of the film was measured with a J. A. Woolam multi-incidence spectroscopy ellipsometer VASE. The prepared film was evaluated as "A" when the refractive index is 1.65 or more, "B" when it is 1.6 or more and less than 1.65, and "C" when it is less than 1.6. . Moreover, when the transmittance | permeability ((lambda) = 632.8 nm) is 90% or more, it evaluated as "A", and when less than 90%, it evaluated as "C."

[Examples 57 to 60]
A resist composition was prepared by using the compounds synthesized in the above synthesis examples and the formulations shown in Table 12 below. Among the components of the resist composition in Table 12, the following were used as the radical generator, the radical diffusion inhibitor, and the solvent.
Radical generator: BASF IRGACURE 184
Radical diffusion control agent: BASF IRGACURE 1010
Organic solvent: Propylene glycol monomethyl ether acetate (PGMEA)

[Evaluation method]
(1) Storage stability of the resist composition and thin film formation The storage stability of the resist composition is allowed to stand at 23 ° C., 50% RH for 3 days after forming the resist composition, and the presence or absence of precipitation is visually observed. It evaluated by observing. The resist composition after standing for 3 days was evaluated as “A” when it was a homogeneous solution and there was no precipitation, and “C” when there was precipitation. Further, the resist composition in a uniform state 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 formed resist composition was evaluated as A when the thin film formation was good, and C when the formed film had a defect.

(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 60 nm-thick resist film. The obtained resist film was irradiated with an electron beam of 1: 1 line and space setting at intervals of 50 nm, 40 nm and 30 nm using an electron beam lithography system (ELS-7500, manufactured by Elionix Inc.) . After the irradiation, the resist film was heated for 90 seconds at each predetermined temperature, and immersed in PGME for 60 seconds to perform development. Thereafter, the resist film was washed with ultrapure water for 30 seconds and dried to form a negative resist pattern. The formed resist pattern was observed for line and space by a scanning electron microscope (S-4800 manufactured by Hitachi High-Technologies Corporation) to evaluate the reactivity of the resist composition by electron beam irradiation.
The sensitivity is indicated by the minimum amount of energy per unit area required 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 In the pattern formation, the obtained pattern shape is used for SEM (Scanning Electron Microscope) Observed and evaluated according to the following.
A: A rectangular pattern is obtained B: A nearly rectangular pattern is obtained C: A non-rectangular pattern is obtained

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

The compound and resin of this embodiment have high solubility in a safe solvent, good heat resistance and etching resistance, and the resist composition of this embodiment gives a good resist pattern shape.
Moreover, a wet process is applicable, and it is possible to realize a compound, a resin and a film forming composition for lithography useful for forming a photoresist underlayer film excellent in heat resistance and etching resistance. And since this film formation composition for lithography uses a compound or resin having a specific structure, which is high in heat resistance and high in solvent solubility, deterioration of the film at the time of high temperature baking is suppressed, oxygen plasma etching, etc. It is possible to form a resist and an underlayer film which are also excellent in etching resistance to Furthermore, when the lower layer film is formed, the adhesion to the resist layer is also excellent, so that an excellent resist pattern can be formed.
Furthermore, since the refractive index is high and the coloration is suppressed by low-temperature to high-temperature treatment, it is also useful as various optical component forming compositions.
Therefore, the present invention includes, for example, insulating materials for electricity, resins for resists, sealing resins for semiconductors, adhesives for printed wiring boards, laminates for electricity mounted on electric devices, electronic devices, industrial devices, etc., electric devices · Matrix resin of prepreg mounted on electronic equipment / industrial equipment, build-up laminate material, resin for fiber reinforced plastic, resin for sealing liquid crystal display panel, paint, various coating agents, adhesive, coating for semiconductor Resin, resin for resist for semiconductor, resin for lower layer film formation, film or sheet, plastic lens (prism lens, lenticular lens, microlens, Fresnel lens, viewing angle control lens, contrast improvement lens, etc.) , Retardation film, film for shielding electromagnetic wave, prism, optical fiber, flexible film Solder resist cement lines, plating resist, multilayer printed wiring boards interlayer insulating film, the optical component such as a photosensitive optical waveguide, it is widely and effectively available.

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

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

Claims (28)

The compound represented by following formula (0).

In the formula (0), R ^Y is a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms,
R ^Z is a C 1 to C 60 N valent group or a single bond,
R ^T each independently has an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, and a substituent Alkenyl group having 2 to 30 carbon atoms which may be substituted, alkoxy group having 1 to 30 carbon atoms which may have a substituent, halogen atom, nitro group, amino group, carboxylic acid group, thiol group, hydroxyl group or hydroxyl group Is a group substituted by one group selected from an aryloxyalkyl group, an acryloxyalkyl group or a methacryloxyalkyl group, and the alkyl group, the aryl group, the alkenyl group and the alkoxy group are ethers binding, may contain ketone or ester bond, wherein at least one hydroxyl group of a hydrogen atom allyl oxyalkyl group R ^T, acryloxy a Includes one substituted group with a group selected from the kill group or methacryloxy group,
X represents an oxygen atom, a sulfur atom or no crosslinking,
m is each independently an integer of 0 to 9, wherein at least one of m is an integer of 1 to 9,
N is an integer of 1 to 4, and when N is an integer of 2 or more, structural formulas in N [] may be the same or different.
r is each independently an integer of 0 to 2; ) The compound of Claim 1 whose compound represented by said Formula (0) is a compound represented by following formula (1).

(In formula (1), R ⁰ is synonymous with said R ^Y ,
R ¹ is a C ¹ to C 60 n-valent group or a single bond,
R ^{2 to} R ⁵ each independently represent an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, and a substituent 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, And the hydrogen atom of the hydroxyl group or the hydroxyl group is a group substituted by one group selected from an aryloxy alkyl group, an acryloxy alkyl group or a methacryl oxy alkyl group, and the alkyl group, the aryl group, the alkenyl group, the alkoxy group is an ether bond, may contain ketone or ester bond, wherein at least one hydrogen atom of the hydroxyl group is allyloxy alkyl group R ² to R ^5, a Includes one substituted group with a group selected from Lil oxyalkyl group or methacryloxy 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 can not simultaneously be 0,
n is synonymous with said N, Here, when n is an integer greater than or equal to 2, Structural formula in n [] may be same or different,
p ² ~p ⁵ have the same meanings as defined above r. ) The compound of Claim 1 whose compound represented by said Formula (0) is a compound represented by following formula (2).

(In formula (2), R ^0A is synonymous with said R ^Y ,
R ^1A is a C ¹ to C 60 n ^A valent group or a single bond,
R ^2A each independently has an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, and a substituent Alkenyl group having 2 to 30 carbon atoms which may be substituted, alkoxy group having 1 to 30 carbon atoms which may have a substituent, halogen atom, nitro group, amino group, carboxylic acid group, thiol group, hydroxyl group or hydroxyl group Is a group substituted by one group selected from an aryloxyalkyl group, an acryloxyalkyl group or a methacryloxyalkyl group, and the alkyl group, the aryl group, the alkenyl group and the alkoxy group are ethers binding, it may contain ketone or ester bond, wherein at least one hydroxyl group of a hydrogen atom allyl oxyalkyl group R ^2A, acrylic Oki Includes one substituted group with a group selected from an alkyl or methacryloxyalkyl group,
n ^A has the same meaning as N, and in the case where n ^A is an integer of 2 or more, structural formulas in n ^A [] may be the same or different.
X ^A represents an oxygen atom, a sulfur atom or no crosslinking,
m ^2A is each independently an integer of 0 to 7, provided that at least one m ^2A is an integer of 1 to 7,
Each q ^A is independently 0 or 1. ) The compound of Claim 2 whose compound represented by said Formula (1) is a compound represented by 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 represent an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, and a substituent A C 2-30 alkenyl group which may have a halogen atom, a halogen atom, a nitro group, an amino group, a carboxylic acid group, a thiol group,
R ^{10 to} R ¹¹ each independently represent a hydrogen atom or one group selected from an allyloxyalkyl group, an acryloxyalkyl group or a methacryloxyalkyl group,
Here, at least one of R ^{10 to} R ¹¹ is one group selected from an aryloxyalkyl 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 can not be 0 simultaneously. ) The compound of Claim 4 whose compound represented by said Formula (1-1) is a compound represented by 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, and
R ^{8 to} R ⁹ have the same meaning as R ^{6 to} R ⁷ above,
R ^{12 to} R ¹³ have the same meaning as R ^{10 to} R ¹¹ above,
m ⁸ and m ⁹ are each independently an integer of 0 to 8,
However, m ⁶ , m ⁷ , m ⁸ and m ⁹ can not be 0 at the same time. ) The compound of Claim 3 whose compound represented by said Formula (2) is a compound represented by following formula (2-1).

(In formula (2-1), R ^0A , R ^1A , n ^A , q ^A and X ^A are as defined in the above formula (2),
R ^3A each independently has an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, 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 and a thiol group, which may be
R ^4A is independently a hydrogen atom of hydrogen or hydroxyl allyloxyalkyl group is one substituted group with a group selected from acryloxy group or methacryloxy group, wherein, R ^4A At least one of them is one group selected from an aryloxyalkyl group, an acryloxyalkyl group or a methacryloxyalkyl group,
m ^6A is each independently an integer of 0 to 5; )   A resin obtained by using the compound according to claim 1 as a monomer. The resin according to claim 7, having a structure represented by the following formula (3).

(In the formula (3),
L represents an alkylene group having 1 to 30 carbon atoms which may have a substituent, an arylene group having 6 to 30 carbon atoms which may have a substituent, and a carbon number which may have a substituent 1 to 30 alkoxyl group or single bond, and the alkylene group, the arylene group and the alkoxyl group may contain an ether bond, a ketone bond or an ester bond,
R ⁰ is synonymous with the above R ^Y ,
R ¹ is a C ¹ to C 60 n-valent group or a single bond,
R ^{2 to} R ⁵ each independently represent an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, and a substituent 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, And the hydrogen atom of the hydroxyl group or the hydroxyl group is a group substituted by one group selected from an aryloxy alkyl group, an acryloxy alkyl group or a methacryl oxy alkyl group, and the alkyl group, the aryl group, the alkenyl group, the alkoxy group is an ether bond, may contain ketone or ester bond, wherein at least one hydrogen atom of the hydroxyl group is allyloxy alkyl group R ² to R ^5, a Includes one substituted group with a group selected from Lil oxyalkyl group or methacryloxy 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 do not simultaneously become 0, and at least one of R ^{2 to} R ⁵ is a hydrogen atom of a hydroxyl group being an allyloxy alkyl group, an acryloxy alkyl group or a methacryl oxy alkyl It is a group substituted by one group selected from a group. ) The resin according to claim 7, having a structure represented by the following formula (4).

(In the formula (4), L has 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 a substituent And the alkylene group, the arylene group and the alkoxylene group may contain an ether bond, a ketone bond or an ester bond,
R ^0A is synonymous with the above R ^Y ,
R ^1A is a C ¹ to C 30 n ^A valent group or a single bond,
R ^2A each independently has an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, and a substituent Alkenyl group having 2 to 30 carbon atoms which may be substituted, alkoxy group having 1 to 30 carbon atoms which may have a substituent, halogen atom, nitro group, amino group, carboxylic acid group, thiol group, hydroxyl group or hydroxyl group Is a group substituted by one group selected from an aryloxyalkyl group, an acryloxyalkyl group or a methacryloxyalkyl group, and the alkyl group, the aryl group, the alkenyl group and the alkoxy group are ethers binding, it may contain ketone or ester bond, wherein at least one hydroxyl group of a hydrogen atom allyl oxyalkyl group R ^2A, acrylic Oki Includes one substituted group with a group selected from an alkyl or methacryloxyalkyl group,
n ^A has the same meaning as N, and in the case where n ^A is an integer of 2 or more, structural formulas in n ^A [] may be the same or different.
X ^A represents an oxygen atom, a sulfur atom or no crosslinking,
m ^2A is each independently an integer of 0 to 7, provided that at least one m ^2A is an integer of 1 to 7,
Each q ^A is independently 0 or 1. )   A composition comprising one or more selected from the group consisting of a compound according to any one of claims 1 to 6 and a resin according to any one of claims 7 to 9.   11. The composition of claim 10, further comprising a solvent.   The composition according to claim 10, further comprising an acid generator.   The composition according to any one of claims 10 to 12, further comprising a crosslinking agent.   The crosslinking agent is at least one selected from the group consisting of phenolic compounds, epoxy compounds, cyanate compounds, amino compounds, benzoxazine compounds, melamine compounds, guanamine compounds, glycoluril compounds, urea compounds, isocyanate compounds and azide compounds. The composition according to claim 13.   The composition according to claim 13 or 14, wherein the crosslinking agent has at least one allyl group.   A composition containing at least one selected from the group consisting of a compound according to any one of claims 1 to 6 and a resin according to any one of claims 7 to 9 in a content ratio of the crosslinking agent. 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 substance is 100 parts by mass.   The composition according to any one of claims 13 to 16, further comprising a crosslinking accelerator.   The composition according to claim 17, wherein the crosslinking accelerator is at least one selected from the group consisting of amines, imidazoles, organic phosphines, and Lewis acids.   The content rate of the said crosslinking accelerator contains 1 or more types chosen from the group which consists of a compound of any one of Claims 1-6, and the resin of any one of Claims 7-9. The composition according to claim 17 or 18, which is 0.1 to 5 parts by mass based on 100 parts by mass of the total mass of the composition.   The composition according to any one of claims 10 to 19, further comprising a radical polymerization initiator.   The composition according to claim 20, wherein the radical polymerization initiator is at least one selected from the group consisting of a ketone-based photoinitiator, an organic peroxide-based polymerization initiator, and an azo-based polymerization initiator.   The content ratio of the said radical polymerization initiator contains 1 or more types chosen from the group which consists of a compound of any one of Claims 1-6, and the resin of any one of Claims 7-9. The composition according to claim 20 or 21, which is 0.05 to 25 parts by mass when the total mass of the composition to be mixed is 100 parts by mass.   The composition according to any one of claims 10 to 22, which is used for forming a film for lithography.   The composition according to any one of claims 10 to 22, which is used for forming a resist permanent film.   The composition according to any one of claims 10 to 22, which is used for forming an optical component.   A method for forming a resist pattern, comprising the steps of: 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 to perform development.   An underlayer film is formed on a substrate using the composition according to claim 23, and at least one photoresist layer is formed on the underlayer film, and then radiation is irradiated to a predetermined region of the photoresist layer. A resist pattern forming method comprising the steps of: An underlayer film is formed on a substrate using the composition according to claim 23, an interlayer film is formed on the underlayer film using a resist interlayer film material, and at least one layer is formed on the interlayer film. Forming a photoresist layer of
Irradiating a predetermined area of the photoresist layer with radiation for development 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, including: