TW201819351A - Compound, resin, composition, and pattern forming method - Google Patents

Abstract

A compound represented by the following formula (o).

Description

   Compound, resin, composition and pattern forming method   

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

In the manufacture of semiconductor devices, microfabrication using photolithography technology using photoresist materials is implemented. In recent years, with the increase in the integration and speed of LSIs, it has been required to use pattern rules. More refined. In addition, the light source used for lithography used to form a photoresist pattern is shortened from KrF excimer laser (248nm) to ArF excimer laser (193nm), and extreme ultraviolet is also expected to be introduced. (EUV, 13.5nm).

However, in the lithography technology using a conventional polymer photoresist material, its molecular weight is as high as 10,000 to 100,000, and the molecular weight distribution is also wide. Therefore, it is difficult to control the pattern size due to the roughness on the pattern surface. , Resulting in a limitation on miniaturization. Therefore, in order to provide a photoresist pattern with higher resolution, various low molecular weight photoresist materials have been proposed so far. Since the low molecular weight photoresist material has a small molecular size, a photoresist pattern that can provide high resolution and small roughness is expected.

As such low-molecular-based photoresist materials, there are only various kinds. For example, a negative-type radiation-sensitive composition of an alkali-developing type using a low molecular weight polynuclear polyphenol compound as a main component has been proposed (see, for example, Patent Document 1 and Patent Document 2) as a low molecular weight photoresist having high heat resistance. As a candidate for the material, a negative-type radiation-sensitive composition of alkali development type using a low-molecular-weight cyclic polyphenol compound as a main component has also been proposed (see, for example, Patent Document 3 and Non-Patent Document 1). In addition, as a matrix compound of a photoresist material, it is known that a polyphenol compound can impart high heat resistance although having a low molecular weight, and can be used to improve the resolution or roughness of a photoresist pattern (see, for example, Non-Patent Document 2).

The present inventors have proposed a photoresist composition containing a compound having a specific structure and an organic solvent as a material which is excellent in etching resistance and is soluble in a solvent and suitable for a wet process (see Patent Document 4).

In addition, along with the miniaturization of the photoresist pattern, a problem of resolution or a problem of collapse of the photoresist pattern after development has occurred, and it is desirable to make the photoresist into a thin film. However, if the photoresist is simply formed into a thin film, it becomes difficult to obtain a sufficient photoresist-type film thickness required for substrate processing. Therefore, it becomes necessary not only to make a photoresist pattern, but also to make a photoresist underlayer film between the photoresist and a processed semiconductor substrate, and to make the photoresist underlayer film function as a mask during substrate processing. Process.

Various types of photoresist underlayer films used in such processes are known. For example, as a photoresist underlayer film having a selectivity ratio close to that of a photoresist, and having a dry etching rate close to that of a photoresist, it has been proposed to include at least The resin component of the substituent which generates a sulfonic acid residue by removing the terminal group with energy and an underlayer film forming material for a multilayer photoresist process with a solvent (see Patent Document 5). Moreover, as a photoresist underlayer film for lithography, which realizes a small dry etching speed selection ratio compared to photoresist, a photoresist underlayer film material including a polymer having a specific repeating unit has been proposed (see Patent Document 6). And, as a photoresist underlayer film having a smaller dry etching speed selection ratio compared to a semiconductor substrate, it has been proposed to include a repeating unit of pinene with a repeating unit having a substituted or unsubstituted hydroxyl group. Material of a photoresist underlayer film of a polymer polymerized (see Patent Document 7).

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

In addition, the present inventors have proposed an underlayer film-forming composition for lithography containing a compound having a specific structure and an organic solvent, which is excellent in etching resistance, has high heat resistance, is soluble in solvents, and can be used as a material for wet processes ( (Refer to Patent Document 8).

In addition, as for a method for forming an intermediate layer for forming a photoresist underlayer film in a three-layer process, for example, a method for forming a silicon nitride film (see Patent Document 9), or CVD formation of a silicon nitride film is known. Method (see Patent Document 10). Further, as an intermediate layer material for a three-layer process, a material containing a silicon compound of a silsesquioxane matrix is known (see Patent Documents 11 and 12).

Various optical component forming compositions have been proposed, and examples thereof include acrylic resins (see Patent Documents 13 to 14).

    [Prior technical literature]         [Patent Literature]    

[Patent Document 1] Japanese Patent Laid-Open No. 2005-326838

[Patent Document 2] Japanese Patent Laid-Open No. 2008-145539

[Patent Document 3] Japanese Patent Laid-Open No. 2009-173623

[Patent Document 4] International Publication No. 2013/024778

[Patent Document 5] Japanese Patent Laid-Open No. 2004-177668

[Patent Document 6] Japanese Patent Laid-Open No. 2004-271838

[Patent Document 7] Japanese Patent Laid-Open No. 2005-250434

[Patent Document 8] International Publication No. 2013/024779

[Patent Document 9] Japanese Patent Laid-Open No. 2002-334869

[Patent Document 10] International Publication No. 2004/066377

[Patent Document 11] Japanese Patent Laid-Open No. 2007-226170

[Patent Document 12] Japanese Patent Laid-Open No. 2007-226204

[Patent Document 13] Japanese Patent Laid-Open No. 2010-138393

[Patent Document 14] Japanese Patent Laid-Open No. 2015-174877

    [Non-patent literature]    

[Non-Patent Document 1] T. Nakayama, M. Nomura, K. Haga, M. Ueda: Bull. Chem. Soc. Jpn., 71, 2979 (1998)

[Non-Patent Document 2] Okazaki Shinji and 22 other "New Development of Photoresist Materials Development" Co., Ltd. CMC Publishing, September 2009, p.211-259

As described above, a lithographic film-forming composition for most photoresist applications and a lithographic film-forming composition for lower film applications have been proposed in the past, but there is no one which can be applied to a spin coating method or Screen printing and other wet processes have high solvent solubility and can coexist heat resistance and etching resistance at a high level. Therefore, it is necessary to develop novel materials.

In addition, it is also required to develop a novel material suitable for obtaining a photoresistive permanent film excellent in alkali developability, light sensitivity and resolution.

In addition, many compositions using optical members have been proposed in the past, but there is no coexistence of heat resistance, transparency, and refractive index at a high level. Therefore, development of novel materials is required.

The present invention has been made in view of the above-mentioned problems, and an object thereof is to provide a compound, a resin, a useful compound for forming a photoresist and an underlayer film for photoresist which are suitable for a wet process and have excellent heat resistance, solubility, and etching resistance. Film-forming composition for lithography. The present invention also provides a photoresist film, a photoresist underlayer film, a photoresistive permanent film, and a pattern forming method using the composition. Furthermore, it aims at providing the composition used for an optical member.

As a result of repeated elaborate studies by the present inventors in order to solve the above-mentioned problems, they have found that the above-mentioned problems can be solved by using a compound or resin having a specific structure, and have completed the present invention.

That is, the present invention is as follows.

[1] A compound represented by the following formula (0).

(In formula (0), R ^Y is a hydrogen atom, an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, R ^Z is an N-valent group or a single bond having 1 to 60 carbon atoms, and R ^T Each is independently an alkyl group having 1 to 30 carbons which may have a substituent, an aryl group having 6 to 30 carbons which may have a substituent, an alkenyl group having 2 to 30 carbons which may have a substituent, and may have a substituent An alkoxy group, a halogen atom, a nitro group, an amine group, a carboxylic acid group, a mercapto group, a hydroxyl group, or a group represented by formula (0-1) having 1 to 30 carbon atoms, the aforementioned alkyl group, the aforementioned aryl group, the aforementioned alkenyl group The aforementioned alkoxy group may also include an ether bond, a ketone bond, or an ester bond. Here, at least one of R ^T includes a group represented by formula (0-1), X represents an oxygen atom, a sulfur atom, or an uncrosslinked group, and m is Each of them is an integer of 0-9. Here, at least one of m is an integer of 1-9, and N is an integer of 1-4. Here, when N is an integer of 2 or more, there are N structural expressions in []. (It may be the same or different. R is an integer independently from 0 to 2.)

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

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

(In formula (1), R ⁰ is synonymous with the aforementioned R ^Y , R ¹ is an n-valent group or single bond having a carbon number of 1 to 60, and R ² to R ⁵ are each independently a carbon number 1 which may have a substituent. Alkyl group of 30 to 30, aryl group of 6 to 30 carbons which may have a substituent, alkenyl group of 2 to 30 carbons which may have a substituent, alkoxy group of 1 to 30 carbons which may have a substituent, halogen An atom, a nitro group, an amine group, a carboxylic acid group, a mercapto group, a hydroxyl group, or a group represented by the formula (0-1). The aforementioned alkyl group, the aforementioned aryl group, the aforementioned alkenyl group, and the aforementioned alkoxy group may also include an ether bond or a ketone. Bond or ester bond, where at least one of R ² to R ⁵ includes a group represented by formula (0-1), m ² and m ³ are each independently an integer of 0 to 8, and m ⁴ and m ⁵ are each Independently, it is an integer from 0 to 9. However, m ² , m ³ , m ^4, and m ⁵ do not become 0 at the same time. N is synonymous with N. Here, when n is an integer of 2 or more, n [] The structural formulas may be the same or different, and p ² to p ⁵ are synonymous with r.)

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

(In formula (2), R ^0A is synonymous with the aforementioned R ^Y , R ^1A is an n ^A valence or single bond having a carbon number of 1 to 60, and R ^2A is each independently a carbon number of 1 to 30 which may have a substituent. An alkyl group, an aryl group having 6 to 30 carbons which may have a substituent, an alkenyl group having 2 to 30 carbons which may have a substituent, an alkoxy group having 1 to 30 carbons which may have a substituent, a halogen atom, A nitro group, an amino group, a carboxylic acid group, a mercapto group, a hydroxyl group, or a group represented by the formula (0-1), the alkyl group, the aryl group, the alkenyl group, and the alkoxy group may further include an ether bond, a ketone bond, or An ester bond, where at least one of R ^2A includes a group represented by formula (0-1), n ^A is synonymous with the aforementioned N, and here, when n ^A is an integer of 2 or more, one of n ^A [] The structural formulas may be the same or different. X ^A represents an oxygen atom, a sulfur atom, or uncrosslinked, m ^2A is an integer of 0 to 7 independently, but at least one m ^2A is an integer of 1 to 7, q ^A is independently 0 or 1.)

[4] The compound as described in [2] above, wherein the compound represented by the aforementioned formula (1) is a compound represented by the following formula (1-1).

(In formula (1-1), R ⁰ , R ¹ , R ⁴ , R ⁵ , n, p ² to p ⁵ , m ⁴ and m ⁵ are synonymous with the foregoing, and R ⁶ to R ⁷ are each independently Alkyl group having 1 to 30 carbon atoms in the substituent, aryl group having 6 to 30 carbon atoms in the substituent group, alkenyl group having 2 to 30 carbon atoms in the substituent group, halogen atom, nitro group, amine group, carboxyl group Acid group and mercapto group, R ¹⁰ to R ¹¹ are each independently a hydrogen atom or a group represented by formula (0-2), and at least one of R ¹⁰ to R ¹¹ is a group represented by formula (0-2) , M ⁶ and m ⁷ are each independently an integer of 0 to 7, but m ⁴ , m ⁵ , m ⁶ and m ⁷ do not become 0 at the same time.)

(In formula (0-2), R ^X is synonymous with the foregoing, R ^W is a linear, branched or cyclic alkylene group having 1 to 30 carbon atoms, and s is an integer of 0 to 30.)

[5] The compound according to the above [4], wherein the compound represented by the aforementioned 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 synonymous with the foregoing, R ⁸ to R ⁹ Are synonymous with the aforementioned R ⁶ to R ⁷ , R ¹² to R ¹³ are synonymous with the aforementioned R ¹⁰ to R ¹¹ , m ⁸ and m ⁹ are each independently an integer of 0 to 8, but m ⁶ , m ⁷ , m ⁸ And m ⁹ will not become 0 at the same time.)

[6] The compound according to the above [3], wherein the compound represented by the aforementioned 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 synonymous with those described in the formula (2), and R ^3A is each independently a carbon number of 1 to 30 which may have a substituent. Linear, branched or cyclic alkyl groups, aryl groups having 6 to 30 carbon atoms which may have a substituent, alkenyl groups having 2 to 30 carbon atoms which may have a substituent, halogen atom, nitro, amine Group, carboxylic acid group, mercapto group, R ^4A is each independently a hydrogen atom or a group represented by formula (0-2), and at least one of R ^4A is a group represented by formula (0-2), and m ^6A (Each is an integer from 0 to 5.)

[7] A resin obtained by using the compound of the above-mentioned [1] as a monomer.

[8] The resin according to the above [7], which has a structure represented by the following formula (3).

(In formula (3), L is an alkylene group having 1 to 30 carbon atoms which may have a substituent, an arylene group having 6 to 30 carbon atoms which may have a substituent, and 1 to 30 carbon atoms which may have a substituent. An alkoxy group or a single bond, the aforementioned alkylene group, the aforementioned aryl group, or the aforementioned alkylene group may also include an ether bond, a ketone bond, or an ester bond, R ⁰ is synonymous with the aforementioned R ^Y , and R ¹ is a carbon number 1 A n-valent radical or single bond of ~ 60, R ² to R ⁵ are each independently an alkyl group having 1 to 30 carbons which may have a substituent, an aryl group having 6 to 30 carbons which may have a substituent, and may have Alkenyl groups having 2 to 30 carbon atoms in the substituent, alkoxy groups having 1 to 30 carbon atoms in the substituent group, halogen atom, nitro group, amine group, carboxylic acid group, mercapto group, hydroxyl group or formula (0-1) In the illustrated group, the aforementioned alkyl group, the aforementioned aryl group, the aforementioned alkenyl group, and the aforementioned alkoxy group may also include an ether bond, a ketone bond, or an ester bond. Here, at least one of R ² to R ⁵ includes a formula (0-1 ), M ² and m ³ are each independently an integer of 0 to 8, m ⁴ and m ⁵ are each independently an integer of 0 to 9, but m ² , m ³ , m ⁴ and m ^{5 are} not Will become 0 at the same time, and at least one of R ² to R ⁵ is a base represented by formula (0-2).)

[9] The resin according to the above [7], which has a structure represented by the following formula (4).

(In formula (4), L is an alkylene group having 1 to 30 carbon atoms which may have a substituent, an arylene group having 6 to 30 carbon atoms which may have a substituent, and 1 to 30 carbon atoms which may have a substituent. An alkoxy group or a single bond, the aforementioned alkylene group, the aforementioned aryl group, or the aforementioned alkyleneoxy group may also include an ether bond, a ketone bond, or an ester bond, R ^0A is synonymous with the aforementioned R ^Y , and R ^1A is a carbon number 1 ~ 30 n ^A valent radical or single bond, R ^2A is each independently an alkyl group having 1 to 30 carbons which may have a substituent, an aryl group having 6 to 30 carbons which may have a substituent, and may have a substituent Alkenyl group having 2 to 30 carbon atoms, alkoxy group having 1 to 30 carbon atoms which may have a substituent, a halogen atom, a nitro group, an amine group, a carboxylic acid group, a mercapto group, a hydroxyl group, or a hydrogen atom of a hydroxyl group are vinylbenzene A methyl-substituted group, the aforementioned alkyl group, the aforementioned aryl group, the aforementioned alkenyl group, and the aforementioned alkoxy group may also include an ether bond, a ketone bond, or an ester bond. Here, at least one of R ^2A includes the formula (0-1) In the base shown, n ^A is synonymous with the aforementioned N. Here, when n ^A is an integer of 2 or more, the structural formulas in n ^A [] may be the same or different, and X ^A represents an oxygen atom and sulfur. Atomic or uncrosslinked, m ^2A is independently an integer from 0 to 7 However, at least one m ^2A is an integer from 1 to 7, and q ^A is independently 0 or 1.)

[10] A composition containing one or more members 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].

[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 composition according to the aforementioned [13], wherein the crosslinking agent is selected from the group consisting of a phenol compound, an epoxy compound, a cyanate compound, an amine compound, a benzoxazine compound, a melamine compound, a guanamine compound, and acetylene. At least one of a group consisting of a urea compound, a urea compound, an isocyanate compound, and an azide compound.

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

[16] The composition according to any one of the aforementioned [13] to [15], which will contain a compound selected from any one of the aforementioned [1] to [6] and the aforementioned [7] to [9] When the total mass of one or more types of the composition of any one of the resins is 100 parts by mass, the content ratio of the crosslinking agent is 0.1 to 100 parts by mass.

[17] The composition according to any one of [13] to [16], further comprising a crosslinking accelerator.

[18] The composition according to the aforementioned [17], wherein the crosslinking accelerator is at least one selected from the group consisting of amines, imidazoles, organic phosphines, and Lewis acids.

[19] The composition according to the aforementioned [17] or [18], which will contain a compound selected from any one of the aforementioned [1] to [6] and any one of the aforementioned [7] to [9] When the total mass of one or more of the components in the resin group is 100 parts by mass, the content of the crosslinking accelerator is 0.1 to 5 parts by mass.

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

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

[22] The composition according to any one of the aforementioned [10] to [21], which will contain a compound selected from the group consisting of any one of the aforementioned [1] to [6] and the aforementioned [7] to [9] When the total mass of one or more kinds of the composition of any one of the resin groups is 100 parts by mass, the content ratio of the radical polymerization initiator is 0.05 to 25 parts by mass.

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

[24] The composition according to any one of [10] to [22], which is used for forming a photoresistive permanent film.

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

[26] A method for forming a photoresist pattern, comprising: after forming a photoresist layer on a substrate using the composition as described in [23], irradiating a predetermined area of the photoresist layer with radiation, and performing development steps .

[27] A method for forming a photoresist pattern, comprising: forming an underlayer film on a substrate using the composition as described in [23] above, and forming at least one photoresist layer on the underlayer film, and then forming a photoresist layer on the substrate. A predetermined area is irradiated with radiation and developed.

[28] A method for forming a circuit pattern, comprising: forming an underlayer film on a substrate using the composition as described in [23], forming an intermediate layer film using a photoresist intermediate layer film material on the foregoing lower layer film, and forming an intermediate layer on the intermediate layer. A step of forming at least one photoresist layer on the film; a step of irradiating a predetermined area of the aforementioned photoresist layer with a radiation and developing an image to form a photoresist pattern; and etching the aforementioned intermediate by using the photoresist pattern as a mask In the layer film, the intermediate layer film pattern obtained is used as an etching mask to etch the aforementioned lower layer film, the obtained lower layer film pattern is used as an etching mask to etch the substrate, and then forming a pattern on the substrate.

The compound and resin of the present invention have high solubility in a safe solvent, and have good heat resistance and etching resistance. In addition, a photoresist composition containing the compound and / or resin of the present invention provides a good photoresist-type shape.

Hereinafter, the form for implementing this invention (henceforth the "this embodiment") is demonstrated. In addition, the following embodiments are merely examples for explaining the present invention, and the present invention is not limited only to the embodiments.

The compound, resin, and composition containing this embodiment can be applied to a wet process, and are useful for forming a photoresist underlayer film having excellent heat resistance and etching resistance. In addition, since the composition of this embodiment uses a compound or resin having a specific structure with high heat resistance and solvent solubility, it is possible to suppress film degradation during high-temperature baking and to resist etching such as oxygen plasma etching. It is also an excellent photoresist and underlayer film. In addition, since the adhesion to the photoresist layer is also excellent when forming the underlayer film, an excellent photoresist pattern can be formed.

In addition, the compounds and resins of this embodiment are excellent in sensitivity or resolution when used in a photosensitive material, and are formed to maintain high heat resistance, and are compatible with general organic solvents or other compounds, resin components, and additives. It is extremely useful on permanent photoresist films with excellent compatibility.

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

    [Compound represented by formula (0)]    

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

(In formula (0), R ^Y is a hydrogen atom, an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, R ^Z is an N-valent group or a single bond having 1 to 60 carbon atoms, and R ^T Each is independently a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, and a carbon number which may have substituents An alkenyl group of 2 to 30, an alkoxy group of 1 to 30 carbon atoms which may have a substituent, a halogen atom, a nitro group, an amine group, a carboxylic acid group, a mercapto group, a hydroxyl group, or a group represented by the formula (0-1), The alkyl group, the aryl group, the alkenyl group, and the alkoxy group may further include an ether bond, a ketone bond, or an ester bond. Here, at least one of R ^T includes a group represented by the formula (0-1), and X represents Oxygen atom, sulfur atom, or uncrosslinked, m is an integer of 0 to 9 independently, here, at least one of m is an integer of 1 to 9, and N is an integer of 1 to 4, where N is an integer of 2 or more For integers, the structural formulas in N [] may be the same or different, and r is an integer of 0 to 2 each independently.)

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

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. R ^Y is a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms, thereby providing excellent heat resistance and solvent solubility.

R ^z is an N-valent radical or single bond having 1 to 60 carbon atoms, and is bonded to each aromatic ring via this R ^z . N is an integer of 1 to 4, and when N is an integer of 2 or more, the structural formulas in N [] may be the same or different. Moreover, the aforementioned N-valent radical refers to an alkyl group having 1 to 60 carbon atoms when N = 1, an alkylene group having 1 to 30 carbon atoms when N = 2, and an alkane having 2 to 60 carbon atoms when N = 3. Triyl, N = 4 means alkane tetrayl with 3 to 60 carbons. Examples of the N-valent group include those having a linear hydrocarbon group, a branched hydrocarbon group, or an alicyclic hydrocarbon group. Here, the alicyclic hydrocarbon group also includes a bridged alicyclic hydrocarbon group. 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 is each independently an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, and 1 to 30 carbon atoms of the substituent group, alkoxy group, halogen atom, nitro group, amine group, carboxylic acid group, mercapto group, hydroxyl group or group represented by formula (0-1), the aforementioned alkyl group, the aforementioned aryl group, the aforementioned group The alkenyl group and the aforementioned alkoxy group may include an ether bond, a ketone bond, or an ester bond. Here, at least one of R ^T includes a group represented by the formula (0-1). The alkyl, alkenyl, and alkoxy groups may be linear, branched, or cyclic groups. Here, the group containing a group represented by formula (0-1) means a group having a group represented by formula (0-1), and examples include a group represented by formula (0-1), -1) a methoxy group substituted with a group represented by the formula, an ethoxy group substituted with a group represented by the formula (0-1), a propoxy group substituted with a group represented by the formula (0-1), and a formula ( Ethoxyethoxy substituted with a group represented by 0-1), propoxypropoxy substituted with a group represented by formula (0-1), and ethoxyethoxy substituted with a group represented by formula (0-1) Phenyloxy and the like.

X represents an oxygen atom, a sulfur atom, or uncrosslinked, and when X is an oxygen atom or a sulfur atom, it is preferred to exhibit high heat resistance, and an oxygen atom is more preferred. X is preferably uncrosslinked from the viewpoint of solubility. In addition, m is 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 the naphthalene structure becomes a monocyclic structure when r = 0, a bicyclic structure when r = 1, and a tricyclic structure when r = 2. r is an integer of 0 to 2 independently. The above m is determined by the ring structure determined by r to determine its numerical range.

    [Compound represented by formula (1)]    

The compound (0) of this embodiment is preferably a compound represented by the following formula (1) from the viewpoints of heat resistance and solvent solubility.

In the formula (1), R ⁰ is a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms. When R ⁰ is a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms, heat resistance becomes higher, and solvent solubility is improved. tendency. In addition, R ^{0 is a} linear, branched, or cyclic alkyl group having 1 to 30 carbon atoms or a carbon number of 6 from the viewpoint of suppressing the coloration of the compound by inhibiting oxidative decomposition and improving heat resistance and solvent solubility. ~ 30 aryl is preferred.

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

R ² to R ⁵ are each independently an alkyl group having 1 to 30 carbons which may have a substituent, an aryl group having 6 to 30 carbons which may have a substituent, and an alkenyl group having 2 to 30 carbons which may have a substituent , An alkoxy group having 1 to 30 carbon atoms, a halogen atom, a nitro group, an amine group, a carboxylic acid group, a mercapto group, a hydroxyl group, or a group represented by the formula (0-1), which may have a substituent, the alkyl group, the aromatic group, The group, the alkenyl group, and the alkoxy group may include an ether bond, a ketone bond, or an ester bond. Here, at least one of R ² to R ⁵ includes a group represented by the formula (0-1).

m ² and m ³ are each independently an integer of 0-8, and m ⁴ and m ⁵ are each independently an integer of 0-9. However, m ² , m ³ , m ⁴ and m ⁵ do not become 0 at the same time.

n is an integer from 1 to 4. Here, when n is an integer of 2 or more, the structural formulas in n [] may be the same or different.

p ² to p ⁵ are each independently an integer of 0 to 2.

Moreover, the aforementioned n-valent radical refers to an alkyl group having 1 to 60 carbon atoms when n = 1, an alkylene group having 1 to 30 carbon atoms when n = 2, and an alkane having 2 to 60 carbon atoms when n = 3. Three groups, n = 4 represents an alkane tetrayl group having 3 to 60 carbon atoms. Examples of the n-valent group include those having a linear hydrocarbon group, a branched hydrocarbon group, or an alicyclic hydrocarbon group. Here, the aforementioned alicyclic hydrocarbon group also includes a bridged alicyclic hydrocarbon group. The n-valent group may have an aromatic group having 6 to 60 carbon atoms.

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

The compound represented by the above formula (1) can be used under high-temperature baking conditions because of its low molecular weight and high heat resistance due to its structural rigidity. In addition, the molecule has a third-order carbon or a fourth-order carbon, and crystallinity is suppressed. Therefore, it is suitable for use as a lithographic film-forming composition that can be used for producing a lithographic film.

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

In addition, because of its low molecular weight and low viscosity, even substrates with step differences (especially fine spaces or hole patterns) can be easily filled uniformly to all corners of the steps to improve the flatness of the film. As a result, The burying and planarization characteristics of the underlayer film-forming composition for this lithography are good. 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 even if subjected to a wide range of heat treatment from low temperature to high temperature, coloration is still suppressed, so it is also useful as a composition for forming various optical parts. Among them, from the viewpoint of suppressing oxidative decomposition of the compound to suppress coloration, and improving heat resistance and solvent solubility, a compound having a grade 4 carbon is preferred. As an optical component, it can be useful not only as a film-shaped or sheet-shaped component, but also as a plastic lens (e.g., a lenticular lens, a lenticular lens, a micro lens, a Freyna lens, a viewing angle control lens, a contrast lifting lens, etc.), Phase difference film, film for shielding electromagnetic waves, tritium, optical fiber, solder resist for flexible printed wiring, anti-plating agent, interlayer insulating film for multilayer printed wiring board, photosensitive optical waveguide.

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

In formula (1-1), R ⁰ , R ¹ , R ⁴ , R ⁵ , n, p ² to p ⁵ , m ⁴ and m ⁵ are synonymous with the foregoing, and R ⁶ to R ⁷ are each independently and may have a substitution. A linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms that may have a substituent, an alkenyl group having 2 to 30 carbon atoms that may have a substituent, A halogen atom, a nitro group, an amine group, a carboxylic acid group, and a thiol group, and R ¹⁰ to R ¹¹ are each independently a hydrogen atom or a group represented by formula (0-2). Here, at least one of R ¹⁰ to R ¹¹ is In the base represented by the formula (0-2), m ⁶ and m ⁷ are each independently an integer of 0 to 7, but m ⁴ , m ⁵ , m ⁶ and m ⁷ do not become 0 at the same time.

(In formula (0-2), R ^X is synonymous with the foregoing, R ^W is a linear, branched, or cyclic alkylene group having 1 to 30 carbon atoms, and s is an integer of 0 to 30.)

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

In formula (1-2), R ⁰ , R ¹ , R ⁶ , R ⁷ , R ¹⁰ , R ¹¹ , n, p ² to p ⁵ , m ⁶ and m ⁷ are synonymous with the foregoing, and R ⁸ to R ⁹ are It is synonymous with the aforementioned R ⁶ to R ⁷ , R ¹² to R ¹³ are synonymous with the aforementioned R ¹⁰ to R ¹¹ , and m ⁸ and m ⁹ are each independently an integer of 0 to 8.

However, m ⁶ , m ⁷ , m ⁸ and m ⁹ do not become 0 at the same time.

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

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

The compound represented by the formula (1a) is 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 synonymous with those described in the above formula (1), and R ⁶ , R ⁷ , R ¹⁰ , R ¹¹ , m ⁶ and m ⁷ are synonymous with those described in the above 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 formula (1b '), R ⁰ , R ¹ , R ⁴ , R ⁵ , m ⁴ , m ⁵ , and n are synonymous with those described in the formula (1), and R ⁶ , R ⁷ , R ¹⁰ , and R ¹¹ , M ⁶ and m ⁷ are synonymous with those described in the above formula (1-1).

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

In the formula (1c), R ⁰ , R ¹ , R ⁶ to R ¹³ , m ⁶ to m ⁹ , and n are synonymous with those described in the formula (1-2).

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

In the formula (1c '), R ⁰ , R ¹ , R ⁶ to R ¹³ , m ⁶ to m ⁹ , and n are synonymous with those described in the formula (1-2).

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

In the above formulas, X system and the above described formula (0) are synonymous, R ^{T 'and} R ^T system described in the above formula is synonymous (0), m is independently an integer of lines 1 to 6 of.

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

In the above formulas, X system and the above described formula (0) are synonymous, and, R ^{Y ',} R ^Z' lines and the above described formula (0) R ^Y, R ^Z synonymous. In addition, at least one of OR ^4A includes a base represented by formula (0-1).

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

Hereinafter, specific examples of the compound represented by the formula (1) are exemplified, but the compound represented by the formula (1) is not limited to the compounds listed here.

In the aforementioned formula, R ² , R ³ , R ⁴ , and R ⁵ are synonymous with those described in the formula (1). m ² and m ³ are integers from 0 to 6, and m ⁴ and m ⁵ are integers from 0 to 7. However, at least one selected from R ² , R ³ , R ⁴ , and R ⁵ includes a group represented by (0-1), and m ² , m ³ , m ⁴ , and m ⁵ do not become 0 at the same time.

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

In the aforementioned formula, R ¹⁰ , R ¹¹ , R ¹² , and R ¹³ are synonymous with those described in the formula (1-2), and at least one of R ¹⁰ to R ¹³ includes a base represented by the formula (0-2).

(In formula (0-2), R ^X is synonymous with the foregoing, R ^W is a linear, branched, or cyclic alkylene group having 1 to 30 carbon atoms, and s is an integer of 0 to 30.)

From the viewpoint of deeper solubility of the compound represented by the formula (1) in an organic solvent, compounds represented by the following formulae (BiF-1) to (BiF-10) are particularly preferred.

In the aforementioned formula, R ¹⁰ , R ¹¹ , R ¹² , and R ¹³ are synonymous with those described in the formula (1-2), and at least one of R ¹⁰ to R ¹³ includes a base represented by the formula (0-2).

(In formula (0-2), R ^X is synonymous with the foregoing, R ^W is a linear, branched, or cyclic alkylene group having 1 to 30 carbon atoms, and s is an integer of 0 to 30.)

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

In the ^formula, R ^0, R ^1, n lines as described in the formula (1-1) are synonymous, R ^{10 'and} R ^11' is synonymous with the system described in the above-described formula (1-1) R ¹⁰ and R ¹¹ , R ^{4 ′} and R ^{5 ′} are each independently an alkyl group having 1 to 30 carbons which may have a substituent, an aryl group having 6 to 30 carbons which may have a substituent, and 2 to 30 carbons which may have a substituent Alkenyl group, alkoxy group having 1 to 30 carbon atoms which may have a substituent, halogen atom, nitro group, amine group, carboxylic acid group, mercapto group, hydroxyl group or a group represented by formula (0-1), the aforementioned alkyl group The aryl group, the alkenyl group, and the alkoxy group may include an ether bond, a ketone bond, or an ester bond, and at least one of R ^{10 ′} and R ^{11 ′} includes a group represented by formula (0-2). m ^{4 '} and m ^5' are integers from 0 to 8, m ^{10 '} and m ^11' are integers from 1 to 9, m ^{4 '} + m ^10' and m ^{4 '} + m ^11' are each independently 1 to 9 Integer.

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

(In formula (0-2), R ^X is synonymous with the foregoing, R ^W is a linear, branched, or cyclic alkylene group having 1 to 30 carbon atoms, and s is an integer of 0 to 30.)

Examples of R ⁰ include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, Phenyl, naphthyl, anthryl, fluorenyl, biphenyl, fused heptyl.

Examples of R ^{4 ′} and R ^{5 ′} include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl. , Tridecyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, cyclododecyl, cyclotridecyl , Norbornyl, adamantyl, phenyl, naphthyl, anthryl, fluorenyl, biphenyl, fused heptyl, vinyl, allyl, tridecenyl, methoxy, ethoxy, tris Decadecyloxy, fluorine atom, chlorine atom, bromine atom, iodine atom, and mercapto group.

Each of the examples of R ⁰ , R ^{4 ′} and R ^{5 ′} includes an isomer. For example, the butyl group includes n-butyl, isobutyl, sec-butyl, and tert-butyl.

In the foregoing formula, R ¹⁰ to R ¹³ are synonymous with those described in the formula (1-2), and R ¹⁶ is a linear, branched or cyclic alkylene group having 1 to 30 carbon atoms, and a carbon number of 6 A divalent aryl group of ~ 30, or a divalent alkenyl group of 2 to 30 carbon atoms.

Examples of R ¹⁶ include methylene, vinyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, and undecenyl. Base, dodecenyl, trienyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, cyclooctenyl, cyclononenyl, cyclodecenyl , Cycloundecenyl, cyclododecenyl, cyclosesquienyl, divalent norbornyl, divalent adamantyl, divalent phenyl, divalent naphthyl, divalent anthracenyl , Divalent fluorenyl, divalent biphenyl, divalent thick heptyl, divalent vinyl, divalent allyl, divalent triacontenyl.

Each of the examples of R ¹⁶ described above includes an isomer. For example, the butyl group includes n-butyl, isobutyl, sec-butyl, and tert-butyl.

In the foregoing formula, R ¹⁰ to R ¹³ are synonymous with those described in the formula (1-2), and R ¹⁴ is independently a linear, branched, or cyclic alkyl or carbon having 1 to 30 carbon atoms. An aryl group having 6 to 30 or an alkenyl group having 2 to 30 carbons, an alkoxy group having 1 to 30 carbon atoms, a halogen atom, and a mercapto group, m ¹⁴ is an integer of 0 to 5, and m ^{14 '} is an integer of 0 to 4 Integer.

Examples of R ¹⁴ include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, Cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, cyclododecyl, cyclotridecyl, norbornyl, Adamantyl, phenyl, naphthyl, anthryl, fluorenyl, biphenyl, fused heptyl, vinyl, allyl, tridecenyl, methoxy, ethoxy, tridecyloxy, A fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and a mercapto group.

Each of the examples of R ¹⁴ includes an isomer. For example, the butyl group includes n-butyl, isobutyl, sec-butyl, and tert-butyl.

In the foregoing formula, R ⁰ , R ^{4 ′} , R ^{5 ′} , m ^{4 ′} , m ^{5 ′} , m ^{10 ′} , and m ^{11 ′} are synonymous with the foregoing, and R ^{1 ′} is a group having 1 to 60 carbon atoms.

In the foregoing formula, R ¹⁰ to R ¹³ are synonymous with those described in the formula (1-2), and R ¹⁴ is independently a linear, branched, or cyclic alkyl or carbon having 1 to 30 carbon atoms. An aryl group having 6 to 30 or an alkenyl group having 2 to 30 carbons, an alkoxy group having 1 to 30 carbon atoms, a halogen atom, and a mercapto group, m ¹⁴ is an integer of 0 to 5, and m ^{14 '} is an integer of 0 to 4 Integer, m ¹⁴ ”is an integer from 0 to 3.

Examples of R ¹⁴ include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, Cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, cyclododecyl, cyclotridecyl, norbornyl, Adamantyl, phenyl, naphthyl, anthryl, fluorenyl, biphenyl, fused heptyl, vinyl, allyl, tridecenyl, methoxy, ethoxy, tridecyloxy, A fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and a mercapto group.

Each of the examples of R ¹⁴ includes an isomer. For example, the butyl group includes n-butyl, isobutyl, sec-butyl, and tert-butyl.

In the foregoing formula, R ¹⁰ to R ¹³ are synonymous with those described in the formula (1-2), and R ¹⁵ is a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, and 6 to carbon atoms. Aryl group of 30, alkenyl group of 2-30 carbon, alkoxy group of 1-30 carbon, halogen atom, mercapto group.

Examples of R ¹⁵ include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, Cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, cyclododecyl, cyclotridecyl, norbornyl, Adamantyl, phenyl, naphthyl, anthryl, fluorenyl, biphenyl, fused heptyl, vinyl, allyl, tridecenyl, methoxy, ethoxy, tridecyloxy, A fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and a mercapto group.

Each of the examples of R ¹⁵ includes an isomer. For example, the butyl group includes n-butyl, isobutyl, sec-butyl, and tert-butyl.

In the aforementioned formula, R ¹⁰ to R ¹³ are synonymous with those described in the aforementioned formula (1-2).

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

In the aforementioned formula, R ¹⁰ to R ¹³ are synonymous with those described in the aforementioned formula (1-2).

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

In the foregoing formula, R ^0A is synonymous with R ^Y in the foregoing formula (0), R ^{1A ′} is synonymous with R ^Z in the foregoing formula (0), and R ¹⁰ to R ¹³ are the same as those in the foregoing formula (1-2) The explainer is synonymous.

In the aforementioned formula, R ¹⁰ to R ¹³ are synonymous with those described in the aforementioned formula (1-2). R ¹⁴ is each independently 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 and 1 to 30 carbon atoms Alkoxy group, halogen atom, and mercapto group, m ¹⁴ is an integer of 0 to 4.

Examples of R ¹⁴ include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, Cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, cyclododecyl, cyclotridecyl, norbornyl, Adamantyl, phenyl, naphthyl, anthryl, fused heptyl, vinyl, allyl, tridecenyl, methoxy, ethoxy, tridecyloxy, fluorine atom, chlorine atom, Bromine atom, iodine atom, mercapto group.

Each of the examples of R ¹⁴ includes an isomer. For example, the butyl group includes n-butyl, isobutyl, sec-butyl, and tert-butyl.

In the foregoing formula, R ¹⁰ to R ¹³ are synonymous with those described in the formula (1-2), and R ¹⁵ is a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, and 6 to carbon atoms. Aryl group of 30, alkenyl group of 2-30 carbon, alkoxy group of 1-30 carbon, halogen atom, mercapto group.

Examples of R ¹⁵ include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, Cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, cyclododecyl, cyclotridecyl, norbornyl, Adamantyl, phenyl, naphthyl, anthryl, fused heptyl, vinyl, allyl, tridecenyl, methoxy, ethoxy, tridecyloxy, fluorine atom, chlorine atom, Bromine atom, iodine atom, mercapto group.

Each of the examples of R ¹⁵ includes an isomer. For example, the butyl group includes n-butyl, isobutyl, sec-butyl, and tert-butyl.

In the foregoing formula, R ¹⁰ to R ¹³ are synonymous with those described in the formula (1-2), and R ¹⁶ is a linear, branched or cyclic alkylene group having 1 to 30 carbon atoms, and a carbon number of 6 A divalent aryl group of ~ 30, or a divalent alkenyl group of 2 to 30 carbon atoms.

Examples of R ¹⁶ include methylene, vinyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, and undecenyl. Base, dodecenyl, trienyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, cyclooctenyl, cyclononenyl, cyclodecenyl , Cycloundecenyl, cyclododecenyl, cyclosesquienyl, divalent norbornyl, divalent adamantyl, divalent phenyl, divalent naphthyl, divalent anthracenyl , Divalent thick heptyl, divalent vinyl, divalent allyl, divalent triacontenyl.

Each of the examples of R ¹⁶ described above includes an isomer. For example, the butyl group includes n-butyl, isobutyl, sec-butyl, and tert-butyl.

In the foregoing formula, R ¹⁰ to R ¹³ are synonymous with those described in the formula (1-2), and R ¹⁴ is independently a linear, branched, or cyclic alkyl or carbon having 1 to 30 carbon atoms. An aryl group having 6 to 30 or an alkenyl group having 2 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a halogen atom, and a mercapto group, m ^{14 ′} is an integer of 0 to 4.

Examples of R ¹⁴ include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, Cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, cyclododecyl, cyclotridecyl, norbornyl, Adamantyl, phenyl, naphthyl, anthryl, fused heptyl, vinyl, allyl, tridecenyl, methoxy, ethoxy, tridecyloxy, fluorine atom, chlorine atom, Bromine atom, iodine atom, mercapto group.

Each of the examples of R ¹⁴ includes an isomer. For example, the butyl group includes n-butyl, isobutyl, sec-butyl, and tert-butyl.

In the foregoing formula, R ¹⁰ to R ¹³ are synonymous with those described in the formula (1-2), and R ¹⁴ is independently a linear, branched, or cyclic alkyl or carbon having 1 to 30 carbon atoms. An aryl group having 6 to 30 or an alkenyl group having 2 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a halogen atom, and a mercapto group, m ¹⁴ is an integer of 0 to 5.

Examples of R ¹⁴ include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, Cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, cyclododecyl, cyclotridecyl, norbornyl, Adamantyl, phenyl, naphthyl, anthryl, fused heptyl, vinyl, allyl, tridecenyl, methoxy, ethoxy, tridecyloxy, fluorine atom, chlorine atom, Bromine atom, iodine atom, mercapto group.

Each of the examples of R ¹⁴ includes an isomer. For example, the butyl group includes n-butyl, isobutyl, sec-butyl, and tert-butyl.

In the aforementioned formula, R ¹⁰ to R ¹³ are synonymous with those described in the aforementioned formula (1-2).

Among the compounds listed above, a compound having a dibenzoxanthene skeleton is more preferred from the viewpoint of heat resistance.

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

In the aforementioned formulae, R ¹⁰ to R ¹³ are synonymous with those described in the aforementioned formula (1-2).

Among the compounds listed above, a compound having a dibenzoxanthene skeleton is preferred from the viewpoint of heat resistance.

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

In the foregoing formula, R ^0A is synonymous with R ^Y in the foregoing formula (0), R ^{1A ′} is synonymous with R ^Z in the foregoing formula (0), and R ¹⁰ to R ¹³ are the same as those in the foregoing formula (1-2) The explainer is synonymous.

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

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

In the foregoing formulae, R ¹⁰ to R ¹³ are synonymous with those described in the foregoing formula (1-2), and R ¹⁴ , R ¹⁵ , R ¹⁶ , m ¹⁴ , and m ^{14 ′} are synonymous with those described in the foregoing formula.

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 the formula (1) in this embodiment can be suitably synthesized by a known method, and the synthesis method is not particularly limited.

For example, it can be obtained by performing a polycondensation reaction of biphenols, binaphthols, or bianthracenol with corresponding aldehydes or ketones under an acid catalyst under normal pressure. The phenol compound is obtained by introducing a group represented by formula (0-1A) into at least one phenolic hydroxyl group of the polyphenol compound. Alternatively, it can be obtained by introducing a group represented by the formula (0-1B) and introducing a hydroxyl group into the group represented by the formula (0-1A). If necessary, it may be performed under pressure.

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

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

Examples of the biphenols include, but are not limited to, biphenol, methylbiphenol, and methoxybinaphthol. These systems can be used alone or in combination of two or more. Among these, it is preferable to use biphenol from the viewpoint of stability of the raw materials.

Examples of the binaphthols include, but are not limited to, binaphthol, methylbinaphthol, and methoxybinaphthol. These systems can be used alone or in combination of two or more. Among these, the use of binaphthol is preferred from the viewpoint of increasing the carbon atom concentration and improving heat resistance.

Examples of the aldehydes include formaldehyde, trioxane, paraformaldehyde, benzaldehyde, acetaldehyde, propylaldehyde, phenylacetaldehyde, phenylpropylaldehyde, hydroxybenzaldehyde, chlorobenzaldehyde, and nitrate. Butylbenzaldehyde, methylbenzaldehyde, ethylbenzaldehyde, butylbenzaldehyde, biphenylaldehyde, naphthaldehyde, anthracenaldehyde, phenanthraldehyde, pyrene formaldehyde, furfural, etc. are not limited thereto. These systems can be used alone or in combination of two or more. Among these, from the viewpoint of imparting high heat resistance, benzaldehyde, phenylacetaldehyde, phenylpropylaldehyde, hydroxybenzaldehyde, chlorobenzaldehyde, nitrobenzaldehyde, methylbenzaldehyde, and ethylbenzaldehyde are used. , Butylbenzaldehyde, cyclohexylbenzaldehyde, biphenylaldehyde, naphthaldehyde, anthracenaldehyde, phenanthraldehyde, pyrene formaldehyde, furfural are preferred. From the viewpoint of improving etching resistance, benzaldehyde, hydroxybenzaldehyde, chlorine Benzaldehyde, nitrobenzaldehyde, methylbenzaldehyde, ethylbenzaldehyde, butylbenzaldehyde, cyclohexylbenzaldehyde, biphenylaldehyde, naphthaldehyde, anthracenaldehyde, phenanthraldehyde, pyrene formaldehyde, and furfural are preferred.

Examples of the ketones include acetone, methyl ethyl ketone, cyclobutanone, cyclopentanone, cyclohexanone, norbornanone, tricyclohexanone, tricyclodecanone, amantadone, and fluorenone. , Benzofluorenone, fluorenone, ethanenaphthone, anthraquinone, acetophenone, diethylfluorenylbenzene, triethylfluorenylbenzene, naphthylacetone, diphenylcarbonylnaphthalene, phenylcarbonylbiphenyl, Diphenylcarbonylbiphenyl, benzophenone, diphenylcarbonylbenzene, triphenylcarbonylbenzene, naphthylphenylketone, diphenylcarbonylnaphthalene, phenylcarbonylbiphenyl, diphenylcarbonylbiphenyl, etc. But it is not limited to these. These systems can be used alone or in combination of two or more. Among these, from the viewpoint of imparting high heat resistance, cyclopentanone, cyclohexanone, norbornanone, tricyclohexanone, tricyclodecanone, amantadone, fluorenone, benzofluorenone, and fluorene are used. Quinone, ethanenaphthone, anthraquinone, acetophenone, diethylfluorenylbenzene, triethylfluorenylbenzene, naphthylacetone, diphenylcarbonylnaphthalene, phenylcarbonylbiphenyl, diphenylcarbonylbiphenyl, Benzophenone, diphenylcarbonylbenzene, triphenylcarbonylbenzene, naphthylphenone, diphenylcarbonylnaphthalene, phenylcarbonylbiphenyl, and diphenylcarbonylbiphenyl are preferred. From the viewpoint of using acetophenone, diethylfluorenylbenzene, triethylfluorenylbenzene, naphthylacetone, diphenylcarbonylnaphthalene, phenylcarbonylbiphenyl, diphenylcarbonylbiphenyl, benzophenone, diphenyl Phenylcarbonylbenzene, triphenylcarbonylbenzene, naphthylphenone, diphenylcarbonylnaphthalene, phenylcarbonylbiphenyl, and diphenylcarbonylbiphenyl are preferred.

As the aldehydes or ketones, it is preferable to use an aldehyde having an aromatic ring or an aromatic ketone from the viewpoint of having both high heat resistance and high etching resistance.

The acid catalyst used in the above reaction can be appropriately selected and used from known ones, and is not particularly limited. As such an acid catalyst, inorganic or organic acids have been widely known, and examples include inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, hydrofluoric acid, and the like; oxalic acid, malonic acid, succinic acid, and adipic acid. Acid, sebacic acid, citric acid, fumaric acid, maleic acid, formic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoromethanesulfonic acid, benzenesulfonic acid Organic acids such as naphthalenesulfonic acid, naphthalenesulfonic acid, naphthalenesulfonic acid, etc .; Lewis acids such as zinc chloride, aluminum chloride, iron chloride, boron trifluoride, or silicotungstic acid, phosphotungstic acid, silomolybdic acid, or molybdenum phosphorus Solid acids and the like are not limited to these. Among these, organic acids and solid acids are preferred from a manufacturing point of view, and hydrochloric acid or sulfuric acid is more preferred from a manufacturing point of view of obtaining ease or ease of handling. The acid catalysts may be used alone or in combination of two or more. The amount of the acid catalyst to be used is appropriately set depending on the types of raw materials and catalysts used, reaction conditions, and the like, and is not particularly limited. It is preferably 0.01 to 100 parts by mass relative to 100 parts by mass of the reaction raw materials.

In the above reaction, a reaction solvent may be used. The reaction solvent is not particularly limited as long as the reaction of the aldehydes or ketones used with the biphenols, binaphthols, or bianthrene glycols proceeds, and it can be appropriately selected and used from known ones. Examples of the reaction solvent include water, methanol, ethanol, propanol, butanol, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and mixed solvents thereof. Moreover, a solvent system may be used individually by 1 type, and may use 2 or more types together.

The amount of these reaction solvents can be appropriately set according to the types of raw materials and catalysts used, reaction conditions, and the like, and is not particularly limited. The range is 0 to 2000 parts by mass relative to 100 parts by mass of the reaction raw materials. Better. In addition, the reaction temperature of the above reaction can be appropriately selected depending on the reactivity of the reaction raw materials, and is not particularly limited, but is usually in the range of 10 to 200 ° C.

In order to obtain a polyphenol compound, the reaction temperature is preferably high, and specifically, it is preferably in a range of 60 to 200 ° C. In addition, the reaction method can be selected by using a known method as appropriate, and is not particularly limited, and examples thereof include a method in which biphenols, binaphthols or dianthrene glycols, aldehydes or ketones, and catalysts are put in one time. Or a method of continuously dripping biphenols, binaphthols or bianthrene glycols, or aldehydes or ketones in the presence of a catalyst. After the polycondensation reaction is completed, the separation of the obtained compound can be performed according to a conventional method, and is not particularly limited. For example, in order to remove unreacted raw materials or catalysts existing in the system, the general method of raising the temperature of the reactor to 130 to 230 ° C and removing volatile components at a level of 1 to 50 mmHg can be used for separation. The compound of the object.

Preferred reaction conditions include, for example, 1 mole of biphenols, binaphthols, or bianthrene glycol relative to 1 mole of aldehydes or ketones, and an excess of 0.001 to 1 mole of acid catalyst. The ear can react at 50 to 150 ° C for 20 minutes to 100 hours under normal pressure.

After completion of the reaction, the target substance is isolated by a known method. For example, the reaction solution can be concentrated, and pure water can be added to precipitate the reaction product. After cooling to room temperature, filtration is performed to separate the solid matter obtained by filtration, and the dried solid is separated and purified by column chromatography. The solvent is distilled off, filtered, and dried to obtain the target compound represented by the formula (1).

A method for introducing a group represented by the formula (0-1A) into at least one phenolic hydroxyl group of a polyphenol compound is known. For example, a group represented by formula (0-1A) can be introduced into at least one phenolic hydroxyl group of the compound by the following operation. The compound for introducing the group represented by the formula (0-1A) can be synthesized by a known method or can be easily obtained, and examples thereof include epoxy acrylate and epoxy methacrylate. No special restrictions.

First, the compound is dissolved or suspended in an aprotic solvent such as acetone, tetrahydrofuran (THF), propylene glycol monomethyl ether acetate, or the like. Next, in the presence of a base catalyst such as sodium hydroxide, potassium hydroxide, sodium methoxylate, sodium ethoxylate, etc., the reaction is allowed to proceed at a normal pressure of 20 to 150 ° C for 6 to 72 hours. Use an acid to neutralize the reaction solution, add distilled water to precipitate a white solid, wash the separated solid with distilled water, or evaporate the solvent to dry and solidify. If necessary, by washing and drying with distilled water, the hydrogen atom of the hydroxyl group can be obtained. (0-1A) A compound substituted with the group represented by the group.

In addition, the timing of introducing a group substituted with a group represented by the formula (0-1A) may be after the condensation reaction of binaphthols with aldehydes or ketones, or before the condensation reaction. In addition, it may be introduced after the production of the resin described later is carried out.

A method of introducing a group represented by the formula (0-1B) into at least one phenolic hydroxyl group of a polyphenol compound, and introducing a group represented by the formula (0-1A) into the hydroxyl group is also known. For example, a group represented by formula (0-1B) can be introduced into at least one phenolic hydroxyl group of the aforementioned compound, and a group represented by formula (0-1A) can be introduced into its hydroxyl group by the following operations.

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

First, the aforementioned compound is dissolved or suspended in an aprotic solvent such as acetone, tetrahydrofuran (THF), propylene glycol monomethyl ether acetate, or the like. Secondly, in the presence of an alkali catalyst such as sodium hydroxide, potassium hydroxide, sodium methoxylate, sodium ethoxylate, etc., the reaction is performed at a normal pressure of 20 to 150 ° C for 6 to 72 hours. By using an acid to neutralize the reaction solution and adding distilled water to precipitate a white solid, the separated solid can be washed with distilled water, or the solvent can be evaporated to dry and solidify. If necessary, it can be washed with distilled water and dried to obtain the hydrogen atom of hydroxyl group. A compound substituted with a group represented by formula (0-1B).

When 2-chloroethyl acetate, 2-bromoethyl acetate, and 2-iodoethyl acetate are used, hydroxyethyl group is introduced by introducing a defluorination reaction after introducing ethoxyethyl group. .

When using ethylene carbonate, propylene carbonate, and butyl carbonate, the addition of alkylene carbonate causes a decarbonation reaction to introduce a hydroxyalkyl group.

First, the compound is dissolved or suspended in an aprotic solvent such as acetone, tetrahydrofuran (THF), propylene glycol monomethyl ether acetate, or the like. Secondly, in the presence of a base catalyst such as sodium hydroxide, potassium hydroxide, sodium methoxylate, sodium ethoxylate, etc., the reaction is performed at a normal pressure of 20 to 150 ° C for 6 to 72 hours. By using an acid to neutralize the reaction solution and adding distilled water to precipitate a white solid, the separated solid is washed with distilled water, or the solvent is evaporated to dry and solidify. If necessary, the distilled water is used for washing and drying to obtain a hydrogen atom of a hydroxyl group. A compound substituted with a group substituted with a group represented by the formula (0-1A).

In this embodiment, the group substituted with the group represented by the formula (0-1A) is reacted in the presence of a radical or an acid / base, and the acid, alkali or organic solvent used for the coating solvent or the developing solution Changes in solubility. In order to achieve a higher sensitivity, the substituted group represented by the aforementioned formula (0-1A) can be achieved. The high-resolution pattern is preferably a chain reaction in the presence of free radicals or acids / bases.

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

The compound represented by the aforementioned formula (1) can be directly used as a composition for forming a lithography film or forming an optical component (hereinafter, also simply referred to as a "composition"). Moreover, the resin system obtained using the compound represented by the said Formula (1) as a monomer can also be used as a composition. The resin is obtained by reacting, for example, a compound represented by the aforementioned formula (1) with a compound having cross-linking reactivity.

Examples of the resin obtained by using the compound represented by the formula (1) as a monomer include those having a structure represented by the following formula (3). That is, the composition of the present embodiment may be one containing a resin having a structure represented by the following formula (3).

In the formula (3), L is a linear, branched or cyclic 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, may be The alkoxy group or single bond having 1 to 30 carbon atoms having a substituent, the aforementioned alkylene group, the aforementioned aryl group, or the aforementioned alkylene group may further include an ether bond, a ketone bond, or an ester bond.

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 synonymous with those described in the formula (1).

However, m ² , m ³ , m ^4, and m ⁵ do not become 0 at the same time, and a hydrogen atom of at least one hydroxyl group of R ² to R ⁵ is a group represented by formula (0-2).

    [Production method of resin obtained by using compound represented by formula (1) as monomer]    

The resin of this embodiment can be obtained by reacting a compound represented by the above formula (1) with a compound having cross-linking reactivity. As the compound having cross-linking reactivity, a known one can be used without particular limitation as long as it can oligomerize or polymerize the compound represented by the formula (1). Specific examples thereof include, but are not limited to, aldehydes, ketones, carboxylic acids, carboxylic acid halides, halogen-containing compounds, amine compounds, imine compounds, isocyanates, and unsaturated hydrocarbon group-containing compounds. Limited to these.

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

Here, examples of the aldehyde used when the compound represented by the formula (1) is phenol-formaldehyde include formaldehyde, trioxane, paraformaldehyde, benzaldehyde, acetaldehyde, propylaldehyde, and benzene. Methyl acetaldehyde, phenylpropyl aldehyde, hydroxybenzaldehyde, chlorobenzaldehyde, nitrobenzaldehyde, methylbenzaldehyde, ethylbenzaldehyde, butylbenzaldehyde, biphenylaldehyde, naphthaldehyde, anthracenaldehyde, phenanthrene Formaldehyde, pyrene formaldehyde, furfural, etc. are not limited to these. Examples of the ketone include the aforementioned ketones. Among these, formaldehyde is preferred. These aldehydes and / or ketones may be used alone or in combination of two or more. The amount of the aldehydes and / or ketones used is not particularly limited, and is preferably 0.2 to 5 moles, more preferably 0.5 to 2 moles, relative to 1 mole of the compound represented by the formula (1).

In the condensation reaction of the compound represented by the formula (1) with an aldehyde and / or a ketone, an acid catalyst may be used. The acid catalyst used here can be appropriately selected and used from known ones, and is not particularly limited. As such an acid catalyst, inorganic or organic acids have been widely known, and examples include inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, hydrofluoric acid, and the like; oxalic acid, malonic acid, succinic acid, and adipic acid. Acid, sebacic acid, citric acid, fumaric acid, maleic acid, formic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoromethanesulfonic acid, benzenesulfonic acid Organic acids such as naphthalenesulfonic acid, naphthalenesulfonic acid, naphthalenesulfonic acid, etc .; Lewis acids such as zinc chloride, aluminum chloride, iron chloride, boron trifluoride, or silicotungstic acid, phosphotungstic acid, silomolybdic acid, or molybdenum phosphorus Solid acids and the like are not limited to these. Among these, organic acids and solid acids are preferred from a manufacturing point of view, and hydrochloric acid or sulfuric acid is preferred from a manufacturing point of view in terms of availability and ease of handling. The acid catalysts may be used alone or in combination of two or more.

In addition, the amount of the acid catalyst used can be appropriately set depending on the types of raw materials and catalysts used, reaction conditions, and the like, and is not particularly limited. It is preferably 0.01 to 100 parts by mass relative to 100 parts by mass of the reaction raw materials. However, when used with indene, hydroxyindene, benzofuran, hydroxyanthracene, pinene, biphenyl, bisphenol, phenol, dicyclopentadiene, tetrahydroindene, 4-vinylcyclohexene, norbornadiene When a compound having a non-conjugated double bond such as 1,5-norbornene, α-pinene, β-pinene, and limonene is used for copolymerization reaction, aldehydes are not necessarily required.

In the condensation reaction of the compound represented by the formula (1) with an aldehyde and / or a ketone, a reaction solvent may be used. The reaction solvent for the polycondensation can be appropriately selected from known ones and is not particularly limited, and examples thereof include water, methanol, ethanol, propanol, butanol, tetrahydrofuran, dioxane, and mixed solvents thereof. . Moreover, a solvent system may be used individually by 1 type, and may use 2 or more types together.

The amount of these solvents can be appropriately set according to the types of raw materials and catalysts used, reaction conditions, and the like, and is not particularly limited. It is preferably in the range of 0 to 2000 parts by mass relative to 100 parts by mass of the reaction raw materials. . In addition, the reaction temperature may be appropriately selected depending on the reactivity of the reaction raw materials, and is not particularly limited, but is usually in the range of 10 to 200 ° C. In addition, the reaction method can be selected by using a known method as appropriate, and is not particularly limited, and examples thereof include a method in which the compound represented by the above formula (1), aldehydes and / or ketones, and a catalyst are put in once, or A method of continuously dropping a compound represented by the above formula (1) or an aldehyde and / or a ketone in the presence of a vehicle.

After the polycondensation reaction is completed, the separation of the obtained compound can be performed according to a conventional method, and is not particularly limited. For example, in order to remove unreacted raw materials or catalysts existing in the system, the general method of raising the temperature of the reactor to 130 to 230 ° C and removing volatile components at a level of 1 to 50 mmHg can be used for separation. A phenolic resin that yields the desired product.

Here, the resin having the structure represented by the formula (3) may be a homopolymer of the compound represented by the formula (1), or may be a copolymer with other phenols. Examples of copolymerizable phenols include phenol, cresol, dimethylphenol, trimethylphenol, butylphenol, phenylphenol, diphenylphenol, naphthylphenol, and resorcinol. Phenol, methyl resorcinol, catechol, butyl catechol, methoxyphenol, methoxyphenol, propylphenol, pyrogallol, thymol, etc. are not limited to these .

The resin having the structure represented by the formula (3) may be one obtained by copolymerizing with a polymerizable monomer in addition to the other phenols. Examples of the comonomer include naphthol, methylnaphthol, methoxynaphthol, dihydroxynaphthalene, indene, hydroxyindene, benzofuran, hydroxyanthracene, pinene, biphenyl, and bisphenol , Phenol, dicyclopentadiene, tetrahydroindene, 4-vinylcyclohexene, norbornadiene, vinylnorbornene, pinene, limonene, etc., but it is not limited to these. In addition, the resin having the structure represented by the formula (3) may be a 2- or more (for example, 2- to 4-membered) copolymer of the compound represented by the formula (1) and the phenols, or may be the formula (2) A copolymer of the compound represented by (1) and the above-mentioned comonomer, which is at least 2 members (for example, a 2- to 4-member system), and is the compound represented by the aforementioned formula (1), the above-mentioned phenols, and the above-mentioned copolymerized monomer. Copolymers having 3 or more members (for example, 3 to 4 members) are also acceptable.

Moreover, the molecular weight of the resin having the structure represented by the formula (3) is not particularly limited, and the weight average molecular weight (Mw) in terms of polystyrene is preferably 500 to 30,000, and more preferably 750 to 20,000. In addition, from the viewpoint of improving the crosslinking efficiency and suppressing the volatile components in baking, the resin having the structure represented by the formula (3) has a dispersion degree (weight average molecular weight Mw / number average molecular weight Mn) of 1.2 to 7. Within the range is better. In addition, the Mw and Mn can be obtained according to the method described in the examples described later.

From the viewpoint that the resin having the structure represented by the formula (3) can be more easily applied to a wet process, etc., it is preferable that the resin has high solubility in a solvent. More specifically, the solubility of these compounds and / or resins with 1-methoxy-2-propanol (PGME) and / or propylene glycol monomethyl ether acetate (PGMEA) as a solvent It is preferably 10% by mass or more. Here, the solubility in PGMEA and / or PGMEA is defined as "mass of resin ÷ (mass of resin + mass of solvent) x 100 (mass%)". For example, when 10 g of the resin is dissolved in 90 g of PGMEA, the solubility of the resin in PGMEA becomes "10% by mass or more", and when it is insoluble, it becomes "less than 10% by mass".

    [Compound represented by formula (2)]    

The compound (0) of this embodiment is preferably a compound represented by the following formula (2) from the viewpoints of heat resistance and solvent solubility.

In formula (2), R ^0A 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.

R ^1A is a radical or single bond of n ^A valence having 1 to 60 carbons, and R ^2A is each independently a linear, branched or cyclic alkyl having 1 to 30 carbons which may have a substituent, and may be An aryl group having 6 to 30 carbon atoms having a substituent, an alkenyl group having 2 to 30 carbon atoms having a substituent, an alkoxy group having 1 to 30 carbon atoms having a substituent, a halogen atom, a nitro group, and an amine group , A carboxylic acid group, a mercapto group, a hydroxyl group, or a group represented by formula (0-1), the alkyl group, the aryl group, the alkenyl group, and the alkoxy group may further include an ether bond, a ketone bond, or an ester bond. At least one of R ^2A includes a group represented by formula (0-1).

n ^A is an integer of 1 to 4. Here, in formula (2), when n ^A is an integer of 2 or more, the structural formulas in n ^A [] may be the same or different.

X ^A each independently represents an oxygen atom, a sulfur atom, or uncrosslinked. Here, X ^A tends to exhibit excellent heat resistance, so an oxygen atom or a sulfur atom is preferred, and an oxygen atom is more preferred. X ^{A is} preferably uncrosslinked from the viewpoint of solubility.

m ^2A is an integer of 0 to 6 independently. However, at least one m ^2A is an integer from 1 to 6.

q ^A is independently 0 or 1.

Furthermore, the aforementioned n-valent radical refers to an alkyl group having 1 to 60 carbon atoms when n = 1, an alkylene group having 1 to 30 carbon atoms when n = 2, and an alkyl group having 2 to 60 carbon atoms when n = 3. Alkane triyl, n = 4 means alkane tetrayl having 3 to 60 carbon atoms. Examples of the n-valent group include those having a linear hydrocarbon group, a branched hydrocarbon group, or an alicyclic hydrocarbon group. Here, the aforementioned alicyclic hydrocarbon group also includes a bridged alicyclic hydrocarbon group. The n-valent group may have an aromatic group having 6 to 60 carbon atoms.

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

The n-valent hydrocarbon group may have an alicyclic hydrocarbon group, a double bond, a hetero atom, or an aromatic group having 6 to 30 carbon atoms. Here, the aforementioned alicyclic hydrocarbon group also includes a bridged alicyclic hydrocarbon group.

The compound represented by the above formula (2) has a low molecular weight and high heat resistance due to the rigidity of its structure, so it can also be used under high-temperature baking conditions. Moreover, since the crystallinity is suppressed by having a third-order carbon or a fourth-order carbon in the molecule, it can be suitably used as a lithographic film-forming composition that can be used to produce a lithographic film.

In addition, since the solubility in a safe solvent is high and heat resistance and etching resistance are good, a photoresist-forming composition for lithography containing the compound shown in the above (2) can provide a good photoresist-like shape.

In addition, because of its low molecular weight and low viscosity, even substrates with step differences (especially fine spaces or hole patterns) can be easily filled uniformly to all corners of the steps to improve the flatness of the film. As a result, The burying and planarization characteristics of the underlayer film-forming composition for this lithography are good. 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 even if subjected to a wide range of heat treatment from low temperature to high temperature, coloration is still suppressed, so it is also useful as a composition for forming various optical parts. Among them, from the viewpoint of suppressing oxidative decomposition of the compound to suppress coloration, and improving heat resistance and solvent solubility, a compound having a grade 4 carbon is preferred. As an optical component, it can be useful not only as a film-shaped or sheet-shaped component, but also as a plastic lens (e.g., a lenticular lens, a lenticular lens, a micro lens, a Freyna lens, a viewing angle control lens, a contrast lifting lens, etc.), Phase difference film, film for shielding electromagnetic waves, tritium, optical fiber, solder resist for flexible printed wiring, anti-plating agent, interlayer insulating film for multilayer printed wiring board, photosensitive optical waveguide.

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

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

R ^3A is a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, and 2 carbon atoms which may have a substituent The alkenyl group, halogen atom, nitro group, amine group, carboxylic acid group, and mercapto group of ~ 30 may be the same or different on the same naphthalene ring or benzene ring.

R ^4A is each independently a hydrogen atom or a group represented by formula (0-2). Here, at least one of R ^4A is a group represented by formula (0-2), and m ^6A is each independently 0 to 5 Integer.

When the compound represented by the above formula (2-1) is used as a film-forming composition for positive photoresist for alkali imaging or negative photolithography for organic imaging, at least one of R ^4A is acid dissociation Sex-based. On the other hand, the compound represented by the formula (2-1) is used as a film-forming composition for lithography for alkali imaging negative photoresist, a film-forming composition for lithography for an underlayer film, or an optical component. At least one of R ^4A is a hydrogen atom.

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

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

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

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

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

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

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

    [Method for producing compound represented by formula (2)]    

The compound represented by the formula (2) in this embodiment can be suitably synthesized by applying a known method, and the synthesis method is not particularly limited.

For example, polyphenol compounds can be obtained by performing polycondensation reaction of phenols, naphthols and corresponding aldehydes or ketones under an acid catalyst under normal pressure, followed by at least one phenol of the polyphenol compound A sexual hydroxyl group is obtained by introducing a group represented by the formula (0-1A). Alternatively, it can be obtained by introducing a group represented by the formula (0-1B) and introducing a group represented by the formula (0-1A) into its hydroxyl group. If necessary, it may be carried out under pressure.

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

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

The aforementioned naphthols are not particularly limited, and examples thereof include naphthol, methylnaphthol, methoxynaphthol, and naphthyl glycol. Among them, naphthalene is used from the viewpoint that it can easily be a xanthene structure. Diols are preferred.

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

Examples of the aldehydes include formaldehyde, trioxane, paraformaldehyde, benzaldehyde, acetaldehyde, propylaldehyde, phenylacetaldehyde, phenylpropylaldehyde, hydroxybenzaldehyde, chlorobenzaldehyde, and nitrate. Butylbenzaldehyde, methylbenzaldehyde, ethylbenzaldehyde, butylbenzaldehyde, biphenylaldehyde, naphthaldehyde, anthracenaldehyde, phenanthraldehyde, pyrene formaldehyde, furfural, etc. are not limited thereto. These systems can be used alone or in combination of two or more. Among these, from the viewpoint of imparting high heat resistance, benzaldehyde, phenylacetaldehyde, phenylpropylaldehyde, hydroxybenzaldehyde, chlorobenzaldehyde, nitrobenzaldehyde, methylbenzaldehyde, and ethylbenzene are used. Formaldehyde, butylbenzaldehyde, cyclohexylbenzaldehyde, biphenylaldehyde, naphthaldehyde, anthracenaldehyde, phenanthraldehyde, pyrene formaldehyde, and furfural are preferred. From the viewpoint of improving etching resistance, benzaldehyde, hydroxybenzaldehyde, Chlorobenzaldehyde, nitrobenzaldehyde, methylbenzaldehyde, ethylbenzaldehyde, butylbenzaldehyde, cyclohexylbenzaldehyde, biphenylaldehyde, naphthaldehyde, anthracenaldehyde, phenanthraldehyde, indaldehyde, and furfural are preferred .

Examples of the ketones include acetone, methyl ethyl ketone, cyclobutanone, cyclopentanone, cyclohexanone, norbornanone, tricyclohexanone, tricyclodecanone, amantadone, and fluorenone. , Benzofluorenone, fluorenone, ethanenaphthone, anthraquinone, acetophenone, diethylfluorenylbenzene, triethylfluorenylbenzene, naphthylacetone, diphenylcarbonylnaphthalene, phenylcarbonylbiphenyl, Diphenylcarbonylbiphenyl, benzophenone, diphenylcarbonylbenzene, triphenylcarbonylbenzene, naphthylphenylketone, diphenylcarbonylnaphthalene, phenylcarbonylbiphenyl, diphenylcarbonylbiphenyl, etc. But it is not limited to these. These systems can be used alone or in combination of two or more. Among these, from the viewpoint of imparting high heat resistance, cyclopentanone, cyclohexanone, norbornanone, tricyclohexanone, tricyclodecanone, amantadone, fluorenone, benzofluorenone, and fluorene are used. Quinone, ethanenaphthone, anthraquinone, acetophenone, diethylfluorenylbenzene, triethylfluorenylbenzene, naphthylacetone, diphenylcarbonylnaphthalene, phenylcarbonylbiphenyl, diphenylcarbonylbiphenyl, Benzophenone, diphenylcarbonylbenzene, triphenylcarbonylbenzene, naphthylphenone, diphenylcarbonylnaphthalene, phenylcarbonylbiphenyl, and diphenylcarbonylbiphenyl are preferred. From the viewpoint of using acetophenone, diethylfluorenylbenzene, triethylfluorenylbenzene, naphthylacetone, diphenylcarbonylnaphthalene, phenylcarbonylbiphenyl, diphenylcarbonylbiphenyl, benzophenone, diphenyl Phenylcarbonylbenzene, triphenylcarbonylbenzene, naphthylphenone, diphenylcarbonylnaphthalene, phenylcarbonylbiphenyl, and diphenylcarbonylbiphenyl are preferred.

As the ketones, it is preferable to use a ketone having an aromatic ring from the viewpoint of having both high heat resistance and high etching resistance.

The acid catalyst used in the above reaction can be appropriately selected and used from known ones, and is not particularly limited. The acid catalyst may be appropriately selected from well-known inorganic acids and organic acids. Examples include inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, and hydrofluoric acid; oxalic acid, formic acid, p-toluenesulfonic acid, Organic acids such as methanesulfonic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid, naphthalenedisulfonic acid, etc .; Lewis acid of zinc chloride, aluminum chloride, ferric chloride, boron trifluoride, etc. Acid; or a solid acid such as silicotungstic acid, phosphotungstic acid, silomolybdic acid, or phosphomolybdic acid. Among these, the use of hydrochloric acid or sulfuric acid is preferred from the standpoint of manufacturing easiness of obtaining or handling. The acid catalyst may be used alone or in combination of two or more.

In the above reaction, a reaction solvent can be used. The reaction solvent is not particularly limited as long as the reaction between the aldehydes or ketones used and the naphthols proceeds, and for example, water, methanol, ethanol, propanol, butanol, tetrahydrofuran, and dioxin can be used. Alkane or a mixed solvent of these. The amount of the reaction solvent is not particularly limited, and for example, it ranges from 0 to 2000 parts by mass based on 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 materials, and a range of 10 to 200 ° C is preferred. From the viewpoint that the polyphenol compound of the present embodiment can be synthesized with good selectivity, a low temperature is preferable, and a range of 10 to 60 ° C is more preferable.

The reaction method is not particularly limited, and examples thereof include a method in which naphthols or the like, aldehydes or ketones, and a catalyst are put in one time, or naphthols or aldehydes or ketones are continuously dropped in the presence of the catalyst. Class method. After the completion of the polycondensation reaction, in order to remove unreacted raw materials and catalysts existing in the system, the temperature of the reaction kettle may be raised to 130-230 ° C and the volatile components at a level of 1-50mmHg.

The amount of the raw material is not particularly limited. For example, with respect to 1 mol of aldehydes or ketones, 2 mol to an excess of naphthol and the like, and 0.001 to 1 mol of an acid catalyst are used. It is better to react at ~ 60 ° C for 20 minutes to 100 hours.

After completion of the reaction, the target substance is isolated by a known method. The method of separating the target is not particularly limited, and examples thereof include concentrating the reaction solution, adding pure water to precipitate the reaction product, and cooling to room temperature, followed by filtration and separation. The obtained solid is filtered and dried. A method of separating and purifying the by-products by column chromatography, distilling off the solvent, filtering and drying to isolate the target compound.

A method for introducing at least one phenolic hydroxyl group of a polyphenol compound into a group represented by the formula (0-1A) is known. For example, a group represented by formula (0-1A) can be introduced into at least one phenolic hydroxyl group of the aforementioned compound by the following operation. The compound for introducing the base represented by the formula (0-1A) is synthesized by a known method or can be easily obtained, and examples thereof include epoxy acrylate and epoxy methacrylate. Limited 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. Next, in the presence of an alkali catalyst such as sodium hydroxide, potassium hydroxide, sodium methoxylate, sodium ethoxylate, etc., the reaction is allowed to proceed for 6 to 72 hours at a normal pressure of 20 to 150 ° C. Use an acid to neutralize the reaction solution, add distilled water to precipitate a white solid, wash the separated solid with distilled water, or evaporate the solvent to dry and solidify. If necessary, use distilled water to wash and dry to obtain the hydrogen atom of the hydroxyl group. 1A) The compound substituted with a group shown in FIG.

In addition, the timing of introducing a group substituted with a group represented by the formula (0-1A) may be after the condensation reaction of binaphthols with aldehydes or ketones, or before the condensation reaction. In addition, it may be introduced after the production of the resin described later is carried out.

A method of introducing a group represented by the formula (0-1B) into at least one phenolic hydroxyl group of a polyphenol compound, and introducing a group represented by the formula (0-1A) into the hydroxyl group is also known.

For example, a group represented by formula (0-1B) can be introduced into at least one phenolic hydroxyl group of the aforementioned compound, and a group represented by formula (0-1A) can be introduced into its hydroxyl group by the following operations.

The compound used as the introduction formula (0-1B) can be synthesized by a known method or can be easily obtained, and examples thereof include chloroethanol, bromoethanol, 2-chloroethyl acetate, and 2-bromoethyl acetate. Ester, 2-iodoethyl acetate, ethylene oxide, propylene oxide, butylene oxide, butylene carbonate, butylene carbonate, butylene carbonate.

For example, the aforementioned compound is dissolved or suspended in an aprotic solvent such as acetone, tetrahydrofuran (THF), propylene glycol monomethyl ether acetate, or the like. Next, in the presence of an alkali catalyst such as sodium hydroxide, potassium hydroxide, sodium methoxylate, sodium ethoxylate, etc., the reaction is performed at a normal pressure of 20 to 150 ° C for 6 to 72 hours. By using an acid to neutralize the reaction solution and adding distilled water to precipitate a white solid, the separated solid can be washed with distilled water, or the solvent can be evaporated to dry and solidify. If necessary, it can be washed with distilled water and dried to obtain the hydrogen atom of hydroxyl group. A compound substituted with a group represented by formula (0-1B).

When 2-chloroethyl acetate, 2-bromoethyl acetate, and 2-iodoethyl acetate are used, hydroxyethyl group is introduced by introducing a defluorination reaction after introducing ethoxyethyl group. .

When using ethylene carbonate, propylene carbonate, and butyl carbonate, the addition of alkylene carbonate causes a decarbonation reaction to introduce a hydroxyalkyl group.

Thereafter, the aforementioned compound is dissolved or suspended in an aprotic solvent such as acetone, tetrahydrofuran (THF), propylene glycol monomethyl ether acetate, or the like. Secondly, in the presence of an alkali catalyst such as sodium hydroxide, potassium hydroxide, sodium methoxylate, sodium ethoxylate, etc., the reaction is performed at a normal pressure of 20 to 150 ° C for 6 to 72 hours. By using an acid to neutralize the reaction solution and adding distilled water to precipitate a white solid, the separated solid can be washed with distilled water, or the solvent can be evaporated to dry and solidify. If necessary, it can be washed with distilled water and dried to obtain the hydrogen atom of the hydroxyl group. A compound substituted with a group represented by formula (0-1A).

In this embodiment, the group substituted with the group represented by the formula (0-1A) is reacted in the presence of a radical or an acid / base, and the acid, alkali or organic solvent used for the coating solvent or the developing solution Changes in solubility. In order to achieve a higher sensitivity, the group substituted by the aforementioned group represented by the formula (0-1A) can be achieved. The high-resolution pattern is preferably a chain reaction in the presence of free radicals or acids / bases.

    [Resin obtained by using the compound represented by formula (2) as a monomer]    

The compound represented by the aforementioned formula (2) can be directly used as a composition for forming a lithography film or forming an optical component. Moreover, the resin system obtained using the compound represented by the said Formula (2) as a monomer can also be used as a composition. The resin is obtained by reacting, for example, a compound represented by the formula (2) with a compound having cross-linking reactivity.

Examples of the resin obtained by using the compound represented by the formula (2) as a monomer include those having a structure represented by the following formula (4). That is, the composition of this embodiment may be one containing a resin having a structure represented by the following formula (4).

In the formula (4), L is a linear, branched or cyclic 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, may be The alkylene group having 1 to 30 carbon atoms or a single bond having a substituent, the alkylene group, the alkylene group, and the alkylene group may also include an ether bond, a ketone bond, or an ester bond.

R ^0A , R ^1A , R ^2A , m ^2A , n ^A , q ^A, and X ^A are synonymous with those described in the above formula (2), but when n ^A is an integer of 2 or more, n ^A of [] The structural formulas may be the same or different. At least one m ^2A is an integer of 1 to 6, and at least one of R ^2A is a base represented by formula (0-2).

    [Manufacturing method of resin using compound represented by formula (2) as monomer]    

The resin of this embodiment can be obtained by reacting a compound represented by the above formula (2) with a compound having cross-linking reactivity. As the compound having cross-linking reactivity, a known one can be used without particular limitation as long as it can oligomerize or polymerize the compound represented by the formula (2). Specific examples thereof include, but are not limited to, aldehydes, ketones, carboxylic acids, carboxylic acid halides, halogen-containing compounds, amine compounds, imine compounds, isocyanates, and unsaturated hydrocarbon group-containing compounds. Limited to these.

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

Here, examples of the aldehyde used when the compound represented by the formula (2) is phenol-formaldehyde include formaldehyde, trioxane, paraformaldehyde, benzaldehyde, acetaldehyde, propylaldehyde, and benzene. Methyl acetaldehyde, phenylpropyl aldehyde, hydroxybenzaldehyde, chlorobenzaldehyde, nitrobenzaldehyde, methylbenzaldehyde, ethylbenzaldehyde, butylbenzaldehyde, biphenylaldehyde, naphthaldehyde, anthracenaldehyde, phenanthrene Formaldehyde, pyrene formaldehyde, furfural, etc. are not limited to these. Examples of the ketone include the aforementioned ketones. Among these, formaldehyde is preferred. These aldehydes and / or ketones may be used alone or in combination of two or more. The amount of the aldehydes and / or ketones used is not particularly limited, but is preferably 0.2 to 5 moles, and more preferably 0.5 to 2 moles, relative to 1 mole of the compound represented by the formula (2).

In the condensation reaction of the compound represented by the formula (2) with an aldehyde and / or a ketone, an acid catalyst may be used. The acid catalyst used here can be appropriately selected and used from known ones, and is not particularly limited. As such an acid catalyst, inorganic or organic acids have been widely known, and examples include inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, hydrofluoric acid, and the like; oxalic acid, malonic acid, succinic acid, and adipic acid. Acid, sebacic acid, citric acid, fumaric acid, maleic acid, formic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoromethanesulfonic acid, benzenesulfonic acid Organic acids such as naphthalenesulfonic acid, naphthalenesulfonic acid, naphthalenesulfonic acid, etc .; Lewis acids such as zinc chloride, aluminum chloride, iron chloride, boron trifluoride, or silicotungstic acid, phosphotungstic acid, silomolybdic acid, or molybdenum phosphorus Solid acids and the like are not limited to these. Among these, organic acids and solid acids are preferred from a manufacturing point of view, and hydrochloric acid or sulfuric acid is preferred from a manufacturing point of view in terms of availability and ease of handling. The acid catalysts may be used alone or in combination of two or more.

The amount of the acid catalyst to be used can be appropriately set depending on the types of raw materials and catalysts used, reaction conditions, and the like, and is not particularly limited. It is preferably 0.01 to 100 parts by mass relative to 100 parts by mass of the reaction raw materials. However, when used with indene, hydroxyindene, benzofuran, hydroxyanthracene, pinene, biphenyl, bisphenol, phenol, dicyclopentadiene, tetrahydroindene, 4-vinylcyclohexene, norbornadiene When a compound having a non-conjugated double bond such as 1,5-norbornene, α-pinene, β-pinene, and limonene is used for copolymerization reaction, aldehydes are not necessarily required.

In the condensation reaction of the compound represented by the formula (2) with an aldehyde and / or a ketone, a reaction solvent may be used. The reaction solvent for the polycondensation can be appropriately selected from known ones and is not particularly limited, and examples thereof include water, methanol, ethanol, propanol, butanol, tetrahydrofuran, dioxane, and mixed solvents thereof. . Moreover, a solvent system may be used individually by 1 type, and may use 2 or more types together.

The amount of these solvents can be appropriately set according to the types of raw materials and catalysts used, reaction conditions, and the like, and is not particularly limited. It is preferably in the range of 0 to 2000 parts by mass relative to 100 parts by mass of the reaction raw materials. . In addition, the reaction temperature may be appropriately selected depending on the reactivity of the reaction raw materials, and is not particularly limited, but is usually in the range of 10 to 200 ° C. In addition, the reaction method can be selected by using a known method as appropriate, and is not particularly limited, and examples thereof include a method in which the compound represented by the formula (2), an aldehyde and / or a ketone, and a catalyst are put in one time, or A method of continuously dropping a compound represented by the above formula (2) or an aldehyde and / or a ketone in the presence of a vehicle.

After the polycondensation reaction is completed, the separation of the obtained compound can be performed according to a conventional method, and is not particularly limited. For example, in order to remove unreacted raw materials or catalysts existing in the system, the general method of raising the temperature of the reactor to 130 to 230 ° C and removing volatile components at a level of 1 to 50 mmHg can be used for separation. A phenolic resin that yields the desired product.

Here, the resin having the structure represented by the formula (4) may be a homopolymer of the compound represented by the formula (2), or may be a copolymer with other phenols. Examples of copolymerizable phenols include phenol, cresol, dimethylphenol, trimethylphenol, butylphenol, phenylphenol, diphenylphenol, naphthylphenol, and resorcinol. Phenol, methyl resorcinol, catechol, butyl catechol, methoxyphenol, methoxyphenol, propylphenol, pyrogallol, thymol, etc. are not limited to these .

In addition, the resin having a structure represented by the formula (4) may be one obtained by copolymerization with a polymerizable monomer in addition to the other phenols. Examples of the comonomer include naphthol, methylnaphthol, methoxynaphthol, dihydroxynaphthalene, indene, hydroxyindene, benzofuran, hydroxyanthracene, pinene, biphenyl, and bisphenol , Phenol, dicyclopentadiene, tetrahydroindene, 4-vinylcyclohexene, norbornadiene, vinylnorbornene, pinene, limonene, etc., but it is not limited to these. In addition, the resin having the structure represented by the formula (4) may be a copolymer of a compound of the compound represented by the formula (2) and the above-mentioned phenols of two or more members (for example, a 2- to 4-membered system), or the aforementioned formula (2) A copolymer of a compound represented by (2) or more (for example, a 2- to 4-membered system) with the above-mentioned comonomer, and the compound represented by the above formula (2), the above-mentioned phenols, and the above-mentioned copolymerized monomer Copolymers having 3 or more members (for example, 3 to 4 members) are also acceptable.

Moreover, the molecular weight of the resin having the structure represented by the formula (4) is not particularly limited, and the weight average molecular weight (Mw) in terms of polystyrene is preferably 500 to 30,000, and more preferably 750 to 20,000. From the viewpoint of improving the crosslinking efficiency and suppressing the volatile components in baking, the resin having the structure represented by the formula (4) has a dispersion degree (weight average molecular weight Mw / number average molecular weight Mn) of 1.2 to 7. Within the range is better. In addition, the Mw and Mn can be obtained according to the method described in the examples described later.

From the viewpoint that the resin having the structure represented by the formula (4) can be more easily applied to a wet process and the like, it is preferably one having high solubility in a solvent. More specifically, the solubility of these compounds and / or resins with 1-methoxy-2-propanol (PGME) and / or propylene glycol monomethyl ether acetate (PGMEA) as a solvent It is preferably 10% by mass or more. Here, the solubility in PGMEA and / or PGMEA is defined as "mass of resin ÷ (mass of resin + mass of solvent) x 100 (mass%)". For example, when 10 g of the resin is dissolved in 90 g of PGMEA, the solubility of the resin in PGMEA becomes "10% by mass or more", and when it is insoluble, it becomes "less than 10% by mass".

    [Purification method of compound and / or resin]    

The method for purifying the compound and / or resin according to this embodiment includes a resin selected from the compound represented by the formula (1), a resin obtained by using the compound represented by the formula (1) as a monomer, and the aforementioned formula (2). ) And a solution (S) obtained by dissolving one or more resins obtained by using the compound represented by the above formula (2) as a monomer in a solvent; obtaining the solution (S); and obtaining the solution (S) and an acidic aqueous solution The step of contacting and extracting impurities in the aforementioned compound and / or the aforementioned resin (first extraction step), and the solvent used in the aforementioned step of obtaining the solution (S) includes a solvent which will not be arbitrarily mixed with water.

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

More specifically, in the purification method according to this embodiment, the compound and / or the resin are dissolved in an organic solvent that will not be arbitrarily mixed with water to obtain a solution (S), and the solution (S) and an acidic aqueous solution are further obtained. Contact and can be extracted. Thereby, after the metal component contained in the solution (S) is transferred to the water phase, the organic phase and the water phase are separated to obtain a compound and / or resin having a reduced metal content.

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

The solvent used in the purification method of this embodiment does not specifically mix with water, and is not particularly limited. An organic solvent suitable for a semiconductor manufacturing process is preferred. Specifically, the solubility in water at room temperature is not limited. An organic solvent of 30% or more, preferably 20% or less, and more preferably 10% or less. The amount of the organic solvent used is preferably 1 to 100 times by mass based on the total amount of the compound and resin used.

Specific examples of solvents that do not arbitrarily mix with water are not limited to the following, but examples include ethers such as diethyl ether and diisopropyl ether; ethyl acetate and n-butyl acetate Esters, esters such as isoamyl acetate, methyl ethyl ketone, methyl isobutyl ketone, ethyl isobutyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 2-pentanone, etc. Ketones; glycol ethers of ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, etc. Acetates; aliphatic hydrocarbons such as n-hexane, n-heptane; aromatic hydrocarbons such as toluene and stubble; halogenated hydrocarbons such as dichloromethane and chloroform. Among these, toluene, 2-heptanone, cyclohexanone, cyclopentanone, methyl isobutyl ketone, propylene glycol monomethyl ether acetate, and ethyl acetate are preferred, and methyl isobutyl ketone is preferred. , Ethyl acetate, cyclohexanone, and propylene glycol monomethyl ether acetate are more preferred, and methyl isobutyl ketone and ethyl acetate are more preferred. When methyl isobutyl ketone, ethyl acetate, etc. are used, the above compounds and resins containing the compounds as constituents have high saturation solubility and low boiling points, so they can be reduced in industrial distillation of solvents. In some cases, the load can be removed by drying. These solvents may be used alone or in combination of two or more.

The acidic aqueous solution used in the purification method of the present embodiment can be appropriately selected from aqueous solutions generally prepared by dissolving an organic compound or an inorganic compound in water. The acidic aqueous solution is not limited to the following, and examples thereof include a mineral acid aqueous solution obtained by dissolving mineral acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid in water; , Succinic acid, fumaric acid, maleic acid, tartaric acid, citric acid, methanesulfonic acid, phenolsulfonic acid, p-toluenesulfonic acid, trifluoroacetic acid and other organic acids dissolved in water. These acidic aqueous solutions can be used alone or in combination of two or more kinds. Among these acidic aqueous solutions, one or more types of mineral acid aqueous solutions are selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid, or they are selected from acetic acid, propionic acid, oxalic acid, malonic acid, succinic acid, fumaric acid, One or more organic acid aqueous solutions of maleic acid, tartaric acid, citric acid, methanesulfonic acid, phenolsulfonic acid, p-toluenesulfonic acid and trifluoroacetic acid are preferred. Sulfuric acid, nitric acid, and acetic acid, oxalic acid, An aqueous solution of a carboxylic acid such as tartaric acid, citric acid and the like is 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 more preferable. Polyvalent carboxylic acids such as oxalic acid, tartaric acid, and citric acid are considered to have a tendency to more effectively remove metals because they can be combined with metal ions to produce a chelate effect. In addition, for the purpose of the purification method according to the embodiment of the present invention, it is preferable to use water with a low metal content, such as ion-exchanged water.

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

The amount of the acidic aqueous solution used in the purification method of the present embodiment is not particularly limited. It is preferable to adjust the amount of use from the viewpoint of reducing the number of extractions for removing metals and ensuring the operability in consideration of the total amount of liquid. From the above point of view, the amount of the acidic aqueous solution used is preferably 10 to 200% by mass, and more preferably 20 to 100% by mass based on 100% by mass of the solution (S).

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

In the purification method of this embodiment, it is preferable that the solution (S) is further mixed with an organic solvent that can be arbitrarily mixed with water. When the solution (S) contains an organic solvent that can be arbitrarily mixed with water, the amount of the compound and / or resin to be added can be increased, and the liquid separation property can be improved, and purification with high kettle efficiency tends to be performed. The method of adding an organic solvent that can be arbitrarily mixed with water is not particularly limited, and may be, for example, a method of adding to a solution containing an organic solvent in advance, a method of adding to a water or an acidic aqueous solution in advance, a solution containing an organic solvent with water or Either of the methods of adding an acidic aqueous solution after contact. Among these, from the standpoint of ease of handling and management of the amount of insertion, a method of adding to a solution containing an organic solvent in advance is preferable.

The organic solvent that can be arbitrarily mixed with water used in the purification method of this embodiment is not particularly limited, and an organic solvent that can be safely applied to a semiconductor manufacturing process is preferred. The amount of the organic solvent that can be arbitrarily mixed with water is not particularly limited as long as it is a range where the solution phase and the water phase will separate, and it is preferably 0.1 to 100 times the mass of the total amount of the compound and resin used. 0.1 to 50 times the mass is better, and 0.1 to 20 times the mass is better.

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

The temperature during the extraction process is usually in the range of 20 to 90 ° C, preferably in the range of 30 to 80 ° C. The extraction operation is performed by, for example, mixing well with stirring, and then leaving it to stand still. Thereby, the metal component contained in the solution (S) is transferred to the water phase. In addition, by this operation, the acidity of the solution is low, and the deterioration of the compound and / or the resin can be suppressed.

Since the aforementioned mixed solution is separated into a solution phase containing a compound and / or a resin and a solvent, and a water phase by standing, the solution phase is recovered by decantation or the like. The time for standing is not particularly limited, and it is preferable to adjust the time for standing from the standpoint of better separating the solution phase containing the solvent from the water phase. Generally, the standing time is 1 minute or more, preferably 10 minutes or more, and more preferably 30 minutes or more. In addition, the extraction process may be performed only once, and it is effective to repeat the operations of mixing, standing, and separating a plurality of times.

In the purification method of this embodiment, after the first extraction step, a step of extracting impurities in the compound or the resin by bringing a solution phase containing the compound or the resin into contact with water (a second extraction step) is included. Better. Specifically, for example, after performing the above-mentioned extraction treatment using an acidic aqueous solution, it is preferable to provide a solution phase containing a compound and / or a resin and a solvent extracted and recovered from the aqueous solution to an extraction treatment using more water. This extraction process using water is not particularly limited. For example, after the aforementioned solution phase is well mixed with water by stirring or the like, the mixed solution obtained by standing is carried out. Since the mixed solution after standing is separated into a solution phase and an aqueous phase containing a compound and / or a resin and a solvent, the solution phase can be recovered by decantation or the like.

The water used here is preferably water having a low metal content, for example, ion-exchanged water, in accordance with the purpose of this embodiment. The extraction process may be performed only once, and it is also effective to repeat the operations of mixing, standing and separating for many times. In addition, the use ratio of the two in the extraction treatment, or conditions such as temperature and time are not particularly limited, and it may be the same as in the case of the previous contact treatment with an acidic aqueous solution.

The moisture contained in the solution containing the compound and / or the resin and the solvent thus obtained can be easily removed by performing operations such as reduced-pressure distillation. If necessary, a solvent may be added to the solution to adjust the concentration of the compound and / or resin to an arbitrary concentration.

The method of separating the compound and / or resin from the obtained solution containing the compound and / or resin and solvent is not particularly limited, and it can be removed under reduced pressure, separated by reprecipitation, and known methods such as combinations thereof. get on. Therefore, if necessary, well-known processes such as a concentration operation, a filtration operation, a telecentric separation operation, and a drying operation can be performed.

    [Film-forming composition for lithography]    

The lithographic film-forming composition of this embodiment contains a resin selected from the compound represented by the aforementioned formula (1), a resin obtained by using the compound represented by the aforementioned formula (1) as a monomer, and represented by the aforementioned formula (2). One or more compounds of the compound and the resin obtained by using the compound represented by the formula (2) as a monomer.

    [Film-forming composition for lithography for chemically amplified photoresist]    

The film-forming composition for lithography (hereinafter also referred to as a "photoresist composition") for use in chemically amplified photoresist in this embodiment contains a compound selected from the group consisting of the compound represented by the formula (1), One or more resins obtained by using a compound represented by (1) as a monomer, a compound represented by the aforementioned formula (2), and a resin obtained by using the compound represented by the aforementioned formula (2) as a monomer. As a photoresist substrate.

The photoresist composition of this embodiment preferably contains a solvent. The solvent is not particularly limited, and examples thereof include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, and ethyl acetate. Ethylene glycol monoalkyl ether acetates such as glycol mono-n-butyl ether acetate; Ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, etc. ; Propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether acetate, propylene glycol mono-n-butyl ether acetate, and other propylene glycol monoalkanes Ether ether acetates; propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether, etc .; methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, lactic acid Lactates such as n-pentyl esters; methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, n-pentyl acetate, n-hexyl acetate, methyl propionate, ethyl propionate Esters of aliphatic carboxylic acid esters; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, Methyl 3-methoxy-2-methylpropanoate, 3-methoxybutyl acetate, 3 -Methyl-3-methoxybutyl acetate, 3-methoxy-3-methylpropanoate, 3-methoxy-3-methylbutanoate, acetamidine methyl acetate , Methyl pyruvate, ethyl pyruvate and other esters; aromatic hydrocarbons such as toluene and stubble; 2-heptanone, 3-heptanone, 4-heptanone, cyclopentanone (CPN), cyclohexyl Ketones such as ketones (CHN); N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, etc. And lactones, such as γ-lactone, are not particularly limited. These solvents may be used alone or in combination of two or more.

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

In this embodiment, the amount of the solid content and the amount of the solvent are not particularly limited, and the solid content and the total mass of the solvent are 100% by mass, preferably 1 to 80% by mass and 20 to 99% by mass of the solvent. , Preferably 1-50% by mass of solids and 50-99% by mass of solvents, more preferably 2-40% by mass of solids and 60-98% by mass of solvents, particularly preferably 2-10% by mass of solids and solvents 90 ~ 98% by mass.

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

Here, the acid generator (C), the cross-linking agent (G), the acid diffusion control agent (E), and the other components (F) can be any known ones, and are not particularly limited. For example, International Publication No. 2013/024778 Number recorded is better.

    [Mixing ratio of each component]    

In the photoresist composition of this embodiment, the content of the compound and / or resin used as the photoresist substrate is not particularly limited, and the total mass of the solid content (including the photoresist substrate, the acid generator (C), The total solid content of any of the components (G), acid diffusion control agent (E), and other components (F), etc., is the same below.) 50 to 99.4% by mass is preferable, and 55 to 99.4% is preferable. 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 photoresist substrate is within the above range, the resolution is further improved, and the line edge roughness (LER) tends to be smaller.

When both the compound and the resin are used as the photoresist substrate, the aforementioned content is the total amount of the two components.

    [Other ingredients (F)]    

As long as the photoresist composition of this embodiment does not hinder the object of the present invention, a dissolution accelerator, a dissolution control agent, a sensitizer, a surfactant, an organic carboxylic acid, or an oxo acid of phosphorus or the like may be added as necessary. Derivatives, heat and / or light hardening catalysts, polymerization inhibitors, flame retardants, fillers, coupling agents, thermosetting resins, light hardening resins, dyes, pigments, thickeners, slip agents, defoamers Various additives such as leveling agents, ultraviolet absorbers, surfactants, colorants, non-ionic surfactants, etc. as one or two or more kinds of photoresist substrates, acid generators (C), and cross-linking agents (G ) And components other than the acid diffusion control agent (E). In addition, in this specification, other components (F) may be called arbitrary components (F).

In the photoresist composition of this embodiment, a photoresist substrate (hereinafter also referred to as "component (A)"), an acid generator (C), a crosslinking agent (G), an acid diffusion control agent (E), When the content of the component (F) (component (A) / acid generator (C) / crosslinking agent (G) / acid diffusion control agent (E) / optional component (F)) is expressed in terms of mass% of solid basis, 50 ~ 99.4 / 0.001 ~ 49 / 0.5 ~ 49 / 0.001 ~ 49/0 ~ 49 is preferable, 55 ~ 90/1 ~ 40 / 0.5 ~ 40 / 0.01 ~ 10/0 ~ 5 is more preferable, and 60 is more preferable. ~ 80/3 ~ 30/1 ~ 30 / 0.01 ~ 5/0 ~ 1, especially preferred is 60 ~ 70/10 ~ 25/2 ~ 20 / 0.01 ~ 3/0.

The blending ratio of each component is selected from each range so that the sum may be 100% by mass. When the blending ratio of each component is within the above range, there is a tendency that the performance such as sensitivity, resolution, and developability is excellent.

The photoresist composition of this embodiment is generally prepared by dissolving each component in a solvent to make a homogeneous solution during use, and thereafter, it is necessary to perform filtration by using, for example, a filter having a pore size of about 0.2 μm.

The photoresist composition of this embodiment may contain resins other than the resin of this embodiment, as long as the object of the present invention is not hindered. The other resins are not particularly limited, and examples thereof include phenol resins, polyvinyl phenols, polyacrylic acid, polyvinyl alcohol, styrene-anhydrous maleic acid resins, and acrylic, vinyl alcohol, or vinyl-containing resins. A polymer of phenol as a monomer unit or a derivative thereof. The content of other resins is not particularly limited, and is appropriately adjusted according to the type of the component (A) to be used. It is preferably 30 parts by mass or less, more preferably 10 parts by mass or less, with respect to 100 parts by mass of the component (A). It is preferably 5 parts by mass or less, and particularly preferably 0 part by mass.

    [Physical properties of photoresist composition]    

The photoresist composition of this embodiment can be used to form an amorphous film by spin coating. The photoresist composition of this embodiment can be applied to general semiconductor manufacturing processes. Positive photoresist patterns can be separately prepared according to the type of the compound represented by the above formula (1) and / or formula (2), the type of resin obtained by using these as monomers, and / or the type of developing solution used. Either a photoresist pattern or a negative photoresist pattern.

In the case of a positive photoresist pattern, the dissolution rate of the amorphous film formed by spin-coating the photoresist composition of this embodiment in a developing solution at 23 ° C is preferably 5 Å / sec or less, and 0.05 ~ 5Å / sec is preferred, and 0.0005 ~ 5Å / sec is more preferred. When the dissolution rate is 5 Å / sec or less, the photoresist tends to be insoluble in the developing solution and easily become a photoresist. When the dissolution rate is 0.0005 Å / sec or more, the resolution may be improved. This presumption is due to the change in the solubility of the compound represented by the above formulae (1) and (2) and / or the solubility of the resin containing the compound as a constituent component before and after exposure. The contrast at the interface of the unexposed portion dissolved in the developing solution becomes large. The effect of reducing LER and reducing defects can also be found.

In the case of a negative photoresist pattern, the dissolution rate of the amorphous film formed by spin-coating the photoresist composition of this embodiment in a developing solution at 23 ° C is preferably 10 Å / sec or more. When the dissolution rate is 10 Å / sec or more, it is easily soluble in a developing solution and suitable as a photoresist. When the dissolution rate is 10 Å / sec or more, the resolution may be improved. This is presumably due to the fact that the compound represented by the formulae (1) and (2) and / or the microscopic surface portion of the resin containing the compound as a constituent component is dissolved, and the LER is reduced. Defect reduction effects were also found.

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

In the case of a positive photoresist pattern, an amorphous film formed by spin-coating the photoresist composition of this embodiment is exposed by radiation such as KrF excimer laser, extreme ultraviolet rays, electron rays, or X-rays. The dissolution rate of the developing solution at 23 ° C is preferably 10 Å / sec or more. When the dissolution rate is above 10 Å / sec, it is easily soluble in the developing solution and is suitable as a photoresist. When the dissolution rate is 10 Å / sec or more, the resolution may be improved. This is presumably due to the fact that the compound represented by the formulae (1) and (2) and / or the microscopic surface portion of the resin containing the compound as a constituent component is dissolved, and the LER is reduced. Defect reduction effects were also found.

In the case of a negative photoresist pattern, an amorphous film formed by spin-coating the photoresist composition of this embodiment is exposed by radiation such as KrF excimer laser, extreme ultraviolet rays, electron rays, or X-rays. The dissolution rate of the developing solution at 23 ° C is preferably 5 Å / sec or less, more preferably 0.05 to 5 Å / sec, and more preferably 0.0005 to 5 Å / sec. When the dissolution rate is 5 Å / sec or less, the photoresist tends to be insoluble in the developing solution and easily become a photoresist. When the dissolution rate is 0.0005 Å / sec or more, the resolution may be improved. This presumption is due to the change in the solubility of the compound represented by the above formulae (1) and (2) and / or the solubility of the resin containing the compound as a constituent component before and after exposure. The contrast at the interface of the exposed portion that is not dissolved in the developing solution is increased. It can also reduce LER and reduce defects.

    [Film-forming composition for lithography for non-chemically amplified photoresist applications]    

The component (A) contained in the lithographic film-forming composition (hereinafter also referred to as a "radiosensitive composition") for the non-chemically amplified photoresist use of this embodiment contains a diazonium compound as described below. The naphthoquinone photoactive compound (B) is used in combination, and it is useful to become soluble by irradiating g-line, h-line, i-line, KrF excimer laser, ArF excimer laser, extreme ultraviolet rays, electron rays or X-rays. Base material for positive photoresist of compound in developer. The nature of the component (A) does not change greatly due to g-line, h-line, i-line, KrF excimer laser, ArF excimer laser, extreme ultraviolet, electron or X-ray, but it is difficult to dissolve in the imaging solution. The diazonaphthoquinone photoactive compound (B) is changed into an easily soluble compound, so that it becomes possible to make a photoresist pattern through a development step.

Since the component (A) contained in the radiation-sensitive composition of this embodiment is a compound having a relatively low molecular weight, the roughness of the obtained photoresist pattern is very small. In the formula (1), at least one selected from the group consisting of R ⁰ to R ⁵ is preferably a group containing an iodine atom. In the formula (2), R ^0A , R ^1A, and R are freely selected. Preferably, at least one of the clusters of ^2A is a group containing an iodine atom. When the radiation-sensitive composition of this embodiment is applied to the component (A) having a base containing an iodine atom in such a preferable aspect, it becomes possible to make it easier for electron rays, extreme ultraviolet rays (EUV), X-rays, etc. The radiation absorption capacity is increased, and as a result, the sensitivity is improved, which is desirable.

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

The glass transition temperature of the component (A) contained in the radiation-sensitive composition of this embodiment is preferably less than 20 J / g, and the crystallized calorific value obtained by differential scanning calorimetry analysis. The (crystallization temperature)-(glass transition temperature) is preferably 70 ° C or higher, more preferably 80 ° C or higher, more preferably 100 ° C or higher, and particularly preferably 130 ° C or higher. When the heat of crystallization is less than 20 J / g, or (crystallization temperature)-(glass transition temperature) is within the above range, an amorphous film is easily formed by spin-coating a radiation-sensitive composition, and light The film-forming properties necessary for resistance can be maintained over a long period of time, and the resolution can be improved.

In this embodiment, the aforementioned crystallization heat value, crystallization temperature, and glass transition temperature can be obtained by differential scanning calorimetry analysis using DSC / TA-50WS manufactured by Shimadzu Corporation. About 10 mg of the sample was placed in an aluminum non-sealed container, and the temperature was raised to a melting point or higher at a temperature increase rate of 20 ° C / min in a nitrogen gas flow (50 mL / min). After the rapid cooling, the temperature was raised again to a melting point or higher in a nitrogen gas flow (30 mL / min) at a temperature increase rate of 20 ° C / min. After further rapid cooling, the temperature was increased again to 400 ° C at a temperature increase rate of 20 ° C / min in a nitrogen gas flow (30 mL / min). The temperature at the midpoint of the stepped baseline (when the specific heat was changed by half) was set as the glass transition temperature (Tg), and the temperature of the exothermic peak that followed appeared as the crystallization temperature. Calculate the heat value from the area of the heating peak and the area surrounded by the baseline, and set it as the crystallization heat value.

The component (A) contained in the radiation-sensitive composition of this embodiment is preferably 100 ° C or lower and 120 ° C or lower under normal pressure, preferably 130 ° C or lower, more preferably 140 ° C or lower, and particularly preferably Low sublimation properties below 150 ° C are preferred. Low sublimation means that in thermogravimetric analysis, the weight reduction after holding at the specified temperature for 10 minutes shows less than 10%, preferably less than 5%, more preferably less than 3%, and more preferably less than 1%. The best display is below 0.1%. With low sublimation, pollution to the exposure device caused by the gas released during exposure can be prevented. And can obtain good pattern shape under low roughness.

The component (A) contained in the radiation-sensitive composition of this embodiment is selected from the group consisting of propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone (CHN), and cyclopentanone. (CPN), 2-heptanone, anisole, butyl acetate, ethyl propionate, and ethyl lactate, and in a solvent that exhibits the highest solubility in component (A), It is preferable to dissolve 1 mass% or more, it is preferable to dissolve 5 mass% or more, and it is more preferable to dissolve 10 mass% or more. Particularly preferred is a solvent selected from the group consisting of PGMEA, PGMEA, and CHN, and which dissolves at least 20% by mass at 23 ° C. in a solvent exhibiting the highest dissolving power for the (A) photoresist substrate. It dissolves at 20% by mass or more at 23 ° C. By satisfying the above conditions, it becomes easy to use the semiconductor manufacturing steps in actual production.

    [Diazonaphthoquinone photoactive compound (B)]    

The diazonaphthoquinone photoactive compound (B) contained in the radiation-sensitive composition of this embodiment is a diazonaphthoquinone substance containing a polymeric and non-polymeric diazonaphthoquinone photoactive compound. Generally, as long as it is a positive type The photoresist composition is not particularly limited as long as it is used as a photosensitive component (photosensitizer), and one kind or two or more kinds can be arbitrarily selected and used.

As the component (B), a low-molecular compound or a polymer having a functional group capable of reacting with the condensation of the acid chloride by making naphthoquinonediazidesulfonic acid chloride or benzoquinonediazidesulfonic acid chloride and the like The compound obtained by reacting the compounds is preferred. Here, the functional group capable of condensing with an acid chloride is not particularly limited, and examples thereof include a hydroxyl group and an amino group, and a hydroxyl group is particularly suitable. The compound capable of condensing with an acid chloride containing a hydroxyl group is not particularly limited, and examples thereof include hydroquinone, resorcinol, 2,4-dihydroxybenzophenone, and 2,3,4-trihydroxy group. Benzophenone, 2,4,6-trihydroxybenzophenone, 2,4,4'-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2, 2 ', 4,4'-tetrahydroxybenzophenone, 2,2', 3,4,6'-pentahydroxybenzophenone and other hydroxybenzophenones; bis (2,4-dihydroxy Phenyl) methane, bis (2,3,4-trihydroxyphenyl) methane, bis (2,4-dihydroxyphenyl) propane, and other hydroxyphenylalkanes; 4,4 ', 3 ", 4" -Tetrahydroxy-3,5,3 ', 5'-tetramethyltriphenylmethane, 4,4', 2 ", 3", 4 "-pentahydroxy-3,5,3 ', 5'-tetra Hydroxytriphenylmethanes, such as methyltriphenylmethane.

Further, as acid chlorides such as naphthoquinonediazidesulfonic acid chloride or benzoquinonediazidesulfonic acid chloride, preferred examples include 1,2-naphthoquinonediazide-5-sulfonyl chloride , 1,2-naphthoquinonediazide-4-sulfonyl chloride and the like.

The radiation-sensitive composition of the present embodiment is preferably prepared by dissolving each component in a solvent to form a homogeneous solution during use, and thereafter, it is preferably prepared by filtering with a filter having a pore size of about 0.2 μm, if necessary.

    [Characteristics of radiation-sensitive composition]    

By using the radiation-sensitive composition of this embodiment, an amorphous film can be formed by spin coating. The radioactive composition of this embodiment can be applied to general semiconductor manufacturing processes. Depending on the type of imaging solution used, either a positive photoresist pattern or a negative photoresist pattern can be produced separately.

In the case of a positive photoresist pattern, the dissolution rate of the amorphous film formed by spin-coating the radiation-sensitive composition of this embodiment in a developing solution at 23 ° C is preferably 5 Å / sec or less. 0.05 to 5 Å / sec is preferred, and 0.0005 to 5 Å / sec is more preferred. When the dissolution rate is 5 Å / sec or less, it tends to be insoluble in the developing solution and tends to become a photoresist. When the dissolution rate is 0.0005 Å / sec or more, the resolution may be improved. This speculation is that the solubility of the compound represented by the formulae (1) and (2) and / or the solubility of the resin containing the compound as a constituent component before and after exposure changes, so that it dissolves in the exposed portion of the developing solution and does not dissolve in the The contrast at the interface of the unexposed portion of the developing solution is increased. It can also be found that the reduction of LER and the effect of reducing defects.

In the case of a negative photoresist pattern, the dissolution rate of the amorphous film formed by spin-coating the radiation-sensitive composition of this embodiment in a developing solution at 23 ° C. is preferably 10 Å / sec or more. When the dissolution rate is 10 Å / sec or more, it is easily soluble in a developing solution and is suitable as a photoresist. When the dissolution rate is 10 Å / sec or more, the resolution may be improved. This is presumably due to the fact that the compound represented by the formulae (1) and (2) and / or the microscopic surface portion of the resin containing the compound as a constituent component is dissolved, and LER is reduced. The defect reduction effect was also found.

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

In the case of a positive photoresist 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 rays, electron rays, or X-rays. After that, or, the dissolution rate of the developer in the exposed portion after heating at 20 to 500 ° C at 23 ° C is preferably 10 Å / sec or more, more preferably 10 to 10,000 Å / sec, and 100 to 1000 Å. / sec is better. When the dissolution rate is 10 Å / sec or more, it is easily soluble in a developing solution and is suitable as a photoresist. When the dissolution rate is 10,000 Å / sec or less, the resolution may be improved. This is presumably due to the fact that the compound represented by the formulae (1) and (2) and / or the microscopic surface portion of the resin containing the compound as a constituent component is dissolved, and the LER is reduced. The defect reduction effect was also found.

In the case of a negative photoresist 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 rays, electron rays, or X-rays. After that, or, the dissolution rate of the developer in the exposed portion after heating at 20 to 500 ° C at 23 ° C is preferably 5 Å / sec or less, more preferably 0.05 to 5 Å / sec, or 0.0005 to 5 Å. / sec is better. When the dissolution rate is 5 Å / sec or less, it tends to be insoluble in the developing solution and tends to become a photoresist. When the dissolution rate is 0.0005 Å / sec or more, the resolution may be improved. This presumption is due to the change in the solubility of the compound represented by the formulae (1) and (2) and / or the resin containing the compound as a constituent component before and after exposure, so that it is dissolved in the unexposed portion of the developing solution and insoluble. The contrast at the interface of the exposure portion of the developing solution becomes large. It can also be found that the reduction of LER and the effect of reducing defects.

    [Mixing ratio of each component]    

In the radiation-sensitive composition of this embodiment, with respect to the total weight of the solid components (the sum of any solid components used in the component (A), the diazonaphthoquinone photoactive compound (B), and other components (D)), The same applies hereinafter), and the content of the component (A) is preferably 1 to 99% by mass, more preferably 5 to 95% by mass, more preferably 10 to 90% by mass, and particularly preferably 25 to 75% by mass. When the content of the component (A) is within the above range in the radiation-sensitive composition of this embodiment, a pattern with a small roughness can be obtained with high sensitivity.

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

    [Other ingredients (D)]    

As long as the radiation-sensitive composition of this embodiment does not hinder the object of the present invention, it may be added as an ingredient other than the component (A) and the diazonaphthoquinone photoactive compound (B), and an acid generator and a cross-linking may be added. Agents, acid diffusion control agents, dissolution accelerators, dissolution control agents, sensitizers, surfactants, organic carboxylic acids or phosphorus oxo acids or derivatives thereof, heat and / or light hardening catalysts, polymerization inhibitors, Flame retardants, fillers, coupling agents, thermosetting resins, photocurable resins, dyes, pigments, thickeners, slip agents, defoamers, levelers, ultraviolet absorbers, surfactants, colorants, Various additives such as non-ionic surfactants, or two or more thereof. In addition, in this specification, other components (D) may be made into arbitrary components (D).

In the radiation-sensitive composition of this embodiment, the proportion of each component (component (A) / diazonaphthoquinone photoactive compound (B) / arbitrary component (D)) is expressed as mass% based on solid content. 1 ~ 99/99 ~ 1/0 ~ 98 is preferred, 5 ~ 95/95 ~ 5/0 ~ 49 is preferred, 10 ~ 90/90 ~ 10/0 ~ 10 is more preferred, and 20 ~ 80/80 ~ 20/0 ~ 5, especially preferred is 25 ~ 75/75 ~ 25/0.

The blending ratio of each component is selected from each range so that the sum may be 100% by mass. When the compounding ratio of each component of the radiation-sensitive composition of this embodiment is within the above-mentioned range, there is a tendency that the properties such as roughness, sensitivity, resolution, and developability are excellent.

The radiation-sensitive composition of the present embodiment may include other resins other than the present embodiment so long as the object of the present invention is not hindered. Examples of such other resins include phenolic resin, polyvinyl phenols, polyacrylic acid, polyvinyl alcohol, styrene-anhydrous maleic acid resin, and acrylic acid, vinyl alcohol, or vinyl phenol as monomers. Units of polymers or derivatives thereof. The blending amount of these resins is appropriately adjusted according to the type of the component (A) to be used, and is preferably 30 parts by mass or less, more preferably 10 parts by mass or less, more preferably 100 parts by mass of the component (A). 5 parts by mass or less, particularly preferably 0 parts by mass.

    [Formation method of photoresist pattern]    

The method for forming a photoresist pattern of this embodiment mode includes: using the photoresist composition or radiation-sensitive composition of the above embodiment to form a photoresist layer on a substrate, and irradiating a predetermined area of the photoresist layer with radiation. Development steps.

More specifically, the method includes the steps of forming a photoresist film on a substrate by using the photoresist composition or the radiation-sensitive composition of the embodiment described above; a step of exposing the formed photoresist film; Step of forming a photoresist pattern. The photoresist pattern of this embodiment can also be formed as an upper photoresist in a multilayer process.

The method for forming a photoresist pattern is not particularly limited, and examples thereof include the following methods. First, a photoresist film or a radiation-sensitive composition is formed on a conventionally known substrate by applying a coating method such as spin coating, cast coating, or roll coating. The conventionally known substrate is not particularly limited, and examples thereof include a substrate for an electronic component, or a predetermined wiring pattern formed thereon. More specifically, a metal substrate such as a silicon wafer, copper, chromium, iron, aluminum, or a glass substrate may be used. Examples of the wiring pattern material include copper, aluminum, nickel, and gold. If necessary, an inorganic and / or organic film may be provided on the substrate. Examples of the inorganic film include an inorganic antireflection film (inorganic BARC). Examples of the organic film include an organic anti-reflection film (organic BARC). Surface treatment with hexamethylene disilazane or the like may be performed on the substrate.

Second, the substrate on which the photoresist composition or the radiation-sensitive composition has been applied is heated as necessary. The heating conditions are changed according to the composition of the photoresist composition or the radiation-sensitive composition, but it is preferably 20 to 250 ° C, and more preferably 20 to 150 ° C. Since the adhesion of the photoresist to the substrate tends to increase by heating, it is preferable. Second, the photoresist film is exposed to a desired pattern by using any type of radiation selected from the group consisting of visible light, ultraviolet rays, excimer lasers, electron rays, extreme ultraviolet rays (EUV), X-rays, and ion beams. . The exposure conditions and the like are appropriately selected in accordance with the composition of the photoresist composition or the radiation-sensitive composition. In this embodiment, in order to form a fine pattern with high accuracy under exposure, it is preferable to perform heating after radiation irradiation. The heating conditions are changed according to the composition of the photoresist composition or the radiation-sensitive composition, but it is preferably 20 to 250 ° C, and more preferably 20 to 150 ° C.

Next, a predetermined photoresist pattern is formed by developing the exposed photoresist film with a developing solution. As a developing solution, a solubility parameter (for a compound represented by the formula (1) or the formula (2) or a resin obtained by using the compound represented by the formula (1) or the formula (2) as a monomer is selected. Solvents having a similar SP value) are preferred. Polar solvents such as ketone solvents, ester solvents, alcohol solvents, amidine solvents, ether solvents, hydrocarbon solvents, or alkaline aqueous solutions can be used.

Examples of the ketone-based solvent include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 4-heptanone, 1-hexanone, 2-hexanone, and diisobutyl Methyl ketone, cyclohexanone, methyl cyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetoacetone, acetone acetone, ionone, diacetone alcohol, acetamidine Methyl alcohol, acetophenone, methylnaphthyl ketone, isophorone, propylene carbonate and the like.

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

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

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

Examples of the amidine-based solvent include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, and trimethylphosphonium hexamethyl phosphate. Amine, 1,3-dimethyl-2-imidazolinone and the like.

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

The above-mentioned solvents may be mixed in plural, and within a range of performance, they may be mixed with a solvent or water other than the above and used. However, from the viewpoint of sufficiently achieving the effects of the invention, the moisture content of the entire developing solution is preferably less than 70% by mass, more preferably less than 50% by mass, and even more preferably less than 30% by mass. It is also better to be less than 10% by mass, and it is particularly preferable that it does not substantially contain water. That is, with respect to the total amount of the developing solution, the content of the organic solvent in the developing solution is preferably 30% by mass or more and 100% by mass or less, more preferably 50% by mass or more and 100% by mass or less, and 70% by mass or more. 100% by mass or less is more preferred, 90% by mass or more and 100% by mass is more preferred, and 95% by mass or more and 100% by mass is particularly preferred.

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

In particular, as a developing solution, from the viewpoint of improving the photoresistance performance such as the resolvability of the photoresist pattern and the roughness, it contains a solvent selected from the group consisting of a ketone solvent, an ester solvent, an alcohol solvent, an amidine solvent, and The developer of at least one of the ether-based solvents is preferred.

The vapor pressure of the developing solution is preferably 20 kC or lower, 5 kPa or lower, 3 kPa or lower, and 2 kPa or lower. When the vapor pressure of the developing solution is 5 kPa or less, evaporation on the substrate or in the developing cup of the developing solution is suppressed, and the temperature uniformity in the wafer surface is improved. As a result, the size uniformity in the wafer surface is excellent. Tendency.

Examples of specific developing solutions having a vapor pressure of 5 kPa or lower at 20 ° C include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 4-heptanone, and 2-hexanone , Diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl isobutyl ketone and other ketone solvents; 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-methyl Ester solvents such as oxybutyl acetate, 3-methyl-3-methoxybutyl acetate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, etc .; n -Propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, 4-methyl-2-pentanol, n- Alcohol solvents such as heptyl alcohol, n-octyl alcohol, n-decanol; glycol solvents such as ethylene glycol, diethylene glycol, and triethylene glycol; ethylene glycol monomethyl ether, propylene glycol mono Methyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, Glycol ether solvents such as oxymethyl butanol; ether solvents such as tetrahydrofuran; N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethyl Amidamine-based solvents for formamidine; aromatic hydrocarbon-based solvents such as toluene and stubble; aliphatic hydrocarbon-based solvents such as octane and decane.

Examples of specific developing solutions having a vapor pressure of 2 kPa or lower at 20 ° C include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 4-heptanone, and 2-hexanone , Diisobutyl ketone, cyclohexanone, methyl cyclohexanone, phenylacetone and other ketone solvents; butyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether Acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate , 3-methyl-3-methoxybutyl acetate, ethyl lactate, butyl lactate, propyl lactate and other ester-based solvents; n-butyl alcohol, sec-butyl alcohol, tert-butyl Alcohol solvents such as alcohols, isobutyl alcohol, n-hexyl alcohol, 4-methyl-2-pentanol, n-heptyl alcohol, n-octyl alcohol, n-decanol; ethylene glycol, diethyl alcohol Diol-based solvents such as glycols and triethylene glycol; ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, and diethylene glycol monomethyl ether Glycol ether solvents, such as triethylene glycol monoethyl ether, methoxymethyl butanol; N-methyl-2-pyrrolidone, N, N- Aliphatic hydrocarbon solvents octane, decane, etc.; methyl as acetamide, N, N- dimethylformamide Amides of the solvents, the crop and other aromatic hydrocarbon solvents.

An appropriate amount of a surfactant may be added to the developing solution as necessary. The surfactant is not particularly limited, and, for example, an ionic or nonionic fluorine-based and / or silicon-based surfactant can be used. Examples of such fluorine and / or silicon-based surfactants include Japanese Patent Laid-Open No. 62-36663, Japanese Patent Laid-Open No. 61-226746, Japanese Patent Laid-Open No. 61-226745, and Japan Japanese Patent Laid-Open No. 62-170950, Japanese Patent Laid-Open No. 63-34540, Japanese Patent Laid-Open No. 7-230165, Japanese Patent Laid-Open No. 8-62834, Japanese Patent Laid-Open No. 9-54432, Japanese Patent Laid-Open No. 9 -5988, US Patent No. 5,457,920, Same as No. 5360692, Same as No. 5529681, Same as No. 5296330, Same as No. 5436098, Same as No. 5576143, Same as No. 5294511, and Same as No. 5284451 The agent is preferably a nonionic surfactant. The nonionic surfactant is not particularly limited, but a fluorine-based surfactant or a silicon-based surfactant is preferred.

Relative to the total amount of the developing solution, the amount of the surfactant used is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, and more preferably 0.01 to 0.5% by mass.

As the developing method, for example, a method of immersing a substrate in a tank filled with a developing solution for a certain period of time (immersion method) can be applied; a developing solution is floated on the surface of the substrate by surface tension to stand still for a certain period of time for development. Method (liquid holding method); method for spraying imaging liquid on the substrate surface (spray method); on a substrate rotating at a certain speed, scan the imaging liquid with a nozzle at a certain speed and continue to spit out the imaging liquid at the same time Method (dynamic allocation method) and so on. The pattern development time is not particularly limited, but is preferably 10 seconds to 90 seconds.

In addition, after the step of performing development, a step of performing development by using another solvent for substitution may be performed.

It is preferable to include a step of washing with a rinse solution containing an organic solvent after development.

As the rinse solution used in the rinse step after development, as long as it does not dissolve the photoresist pattern that is hardened by cross-linking, there is no particular limitation, and a solution containing general organic solvents or water can be used. As the aforementioned rinse solution, a rinse solution using at least one type of organic solvent selected from the group consisting of a hydrocarbon-based solvent, a ketone-based solvent, an ester-based solvent, an alcohol-based solvent, an amidine-based solvent, and an ether-based solvent is preferred. After the development, it is preferable to perform a step of washing with a rinse solution containing at least one type of organic solvent selected from the group consisting of a ketone solvent, an ester solvent, an alcohol solvent, and an amidine solvent. More preferably, after the development, a step of washing with an rinse solution containing an alcohol-based solvent or an ester-based solvent is performed. More preferably, after the development, a step of washing with a rinse solution containing a monovalent alcohol is performed. Particularly preferred is a step of washing with a rinse solution containing a monovalent alcohol having 5 or more carbon atoms after development. There is no particular limitation on the time for implementing the rinse pattern, and it is preferably 10 seconds to 90 seconds.

Here, examples of the monovalent alcohol used in the rinse step after development include linear, branched, and cyclic monovalent alcohols. Specifically, 1-butanol and 2-butanol can be used. Alcohol, 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, etc. are particularly preferred as having a carbon number of 5 or more Examples of the monovalent alcohol include 1-hexanol, 2-hexanol, 4-methyl-2-pentanol, 1-pentanol, and 3-methyl-1-butanol.

Each of the aforementioned components may be mixed in plural, or may be used after being mixed with an organic solvent other than the above.

The moisture content in the lotion is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 3% by mass or less. When the water content in the lotion is 10% by mass or less, there is a tendency that a better developing characteristic can 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 more preferably 0.12 kPa or more and 3 kPa or less. When the vapor pressure of the rinse solution is above 0.05 kPa and less than 5 kPa, the temperature uniformity in the wafer surface is further improved, and the swelling caused by the penetration of the rinse liquid is further suppressed, and the size uniformity in the wafer surface is uniform. The tendency to become better.

An appropriate amount of a surfactant may be added to the lotion and used.

In the rinse step, the developed wafer is cleaned using a rinse solution containing the organic solvent. The method of cleaning treatment is not particularly limited, and it can be applied, for example, a method of continuously discharging a rinse solution on a substrate rotating at a certain speed (spin coating method); immersing the substrate in a tank filled with the rinse solution for a certain period of time. Method (dipping method); a method of spraying a cleaning solution on the surface of the substrate (spray method), etc., in which a cleaning process is performed by a spin coating method, and the substrate is rotated at a rotation number of 2000 rpm to 4000 rpm after cleaning, It is better to remove the rinse solution from the substrate.

After the photoresist pattern is formed, a pattern wiring board is obtained by etching. The etching method can be carried out by a known method such as dry etching using a plasma gas and wet etching using an alkali solution, a second copper chloride solution, a second iron chloride solution, and the like.

After the photoresist pattern is formed, plating can also be performed. Examples of the plating method include copper plating, flux plating, nickel plating, and gold plating.

The residual photoresist 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), and EL (ethyl lactate). Examples of the peeling method include a dipping method and a spray method. In addition, the wiring substrate on which the photoresist pattern has been formed may be a multilayer wiring substrate or may have a small-diameter through hole.

The wiring substrate according to this embodiment can also be formed by a method of lift-off method in which a metal is evaporated in a vacuum after the photoresist pattern is formed, and then the photoresist pattern is dissolved by a solution.

    [Film-forming composition for lithography for lower film use]    

The lithographic film-forming composition (hereinafter also referred to as "underlayer film-forming material") for use in the underlayer film of this embodiment contains a compound selected from the group consisting of the compound represented by the above formula (1), At least one of a group consisting of a resin represented by the compound shown as a monomer, a compound represented by the formula (2), and a resin obtained by using the compound represented by the formula (2) as a monomer. From the viewpoints of coating properties and quality stability, the foregoing substances in this embodiment are preferably 1 to 100% by mass, more preferably 10 to 100% by mass, and 50 to 100% by mass in the lower layer film forming material. For better performance, 100% by mass is particularly preferred.

The underlayer film forming material of this embodiment can be applied to a wet process, and has excellent heat resistance and etching resistance. In addition, since the underlayer film forming material of the present embodiment uses the above-mentioned materials, it is possible to form an underlayer film with suppressed film degradation during high-temperature baking, and has excellent resistance to etching such as oxygen plasma etching. Furthermore, since the underlayer film forming material of this embodiment is also excellent in adhesion with the photoresist layer, an excellent photoresist pattern can be obtained. In addition, the underlayer film-forming material of this embodiment may include a known underlayer film-forming material for lithography within a range that does not impair the effect of the present invention.

    [Solvent]    

The underlayer film forming material of this embodiment may contain a solvent. As the solvent used as the material for forming the underlayer film, a known one can be suitably used as long as it dissolves at least the above substances.

Specific examples of the solvent are not particularly limited, and examples thereof include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; propylene glycol monomethyl ether and propylene glycol monomethyl Solvent solvents such as ether acetate; ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, isoamyl acetate, ethyl lactate, methyl methoxypropionate, methyl hydroxyisobutyrate Ester-based solvents such as esters; alcohol-based solvents such as methanol, ethanol, isopropanol, 1-ethoxy-2-propanol; aromatic hydrocarbons such as toluene, stubble, and 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 preferred from the viewpoint of safety.

The content of the solvent is not particularly limited. From the viewpoints of solubility and film formation, it is preferably 100 to 10,000 parts by mass, and more preferably 200 to 5,000 parts by mass relative to 100 parts by mass of the aforementioned lower layer film forming material. 200 to 1,000 parts by mass is more preferable.

    [Crosslinking agent]    

The layer film-forming material under the present embodiment may contain a cross-linking agent as necessary from the viewpoint of suppressing intermixing and the like. The crosslinking agent is not particularly limited, and examples thereof include those described in International Publication No. 2013/024779.

Specific examples of the crosslinking agent that can be used in this embodiment include, for example, a phenol compound, an epoxy compound, a cyanate compound, an amine compound, a benzoxazine compound, an acrylate compound, a melamine compound, and guanidine. Amine compounds, acetylene urea compounds, urea compounds, isocyanate compounds, azide compounds, etc. are not limited thereto. These crosslinking agents may be used singly or in combination of two or more kinds. Among these, a benzoxazine compound, an epoxy compound, or a cyanate compound is preferable, and a benzoxazine compound is more preferable from the viewpoint of improvement in etching resistance.

As said phenol compound, a well-known thing can be used. For example, as the phenols, in addition to phenols, alkylphenols such as cresols and phenols, polyvalent phenols such as hydroquinone, naphthols, and naphthalene glycols Polycyclic phenols such as bisphenols, bisphenols such as bisphenol A and bisphenol F, and polyfunctional phenol compounds such as phenol novolac and phenol aralkyl resins. Among them, from the viewpoints of heat resistance and solubility, an aralkyl-type phenol resin is preferred.

As said epoxy compound, a well-known thing can be used, for example, it can select from the thing which has 2 or more epoxy groups in 1 molecule. Examples include bisphenol A, bisphenol F, 3,3 ', 5,5'-tetramethyl-bisphenol F, bisphenol S, bisphenol, 2,2'-biphenol, 3,3 ', 5,5'-tetramethyl-4,4'-dihydroxybiphenol, resorcinol, naphthalene glycols and other bivalent phenols, epoxides, and gins- (4-hydroxyphenyl ) Methane, 1,1,2,2- (4-hydroxyphenyl) ethane, ginseng (2,3-epoxypropyl) isocyanurate, trimethylolmethane tripropylene oxide Ethers, trimethylolpropane triglycidyl ether, triethylhydroxyethane triglycidyl ether, phenol novolac, o-cresol novolac, trivalent or higher phenolic epoxides, dicyclopentyl Epoxides of co-condensation resins of dienes and phenols, epoxides of phenol aralkyl resins synthesized from phenols and dichloroparaxylene, etc., from phenols and bischloromethyl biphenyls, etc. Synthetic epoxides of biphenylaralkyl phenol resins, naphthol aralkyl resins synthesized from naphthols and dichloro-p-xylene, etc. These epoxy resins can be used alone or in combination of two or more. Among them, from the viewpoints of heat resistance and solubility, solid epoxy resins at room temperature, such as epoxy resins obtained from phenolaralkyl resins and biphenylaralkyl resins, are used.

As said cyanate ester compound, if it is a compound which has 2 or more cyanate esters in 1 molecule, a well-known thing can be used without a restriction | limiting. In this embodiment, as a preferable cyanate ester compound, the structure which substituted the hydroxyl group of the compound which has 2 or more hydroxyl groups in one molecule with a cyanate ester is mentioned. The cyanate compound is preferably one having an aromatic group, and a structure in which a cyanate is directly bonded to the aromatic group can be suitably used. Examples of such a cyanate ester compound include bisphenol A, bisphenol F, bisphenol M, bisphenol P, bisphenol E, phenol novolac resin, cresol novolac resin, dicyclopentadiene novolac resin, Tetramethyl bisphenol F, bisphenol A phenolic resin, brominated bisphenol A, brominated phenolic resin, trifunctional phenol, 4-functional phenol, naphthalene phenol, biphenyl phenol, phenol aralkyl resin, biphenyl A structure in which hydroxy groups such as phenylaralkyl resin, naphthol aralkyl resin, dicyclopentadiene aralkyl resin, alicyclic phenol, and phosphorus-containing phenol are substituted by cyanate esters. These cyanate ester compounds may be used alone or in a suitable combination of two or more. The cyanate ester compound may be in any form of a monomer, an oligomer, and a resin.

Examples of the amine-based compound include m-phenylene diamine, p-phenylene diamine, 4,4'-diaminodiphenylmethane, and 4,4'-diaminodiphenylpropane. , 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl Hydrazone, 3,4'-diaminodiphenylphosphonium, 3,3'-diaminodiphenylphosphonium, 4,4'-diaminodiphenylsulfide, 3,4'-diamine Diphenyl 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 ] 碸, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 4,4 '-Bis (4-aminophenoxy) biphenyl, 4,4'-bis (3-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] ether , Bis [4- (3-aminophenoxy) phenyl] ether, 9,9-bis (4-aminophenyl) fluorene, 9,9-bis (4-amino-3-chlorophenyl) ) Pyrene, 9,9-bis (4-amino-3-fluorophenyl) pyrene, O-bistoluidine, m-toluidine, 4,4'-diaminobenzene Aniline, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 4-aminophenyl-4-aminobenzoate, 2- (4-amino Phenyl) -6-aminobenzoxazole and the like. Furthermore, examples include 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenyl ether, 3,4 ' -Diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenylphosphonium, 3,3'-diaminodiphenylphosphonium, 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] fluorene, 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 -Aromatic amines such as -aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] ether, bis [4- (3-aminophenoxy) phenyl] ether, etc. Class, diaminocyclohexane, diaminodicyclohexylmethane, dimethyldiaminodicyclohexylmethane, tetramethyldiaminodicyclohexylmethane, diaminodicyclohexylpropane, diamine Bicyclo [2.2.1] heptane, bis (aminomethyl) -bicyclo [2.2.1] heptane, 3 (4), 8 (9) -bis (aminomethyl) tricyclo [5.2.1.02, 6] decane, 1,3-bisaminomethylcyclohexane, iso Alicyclic amines such as ketone diamine, ethylenediamine, hexamethylenediamine, octamethylenediamine, decamethylenediamine, diethylene glycol triamine, triethylene glycol tetraamine, etc. Aliphatic amines and so on.

Examples of the benzoxazine compounds include Pd-type benzoxazines obtained from difunctional diamines and monofunctional phenols, and Fa-types obtained from monofunctional diamines and difunctional phenols. Benzoxazine and so on.

Specific examples of the melamine compound include, for example, compounds obtained by methoxymethylating 1 to 6 methylol groups of hexamethylolmelamine, hexamethoxymethylmelamine, and hexamethylolmelamine. Or its mixture, hexamethoxyethylmelamine, hexamethoxymethylmelamine, 1 to 6 methylol groups of hexamethylolmelamine, or mixtures thereof.

Specific examples of the guanamine compound include, for example, tetramethylolguanamine, tetramethoxymethylguanamine, and one to four methylol groups of tetramethylolguanamine via a methoxymethyl group. Compounds or mixtures thereof, compounds in which one to four methylol groups of tetramethoxyethylguanamine, tetramethoxyguanamine, and tetramethylolguanamine are methylated with methoxy groups Or a mixture thereof.

Specific examples of the acetylene urea compound include, for example, tetramethylol acetylene urea, tetramethoxy acetylene urea, tetramethoxymethyl acetylene urea, and methylol groups 1 to 4 of tetramethylol acetylene urea. Methoxymethylated compounds or mixtures thereof, 1 to 4 methylol groups of tetramethylolacetylacetylurea, or mixtures thereof.

Specific examples of the urea compound include, for example, methoxymethylation of one to four methylol groups of tetramethylolurea, tetramethoxymethylurea, and tetramethylolurea. Compounds or mixtures thereof, tetramethoxyethylurea, and the like.

In this embodiment, a crosslinking agent having at least one allyl group may be used from the viewpoint of improving the crosslinkability. Specific examples of the crosslinking agent having at least one allyl group include 2,2-bis (3-allyl-4-hydroxyphenyl) propane, 1,1,1,3,3, 3-hexafluoro-2,2-bis (3-allyl-4-hydroxyphenyl) propane, bis (3-allyl-4-hydroxyphenyl) fluorene, bis (3-allyl-4 -Allylphenols such as -hydroxyphenyl) sulfide, bis (3-allyl-4-hydroxyphenyl) ether, 2,2-bis (3-allyl-4-cyanooxyphenyl) ) Propane, 1,1,1,3,3,3-hexafluoro-2,2-bis (3-allyl-4-cyanoxyphenyl) propane, bis (3-allyl-4- Allyl cyanide, such as cyanooxyphenyl) fluorene, bis (3-allyl-4-cyanoxyphenyl) sulfide, bis (3-allyl-4-cyanoxyphenyl) ether, etc. Acid esters, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, triallyl isotricyanate, trimethylolpropane diallyl ether , Pentaerythritol allyl ether, etc., but it is not limited to these exemplifiers. These systems may be used alone or as a mixture of two or more types. Among these are 2,2-bis (3-allyl-4-hydroxyphenyl) propane, 1,1,1,3,3,3-hexafluoro-2,2-bis (3-ene Propyl-4-hydroxyphenyl) propane, bis (3-allyl-4-hydroxyphenyl) fluorene, bis (3-allyl-4-hydroxyphenyl) sulfide, bis (3-allyl Allyl phenols such as methyl-4-hydroxyphenyl) ether are preferred.

The content of the cross-linking agent in the lower-layer film forming material is not particularly limited, and is preferably 0.1 to 100 parts by mass, more preferably 5 to 50 parts by mass, and more preferably 10 to 100 parts by mass of the lower layer film forming material. 40 parts by mass. By setting the content of the cross-linking agent to the above range, the occurrence of the mixing phenomenon with the photoresist layer tends to be suppressed, and the antireflection effect is improved, and the film formability after cross-linking tends to be improved.

    [Crosslinking accelerator]    

In the underlayer film forming material of this embodiment, a cross-linking accelerator for promoting cross-linking and hardening reaction may be used as necessary.

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

The above-mentioned crosslinking accelerator is not limited to the following, and examples thereof include 1,8-diazinebicyclo (5,4,0) undecene-7, triethylenediamine, and benzyldimethyl. Tertiary amines such as amines, triethanolamine, dimethylaminoethanol, ginseng (dimethylaminomethyl) phenol, 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methyl Imidazole, 2-phenyl-4-methylimidazole, 2-heptylimidazole, 2,4,5-triphenylimidazole and other imidazoles, tributylphosphine, methyldiphenylphosphine, triphenyl Phosphine, diphenylphosphine, phenylphosphine and other organic phosphines, tetraphenylphosphonium. Tetraphenylborate, tetraphenylphosphonium. Ethyltriphenylborate, tetrabutylphosphonium. Tetrabutyl borate and other tetra-substituted hydrazones. Tetra-substituted borate, 2-ethyl-4-methylimidazole. Tetraphenylborate, N-methylmorpholine. Tetraphenylborate and the like.

As the compounding amount of the cross-linking accelerator, when the entire lower-layer film-forming material is generally set to 100 parts by mass, it is preferably 0.1 to 10 parts by mass, and from the viewpoint of ease of control and economy, it is preferably 0.1 to 5 parts by mass. Parts, more preferably 0.1 to 3 parts by mass.

    [Free radical polymerization initiator]    

A free-radical polymerization initiator may be blended into the underlayer film-forming material of this embodiment as necessary. The radical polymerization initiator may be a photopolymerization initiator that starts radical polymerization by light, or a thermal polymerization initiator that starts radical polymerization by heat.

There is no particular limitation on such a radical polymerization initiator, and a conventional user can be suitably used. Examples include 1-hydroxycyclohexylphenyl ketone, benzyldimethylketal, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1- [4- (2-hydroxy Ethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propanone) ) -Benzyl] phenyl} -2-methylpropane-1-one, 2,4,6-trimethylbenzylfluorenyl-diphenyl-phosphine oxide, bis (2,4,6-tri Ketone-based photopolymerization initiators such as methyl benzamidine) -phenylphosphine oxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, methyl cyclohexanone peroxide, methyl ethyl Hydrazone acetate peroxide, acetamyl 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-butyl (Peryloxy) -2-methylcyclohexane, 1,1-bis (t-butylperoxy) -cyclohexane, 1,1-bis (t-butylperoxy) cyclododecyl Alkane, 1,1-bis (t-butylperoxy) butane, 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane, p-menthane hydroperoxide Compounds, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydrogen Oxide, cumene hydroperoxide, t-hexyl hydroperoxide, t-butyl hydroperoxide, α, α'-bis (t-butylperoxy) diisopropylbenzene, di Cumene peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, t-butylcumyl peroxide, di-t-butyl Methyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3, isobutylfluorenyl peroxide, 3,5,5-trimethylhexyl Peroxide, octyl peroxide, lauryl peroxide, stearyl peroxide, succinate peroxide, m-toluenyl benzyl peroxide, benzyl peroxide , Di-n-propylperoxydicarbonate, diisopropylperoxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, di-2-ethoxy Ethylperoxydicarbonate, di-2-ethoxyhexylperoxydicarbonate, di-3-methoxybutylperoxydicarbonate, di-s-butylperoxydicarbonate Carbonate, bis (3-methyl-3-methoxybutyl) peroxydicarbonate, α, α'-bis (neodecanylperoxy) diisopropylbenzene, cumyl Peroxyneodecanoate 1,1,3,3-tetramethylbutylperoxy neodecanoate, 1-cyclohexyl-1-methylethylperoxy neodecanoate, t-hexylperoxy neodecanoate , T-butylperoxy neodecanoate, t-hexylperoxy tert-valerate, t-butylperoxy t-valerate, 1,1,3,3-tetramethylbutyl peroxy Oxy-2-ethylhexanoate, 2,5-dimethyl-2,5-bis (2-ethylhexylperoxy) hexanoate, 1-cyclohexyl-1-methylethyl Peroxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-hexylperoxy Isopropyl monocarbonate, t-butylperoxyisobutyrate, t-butylperoxymaleate, t-butylperoxy-3,5,5-trimethylhexanoate Ester, t-butylperoxylaurate, t-butylperoxyisopropylmonocarbonate, t-butylperoxy-2-ethylhexylmonocarbonate, t-butylperoxy Acetate, t-butylperoxy-m-toluenylbenzoate, t-butylperoxybenzoate, bis (t-butylperoxy) isophthalate , 2,5-dimethyl-2,5-bis (m-toluenylperoxy) hexane, t-hexylperoxybenzoate, 2,5-dimethyl-2,5 - Bis (benzylfluorenylperoxy) hexane, t-butylperoxyallyl monocarbonate, t-butyltrimethylsilyl peroxide, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 2,3-dimethyl-2,3-diphenylbutane and other organic peroxide-based polymerization initiators.

Further examples include 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile and 1-[(1-cyano-1-methylethyl) azo] methyl. Amidine, 1,1'-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobisisobutyronitrile , 2,2'-Azobis (2,4-dimethylvaleronitrile), 2,2'-Azobis (2-methylpropane) dihydrochloride, 2,2'-Azobis (2-methyl-N-phenylpropionamidine) dihydrochloride, 2,2'-azobis [N- (4-chlorophenyl) -2-methylpropionamidine] dihydrochloride, 2 , 2'-Azobis [N- (4-hydrophenyl) -2-methylpropionamidine] dihydrochloride, 2,2'-Azobis [2-methyl-N- (phenylmethyl) Propyl) propanyl] dihydrochloride, 2,2'-azobis [2-methyl-N- (2-propenyl) propanyl] dihydrochloride, 2,2'-azobis [N -(2-hydroxyethyl) -2-methylpropanidine] dihydrochloride, 2,2'-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] di Hydrochloride, 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-tetrahydropyrimidine- 2-yl) propane] dihydrochloride, 2,2'-azobis [2- (5-hydroxy-3,4,5,6-tetra Hydropyrimidin-2-yl) propane] dihydrochloride, 2,2'-azobis [2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl] propane] dihydrochloride Salt, 2,2'-azobis [2- (2-imidazolin-2-yl) propane], 2,2'-azobis [2-methyl-N- [1,1-bis (hydroxyl (Methyl) -2-hydroxyethyl] propanamide], 2,2'-azobis [2-methyl-N- [1,1-bis (hydroxymethyl) ethyl] propanamine], 2,2'-Azobis [2-methyl-N- (2-hydroxyethyl) propanilamine], 2,2'-Azobis (2-methylpropylamine), 2,2 ' -Azobis (2,4,4-trimethylpentane), 2,2'-azobis (2-methylpropane), dimethyl-2,2-azobis (2-methyl Propionate), 4,4'-azobis (4-cyanovaleric acid), 2,2'-azobis [2- (hydroxymethyl) propionitrile], etc. . As the radical polymerization initiator of this embodiment, one of these may be used alone, or two or more thereof may be used in combination, and other known polymerization initiators may be used in combination.

The content of the radical polymerization initiator may be a stoichiometrically necessary amount. When the lower layer film forming material is set to 100 parts by mass, it is preferably 0.05 to 25 parts by mass, and 0.1 to 10 parts by mass. Serving is better. When the content of the radical polymerization initiator is 0.05 parts by mass or more, the curing tends to be insufficient, and when the content of the radical polymerization initiator is 25 parts by mass or less, the lower layer may be prevented from being damaged. The long-term storage stability of the film-forming material at room temperature tends to be stable.

    [Acid generator]    

The layer film-forming material under the present embodiment may contain an acid generator, if necessary, from the viewpoint of further promoting a crosslinking reaction due to heat and the like. As the acid generator, there are known that an acid is generated by thermal decomposition and an acid is generated by light irradiation, and any of them can be used. As the acid generator, for example, those described in International Publication No. 2013/024779 can be used.

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

    [Basic compound]    

The underlayer film-forming material of this embodiment may contain a basic compound from the viewpoint of improving storage stability and the like.

The basic compound is used to prevent the acid from the trace amount of acid produced by the acid generator from promoting the cross-linking reaction to the quencher of the acid. The basic compound is not particularly limited, and examples thereof include those described in International Publication No. 2013/024779.

The content of the basic compound in the lower-layer film-forming material is not particularly limited, and is preferably 0.001 to 2 parts by mass, and more preferably 0.01 to 1 part by mass, relative to 100 parts by mass of the lower-layer film forming material. By setting the content of the basic compound to the above range, there is a tendency that the cross-linking reaction is not excessively impaired and storage stability is improved.

    [Other additives]    

In addition, the underlayer film forming material of this embodiment may contain other resins and / or compounds for the purpose of controlling the hardening or absorbance imparted by heat or light. Examples of such other resins and compounds include naphthol resins, naphthol denatured resins, and phenol denatured resins of naphthalene resins; polyhydroxystyrene, dicyclopentadiene resins, and (meth) acrylates , Dimethacrylate, trimethacrylate, tetramethacrylate, vinyl naphthalene, polynaphthalene, naphthalene ring, phenanthrenequinone, fluorene, biphenyl ring, thiophene, indene, etc. Atomic heterocyclic resins or resins that do not contain aromatic rings; rosin-based resins, cyclodextrin, adamantane (poly) alcohols, tricyclodecane (poly) alcohols, and derivatives containing alicyclic structures Resins, compounds, etc. are not limited to these. In addition, the underlayer film forming material of this embodiment may contain a known additive. The known additives are not limited to the following, and examples thereof include heat and / or photocuring catalysts, polymerization inhibitors, flame retardants, fillers, coupling agents, thermosetting resins, and photocuring resins. , Dyes, pigments, thickeners, slip agents, defoamers, leveling agents, UV absorbers, surfactants, colorants, non-ionic surfactants, etc.

    [Formation method of lower layer film and multilayer photoresist pattern for lithography]    

The underlayer film for lithography according to this embodiment is formed from the above-mentioned underlayer film forming material.

In addition, the photoresist pattern forming method of this embodiment includes forming an underlayer film on a substrate using the composition, forming at least one photoresist layer on the underlayer film, and irradiating a predetermined area of the photoresist layer with radiation. Perform the development steps. More specifically, the method includes the step (A-1) of forming an underlayer film using the underlayer film forming material of this embodiment on a substrate; and the step (A-2) of forming at least one photoresist layer on the aforementioned underlayer film; After the step (A-2), a step (A-3) of irradiating a predetermined area of the photoresist layer with radiation and performing development is performed.

In addition, the method for forming a circuit pattern according to this embodiment includes forming an underlayer film on a substrate using the composition, forming an intermediate layer film using a photoresist intermediate layer film material on the lower layer film, and forming at least one layer on the intermediate layer film. Step of photoresist layer; step of irradiating a predetermined area of the photoresist layer with radiation to develop a photoresist pattern; and using the photoresist pattern as a mask to etch the intermediate layer film to obtain the intermediate The layer film pattern is used as an etching mask to etch the aforementioned lower layer film, and the lower layer film pattern is obtained as an etching mask to etch the substrate to form a pattern on the substrate.

More specifically, the method includes the steps (B-1) of forming an underlayer film using the underlayer film forming material of this embodiment on a substrate; and forming an interlayer film using a photoresist interlayer film material containing silicon atoms on the aforementioned underlayer film. Step (B-2); step (B-3) of forming at least one photoresist layer on the aforementioned intermediate layer film; after the aforementioned step (B-3), irradiating a predetermined area of the aforementioned photoresist layer with radiation and displaying Step (B-4) of forming a photoresist pattern on the image; after the aforementioned step (B-4), the intermediate layer film is etched by using the photoresist pattern as a mask to obtain the intermediate layer pattern Step (B-5) of etching the aforementioned lower layer film as an etching mask, and obtaining the pattern of the lower layer film as an etching mask to etch the substrate to form a pattern on the substrate.

As long as the underlayer film for lithography according to this embodiment is formed from an underlayer film forming material according to this embodiment, the formation method is not particularly limited, and a known method can be applied. For example, after applying the underlayer film material of the present embodiment to a substrate by a known coating method or printing method such as spin coating or screen printing, the organic solvent is removed by volatilization, etc., followed by a known method. Cross-linking and hardening can form an underlayer film for lithography in this embodiment. Examples of the crosslinking method include methods such as thermal curing and light curing. By removing the organic solvent and removing it, an underlayer film can be formed.

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

After making the lower layer film, in the case of the two-layer process, it is better to make a silicon-containing photoresist layer or a single-layer photoresist composed of ordinary hydrocarbons. In the case of the three-layer process, it is made on it. It is better to use a silicon-containing intermediate layer and then make a single-layer photoresist layer without silicon on it. In this case, a known material can be used as the photoresist material for forming the photoresist layer.

After the lower film is made on the substrate, in the case of a two-layer process, a silicon-containing photoresist layer or a single-layer photoresist composed of ordinary hydrocarbons can be produced on the lower film. In the case of a three-layer process, a silicon-containing intermediate layer can be fabricated on the underlying film, and a silicon-free single-layer photoresist layer can be fabricated on the silicon-containing intermediate layer. In these cases, the photoresist material for forming the photoresist layer can be appropriately selected and used from known ones, and is not particularly limited.

As a silicon-containing photoresist material for a two-layer process, it is preferable to use a silicon atom-containing polymer including a polysilsesquioxane derivative or a vinyl silane derivative from the viewpoint of oxygen gas etching resistance. It is used as a matrix polymer, as well as positive photoresist materials such as organic solvents, acid generators, and necessary basic compounds. As the silicon atom-containing polymer, a known polymer used in this photoresist material can be used.

As a silicon-containing intermediate layer for a three-layer process, it is preferable to use a polysilsesquioxane-based intermediate layer. When the intermediate layer has an effect as an anti-reflection film, there is a tendency to effectively suppress reflection. For example, in the 193nm exposure process, when the lower layer film uses a material containing a large number of aromatic groups and has high substrate etching resistance, the k value tends to increase and the substrate reflection becomes higher. However, by using an intermediate layer to suppress reflection, Then, the substrate reflection pressure can be lower than 0.5%. As an intermediate layer having such an anti-reflection effect, it is not limited to the following. For 193 nm exposure, it is preferable to use a cross-linking with acid or heat by introducing a light-absorbing group having a phenyl group or a silicon-silicon bond. Polysilsesquioxane.

Alternatively, an intermediate layer formed by a Chemical Vapour Deposition (CVD) method may be used. The intermediate layer having a high effect as an antireflection film produced by the CVD method is not limited to the following, and for example, a SiON film is known. Generally, forming an intermediate layer by a CVD method and a wet process such as a spin coating method or screen printing has the advantages of simplicity and cost. In addition, in the three-layer process, the upper layer photoresist may be any of a positive type and a negative type, and the same as a commonly used single layer photoresist may be used.

In addition, the underlayer film of this embodiment can also be used as an ordinary antireflection film for a single-layer photoresist or a base material for suppressing pattern collapse. Since the underlayer film of this embodiment has excellent etching resistance for substrate processing, it can also be expected to function as a hard mask for substrate processing.

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

In addition, the exposure light may be appropriately selected and used according to the photoresist material used. Generally, it is a high-energy line with a wavelength of 300 nm or less. Specific examples include excimer lasers of 248 nm, 193 nm, and 157 nm, soft X-rays of 3 to 20 nm, electron beams, and X-rays.

The photoresist pattern formed by the above method becomes a person whose pattern collapse is suppressed by the underlying film. Therefore, by using the underlayer film of this embodiment, a finer pattern can be obtained, and the exposure amount necessary to obtain the photoresist pattern can be reduced.

Next, etching is performed using the obtained photoresist pattern as a mask. As the etching of the lower film in the two-layer process, gas etching is preferably used. The gas etching is preferably an etching using oxygen. In addition to oxygen, inert gases such as He, Ar, or CO, CO ₂ , NH ₃ , SO ₂ , N ₂ , NO ₂ , H ₂ gases can be added. Moreover, instead of using oxygen, gas etching may be performed using only CO, CO ₂ , NH ₃ , N ₂ , NO ₂ , and H ₂ gas. In particular, the latter gas is preferably used for side wall protection in order to prevent low cut of the pattern side wall.

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

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

As the intermediate layer, a polysilsesquioxane-based intermediate layer is preferably used. When the photoresist interlayer film has an effect as an antireflection film, there is a tendency that reflection can be effectively suppressed. The specific material of the polysilsesquioxane-based intermediate layer is not limited to the following. For example, Japanese Patent Application Laid-Open No. 2007-226170 (Patent Document 8) and Japanese Patent Application Laid-Open No. 2007-226204 (Patent Document 9) can be used. Recorder.

In addition, the etching of the second substrate can also be performed by a conventional method. For example, if the substrate is SiO ₂ or SiN, it is etched mainly with a chlorofluorocarbon gas, and if it is p-Si or Al or W, the substrate is etched. Etching mainly with chlorine-based and bromine-based gases is performed. When the substrate is etched with a chlorofluorocarbon-based gas, the silicon-containing photoresist in the two-layer photoresist process and the silicon-containing intermediate layer in the three-layer process are peeled simultaneously with the substrate processing. On the other hand, when the substrate is etched with a chlorine-based or bromine-based gas, the stripping of the silicon-containing photoresist layer or the silicon-containing intermediate layer is performed separately. Generally, after the substrate is processed, dry-etching stripping with a chlorofluorocarbon gas is performed. .

The underlayer film of this embodiment has a feature of excellent substrate etching resistance. In addition, as the substrate, a known one can be appropriately selected and used without particular limitation, and examples thereof include Si, α-Si, p-Si, SiO ₂ , SiN, SiON, W, TiN, and Al. The substrate may be a laminated body having a film to be processed (substrate to be processed) on a substrate (support). Examples of such processed films include various low-k films such as Si, SiO ₂ , SiON, SiN, p-Si, α-Si, W, W-Si, Al, Cu, Al-Si, and the like, and The stop film and the like are usually made of a material different from the base material (support). In addition, the thickness of the substrate or film to be processed is not particularly limited, but it is usually about 50 to 10,000 nm, and more preferably 75 to 5,000 nm.

The photoresistive permanent film formed by coating the composition of this embodiment mode is preferably a permanent film that remains in the final product after a photoresist pattern is formed as necessary. As a specific example of the permanent film, in a semiconductor device, a package bonding layer such as a solder resist, a packaging material, an underfill material, and a circuit element, or a bonding layer of an integrated circuit element and a circuit substrate may be mentioned. For a thin display, Examples thereof include a thin film transistor protective film, a liquid crystal color filter protective film, a black matrix, and a spacer. In particular, the permanent film composed of the composition of this embodiment is not only excellent in heat resistance and moisture resistance, but also has a very excellent advantage that the pollution caused by the sublimation component is small. In particular, it is a display material that has less deterioration in image quality due to severe pollution, and has both high sensitivity, high heat resistance, and moisture absorption reliability.

When the composition of this embodiment is used for a permanent photoresist film application, in addition to the hardener, various additives such as other resins, surfactants or dyes, fillers, cross-linking agents, and dissolution accelerators are added as necessary. By dissolving in an organic solvent, it can be used as a composition for a permanent photoresist film.

The film-forming composition for lithography or the composition for a photoresistive permanent film according to this embodiment can be prepared by blending the above-mentioned components with a mixer or the like. In addition, when the composition for a photoresist underlayer film or the composition for a photoresistive permanent film of this embodiment contains a filler or a pigment, it can be dispersed or mixed using a dispersing device such as a dissolver, a homogenizer, and a three-roll mill. Perform modulation.

    [Example]    

Hereinafter, this embodiment will be described in more detail based on synthesis examples and examples. However, this embodiment is not intended to be limited by these examples.

    (Carbon concentration and oxygen concentration)    

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

Device: CHN Corder MT-6 (Yanko Analytical Industry Co., Ltd.)

    (Molecular weight)    

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

Further, a gel permeation chromatography (GPC) analysis was performed under the following conditions to obtain a weight average molecular weight (Mw), a number average molecular weight (Mn), and a dispersion (Mw / Mn) in terms of polystyrene.

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

Column: KF-80M × 3

Eluent: THF 1mL / min

Temperature: 40 ° C

    (Solubility)    

At 23 ° C, make the compound 3 to propylene glycol monomethyl ether (PGME), cyclohexanone (CHN), ethyl lactate (EL), methylpentyl ketone (MAK) or tetramethylurea (TMU). The solution was stirred and dissolved in a mass% solution, and the results after 1 week were evaluated based on the following criteria.

Evaluation A: It was visually confirmed that no precipitate was found in any of the solvents

Evaluation C: Precipitation was visually confirmed in all solvents

    (Structure of the compound)    

The structure of the compound was measured and confirmed by ¹ H-NMR using the "Advance600II spectrometer" manufactured by Bruker under the following conditions.

Frequency: 400MHz

Solvent: d6-DMSO

Internal standard: TMS

Measuring temperature: 23 ℃

    <Synthesis Example 1> Synthesis of XBisN-1    

In a 100-ml container equipped with a stirrer, a cooling tube, and a buret, 3.20 g (20 mmol) of 2,6-naphthalene glycol (a test reagent manufactured by Sigma-Aldrich) and 4-biphenylcarboxaldehyde (Mitsubishi Gas (1.82 g (10 mmol) manufactured by Chemical Co., Ltd.) was put in 30 ml of methyl isobutyl ketone, 5 ml of 95% sulfuric acid was added, and the reaction solution was stirred at 100 ° C. for 6 hours to perform a reaction. Next, the reaction solution was concentrated, and 50 g of pure water was added to precipitate a reaction product. After cooling to room temperature, filtration was performed to isolate the reaction product. The solid obtained was filtered and dried, and then separated and purified by column chromatography to obtain 3.05 g of the target compound represented by the following formula. It was confirmed by 400 MHz- ¹ H-NMR that it has a chemical structure of the following formula.

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

δ (ppm) 9.7 (2H, O-H), 7.2 ~ 8.5 (19H, Ph-H), 6.6 (1H, C-H)

Furthermore, from the fact that the proton signals at the 3rd and 4th positions are double peaks, the substitution position of 2,6-naphthalenediol was confirmed to be the 1st position.

    <Synthesis Example 1A> Synthesis of E-XBisN-1    

In a 100-ml container equipped with a stirrer, a cooling tube, and a burette, put 10 g (21 mmol) of the compound represented by the formula (XBisN-1) and 14.8 g (107 mmol) of potassium carbonate in 50 ml of dimethylformamide. Then, 6.56 g (54 mmol) of 2-chloroethyl acetate was added, and the reaction solution was stirred at 90 ° C. for 12 hours to perform a reaction. Next, the reaction solution was cooled in an ice bath to precipitate crystals, and then separated by filtration. Thereafter, 40 g of the above crystals, 40 g of methanol, 100 g of THF, and a 24% aqueous sodium hydroxide solution were placed in a 100 ml container equipped with a stirrer, a cooling tube, and a burette, and the reaction solution was stirred under reflux for 4 hours and reacted. Thereafter, the reaction solution was cooled in an ice bath, and the precipitated solid was filtered and dried, and then separated and purified by column chromatography to obtain 5.9 g of the target compound represented by the following formula. A chemical structure having the following formula was confirmed by 400 MHz- ¹ H-NMR.

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

δ (ppm) 8.6 (2H, OH), 7.2 ~ 7.8 (19H, Ph-H), 6.7 (1H, C-H), 4.0 (4H, -O-CH _2- ), 3.8 (4H, -CH ₂ -OH)

    <Synthesis Example 2> Synthesis of BisF-1    

Prepare a 200 ml container with a blender, cooling tube, and burette. In this container, 30 g (161 mmol) of 4,4-biphenol (test reagent manufactured by Tokyo Chemical Industry Co., Ltd.), 15 g (82 mmol) of 4-biphenylaldehyde (manufactured by Mitsubishi Gas Chemical Co., Ltd.), and 100 ml of butyl acetate were added, and added. 3.9 g (21 mmol) of p-toluenesulfonic acid (test reagent manufactured by Kanto Chemical Co., Ltd.) was prepared as a reaction solution. The reaction solution was stirred at 90 ° C for 3 hours and reacted. Next, the reaction solution was concentrated, and 50 g of heptane was added to precipitate a reaction product. After cooling to room temperature, filtration was performed to isolate the reaction product. The solid obtained by filtration was dried, and then separated and purified by column chromatography to obtain 5.8 g of the target compound (BisF-1) represented by the following formula.

Furthermore, the following peaks were found by 400 MHz- ¹ H-NMR, and it was confirmed that the chemical structure has the following formula.

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

δ (ppm) 9.4 (4H, O-H), 6.8 ~ 7.8 (22H, Ph-H), 6.2 (1H, C-H)

As for the obtained compound, the molecular weight measured by the aforementioned method was 536.

    <Synthesis example 2A>    

In a 100-ml container equipped with a stirrer, a cooling tube, and a burette, put 11.2 g (21 mmol) of the compound represented by the above formula (BisF-1) and 14.8 g (107 mmol) of potassium carbonate in 50 ml of dimethylformamidine To the amine, 6.56 g (54 mmol) of 2-chloroethyl acetate was added, and the reaction solution was stirred at 90 ° C. for 12 hours to perform a reaction. Next, the reaction solution was cooled in an ice bath to precipitate crystals, and then separated by filtration. Thereafter, 40 g of the above crystals, 40 g of methanol, 100 g of THF, and a 24% aqueous sodium hydroxide solution were placed in a 100 ml container equipped with a stirrer, a cooling tube, and a burette, and the reaction solution was stirred under reflux for 4 hours and reacted. Thereafter, the reaction solution was cooled in an ice bath, and the precipitated solid matter was filtered and dried. Then, separation and purification by column chromatography were performed to obtain the objective represented by the following formula (E-BisF-1). Compound 5.9 g.

A chemical structure having the following formula (E-BisF-1) was confirmed by 400 MHz- ¹ H-NMR.

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

δ (ppm) 8.6 (4H, OH), 6.8 ~ 7.8 (22H, Ph-H), 6.2 (1H, CH), 4.0 (8H, -O-CH _2- ), 3.8 (8H, -CH ₂ -OH )

As for the obtained compound, the molecular weight measured by the aforementioned method was 712.

    <Synthesis Example 1-1> Synthesis of EaXBisN-1    

In a 100 ml container equipped with a stirrer, a cooling tube and a burette, 10.0 g (21 mmol) of the compound represented by the above formula (XBisN-1), 6.1 g of epoxypropylmethacrylate, and 0.5 of triethylamine g, 0.05 g of p-methoxyphenol was put into 50 ml of methyl isobutyl ketone, and the reaction was carried out with stirring for 24 hours while being heated to 80 ° C with stirring.

The reaction solution was cooled to 50 ° C., and the reaction solution was dropped into a solid precipitated in pure water and dried, and then separated and purified by column chromatography to obtain the following formula (EaXBisN-1) 3.0 g of the target compound.

By 400 MHz- ¹ H-NMR, a chemical structure having the following formula (EaXBisN-1) was confirmed.

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

δ (ppm) 7.2 ~ 7.8 (19H, Ph-H), 6.7 (1H, CH), 6.5 (4H, = CH2), 5.7 (2H, -OH), 4.1 ~ 4.7 (10H, -O-CH2-CH -CH2-O-), 2.0 (6H, -CH3)

The obtained compound had a molecular weight measured by the aforementioned method of 750.

The thermal decomposition temperature was 370 ° C, the glass transition temperature was 95 ° C, and the melting point was 200 ° C. High heat resistance was successfully confirmed.

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

A compound was reacted in the same manner as in Synthesis Example 1-1 except that the compound represented by the above formula (E-XBisN-1) was replaced with the compound represented by the above formula (XBisN-1), and the following was obtained 3.2 g of the target compound represented by the formula (EaE-XBisN-1).

By 400 MHz- ¹ H-NMR, a chemical structure having the following formula (EaE-XBisN-1) was confirmed.

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

7.2 ~ 7.8 (19H, Ph-H), 6.7 (1H, CH), 6.5 (4H, = CH2), 5.7 (2H, -OH), 4.1 ~ 4.7 (10H, -O-CH2-CH-CH2-O -), 4.0 (4H, -O-CH _2- ), 3.8 (4H, -CH ₂ -OH), 2.0 (6H, -CH3)

As for the obtained compound, the molecular weight measured by the aforementioned method was 838.

The thermal decomposition temperature was 360 ° C, the glass transition temperature was 90 ° C, and the melting point was 195 ° C, and high heat resistance was successfully confirmed.

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

A reaction was carried out in the same manner as in Synthesis Example 1-1 except that the compound represented by the above formula (BisF-1) was replaced with the compound represented by the above formula (XBisN-1), and the following formula ( 2.5 g of the target compound shown by EaBisF-1).

By 400 MHz- ¹ H-NMR, a chemical structure having the following formula (EaBisF-1) was confirmed.

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

δ (ppm) 6.8 ~ 7.8 (22H, Ph-H), 6.5 (8H, = CH2), 6.2 (1H, CH), 5.7 (4H, -OH), 4.1 ~ 4.7 (2OH, -O-CH2-CH -CH2-O-), 2.0 (12H, -CH3)

As for the obtained compound, the molecular weight measured by the aforementioned method was 1104.

The thermal decomposition temperature was 365 ° C, the glass transition temperature was 60 ° C, and the melting point was 185 ° C. High heat resistance was successfully confirmed.

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

A compound was reacted in the same manner as in Synthesis Example 1-1, except that the compound represented by the formula (E-BisF-1) was replaced with the compound represented by the formula (XBisN-1), and the following was obtained. 2.6 g of the target compound represented by the formula (EaE-BisF-1).

By 400 MHz- ¹ H-NMR, a chemical structure having the following formula (EaE-BisF-1) was confirmed.

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

δ (ppm) 6.8 ~ 7.8 (22H, Ph-H), 6.5 (8H, = CH2), 6.2 (1H, C-H), 5.7 (4H, -OH), 4.1 ~ 4.7 (2OH, -O-CH2 -CH-CH2-O-), 4.0 (8H, -O-CH _2- ), 3.8 (8H, -CH ₂ -OH), 2.0 (12H, -CH3)

As for the obtained compound, the molecular weight measured by the aforementioned method was 1281.

The thermal decomposition temperature was 355 ° C, the glass transition temperature was 55 ° C, and the melting point was 175 ° C. High heat resistance was successfully confirmed.

    <Synthesis Example 3> Synthesis of BiN-1    

In a 300-mL container equipped with a stirrer, a cooling tube, and a burette, 10 g (69.0 mmol) of 2-naphthol (test reagent manufactured by Sigma-Aldrich) was melted at 120 ° C, and 0.27 g of sulfuric acid was added and added. 2.7 g (13.8 mmol) of 4-ethenylbiphenyl (reagent manufactured by Sigma-Aldrich), and the contents were stirred at 120 ° C for 6 hours and reacted to obtain a reaction solution. Next, 100 mL of N-methyl-2-pyrrolidone (manufactured by Kanto Chemical Co., Ltd.) and 50 mL of pure water were added to the reaction solution, and then extracted with ethyl acetate. Next, pure water was added until it became neutral, and after liquid separation, it concentrated and obtained the solution.

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

As for the obtained compound (BiN-1), the molecular weight measured by the above method was 466.

With respect to the obtained compound (BiN-1), when the NMR measurement was performed under the above-mentioned measurement conditions, the following peaks were found, and a chemical structure having the following formula (BiN-1) was confirmed.

δ (ppm) 9.69 (2H, O-H), 7.01 ~ 7.67 (21H, Ph-H), 2.28 (3H, C-H)

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

In a 100 ml container equipped with a stirrer, a cooling tube, and a burette, 10.5 g (21 mmol) of the compound (BiN-1) represented by the above formula and 14.8 g (107 mmol) of potassium carbonate were placed in 50 ml of dimethylformamidine. To the amine, 6.56 g (54 mmol) of 2-chloroethyl acetate was added, and the reaction solution was stirred at 90 ° C. for 12 hours to perform a reaction. Next, the reaction solution was cooled in an ice bath to precipitate crystals, and then separated by filtration. Thereafter, the above-mentioned crystals 40 g, 40 g of methanol, 100 g of THF, and 24% aqueous sodium hydroxide solution were placed in a 100-ml container equipped with a stirrer, a cooling tube, and a burette, and the reaction solution was stirred under reflux for 5 hours and reacted. Thereafter, the reaction solution was cooled in an ice bath, and the precipitated solid was filtered and dried, and then separated and purified by column chromatography to obtain 4.6 g of the target compound represented by the following formula. A chemical structure having the following formula was confirmed by 400 MHz- ¹ H-NMR.

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

δ (ppm) 8.6 (2H, OH), 7.2 ~ 7.8 (19H, Ph-H), 6.7 (1H, CH), 4.0 (4H, -O-CH _2- ), 3.8 (4H, -CH ₂ -OH )

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

A reaction was carried out in the same manner as in Synthesis Example 1-1 except that the compound represented by the above formula (BiN-1) was replaced with the compound represented by the above formula (XBisN-1), and the following formula ( 3.5 g of the target compound shown by EaBiN-1).

By 400 MHz- ¹ H-NMR, a chemical structure having the following formula (EaBiN-1) was confirmed.

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

δ (ppm) 7.2 ~ 7.8 (21H, Ph-H), 6.5 (4H, = CH2), 5.7 (2H, -OH), 4.1 ~ 4.7 (10H, -O-CH2-CH-CH2-O-), 2.3 (3H, -CH3), 2.0 (6H, -CH3)

The obtained compound had a molecular weight measured by the aforementioned method of 750.

The thermal decomposition temperature was 380 ° C, the glass transition temperature was 85 ° C, and the melting point was 203 ° C. High heat resistance was successfully confirmed.

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

A compound was reacted in the same manner as in Synthesis Example 1-1 except that the compound represented by the above formula (E-BiN-1) was replaced with the compound represented by the above formula (XBisN-1), and the following was obtained 2.9 g of the target compound represented by formula (EaE-BiN-1).

By 400 MHz- ¹ H-NMR, a chemical structure having the following formula (EaE-BiN-1) was confirmed.

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

δ (ppm) 7.2 ~ 7.8 (21H, Ph-H), 6.5 (4H, = CH2), 5.7 (2H, -OH), 4.1 ~ 4.7 (10H, -O-CH2-CH-CH2-O-), 4.0 (4H, -O-CH _2- ), 3.8 (4H, -CH ₂ -OH), 2.3 (3H, -CH3), 2.0 (6H, -CH3)

As for the obtained compound, the molecular weight measured by the aforementioned method was 838.

The thermal decomposition temperature was 371 ° C, the glass transition temperature was 72 ° C, and the melting point was 221 ° C. High heat resistance was successfully confirmed.

    <Synthesis Example 4> Synthesis of BiP-1    

1.0 g of the objective compound represented by following formula (BiP-1) was obtained by making it react similarly to the synthesis example 3 except having replaced 2-naphthol with o-phenylphenol.

The obtained compound (BiP-1) had a molecular weight measured by the above method of 466.

The obtained compound (BiP-1) was found to have a chemical structure of the following formula (BiP-1) when the following peaks were found when the NMR measurement was performed under the above measurement conditions.

δ (ppm) 9.67 (2H, O-H), 6.98 ~ 7.60 (25H, Ph-H), 2.25 (3H, C-H)

    <Synthesis Example 4A> Synthesis of E-BiP-1    

In a 100-ml container equipped with a stirrer, a cooling tube, and a burette, put 11.2 g (21 mmol) of the compound represented by the above formula (BiP-1) and 14.8 g (107 mmol) of potassium carbonate in 50 ml of dimethylformamidine To the amine, 6.56 g (54 mmol) of 2-chloroethyl acetate was added, and the reaction solution was stirred at 90 ° C. for 12 hours to perform a reaction. Next, the reaction solution was cooled in an ice bath to precipitate crystals, and then separated by filtration. Thereafter, 40 g of the above crystals, 40 g of methanol, 100 g of THF, and a 24% aqueous sodium hydroxide solution were placed in a 100 ml container equipped with a stirrer, a cooling tube, and a burette, and the reaction solution was stirred under reflux for 4 hours and reacted. Thereafter, the reaction solution was cooled in an ice bath, and the precipitated solid was filtered and dried, and then separated and purified by column chromatography to obtain a compound represented by the following formula (E-BiP-1). 5.9 g of the target compound.

By 400 MHz- ¹ H-NMR, a chemical structure having the following formula (E-BiP-1) was confirmed.

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

δ (ppm) 8.6 (4H, OH), 6.8 ~ 7.6 (25H, Ph-H), 4.0 (4H, -O-CH _2- ), 3.8 (4H, -CH ₂ -OH), 2.2 (3H, CH )

As for the obtained compound, the molecular weight measured by the aforementioned method was 606.

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

A compound was reacted in the same manner as in Synthesis Example 1-1 except that the compound represented by the formula (XBisN-1) was replaced with the compound represented by the formula (BiP-1), and the following formula ( 3.5 g of the target compound shown by EaBiP-1).

By 400 MHz- ¹ H-NMR, a chemical structure having the following formula (EaBiP-1) was confirmed.

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

δ (ppm) 6.8 ~ 7.8 (25H, Ph-H), 6.5 (4H, = CH2), 5.7 (2H, -OH), 4.1 ~ 4.7 (10H, -O-CH2-CH-CH2-O-), 2.3 (3H, -CH3), 2.2 (3H, CH), 2.0 (6H, -CH3)

The thermal decomposition temperature was 371 ° C, the glass transition temperature was 78 ° C, and the melting point was 212 ° C. High heat resistance was successfully confirmed.

As for the obtained compound, the molecular weight measured by the aforementioned method was 802.

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

A reaction was performed in the same manner as in Synthesis Example 1-1 except that the compound represented by the above formula (E-BiP-1) was replaced with the compound represented by the above formula (XBisN-1), and the following was obtained. 3.2 g of the target compound represented by formula (EaE-BiP-1).

By 400 MHz- ¹ H-NMR, a chemical structure having the following formula (EaE-BiP-1) was confirmed.

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

δ (ppm) 6.8 ~ 7.8 (25H, Ph-H), 6.5 (4H, = CH2), 5.7 (2H, -OH), 4.1 ~ 4.7 (10H, -O-CH2-CH-CH2-O-), 4.0 (4H, -O-CH _2- ), 3.8 (4H, -CH ₂ -OH), 2.3 (3H, -CH3), 2.0 (6H, -CH3)

As for the obtained compound, the molecular weight measured by the aforementioned method was 890.

The thermal decomposition temperature was 362 ° C, the glass transition temperature was 75 ° C, and the melting point was 220 ° C, and high heat resistance was successfully confirmed.

    (Synthesis examples 5 to 17)    

Except that 2-naphthol (raw material 1) and 4-ethylfluorenylbiphenyl (raw material 2), which are the raw materials of Synthesis Example 3, were changed to those shown in Table 1, other systems were carried out in the same manner as in Synthesis Example 3 to obtain Each compound of interest.

Each target compound was identified by 1H-NMR.

    (Synthesis examples 18-20)    

Except changing 2-naphthol (raw material 1) and 4-biphenylaldehyde (raw material 2), which are the raw materials of Synthesis Example 3, as shown in Table 3, the other systems were implemented in the same manner as in Synthesis Example 3, and each purpose was achieved. Compound.

Each target compound was identified by 1H-NMR.

    (Synthesis examples 21 to 22)    

In addition to changing the 2-naphthol (raw material 1) and 4-ethylfluorenylbiphenyl (raw material 2), which are the raw materials of Synthesis Example 3, to Table 5 and adding 1.5 mL of water and 73 mg of dodecyl mercaptan ( 0.35 mmol), 2.3 g (22 mmol) of 37% hydrochloric acid, and the reaction temperature was changed to other than 55 ° C. The rest of the system was carried out in the same manner as in Synthesis Example 3 to obtain each target compound.

Each target compound was identified by 1H-NMR.

    (Synthesis example 5A ~ 22A)    

The target compound was obtained under the same conditions as in Synthesis Example 3A, except that the compound represented by the aforementioned formula (BiN-1), which is the raw material of Synthesis Example 3A, was changed to that shown in Table 7. The structure of each target compound was confirmed and identified by 400 MHz- ¹ H-NMR (d-DMSO, internal standard TMS) and LC-MS.

    (Synthetic Examples 5-1 to 22-1)    

Except that the compound represented by the aforementioned formula (BiN-1), which is the raw material of Synthesis Example 3-1, was changed to that shown in Table 7, the rest were synthesized under the same conditions as those of Synthesis Example 3-1, and were separately Obtain each target compound. The structure of each target compound was confirmed and identified by 400 MHz- ¹ H-NMR (d-DMSO, internal standard TMS) and LC-MS.

    (Synthesis Examples 5-2 to 22-2)    

The synthesis was performed under the same conditions as in Synthesis Example 3-2, except that the compound represented by the aforementioned formula (E-BiN-1), which is the raw material of Synthesis Example 3-2, was changed to that shown in Table 7. And obtain each object. The structure of each target compound was confirmed and identified by 400 MHz- ¹ H-NMR (d-DMSO, internal standard TMS) and LC-MS.

    (Synthesis example 23) Synthesis of resin (R1-XBisN-1)    

Prepare a 1-liter four-neck flask with an openable inner volume equipped with a Dessert cooling tube, a thermometer, and a stirring wing. 32.6 g (70 mmol, manufactured by Mitsubishi Gas Chemical Co., Ltd.) and 21.0 g of a 40% by mass aqueous formaldehyde solution (280 mmol of formaldehyde, Mitsubishi Mitsubishi) were placed in this four-necked flask under a nitrogen stream. Gas Chemical Co., Ltd.) and 98% by mass of sulfuric acid (manufactured by Kanto Chemical Co., Ltd.) 0.97 mL, which were refluxed at 100 ° C. under normal pressure and reacted simultaneously for 7 hours. Thereafter, 180.0 g of neighbouring stubble (special grade of test reagent manufactured by Wako Pure Chemical Industries, Ltd.) was added to the reaction solution as a diluting solvent, and the aqueous phase of the lower phase was removed after standing. In addition, neutralization and washing with water were performed, and adjacent stubble was distilled off under reduced pressure to obtain 34.1 g of a resin (R1-XBisN-1) as a brown solid.

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

    (Synthesis example 24) Synthesis of resin (R2-XBisN-1)    

Prepare a 1-liter four-neck flask with an openable inner volume equipped with a Dessert cooling tube, a thermometer, and a stirring wing. In a nitrogen flow, 32.6 g of the compound (XBisN-1) obtained in Synthesis Example 1 (70 mmol, manufactured by Mitsubishi Gas Chemical Co., Ltd.) and 50.9 g of 4-biphenylaldehyde (280 mmol, Mitsubishi Gas Chemical Co., Ltd.) were placed in a nitrogen flow. (Product), 100 mL of anisole (manufactured by Kanto Chemical Co., Ltd.), and 10 mL of oxalic acid dihydrate (manufactured by Kanto Chemical Co., Ltd.). The mixture was refluxed at 100 ° C. under normal pressure and reacted simultaneously for 7 hours. Thereafter, 180.0 g of neighbouring stubble (special grade of test reagent manufactured by Wako Pure Chemical Industries, Ltd.) was added to the reaction solution as a diluting solvent, and the aqueous phase of the lower phase was removed after standing. Then, neutralization and washing with water were performed, and the solvent and unreacted 4-biphenylaldehyde in the organic phase were distilled off under reduced pressure to obtain 34.7 g of a resin (R2-XBisN-1) as a brown solid.

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

    <Synthesis Example 23A> Synthesis of E-R1-XBisN-1    

In a 500 ml container equipped with a stirrer, a cooling tube and a burette, put 30 g of the above resin (R1-XBisN-1) and 29.6 g (214 mmol) of potassium carbonate in 100 ml of dimethylformamide, and add acetic acid-2 -13.12 g (108 mmol) of chloroethyl ester, the reaction solution was stirred at 90 ° C. for 12 hours, and the reaction was performed. Next, the reaction solution was cooled in an ice bath to precipitate crystals, and then separated by filtration. Thereafter, 40 g of the above crystals, 80 g of methanol, 100 g of THF, and a 24% aqueous sodium hydroxide solution were placed in a 100 ml container equipped with a stirrer, a cooling tube, and a burette, and the reaction solution was stirred under reflux for 4 hours and reacted. Thereafter, the reaction solution was concentrated in an ice bath, and the precipitated solid was filtered and dried to obtain 26.5 g of a resin (E-R1-XBisN-1) as a brown solid.

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

    <Synthesis Example 23-1> Synthesis of EaR1-XBisN-1    

In a 500 ml container equipped with a stirrer, a cooling tube and a burette, 20.0 g of the resin represented by the above formula (R1-XBisN-1), 12.2 g of epoxypropylmethacrylate, and 1.0 g of triethylamine 0.1 g of p-methoxyphenol was put into 100 ml of methyl isobutyl ketone, and the reaction was stirred for 24 hours while being heated to 80 ° C with stirring.

After cooling to 50 ° C., the reaction solution was dropped into a solid precipitated in pure water and dried to obtain 26.2 g of a resin represented by (EaR1-XBisN-1) as a gray solid.

The obtained resin (EaR1-XBisN-1) was Mn: 2219, Mw: 3540, and Mw / Mn: 1.59.

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

In addition to replacing the resin shown in the above formula (R1-XBisN-1) obtained in Synthesis Example 23 and using the above formula (E-R1-XBisN-1) obtained in Synthesis Example 23A, the rest are the same as in Synthesis Example 23-1 By reacting in the same manner, 25.0 g of a resin represented by (EaE-R1-XBisN-1) was obtained as a brown solid.

The obtained resin (EaE-R1-XBisN-1) was Mn: 2678, Mw: 4330, and Mw / Mn: 1.61.

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

In a 500 ml container equipped with a stirrer, a cooling tube, and a burette, put 30 g of the resin (R2-XBisN-1) and 29.6 g (214 mmol) of potassium carbonate in 100 ml of dimethylformamide, and add acetic acid-2 -13.12 g (108 mmol) of chloroethyl ester, the reaction solution was stirred at 90 ° C. for 12 hours, and the reaction was performed. Next, the reaction solution was cooled in an ice bath to precipitate crystals, and then separated by filtration. Thereafter, 40 g of the above crystals, 80 g of methanol, 100 g of THF, and a 24% aqueous sodium hydroxide solution were placed in a 100 ml container equipped with a stirrer, a cooling tube, and a burette, and the reaction solution was stirred under reflux for 4 hours and reacted. Thereafter, the reaction solution was cooled in an ice bath, and the precipitated solid was filtered and dried to obtain 22.3 g of a resin (E-R2-XBisN-1) as a brown solid.

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

    <Synthesis Example 24-1> Synthesis of EaR2-XBisN-1    

Except for replacing the above-mentioned formula (R1-XBisN-1) obtained in Synthesis Example 23 and using 31.2 g of the compound shown in the above-mentioned formula (R2-XBisN-1) obtained in Synthesis Example 24, it is the same as in Synthesis Example 23-1 By reacting in the same manner, 37.1 g of a resin represented by (EaR2-XBisN-1) as a gray solid was obtained.

The obtained resin (EaR2-XBisN-1) was Mn: 2641, Mw: 4415, and Mw / Mn: 1.67.

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

Except for replacing the resin shown in the above formula (R1-XBisN-1) obtained in Synthesis Example 23 and using the above formula (E-R2-XBisN-1) obtained in Synthesis Example 24A, the rest are the same as in Synthesis Example 23-1 By reacting in the same manner, 27.0 g of a resin represented by (EaE-R2-XBisN-1) was obtained as a brown solid.

The obtained resin (EaE-R2-XBisN-1) was Mn: 2576, Mw: 4230, and Mw / Mn: 1.64.

    (Synthetic Comparative Example 1)    

Prepare a four-necked flask with a 10-liter inner volume with a Dessert cooling tube, a thermometer, and a stirring wing. 1.09 kg of 1,5-dimethylnaphthalene (7 mol, manufactured by Mitsubishi Gas Chemical Co., Ltd.) and 2.1 kg of a 40% by mass aqueous formaldehyde solution (28 mol of formaldehyde, Mitsubishi Gas Chemical ( ) And 98% by mass of sulfuric acid (manufactured by Kanto Chemical Co., Ltd.) 0.97 ml, and refluxed at 100 ° C. under normal pressure and reacted simultaneously for 7 hours. Thereafter, 1.8 kg of ethylbenzene (Wako Pure Chemical Industries, Ltd. test reagent special grade) was added as a diluting solvent to the reaction solution, and after standing, the aqueous phase of the lower phase was removed. Then, 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 dimethylnaphthalene formaldehyde resin as a light brown solid.

The molecular weight of the obtained dimethylnaphthaldehyde was Mn: 562.

Next, prepare a 0.5-liter four-necked flask with a Dirichlet cooling tube, a thermometer, and a stirring wing. Under a nitrogen stream, 100 g (0.51 mol) of dimethylnaphthalene formaldehyde resin and 0.05 g of p-toluenesulfonic acid obtained in the above-mentioned operation were put into this four-necked flask, and the temperature was raised to 190 ° C for 2 hours. Stir. Thereafter, 52.0 g (0.36 mol) of 1-naphthol was further added, the temperature was raised to 220 ° C., and the reaction was performed for 2 hours. After the solvent was diluted, neutralization and water washing were performed, and the solvent was removed under reduced pressure to obtain 126.1 g of a denatured resin (CR-1) as a dark brown solid.

The obtained resin (CR-1) was Mn: 885, Mw: 2220, and Mw / Mn: 4.17.

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

The compounds or resins described in Synthesis Examples 1-1 to 24-2 and CR-1 described in Synthesis Comparative Example 1 were used for the solubility test. The results are shown in Table 8.

The lithography underlayer film-forming materials having the compositions shown in Table 8 were individually prepared.

Next, these underlayer film-forming materials for lithography were spin-coated on a silicon substrate, and then baked at 240 ° C for 60 seconds, and then baked at 400 ° C for 120 seconds to produce a film thickness of 200 nm. Underlayer film. As the acid generator, the crosslinking agent and the organic solvent, the following are used.

Acid generator: third butyl diphenylsulfonium nonafluoromethane cyclic salt (DTDPI) manufactured by Tsui Chemical Co., Ltd.

Crosslinking agent: NikalacMX270 (Nikalac) manufactured by Sanwa Chemical Co., Ltd.

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

    (Examples 25 to 44)    

In addition, a lithography underlayer film-forming material having a composition shown in Table 9 below was prepared separately. Next, these lower lithography film-forming materials are spin-coated on a silicon substrate, and thereafter, baked at 110 ° C for 60 seconds to remove the coating film's solvent, and then a high-pressure mercury lamp is used to accumulate exposure An amount of 600 mJ / cm ² and an irradiation time of 20 seconds were used to harden, and an underlayer film having a thickness of 200 nm was individually produced. The photo-radical polymerization initiator, crosslinking agent, and organic solvent are the following.

Radical polymerization initiator: IRGACURE184 manufactured by BASF

Crosslinking agent:

(1) NikalacMX270 (Nikalac) manufactured by Sanwa Chemical Co., Ltd.

(2) diallyl bisphenol A cyanate (DABPA-CN) manufactured by Mitsubishi Gas Chemical

(3) diallyl bisphenol A (BPA-CA) manufactured by Konishi Chemical Industry

(4) Benzoxazine (BF-BXZ) manufactured by Konishi Chemical Industry

(5) Biphenylaralkyl epoxy resin (NC-3000-L)

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

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

(In the above formula, n is an integer from 1 to 4.)

Then, an etching test was performed under the conditions shown below to evaluate the etching resistance. The evaluation results are shown in Tables 8 and 9.

    [Etching test]    

Etching device: RIE-10NR, manufactured by Nico International Corporation

Output: 50W

Pressure: 20Pa

Time: 2min

Etching gas

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

    [Evaluation of etching resistance]    

The evaluation of the etching resistance is performed in accordance with the following procedure.

First, except that the compound (EaXBisN-1) was replaced with a phenolic compound (PSM4357 manufactured by Gunrong Chemical Co., Ltd.), a phenolic underlayer film was produced under the same conditions as in Example 1. Then, using this phenolic underlayer film as an object, the above-mentioned etching test was performed, and the etching rate at this time was measured.

Next, the above-mentioned etching test was performed in the same manner as the target of the lower layer film of each of Examples and Comparative Example 1, and the etching rate at this time was measured.

Then, using the etching rate of the phenolic underlayer film as a reference, the etching resistance was evaluated according to the following evaluation criteria.

    [Evaluation criteria]    

A: Compared with the phenolic underlayer film, the etching rate is less than -10%

B: Compared with the phenolic underlayer film, the etching rate is -10% ~ + 5%

C: Compared with the phenolic underlayer film, the etching rate exceeds + 5%

    (Examples 45 to 48)    

Next, each solution of the underlying film-forming material for lithography including EaXBisN-1, EaE-XBisN-1, EaBisF-1, and EaE-BisF-1 was coated on a SiO ₂ substrate having a film thickness of 300 nm. Bake at 60 ° C for 60 seconds, and then bake at 400 ° C for 120 seconds to form a film with a film thickness of 70 nm. The photoresist 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 thickness of 140 nm. In addition, the ArF photoresist solution is a compound compounded with the following formula (11): 5 parts by mass, triphenylsulfonium nonafluoromethane cyclic salt: 1 part by mass, tributylamine: 2 parts by mass, and PGMEA: 92 Made by mass.

The compound of formula (11) uses 2-methyl-2-methacryloxy adamantane 4.15 g, methyl propoxyl-γ-butyrolactone 3.00 g, and 3-hydroxy-1-adamantyl 2.08 g of methacrylate and 0.38 g of azobisisobutyronitrile were dissolved in 80 mL of tetrahydrofuran to prepare a reaction solution. In a nitrogen environment, this reaction solution was kept at a reaction temperature of 63 ° C., and after being polymerized for 22 hours, the reaction solution was dropped into 400 ml of n-hexane. The resulting resin obtained was solidified and purified, and the resulting white powder was filtered and dried under reduced pressure at 40 ° C. overnight.

In the above formula (11), 40, 40, and 20 are ratios of constituent units, and do not represent block copolymers.

Next, the photoresist layer was exposed by using an electron beam drawing device (manufactured by Elionix; ELS-7500, 50keV), baked at 115 ° C for 90 seconds (PEB), and 2.38 mass% tetramethylammonium hydroxide ( TMAH) aqueous solution was developed for 60 seconds to obtain a positive photoresist pattern.

Regarding the shape of the photoresist pattern after development, those with no pattern collapse and good rectangularity were evaluated as "good", and the others were evaluated as "bad". In addition, based on the results of the foregoing observations, the smallest line width with no pattern collapse and good rectangularity is taken as the "resolution" and is set as an evaluation index. In addition, the minimum electron beam energy that can draw a good pattern shape is regarded as "sensitivity" and set as an index for evaluation.

The evaluation results are shown in Table 10.

    (Comparative example 2)    

A photoresist layer was directly formed on the SiO ₂ substrate in the same manner as in Example 45 except that the formation of the lower layer film was not performed to obtain a positive photoresist pattern. The results are shown in Table 2.

From Table 8, it can be clearly confirmed that in Examples 1 to 24 using the compound or resin of the present embodiment, the heat resistance, solubility, and etching resistance were all good. On the other hand, in Comparative Example 1 using CR-1 (phenol-denatured dimethylnaphthalene formaldehyde resin), the etching resistance was poor.

In addition, in Examples 45 to 48, it was confirmed that the photoresist pattern shape after development was good, and no defect was found. Compared with Comparative Example 2 in which the formation of the underlayer film was omitted, it was confirmed that both the resolving power and the sensitivity were significantly excellent.

Due to the difference in the shape of the photoresist pattern after development, the underlayer film-forming material for lithography used in Examples 45 to 48 showed good adhesion to the photoresist material.

    <Examples 49 to 52>    

The SiO ₂ substrate having a film thickness of 300 nm was coated with the solution of the lower film-forming material for lithography of Examples 1-1 to 2-2, and baked at 240 ° C for 60 seconds, and then baked at 400 ° C for 120 seconds. In seconds, a film with a film thickness of 80 nm is formed. An intermediate layer film having a thickness of 35 nm was formed by coating a silicon-containing intermediate layer material on this lower layer film and baking at 200 ° C. for 60 seconds. Then, the photoresist 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 thickness of 150 nm. The silicon-containing intermediate layer material is a silicon atom-containing polymer described in Japanese Patent Application Laid-Open No. 2007-226170 <Synthesis Example 1>.

Next, the photoresist layer was masked and exposed by using an electronic wire drawing device (manufactured by Elionix; ELS-7500, 50keV), baked at 115 ° C for 90 seconds (PEB), and 2.38% by mass of hydrogen was used. Tetramethylammonium oxide (TMAH) aqueous solution was developed for 60 seconds, and a positive photoresist pattern of 55nmL / S (1: 1) was obtained.

Thereafter, dry etching of the silicon-containing interlayer film (SOG) was performed using the obtained photoresist pattern as a mask using RIE-10NR manufactured by Sakko International, and then the obtained silicon-containing interlayer was sequentially performed. The film pattern is used as a dry etching process for the underlying film and the dry etching process for the SiO ₂ film that is used as the mask to obtain the underlying film pattern.

The individual etching conditions are as follows.

Photoresist Pattern Etching Conditions for Photoresist Interlayer Film

Output: 50W

Pressure: 20Pa

Time: 1min

Etching gas

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

Photoresist Interlayer Pattern Etching Conditions for Photoresist Underlayer Film

Output: 50W

Pressure: 20Pa

Time: 2min

Etching gas

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

Photoresist Underlayer Film Pattern Etching Conditions for SiO ₂ Film

Output: 50W

Pressure: 20Pa

Time: 2min

Etching gas

Ar gas flow: C ₅ F ₁₂ gas flow: C ₂ F ₆ gas flow: O ₂ gas flow = 50: 4: 3: 1 (sccm)

    [Evaluation]    

When the pattern cross section (shape of the SiO ₂ film after etching) obtained by the above operation was observed with an electron microscope (S-4800) manufactured by Hitachi, it was confirmed that the example of using the underlayer film of this embodiment was reused. In the middle, the shape of the SiO ₂ film after the multilayer photoresist processing is rectangular, and no defect is found and it is good.

    [Examples 53 to 56]    

Using each compound synthesized in the aforementioned Synthesis Example, an optical component forming composition was prepared with the blend shown in Table 11 below. In addition, among the components of the optical component forming composition in Table 11, the acid generator, cross-linking agent, acid diffusion inhibitor, and solvent are the following.

Acid generator: third butyl diphenylsulfonium nonafluoromethane cyclic salt (DTDPI) manufactured by Tsui Chemical Co., Ltd.

Crosslinking agent: NikalacMX270 (Nikalac) manufactured by Sanwa Chemical Co., Ltd.

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

    [Evaluation of film formation]    

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

    [Evaluation of refractive index and transmittance]    

After the uniform optical component forming composition was spin-coated on a clean silicon wafer, PB was performed in an oven at 110 ° C. to form a film having a thickness of 1 μm. For this film, a multiple incidence angle spectroscopic ellipsometry VASE manufactured by J.A. Woollam was used to measure the refractive index at 25 ° C. (λ = 589.3 nm). Regarding the prepared film, the case where the refractive index was 1.65 or more was evaluated as "A", the case where the refractive index was 1.6 or less and 1.65 was evaluated as "B", and the case where the refractive index was less than 1.6 was evaluated as "C". When the transmittance (λ = 632.8 nm) is 90% or more, it is evaluated as "A", and when it is less than 90%, it is evaluated as "C".

    [Examples 57 to 60]    

Using each compound synthesized in the aforementioned Synthesis Example, a photoresist composition was prepared with the blend shown in Table 12 below. In addition, among the components of the photoresist composition in Table 12, a radical generator, a radical diffusion inhibitor, and a solvent are the following.

Free radical generator: IRGACURE184 manufactured by BASF

Radical diffusion control agent: IRGACURE1010 manufactured by BASF

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

    [Evaluation method]         (1) Storage stability and film formation of photoresist composition    

The storage stability of the photoresist composition is that after the photoresist composition is prepared, it is left to stand at 23 ° C. and 50% RH for 3 days, and the presence or absence of precipitation is visually observed and evaluated. In the photoresist composition after standing for 3 days, the case where the solution was uniform and not precipitated was evaluated as A, and the case where the solution was precipitated was evaluated as C. In addition, the photoresist composition in a uniform state was spin-coated on a clean silicon wafer, and then baked before exposure (PB) in an oven at 110 ° C. to form a photoresist film having a thickness of 40 nm. The prepared photoresist composition was evaluated as A when the film formation was good, and evaluated as C when the formed film had defects.

    (2) Pattern evaluation of photoresist pattern    

The uniform photoresist composition was spin-coated on a clean silicon wafer, and then baked before exposure (PB) in an oven at 110 ° C. to form a photoresist film with a thickness of 60 nm. An electron beam drawing device (ELS-7500, manufactured by Elionix Co., Ltd.) was used to irradiate the obtained photoresist film with electron beams set to a line width and a line pitch of 1: 1 at 50 nm, 40 nm, and 30 nm intervals. After this irradiation, the photoresist film was heated at a predetermined temperature for 90 seconds, and immersed in PGME for 60 seconds for development. Thereafter, the photoresist film was washed with ultrapure water for 30 seconds and dried to form a negative photoresist pattern. With respect to the formed photoresist pattern, the line width and line pitch were observed with a scanning electron microscope (S-4800, manufactured by Hitachi Hi-Tech), and the reactivity of the photoresist composition by irradiation with electron rays was evaluated.

Sensitivity is expressed as the minimum energy per unit area necessary to obtain a pattern, and is evaluated according to the following criteria.

A: When the pattern can be obtained under 50μC / cm ²

C: When the pattern is obtained after 50μC / cm ² or more

The pattern formation system observed the shape of the pattern using a SEM (Scanning Electron Microscope), and evaluated it according to the following criteria.

A: When obtaining a rectangular pattern

B: When obtaining almost rectangular pattern

C: When obtaining a non-rectangular pattern

As described above, the present invention is not limited to the above-mentioned embodiments and examples, and appropriate changes can be added without departing from the gist thereof.

The compound and resin of this embodiment have high solubility in a safe solvent, and have good heat resistance and etching resistance, and the photoresist composition of this embodiment will give a good photoresist-type shape.

In addition, it can be applied to a wet process, and can realize a compound, a resin, and a lithography film-forming composition that are useful for forming a photoresist underlayer film excellent in heat resistance and etching resistance. In addition, since this lithography film-forming composition uses a compound or resin having a specific structure that has high heat resistance and high solvent solubility, it is possible to suppress degradation of the film during high-temperature baking. Photoresist and underlayer film with excellent etching resistance such as etching. Furthermore, when forming an underlayer film, since the adhesion with the photoresist layer is also excellent, an excellent photoresist pattern can be formed.

In addition, since the refractive index is high and the coloring caused by low-temperature to high-temperature processing is suppressed, it can also be used as a composition for forming various optical parts.

Therefore, in addition to the present invention, for example, electrical insulation materials, photoresist resins, semiconductor sealing resins, adhesives for printed wiring boards, and electrical equipment can be used. Electronic machines. Laminates for electrical appliances and electrical equipment mounted on industrial equipment. Electronic machines. Matrix resins for pre-stained bodies mounted on industrial equipment, laminated laminate materials, resins for fiber-reinforced plastics, resins for sealing liquid crystal display panels, coatings, various coating agents, adhesives, coating agents for semiconductors, In addition to resins for semiconductors, resins for lower film formation, film and sheet forms, they can be widely and effectively used in plastic lenses (e.g., lenticular lenses, lenticular lenses, microlenses, Fresnel lenses, Viewing angle control lens, contrast enhancement lens, etc.), phase difference film, film for electromagnetic wave shielding, chirp, optical fiber, solder resist for flexible printed wiring, anti-plating agent, interlayer insulating film for multilayer printed wiring board, photosensitive optical waveguide And other optical parts.

This application is based on a Japanese patent application (Japanese Patent Application No. 2016-143684) filed with the Japan Patent Office on July 21, 2016, and the contents thereof are incorporated herein by reference.

    [Industrial availability]    

The present invention has industrial applicability in the fields of lithography photoresist, lithography underlayer film, multilayer photoresist underlayer film, and optical parts.

Claims (28)

A compound represented by the following formula (0); In formula (0), R ^Y is a hydrogen atom, an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, R ^Z is an N-valent group or single bond having 1 to 60 carbon atoms, and R ^T is Each independently is an alkyl group having 1 to 30 carbons which may have a substituent, an aryl group having 6 to 30 carbons which may have a substituent, an alkenyl group having 2 to 30 carbons which may have a substituent, and an 1 to 30 carbon alkoxy, halogen atom, nitro, amine, carboxylic acid, mercapto, hydroxyl, or group represented by formula (0-1), the aforementioned alkyl group, the aforementioned aryl group, the aforementioned alkenyl group, The aforementioned alkoxy group may also include an ether bond, a ketone bond, or an ester bond. Here, at least one of R ^T includes a group represented by formula (0-1), X represents an oxygen atom, a sulfur atom, or an uncrosslinked, m Are each independently an integer of 0-9, where at least one of m is an integer of 1-9, and N is an integer of 1-4. Here, when N is an integer of 2 or more, one of N [] The structural formulas may be the same or different, and r is an integer of 0 to 2 each independently; In the formula (0-1), R ^X is a hydrogen atom or a methyl group. The compound according to claim 1, wherein the compound represented by the aforementioned formula (0) is a compound represented by the following formula (1); In formula (1), R ⁰ is synonymous with the aforementioned R ^Y , R ¹ is an n-valent group or a single bond having a carbon number of 1 to 60, and R ² to R ⁵ are each independently a carbon number of 1 to ⁵ which may have a substituent. Alkyl group of 30, aryl group of 6 to 30 carbons which may have a substituent, alkenyl group of 2 to 30 carbons which may have a substituent, alkoxy group of 1 to 30 carbons which may have a substituent, halogen atom , Nitro, amine, carboxylic acid, mercapto, hydroxyl, or a group represented by formula (0-1), the alkyl group, the aryl group, the alkenyl group, and the alkoxy group may further include an ether bond or a ketone bond Or an ester bond, where at least one of R ² to R ⁵ includes a group represented by formula (0-1), m ² and m ³ are each independently an integer of 0 to 8, and m ⁴ and m ⁵ are each Independently, it is an integer from 0 to 9. However, m ² , m ³ , m ^4, and m ⁵ will not become 0 at the same time. N is synonymous with N. Here, when n is an integer of 2 or more, n [] The structural formulas may be the same or different, and p ² to p ⁵ are synonymous with the foregoing r. The compound according to claim 1, wherein the compound represented by the aforementioned formula (0) is a compound represented by the following formula (2). In formula (2), R ^0A is synonymous with the aforementioned R ^Y , R ^1A is an n ^A valence group or a single bond having a carbon number of 1 to 60, and R ^2A is each independently a carbon number of 1 to 30 which may have a substituent. Alkyl, aryl having 6 to 30 carbons which may have substituents, alkenyl having 2 to 30 carbons which may have substituent, alkoxy groups having 1 to 30 carbons which may have substituent, halogen atom, nitrate Group, amino group, carboxylic acid group, mercapto group, hydroxyl group or group represented by formula (0-1), the alkyl group, the aryl group, the alkenyl group, and the alkoxy group may further include an ether bond, a ketone bond, or an ester Here, at least one of R ^2A includes a group represented by formula (0-1), n ^A is synonymous with the aforementioned N. Here, when n ^A is an integer of 2 or more, one of n ^A [] The structural formulas may be the same or different. X ^A represents an oxygen atom, a sulfur atom, or uncrosslinked, m ^2A is an integer of 0 to 7 independently, but at least one m ^2A is an integer of 1 to 7, q ^A is independently 0 or 1. The compound according to claim 2, wherein the compound represented by the aforementioned formula (1) is a compound represented by the following formula (1-1); In formula (1-1), R ⁰ , R ¹ , R ⁴ , R ⁵ , n, p ² to p ⁵ , m ⁴ and m ⁵ are synonymous with the foregoing, and R ⁶ to R ⁷ are each independently and may have a substitution. Alkyl group having 1 to 30 carbon atoms, aryl group having 6 to 30 carbon atoms having substituents, alkenyl group having 2 to 30 carbon atoms having substituents, halogen atom, nitro group, amine group, carboxylic acid Group, mercapto group, R ¹⁰ to R ¹¹ are each independently a hydrogen atom or a group represented by formula (0-2), and at least one of R ¹⁰ to R ¹¹ is a group represented by formula (0-2) , M ⁶ and m ⁷ are each independently an integer of 0 to 7, but m ⁴ , m ⁵ , m ⁶ and m ⁷ will not become 0 at the same time; In formula (0-2), R ^X is synonymous with the foregoing, R ^W is a linear, branched, or cyclic alkylene group having 1 to 30 carbon atoms, and s is an integer of 0 to 30. The compound according to claim 4, wherein the compound represented by the aforementioned 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 synonymous with the foregoing, and R ⁸ to R ⁹ are Synonymous with R ⁶ to R ⁷ , R ¹² to R ¹³ are synonymous with R ¹⁰ to R ¹¹ , and m ⁸ and m ⁹ are each independently an integer of 0 to 8, but m ⁶ , m ⁷ , m ⁸ and m ⁹ does not become 0 at the same time. The compound according to claim 3, wherein the compound represented by the aforementioned 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 synonymous with those described in the formula (2), and R ^3A is each independently a carbon number of 1 to 30 which may have a substituent. Linear, branched or cyclic alkyl groups, aryl groups having 6 to 30 carbon atoms which may have a substituent, alkenyl groups having 2 to 30 carbon atoms which may have a substituent, halogen atom, nitro, amine Group, carboxylic acid group, mercapto group, R ^4A is each independently a hydrogen atom or a group represented by formula (0-2), and at least one of R ^4A is a group represented by formula (0-2), m ^6A is independently an integer of 0-5.     A resin obtained by using a compound as claimed in claim 1 as a monomer.     The resin according to claim 7, which has a structure represented by the following formula (3); In the formula (3), L is an alkylene group having 1 to 30 carbon atoms which may have a substituent, an alkylene group having 6 to 30 carbon atoms which may have a substituent, and an alkylene group having 1 to 30 carbon atoms which may have a substituent. An alkoxy group or a single bond, the aforementioned alkylene group, the aforementioned aryl group, or the aforementioned alkylene group may also include an ether bond, a ketone bond, or an ester bond, R ⁰ is synonymous with the aforementioned R ^Y , and R ¹ is a carbon number of 1 to A n-valent radical or single bond of 60, R ² to R ⁵ are each independently 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 may have a substituent Alkenyl group having 2 to 30 carbon atoms, alkoxy group having 1 to 30 carbon atoms which may have a substituent, a halogen atom, a nitro group, an amine group, a carboxylic acid group, a mercapto group, a hydroxyl group, or a compound of formula (0-1) The aforementioned alkyl group, the aforementioned aryl group, the aforementioned alkenyl group, and the aforementioned alkoxy group may also include an ether bond, a ketone bond, or an ester bond. Here, at least one of R ² to R ⁵ includes ), 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, but m ² , m ³ , m ⁴ and m ^{5 are} not Will become 0 at the same time, and at least one of R ² to R ⁵ is a base represented by formula (0-2). The resin according to claim 7, which has a structure represented by the following formula (4); In the formula (4), L is an alkylene group having 1 to 30 carbons which may have a substituent, an alkylene group having 6 to 30 carbons which may have a substituent, and an alkylene group having 1 to 30 carbons which may have a substituent. An alkoxy group or a single bond, the aforementioned alkylene group, the aforementioned aryl group, or the aforementioned alkylene group may also include an ether bond, a ketone bond, or an ester bond. R ^0A is synonymous with the aforementioned R ^Y , and R ^1A is a carbon number of 1 to ^A value of the n-30 group or a single bond, R ^2A are each independently based carbon may have a substituent group of the alkyl group having 1 to 30, may have a substituent group of carbon number of 6 to 30 aryl group, the group may have a substituent Alkenyl group having 2 to 30 carbon atoms, alkoxy group having 1 to 30 carbon atoms which may have a substituent, a halogen atom, a nitro group, an amine group, a carboxylic acid group, a mercapto group, a hydroxyl group or a hydrogen atom of a hydroxyl group are vinyl phenyl The methyl-substituted group, the aforementioned alkyl group, the aforementioned aryl group, the aforementioned alkenyl group, and the aforementioned alkoxy group may also include an ether bond, a ketone bond, or an ester bond. Here, at least one of R ^2A includes the formula (0-1) In the base shown, n ^A is synonymous with the aforementioned N. Here, when n ^A is an integer of 2 or more, the structural formulas in n ^A [] may be the same or different, and X ^A represents an oxygen atom and sulfur. atom or uncrosslinked, m ^2A lines each independently integers of 0 to 7 of the However, at least 1 m ^2A is an integer of 1-7, q ^A is based is independently 0 or 1.     A composition containing one or more members 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.         The composition of claim 10, further comprising a solvent.         The composition according to claim 10 or 11, further comprising an acid generator.         The composition of claim 10 or 11 further contains a cross-linking agent.         The composition according to claim 13, wherein the cross-linking agent is selected from the group consisting of a phenol compound, an epoxy compound, a cyanate compound, an amine compound, a benzoxazine compound, a melamine compound, a guanamine compound, an acetylene urea compound, and urea At least one of the group consisting of a compound, an isocyanate compound, and an azide compound.         The composition according to claim 13, wherein the crosslinking agent has at least one allyl group.         The composition according to claim 13, which contains a total of one or more components selected from the group consisting of the compound according to any of claims 1 to 6, and the resin according to any of claims 7 to 9. When the mass is 100 parts by mass, the content ratio of the crosslinking agent is 0.1 to 100 parts by mass.         The composition according to claim 13, 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 composition according to claim 17, which contains a total of one or more compositions 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. When the mass is 100 parts by mass, the content of the crosslinking accelerator is 0.1 to 5 parts by mass.         The composition according to claim 10 or 11, further comprising a radical polymerization initiator.         The composition according to claim 20, wherein the aforementioned radical polymerization initiator is at least 1 selected from the group consisting of a ketone-based photopolymerization initiator, an organic peroxide-based polymerization initiator, and an azo-based polymerization initiator. Species.         The composition according to claim 20, which contains a total of one or more compositions 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. When the mass is 100 parts by mass, the content ratio of the radical polymerization initiator is 0.05 to 25 parts by mass.         The composition according to claim 10 or 11, wherein the composition is used for forming a lithography film.         The composition of claim 10 or 11, wherein the composition is used for forming a photoresistive permanent film.         The composition of claim 10 or 11 is used for forming optical parts.         A photoresist pattern forming method includes the steps of: after forming a photoresist layer on a substrate by using the composition of claim 23, irradiating a predetermined area of the photoresist layer with radiation, and performing development.         A method for forming a photoresist pattern, comprising: forming a lower layer film on a substrate by using the composition of claim 23; and after forming at least one photoresist layer on the lower layer film, irradiating a predetermined area of the photoresist layer Steps of radiation and development.         A method for forming a circuit pattern, comprising: forming a lower layer film on a substrate using the composition as claimed in claim 23; forming a middle layer film using a photoresist intermediate layer film material on the lower layer film; and forming at least the middle layer film A step of one photoresist layer; a step of irradiating a predetermined area of the photoresist layer with radiation to develop a photoresist pattern; and using the photoresist pattern as a mask to etch the intermediate layer film, The obtained intermediate layer film pattern is used as an etching mask to etch the aforementioned lower layer film, and the obtained lower layer film pattern is used as an etching mask to etch the substrate, thereby forming a pattern on the substrate.