TW201817721A - Compound, resin, composition, method for forming resist pattern, and method for forming circuit pattern - Google Patents

Abstract

The invention provides a compound represented by the following formula (0), (in formula (0), R<SP>Y</SP> represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms; R<SP>Z</SP> represents a N-valent group having 1 to 60 carbon atoms or a single bond; R<SP>T</SP> each independently represents an alkyl group having 1 to 30 carbon atoms which may have substitution, an aryl group having 6 to 30 carbon atom which may have substitution, an alkenyl group having 2 to 30 carbon atoms which may have substitution, an alkoxy group having 1 to 30 carbon atoms which may have substitution, a halogen atom, a nitro group, an amino group, a carboxyl group, a thiol group, a hydroxyl group, or a group in which the hydrogen atom of an hydroxyl group is substituted with a group represented by following formula (0-1), wherein said alkyl, aryl, alkenyl and alkoxy groups may contain an ether bond, a keto bond or an ester bond, and wherein at least one R<SP>T</SP> contains a group represented by following formula (0-1); X represents an oxygen atom, a sulfur atom or is uncrosslinked; m each independently represents an integer of 0 to 9, wherein at least one m is an integer of 1 to 9; N is an integer of 1 to 4, and when N is an integer of 2 or greater, the structural formulae included in N [ ]'s may be the same or different; and r each independently represents an integer of 0 to 2), (in formula (0-1), R<SP>X</SP> is a hydrogen atom or a methyl group).

Description

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

The present invention relates to compounds having specific configurations, resins, and compositions containing the same. Further, a method of forming a pattern of the composition (a method of forming a resist pattern and a method of forming a circuit pattern) is used.

In the production of a semiconductor device, fine processing is performed by using a lithography of a photoresist material. However, in recent years, with the increase in the integration and speed of LSI, it is required to further refine the pattern due to the pattern rule. Moreover, the light source for lithography used in the formation of the resist pattern is short-wavelength from KrF excimer laser (248 nm) to ArF excimer laser (193 nm), and may also be introduced into extreme ultraviolet light (EUV, 13.5). Nm).

However, when the lithography of the conventional polymer-based resist material is used, the molecular weight is about 10,000 to 100,000, and the molecular weight distribution is also wide. Therefore, the surface of the pattern is rough, the control of the pattern size is difficult, and the micronization has a limit. Therefore, various low molecular weight resist materials have been proposed so far in order to provide a higher resolution resist pattern. Since the low molecular weight resist material is small in molecular size, it is expected to provide a resist pattern having high resolution and low roughness.

Now, such low molecular resistance materials are known in various ways. For example, an alkali-developing type negative radiation-sensitive composition using a low-molecular-weight polynuclear polyphenol compound as a main component (see, for example, Patent Document 1 and Patent Document 2) has been proposed as a low molecular weight resistance having high heat resistance. For example, the alkali-developing type negative radiation-sensitive composition using a low-molecular-weight cyclic polyphenol compound as a main component (see, for example, Patent Document 3 and Non-Patent Document 1). In addition, the polyphenol compound which is a base compound of a resist material has a low molecular weight, but can provide high heat resistance, and is known for improving the resolution or roughness of a resist pattern (see, for example, Non-Patent Document 2).

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

Further, as the refinement pattern is made finer, there is a problem of resolution or a problem such as collapse of the resist pattern after development, and thus it is expected that the resist is thinned. However, when only the film of the resist is formed, it becomes difficult to obtain a sufficient film thickness of the resist pattern in the substrate processing. Therefore, not only the resist pattern but also the resist underlayer film is formed between the resist and the processed semiconductor substrate, and the resist underlayer film also has a function as a mask for processing the substrate.

Now, as a resist underlayer film for such a process, various kinds are known. For example, it is proposed that, unlike a resist underlayer film having a relatively fast etching speed, a lithographic resist underlayer film having a selectivity ratio close to a dry etching rate of a resist, for example, contains at least a terminal group by applying a specific energy. The underlayer film forming material for the multilayer resist process for producing a resin component having a substituent of a sulfonic acid residue and a solvent (for example, see Patent Document 5). Further, it is proposed to realize a lithographic resist underlayer film having a selection ratio of a dry etching rate smaller than that of a resist, for example, a resist underlayer film material containing a polymer having a specific repeating unit (see, for example, Patent Document 6). Further, it is proposed that a lithographic resist underlayer film having a selection ratio of a dry etching rate smaller than that of a semiconductor substrate can be realized, for example, including a repeating unit of a terpene group and a repeating unit having a substituted or unsubstituted hydroxyl group. A resist underlayer film material of a polymer obtained by polymerization (for example, see Patent Document 7).

On the other hand, in such a resist underlayer film, a material having high etching resistance, for example, an amorphous carbon underlayer film formed by CVD using methane gas, ethane gas, acetylene gas or the like for a raw material is quite People know. However, from the viewpoint of the process, it is required to form a resist underlayer film material of a resist underlayer film by a wet process such as spin coating or screen printing.

Further, the inventors of the present invention have proposed a composition for forming a lower layer film for lithography which is excellent in etching resistance, high in heat resistance, soluble in a solvent, and applicable to a wet process, and a compound containing a specific structure and an organic solvent. (For example, refer to Patent Document 8).

Further, as a method of forming the intermediate layer used for forming the resist underlayer film in the three-layer process, for example, a method of forming a tantalum nitride film (for example, refer to Patent Document 9) or a CVD method for forming a tantalum nitride film is known. (For example, refer to Patent Document 10). In addition, a material containing a sesquiterpene oxyalkylene compound is known as an intermediate layer material for a three-layer process (see, for example, Patent Document 11 and Patent Document 12).

Further, various constituents are proposed as optical components. For example, an acrylic resin is mentioned (for example, refer patent documents 13-14).

 Prior technical literature    Patent literature  

Patent Document 1: Japanese Laid-Open Patent Publication No. 2005-326838

Patent Document 2: Japanese Laid-Open Patent Publication No. 2008-145539

Patent Document 3: Japanese Laid-Open Patent Publication No. 2009-173623

Patent Document 4: International Publication No. 2013/024778

Patent Document 5: Japanese Laid-Open Patent Publication No. 2004-177668

Patent Document 6: Japanese Laid-Open Patent Publication No. 2004-271838

Patent Document 7: Japanese Laid-Open Patent Publication No. 2005-250434

Patent Document 8: International Publication No. 2013/024779

Patent Document 9: Japanese Laid-Open Patent Publication No. 2002-334869

Patent Document 10: International Publication No. 2004/066377

Patent Document 11: Japanese Laid-Open Patent Publication No. 2007-226170

Patent Document 12: Japanese Laid-Open Patent Publication No. 2007-226204

Patent Document 13: Japanese Laid-Open Patent Publication No. 2010-138393

Patent Document 14: Japanese Laid-Open Patent Publication No. 2015-174877

 Non-patent literature  

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

Non-Patent Document 2: Okazaki Shinji and 22 other "New Prospects for Resist Material Development" Joint Stock Company CMC Publishing, September 2009, p.211-259

 [Summary of the Invention]  

As described above, a film forming composition for a lithography film for a plurality of resisting agents and a film for lithography for use in a lower film has been proposed. However, it is not limited to a wet type which is applicable not only to spin coating or screen printing. Since the solvent of the process has high solubility and high heat resistance and etching resistance, it is necessary to develop new materials. Further, it has been demanded to develop a new material suitable for obtaining a permanent film of a resist which is excellent in alkali developability, light sensitivity, and resolution.

Further, many compositions for optical members have been proposed in the past, but they are not high-order materials having heat resistance, transparency, and refractive index, and therefore it is necessary to develop new materials.

The present invention has been made in view of the above-described problems of the prior art, and an object of the present invention is to provide a compound which can be used in a wet process and which can form an underlayer film for photoresist and photoresist which is excellent in heat resistance and solubility and etching resistance. Resin, composition. Further, a resist film using the composition, a resist underlayer film, a resist permanent film, and a pattern forming method are provided. Further, a composition for an optical member is provided.

As a result of careful examination of the above-mentioned conventional problems, the present inventors have found that the above-described conventional problems can be solved by using a compound or a resin having a specific structure, and the present invention has been completed.

That is, the present invention is as follows.

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

(In the formula (0), R ^Y is a hydrogen atom, an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, and R ^Z is an N-valent group or a single bond having 1 to 60 carbon atoms, and each of R ^T 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 a carbon which may have a substituent a hydrogen atom having 1 to 30 alkoxy groups, a halogen atom, a nitro group, an amine group, a carboxylic acid group, a thiol group, a hydroxyl group or a hydroxyl group is substituted with a group represented by the following formula (0-1), and the aforementioned alkyl group, The aryl group, the above alkenyl group, and the alkoxy group may further contain an ether bond, a ketone bond or an ester bond. Here, at least one of R ^T contains a group represented by the following formula (0-1), and X represents an oxygen atom. , sulfur atom or no cross-linking, m is independently an integer from 0 to 9, where at least one of m is an integer from 1 to 9, N is an integer from 1 to 4, and N is an integer of two or more, N The structural formulas in [ ] may be the same or different, and r is independently an integer of 0~2).

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

[2] The compound of the above formula (1), wherein the compound represented by the above formula (0) is a compound represented by the following formula (1),

(In the formula (1), R ⁰ is synonymous with the above R ^Y , R ¹ is an n-valent group or a single bond having 1 to 60 carbon atoms, and R ² to R ⁵ are each independently a carbon number 1 to 30 which may have a substituent. An alkyl group, an aryl group having 6 to 30 carbon atoms which may have a substituent, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, an alkoxy group having 1 to 30 carbon atoms which may have a substituent, a halogen atom, a hydrogen atom of a nitro group, an amine group, a carboxylic acid group, a thiol group, a hydroxyl group or a hydroxyl group is substituted with a group represented by the above formula (0-1), and the aforementioned alkyl group, the aforementioned aryl group, the aforementioned alkenyl group, and the aforementioned alkoxy group may be used. The ether bond, the ketone bond or the ester bond is contained. Here, at least one of R ² to R ⁵ contains a group represented by the above formula (0-1), and m ² and m ³ are each independently an integer of 0-8, 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 0 at the same time, and n is synonymous with the above N. Here, when n is an integer of 2 or more, n The structural formulae in [ ] may be the same or different, and p ² to p ⁵ are synonymous with the aforementioned r).

[3] The compound of the above formula (1), wherein the compound represented by the above formula (0) is a compound represented by the following formula (2),

(In the formula (2), R ^0A is synonymous with the above R ^Y , R ^1A is a n ^A valent group or a single bond having a carbon number of 1 to 60, and each of R ^{2A is} 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, an alkoxy group having 1 to 30 carbon atoms which may have a substituent, a halogen atom, and a nitro group a hydrogen atom of an amine group, a carboxylic acid group, a thiol group, a hydroxyl group or a hydroxyl group is substituted with a group represented by the above formula (0-1), and the alkyl group, the above aryl group, the aforementioned alkenyl group, and the alkoxy group may also contain Here, at least one of R ^2A contains a group represented by the above formula (0-1), and n ^A is synonymous with the above N, and when n ^A is an integer of 2 or more, n ^A number of [formula] may be within the same or different, X ^A represents an oxygen atom, a sulfur atom or noncrosslinked, m ^2A are each independently an integer of 0 to 7, but at least one of 1 to m ^2A An integer of 7, q ^{A is} independently 0 or 1).

[4] The compound of the above formula (1), wherein the compound represented by the above formula (1) is a compound represented by the following formula (1-1),

(In the formula (1-1), R ⁰ , R ¹ , R ⁴ , R ⁵ , n, p ² to p ⁵ , m ⁴ and m ⁵ are synonymous with the definitions described in the above formula (1), R ⁶ Each of -R ^{7 is} 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 a halogen atom And a nitro group, an amine group, a carboxylic acid group or a fluorenyl group, and each of R ¹⁰ to R ^{11 is} independently a hydrogen atom or a group represented by the following formula (0-2), wherein at least one of R ¹⁰ to R ¹¹ is a lower one. The formula (0-2) represents a group, and m ⁶ and m ⁷ are each independently an integer of 0 to 7, but m ⁴ , m ⁵ , m ⁶ and m ^{7 are} not 0).

(In the formula (0-2), R ^X is synonymous with the definition described in the above formula (0-1), and s is an integer of 0 to 30).

[5] The compound of the above formula (1-1), wherein the compound represented by the above formula (1-1) is a compound represented by the following formula (1-2),

(In the formula (1-2), R ⁰ , R ¹ , R ⁶ , R ⁷ , R ¹⁰ , R ¹¹ , n, p ² to p ⁵ , m ⁶ and m ⁷ are the same as in the above formula (1-1) The definitions are synonymous, R ⁸ ~ R ⁹ are synonymous with the above R ⁶ ~ R ⁷ , R ¹² ~ R ¹³ are synonymous with the above R ¹⁰ ~ R ¹¹ , and m ⁸ and m ⁹ are each independently an integer of 0-8. However, m ⁶ , m ⁷ , m ⁸ and m ^{9 are} not 0) at the same time.

[6] The compound of the above formula (2), wherein the compound represented by the above formula (2) is a compound represented by the following formula (2-1),

(In the formula (2-1), R ^0A , R ^1A , n ^A , q ^A and X ^A are synonymous with the definitions described in the above formula (2), and each of R ^{3A is} independently a carbon number which may have a substituent 1 a linear, branched or cyclic alkyl group of ~30, an aryl group having 6 to 30 carbon atoms which may have a substituent, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, a halogen atom, a nitro group, The amine group, the carboxylic acid group, the fluorenyl group, and each of R ^4A are each independently a hydrogen atom or a group represented by the following formula (0-2). Here, at least one of R ^4A is a group represented by the following formula (0-2). , m ^6A are each independently an integer of 0 to 5).

(In the formula (0-2), R ^X is synonymous with the definition described in the above formula (0-1), and s is an integer of 0 to 30).

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

[8] The resin according to [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 extended aryl group having 6 to 30 carbon atoms which may have a substituent, and a carbon number of 1 to 30 which may have a substituent. An alkyleneoxy group or a single bond, the above alkylene group, the above-mentioned extended aryl group, the aforementioned alkyleneoxy group may also contain 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. And a single bond, 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. An alkenyl group having 2 to 30 carbon atoms, a substituted alkoxy group having 1 to 30 carbon atoms, a halogen atom, a nitro group, an amine group, a carboxylic acid group, a fluorenyl group, a hydroxyl group or a hydroxyl group by the above formula ( The group represented by 0-1), wherein the alkyl group, the aryl group, the alkenyl group, and the alkoxy group may further contain an ether bond, a ketone bond or an ester bond, and here, at least 1 of R ² to R ⁵ Each of the groups represented by the above 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 an integer of 0 to 9, but m ² , m ³ , m ⁴ And m ^{5 is} not 0 at the same time, and n is synonymous with the above N. Here, when n is an integer of 2 or more, n The structural formulae in [ ] may be the same or different, and p ² ~ p ⁵ are synonymous with the aforementioned r).

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

(In the formula (4), L is an alkylene group having 1 to 30 carbon atoms which may have a substituent, an extended aryl group having 6 to 30 carbon atoms which may have a substituent, and a carbon number of 1 to 30 which may have a substituent An alkylene group or a single bond, the alkylene group, the above-mentioned extended aryl group, and the aforementioned alkyleneoxy group may also contain 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. ~30 nA ^A valent group or single bond, R ^2A each independently is an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, and a carbon which may have a substituent a hydrogen atom having 2 to 30 alkenyl groups, an alkoxy group having 1 to 30 carbon atoms, a halogen atom, a nitro group, an amine group, a carboxylic acid group, a fluorenyl group, a hydroxyl group or a hydroxyl group which may have a substituent (0- 1) a group substituted by a group, wherein the alkyl group, the aryl group, the alkenyl group, and the alkoxy group may further contain an ether bond, a keto bond or an ester bond, and at least one of R ^2A contains the above formula ( 0-1) represents a group, and n ^A is synonymous with the above N. Here, when n ^A is an integer of 2 or more, the structural formulas in n ^A of [ ] may be the same or different, and X ^A represents an oxygen atom, Sulfur atoms or no crosslinks, m ^2A are each independently an integer from 0 to 7, but It is at least one m ^2A is an integer of 1 to 6, and q ^{A is} independently 0 or 1).

[10] A composition comprising one or more selected from the group consisting of a compound according to any one of [1] to [6] and a resin according to any one of [7] to [9].

[11] The composition according to [10], which further contains a solvent.

[12] The composition of [10] or [11], which further contains an acid generator.

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

[14] The composition according to [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 a glycoluril. At least one of a compound, a urea compound, an isocyanate compound, and an azide compound.

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

[16] The composition according to any one of [13] to [15] which contains a compound selected from any one of [1] to [6] and such as [7] to [9] When the total mass of the composition of one or more kinds of the resin is 100 parts by mass, the content 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 [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 of [17] or [18], which comprises a resin selected from any one of [1] to [6] and a resin according to any one of [7] to [9] When the total mass of the one or more components in the 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] which further contains a radical polymerization initiator.

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

[22] The composition according to any one of [10] to [21] which contains a compound selected from any one of [1] to [6] and such as [7] to [9] When the total mass of the one or more components of the resin is 100 parts by mass, the content 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 film for lithography.

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

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

[26] A method for forming a resist pattern, comprising the steps of: forming a photoresist layer on a substrate using a composition such as [23], irradiating a specific region of the photoresist layer with radiation, and performing development A step of.

[27] A method for forming a resist pattern, comprising the steps of: forming an underlayer film on a substrate using a composition such as [23], and forming at least one photoresist layer on the underlayer film, The specific region of the photoresist layer is irradiated with radiation to perform development.

[28] A method of forming a circuit pattern, comprising the steps of: forming a lower film using a composition such as [23] on a substrate, and using a resist intermediate film material on the underlying film to form an intermediate layer; a film, after forming at least one photoresist layer on the intermediate layer film, irradiating a specific region of the photoresist layer with radiation, developing to form a resist pattern, and using the resist pattern as a mask And etching the intermediate layer film, using the obtained interlayer film pattern as an etching mask, etching the underlying film, using the underlying film pattern as an etching mask, etching the substrate, and forming a pattern on the substrate.

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

 Form of implementing the invention  

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

The compound of the present embodiment is a compound represented by the following formula (0) or a resin obtained by using the compound as a monomer. The compound and resin of the present invention can be applied to a wet process and can be used to form a photoresist underlayer film excellent in heat resistance and etching resistance. Further, since the film forming composition for lithography is high in heat resistance and solvent solubility, and has a compound or a resin having a specific structure, deterioration of the film at the time of high-temperature baking is suppressed, and oxygen plasma can be formed. A resist and an underlayer film excellent in etching resistance such as etching. Further, in the case where the underlayer film is formed, since it is excellent in adhesion to the resist layer, an excellent resist pattern can be formed. Further, in the case where the compound and the resin in the present embodiment are excellent in sensitivity or resolution when used for a photosensitive material, they can be used to form a high heat resistance, and can be used together with a general organic solvent or other compounds, a resin component, and A permanent film of a resist that is excellent in compatibility with additives. Further, since the refractive index is high and the coloring is suppressed by heat treatment in a wide range from low temperature to high temperature, it can be used as various optical forming compositions.

 [Compound represented by formula (0)]  

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

(In the formula (0), R ^Y is a hydrogen atom, an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, and R ^Z is an N-valent group or a single bond having 1 to 60 carbon atoms, and each of R ^T 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 a carbon which may have a substituent a hydrogen atom having 1 to 30 alkoxy groups, a halogen atom, a nitro group, an amine group, a carboxylic acid group, a thiol group, a hydroxyl group or a hydroxyl group is substituted with a group represented by the following formula (0-1), and the aforementioned alkyl group, The aryl group, the above alkenyl group, and the alkoxy group may further contain an ether bond, a ketone bond or an ester bond. Here, at least one of R ^T contains a group represented by the following formula (0-1), and X represents an oxygen atom. , sulfur atom or no cross-linking, m is independently an integer from 0 to 9, where at least one of m is an integer from 1 to 9, N is an integer from 1 to 4, and N is an integer of two or more, N The structural formulas in [ ] may be the same or different, and r is independently an integer of 0~2).

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

The group containing a group represented by the formula (0-1) means a group having a group represented by the formula (0-1), and examples thereof include a group represented by the formula (0-1), and a formula (0-1) a methoxy group substituted by a group, a ethoxy group substituted by a group represented by the formula (0-1), a propoxy group substituted by a group represented by the formula (0-1), and a group represented by the formula (0-1) A substituted ethoxyethoxy group, a propyloxypropoxy group substituted by a group represented by the formula (0-1), and a phenoxy group substituted by a group represented by the formula (0-1).

R ^Y is a hydrogen atom, an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms. The alkyl group may be a linear, branched or cyclic alkyl group. R ^Y is excellent in heat resistance and solvent solubility by 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 ^z is an N-valent group or a single bond having a carbon number of 1 to 60, and a bond is formed through the respective aromatic rings via R ^z . N is an integer of 1 to 4, and N is an integer of 2 or more, and the structural formulae of N [ ] may be the same or different. Further, the above-mentioned N-valent group means an alkyl group having 1 to 60 carbon atoms when N=1, an alkylene group having 1 to 30 carbon atoms when N=2, and an alkane hydrocarbon having 2 to 60 carbon atoms when N=3. Base, when N=4, an alkane tetrayl group having a carbon number of 3 to 60. Examples of the above-mentioned 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 contains a bridged aliphatic hydrocarbon group. Further, 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 may have a substitution a group in which a hydrogen atom having 1 to 30 carbon atoms, a halogen atom, a nitro group, an amine group, a carboxylic acid group, a thiol group, a hydroxyl group or a hydroxyl group is substituted with a group represented by the above formula (0-1), the above alkane The aryl group, the above alkenyl group, and the alkoxy group may further contain an ether bond, a ketone bond or an ester bond, and at least one hydrogen atom containing a hydroxyl group of R ^T is selected from an allyloxyalkyl group. A group substituted with a propylene methoxyalkyl group and an acryloxyalkyl group. Further, the alkyl group, the alkenyl group and the alkoxy group may be a linear chain, a branched chain or a cyclic group. Here, the group in which the hydrogen atom of the hydroxy group is substituted with a vinyl phenylmethyl group means a group having a vinyl phenylmethyl group, and examples thereof include a vinyl phenylmethyl group, a vinyl phenylmethyl methyl group, and a vinyl group. Phenylmethylphenyl and the like.

X represents an oxygen atom, a sulfur atom or no cross-linking, and when X is an oxygen atom or a sulfur atom, it tends to exhibit high heat resistance, and therefore it is preferably an oxygen atom. From the viewpoint of solubility, X is preferably not crosslinked. Further, m is independently an integer of 0 to 9, and at least one of m is an integer of 1 to 9.

In the formula (0), when the moiety represented by the naphthalene structure is r=0, it is a single ring structure, when r=1, it is a bicyclic structure, and when r=2, it is a tricyclic structure. r is independently an integer from 0 to 2. The above m is determined by the ring structure determined by r.

The compound represented by the above formula (0), although having a relatively low molecular weight, has higher heat resistance due to the rigidity of its structure, and thus can be used for high-temperature baking conditions. Further, the molecule has tertiary carbon or quaternary carbon, and the crystallinity is suppressed, and it can be suitably used as a film forming composition for use in the production of a film for lithography.

Further, it has high solubility in a safe solvent, and is excellent in heat resistance and etching resistance. The composition containing a lithographic resist represented by the formula (0) forms a composition and provides a good resist pattern shape.

In addition, since the molecular weight is relatively low and the viscosity is low, even if the substrate has a step (especially a fine space or a hole pattern, etc.), it can be uniformly filled to the corners of the step, and the flatness of the film is easily improved. As a result, the lithography of the compound represented by the formula (0) was used to form a composition embedding and planarizing property using the underlayer film. Further, since the compound represented by the formula (0) has a compound having a relatively high carbon concentration, it can impart high etching resistance.

Further, since the composition containing the compound represented by the formula (0) has a high aromatic density, the refractive index is high, and the coloring is suppressed by heat treatment in a wide range from low temperature to high temperature, so that it can be used as various kinds of optics. The component forming composition is used. Among them, a compound having a quaternary carbon suppresses oxidative decomposition, suppresses coloration of a compound, and has high heat resistance, and is preferable from the viewpoint of improving solvent solubility. In addition to being used in the form of a film or a sheet, the optical element can also be used as a plastic lens (稜鏡 lens, lenticular lens, microlens, Fresnel lens, viewing angle control lens, contrast lifting lens, etc.), retardation film. A film for electromagnetic wave shielding, germanium, an optical fiber, a solder resist for printed wiring, a plating resist, an interlayer insulating film for a multilayer printed wiring board, and a photosensitive optical waveguide.

 [Compound represented by formula (1)]  

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

In the above formula (1), R ⁰ is synonymous with the above R ^Y and is a hydrogen atom, an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms. Since R ⁰ is a hydrogen atom, an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, the heat resistance is relatively high, and the solvent solubility tends to be improved. Further, R ⁰ is an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, which suppresses oxidative decomposition and suppresses coloring of the compound, and is preferred from the viewpoint of improving heat resistance and solvent solubility. R ¹ is an n-valent group or a single bond having 1 to 60 carbon atoms, and via these R ¹ , each of the aromatic rings generates a bond.

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 an alkenyl group having 2 to 30 carbon atoms which may have a substituent. a group in which a hydrogen atom having 1 to 30 carbon atoms, a halogen atom, a nitro group, an amine group, a carboxylic acid group, a fluorenyl group, a hydroxyl group or a hydroxyl group which may have a substituent is substituted with a group represented by the above formula (0-1) The alkyl group, the aryl group, the alkenyl group, and the alkoxy group may contain an ether bond, a ketone bond or an ester bond. Here, at least one of R ² to R ⁵ includes the formula (0-1). base.

m ² and m ³ are each independently an integer of 0 to 8, and m ⁴ and m ⁵ are each independently an integer of 0 to 9. However, m ² , m ³ , m ⁴ and m ^{5 are} not 0 at the same time. The n system is synonymous with the above N and is an integer of 1 to 4. Here, when n is an integer of 2 or more, the structural formulae in n [ ] may be the same or different, and p ² to p ⁵ are each independently an integer of 0 to 2. Further, the alkyl group, the alkenyl group and the alkoxy group may be a linear chain, a branched chain or a cyclic group.

Further, the above n-valent group means an alkyl group having 1 to 60 carbon atoms when n = 1, and an alkylene group having 1 to 60 carbon atoms when n = 2, and 2 to 60 carbon atoms when n = 3; The alkane triyl group, when n=4, represents an alkane tetra group having a carbon number of 3 to 60. Examples of the above-mentioned n-valent group include those having a linear hydrocarbon group, a branched hydrocarbon group or an alicyclic hydrocarbon group. Here, the above alicyclic hydrocarbon group also contains a bridged aliphatic hydrocarbon group. Further, the n-valent group may have an aromatic group having 6 to 60 carbon atoms.

Further, 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 above alicyclic hydrocarbon group also contains a bridged aliphatic hydrocarbon group.

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

Moreover, since it has high solubility in a safe solvent and is excellent in heat resistance and etching resistance, a composition for forming a lithographic resist containing a compound represented by the above formula (1) can provide a favorable resist pattern shape.

In addition, because of the relatively low molecular weight and low viscosity, even a substrate having a step (especially a fine space or a hole pattern) can be uniformly filled to each corner of the step, and the flatness of the film is easily improved. As a result, the composition was formed using the underlayer film using this lithography, and the embedding and planarization characteristics were good. Further, since the compound has a relatively high carbon concentration, it can impart high etching resistance.

Further, since the aromatic density is high, the refractive index is high, and the coloring is suppressed by heat treatment in a wide range from low temperature to high temperature. Therefore, it can be used as a composition for forming various optical elements. Among them, a compound having a quaternary carbon suppresses oxidative decomposition, suppresses coloration of a compound, and has high heat resistance, and is preferable from the viewpoint of improving solvent solubility. In addition to being used in the form of a film or a sheet, the optical element can also be used as a plastic lens (稜鏡 lens, lenticular lens, microlens, Fresnel lens, viewing angle control lens, contrast lifting lens, etc.), retardation film, and electromagnetic wave shielding. Film, germanium, optical fiber, flexible solder resist for printed wiring, anti-plating agent, interlayer insulating film for multilayer printed circuit boards, and photosensitive optical waveguide.

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

In the formula (1-1), R ⁰ , R ¹ , R ⁴ , R ⁵ , n, p ² to p ⁵ , m ⁴ and m ⁵ are synonymous with the definition described in the above formula (1), R ⁶ ~ R ^{7 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, a halogen atom, The nitro group, the amine group, the carboxylic acid group, and the fluorenyl group, each of R ¹⁰ to R ^{11 is} independently a hydrogen atom or a group represented by the following formula (0-2), and at least one of R ¹⁰ to R ¹¹ is as follows. The formula (0-2) represents a group, and m ⁶ and m ⁷ are each independently an integer of 0 to 7, but m ⁴ , m ⁵ , m ⁶ and m ^{7 are} not 0 at the same time.

(In the formula (0-2), R ^X is synonymous with the definition described in the above formula (0-1), and s is an integer of 0 to 30).

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

In the formula (1-2), R ⁰ , R ¹ , R ⁶ , R ⁷ , R ¹⁰ , R ¹¹ , n, p ² to p ⁵ , m ⁶ and m ⁷ are the same as those in the above formula (1-1) The definitions are synonymous, R ⁸ to R ⁹ are synonymous with R ⁶ to R ⁷ described above, R ¹² to R ¹³ are synonymous with R ¹⁰ to R ¹¹ described above, and m ⁸ and m ⁹ are each independently an integer of 0-8. However, m ⁶ , m ⁷ , m ⁸ and m ^{9 are} not 0 at the same time.

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

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

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

In the above formula (1b), R ⁰ , R ¹ , R ⁴ , R ⁵ , R ¹⁰ , R ¹¹ , m ⁴ , m ⁵ and n are synonymous with those described in the above formula (1), and R ⁶ and R ^{7 are} 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 above formula (1a) is more preferably a compound represented by the following formula (1b') from the viewpoint of reactivity.

In the above formula (11), 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 and m ^{6. The} m ⁷ system is synonymous with the above formula (1-1).

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

In the above 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 above formula (1-2).

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

In the above 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 above formula (1-2).

Specific examples of the compound represented by the above formula (0) are as follows, but the compound represented by the formula (0) is not limited to the specific examples listed herein.

In the above formula, X's system and the above-described formula (0) described synonymous, R ^{T 'system} and the above-described formula (0) described the same meaning as R ^T, m is independently an integer of 1 to 6.

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

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

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

Among the above compounds, R ² , R ³ , R ⁴ and R ⁵ are synonymous with those described in the above 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 the group consisting of R ² , R ³ , R ⁴ and R ⁵ includes a group represented by the following formula (0-1), and when m ² , m ³ , m ⁴ and m ^{5 are} not different, it is 0.

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

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

(In the formula (0-2), R ^X is synonymous with the above formula (0-1), and s is an integer of 0 to 30).

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

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

(In the formula (0-2), R ^X is synonymous with the above formula (0-1), and s is an integer of 0 to 30).

In the following, a specific example of the compound represented by the above formula (0) is further exemplified, but the compound represented by the formula (0) is not limited to the specific examples listed herein.

In the ^formula, R ^0, R ^1, n lines of the above formula (1-1) described by synonymous, R ^{10 'and} R ^11' and the system described above of R ¹⁰ and R of formula (1-1) is synonymous ^11, R ^4' and 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 an alkenyl group having 2 to 30 carbon atoms which may have a substituent a hydrogen atom having an alkoxy group having 1 to 30 carbon atoms, a halogen atom, a nitro group, an amine group, a carboxylic acid group, a thiol group, a hydroxyl group or a hydroxyl group which may have a substituent, which is substituted by the following formula (0-1), The alkyl group, the aryl group, the alkenyl group, and the alkoxy group may further contain an ether bond, a ketone bond or an ester bond, and at least one of R ^{10 '} and R ^{11 ' may} be substituted by the following formula (0-2) The basis. 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 the formula (0-2), R ^X is synonymous with the above formula (0-1), and s is an integer of 0 to 30).

R ⁰ may, for example, be methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, decyl, undecyl, dodecyl, tridecyl, benzene Base, naphthyl, anthracenyl, fluorenyl, biphenyl, and heptyl.

R ^{4 '} and R ^{5 '} may, for example, be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a decyl group, an undecyl group, a dodecyl group, or a trisyl group. Decaalkyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, cyclodecyl, cycloundecyl, cyclododecyl, cyclo 30 Alkyl, norbornyl, adamantyl, phenyl, naphthyl, anthracenyl, fluorenyl, biphenyl, heptyl, vinyl, allyl, tridecenyl, methoxy, ethoxy A group, a triacontyloxy group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a fluorenyl group.

Each of R ⁰ , R ^{4 '} and R ^5' is exemplified to include an isomer. For example, butyl includes n-butyl, isobutyl, sec-butyl, tert-butyl.

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

R ¹⁶ may, for example, be a methylene group, an exoethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, a decyl group, a hydrazine group, a hydrazine group, an eleven group group, and a stretching group. Twelve base, extens 30, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, fluorenyl, fluorenyl, extensible Eleven base, extended ring twelve base, extended ring thirty base, divalent thiol group, divalent adamantyl group, divalent phenyl group, divalent naphthyl group, divalent thiol group, divalent A mercapto group, a divalent biphenyl group, a divalent heptyl group, a divalent vinyl group, a divalent allyl group, and a divalent thirteen carbon group.

Each of the foregoing R ¹⁶ is illustrative of an isomer. For example, butyl includes n-butyl, isobutyl, sec-butyl, tert-butyl.

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

R ¹⁴ may, for example, be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a decyl group, an undecyl group, a dodecyl group, a triaconyl group or a ring Propyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, cyclodecyl, cycloundecyl, cyclododecyl, cyclotridecyl, halo Adamantyl, phenyl, naphthyl, anthracenyl, fluorenyl, biphenyl, heptyl, vinyl, allyl, tridecyl, methoxy, ethoxy, triacontane An oxy group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom or a fluorenyl group.

Each of the foregoing R ¹⁴ is illustrative of an isomer. For example, butyl includes n-butyl, isobutyl, sec-butyl, tert-butyl.

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

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

R ¹⁴ may, for example, be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a decyl group, an undecyl group, a dodecyl group, a triaconyl group or a ring Propyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, cyclodecyl, cycloundecyl, cyclododecyl, cyclotridecyl, halo Adamantyl, phenyl, naphthyl, anthracenyl, fluorenyl, biphenyl, heptyl, vinyl, allyl, tridecyl, methoxy, ethoxy, triacontane An oxy group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom or a fluorenyl group.

Each of the foregoing R ¹⁴ is illustrative of an isomer. For example, butyl includes n-butyl, isobutyl, sec-butyl, tert-butyl.

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

R ¹⁵ may, for example, be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a decyl group, an undecyl group, a dodecyl group, a triaconyl group or a ring Propyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, cyclodecyl, cycloundecyl, cyclododecyl, cyclotridecyl, halo Adamantyl, phenyl, naphthyl, anthracenyl, fluorenyl, biphenyl, heptyl, vinyl, allyl, tridecyl, methoxy, ethoxy, triacontane An oxy group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom or a fluorenyl group.

Each of the foregoing R ¹⁵ is illustrative of an isomer. For example, butyl includes n-butyl, isobutyl, sec-butyl, tert-butyl.

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

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

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

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

In the above formula, R ^0A is synonymous with R ^Y in the above formula (0), R ^1A′ is synonymous with R ^Z in the above formula (0), and R ¹⁰ to R ¹³ are the same as the above formula (1-2). Synonymous.

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

R ¹⁴ may, for example, be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a decyl group, an undecyl group, a dodecyl group, a triaconyl group or a ring Propyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, cyclodecyl, cycloundecyl, cyclododecyl, cyclotridecyl, halo Alkyl, adamantyl, phenyl, naphthyl, anthracenyl, heptyl, vinyl, allyl, tridecenyl, methoxy, ethoxy, octadecyloxy, fluoro, chloro Atom, bromine atom, iodine atom, sulfhydryl group.

Each of the foregoing R ¹⁴ is illustrative of an isomer. For example, butyl includes n-butyl, isobutyl, sec-butyl, tert-butyl.

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

R ¹⁵ may, for example, be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a decyl group, an undecyl group, a dodecyl group, a triaconyl group or a ring Propyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, cyclodecyl, cycloundecyl, cyclododecyl, cyclotridecyl, halo Alkyl, adamantyl, phenyl, naphthyl, anthracenyl, heptyl, vinyl, allyl, tridecenyl, methoxy, ethoxy, octadecyloxy, fluoro, chloro Atom, bromine atom, iodine atom, sulfhydryl group.

Each of the foregoing R ¹⁵ is illustrative of an isomer. For example, butyl includes n-butyl, isobutyl, sec-butyl, tert-butyl.

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

R ¹⁶ may, for example, be a methylene group, an exoethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, a decyl group, a hydrazine group, a hydrazine group, an eleven group group, and a stretching group. Twelve base, extens 30, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, fluorenyl, fluorenyl, extensible Eleven base, extended ring twelve base, extended ring thirty base, divalent thiol group, divalent adamantyl group, divalent phenyl group, divalent naphthyl group, divalent thiol group, divalent A heptyl group, a divalent vinyl group, a divalent allyl group, and a divalent 30-carbon alkenyl group.

Each of the foregoing R ¹⁶ is illustrative of an isomer. For example, butyl includes n-butyl, isobutyl, sec-butyl, tert-butyl.

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

R ¹⁴ may, for example, be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a decyl group, an undecyl group, a dodecyl group, a triaconyl group or a ring Propyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, cyclodecyl, cycloundecyl, cyclododecyl, cyclotridecyl, halo Alkyl, adamantyl, phenyl, naphthyl, anthracenyl, heptyl, vinyl, allyl, tridecenyl, methoxy, ethoxy, octadecyloxy, fluoro, chloro Atom, bromine atom, iodine atom, sulfhydryl group.

Each of the foregoing R ¹⁴ is illustrative of an isomer. For example, butyl includes n-butyl, isobutyl, sec-butyl, tert-butyl.

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

R ¹⁴ may, for example, be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a decyl group, an undecyl group, a dodecyl group, a triaconyl group or a ring Propyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, cyclodecyl, cycloundecyl, cyclododecyl, cyclotridecyl, halo Alkyl, adamantyl, phenyl, naphthyl, anthracenyl, heptyl, vinyl, allyl, tridecenyl, methoxy, ethoxy, octadecyloxy, fluoro, chloro Atom, bromine atom, iodine atom, sulfhydryl group.

Each of the foregoing R ¹⁴ is illustrative of an isomer. For example, butyl includes n-butyl, isobutyl, sec-butyl, tert-butyl.

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

Among the above-exemplified compounds, a compound having a dibenzoxanthene skeleton is more preferable from the viewpoint of heat resistance.

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

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

Among the above-exemplified compounds, a compound having a dibenzoxanthene skeleton is more preferable from the viewpoint of heat resistance.

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

In the above formula, R ^0A is synonymous with R ^Y in the above formula (0), R ^1A′ is synonymous with R ^Z in the above formula (0), and R ¹⁰ to R ¹³ are the same as the above formula (1-2). Synonymous.

Among the above-exemplified compounds, a compound having a xanthene skeleton is more preferable from the viewpoint of heat resistance.

Further, examples of the compound represented by the above formula (0) include compounds represented by the following formulas.

Among the above compounds, R ¹⁰ to R ¹³ are synonymous with those described in the above formula (1-2). R ¹⁴ , R ¹⁵ , R ¹⁶ , m ¹⁴ and m ^14' are synonymous with those described in the above formula.

 [Method for Producing Compound represented by Formula (1)]  

The compound represented by the formula (1) used in the present embodiment can be suitably synthesized by a conventional method, and the synthesis method is not particularly limited. For example, under normal pressure, a polyphenol compound is obtained by subjecting a biphenyldiol, a binaphthol or a hydrazin to a corresponding aldehyde or a ketone under a acid catalyst to obtain a polyphenol compound, and then, At least one phenolic hydroxyl group of the polyphenol compound is obtained by introducing a group represented by the following formula (0-1A). Further, a group represented by the following formula (0-1B) is introduced, and the hydroxyl group is also obtained by introducing a group represented by the following formula (0-1A). Further, if necessary, it can also be carried out under pressure.

(In the 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 alkyl group having 1 to 30 carbon atoms, and s is an integer of 0 to 30).

Examples of the biphenyldiols include, but are not limited to, biphenyldiol, methylbiphenol, methoxybiphenol, and the like. These may be used alone or in combination of two or more. Among these, it is more preferable to use biphenyldiol from the viewpoint of stability of supply of raw materials.

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

Examples of the aldehydes include formaldehyde, trioxane, polyoxymethylene, benzaldehyde, acetaldehyde, propionaldehyde, phenylacetaldehyde, phenylpropanal, hydroxybenzaldehyde, chlorobenzaldehyde, nitrobenzaldehyde, Methyl benzaldehyde, ethyl benzaldehyde, butyl benzaldehyde, biphenyl formaldehyde, naphthaldehyde, indole formaldehyde, phenanthrene formaldehyde, indole formaldehyde, furfural, etc., but are not limited thereto. These may be used alone or in combination of two or more. Among these, from the viewpoint of providing high heat resistance, it is preferred to use benzaldehyde, phenylacetaldehyde, phenylpropanal, hydroxybenzaldehyde, chlorobenzaldehyde, nitrobenzaldehyde, methylbenzaldehyde, and B. Benzoaldehyde, butyl benzaldehyde, cyclohexylbenzaldehyde, biphenylformaldehyde, naphthaldehyde, anthracene formaldehyde, phenanthrene, anthracene formaldehyde, furfural, and benzaldehyde, hydroxybenzaldehyde, chlorobenzaldehyde, nitrobenzaldehyde, Methyl benzaldehyde, ethyl benzaldehyde, butyl benzaldehyde, cyclohexylbenzaldehyde, biphenyl formaldehyde, naphthaldehyde, anthracene formaldehyde, phenanthrene, anthracene formaldehyde, furfural, high etching resistance, and better.

Examples of the ketones include acetone, methyl ethyl ketone, cyclobutanone, cyclopentanone, cyclohexanone, norbornene, tricyclohexanone, tricyclic fluorenone, adamantanone, anthrone, and benzopyrene. Ketone, anthracene, ethane naphthone, anthracene, acetophenone, diethyl benzene benzene, triethylene phenyl benzene, naphthyl ethyl ketone, diphenyl carbonyl naphthalene, phenyl carbonyl biphenyl, diphenyl carbonyl Biphenyl, benzophenone, diphenylcarbonylbenzene, triphenylcarbonylbenzene, naphthylphenyl ketone, diphenylcarbonylnaphthalene, phenylcarbonylbiphenyl, diphenylcarbonylbiphenyl, etc., but not limited This is the case. These may be used alone or in combination of two or more. Among these, from the viewpoint of providing high heat resistance, it is preferred to use cyclopentanone, cyclohexanone, norbornene, tricyclohexanone, tricyclic fluorenone, adamantanone, anthrone, benzofluorene. Ketone, anthracene, ethane naphthone, anthracene, acetophenone, diethyl benzene benzene, triethylene phenyl benzene, naphthyl ethyl ketone, diphenyl carbonyl naphthalene, phenyl carbonyl biphenyl, diphenyl carbonyl Biphenyl, benzophenone, diphenylcarbonylbenzene, triphenylcarbonylbenzene, naphthylphenyl ketone, diphenylcarbonylnaphthalene, phenylcarbonylbiphenyl, diphenylcarbonylbiphenyl, and phenylethyl Ketone, diethyl benzene benzene, triethylene phenyl benzene, naphthyl ethyl ketone, diphenyl carbonyl naphthalene, phenyl carbonyl biphenyl, diphenyl carbonyl biphenyl, benzophenone, diphenyl carbonyl benzene, triphenyl The carbonyl benzene, naphthyl phenyl ketone, diphenyl carbonyl naphthalene, phenyl carbonyl biphenyl, and diphenyl carbonyl biphenyl have high etching resistance and are more preferable. An aldehyde or a ketone is preferably an aldehyde having an aromatic ring or an aromatic ketone, and has both high heat resistance and high etching resistance.

The acid catalyst used in the above reaction can be appropriately selected from the conventional ones, and is not particularly limited. Such an acid catalyst, for example, an inorganic acid or an organic acid, is widely known, and examples thereof include inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, and hydrofluoric acid; oxalic acid, malonic acid, succinic acid, adipic acid, and hydrazine; Diacid, citric acid, fumaric acid, maleic acid, formic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, naphthalenesulfonate An organic acid such as acid or naphthalene disulfonic acid; a Lewis acid such as zinc chloride, aluminum chloride, iron chloride or boron trifluoride; or a solid such as tungstic acid, phosphotungstic acid, lanthanum molybdate or phosphomolybdic acid Acid or the like, but is not particularly limited thereto. Among these, from the viewpoint of production, organic acids and solid acids are preferred, and hydrochloric acid or sulfuric acid is preferably used from the viewpoint of ease of production, ease of handling, and the like. In addition, the acid catalyst may be used singly or in combination of two or more. In addition, the amount of the acid catalyst to be used is appropriately set in accordance with the type of the raw material to be used, the type of the catalyst to be used, and the reaction conditions, and is not particularly limited, and is preferably 0.01 to 100 parts by mass based on 100 parts by mass of the reaction raw material.

In the above reaction, a reaction solvent can also be used. The reaction solvent is not particularly limited as long as it is a reaction with an aldehyde or a ketone to be used with a biphenyldiol, a binaphthol or a hydrazine diol, and can be appropriately selected from the conventional ones. The reaction solvent may, for example, be water, methanol, ethanol, propanol, butanol, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether or a mixed solvent thereof. Further, the solvent may be used alone or in combination of two or more.

In addition, the amount of the reaction solvent to be used may be appropriately set in accordance with the raw material to be used, the type of the catalyst to be used, the reaction conditions, and the like, and is not particularly limited. However, it is preferably 0 to 2000 by mass based on 100 parts by mass of the reaction raw material. The scope of the share. Further, the reaction temperature in the above reaction can be appropriately selected in accordance with the reactivity of the reaction raw material, and is not particularly limited, but is usually in the range of 10 to 200 °C.

In order to obtain a polyphenol compound, the reaction temperature is preferably higher, and specifically, it is preferably in the range of 60 to 200 °C. Further, the reaction method can be suitably selected by a conventional method, and is not particularly limited, and examples thereof include a method in which a biphenyldiol, a binaphthol or a hydrazine diol, an aldehyde or a ketone, and a catalyst are introduced together. Or a method in which a biphenyldiol, a binaphthol or a hydrazine diol or an aldehyde or a ketone is dropped in the presence of a catalyst. After completion of the polycondensation reaction, the isolation of the obtained compound can be carried out according to a usual method, and is not particularly limited. For example, in order to remove unreacted raw materials or catalysts present in the system, by using a general method of removing the volatile matter by using the temperature of the reaction vessel to 130 to 230 ° C and removing the volatile matter at about 1 to 50 mmHg, the object can be separated from the target. Compound.

The preferred reaction conditions are 1.0 moles to excess of aldehydes or ketones, 0.00 moles to excess of biphenyldiols, binaphthols or hydrazide diols, and 0.001 to 1 moles of acid catalyst. Under normal pressure, the reaction is carried out at 50 to 150 ° C for about 20 minutes to 100 hours.

After the reaction is completed, the object can be isolated by a conventional method. For example, the reaction solution is concentrated, pure water is added to precipitate the reaction product, and after cooling to room temperature, the mixture is filtered and separated, and the obtained solid matter is filtered, dried, and separated and purified by by-column chromatography. The compound represented by the above formula (1) is obtained by subjecting the solvent to distillation, filtration, and drying to obtain the object.

A method of introducing a group represented by the above formula (0-1A) into at least one phenolic hydroxyl group of the polyphenol compound is conventional. For example, as shown below, a group represented by the formula (0-1A) can be introduced into at least one phenolic hydroxyl group of the above compound. The compound for the group represented by the formula (0-1A) can be synthesized or easily obtained by a known method, and examples thereof include ethyl 2-methacrylate isocyanate and ethyl 2-ethyl acrylate. This is the case.

For example, the above compound is dissolved or suspended in an aprotic solvent such as acetone, tetrahydrofuran (THF) or propylene glycol monomethyl ether acetate. Next, the reaction is carried out for 6 to 72 hours in the presence of an alkali catalyst such as sodium hydroxide, potassium hydroxide, sodium methoxide or sodium ethoxide at a normal pressure of 20 to 150 °C. The reaction solution is neutralized with an acid, added to distilled water, and precipitated as a white solid. After the separated solid is washed with distilled water or the solvent is evaporated to dryness, if necessary, it is washed with distilled water and dried. A compound in which a hydrogen atom of a hydroxyl group is substituted with a group represented by the above formula (0-1A).

Further, the timing of introducing the group substituted by the group represented by the above formula (0-1A) can be carried out not only after the condensation reaction of the binaphthol with the aldehyde or the ketone but also before the condensation reaction. Further, it may be carried out after the resin is produced as will be described later.

Further, a method in which a group represented by the above formula (0-1B) is introduced into at least one of the phenolic hydroxyl groups of the polyphenol compound, and a group represented by the formula (0-1A) is introduced into the hydroxyl group is also known. For example, in the phenolic hydroxyl group of at least one of the above compounds, a group represented by the formula (0-1B) may be introduced, and a group represented by the formula (0-1A) may be introduced into the hydroxyl group.

The compound represented by the formula (0-1B) can be synthesized or easily obtained by a known method, and examples thereof include chlorohydrin, bromoethanol, 2-chloroethyl acetate, 2-bromoethyl acetate, and acetic acid. -2-iodoethyl ester, ethylene oxide, propylene oxide, butylene oxide, ethylene carbonate, propylene carbonate, butylene carbonate, but is not limited thereto.

For example, the above compound is dissolved or suspended in an aprotic solvent such as acetone, tetrahydrofuran (THF) or propylene glycol monomethyl ether acetate. Next, the reaction is carried out for 6 to 72 hours in the presence of an alkali catalyst such as sodium hydroxide, potassium hydroxide, sodium methoxide or sodium ethoxide at a normal pressure of 20 to 150 °C. The reaction solution is neutralized with an acid, added to distilled water, and precipitated as a white solid. After the separated solid is washed with distilled water or the solvent is evaporated to dryness, if necessary, it is washed with distilled water and dried. A compound in which a hydrogen atom of a hydroxyl group is substituted by a group represented by the formula (0-1B).

In the case of using 2-chloroethyl acetate, 2-bromoethyl acetate or 2-iodoethyl acetate, after introducing an ethyl ethoxyethyl group, a hydroxyethyl group is introduced by deacylation. .

In the case of using ethylene carbonate, propylene carbonate or butylene carbonate, a decarboxylation reaction is initiated by addition of an alkylene carbonate to introduce a hydroxyalkyl group.

Then, the above compound is dissolved or suspended in an aprotic solvent such as acetone, tetrahydrofuran (THF) or propylene glycol monomethyl ether acetate. Next, the reaction is carried out for 6 to 72 hours in the presence of an alkali catalyst such as sodium hydroxide, potassium hydroxide, sodium methoxide or sodium ethoxide at a normal pressure of 20 to 150 °C. The reaction solution is neutralized with an acid, added to distilled water, and precipitated as a white solid. After the separated solid is washed with distilled water or the solvent is evaporated to dryness, if necessary, it is washed with distilled water and dried. A compound in which a hydrogen atom of a hydroxyl group is substituted with a group represented by the formula (0-1A).

In the present embodiment, the group substituted by the formula represented by the formula (0-1A) means that the reaction is carried out in the presence of a radical or an acid/base, and is used for an acid, a base or an organic solvent used for coating a solvent or a developing solution. Solubility changes. The base substituted by the above formula (0-1A), in order to form a higher sensitivity. In the case of a high-resolution pattern, it is preferred to have a property of performing a chain reaction in the presence of a radical or in the presence of an acid/base.

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

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

The resin obtained by using the compound represented by the above formula (1) as a monomer may, for example, be a structure represented by the following formula (3). In other words, the composition of the present embodiment may be a resin containing 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, a aryl group having 6 to 30 carbon atoms which may have a substituent, and a carbon number of 1 to 30 which may have a substituent. An alkoxy group or a single bond, the above alkyl group, and the above-mentioned extended aryl group, and the above alkyleneoxy group may also contain an ether bond, a ketone bond or an ester bond. Further, the alkylene group or the alkoxy group may be a linear, branched or cyclic group.

R ⁰ is synonymous with R ^Y described above, R ¹ is an n-valent or a single bond having 1 to 60 carbon atoms, and R ² to R ⁵ are each independently an alkyl group having 1 to 30 carbon atoms which may have a substituent, and may have a substitution. An aryl group having 6 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, an alkoxy group having 1 to 30 carbon atoms which may have a substituent, a halogen atom, a nitro group, an amine group, and a carboxyl group The acid group, the thiol group, the hydroxyl group or the hydrogen atom of the hydroxy group is substituted with an acid dissociable group, and the alkyl group, the aryl group, the above alkenyl group, and the alkoxy group may further contain an ether bond, a ketone bond or an ester bond. , at least one of R ² to R ⁵ contains a group represented by the above 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 an integer of 0 to 9. However, m ² , m ³ , m ⁴ and m ^{5 are} not 0 at the same time, and n is synonymous with the above N. Here, when n is an integer of 2 or more, the structural formulas in n [ ] may be the same or different, p ² ~ p ⁵ is synonymous with the above r.

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

The resin of the present embodiment is obtained by reacting a compound represented by the above formula (1) with a compound having crosslinking reactivity. The compound having a crosslinking reactivity is not particularly limited as long as it can oligomerize or polymerize the compound represented by the above formula (1). Specific examples thereof include, but are not particularly limited to, an aldehyde, a ketone, a carboxylic acid, a carboxylic acid halide, a halogen-containing compound, an amine compound, an imine compound, an isocyanate, and an unsaturated hydrocarbon group-containing compound.

Specific examples of the resin having the structure represented by the above formula (3) include phenolic aldehydes by a condensation reaction between a compound represented by the above formula (1) and an aldehyde and/or a ketone having a compound having crosslinking reactivity. Varnished resin.

Here, examples of the aldehyde used in the novolak-forming of the compound represented by the above formula (1) include formaldehyde, trioxane, polyoxymethylene, benzaldehyde, acetaldehyde, propionaldehyde, phenylacetaldehyde, and phenylpropanal. , hydroxybenzaldehyde, chlorobenzaldehyde, nitrobenzaldehyde, methyl benzaldehyde, ethyl benzaldehyde, butyl benzaldehyde, biphenyl formaldehyde, naphthaldehyde, anthracene formaldehyde, phenanthrene, anthracene formaldehyde, furfural, etc., but not It is particularly limited to these. The ketones include the above ketones. Among these, it is more preferably formaldehyde. In addition, these aldehydes and/or ketones may be used alone or in combination of two or more. Further, the amount of the aldehyde and/or ketone used is not particularly limited, and is preferably 0.2 to 5 moles, more preferably 0.5 to 2 moles, per mole of the compound 1 represented by the above formula (1).

In the condensation reaction of the compound represented by the above formula (1) with an aldehyde and/or a ketone, a catalyst may also be used. The acid catalyst used herein can be suitably selected from the conventional ones without particular limitation. Such an acid catalyst is widely known as an inorganic acid or an organic acid, and examples thereof include inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, and hydrofluoric acid; oxalic acid, malonic acid, succinic acid, adipic acid, and bismuth; Acid, citric acid, fumaric acid, maleic acid, formic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid An organic acid such as naphthalene disulfonic acid; a Lewis acid such as zinc chloride, aluminum chloride, iron chloride or boron trifluoride; a solid acid such as tungstic acid, phosphotungstic acid, lanthanum molybdate or phosphomolybdic acid; Etc., but it is not particularly limited to this. Among these, from the viewpoint of production, organic acids and solid acids are preferred, and hydrochloric acid or sulfuric acid is preferred from the viewpoint of ease of production, ease of handling, and the like. In addition, the acid catalyst may be used singly or in combination of two or more.

In addition, the amount of the acid catalyst to be used may be appropriately set in accordance with the type of the raw material to be used, the type of the catalyst to be used, and the reaction conditions, and is not particularly limited. However, it is preferably 0.01 to 100 parts by mass based on 100 parts by mass of the reaction raw material. However, with hydrazine, hydroxy hydrazine, benzofuran, hydroxy hydrazine, decene, biphenyl, bisphenol, trisphenol, dicyclopentadiene, tetrahydroanthracene, 4-vinylcyclohexene, decadiene, 5- In the case of a copolymerization reaction of a compound having a non-conjugated double bond such as vinyl norquin-2-ene, α-pinene, β-pinene or limonene, an aldehyde is not necessarily required.

In the condensation reaction of the compound represented by the above formula (1) with an aldehyde and/or a ketone, a reaction solvent can also be used. The reaction solvent in the polycondensation can be appropriately selected from the conventional ones, and is not particularly limited. For example, water, methanol, ethanol, propanol, butanol, tetrahydrofuran, dioxane or a mixed solvent of these may be mentioned. Further, the solvent may be used alone or in combination of two or more.

In addition, the amount of the solvent to be used may be appropriately set in accordance with the raw material to be used, the type of the catalyst to be used, the reaction conditions, and the like, and is not particularly limited. However, it is preferably 0 to 2000 parts by mass based on 100 parts by mass of the reaction raw material. The scope. Further, the reaction temperature is appropriately selected depending on the reactivity of the reaction raw material, and is not particularly limited, but is usually in the range of 10 to 200 °C. In addition, the reaction method can be appropriately selected from the conventional methods, and is not particularly limited, and examples thereof include a method of introducing a compound represented by the above formula (1), an aldehyde and/or a ketone, and a catalyst, or expressing the above formula (1). A method in which a compound or an aldehyde and/or a ketone is dropped in the presence of a catalyst.

After completion of the polycondensation reaction, the isolation of the obtained compound can be carried out according to a usual method, and is not particularly limited. For example, in order to remove unreacted raw materials or catalysts present in the system, a general method of removing volatiles such as 1 to 50 mmHg by raising the temperature of the reaction vessel to 130 to 230 ° C can be used to separate the target. A phenolic varnished resin.

Here, the resin having the structure represented by the above formula (3) may be a homopolymer of the compound represented by the above formula (1), or may be a copolymer with other phenols. Here, examples of the phenol which can be copolymerized include phenol, cresol, dimethylphenol, trimethylphenol, butylphenol, phenylphenol, diphenylphenol, naphthylphenol, resorcin, Methyl resorcinol, catechol, butyl catechol, methoxy phenol, methoxy phenol, propyl phenol, pyrogallol, thymol, and the like are not particularly limited thereto.

Further, the resin having the structure represented by the above formula (3) may be copolymerized with a polymerizable monomer in addition to the above other phenols. Examples of the comonomer include naphthol, methylnaphthol, methoxynaphthol, dihydroxynaphthalene, anthracene, hydroxyindole, benzofuran, hydroxyindole, terpene, biphenyl, bisphenol, triphenol, Dicyclopentadiene, tetrahydroanthracene, 4-vinylcyclohexene, decadiene, vinyl norbornene, decene, limonene, etc., but are not particularly limited thereto. Further, the resin having the structure represented by the above formula (2) may be a copolymer of the compound represented by the above formula (1) and two or more (for example, two to four members) of the above phenol, or may be the above formula ( 1) a copolymer of the compound represented by the above-mentioned comonomer of 2 or more (for example, 2 to 4 member), or a compound represented by the above formula (1), the phenol and the comonomer of 3 or more A copolymer (for example, a 3 to 4 member system).

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

The resin having the structure represented by the above formula (3) is preferably one having a high solvent solubility from the viewpoint of being more easily applied to a wet process or the like. More specifically, when 1-methoxy-2-propanol (PGME) and/or propylene glycol monomethyl ether acetate (PGMEA) is used as a solvent, the solubility of the solvent is preferably 10% by mass or more. . Here, the solubility of PGME and/or PGMEA is defined as "the mass of the resin (the mass of the resin + the mass of the solvent) × 100 (% by mass)". For example, when 10 g of the resin is dissolved in 90 g of PGMEA, the solubility of the resin to PGMEA is "10 mass% or more", and when it is not dissolved, it is "less than 10 mass%".

 [Compound represented by formula (2)]  

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

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

R ^1A is an n ^A valent group or a single bond having 1 to 60 carbon atoms, and each of R ^{2A is} independently an alkyl group having 1 to 30 carbon atoms which may have a substituent, and an aryl group having 6 to 30 carbon atoms which may have a substituent. An alkenyl group having 2 to 30 carbon atoms which may have a substituent, an 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 fluorenyl group, a hydroxyl group or a hydroxyl group The alkyl group, the aryl group, the alkenyl group, and the alkoxy group may further contain an ether bond, a ketone bond or an ester bond, and the R ^2A may contain at least one of the above. The formula (0-1) represents the base.

n ^A is an integer of 1 to 4. Here, in the 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 no crosslinking. Here, when X ^A is an oxygen atom or a sulfur atom, it tends to exhibit high heat resistance, and therefore it is preferably an oxygen atom. From the viewpoint of solubility, X ^{A is} preferably not crosslinked.

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

q ^{A is} independently 0 or 1.

Further, the n-valent group means an alkyl group having 1 to 60 carbon atoms when n=1, an alkylene group having 1 to 30 carbon atoms when n=2, and a carbon number 2 when n=3. The alkane triyl group of 60, when n=4, represents an alkane tetrayl group having 3 to 60 carbon atoms. Examples of the above-mentioned n-valent group include those having a linear hydrocarbon group, a branched hydrocarbon group or an alicyclic hydrocarbon group. Here, the above-mentioned alicyclic hydrocarbon group also contains a bridged aliphatic hydrocarbon group. Further, the above n-valent group may contain an aromatic group having 6 to 60 carbon atoms.

Further, 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 above alicyclic hydrocarbon group also contains a bridged aliphatic hydrocarbon group.

Further, 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 above alicyclic hydrocarbon group also contains a bridged aliphatic hydrocarbon group.

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

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

In addition, since it has a relatively low molecular weight and a low viscosity, even if it is a substrate having a step (especially a fine space or a hole pattern), it can be uniformly filled to each corner of the step, and the flatness of the film is easily improved. The composition was formed using the underlayer film using this lithography, and the embedding and planarization characteristics were good. Further, since the compound has a relatively high carbon concentration, it can impart high etching resistance.

Further, since the aromatic density is high, the refractive index is high, and the coloring is suppressed by heat treatment in a wide range from low temperature to high temperature, and therefore it can be used as a composition for forming various optical elements. Among them, a compound having a quaternary carbon suppresses oxidative decomposition, suppresses coloration of a compound, and has high heat resistance, and is preferable from the viewpoint of improving solvent solubility. In addition to being used in the form of a film or a sheet, the optical element can also be used as a plastic lens (稜鏡 lens, lenticular lens, microlens, Fresnel lens, viewing angle control lens, contrast lifting lens, etc.), retardation film, and electromagnetic wave shielding. Film, germanium, optical fiber, flexible solder resist for printed wiring, anti-plating agent, interlayer insulating film for multilayer printed circuit boards, and photosensitive optical waveguide.

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

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

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

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

(In the formula (0-2), R ^X is synonymous with the definition described in the above formula (0-1), and s is an integer of 0 to 30).

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

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

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

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

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

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

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

The compound represented by the above formula (2) is further preferably a formula (BisN-1) to (BisN-4) or (XBisN-1) to (XBisN-3) from the viewpoint of solubility in an organic solvent. A compound represented by (BiN-1)~(BiN-4) or (XBiN-1)~(XBiN-3).

 [Method for Producing Compound represented by Formula (2)]  

The compound represented by the formula (2) used in the present embodiment can be appropriately synthesized by a conventional method, and the synthesis method is not particularly limited. For example, under normal pressure, a polyphenol compound can be obtained by subjecting a phenol or a naphthol to a corresponding aldehyde or ketone to a polycondensation reaction under an acid catalyst, and then, the following formula (0-1A) is obtained. The group indicated by the introduction of at least one phenolic hydroxyl group of the polyphenol compound.

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

(In the 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 alkyl group having 1 to 30 carbon atoms, and s is an integer of 0 to 30).

The naphthols are not particularly limited, and examples thereof include naphthol, methylnaphthol, methoxynaphthol, and naphthalenediol. From the viewpoint of easily producing a xanthene structure, naphthalenediol is more preferable.

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

Examples of the above aldehydes include formaldehyde, trioxane, polyoxymethylene, benzaldehyde, acetaldehyde, propionaldehyde, phenylacetaldehyde, phenylpropanal, hydroxybenzaldehyde, chlorobenzaldehyde, nitrobenzaldehyde, and methylbenzene. Formaldehyde, ethyl benzaldehyde, butyl benzaldehyde, biphenyl formaldehyde, naphthaldehyde, anthraquinone, phenanthrene, anthracene, furfural, etc., but are not limited thereto. These may be used alone or in combination of two or more. Among these, from the viewpoint of providing high heat resistance, it is preferred to use benzaldehyde, phenylacetaldehyde, phenylpropanal, hydroxybenzaldehyde, chlorobenzaldehyde, nitrobenzaldehyde, methylbenzaldehyde, and B. Benzoaldehyde, butyl benzaldehyde, cyclohexylbenzaldehyde, biphenylformaldehyde, naphthaldehyde, anthracene formaldehyde, phenanthrene, anthracene formaldehyde, furfural, and benzaldehyde, hydroxybenzaldehyde, chlorobenzaldehyde, nitrobenzaldehyde, Methyl benzaldehyde, ethyl benzaldehyde, butyl benzaldehyde, cyclohexylbenzaldehyde, biphenyl formaldehyde, naphthaldehyde, anthracene formaldehyde, phenanthrene, anthracene formaldehyde, furfural, high etching resistance, and better.

Examples of the ketones include acetone, methyl ethyl ketone, cyclobutanone, cyclopentanone, cyclohexanone, norbornene, tricyclohexanone, tricyclic fluorenone, adamantanone, anthrone, and benzopyrene. Ketone, anthracene, ethane naphthone, anthracene, acetophenone, diethyl benzene benzene, triethylene phenyl benzene, naphthyl ethyl ketone, diphenyl carbonyl naphthalene, phenyl carbonyl biphenyl, diphenyl carbonyl Biphenyl, benzophenone, diphenylcarbonylbenzene, triphenylcarbonylbenzene, naphthylphenyl ketone, diphenylcarbonylnaphthalene, phenylcarbonylbiphenyl, diphenylcarbonylbiphenyl, etc., but not limited This is the case. These may be used alone or in combination of two or more. Among these, from the viewpoint of providing high heat resistance, it is preferred to use cyclopentanone, cyclohexanone, norbornene, tricyclohexanone, tricyclic fluorenone, adamantanone, anthrone, benzofluorene. Ketone, anthracene, ethane naphthone, anthracene, acetophenone, diethyl benzene benzene, triethylene phenyl benzene, naphthyl ethyl ketone, diphenyl carbonyl naphthalene, phenyl carbonyl biphenyl, diphenyl carbonyl Biphenyl, benzophenone, diphenylcarbonylbenzene, triphenylcarbonylbenzene, naphthylphenyl ketone, diphenylcarbonylnaphthalene, phenylcarbonylbiphenyl, diphenylcarbonylbiphenyl, and phenylethyl Ketone, diethyl benzene benzene, triethylene phenyl benzene, naphthyl ethyl ketone, diphenyl carbonyl naphthalene, phenyl carbonyl biphenyl, diphenyl carbonyl biphenyl, benzophenone, diphenyl carbonyl benzene, triphenyl The carbonylbenzene, naphthylphenyl ketone, diphenylcarbonylnaphthalene, phenylcarbonylbiphenyl, and diphenylcarbonylbiphenyl have high etching resistance and are more preferable.

A ketone having a ketone having an aromatic ring is preferred 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 from the conventional ones, and is not particularly limited. The acid catalyst is not particularly limited, and a conventional inorganic acid or organic acid can be suitably selected. Examples thereof include inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, and hydrofluoric acid; oxalic acid, formic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, and naphthalenesulfonic acid; An organic acid such as acid or naphthalene disulfonic acid; a Lewis acid such as zinc chloride, aluminum chloride, iron chloride or boron trifluoride; or a solid such as tungstic acid, phosphotungstic acid, lanthanum molybdate or phosphomolybdic acid Acid, etc. From the viewpoint of production availability such as ease of handling or ease of handling, hydrochloric acid or sulfuric acid is preferably used. Further, the acid catalyst may be used alone or in two or more types.

In the above reaction, a reaction solvent can also be used. The reaction solvent is not particularly limited as long as it is an aldehyde or a ketone to be used with a naphthol or the like, and for example, water, methanol, ethanol, propanol, butanol, tetrahydrofuran, dioxane or a mixture thereof can be used. Solvents, etc. The amount of the solvent is not particularly limited, and is, for example, preferably in the range of 0 to 2000 parts by mass based on 100 parts by mass of the reaction raw material.

When the polyphenol compound is produced, the reaction temperature is not particularly limited, and may be appropriately selected in accordance with the reactivity of the reaction raw material, and is preferably in the range of 10 to 200 °C. In order to selectively synthesize the above polyphenol compound, the effect is high, and it is more preferably in the range of 10 to 60 °C.

The method for producing the polyphenol compound is not particularly limited, and examples thereof include a method in which a naphthol or the like, an aldehyde or a ketone, or a catalyst are introduced together, or a binaphthol or an aldehyde or a ketone in the presence of a catalyst. The method of dropping. After the completion of the polycondensation reaction, in order to remove unreacted raw materials or catalysts present in the system, the temperature of the reaction vessel is raised to 130 to 230 ° C, and the volatile matter can be removed at about 1 to 50 mmHg.

The amount of the raw material in the production of the above polyphenol compound is not particularly limited. For example, it is used in an amount of 2 moles to an excess amount with respect to an aldehyde or a ketone, a naphthol or the like, and an acid catalyst is used in an amount of 0.001 to 1 mole. Under normal pressure, the reaction is carried out at 20 to 60 ° C for about 20 minutes to 100 hours.

When the above polyphenol compound is produced, after the completion of the above reaction, the object can be isolated by a conventional method. The method for separating the target product is not particularly limited, and for example, the reaction solution is concentrated, pure water is added to precipitate the reaction product, and after cooling to room temperature, the mixture is filtered and separated, and the obtained solid component is filtered to be dried. A method of obtaining a target compound by column chromatography, separation and purification from by-products, solvent distillation, filtration, and drying.

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

For example, the above compound is dissolved or suspended in an aprotic solvent such as acetone, tetrahydrofuran (THF) or propylene glycol monomethyl ether acetate. Next, the reaction is carried out at a normal pressure of 20 to 150 ° C for 6 to 72 hours in the presence of a base catalyst such as sodium hydroxide, potassium hydroxide, sodium methoxide or sodium ethoxide. The reaction solution is neutralized with an acid, added to distilled water, and precipitated as a white solid. The separated solid is washed with distilled water or evaporated to dryness. If necessary, it is washed with distilled water and dried to obtain a hydroxyl group. A compound in which a hydrogen atom is substituted by a group represented by the formula (0-1A).

Further, the timing of introducing the group substituted by the formula represented by the formula (0-1A) may be carried out not only after the condensation reaction of the binaphthols with the aldehydes or the ketones but also before the condensation reaction. Further, it may be carried out after the resin is produced as will be described later.

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

For example, in the phenolic hydroxyl group of at least one of the above compounds, a group represented by the formula (0-1B) may be introduced, and a group represented by the formula (0-1A) may be introduced into the hydroxyl group.

The compound represented by the formula (0-1B) can be synthesized or easily obtained by a known method, and examples thereof include chlorohydrin, bromoethanol, 2-chloroethyl acetate, 2-bromoethyl acetate, and acetic acid. -2-iodoethyl ester, ethylene oxide, propylene oxide, butylene oxide, ethylene carbonate, propylene carbonate, butylene carbonate, but is not limited thereto.

For example, the above compound is dissolved or suspended in an aprotic solvent such as acetone, tetrahydrofuran (THF) or propylene glycol monomethyl ether acetate. Next, the reaction is carried out for 6 to 72 hours in the presence of an alkali catalyst such as sodium hydroxide, potassium hydroxide, sodium methoxide or sodium ethoxide at a normal pressure of 20 to 150 °C. The reaction solution is neutralized with an acid, added to distilled water, and precipitated as a white solid. After the separated solid is washed with distilled water or the solvent is evaporated to dryness, if necessary, it is washed with distilled water and dried. A compound in which a hydrogen atom of a hydroxyl group is substituted with a group represented by the above formula (0-1B).

In the case of using 2-chloroethyl acetate, 2-bromoethyl acetate or 2-iodoethyl acetate, after introducing an ethyl ethoxyethyl group, a hydroxyethyl group is introduced by deacylation. .

In the case of using ethylene carbonate, propylene carbonate or butylene carbonate, a decarboxylation reaction is initiated by addition of an alkylene carbonate to introduce a hydroxyalkyl group.

Then, the above compound is dissolved or suspended in an aprotic solvent such as acetone, tetrahydrofuran (THF) or propylene glycol monomethyl ether acetate. Next, the reaction is carried out for 6 to 72 hours in the presence of an alkali catalyst such as sodium hydroxide, potassium hydroxide, sodium methoxide or sodium ethoxide at a normal pressure of 20 to 150 °C. The reaction solution is neutralized with an acid, added to distilled water, and precipitated as a white solid. After the separated solid is washed with distilled water or the solvent is evaporated to dryness, if necessary, it is washed with distilled water and dried. A compound in which a hydrogen atom of a hydroxyl group is substituted with a group represented by the formula (0-1A).

In the present embodiment, the group substituted by the formula represented by the formula (0-1A) means that the reaction is carried out in the presence of a radical or an acid/base, and is used for an acid, a base or an organic solvent used for coating a solvent or a developing solution. Solubility changes. The base substituted by the above formula (0-1A), in order to form a higher sensitivity. In the case of a high-resolution pattern, it is preferably a radical or a property of reacting in a chain in the presence of an acid/base.

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

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

The resin obtained by using the compound represented by the above formula (2) as a monomer may, for example, be a structure represented by the following formula (4). In other words, the composition for forming a lithography film of the present embodiment may be a resin containing a structure represented by the following formula (4).

In the formula (4), L is an alkylene group having 1 to 30 carbon atoms which may have a substituent, a aryl group having 6 to 30 carbon atoms which may have a substituent, and a carbon number of 1 to 30 which may have a substituent. The alkoxy group or a single bond, the above alkylene group, the above-mentioned extended aryl group, and the above alkyleneoxy group may also contain an ether bond, a ketone bond or an ester bond. Further, the alkylene group or the alkyleneoxy group may be a linear, branched or cyclic group.

R ^0A is synonymous with R ^Y described above, R ^1A is a n ^A valent group or a single bond having 1 to 30 carbon atoms, and R ^{2A is} each independently an alkyl group having 1 to 30 carbon atoms which may have a substituent, and may have a substituent. An aryl group having 6 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, an alkoxy group having 1 to 30 carbon atoms which may have a substituent, a halogen atom, a nitro group, an amine group, and a carboxylic acid group a hydrogen atom of a mercapto group, a hydroxyl group or a hydroxyl group is substituted with a group represented by the above formula (0-1), and the alkyl group, the above aryl group, the above alkenyl group, and the above alkoxy group may further contain an ether bond, a ketone bond or an ester. Here, at least one of R ^2A contains a group represented by the above formula (0-1), and n ^A is synonymous with the above N. Here, when n ^A is an integer of 2 or more, n ^{A is} in [ ] The structural formulas may be the same or different, X ^A represents an oxygen atom, a sulfur atom or no cross-linking, and m ^2A are each independently an integer of 0 to 7, but at least one of m ^2A is an integer of 1 to 6, and q ^{A is} independently Is 0 or 1.

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

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

The compound having a crosslinking reactivity is not particularly limited as long as it can oligomerize or polymerize the compound represented by the above formula (2). Specific examples thereof include, but are not particularly limited to, an aldehyde, a ketone, a carboxylic acid, a carboxylic acid halide, a halogen-containing compound, an amine compound, an imine compound, an isocyanate, and an unsaturated hydrocarbon group-containing compound.

Specific examples of the resin having a structure represented by the above formula (4) include phenolic aldehydes by a condensation reaction between a compound represented by the above formula (2) and an aldehyde and/or a ketone having a compound having crosslinking reactivity. Varnished resin.

Here, examples of the aldehyde used in the novolak formation of the compound represented by the above formula (2) include formaldehyde, trioxane, polyoxymethylene, benzaldehyde, acetaldehyde, propionaldehyde, phenylacetaldehyde, and phenylpropanal. , hydroxybenzaldehyde, chlorobenzaldehyde, nitrobenzaldehyde, methyl benzaldehyde, ethyl benzaldehyde, butyl benzaldehyde, biphenyl formaldehyde, naphthaldehyde, anthracene formaldehyde, phenanthrene, anthracene formaldehyde, furfural, etc., but not It is particularly limited to these. The ketones include the above ketones. Among these, it is more preferably formaldehyde. In addition, these aldehydes and/or ketones may be used alone or in combination of two or more. Further, the amount of the aldehyde and/or ketone used is not particularly limited, and is preferably 0.2 to 5 moles, more preferably 0.5 to 2 moles, per mole of the compound 1 represented by the above formula (2).

In the condensation reaction of the compound represented by the above formula (2) with an aldehyde and/or a ketone, an acid catalyst can also be used. The acid catalyst used herein can be suitably selected from the conventional ones without particular limitation. Such an acid catalyst is widely known as an inorganic acid or an organic acid, and examples thereof include inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, and hydrofluoric acid; oxalic acid, malonic acid, succinic acid, adipic acid, and bismuth; Acid, citric acid, fumaric acid, maleic acid, formic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid An organic acid such as naphthalene disulfonic acid; a Lewis acid such as zinc chloride, aluminum chloride, iron chloride or boron trifluoride; a solid acid such as tungstic acid, phosphotungstic acid, lanthanum molybdate or phosphomolybdic acid; Etc., but it is not particularly limited to this. Among these, from the viewpoint of production, organic acids and solid acids are preferred, and hydrochloric acid or sulfuric acid is preferred from the viewpoint of ease of production, ease of handling, and the like. In addition, the acid catalyst may be used singly or in combination of two or more.

In addition, the amount of the acid catalyst to be used may be appropriately set in accordance with the type of the raw material to be used, the type of the catalyst to be used, and the reaction conditions, and is not particularly limited. However, it is preferably 0.01 to 100 parts by mass based on 100 parts by mass of the reaction raw material. However, with hydrazine, hydroxy hydrazine, benzofuran, hydroxy hydrazine, decene, biphenyl, bisphenol, trisphenol, dicyclopentadiene, tetrahydroanthracene, 4-vinylcyclohexene, decadiene, 5- In the case of a copolymerization reaction of a compound having a non-conjugated double bond such as vinyl norquin-2-ene, α-pinene, β-pinene or limonene, an aldehyde is not necessarily required.

In the condensation reaction of the compound represented by the above formula (2) with an aldehyde and/or a ketone, a reaction solvent can also be used. The reaction solvent in the polycondensation can be appropriately selected from the conventional ones, and is not particularly limited. For example, water, methanol, ethanol, propanol, butanol, tetrahydrofuran, dioxane or a mixed solvent of these may be mentioned. Further, the solvent may be used alone or in combination of two or more.

In addition, the amount of the solvent to be used may be appropriately set in accordance with the raw material to be used, the type of the catalyst to be used, the reaction conditions, and the like, and is not particularly limited. However, it is preferably 0 to 2000 parts by mass based on 100 parts by mass of the reaction raw material. The scope. Further, the reaction temperature is appropriately selected depending on the reactivity of the reaction raw material, and is not particularly limited, but is usually in the range of 10 to 200 °C. In addition, the reaction method can be appropriately selected from the conventional methods, and is not particularly limited, and examples thereof include a method of introducing a compound represented by the above formula (2), an aldehyde and/or a ketone, and a catalyst, or expressing the above formula (2). A method in which a compound or an aldehyde and/or a ketone is dropped in the presence of a catalyst.

After completion of the polycondensation reaction, the isolation of the obtained compound can be carried out according to a usual method, and is not particularly limited. For example, in order to remove unreacted raw materials or catalysts present in the system, a general method of removing volatiles such as 1 to 50 mmHg by raising the temperature of the reaction vessel to 130 to 230 ° C can be used to separate the target. A phenolic varnished resin.

Here, the resin having the structure represented by the above formula (4) may be a homopolymer of the compound represented by the above formula (2), or may be a copolymer with other phenols. Here, examples of the phenol which can be copolymerized include phenol, cresol, dimethylphenol, trimethylphenol, butylphenol, phenylphenol, diphenylphenol, naphthylphenol, resorcin, Methyl resorcinol, catechol, butyl catechol, methoxy phenol, methoxy phenol, propyl phenol, pyrogallol, thymol, and the like are not particularly limited thereto.

Further, the resin having the structure represented by the above formula (4) may be copolymerized with a polymerizable monomer in addition to the above other phenols. Examples of the comonomer include naphthol, methylnaphthol, methoxynaphthol, dihydroxynaphthalene, anthracene, hydroxyindole, benzofuran, hydroxyindole, terpene, biphenyl, bisphenol, triphenol, Dicyclopentadiene, tetrahydroanthracene, 4-vinylcyclohexene, decadiene, vinyl norbornene, decene, limonene, etc., but are not particularly limited thereto. Further, the resin having the structure represented by the above formula (4) may be a copolymer of a compound represented by the above formula (2) and a diol or a phenol thereof of 2 or more (for example, 2 to 4 member), or may be the above formula ( 2) a copolymer of 2 or more (for example, 2 to 4 member) of the compound and the comonomer, or a compound represented by the above formula (2), the phenol and the comonomer of 3 or more A copolymer (for example, a 3 to 4 member system).

Further, the molecular weight of the resin having the structure represented by the above formula (4) is not particularly limited, and the weight average molecular weight (Mw) in terms of polystyrene is preferably from 500 to 30,000, more preferably from 750 to 20,000. Moreover, from the viewpoint of improving the crosslinking efficiency and suppressing the volatile component during baking, the resin having the structure represented by the above formula (4) preferably has a degree of dispersion (weight average molecular weight Mw / number average molecular weight Mn) of 1.2 to 7 Within the scope of the. Further, the above Mw and Mn can be obtained by the method described in the examples below.

The resin having the structure represented by the above formula (4) is preferably one having a high solubility in a solvent from the viewpoint of being more easily applied to a wet process or the like. More specifically, when 1-methoxy-2-propanol (PGME) and/or propylene glycol monomethyl ether acetate (PGMEA) is used as a solvent, the solubility of the solvent is preferably 10% by mass or more. . Here, the solubility of PGME and/or PGMEA is defined as "the mass of the resin (the mass of the resin + the mass of the solvent) × 100 (% by mass)". For example, when 10 g of the resin is dissolved in 90 g of PGMEA, the solubility of the resin to PGMEA is "10 mass% or more", and when it is not dissolved, it is "less than 10 mass%".

 [Method for Purifying Compound and/or Resin]  

The method for purifying the compound and/or the resin of the present embodiment includes a resin obtained by selecting a compound represented by the above formula (1) and a compound represented by the above formula (1) as a monomer, and a compound represented by the above formula (2). And a method of obtaining a solution (S) by dissolving one or more kinds of resins obtained by using the compound represented by the above formula (2) as a monomer in a solvent; and contacting the obtained solution (S) with an acidic aqueous solution to extract the compound and / a step of the impurities in the above resin (first extraction step); the solvent used in the step of obtaining the above solution (S) contains an organic solvent which is not arbitrarily mixed with water.

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

More specifically, in the purification method of the present embodiment, the above compound and/or the above resin is dissolved in an organic solvent which is not arbitrarily mixed with water, and a solution (S) can be obtained, and the solution (S) and the acidic solution can be obtained. The aqueous solution is contacted and subjected to extraction treatment. Thereby, the metal component contained in the above solution (S) is moved to the aqueous phase, and then the organic phase and the aqueous phase are separated to obtain a compound and/or a resin having a reduced metal content.

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

The solvent used in the embodiment which is not arbitrarily mixed with water is not particularly limited, and is preferably an organic solvent which can be safely applied to a semiconductor manufacturing process. Specifically, the solubility in water at room temperature is less than 30%, more preferably It is less than 20%, and more preferably less than 10% organic solvent. The amount of the organic solvent to be used is preferably from 1 to 100 times by mass based on the total amount of the compound to be used and the resin.

Specific examples of the solvent which is not optionally mixed with water are not limited to the following, and examples thereof include ethers such as diethyl ether and diisopropyl ether; and esters such as ethyl acetate, n-butyl acetate, and isoamyl acetate. a ketone of methyl ethyl ketone, methyl isobutyl ketone, ethyl isobutyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 2-pentanone or the like; ethylene glycol monoethyl ether acetate Glycol ether acetates such as ester, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, etc.; n-hexane, n-heptane, etc. An aliphatic hydrocarbon; an aromatic hydrocarbon such as toluene or xylene; a halogenated hydrocarbon such as dichloromethane or chloroform; Among these, preferred are toluene, 2-heptanone, cyclohexanone, cyclopentanone, methyl isobutyl ketone, propylene glycol monomethyl ether acetate, ethyl acetate, etc., more preferably methyl isobutyl ketone. Ethyl acetate, cyclohexanone, propylene glycol monomethyl ether acetate, more preferably methyl isobutyl ketone or ethyl acetate. The above-mentioned compound, such as methyl isobutyl ketone and ethyl acetate, and the resin containing the compound as a constituent component have a relatively high saturated solubility and a relatively low boiling point, so that the industrial solvent can be reduced or removed by drying. The burden of the steps. These solvents may be used singly or in combination of two or more.

The acidic aqueous solution used in the purification method of the present embodiment is preferably selected from an aqueous solution in which a generally known organic compound or inorganic compound is dissolved in water. The acidic aqueous solution is not limited to the following, and examples thereof include a mineral acid aqueous solution in which a mineral acid such as hydrochloric acid, sulfuric acid, nitric acid or phosphoric acid is dissolved in water, or acetic acid, propionic acid, oxalic acid, malonic acid, succinic acid or fumaric acid. An organic acid aqueous solution in which an organic acid such as maleic acid, tartaric acid, citric acid, methanesulfonic acid, phenolsulfonic acid, p-toluenesulfonic acid or trifluoroacetic acid is dissolved in water. These acidic aqueous solutions may be used alone or in combination of two or more. Among these acidic aqueous solutions, one or more aqueous mineral acid solutions selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid, or selected from the group consisting of acetic acid, propionic acid, oxalic acid, malonic acid, succinic acid, and fumaric acid. An aqueous solution of one or more organic acids of maleic acid, tartaric acid, citric acid, methanesulfonic acid, phenolsulfonic acid, p-toluenesulfonic acid and trifluoroacetic acid is preferred, and more preferably sulfuric acid, nitric acid, and acetic acid. An aqueous solution of a carboxylic acid such as oxalic acid, tartaric acid or citric acid is more preferably an aqueous solution of sulfuric acid, oxalic acid, tartaric acid or citric acid, and more preferably an aqueous solution of oxalic acid. A polycarboxylic acid such as oxalic acid, tartaric acid or citric acid is coordinated to a metal ion to produce a chelate effect, so that the tendency of the metal can be removed more effectively. Further, in the water system used herein, it is preferred to use water having a small metal content, such as ion-exchanged water, for the purpose of the purification method of the present embodiment.

The pH of the acidic aqueous solution used in the purification method of the present embodiment is not particularly limited, and it is preferable to adjust the acidity of the aqueous solution in consideration of the influence on the above compound or resin. The pH of the acidic aqueous solution is preferably about 0 to 5, more preferably about pH 0 to 3.

The amount of the acidic aqueous solution to be used in the purification method of the present embodiment is not particularly limited, and it is preferable to adjust the amount of use from the viewpoint of reducing the number of extractions for removing metals and considering the amount of liquid as a whole to ensure operability. From the above viewpoints, the amount of the acidic aqueous solution used is 100% by mass, preferably 10 to 200% by mass, and more preferably 20 to 100% by mass based on the above solution (S).

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

In the purification method of the present embodiment, the solution (S) further preferably contains an organic solvent which is optionally mixed with water. When the solution (S) contains an organic solvent which is arbitrarily mixed with water, the amount of the above-mentioned compound and/or resin to be added can be increased, and the liquid separation property can be improved, and purification can be performed with high pot efficiency. The method of adding an organic solvent arbitrarily mixed with water is not particularly limited. For example, it may be a method of adding in advance to a solution containing an organic solvent, a method of adding in advance to water or an acidic aqueous solution, or a method of adding an organic solvent-containing solution to water or an acidic aqueous solution, followed by addition. Among these, the method of adding in advance to the solution containing an organic solvent is preferable from the viewpoint of the ease of management of the workability and the amount of the operation.

The organic solvent to be arbitrarily mixed with water used in the purification method of the present embodiment is not particularly limited, and is preferably an organic solvent which can be safely applied to a semiconductor manufacturing process. The amount of the organic solvent to be arbitrarily mixed with water is not particularly limited as long as it is in a range in which the solution phase and the aqueous phase are separated, and is preferably 0.1 to 100 times by mass based on the total amount of the compound to be used and the resin. More preferably, it is 0.1 to 50 times by mass, and more preferably 0.1 to 20 times by mass.

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

The temperature at which the extraction treatment is carried out is usually 20 to 90 ° C, preferably 30 to 80 ° C. The extraction operation is carried out, for example, by stirring or the like, and then allowing to stand. Thereby, the metal component contained in the solution (S) moves to the aqueous phase. Further, due to the operation, the acidity of the solution is lowered, and deterioration of the compound and/or the resin can be suppressed.

The mixed solution is separated into a solution phase containing a compound and/or a resin and a solvent and an aqueous phase by standing, so that the solution phase can be recovered by decantation or the like. The standing time is not particularly limited, and it is preferable to adjust the standing time from the viewpoint that the separation of the solvent-containing solution phase and the aqueous phase is better. Usually, the standing time is 1 minute or longer, preferably 10 minutes or longer, more preferably 30 minutes or longer. Further, the extraction treatment may be performed only once, but the operations of mixing, standing, and separating are repeated a plurality of times, and the effect is also obtained.

In the purification method of the present embodiment, the method further comprises the step of, after the first extraction step, contacting the solution containing the compound or the resin with water to extract impurities in the compound or the resin (second extraction) Step) is better. Specifically, for example, after the extraction treatment is carried out using an acidic aqueous solution, the solution containing the compound and/or the resin and the solvent extracted and recovered from the aqueous solution is further supplied as a water extraction treatment. The extraction treatment with water is not particularly limited. For example, the solution phase and the water may be sufficiently mixed by stirring or the like, and the resulting mixed solution may be allowed to stand. Since the mixed solution after standing is separated into a solution phase containing a compound and/or a resin and a solvent, and an aqueous phase, the solution phase can be recovered by decantation or the like.

Further, in the water system used herein, it is preferred to use water having a small metal content, such as ion-exchanged water, in accordance with the purpose of the present embodiment. Further, the extraction treatment may be performed only once, but the operations of mixing, standing, and separating are repeated a plurality of times, and the effect is also obtained. Further, the ratio of use of the two in the extraction treatment, the temperature, the time, and the like are not particularly limited, and may be the same as in the case of the previous contact treatment with the acidic aqueous solution.

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

The method of separating the compound and/or the resin from the obtained compound-containing compound and/or the resin and the solvent is not particularly limited, and a conventional method such as removal under reduced pressure, separation by reprecipitation, and a combination thereof may be used. Come on. If necessary, a conventional treatment such as a concentration operation, a filtration operation, a centrifugal separation operation, a drying operation, or the like can be performed.

 [composition]  

The composition of the present embodiment contains a resin selected from the compound represented by the above formula (1) and a compound represented by the above formula (1) as a monomer, a compound represented by the above formula (2), and represented by the above formula (2). The compound obtained as a monomer is a group of one or more types of resins. Further, the composition of the present embodiment may be a film forming composition for lithography or an optical element forming composition.

 [Metal forming composition for lithography for chemically amplified photoresist]  

The film forming composition for lithography (hereinafter also referred to as "resist composition") for use in the chemical amplification resist of the present embodiment contains a compound selected from the above formula (1) and is represented by the above formula (1). One or more types of the resin obtained by using the compound as a monomer, the compound represented by the above formula (2), and the compound represented by the above formula (2) as a monomer are used as a resist substrate.

Further, the composition (resist composition) of the present 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 ethylene glycol mono-n-butyl ether. Ethylene glycol monoalkyl ether acetates such as acid esters; ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether Propylene glycol monoalkyl ether acetates such as acetate, propylene glycol mono-n-propyl ether acetate, propylene glycol mono-n-butyl ether acetate; propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether, etc. Alkyl ethers; lactates of methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, n-amyl lactate, etc.; methyl acetate, ethyl acetate, n-propyl acetate, acetic acid An aliphatic carboxylic acid ester of n-butyl ester, n-amyl acetate, n-hexyl acetate, methyl propionate, ethyl propionate, etc.; methyl 3-methoxypropionate, 3-methoxy Ethyl propionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxy-2-methylpropanoate, 3-methoxybutyl acetate , 3-methyl-3-methoxybutyl acetate, 3-methoxy-3-methylpropane Other esters such as butyl ester, butyl 3-methoxy-3-methylbutyrate, methyl acetoacetate, methyl pyruvate, ethyl pyruvate; aromatic hydrocarbons such as toluene and xylene ; 2-ketones, 3-heptanone, 4-heptanone, cyclopentanone (CPN), cyclohexanone (CHN), etc.; N,N-dimethylformamide, N-methyl Examples thereof include decyl amines such as guanamine, N,N-dimethylacetamide and N-methylpyrrolidone; lactones such as γ-lactone, and the like, but are not particularly limited. These solvents may be used alone or in combination of two or more.

The solvent-based safe solvent used in the embodiment is more preferable, and more preferably at least one selected from the group consisting of PGMEA, PGME, CHN, CPN, 2-heptanone, anisole, butyl acetate, ethyl propionate, and ethyl lactate. More preferably, it is at least one selected from the group consisting of PGMEA, PGME, and CHN.

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

The composition (resist composition) of the present embodiment may further contain other solid components selected from the group consisting of an acid generator (C), a crosslinking agent (G), an acid diffusion controlling agent (E), and other components. (F) at least one of the groups. In the present specification, the solid-forming component means a component other than the solvent.

Here, the acid generator (C), the crosslinking agent (G), the acid diffusion controlling agent (E), and other components (F) can be used without any particular limitation, for example, International Publication No. 2013/024778 The ones recorded are better.

 [Preparation ratio of each component]  

In the resist composition of the present embodiment, the content of the compound and/or the resin used as the resist substrate is not particularly limited, and is preferably the total mass of the solid component (including the resist substrate and the acid generator (C). The total solid content of the component used in any of the crosslinking agent (G), the acid diffusion controlling agent (E), and other components (F) is the same as the following.) 50 to 99.4% by mass, more preferably 55 to 90% by mass, more preferably 60 to 80% by mass, and particularly preferably 60 to 70% by mass. When the content of the compound and/or the resin used as the resist substrate is in the above range, the resolution is further improved, and the line edge roughness (LER) is further reduced. Further, in the case where the resist substrate contains both the compound and the resin, the content is the total amount of the two components.

 [Other ingredients (F)]  

In the resist composition of the present embodiment, one or two or more kinds of the resist substrate, the acid generator (C), and the crosslinking agent may be added as needed within the range not inhibiting the object of the present invention. G) and components other than the acid diffusion controlling agent (E): a dissolution promoter, a dissolution controlling agent, a sensitizer, a surfactant, an oxyacid of an organic carboxylic acid or phosphorus or a derivative thereof, heat and/or photohardening Catalyst, polymerization inhibitor, flame retardant, filler, coupling agent, thermosetting resin, photocurable resin, dye, pigment, tackifier, slip agent, antifoaming agent, flat agent, ultraviolet absorber, interface Various additives such as an active agent, a colorant, and a nonionic surfactant. Further, in the present specification, the other component (F) may be referred to as an arbitrary component (F).

In the resist composition of the present embodiment, a resist substrate (hereinafter also referred to as "component (A)"), an acid generator (C), a crosslinking agent (G), an acid diffusion controlling agent (E), or any The content of the component (F) (ingredient (A) / acid generator (C) / crosslinker (G) / acid diffusion controlling agent (E) / optional component (F)) is % by mass based on solids. Good is 50~99.4/0.001~49/0.5~49/0.001~49/0~49, more preferably 55~90/1~40/0.5~40/0.01~10/0~5, and even better 60 ~80/3~30/1~30/0.01~5/0~1, and especially good is 60~70/10~25/2~20/0.01~3/0. The blending ratio of each component is 100% by mass in total, and is selected from the respective ranges. When the mixing ratio of each component is in the above range, the performance such as sensitivity, resolution, and developability tends to be excellent.

In the resist composition of the present embodiment, the components are usually dissolved in a solvent to form a homogeneous solution, and if necessary, they are prepared by, for example, filtration through a filter having a pore size of about 0.2 μm.

The resist composition of the present embodiment may contain other resins than the resin of the present embodiment, within the range not inhibiting the object of the present invention. The other resin is not particularly limited, and examples thereof include a novolac resin, a polyvinyl phenol, a polyacrylic acid, a polyvinyl alcohol, a styrene-maleic anhydride resin, and a monomer containing acrylic acid, vinyl alcohol, or vinyl phenol. A polymer of a unit or such a derivative or the like. The content of the other resin is not particularly limited, and the type of the component (A) to be used is appropriately adjusted. However, it is preferably 30 parts by mass or less, more preferably 10 parts by mass or less, more preferably 100 parts by mass based on the component (A). It is preferably 5 parts by mass or less, and particularly preferably 0 parts by mass.

 [Physical properties of the resist composition, etc.]  

In the resist composition of the present embodiment, an amorphous film is formed by spin coating. Further, the resist composition of the present embodiment can be applied to a general semiconductor manufacturing process. The positive resist pattern and the negative type can be separately produced according to the compound represented by the above formula (1) and/or the formula (2), the kind of the resin obtained as the monomer, and/or the type of the developer used. Any of the resist patterns.

In the case of the positive resist pattern, the amorphous film formed by spin coating the resist composition of the present embodiment preferably has a dissolution rate of the developer at 23 ° C of 5 Å/sec or less, more preferably 0.05. ~5Å/sec, and more preferably 0.0005~5Å/sec. When the dissolution rate is 5 Å/sec or less, it is insoluble in the developer and can be used as a resist. Further, when the dissolution rate is 0.0005 Å/sec or more, the analytical property tends to be improved. It is presumed that the compound represented by the above formula (1) and/or the solubility change of the resin containing the compound as a constituent component before and after exposure, and the exposed portion dissolved in the developer and the undissolved in the developer are not exposed. The contrast of the interface of the ministry has become larger. Further, there is an effect that the LER (line edge roughness) is lowered and the defects are lowered.

In the case of the negative resist pattern, the amorphous film formed by spin coating the resist composition of the present embodiment is preferably 10 Å/sec or more for the dissolution rate of the developer at 23 °C. When the dissolution rate is 10 Å/sec or more, it is easily soluble in the developer, and is more suitable for the resist. Further, when the dissolution rate is 10 Å/sec or more, the resolution may be improved. It is presumed that the compound represented by the above formula (1) and/or the microscopic surface portion containing the resin having the compound as a constituent component are dissolved to lower the LER. There are also effects of reduced defects.

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

In the case of a positive resist pattern, an amorphous film formed by spin coating the resist composition of the present embodiment is exposed by radiation of KrF excimer laser, extreme ultraviolet light, electron beam or X-ray. For the portion, the dissolution rate of the developer at 23 ° C is preferably 10 Å / sec or more. When the dissolution rate is 10 Å/sec or more, it is easily soluble to the developer and is more suitable for the resist. Further, when the dissolution rate is 10 Å/sec or more, the resolution may be improved. It is presumed that this is because the compound represented by the above formulas (1) and (2) and/or the microscopic surface portion of the resin containing the compound as a constituent component are dissolved to lower the LER. Also, there is an effect of reducing defects.

In the case of a negative resist pattern, the amorphous film formed by spin coating the resist composition of the present embodiment is exposed to radiation by KrF excimer laser, extreme ultraviolet light, electron beam or X-ray. In part, the dissolution rate of the developer 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, it is insoluble to the developer and can be used as a resist. Further, when the dissolution rate is 0.0005 Å/sec or more, the resolution may be improved. It is presumed that the solubility of the compound represented by the above formula (1) and/or the resin containing the compound as a constituent component before and after exposure is such that it is dissolved in the unexposed portion of the developer and is not dissolved in the developer. The contrast of the interface of the exposure portion becomes large. Moreover, it has the effect of reducing LER and reducing defects.

 [Film forming composition for lithography for non-chemically amplified resists]  

The component (A) contained in the film forming composition for lithography (hereinafter also referred to as "radiation-sensitive composition") for the non-chemically amplified resist application of the present embodiment and the diazonaphthoquinone photoactive compound described later ( B) In combination, by irradiating a g-line, an h-line, an i-line, a KrF excimer laser, an ArF excimer laser, an extreme ultraviolet ray, an electron beam or an X-ray, it becomes a positive type for a compound which is easily soluble in a developer. The resist is used as a substrate. By g-line, h-line, i-line, KrF excimer laser, ArF excimer laser, extreme ultraviolet light, electron beam or X-ray, the property of component (A) does not change greatly, but it is insoluble to the developer. The diazonaphthoquinone photoactive compound (B) is changed to a readily soluble compound, and a resist pattern can be produced by a development step.

Since the component (A) contained in the radiation-sensitive composition of the present embodiment is a compound having a relatively low molecular weight, the roughness of the resist pattern obtained is extremely small. Further, in the above formula (1), it is preferred that at least one selected from the group consisting of R ⁰ to R ⁵ is a group containing an iodine atom, and in the above formula (2), it is selected from R ^0A , R ^1A and R ^{2A .} It is preferred that at least one of the groups is a group containing an iodine atom. When the radiation-sensitive composition of the present embodiment is used as the component (A) having an iodine atom-containing group in such a preferred embodiment, absorption of radiation such as electron beams, extreme ultraviolet rays (EUV), and X-rays can be increased. The ability, the result can improve the sensitivity, so it is better.

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

The glass transition temperature of the component (A) contained in the radiation-sensitive composition of the present embodiment is preferably less than 20 J/g as determined by differential scanning calorimetry. Further, (crystallization temperature) - (glass transition temperature) is preferably 70 ° C or higher, more preferably 80 ° C or higher, still more preferably 100 ° C or higher, and particularly preferably 130 ° C or higher. When the crystallization heat generation amount is less than 20 J/g, or (crystallization temperature) - (glass transition temperature) is within the above range, the amorphous film can be easily formed by spin coating the radiation-sensitive composition, and can be long The film forming property necessary for the resist is maintained during the period, and the tendency of the resolution is improved.

In the present embodiment, the crystallization heat generation amount, the crystallization temperature, and the glass transition temperature can be determined by using differential scanning calorimetry of DSC/TA-50WS manufactured by Shimadzu Corporation. About 10 mg of the sample was placed in an unsealed container made of aluminum, and the temperature was raised to a melting point or higher in a nitrogen gas stream (50 mL/min) at a temperature increase rate of 20 ° C /min. After quenching, the temperature was raised to a temperature above the melting point in a nitrogen gas stream (30 mL/min) at a temperature increase rate of 20 ° C/min. After quenching, the temperature was raised to 400 ° C in a nitrogen gas stream (30 mL/min) at a temperature increase rate of 20 ° C/min. The temperature at the midpoint of the step (the specific heat is half) which is changed to the step line of the stage is set as the glass transition temperature (Tg), and the temperature of the subsequent heat generation peak is set as the crystallization temperature. The amount of heat generated by the area surrounded by the heat peak and the reference line is taken as heat of crystallization.

The component (A) contained in the radiation-sensitive composition of the present embodiment is 100 ° C or less, preferably 120 ° C or less, more preferably 130 ° C or less, and still more preferably 140 ° C or less, under normal pressure. When the temperature is below 150 ° C, the sublimation is preferred. Low sublimation refers to a weight loss of 10% or less, preferably 5% or less, more preferably 3% or less, and even more preferably 1% or less, in a thermogravimetric analysis at a specific temperature for 10 minutes. Good is less than 0.1%. Due to the low sublimation, the exhaust gas during exposure can be prevented from contaminating the exposure device. Further, a low roughness can be obtained and a good pattern shape can be obtained.

The component (A) contained in the radiation-sensitive composition of the present 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 are grouped, and in the solvent exhibiting the highest solubility in component (A), at 23 ° C, preferably The amount of dissolution is 1% by mass or more, more preferably 5% by mass or more, and still more preferably 10% by mass or more. Particularly preferably, in a solvent selected from the group consisting of PGMEA, PGME, and CHN, and having the highest solubility in the (A) resist substrate, it is dissolved at 20% by mass or more at 23 ° C, particularly preferably for PGMEA. The solution was dissolved at 20% by mass or more at 23 °C. By satisfying the above conditions, the use of the semiconductor manufacturing steps actually produced becomes easy.

 [diazonaphthoquinone photoactive compound (B)]  

The diazonaphthoquinone photoactive compound (B) contained in the radiation-sensitive composition of the present embodiment is a diazonaphthoquinone substance containing a polymerizable or non-polymeric diazonaphthoquinone photoactive compound, and generally, The positive resist composition is not particularly limited as long as it can be used as a photosensitive component (sensitizer), and one or two or more kinds can be used arbitrarily.

The component (B) is preferably a low molecular compound having a functional group capable of condensing with the acid chloride by using naphthoquinonediazidesulfonic acid chloride or benzoquinonediazidesulfonic acid chloride or the like. A compound obtained by reacting a polymer compound is preferred. Here, the functional group which can be condensed with the acid chloride is not particularly limited, and examples thereof include a hydroxyl group and an amine group, and particularly preferably a hydroxyl group. The compound which can be condensed with the hydroxyl group-containing acid chloride is not particularly limited, and examples thereof include hydroquinone, resorcin, 2,4-dihydroxybenzophenone, and 2,3,4-trihydroxybenzophenone. Ketone, 2,4,6-trihydroxybenzophenone, 2,4,4'-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,2', Hydroxybenzophenones such as 4,4'-tetrahydroxybenzophenone, 2,2',3,4,6'-pentahydroxybenzophenone, bis(2,4-dihydroxyphenyl) Hydroxyphenyl alkane such as methane, bis(2,3,4-trihydroxyphenyl)methane or bis(2,4-dihydroxyphenyl)propane, 4,4',3",4"-tetrahydroxyl -3,5,3',5'-tetramethyltriphenylmethane, 4,4',2",3",4"-pentahydroxy-3,5,3',5'-tetramethyl three Hydroxytriphenylmethane or the like such as phenylmethane.

Further, examples of the acid chloride such as naphthoquinonediazidesulfonic acid chloride or benzoquinonediazidesulfonic acid chloride include 1,2-naphthoquinonediazide-5-sulfonium chloride, 1,2. - Naphthoquinonediazide-4-sulfonium chloride or the like is preferred.

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

 [Characteristics of Radiation Sensitive Compositions]  

In the radiation-sensitive composition of the present embodiment, an amorphous film can be formed by spin coating. Further, the radiation-sensitive composition of the present embodiment can be applied to a general semiconductor manufacturing process. Any one of a positive resist pattern and a negative resist pattern may be separately produced depending on the type of developer used.

In the case of a positive resist pattern, the amorphous film formed by spin coating the radiation-sensitive composition of the present embodiment preferably has a dissolution rate of the developer at 23 ° C of 5 Å/sec or less, more preferably 0.05~5Å/sec, and more preferably 0.0005~5Å/sec. When the dissolution rate is 5 Å/sec or less, it is insoluble in the developer and can be used as a resist. Moreover, when the dissolution rate is 0.0005 Å/sec or more, the analytical property tends to be improved. It is presumed that the compound represented by the above formulas (1) and (2) and/or the solubility change of the resin containing the compound as a constituent component before and after exposure are dissolved in the exposed portion of the developing solution and are not dissolved in the developing portion. The contrast of the interface of the unexposed portion of the liquid becomes large. Moreover, there is an effect that the LER is lowered and the defect is lowered.

In the case of the negative resist pattern, the amorphous film formed by spin coating the radiation-sensitive composition of the present embodiment preferably has a dissolution rate of the developer at 23 ° C of 10 Å/sec or more. When the dissolution rate is 10 Å/sec or more, it is easily soluble in the developer, and is more suitable for the resist. Further, when the dissolution rate is 10 Å/sec or more, the resolution may be improved. It is presumed that the compound represented by the above formulas (1) and (2) and/or the microscopic surface portion of the resin containing the compound as a constituent component are dissolved to lower the LER. There are also effects of reduced defects.

The dissolution rate is determined by immersing the amorphous film in a developing solution at 23 ° C for a specific period of time, and measuring the film thickness before and after the immersion by a known method such as a visual, elliptical thickness gauge or QCM method.

In the case of a positive resist pattern, an amorphous film formed by spin coating the radiation-sensitive composition of the present embodiment is irradiated with radiation such as KrF excimer laser, extreme ultraviolet light, electron beam or X-ray. After that, or the exposed portion heated at 20 to 500 ° C, the dissolution rate of the developer at 23 ° C is preferably 10 Å / sec or more, preferably 10 ~ 10000 Å / sec, preferably 100 ~ 1000 Å / sec. For better. When the dissolution rate is 10 Å/sec or more, the developer is easily dissolved, and is more suitable for a resist. Further, when the dissolution rate is 10000 Å/sec or less, the resolution can be improved. It is presumed that the compound represented by the above formulas (1) and (2) and/or the microscopic surface portion of the resin containing the compound as a constituent component are dissolved and the LER is lowered. There are also effects of reduced defects.

In the case of a negative resist pattern, an amorphous film formed by spin coating the radiation-sensitive composition of the present embodiment is irradiated with radiation of KrF excimer laser, extreme ultraviolet light, electron beam or X-ray. After that, the exposure portion heated at 20 to 500 ° C preferably has a dissolution rate of 5 Å/sec or less, more preferably 0.05 to 5 Å/sec, and more preferably 0.0005 to 5 Å for the developer at 23 ° C. /sec. When the dissolution rate is 5 Å/sec or less, it is insoluble in the developer and can be used as a resist. Further, when the dissolution rate is 0.0005 Å/sec or more, the resolution may be improved. It is presumed that the compound represented by the above formulas (1) and (2) and/or the solubility change of the resin containing the compound as a constituent component before and after exposure are dissolved in the unexposed portion of the developer and are not dissolved in the development. The contrast of the interface of the exposure portion of the liquid becomes large. Moreover, there is an effect that the LER is lowered and the defect is lowered.

 [Proportion of each ingredient]  

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

In the radiation-sensitive composition of the present embodiment, the content of the diazonaphthoquinone photoactive compound (B) is relative to the total weight of the solid component (ingredient (A), diazonaphthoquinone photoactive compound (B), and other components ( D) The sum of the solid components used arbitrarily, the same as the following), preferably 1 to 99% by mass, more preferably 5 to 95% by mass, still more preferably 10 to 90% by mass, particularly preferably 25 to 75% by mass. %. In the radiation-sensitive composition of the present embodiment, when the content of the diazonaphthoquinone photoactive compound (B) is within the above range, a pattern having high sensitivity and a small roughness tends to be obtained.

 [Other ingredients (D)]  

In the radiation-sensitive composition of the present embodiment, one or two or more kinds of the component (A) and the diazonaphthoquinone photoactive compound (B) may be added as needed within the range which does not inhibit the object of the present invention. Ingredients: acid generator, crosslinker, acid diffusion control agent, dissolution promoter, dissolution control agent, sensitizer, surfactant, organic carboxylic acid or phosphorus oxyacid or its derivative, heat and / or Photocuring catalyst, polymerization inhibitor, flame retardant, filler, coupling agent, thermosetting resin, photocurable resin, dye, pigment, tackifier, slip agent, antifoaming agent, flat agent, ultraviolet absorber Various additives such as surfactants, colorants, and nonionic surfactants. Further, in the present specification, the other component (D) is sometimes referred to as an optional component (D).

In the radiation-sensitive composition of the present embodiment, the blending ratio of each component (component (A) / diazonaphthoquinone photoactive compound (B) / optional component (D)) is based on the mass % of the solid component basis. Good for 1~99/99~1/0~98, better for 5~95/95~5/0~49, better for 10~90/90~10/0~10, especially good for 20~ 80/80~20/0~5, the best is 25~75/75~25/0. The blending ratio of each component is selected from the range of each component to make the total of 100% by mass. In the radiation-sensitive composition of the present embodiment, when the blending ratio of each component is in the above range, the properties such as sensitivity and resolution are also excellent in addition to the roughness.

The radiation-sensitive composition of the present embodiment may contain a resin other than the present embodiment within a range not inhibiting the object of the present invention. Examples of other resins include novolak resins, polyvinyl phenols, polyacrylic acid, polyvinyl alcohol, styrene-maleic anhydride resins, and polymers containing acrylic acid, vinyl alcohol, or vinyl phenol as monomer units or the like. Derivatives, etc. The amount of the resin to be added may be appropriately adjusted in accordance with 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 or less based on the component (A). It is preferably 5 parts by mass or less, and particularly preferably 0 parts by mass.

 [Formation method of resist pattern]  

The method for forming a resist pattern according to the present embodiment includes the use of the resist composition or the radiation-sensitive composition of the present embodiment, and after forming a photoresist layer on the substrate, irradiating a specific region of the resist layer with radiation. Contains the step of developing. Specifically, the step of forming a resist film on the substrate, the step of exposing the formed resist film, and the step of developing the resist film to form a resist pattern are provided. The resist pattern in this embodiment can also be formed as an upper layer resist in a multilayer process.

The method of forming the resist pattern is not particularly limited, and examples thereof include the following methods. First, the resist composition or the radiation-sensitive composition of the above-described embodiment is applied onto a conventionally known substrate by a coating means such as spin coating, cast coating, or roll coating to form a resistor. Membrane film. The conventionally known substrate is not particularly limited, and examples thereof include a substrate for an electronic component, or a specific wiring pattern formed thereon. More specifically, a metal substrate such as a ruthenium wafer, copper, chromium, iron, or aluminum, or a glass substrate or the like can be given. Examples of the wiring pattern type include copper, aluminum, nickel, gold, and the like. Further, if necessary, an inorganic-based and/or organic-based film may be provided on the substrate. Examples of the inorganic film include an inorganic antireflection film (inorganic BARC). The organic film is an organic antireflection film (organic BARC). Surface treatment can also be carried out using hexamethylene diazane or the like on the substrate.

Next, if necessary, the substrate coated with the resist composition or the radiation-sensitive composition is heated. The heating condition varies depending on the composition of the resist composition or the radiation-sensitive composition, and is preferably 20 to 250 ° C, more preferably 20 to 150 ° C. It is preferable to increase the adhesion of the resist to the substrate by heating. Next, the resist film is exposed to a desired pattern by any radiation selected from the group consisting of visible light, ultraviolet light, excimer laser, electron beam, extreme ultraviolet (EUV), X-ray, and ion beam. The exposure conditions and the like can be appropriately selected depending on the composition of the resist or the composition of the radiation-sensitive composition. In the present embodiment, in order to stably form a high-precision fine pattern at the time of exposure, it is preferable to perform heating after irradiating the radiation. The heating condition is changed depending on the composition of the resist composition or the radiation-sensitive composition, etc., and is preferably 20 to 250 ° C, more preferably 20 to 150 ° C.

Next, the exposed resist film is developed with a developing solution to form a specific resist pattern. The developer is selected from the group consisting of a compound represented by the formula (1) or the formula (2) or a compound represented by the formula (1) or the formula (2) as a monomer, and a solvent having a solubility parameter (SP value) close to that of the solvent. Preferably, a polar solvent such as a ketone solvent, an ester solvent, an alcohol solvent, a guanamine solvent or an ether solvent, a hydrocarbon solvent or an aqueous alkali solution can be used.

Examples of the ketone solvent include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutylketone, and cyclohexanone. , methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetyl ketone, acetonyl acetone, ionone, diacetone alcohol, acetonitrile, phenyl Ketone, methylnaphthyl ketone, isophorone, propylene carbonate, and the like.

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

Examples of the alcohol solvent include methanol, ethanol, n-propanol, isopropanol (2-propanol), n-butanol, sec-butanol, tert-butanol, isobutanol, n-hexanol, and 4- An alcohol such as methyl-2-pentanol, n-heptanol, n-octanol or n-nonanol, or a glycol solvent such as ethylene glycol, diethylene glycol or triethylene glycol, or ethylene glycol a glycol ether solvent such as alcohol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether or methoxymethyl butanol .

Examples of the ether solvent include, for example, the above glycol ether solvent, and examples thereof include dioxane and tetrahydrofuran.

As the amide-based solvent, for example, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, hexamethylphosphonium triamine, and 1,3- can be used. Dimethyl-2-tetrahydroimidazolidinone and the like.

The hydrocarbon-based solvent may, for example, be an aromatic hydrocarbon solvent such as toluene or xylene, or an aliphatic hydrocarbon solvent such as pentane, hexane, octane or decane.

The above solvent may be used in combination or in a range of properties, or may be used in combination with a solvent or water other than the above. However, in order to fully exert the effect of the cost invention, the water content of the entire developer is preferably less than 70% by mass, more preferably less than 50% by mass, still more preferably less than 30% by mass, and even more preferably Up to 10% by mass, particularly preferably not substantially water-containing. In other words, the content of the organic solvent relative to the developer is 30% by mass or more and 100% by mass or less, preferably 50% by mass or more and 100% by mass or less, and more preferably 70% by mass or more and 100% by mass or less based on the total amount of the developer. % or less is more preferably 90% by mass or more and 100% by mass or less, and particularly preferably 95% by mass or more and 100% by mass or less.

Examples of the aqueous alkali solution include bases of mono-, di- or trialkylamines, mono-, di- or trialkanolamines, heterocyclic amines, tetramethylammonium hydroxide (TMAH), choline, and the like. Sex compounds.

In particular, the developer is a developer containing at least one solvent selected from the group consisting of a ketone solvent, an ester solvent, an alcohol solvent, a guanamine solvent, and an ether solvent, thereby improving the resolution or roughness of the resist pattern. It is preferred to have a resisting property.

The vapor pressure of the developer is preferably 20 kPa or less, more preferably 3 kPa or less, and particularly preferably 2 kPa or less. By setting the vapor pressure of the developer to 5 kPa or less, evaporation of the developer onto the substrate or in the developing cup can be suppressed, and temperature uniformity in the wafer surface can be improved, and as a result, uniformity in the wafer surface can be improved. Sexual tendency.

Examples of specific developing solutions having a vapor pressure of 5 kPa or less at 20 ° C include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 4-heptanone, 2-hexanone, and a ketone solvent such as isobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone or methyl isobutyl ketone; butyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether Acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3- An ester solvent such as methyl-3-methoxybutyl acetate, butyl formate, propyl formate, ethyl lactate, butyl lactate or propyl lactate; n-propanol, isopropanol, n- Alcohols such as butanol, sec-butanol, tert-butanol, isobutanol, n-hexanol, 4-methyl-2-pentanol, n-heptanol, n-octanol, n-nonanol Solvent; glycol solvent such as ethylene glycol, diethylene glycol or triethylene glycol; ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl a glycol ether solvent such as ether, triethylene glycol monoethyl ether or methoxymethylbutanol; tetrahydrofuran or the like Ether solvent; amide-based solvent such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide; aromatic hydrocarbons such as toluene and xylene An aliphatic hydrocarbon solvent such as a solvent, octane or decane.

Specific examples of the specific developing solution having a vapor pressure of 2 kPa or less in a particularly excellent range at 20 ° C include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 4-heptanone, and 2-hexyl a ketone solvent such as ketone, diisobutyl ketone, cyclohexanone, methylcyclohexanone or phenylacetone; butyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate , diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxy propionate, 3-methoxybutyl acetate, 3-methyl- An ester solvent such as 3-methoxybutyl acetate, ethyl lactate, butyl lactate or propyl lactate; n-butanol, sec-butanol, tert-butanol, isobutanol, n-hexyl An alcohol solvent such as an alcohol, 4-methyl-2-pentanol, n-heptanol, n-octanol or n-nonanol; or a glycol system such as ethylene glycol, diethylene glycol or triethylene glycol. Solvent; glycol such as ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methoxy methyl butanol Ether solvent; N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, etc. Amides based solvents; xylene, the aromatic hydrocarbon solvents; octane, decane and the like aliphatic hydrocarbon solvents and the like.

In the developer, an appropriate amount of a surfactant may be added as necessary. The surfactant is not particularly limited, and for example, an ionic or nonionic fluorine-based and/or a lanthanoid surfactant can be used. Examples of the fluorine and/or lanthanide surfactants include, for example, JP-A-62-36663, JP-A-61-226746, JP-A-61-226745, and JP-A-2013 Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The surfactants described in the publications, U.S. Patent No. 5,405, 720, the same as No. 5,360,692, the same as No. 5,529,881, the same as No. 5,296,330, the same as No. 5,546,098, the same as No. 5,576,143, the same as No. 5,294,411, and the No. 5,842,451. A non-ionic surfactant. The nonionic surfactant is not particularly limited, and more preferably a fluorine-based surfactant or a quinone-based surfactant is used.

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

For the development method, for example, a method in which a substrate is placed in a tank filled with a developing solution, immersed for a certain period of time (dipping method), a developing solution is applied to cover the surface of the substrate by surface tension, and static for a certain period of time for development (paddle type) The "puddle" method, a method of spraying a surface of a substrate onto a substrate (spray method), and a substrate which is rotated at a constant speed on a substrate which is rotated at a constant speed, and a method of discharging the developer (Dynamic dispense method) or the like is continued. The time for developing the pattern is not particularly limited, and is preferably from 10 seconds to 90 seconds.

Further, after the development step, the step of stopping the development may be carried out by substituting for another solvent.

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

The cleaning liquid used in the cleaning step after development is not particularly limited as long as it does not dissolve the resist pattern which is hardened by crosslinking, and a solution containing a general organic solvent or water can be used. The cleaning liquid is preferably a cleaning liquid containing at least one organic solvent selected from the group consisting of a hydrocarbon solvent, a ketone solvent, an ester solvent, an alcohol solvent, a guanamine solvent, and an ether solvent. More preferably, after the development, a step of washing with a cleaning liquid containing at least one organic solvent selected from the group consisting of a ketone solvent, an ester solvent, an alcohol solvent, and a guanamine solvent is used. More preferably, it is a step of washing with a cleaning liquid containing an alcohol solvent or an ester solvent after development. More preferably, it is a step of washing with a cleaning liquid containing a monohydric alcohol after development. It is particularly preferred to carry out the step of washing with a cleaning liquid containing one or more carbon atoms having a carbon number of 5 or more after development. The time for performing the pattern cleaning is not particularly limited, and is generally preferably from 10 seconds to 90 seconds.

Here, examples of the monohydric alcohol used in the washing step after development include a linear, branched, or cyclic monohydric alcohol. Specifically, 1-butanol, 2-butanol, and 3- can be used. Methyl-1-butanol, tert-butanol, 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, particularly preferred monohydric alcohol having 5 or more carbon atoms, can be used 1 -hexanol, 2-hexanol, 4-methyl-2-pentanol, 1-pentanol, 3-methyl-1-butanol, and the like.

The above components may be used in combination or in combination with an organic solvent other than the above.

The water content in the cleaning liquid is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 3% by mass or less. When the water content is 10% by mass or less, more favorable development characteristics tend to be obtained.

The vapor pressure of the cleaning liquid used after development is preferably 0.05 kPa or more and 5 kPa or less at 20 ° C, more preferably 0.1 kPa or more and 5 kPa or less, and most preferably 0.12 kPa or more and 3 kPa or less. When the vapor pressure of the cleaning liquid is set to 0.05 kPa or more and 5 kPa or less, the temperature uniformity in the wafer surface can be further improved, and the swelling phenomenon caused by the penetration of the cleaning liquid can be further suppressed, and the wafer surface can be made. The tendency for uniformity in size within the interior is better.

An appropriate amount of surfactant can be added to the cleaning solution for use.

In the cleaning step, the developed wafer is washed using a cleaning solution containing the above organic solvent. The method of the cleaning treatment is not particularly limited. For example, a method for continuously discharging the cleaning liquid on a substrate that is rotated at a constant speed (rotary coating method), immersing the substrate in a tank filled with the cleaning liquid, and immersing for a certain period of time can be used. a method (dipping method), a method of spraying a cleaning liquid on a surface of a substrate (spray method), and the like, wherein the cleaning treatment is performed by a spin coating method, and after the cleaning, the substrate is rotated at a number of revolutions of 2000 rpm to 4000 rpm. It is better to remove the cleaning liquid from the substrate.

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

After forming the resist pattern, the plating treatment can be performed. Examples of the plating method include copper plating, solder plating, nickel plating, gold plating, and the like.

The residual resist pattern after etching can be peeled off using 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 above-mentioned peeling method include a dipping method, a spraying method, and the like. Further, the wiring substrate on which the resist pattern is formed may be a multilayer wiring substrate or may have a through hole having a small diameter.

The wiring board obtained in the present embodiment can be formed by forming a resist pattern, vapor-depositing the metal in a vacuum, and then dissolving the solution in a solution pattern, that is, using a liftoff method. .

 [Film forming composition for lithography of lower film use]  

The film forming composition for lithography (hereinafter also referred to as "lower film forming material") for use in a layer film according to the present embodiment contains a compound represented by the above formula (1) and a compound represented by the above formula (1) At least one of a resin obtained from 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. In the present embodiment, the material is preferably from 1 to 100% by mass, more preferably from 10 to 100% by mass, even more preferably from 50 to 100% by mass from the viewpoint of coatability and quality stability. %, particularly preferably 100% by mass.

The underlayer film forming material of the present embodiment can be applied to a wet process and is excellent in heat resistance and etching resistance. Further, in the layer film forming material of the present embodiment, since the above-described substance is used, deterioration of the film at the time of high-temperature baking can be suppressed, and an underlayer film excellent in etching resistance such as oxygen plasma etching can be formed. Further, in the layered film forming material of the present embodiment, the adhesion to the resist layer is also excellent, so that an excellent resist pattern can be obtained. In addition, the layer film forming material of the present embodiment may contain a known underlayer film forming material for lithography, etc., as long as the effects of the present invention are not impaired.

 [solvent]  

The layer film forming material in the present embodiment may contain a solvent. The solvent used for the film forming material of the present embodiment 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 a ketone solvent such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone; propylene glycol monomethyl ether or propylene glycol monomethyl ether acetate; Solvent-based solvent; ester solvent of ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, isoamyl acetate, ethyl lactate, methyl methoxypropionate, methyl hydroxyisobutyrate, etc. An alcohol solvent such as methanol, ethanol, isopropanol or 1-ethoxy-2-propanol; or an aromatic hydrocarbon such as toluene, xylene or 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, and is preferably from 100 to 10,000 parts by mass, more preferably from 200 to 5,000 parts by mass, more preferably from 100 parts by mass to the above-mentioned underlayer film forming material from the viewpoint of solubility and film formation. It is 200 to 1,000 parts by mass.

 [crosslinking agent]  

The layer film forming material of the present embodiment may contain a crosslinking agent as necessary from the viewpoint of suppressing mutual mixing and the like. The crosslinking agent which can be used in the embodiment is not particularly limited, and for example, those described in International Publication No. 2013/024779 can be used.

Specific examples of the crosslinking agent which can be used in the embodiment include a phenol compound, an epoxy compound, a cyanate compound, an amine compound, a benzoxazine compound, an acrylate compound, a melamine compound, a guanamine compound, and the like. The glycoluril compound, the urea compound, the isocyanate compound, the azide compound, and the like are not limited thereto. These crosslinking agents may be used alone or in combination of two or more. Among these, a benzoxazine compound, an epoxy compound or a cyanate compound is preferable, and a benzoxazine compound is more preferable from the viewpoint of improving etching resistance.

The aforementioned phenol compound can be used by a conventional one. For example, phenols include polyphenols such as alkylphenols such as cresols and xylenols, polyphenols such as hydroquinone, naphthols, and naphthalenediols, in addition to phenol. A bisphenol such as bisphenol A or bisphenol F, or a polyfunctional phenol compound such as a phenol novolak or a phenol aralkyl resin. Among them, from the viewpoint of heat resistance and solubility, an aralkyl type phenol resin is preferred.

The epoxy compound can be used by a conventional one, and is selected from those having two or more epoxy groups in one molecule. For example, bisphenol A, bisphenol F, 3,3', 5,5'-tetramethyl-bisphenol F, bisphenol S, bisphenol, 2,2'-biphenol, 3, 3 ',5,5'-tetramethyl-4,4'-dihydroxybiphenol, resorcinol, naphthalenediol, etc., divalent phenolic epoxide, tris-(4-hydroxyl) Phenyl)methane, 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, tris(2,3-epoxypropyl)isocyanate, trishydroxymethylmethane tricyclic An epoxide of a valence of three or more valences such as oxypropyl ether, trimethylolpropane triglycidyl ether, trishydroxyethyl ethane triepoxypropyl ether, phenol novolac, and o-cresol novolac; An epoxide of a co-condensation resin of dicyclopentadiene and a phenol, an epoxide of a phenol aralkyl resin synthesized by a phenol and a p-xylylene dichloride, a phenol, and a bischloromethyl group An epoxide of a biphenyl aralkyl type phenol resin synthesized by biphenyl or the like, an epoxide of a naphthol aralkyl resin synthesized by naphthol and p-xylylene dichloride, or the like. These epoxy resins may be used singly or in combination of two or more. Among them, from the viewpoint of heat resistance and solubility, an epoxy resin obtained from a phenol aralkyl resin or a biphenyl aralkyl resin is preferable, and a solid epoxy resin is used at normal temperature.

The cyanate ester compound is not particularly limited as long as it is a compound having two or more cyanate groups in one molecule, and a conventional one can be used. In the present embodiment, a preferred cyanate compound is a structure in which a hydroxyl group of a compound having two or more hydroxyl groups in one molecule is substituted with a cyanate group. Further, the cyanate compound preferably has an aromatic group, and a structure in which a cyanate group is directly bonded to an aromatic group can be suitably used. Examples of the cyanate ester compound include bisphenol A, bisphenol F, bisphenol M, bisphenol P, bisphenol E, phenol novolak resin, cresol novolak resin, and dicyclopentadiene novolac resin. Tetramethyl bisphenol F, bisphenol A novolac resin, brominated bisphenol A, brominated phenol novolak resin, trifunctional phenol, tetrafunctional phenol, naphthalene phenol, biphenyl phenol, phenol aralkyl resin, A structure in which a hydroxy group such as a biphenyl aralkyl resin, a naphthol aralkyl resin, a dicyclopentadiene aralkyl resin, an alicyclic phenol or a phosphorus-containing phenol is substituted with a cyanate group. These cyanate compounds may be used singly or in combination of two or more kinds as appropriate. Further, the cyanate compound may be in the form of any one of a monomer, an oligomer, and a resin.

Examples of the aforementioned amine compound include m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, and 4,4'- Diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenylanthracene, 3,4'-di Aminodiphenylphosphonium, 3,3'-diaminodiphenylphosphonium, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3' -diaminodiphenyl sulfide, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(3-amine Phenoxy group) benzene, 1,3-bis(3-aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]anthracene, 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)anthracene, 9,9-bis(4-amino-3-chlorophenyl)anthracene, 9,9-bis(4-amine 3-fluorophenyl)anthracene, O-tolidine, m-tolidine, 4,4'-diaminobenzimidamide, 2,2'-bis(trifluoromethyl)- 4,4'-Diaminobiphenyl, 4-aminophenyl-4-aminobenzoate, 2-(4-aminophenyl)-6-aminobenzoxazole, and the like. Further, examples thereof include 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenyl ether, and 3,4'-diamino group. Diphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl fluorene, 3,3'-diaminodiphenyl fluorene, 1,4-bis(4- Aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(3-aminophenoxy)benzene, 1,3-bis(3-amino group Phenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]anthracene, 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) An aromatic amine or diamine ring such as biphenyl, bis[4-(4-aminophenoxy)phenyl]ether or bis[4-(3-aminophenoxy)phenyl]ether Hexane, diaminodicyclohexylmethane, dimethyl-diaminodicyclohexylmethane, tetramethyl-diaminodicyclohexylmethane, diaminodicyclohexylpropane, diaminobicyclo[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-diaminomethylcyclohexane, isophorone diamine, etc. Alicyclic amines, ethylene diamine, hexamethylene diamine, octamethylene diamine, decamethylene diamine, diethylene triamine extending acetate, triethylene tetramine acetate stretch of aliphatic amines.

Examples of the benzoxazine compound include a Pd-type benzoxazine obtained from a difunctional diamine and a monofunctional phenol, and a Fa-type benzoic acid obtained from a monofunctional diamine and a difunctional phenol. And so on.

Specific examples of the melamine compound include a methoxymethylated compound of hexamethylenemethyl melamine, hexamethoxymethyl melamine, and hexamethylol melamine, or a mixture thereof, or a mixture thereof. 1 to 6 methoxymethylated compounds of hexamethoxyethyl melamine, hexamethoxymethyl melamine, hexamethylol melamine, or a mixture thereof, or the like.

Specific examples of the guanamine compound include methoxymethylation of 1 to 4 methylol groups of tetramethylolguanamine, tetramethoxymethylguanamine, and tetrahydroxymethylguanamine. A compound or a mixture thereof, a methoxymethyl group of 1 to 4 hydroxymethyl groups of tetramethoxyethyl decylamine, tetradecyl decylamine or tetrahydroxymethyl decylamine, or a mixture thereof.

Specific examples of the above-mentioned glycoluril compound include, for example, 1 to 4 of hydroxymethyl group of tetramethylol glycoluril, tetramethoxyglycoluril, tetramethoxymethyl glycoluril, and tetramethylol glycoluril. The methoxymethylated compound or a mixture thereof, and 1 to 4 of the methylol group of tetramethylol glycoluril are methoxyoxymethylated compounds or a mixture thereof.

Specific examples of the urea compound include, for example, a compound in which methoxymethylated one or four methylol groups of tetramethylolurea, tetramethoxymethylurea, or tetramethylolurea are methoxymethylated or Mixture, tetramethoxyethyl urea, and the like.

Further, in the present embodiment, a crosslinking agent having at least one allyl group can be used from the viewpoint of improving 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-hexa. Fluorin-2,2-bis(3-allyl-4-hydroxyphenyl)propane, bis(3-allyl-4-hydroxyphenyl)anthracene, bis(3-allyl-4-hydroxybenzene Allyl phenol such as thioether, 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-cyanooxyphenyl)propane, bis(3-allyl-4-cyanooxyl) Allyl cyanate such as phenyl)anthracene, bis(3-allyl-4-cyanooxyphenyl) sulfide, bis(3-allyl-4-cyanooxyphenyl)ether , diallyl phthalate, diallyl isophthalate, diallyl terephthalate, triallyl isocyanurate, trimethylolpropane II Allyl ether, pentaerythritol allyl ether and the like are not limited to these examples. These may be used alone or in a mixture of two or more types. Among these, from the viewpoint of excellent compatibility with the bismaleimide compound and/or the addition polymerization type maleimide resin, 2,2-bis(3-allyl-4- is preferable. Hydroxyphenyl)propane, 1,1,1,3,3,3-hexafluoro-2,2-bis(3-allyl-4-hydroxyphenyl)propane, bis(3-allyl-4 Allyl phenols such as -hydroxyphenyl)anthracene, bis(3-allyl-4-hydroxyphenyl) sulfide, bis(3-allyl-4-hydroxyphenyl)ether.

The content of the crosslinking agent in the underlayer 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, even more preferably 10 to 10 parts by mass, based on 100 parts by mass of the underlayer film forming material. 40 parts by mass. When the content of the crosslinking agent is in the above range, there is a tendency to suppress the occurrence of a phenomenon of mixing with the resist layer, and the antireflection effect is enhanced, and the film formability after crosslinking is increased.

 [Crosslinking accelerator]  

In the layer forming material of the present embodiment, if necessary, a crosslinking accelerator for promoting crosslinking and curing reaction can be used.

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

The crosslinking accelerator is not limited to the following, and examples thereof include 1,8-diazabicyclo(5,4,0)undecene-7, triethylenediamine, benzyldimethylamine, and the like. a tertiary amine such as ethanolamine, dimethylaminoethanol or tris(dimethylaminomethyl)phenol, 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2 - imidazoles such as phenyl-4-methylimidazole, 2-heptadecylimidazole, 2,4,5-triphenylimidazole, tributylphosphine, methyldiphenylphosphine, triphenylphosphine, An organic phosphine such as diphenylphosphine or phenylphosphine, tetraphenylphosphonium. Tetraphenylborate, tetraphenylphosphonium. Ethyltriphenylborate, tetrabutylphosphonium. Tetrabutyl hydride such as tetrabutyl borate. Tetrasubstituted borate, 2-ethyl-4-methylimidazole. Tetraphenylborate, N-methylmorpholine. A tetraphenylboron salt such as tetraphenylborate.

When the total amount of the underlayer film forming material is 100 parts by mass, the amount of the crosslinking agent is preferably 0.1 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass from the viewpoint of ease of control and economy. More preferably, it is 0.1 to 3 parts by mass.

 [Free radical polymerization initiator]  

In the layered film forming material of the present embodiment, a radical polymerization initiator may be blended as necessary. The radical polymerization initiator may be a photopolymerization initiator which initiates radical polymerization by light, or may be a thermal polymerization initiator which initiates radical polymerization by heat.

The radical polymerization initiator is not particularly limited, and can be suitably used in the prior art. For example, 1-hydroxycyclohexyl phenyl ketone, benzyl dimethyl acetal, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxyl) -Phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propenyl) -benzyl]phenyl}-2-methylpropan-1-one, 2,4,6-trimethylbenzylidene-diphenyl-phosphine oxide, bis(2,4,6-trimethyl) Ketone-based photopolymerization initiators such as benzylidene)-phenylphosphine oxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, methyl cyclohexanone peroxide, acetamidine acetic acid Methyl ester peroxide, ethyl acetoxy acetate peroxide, 1,1-bis(t-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-double (t- Hexylperoxy)-cyclohexane, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)- 2-methylcyclohexane, 1,1-bis(t-butylperoxy)-cyclohexane, 1,1-bis(t-butylperoxy)cyclododecane, 1,1-double ( T-butyl peroxy)butane, 2,2-bis(4,4-di-t-butylperoxycyclohexyl)propane, p-menthane hydrogen peroxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene peroxidation , t-hexyl hydroperoxide, t-butyl hydroperoxide, α,α'-bis(t-butylperoxy)diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl -2,5-bis(t-butylperoxy)hexane, t-butylcumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-double (t-butylperoxy) hexyne-3, isobutyl hydrazine peroxide, 3,5,5-trimethylhexyl peroxide, octahydrate peroxide, laurel peroxide, stearyl peroxide, Oxidized succinic acid, peroxy-m-toluene benzamidine, benzammonium peroxide, di-n-propyl peroxydicarbonate, diisopropylperoxydicarbonate, bis(4-t- Butylcyclohexyl)peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, di-2-ethoxyhexylperoxydicarbonate, di-3-methoxybutyl Oxydicarbonate, di-s-butylperoxydicarbonate, bis(3-methyl-3-methoxybutyl)peroxydicarbonate, α,α'-bis(neindyl) Neodecanoyl) peroxy)diisopropylbenzene, cumylperoxy neodecanoate, 1,1,3,3-tetramethylbutyl peroxy neodecanoate, 1-cyclohexyl-1-methyl Base peroxy neodecanoate, t-hexyl peroxy neodecanoate, t-butyl Peroxy neodecanoate, t-hexyl peroxytrimethyl acetate (pivalate), t-butyl peroxytrimethyl acetate, 1,1,3,3-tetramethylbutyl peroxyl -2-ethylhexanoate, 2,5-dimethyl-2,5-bis(2-ethylhexylperoxy)hexanoate, 1-cyclohexyl-1-methyl Base peroxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-hexylperoxyisopropyl Carbonate, t-butyl peroxyisobutyrate, t-butyl peroxymaleate (maleate), t-butyl peroxy-3,5,5-trimethylhexanoate, t- Butyl peroxylaurate (laurate), t-butyl peroxyisopropyl monocarbonate, t-butyl peroxy-2-ethylhexyl monocarbonate, t-butyl peroxyacetate, T-butyl peroxy-m-tolylmethyl benzoate, tert-butyl peroxybenzoate, bis(t-butylperoxy)isophthalate, 2,5-dimethyl -2,5-bis(m-tolylmethyl peroxy)hexane, t-hexylperoxybenzoate, 2,5-dimethyl-2,5-bis(benzhydrylperoxy) Hexane, t-butylperoxyallyl monocarbonate, t-butyltrimethylformamido peroxide, 3,3',4,4'-tetra(t-butylperoxy) Yl) benzophenone, an organic peroxide 2,3-dimethyl-2,3-diphenyl butane and the like of a polymerization initiator.

Further, 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile, 1-[(1-cyano-1-methylethyl)azo]carbamamine, 1, 1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobisisobutyronitrile, 2,2' - azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2-methylpropionamidine) dihydrochloride, 2,2'-azobis (2 -methyl-N-phenylpropionamidine dihydrochloride, 2,2'-azobis[N-(4-chlorophenyl)-2-methylpropionamidine dihydrochloride, 2,2 '-Azobis[N-(4-hydro(hydro)phenyl)-2-methylpropionamidine] dihydrochloride, 2,2'-azobis[2-methyl-N-(phenyl) Methyl)propanoid] dihydrochloride, 2,2'-azobis[2-methyl-N-(2-propenyl)propanoid] dihydrochloride, 2,2'-azobis [ N-(2-hydroxyethyl)-2-methylpropionamidine dihydrochloride, 2,2'-azobis[2-(5-methyl-2-imidazolin-2-yl)propane] Dihydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride, 2,2'-azobis[2-(4,5,6 ,7-tetrahydro-1H-1,3-diazacycloheptatriene (diazepine-2-yl)propane]dihydrochloride, 2,2'-azobis[2-(3,4,5 ,6-tetrahydropyrimidin-2-yl)propane]dihydrochloride, 2,2'-even Bis[2-(5-hydroxy-3,4,5,6-tetrahydropyrimidin-2-yl)propane]dihydrochloride, 2,2'-azobis[2-[1-(2-hydroxyl) Ethyl)-2-imidazolin-2-yl]propane]dihydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane], 2,2'-even Nitrogen bis[2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propanamide], 2,2'-azobis[2-methyl-N-[ 1,1-bis(hydroxymethyl)ethyl]propanamide], 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propanamide], 2,2' - azobis(2-methylpropanamide), 2,2'-azobis(2,4,4-trimethylpentane), 2,2'-azobis(2-methylpropane) ), dimethyl-2,2-azobis(2-methylpropionate), 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis[2] An azo polymerization initiator such as -(hydroxymethyl)propionitrile. One of these may be used singly or in combination of two or more kinds of the above-mentioned radical polymerization initiators. Further, other conventional polymerization initiators may be used in combination.

The content of the radical polymerization initiator may be an amount necessary for the stoichiometric amount, and when the underlayer film forming material is 100 parts by mass, it is preferably 0.05 to 25 parts by mass, more preferably 0.1 to 10 parts by mass. . When the content of the radical polymerization initiator is 0.05 parts by mass or more, the tendency of insufficient curing can be prevented, and when the content of the radical polymerization initiator is 25 parts by mass or less, the formation of the underlayer film can be prevented from being damaged. The tendency of materials to preserve stability over a long period of time at room temperature.

 [acid generator]  

In the layer film forming material of the present embodiment, an acid generator may be contained as necessary from the viewpoint of further promoting a crosslinking reaction by heat or the like. As the acid generator, those which generate an acid by thermal decomposition, and those which generate an acid by light irradiation are known, but any of them may be used. For example, those described in International Publication No. 2013/024779 can be used.

The content of the acid generator in the film forming material of the present embodiment is not particularly limited, and is preferably 0.1 to 50 parts by mass, more preferably 0.5 to 40 parts by mass, per 100 parts by mass of the underlayer film forming material. In the above preferred range, the amount of acid generated is increased to increase the tendency of the crosslinking reaction, and the tendency to suppress the mixing with the resist layer tends to occur.

 [alkaline compound]  

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

The basic compound has a function of a quenching agent for an acid to prevent crosslinking by an acid generated by an acid generator. The basic compound is not particularly limited, and examples thereof include those described in International Publication No. 2013/024779.

In the layer forming material of the present embodiment, the content of the basic compound is not particularly limited, and is preferably 0.001 to 2 parts by mass, more preferably 0.01 to 1 part by mass, per 100 parts by mass of the underlayer film forming material. By setting it as the above preferable range, it exists in the tendency which improves the storage stability without not damaging a crosslinking reaction.

 [Other additives]  

Further, in the present embodiment, the underlayer film forming material may contain other resins and/or compounds in order to impart heat or light curability or control absorbance. Examples of such other resins and/or compounds include naphthol resin, xylene resin naphthol modified resin, phenol modified resin of naphthalene resin, polyhydroxystyrene, dicyclopentadiene resin, and (meth)acrylic acid. Ester, dimethacrylate, trimethacrylate, tetramethacrylate, vinyl naphthalene, naphthalene ring containing polydecene, biphenyl ring of phenanthrenequinone, anthracene, etc., thiophene, anthracene, etc. Atomic heterocyclic resin or aromatic ring-free resin; rosin-based resin, cyclodextrin, adamantane (poly)ol, tricyclodecane (poly)ol, and derivatives thereof, etc. The resin, the compound, and the like are not particularly limited thereto. Further, the underlayer film forming material in the present embodiment may contain a conventional additive. The above-mentioned additives are not limited to the following, and examples thereof include heat and/or photo-curing catalyst, polymerization inhibitor, flame retardant, filler, coupling agent, thermosetting resin, photocurable resin, dye, and the like. Pigments, tackifiers, slip agents, antifoaming agents, flat agents, ultraviolet absorbers, surfactants, colorants, nonionic surfactants, and the like.

 [Formation method of underlayer film and multilayer resist pattern for lithography]  

The underlayer film for lithography in the present embodiment is formed of the underlayer film forming material.

Further, the method of forming the pattern of the present embodiment includes the following steps.

The above composition is used on the substrate to form an underlayer film, and at least one photoresist layer is formed on the underlayer film, and then a specific region of the photoresist layer is irradiated with radiation for development. More specifically, the method includes the steps of: forming a lower film using the underlayer film forming material of the present embodiment on the substrate (A-1); and forming at least one photoresist layer on the underlying film (A-2). And after the step (A-2), the step (A-3) of irradiating the specific region of the photoresist layer with radiation is performed.

Further, the method of forming the circuit pattern of the present embodiment includes the following steps.

Forming an underlayer film on the substrate using the above composition, using a resist interlayer film material on the underlayer film, forming an intermediate layer film, and forming at least one layer of the photoresist layer on the intermediate layer film; a specific region of the photoresist layer is irradiated with radiation, and is developed to form a resist pattern; the intermediate layer film is etched by using the resist pattern as a mask, and the obtained interlayer film pattern is used as an etching mask And etching the underlayer film, using the obtained underlying film pattern as an etch mask, etching the substrate, and forming a pattern on the substrate.

In more detail, the following steps are performed. a step (B-1) of forming a lower layer film using the underlayer film forming material of the present embodiment on the substrate; and a step of forming an intermediate layer film using a resist layer intermediate layer film material containing germanium atoms on the underlayer film (B-2) a step (B-3) of forming at least one photoresist layer on the intermediate layer film; after the step (B-3), irradiating a specific region of the photoresist layer with radiation and developing to form a resist pattern After the step (B-4); and the step (B-4), the intermediate layer film is etched by using the resist pattern as a mask, and the obtained interlayer film pattern is used as an etching mask and etched. In the underlayer film, the obtained underlayer film pattern is used as an etching mask, and the substrate is etched to form a pattern (B-5) on the substrate.

The underlayer film for lithography in the present embodiment is not particularly limited as long as it is formed of the underlayer film forming material of the present embodiment, and a conventional method can be applied. For example, after the layer film material of the present embodiment is applied to a substrate by a conventional coating method such as spin coating or screen printing, or a printing method, the organic solvent is removed by volatilization or the like, and then conventionally known. According to the method, the underlayer film for lithography of the present embodiment can be formed by crosslinking and hardening. Examples of the crosslinking method include methods such as thermosetting and photocuring.

In the formation of the underlayer film, baking is preferably performed in order to suppress the occurrence of a mixing phenomenon with the upper layer resist and promote the crosslinking reaction. In this case, the baking temperature is not particularly limited, but is preferably in the range of 80 to 450 ° C, preferably 200 to 400 ° C. Further, the baking time is not particularly limited, but it is preferably in the range of 10 to 300 seconds. Further, the thickness of the underlayer film is appropriately selected depending on the desired properties, and is not particularly limited, and is usually about 30 to 20,000 nm, more preferably 50 to 15,000 nm.

After the underlayer film is formed, in the case of a two-layer process, a resist layer containing ruthenium or a single-layer resist composed of a usual hydrocarbon is formed thereon, and in the case of a three-layer process, ruthenium is formed thereon. It is preferable that the intermediate layer is made of a single-layer resist layer containing no antimony thereon. At this time, a photoresist material for forming the resist layer can be used.

After the underlayer film is formed on the substrate, in the case of a two-layer process, a resist layer containing ruthenium or a single-layer resist composed of a usual hydrocarbon can be formed on the underlayer film. In the case of a three-layer process, a ruthenium-containing intermediate layer can be formed on the underlayer film, and a ruthenium-free single-layer resist layer can be formed on the ruthenium-containing intermediate layer. In these cases, the photoresist material for forming the resist layer can be appropriately selected from those skilled in the art, and is not particularly limited.

A ruthenium-containing polymer containing a polysilsesquioxane derivative or a vinyl decane derivative or the like as a matrix polymer from the viewpoint of oxygen gas etching resistance from the viewpoint of oxygen gas etching resistance, and It is preferred to use a positive photoresist material containing an organic solvent, an acid generator, a basic compound if necessary, and the like. here. As the polymer containing a ruthenium atom, a conventional polymer used for such a resist material can be used.

The intermediate layer containing ruthenium for the three-layer process is preferably an intermediate layer using polysilsesquioxane. By providing the intermediate layer with an effect as an antireflection film, the tendency of reflection can be effectively suppressed. For example, in the 193 nm exposure process, when a material containing a large number of aromatic groups and having high substrate etching resistance is used as the underlayer film, the k value tends to be high, and the substrate reflection tends to be high. However, by suppressing the reflection by the intermediate layer, The substrate reflection was set to 0.5% or less. The intermediate layer having such an antireflection effect is not particularly limited to the following. For 193 nm exposure, it is preferred to use a phenyl group or a light-absorbing group having a fluorene-ruthenium bond to crosslink with acid or heat. Sesquiterpene oxide.

Further, an intermediate layer formed by a chemical vapor deposition (CVD) method can also be used. The intermediate layer having a high effect as an antireflection film produced by the CVD method is not limited to the following, and for example, an SiON film is known. In general, the intermediate layer is formed by a wet process such as spin coating or screen printing as compared with the CVD method, which is relatively simple and cost-effective. Further, the resist agent may be either a positive type or a negative type in the three-layer process, or may be the same as the single-layer resist which is usually used.

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

In the case where the resist layer is formed of the above-mentioned photoresist material, as in the case of forming the underlayer film, a wet process such as a spin coating method or screen printing is preferably used. Further, after the resist material is applied by a spin coating method or the like, prebaking is usually carried out, but the prebaking is preferably carried out at 80 to 180 ° C for 10 to 300 seconds. Then, exposure is carried out in accordance with a conventional method, and a resist pattern is obtained by post-exposure baking (PEB) and development. Further, the thickness of the resist film is not particularly limited, but is preferably 30 to 500 nm, more preferably 50 to 400 nm.

Further, the exposure light source may be appropriately selected and used according to the photoresist material to be used. In general, high-energy rays having a wavelength of 300 nm or less include, for example, excimer lasers of 248 nm, 193 nm, and 157 nm, soft X-rays of 3 to 20 nm, electron beams, and X-rays.

The resist pattern formed by the above method is a pattern in which the pattern is suppressed by the underlayer film of the present embodiment. Therefore, by using the underlayer film of the present embodiment, a more fine pattern can be obtained, and the amount of exposure necessary for obtaining the resist pattern can be reduced.

Next, etching is performed using the obtained resist pattern as a mask. The etching of the underlying film in the 2-layer process is preferably performed using a gas etch. The gas etching is preferably an etching using oxygen. In addition to oxygen, an inert gas such as He, Ar or the like, or CO, CO ₂ , NH ₃ , SO ₂ , N ₂ , NO ₂ or H ₂ gas may be added. Further, it is also possible to perform gas etching using only CO, CO ₂ , NH ₃ , N ₂ , NO ₂ , and H ₂ gas without using oxygen. In particular, in order to prevent side wall protection for undercut of the pattern side wall, it is preferred to use the latter gas.

On the other hand, etching of the intermediate layer in the 3-layer process is also preferably performed using gas etching. The gas etching can be applied to the same as those described in the above two-layer process. In particular, it is preferred that the intermediate layer in the three-layer process be processed using a chlorofluorocarbon-based gas and a resist pattern as a mask. Thereafter, as described above, the underlayer film can be processed by using an intermediate layer pattern as a mask, for example, by oxygen gas etching.

Here, when an inorganic hard mask intermediate layer film is formed as an intermediate layer, a tantalum oxide film, a tantalum nitride film, or a tantalum oxide nitride film (SiON film) is formed by a CVD method, an ALD method, or the like. The method of forming the nitride film is not limited to the following, and the methods described in, for example, JP-A-2002-334869 (Patent Document 6) and WO2004/066377 (Patent Document 7) can be used. A photoresist film may be formed directly on the interlayer film, but an organic anti-reflection film (BARC) may be formed by spin coating on the interlayer film, and a photoresist film may be formed thereon.

The intermediate layer is also preferably an intermediate layer using a polysescappoxyalkylene bottom. By having the effect of the resist intermediate layer film as an antireflection film, the tendency of reflection can be effectively suppressed. The specific material of the intermediate layer of the poly-sesquiterpoxyalkylene group is not limited to the following, and is described in, for example, JP-A-2007-226170 (Patent Document 8) and JP-A-2007-226204 (Patent Document 9). By.

Further, the following substrate etching can be carried out according to a conventional method. For example, when the substrate is SiO ₂ or SiN, etching using a chlorofluorocarbon-based gas as a main component can be performed, and if p-Si, Al or W is used, The chlorine-based or bromine-based gas is mainly etched. In the case of etching a substrate using a chlorofluorocarbon-based gas, the ruthenium-containing resist of the two-layer resist process and the ruthenium-containing intermediate layer of the three-layer process are simultaneously peeled off from the substrate processing. Further, when a substrate is etched using a chlorine-based or bromine-based gas, the stripping layer containing the resist layer or the tantalum-containing intermediate layer is additionally performed, and generally, after the substrate processing, dry etching is performed by a chlorofluorocarbon-based gas. Stripped.

The layer film under the present embodiment has such a feature that the substrate is excellent in etching resistance. Further, the substrate can be appropriately selected from those skilled in the art, and is not particularly limited, and examples thereof include Si, α-Si, p-Si, SiO ₂ , SiN, SiON, W, TiN, and Al. Further, the substrate may be a laminate having a film to be processed (substrate to be processed) on a substrate (support). Examples of such a film to be processed include various Low-k films such as Si, SiO ₂ , SiON, SiN, p-Si, α-Si, W, W-Si, Al, Cu, and Al-Si, and a stopper film thereof. Usually, a material different from the substrate (support) is used. Further, the thickness of the substrate to be processed or the film to be processed is not particularly limited, and is usually about 50 to 10,000 nm, more preferably 75 to 5,000 nm.

It is preferable to apply the resist permanent film formed by the composition of the present embodiment, and if necessary, to form a resist pattern, it is preferable to use it as a permanent film remaining in the final product. Specific examples of the permanent film include a semiconductor device, and a package adhesion layer or an integrated circuit element such as a solder resist, a package material, an underfill material, and a circuit element is associated with an adhesive layer of a circuit board or a thin display. Crystal protective film, liquid crystal color filter protective film, black matrix, spacer, and the like. In particular, the permanent film formed of the composition of the present embodiment is also excellent in heat resistance and moisture resistance, and is extremely excellent in contamination due to sublimation components. In particular, among the display materials, it is a material having high sensitivity, high heat resistance, and moisture absorbing reliability which are both important due to deterioration of image quality due to contamination.

When the composition of the present embodiment is used for the use of a resist permanent film, in addition to the curing agent, other resins, surfactants or dyes, fillers, crosslinking agents, dissolution promoters, etc. may be added as necessary. The various additives can be used as a resistive permanent film composition by dissolving in an organic solvent.

In the film for lithography of the present embodiment, a composition for forming a composition or a film for a permanent film of a resist is prepared by mixing the above components and mixing them by using a stirrer or the like. In the case where the composition for a resist underlayer film or the composition for a resist permanent film of the present embodiment contains a filler or a pigment, dispersion can be carried out using a dispersing device such as a dissolver, a homogenizer or a three-roll mill. Or mix to modulate.

 Example  

Hereinafter, the present embodiment will be described in more detail by way of Synthesis Examples and Examples, but the present embodiment is not limited to such examples.

 (carbon concentration and oxygen concentration)  

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

Device: CHN Corder MT-6 (Yanaco 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, gel permeation chromatography (GPC) analysis was carried out under the following conditions to obtain a weight average molecular weight (Mw), a number average molecular weight (Mn), and a dispersity (Mw/Mn) in terms of polystyrene.

Device: Shodex GPC-101 (Showa Denko (share) system)

Column: KF-80M×3

Dissolved solution: THF 1mL/min

Temperature: 40 ° C

 (solubility)  

The compound is dissolved in propylene glycol monomethyl ether (PGME), cyclohexanone (CHN), ethyl lactate (EL), methyl amyl ketone (MAK) or tetramethyl urea (TMU) at 23 ° C. The solution was stirred at 3% by mass, and the results after one week were evaluated based on the following criteria.

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

Evaluation C: It was visually confirmed that precipitates were present in any of the solvents.

 [Structure of compound]  

The structure of the compound was confirmed by 1H-NMR measurement using the "Advance 600 II spectrometer" manufactured by Bruker Co., Ltd. under the following conditions.

Frequency: 400MHz

Solvent: d6-DMSO

Internal standard: TMS

Measuring temperature: 23 ° C

 <Synthesis Example 1> Synthesis of XBisN-1  

2,6-naphthol (a reagent manufactured by Sigma-Aldrich Co., Ltd.) 3.20 g (20 mmol) and 4-biphenylcarboxyaldehyde (Mitsubishi Gas Chemical Co., Ltd.) in a container having an internal volume of 100 mL equipped with a stirrer, a condenser, and a burette 1.82 g (10 mmol) was placed in 30 mL of methyl isobutyl ketone, and 5 mL of 95% sulfuric acid was added, and the reaction liquid was stirred at 100 ° C for 6 hours to carry out a reaction. Next, the reaction liquid was concentrated, 50 g of pure water was added, and the reaction product was precipitated, and after cooling to room temperature, it was filtered and separated. The obtained solid matter was filtered, dried, and then separated and purified by column chromatography to obtain 3.05 g of the objective compound of the formula (XBisN-1). The chemical structure having the following formula (XBisN-1) was confirmed by 400 MHz - ¹ H-NMR.

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)

Further, the substitution position of 2,6-naphthol was confirmed by the doublet of the 3rd and 4th proton signals (signal).

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

10 g (21 mmol) of the compound represented by the above formula (XBisN-1) and 14.8 g (107 mmol) of potassium carbonate were placed in 50 mL of dimethylformamide in a container having an internal volume of 100 mL equipped with a stirrer, a condenser, and a burette. 6.56 g (54 mmol) of 2-chloroethyl acetate was added, and the reaction liquid was stirred at 90 ° C for 12 hours to carry out a reaction. Next, the reaction liquid was cooled in an ice bath to precipitate crystals, which were filtered and separated. Then, 40 g of the above-mentioned crystals, 40 g of methanol, 100 g of THF, and a 24% aqueous sodium hydroxide solution were placed in a container having an internal volume of 100 mL of a stirrer, a condenser, and a burette, and the reaction liquid was stirred under reflux for 4 hours to carry out a reaction. Then, the mixture is cooled in an ice bath, and the reaction mixture is concentrated, and the precipitated solid is filtered, dried, and then purified by column chromatography to obtain the objective compound 5.9 (E-XBisN-1). g. The chemical structure having the following formula (E-XBisN-1) was confirmed by 400 MHz - ¹ H-NMR.

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

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

 <Synthesis Example 2> Synthesis of BisF-1  

A 200 mL inner container having a stirrer, a condenser, and a burette was prepared. Into this container, 30 g (161 mmol) of 4,4-biphenol (a reagent manufactured by Tokyo Chemical Industry Co., Ltd.), 15 g (82 mmol) of 4-benzaldehyde (manufactured by Mitsubishi Gas Chemical Co., Ltd.), and 100 mL of butyl acetate were charged, and p was added thereto. -toluenesulfonic acid (reagent manufactured by Kanto Chemical Co., Ltd.) 3.9 g (21 mmol), and the reaction liquid was prepared. The reaction solution was stirred at 90 ° C for 3 hours to carry out a reaction. Next, the reaction liquid was concentrated, 50 g of heptane was added, and the reaction product was precipitated, and after cooling to room temperature, it was filtered and separated. The solid obtained by filtration was dried and then separated and purified by column chromatography to obtain 5.8 g of the objective compound of the formula (BisF-1). The following peaks were found by 400 MHz - ¹ H-NMR, and the chemical structure of the following formula (BisF-1) was confirmed.

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)

Further, with respect to the obtained compound, the molecular weight was measured by the above method and found to be 536.

 <Synthesis Example 2A> Synthesis of E-BisF-1  

In a container having a volume of 100 mL equipped with a stirrer, a condenser, and a burette, 11.2 g (21 mmol) of the compound represented by the above formula (BisF-1) and 14.8 g (107 mmol) of potassium carbonate were placed in 50 mL of dimethylformamide. In the above, 6.56 g (54 mmol) of 2-chloroethyl acetate was added, and the reaction mixture was stirred at 90 ° C for 12 hours to carry out a reaction. Next, the reaction liquid was cooled in an ice bath to precipitate crystals, which were filtered and separated. Then, 40 g of the above-mentioned crystals, 40 g of methanol, 100 g of THF, and a 24% aqueous sodium hydroxide solution were placed in a container having an internal volume of 100 mL of a stirrer, a condenser, and a burette, and the reaction liquid was stirred under reflux for 4 hours to carry out a reaction. Then, it is cooled in an ice bath, and the reaction liquid is concentrated, and the precipitated solid matter is filtered, and after drying, it is separated and purified by column chromatography to obtain the objective compound 5.9 represented by the following formula (E-BisF-1). g. The 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 to 7.8 (22H, Ph-H), 6.2 (1H, CH), 4.0 (8H, -O-CH ₂ -), 3.8 (8H, -CH ₂ -OH )

Further, with respect to the obtained compound, the molecular weight was measured by the above method and found to be 712.

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

10.0 g (21 mmol) of the compound represented by the above formula (XBisN-1), 6.1 g of 2-isocyanatoethyl methacrylate, and the like, in a container having an internal volume of 100 mL equipped with a stirrer, a condenser, and a burette 0.5 g of ethylamine and 0.05 g of p-methoxyphenol were placed in 50 mL of methyl isobutyl ketone, and the mixture was heated to 80 ° C, and stirred for 24 hours to carry out a reaction. After cooling to 50 ° C, the reaction liquid was dropped into pure water, and the precipitated solid matter was filtered and dried, and then separated and purified by column chromatography to obtain a target compound represented by the following formula (UaXBisN-1): 3.0 g. . The chemical structure having the following formula (UaXBisN-1) was confirmed by 400 MHz- ¹ H-NMR.

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

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

Further, with respect to the obtained compound, the molecular weight was measured by the above method and found to be 776. The thermal decomposition temperature was 370 ° C, the glass transition temperature was 90 ° C, and the melting point was 200 ° C, which was confirmed to be high heat resistance.

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

In the same manner as in the synthesis of Example 1, except that the compound represented by the above formula (E-XBisN-1) was used instead of the compound represented by the above formula (XBisN-1), the following formula (UaE-XBisN-1) was obtained. The target compound was 3.2 g. The chemical structure of the following formula (UaE-XBisN-1) was confirmed by 400 MHz- ¹ H-NMR.

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

7.2~7.8(19H, Ph-H), 6.8(2H, NH), 6.7(1H,CH), 6.5(4H,=CH ₂ ), 3.1~4.6(16H,-OCH ₂ -CH ₂ -O-, -O-CH ₂ -CH ₂ -N-), 2.0 (6H, -CH ₃ )

Further, with respect to the obtained compound, the molecular weight was measured by the above method and found to be 864. The thermal decomposition temperature was 360 ° C, the glass transition temperature was 85 ° C, and the melting point was 195 ° C, which was confirmed to be high heat resistance.

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

In addition to the compound represented by the above formula (BisF-1), in place of the compound represented by the above formula (XBisN-1), the same reaction as in the synthesis example 1-1 can be carried out to obtain the following formula (UaBisF-1). Compound 2.5 g. The chemical structure having the following formula (UaBisF-1) was confirmed by 400 MHz - ¹ H-NMR.

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

δ (ppm) 6.8 to 7.8 (22H, Ph-H), 6.5 (8H, =CH ₂ ), 6.2 (1H, CH), 4.1 to 4.7 (16H, -O-CH ₂ -CH ₂ -N-), 2.0(12H,-CH ₃ )

Further, with respect to the obtained compound, the molecular weight was measured by the above method and found to be 1156. The thermal decomposition temperature was 365 ° C, the glass transition temperature was 65 ° C, and the melting point was 185 ° C, which was confirmed to be high heat resistance.

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

In addition to the compound represented by the above formula (E-BisF-1), in the same manner as in the synthesis example 1-2 except for the compound represented by the above formula (XBisN-1), the following formula (UaE-BisF-1) can be obtained. ) The target compound represented by 2.6 g. The chemical structure having the following formula (UaE-BisF-1) was confirmed by 400 MHz - ¹ H-NMR.

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

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

Further, with respect to the obtained compound, the molecular weight was measured by the above method and found to be 1133. The thermal decomposition temperature was 355 ° C, the glass transition temperature was 60 ° C, and the melting point was 175 ° C, which was confirmed to be high heat resistance.

 <Synthesis Example 3> Synthesis of BiN-1  

In a container having a volume of 300 mL equipped with a stirrer, a condenser, and a burette, 10 g (69.0 mmol) of 2-naphthol (a reagent manufactured by Sigma-Aldrich Co., Ltd.) was melted at 120 ° C, and then 0.27 g of sulfuric acid was added thereto, followed by addition. 4-Ethylbiphenyl (a reagent manufactured by Sigma-Aldrich Co., Ltd.) was 2.7 g (13.8 mmol), and the content was stirred at 120 ° C for 6 hours to carry out a reaction to obtain a reaction liquid. 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 mixture, followed by extraction with ethyl acetate. Next, pure water was added until it was neutral, and liquid was separated and concentrated to prepare a solution. After the obtained solution was separated through a column chromatography layer, 1.0 g of the objective compound (BiN-1) represented by the following formula (BiN-1) was obtained.

With respect to the obtained compound (BiN-1), the molecular weight was measured by the above method and found to be 466.

The obtained compound (BiN-1) was subjected to NMR measurement under the above-mentioned measurement conditions, and the following peaks were observed, and the chemical structure of 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  

10.5 g (21 mmol) of the compound (BisN-1) represented by the above formula and 14.8 g (107 mmol) of potassium carbonate were placed in 50 mL of dimethylformamide in a container having an internal volume of 100 mL equipped with a stirrer, a condenser, and a burette. In the above, 6.56 g (54 mmol) of 2-chloroethyl acetate was added, and the reaction mixture was stirred at 90 ° C for 12 hours to carry out a reaction. Next, the reaction liquid was cooled in an ice bath to precipitate crystals, which were filtered and separated. Then, 40 g of the crystal, 40 g of methanol, 100 g of THF, and a 24% aqueous sodium hydroxide solution were placed in a container having a volume of 100 mL of a condenser, a condenser, and a burette, and the reaction solution was stirred under reflux for 5 hours to carry out a reaction. Then, the mixture was cooled in an ice bath, and the reaction mixture was concentrated, and the precipitated solid was filtered, and dried and then purified by column chromatography to obtain 4.6 g of the desired compound. The 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 to 7.8 (19H, Ph-H), 6.7 (1H, CH), 4.0 (4H, -O-CH ₂ -), 3.8 (4H, -CH ₂ -OH )

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

In addition to the compound represented by the above formula (BiN-1), the compound represented by the following formula (UaBiN-1) is obtained by the same reaction as in the synthesis example 1-1 except for the compound represented by the above formula (XBisN-1). 3.5g.

The chemical structure of the following formula (UaBiN-1) was confirmed by 400 MHz - ¹ H-NMR.

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

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

With respect to the obtained compound, the molecular weight was measured by the aforementioned method and found to be 776. The thermal decomposition temperature was 390 ° C, the glass transition temperature was 72 ° C, and the melting point was 224 ° C, which was confirmed to have high heat resistance.

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

In the same manner as in Synthesis Example 1-2 except that the compound represented by the above formula (E-BiN-1) was used instead of the compound represented by the above formula (XBisN-1), the following formula (UaE-BiN-1) was obtained. The target compound represented by 3.9 g.

The chemical structure of the following formula (UaE-BiN-1) was confirmed by 400 MHz - ¹ H-NMR.

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

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

With respect to the obtained compound, the molecular weight was measured by the aforementioned method and found to be 864. The thermal decomposition temperature was 362 ° C, the glass transition temperature was 70 ° C, and the melting point was 226 ° C, which was confirmed to have high heat resistance.

 <Synthesis Example 4> Synthesis of BiP-1  

In the same manner as in Synthesis Example 1, except that 2-phenylphenol was used instead of 2-naphthol, 1.0 g of the objective compound represented by the following formula (BiP-1) was obtained.

With respect to the obtained compound (BiP-1), the molecular weight was measured by the above method and found to be 466. The obtained compound (BiP-1) was subjected to NMR measurement using the above measurement conditions. As a result, the following peak was observed, and the chemical structure of the following formula (BiP-1) was confirmed.

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 container having a volume of 100 mL equipped with a stirrer, a condenser, and a burette, 11.2 g (21 mmol) of the compound represented by the above formula (BiP-1) and 14.8 g (107 mmol) of potassium carbonate were placed in 50 mL of dimethylformamide. In the above, 6.56 g (54 mmol) of 2-chloroethyl acetate was added, and the reaction mixture was stirred at 90 ° C for 12 hours to carry out a reaction. Next, the reaction liquid was cooled in an ice bath to precipitate crystals, which were filtered and separated. Then, 40 g of the crystal, 40 g of methanol, 100 g of THF, and a 24% aqueous sodium hydroxide solution were placed in a container having an internal volume of 100 mL equipped with a stirrer, a condenser, and a burette, and the reaction liquid was stirred under reflux for 4 hours to carry out a reaction. Then, it was cooled in an ice bath, and the reaction liquid was concentrated, and the precipitated solid was filtered, dried, and then purified by column chromatography to obtain the objective compound 5.9 g (E-BisF-1). . The chemical structure of the following formula (E-BiP-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 to 7.6 (25H, Ph-H), 4.0 (4H, -O-CH ₂ -), 3.8 (4H, -CH ₂ -OH), 2.2 (3H, CH )

With respect to the obtained compound, the molecular weight was measured by the aforementioned method and found to be 606.

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

In addition to the compound represented by the above formula (BiP-1), the compound represented by the following formula (UaBiP-1) is obtained by the same reaction as in the synthesis example 1-2 except for the compound represented by the above formula (XBisN-1). 6.6g.

The chemical structure of the following formula (UaBiP-1) was confirmed by 400 MHz- ¹ H-NMR.

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

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

The thermal decomposition temperature was 371 ° C, the glass transition temperature was 84 ° C, and the melting point was 232 ° C, which was confirmed to have high heat resistance.

With respect to the obtained compound, the molecular weight was measured by the aforementioned method and found to be 828.

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

The compound represented by the above formula (E-BiP-1) was used in the same manner as in the synthesis example 1-2 except that the compound represented by the above formula (XBisN-1) was used, and the following formula (UaE-BiP-1) was obtained. The target compound represented by 4.6 g.

The chemical structure of the following formula (UaE-BiP-1) was confirmed by 400 MHz- ¹ H-NMR.

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

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

With respect to the obtained compound, the molecular weight was measured by the aforementioned method and found to be 916.

The thermal decomposition temperature was 372 ° C, the glass transition temperature was 70 ° C, and the melting point was 210 ° C, which was confirmed to have high heat resistance.

 (Synthesis Examples 5 to 17)  

2-naphthol (raw material 1) and 4-ethyl fluorenylbiphenyl (raw material 2) of the raw material of Synthesis Example 3 were changed as shown in Table 1, and the same as in Synthesis Example 3, and each object was obtained.

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

 (Synthesis Examples 18 to 20)  

The 4-bi-benzaldehyde (raw material 2) of the raw material of Synthesis Example 1 was changed as shown in Table 3, and the same procedure as in Synthesis Example 3 was carried out to obtain each compound of interest. Each compound of interest was identified by ¹ H-NMR (Table 4).

 (Synthesis Examples 21 to 22)  

The 2-naphthol (raw material 1) and 4-ethylhydrazine biphenyl (raw material 2) of the raw material of Synthesis Example 3 were changed as shown in Table 5, and 1.5 mL of water and 73 mg (0.35 mmol) of dodecyl mercaptan were added, 37. 2.3 g (22 mmol) of hydrochloric acid, and the reaction temperature was changed to 55 ° C, and the same procedure as in Synthesis Example 3 was carried out to obtain the objective compound. Each compound of interest was identified by ¹ H-NMR (Table 6).

 (Synthesis Example 5A to 22A)  

The compound represented by the above formula (BiN-1) of the starting material of Synthesis Example 3A was changed as shown in Table 7, and the other compounds were synthesized under the same conditions as in Synthesis Example 3A to obtain the objective compound. The structure of each compound of interest was identified by confirming the molecular weight by 400 MHz - ¹ H-NMR (d-DMSO, internal standard TMS) and LC-MS.

 (Synthesis Examples 5-1 to 22-1)  

The compound represented by the above formula (E-BiN-1) of the starting material of Synthesis Example 3-1 was changed as shown in Table 7, and the same conditions as those in Synthesis Example 3-1 were carried out to obtain the objective compound. The structure of each of the objective compounds was identified by confirming the molecular weight by 400 MHz - ¹ H-NMR (d-DMSO, internal standard TMS) and LC-MS.

 (Synthesis Example 5-2 to 22-2)  

The compound represented by the above formula (E-BiN-1) of the starting material of Synthesis Example 3-2 was changed as shown in Table 7, and the other compounds were synthesized under the same conditions as in Synthesis Example 3-2 to obtain each compound of interest. The structure of each of the objective compounds was identified by confirming the molecular weight by 400 MHz - ¹ H-NMR (d-DMSO, internal standard TMS) and LC-MS.

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

A four-necked flask having a 1 L inner volume discharged from the bottom with a Dimroth condenser, a thermometer, and a stirring blade was prepared. In the four-necked flask, 32.6 g (70 mmol, manufactured by Mitsubishi Gas Chemical Co., Ltd.) and 21.0 g of a 40% by mass aqueous solution of Formalin (formaldehyde: 280 mmol) of the compound (XBisN-1) obtained in Synthesis Example 1 were placed under a nitrogen flow. Mitsubishi Gas Chemical Co., Ltd.) and 98% by mass of sulfuric acid (manufactured by Kanto Chemical Co., Ltd.) were reacted at 0.97 mL under normal pressure at 100 ° C for 7 hours while refluxing. Then, 180.0 g of o-xylene (Special grade of reagent manufactured by Wako Pure Chemical Industries, Ltd.) as a diluent solvent was added to the reaction liquid, and after standing, the aqueous phase of the lower phase was removed. Further, neutralization and washing with water were carried out, and o-xylene was distilled off under reduced pressure to obtain 34.1 g of a brown solid resin (R1-XBisN-1).

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

 (Synthesis Example 24) Synthesis of Resin (R2-XBisN-1)  

A four-necked flask having a 1 L inner volume discharged from the bottom with a Dimroth condenser, a thermometer, and a stirring blade was prepared. In the four-necked flask, 32.6 g (70 mmol, manufactured by Mitsubishi Gas Chemical Co., Ltd.), 4-bibenzaldehyde 50.9 g (280 mmol, Mitsubishi Gas Chemistry) of the compound (XBisN-1) obtained in Synthesis Example 1 was placed under a nitrogen flow. 100 mL of anisole (manufactured by Kanto Chemical Co., Ltd.) and 10 mL of oxalic acid dihydrate (manufactured by Kanto Chemical Co., Ltd.) were reacted at 100 ° C for 7 hours under reflux at 100 ° C. Then, 180.0 g of o-xylene (Special grade of reagent manufactured by Wako Pure Chemical Industries, Ltd.) as a diluent solvent was added to the reaction liquid, and after standing, the aqueous phase of the lower phase was removed. Further, the mixture was neutralized and washed with water, and the solvent of the organic phase and the unreacted 4-benzaldehyde were distilled off under reduced pressure to obtain 34.7 g of a brown solid resin (R2-XBisN-1).

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

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

30 g of the resin (R1-XBisN-1) obtained in Synthesis Example 23 and 29.6 g (214 mmol) of potassium carbonate were placed in 100 mL of dimethylformamide in a 500 mL container equipped with a stirrer, a condenser, and a burette. Among them, 13.12 g (108 mmol) of 2-chloroethyl acetate was added, and the reaction liquid was stirred at 90 ° C for 12 hours to carry out a reaction. Next, the reaction liquid was cooled in an ice bath to precipitate crystals, which were filtered and separated. Then, 40 g of the crystal, 80 g of methanol, 100 g of THF, and a 24% aqueous sodium hydroxide solution were placed in a container having an internal volume of 100 mL of a stirrer, a condenser, and a burette, and the reaction liquid was stirred under reflux for 4 hours to carry out a reaction. Then, the mixture was cooled in an ice bath, and the reaction mixture was concentrated, and the precipitated solid was filtered, and dried to give 26.5 g of a brown solid resin (E-R1-XBisN-1).

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

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

20.0 g of the resin represented by the above formula (R1-XBisN-1), 12.2 g of 2-isocyanatoethyl methacrylate, and triethyl acetate in a 500 mL container equipped with a stirrer, a condenser, and a burette 1.0 g of a base amine and 0.1 g of p-methoxyphenol were placed in 100 mL of methyl isobutyl ketone, and the mixture was heated to 80 ° C, and stirred under stirring for 24 hours to carry out a reaction. The mixture was cooled to 50 ° C, and the reaction liquid was dropped into pure water, and the precipitated solid matter was filtered and dried to obtain 23.6 g of a resin (UaR1-XBisN-1) as a brown solid.

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

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

The reaction of the above formula (E-R1-XBisN-1) obtained in Synthesis Example 23A was carried out in the same manner as in Synthesis Example 23-1 except that the resin represented by the above formula (R1-XBisN-1) obtained in Synthesis Example 23 was used. The resin represented by a brown solid (UaE-R1-XBisN-1) was 25.0 g.

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

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

30 g of the above-mentioned resin (R2-XBisN-1) and 29.6 g (214 mmol) of potassium carbonate were placed in 100 mL of dimethylformamide in a container having an internal volume of 500 mL equipped with a stirrer, a condenser, and a burette, and acetic acid was added thereto. 13.12 g (108 mmol) of 2-chloroethyl ester, and the reaction mixture was stirred at 90 ° C for 12 hours to carry out a reaction. Next, the reaction liquid was cooled in an ice bath to precipitate crystals, which were filtered and separated. Then, 40 g of the crystal, 80 g of methanol, 100 g of THF, and a 24% aqueous sodium hydroxide solution were placed in a container having an internal volume of 100 mL of a stirrer, a condenser, and a burette, and the reaction liquid was stirred under reflux for 4 hours to carry out a reaction. Then, it was cooled in an ice bath, and the reaction liquid was concentrated, and the precipitated solid matter 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 UaR2-XBisN-1  

33.2 g of the compound represented by the above formula (R2-XBisN-1) obtained in Synthesis Example 24 was used, and the same formula (R1-XBisN-1) obtained in Synthesis Example 23 was used, and reacted in the same manner as in Synthesis Example 23-1. 40.1 g of a resin represented by a brown solid (UaR2-XBisN-1).

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

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

The reaction of the above formula (E-R2-XBisN-1) obtained in Synthesis Example 24A was carried out in the same manner as in Synthesis Example 23-1 except that the resin represented by the above formula (R1-XBisN-1) obtained in Synthesis Example 23 was obtained. The resin represented by a brown solid (UaE-R2-XBisN-1) was 29.0 g.

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

 (Synthesis Comparative Example 1)  

A four-necked flask having a 10 L inner volume discharged from the bottom with a Dimroth condenser, a thermometer, and a stirring blade was prepared. In this four-necked flask, 1.09 kg of 1,5-dimethylnaphthalene (7 mol, manufactured by Mitsubishi Gas Chemical Co., Ltd.) and 2.1 kg of a 40% by mass aqueous solution of Formalin (formaldehyde: 28 mol, Mitsubishi Gas Chemistry) were placed under a nitrogen stream. (manufactured by the company) and 0.97 mL of 98% by mass of sulfuric acid (manufactured by Kanto Chemical Co., Ltd.), and reacted under reflux at 100 ° C for 7 hours while refluxing. Then, 1.8 kg of ethylbenzene (a special grade manufactured by Wako Pure Chemical Industries, Ltd.) as a diluent solvent was added to the reaction liquid, and after standing, the aqueous phase of the lower phase was removed. Further, neutralization and washing with water were carried out, and ethylbenzene and unreacted 1,5-dimethylnaphthalene were distilled off under reduced pressure to obtain 1.25 kg of dimethylnaphthalene formaldehyde resin as a pale brown solid. The molecular weight of the obtained dimethylnaphthalene formaldehyde was Mn: 562.

Next, a four-necked flask equipped with a volume of 0.5 L of a Dimroth condenser, a thermometer, and a stirring blade was prepared. Into the four-necked flask, 100 g (0.51 mol) of the dimethylnaphthalene formaldehyde resin and 0.05 g of p-toluenesulfonic acid obtained above were placed under a nitrogen stream, and the mixture was heated to 190 ° C for 2 hours, and then stirred. Then, 52.0 g (0.36 mol) of 1-naphthol was further added, and the temperature was further raised to 220 ° C to carry out a reaction for 2 hours. After the solvent was diluted, it was neutralized and washed with water, and the solvent was removed under reduced pressure to give 126.1 g of a modified 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 solubility test was carried out by using the compound or resin described in the above Synthesis Examples 1-1 to 24-2 and synthesizing CR-1 described in Comparative Example 1. The results are shown in Table 8. Further, each of the lithographic underlayer film forming materials having the composition shown in Table 8 was prepared. Next, these lithography were spin-coated on the ruthenium substrate with the underlayer film forming material, and then baked at 240 ° C for 60 seconds and further baked at 400 ° C for 120 seconds to form an underlayer film having a film thickness of 200 nm. . The following are used for the acid generator, the crosslinking agent, and the organic solvent.

Acid generator: Dibutyl butyl diphenyl sulfonium hexafluoromethane sulfonate (DTDPI) manufactured by Green Chemical Co., Ltd.

Crosslinking agent: Nikalac MX270 (Nikalac) manufactured by Sanwa Chemical Co., Ltd.

Organic solvent: propylene glycol monomethyl ether acetate (PGMEA)

 (Examples 25 to 44)  

Further, each of the underlayer film forming materials for lithography having the composition shown in Table 9 below was prepared. Next, the lithography is spin-coated on the ruthenium substrate with the underlayer film forming material, and then baked at 110 ° C for 60 seconds to remove the solvent of the coating film, and the integrated exposure amount is 600 mJ/by the high pressure mercury lamp. The cm2 was irradiated for 20 seconds to be hardened, and an underlayer film having a film thickness of 200 nm was produced. The following are used for the photoradical polymerization initiator, the crosslinking agent, and the organic solvent.

Radical polymerization initiator: IRGACURE 184 manufactured by BASF

Crosslinker:

(1) Nikalac MX270 (Nikalac) manufactured by Sanwa Chemical Co., Ltd.

(2) Mitsubishi Gas Chemically produces diallyl bisphenol A type cyanate (DABPA-CN)

(3) Dipropylene bisphenol A (BPA-CA) manufactured by Xiaoxi Chemical Industry Co., Ltd.

(4) benzoxazine (BF-BXZ) manufactured by Xiaoxi Chemical Industry

(5) Biphenyl aralkyl type epoxy resin (NC-3000-L) made by Nippon Chemical Co., Ltd.

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

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

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

 [etching resistance]  

Etching tests were performed under the conditions shown below to evaluate the etching resistance. The evaluation results are shown in Table 1 and Tables 8 and 9.

 (etching test conditions)  

Etching device: RIE-10NR manufactured by Samco International

Output: 50W

Pressure: 20Pa

Time: 2min

Etching gas

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

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

First, a novolac underlayer film was produced under the same conditions as in Example 1-1 except that a novolac (PSM 4357 manufactured by Kyoei Chemical Co., Ltd.) was used instead of the compound (UaXBisN-1) used in Example 1-1. Then, the etching test was performed on the underlayer film of the novolac, and the etching rate at this time was measured.

Next, the etching test was performed in the same manner as in the layer films of Example 1-1 and Comparative Example 1, and the etching rate at this time was measured. Then, the etching resistance was evaluated based on the etching rate of the film under the novolac layer using the following evaluation criteria.

 [evaluation benchmark]  

A: The etching rate is less than -10% compared to the film under the novolac

B: The etching rate is -10% to +5% compared to the film under the novolac

C: The etching rate is more than +5% compared to the film under the novolac

 [Examples 45 to 48]  

Next, each solution containing the underlayer film forming material of lithography containing UaXBisN-1, UaE-XBisN-1, UaBisF-1, or UaE-BisF-1 was applied onto a SiO ₂ substrate having a thickness of 300 nm by 240. The film was baked at ° C for 60 seconds and further baked at 400 ° C for 120 seconds to form an underlayer film having a film thickness of 70 nm. The underlayer film was coated with a resist solution for ArF, and baked at 130 ° C for 60 seconds to form a photoresist layer having a film thickness of 140 nm. Further, as the ArF resist solution, a compound in which the following formula (11) is blended is used: 5 parts by mass, triphenylsulfonium nonafluoromethanesulfonate: 1 part by mass, and tributylamine: 2 parts by mass, and PGMEA: 92 parts by mass.

The compound of the formula (11) is 4-methyl-2-methylpropenyloxyadamantane 4.15 g, methacryloxy-γ-butyrolactone 3.00 g, 3-hydroxy-1-adamantyl group 2.08 g of methacrylate and 0.38 g of azobisisobutyronitrile were dissolved in 80 mL of tetrahydrofuran as a reaction solution. The reaction solution was kept at 63 ° C under a nitrogen atmosphere, and after polymerization for 22 hours, the reaction solution was dropped into 400 mL of n-hexane. The resulting resin thus 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" indicate the ratio of each constituent unit, and are not indicative of the block copolymer).

Next, using an electron beam drawing apparatus (ELION-7500, 50 keV), the photoresist layer was exposed, baked at 115 ° C for 90 seconds (PEB), and developed with a 2.38 mass% aqueous solution of tetramethylammonium hydroxide (TMAH). For 60 seconds, a positive resist pattern was obtained.

The shape and defects of the obtained resist pattern of 55nmL/S (1:1) and 80nmL/S (1:1) were observed using an electron microscope (S-4800) manufactured by Hitachi, Ltd. Regarding the shape of the resist pattern after development, no pattern collapsed, and those having good squareness were evaluated as "good", and others were evaluated as "poor". Further, as a result of the above observation, there was no pattern collapse, and the minimum line width with good squareness was used as an evaluation index of "analytical properties". In addition, the minimum electron beam energy of a good pattern shape can be depicted as an evaluation index of "sensitivity". The results are shown in Table 10.

 (Comparative Example 2)  

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

As is clear from Table 10, it was confirmed that the examples of the compounds UaXBisN-1, UaE-XBisN-1, UaBisF-1, and UaE-BisF-1 of the present embodiment were excellent in any of heat resistance, solubility, and etching resistance. Further, in Comparative Example 1 using CR-1 (phenol-modified dimethylnaphthalene formaldehyde resin), the etching resistance was poor.

Further, in Examples 45 to 48, it was confirmed that the shape of the resist pattern after development was good, and no defects were observed. In comparison with Comparative Example 2 in which the underlayer film was formed, it was confirmed that the resolution and the sensitivity were excellent. Further, since the shape of the resist pattern after development was different, in the examples 45 to 48, the underlying film forming material for lithography used was used, and the adhesion to the resist material was excellent.

 <Examples 49 to 52>  

The lithography obtained in Examples 1-1 to 2-2 was applied onto a SiO ₂ substrate having a thickness of 300 nm on a SiO ₂ substrate having a thickness of 300 nm, and baked at 240 ° C for 60 seconds and further baked at 400 ° C. In the second, an underlayer film having a film thickness of 80 nm was formed. The underlayer film was coated with a ruthenium-containing intermediate layer material, and baked at 200 ° C for 60 seconds to form an intermediate layer film having a film thickness of 35 nm. Further, the above-mentioned ArF resist solution was applied onto the interlayer film, and baked at 130 ° C for 60 seconds to form a photoresist layer having a film thickness of 150 nm. Further, as the ruthenium-containing intermediate layer material, a ruthenium atom-containing polymer described in <Synthesis Example 1> of JP-A-2007-226170 is used.

Next, the photoresist layer was subjected to mask exposure using an electron beam drawing apparatus (ELS-7500, ELK-7500, 50 keV), and baked at 230 ° C for 90 seconds (PEB) to 2.38 mass% of tetramethylammonium hydroxide ( The TMAH aqueous solution was developed for 60 seconds to obtain a positive resist pattern of 55 nmL/s (1:1).

Then, using RIE-10NR manufactured by Samco International Co., Ltd., using the obtained resist pattern as a mask, a dry etching process using a ruthenium-containing interlayer film (SOG), followed by sequentially obtaining a ruthenium-containing interlayer film pattern Dry etching of the underlying film is performed for the mask, and dry etching of the SiO ₂ film is performed by using the obtained underlying film pattern as a mask.

The respective etching conditions are as follows.

 Etching conditions for the resist film intermediate film of the resist pattern  

Output: 50W

Pressure: 20Pa

Time: 1min

Etching gas

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

 Etching conditions of the underlayer film of the resist intermediate film pattern  

Output: 50W

Pressure: 20Pa

Time: 2min

Etching gas

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

Etching conditions for SiO ₂ film of resist underlayer film pattern

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 cross-section of the pattern (the shape of the SiO ₂ film after etching) obtained as described above was observed using an electron microscope (S-4800) manufactured by Hitachi, Ltd., it was confirmed that the layer film of the present embodiment was used, and the multilayer resist was used. The etched SiO ₂ film after processing has a rectangular shape and is free from defects and is in a good state.

 [Examples 53 to 56]  

Using the respective compounds synthesized in the above Synthesis Examples, the composition was formed by blending the modulating optical elements shown in Table 11 below. Further, among the components of the optical element forming composition in Table 11, the following were used for the acid generator, the crosslinking agent, the acid diffusion inhibitor, and the solvent.

Acid generator: Dibutyl butyl diphenyl sulfonium hexafluoromethane sulfonate (DTDPI) manufactured by Green Chemical Co., Ltd.

Crosslinking agent: Nikalac MX270 (Nikalac) manufactured by Sanwa Chemical Co., Ltd.

Organic solvent: propylene glycol monomethyl ether acetate (PGMEA)

 [Evaluation of film formation]  

The optical element forming composition in a uniform state was spin-coated on a clean tantalum wafer, and then prebaked (prebake: PB) in an oven at 110 ° C to form an optical element forming film having a thickness of 1 μm. When the composition of the optical element after the preparation is formed and the film is formed to be good, it is evaluated as "A", and when the formed film is defective, it is evaluated as "C".

 [Evaluation of refractive index and transmittance]  

After the uniform optical element forming composition was spin-coated on a clean tantalum wafer, prebaking (PB) was performed in an oven at 110 ° C to form a film having a thickness of 1 μm. For the film, a refractive index (λ = 589.3 nm) at 25 ° C was measured using a multi-incidence angle spectroscopic thickness gauge VASE manufactured by J.A. Woollam Japan Co., Ltd. When the refractive index of the film to be prepared is 1.6 or more, it is evaluated as "A" and 1.55 or more. When it is less than 1.6, it is evaluated as "B", and when it is less than 1.55, it is evaluated as "C". In the case where the transmittance (λ = 632.8 nm) is 90% or more, the evaluation is "A", and when it is less than 90%, the evaluation is "C".

 [Examples 57 to 60]  

Each of the compounds synthesized in the above Synthesis Examples was used to prepare a resist composition as shown in the following Table 12. Further, among the components of the composition of the resist agent in Table 12, the following were used for the radical generator, the radical diffusion inhibitor, and the solvent.

Free radical generator: IRGACURE 184 manufactured by BASF

Free radical diffusion control agent: IRGACURE1010 manufactured by BASF

Organic solvent: propylene glycol monomethyl ether acetate (PGMEA)

 [Evaluation method]    (1) Preservation stability and film formation of resist composition  

The storage stability of the resist composition was determined by preparing a resist composition, and then standing at 23 ° C and 50% RH for 3 days, and visually observing the presence or absence of precipitation. The resist composition after standing for 3 days was a uniform solution, and when it was not precipitated, it was evaluated as A, and when it was precipitated, it was evaluated as C. Further, after the resist composition in a uniform state was spin-coated on a clean tantalum wafer, pre-bake pre-baking (PB) was performed in an oven at 110 ° C to form a resist film having a thickness of 40 nm. When the film was formed to be good, the film composition was evaluated as A, and when the formed film was defective, it was evaluated as C.

 (2) Pattern evaluation of resist pattern  

After the uniform resist composition was spin-coated on a clean tantalum wafer, pre-exposure pre-baking (PB) was performed in an oven at 110 ° C to form a resist film having a thickness of 60 nm. To the obtained resist film, an electron beam set by a line width/pitch of 1:1 at intervals of 50 nm, 40 nm, and 30 nm was irradiated using an electron beam drawing apparatus (ELS-7500, manufactured by ELIONIX Co., Ltd.). After the irradiation, the resist films were each heated at a specific temperature for 90 seconds, and immersed in PGME for 60 seconds for development. Then, the resist film was washed with ultrapure water for 30 seconds and dried to form a negative resist pattern. With respect to the formed resist pattern, the line width/pitch was observed by a scanning electron microscope (S-4800, Hitachi High-Tech Co., Ltd.), and the reactivity was evaluated by electron beam irradiation of the resist composition. The sensitivity is expressed by the minimum energy per unit area necessary for obtaining the pattern, and is evaluated according to the following.

A: A case where a pattern is obtained at a temperature of less than 50 μC/cm ²

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

The pattern formation was observed by SEM (Scanning Electron Microscope), and the following pattern was evaluated.

A: The case where a rectangle pattern can be obtained

B: A situation in which a roughly rectangular pattern can be obtained

C: the case where a non-rectangular pattern can be obtained

As described above, the present invention is not limited to the above-described embodiments and examples, and may be modified as appropriate without departing from the scope of the invention.

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

Further, a wet process can be applied, and a compound for forming a photoresist underlayer film excellent in heat resistance and etching resistance, a resin, and a film for lithography can be obtained. Further, since the film forming composition for lithography uses a compound or a resin having a high heat resistance and a high solvent solubility and having a specific structure, deterioration of the film at the time of high-temperature baking can be suppressed, and oxygen plasma etching or the like is performed. The resist and the underlayer film are also excellent in etching resistance. Further, in the case where the underlayer film is formed, the adhesion to the resist layer is also excellent, so that an excellent resist pattern can be formed.

Further, since the refractive index is high and the coloring is suppressed by the low temperature to high temperature treatment, it can be used as a composition for forming various optical elements.

Therefore, the present invention can be used, for example, in electrical insulating materials, resist resins, semiconductor encapsulating resins, adhesives for printed circuit boards, and electrical equipment. Electronic machine. Electrical laminates and electrical equipment installed in industrial equipment. Electronic machine. Matrix resin for prepreg mounted on industrial equipment, build-up laminate material, resin for fiber reinforced plastic, resin for encapsulation of liquid crystal display panel, paint, various coating agents, adhesives, and semiconductors The coating agent, the resin for a resist for a semiconductor, the resin for forming a lower layer film, a film or a sheet, can also be widely and effectively used for a plastic lens (a lens, a lenticular lens, a microlens, a Fresnel). Lens, viewing angle control lens, contrast lifting lens, etc., retardation film, electromagnetic shielding film, germanium, optical fiber, flexible solder resist for printed wiring, anti-plating agent, interlayer insulating film for multilayer printed circuit board, and photosensitive Optical elements such as optical waveguides.

In particular, the present invention is particularly useful in the field of lithographic resists, underlayer films for lithography, underlayer films for multilayer resists, and optical elements.

The present application is based on the Japanese Patent Application No. Hei. No. Hei. No. Hei.

 Industrial availability  

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

Claims (28)

a compound represented by the following formula (0), (In the formula (0), R ^Y is a hydrogen atom, an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, and R ^Z is an N-valent group or a single bond having 1 to 60 carbon atoms, and each of R ^T 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 a carbon which may have a substituent a hydrogen atom having 1 to 30 alkoxy groups, a halogen atom, a nitro group, an amine group, a carboxylic acid group, a thiol group, a hydroxyl group or a hydroxyl group is substituted with a group represented by the following formula (0-1), and the aforementioned alkyl group, The aryl group, the above alkenyl group, and the alkoxy group may further contain an ether bond, a ketone bond or an ester bond. Here, at least one of R ^T contains a group represented by the following formula (0-1), and X represents an oxygen atom. , sulfur atom or no cross-linking, m is independently an integer from 0 to 9, where at least one of m is an integer from 1 to 9, N is an integer from 1 to 4, and N is an integer of two or more, N The structural formulas in [ ] can be the same or different, r are each an integer of 0~2) (In the formula (0-1), R ^X is a hydrogen atom or a methyl group). The compound of claim 1, wherein the compound represented by the above formula (0) is a compound represented by the following formula (1), (In the formula (1), R ⁰ is synonymous with the above R ^Y , R ¹ is an n-valent group or a single bond having 1 to 60 carbon atoms, and R ² to R ⁵ are each independently a carbon number 1 to 30 which may have a substituent. An alkyl group, an aryl group having 6 to 30 carbon atoms which may have a substituent, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, an alkoxy group having 1 to 30 carbon atoms which may have a substituent, a halogen atom, a hydrogen atom of a nitro group, an amine group, a carboxylic acid group, a thiol group, a hydroxyl group or a hydroxyl group is substituted with a group represented by the above formula (0-1), and the alkyl group, the aforementioned aryl group, the aforementioned alkenyl group, and the aforementioned alkoxy group are also The ether bond, the ketone bond or the ester bond may be contained. Here, at least one of R ² to R ⁵ contains a group represented by the above formula (0-1), and 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} different at 0, and n is synonymous with the above N. Here, when n is an integer of 2 or more, n The structural formulas in [ ] may be the same or different, and p ² to p ⁵ are synonymous with the aforementioned r). The compound of claim 1, wherein the compound represented by the above formula (0) is a compound represented by the following formula (2), (In the formula (2), R ^0A is synonymous with the above R ^Y , R ^1A is a n ^A valent group or a single bond having a carbon number of 1 to 60, and each of R ^{2A is} 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, an alkoxy group having 1 to 30 carbon atoms which may have a substituent, a halogen atom, and a nitro group a hydrogen atom of an amine group, a carboxylic acid group, a thiol group, a hydroxyl group or a hydroxyl group is substituted with a group represented by the above formula (0-1), and the alkyl group, the above aryl group, the aforementioned alkenyl group, and the alkoxy group may also contain Here, at least one of R ^2A contains a group represented by the above formula (0-1), and n ^A is synonymous with the above N, and when n ^A is an integer of 2 or more, n ^A number of [formula] may be within the same or different, X ^A represents an oxygen atom, a sulfur atom or noncrosslinked, m ^2A are each independently an integer of 0 to 7, but at least one of 1 to m ^2A An integer of 7, q ^{A is} independently 0 or 1). The compound of the above formula (1), wherein the compound represented by the above formula (1) is a compound represented by the following formula (1-1), (In the formula (1-1), R ⁰ , R ¹ , R ⁴ , R ⁵ , n, p ² to p ⁵ , m ⁴ and m ⁵ are synonymous with the definitions described in the above formula (1), R ⁶ Each of -R ^{7 is} 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 a halogen atom And a nitro group, an amine group, a carboxylic acid group or a fluorenyl group, and each of R ¹⁰ to R ^{11 is} independently a hydrogen atom or a group represented by the following formula (0-2), wherein at least one of R ¹⁰ to R ¹¹ is a lower one. The formula (0-2) represents a base, and m ⁶ and m ⁷ are each independently an integer of 0 to 7, but m ⁴ , m ⁵ , m ⁶ and m ^{7 are} not 0) (In the formula (0-2), R ^X is synonymous with the definition described in the above formula (0-1), and s is an integer of 0 to 30). The compound of the above formula (1-1), wherein the compound represented by the above formula (1-1) is a compound represented by the following formula (1-2), (In the formula (1-2), R ⁰ , R ¹ , R ⁶ , R ⁷ , R ¹⁰ , R ¹¹ , n, p ² to p ⁵ , m ⁶ and m ⁷ are the same as in the above formula (1-1) The definitions are synonymous, R ⁸ ~ R ⁹ are synonymous with the above R ⁶ ~ R ⁷ , R ¹² ~ R ¹³ are synonymous with the above R ¹⁰ ~ R ¹¹ , and m ⁸ and m ⁹ are each independently an integer of 0-8. However, m ⁶ , m ⁷ , m ⁸ and m ^{9 are} not 0) at the same time. The compound of the above formula (2), wherein the compound represented by the above formula (2) is a compound represented by the following formula (2-1), (In the formula (2-1), R ^0A , R ^1A , n ^A , q ^A and X ^A are synonymous with the definitions described in the above formula (2), and each of R ^{3A is} independently a carbon number which may have a substituent 1 a linear, branched or cyclic alkyl group of ~30, an aryl group having 6 to 30 carbon atoms which may have a substituent, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, a halogen atom, a nitro group, The amine group, the carboxylic acid group, the fluorenyl group, and each of R ^4A are each independently a hydrogen atom or a group represented by the following formula (0-2). Here, at least one of R ^4A is a group represented by the following formula (0-2). , m ^6A are each independently an integer from 0 to 5) (In the formula (0-2), R ^X is synonymous with the definition described in the above formula (0-1), and s is an integer of 0 to 30).  A resin obtained by using the compound of claim 1 as a monomer.   The resin of claim 7, which has the 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 extended aryl group having 6 to 30 carbon atoms which may have a substituent, and a carbon number of 1 to 30 which may have a substituent. An alkyleneoxy group or a single bond, the above alkylene group, the above-mentioned extended aryl group, the aforementioned alkyleneoxy group may also contain 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. And a single bond, 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. An alkenyl group having 2 to 30 carbon atoms, a substituted alkoxy group having 1 to 30 carbon atoms, a halogen atom, a nitro group, an amine group, a carboxylic acid group, a fluorenyl group, a hydroxyl group or a hydroxyl group by the above formula ( The group represented by 0-1), wherein the alkyl group, the aryl group, the alkenyl group, and the alkoxy group may further contain an ether bond, a keto bond or an ester bond, and here, R ² to R ^{5 are} at least 1 Each of the groups represented by the above 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 an integer of 0 to 9, but m ² , m ³ , m ⁴ when m ⁵ and are not simultaneously 0, n and the N lines synonymous herein, n is an integer of 2 or more, n-th Structural formula [] may be within the same or different, p ² ~ p ⁵ is synonymous with the r). The resin of claim 7, which has the structure represented by the following formula (4), (In the formula (4), L is an alkylene group having 1 to 30 carbon atoms which may have a substituent, an extended aryl group having 6 to 30 carbon atoms which may have a substituent, and a carbon number of 1 to 30 which may have a substituent An alkylene group or a single bond, the alkylene group, the above-mentioned extended aryl group, and the aforementioned alkyleneoxy group may also contain 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. ~30 nA ^A valent group or single bond, R ^2A each independently is an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, and a carbon which may have a substituent a hydrogen atom having 2 to 30 alkenyl groups, an alkoxy group having 1 to 30 carbon atoms, a halogen atom, a nitro group, an amine group, a carboxylic acid group, a fluorenyl group, a hydroxyl group or a hydroxyl group which may have a substituent (0- 1) a group substituted by a group, wherein the alkyl group, the aryl group, the alkenyl group, and the alkoxy group may further contain an ether bond, a keto bond or an ester bond, and at least one of R ^2A contains the above formula ( 0-1) represents a group, and n ^A is synonymous with the above N. Here, when n ^A is an integer of 2 or more, the structural formulas in n ^A of [ ] may be the same or different, and X ^A represents an oxygen atom, a sulfur atom or noncrosslinked, m ^2A are each independently an integer of 0 to 7, At least one of m ^2A is an integer of 1 to 6, q ^A are each independently 0 or 1).  A composition comprising one or more selected from the group consisting of a compound according to any one of claims 1 to 6 and a resin according to any one of claims 7 to 9.    The composition of claim 10, which further comprises a solvent.    The composition of claim 10 or 11, which further comprises an acid generator.    The composition of any one of claims 10 to 12, further comprising a crosslinking agent.    The composition of claim 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, a glycoluril compound, and a urea. At least one of a compound, an isocyanate compound, and an azide compound.    The composition of claim 13, wherein the aforementioned crosslinking agent has at least one allyl group.    The composition of claim 13 which is a total of one or more components selected from the group consisting of the compound of any one of claims 1 to 6 and the resin of any one of claims 7 to 9. When the mass is 100 parts by mass, the content of the crosslinking agent is from 0.1 to 100 parts by mass.    The composition of claim 13, which further comprises a crosslinking accelerator.    The composition of claim 17, wherein the crosslinking accelerator is at least one selected from the group consisting of amines, imidazoles, organic phosphines, and Lewis acids.    The composition of claim 17 or 18, which is a composition comprising one or more selected from the group consisting of the compound of any one of claims 1 to 6 and the resin of any one of claims 7 to 9. When the total mass is 100 parts by mass, the content of the crosslinking accelerator is 0.1 to 5 parts by mass.    The composition of any one of claims 10 to 12 further comprising a radical polymerization initiator.    The composition according to any one of claims 10 to 12, wherein the radical polymerization initiator is selected from the group consisting of a ketone photopolymerization initiator, an organic peroxide polymerization initiator, and an azo polymerization initiator. At least one of the groups.    The composition according to any one of claims 10 to 12, which is a group of the resin selected from the group consisting of the compound of any one of claims 1 to 6 and the resin of any one of claims 7 to When the total mass of the above composition is 100 parts by mass, the content of the radical polymerization initiator is 0.05 to 25 parts by mass.    The composition according to any one of claims 10 to 12, which is used for forming a film for lithography.    The composition of any one of claims 10 to 12 for use in forming a permanent film of a resist.    The composition of any one of claims 10 to 12 for forming an optical element.    A method for forming a resist pattern, comprising the steps of: developing a photoresist layer on a substrate using the composition of claim 23, irradiating a specific region of the photoresist layer, and performing development.    A method for forming a resist pattern, comprising the steps of: forming an underlayer film on a substrate using the composition of claim 23, forming at least one photoresist layer on the underlayer film, and performing the photoresist layer on the underlayer film The specific region is irradiated with radiation and subjected to development.    A method for forming a circuit pattern, comprising the steps of: forming a lower layer film on a substrate using the composition of claim 23, and forming a middle layer film on the underlying film using a resist intermediate layer film material, in the middle After at least one layer of the photoresist layer is formed on the layer film, the specific region of the photoresist layer is irradiated with radiation, developed to form a resist pattern, and then the middle portion is etched by using the resist pattern as a mask. The layer film is formed by etching the underlayer film with the obtained interlayer film pattern as an etching mask, etching the substrate with the underlying film pattern as an etching mask, and forming a pattern on the substrate.