JP4292910B2 - Acenaphthylene derivative, polymer and antireflection film-forming composition - Google Patents

Description

  The present invention relates to acetoxymethyl acenaphthylene and hydroxymethyl acenaphthylene, a polymer that can be produced from the acetoxymethyl acenaphthylene or the hydroxymethyl acenaphthylene, and the polymer. The present invention relates to a composition for forming an antireflection film suitable for microfabrication in a lithography process to be used, particularly for manufacturing highly integrated circuit elements.

It is well known that acenaphthylene is polymerized to obtain polyacenaphthylene, and that acenaphthylene is copolymerized with styrene, maleic anhydride or the like to obtain a copolymer.
Since such acenaphthylene-based (co) polymers have a unique structure and are highly reactive, not only chemical modification by reaction with various reactive reagents has been studied, but also various physical properties such as luminescence behavior. Various materials and applications have been developed that are reported in detail, and that focus on characteristics such as low hygroscopicity, low birefringence, and low dielectric constant.
And in terms of developing acenaphthylene-based (co) polymers that are expected to have a variety of reactive properties, it is important to provide acenaphthylene derivatives having various functional groups that are useful as raw materials for production thereof. From the general viewpoint, the acenaphthylene derivative in which the aromatic ring is substituted with, for example, a hydroxyl group, an alkyl group, a halomethyl group, a halogen or the like has already been synthesized.
However, no acenaphthylene derivative in which the aromatic ring is substituted with an acetoxymethyl group or a hydroxymethyl group has been reported so far.

  Further, in the manufacturing method of an integrated circuit element, in order to obtain a higher degree of integration, the processing size in the lithography process is miniaturized. In this lithography process, a resist composition solution is applied onto a substrate, a mask pattern is transferred by a reduction projection exposure apparatus (stepper), and developed with an appropriate developer to obtain a desired pattern. However, high-reflectance substrates such as aluminum, aluminum-silicon alloy, aluminum-silicon-copper alloy, polysilicon, and tungsten silicide used in this process reflect the exposed radiation on the substrate surface. There is a problem that halation occurs and a fine resist pattern cannot be accurately reproduced.

  In order to solve this problem, it has been proposed to provide an antireflection film having a property of absorbing radiation reflected from the substrate surface under a resist film to be formed on the substrate. As such an antireflection film, an inorganic film such as a titanium film, a titanium dioxide film, a titanium nitride film, a chromium oxide film, a carbon film, or an α-silicon film formed by a method such as vacuum deposition, CVD, or sputtering. Although known, these inorganic antireflection films have conductivity, so they cannot be used in the production of integrated circuits, or are specially used for the formation of antireflection films such as vacuum deposition equipment, CVD equipment, and sputtering equipment. There were drawbacks such as the need for a device.

In order to solve the disadvantages of this inorganic antireflection film, an organic antireflection film comprising a polyamic acid (co) polymer or polysulfone (co) polymer and a dye has been proposed (for example, see Patent Document 1). ). This antireflection film has no electrical conductivity, and the composition used for its formation is dissolved in a general solvent. Therefore, a special apparatus as described above is not required, and the solution is the same as in the case of the resist composition solution. Can be easily applied to the substrate.
However, the antireflection film composed of a polyamic acid (co) polymer or polysulfone (co) polymer and a dye cannot sufficiently prevent halation and standing waves because the amount of the dye added is limited, and the resist film (This is called intermixing), and there is a problem in that the resist pattern cross-sectional shape (pattern profile) is deteriorated, such as omission defects and skirting.

On the other hand, when a polymer having an acenaphthylene skeleton is applied to an antireflection film, it is known that the above-described problems can be considerably solved (see, for example, Patent Document 2 and Patent Document 3). Even in the prevention film, the problem of intermixing has not been sufficiently solved.
Therefore, as a method for solving this problem, a method of crosslinking a polymer having an acenaphthylene skeleton with formaldehyde or the like can be considered, but when such a method is used, the storage stability of the antireflection film-forming composition in a solution state is considered. The disadvantage of lowering.
Therefore, it has been desired to develop an improved antireflection film capable of solving various problems in the prior art and a polymer particularly useful as a polymer component of the antireflection film.

JP 59-93448 A JP 2000-143937 A JP 2001-40293 A

  An object of the present invention is to provide an antireflection film-forming composition capable of overcoming the above-mentioned conventional problems, having a high antireflection effect, without causing intermixing, and forming a resist pattern excellent in resolution, pattern shape, etc. In particular, it is an object of the present invention to provide a polymer useful as a component of the antireflection film-forming composition, and an acenaphthylene derivative particularly useful as a raw material or an intermediate of the polymer.

  As a result of intensive studies to solve the above problems, the present inventors have obtained a new acenaphthylene derivative that can be easily synthesized through a process well known as an organic synthesis reaction, starting from readily available acenaphthene, A novel polymer having an aromatic ring introduced with a specific substituent, which is extremely useful as a raw material or intermediate of a polymer that can effectively solve the above-mentioned problems in an antireflection film, and can be produced from the acenaphthylene derivative. It has a high absorbance with respect to an excimer laser, etc., and a high refractive index compared to a conventional antireflection film, and an excellent antireflection film can be obtained by using the polymer in an antireflection film forming composition. As a result, the present invention has been accomplished.

The present invention, first,
It consists of acetoxymethyl acenaphthylene represented by the following formula (1).

The present invention secondly,
It consists of hydroxymethyl acenaphthylene represented by the following formula (2).

Third, the present invention
Weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC) having a structural unit represented by the structural unit represented by the following formula (3) (hereinafter referred to as “structural unit (3)”) is 500. To 10,000 polymers (hereinafter referred to as “polymer (I)”).

〔式（３）において、Ｒ¹ は水素原子、フェニル基、炭素数１〜１０のアルキル基、炭素数２〜１０のアルケニル基または炭素数２〜１０のアシル基を示し、前記フェニル基、アルキル基およびアルケニル基はそれぞれハロゲン原子、ヒドロキシル基、メルカプト基、カルボキシル基、ニトロ基もしくはスルホン酸基の１個以上ないし１種以上で置換されていてもよく（但し、置換されたフェニル基、置換されたアルキル基および置換されたアルケニル基の炭素数は１０以下である。）、Ｒ² およびＲ³ は相互に独立に水素原子、ハロゲン原子、フェニル基、炭素数１〜１０のアルキル基、炭素数２〜１０のアルケニル基または炭素数２〜１０のアシル基を示し、前記フェニル基、アルキル基およびアルケニル基はそれぞれハロゲン原子、ヒドロキシル基、メルカプト基、カルボキシル基、ニトロ基もしくはスルホン酸基の１個以上ないし１種以上で置換されていてもよい（但し、置換されたフェニル基、置換されたアルキル基および置換されたアルケニル基の炭素数は１０以下である。）。〕

[In the formula (3), R ¹ represents a hydrogen atom , a phenyl group, an alkyl group having 1 to 10 carbon atoms , an alkenyl group having 2 to 10 carbon atoms, or an acyl group having 2 to 10 carbon atoms. The group and the alkenyl group may each be substituted with one or more of a halogen atom, a hydroxyl group, a mercapto group, a carboxyl group, a nitro group or a sulfonic acid group (provided that a substituted phenyl group, The alkyl group and the substituted alkenyl group have 10 or less carbon atoms.) , R ² and R ³ are each independently a hydrogen atom, a halogen atom, a phenyl group, an alkyl group having 1 to 10 carbon atoms, or a carbon number. Represents an alkenyl group having 2 to 10 carbon atoms or an acyl group having 2 to 10 carbon atoms, wherein the phenyl group, alkyl group and alkenyl group are each a halogen atom or a hydride; May be substituted with one or more of a roxyl group, a mercapto group, a carboxyl group, a nitro group or a sulfonic acid group (however, a substituted phenyl group, a substituted alkyl group and a substituted alkenyl group) The number of carbon atoms is 10 or less.) ]

The present invention fourthly,
It comprises a polymer (I) and an antireflection film-forming composition characterized by containing a solvent.

The present invention fifthly ,
The structural unit (3) and the following formula (4) structural unit represented by (hereinafter referred to as "structural unit (4)".) (Hereinafter referred to as "polymer (III)".) Polymer having a, and A group of polymers (hereinafter referred to as “polymer (IV)”) having a structural unit (3) and a structural unit represented by the following formula (5) (hereinafter referred to as “structural unit (5)”). And an antireflection film-forming composition characterized by containing a solvent.

〔式（４）において、Ｒ ⁴ は水素原子、フェニル基、炭素数１〜１０のアルキル基、炭素数２〜１０のアルケニル基または炭素数２〜１０のアシル基を示し、前記フェニル基、アルキル基およびアルケニル基はそれぞれハロゲン原子、ヒドロキシル基、メルカプト基、カルボキシル基、ニトロ基もしくはスルホン酸基の１個以上ないし１種以上で置換されていてもよく（但し、置換されたフェニル基、置換されたアルキル基および置換されたアルケニル基の炭素数は１０以下である。）、Ｒ ⁵ は水素原子、ハロゲン原子、フェニル基、炭素数１〜１０のアルキル基、炭素数２〜１０のアルケニル基または炭素数２〜１０のアシル基を示し、前記フェニル基、アルキル基およびアルケニル基はそれぞれハロゲン原子、ヒドロキシル基、メルカプト基、カルボキシル基、ニトロ基もしくはスルホン酸基の１個以上ないし１種以上で置換されていてもよく（但し、置換されたフェニル基、置換されたアルキル基および置換されたアルケニル基の炭素数は１０以下である。）、ｎは０または１である。〕

〔式（５）において、Ｒ⁶ およびＲ⁷ は相互に独立に水素原子、ハロゲン原子、フェニル基、炭素数１〜１０のアルキル基、炭素数２〜１０のアルケニル基または炭素数２〜１０のアシル基を示し、前記フェニル基、アルキル基およびアルケニル基はそれぞれハロゲン原子、ヒドロキシル基、メルカプト基、カルボキシル基、ニトロ基もしくはスルホン酸基の１個以上ないし１種以上で置換されていてもよい（但し、置換されたフェニル基、置換されたアルキル基および置換されたアルケニル基の炭素数は１０以下である。）。〕

[In the formula (4), R ⁴ represents a hydrogen atom, a phenyl group, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an acyl group having 2 to 10 carbon atoms. The group and the alkenyl group may each be substituted with one or more of a halogen atom, a hydroxyl group, a mercapto group, a carboxyl group, a nitro group or a sulfonic acid group (provided that a substituted phenyl group, R ⁵ is a hydrogen atom, a halogen atom, a phenyl group, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or An acyl group having 2 to 10 carbon atoms, wherein the phenyl group, alkyl group and alkenyl group are a halogen atom, a hydroxyl group and a mercapto group, respectively; Group, carboxyl group, nitro group or sulfonic acid group may be substituted with one or more kinds (provided that the number of carbon atoms of the substituted phenyl group, the substituted alkyl group and the substituted alkenyl group is N is 0 or 1. ]

[In Formula (5), R < ⁶ > and R < ⁷ > are mutually independently a hydrogen atom, a halogen atom, a phenyl group, a C1-C10 alkyl group, a C2-C10 alkenyl group, or C2-C10. Represents an acyl group, and each of the phenyl group, alkyl group and alkenyl group may be substituted with one or more of halogen atom, hydroxyl group, mercapto group, carboxyl group, nitro group or sulfonic acid group ( However, the carbon number of the substituted phenyl group, the substituted alkyl group, and the substituted alkenyl group is 10 or less.) ]

Hereinafter, the present invention will be described in detail.
Acetoxymethyl acenaphthylene and hydroxymethyl acenaphthylene The acetoxymethyl group in the formula (1) and the hydroxylmethyl group in the formula (2) are bonded to any of the 3 to 5 positions of acenaphthylene, respectively.
The acetoxymethyl acenaphthylene represented by the formula (1) (hereinafter referred to as “acetoxymethyl acenaphthylene (1)”) can be synthesized, for example, by the following first to fourth steps. The hydroxymethyl acenaphthylene represented by (2) (hereinafter referred to as “hydroxymethyl acenaphthylene (2)”) can be synthesized, for example, by the following fifth step.

First step: As shown in the following formula (i), acenaphthene is formylated by a conventional method.

Second step: As shown in the following formula (ii), the formyl group of formylacenaphthene obtained in the first step is reduced by a conventional method to obtain hydroxymethylacenaphthene.

Third step: As shown in the following formula (iii), the hydroxyl group of hydroxymethylacenaphthene obtained in the second step is acetylated by a conventional method to obtain acetoxymethylacenaphthene.

Fourth step: As shown in the following formula (iv), the acetoxymethylacenaphthene obtained in the third step is dehydrogenated by a conventional method to obtain acetoxymethylacenaphthylene (1).

Fifth step: As shown in the following formula (v), the acetoxy group of the acetoxymethylacenaphthylene obtained in the fourth step is hydrolyzed by a conventional method to obtain hydroxymethylacenaphthylene (2).

  The acetoxymethyl acenaphthylene (1) can be used very suitably as a raw material or intermediate for producing the polymer (I), and is also used as a raw material or intermediate for producing the polymer (III) and the polymer (IV). In addition to being useful as a raw material, it can be very suitably used as a raw material for synthesizing hydroxymethylacenaphthylene (2), and is also useful as a raw material or an intermediate for synthesizing other related acenaphthylene derivatives.

  Hydroxymethylacenaphthylene (2) can be used very suitably as a raw material or intermediate for producing the polymer (I), and is also a raw material or intermediate for producing the polymer (III) and the polymer (IV). In addition to being useful as a raw material, it can be used very suitably as a raw material for synthesizing acetoxymethylacenaphthylene (1), and also useful as a raw material or intermediate for synthesizing other related acenaphthylene derivatives.

Polymer (I)
In the structural unit (3), the alkyl group having 1 to 10 carbon atoms of R ¹ is preferably a linear or branched alkyl group having 1 to 6 carbon atoms, and more preferably a methyl group, an ethyl group, n -Propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group and the like.
As the alkenyl group having a carbon number 2 to 10 R ^1, preferably a linear or branched alkenyl group having 2 to 6 carbon atoms, more preferably, a vinyl group, an allyl group, methallyl group, 1-butenyl Group, 2-butenyl group and the like.
In addition, the acyl group having 2 to 10 carbon atoms of R ¹ is preferably an aliphatic or aromatic acyl group having 2 to 6 carbon atoms, and more preferably an acetyl group, a propionyl group, a butyryl group, a benzoyl group, or the like. is there.

In the structural unit (3), examples of the halogen atom for R ² and R ³ include a fluorine atom, a chlorine atom, and a bromine atom.
In addition, examples of the alkyl group having 1 to 10 carbon atoms, the alkenyl group having 2 to 10 carbon atoms, and the acyl group having 2 to 10 carbon atoms of R ² and R ³ include, for example, alkyl having 1 to 10 carbon atoms of R ¹ The same groups as those exemplified for the group, the alkenyl group having 2 to 10 carbon atoms and the acyl group having 2 to 10 carbon atoms can be mentioned. Examples of the substituent for the phenyl group, the alkyl group and the alkenyl group include the R ¹ phenyl group, Ru can be the same as the groups exemplified for a substituent for the alkyl and alkenyl groups.

In the structural unit (3), R ¹ is particularly preferably a hydrogen atom, a methyl group, an acetyl group, or the like.
R ² and R ³ are each preferably a hydrogen atom, a methyl group, a phenyl group, or the like.

Polymer (I) is, for example, bulk polymerization, solution polymerization of acenaphthylenes corresponding to structural unit (3), optionally together with other copolymerizable unsaturated compounds, by radical polymerization, anionic polymerization, cationic polymerization, etc. It can manufacture by superposing | polymerizing with appropriate polymerization forms, such as.
In addition, the polymer (I) having the structural unit (3) in which R ¹ is a hydrogen atom is obtained by subjecting the acetoxy group of the polymer (I) having the structural unit (3) in which R ¹ is an acetyl group to a hydrolyzing by a conventional method. The polymer (I) having a structural unit (3) in which R ¹ is an acetyl group can also be produced by decomposing the polymer (I) having a structural unit (3) in which R ¹ is a hydrogen atom. ) Can be also produced by acetylation by a conventional method.

As acenaphthylenes corresponding to the structural unit (3), for example,
3-hydroxymethyl acenaphthylene, 4-hydroxymethyl acenaphthylene, 5-hydroxymethyl acenaphthylene,
1-methyl-3-hydroxymethylacenaphthylene, 1-methyl-4-hydroxymethylacenaphthylene, 1-methyl-5-hydroxymethylacenaphthylene, 1-methyl-6-hydroxymethylacenaphthylene, 1- Methyl-7-hydroxymethylacenaphthylene, 1-methyl-8-hydroxymethylacenaphthylene, 1,2-dimethyl-3-hydroxymethylacenaphthylene, 1,2-dimethyl-4-hydroxymethylacenaphthylene, 1,2-dimethyl-5-hydroxymethylacenaphthylene, 1-phenyl-3-hydroxymethylacenaphthylene, 1-phenyl-4-hydroxymethylacenaphthylene, 1-phenyl-5-hydroxymethylacenaphthylene, 1-phenyl-6-hydroxymethylacenaphthylene, 1-phenyl-7 Hydroxymethyl acenaphthylene, 1-phenyl-8-hydroxymethyl acenaphthylene, 1,2-diphenyl-3-hydroxymethyl acenaphthylene, 1,2-diphenyl-4-hydroxymethyl acenaphthylene, 1,2- Hydroxymethylacenaphthylenes such as diphenyl-5-hydroxymethylacenaphthylene;

3-acetoxymethyl acenaphthylene, 4-acetoxymethyl acenaphthylene, 5-acetoxymethyl acenaphthylene,
1-methyl-3-acetoxymethyl acenaphthylene, 1-methyl-4-acetoxymethyl acenaphthylene, 1-methyl-5-acetoxymethyl acenaphthylene, 1-methyl-6-acetoxymethyl acenaphthylene, 1- Methyl-7-acetoxymethyl acenaphthylene, 1-methyl-8-acetoxymethyl acenaphthylene, 1,2-dimethyl-3-acetoxymethyl acenaphthylene, 1,2-dimethyl-4-acetoxymethyl acenaphthylene, 1,2-dimethyl-5-acetoxymethyl acenaphthylene, 1-phenyl-3-acetoxymethyl acenaphthylene, 1-phenyl-4-acetoxymethyl acenaphthylene, 1-phenyl-5-acetoxymethyl acenaphthylene, 1-phenyl-6-acetoxymethyl acenaphthylene, 1-phenyl-7 Acetoxymethyl acenaphthylene, 1-phenyl-8-acetoxymethyl acenaphthylene, 1,2-diphenyl-3-acetoxymethyl acenaphthylene, 1,2-diphenyl-4-acetoxymethyl acenaphthylene, 1,2- Acetoxymethyl acenaphthylenes such as diphenyl-5-acetoxymethyl acenaphthylene;

3-methoxymethyl acenaphthylene, 4-methoxymethyl acenaphthylene, 5-methoxymethyl acenaphthylene,
1-methyl-3-methoxymethyl acenaphthylene, 1-methyl-4-methoxymethyl acenaphthylene, 1-methyl-5-methoxymethyl acenaphthylene, 1-methyl-6-methoxymethyl acenaphthylene, 1- Methyl-7-methoxymethylacenaphthylene, 1-methyl-8-methoxymethylacenaphthylene, 1,2-dimethyl-3-methoxymethylacenaphthylene, 1,2-dimethyl-4-methoxymethylacenaphthylene, 1,2-dimethyl-5-methoxymethylacenaphthylene, 1-phenyl-3-methoxymethylacenaphthylene, 1-phenyl-4-methoxymethylacenaphthylene, 1-phenyl-5-methoxymethylacenaphthylene, 1-phenyl-6-methoxymethyl acenaphthylene, 1-phenyl-7-methoxymethyl acenaphthylene 1-phenyl-8-methoxymethylacenaphthylene, 1,2-diphenyl-3-methoxymethylacenaphthylene, 1,2-diphenyl-4-methoxymethylacenaphthylene, 1,2-diphenyl-5 Methoxymethyl acenaphthylenes such as methoxymethyl acenaphthylene,

3-phenoxymethyl acenaphthylene, 4-phenoxymethyl acenaphthylene, 5-phenoxymethyl acenaphthylene, 3-vinyloxymethyl acenaphthylene, 4-vinyloxymethyl acenaphthylene, 5-vinyloxymethyl acenaphthylene Etc.

Among these acenaphthylenes, in particular, 3-hydroxymethyl acenaphthylene, 4-hydroxymethyl acenaphthylene, 5-hydroxymethyl acenaphthylene, 3-acetoxymethyl acenaphthylene, 4-acetoxymethyl acenaphthylene, 5 -Acetoxymethyl acenaphthylene, 3-methoxymethyl acenaphthylene, 4-methoxymethyl acenaphthylene, 5-methoxymethyl acenaphthylene and the like are preferable.
The acenaphthylenes can be used alone or in admixture of two or more.

Moreover, as another copolymerizable unsaturated compound in polymer (I), the aromatic vinyl compound corresponding to the structural unit (4) mentioned later and the acenaphthylene corresponding to the structural unit (5) mentioned later are preferable.
Further, as other copolymerizable unsaturated compounds, for example,
Other aromatic vinyl compounds such as styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 1-vinylnaphthalene, 2-vinylnaphthalene, 9-vinylanthracene, 9-vinylcarbazole ;
Vinyl ester compounds such as vinyl acetate, vinyl propionate and vinyl caproate;
Vinyl cyanide compounds such as (meth) acrylonitrile, α-chloroacrylonitrile, vinylidene cyanide;
Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) Unsaturated carboxylic acid ester compounds such as acrylate and glycidyl (meth) acrylate;

Unsaturated group-containing unsaturated carboxylic acid ester-based compounds such as ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, vinyl (meth) acrylate, dimethyl vinyl (meth) acryloyloxymethylsilane;
Halogen-containing vinyl compounds such as 2-chloroethyl vinyl ether, vinyl chloroacetate, and allyl chloroacetate;
Hydroxyl group-containing vinyl compounds such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and (meth) allyl alcohol;
Amide group-containing vinyl compounds such as (meth) acrylamide and crotonic amide; succinic acid mono [2- (meth) acryloyloxyethyl], maleic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2 -(Meth) acryloyloxyethyl] and other carboxyl group-containing vinyl compounds.
The said other copolymerizable unsaturated compound can be used individually or in mixture of 2 or more types.

The content of structural units derived from other copolymerizable unsaturated compounds in the polymer (I) is preferably 80 mol% or less, more preferably 60 mol% or less, particularly preferably 40, based on all structural units. It is below mol%.
The weight average molecular weight in terms of polystyrene (hereinafter referred to as “Mw”) measured by gel permeation chromatography of the polymer (I) is 500 to 10,000, preferably 1,000 to 5,000.

  The polymer (I) has a property of causing a cross-linking reaction between molecular chains by heating or exposure, and is particularly useful for an antireflection film-forming composition to be described later, alone or in other curability. It can be mixed with resin and curable rubber and used for paints, adhesives, insulating materials, molded products and the like.

Antireflective film-forming composition The antireflective film-forming composition of the present invention contains (a) a polymer (I) and a solvent, or (c) a polymer (III) and a polymer (IV). It contains at least one selected as well as a solvent.
Hereinafter, the polymers (II) to ( IV ) and the solvent, which are constituent components of each antireflection film-forming composition, will be described in order.

-Polymers (III) to ( IV )-
The structural unit (3) in the polymer (III) and the polymer (IV) is the same as the structural unit (3) in the polymer (I).
In the structural unit (4) , examples of the alkyl group having 1 to 10 carbon atoms, the alkenyl group having 2 to 10 carbon atoms, and the acyl group having 2 to 10 carbon atoms in R ⁴ include, for example, the structural unit (3).
Alkyl group having 1 to 10 carbon atoms of R ^1, can be the same as the groups exemplified for an alkenyl group and an acyl group having 2 to 10 carbon atoms from 2 to 10 carbon atoms, a phenyl group R ^4, an alkyl As the substituent for the group and the alkenyl group, the same groups as those exemplified for the substituent for the phenyl group, alkyl group and alkenyl group of R ¹ in the structural unit (3) can be mentioned , and the halogen atom of R ⁵ , An alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and an acyl group having 2 to 10 carbon atoms, for example, a halogen atom and a carbon number of R ² and R ³ in the structural unit (3) , respectively. The same thing as illustrated about the alkyl group of 1-10, a C2-C10 alkenyl group, and a C2-C10 acyl group can be mentioned, ⁵ of the phenyl group, the substituents for alkyl and alkenyl group include the same groups as those exemplified for the substituent for the phenyl group, an alkyl group and the alkenyl group R ¹ in the structural unit (3).
In the structural unit (4), R ⁴ is particularly preferably a hydrogen atom, a methyl group or the like.
R ⁵ is particularly preferably a hydrogen atom, a methyl group or the like.

In the structural unit (5), examples of the halogen atom of R ⁶ and R ⁷ , a phenyl group, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and an acyl group having 2 to 10 carbon atoms include Examples of the halogen atom, phenyl group, alkyl group having 1 to 10 carbon atoms, alkenyl group having 2 to 10 carbon atoms, and acyl group having 2 to 10 carbon atoms for R ² and R ³ in the structural unit (3) can include the same ones, the phenyl group of R ⁶ and R ^7, examples of the substituent for the alkyl group and alkenyl group, a phenyl group of R ¹ in the structural unit (3), the substituents for alkyl and alkenyl groups Ru can be the same as the group exemplified.

In the structural unit (5), each of R ⁶ and R ⁷ is particularly preferably a hydrogen atom, a methyl group, or the like.

Polymer (III) polymerizes acenaphthylenes corresponding to structural unit (3) and an aromatic vinyl compound corresponding to structural unit (4), optionally together with other copolymerizable unsaturated compounds. The polymer (IV) can be prepared from acenaphthylenes corresponding to the structural unit (3) and acenaphthylenes corresponding to the structural unit (5), optionally together with other copolymerizable unsaturated compounds. It can be produced by polymerization.
Each polymerization for producing the polymers (III) to ( IV ) can be carried out in an appropriate polymerization form such as bulk polymerization, solution polymerization or the like, for example, by radical polymerization, anionic polymerization, cationic polymerization or the like.

Also, heavy the polymer structural units R ¹ is a hydrogen atom (3) or R ⁴ has the structural unit (4) is a hydrogen atom (III) and R ¹ having the structural unit (3) is a hydrogen atom The compound ( IV ) can also be produced by hydrolyzing the acetoxymethyl group in the polymers (III) to ( IV ) each having an acetoxymethyl group by a conventional method, and R ¹ is an acetyl group. the structural unit (3) or R ⁴ is a polymer having a polymer having the structural unit (4) is an acetyl group (III) and the structural unit R ¹ is an acetyl group (3) (IV) are each hydroxymethyl It can also be produced by acetylating each hydroxyl group in the polymers (III) to ( IV ) having a group by a conventional method.

In the polymers (III) and (IV), examples of the acenaphthylenes corresponding to the structural unit (3) are the same as the compounds exemplified for the acenaphthylenes corresponding to the structural unit (3) in the polymer (I). Can be mentioned. Among these acenaphthylenes, in particular, 3-hydroxymethyl acenaphthylene, 4-hydroxymethyl acenaphthylene, 5-hydroxymethyl acenaphthylene, 3-methoxymethyl acenaphthylene, 4-methoxymethyl acenaphthylene, 5 -Methoxymethylacenaphthylene and the like are preferable.
The acenaphthylenes can be used alone or in admixture of two or more.

In the polymer (III), preferable aromatic vinyl compounds corresponding to the structural unit (4) include, for example, 2-hydroxymethylstyrene, 3-hydroxymethylstyrene, 4-hydroxymethylstyrene, 2-hydroxymethyl. -Hydroxymethylstyrene compounds such as α-methylstyrene, 3-hydroxymethyl-α-methylstyrene, 4-hydroxymethyl-α-methylstyrene;
Methoxy such as 2-methoxymethylstyrene, 3-methoxymethylstyrene, 4-methoxymethylstyrene, 2-methoxymethyl-α-methylstyrene, 3-methoxymethyl-α-methylstyrene, 4-methoxymethyl-α-methylstyrene Methylstyrene compounds;
4-phenoxymethylstyrene, 4-phenoxymethyl-α-methylstyrene, 4-vinyloxymethylstyrene, 4-vinyloxymethyl-α-methylstyrene, 4-acetoxymethylstyrene, 4-acetoxymethyl-α-methylstyrene, etc. Other styrenic compounds;
4-hydroxymethyl-1-vinylnaphthalene, 7-hydroxymethyl-1-vinylnaphthalene, 8-hydroxymethyl-1-vinylnaphthalene, 4-hydroxymethyl-1-isopropenylnaphthalene, 7-hydroxymethyl-1-isopropenyl Naphthalene, 8-hydroxymethyl-1-isopropenylnaphthalene, 1-hydroxymethyl-2-vinylnaphthalene, 1-hydroxymethyl-3-vinylnaphthalene, 1-hydroxymethyl-4-vinylnaphthalene, 1-hydroxymethyl-5 Vinylnaphthalene, 1-hydroxymethyl-6-vinylnaphthalene, 1-hydroxymethyl-7-vinylnaphthalene, 1-hydroxymethyl-8-vinylnaphthalene, 2-hydroxymethyl-3-vinylnaphthalene, 2-hydroxymethyl-4- Sulfonyl naphthalene, 2-hydroxymethyl-5-vinylnaphthalene, 2-hydroxymethyl-6-vinylnaphthalene, 2-hydroxymethyl-7-vinylnaphthalene hydroxymethyl - vinylnaphthalene compounds;
4-methoxymethyl-1-vinylnaphthalene, 7-methoxymethyl-1-vinylnaphthalene, 8-methoxymethyl-1-vinylnaphthalene, 4-methoxymethyl-1-isopropenylnaphthalene, 7-methoxymethyl-1-isopropenyl Methoxymethyl-1-vinylnaphthalene compounds such as naphthalene and 8-methoxymethyl-1-isopropenylnaphthalene;
4-phenoxymethyl-1-vinylnaphthalene, 4-vinyloxymethyl-1-vinylnaphthalene, 4-acetoxymethyl-1-vinylnaphthalene, 4-phenoxymethyl-1-isopropenylnaphthalene, 4-vinyloxymethyl-1- Other vinylnaphthalene compounds such as isopropenylnaphthalene and 4-acetoxymethyl-1-isopropenylnaphthalene
Can be mentioned.
Of these aromatic vinyl compounds, 4-hydroxymethylstyrene, 4-methoxymethylstyrene and the like are particularly preferable.
The said aromatic vinyl type compound can be used individually or in mixture of 2 or more types.

In the polymer (IV), preferable acenaphthylenes corresponding to the structural unit (5) include, for example, acenaphthylene, 1-methylacenaphthylene, 1,2-dimethylacenaphthylene, 1-phenylacenaphthylene, Examples include 1,2-diphenylacenaphthylene and 1-methyl-2-phenylacenaphthylene.
Of these acenaphthylenes, acenaphthylene is particularly preferable.
The acenaphthylenes can be used alone or in admixture of two or more.
Examples of the other copolymerizable unsaturated compounds in the polymers (III) to ( IV ) include those similar to the other copolymerizable unsaturated compounds in the polymer (I), respectively. it can.
These other copolymerizable unsaturated compounds can be used alone or in admixture of two or more.

  In the polymer (III), the content of the structural unit (3) is preferably from 5 to 80 mol%, more preferably from 10 to 60 mol%, particularly preferably from 10 to 40 mol%, based on all structural units. And the content of the structural unit (4) is preferably from 5 to 80 mol%, more preferably from 5 to 60 mol%, particularly preferably from 5 to 40 mol%, based on the total structural units. The content of the structural unit derived from the polymerizable unsaturated compound is preferably 50 mol% or less, more preferably 30 mol% or less, based on all the structural units.

  In the polymer (IV), the content of the structural unit (3) is preferably from 5 to 80 mol%, more preferably from 10 to 60 mol%, particularly preferably from 10 to 40 mol%, based on all structural units. The content of the structural unit (5) is preferably 5 to 95 mol%, more preferably 10 to 90 mol%, particularly preferably 20 to 90 mol%, based on the total structural units. The content of the structural unit derived from the polymerizable unsaturated compound is preferably 50 mol% or less, more preferably 30 mol% or less, based on all the structural units.

The Mw of the polymer (III) and the polymer (IV) is appropriately selected according to the desired properties of the antireflection film, but is usually 500 to 10,000, preferably 500 to 5,000.

-Solvent-
The solvent used in each antireflective film forming composition of the present invention is not particularly limited as long as it can dissolve the respective polymers and additive components described below.
Ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether;
Ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, ethylene glycol mono-n-butyl ether acetate;
Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol di-n-propyl ether, diethylene glycol di-n-butyl ether;
Triethylene glycol dialkyl ethers such as triethylene glycol dimethyl ether and triethylene glycol diethyl ether;

Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether;
Propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol di-n-propyl ether, propylene glycol di-n-butyl ether;
Propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoether ether acetate, propylene glycol mono-n-propyl ether acetate, propylene glycol mono-n-butyl ether acetate;

Lactic acid esters such as methyl lactate, ethyl lactate, n-propyl lactate, i-propyl lactate, n-butyl lactate, i-butyl lactate;
Methyl formate, ethyl formate, n-propyl formate, i-propyl formate, n-butyl formate, i-butyl formate, n-amyl formate, i-amyl formate, methyl acetate, ethyl acetate, n-propyl acetate, i-acetate Propyl, n-butyl acetate, i-butyl acetate, n-amyl acetate, i-amyl acetate, n-hexyl acetate, methyl propionate, ethyl propionate, n-propyl propionate, i-propyl propionate, n propionate -Aliphatic carboxylic acid esters such as butyl, i-butyl propionate, methyl butyrate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, i-butyl butyrate;

Ethyl hydroxyacetate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutyrate, ethyl methoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate , Ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-methoxypropyl acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, 3 -Other esters such as methyl-3-methoxybutyl butyrate, methyl acetoacetate, methyl pyruvate, ethyl pyruvate;
Aromatic hydrocarbons such as toluene and xylene;
Ketones such as methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, 2-heptanone, 3-heptanone, 4-heptanone, cyclohexanone;
Amides such as N-methylformamide, N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone;
Lactones such as γ-butyrolactone are appropriately selected and used.

Among these solvents, ethylene glycol monoethyl ether acetate, ethyl lactate, n-butyl acetate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone and the like are preferable.
The said solvent can be used individually or in mixture of 2 or more types.

  The amount of the solvent used is such that the solid content concentration of the resulting composition is usually 0.01 to 70% by weight, preferably 0.05 to 60% by weight, more preferably 0.1 to 50% by weight. is there.

-Additives-
In the antireflection film-forming composition of the present invention, various kinds of agents such as an acid generator, a cross-linking agent, a binder resin, a radiation absorber, and a surfactant are used as necessary as long as the intended effect in the present invention is not impaired. An additive can be blended, and it is particularly preferable to blend an acid generator and / or a crosslinking agent.

The acid generator is a component that generates an acid upon exposure or heating.
Examples of the acid generator that generates an acid upon exposure (hereinafter referred to as “photo acid generator”) include:
Diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium pyrenesulfonate, diphenyliodonium n-dodecylbenzenesulfonate, diphenyliodonium 10-camphorsulfonate, diphenyliodonium naphthalenesulfonate, diphenyliodonium hexafluoroantimonate,
Bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium nonafluoro-n-butanesulfonate, bis (4-t-butylphenyl) iodonium n-dodecylbenzenesulfonate, bis ( 4-t-butylphenyl) iodonium 10-camphorsulfonate, bis (4-t-butylphenyl) iodonium naphthalenesulfonate, bis (4-t-butylphenyl) iodonium hexafluoroantimonate,
Triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium n-dodecylbenzenesulfonate, triphenylsulfonium naphthalenesulfonate, triphenylsulfonium 10-camphorsulfonate, triphenylsulfonium hexafluoroantimonate,
4-hydroxyphenyl phenyl methylsulfonium p-toluenesulfonate, 4-hydroxyphenyl benzyl methylsulfonium p-toluenesulfonate,

Cyclohexyl methyl 2-oxocyclohexylsulfonium trifluoromethanesulfonate, 2-oxocyclohexyldicyclohexylsulfonium trifluoromethanesulfonate, 2-oxocyclohexyldimethylsulfonium trifluoromethanesulfonate,
1-naphthyldimethylsulfonium trifluoromethanesulfonate, 1-naphthyldiethylsulfonium trifluoromethanesulfonate, 4-cyano-1-naphthyldimethylsulfonium trifluoromethanesulfonate, 4-cyano-1-naphthyldiethylsulfonium trifluoromethanesulfonate, 4-nitro-1- Naphthyldimethylsulfonium trifluoromethanesulfonate, 4-nitro-1-naphthyldiethylsulfonium trifluoromethanesulfonate, 4-methyl-1-naphthyldimethylsulfonium trifluoromethanesulfonate, 4-methyl-1-naphthyldiethylsulfonium trifluoromethanesulfonate, 4-hydroxy- 1-naphthyldimethylsulfonium trifluoromethanesulfonate, 4 Hydroxy-1-naphthyl diethyl sulfonium trifluoromethane sulfonate,

1- (4-hydroxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-methoxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-ethoxynaphthalene-1- Yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-methoxymethoxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-ethoxymethoxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethane Sulfonate,
1- [4- (1-methoxyethoxy) naphthalen-1-yl] tetrahydrothiophenium trifluoromethanesulfonate, 1- [4- (2-methoxyethoxy) naphthalen-1-yl] tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-methoxycarbonyloxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-ethoxycarbonyloxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-n -Propoxycarbonyloxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate,

1- (4-i-propoxycarbonyloxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-n-butoxycarbonyloxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1 -(4-t-butoxycarbonyloxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- [4- (2-tetrahydrofuranyloxy) naphthalen-1-yl] tetrahydrothiophenium trifluoromethanesulfonate, 1 -[4- (2-tetrahydropyranyloxy) naphthalen-1-yl] tetrahydrothiophenium trifluoromethanesulfonate,
Onium salt photoacid generators such as 1- (4-benzyloxy) tetrahydrothiophenium trifluoromethanesulfonate, 1- (naphthylacetomethyl) tetrahydrothiophenium trifluoromethanesulfonate;

Halogen-containing compound-based photoacid generators such as phenylbis (trichloromethyl) -s-triazine, 4-methoxyphenylbis (trichloromethyl) -s-triazine, 1-naphthylbis (trichloromethyl) -s-triazine;
1,2-naphthoquinonediazide-4-sulfonyl chloride, 1,2-naphthoquinonediazide-5-sulfonyl chloride, 1,2, naphthoquinonediazide-4-sulfonic acid ester of 2,3,4,4′-tetrahydroxybenzophenone or Diazoketone compound-based photoacid generators such as 1,2-naphthoquinonediazide-5-sulfonic acid ester;
Sulfone compound photoacid generators such as 4-trisphenacylsulfone, mesitylphenacylsulfone, bis (phenylsulfonyl) methane;
Benzoin tosylate, pyrogallol tris (trifluoromethanesulfonate), nitrobenzyl-9,10-diethoxyanthracene-2-sulfonate, trifluoromethanesulfonylbicyclo [2,2,1] hept-5-ene-2,3-di Examples thereof include sulfonic acid compound photoacid generators such as carbodiimide, N-hydroxysuccinimide trifluoromethanesulfonate, and 1,8-naphthalenedicarboxylic acid imide trifluoromethanesulfonate.

Among these photoacid generators, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium pyrenesulfonate, diphenyliodonium n-dodecylbenzenesulfonate, diphenyliodonium 10-camphorsulfonate, diphenyliodonium naphthalenesulfonate, Bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium nonafluoro-n-butanesulfonate, bis (4-t-butylphenyl) iodonium n-dodecylbenzenesulfonate, bis ( 4-t-butylphenyl) iodonium 10-camphorsulfonate, bis (4-t-butylphenyl) Etc. iodonium naphthalene sulfonate is preferred.
The photoacid generators can be used alone or in admixture of two or more.

Examples of the acid generator that generates an acid by heating (hereinafter referred to as “thermal acid generator”) include 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl, and the like. Tosylate, alkyl sulfonates and the like can be mentioned.
These thermal acid generators can be used alone or in admixture of two or more.
Moreover, a photo-acid generator and a thermal acid generator can also be used together as an acid generator.

  The compounding amount of the acid generator is usually 5,000 parts by weight or less, preferably 0.1 to 1,000 parts by weight, more preferably 0.1 to 100 parts by weight per 100 parts by weight of the solid content of the antireflection film-forming composition. 100 parts by weight. The antireflective film-forming composition of the present invention contains a photoacid generator and / or a thermal acid generator, thereby effectively causing a crosslinking reaction between the molecular chains of each polymer at a relatively low temperature including normal temperature. It becomes possible.

The cross-linking agent is a component having an action of preventing intermixing between the obtained antireflection film and the resist film formed thereon, and further preventing cracking of the antireflection film.
As such a crosslinking agent, polynuclear phenols and various commercially available curing agents can be used.
Examples of the polynuclear phenols include binuclear phenols such as 4,4′-biphenyldiol, 4,4′-methylene bisphenol, 4,4′-ethylidene bisphenol, and bisphenol A; 4,4 ′, 4 ″. -Trinuclear phenols such as methylidenetrisphenol, 4,4 '-[1- {4- (1- [4-hydroxyphenyl] -1-methylethyl) phenyl} ethylidene] bisphenol; polyphenols such as novolak Can be mentioned.
Of these polynuclear phenols, 4,4 ′-[1- {4- (1- [4-hydroxyphenyl] -1-methylethyl) phenyl} ethylidene] bisphenol, novolac and the like are preferable.
The polynuclear phenols can be used alone or in admixture of two or more.

Examples of the curing agent include 2,3-tolylene diisocyanate, 2,4-tolylene diisocyanate, 3,4-tolylene diisocyanate, 3,5-tolylene diisocyanate, and 4,4 ′. -Diisocyanates such as diphenylmethane diisocyanate, hexamethylene diisocyanate, 1,4-cyclohexane diisocyanate, and the following trade names: Epicoat 812, 815, 826, 828, 834, 834 871, 1001, 1004, 1007, 1007, 1009, 1031 (Oilized Shell Epoxy), Araldite 6600, 6700, 6800, 502, 6071, 6084, 6097, 6099 (above, manufactured by Ciba Geigy), DER331, 332, 333, 66 1, epoxy compound such as 644, 667 (manufactured by Dow Chemical Co.); Cymel 300, 301, 303, 350, 370, 771, 325, 327, 703, 712, Melting agents such as 701, 272, 202, My Coat 506, 508 (above, manufactured by Mitsui Cyanamid Co., Ltd.); Cymel 1123, 1123-10, 1128, My Coat 102, 105, Benzoguanamine type curing agents such as 106, 130 (above, Mitsui Cyanamid Co., Ltd.), etc .; Cymel 1170, 1172 (above, Mitsui Cyanamid Co., Ltd.), Nicarak N-2702 (Sanwa Chemical Co., Ltd.) ) And the like.
Of these curing agents, melamine curing agents, glycoluril curing agents and the like are preferable. The said hardening | curing agent can be used individually or in mixture of 2 or more types.
Moreover, polynuclear phenols and a hardening | curing agent can also be used together as a crosslinking agent.

  The amount of the crosslinking agent is usually 5,000 parts by weight or less, preferably 1,000 parts by weight or less per 100 parts by weight of the solid content of the antireflection film-forming composition.

As the binder resin, various thermoplastic resins and thermosetting resins can be used.
As the thermoplastic resin, for example,
Polyethylene, polypropylene, poly-1-butene, poly-1-pentene, poly-1-hexene, poly-1-heptene, poly-1-octene, poly-1-decene, poly-1-dodecene, poly-1- Α-Olefin polymers such as tetradecene, poly-1-hexadecene, poly-1-octadecene, and polyvinylcycloalkane; poly-1,4-pentadiene, poly-1,4-hexadiene, poly-1,5-hexadiene Non-conjugated diene polymers such as
α, β-unsaturated aldehyde polymers; α, β-unsaturated ketone polymers such as poly (methyl vinyl ketone), poly (aromatic vinyl ketone), poly (cyclic vinyl ketone); (meth) acrylic acid Polymers of α, β-unsaturated carboxylic acids or derivatives thereof such as, α-chloroacrylic acid, (meth) acrylate, (meth) acrylic acid ester, (meth) acrylic acid halide; Polymers of α, β-unsaturated carboxylic acid anhydrides such as copolymers of acrylic acid anhydride and maleic anhydride; Polymers of unsaturated polybasic carboxylic acid esters such as methylenemalonic acid diester and itaconic acid diester Kind;

Polymers of diolefin carboxylic acid esters such as sorbic acid ester and muconic acid ester; Polymers of α, β-unsaturated carboxylic acid thioesters such as (meth) acrylic acid thioester and α-chloroacrylic acid thioester; ) Polymers of (meth) acrylonitrile such as acrylonitrile and α-chloroacrylonitrile or derivatives thereof; Polymers of (meth) acrylamide or derivatives thereof such as (meth) acrylamide, N, N-dimethyl (meth) acrylamide; Polymers of metal compounds; Polymers of vinyloxy metal compounds;
Polyimines; polyethers such as polyphenylene oxide, poly-1,3-dioxolane, polyoxirane, polytetrahydrofuran, polytetrahydropyran; polysulfides; polysulfonamides; polypeptides; nylon 66, nylon 1 to nylon 12, etc. Polyamides; Polyesters such as aliphatic polyesters, aromatic polyesters, alicyclic polyesters and polycarbonates; Polyureas; Polysulfones; Polyazines; Polyamines; Polyaromatic ketones; Polyimides; Polybenzoxazoles; polybenzothiazoles; polyaminotriazoles; polyoxadiazoles; polypyrazoles; polytetrazoles; polyquinoxalines; polytriazines; Down like; quinoline compounds; mention may be made of a poly-Anne tiger gelsolin, and the like.

Further, the thermosetting resin is a component that has an action of preventing intermixing between the antireflection film obtained and the resist film formed thereon, which is cured by heating and becomes insoluble in a solvent. It can be preferably used as a binder resin.
Examples of such thermosetting resins include thermosetting acrylic resins, phenol resins, urea resins, melamine resins, amino resins, aromatic hydrocarbon resins, epoxy resins, alkyd resins. And the like.
Of these thermosetting resins, urea resins, melamine resins, aromatic hydrocarbon resins and the like are preferable.

The said binder resin can be used individually or in mixture of 2 or more types.
The blending amount of the binder resin is usually 20 parts by weight or less, preferably 10 parts by weight or less per 100 parts by weight of the polymer of each antireflection film forming composition.

Examples of the radiation absorber include oil-soluble dyes, disperse dyes, basic dyes, methine dyes, pyrazole dyes, imidazole dyes, hydroxyazo dyes, and the like; bixin derivatives, norbixine, stilbene, Fluorescent brighteners such as 4,4′-diaminostilbene derivatives, coumarin derivatives, pyrazoline derivatives; hydroxyazo dyes, tinuvin 234 (trade name, manufactured by Ciba Geigy), tinuvin 1130 (trade name, manufactured by Ciba Geigy), etc. Ultraviolet absorbers; aromatic compounds such as anthracene derivatives and anthraquinone derivatives.
These radiation absorbers can be used alone or in admixture of two or more.
The compounding amount of the radiation absorber is usually 100 parts by weight or less, preferably 50 parts by weight or less per 100 parts by weight of the solid content of the antireflection film-forming composition.

The surfactant is a component having an effect of improving coatability, striation, wettability, developability and the like.
Examples of such surfactants include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene-n-octylphenyl ether, polyoxyethylene-n-nonylphenyl ether, and polyethylene. Nonionic surfactants such as glycol dilaurate and polyethylene glycol distearate, and KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow No. 75, no. 95 (above, manufactured by Kyoeisha Yushi Chemical Co., Ltd.), Ftop EF101, EF204, EF303, EF352 (above, manufactured by Tochem Products), MegaFuck F171, F172, F173 (above, Dainippon) Ink Chemical Industry Co., Ltd.), Florard FC430, FC431, FC135, FC135, FC93 (above, manufactured by Sumitomo 3M), Asahi Guard AG710, Surflon S382, SC101, SC102, SC103, SC104, SC105, SC106 (above, manufactured by Asahi Glass Co., Ltd.) and the like.
These surfactants can be used alone or in admixture of two or more.
The compounding amount of the surfactant is usually 15 parts by weight or less, preferably 10 parts by weight or less per 100 parts by weight of the solid content of the antireflection film-forming composition.
Furthermore, examples of additives other than those described above include storage stabilizers, antifoaming agents, and adhesion aids.

Method for Forming Antireflection Film A method for forming an antireflection film from each antireflection film forming composition (hereinafter simply referred to as “composition”) of the present invention is usually, for example, 1) coating the composition on a substrate. And a step of forming an antireflection film by curing the obtained coating film, 2) a step of applying a resist composition solution on the antireflection film, and prebaking the obtained coating film to form a resist coating film. 3) a step of selectively exposing the resist film through a photomask, 4) a step of developing the exposed resist film, and 5) a step of etching the antireflection film.

In step 1), for example, a silicon wafer, a wafer coated with aluminum, or the like can be used as the substrate. The composition can be applied by an appropriate method such as spin coating, cast coating, roll coating or the like.
Thereafter, the coating film is cured by exposure and / or heating. The radiation to be exposed is appropriately selected from visible light, ultraviolet light, far ultraviolet light, X-ray, electron beam, γ-ray, molecular beam, ion beam and the like according to the type of photoacid generator used. When the composition contains a photoacid generator and is exposed, the coating film can be effectively cured even at room temperature. The heating temperature is usually about 90 to 350 ° C., preferably about 200 to 300 ° C. When the composition contains a thermal acid generator, the coating film can be effectively used even at about 90 to 150 ° C., for example. It can be cured.
1) The thickness of the antireflection film formed in the step is usually 0.1 to 5 μm.

  Next, in step 2), the resist composition solution is applied on the antireflection film so that the resulting resist film has a predetermined thickness, and then pre-baked to volatilize the solvent in the film, thereby resisting the resist. Form a film. The prebaking temperature at this time is appropriately adjusted according to the type of the resist composition to be used, and is usually about 30 to 200 ° C, preferably 50 to 150 ° C.

  Examples of the resist composition include a positive or negative chemically amplified resist composition containing a photoacid generator, a positive resist composition comprising an alkali-soluble resin and a quinonediazide-based photosensitizer, and an alkali-soluble resin. Examples thereof include a negative resist composition comprising a crosslinking agent.

  The resist composition solution used for forming the resist film on the antireflection film has a solid concentration of usually about 5 to 50% by weight, and is generally filtered with a filter having a pore size of about 0.2 μm, for example. And used for forming a resist film. In this step, a commercially available resist composition solution can be used as it is.

Next, in the step 3), as the radiation used for exposure, visible light, ultraviolet light, far ultraviolet light, X-rays, electron beams, gamma rays, molecules are used depending on the type of photoacid generator used in the resist composition. It is suitably selected from a line, an ion beam, etc., but is preferably far ultraviolet rays, and in particular, KrF excimer laser (248 nm), ArF excimer laser (193 nm), F ₂ excimer laser (wavelength 157 nm), Kr ₂ excimer laser ( A wavelength of 147 nm), an ArKr excimer laser (wavelength of 134 nm), extreme ultraviolet light (wavelength of 13 nm, etc.) and the like are preferable.

  Next, in step 4), the resist film after exposure is developed, washed, and dried to form a predetermined resist pattern. In this step, post-baking can be performed after exposure and before development in order to improve resolution, pattern profile, developability, and the like.

  The developer used in this step is appropriately selected according to the type of resist composition used, but development in the case of a positive chemically amplified resist composition or a positive resist composition containing an alkali-soluble resin. Examples of the liquid include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, dimethyl / ethanol. Amine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, choline, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3. 0] -5-none Alkaline aqueous solution etc. may be mentioned. In addition, an appropriate amount of a water-soluble organic solvent, for example, an alcohol such as methanol or ethanol, or a surfactant can be added to these alkaline aqueous solutions.

  Next, in step 5), the resist pattern obtained is used as a mask, and dry etching of the antireflection film is performed using, for example, gas plasma such as oxygen plasma, thereby obtaining a resist pattern for processing a predetermined substrate.

The acetoxymethyl acenaphthylene (1) and hydroxymethyl acenaphthylene (2) of the present invention can be used particularly suitably as a raw material or an intermediate for producing the polymer (I).
The polymer (I) of the present invention can be particularly suitably used as a polymer component in each antireflection film-forming composition of the present invention.
Since the antireflection film formed using each antireflection film forming composition of the present invention has a high antireflection effect and does not cause intermixing with the resist film, various positive and negative resist compositions. In cooperation with, a resist pattern having excellent resolution, pattern shape, and the like can be provided. Therefore, each antireflection film forming composition of the present invention greatly contributes particularly to the production of highly integrated circuits.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples. In the following, “parts” and “%” are based on weight unless otherwise specified.
Example 1 (Synthesis of acenaphthylene derivative)
-First step-
Under a dry atmosphere, 150 g of tin chloride was added dropwise at −5 ° C. with stirring to a solution of 70 g of dichloromethyl methyl ether in 300 g of dichloroethane, and then a solution of 77 g of acenaphthene in 300 g of dichloroethane was added dropwise. Thereafter, the reaction solution was stirred at room temperature for 2 hours, and then 5% calcium chloride aqueous solution was gradually added dropwise. Thereafter, the organic phase was washed until the aqueous phase became neutral, and then the organic layer was separated and the solvent was distilled off to obtain 90.5 g of a pale yellow solid compound.
This compound had the following ¹ H-NMR spectrum (δ) (solvent: deuterated chloroform, the same applies hereinafter) and infrared absorption spectrum (IR), and was identified as formylacenaphthene.
δ (unit: ppm): 3.4 (CH ₂ group);
7.3-8.8, 10.5 (above, CHO group).
IR (unit cm ⁻¹ ): 1677 (C═O group).

-Second step-
To a solution obtained by dissolving 73 g of formylacenaphthene obtained in the first step in a tetrahydrofuran / ethanol mixed solvent (tetrahydrofuran 550 g, ethanol 110 g), 7.6 g of sodium borohydride was added and stirred at room temperature for 2 hours. Thereafter, the reaction solution was concentrated, water was added, and the precipitated compound was filtered off and dried under reduced pressure to obtain 71 g of a white solid compound.
This compound had the following ¹ H-NMR spectrum (δ) and infrared absorption spectrum (IR), and was identified as hydroxymethylacenaphthene.
δ (unit: ppm): 3.3 (CH ₂ group);
4.8 to 4.9 (CH ₂ —O group);
5.2-5.3 (OH group);
7.2 to 7.8 (aromatic hydrogen atom).
IR (unit cm ⁻¹ ): 3372, 3297 (above, OH group).

-Third step-
To a solution obtained by dissolving 55 g of hydroxymethylacenaphthene obtained in the second step in 1,200 g of dioxane, 26 g of acetyl chloride and 36 g of triethylamine were dropped in this order while maintaining the liquid temperature at 50 ° C. or lower. Stir for 3 hours. Thereafter, the insoluble matter was filtered off, the organic phase was concentrated, and then the solvent was replaced with toluene. Thereafter, this toluene solution was washed with water until the aqueous phase became neutral, and then the solvent was distilled off to obtain 65 g of a yellow solid compound.
This compound had the following ¹ H-NMR spectrum (δ) and infrared absorption spectrum (IR), and was identified as acetoxymethylacenaphthene.
δ (unit: ppm): 2.1 (CH ₃ group);
3.3-3.4 (CH ₂ group);
5.5 (CH ₂ —O group);
7.2 to 7.5 (hydrogen atom of an aromatic ring).
IR (unit: cm ⁻¹ ): 1725 (C═O group).

-Fourth step-
After adding 60 g of dichlorodicyanobenzoquinone to a solution obtained by dissolving 45 g of acetoxymethylacenaphthene obtained in the third step in 450 g of dioxane, the mixture was stirred at 95 ° C. for 7 hours. Then, after filtering the reaction solution, the solvent was distilled off to obtain 54 g of brown solid acetoxymethylacenaphthylene.

-Fifth process-
110 g of 10% NaOH aqueous solution was added dropwise to a solution of 44 g of acetoxymethylacenaphthylene in 300 g of methanol, followed by stirring at 60 ° C. for 2 hours. Thereafter, methanol was distilled off from the reaction solution, and the solvent was replaced with 350 g of methyl ethyl ketone. Thereafter, this methyl ethyl ketone solution was washed with water until the aqueous phase became neutral, and then the solvent was distilled off to obtain a yellow solid. Then, this yellow solid was recrystallized and purified to obtain 10 g of a compound.
This compound had the following ¹ H-NMR spectrum (δ) and infrared absorption spectrum (IR), and was identified as hydroxymethylacenaphthylene.
δ (unit: ppm): 5.1 (CH ₂ —O group),
5.4 (OH group),
7.2 (HC = CH group),
7.6-8.2 (hydrogen atom of an aromatic ring).
IR (unit cm < ^-1 >): 3423 (OH group).

Synthesis Example 1 (Synthesis of 2-hydroxymethyl-6-vinylnaphthalene)
Under a nitrogen atmosphere, 98 g of methyl 6-bromo-2-naphthalenecarboxylate was dissolved in 2 liters of 1,2-dimethoxyethane, 44 g of tetrakis (triphenylphosphine) palladium was added, and the mixture was stirred at room temperature for 30 minutes. Thereafter, 52 g of potassium carbonate, 1 liter of water, and 91 g of 2,4,6-trivinylcyclotriboroxane / pyridine complex were added, and the mixture was stirred for 24 hours while heating under reflux. Thereafter, the reaction solution was returned to room temperature and passed through an activated alumina layer to obtain 77 g of methyl 2-vinyl-6-naphthalenecarboxylate.
Next, 400 ml of a tetrahydrofuran solution of di-i-butylaluminum hydride having a concentration of 1 mol / liter was added at −78 ° C. to a solution of 30 g of methyl 2-vinyl-6-naphthalenecarboxylate dissolved in 500 ml of tetrahydrofuran. Stir for 1 hour. Thereafter, completion of the reaction was confirmed by thin layer chromatography, methanol and water were added and mixed, and the organic layer was extracted with ethyl acetate. The organic layer was then washed with brine, dried over anhydrous magnesium sulfate, filtered and concentrated. Thereafter, the concentrate was purified by silica gel chromatography to obtain 18.5 g of a compound.
This compound had the following ¹ H-NMR spectrum (δ) and was identified as 2-hydroxymethyl-6-vinylnaphthalene.
δ (unit: ppm): 4.9 (CH ₂ —O group),
5.3, 5.9, 6.9 (vinyl group),
7.6-7.8 (hydrogen atom of an aromatic ring).

  In the following Preparation Example 1 and Examples 2 to 4, the Mw of the obtained resin and polymer was a Tosoh Co., Ltd. GPC column (G2000HXL: 2, G3000HXL: 1), flow rate: 1.0 ml / Min, elution solvent: tetrahydrofuran, column temperature: Measured by gel permeation chromatography (detector: differential refractometer) using monodisperse polystyrene as a standard under the analysis conditions of 40 ° C.

The performance evaluation of the composition for forming an antireflection film was performed as follows.
optical properties:
An antireflection film-forming composition was spin-coated on an 8 inch diameter silicon wafer, and then heated on a hot plate at 345 ° C. for 120 seconds to form an antireflection film having a thickness of 0.1 μm. The film was measured for refractive index (n value) and absorbance (k value) at a wavelength of 248 nm using KLA-TENCOR spectroscopic ellipsometer UV-1280E, and using SOPRA spectroscopic ellipsometer MOSS-ESVG DEEP UV. Then, the n value and the k value at a wavelength of 193 nm were measured.

Formation of positive resist pattern for KrF:
An antireflection film-forming composition was spin-coated on a silicon wafer having a diameter of 8 inches, and then heated on a hot plate at 345 ° C. for 120 seconds to form an antireflection film having a thickness of 0.6 μm. Thereafter, a resist composition solution for KrF (trade name KRFM20G, manufactured by JSR Corporation) is spin-coated on this antireflection film, and prebaked on a hot plate at 140 ° C. for 60 seconds to obtain a film thickness of 0.61 μm. A resist film was formed. Then, using a Nikon stepper NSR2005EX12B (wavelength of 248 nm), an exposure time for forming a line-and-space pattern with a line width of 0.22 μm with a KrF excimer laser through the mask pattern with a one-to-one line width ( Hereinafter, only the “optimum exposure time” was exposed). Then, after post-baking on a hot plate at 140 ° C. for 90 seconds, using a 2.38 wt% tetramethylammonium hydroxide aqueous solution, developing at 23 ° C. for 30 seconds, washing with water and drying, a positive resist pattern is formed. Formed.

Formation of positive resist pattern for ArF:
An antireflection film composition was spin-coated on an 8-inch diameter silicone wafer and baked on a 345 ° C. hot plate for 120 seconds to form an antireflection film having a thickness of 0.6 μm. Thereafter, the ArF resist composition solution obtained in Reference Example 1 described later is spin-coated on this antireflection film, and pre-baked on a hot plate at 130 ° C. for 90 seconds to form a resist film having a thickness of 0.5 μm. Formed. Thereafter, using an ArF excimer laser exposure apparatus (lens numerical aperture 0.60, exposure wavelength 193 nm) manufactured by ISI, exposure was performed for an optimal exposure time through a mask pattern. Then, after post-baking on a hot plate at 130 ° C. for 90 seconds, using a 2.38 wt% aqueous solution of tetramethylammonium hydroxide, developing at 25 ° C. for 1 minute, washing with water and drying, a positive resist A pattern was formed.

Standing wave prevention effect:
In the manner described above, an antireflection film and a resist film were formed, exposed and developed, and the presence or absence of a standing wave on the resist film was observed and evaluated with a scanning electron microscope.
Intermixing prevention effect:
The antireflection film was formed as described above, and the obtained antireflection film was immersed in propyl glycol monomethyl ether acetate at room temperature for 1 minute, and the change in film thickness before and after immersion was measured using a spectroscopic ellipsometer UV1280E (KLA-TENCOR). When the film thickness was measured using “manufactured”, the case where no change in film thickness was observed was evaluated as “◯”, and the case where a film thickness change was observed was evaluated as “x”.

Preparation Example 1 (Preparation of resist composition solution for ArF)
In a separable flask equipped with a reflux tube, 8-methyl-8-t-butoxycarbonylmethoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] 29 parts dodec-3-ene, 8-methyl-8-hydroxytetracyclo [4.4.0.1 ^2,5 .
[1 ^7,10 ] 10 parts dodec-3-ene, 18 parts maleic anhydride, 4 parts 2,5-dimethyl-2,5-hexanediol diacrylate, 1 part t-dodecyl mercaptan, 4 azobisisobutyronitrile And 60 parts of 1,2-diethoxyethane were charged and polymerized at 70 ° C. for 6 hours with stirring. Thereafter, the reaction solution is poured into a large amount of a mixed solvent of n-hexane / i-propyl alcohol (weight ratio = 1/1) to solidify the resin, and the solidified resin is washed several times with the mixed solvent, and then vacuumed. When dried, the content of the structural unit represented by the following formula (a), formula (b) or formula (c) is 64 mol%, 18 mol% and 18 mol%, respectively, and Mw is 27,000. The resin was obtained in 60% yield.

  80 parts of the resin obtained, 1.5 parts of 1- (4-methoxynaphthalen-1-yl) tetrahydrothiophenium nonafluoro-n-butanesulfonate and 0.04 part of tri-n-octylamine were mixed with propylene glycol monomethyl ether An ArF resist composition solution was prepared by dissolving in 533 parts of acetate.

Example 2 (Synthesis of polymer (III))
A separable flask equipped with a thermometer was charged with 8 parts of acenaphthylene, 4 parts of 5-hydroxymethylacenaphthylene, 50 parts of n-butyl acetate and 4 parts of azobisisobutyronitrile in a nitrogen atmosphere while stirring. Polymerization was carried out at 80 ° C. for 7 hours. Thereafter, the reaction solution was diluted with 100 parts of n-butyl acetate, and the organic layer was washed with a large amount of a mixed solvent of water / methanol (weight ratio = 1/2), and then the solvent was distilled off to obtain an Mw of 1,000. The polymer (III) was obtained.

Example 3 (Synthesis of polymer (IV))
A separable flask equipped with a thermometer was charged with 6 parts of acenaphthylene, 5 parts of 4-hydroxymethylstyrene, 48 parts of n-butyl acetate and 4 parts of azobisisobutyronitrile in a nitrogen atmosphere and stirred at 75 ° C. For 7 hours. Thereafter, the reaction solution was diluted with 100 parts of n-butyl acetate, and the organic layer was washed with a large amount of a water / methanol (weight ratio = 1/2) mixed solvent. The polymer (IV) was obtained.

Example 5 (Evaluation of antireflection film-forming composition)
10 parts of the polymer (III) obtained in Example 2, 0.5 part of bis (4-t-butylphenyl) iodonium 10-camphorsulfonate and 4,4 ′-[1- {4- (1- [4- Hydroxyphenyl] -1-methylethyl) phenyl} ethylidene] bisphenol 0.5 part is dissolved in 89 parts of ethyl lactate, and the solution is filtered through a membrane filter having a pore size of 0.1 μm to obtain an antireflection film-forming composition. Prepared. Subsequently, performance evaluation was performed about this composition. The evaluation results are shown in Table 1.

Example 6 (Evaluation of composition for forming antireflection film)
10 parts of the polymer (III) obtained in Example 2, 0.5 part of bis (4-t-butylphenyl) iodonium nonafluoro-n-butanesulfonate and 4,4 ′-[1- {4- (1- [4-Hydroxyphenyl] -1-methylethyl) phenyl} ethylidene] bisphenol 0.5 part is dissolved in 89 parts of ethyl lactate, and the solution is filtered through a membrane filter having a pore size of 0.1 μm to form an antireflection film. A composition was prepared. Subsequently, performance evaluation was performed about this composition. The evaluation results are shown in Table 1.

Example 7 (Evaluation of composition for forming antireflection film)
In Example 5, reflection was carried out in the same manner as in Example 5 except that 10 parts of the polymer (IV) obtained in Example 3 was used instead of 10 parts of the polymer (III) obtained in Example 2. An anti-film forming composition was prepared. Subsequently, performance evaluation was performed about this composition. The evaluation results are shown in Table 1.

Example 8 (Evaluation of composition for forming antireflection film)
In Example 6, reflection was conducted in the same manner as in Example 6 except that 10 parts of the polymer (IV) obtained in Example 3 was used instead of 10 parts of the polymer (III) obtained in Example 2. An anti-film forming composition was prepared. Subsequently, performance evaluation was performed about this composition. The evaluation results are shown in Table 1.

Comparative Example 1
Without using the antireflection film forming composition, a positive resist pattern for KrF and a positive resist pattern for ArF were formed, and performance evaluation was performed. The evaluation results are shown in Table 1.

Claims (7)

Acetoxymethylacenaphthylene represented by the following formula (1).

Hydroxymethylacenaphthylene represented by the following formula (2).

A polymer having a structural unit represented by the following formula (3) and having a polystyrene-equivalent weight average molecular weight of 500 to 10,000 measured by gel permeation chromatography.

[In the formula (3), R ¹ represents a hydrogen atom , a phenyl group, an alkyl group having 1 to 10 carbon atoms , an alkenyl group having 2 to 10 carbon atoms, or an acyl group having 2 to 10 carbon atoms. The group and the alkenyl group may each be substituted with one or more of a halogen atom, a hydroxyl group, a mercapto group, a carboxyl group, a nitro group or a sulfonic acid group (provided that a substituted phenyl group, The alkyl group and the substituted alkenyl group have 10 or less carbon atoms.) , R ² and R ³ are each independently a hydrogen atom, a halogen atom, a phenyl group, an alkyl group having 1 to 10 carbon atoms, or a carbon number. Represents an alkenyl group having 2 to 10 carbon atoms or an acyl group having 2 to 10 carbon atoms, wherein the phenyl group, alkyl group and alkenyl group are each a halogen atom or a hydride; May be substituted with one or more of a roxyl group, a mercapto group, a carboxyl group, a nitro group or a sulfonic acid group (however, a substituted phenyl group, a substituted alkyl group and a substituted alkenyl group) The number of carbon atoms is 10 or less.) ]   An antireflection film-forming composition comprising the polymer according to claim 3 and a solvent. Polymer having a structural unit represented by the structural unit formula of the formula (3) according to claim 3 (4), and the formula (3) according to claim 3 Structure An antireflective film-forming composition comprising at least one selected from the group of polymers having a unit and a structural unit represented by the following formula (5), and a solvent.

[In the formula (4), R ⁴ represents a hydrogen atom, a phenyl group, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an acyl group having 2 to 10 carbon atoms. Group and alkenyl group may each be substituted (provided that the substituted phenyl group, substituted alkyl group and substituted alkenyl group have 10 or less carbon atoms), R ⁵ represents a hydrogen atom, halogen atom An atom, a phenyl group, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms or an acyl group having 2 to 10 carbon atoms, wherein the phenyl group, the alkyl group and the alkenyl group are a halogen atom and a hydroxyl group, respectively. , A mercapto group, a carboxyl group, a nitro group or a sulfonic acid group may be substituted with one or more kinds (provided that the substituted The phenyl group, the substituted alkyl group and the substituted alkenyl group have 10 or less carbon atoms.), N is 0 or 1. ]

[In Formula (5), R < ⁶ > and R < ⁷ > are mutually independently a hydrogen atom, a halogen atom, a phenyl group, a C1-C10 alkyl group, a C2-C10 alkenyl group, or C2-C10. Represents an acyl group, and each of the phenyl group, alkyl group and alkenyl group may be substituted with one or more of halogen atom, hydroxyl group, mercapto group, carboxyl group, nitro group or sulfonic acid group ( However, the carbon number of the substituted phenyl group, the substituted alkyl group, and the substituted alkenyl group is 10 or less.) ] The antireflection film-forming composition according to claim 4 or 5 , further comprising an acid generator. Further contains a crosslinking agent, anti-reflective coating forming composition according to any one of claims 4-6.