JPWO2020059603A1 - Imprint laminate, imprint laminate manufacturing method, pattern formation method and kit - Google Patents

Abstract

It contains a lower layer film 11 formed from a composition for forming a lower layer film containing a polymer having an aromatic ring and a polymerizable group, and a polymerizable compound provided on the surface of the lower layer film 11 and liquid at 23 ° C. and 1 atm. An imprint laminate 10 having a liquid film 12 and a photocurable composition 13 for imprint provided on the surface of the liquid film 12. Manufacturing method, pattern forming method and kit for imprint laminate.

Description

The present invention relates to an imprint laminate. More specifically, the present invention relates to an imprint laminate used for forming a pattern in imprint. The present invention also relates to a method for producing an imprint laminate, a pattern forming method, and a kit.

The imprint method is a mechanical process in which a mold prototype (generally called a mold, stamper, template, etc.) that has formed an uneven pattern by developing the embossing technology that is well known in optical disc manufacturing is pressed against a resist. It is a technology that transforms into a fine pattern and transfers it precisely. Once the mold is manufactured, it is economical because fine structures such as nanostructures can be easily and repeatedly molded, and because it is a nanoprocessing technology with less harmful waste and emissions, it has been applied to various fields in recent years. It is expected to be applied.

In the imprint method, a light-transmitting mold or a light-transmissive substrate is irradiated with light to cure the photocurable composition for imprint, and then the mold is peeled off to transfer a fine pattern to the photo-cured product. be. Since this method enables imprinting at room temperature, it can be applied to the field of precision processing of ultrafine patterns such as fabrication of semiconductor integrated circuits. Recently, new developments such as a nanocasting method that combines these advantages and a reversal imprint method for producing a three-dimensional laminated structure have been reported.

On the other hand, with the activation of the imprinting method, the adhesion between the substrate and the photocurable composition for imprinting has become a problem. That is, in the imprint method, the photocurable composition for imprint is applied to the surface of the substrate, and the photocurable composition for imprint is cured by irradiating light with the mold in contact with the surface. , The mold is peeled off, but in the process of peeling off the mold, the cured product may be peeled off from the substrate and adhered to the mold. It is considered that this is because the adhesion between the substrate and the cured product is lower than the adhesion between the mold and the cured product. Therefore, an attempt to form an underlayer film on a substrate and apply a photocurable composition for imprinting on the substrate to improve the adhesion between the substrate and the cured product has been studied (see Patent Documents 1 and 2). ).

International Publication WO 2013/191118 Japanese Unexamined Patent Publication No. 2014-192178

In pattern formation by the imprint method, the cured product formed from the photocurable composition for imprint has good adhesion to the substrate, and the photocurable composition for imprint has good wettability. In recent years, it has been desired to achieve both of these characteristics at a higher level.

Therefore, an object of the present invention is to provide excellent adhesion of a cured product formed from a photocurable composition for imprinting to a substrate or the like, and to provide excellent wettability of the photocurable composition for imprinting. It is an object of the present invention to provide an imprint laminate, a method for producing an imprint laminate, a pattern forming method, and a kit.

式（１）中、Ｒ¹¹は置換基を表し、ｍ１は０〜４の整数を表す。ｍ１が２以上の場合は、複数のＲ¹¹は同一であってもよく、異なってもよく、２個のＲ¹¹同士が結合して環を形成していてもよい；
式（２）中、Ｒ²は水素原子またはメチル基を表し、Ｒ¹²は置換基を表し、ｍ２は０〜５の整数を表す。ｍ２が２以上の場合は、複数のＲ¹²は同一であってもよく、異なってもよく、２個のＲ¹²同士が結合して環を形成していてもよい；
式（３）中、Ｒ³は水素原子またはメチル基を表し、Ｒ¹³は置換基を表す；
式（４）中、Ｒ⁴は水素原子またはメチル基を表し、Ｒ¹⁴は置換基を表す；
式（５）中、Ｒ¹⁵は置換基を表す。
＜４＞ ポリマーは、９０〜３００℃の温度で重合反応するポリマーである、＜１＞〜＜３＞のいずれか１つに記載のインプリント用積層体。
＜５＞ ポリマーが有する重合性基は、（メタ）アクリロイル基、オキシラニル基およびオキセタニル基から選ばれる少なくとも１種である、＜１＞〜＜４＞のいずれか１つに記載のインプリント用積層体。
＜６＞ 液膜の膜厚が１０ｎｍ以下である、＜１＞〜＜５＞のいずれか１つに記載のインプリント用積層体。
＜７＞ 液膜に含まれる重合性化合物は芳香族環を含む重合性化合物である、＜１＞〜＜６＞のいずれか１つに記載のインプリント用積層体。
＜８＞ 液膜に含まれる重合性化合物は多官能の重合性化合物である、＜１＞〜＜７＞のいずれか１つに記載のインプリント用積層体。
＜９＞ 液膜に含まれる重合性化合物はラジカル重合性化合物である、＜１＞〜＜８＞のいずれか１つに記載のインプリント用積層体。
＜１０＞ インプリント用光硬化性組成物は重合性化合物と光重合開始剤とを含む、＜１＞〜＜９＞のいずれか１つに記載のインプリント用積層体。
＜１１＞ インプリント用光硬化性組成物に含まれる重合性化合物は、芳香族環を含む重合性化合物である＜１０＞に記載のインプリント用積層体。
＜１２＞ 液膜のハンセン溶解度パラメータとインプリント用光硬化性組成物のハンセン溶解度パラメータとに基づき下記数式（Ｈ１）で算出されるΔＨＳＰの値が１０以下である、＜１＞〜＜１１＞のいずれか１つに記載のインプリント用積層体；
ΔＨＳＰ＝（４．０×ΔＤ²＋ΔＰ²＋ΔＨ²）^0.5 （Ｈ１）
上記ΔＤは、インプリント用光硬化性組成物のハンセン溶解度パラメータベクトルの分散項成分と、液膜のハンセン溶解度パラメータベクトルの分散項成分の差であり、上記ΔＰは、インプリント用光硬化性組成物のハンセン溶解度パラメータベクトルの極性項成分と、液膜のハンセン溶解度パラメータベクトルの極性項成分の差であり、上記ΔＨは、インプリント用光硬化性組成物のハンセン溶解度パラメータベクトルの水素結合項成分と、液膜のハンセン溶解度パラメータベクトルの水素結合項成分の差である。
＜１３＞ 基板上に芳香族環と重合性基とを有するポリマーを含む下層膜形成用組成物を適用して下層膜を形成する工程と、
下層膜上に２３℃、１気圧で液体である重合性化合物を含む液膜形成用組成物を適用して液膜を形成する工程と、
液膜上にインプリント用光硬化性組成物を適用する工程と、
を含むインプリント用積層体の製造方法。
＜１４＞ 基板上に芳香族環と重合性基とを有するポリマーを含む下層膜形成用組成物を適用して下層膜を形成する工程と、
下層膜上に２３℃、１気圧で液体である重合性化合物を含む液膜形成用組成物を適用して液膜を形成する工程と、
液膜上にインプリント用光硬化性組成物を適用する工程と、
液膜上のインプリント用光硬化性組成物とパターンを有するモールドとを接触させる工程と、
モールドを接触させた状態でインプリント用光硬化性組成物を露光する工程と、
露光したインプリント用光硬化性組成物からモールドを剥離する工程と、
を含むパターン形成方法。
＜１５＞ ＜１＞〜＜１２＞のいずれか１つに記載のインプリント用積層体に用いられるキットであって、
芳香族環と重合性基とを有するポリマーを含む下層膜形成用組成物と、
２３℃、１気圧で液体である重合性化合物を含む液膜形成用組成物と、
インプリント用光硬化性組成物と、を含むキット。Based on the above problems, it has been found that the above problems can be solved by using an imprint laminate having a configuration described later. Therefore, the present invention provides the following.
<1> An underlayer film formed from a composition for forming an underlayer film containing a polymer having an aromatic ring and a polymerizable group, and
A liquid film containing a polymerizable compound that is liquid at 23 ° C. and 1 atm provided on the surface of the lower layer film, and
A photocurable composition for imprinting provided on the surface of the liquid film,
Laminated body for imprinting.
<2> The laminate for imprint according to <1>, wherein the polymer contains a structural unit containing an aromatic ring and a polymerizable group.
<3> The imprint laminate according to <1> or <2>, wherein the polymer contains at least one of the structural units represented by any of the following formulas (1) to (5);

In formula (1), R ¹¹ represents a substituent and m1 represents an integer from 0 to 4. If m1 is 2 or more, plural R ¹¹ may be the same, or different, may have the two R ¹¹ are bonded to each other to form a ring;
In formula (2), R ² represents a hydrogen atom or a methyl group, R ¹² represents a substituent, and m2 represents an integer from 0 to 5. When m2 is 2 or more, the plurality of R ^12s may be the same or different, and the two R ^12s may be bonded to each other to form a ring;
In formula (3), R ³ represents a hydrogen atom or a methyl group and R ¹³ represents a substituent;
In formula (4), R ⁴ represents a hydrogen atom or a methyl group, and R ¹⁴ represents a substituent;
In formula (5), R ¹⁵ represents a substituent.
<4> The imprint laminate according to any one of <1> to <3>, wherein the polymer is a polymer that undergoes a polymerization reaction at a temperature of 90 to 300 ° C.
<5> The imprint laminate according to any one of <1> to <4>, wherein the polymerizable group of the polymer is at least one selected from a (meth) acryloyl group, an oxylanyl group, and an oxetanyl group. body.
<6> The laminate for imprint according to any one of <1> to <5>, wherein the film thickness of the liquid film is 10 nm or less.
<7> The imprint laminate according to any one of <1> to <6>, wherein the polymerizable compound contained in the liquid film is a polymerizable compound containing an aromatic ring.
<8> The imprint laminate according to any one of <1> to <7>, wherein the polymerizable compound contained in the liquid film is a polyfunctional polymerizable compound.
<9> The imprint laminate according to any one of <1> to <8>, wherein the polymerizable compound contained in the liquid film is a radically polymerizable compound.
<10> The laminate for imprint according to any one of <1> to <9>, wherein the photocurable composition for imprint contains a polymerizable compound and a photopolymerization initiator.
<11> The laminate for imprint according to <10>, wherein the polymerizable compound contained in the photocurable composition for imprint is a polymerizable compound containing an aromatic ring.
<12> The value of ΔHSP calculated by the following mathematical formula (H1) based on the Hansen solubility parameter of the liquid film and the Hansen solubility parameter of the photocurable composition for imprinting is 10 or less, <1> to <11>. The imprint laminate according to any one of the above;
ΔHSP = (4.0 × ΔD ² + ΔP ² + ΔH ² ) ^0.5 (H1)
The above ΔD is the difference between the dispersion term component of the Hansen solubility parameter vector of the photocurable composition for imprint and the dispersion term component of the Hansen solubility parameter vector of the liquid film, and the above ΔP is the photocurable composition for imprint. The difference between the polar term component of the Hansen solubility parameter vector of the product and the polar term component of the Hansen solubility parameter vector of the liquid film, and the above ΔH is the hydrogen bond term component of the Hansen solubility parameter vector of the photocurable composition for imprint. And the difference between the hydrogen bond term components of the Hansen solubility parameter vector of the liquid film.
<13> A step of applying a composition for forming an underlayer film containing a polymer having an aromatic ring and a polymerizable group on a substrate to form an underlayer film, and a step of forming the underlayer film.
A step of forming a liquid film by applying a liquid film forming composition containing a polymerizable compound that is liquid at 23 ° C. and 1 atm on the lower layer film.
The process of applying the photocurable composition for imprinting on the liquid film, and
A method for manufacturing an imprint laminate including.
<14> A step of applying a composition for forming an underlayer film containing a polymer having an aromatic ring and a polymerizable group on a substrate to form an underlayer film, and a step of forming the underlayer film.
A step of forming a liquid film by applying a liquid film forming composition containing a polymerizable compound that is liquid at 23 ° C. and 1 atm on the lower layer film.
The process of applying the photocurable composition for imprinting on the liquid film, and
The process of contacting the photocurable composition for imprinting on the liquid film with the mold having a pattern,
The process of exposing the photocurable composition for imprinting in contact with the mold, and
The process of peeling the mold from the exposed photocurable composition for imprinting,
Pattern forming method including.
<15> A kit used for the imprint laminate according to any one of <1> to <12>.
A composition for forming an underlayer film containing a polymer having an aromatic ring and a polymerizable group, and
A composition for forming a liquid film containing a polymerizable compound that is liquid at 23 ° C. and 1 atm, and
A kit containing a photocurable composition for imprinting.

INDUSTRIAL APPLICABILITY The present invention can provide excellent adhesion of a cured product formed from a photocurable composition for imprinting to a substrate or the like, and can also provide excellent wettability of the photocurable composition for imprinting. A method for producing a laminate for printing, a method for producing an imprint laminate, a pattern forming method, and a kit can be provided.

It is the schematic of the laminate for imprint of this invention. It is a figure which shows the state in which the photocurable composition for imprint and the mold which has a pattern are in contact with each other in the pattern forming method of this invention. It is a schematic diagram which shows an example of the pattern formed by using the pattern forming method of this invention.

Hereinafter, the contents of the present invention will be described in detail. In addition, in this specification, "~" is used in the meaning that the numerical values described before and after it are included as the lower limit value and the upper limit value.
As used herein, "(meth) acrylate" refers to acrylate and methacrylate.
As used herein, "imprint" preferably refers to a pattern transfer having a size of 1 nm to 10 mm, and more preferably a pattern transfer having a size of about 10 nm to 100 μm (nanoimprint).
In the notation of a group (atomic group) in the present specification, the notation that does not describe substitution and non-substitution includes those having no substituent as well as those having a substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In the present specification, "light" includes not only light having wavelengths in the ultraviolet, near-ultraviolet, far-ultraviolet, visible, and infrared regions, and electromagnetic waves, but also radiation. Radiation includes, for example, microwaves, electron beams, extreme ultraviolet rays (EUV), and X-rays. Further, laser light such as a 248 nm excimer laser, a 193 nm excimer laser, and a 172 nm excimer laser can also be used. As these lights, monochrome light (single wavelength light) that has passed through an optical filter may be used, or light having a plurality of different wavelengths (composite light) may be used.
Unless otherwise specified, the weight average molecular weight (Mw) in the present invention refers to those measured by gel permeation chromatography (GPC).
The boiling point in the present invention means the boiling point at 1 atm (1 atm = 1013.25 hPa).
Unless otherwise specified, the temperature in the present invention is 23 ° C.

<Laminate for imprint>
The imprint laminate of the present invention is
An underlayer film formed from a composition for forming an underlayer film containing a polymer having an aromatic ring and a polymerizable group,
A liquid film containing a polymerizable compound that is liquid at 23 ° C. and 1 atm provided on the surface of the lower layer film, and
A photocurable composition for imprinting provided on the surface of the liquid film,
It is characterized by having.

The imprint laminate of the present invention has a lower layer film formed from a lower layer film forming composition containing a polymer having an aromatic ring and a polymerizable group. Since the polymer contained in the composition for forming an underlayer film contains an aromatic ring, it is considered that the aromatic ring contained in the polymer and the substrate or the like are likely to interact with each other. Further, since this polymer also contains a polymerizable group, it is considered that an interaction between the substrate and the polymerizable group contained in the polymer can be obtained. Therefore, the adhesion between the substrate and the lower layer film can be further improved. Further, since the polymer contains a polymerizable group, it is presumed that a crosslinked structure is formed in the lower layer film formed from the lower layer film forming composition. Therefore, it is presumed that it is possible to suppress the cohesive failure of the lower layer film at the time of mold peeling.
Further, the imprint laminate of the present invention has a liquid film containing a polymerizable compound that is liquid at 23 ° C. and 1 atm on the surface of the lower layer film. As described above, since the liquid film contains the above-mentioned polymerizable compound, it is presumed that the polymerizable compound contained in the liquid film interacts with the underlayer film and the photocurable composition for imprinting, and the liquid film and the liquid film are presumed to interact with each other. It is possible to improve the adhesion to the lower layer film and the adhesion between the liquid film and the cured product obtained from the photocurable composition for imprint formed on the liquid film. Therefore, it is presumed that the imprint laminate of the present invention can provide excellent adhesion to a substrate or the like of a cured product formed from the imprint photocurable composition. In the present invention, the liquid means a liquid having a viscosity at 23 ° C. of 100,000 mPa · s or less.
Further, since the imprint laminate of the present invention has the imprint photocurable composition on the liquid film, the imprint photocurable composition easily wets and spreads on the liquid film, and the imprint The photocurable composition for use has excellent wettability. Therefore, when the mold is brought into contact with the surface of the photocurable composition for imprint to form a pattern, it is possible to provide excellent filling property of the photocurable composition for imprint into the mold.

The imprint laminate of the present invention will be described in more detail with reference to FIG. In FIG. 1, the imprint laminate 10 of the present invention is formed on the substrate 1. That is, in FIG. 1, the lower layer film 11 is formed on the substrate 1, and the liquid film 12 is formed on the lower layer film. Then, the photocurable composition 13 for imprinting is arranged on the liquid film 12. The laminate of the underlayer film 11, the liquid film 12, and the photocurable composition for imprint 13 is the laminate 10 for imprint of the present invention.

The material of the substrate 1 on which the imprint laminate is formed is not particularly specified, and the description in paragraph 0103 of JP-A-2010-109092 (the publication number of the corresponding US application is US2011 / 0183127) is described. These contents can be taken into consideration and are incorporated herein by reference. Specific examples of the substrate 1 include a silicon substrate, a glass substrate, a quartz substrate, a sapphire substrate, a silicon carbide (silicon carbide) substrate, a gallium nitride substrate, an aluminum substrate, an amorphous aluminum oxide substrate, a polycrystalline aluminum oxide substrate, and GaAsP. Examples thereof include a substrate composed of GaP, AlGaAs, InGaN, GaN, AlGaN, ZnSe, AlGa, InP, or ZnO. Specific examples of the material of the glass substrate include aluminosilicate glass, aluminoborosilicate glass, and barium borosilicate glass. In the present invention, a silicon substrate is preferable.

In the present invention, it is also preferable to use a substrate having a carbon film on the surface as the substrate 1. The carbon film is preferably provided on the outermost layer of the substrate. Examples of the carbon film include an amorphous carbon film and a spin-on carbon film. As an example of the spin-on carbon film, the description in paragraph 0126 of JP2011-164345A can be referred to, and the contents thereof are incorporated in the present specification.

The contact angle of water on the surface of the substrate is preferably 1 ° or more, more preferably 20 ° or more, and even more preferably 40 ° or more. It is practical that the upper limit is 90 ° or less.

The thickness of the underlayer film 11 is preferably 2 nm or more, more preferably 3 nm or more, further preferably 4 nm or more, 5 nm or more, or 7 nm or more. It may be 10 nm or more. The thickness of the underlayer film is preferably 40 nm or less, more preferably 30 nm or less, further preferably 20 nm or less, and may be 15 nm or less. By setting the film thickness to the above lower limit value or more, the wettability of the photocurable composition for imprinting can be enhanced. By setting the film thickness to the above upper limit value or less, the residual film after imprinting becomes thin, uneven film thickness is less likely to occur, and the uniformity of the residual film can be improved.

The surface free energy of the underlayer film 11 is preferably 30 mN / m or more, more preferably 40 mN / m or more, and further preferably 50 mN / m or more. The upper limit is preferably 200 mN / m or less, more preferably 150 mN / m or less, and even more preferably 100 mN / m or less. The surface free energy can be measured at 23 ° C. using a surface tension meter SURFACE TENS-IOMETER CBVP-A3 manufactured by Kyowa Interface Science Co., Ltd. and a glass plate.

In the imprint laminate of the present invention, the underlayer film 11 is formed from a composition for forming an underlayer film containing a polymer having an aromatic ring and a polymerizable group. Details of the composition for forming an underlayer film will be described later.

The thickness of the liquid film 12 is preferably 20 nm or less, more preferably 15 nm or less, and even more preferably 10 nm or less. The thickness of the liquid film is preferably 2 nm or more. By setting the film thickness to the above lower limit value or more, the wettability of the photocurable composition for imprinting can be enhanced. By setting the film thickness to the above upper limit value or less, it is possible to suppress the occurrence of pattern collapse and the like.

In the imprint laminate of the present invention, the liquid film 12 contains a polymerizable compound (hereinafter, also referred to as polymerizable compound A) that is liquid at 23 ° C. and 1 atm. The content of the non-volatile component (meaning a component other than the solvent) of the liquid film 12 is preferably 0.01% by mass or more, and more preferably 0.1% by mass or more. The content of the polymerizable compound A in the liquid film 12 is preferably 50% by mass or more, and more preferably 80% by mass or more.

The liquid film 12 can be formed by using a liquid film forming composition containing a polymerizable compound that is liquid at 23 ° C. and 1 atm. Details of the liquid film forming composition will be described later.

Although the photocurable composition 13 for imprinting is arranged only in a part of the surface of the liquid film 12 in FIG. 1, it may be arranged on the entire surface of the liquid film 12. Further, in FIG. 1, the photocurable composition 13 for imprint is arranged in dots on the surface of the liquid film 12, but the shape of the photocurable composition 13 for imprint is not particularly limited and is striped. , Square, rectangular, oval, rhombus, etc. Details of the photocurable composition for imprint will be described later.

<< Composition for forming a lower layer film >>
Next, the composition for forming an underlayer film used in the imprint laminate of the present invention will be described.

[Specific polymer]
The composition for forming an underlayer film contains a polymer having an aromatic ring and a polymerizable group (hereinafter, also referred to as a specific polymer). In the specific polymer, the aromatic ring may be contained in the main chain of the constituent unit or in the side chain. Further, in the specific polymer, the polymerizable group may be contained in a structural unit containing an aromatic ring, or may be contained in a structural unit not containing an aromatic ring. Further, the specific polymer may be a mixture of a polymer having an aromatic ring and no polymerizable group and a polymer having a polymerizable group and not having an aromatic ring. .. The specific polymer preferably contains a structural unit containing an aromatic ring and a polymerizable group because of its adhesion to the photocurable composition 13 for imprinting and its adhesion to the substrate 1. Further, the specific polymer is preferably a polymer that polymerizes at a temperature of 90 to 300 ° C., and more preferably a polymer that polymerizes at a temperature of 150 to 200 ° C.

The aromatic ring contained in the specific polymer may be either an aromatic hydrocarbon ring or an aromatic heterocycle, but is preferably an aromatic hydrocarbon ring. The aromatic ring may be a monocyclic ring or a condensed ring, but is preferably a monocyclic ring. In the case of condensed rings, the number of rings is preferably two or three. The ring is preferably a 3- to 8-membered ring, more preferably a 5-membered ring or a 6-membered ring, and even more preferably a 6-membered ring.

Specific examples of the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a phenanthrene ring, a fluorene ring, an acenaphthalene ring, a biphenyl ring, a terphenyl ring, an indene ring, an indan ring, a triphenylene ring, and a tetraphenylene. Examples thereof include a ring, a pyrene ring, a chrysene ring, a perylene ring, and a tetrahydronaphthalene ring. Specific examples of the aromatic heterocycle include a thiophene ring, a furan ring, a pyrrol ring, an imidazole ring, a pyrazole ring, a triazole ring, a tetrazole ring, a thiazole ring, an oxazole ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, and a triazine ring. Ring, isoindole ring, indole ring, indazole ring, purine ring, quinolidine ring, isoquinoline ring, quinoline ring, phthalazine ring, naphthylidine ring, quinoxaline ring, quinazoline ring, cinnoline ring, carbazole ring, acrydin ring, phenazine ring, phenothiazine ring. , Phenoxazine ring and the like. The aromatic ring contained in the specific polymer is preferably a benzene ring.

Examples of the polymerizable group contained in the specific polymer include (meth) acryloyl group, oxylanyl group, oxetanyl group, methylol group, methylol ether group, vinyl ether group, isocyanate group, oxazoline group and the like, and include (meth) acryloyl group and oxylanyl group. , Oxetanyl group is preferred, and (meth) acryloyl group is more preferred.

In the specific polymer, the proportion of the structural unit having a polymerizable group is preferably 10 to 100 mol%, more preferably 20 to 100 mol%, and 30 to 100 mol% in all the structural units. Is more preferable, and 50 to 100 mol% is particularly preferable. The specific polymer may contain only one type of structural unit having a polymerizable group, or may contain two or more types. When two or more kinds are included, the total amount is preferably in the above range.

The specific polymer preferably contains at least one of the structural units represented by any of the following formulas (1) to (5).

In formula (1), R ¹¹ represents a substituent and m1 represents an integer from 0 to 4. If m1 is 2 or more, plural R ¹¹ may be the same, or different, may form two R ¹¹ are bonded to each other ring.
In formula (2), R ² represents a hydrogen atom or a methyl group, R ¹² represents a substituent, and m2 represents an integer from 0 to 5. When m2 is 2 or more, the plurality of R ^12s may be the same or different, and the two R ^12s may be bonded to each other to form a ring.
In formula (3), R ³ represents a hydrogen atom or a methyl group, and R ¹³ represents a substituent.
In formula (4), R ⁴ represents a hydrogen atom or a methyl group, and R ¹⁴ represents a substituent.
In formula (5), R ¹⁵ represents a substituent.

In the above formula, the ^{substituents represented by R 11 to} R ¹⁵ include the substituent T described later and the group represented by the following formula (T1). Further, the ^{substituent represented by R 13 to} R ¹⁵ is preferably a group containing an aromatic ring, and more preferably a group represented by the formula (T1). m1 represents an integer of 0 to 4, preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and even more preferably 1 or 2. m2 represents an integer of 0 to 5, preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and even more preferably 1 or 2. When m1 is 1, R ¹¹ is preferably a group represented by the following formula (T1). Also, in the case of m1 is 2 or more, it is preferable that at least one of the plurality of R ¹¹ is a group represented by the following formula (T1). When m2 is 1, R ¹² is preferably a group represented by the following formula (T1). When m2 is 2 or more, ^{it is preferable that at least one of the plurality of R 12s} is a group represented by the following formula (T1).

(Group represented by the formula (T1))
The group represented by the formula (T1) will be described.

− (L ³ ) _n5 − (L ¹ ) _n1 −La − [(L ² ) _n2 − (P) _n3 ] _n4・ ・ ・ (T1)
L ¹ and L ² are each independently the following linking group L, preferably a linking group Lh containing a heteroatom. However, when n3 is 0, L ^{2 at} the terminal is a substituent. La is a linking group containing an aromatic ring. However, when n2 is 0 and n3 is 0, La is a substituent containing an aromatic ring. P is a polymerizable group. n1 is 0 to 4. n2 is 0 to 4. When n1 or n2 is 2 or more, a plurality of linking groups L ¹ and L ² can be the same or be different. n3 is 0 to 6. When n3 is 2 or more, the linking group L ² may be linked with a trivalent or higher value. For example, a group having an alkane structure having a trivalent value or higher (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms). 1-3 are more preferred), alkene-structured groups (2-12 carbon atoms are preferred, 2-6 are more preferred, 2-3 are more preferred), or aryl-structured groups (6-22 carbon atoms are preferred. 6-18 is more preferred, 6-10 is even more preferred). n4 is an integer of 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 6, even more preferably an integer of 1 to 4, and particularly preferably an integer of 1 to 3. L ³ is a divalent linking group, and it is preferable that L 3 is a linking group L described in detail later. n5 is 0 or 1.

Two or more of the above "(L ¹ ) _n1 − La − [(L ² ) _n2 − (P) _n3 ] _n4 " ^{may be substituted via L 3.} That is, a form of − (L ³ ) _n5 − {(L ¹ ) _n1 − La − [(L ² ) _n2 − (P) _n3 ] _n4 } _n11 (n11 = an integer of 2 or more) is also a preferred embodiment of the present invention. Can be mentioned. At this time, L ³ may be a linking group having a trivalent or higher valence. For example, a group having an alkane structure having a trivalent or higher valence (1 to 12 carbon atoms is preferable, 1 to 6 is more preferable, and 1 to 3 is further. (Preferably), an alkene-structured group (preferably 2-12 carbon atoms, more preferably 2-6, more preferably 2-3), or an aryl-structured group (preferably 6-22 carbon atoms, more preferably 6-18 carbon atoms). Preferably, 6-10 are more preferred).

Examples of the linking group Lh containing a hetero atom include an oxygen atom, a sulfur atom, a carbonyl group, a thiocarbonyl group, a sulfonyl group, a sulfinyl group, -NR ^N- , and an (oligo) alkyleneoxy group (an alkylene group in one structural unit). The carbon number is preferably 1-12, more preferably 1-6, even more preferably 1-3; the number of repetitions is preferably 1-50, more preferably 1-40, even more preferably 1-30), or any of these. Examples include linking groups consisting of combinations. The number of atoms constituting the linking group Lh containing a hetero atom is preferably 1 to 100, more preferably 1 to 70, and particularly preferably 1 to 50, excluding hydrogen atoms. The number of linked atoms of Lh is preferably 1 to 25, more preferably 1 to 20, further preferably 1 to 15, further preferably 1 to 10. The (oligo) alkyleneoxy group may be an alkyleneoxy group or an oligoalkyleneoxy group. The (oligo) alkyleneoxy group and the like may be chain-like or cyclic, and may be linear or branched. If the linking group is a ^{group capable of forming a salt, such as when −NR N} − or a carboxyl group is substituted, the group may form a salt. ^RN is a hydrogen atom or an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms), and a hydrogen atom, a methyl group, an ethyl group, or a propyl group is preferable.

L ¹ and L ² may each independently have a substituent T. For example, a preferred example may be an embodiment in which a hydroxyl group is substituted in the portion of the alkylene group of the alkyleneoxy group.

n3 is atom or group L ² enters the position of P when become substituent 0 may be of any, for example, a hydrogen atom, an alkyl group (having 1 to 12 carbon atoms are preferred, 1 to 6 More preferably, 1 to 3 are even more preferable).

Examples of the polymerizable group represented by P include the above-mentioned polymerizable group, and a (meth) acryloyl group, an oxylanyl group, and an oxetanyl group are preferable, and a (meth) acryloyl group is more preferable.

La is a linking group containing an aromatic ring. La may be composed only of an aromatic ring, or may have a non-aromatic hydrocarbon linking group. Examples of the non-aromatic hydrocarbon linking group include non-aromatic hydrocarbon linking groups among the linking groups L described in detail later, which may be chain or cyclic, linear or branched, and may be an alkylene group (1 carbon number). ~ 24 is preferable, 1 to 12 is more preferable, 1 to 6 is more preferable), an alkaneylene group which may be chain or cyclic, linear or branched (preferably 2 to 24 carbon atoms, more preferably 2 to 12). , 2 to 6 are more preferable). The non-aromatic hydrocarbon linking group shown here is called a linking group Lt.
When n2 = 0 and n3 = 0, the aromatic ring La serves as a terminal substituent. At that time, the terminal may be any atom or atomic group, and examples thereof include a hydrogen atom or an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 3 carbon atoms).
La may be a linking group having an aromatic ring, and may be in a form in which the aromatic ring is not in the linking position. For example, an ^{alkylene group may be connected between L 21} and L ²¹ , and the alkylene group may be substituted with an aromatic ring.

The formula amount of the group represented by the formula (T1) is preferably 80 or more, more preferably 100 or more, further preferably 130 or more, and particularly preferably 150 or more. It is practical that the upper limit is 500 or less.

(Substituent T)
As the substituent T, an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, further preferably 1 to 6 carbon atoms) and an arylalkyl group (preferably 7 to 21 carbon atoms, more preferably 7 to 15 carbon atoms). , 7-11 is more preferred), an alkenyl group (preferably 2 to 24 carbon atoms, more preferably 2 to 12 and even more preferably 2 to 6), an alkynyl group (preferably 2 to 12 carbon atoms, 2 to 6 carbon atoms). More preferably, 2-3), hydroxyl group, amino group (preferably 0 to 24 carbon atoms, more preferably 0 to 12 and even more preferably 0 to 6), thiol group, carboxyl group, aryl group (carbon). Numbers 6 to 22 are preferred, 6 to 18 are more preferred, 6 to 10 are even more preferred), alkoxyl groups (1 to 12 carbon atoms are preferred, 1 to 6 are more preferred, 1-3 are more preferred), aryloxy. Group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 10), acyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, further preferably 2 to 3) , Acyloxy group (preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, further preferably 2 to 3 carbon atoms), allyloyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, further preferably 7 to 11 carbon atoms). (Preferably), allyloyloxy group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, further preferably 7 to 11), carbamoyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms 1). ~ 3 is more preferable), sulfamoyl group (preferably 0 to 12 carbon atoms, more preferably 0 to 6 and even more preferably 0 to 3), sulfo group, alkylsulfonyl group (preferably 1 to 12 carbon atoms, 1 to 1). 6 is more preferable, 1 to 3 are more preferable), an arylsulfonyl group (6 to 22 carbon atoms is preferable, 6 to 18 is more preferable, 6 to 10 is more preferable), and a heterocyclic group (1 to 12 carbon atoms is preferable). Preferably, 1 to 8 are more preferable, 2 to 5 are even more preferable, and a 5-membered ring or a 6-membered ring is preferably contained), a (meth) acryloyl group, a (meth) acryloyloxy group, a halogen atom (for example, a fluorine atom). , a chlorine atom, a bromine atom, an iodine atom), oxo (= O), imino (= NR ^N), an alkylidene group _{^{(= C (R N) 2}} ) , and the like. ^RN is a hydrogen atom or an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms), and a hydrogen atom, a methyl group, an ethyl group, or a propyl group is preferable. The alkyl moiety, alkenyl moiety, and alkynyl moiety contained in each substituent may be chain or cyclic, and may be linear or branched. When the substituent T is a group capable of taking a substituent, it may further have a substituent T. For example, the alkyl group may be an alkyl halide group, a (meth) acryloyloxyalkyl group, an aminoalkyl group or a carboxyalkyl group. When the substituent is a group capable of forming a salt such as a carboxyl group or an amino group, the group may form a salt.

(Connecting group L)
As the linking group L, an alkylene group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, further preferably 1 to 6 carbon atoms) and an alkenylene group (preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms). 2-3 are more preferred), alkynylene groups (2-12 carbon atoms are preferred, 2-6 are more preferred, 2-3 are more preferred), (oligo) alkyleneoxy groups (alkylene groups in one building block. The number of carbon atoms is preferably 1-12, more preferably 1-6, still more preferably 1-3; the number of repetitions is preferably 1-50, more preferably 1-40, even more preferably 1-30), arylene group ( It consists of an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, a thiocarbonyl group, -NR ^N- , and a combination thereof. Linking groups can be mentioned. The alkylene group may have a substituent T described later. For example, the alkylene group may have a hydroxyl group. The number of atoms contained in the linking group L is preferably 1 to 50, more preferably 1 to 40, and even more preferably 1 to 30, excluding hydrogen atoms. The number of linked atoms means the number of atoms located in the shortest path among the atomic groups involved in the linking. For example, in the case of −CH _2- (C = O) −O−, the number of atoms involved in the connection is 6, and even excluding the hydrogen atom, it is 4. On the other hand, the shortest atom involved in the connection is -C-C-O-, which is three. The number of connected atoms is preferably 1 to 24, more preferably 1 to 12, and even more preferably 1 to 6. The alkylene group, alkenylene group, alkynylene group, and (oligo) alkyleneoxy group may be chain or cyclic, and may be linear or branched. If the linking group is a group ^{capable of forming a salt such as −NR N} −, the group may form a salt. ^RN is a hydrogen atom or an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms), and a hydrogen atom, a methyl group, an ethyl group, or a propyl group is preferable.

The particular polymer is also preferably a copolymer. The copolymerization component preferably contains at least one of the structural units represented by any of the following formulas (11) to (15) (hereinafter, may be referred to as other structural units).

In formula (11), R ^11a represents a substituent and m11 represents an integer of 1 to 4. When m11 is 2 or more, the plurality of R ^11a may be the same or different, and the two R ^11a may be bonded to each other to form a ring. However, ^{at least one of m11 R 11a} represents a group represented by the formula (T2) described later.
In formula (12), R ^2a represents a hydrogen atom or a methyl group, R ^12a represents a substituent, and m12 represents an integer of 1-5. When m12 is 2 or more, the plurality of R ^12a may be the same or different, and the two R ^12a may be bonded to each other to form a ring. However, ^{at least one of m12 R 12a} represents a group represented by the formula (T2).
In formula (13), R ^3a represents a hydrogen atom or a methyl group, and R ^13a represents a group represented by formula (T2).
In formula (14), R ^4a represents a hydrogen atom or a methyl group, and R ^14a represents a group represented by formula (T2).
In formula (15), R ^15a represents a group represented by formula (T2).

^{Examples of the} substituent represented by R 11a and R ^12a include the above-mentioned substituent T and the group represented by the following formula (T2).

(Group represented by the formula (T2))
− (L ⁴ ) _n6 − (P) _n7 (T2)
L ⁴ is the above-mentioned linking group L, and among them, an alkylene group, an arylene group, a (oligo) alkyleneoxy group, a carbonyl group, an oxygen atom, and a linking group related to a combination thereof are preferable. n6 is 0 or 1, preferably 1. P is synonymous with equation (T1). n7 is an integer of 1 to 6, preferably 1 or 2. When n7 is 2 or more, L ⁴ may be a linking group having a valence of 3 or more. For example, a group having an alkane structure having a valence of 3 or more (preferably 1 to 12 carbon atoms, 1 to 6 are preferable). More preferably, 1 to 3 is more preferable), an alkene structure group (2 to 12 carbon atoms is preferable, 2 to 6 is more preferable, and 2 to 3 is more preferable), or an aryl structure group (6 to 22 carbon atoms is preferable). , 6-18 is more preferred, and 6-10 is even more preferred).

The formula amount of the group represented by the formula (T2) is preferably 80 or more, more preferably 100 or more, further preferably 130 or more, and particularly preferably 150 or more. It is practical that the upper limit is 500 or less.

When the specific polymer contains the structural unit represented by the formula (1), the structural unit represented by the formula (11) is preferable as the other structural unit. Similarly, it is preferable that the formulas (2) to (5) also include the structural units represented by the formulas (12) to (15), respectively.

It is also preferred that the particular polymer further comprises a structural unit without a polymerizable group (sometimes referred to as "another structural unit"). Further, examples of the structural unit include the structural units represented by the formulas (21) to (25).

In formula (21), R ^11b represents a substituent and m21 represents an integer of 1-4. When m21 is 2 or more, the plurality of R ^11b may be the same or different, and the two R ^11b may be bonded to each other to form a ring. However, ^{at least one of m21 R 11b} represents a group represented by the formula (T3).
In formula (22), R ^2b represents a hydrogen atom or a methyl group, R ^12b represents a substituent, and m22 represents an integer of 1-5. When m22 is 2 or more, the plurality of R ^12b may be the same or different, and the two R ^12b may be bonded to each other to form a ring. However, ^{at least one of m22 R 12b} represents a group represented by the formula (T3).
In formula (23), R ^3b represents a hydrogen atom or a methyl group, and R ^13b represents a group represented by formula (T3).
In formula (24), R ^4b represents a hydrogen atom or a methyl group, and R ^14b represents a group represented by formula (T3).
In formula (25), R ^15b represents a group represented by formula (T3).

^{Examples of the} substituent represented by R 11b and R ^12b include the above-mentioned substituent T and the group represented by the following formula (T3).

(Group represented by the formula (T3))
_{^{- (L 5) n8 - (}} T 1) n9 (T3)
L ⁵ is the above-mentioned linking group L, and among them, an alkylene group, an arylene group, a (oligo) alkyleneoxy group, a carbonyl group, an oxygen atom, and a linking group related to a combination thereof are preferable. n8 is 0 or 1. T ¹ is the above-mentioned substituent T, and among them, an alkyl group that may be substituted with a halogen atom, an aryl group that may be substituted with a halogen atom, and an arylalkyl group that may be substituted with a halogen atom. preferable. n9 is an integer of 1 to 6, preferably 1 or 2. When n9 is 2 or more, L ⁵ may be a linking group having a trivalent or higher value. For example, a group having an alkane structure having a trivalent or higher valence (1 to 12 carbon atoms is preferable, 1 to 6 is more preferable). , 1-3 are more preferred), alkene-structured groups (preferably 2-12 carbon atoms, more preferably 2-6, more preferably 2-3), or aryl-structured groups (preferably 6-22 carbon atoms). , 6-18 is more preferred, 6-10 is even more preferred).

In a specific polymer, the structural unit represented by any of the formulas (1) to (5) may constitute all of the polymer (hompolymer having a composition ratio of 100 mol%), or other structural units or the like. Further, it may be a copolymer with other constituent units.
In a specific polymer, the constituent units represented by the formulas (1) to (5) / other structural units (constituent units having a polymerizable group) / the constituent ratios of the other structural units are based on the molar ratio. It is preferably 10 to 100/0 to 80/0 to 50, more preferably 30 to 100/0 to 70/0 to 30, and even more preferably 50 to 100/0 to 50/0 to 10/0.
In a specific polymer, the proportion of the structural units having a polymerizable group is preferably 10 to 100 mol%, more preferably 50 to 100 mol% of all the structural units.
The specific polymer contains only one type of structural unit represented by the formulas (1) to (5), other structural units (constituent units having a polymerizable group), and other structural units. It may contain two or more kinds. When two or more kinds are included, it is preferable that the total is the above ratio.

The weight average molecular weight of the specific polymer is preferably 4000 or more, more preferably 5000 or more, further preferably 7000 or more, and even more preferably 10000 or more. The upper limit is preferably 20000 or less, more preferably 1500,000 or less, and even more preferably 1,000,000 or less. The method for measuring the weight average molecular weight shall be the method shown in Examples described later.

The content of the specific polymer in the composition for forming the underlayer film is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and preferably 0.1% by mass or more. More preferred. The upper limit is preferably 10% by mass or less, more preferably 7% by mass or less, further preferably 5% by mass or less, further preferably 4% by mass or less, and 3% by mass. % Or less is even more preferable, and it may be 1% by mass or less, or 0.7% by mass or less.
The content of the specific polymer in the non-volatile component (meaning the component other than the solvent in the composition, the same applies hereinafter) of the composition for forming the underlayer film is preferably 5% by mass or more, preferably 20% by mass or more. More preferably, it is more preferably 30% by mass or more, further preferably 50% by mass or more, further preferably 80% by mass or more, and even more preferably 90% by mass or more. , 95% by mass or more, or 99% by mass or more. The upper limit may be 100% by mass. By setting this amount to the above lower limit value or more, the effect of blending the polymer can be suitably exhibited, and a uniform thin film can be easily prepared. On the other hand, when the value is not more than the above upper limit, the effect of using the solvent is preferably exhibited, and it becomes easy to form a uniform film over a wide area. Only one type of specific polymer may be used, or two or more types may be used. When two or more types are used, the total amount is preferably in the above range.

[Thermosetting accelerator]
The composition for forming an underlayer film preferably contains a thermosetting accelerator. According to this aspect, it is easy to form a lower layer film having a high crosslink density, and diffusion of a liquid film provided on the lower layer film into the lower layer film can be effectively suppressed.

The thermosetting accelerator is preferably a compound that generates an acid or a cation at a temperature of 100 ° C. or higher (preferably 100 to 180 ° C., more preferably 120 to 180 ° C., still more preferably 120 to 160 ° C.).

The thermosetting accelerator is preferably a compound that generates an acid having a pKa of 4 or less, more preferably a compound that generates an acid having a pKa of 3 or less, and most preferably a compound that generates an acid of 2 or less. In the present invention, pKa basically refers to pKa in water at 25 ° C. Those that cannot be measured in water refer to those measured by changing to a solvent suitable for measurement. Specifically, pKa described in the Chemistry Handbook and the like can be referred to. The acid having a pKa of 3 or less is preferably a sulfonic acid or a phosphonic acid, and more preferably a sulfonic acid.

Examples of the heat curing accelerator include compounds that generate low nucleophilic acids such as sulfonic acid, carboxylic acid, and disulfonylimide by heating. As the above-mentioned acid, an acid having a pKa of 4 or less is preferable, an acid having a pKa of 3 or less is more preferable, and an acid having a pKa of 2 or less is further preferable. In the present invention, pKa basically refers to pKa in water at 25 ° C. Those that cannot be measured in water refer to those measured by changing to a solvent suitable for measurement.

Examples of the heat curing accelerator include onium salts such as sulfonium salt, benzothiazonium salt, ammonium salt and phosphonium salt, and sulfonium salt is preferable. Examples of the sulfonium salt include an alkyl sulfonium salt, a benzyl sulfonium salt, a dibenzyl sulfonium salt, a substituted benzyl sulfonium salt and the like. Examples of commercially available thermosetting accelerators include Sun Aid SI-60, 100, 110, 150 (all manufactured by Sanshin Chemical Industry Co., Ltd.).

Further, in the present invention, the compounds described in paragraphs 0033 to 0047 of JP-A-2017-088866 can also be used as the thermosetting accelerator.

The content of the thermosetting accelerator in the composition for forming the underlayer film is preferably 0.0001% by mass or more, more preferably 0.001% by mass or more, and 0.003% by mass or more. Is even more preferable. The upper limit is preferably 0.03% by mass or less, more preferably 0.02% by mass or less, and further preferably 0.01% by mass or less.
The content of the thermosetting accelerator in the non-volatile component (meaning the component other than the solvent in the composition, the same applies hereinafter) of the composition for forming the underlayer film is preferably 0.1% by mass or more, and is preferably 1% by mass. % Or more is more preferable, and 3% by mass or more is further preferable. The upper limit is preferably 30% by mass or less, more preferably 20% by mass or less, and further preferably 10% by mass or less.
The content of the thermosetting accelerator is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the above-mentioned specific polymer. The lower limit is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and further preferably 3 parts by mass or more. The upper limit is preferably 25 parts by mass or less, more preferably 20 parts by mass or less, and further preferably 10 parts by mass or less. Only one type of thermosetting accelerator may be used, or two or more types may be used. When two or more types are used, the total amount is preferably in the above range.

[solvent]
The composition for forming an underlayer film preferably contains a solvent (hereinafter, may be referred to as a "solvent for an underlayer film"). The solvent is preferably, for example, a compound that is liquid at 23 ° C. and has a boiling point of 250 ° C. or lower. Usually, the non-volatile component finally forms the underlayer film. The composition for forming the lower layer film preferably contains 99.0% by mass or more of the solvent for the lower layer film, more preferably 99.5% by mass or more, and may contain 99.6% by mass or more. When the content of the solvent is within the above range, it is easy to form a thin underlayer film. Only one type of solvent may be contained in the composition for forming the lower layer film, or two or more types of the solvent may be contained. When two or more kinds are included, the total amount is preferably in the above range.
The boiling point of the solvent for the underlayer film is preferably 230 ° C. or lower, more preferably 200 ° C. or lower, further preferably 180 ° C. or lower, further preferably 160 ° C. or lower, and 130 ° C. or lower. Is even more preferable. It is practical that the lower limit is 23 ° C, but it is more practical that it is 60 ° C or higher. By setting the boiling point in the above range, the solvent can be easily removed from the underlayer film, which is preferable.

The solvent for the underlayer film is preferably an organic solvent. The solvent is preferably a solvent having at least one of an ester group, a carbonyl group, a hydroxyl group and an ether group. Of these, it is preferable to use an aprotic polar solvent.

As specific examples, alkoxy alcohols, propylene glycol monoalkyl ether carboxylates, propylene glycol monoalkyl ethers, lactic acid esters, acetate esters, alkoxypropionic acid esters, chain ketones, cyclic ketones, lactones, and alkylene carbonates are selected.

Examples of the alkoxy alcohol include methoxyethanol, ethoxyethanol, methoxypropanol (for example, 1-methoxy-2-propanol), ethoxypropanol (for example, 1-ethoxy-2-propanol), and propoxypropanol (for example, 1-propanol-2-. (Propanol), methoxybutanol (eg 1-methoxy-2-butanol, 1-methoxy-3-butanol), ethoxybutanol (eg 1-ethoxy-2-butanol, 1-ethoxy-3-butanol), methylpentanol (For example, 4-methyl-2-pentanol) and the like.

As the propylene glycol monoalkyl ether carboxylate, at least one selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, and propylene glycol monoethyl ether acetate is preferable, and propylene glycol monomethyl ether acetate (propylene glycol monomethyl ether acetate). PGMEA) is particularly preferable.

Further, as the propylene glycol monoalkyl ether, propylene glycol monomethyl ether (PGME) or propylene glycol monoethyl ether is preferable.
As the lactate ester, ethyl lactate, butyl lactate, or propyl lactate is preferable.
As the acetic acid ester, methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, isoamyl acetate, methyl acetate, ethyl formate, butyl acetate, propyl acetate, or 3-methoxybutyl acetate are preferable.
As the alkoxypropionate ester, methyl 3-methoxypropionate (MMP) or ethyl 3-ethoxypropionate (EEP) is preferable.
Chain ketones include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutylketone, phenylacetone, methylethylketone, methylisobutylketone, acetylacetone, Acetoneacetone, ionone, diacetonyl alcohol, acetylcarbinol, acetophenone, methylnaphthyl ketone or methyl amyl ketone are preferred.
As the cyclic ketone, methylcyclohexanone, isophorone or cyclohexanone is preferable.
As the lactone, γ-butyrolactone (γBL) is preferable.
As the alkylene carbonate, propylene carbonate is preferable.

In addition to the above components, it is preferable to use an ester solvent having 7 or more carbon atoms (preferably 7 to 14, more preferably 7 to 12 and even more preferably 7 to 10) and having a heteroatom number of 2 or less.

Preferred examples of ester-based solvents having 7 or more carbon atoms and 2 or less heteroatomic atoms include amyl acetate, 2-methylbutyl acetate, 1-methylbutyl acetate, hexyl acetate, pentyl propionate, hexyl propionate, and butyl propionate. Examples thereof include isobutyl isobutyrate, heptyl propionate, butyl butanoate and the like, and isoamyl acetate is particularly preferable.

It is also preferable to use a solvent having a flash point (hereinafter, also referred to as p component) of 30 ° C. or higher. Examples of such components include propylene glycol monomethyl ether (p component: 47 ° C.), ethyl lactate (p component: 53 ° C.), ethyl 3-ethoxypropionate (p component: 49 ° C.), and methylamyl ketone (p component: 49 ° C.). 42 ° C.), cyclohexanone (p component: 30 ° C.), pentyl acetate (p component: 45 ° C.), methyl 2-hydroxyisobutyrate (p component: 45 ° C.), γ-butyrolactone (p component: 101 ° C.) or propylene carbonate. (P component: 132 ° C.) is preferable. Of these, propylene glycol monoethyl ether, ethyl lactate, pentyl acetate or cyclohexanone are more preferred, and propylene glycol monoethyl ether or ethyl lactate is particularly preferred.

Among the preferred solvents for the underlayer film are alkoxyalcohol, propylene glycol monoalkyl ether carboxylate, propylene glycol monoalkyl ether, lactic acid ester, acetate ester, alkoxypropionic acid ester, chain ketone, cyclic ketone, lactone, and alkylene. Examples include carbonates.

[Alkylene glycol compound]
The composition for forming an underlayer film may contain an alkylene glycol compound. The alkylene glycol compound preferably has 3 to 1000 alkylene glycol constituent units, more preferably 4 to 500, still more preferably 5 to 100, and 5 to 100. It is more preferable to have 50 of them. The weight average molecular weight (Mw) of the alkylene glycol compound is preferably 150 to 10000, more preferably 200 to 5000, further preferably 300 to 3000, and even more preferably 300 to 1000.
The alkylene glycol compounds are polyethylene glycol, polypropylene glycol, these mono or dimethyl ethers, mono or dioctyl ethers, mono or dinonyl ethers, mono or didecyl ethers, monostearic acid esters, monooleic acid esters, monoadiponic acid esters, monosuccinates. Acid esters are exemplified, and polyethylene glycol and polypropylene glycol are preferable.
The surface tension of the alkylene glycol compound at 23 ° C. is preferably 38.0 mN / m or more, and more preferably 40.0 mN / m or more. The upper limit of surface tension is not particularly specified, but is, for example, 48.0 mN / m or less. By blending such a compound, the wettability of the photocurable composition for imprinting can be further improved.
The surface tension of the alkylene glycol compound is measured by using a surface tension meter SURFACE TENS-IOMETER CBVP-A3 manufactured by Kyowa Interface Science Co., Ltd. and using a glass plate at 23 ° C. The unit is mN / m. Two samples are prepared for each level and measured three times each. The arithmetic mean value of a total of 6 times is adopted as the evaluation value.

When blended, the content of the alkylene glycol compound is preferably 40% by mass or less, more preferably 30% by mass or less, and 20% by mass or less of the non-volatile component in the composition for forming an underlayer film. It is more preferable that there is, and it is particularly preferable that it is 15% by mass or less. The lower limit can be 0.5% by mass or more, and can be 1% by mass or more. Only one kind of alkylene glycol compound may be used, or two or more kinds may be used. When two or more types are used, the total amount is preferably in the above range.

[Polymerization initiator]
The composition for forming an underlayer film may contain a polymerization initiator. Examples of the polymerization initiator include a thermal polymerization initiator and a photopolymerization initiator, and a photopolymerization initiator is preferable. Examples of the photopolymerization initiator include a photoradical polymerization initiator and a photocationic polymerization initiator, and a photoradical polymerization initiator is more preferable. When the composition for forming the lower layer film contains a polymerization initiator, the reaction of the polymerizable groups contained in the composition for forming the lower layer film is promoted, and the crosslink density of the lower layer film can be further improved.

As the photopolymerization initiator, a known compound can be arbitrarily used. For example, halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds, hexaarylbiimidazole compounds, oxime compounds, organic peroxides. , Thio compounds, ketone compounds, aromatic onium salts, acetophenone compounds, azo compounds, azide compounds, metallocene compounds, organic boron compounds, iron arene complexes and the like. For details thereof, the description in paragraphs 0165 to 0182 of JP-A-2016-0273557 can be referred to, and the contents thereof are incorporated in the present specification. Of these, acetophenone compounds, acylphosphine compounds, and oxime compounds are preferable. Commercially available products include IRGACURE-OXE01, IRGACURE-OXE02, IRGACURE-127, IRGACURE-819, IRGACURE-379, IRGACURE-369, IRGACURE-754, IRGACURE-1800, IRGACURE-651, IRGACURE-907, IRGACURE-907. -1173 and the like (above, manufactured by BASF), Omnirad 184, Omnirad TPO H, Omnirad 819, Omnirad 1173 (all manufactured by IGM Resins BV).

When the polymerization initiator is contained, it is preferably 0.0001 to 5% by mass, more preferably 0.0005 to 3% by mass, and 0.01. It is more preferably ~ 1% by mass. When two or more kinds of polymerization initiators are used, the total amount thereof is preferably in the above range.

[Other ingredients]
In addition to the above, the composition for forming an underlayer film may contain one or more kinds of polymerization inhibitors, antioxidants, leveling agents, thickeners, surfactants and the like. As for these components, each component described in JP-A-2013-036027, JP-A-2014-090133, and JP-A-2013-189537 can be used. Regarding the content and the like, the description in the above publication can be taken into consideration.

<< Composition for forming a liquid film >>
Next, the liquid film forming composition used for the imprint laminate of the present invention will be described.

The viscosity of the liquid film forming composition is preferably 1,000 mPa · s or less, more preferably 800 mPa · s or less, further preferably 500 mPa · s or less, and 100 mPa · s or less. Is even more preferable. The lower limit of the viscosity is not particularly limited, but can be, for example, 1 mPa · s or more. Viscosity is measured according to the method below.
The viscosity is measured by adjusting the temperature of the sample cup to 23 ° C. using an E-type rotational viscometer RE85L manufactured by Toki Sangyo Co., Ltd. and a standard cone rotor (1 ° 34'x R24). The unit is mPa · s. Other details regarding the measurement are in accordance with JISZ8803: 2011. Two samples are prepared for each level and measured three times each. The arithmetic mean value of a total of 6 times is adopted as the evaluation value.

[Polymerizable compound A]
The liquid film forming composition contains a polymerizable compound (polymerizable compound A) that is liquid at 23 ° C. and 1 atm.

The viscosity of the polymerizable compound A at 23 ° C. is preferably 1 to 100,000 mPa · s. The lower limit is preferably 5 mPa · s or more, and more preferably 11 mPa · s or more. The upper limit is preferably 1,000 mPa · s or less, and more preferably 600 mPa · s or less.

The polymerizable compound A may be a monofunctional polymerizable compound having only one polymerizable group in one molecule, or a polyfunctional polymerizable compound having two or more polymerizable groups in one molecule. You may. A monofunctional polymerizable compound and a polyfunctional polymerizable compound may be used in combination. Among them, the polymerizable compound A contained in the liquid film forming composition preferably contains a polyfunctional polymerizable compound for the reason of suppressing pattern collapse, and is polymerizable containing 2 to 5 polymerizable groups in one molecule. It is more preferable to contain a compound, further preferably to contain a polymerizable compound containing 2 to 4 polymerizable groups in one molecule, and particularly preferably to contain a polymerizable compound containing two polymerizable groups in one molecule. preferable.

The polymerizable compound A includes an aromatic ring (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 10 carbon atoms) and an alicyclic ring (preferably 3 to 24 carbon atoms, 3 to 18 carbon atoms). More preferably, 3 to 6 is more preferable), and it is more preferable to contain an aromatic ring. The aromatic ring is preferably a benzene ring. The molecular weight of the polymerizable compound A is preferably 100 to 900.

Examples of the polymerizable group contained in the polymerizable compound A include a (meth) acryloyl group, an oxylanyl group, and an oxetanyl group, and a (meth) acryloyl group is preferable. Further, the polymerizable compound A is preferably a radically polymerizable compound.

The polymerizable compound A is also preferably a compound represented by the following formula (I-1).

L ²⁰ is a 1 + q2-valent linking group, for example, a 1 + q2-valent group having an alkane structure (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 3 carbon atoms), and an alkene structure group. (Preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, further preferably 2 to 3 carbon atoms), Group having an aryl structure (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 10 carbon atoms). ), A group having a heteroaryl structure (preferably 1 to 22 carbon atoms, more preferably 1 to 18 carbon atoms, further preferably 1 to 10 carbon atoms, and examples of the heteroatom include a nitrogen atom, a sulfur atom, and an oxygen atom. , 6-membered ring, 7-membered ring is preferable), or a linking group containing a group combining these. Examples of the group in which two aryl groups are combined include a group having a structure such as biphenyl, diphenylalkane, biphenylene, and indene. Examples of the combination of the heteroaryl structure group and the aryl structure group include groups having a structure such as indole, benzimidazole, quinoxaline, and carbazole.
L ²⁰ is preferably a linking group containing at least one selected from an aryl structure group and a heteroaryl structure group, and more preferably a linking group containing an aryl structure group.

R ²¹ and R ²² independently represent a hydrogen atom or a methyl group, respectively.

L ²¹ and L ²² each independently represent a single bond or the above-mentioned linking group L, and are preferably a single bond or an alkylene group.
L ²⁰ and L ²¹ or L ²² may be combined with or without the linking group L to form a ring. L ²⁰ , L ²¹ and L ²² may have the above-mentioned substituent T. A plurality of substituents T may be bonded to form a ring. When there are a plurality of substituents T, they may be the same or different from each other.
q2 is an integer of 0 to 5, preferably an integer of 0 to 3, more preferably an integer of 0 to 2, even more preferably 0 or 1, and particularly preferably 1.

Examples of the polymerizable compound A include the compounds described in paragraphs 0017 to 0024 and Examples of JP-A-2014-090133, the compounds described in paragraphs 0024 to 0089 of JP-A-2015-009171, and JP-A-2015-070145. The compounds described in paragraphs 0023 to 0037 of the publication and the compounds described in paragraphs 0012 to 0039 of the International Publication WO2016 / 152597 can also be used.

The content of the polymerizable compound A in the liquid film forming composition is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and 0.1% by mass or more. Is even more preferable. The upper limit is preferably 10% by mass or less, more preferably 5% by mass or less, and further preferably 1% by mass or less.
The content of the polymerizable compound A in the non-volatile components of the liquid film forming composition (referring to components other than the solvent in the composition, the same applies hereinafter) is preferably 0.01% by mass or more, and 0. It is more preferably 05% by mass or more, and further preferably 0.1% by mass or more. The upper limit may be 100% by mass. Only one type of the polymerizable compound A may be used, or two or more types may be used. When two or more types are used, the total amount is preferably in the above range.
Further, it is also preferable that the non-volatile component of the liquid film forming composition is substantially composed of only the polymerizable compound A. When the non-volatile component of the liquid film-forming composition is substantially composed of the polymerizable compound A only, the content of the polymerizable compound A in the non-volatile component of the liquid film-forming composition is 99.9% by mass. This means that the content is more preferably 99.99% by mass or more, and further preferably composed of only the polymerizable compound A.

[solvent]
The liquid film forming composition preferably contains a solvent (hereinafter, may be referred to as "liquid film solvent"). Examples of the solvent for the liquid film include those described in the above-mentioned solvent for the underlayer film, and these can be used. The liquid film forming composition preferably contains a liquid film solvent in an amount of 90% by mass or more, more preferably 99% by mass or more, and may contain 99.99% by mass or more.
The boiling point of the liquid film solvent is preferably 230 ° C. or lower, more preferably 200 ° C. or lower, further preferably 180 ° C. or lower, further preferably 160 ° C. or lower, and 130 ° C. or lower. Is even more preferable. It is practical that the lower limit is 23 ° C, but it is more practical that it is 60 ° C or higher. By setting the boiling point in the above range, the solvent can be easily removed from the liquid film, which is preferable.

[Polymerization initiator]
The liquid film forming composition may contain a polymerization initiator. Examples of the polymerization initiator include a thermal polymerization initiator and a photopolymerization initiator, and a photopolymerization initiator is preferable, and a photoradical polymerization initiator is more preferable. Examples of the polymerization initiator include those described in the section of the composition for forming an underlayer film described above, and these can be used.

When the polymerization initiator is contained, it is preferably 0.1 to 10% by mass, more preferably 1 to 8% by mass, and 2 to 5% by mass of the non-volatile component of the liquid film forming composition. Is more preferable. When two or more kinds of polymerization initiators are used, the total amount thereof is preferably in the above range.

[Other ingredients]
In addition to the above, the liquid film forming composition may contain one or more kinds of polymerization inhibitors, antioxidants, leveling agents, thickeners, surfactants and the like.

<< Photocurable composition for imprint >>
Next, the photocurable composition for imprint used in the laminate for imprint of the present invention will be described. In the present invention, the photocurable composition for imprint is not particularly specified, and a known photocurable composition for imprint can be used. The photocurable composition for imprint preferably contains at least a polymerizable compound.

The viscosity of the photocurable composition for imprint is preferably 20 mPa · s or less, more preferably 15 mPa · s or less, further preferably 11 mPa · s or less, and 9 mPa · s or less. Is even more preferable. The lower limit of the viscosity is not particularly limited, but may be, for example, 5 mPa · s or more. Viscosity is measured according to the method below.
The viscosity is measured by adjusting the temperature of the sample cup to 23 ° C. using an E-type rotational viscometer RE85L manufactured by Toki Sangyo Co., Ltd. and a standard cone rotor (1 ° 34'x R24). The unit is mPa · s. Other details regarding the measurement are in accordance with JISZ8803: 2011. Two samples are prepared for each level and measured three times each. The arithmetic mean value of a total of 6 times is adopted as the evaluation value.

The surface tension of the photocurable composition for imprint is preferably 28 mN / m or more, more preferably 30 mN / m or more, and further preferably 32 mN / m or more. By using the photocurable composition for imprint having a high surface tension, the capillary force is increased, and the photocurable composition for imprint can be filled into the mold pattern at high speed. The upper limit of the surface tension is not particularly limited, but from the viewpoint of imparting inkjet suitability, it is preferably 40 mN / m or less, more preferably 38 mN / m or less, and 36 mN / m. It may be m or less. The surface tension of the photocurable composition for imprinting is measured according to the following method.
The surface tension was measured at 23 ° C. using a glass plate using a surface tension meter SURFACE TENS-IOMETER CBVP-A3 manufactured by Kyowa Interface Science Co., Ltd. The unit is expressed in mN / m. Two samples were prepared for each level and measured three times each. The arithmetic mean value of a total of 6 times is adopted as the evaluation value.

The Onishi parameter of the photocurable composition for imprint is preferably 5 or less, more preferably 4 or less, and further preferably 3.7 or less. The lower limit of the Onishi parameter of the photocurable composition for imprint is not particularly specified, but may be, for example, 1 or more, or 2 or more.
The Onishi parameter can be obtained by substituting the numbers of carbon atoms, hydrogen atoms, and oxygen atoms of all the constituents into the following equations for the non-volatile components of the photocurable composition for imprint.
Onishi parameter = sum of the number of carbon atoms, hydrogen atoms and oxygen atoms / (number of carbon atoms-number of oxygen atoms)

The imprint photocurable composition used in the present invention has a ΔHSP value calculated by the following mathematical formula (H1) based on the Hansen solubility parameter of the liquid film and the Hansen solubility parameter of the imprint photocurable composition. It is preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less. The lower limit may be 0. When the value of ΔHSP is 10 or less, the effect of droplet expandability of the photocurable composition 13 for imprint can be expected.
ΔHSP = (4.0 × ΔD ² + ΔP ² + ΔH ² ) ^0.5 (H1)
ΔD is the difference between the dispersion term component of the Hansen solubility parameter vector of the photocurable composition for imprint and the dispersion term component of the Hansen solubility parameter vector of the liquid film, and ΔP is the photocurable composition for imprint. The difference between the polar term component of the Hansen solubility parameter vector and the polar term component of the Hansen solubility parameter vector of the liquid film, where ΔH is the hydrogen bond term component of the Hansen solubility parameter vector of the photocurable composition for imprint and the liquid. It is the difference of the hydrogen bond term component of the Hansen solubility parameter vector of the film.

The dispersion term component of the Hansen solubility parameter vector of the photocurable composition for imprint is preferably 8 to 25, more preferably 10 to 20, and even more preferably 14 to 18.
The polar term component of the Hansen solubility parameter vector of the photocurable composition for imprint is preferably 1 to 10, more preferably 2 to 8, and even more preferably 3 to 5.
The hydrogen bond term component of the Hansen solubility parameter vector of the photocurable composition for imprint is preferably 1 to 15, more preferably 3 to 10, and even more preferably 3 to 8.

The dispersion term component, the polar term component, and the hydrogen bond term component of the Hansen solubility parameter vector of the liquid film and the photocurable composition for imprint are set by the methods described in Examples described later, respectively. Further, in the present invention, the dispersion term component, the polar term component and the hydrogen bond term component of the Hansen solubility parameter vector of the liquid film are the dispersion of the Hansen solubility parameter of the non-volatile component (component other than the solvent) of the liquid film forming composition. The values of the term component, the polar term component and the hydrogen bond term component shall be used.

[Polymerizable compound]
The photocurable composition for imprint preferably contains a polymerizable compound. The polymerizable group contained in the polymerizable compound is preferably a (meth) acryloyl group. Further, the polymerizable compound is preferably a radically polymerizable compound.

The polymerizable compound may be a monofunctional polymerizable compound having only one polymerizable group in one molecule, or a polyfunctional polymerizable compound having two or more polymerizable groups in one molecule. May be good. A monofunctional polymerizable compound and a polyfunctional polymerizable compound may be used in combination. The polymerizable compound contained in the photocurable composition for imprint preferably contains a polyfunctional polymerizable compound, and more preferably contains a polymerizable compound containing 2 to 5 polymerizable groups in one molecule. It is more preferable to contain a polymerizable compound containing 2 to 4 polymerizable groups in one molecule, and it is particularly preferable to contain a polymerizable compound containing two polymerizable groups in one molecule.

Further, at least one of the polymerizable compounds contained in the photocurable composition for imprint includes an aromatic ring (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 10 carbon atoms) and an alicyclic compound. It preferably contains at least one of the rings (preferably 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, still more preferably 3 to 6 carbon atoms), and even more preferably an aromatic ring. The aromatic ring is preferably a benzene ring. The molecular weight of the polymerizable compound is preferably 100 to 900.

It is also preferable that at least one of the above-mentioned polymerizable compounds is a compound represented by the following formula (I-1).

L ²⁰ is a 1 + q2-valent linking group, for example, a 1 + q2-valent group having an alkane structure (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 3 carbon atoms), and an alkene structure group. (Preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, further preferably 2 to 3 carbon atoms), Group having an aryl structure (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 10 carbon atoms). ), A group having a heteroaryl structure (preferably 1 to 22 carbon atoms, more preferably 1 to 18 carbon atoms, further preferably 1 to 10 carbon atoms, and examples of the heteroatom include a nitrogen atom, a sulfur atom, and an oxygen atom. , 6-membered ring, 7-membered ring is preferable), or a linking group containing a group combining these. Examples of the group in which two aryl groups are combined include a group having a structure such as biphenyl, diphenylalkane, biphenylene, and indene. Examples of the combination of the heteroaryl structure group and the aryl structure group include groups having a structure such as indole, benzimidazole, quinoxaline, and carbazole.
L ²⁰ is preferably a linking group containing at least one selected from an aryl structure group and a heteroaryl structure group, and more preferably a linking group containing an aryl structure group.

R ²¹ and R ²² independently represent a hydrogen atom or a methyl group, respectively.

L ²¹ and L ²² each independently represent a single bond or the above-mentioned linking group L, and are preferably a single bond or an alkylene group.
L ²⁰ and L ²¹ or L ²² may be combined with or without the linking group L to form a ring. L ²⁰ , L ²¹ and L ²² may have the above-mentioned substituent T. A plurality of substituents T may be bonded to form a ring. When there are a plurality of substituents T, they may be the same or different from each other.
q2 is an integer of 0 to 5, preferably an integer of 0 to 3, more preferably an integer of 0 to 2, even more preferably 0 or 1, and particularly preferably 1.

Examples of the polymerizable compound include the compounds used in Examples described later, paragraphs 0017 to 0024 of JP-A-2014-090133 and the compounds described in Examples, paragraphs 0024-0089 of JP-A-2015-009171. , The compounds described in paragraphs 0023 to 0037 of JP2015-070145A, and the compounds described in paragraphs 0012 to 0039 of International Publication WO2016 / 152597, but the present invention is limited thereto. It is not interpreted as.

The polymerizable compound is preferably contained in the photocurable composition for imprint in an amount of 30% by mass or more, more preferably 45% by mass or more, further preferably 50% by mass or more, further preferably 55% by mass or more, and 60% by mass or more. It may be 70% by mass or more, and may be 70% by mass or more. Further, the upper limit value is preferably less than 99% by mass, more preferably 98% by mass or less, and may be 97% by mass or less.

[Photopolymerization initiator]
The photocurable composition for imprint preferably contains a photopolymerization initiator. As the photopolymerization initiator, any compound that generates an active species that polymerizes the polymerizable compound by light irradiation can be used. The photopolymerization initiator is preferably a radical polymerization initiator. Further, in the present invention, a plurality of types of photopolymerization initiators may be used in combination.

As the photopolymerization initiator, a known compound can be arbitrarily used. For example, halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds, hexaarylbiimidazole compounds, oxime compounds, organic peroxides. , Thio compounds, ketone compounds, aromatic onium salts, acetophenone compounds, azo compounds, azide compounds, metallocene compounds, organic boron compounds, iron arene complexes and the like. For details thereof, the description in paragraphs 0165 to 0182 of JP-A-2016-0273557 can be referred to, and the contents thereof are incorporated in the present specification. Of these, acetophenone compounds, acylphosphine compounds, and oxime compounds are preferable. Commercially available products include IRGACURE-OXE01, IRGACURE-OXE02, IRGACURE-127, IRGACURE-819, IRGACURE-379, IRGACURE-369, IRGACURE-754, IRGACURE-1800, IRGACURE-651, IRGACURE-907, IRGACURE-907. -1173 and the like (above, manufactured by BASF), Omnirad 184, Omnirad TPO H, Omnirad 819, Omnirad 1173 (all manufactured by IGM Resins BV).

The photopolymerization initiator is preferably contained in the photocurable composition for imprint in an amount of 0.01 to 15% by mass, more preferably 0.1 to 12% by mass, still more preferably 0.2 to 7% by mass. It is mass%.

[Other ingredients]
The photocurable composition for imprint may further contain a surfactant, a sensitizer, a mold release agent, an antioxidant, a polymerization inhibitor and the like. Specific examples of the photocurable composition for imprint that can be used in the present invention include the compositions described in JP2013-036027, JP2014-090133, and JP2013-189537. Illustrated, these contents are incorporated herein. Further, regarding the method for preparing the photocurable composition for imprint, the description in the above publication can be taken into consideration, and these contents are incorporated in the present specification.

The content of the solvent in the photocurable composition for imprint is preferably 5% by mass or less, more preferably 3% by mass or less, and 1% by mass or less. It is more preferable to have.
The photocurable composition for imprint has a polymer (preferably a weight average molecular weight of more than 1,000, more preferably a weight average molecular weight of more than 2,000, still more preferably a weight average molecular weight of 10,000 or more. It is also possible to have a mode in which the polymer) is substantially not contained. The term "substantially free of polymer" means, for example, that the content of the polymer is 0.01% by mass or less of the photocurable composition for imprinting, preferably 0.005% by mass or less, and does not contain the polymer at all. Is more preferable.

<Kit>
Next, the kit of the present invention will be described. The kit of the present invention is a kit used for the above-mentioned imprint laminate of the present invention, and is a composition for forming an underlayer film containing a polymer having an aromatic ring and a polymerizable group, and 23 ° C. and 1 atm. A composition for forming a liquid film containing a polymerizable compound which is liquid in the above, and a photocurable composition for imprinting are included. Examples of the underlayer film forming composition, the liquid film forming composition, and the photocurable composition for imprinting include those described above, and the preferred ranges are also the same.

<Manufacturing method of laminate for imprint>
Next, a method for producing the imprint laminate of the present invention will be described.
The method for producing an imprint laminate of the present invention includes a step of applying a composition for forming an underlayer film containing a polymer having an aromatic ring and a polymerizable group on a substrate to form an underlayer film.
A step of forming a liquid film by applying a liquid film forming composition containing a polymerizable compound that is liquid at 23 ° C. and 1 atm on the lower layer film.
It includes a step of applying a photocurable composition for imprinting on a liquid film. Hereinafter, each step will be described.

In the step of forming the lower layer film, a lower layer film forming composition containing a polymer having an aromatic ring and a polymerizable group is applied on the substrate to form the lower layer film. The substrate to which the composition for forming the underlayer film is applied is not particularly limited. The one described in the section of the laminate for imprint described above is used. Further, as the composition for forming the underlayer film, the composition described in the above-mentioned section of the laminate for imprinting is used. The lower layer film is preferably formed by applying the lower layer film forming composition on the substrate in a layered manner. An adhesive film may be provided on the surface of the substrate under the lower layer film.

The application method of the composition for forming an underlayer film is not particularly specified, and a generally well-known application method can be adopted. For example, a dip coating method, an air knife coating method, a curtain coating method, a wire bar coating method, a gravure coating method, an extrusion coating method, a spin coating method, a slit scan method, and an inkjet method are exemplified, and the spin coating method is preferable. It is also preferable that the composition for forming an underlayer film is applied in a layered manner on the substrate, and then the solvent is preferably volatilized (dried) by heat to form the underlayer film. Further, after drying, it is also preferable to further heat (bake) at a temperature of 100 to 300 ° C. (preferably 130 to 260 ° C., more preferably 150 to 230 ° C.). The heating time is preferably 30 seconds to 5 minutes.

Next, a liquid film forming composition containing a polymerizable compound that is liquid at 23 ° C. and 1 atm is applied onto the lower layer film to form a liquid film. The liquid film is preferably formed by applying the liquid film forming composition on the lower layer film in a layered manner. As the liquid film forming composition, the composition described in the above-mentioned section of the imprint laminate is used.

The application method of the liquid film forming composition is not particularly specified, and a generally well-known application method can be adopted. For example, a dip coating method, an air knife coating method, a curtain coating method, a wire bar coating method, a gravure coating method, an extrusion coating method, a spin coating method, a slit scan method, and an inkjet method are exemplified, and the spin coating method is preferable. It is also preferable that the liquid film forming composition is applied in layers on the lower layer film, and then the solvent is preferably volatilized (dried) by heat to form a liquid film. When the solvent is volatilized by heat, the heating temperature is preferably 80 to 200 ° C, more preferably 80 to 180 ° C, still more preferably 80 to 150 ° C. Further, the heating temperature is preferably a temperature lower than the temperature at which the polymerizable compound contained in the liquid film forming composition is reactively cured. The heating time is preferably 30 seconds to 5 minutes.

Next, the photocurable composition for imprinting is applied on the liquid film. As the photocurable composition for imprint, the one described in the above-mentioned section of the laminate for imprint is used. The method of applying the photocurable composition for imprint is not particularly specified, and the description in paragraph 0102 of JP-A-2010-109092 (the publication number of the corresponding US application is US2011 / 0183127) can be referred to. The contents are incorporated herein by reference. The photocurable composition for imprinting is preferably applied to the surface of the liquid film by an inkjet method. Further, the photocurable composition for imprint may be applied by multiple coating. In a method of arranging droplets on the surface of a liquid film by an inkjet method or the like, the amount of droplets is preferably about 1 to 20 pL, and it is preferable to arrange the droplets on the surface of the liquid film at intervals. The droplet interval is preferably 10 to 1000 μm. In the case of the inkjet method, the droplet interval is the arrangement interval of the inkjet nozzles.

In this way, the imprint laminate of the present invention can be produced.

<Pattern formation method>
Next, the pattern forming method of the present invention will be described.
The pattern forming method of the present invention includes a step of applying a composition for forming an underlayer film containing a polymer having an aromatic ring and a polymerizable group on a substrate to form an underlayer film.
A step of forming a liquid film by applying a liquid film forming composition containing a polymerizable compound that is liquid at 23 ° C. and 1 atm on the lower layer film.
The process of applying the photocurable composition for imprinting on the liquid film, and
The process of contacting the photocurable composition for imprinting on the liquid film with the mold having a pattern,
The process of exposing the photocurable composition for imprinting in contact with the mold, and
The step of peeling the mold from the exposed photocurable composition for imprint and
including. By going through such a step, a desired cured product pattern (imprint pattern) can be obtained. Hereinafter, the pattern forming method of the present invention will be described with reference to the drawings.

The step of forming the underlayer film, the step of forming the liquid film, and the step of applying the photocurable composition for imprinting are synonymous with the contents described in the above-mentioned section of the method for producing a laminate for imprinting. In this way, the imprint laminate shown in FIG. 1 is formed.

Next, as shown in FIG. 2, the photocurable composition 13 for imprinting on the liquid film 12 and the mold 20 having a pattern are brought into contact with each other. Specifically, the mold 20 is pressed against the surface of the photocurable composition 13 for imprinting.

The mold 20 may be a light-transmitting mold or a light-impermeable mold. When a light-transmitting mold is used, it is preferable to irradiate the photocurable composition 13 for imprinting with light from the mold 20 side. On the other hand, when a light-transmissive mold is used, it is preferable to use a light-transparent substrate as the substrate 1 and irradiate light from the substrate 1 side. In the present invention, it is more preferable to use a light-transmitting mold and irradiate light from the mold 20 side.

The mold that can be used in the present invention is a mold having a pattern to be transferred. The pattern possessed by the mold can be formed according to a desired processing accuracy by, for example, photolithography or an electron beam drawing method, but the mold pattern manufacturing method is not particularly limited in the present invention. Further, the pattern formed by the cured product pattern manufacturing method according to the preferred embodiment of the present invention can also be used as a mold.
The material constituting the light-transmitting mold used in the present invention is not particularly limited, but is limited to glass, quartz, polymethylmethacrylate (PMMA), light-transmitting resin such as polycarbonate resin, transparent metal vapor-deposited film, polydimethylsiloxane, and the like. A flexible film, a photocurable film, a metal film and the like are exemplified, and quartz is preferable.
The non-light-transmitting mold material used when the light-transmitting substrate is used in the present invention is not particularly limited, but may be any material having a predetermined strength. Specific examples include ceramic materials, vapor-deposited films, magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, and Fe, and substrates such as SiC, silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon. It is not particularly restricted.

When the photocurable composition 13 for imprinting on the liquid film 12 and the mold 20 having a pattern are brought into contact with each other, the mold pressure is preferably 10 atm or less. By setting the mold pressure to 10 atm or less, the mold 20 and the substrate 1 are less likely to be deformed, and the pattern accuracy tends to be improved. It is also preferable because the pressing force is low and the device tends to be reduced in size.
It is also preferable that the contact between the photocurable composition 13 for imprinting and the mold 20 is performed in an atmosphere containing helium gas or condensable gas, or both helium gas and condensable gas.

Next, the imprinting photocurable composition 13 is exposed in a state where the mold 20 is in contact with the imprinting photocurable composition 13. The irradiation amount at the time of exposure may be sufficiently larger than the minimum irradiation amount required for curing the photocurable composition 13 for imprinting. The irradiation amount required for curing the photocurable composition 13 for imprinting is appropriately determined by examining the consumption amount of unsaturated bonds of the photocurable composition 13 for imprinting. The type of light used for exposure is not particularly specified, but ultraviolet light is exemplified. The substrate temperature at the time of exposure is usually room temperature, but exposure may be performed while heating in order to enhance reactivity. A vacuum state as a pre-exposure step is effective in preventing air bubbles from being mixed in, suppressing a decrease in reactivity due to oxygen mixing, and improving the adhesion between the mold 20 and the photocurable composition 13 for imprinting. Light may be irradiated in the state. The preferred degree of vacuum during exposure is in ^{the range of 10 -1} Pa to normal pressure.
In photoexposure, the light intensity is preferably in the range of 1 to 500 mW / cm ^2, and more preferably in the range of 10~400mW / cm ^2. The exposure time is not particularly limited, but is preferably 0.01 to 10 seconds, more preferably 0.5 to 1 second. Exposure amount is preferably in a range of 5~1000mJ / cm ^2, and more preferably in the range of 10 to 500 mJ / cm ^2.

After the exposure, if necessary, a step of applying heat to the photocurable composition 13 for imprinting after the exposure to further cure the composition may be included. The heating temperature is preferably 150 to 280 ° C, more preferably 200 to 250 ° C. The heating time is preferably 5 to 60 minutes, more preferably 15 to 45 minutes.

Next, the mold 20 is peeled off from the exposed photocurable composition for imprint (FIG. 3). In this way, a pattern having a shape along the pattern of the mold 20 (hereinafter, also referred to as a cured product pattern) is formed. The obtained cured product pattern can be used for various purposes as described later. The present invention is particularly advantageous in that a nano-order fine pattern can be formed, and a pattern having a size of 50 nm or less, particularly 30 nm or less can be formed. The lower limit of the size of the cured product pattern formed by the above-mentioned cured product pattern manufacturing method is not particularly specified, but can be, for example, 1 nm or more.

<Application of cured product pattern>
The pattern (cured product pattern) formed by the pattern forming method of the present invention can be used as a permanent film used in a liquid crystal display (LCD) or the like, or as an etching resist (lithography mask) for manufacturing a semiconductor element. .. In particular, the present invention discloses a method for manufacturing a circuit board, which includes a step of obtaining a pattern (cured product pattern) by the pattern forming method according to a preferred embodiment of the present invention. Further, in the method for manufacturing a circuit board according to a preferred embodiment of the present invention, a step of etching or ion-implanting the substrate using the pattern (cured product pattern) obtained by the above pattern forming method as a mask and forming an electronic member are formed. It may have a step of performing. The circuit board is preferably a semiconductor element. That is, the present invention discloses a method for manufacturing a semiconductor device including the above pattern forming method. Further, the present invention discloses a method for manufacturing an electronic device having a step of obtaining a circuit board by the method for manufacturing a circuit board and a step of connecting the circuit board and a control mechanism for controlling the circuit board. Further, by forming a grid pattern on the glass substrate of the liquid crystal display device using the pattern forming method of the present invention, a polarizing plate having a large screen size (for example, 55 inches or more than 60 inches) with less reflection or absorption can be inexpensively used. Can be manufactured. For example, the polarizing plate described in JP-A-2015-132825 and WO2011 / 132649 can be manufactured. In addition, 1 inch is 25.4 mm.

The pattern (cured product pattern) formed by the pattern forming method of the present invention is also useful as an etching resist (mask for lithography). When the cured product pattern is used as an etching resist, first, a pattern (cured product pattern) is formed by applying the pattern forming method of the present invention on a substrate, and the obtained cured product pattern is used as an etching mask. An aspect of etching the substrate can be mentioned. By etching with an etching gas such as hydrogen fluoride in the case of wet etching and CF _{4 in} the case of dry etching, it is possible to form a pattern on the substrate along the shape of the desired cured product pattern. can.

The pattern (cured product pattern) formed by the pattern forming method of the present invention includes a recording medium such as a magnetic disk, a light receiving element such as a solid-state imaging device, an LED (light emitting diode), an organic EL (organic electroluminescence), and the like. Light emitting elements, optical devices such as liquid crystal displays (LCDs), diffraction grids, relief holograms, optical waveguides, optical filters, optical components such as microlens arrays, thin films, organic transistors, color filters, antireflection films, polarizing plates, Fine pattern formation using self-assembly of polarizing elements, optical films, flat panel display members such as pillars, nanobiodevices, immunoanalytical chips, deoxyribonucleic acid (DNA) separation chips, microreactors, photonic liquid crystals, and block copolymers. It can also be preferably used for producing a guide pattern or the like for (directed self-assembury, DSA).

Hereinafter, the present invention will be described in more detail with reference to examples. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

<Measurement method of weight molecular weight (Mw)>
The weight average molecular weight (Mw) of the polymer was defined as a polystyrene-equivalent value according to gel permeation chromatography (GPC measurement). The apparatus used was HLC-8220 (manufactured by Tosoh Corporation), and guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000 and TSKgel Super HZ2000 (manufactured by Tosoh Co., Ltd.) were used as columns. .. The eluate used was THF (tetrahydrofuran). For detection, an RI (Refractive Index) detector was used.

<Calculation of Hansen solubility parameter>
The Hansen solubility parameter of the liquid film and the photocurable composition for imprint was calculated by the HSP calculation software HSPiP. Specifically, by inputting the structural formula of each compound contained in the liquid film and the photocurable composition for imprint into the above software in the SMILES format, Hansen of the photocurable composition for the liquid film and imprint can be input. The dispersion term component (hereinafter, also referred to as D component), the polar term component (hereinafter, also referred to as P component) and the hydrogen bond term component (hereinafter, also referred to as H component) of the solubility parameter vector were calculated. Further, the distance (ΔHSP) between the Hansen solubility parameter between the photocurable composition for imprint and the liquid film was calculated by applying the calculated Hansen solubility parameter to the following formula.
ΔHSP = (4.0 × ΔD ² + ΔP ² + ΔH ² ) ^0.5
The above ΔD is the difference between the dispersion term component of the Hansen solubility parameter vector of the photocurable composition for imprint and the dispersion term component of the Hansen solubility parameter vector of the liquid film, and the above ΔP is the photocurable composition for imprint. The difference between the polar term component of the Hansen solubility parameter vector of the product and the polar term component of the Hansen solubility parameter vector of the liquid film, and the above ΔH is the hydrogen bond term component of the Hansen solubility parameter vector of the photocurable composition for imprint. And the difference between the hydrogen bond term components of the Hansen solubility parameter vector of the liquid film.
The D component, H component, and P component of the Hansen solubility parameter of the liquid film are the values of the D component, H component, and P component of the Hansen solubility parameter of the non-volatile component (component other than the solvent) of the liquid film forming composition. Was used.

<Measurement of viscosity>
The viscosity was measured by adjusting the temperature of the sample cup to 23 ° C. using an E-type rotational viscometer RE85L manufactured by Toki Sangyo Co., Ltd. and a standard cone rotor (1 ° 34'x R24). The unit is mPa · s. Regarding the viscosity (ηUL) of the non-volatile component of the composition for forming an underlayer film for imprinting, the viscosity was measured with a composition in which components other than the solvent were mixed. Other details regarding the measurements were in accordance with JISZ8803: 2011. Two samples were prepared for each level and measured three times each. A total of 6 arithmetic mean values were adopted as evaluation values.

(Synthesis of polymer)
<Synthesis of P-1>
Dichloromethane (200 mL), 4-Vinylbenzoic Acid (manufactured by Tokyo Chemical Industry Co., Ltd., 10.0 g, 67.5 mmol), Glycidol (manufactured by Tokyo Chemical Industry Co., Ltd., 5.5 g,) in a three-necked flask with N _{2 flow.} 74.2 mmol) was added, and the mixture was cooled to 0 ° C. There, 1- (3-Dimethylaminopropanol) -3-ethylcarbodiimide Hydrochloride (manufactured by Tokyo Chemical Industry Co., Ltd., 14.2 g, 74.2 mmol), 4-Dimethylaminopyridine (manufactured by Tokyo Chemical Industry Co., Ltd., 1.6 g, 13. 5 mmol) was added, and the mixture was further aged at 0 ° C. for 4 hours. Then, 1% _{aqueous NaHCO 3} solution (200 mL) was added to separate the liquids. The aqueous layer was removed, and a 1% _{aqueous solution of NaHCO 3} (500 mL) was further added to separate the solutions. The aqueous layer was removed, and 500 mL of distilled water was added to separate the liquids. The organic layer was concentrated and purified by silica gel chromatography to synthesize the target compound (intermediate P-1A).
Next, _{20.4 g of propylene glycol monomethyl ether acetate (PGMEA) was added to the N 2} flowing three-necked flask, and the mixture was heated to 90 ° C. Intermediate P-1A (10.2 g, 49.4 mmol) and photoradical polymerization initiator (manufactured by Wako Pure Chemical Industries, Ltd., V-601, 0.92 g, 8.0 mmol) are dissolved in PGMEA (20.4 g). Then, the obtained mixture was added dropwise at a temperature at which the internal temperature of the flask did not exceed 95 ° C. over 2 hours, and further aged at 90 ° C. for 4 hours. Then, it cooled to 25 degreeC. Diisopropyl ether (435.5 g) and hexane (186.6 g) were added to another three-necked flask, cooled to 0 ° C., and stirred. The reaction solution in the flask was added dropwise over 30 minutes at a temperature not exceeding 5 ° C., and the mixture was stirred for 1 hour. Then, it was allowed to stand still for 1 hour and filtered under reduced pressure. The obtained powder was dried under reduced pressure to synthesize the target compound (intermediate P-1B).
Next, PGMEA (40.8 g), intermediate P-1B (4.1 g, 20.0 mmol), Acrylic Acid (manufactured by Tokyo Chemical Industry Co., Ltd., 1.6 g, 22) were placed in a three-necked flask with _{N 2 flow.} .0 mmol), tetraethylammonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd., 0.1 g, 0.7 mmol), 4-OH-TEMPO (manufactured by Tokyo Chemical Industry Co., Ltd., 1.72 mg, 0.01 mmol) are added and 90 Aging was carried out at ° C. for 7 hours. Then, it cooled to 25 degreeC. Diisopropyl ether (435.5 g) and hexane (186.6 g) were added to another three-necked flask, cooled to 0 ° C., and stirred. The reaction solution in the flask was added dropwise over 30 minutes at a temperature not exceeding 5 ° C., and the mixture was stirred for 1 hour. Then, it was allowed to stand still for 1 hour and filtered under reduced pressure. The obtained powder was dried under reduced pressure to synthesize the target compound (P-1).

<Synthesis of P-2 to P25, H-1, H-2>
P-2 to P-25, H-1, and H-2 were synthesized in the same manner as in the method for synthesizing P-1.

<Preparation of composition for forming underlayer film>
Each compound shown in the table below is mixed and subjected to two-stage filtration with a polytetrafluoroethylene (PTFE) filter having a pore size of 0.1 μm and a PTFE filter having a pore size of 0.003 μm. ~ X-31 was prepared.

The raw materials listed in the above table are as follows.
(polymer)
P-1: Polymer having the following structure (Mw = 30,000)
P-2: Polymer having the following structure (Mw = 20,000)
P-3: Polymer having the following structure (Mw = 20,000)
P-4: Polymer having the following structure (Mw = 30,000)
P-5: Polymer with the following structure (Mw = 50,000)
P-6: Polymer having the following structure (Mw = 10,000)
P-7: Polymer having the following structure (Mw = 80,000)
P-8: Polymer having the following structure (Mw = 40,000)
P-9: Polymer having the following structure (Mw = 30,000)
P-10: Polymer having the following structure (Mw = 100,000)
P-11: Polymer with the following structure (Mw = 35,000)
P-12: Polymer having the following structure (Mw = 10,000)
P-13: Polymer having the following structure (Mw = 30,000)
P-14: Polymer having the following structure (Mw = 80,000)
P-15: Polymer having the following structure (Mw = 55,000)
P-16: Polymer having the following structure (Mw = 30,000)
P-17: Polymer having the following structure (Mw = 40,000)
P-18: Polymer having the following structure (Mw = 8,000)
P-19: Polymer having the following structure (Mw = 4,500)
P-20: Polymer having the following structure (Mw = 27,000)
P-21: Polymer with the following structure (Mw = 10,000)
P-22: Polymer having the following structure (Mw = 40,000)
P-23: Polymer having the following structure (Mw = 15,000)
P-24: Polymer having the following structure (Mw = 15,000)
P-25: Polymer having the following structure (Mw = 15,000)
H-1: Polymer having the following structure (Mw = 20,000)
H-2: Polymer having the following structure (Mw = 20,000)

(Additive)
T-1: IRGACURE OXE01 (manufactured by BASF)
T-2: Omnirad TPO H (manufactured by IGM Resins BV)
T-3: Sun Aid SI-150L (manufactured by Sanshin Chemical Industry Co., Ltd.)

(solvent)
PGMEA: Propylene Glycol Monomethyl Ether Acetate PGME: Propylene Glycol Monomethyl Ether GBL: γ-Butyrolactone

<Preparation of composition for liquid film formation>
Each of the compounds shown in the table below is mixed and subjected to two-stage filtration with a polytetrafluoroethylene (PTFE) filter having a pore size of 0.1 μm and a PTFE filter having a pore size of 0.003 μm. ~ W-29 was prepared. The Hansen solubility parameter of the non-volatile component of the liquid film forming composition is shown in the table below.

The raw materials listed in the above table are as follows.
J-1 to J-24: Compounds with the following structure (polymerizable compounds that are liquid at 23 ° C and 1 atm)

(Additive)
T-2: Omnirad TPO H (manufactured by IGM Resins BV)
T-3: Sun Aid SI-150L (manufactured by Sanshin Chemical Industry Co., Ltd.)
T-4: Omnirad 184 (manufactured by IGM Resins BV)
T-5: BLAUNON SR-705 (manufactured by Aoki Yushi Kogyo Co., Ltd., polyoxyethylene stearyl ether)

(solvent)
PGMEA: Propylene Glycol Monomethyl Ether Acetate PGME: Propylene Glycol Monomethyl Ether GBL: γ-Butyrolactone

<Preparation of photocurable composition for imprint>
Various compounds shown in the structural formulas in Table 3 are mixed, and two-stage filtration is performed with a polytetrafluoroethylene (PTFE) filter having a pore size of 0.1 μm and a PTFE filter having a pore size of 0.003 μm, and a photocurable composition for imprinting is performed. Substances V-1 to V-6 were prepared.

The Hansen solubility parameter of the photocurable composition for imprint is as follows.

<Calculation of ΔHSP value between Hansen solubility parameter of liquid film and Hansen solubility parameter of photocurable composition for imprint>
The Hansen solubility parameter of the liquid film and the photocurable composition for imprint was calculated by the HSP calculation software HSPiP. Specifically, by inputting the structural formula of each compound contained in the liquid film and the photocurable composition for imprint into the above software in the SMILES format, Hansen of the photocurable composition for the liquid film and imprint can be input. Each component (ΔD, ΔP, ΔH) of the solubility parameter was calculated. As the Hansen solubility parameter of the liquid film, the Hansen solubility parameter of the non-volatile component (component other than the solvent) of the liquid film forming composition was used.
By applying the calculated Hansen solubility parameter to the following formula, the ΔHSP value of the Hansen solubility parameter of the liquid film and the Hansen solubility parameter of the photocurable composition for imprint was calculated.
ΔHSP = (4.0 × ΔD ² + ΔP ² + ΔH ² ) ^0.5

<Evaluation>

<Evaluation of adhesion>
The composition for forming an underlayer film shown in the table below was spin-coated on a silicon wafer, heated for 1 minute using a hot plate at 220 ° C., and the solvent was dried to form an underlayer film having a thickness of 5 nm. Next, the liquid film forming composition shown in the table below is spin-coated on the surface of the underlayer film, heated for 1 minute using a hot plate at 100 ° C., and the solvent is dried to obtain a liquid having the film thickness shown in the table below. A film was formed. The film thicknesses of the underlayer and liquid films were measured by an ellipsometer and an atomic force microscope.
On the surface of the liquid film obtained above, the photocurable composition for imprint shown in the table below, whose temperature was adjusted to 25 ° C., was applied to 1 pL per nozzle using an inkjet printer DMP-2831 manufactured by Fujifilm Dimatics. The droplets were discharged in the amount of the droplets of the above, and were applied to the surface of the liquid film so that the droplets were arranged in a square at intervals of about 100 μm. Next, a quartz mold (rectangular line / space pattern (1/1), line width 60 nm, groove depth 100 nm, line edge roughness 3.5 nm) is pressed against the photocurable composition for imprinting on the liquid film. , The photocurable composition for imprint was filled in the mold. Further, after exposure from the mold side using a high-pressure mercury lamp under ^{the condition of 300 mJ / cm 2} , the pattern was transferred to the photocurable composition for imprint by peeling the mold.
The pattern transferred to the photocurable composition for imprint was observed using an optical microscope (manufactured by Olympus, STM6-LM), and the pattern peeling failure was evaluated according to the following criteria.
A: No peeling failure was observed in the entire pattern.
B: Peeling failure was observed in the region of less than 10% of the pattern.
C: Peeling failure was observed in the region of 10% or more of the pattern.

<Evaluation of wettability>
The composition for forming an underlayer film shown in the table below was spin-coated on a silicon wafer, heated for 1 minute using a hot plate at 220 ° C., and the solvent was dried to form an underlayer film having a thickness of 5 nm. Next, the liquid film forming composition shown in the table below is spin-coated on the surface of the underlayer film, heated for 1 minute using a hot plate at 100 ° C., and the solvent is dried to obtain a liquid having the film thickness shown in the table below. A film was formed. The film thicknesses of the underlayer and liquid films were measured by an ellipsometer and an atomic force microscope. In Comparative Example 4 using the liquid film forming composition W-2, a solid film was formed.
On the surface of the liquid film obtained above, the photocurable composition for imprint shown in the table below, whose temperature was adjusted to 25 ° C., was applied to 1 pL per nozzle using an inkjet printer DMP-2831 manufactured by Fujifilm Dimatics. The droplets were discharged in the amount of the droplets of the above, and were applied to the surface of the liquid film so that the droplets were arranged in a square at intervals of about 100 μm. Next, a quartz substrate was pressed against the photocurable composition for imprint on the liquid film to flatten the photocurable composition for imprint. Further, after exposure from the mold side using a high-pressure mercury lamp under ^{the condition of 300 mJ / cm 2} , a flat film was obtained by peeling off the quartz substrate.
The surface of the flat film was observed with an optical microscope (STM6-LM manufactured by Olympus), and the wettability was evaluated according to the following criteria.
A: In the imprint area, an unfilled region (a region in which a cured product of the photocurable composition for imprint does not exist) was not generated.
B: Unfilling at the inkjet droplet boundary was confirmed in a part of the imprint area.
C: Unfilling at the inkjet droplet boundary was confirmed over the entire surface of the imprint area.
D: A region was confirmed in which the inkjet droplets were not connected to each other and a flat film could not be formed.

As is clear from the above results, the examples were excellent in the evaluation of wettability and adhesion.
On the other hand, Comparative Example 1 in which a polymer containing no aromatic ring was used as the composition for forming the lower layer film, and Comparative Example 2 in which a polymer containing no polymerizable group was used as the composition for forming the lower layer film had insufficient adhesion. there were. In addition, Comparative Example 3 in which the liquid film was not provided had insufficient wettability. Further, in Comparative Example 4 in which a solid film was formed instead of the liquid film, the wettability was insufficient. Further, Comparative Example 5 using the liquid film forming composition containing no polymerizable compound had insufficient adhesion.

The value of ΔHSP in the above table is the distance between the Hansen solubility parameters (ΔHSP) between the photocurable composition for imprinting and the liquid film, and was calculated by the method described above.

1: Substrate 10: Laminate for imprint 11: Underlayer film 12: Liquid film 13: Photocurable composition for imprint 20: Mold

Claims (15)

An underlayer film formed from a composition for forming an underlayer film containing a polymer having an aromatic ring and a polymerizable group,
A liquid film containing a polymerizable compound that is liquid at 23 ° C. and 1 atm provided on the surface of the lower layer film, and
A photocurable composition for imprinting provided on the surface of the liquid film and
Laminated body for imprinting. The imprint laminate according to claim 1, wherein the polymer contains a structural unit containing an aromatic ring and a polymerizable group. The imprint laminate according to claim 1 or 2, wherein the polymer contains at least one of the structural units represented by any of the following formulas (1) to (5).

In formula (1), R ¹¹ represents a substituent and m1 represents an integer from 0 to 4. If m1 is 2 or more, plural R ¹¹ may be the same, or different, may have the two R ¹¹ are bonded to each other to form a ring;
In formula (2), R ² represents a hydrogen atom or a methyl group, R ¹² represents a substituent, and m2 represents an integer from 0 to 5. When m2 is 2 or more, the plurality of R ^12s may be the same or different, and the two R ^12s may be bonded to each other to form a ring;
In formula (3), R ³ represents a hydrogen atom or a methyl group and R ¹³ represents a substituent;
In formula (4), R ⁴ represents a hydrogen atom or a methyl group, and R ¹⁴ represents a substituent;
In formula (5), R ¹⁵ represents a substituent. The imprint laminate according to any one of claims 1 to 3, wherein the polymer is a polymer that undergoes a polymerization reaction at a temperature of 90 to 300 ° C. The imprint laminate according to any one of claims 1 to 4, wherein the polymerizable group contained in the polymer is at least one selected from a (meth) acryloyl group, an oxylanyl group and an oxetanyl group. The imprint laminate according to any one of claims 1 to 5, wherein the liquid film has a film thickness of 10 nm or less. The imprint laminate according to any one of claims 1 to 6, wherein the polymerizable compound contained in the liquid film is a polymerizable compound containing an aromatic ring. The imprint laminate according to any one of claims 1 to 7, wherein the polymerizable compound contained in the liquid film is a polyfunctional polymerizable compound. The imprint laminate according to any one of claims 1 to 8, wherein the polymerizable compound contained in the liquid film is a radically polymerizable compound. The imprint laminate according to any one of claims 1 to 9, wherein the imprint photocurable composition contains a polymerizable compound and a photopolymerization initiator. The imprint laminate according to claim 10, wherein the polymerizable compound contained in the imprint photocurable composition is a polymerizable compound containing an aromatic ring. Any of claims 1 to 11, wherein the value of ΔHSP calculated by the following mathematical formula (H1) based on the Hansen solubility parameter of the liquid film and the Hansen solubility parameter of the photocurable composition for imprinting is 10 or less. The imprint laminate according to item 1;
ΔHSP = (4.0 × ΔD ² + ΔP ² + ΔH ² ) ^0.5 (H1)
The above ΔD is the difference between the dispersion term component of the Hansen solubility parameter vector of the photocurable composition for imprint and the dispersion term component of the Hansen solubility parameter vector of the liquid film, and the above ΔP is the light for imprint. The difference between the polar term component of the Hansen solubility parameter vector of the curable composition and the polar term component of the Hansen solubility parameter vector of the liquid film, where ΔH is the Hansen solubility parameter vector of the photocurable composition for imprint. This is the difference between the hydrogen bond term component of the above and the hydrogen bond term component of the Hansen solubility parameter vector of the liquid film. A step of applying a composition for forming an underlayer film containing a polymer having an aromatic ring and a polymerizable group on a substrate to form an underlayer film, and a step of forming the underlayer film.
A step of forming a liquid film by applying a liquid film forming composition containing a polymerizable compound that is liquid at 23 ° C. and 1 atm on the lower layer film.
The step of applying the photocurable composition for imprinting on the liquid film, and
A method for manufacturing an imprint laminate including. A step of applying a composition for forming an underlayer film containing a polymer having an aromatic ring and a polymerizable group on a substrate to form an underlayer film, and a step of forming the underlayer film.
A step of forming a liquid film by applying a liquid film forming composition containing a polymerizable compound that is liquid at 23 ° C. and 1 atm on the lower layer film.
The step of applying the photocurable composition for imprinting on the liquid film, and
A step of bringing the photocurable composition for imprinting on the liquid film into contact with a mold having a pattern, and
A step of exposing the photocurable composition for imprinting in a state where the molds are in contact with each other.
A step of peeling the mold from the exposed photocurable composition for imprinting,
Pattern forming method including. A kit used for the imprint laminate according to any one of claims 1 to 12.
A composition for forming an underlayer film containing a polymer having an aromatic ring and a polymerizable group, and
A composition for forming a liquid film containing a polymerizable compound that is liquid at 23 ° C. and 1 atm, and
A kit containing a photocurable composition for imprinting.

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