JP7017623B2 - Underlayer film forming composition for imprint, curable composition for imprint, kit - Google Patents

Description

The present invention relates to the provision of an imprint underlayer film forming composition, an imprint curable composition, and a kit.

In the imprint method, a mold is pressed against a curable composition, the composition is cured, and then the mold is peeled off to transfer a fine pattern. Attempts are underway to apply this method to precision processing fields such as the manufacture of semiconductor integrated circuits. The imprint method eliminates the need for expensive microfabrication equipment such as steppers and electron beams. Since the manufacturing cost is reduced, the process is simple, high resolution and high throughput can be realized, research for mass production of devices is being vigorously conducted in various fields.

In the imprint method, there is a technique of using a photosensitive resin composition as a material applied to patterning and processing by combining a light-transmitting mold. In this manufacturing method, a pattern is formed on a cured film of a photosensitive resin composition disposed on a substrate by irradiating light through a mold, and the pattern is used as an insulating member or a mask for further processing. .. A method that uses ultraviolet rays (UV: Ultraviolet) as the light to irradiate is particularly called a UV nanoimprint method. Unlike the thermal nanoimprint method, which uses a thermosetting resin composition and requires heating, the optical nanoimprint method including the UV nanoimprint method enables processing at room temperature. Therefore, it can be widely used as a technology for achieving high quality in the manufacture of semiconductor devices that dislike heat.

In the optical nanoimprint method using a photosensitive resin composition, a technique using an underlayer film has been proposed (see Patent Document 1). For example, Patent Document 1 contains a resin having a (meth) acryloyloxy group, an alkoxycarbonyl group, an oxylanyl group, and at least one group selected from an oxetanyl group, a nonionic surfactant, and a solvent. A resin composition for forming a lower layer film is disclosed. As a result, it is described that the variation in the residual film thickness after pressing the mold is small, and the variation in the line width distribution of the pattern after pressing is less likely to occur.

International Publication No. 2016/027843

As described above, the formation of fine patterns by imprinting is extremely efficient as compared with the technique by photolithography, and the manufacturing cost and productivity related to the manufacturing of semiconductor devices can be significantly improved. With the progress of semiconductor technology, further improvement in pattern miniaturization and manufacturing quality is required. For example, in the manufacturing process by imprinting, in order to improve the adhesion between the substrate and the curable composition for imprinting, the underlayer film forming composition for imprinting is used, and the coating film of the underlayer film forming composition for imprinting is used. It has been studied to apply a curable composition for imprinting on the surface to form a film, but there is a demand for further improvement in the wettability of the film. In addition, as a matter of course, the adhesion between the underlayer film formed from these compositions and the imprint layer is also required.
Therefore, the present invention is superior in the wettability of the curable composition for imprint to the coating film of the underlayer film forming composition for imprint, and the adhesion between the underlayer film formed from these compositions and the imprint layer. It is an object of the present invention to provide an excellent underlayer film forming composition for imprinting, a curable composition for imprinting, and a kit using these.

式中、Ｒ^ｒ１、Ｒ^ｒ２、Ｒ^ｒ４、Ｒ^ｒ５、およびＲ^ｒ６はそれぞれ独立に水素原子または１価の置換基であり、Ｒ^ｒ１およびＲ^ｒ２の少なくとも一方は置換基であり、Ｒ^ｒ４、Ｒ^ｒ５、およびＲ^ｒ６の少なくとも１つは置換基であり、Ｒ^ｒ３は２価の置換基である。
＜２＞ 上記式（ｒ１）または（ｒ２）で表される化合物が式（ｒ１－１）で表される、＜１＞に記載のインプリント用下層膜形成組成物；

式中、Ｒ^ｒ１およびＲ^ｒ２はそれぞれ独立に水素原子または１価の置換基であり、Ｒ^ｒ１およびＲ^ｒ２の少なくとも一方は置換基である。
＜３＞ 上記ポリマーが下記式（Ｒ－１）～（Ｒ－４）のいずれかで表される基を含む、＜１＞また＜２＞に記載のインプリント用下層膜形成組成物；

式中、Ｒ^１～Ｒ^３はそれぞれ独立に１価の置換基であり、Ｒ^４～Ｒ^１２はそれぞれ独立に水素原子または１価の置換基であり、Ｘはポリマーの主鎖への結合位置を表す。
＜４＞ 上記式（Ｒ－１）～（Ｒ－４）のいずれかで表される置換基を含むポリマーから、式中のＣ－Ｏ結合が分解して、上記式（ｒ１）または（ｒ２）で表され、かつ、分子量２１０以上の化合物が脱離する、＜３＞に記載のインプリント用下層膜形成組成物。
＜５＞ 上記ポリマーが重合性基を含む、＜１＞～＜４＞のいずれか１つに記載のインプリント用下層膜形成組成物。
＜６＞ 上記重合性基が（メタ）アクリロイル基を含む、＜５＞に記載のインプリント用下層膜形成組成物。
＜７＞ 上記ポリマーが芳香環を含む、＜１＞～＜６＞のいずれか１つに記載のインプリント用下層膜形成組成物。
＜８＞ 上記ポリマーが下記式（１）～式（６）のいずれかで表される構成単位の少なくとも１種を含む、＜１＞～＜７＞のいずれか１つに記載のインプリント用下層膜形成組成物；

式中、Ｒ^Ｐ４は水素原子またはメチル基である；Ｒ^Ｐ１は、式（ｒ１）または（ｒ２）で表される化合物を脱離可能な基を表す。
＜９＞ 上記式（ｒ１）または（ｒ２）で表される化合物が芳香環を含む、＜１＞～＜８＞のいずれか１つに記載のインプリント用下層膜形成組成物。
＜１０＞ 上記式（ｒ１）または（ｒ２）で表される化合物が重合性基を含む、＜１＞～＜９＞のいずれか１つに記載のインプリント用下層膜形成組成物。
＜１１＞ 上記重合性基が（メタ）アクリロイル基を含む、＜１０＞に記載のインプリント用下層膜形成組成物。
＜１２＞ 上記式（ｒ１）のＲ^ｒ１およびＲ^ｒ２の少なくとも１つ、および、式（ｒ２）のＲ^ｒ４～Ｒ^ｒ６の少なくとも１つの少なくとも１つが重合性基を含む、＜１＞～＜１１＞のいずれか１つに記載のインプリント用下層膜形成組成物。
＜１３＞ 上記式（ｒ１）または（ｒ２）で表される化合物の分子量が１０００以下である、＜１＞～＜１２＞のいずれか１つに記載のインプリント用下層膜形成組成物。
＜１４＞ さらに、脱離反応促進剤またはその前駆体を含む、＜１＞～＜１３＞のいずれか１つに記載のインプリント用下層膜形成組成物。
＜１５＞ さらに、光重合開始剤を含む、＜１＞～＜１４＞のいずれか１つに記載のインプリント用下層膜形成組成物。
＜１６＞ 上記式（ｒ１）または（ｒ２）で表される化合物の表面張力が３５～５５ｍＮ／ｍである、＜１＞～＜１５＞のいずれか１つに記載のインプリント用下層膜形成組成物。
＜１７＞ 溶剤を９５．０質量％以上の割合で含む、＜１＞～＜１６＞のいずれか１つに記載のインプリント用下層膜形成組成物。
＜１８＞ ＜１＞～＜１７＞のいずれか１つに記載のインプリント用下層膜形成組成物と組み合わせて用いる、重合性化合物を含むインプリント用硬化性組成物。
＜１９＞ ＜１＞～＜１７＞のいずれか１つに記載のインプリント用下層膜形成組成物と、重合性化合物を含むインプリント用硬化性組成物とを含むキット。
＜２０＞ 上記式（ｒ１）または（ｒ２）で表される化合物のハンセン溶解度パラメータと上記インプリント用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値が５以下である、＜１９＞に記載のキット；
ΔＨＳＰ＝（４．０×ΔＤ^２＋ΔＰ^２＋ΔＨ^２）^０．５ （Ｈ１）
上記ΔＤは、インプリント用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、式（ｒ１）または（ｒ２）で表される化合物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、式（ｒ１）または（ｒ２）で表される化合物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、式（ｒ１）または（ｒ２）で表される化合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の差である。
＜２１＞ ＜１＞～＜１７＞のいずれか１つに記載の下層膜形成組成物から形成された下層膜。
＜２２＞ ＜１９＞または＜２０＞に記載のキットから形成される積層体であって、
上記インプリント用下層膜形成組成物から形成された下層膜と、上記インプリント用硬化性組成物から形成され、上記下層膜の表面に位置するインプリント層とを有する、積層体。
＜２３＞ ＜１９＞または＜２０＞に記載のキットを用いて積層体を製造する方法であって、上記インプリント用下層膜形成組成物から形成された下層膜の表面に、インプリント用硬化性組成物を適用することを含む、積層体の製造方法。
＜２４＞ 上記インプリント用硬化性組成物は、インクジェット法により、上記下層膜の表面に適用する、＜２３＞に記載の積層体の製造方法。
＜２５＞ さらに、上記インプリント用下層膜形成組成物を基板上に層状に適用する工程を含み、上記層状に適用したインプリント用下層膜形成組成物を８０～２５０℃で、加熱することを含む、＜２３＞または＜２４＞に記載の積層体の製造方法。
＜２６＞ ＜１９＞または＜２０＞に記載のキットを用いて硬化物パターンを製造する方法であって、基板上に、インプリント用下層膜形成組成物を適用して下層膜を形成する下層膜形成工程と、上記下層膜の表面に、インプリント用硬化性組成物を適用する適用工程と、上記インプリント用硬化性組成物と、パターン形状を転写するためのパターンを有するモールドとを接触させるモールド接触工程と、上記インプリント用硬化性組成物に光を照射して硬化物を形成する光照射工程と、上記硬化物と上記モールドとを引き離す離型工程と、を有する硬化物パターンの製造方法。
＜２７＞ ＜２６＞に記載の製造方法により硬化物パターンを得る工程を含む、回路基板の製造方法。As a result of studies by the present inventors based on the above problems, it has been found that the above problems can be solved by adopting a polymer capable of producing a specific desorption component in the underlayer film forming composition for imprinting. rice field. Specifically, the above problems were solved by the following means <1>, preferably <2> to <27>.
<1> An imprint underlayer film-forming composition containing a polymer and a solvent. When the imprint underlayer film-forming composition is formed into a film and baked at 80 ° C., the following formula (r1) is obtained from the polymer. Alternatively, the underlayer film forming composition for imprint, wherein the compound represented by (r2) and having a molecular weight of 210 or more is eliminated;

In the formula, R ^r1 , R ^r2 , R ^r4 , R ^r5 , and R ^r6 are independently hydrogen atoms or monovalent substituents, and at least one of R ^r1 and R ^r2 is a substituent, R ^r4 , At least one of R ^r5 and R ^r6 is a substituent and R ^r3 is a divalent substituent.
<2> The underlayer film forming composition for imprint according to <1>, wherein the compound represented by the above formula (r1) or (r2) is represented by the formula (r1-1);

In the formula, R ^r1 and R ^r2 are independently hydrogen atoms or monovalent substituents, and at least one of R ^r1 and R ^r2 is a substituent.
<3> The underlayer film forming composition for imprint according to <1> or <2>, wherein the polymer contains a group represented by any of the following formulas (R-1) to (R-4);

In the formula, R ¹ to R ³ are independently monovalent substituents, R ⁴ to R ¹² are independently hydrogen atoms or monovalent substituents, and X is the bonding position of the polymer to the main chain. Represents.
<4> The CO bond in the formula is decomposed from the polymer containing the substituent represented by any of the above formulas (R-1) to (R-4), and the above formula (r1) or (r2) is decomposed. ), And the underlayer film forming composition for imprint according to <3>, wherein the compound having a molecular weight of 210 or more is eliminated.
<5> The underlayer film forming composition for imprint according to any one of <1> to <4>, wherein the polymer contains a polymerizable group.
<6> The underlayer film forming composition for imprint according to <5>, wherein the polymerizable group contains a (meth) acryloyl group.
<7> The underlayer film forming composition for imprint according to any one of <1> to <6>, wherein the polymer contains an aromatic ring.
<8> The imprint according to any one of <1> to <7>, wherein the polymer contains at least one of the structural units represented by any of the following formulas (1) to (6). Underlayer film forming composition;

In the formula, ^RP4 is a hydrogen atom or a methyl group; ^RP1 represents a group capable of desorbing the compound represented by the formula (r1) or (r2).
<9> The underlayer film forming composition for imprint according to any one of <1> to <8>, wherein the compound represented by the above formula (r1) or (r2) contains an aromatic ring.
<10> The underlayer film forming composition for imprint according to any one of <1> to <9>, wherein the compound represented by the above formula (r1) or (r2) contains a polymerizable group.
<11> The underlayer film forming composition for imprint according to <10>, wherein the polymerizable group contains a (meth) acryloyl group.
<12><1> to <11, wherein at least one of R ^r1 and R ^r2 of the above formula (r1) and at least one of R ^r4 to R ^r6 of the formula (r2) contain a polymerizable group. > The underlayer film forming composition for imprint according to any one of.
<13> The underlayer film forming composition for imprint according to any one of <1> to <12>, wherein the compound represented by the above formula (r1) or (r2) has a molecular weight of 1000 or less.
<14> The underlayer film forming composition for imprint according to any one of <1> to <13>, further comprising a desorption reaction accelerator or a precursor thereof.
<15> The underlayer film forming composition for imprint according to any one of <1> to <14>, further comprising a photopolymerization initiator.
<16> The underlayer film formation for imprint according to any one of <1> to <15>, wherein the surface tension of the compound represented by the above formula (r1) or (r2) is 35 to 55 mN / m. Composition.
<17> The underlayer film forming composition for imprint according to any one of <1> to <16>, which contains a solvent in a proportion of 95.0% by mass or more.
<18> A curable composition for imprint containing a polymerizable compound, which is used in combination with the underlayer film forming composition for imprint according to any one of <1> to <17>.
<19> A kit containing the imprint underlayer film forming composition according to any one of <1> to <17> and the imprint curable composition containing a polymerizable compound.
<20> The ΔHSP value calculated by the following formula (H1) based on the Hansen solubility parameter of the compound represented by the above formula (r1) or (r2) and the Hansen solubility parameter of the curable composition for imprinting is 5 The kit according to <19>, which is as follows;
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 curable composition for imprint and the dispersion term component of the Hansen solubility parameter vector of the compound represented by the formula (r1) or (r2). ΔP is the difference between the polar term component of the Hansen solubility parameter vector of the curable composition for imprint and the polar term component of the Hansen solubility parameter vector of the compound represented by the formula (r1) or (r2). Is the difference between the hydrogen bond term component of the Hansen solubility parameter vector of the curable composition for imprint and the hydrogen bond term component of the Hansen solubility parameter vector of the compound represented by the formula (r1) or (r2).
<21> A lower layer film formed from the lower layer film forming composition according to any one of <1> to <17>.
<22> A laminate formed from the kit according to <19> or <20>.
A laminate having an imprint film formed from the imprint underlayer film forming composition and an imprint layer formed from the imprint curable composition and located on the surface of the underlayer film.
<23> A method for producing a laminate using the kit according to <19> or <20>, wherein the surface of the underlayer film formed from the above-mentioned underlayer film forming composition for imprint is cured for imprinting. A method for producing a laminate, which comprises applying a sex composition.
<24> The method for producing a laminate according to <23>, wherein the curable composition for imprint is applied to the surface of the underlayer film by an inkjet method.
<25> Further, the step of applying the imprint underlayer film forming composition on the substrate in a layered manner is included, and the imprinting underlayer film forming composition applied in the layered form is heated at 80 to 250 ° C. The method for producing a laminate according to <23> or <24>, which comprises.
<26> A method for producing a cured product pattern using the kit according to <19> or <20>, wherein a lower layer film forming composition for imprinting is applied onto a substrate to form a lower layer film. The film forming step, the application step of applying the curable composition for imprint to the surface of the lower layer film, the curable composition for imprint, and the mold having a pattern for transferring the pattern shape are brought into contact with each other. A cured product pattern having a mold contacting step of forming a cured product by irradiating the curable composition for imprinting with light, and a mold separating step of separating the cured product from the mold. Production method.
<27> A method for manufacturing a circuit board, which comprises a step of obtaining a cured product pattern by the manufacturing method according to <26>.

INDUSTRIAL APPLICABILITY According to the present invention, the wettability of the curable composition for imprint to the coating film of the underlayer film forming composition for imprint and the adhesion between the underlayer film formed from these compositions and the imprint layer are improved. Is now possible. In addition, it has become possible to provide an imprint underlayer film forming composition, an imprint curable composition, and a kit using these to which the technique is applied.

It is a process explanatory drawing which shows an example of the manufacturing process in the case of forming a cured product pattern, and using the obtained cured product pattern for processing a substrate by etching. It is a top view which shows typically the state of the wetting spread of the curable composition for imprint when the curable composition for imprint is applied to the surface of the underlayer film with low wettability by the inkjet method.

Hereinafter, the contents of the present invention will be described in detail. In addition, in this specification, "-" is used in the sense 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 refers to a pattern transfer having a size of approximately 10 nm to 100 μm (nanoimprint).
In the notation of a group (atomic group) in the present specification, the notation not describing 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 (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 temperature in the present invention is 23 ° C.
The boiling point in the present invention means the boiling point at 1 atm (1 atm = 1013.25 hPa).

The underlayer film-forming composition for imprint of the present invention contains a polymer and a solvent, and when the underlayer film-forming composition for imprint is formed into a film and baked at 80 ° C., the following formula (r1) or (r2) is obtained from the polymer. It is characterized in that the compound represented by (hereinafter, may be referred to as a desorption component) is desorbed. As a result, the wettability of the curable composition for imprint to the coating film of the underlayer film forming composition for imprint in imprint is improved, and the underlayer film and the imprint layer formed from these compositions adhere to each other. Sex improves. The reason for this is presumed as follows. That is, it is considered that the formation of the small molecule component causes a decrease in the interfacial tension on the surface of the underlayer film, and the wettability is improved accordingly. In addition, the curable component of the curable composition for imprint infiltrates into the region where the small molecule component was present due to the generation of a diffusion path in the lower layer film, and the portion is cured to cure the lower layer film. It is considered that the adhesion between the and the cured product is improved.

<Underlayer film forming composition for imprint>
In the present invention, when the underlayer film forming composition for imprint is formed into a film and baked at 80 ° C., a compound represented by the following formula (r1) or (r2) and having a molecular weight of 210 or more is eliminated from the polymer. do. Hereinafter, in the present specification, the above compound is referred to as an elimination component.

<< Desorption component >>
The desorption component is a component that desorbs from the polymer when the underlayer film forming composition for imprint is formed into a film and baked at 80 ° C., and is a compound having a predetermined structure and having a molecular weight of 210 or more. be.

式中、Ｒ^ｒ１、Ｒ^ｒ２、Ｒ^ｒ４、Ｒ^ｒ５、およびＲ^ｒ６はそれぞれ独立に水素原子または１価の置換基であり、Ｒ^ｒ１およびＲ^ｒ２の少なくとも一方は置換基であり、Ｒ^ｒ４、Ｒ^ｒ５、およびＲ^ｒ６の少なくとも１つは置換基であり、Ｒ^ｒ３は２価の置換基である。The desorption component in the first embodiment of the present invention is represented by the following formula (r1) or (r2). When the desorption component is a compound represented by the formula (r1) or (r2), the polymerization initiator in the curable composition for imprint diffuses into the underlayer film forming composition for imprint, and is used for imprint. At the same time as the curing of the curable composition, the underlayer film forming composition for imprinting is also cured, and the adhesion between the curable composition for imprinting and the underlayer film is more excellent.

In the formula, R ^r1 , R ^r2 , R ^r4 , R ^r5 , and R ^r6 are independently hydrogen atoms or monovalent substituents, and at least one of R ^r1 and R ^r2 is a substituent, R ^r4 , At least one of R ^r5 and R ^r6 is a substituent and R ^r3 is a divalent substituent.

式中、Ｒ^ｒ１およびＲ^ｒ２はそれぞれ独立に水素原子または１価の置換基であり、Ｒ^ｒ１およびＲ^ｒ２の少なくとも一方は置換基である。The compound represented by the formula (r1) or (r2) is preferably represented by the following formula (r1-1).

In the formula, R ^r1 and R ^r2 are independently hydrogen atoms or monovalent substituents, and at least one of R ^r1 and R ^r2 is a substituent.

The desorption component (compound represented by the formula (r1) or (r2) or the compound represented by the formula (r1-1)) preferably contains an aromatic ring (preferably the ring aCy or hCy below).
In particular, at least one of R ^r1 and R ^r2 of the formula (r1), at least one of R ^r4 to R ^r6 of the formula (r2), and at least one of R ^r1 and R ^r2 of the formula (r1-1) are aromatic rings. It is preferable to include. The aromatic ring is preferably the following ring aCy or hCy.

上記化学式のものを含め、ここで例示した芳香族環の例を環ａＣｙと呼ぶ。Specific examples of the aromatic ring when it is an aromatic 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 inden ring, an indan ring, and a triphenylene. Examples thereof include a ring, a tetraphenylene ring, a pyrene ring, a chrysene ring, a perylene ring, and a tetrahydronaphthalene ring. The aromatic ring may have a structure in which a plurality of aromatic rings are linked with or without a linking group L, and examples thereof include a biphenyl ring, a diphenylmethane ring, and a triphenylmethane ring. Alternatively, examples of the structure in which a plurality of benzene rings are linked, including those partially exemplified above, include those having the following formulas Ar1 to Ar5. In the formula, the straight line drawn outward from the vicinity of the center of the benzene ring indicates the bond. It is attached to any linking group via this single bond, or is attached to the main chain of L ¹ , L ² , P, or a polymer of the following formula (T1) with or without it. Means that. A ¹ is a divalent linking group, and the example of the linking group L is preferable, and an alkylene group which may be substituted with a fluorine atom (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, 1 to 3 is preferable. Further preferred), a carbonyl group, an oxygen atom, a sulfonyl group, a sulfinyl group, and -NR ^N- are more preferred. A ² means a trivalent linking group containing a nitrogen atom or a phosphorus atom, or a methine group. In the formulas Ar1 to Ar5, it is shown that there are arbitrarily two or three bonds, but it means that the bonds may be formed at the required part according to the required number of bonds. For example, extending two bonds from one benzene ring can be mentioned as a preferred embodiment of the present invention. Further, it can be mentioned as a preferred embodiment of the present invention that Ar2 having three rings is a divalent linking group.

Examples of the aromatic ring exemplified here, including those having the above chemical formula, are referred to as a ring aCy.

When the aromatic ring is an aromatic heterocycle, the number of carbon atoms thereof is preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 5. Specific examples thereof include thiophene ring, furan ring, pyrrol ring, imidazole ring, pyrazole ring, triazole ring, tetrazole ring, thiazole ring, oxazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, triazine ring, and isoindole. Ring, indole ring, indazole ring, purine ring, quinolidine ring, isoquinoline ring, quinoline ring, phthalazine ring, naphthylidine ring, quinoxalin ring, quinazoline ring, cinnoline ring, carbazole ring, aclysine ring, phenazine ring, phenothiazine ring, phenoxazine ring. And so on.
The aromatic heterocycle may be a structure in which a plurality of ring structures are linked with or without a linking group L.
The aromatic heterocycle shown here is referred to as a ring hCy.

As the aromatic ring contained in the desorbed component, a benzene ring is particularly preferable.
The aromatic ring may have a substituent T as long as the effect of the present invention is exhibited. When there are a plurality of substituents T, they may be bonded to each other, or may be bonded to the ring in the formula with or without the linking group L to form a ring. For example, an alkyl group, an alkenyl group, an aryl group, an arylalkyl group and the like may be further substituted with a halogen atom (preferably a fluorine atom).

Moreover, it is preferable that the desorbed component contains a polymerizable group. Examples of the polymerizable group include a group containing an ethylenically unsaturated group, an epoxy group, a glycidyl group, an oxetane group and the like. Examples of the ethylenically unsaturated group include a vinyl group, an allyl group, a vinylphenyl group, a (meth) acryloyl group, and a group containing a (meth) acryloyloxy group. The polymerizable group exemplified here is referred to as a polymerizable group Ps. In the present invention, the polymerizable group Ps preferably contains a (meth) acryloyl group or a (meth) acryloyloxy group.
In particular, at least one of R ^r1 and R ^r2 of the formula (r1), at least one of R ^r4 to R ^r6 of the formula (r2), and at least one of R ^r1 and R ^r2 of the formula (r1-1) are polymerizable. It preferably contains a group. As the polymerizable group, the above-mentioned polymerizable group Ps is preferable.
Further, the desorption component preferably contains an ethylenic double bond. In particular, it is preferable to form an ethylenic double bond by desorbing from the polymer. By such desorption, the effect of adhesion is exhibited.

When R ^r1 , R ^r2 , R ^r4 , R ^r5 , and R ^r6 are substituents in the formula (r1) or (r2) or the formula (r1-1), an example of the substituent T described later is used as the substituent. Among them, alkyl groups (preferably 1 to 12 carbon atoms are preferable, 1 to 6 are more preferable, 1 to 3 are more preferable) and alkenyl groups (preferably 2 to 12 carbon atoms, 2 to 6 carbon atoms are preferable, respectively). More preferably, 2 to 3 are more preferable), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 10), an arylalkyl group (preferably 7 to 23 carbon atoms, 7). ~ 19 is more preferable, and 7 to 11 are more preferable), or a group represented by the following formula (RL-1) is preferable. Further, in the formulas (r1) and (r2), it is particularly preferable that at least R ^r2 or R ^r6 is a group represented by the following formula (RL-1).

Ｌ^Ｒ１およびＬ^Ｒ２はそれぞれ独立に単結合または連結基であり、Ａｒ^Ｒは芳香環を含む連結基であり、Ｐ^Ｒは重合性基を有する基である。ｎｒは０～８の整数であり、ｍｒは１～４の整数である。

L ^R1 and L ^{R 2} are independent single bonds or linking groups, Ar ^R is a linking group containing an aromatic ring, and ^PR is a group having a polymerizable group. nr is an integer of 0 to 8, and mr is an integer of 1 to 4.

LR1 is a 1 + mr-valent aromatic ring (preferably the above ^aCy or hCy example), an alicyclic ring (preferably the following alicyclic fCy example), and a group having a linear or branched alkane structure (preferably 1 to 40 carbon atoms). 1 to 30 is more preferred, 1 to 20 is more preferred), a linear or branched alkyne structure group (2 to 40 carbon atoms is preferred, 2 to 30 is more preferred, 2 to 20 is even more preferred), or It is preferably a linear or branched alkyne-structured group (preferably 2 to 40 carbon atoms, more preferably 2 to 30 carbon atoms, still more preferably 2 to 20 carbon atoms).

As the linking group of ^LR2 , an example of the following linking group L or the linking group Lh containing the following heteroatom is preferable. Among them, an alkylene group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 3 carbon atoms) and an arylene group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, 6 to 10 carbon atoms). (More preferably), (oligo) alkyleneoxy group (the number of carbon atoms of the alkylene group in one structural unit is preferably 1 to 12, more preferably 1 to 6, further preferably 1 to 3; the number of repetitions is 1 to 50. Of the above, 1 to 40 is more preferable, and 1 to 30 is even more preferable), a carbonyl group, an oxygen atom, or a group in which these are combined is preferable.
L ^R2 may be coupled to L ^R1 with or without the linking group L to form a ring.

Ar ^R is a linking group containing an aromatic ring. However, when nr is 0, Ar ^R is a substituent containing an aromatic ring. As the aromatic ring, the above-mentioned ring aCy or hCy is preferable. When Ar ^R contains a substituent other than the aromatic ring, the following examples of the linking group L are given as the linking group, and among them, the alkylene group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms 1 to 12). 6 is more preferred), an alkenylene group (preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms), an alkynylene group (preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms). (2 to 3 is more preferable), (oligo) alkyleneoxy group (the number of carbon atoms of the alkylene group in one structural unit is preferably 1 to 12, more preferably 1 to 6, further preferably 1 to 3; the number of repetitions is 1 to 50 is preferred, 1 to 40 is more preferred, 1 to 30 is even more preferred), an arylene group (6 to 22 carbon atoms is preferred, 6 to 18 is more preferred, 6 to 10 is even more preferred), or a combination thereof. Examples thereof include the linking group according to the above. Ar ^R may be coupled to L ^R1 , L ^R2 , or ^PR to form a ring with or without the linking group L.

PR is a volatile group having a polymerizable group, and the polymerizable group is preferably the example of the above-mentioned polymerizable group ^Ps . ^PR may be coupled with ^LR1 and ^LR2 to form a ring with or without the linking group L.

L ^R1 , L ^R2 , Ar ^R , and ^PR may have a substituent T as long as the effects of the present invention are exhibited. For example, an alkyl group, an alkenyl group, an aryl group, an arylalkyl group and the like may be further substituted with a halogen atom (preferably a fluorine atom).

nr is an integer of 0 to 8, preferably 0 to 6, more preferably 0 to 4, and even more preferably 0 to 2. mr is an integer of 1 to 4, preferably 1 to 2.

Examples of the divalent substituent of R ^r3 include CH ₂ (the second embodiment below), CHR ^r8 , or C (R ^r9 ) ₂ . Here, R ^r8 and R ^r9 are each independently a substituent T described later, and among them, an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3), and an alkenyl. Group (preferably 2 to 12 carbon atoms, more preferably 2 to 6), alkynyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms) , Aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 10 carbon atoms), arylalkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, 7 to 11 carbon atoms). Further preferred) is preferred. The two R ^r9s of C (R ^r9 ) ₂ may be the same or different from each other.

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 (the alkylene group in one structural unit. The number of carbon atoms is preferably 1 to 12, more preferably 1 to 6, further preferably 1 to 3, and the number of repetitions is preferably 1 to 50, more preferably 1 to 40 (more preferably 1 to 30), or these. Examples include a linking group consisting of a combination. 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, and even more preferably 1 to 10. The (oligo) alkyleneoxy group means that it may be either an alkyleneoxy group or an oligoalkyleneoxy group. The (oligo) alkyleneoxy group 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.

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 carbon atoms), an alkynyl group (preferably 2 to 12 carbon atoms, 2 to 6 carbon atoms). More preferably, 2 to 3 are more preferable), a hydroxyl group, an amino group (preferably 0 to 24 carbon atoms, more preferably 0 to 12 and even more preferably 0 to 6), a thiol group, a carboxyl group and an aryl group (carbon). The number 6 to 22 is preferable, 6 to 18 is more preferable, 6 to 10 is more preferable), an alkoxyl group (1 to 12 carbon atoms is preferable, 1 to 6 is more preferable, 1 to 3 is more preferable), and aryloxy. Group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 10), acyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, still more preferably 2 to 3). , Acyloxy group (preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, further preferably 2 to 3), allylloyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, further preferably 7 to 11 carbon atoms). ), Allyloyloxy group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, still more 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). 6 is more preferable, 1 to 3 is 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 more preferable). Preferably, 1-8 is more preferred, 2-5 is even more preferred, a 5-membered or 6-membered ring is preferred), a (meth) acryloyl group, a (meth) acryloyloxy group, a halogen atom (eg, a fluorine atom). , Chlorine atom, bromine atom, iodine atom), oxo group (= O), imino group (= NR ^N ), alkylidene group (= C ( ^RN ) ₂ ) and the like. ^RN is a hydrogen atom, an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 3 carbon atoms), an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms). 2 to 3 is more preferable), an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms), an aryl group (preferably 6 to 22 carbon atoms, 6 to 18 carbon atoms are more preferable). It is preferably 6 to 10) or an arylalkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, still more preferably 7 to 11 carbon atoms), a hydrogen atom, a methyl group, an ethyl group, or A propyl group is preferred. 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.

As the linking group L, an alkylene group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms) and an alkenylene group (preferably 2 to 12 carbon atoms, 2 to 6 carbon atoms are more preferable). 2 to 3 are more preferred), alkynylene group (preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, still more preferably 2 to 3), (oligo) alkyleneoxy group (alkylene group in one structural unit). The number of carbon atoms is preferably 1 to 12, more preferably 1 to 6, further preferably 1 to 3, and the number of repetitions is preferably 1 to 50, more preferably 1 to 40), an arylene group (more preferably 1 to 30). 6 to 22 carbon atoms are preferred, 6 to 18 are more preferred, 6 to 10 are even more preferred), oxygen atoms, sulfur atoms, sulfonyl groups, carbonyl groups, thiocarbonyl groups, -NR ^N- , and combinations thereof. A linking group may be mentioned. The alkylene group may have the above-mentioned substituent T. 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 -CCO-, 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-like or cyclic, and may be linear or branched. When the linking group is a group capable of forming a salt such as −NR ^N −, the group may form a salt.

The desorbed component has a molecular weight of 210 or more. When the molecular weight is at least this lower limit, volatilization during baking is suppressed, which is preferable. The molecular weight of the desorbed component is preferably 210 or more, more preferably 250 or more, and even more preferably 300 or more. It is practical that the upper limit is 1000 or less.

The surface tension of the desorbed component is preferably 28 mN / m or more, more preferably 30 mN / m or more, further preferably 36 mN / m or more, and even more preferably 38 mN / m or more. , 40 mN / m or more is even more preferable, and 42 mN / m or more is even more preferable. The upper limit is preferably 80 mN / m or less, more preferably 60 mN / or less, and even more preferably 50 mN / m or less.

Of the Hansen solubility parameter (HSP) vector of the desorbed component:
(I) The dispersion term component (d component) is preferably 14.0 to 20.0, more preferably 15.0 to 19.0, and preferably 16.0 to 19.5. More preferred;
(Ii) The polar term component (p component) is preferably 2.0 to 9.0, more preferably 3.0 to 6.0, and preferably 3.5 to 5.0. More preferred;
(Iii) The hydrogen bond term component (h component) is preferably 3.0 to 12.0, more preferably 4.7 to 7.0, and 5.0 to 6.5. Is even more preferable.

<< Specific polymer >>
The polymer used in the present invention (hereinafter, this polymer may be referred to as a specific polymer) is a case where the underlayer film forming composition for imprint containing this specific polymer is formed into a film and baked at 80 to 250 ° C. , Polymers that desorb desorbing components from the polymer can be widely used. More specifically, the specific polymer is preferably a polymer having a group as a desorption component in the side chain.
In the present invention, preferably 30% by mass or more, more preferably 40% by mass or more of all the structural units constituting the polymer are structural units capable of desorbing the desorbing component. The upper limit value is not particularly specified and may be 100% by mass. In the present invention, it is not necessary that all the constituent units having a group capable of desorbing the desorbed component are desorbed by heating at 80 to 250 ° C., and at least 70% by mass may be desorbed, 80 mass by mass. % Or more is preferably desorbed, 90% by mass or more is more preferably desorbed, and 99% by mass or more is more preferably desorbed.
Further, in the present invention, the desorption component of a specific polymer, preferably 20% by mass or more, more preferably 30% by mass or more, still more preferably 50% by mass or more, is desorbed. The upper limit is not particularly determined, but is, for example, 80% by mass or less, preferably 70% by mass or less, more preferably 60% by mass or less, and further preferably 50% by mass or less.
The specific polymer preferably contains a substituent represented by any of the following formulas (R-1) to (R-4).

In the formula, R ¹ to R ³ are independently monovalent substituents, R ⁴ to R ¹² are independently hydrogen atoms or monovalent substituents, and X is the bonding position of the polymer to the main chain. Represents.

^In the formulas (R-2) to (R ^{- 4} ), it is preferable that all of ^R4 to R6, ^R7 to R9, and R10 to ^R12 are not hydrogen atoms. The group containing the carbon atom bonded to the oxygen atom in the formula (R-1), that is, the carbon atom substituted by R ¹ to R ³ (hereinafter, the carbon atom at this position is referred to as an α carbon atom in each formula) is the second. It is preferably a tertiary alkyl group or a tertiary alkyl group. This also applies to the formula (R-2), and the group containing an α carbon atom is preferably a secondary alkyl group or a tertiary alkyl group. Unlike this, the group containing an α carbon atom in the formulas (R-3) and (R-4) is preferably a primary alkyl group or a secondary alkyl group.

It is preferable that at least one of R ¹ to R ³ is a substituent, and it is preferable that at least two are substituents. It is preferable that at least one of ^R4 to R6 is a substituent, and it is preferable that at least ^two are substituents. It is preferable that at least one of R ⁷ to R ⁹ is a substituent, two are hydrogen atoms and one is a substituent. It is preferable that at least one of R ¹⁰ to R ¹² is a substituent, two are hydrogen atoms and one is a substituent. When R ¹ to R ³ , R ⁴ to R ⁶ , R ⁷ to R ⁹ , and R ¹⁰ to R ¹² are substituents, examples of the substituents include groups having the same meaning as R ^r1 and a preferable range. It is the same.
R ¹ to R ³ , R ⁴ to R ⁶ , R ⁷ to R ⁹ , and R ¹⁰ to R ¹² may be coupled to each other to form a ring. When R ¹ to R ¹² are substituents, the substituent T may be further provided as long as the effects of the present invention are exhibited. For example, an alkyl group, an alkenyl group, an aryl group, an arylalkyl group and the like may be further substituted with a halogen atom (preferably a fluorine atom).

In the present invention, the CO bond in the formula is decomposed from the polymer containing the substituent represented by any of the formulas (R-1) to (R-4), and the formula (r1) or (r2) is used. Alternatively, it is preferable that a compound represented by the formula (r1-1) and having a molecular weight of 210 or more is eliminated.
In particular, the carbon atom substituted by R ^r1 and R ^r2 in the formula (r1) (the carbon atom in the second position with the carbon atom contained in R ^r3 as the first position) is R in the formula (R-1) before desorption. It is preferable that ¹ to R ³ are substituted carbon atoms (α carbon atoms). Further, it is preferable that the carbon atom at the 2-position of the formula (r1) is a carbon atom substituted with ^R4 to R6 of the formula (R ^- 2) before desorption. Regarding the formula (r2), the tertiary carbon atoms substituted by R ^r4 to R ^r6 are the carbons substituted by each of the above α carbon atoms, that is, R ¹ to R ³ of the formula (R-1) before desorption. It is preferably an atom or a carbon atom substituted by R ⁴ to R ⁶ of the formula (R-2).

^At least one of ^R1 to R3 is set so that it decomposes at the position of CO in the formula (R-1) and a double bond is formed at the desorption position (position of the α carbon atom) on the desorption component side. , An alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms), more preferably an ethyl group, still more preferably a methyl group. The same applies to the formula (R-2), and it is preferable that at least one of R ⁴ to R ⁶ is an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms). It is more preferably an ethyl group, and even more preferably a methyl group.

The specific polymer also preferably contains a polymerizable group, preferably the polymerizable group is a polymerizable group Ps, and more preferably contains a (meth) acryloyl group. The polymerizable group may be contained in a structural unit having a group capable of desorbing a desorbing component, or may be contained in another structural unit. In the present invention, it is preferable that at least a structural unit other than the structural unit having a group capable of desorbing a desorbing component has a polymerizable group.
In the specific polymer, the proportion of the structural units having a polymerizable group is preferably 10 to 100 mol%, more preferably 50 to 100 mol%, and 80 to 100 mol% of all the structural units. Is even more preferable.

Further, the specific polymer preferably contains an aromatic ring, and the aromatic ring is preferably a ring aCy or hCy. The aromatic ring may be contained by a structural unit having a group capable of desorbing a desorbing component, or may be contained by another structural unit. In the present invention, it is preferable that at least the structural unit having a group capable of desorbing the desorbing component has an aromatic ring.
In the specific polymer, the proportion of the structural unit containing the aromatic ring is preferably 10 to 100 mol%, more preferably 40 to 100 mol% of the total structural unit.

The type of the specific polymer is not particularly limited, but for example, (meth) acrylate resin, polyolefin resin, polystyrene resin, phenol resin (Novolak resin), cyclic polyolefin resin, polyamide resin, polyimide resin, polyacetal resin, polycarbonate resin, polyester resin. , Polyurethane resin, silicone resin and the like.

It is more preferable that the specific polymer contains at least one of the structural units represented by any of the following formulas (1) to (6).

^RP4 is a hydrogen atom or a methyl group.
RP1 represents a group capable of desorbing a compound represented by the formula (r1) or (r2) or a compound represented by the formula ( ^r1-1 ), and preferably formulas (R-1) to (R-1). It is a group containing the group represented by -4). In ^RP1 , a linking group may be interposed between the X of the formulas (R-1) to (R-4) and the atom of the main chain. Examples of the linking group include the linking group L. The linking group at this time may be trivalent or higher. In that case, the structural unit of the polymer is a plurality of groups represented by the formulas (R-1) to (R-4) via the linking group. Examples of the trivalent or higher linking group include an aromatic ring (aCy, hCy) structure group, an alkane structure group (preferably 1 to 40 carbon atoms, more preferably 1 to 30 carbon atoms), and an alkene structure. Group (preferably 2 to 40 carbon atoms, more preferably 2 to 30 carbon atoms, further preferably 2 to 20), group having an alkyne structure (preferably 2 to 40 carbon atoms, more preferably 2 to 30 carbon atoms). Further preferred), or a group relating to a combination thereof, or a group relating to a combination thereof and a linking group Lh can be mentioned. The group having an alkane structure, the group having an alkene structure, and the group having an alkyne structure may be chain-like or cyclic, and may be linear or branched. Hereinafter, the linking group having a valence of 3 or more is referred to as a linking group Lm.

In the formulas (1) to (6), two or more substituents ^RP1 may be substituted in the same structural unit. For example, in the formulas (1) and (2), a benzene ring in which two or more ^RP1s are substituted is also mentioned as a preferred embodiment of the present invention.

The main chain of the polymer and the substituent ^RP1 in the formulas (1) to (6) may have a substituent T as long as the effect of the present invention is exhibited.

式（１－１）～式（１－６）中、置換基Ｒ^Ｐ２はそれぞれ独立に重合性基を含む置換基であり、Ｒ^Ｐ４は水素原子またはメチル基である。Ｒ^Ｐ２に含まれる重合性基は上記Ｐｓであることが好ましい。Ｒ^Ｐ２は重合性基と主鎖との間に連結基をともなっていてもよく、２価の連結基の場合は連結基Ｌの例が挙げられ、３価以上の連結基の場合は連結基Ｌｍの例が挙げられる。式（１－１）～式（１－６）におけるＲ^Ｐ２が２つ以上ある場合、すなわち（Ｒ^Ｐ２）_ｎ（ｎは１以上の自然数）となるとき、複数のＲ^Ｐ２は互いに結合して環を形成していてもよい。また、Ｒ^Ｐ２は主鎖に結合して環を形成していてもよい。また、式（１－１）～式（１－６）の主鎖および置換基Ｒ^Ｐ２には本発明の効果を奏する範囲で置換基Ｔが置換していてもよい。
Ｒ^Ｐ２としては下記式（Ｔ２）であることが好ましい。Ｒ^Ｐ２の式量は、８０以上１０００以下が好ましく、１００以上８００以下がより好ましく、１５０以上６００以下がさらに好ましい。
－（Ｌ^４）_ｎ６－（Ｐ）_ｎ７ （Ｔ２）
Ｌ^４は上記の連結基ＬまたはＬｍであり、なかでもアルキレン基、アリーレン基、(オリゴ)アルキレンオキシ基、カルボニル基、酸素原子、アルカン構造の基、アルケン構造の基、アリール構造の基、これらの組合せに係る連結基が好ましい。ｎ６は０～６の整数である。Ｐは重合性基Ｐｓである。ｎ７は１～６の整数であり、１または２が好ましい。なお、ｎ７が３以上のときは、末端のＬ^４が４価以上の連結基になってすべてのＰが置換していてもよいが、２つ以上のＬ^４にＰが置換していてもよい。
特定のポリマーが式（１）で表される構成単位を含む場合、他の構成単位としては、式（１－１）で表される構成単位が好ましい。式（２）～式（６）についても、同様に、それぞれ、式（１－２）～式（１－６）で表される構成単位を含むことが好ましい。The specific 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 (1-1) to (1-6) (hereinafter, may be referred to as other structural units).

In the formulas (1-1) to (1-6), the substituent ^RP2 is a substituent containing a polymerizable group independently, and ^RP4 is a hydrogen atom or a methyl group. The polymerizable group contained in ^RP2 is preferably Ps. ^RP2 may have a linking group between the polymerizable group and the main chain, and in the case of a divalent linking group, an example of a linking group L is given, and in the case of a trivalent or higher linking group, a linking group is given. An example of Lm is given. When there are two or more ^RP2s in the equations (1-1) to (1-6), that is, ( ^RP2 ) _n (n is a natural number of 1 or more), the plurality of ^RP2s are combined with each other. It may form a ring. Further, ^RP2 may be bonded to the main chain to form a ring. Further, the main chain of the formulas (1-1) to (1-6) and the substituent ^RP2 may be substituted with the substituent T within the range in which the effect of the present invention is exhibited.
The ^RP2 is preferably the following formula (T2). The formula amount of ^RP2 is preferably 80 or more and 1000 or less, more preferably 100 or more and 800 or less, and further preferably 150 or more and 600 or less.
-(L ⁴ ) _n6- (P) _n7 (T2)
L ⁴ is the above-mentioned linking group L or Lm, and among them, an alkylene group, an arylene group, a (oligo) alkyleneoxy group, a carbonyl group, an oxygen atom, an alkane structure group, an alkane structure group, an aryl structure group, and the like. The linking group according to the combination of the above is preferable. n6 is an integer from 0 to 6. P is a polymerizable group Ps. n7 is an integer of 1 to 6, preferably 1 or 2. When n7 is 3 or more, L4 at the terminal may be a linking group having a valence of ⁴ or more and all Ps may be substituted, but even if P is substituted with two or more ^L4s . good.
When the specific polymer contains the structural unit represented by the formula (1), the structural unit represented by the formula (1-1) is preferable as the other structural unit. Similarly, it is preferable that the formulas (2) to (6) also include the structural units represented by the formulas (1-2) to (1-6), 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"). Still other structural units preferably have the skeletons of the formulas (1-1) to (1-6) defined by the other structural units. However, the substituent ^RP2 is a substituent ^RP3 without a polymerizable group. In addition, two or more ^RP2s in the other structural units, formulas (1-1), (1-2), (1-4), and (1-6), may be substituted with ring structural groups. In addition, the substituent T may be substituted in the portion of the main chain and ^RP3 of the other structural unit within the range in which the effect of the present invention is exhibited.
It is preferable that ^RP3 has the following formula (T3). The formula amount of ^RP3 is preferably 80 or more and 1000 or less, more preferably 100 or more and 800 or less, and further preferably 150 or more and 600 or less.
-(L ⁵ ) _n8- (T ¹ ) _n9 (T3)
L ⁵ is the above-mentioned linking group L or Lm, and among them, an alkylene group, an arylene group, a (oligo) alkyleneoxy group, a carbonyl group, an oxygen atom, an alkane structure group, an alkane structure group, an aryl structure group, and the like. The linking group according to the combination of the above is preferable. T ¹ is the above-mentioned substituent T, and examples thereof include an alkyl group, an aryl group, an alkoxy group, and an acyl group. n9 is an integer of 1 to 6, preferably 1 or 2. When n9 is 3 or more, L ⁵ at the terminal may be a linking group having a valence of 4 or more and all T ^1s may be substituted, but even if T ¹ is substituted with two or more L ^5s . good.

^In the formulas T2 and T3, L4, ^L5 , P and T1 may have the above ^- mentioned substituent T as long as the effect of the present invention is exhibited. For example, a group having an alkane structure, a group having an alkene structure, a group having an aryl structure and the like may be further substituted with a halogen atom (preferably a fluorine atom).

In a specific polymer, the structural unit represented by any of the formulas (1) to (6) may constitute all of the polymer (homoromer having a composition ratio of 100 mol%), or other structural units or the like. Further, it may be a copolymer with other structural units.

In a specific polymer, a structural unit having a group capable of desorbing a desorbing component (for example, a structural unit represented by the formulas (1) to (6)) / other structural units (a structural unit having a polymerizable group). ) / The composition ratio of the other structural units is preferably 10 to 100/0 to 80/0 to 50, more preferably 30 to 100/0 to 70/0 to 30, and 50 to 100 / based on the molar ratio. It is more preferably 0 to 50/0 to 10, and may be 50 to 90/10 to 50/0 to 10.
In a specific polymer, only one type of a structural unit having a group capable of desorbing a desorbing component, another structural unit (a structural unit having a polymerizable group), and another structural unit may be contained. However, it may contain two or more kinds. When two or more types are included, it is preferable that the total is the above ratio.
Further, in the present invention, it is also preferable that the constitution does not substantially contain other structural units other than the structural unit having a group capable of desorbing the desorbing component and the structural unit having a polymerizable group. The term "substantially free" means, for example, 5% by mass or less of all the constituent units, preferably 3% by mass or less, and further preferably 1% by mass or less.

The weight average molecular weight of the specific polymer is preferably 4,000 or more, more preferably 5,000 or more, still more preferably 7,000 or more, and even more preferably 10,000 or more. The upper limit is preferably 2,000,000 or less, more preferably 1,500,000 or less, still more preferably 1,000,000 or less. The method for measuring the weight average molecular weight shall be the method shown in the following examples.

The content of the specific polymer in the underlayer film forming composition for imprint is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and 1.0% by mass or more. Is even more preferable, and 1.5% by mass or more is even more preferable. 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. 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 suitably exhibited, and it becomes easy to form a uniform film over a wide area.
Further, the content of the specific polymer with respect to the non-volatile component (meaning the solid content excluding the solvent in the composition) in the underlayer film forming composition for imprint is preferably 90% by mass or more. It is more preferably 95% by mass or more, and further preferably 99% by mass or more. The upper limit is 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 suitably 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.

The substituent ^RP1 forming the elimination component in the above polymer can be introduced into the main chain by a conventional method.

<< Desorption reaction accelerator or precursor thereof >>
The desorption reaction accelerator is a compound that, by coexisting with a specific polymer in the system, acts on the specific polymer by a predetermined trigger and promotes a reaction of desorbing the desorption component from the specific polymer. The elimination reaction accelerator is a compound having an acidic functional group or a basic functional group. The elimination reaction accelerator is preferably present as a precursor thereof in the composition. Examples of the precursor include a compound that reacts by applying external energy such as heat or light and is converted into an elimination reaction accelerator compound. Specific examples include a thermoacid generator, a photoacid generator, a thermobase generator, a photobase generator, and the like, a thermoacid generator and a photoacid generator are preferable, and a thermoacid generator is more preferable.
When the desorption reaction accelerator has an acidic functional group, the pKa of the desorption accelerator is preferably 2 or less, more preferably 1 or less, still more preferably 0 or less. The lower limit value is not particularly specified, but may be, for example, -10 or more. When having a basic functional group, the pKa of the conjugate acid is preferably 5 or more, more preferably 7 or more, still more preferably 8 or more. The upper limit value is not particularly specified, but may be, for example, 15 or less.
In the present invention, specific examples of the desorption reaction accelerator or a precursor thereof are the acid growth agents described in paragraphs 0012, 0017, 0026 to 0037 of JP-A-2014-047329, and the light described in paragraphs 0038 to 0040. The acid generator, the thermal acid generator described in paragraph 0041, the photobase propagating agent described in paragraphs 0029 to 0066 of JP2012-237776, the photobase generator described in paragraphs 0073 to 0087, paragraphs 0087 to 0090. The thermal base generator according to Japanese Patent Publication No. 5687442, paragraphs 0012 to 0015, 0023 to 0029, and the base generator according to International Publication No. 2009/123122, paragraphs 0033 to 0075. The base generators described in paragraphs 0038-0069 of JP-A-2011-236416 can be used and their contents are incorporated herein.

The content of the desorption reaction accelerator or its precursor is preferably 0.1% by mass or more, more preferably 1.0% by mass or more, and 2.0% by mass or more of the non-volatile component. It is more preferable to have. As the upper limit, it is practical that it is 10.0% by mass or less, and it may be 5.0% by mass or less.
The desorption reaction accelerator or a precursor thereof may be used alone or in combination of two or more. When two or more types are used, the total amount is preferably in the above range.

<< alkylene glycol compound >>
The underlayer film forming composition for imprint may contain an alkylene glycol compound. The alkylene glycol compound preferably has 3 to 1000 alkylene glycol constituent units, more preferably 4 to 500, and even more preferably 5 to 100. It is more preferable to have 50 pieces. The weight average molecular weight (Mw) of the alkylene glycol compound is preferably 150 to 10000, more preferably 200 to 5000, still more 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, monostearate esters, monooleic acid esters, monoadipic 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 the 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 curable composition for imprint provided directly above the underlayer film can be further improved.

When the alkylene glycol compound is contained, it is 40% by mass or less of the non-volatile component, preferably 30% by mass or less, more preferably 20% by mass or less, and preferably 1 to 15% by mass. More preferred.
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 >>
A polymerization initiator may be contained as a non-volatile component. Examples of the polymerization initiator include a thermal polymerization initiator and a photopolymerization initiator, but a photopolymerization initiator is preferable from the viewpoint of improving the cross-linking reactivity with the curable composition for imprint. As the photopolymerization initiator, a radical polymerization initiator and a cationic polymerization initiator are preferable, and a radical polymerization initiator is more preferable. 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 containing a triazine skeleton, compounds containing an oxadiazole skeleton, compounds containing a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazoles, oxime derivatives and the like. Oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketooxime ethers, aminoacetophenone compounds, hydroxyacetophenones, azo compounds, azido compounds, metallocene compounds, organic boron compounds, iron arene complexes, etc. Can be mentioned. Of these, oxime compounds are preferred. 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.
Examples of the acylphosphine compound include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide. Further, commercially available products such as IRGACURE-819, IRGACURE1173, and IRGACURE-TPO (trade names: all manufactured by BASF) can be used.

The content of the photopolymerization initiator used in the above-mentioned underlayer film forming composition for imprint is, for example, 0.01 to 15% by mass, preferably 0.1 to 12% by mass, among the non-volatile components when blended. %, More preferably 0.2 to 7% by mass. When two or more kinds of photopolymerization initiators are used, the total amount thereof is within the above range.

<< Polymerization inhibitor >>
A polymerization inhibitor may be contained as a non-volatile component. The polymerization inhibitor (B) according to the present embodiment is a compound having an ability to trap radicals generated in the curable main agent (A) before they cause a growth reaction. As a result, the polymerization inhibitor (B) acts to inhibit the polymerization of the curable main agent (A).

The polymerization inhibitor (B) can be any of hydroquinones, catechols, phenothiazines, and phenoxazines. Specific examples of the polymerization inhibitor (B) include 4-methoxyphenol, 4-methoxy-1-naphthol, 4-tert-butylcatechol, 2,6-di-tert-butylphenol, and 2,6-di-tert-. Examples thereof include phenolic compounds such as butyl-p-cresol, 2-tert-butyl-4,6-dimethylphenol, 2,4,6-tri-tert-butylphenol, hydroquinone, and tert-butylhydroquinone. Specific examples of the polymerization inhibitor (B) include quinone compounds such as naphthoquinone and benzoquinone. Specific examples of the polymerization inhibitor (B) include amine compounds such as phenothiazine, phenoxazine, 4-hydroxy-2,2,6,6-tetramethylpiperidine. Specific examples of the polymerization inhibitor (B) include N such as 2,2,6,6-tetramethylpiperidine-N-oxyl and 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl. -Oxyl compounds can also be mentioned. The compounds listed here are merely examples, and the polymerization inhibitor (B) may be another compound.

The content of the polymerization inhibitor is preferably 0.0001% by mass or more and 10.0% by mass or less, more preferably 0.001% by mass or more and 1.0% by mass or less, and 0. It is more preferably 005% by mass or more and 0.1% by mass or less. Only one kind of polymerization inhibitor may be used, or two or more kinds may be used. When two or more types are used, it is preferable that the total amount thereof is within the above range.

<< Other ingredients >>
In addition to the above compounds, one or two types of non-volatile components to be blended in the underlayer film forming composition for imprint include a thermal polymerization initiator, an antioxidant, a leveling agent, a thickener, and a surfactant. The above may be included.
As the thermal polymerization initiator and the like, 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.
Further, in the present invention, the underlayer film forming composition for imprinting may be configured to be substantially free of a surfactant. The term "substantially free" means that the amount is 0.1% by mass or less of the non-volatile component in the underlayer film forming composition for imprinting.

<< Solvent for Underlayer Membrane >>
The underlayer film forming composition for imprint contains a solvent. The solvent preferably contains, for example, a compound (solvent for an underlayer film) that is liquid at 23 ° C. and has a boiling point of 250 ° C. or lower in a proportion of 70.0% by mass or more. Usually, the non-volatile component eventually forms the underlayer. The underlayer film forming composition for imprint preferably contains 80.0% by mass or more of the underlayer film solvent, more preferably 90.0% by mass or more, and more preferably 93.0% by mass or more. It is more preferably 94.0% by mass or more, and may be 95.0% by mass or more, 98.0% by mass or more, or 99.0% by mass or more.
The solvent may be contained in only one kind or two or more kinds in the underlayer film forming composition for imprinting. When two or more kinds are contained, it is preferable that the total amount is within 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. The lower limit is 23 ° C, but it is 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 containing any one or more of an ester group, a carbonyl group, a hydroxyl group and an ether group. Above all, 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 is used. It is particularly preferable to have.

Further, as the propylene glycol monoalkyl ether, propylene glycol monomethyl ether or propylene glycol monoethyl ether is preferable.
As the lactic acid 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 acetate, butyl acetate, propyl acetate, or 3-methoxybutyl acetate are preferable.
As the alkoxypropionic acid 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 ketones or methylamyl ketones are preferred.
As the cyclic ketone, methylcyclohexanone, isophorone or cyclohexanone is preferable.
As the lactone, γ-butyrolactone 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, 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 fp) of 30 ° C. or higher. Examples of such components include propylene glycol monomethyl ether (fp: 47 ° C.), ethyl lactate (fp: 53 ° C.), ethyl 3-ethoxypropionate (fp: 49 ° C.), methyl amyl ketone (fp: 42 ° C.), and the like. Cyclohexanone (fp: 30 ° C.), pentyl acetate (fp: 45 ° C.), methyl 2-hydroxyisobutyrate (fp: 45 ° C.), γ-butyrolactone (fp: 101 ° C.) or propylene carbonate (fp: 132 ° C.) are preferred. .. 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, water, 1-methoxy-2-propanol, propylene glycol monomethyl ether acetate (PGMEA), ethoxyethyl propionate, cyclohexanone, 2-heptanone, γ-butyrolactone, butyl acetate, propylene At least one selected from the group consisting of glycol monomethyl ether (PGME), ethyl lactate and 4-methyl-2-pentanol, and selected from the group consisting of 1-methoxy-2-propanol, PGMEA and butyl acetate. At least one is more preferred.

A conventionally known storage container can be used as the storage container for the underlayer film forming composition for imprint. In addition, as a storage container, a multi-layer bottle composed of 6 types and 6 layers of resin and a 7-layer structure of 6 types of resin are used for the inner wall of the container for the purpose of suppressing impurities from being mixed into raw materials and compositions. It is also preferable to use a bottle of plastic. Examples of such a container include the container described in Japanese Patent Application Laid-Open No. 2015-123351.

<Curing composition for imprint>
<< Polymerizable compound >>
The curable composition for imprint preferably contains a polymerizable compound, and preferably contains a polymerizable compound having an aromatic ring. The polymerizable compound may be a monofunctional polymerizable compound or a polyfunctional polymerizable compound. Further, it is preferable to contain both a monofunctional polymerizable compound and a polyfunctional polymerizable compound.

<<< Monofunctional Polymerizable Compound >>>
The molecular weight of the monofunctional polymerizable compound used in the curable composition for imprint is preferably 50 or more, more preferably 100 or more, still more preferably 150 or more. The molecular weight is also preferably 1,000 or less, more preferably 800 or less, still more preferably 300 or less, still more preferably 270 or less. Volatility tends to be suppressed by setting the molecular weight to the above lower limit or higher. By setting the molecular weight to the above upper limit or less, the viscosity tends to be reduced.
The boiling point of the monofunctional polymerizable compound used in the curable composition for imprint is preferably 85 ° C. or higher, more preferably 110 ° C. or higher, and even more preferably 130 ° C. or higher. Volatility can be suppressed by setting the boiling point to the above lower limit or higher. The upper limit of the boiling point is not particularly specified, but for example, the boiling point can be 350 ° C. or lower.

The type of the polymerizable group contained in the monofunctional polymerizable compound used in the curable composition for imprint is not particularly specified, but an ethylenically unsaturated group, an epoxy group and the like are exemplified, and an ethylenically unsaturated group is preferable. As the ethylenically unsaturated group, a (meth) acryloyl group is preferable, and an acryloyl group is more preferable.

The type of atom constituting the monofunctional polymerizable compound used in the curable composition for imprint is not particularly specified, but it is composed only of atoms selected from carbon atom, oxygen atom, hydrogen atom and halogen atom. Is preferable, and it is more preferable that the atom is composed of only an atom selected from a carbon atom, an oxygen atom and a hydrogen atom.

A preferred first embodiment of the monofunctional polymerizable compound used in the curable composition for imprint is a compound having a linear or branched hydrocarbon chain having 4 or more carbon atoms.
The hydrocarbon chain in the present invention represents an alkyl chain, an alkenyl chain, or an alkynyl chain, and an alkyl chain or an alkenyl chain is preferable, and an alkyl chain is more preferable.
In the present invention, the alkyl chain represents an alkyl group and an alkylene group. Similarly, the alkenyl chain represents an alkenyl group and an alkynylene group, and the alkynyl chain represents an alkynyl group and an alkynylene group. Among these, a linear or branched alkyl group or alkenyl group is more preferable, a linear or branched alkyl group is further preferable, and a linear alkyl group is further preferable.
The linear or branched hydrocarbon chain (preferably an alkyl group) has 4 or more carbon atoms, preferably 6 or more carbon atoms, more preferably 8 or more carbon atoms, further preferably 10 or more carbon atoms, and further preferably 10 or more carbon atoms. 12 or more is more preferable. The upper limit of the number of carbon atoms is not particularly specified, but may be, for example, 25 or less carbon atoms.
The linear or branched hydrocarbon chain may contain an ether group (—O—), but it is preferable that the linear or branched hydrocarbon chain does not contain an ether group from the viewpoint of improving releasability.
By using a monofunctional polymerizable compound having such a hydrocarbon chain, the elastic modulus of the cured product (pattern) is reduced and the releasability is improved with a relatively small amount of addition. Further, when a monofunctional polymerizable compound having a linear or branched alkyl group is used, the interfacial energy between the mold and the cured product (pattern) can be reduced, and the releasability can be further improved.
Preferred hydrocarbon groups of the monofunctional polymerizable compound used in the curable composition for imprint include (1) to (3).
(1) A linear alkyl group having 8 or more carbon atoms (2) A branched alkyl group having 10 or more carbon atoms (3) An alicyclic, aromatic ring or aromatic ring substituted with a linear or branched alkyl group having 1 or more carbon atoms. Heterocycle

(1) Linear alkyl group having 8 or more carbon atoms The linear alkyl group having 8 or more carbon atoms is more preferably 10 or more carbon atoms, further preferably 11 or more carbon atoms, and further preferably 12 or more carbon atoms. Further, the carbon number of 20 or less is preferable, the carbon number of 18 or less is more preferable, the carbon number of 16 or less is further preferable, and the carbon number of 14 or less is further preferable.
(2) Branched alkyl group having 10 or more carbon atoms The branched alkyl group having 10 or more carbon atoms is preferably 10 to 20 carbon atoms, more preferably 10 to 16 carbon atoms, and even more preferably 10 to 14 carbon atoms. 10 to 12 carbon atoms are more preferable.
(3) Alicyclic, aromatic ring or aromatic heterocycle substituted with a linear or branched alkyl group having 1 or more carbon atoms The linear or branched alkyl group having 1 or more carbon atoms is more composed of a linear alkyl group. preferable. The number of carbon atoms of the alkyl group is preferably 14 or less, more preferably 12 or less, still more preferably 10 or less.
The alicyclic ring, aromatic ring or aromatic heterocyclic 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 ring include an example of the ring Cz described later.

The monofunctional polymerizable compound used in the curable composition for imprint is preferably a compound in which a linear or branched hydrocarbon chain having 4 or more carbon atoms and a polymerizable group are directly bonded or via a linking group. , A compound in which any one of the groups (1) to (3) and the polymerizable group are directly bonded is more preferable. Examples of the linking group include -O-, -C (= O)-, -CH _2- , or a combination thereof. As the monofunctional polymerizable compound used in the present invention, (1) a linear alkyl (meth) acrylate in which a linear alkyl group having 8 or more carbon atoms and a (meth) acryloyloxy group are directly bonded is particularly used. preferable.

Ｒ^１２は、アルキル基（炭素数１～３６が好ましく、１～３０がより好ましく、１～２４がさらに好ましい）、脂環（炭素数３～２４が好ましく、３～１２がより好ましく、３～６がさらに好ましい）、芳香族環（炭素数６～２２が好ましく、６～１８がより好ましく、６～１０がさらに好ましい）および芳香族複素環（炭素数２～１２が好ましく、２～６がより好ましく、２～５がさらに好ましい）から選ばれる少なくとも１種、またはそれらの組合せによる基を表す。Ｒ^１１は水素原子またはメチル基を表す。Ｌ^１１は単結合または上記連結基Ｌを表し、アルキレン基またはアルケニレン基が好ましい。Ｒ^１２とＬ^１１は連結基Ｌを介してまたは介さずに結合して環を形成していてもよい。Ｒ^１２、Ｌ^１１は上記置換基Ｔを有していてもよい。置換基Ｔは複数が結合して環を形成してもよく、Ｒ^１２と結合して、またはＬ^１１と結合して環を形成してもよい。置換基Ｔが複数あるとき互いに同じでも異なっていてもよい。Ｒ^１２における脂環、芳香族環または芳香族複素環の好ましい範囲は、後述する環Ｃｚと同様である。The monofunctional polymerizable compound is preferably a compound represented by the following formula (I-1).

R ¹² has an alkyl group (preferably 1 to 36 carbon atoms, more preferably 1 to 30 carbon atoms, further preferably 1 to 24 carbon atoms) and an alicyclic (preferably 3 to 24 carbon atoms, more preferably 3 to 12 carbon atoms) and 3 to 12 carbon atoms. 6 is more preferred), aromatic rings (preferably 6 to 22 carbons, more preferably 6 to 18 and even more preferably 6 to 10) and aromatic heterocycles (preferably 2 to 12 carbons, 2 to 6 are preferred. More preferably, it represents a group of at least one selected from 2 to 5), or a combination thereof. R ¹¹ represents a hydrogen atom or a methyl group. L ¹¹ represents a single bond or the above-mentioned linking group L, and an alkylene group or an alkaneylene group is preferable. R ¹² and L ¹¹ may be bonded to each other with or without the linking group L to form a ring. R ¹² and L ¹¹ may have the above-mentioned substituent T. A plurality of substituents T may be bonded to form a ring, or may be bonded to R ¹² or L ¹¹ to form a ring. When there are a plurality of substituents T, they may be the same or different from each other. The preferred range of the alicyclic, aromatic ring or aromatic heterocycle in ^R12 is the same as that of the ring Cz described later.

Examples of the monofunctional polymerizable compound of the first embodiment include the following groups 1 and 2. However, it goes without saying that the present invention is not limited to these. Also, the first group is more preferable than the second group.
Group 1

Group 2

A preferred second embodiment of the monofunctional polymerizable compound used in the curable composition for imprinting is a compound having a cyclic structure. As the cyclic structure, a monocyclic ring or a fused ring having 3 to 8 membered rings is preferable. The number of rings constituting the fused ring is preferably two or three. The annular structure is more preferably a 5-membered ring or a 6-membered ring, and even more preferably a 6-membered ring. Also, a single ring is more preferable.
The number of cyclic structures in one molecule of the polymerizable compound may be one or two or more, but one or two is preferable, and one is more preferable. In the case of a fused ring, the fused ring is considered as one cyclic structure.

The following compounds can be exemplified as the monofunctional polymerizable compound of the second embodiment. However, it goes without saying that the present invention is not limited to these. Further, among the compounds described in the first embodiment, the compound having a cyclic structure is also exemplified as a preferable compound of the present embodiment.

In the present invention, a monofunctional polymerizable compound other than the above monofunctional polymerizable compound may be used as long as the gist of the present invention is not deviated, and monofunctional among the polymerizable compounds described in JP-A-2014-170949. Polymerizable compounds are exemplified and these contents are included herein.

The content of the monofunctional polymerizable compound used in the curable composition for imprint with respect to the total polymerizable compound is preferably 6% by mass or more, more preferably 8% by mass or more, still more preferably 10% by mass or more. , 12% by mass or more is more preferable. Further, the content is more preferably 60% by mass or less, and may be 55% by mass or less.
In the present invention, only one type of monofunctional polymerizable compound may be contained, or two or more types may be contained. When two or more kinds are contained, it is preferable that the total amount is within the above range.

<<< Polyfunctional Polymerizable Compound >>>
The polyfunctional polymerizable compound used in the curable composition for imprint is not particularly specified, but preferably contains at least one of an alicyclic ring, an aromatic ring and an aromatic heterocycle, and is preferably an aromatic ring and an aromatic ring. It is more preferable to contain at least one of the heterocycles. A compound containing at least one of an alicyclic ring, an aromatic ring and an aromatic heterocycle may be referred to as a ring-containing polyfunctional polymerizable compound in the following description.

The molecular weight of the ring-containing polyfunctional polymerizable compound used in the curable composition for imprint is preferably 1,000 or less, more preferably 800 or less, further preferably 500 or less, still more preferably 350 or less. .. By setting the upper limit of the molecular weight to 1,000 or less, the viscosity tends to be reduced. The lower limit of the molecular weight is not particularly specified, but may be, for example, 200 or more.

The number of polymerizable groups contained in the ring-containing polyfunctional polymerizable compound used in the curable composition for imprint is 2 or more, preferably 2 to 7, more preferably 2 to 4, further preferably 2 or 3. 2 is more preferable.

The type of the polymerizable group of the ring-containing polyfunctional polymerizable compound used in the curable composition for imprint is not particularly specified, but ethylenically unsaturated groups, epoxy groups and the like are exemplified, and the ethylenically unsaturated group is used. preferable. As the ethylenically unsaturated group, a (meth) acryloyl group is more preferable, and an acryloyl group is further preferable. One molecule may contain two or more kinds of polymerizable groups, or may contain two or more kinds of polymerizable groups of the same type.

The types of atoms constituting the ring-containing polyfunctional polymerizable compound used in the curable composition for imprint are not particularly specified, but are composed only of atoms selected from carbon atoms, oxygen atoms, hydrogen atoms and halogen atoms. It is more preferable that the atom is composed of only an atom selected from a carbon atom, an oxygen atom and a hydrogen atom.

The ring contained in the ring-containing polyfunctional polymerizable compound used in the curable composition for imprint 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. Further, the ring may be an alicyclic ring, an aromatic ring or an aromatic heterocycle, but is preferably an aromatic ring or an aromatic heterocycle, and more preferably an aromatic ring. .. Specific examples of the ring include an example of the ring Cz.
The number of rings in the ring-containing polyfunctional polymerizable compound used in the curable composition for imprint may be one or two or more, but one or two is preferable, and one is more preferable. .. In the case of a fused ring, the fused ring is considered as one.
The structure of the ring-containing polyfunctional polymerizable compound used in the curable composition for imprint is (polymerizable group)-(single bond or divalent linking group)-(divalent group having a ring)-(single bond). Alternatively, it is preferably represented by a divalent linking group)-(polymerizable group). Here, as the linking group, an alkylene group is more preferable, and an alkylene group having 1 to 3 carbon atoms is further preferable.

Ｑは、脂環（炭素数３～２４が好ましく、３～１２がより好ましく、３～６がさらに好ましい）、芳香族環（炭素数６～２２が好ましく、６～１８がより好ましく、６～１０がさらに好ましい）および芳香族複素環（炭素数２～１２が好ましく、２～６がより好ましく、２～５がさらに好ましい）から選ばれる少なくとも１種を有する１＋ｑ価の基を表す。Ｒ^２１およびＲ^２２はそれぞれ独立に水素原子またはメチル基を表す。Ｌ^２１およびＬ^２２はそれぞれ独立に単結合または上記連結基Ｌを表す。ＱとＬ^２１またはＬ^２２は連結基Ｌを介してまたは介さずに結合して環を形成していてもよい。Ｑ、Ｌ^２１およびＬ^２２は上記置換基Ｔを有していてもよい。置換基Ｔは複数が結合して環を形成してもよく、Ｑと結合して、またはＬ^２１またはＬ^２２と結合して環を形成してもよい。置換基Ｔが複数あるとき互いに同じでも異なっていてもよい。Ｑにおける脂環、芳香族環または芳香族複素環の好ましい範囲は、後述する環Ｃｚが挙げられる。ｑは１～５の整数であり、１～３の整数が好ましく、１または２がより好ましく、１がさらに好ましい。
Ｑは、複数の脂環、複数の芳香族環、複数の芳香族複素環、脂環と芳香族環、脂環と芳香族複素環、芳香族環と芳香族複素環が連結した構造を有していてもよい。芳香族環が連結した構造としては、上記式Ａｒ１～Ａｒ５の構造が挙げられる。The ring-containing polyfunctional polymerizable compound used in the curable composition for imprint is preferably represented by the following formula (I-2).

Q is an alicyclic ring (preferably 3 to 24 carbon atoms, more preferably 3 to 12 carbon atoms, further preferably 3 to 6 carbon atoms), an aromatic ring (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, 6 to 6 to 6). Represents a 1 + q-valent group having at least one selected from (preferably 10) and aromatic heterocycles (preferably 2-12 carbon atoms, more preferably 2-6, more preferably 2-5). 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 linking group L. Q and L ²¹ or L ²² may be bonded to each other with or without the linking group L to form a ring. Q, L ²¹ and L ²² may have the above-mentioned substituent T. A plurality of substituents T may be bonded to form a ring, bonded to Q, or bonded to L ²¹ or L ²² to form a ring. When there are a plurality of substituents T, they may be the same or different from each other. A preferable range of the alicyclic ring, the aromatic ring or the aromatic heterocycle in Q is the ring Cz described later. q is an integer of 1 to 5, preferably an integer of 1 to 3, more preferably 1 or 2, and even more preferably 1.
Q has a structure in which a plurality of alicyclic rings, a plurality of aromatic rings, a plurality of aromatic heterocycles, an alicyclic and an aromatic ring, an alicyclic and an aromatic heterocycle, and an aromatic ring and an aromatic heterocycle are linked. You may be doing it. Examples of the structure in which the aromatic rings are linked include the structures of the above formulas Ar1 to Ar5.

第２群

Examples of the polyfunctional polymerizable compound used in the curable composition for imprint include the following groups 1 and 2. However, it goes without saying that the present invention is not limited to these. The first group is more preferable.
Group 1

Group 2

Ｌ^３０は、直鎖もしくは分岐のアルカン構造の基（炭素数１～１２が好ましく、１～６がより好ましく、１～３がさらに好ましい）、直鎖もしくは分岐のアルケン構造の基（炭素数２～１２が好ましく、２～６がより好ましく、２～３がさらに好ましい）、直鎖もしくは分岐のアルキン構造の基（炭素数２～１２が好ましく、２～６がより好ましく、２～３がさらに好ましい）から選ばれる少なくとも１種を有する１＋ｒ価の基を表す。Ｒ^２５およびＲ^２６はそれぞれ独立に水素原子またはメチル基を表す。Ｌ^２５およびＬ^２６はそれぞれ独立に単結合または上記連結基Ｌを表す。Ｌ^３０とＬ^２５またはＬ^２６とは連結基Ｌを介してまたは介さずに結合して環を形成していてもよい。Ｌ^２５、Ｌ^２６およびＬ^３０は上記置換基Ｔを有していてもよい。置換基Ｔは複数が結合して環を形成してもよく、他の連結基と結合して環を形成してもよい。置換基Ｔが複数あるとき互いに同じでも異なっていてもよい。ｒは１～４の整数であり、１～３の整数が好ましく、１または２がより好ましく、１がさらに好ましい。なお、Ｌ^３０にはヘテロ連結基（Ｏ、Ｓ、ＮＲ^Ｎ）が介在していてもよい。ヘテロ連結基が介在する数は、Ｌ^３０の炭素数１～６個に１つの割合であることが好ましい。The curable composition for imprint may contain a polyfunctional polymerizable compound other than the ring-containing polyfunctional polymerizable compound. As the other polyfunctional polymerizable compound, a compound represented by the following formula (I-3) is preferable.

L ³⁰ is a linear or branched alkyne structure group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms), and a linear or branched alkyne structure group (carbon number 2). ~ 12 is preferable, 2 to 6 is more preferable, 2 to 3 is more preferable), and a linear or branched alkyne structure group (2 to 12 carbon atoms is preferable, 2 to 6 is more preferable, and 2 to 3 is further preferable. Represents a 1 + r valence group having at least one selected from). R ²⁵ and R ²⁶ independently represent a hydrogen atom or a methyl group, respectively. L ²⁵ and L ²⁶ each independently represent a single bond or the linking group L. L ³⁰ and L ²⁵ or L ²⁶ may be bonded to each other with or without the linking group L to form a ring. L ²⁵ , L ²⁶ and L ³⁰ may have the above-mentioned substituent T. A plurality of substituents T may be bonded to form a ring, or may be bonded to another linking group to form a ring. When there are a plurality of substituents T, they may be the same or different from each other. r is an integer of 1 to 4, preferably an integer of 1 to 3, more preferably 1 or 2, and even more preferably 1. A heterolinking group (O, S, NR ^N ) may be interposed in L ³⁰ . The number of intervening heterolinking groups is preferably 1 in 1 to 6 carbon atoms of ^L30 .

Examples of other polyfunctional polymerizable compounds used in the curable composition for imprint include polyfunctional polymerizable compounds having no ring among the polymerizable compounds described in JP-A-2014-170949. The contents of are included herein. More specifically, for example, the following compounds are exemplified.

Examples of the ring Cz include the following aromatic rings, aromatic heterocycles and alicyclic rings.
As the aromatic ring contained in the compound containing an aromatic ring, one having 6 to 22 carbon atoms is preferable, 6 to 18 is more preferable, and 6 to 10 is even more preferable. Specific examples of the aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a phenalene ring, a fluorene ring, an acenaphthylene ring, a biphenylene ring, an indene ring, an indane ring, a triphenylene ring, a pyrene ring, a chrysene ring, and a perylene ring. , Tetrahydronaphthalene ring and the like. Of these, a benzene ring or a naphthalene ring is preferable, and a benzene ring is more preferable. The aromatic ring may have a structure in which a plurality of aromatic rings are linked, and examples thereof include a biphenyl ring and a bisphenyl ring.
The aromatic heterocycle preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 5 carbon atoms. Specific examples thereof include thiophene ring, furan ring, pyrrol ring, imidazole ring, pyrazole ring, triazole ring, tetrazole ring, thiazole ring, oxazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, isoindole ring, and indole. Ring, indazole ring, purine ring, quinolidine ring, isoquinoline ring, quinoline ring, phthalazine ring, naphthylidine ring, quinoxalin ring, quinazoline ring, cinnoline ring, carbazole ring, aclysine ring, phenazine ring, phenothiazine ring, phenoxazine ring and the like. Be done.
The alicyclic has preferably 3 to 22 carbon atoms, more preferably 4 to 18 carbon atoms, and even more preferably 6 to 10 carbon atoms. Specific examples thereof include a cyclopropane ring, a cyclobutane ring, a cyclobutene ring, a cyclopentane ring, a cyclohexane ring, a cyclohexene ring, a cycloheptane ring, a cyclooctane ring, a dicyclopentadiene ring, a tetrahydrodicyclopentadiene ring, and an octahydronaphthalene ring. Examples thereof include a decahydronaphthalene ring, a hexahydroindane ring, a bornan ring, a norbornene ring, a norbornene ring, an isobornane ring, a tricyclodecane ring, a tetracyclododecane ring, and an adamantane ring.

The polyfunctional polymerizable compound is preferably contained in an amount of 30% by mass or more, more preferably 45% by mass or more, still more preferably 50% by mass or more, based on the total polymerizable compound in the curable composition for imprint. 55% by mass or more is more preferable, 60% by mass or more may be used, and 70% by mass or more may be further used. Further, the upper limit value is preferably less than 95% by mass, more preferably 90% by mass or less, and may be 85% by mass or less.
The curable composition for imprint may contain only one kind of polyfunctional polymerizable compound, or may contain two or more kinds. When two or more kinds are contained, it is preferable that the total amount is within the above range.

In the curable composition for imprint used in the present invention, 85% by mass or more of the composition is preferably a polymerizable compound, more preferably 90% by mass or more is a polymerizable compound, and 93% by mass or more is. More preferably, it is a polymerizable compound.

Hansen solubility parameter (HSP) vector of curable composition for imprint:
(I) The dispersion term component (d component) is preferably 14.0 to 20.0, more preferably 15.0 to 19.0, and preferably 16.0 to 18.5. More preferred;
(Ii) The polar term component (p component) is preferably 3.5 to 8.0, more preferably 3.8 to 6.0, and preferably 4.0 to 5.0. More preferred;
(Iii) The hydrogen bond term component (h component) is preferably 4.0 to 8.0, more preferably 4.7 to 7.0, and 5.2 to 6.5. Is even more preferable.
The dispersion term component, the polar term component, and the hydrogen bond term component of the HSP vector of the curable composition for imprint are set by the methods described in Examples described later.

<< Other ingredients >>
The curable composition for imprint may contain additives other than the polymerizable compound. Other additives may include a polymerization initiator, a surfactant, a sensitizer, a mold release agent, an antioxidant, a polymerization inhibitor and the like.
Specific examples of the curable composition for imprint that can be used in the present invention include the compositions described in JP-A-2013-036027, JP-A-2014-090133, and JP-A-2013-189537. And these contents are incorporated herein. Further, the description of the above-mentioned publication can be referred to with respect to the preparation of the curable composition for imprint and the method of forming the film (pattern forming layer), and these contents are incorporated in the present specification.

<< Physical characteristics, etc. >>
The viscosity of the curable composition for imprint is preferably 20.0 mPa · s or less, more preferably 15.0 mPa · s or less, and may be 11.0 mPa · s or less, and further. It may be 9.0 mPa · s or less. The lower limit of the viscosity is not particularly limited, but may be, for example, 4.0 mPa · or more, and further 5.0 mPa · s or more.

The surface tension (γResist) of the curable composition for imprint is preferably 29.0 mN / m or more, more preferably 30.0 mN / m or more, and further preferably 31.0 mN / m or more. preferable. By using the curable composition for imprint having a high surface tension, the capillary force is increased, and the curable 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 is preferably 42.0 mN / m or less, preferably 40.0 mN / m, from the viewpoint of imparting the relationship with the underlying film and inkjet suitability. It is more preferably 38.0 mN / m or less, and may be 38.0 mN / m or less.

The Onishi parameter of the curable composition for imprint is preferably 5.0 or less, more preferably 4.0 or less, and further preferably 3.7 or less. The lower limit of the Onishi parameter of the curable composition for imprint is not particularly specified, but may be, for example, 1.0 or more, and further may be 2.0 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 polymerizable compound of the curable 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 Hansen solubility parameter (HSP) vector of the polymerizable compound contained in the curable composition for imprint:
(I) The dispersion term component (d component) is preferably 14.0 to 20.0, more preferably 15.0 to 19.0, and preferably 16.0 to 18.5. More preferred;
(Ii) The polar term component (p component) is preferably 3.5 to 8.0, more preferably 3.8 to 6.0, and preferably 4.0 to 5.0. More preferred;
(Iii) The hydrogen bond term component (h component) is preferably 4.0 to 8.0, more preferably 4.7 to 7.0, and 5.2 to 6.5. Is even more preferable.
The dispersion term component, the polarity term component, and the hydrogen bond term component of the HSP vector are each set by the methods described in Examples described later. When there are a plurality of applicable components in the calculation of the HSP vector, it is preferable that at least one of them satisfies the above range, and it is more preferable that the largest amount of components satisfy the above range.

In the present invention, the content of the solvent in the curable composition for imprint is preferably 5% by mass or less, more preferably 3% by mass or less, and 1% by mass. The following is more preferable.
The curable composition for imprint is a polymer (preferably a polymer having 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. ) Can be 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, preferably 0.005% by mass or less, and is not contained at all. Is more preferable.

As a container for the curable composition for imprint used in the present invention, a conventionally known container can be used. In addition, as a storage container, a multi-layer bottle composed of 6 types and 6 layers of resin and a 7-layer structure of 6 types of resin are used for the inner wall of the container for the purpose of suppressing impurities from being mixed into raw materials and compositions. It is also preferable to use a bottle of plastic. Examples of such a container include the container described in Japanese Patent Application Laid-Open No. 2015-123351.

<Kit>
The present invention discloses a kit containing an imprint underlayer film forming composition and an imprint curable composition containing a polymerizable compound.
The kit of the present invention comprises the Hansen solubility parameter of the desorption component (the compound represented by the formula (r1) or (r2) or the compound represented by the formula (r1-1)) and the Hansen of the curable composition for imprint. The ΔHSP value calculated by the following formula (H1) based on the solubility parameter is preferably 5 or less, more preferably 7.0 or less, further preferably 5.0 or less, and 4.0. The following is more preferable. The lower limit may be 0, but it is practically 0.1 or more.
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 curable composition for imprinting and the dispersion term component of the Hansen solubility parameter vector of the elimination component.
ΔP is the difference between the polar term component of the Hansen solubility parameter vector of the curable composition for imprint and the polar term component of the Hansen solubility parameter vector of the desorption component.
ΔH is the difference between the hydrogen bond term component of the Hansen solubility parameter vector of the curable composition for imprint and the hydrogen bond term component of the Hansen solubility parameter vector of the elimination component.

<Laminate and its manufacturing method>
A preferred embodiment of the kit of the present invention is a laminate formed from this kit. The laminate of the present embodiment comprises a lower layer film formed from the imprint lower layer film forming composition and an imprint layer formed from the imprint curable composition and located on the surface of the lower layer film. It is preferable to have. The production method thereof is not particularly limited, but a production method comprising applying the curable composition for imprint to the surface of the underlayer film formed from the underlayer film forming composition for imprint using the above kit. Can be mentioned. At this time, the curable composition for imprinting is preferably applied to the surface of the underlayer film by an inkjet method (IJ method). Further, the method for producing the laminate includes a step of applying the above-mentioned imprint underlayer film forming composition on a substrate in a layered manner, and the imprinting underlayer film forming composition applied in the above-mentioned layered form is applied at 80 to 250 ° C. (preferably). Is preferably included in heating (baking) at (150 to 250 ° C.) (process temperature).

<Cured product pattern and its manufacturing method>
The method for producing a cured product pattern according to a preferred embodiment of the present invention is a method for producing a cured product pattern using the above kit, in which a lower layer film forming composition for imprint is applied on a substrate to form a lower layer. The lower film forming step of forming the film, the application step of applying the curable composition for imprint to the surface of the lower film, the curable composition for imprint, and the pattern for transferring the pattern shape. A mold contacting step of bringing the mold into contact with each other, a light irradiation step of irradiating the curable composition for imprint with light to form a cured product, and a mold separating step of separating the cured product from the mold. Have.
Hereinafter, a method for forming a cured product pattern (a method for producing a cured product pattern) will be described with reference to FIG. 1. Needless to say, the configuration of the present invention is not limited by the drawings.

<< Underlayer film forming process >>
In the lower layer film forming step, the lower layer film 2 is formed on the substrate 1 as shown in FIGS. 1 (1) and 1 (2). The underlayer film is preferably formed by applying the underlayer film forming composition for imprint in a layered manner on the substrate.

The method of applying the underlayer film forming composition for imprinting on the substrate is not particularly specified, and a generally well-known application method can be adopted. Specifically, as the application method, 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, or an inkjet method. Is exemplified, and the spin coating method is preferable.
Further, after applying the imprinting underlayer film forming composition on the substrate in a layered manner, the solvent is preferably volatilized (dried) by heat to form a thin underlayer film.

The thickness of the underlayer film 2 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. The thickness of the underlayer film is preferably 40 nm or less, more preferably 30 nm or less, further preferably 20 nm or less, further preferably 15 nm or less, and further preferably 10 nm or less. May be good. By setting the film thickness to the above lower limit value or more, the expandability (wetting property) of the curable composition for imprinting on the lower film is improved, and a uniform residual film can be formed after imprinting. By setting the film thickness to the above upper limit value or less, the residual film after imprinting becomes thin, the film thickness unevenness is less likely to occur, and the uniformity of the residual film tends to be improved.

The material of the substrate is not particularly specified, and the description in paragraph 0103 of JP-A-2010-109092 (the publication number of the corresponding US application is the specification of US Patent Application Publication No. 2011/0183127) can be referred to. The contents of are incorporated herein by reference. In the present invention, 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, GaP, AlGaAs, Examples thereof include a substrate composed of 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.

<< Application process >>
In the application step, for example, as shown in FIG. 1 (3), the curable composition 3 for imprinting is applied to the surface of the underlayer film 2.
The method of applying the curable composition for imprint is not particularly specified, and paragraph 0102 of JP2010-109092 (the publication number of the corresponding US application is the publication number of US Patent Application Publication No. 2011/0199592). Can be taken into account and this content is incorporated herein by reference. The curable composition for imprint is preferably applied to the surface of the underlayer film by an inkjet method. Further, the curable composition for imprint may be applied by multiple coating. In a method of arranging droplets on the surface of the lower layer film by an inkjet method or the like, the amount of the droplets is preferably about 1 to 20 pL, and it is preferable to arrange the droplets on the surface of the lower layer film at intervals. The droplet spacing is preferably 10 to 1000 μm. In the case of the inkjet method, the droplet spacing is the placement spacing of the inkjet nozzles.
Further, the volume ratio of the lower layer film 2 and the film-like curable composition for imprint 3 applied on the lower layer film is preferably 1: 1 to 500, more preferably 1:10 to 300. It is preferably 1:50 to 200, and more preferably 1:50 to 200.
Further, the method for producing a laminate according to a preferred embodiment of the present invention is a method for producing a laminate using the kit of the present invention, in which the surface of the underlayer film formed from the above-mentioned underlayer film forming composition for imprinting is used. Includes applying a curable composition for imprinting. Further, the method for producing a laminate according to a preferred embodiment of the present invention includes a step of applying the above-mentioned underlayer film forming composition for imprint in a layered manner on a substrate, and the underlayer film forming composition for imprinting applied in the above-mentioned layered form. It is preferable to include heating (baking) the product at 80 to 250 ° C. (preferably 150 ° C. or higher and 250 ° C. or lower). The heating time can be 30 seconds to 5 minutes.

<< Mold contact process >>
In the mold contacting step, for example, as shown in FIG. 1 (4), the imprintable curable composition 3 and the mold 4 having a pattern for transferring the pattern shape are brought into contact with each other. By going through such a step, a desired cured product pattern (imprint pattern) can be obtained.
Specifically, the mold 4 is pressed against the surface of the film-like curable composition for imprint 3 in order to transfer a desired pattern to the film-like curable composition for imprint.

The mold may be a light-transmitting mold or a light-impermeable mold. When a light-transmitting mold is used, it is preferable to irradiate the imprintable curable composition 3 with light from the mold side. On the other hand, when a light-transmissive mold is used, it is preferable to use a light-transmitting substrate as the substrate and irradiate light from the substrate side. In the present invention, it is more preferable to use a light-transmitting mold and irradiate light from the mold 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 in the present invention, the mold pattern manufacturing method is not particularly limited. 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, thin-film deposition 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.

In the above-mentioned method for producing a cured product pattern, it is preferable that the mold pressure is 10 atm or less when performing imprint lithography using the curable composition for imprinting. By setting the mold pressure to 10 atm or less, the mold and the substrate are less likely to be deformed, and the pattern accuracy tends to be improved. It is also preferable because the pressurization is low and the device tends to be reduced. The mold pressure is preferably selected from a range in which the uniformity of the mold transfer can be ensured while the residual film of the curable composition for imprint corresponding to the convex portion of the mold is reduced.
It is also preferable that the contact between the curable composition for imprint and the mold is performed in an atmosphere containing helium gas or condensable gas, or both helium gas and condensable gas.

<< Light irradiation process >>
In the light irradiation step, the curable composition for imprint is irradiated with light to form a cured product. The irradiation amount of light irradiation in the light irradiation step may be sufficiently larger than the minimum irradiation amount required for curing. The irradiation amount required for curing is appropriately determined by examining the consumption of unsaturated bonds of the curable composition for imprinting.
The type of light to be irradiated is not particularly specified, but ultraviolet light is exemplified.
Further, in the imprint lithography applied to the present invention, the substrate temperature at the time of light irradiation is usually room temperature, but light irradiation may be performed while heating in order to enhance the reactivity. If a vacuum state is used as a pre-stage of light irradiation, it 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 and the curable composition for imprinting. You may irradiate with light. Further, in the above-mentioned method for producing a cured product pattern, the preferable degree of vacuum at the time of light irradiation is in the range of 10 ^-1 Pa to normal pressure.
At the time of exposure, the exposure illuminance is preferably in the range of 1 to 500 mW / cm ² , and more preferably in the range of 10 to 400 mW / cm ² . The exposure time is not particularly limited, but is preferably 0.01 to 10 seconds, more preferably 0.5 to 1 second. The exposure amount is preferably in the range of 5 to 1000 mJ / cm ² , and more preferably in the range of 10 to 500 mJ / cm ² .
In the above-mentioned method for producing a cured product pattern, a film-shaped curable composition for imprint (pattern forming layer) is cured by light irradiation, and then, if necessary, heat is applied to the cured pattern to further cure the cured composition. It may include a step. The temperature for heat-curing the imprint-curable composition after light irradiation is preferably 150 to 280 ° C, more preferably 200 to 250 ° C. The time for applying heat is preferably 5 to 60 minutes, more preferably 15 to 45 minutes.

<< Mold release process >>
In the mold release step, the cured product and the mold are separated from each other (FIG. 1 (5)). The obtained cured product pattern can be used for various purposes as described later.
That is, the present invention discloses a laminate having a cured product pattern formed from the curable composition for imprinting on the surface of the underlayer film. The film thickness of the pattern forming layer made of the curable composition for imprint used in the present invention varies depending on the intended use, but is about 0.01 μm to 30 μm.
Further, as will be described later, etching or the like can also be performed.

<Cured product pattern and its application>
As described above, the cured product pattern formed by the above-mentioned cured product pattern manufacturing method shall be used as a permanent film used in a liquid crystal display device (LCD) or the like, or as an etching resist (lithographic mask) for manufacturing a semiconductor device. Can be done.
In particular, the present invention discloses a method for manufacturing a circuit board, which comprises a step of obtaining a cured product pattern by the method for producing a cured product pattern 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 injecting ions into the substrate using the cured product pattern obtained by the above-mentioned method for producing a cured product pattern as a mask and forming an electronic member are formed. It may have a process. The circuit board is preferably a semiconductor element. Further, the present invention discloses a method for manufacturing an electronic device having a step of obtaining a circuit board by the method of manufacturing the circuit board and a step of connecting the circuit board and a control mechanism for controlling the circuit board.
Further, a grid pattern is formed on the glass substrate of the liquid crystal display device by using the pattern formed by the cured product pattern manufacturing method, and the polarizing plate has a large screen size (for example, 55 inches or more than 60 inches) with less reflection or absorption. It is possible to manufacture the plate at low cost. For example, the polarizing plate described in JP-A-2015-132825 and International Publication No. 2011/132649 can be manufactured. In addition, 1 inch is 25.4 mm.
As shown in FIGS. 1 (6) and 1 (7), the cured product pattern formed in 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 silicon substrate (silicon wafer or the like) on which a thin film such as SiO ₂ is formed is used as the substrate, and the cured product pattern manufacturing method is used on the substrate, for example. Form a fine cured product pattern on the order of nano or micron. The present invention is particularly advantageous in that a nano-order fine pattern can be formed, and further, 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 may be, for example, 1 nm or more.
A method for manufacturing an imprint mold, which comprises a step of obtaining a cured product pattern on a substrate by a method for producing a cured product pattern and a step of etching the substrate using the obtained cured product pattern, is also preferable. It is mentioned as an embodiment.
A desired cured product pattern can be formed on the substrate 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. The cured product pattern has particularly good etching resistance to dry etching. That is, the pattern formed by the cured product pattern manufacturing method is preferably used as a mask for lithography.

FIG. 2 is a plan view schematically showing a wet and spread state of the curable composition for imprint when the curable composition for imprint is applied to the surface of the underlayer film by an inkjet method. When the curable composition for imprint is applied by the inkjet (IJ) method, for example, as shown in the figure, droplets of the curable composition 22 for imprint are dropped on the surface of the underlayer film 21 at equal intervals. (Fig. 2 (a)). When the mold is brought into contact there, the droplets spread on the underlayer film 21 and become film-like curable compositions for imprint 22a, 22b, 22c (FIGS. 2 (b) and 2 (c), (D)). However, if the curable composition for imprint does not spread uniformly, for example, when the wet spread stops in FIG. 2C, the state of the curable composition for imprint 22b is completely on the underlayer film 21. A film that does not spread is formed. That is, there may be a region 23 having a thin film thickness or no film. In this case, the pattern of the mold is not sufficiently filled with the curable composition for imprinting, and the imprinting layer has a portion without the pattern. For example, when etching is performed using a pattern of an imprint layer having a defect or an insufficient thickness in such a part as a mask, a region with a thin film thickness or a region without a film 23 and a region 22b other than the film thickness are used. Etching unevenness occurs, and it becomes difficult to uniformly etch and transfer the desired pattern shape over the entire surface of the imprint region.
On the other hand, according to the underlayer film forming composition for imprint of the present invention, the interfacial tension between the underlayer film formed thereby and the curable composition for imprint is improved, and the wettability is improved. Therefore, the curable composition for imprint 22c is more reliably spread to every corner of the state shown in FIG. 2 (d). As a result, the curable composition for imprint is accurately and sufficiently filled in the mold throughout, and good patterning with uniform thickness can be achieved in the formed imprint layer. In addition, the improved fillability enables high-speed imprinting, which can lead to an improvement in throughput.
In the above description, the mechanism of action according to the preferred embodiment of the present invention has been described by giving an example of applying the curable composition for imprint on the underlayer film by the inkjet method, but the present invention is limited thereto. It is not interpreted as. For example, even in screen coating and spin coating, good wettability and excellent filling property lead to advantages in processing and product quality, and the effects of the invention can be suitably exhibited.

Specifically, the pattern formed in the present invention includes a recording medium such as a magnetic disk, a light receiving element such as a solid-state image pickup element, a light emitting element such as an LED (light emitting die) or an organic EL (organic electroluminescence), and a liquid crystal display. Optical devices such as liquid crystal displays, diffraction grids, relief holograms, optical waveguides, optical filters, optical components such as microlens arrays, thin films, organic transistors, color filters, antireflection films, polarizing plates, polarizing elements, optical films, Flat panel display members such as pillars, nanobiodevices, immunoanalytical chips, deoxyribonucleic acid (DNA) separation chips, microreactors, photonic liquid crystals, and fine pattern formation (directed self-assembury) using self-assembly of block copolymers, It can be preferably used for producing a guide pattern or the like for 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.

<Synthesis example of polymer G-1>
Methanol (Methanol) (300 g), 5-Bromoisophthalic Acid (10 g manufactured by Tokyo Chemical Industry Co., Ltd.), and concentrated sulfuric acid (1 mL) are added to an N ₂ flowing three-necked flask, and the mixture is heated to 90 ° C. and aged for 4 hours. Was done. Then, it was concentrated under reduced pressure. The concentrate, ethyl acetate (500 g) and 3% aqueous sodium hydrogen carbonate solution (300 g) were added to the separating funnel, and the mixture was stirred. The organic layer was concentrated to synthesize the target compound (intermediate G-1A).

Tetrahydrofuran (THF) (300 g) and G-1A (10 g) are added to the N ₂ flowing three-necked flask, cooled to 0 ° C., and LiAlH ₄ (manufactured by Wako Pure Chemical Industries, Ltd., 3 g) is added little by little. In addition, it was aged for 2 hours. Then, water (3 g), a 15% aqueous sodium hydroxide solution (3 g) and water (9 g) were added, and the mixture was aged for 1 hour. Then, the target compound (intermediate G-1B) was synthesized by filtering and concentrating the filtrate.

Add DMF (300 g), imidazole (8 g), and G-1B (10 g) to the N ₂ flowing three-necked flask, cool to 0 ° C., and add a little tert-Butyldimethylchlorosilane (manufactured by Tokyo Chemical Industry Co., Ltd., 18 g). It was added one by one and aged for 2 hours. Then, it was concentrated under reduced pressure. The concentrate, ethyl acetate (500 g) and 3% aqueous sodium hydrogen carbonate solution (300 g) were added to the separating funnel, and the mixture was stirred. The organic layer was concentrated and purified by silica gel chromatography to synthesize the desired compound (intermediate G-1C).

Mg (1 g), G-1C (10 g) and THF (100 g) were added to the N ₂ flowing three-necked flask, cooled to 0 ° C., and aged for 1 hour. Then, acetone (2 g) was added little by little, and aging was carried out for 2 hours. Then, it was concentrated under reduced pressure. The concentrate, ethyl acetate (500 g) and 3% aqueous sodium hydrogen carbonate solution (300 g) were added to the separating funnel, and the mixture was stirred. The organic layer was concentrated and purified by silica gel chromatography to synthesize the desired compound (intermediate G-1D).

G-1D (10 g) and cyclohexane (100 g) were added to the N ₂ flowing three-necked flask, cooled to 0 ° C., and a 20% butyllithium cyclohexane solution (manufactured by Tokyo Chemical Industry Co., Ltd., 12 mL) was added dropwise. Time aging was performed. Then, methacrylic acid chloride (3 g manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise and aged for 1 hour. Then, THF (100 g) and a 1M HCl aqueous solution were added, and aging was carried out for 5 hours. Then, ethyl acetate (1000 g) and a 3% aqueous sodium hydrogen carbonate solution (300 g) were added, and the mixture was stirred. The organic layer was concentrated and purified by silica gel chromatography to synthesize the desired compound (intermediate G-1E).

PGMEA (30 g) was added to the N ₂ flowing three-necked flask and heated to 60 ° C. 2-Hydroxyl Metyllate (manufactured by Tokyo Chemical Industry Co., Ltd., 13 g, 100 mmol), G-1E (26 g, 100.0 mmol) and photoradical polymerization initiator (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., V-65, 1) (0.0 g, 4.0 mmol) was dissolved in PGMEA (70 g), and the obtained mixture was added dropwise at a temperature at which the internal temperature of the flask did not exceed 65 ° C. over 2 hours, and further aged at 90 ° C. for 4 hours. rice field. 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. After that, 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 G-1F). )

PGMEA (45.38 g), intermediate G-1F (19.7 g, 100.0 mmol) and triethylamine (manufactured by Tokyo Chemical Industry Co., Ltd., 15 g, 150.0 mmol) were added to the N ₂ flowing three-necked flask, and 0 was added. Cooled to ° C. PGMEA (45.38 g) and Acryloyl Choride (14 g, 150.0 mmol) were mixed, dropped over 2 hours at a temperature at which the internal temperature of the flask did not exceed 10 ° C., and further aged at 20 ° C. for 4 hours. .. Then, it cooled to 0 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. After that, it was allowed to stand still for 1 hour and filtered under reduced pressure. The obtained powder was washed with water and dried under reduced pressure to synthesize the desired compound (G-1).
Other polymers were synthesized according to the above synthetic example.

<Preparation of underlayer film forming composition>
As shown in Tables 1 to 4 below, each component was mixed, and two-step filtration was performed using a polytetrafluoroethylene (PTFE) filter with a pore size of 0.1 μm and an UPE filter (ultra-high molecular weight polyethylene) with a pore size of 0.003 μm. , The underlayer film forming composition for imprint shown in Examples and Comparative Examples was prepared. Tables 1 to 4 also show the numbers of the curable compositions for imprint used in combination.

<Method of confirming desorbed components when baked at 80 ° C>
The underlayer film forming composition for imprint was spin-coated on a silicon wafer (diameter 8 inches). Then, it was heated at 80 ° C. for 3 minutes using a hot plate under baking conditions under an air atmosphere to form an underlayer film on the wafer. The thickness of the obtained underlayer film was about 10 nm. The obtained underlayer film was immersed in tetrahydrofuran (THF) for 30 minutes, and the obtained THF solution was analyzed using LC / MS.
In this way, it was confirmed whether or not the detection of the compound represented by the formula (r1) or (r2) or the formula (r1-1) and having a molecular weight of 210 or more was confirmed.
The compound surrounded by a dotted line under the polymer described later is a desorbed compound. No desorption of compounds having a molecular weight of 210 or more was observed for the polymers H-1 to H-3. With respect to the polymer H-3, desorption of the compound represented by the formula (r1) or (r2) or the compound represented by the formula (r1-1) was not observed.

<Preparation of curable composition for imprint>
Each of the compounds shown in Table 5 is mixed, and 4-hydroxy-2,2,6,6-tetramethylpiperidin-1-oxyl-free radical (manufactured by Tokyo Kasei) is used as a polymerization inhibitor. It was added so as to be 200% by mass (0.02% by mass) with respect to the total amount of the sex compounds, and a curable composition for imprint was obtained. This was filtered in two stages with a polytetrafluoroethylene (PTFE) filter having a pore size of 0.1 μm and a UPE (ultra high molecular weight polyethylene) filter having a pore size of 0.003 μm.

<Surface tension>
The surface tension was measured by using a surface tension meter SURFACETENSIOMETER CBVP-A3 manufactured by Kyowa Interface Science Co., Ltd. and using a glass plate at 23 ° C. The unit is mN / m. Two samples were prepared for each level, each was measured three times, and the arithmetic mean value of a total of six times was adopted as the evaluation value.

<Calculation of Hansen solubility parameter distance (ΔHSP)>
The Hansen solubility parameter was calculated with the HSP calculation software HSPiP.
By inputting the structural formula of each compound into the above software in SMILES format, each component (d component, p component, h component) of the Hansen solubility parameter was calculated. For the calculated Hansen solubility parameter, if necessary, the distance between the Hansen solubility parameters (ΔHSP: ΔD, ΔP, ΔH) was calculated.
ΔHSP = (4.0 × ΔD ² + ΔP ² + ΔH ² ) ^0.5 (H1)
For the Hansen solubility parameter, when there are a plurality of compounds in each calculation target component (for example, when there are two or more desorbed components), the value of the largest amount component (mass basis) among the corresponding compounds is adopted. When there are two or more kinds of the maximum amount of components, it is set as (average value by mixing ratio).
Tables 1 to 4 show the distance (ΔHSP) of the Hansen solubility parameter between the desorbed component calculated by the formula (H1) and the curable composition.

<Measurement method of molecular weight>
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 eluent used was THF (tetrahydrofuran). For the detection, a detector having a wavelength of 254 nm of UV rays (ultraviolet rays) was used.

<Adhesion>
The underlayer film forming composition for imprint was spin-coated on a silicon wafer (diameter 8 inches). Then, it was heated at 150 ° C. for 3 minutes using a hot plate under baking conditions under an air atmosphere to form an underlayer film on the wafer. The thickness of the obtained underlayer film was about 10 nm.
A curable composition for imprint whose temperature was adjusted to 23 ° C. was discharged onto the surface of the underlayer film using an inkjet printer DMP-2831 manufactured by Fujifilm Dimatics in a droplet amount of 1 pL per nozzle. The droplets were applied onto the underlayer film in a square arrangement at intervals of about 100 μm.
A quartz mold (rectangular line / space pattern (1/1), line width 40 nm, groove depth 100 nm, line edge roughness 3.5 nm) is placed on it so as to be in contact with the curable composition layer for imprinting, and a quartz wafer is placed. Exposure was performed from the side using a high-pressure mercury lamp under the condition of 300 mJ / cm ² . After the exposure, the quartz wafer was separated and the peeling force at that time was measured.
This peeling force corresponds to the adhesion force F (unit: N). The peeling force was measured according to the method for measuring the peeling force described in the comparative example described in paragraph Nos. 0102 to 0107 of JP-A-2011-206977. That is, the peeling steps 1 to 6 and 16 to 18 in FIG. 5 of the above publication were performed.
A: F ≧ 45N
B: 45N> F ≧ 30N
C: 30N> F ≧ 20N
D: 20N> F

<Evaluation of wettability>
The underlayer film forming composition for imprint was spin-coated on a silicon wafer (diameter 8 inches). Then, it was heated at 150 ° C. for 3 minutes using a hot plate under baking conditions under an air atmosphere to form an underlayer film on the adhesion layer. The thickness of the obtained underlayer film was about 10 nm.
A curable composition for imprint whose temperature was adjusted to 23 ° C. was discharged onto the surface of the underlayer film using an inkjet printer DMP-2831 manufactured by Fujifilm Dimatics Co., Ltd. with a droplet amount of 1 pL per nozzle. The droplets were applied onto the underlayer film in a square arrangement at intervals of about 100 μm.
The shape of the droplet 3 seconds after application was photographed, and the diameter of the droplet was measured. Two samples were used for each level, and each measurement was performed three times. The arithmetic mean value of 6 times in total was adopted as the evaluation value. The results are shown in Tables 1 to 4.
A: Average diameter of IJ droplets> 500 μm
B: 400 μm <Average diameter of IJ droplet ≤ 500 μm
C: 320 μm <Average diameter of IJ droplet ≤ 400 μm
D: Average diameter of IJ droplets ≤ 320 μm

破線は脱離後の脱離成分を記載している（以下同様である）
Molecular Weightは分子量を意味する。

polymer

The broken line describes the desorption component after desorption (the same applies hereinafter).
Molecular Weight means molecular weight.

Desorption reaction promoters or precursors thereof T-1, T-4, T-5, T-6 and T-7 are photoacid generators. T-2 is a thermal base generator. T-3 is a thermoacid generator.

Photopolymerization initiator

As is clear from the above results, the underlayer film forming composition for imprint of the present invention contains a polymer that desorbs a specific desorbing component, and when used in combination with a curable composition for imprint. , It was found to show excellent wettability and good adhesion (Examples 1 to 21). On the other hand, it was found that if the desorbed component does not desorb, or if the desorbed component does not have a specific chemical structure even if it is desorbed, the wettability or wettability is inferior (Comparative Examples 1 to 3).

A quartz mold having a width of 500 nm was brought into contact with the film of the curable composition for imprint produced in each example. Then, the film was cured by irradiating ultraviolet rays from the mold side. The mold was then pulled apart to obtain a cured product pattern to which the mold pattern was transferred. As a result, it was confirmed that a good pattern could be formed in any of the cured products.

1 Substrate 2 Underlayer film 3 Imprint curable composition 4 Mold 21 Underlayer film 22 Imprint curable composition 23 No film area

Claims (23)

An imprint underlayer film-forming composition containing a polymer and a solvent, and when the imprint underlayer film-forming composition is formed into a film and baked at 80 ° C., the following formula (r1) or (r2) is obtained from the polymer. ), And the compound having a molecular weight of 210 or more and 1000 or less is desorbed;

In the formula, R ^r1 , R ^r2 , R ^r4 , R ^r5 , and R ^r6 are independently represented by a hydrogen atom , an alkyl group, an alkenyl group, an aryl group, an arylalkyl group, or the following formula (RL-1). At least one of R ^r1 and R ^r2 is an alkyl group, an alkenyl group, an aryl group, an arylalkyl group, or a group represented by the following formula (RL-1), and R ^r4 , R ^r5 , and the like. And at least one of R ^r6 is an alkyl group, an alkenyl group, an aryl group, an arylalkyl group, or a group represented by the following formula (RL-1), and R ^r3 is CH ₂ , CHR ^r8 , or C ( R ^r9 ) ₂ , where R ^r8 and R ^r9 independently represent an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or an arylalkyl group, respectively, and the two R ^r9s may be the same or different from each other. ..

L ^R1 and L ^R2 are independently single bonds or linking groups, Ar ^R is a linking group containing an aromatic ring, and ^PR is a group having a polymerizable group. nr is an integer of 0 to 8, and mr is an integer of 1 to 4. The underlayer film forming composition for imprint according to claim 1, wherein the compound represented by the formula (r1) or (r2) is represented by the formula (r1-1);

In the formula, R ^r1 and R ^r2 are independently hydrogen atoms or monovalent substituents, and at least one of R ^r1 and R ^r2 is a substituent. The underlayer film forming composition for imprint according to claim 1 or 2, wherein the polymer contains a group represented by any of the following formulas (R-1) to (R-4);

In the formula, R ¹ to R ³ are independently monovalent substituents, R ⁴ to R ¹² are independently hydrogen atoms or monovalent substituents, and X is the bonding position of the polymer to the main chain. Represents. From the polymer containing a substituent represented by any of the formulas (R-1) to (R-4), the CO bond in the formula is decomposed and represented by the formula (r1) or (r2). The underlayer film forming composition for imprint according to claim 3, wherein the compound having a molecular weight of 210 or more is eliminated. The underlayer film forming composition for imprint according to any one of claims 1 to 4, wherein the polymer contains a polymerizable group. The underlayer film forming composition for imprint according to claim 5, wherein the polymerizable group contains a (meth) acryloyl group. The underlayer film forming composition for imprint according to any one of claims 1 to 6, wherein the polymer contains an aromatic ring. The underlayer film forming composition for imprint according to any one of claims 1 to 7, wherein the polymer contains at least one of the structural units represented by any of the following formulas (1) to (6). ;

In the formula, ^RP4 is a hydrogen atom or a methyl group; ^RP1 represents a group capable of desorbing the compound represented by the formula (r1) or (r2). The underlayer film forming composition for imprint according to any one of claims 1 to 8, wherein the compound represented by the formula (r1) or (r2) contains an aromatic ring. The underlayer film forming composition for imprint according to any one of claims 1 to 9, wherein the compound represented by the formula (r1) or (r2) contains a polymerizable group. The underlayer film forming composition for imprint according to claim 10, wherein the polymerizable group contains a (meth) acryloyl group. The invention according to any one of claims 1 to 11, wherein at least one of R ^r1 and R ^r2 of the formula (r1) and at least one of R ^r4 to R ^r6 of the formula (r2) contain a polymerizable group. Underlayer film forming composition for imprinting. The underlayer film forming composition for imprint according to any one of claims 1 to 12 , further comprising an elimination reaction accelerator or a precursor thereof. The underlayer film forming composition for imprint according to any one of claims 1 to 13 , further comprising a photopolymerization initiator. The underlayer film forming composition for imprint according to any one of claims 1 to 14 , wherein the surface tension of the compound represented by the formula (r1) or (r2) is 35 to 55 mN / m. The underlayer film forming composition for imprint according to any one of claims 1 to 15 , which contains a solvent in a proportion of 95.0% by mass or more. A kit comprising the underlayer film forming composition for imprint according to any one of claims 1 to 16 and a curable composition for imprint containing a polymerizable compound. The ΔHSP value calculated by the following formula (H1) based on the Hansen solubility parameter of the compound represented by the formula (r1) or (r2) and the Hansen solubility parameter of the curable composition for imprinting is 5 or less. , The kit according to claim 17 ;
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 curable composition for imprint and the dispersion term component of the Hansen solubility parameter vector of the compound represented by the formula (r1) or (r2). ΔP is the difference between the polar term component of the Hansen solubility parameter vector of the curable composition for imprint and the polar term component of the Hansen solubility parameter vector of the compound represented by the formula (r1) or (r2). Is the difference between the hydrogen bond term component of the Hansen solubility parameter vector of the curable composition for imprint and the hydrogen bond term component of the Hansen solubility parameter vector of the compound represented by the formula (r1) or (r2). A method for producing a laminate using the kit according to claim 17 or 18 , wherein the curable composition for imprinting is applied to the surface of the underlayer film formed from the underlayer film forming composition for imprinting. A method of manufacturing a laminate, including the process of making a laminate. The method for producing a laminate according to claim 19 , wherein the curable composition for imprint is applied to the surface of the underlayer film by an inkjet method. Further, the present invention comprises a step of applying the imprint underlayer film forming composition on a substrate in a layered manner, and comprising heating the imprinting underlayer film forming composition applied in the layered form at 80 to 250 ° C. Item 19. The method for producing a laminate according to Item 19 . A method for producing a cured product pattern using the kit according to claim 17 or 18 , wherein a lower layer film forming composition for imprinting is applied onto a substrate to form a lower layer film. An application step of applying the curable composition for imprint to the surface of the underlayer film, and a mold contact step of contacting the curable composition for imprint with a mold having a pattern for transferring the pattern shape. A method for producing a cured product pattern, which comprises a light irradiation step of irradiating the curable composition for imprint with light to form a cured product, and a mold release step of separating the cured product from the mold. A method for manufacturing a circuit board, which comprises a step of obtaining a cured product pattern by the manufacturing method according to claim 22 .

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